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1 DR

2 2

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4 5AluVer 3 6 TIMER ENTER 4

5 5

6 1.5 / PH N PH a) 50 / Aluminum Voluette Ampule b) c) / d) / 3 AL / 0.4 / TenSette0.850/Voluette Ampule / 0.013/ / 6

7 300 mg/lcaco mg/lcaco 3 a) 3 b) 5.0 N c) 5.25 N 1000 mg/l CaCO 3 a) 3 b) 5.25N 20 mg/l 50 mg/l 7

8 (100 Tests) : (1) , (1) , (1) AluVer /pkg /pkg Bleaching /pkg ml, w/ cap /pkg OPTIONAL REAGENTS Aluminum Standard Solution, 100 mg/l ml Aluminum Standard Solution, Voluette ampule, 50 mg/l as Al, 10 ml... 16/pkg Hydrochloric Acid Solution, 6N (1:1) ml m-nitrophenol Indicator Solution, 10 g/l ml Nitric Acid, ACS ml Nitric Acid Solution, 1: ml Sodium Hydroxide Standard Solution, 5.0 N ml MDB Sodium Hydroxide Standard Solution, 5.0 N ml SCDB Sulfuric Acid Standard Solution, 5.25 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker Kit... each Brush... each Flask, volumetric, Class A, 100 ml... each Flask, volumetric, Class A, 250 ml... each Fluoride Combination Electrode... each Fluoride Analysis Package... each ph Indicator Paper, 1 to 11 ph... 5 rolls/pkg ph/ise Meter, sension 2, portable... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Pipet, Volumetric, Class A, 1.00 ml... each Thermometer, -10 to 110 C... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 8

9 8079 9

10 10

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12 /pkg UV ml, w/cap /pkg :, 115 V, 60 Hz , 230 V, 50 Hz OPTIONAL REAGENTS Benzotriazole Standard Solution, 500 mg/l ml Rochelle Salt Solution...29 ml* DB Sulfuric Acid Standard Solution, 1.00 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Flask, volumetric, Class A, 1000 ml...each Lamp, UV (lamp only)...each ph Paper, 1 to 11 ph...5 rolls/pkg ph Meter, sension 1, portable...each Pipet Filler, safety bulb...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet Tips, for TenSette Pipet /pkg Pipet, volumetric, 10.0 ml, Class A...each Stopwatch...each Thermometer, mercury-filled, -20 to 110 C...each Timer, interval, 1 second to 99 hours...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 12

13 0 to 1.60 mg/l as B H Boron 13

14 14

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16 1.0/ 0.04/ 40.03/ 16

17 (mg/l) ( 3+ ) Isothiazolin-type 120 Quat-type CaCO ( CaCO 3 ) ( 7+ ) 5 (Mo 6+ ) 60, AMP 20,, HEDP 20 Polyacrylates 20 (as Acumer 1000, 1100) Polymaleic Acid 40 (as Belcene 200) Tolyltriazole 20 ( 2+ ) 10 >500 mg/l (+ -) 11.0NpH (+) ()(+) 17

18 (Fe 3+ or Fe 2+ ), 8 mg/l (+),(+) (+) 18

19 BoroTrace : (1) , (1) , (1) , (1) BoroTrace /pkg BoroTrace /pkg , 1 M ml SCDB , ml ml , for opening powder pillows ,, 50-mL, w/cap , ml, w/cap /pkg OPTIONAL REAGENTS Boron Standard Solution, 250 mg/l as B, 10-mL Voluette Ampule...16/pkg Boron Standard Solution, 1000 mg/l as B ml Dechlorinating Reagent Powder Pillows...100/pkg Eluant Solution... 1 L Phosphate Buffer Solution, ph L Sodium Hydroxide Standard Solution, 5.0 N...50 ml DB Sulfamic Acid g Sulfuric Acid Standard Solution, N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker Kit (for 10-mL ampules)...eacu Filter Holder Assembly...each Flask, volumetric, polypropylene, 100 ml, w/cap...each Flask, volumetric, polypropylene, 1000 ml, w/cap...each Membrane Filters, 3-micron...25/pkg ph Paper, ph each Pipet, Mohr-type, polypropylene, 5 ml...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...each Spoon, measuring, 0.1 g...each Syringe, 30-cc...each Thermometer, -10 to 110 C...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 19

20 Br2 Br2 20

21 21

22 0.1( mg / L 2.25 mg / L) 10.1( 0.2( mg / L 2.25 mg / L) 25.2( 22

23 Pollution Prevention and Waste Management Samples treated with sodium arsenite for manganese or chromium interference will be hazardous wastes as regulated by Federal RCRA for arsenic (D004). See Section 3 for more information on proper disposal of these materials. 23

24 () DPD /pkg () DPD AccuVac /pkg (), mL, w/ cap... 6/pkg (), 50 ml each OPTIONAL REAGENTS Chlorine Standard Solution, PourRite ampule, mg/l, 2 ml... 20/pkg Potassium Iodide Solution, 30 g/l ml* MDB Sodium Arsenite, 5 g/l ml* MDB Sodium Hydroxide Standard Solution, N ml* MDB Sulfuric Acid Standard Solution, 1 N ml* MDB Water, deionized... 4 L OPTIONAL APPARATUS AccuVac Snapper Kit... each PourRite Ampule Breaker... each Cylinder, graduated, 25 ml... each ph Meter, sension 1, portable... each ph Indicator Paper, 1 to 11 ph units... 5 rolls/pkg Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. * Contact Hach for larger sizes 24

25

26 26

27 PH 27

28 DPD 11/ 1 a b(50-75 /) c a1 5%1 2# ) DPD 5 6 )

29 (EDL) 29

30 30

31 () DPD/ (100 tests) : DPD llows, 10 ml /pkg ml (AccuVac ) DPD/AccuVac (25 tests) : DPD AccuVac /pkg ml OPTIONAL REAGENTS Chlorine Standard Solution, Voluette ampule, mg/l, 10 ml... 16/pkg DPD Free Chlorine Reagent w/dispensing cap tests Potassium Iodide Solution, 30 g/l ml* MDB Sodium Arsenite, 5 g/l ml* MDB Sodium Hydroxide Standard Solution, N ml* MDB Sulfuric Acid Standard Solution, N ml* MDB Water, deionized... 4 L Water, sterile, chlorine dioxide-free ml OPTIONAL APPARATUS AccuVac Snapper Kit... each Cylinder, graduated, 25 ml... each ph Meter, sension 1, portable... each ph Paper, 1 to 11 ph units... 5 rolls/pkg Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg PourRite Ampule Breaker... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. * Marked Dropper Bottle - contact Hach for larger sizes. 31

32 8345 ENTER 32

33 25.0/ 0.3/ 77.3/, ml, w/ cap /pkg ml... 4 L For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 33

34 0.00 mg/l Cl2 34

35 PH 5 10 a) LR Chlorine PourRite Ampule b) TenSette0.110 c) d) / 35

36 0.1( mg / L mg / L) 10.1( e) d f) 2.40/ 0.06/ 80.03/2/ 8021 Federal RCRA for arsenic (D004) (Mn4+, Mn7+) (Cr6+) 1 1. ph to (30 g/l)10-ml (5 g/l)

37 (NH2Cl) ph NH2ClHR Free Cl2 (1 mg/l Cl2): C ( F) NH2Cl 5 (41) 10 (50) 20 (68) 30 (86) 1.2 mg/l mg/l mg/l mg/l ph6-7 DPD /pkg ml... 4 L , ml, w/ caps /pkg OPTIONAL REAGENTS Chlorine Standard Solution, PourRite ampule, mg/l, 2 ml...20/pkg Potassium Iodide Solution, 30 g/l ml* MDB Sodium Arsenite, 5 g/l ml* MDB Sodium Hydroxide Standard Solution, N ml* MDB Sulfuric Acid Standard Solution, N ml* MDB OPTIONAL APPARATUS Cylinder, graduated, mixing, 25 ml...each ph Meter, sension 1, portable...each ph Paper, 1 to 11 ph units...5 rolls/pkg Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg PourRite Ampule Breaker...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. * Marked Dropper Bottle (contact Hach for larger sizes) 37

38 0.00 mg/l Cl2 38

39 PH 5 10 a) LR Chlorine PourRite Ampule b) TenSette0.110 c) d) / 0.1( mg / L mg / L) 10.1( 39

40 e) d f) 2.40/ 0.06/ 80.03/2/ 8167 Federal RCRA for arsenic (D004) (Mn4+, Mn7+) (Cr6+) ph 1 1. ph to (30 g/l)10-ml (5 g/l) ph6-7 40

41 DPD /pkg ml...500ml , ml, w/ caps /pkg OPTIONAL REAGENTS Description Unit Cat. No. Chlorine Standard Solution, PourRite ampule, mg/l, 2 ml...20/pkg Potassium Iodide Solution, 30 g/l ml* MDB Sodium Arsenite, 5 g/l ml* MDB Sodium Hydroxide Standard Solution, N ml* MDB Sulfuric Acid Standard Solution, N ml* MDB OPTIONAL APPARATUS Cylinder, graduated, mixing, 25 ml...each ph Meter, sension 1, portable...each ph Paper, 1 to 11 ph units...5 rolls/pkg Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg PourRite Ampule Breaker...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 41

42 ( mg/l) :

43 PH 5 10 a) LR Chlorine PourRite Ampule b) TenSette0.1 c) d) READ e) / 0.1( mg / L mg / L) 10.1( f) d e g) a) LR Chlorine PourRite Ampule b) 25 c) 0.2( ) d) DPD e) f) / 0.2( mg / L mg / L) 25.2( 43

44 g) f h) 1.00/ 0.01/ 1.00/ 0.01/ / Federal RCRA for arsenic (D004) DPD 44

45 () DPD, 10 ml /pkg l, 10, 20, 25 ml, w/ cap /pkg () DPD AccuVac /pkg , 50 ml each OPTIONAL REAGENTS Description Unit Cat. No. Chlorine Standard Solution, PourRite ampule, mg/l, 2 ml... 20/pkg DPD Free Chlorine Reagent w/dispensing cap tests Potassium Iodide Solution, 30 g/l ml* MDB Sodium Arsenite, 5 g/l ml* MDB Sodium Hydroxide Standard Solution, N ml* MDB Sulfuric Acid Standard Solution, N ml* MDB Water, deionized... 4 L OPTIONAL APPARATUS AccuVac Snapper Kit... each Cylinder, graduated, 25 ml... each ph Meter, sension 1, portable... each ph Paper, 1 to 11 ph units... 5 rolls/pkg Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg

46 PourRite Ampule Breaker... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 46

47 :

48 PH 5 10 a) LR Chlorine PourRite Ampule b) TenSette0.1 c) d) READ e) / 0.1( mg / L mg / L) 10.1( f) d e g) a) LR Chlorine PourRite Ampule b) 25 c) 0.2( ) d) DPD e) f) / 48

49 0.2( mg / L mg / L) 25.2( g) f h) 1.00/ 0.01/ 1.00/ 0.01/ / Federal RCRA for arsenic (D004) 49

50 () DPD, 10 ml /pkg l, 10, 20, 25 ml, w/ cap /pkg () DPD AccuVac /pkg , 50 ml each OPTIONAL REAGENTS Description Unit Cat. No. Chlorine Standard Solution, PourRite ampule, mg/l Cl /pkg DPD Total Chlorine Reagent w/dispensing cap tests Potassium Iodide Solution, 30 g/l ml* MDB Sodium Arsenite, 5 g/l ml* MDB Sodium Hydroxide Standard Solution, 1 N ml* MDB Sulfuric Acid Standard Solution, 1 N ml* MDB Water, deionized... 4 L OPTIONAL APPARATUS AccuVac Snapper Kit... each PourRite Ampule Breaker... each Cylinder, graduated, 25 ml... each ph Indicator Paper, 1 to 11 ph units... 5 rolls/pkg ph Meter, sension 1, portable... each

51 Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 51

52 Test N Tube TM 52

53 PH 5 10 a) LR Chlorine PourRite Ampule b) TenSette0.1 c) 8 d) / 0.1( mg / L mg / L) 10.1( e) d e f) 53

54 2.53/ 0.14/ / Federal RCRA for arsenic (D004) 54

55 Test N Tube DPD /pkg Test N Tube...1 l... 6/pkg COD/TNT each OPTIONAL REAGENTS Chlorine Standard Solution, PourRite ampule, mg/l, 2 ml... 20/pkg Potassium Iodide Solution, 30 g/l ml* MDB Sodium Arsenite, 5 g/l ml* MDB Sodium Hydroxide Standard Solution, N ml* MDB Sulfuric Acid Standard Solution, N ml* MDB OPTIONAL APPARATUS Beaker, 50 ml... each ph Meter, sension 1, portable... each ph Paper, ph 1 to 11 ph... 5 rolls/pkg Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg PourRite Ampule Breaker... each Test Tube Rack... each

56 Test N Tube TM 56

57 PH 5 10 a) LR Chlorine PourRite Ampule b) TenSette0.1 c) 8 d) / 0.1( mg / L mg / L) 10.1( e) d e f) 57

58 2.53/ 0.14/ / Federal RCRA for arsenic (D004) 58

59 Test N Tube DPD /pkg Test N Tube /pkg COD/TNT OPTIONAL REAGENTS Chlorine Standard Solution, 2-mL PourRite ampule, mg/l... 20/pkg Potassium Iodide Solution, 30 g/l ml* MDB Sodium Arsenite Solution, 5 g/l ml* MDB Sodium Hydroxide Standard Solution, 1.00 N ml* MDB Sulfuric Acid Standard Solution, N ml* MDB OPTIONAL APPARATUS Beaker, 50 ml... each PourRite Ampule Breaker... each ph Indicator Paper, ph 1 to rolls/pkg ph Meter, sension 1, portable... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Test Tube Rack... each

60 60

61 () a) PourRite 5/ b) TenSette c) / d) a) Voluette12.5/ b) TenSette c) / d) 1050/ / 0.6/ 0.008/ 61

62 0.6/ 0.005/ / 62

63 ChromaVer /pkg , ml, w/ cap /pkg AccuVac ChromaVer 3 AccuVac /pkg , 50 ml each OPTIONAL REAGENTS Description Unit Cat. No Acid Reagent Powder Pillows /pkg Chromium, Hexavalent, Standard Solution, 50 mg/l Cr ml Chromium, Hexavalent, Standard Solution, Voluette Ampule, 12.5 mg/l Cr6+, 10 ml... 16/pkg Chromium, Hexavalent, Standard Solution, PourRite Ampule, 5 mg/l Cr6+, 2 ml... 20/pkg Water, deionized... 4 L OPTIONAL APPARATUS Description Unit Cat. No. AccuVac Snapper Kit... each Ampule Breaker Kit... each Flask, volumetric, Class A, 1000 ml... each ph Paper, 1 to 11 ph units... 5 rolls/pkg ph Meter, EC10, portable... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Pipet, volumetric, 5.00 ml, Class A... each Pipet Filler, safety bulb... each PourRite Ampule Breaker, 2 ml... each In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 63

64 64

65 65

66 c) TenSette d) / 150/ / 0.5/ 0.4/ 0.004/ / 1 ph 2 66

67 (100 Tests) : (1) , (1) , (1) , (1) /pkg ChromaVer /pkg Chromium /pkg Chromium /pkg , 4", 120 V , 4", 240 V , ml, w/ cap /pkg OPTIONAL REAGENTS Chromium, trivalent, Standard Solution, 50 mg/l Cr ml Chromium, trivalent, Standard Solution, PourRite ampule, 12.5 mg/l Cr3+, 2 ml...20/pkg Nitric Acid, ACS ml Nitric Acid Solution 1: ml Sodium Hydroxide Standard Solution 5.0 N ml* DB Water, deionized... 4 L OPTIONAL APPARATUS Cylinder, graduated, polypropylene, 25 ml...each Finger Cots...2/pkg ph Paper, 1 to 11 ph units...5 rolls/pkg ph Meter, EC10, portable...each Pipet, serological, 2 ml...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips for TenSette Pipet...50/pkg Pipet, volumetric, Class A, 1.00 ml...each Pipet Filler, safety bulb...each PourRite Ampule Breaker...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 67

68

69 250Pt-Co Pt-Co 1925Pt-Co 69

70 ml... 4 L each , 47 mm, 300 ml each , 47 mm, /pkg , 500 ml each , ml, w/cap /pkg , No. 7, one hole /pkg OPTIONAL REAGENTS Color Standard Solution, 500 platinum-cobalt units... 1 L OPTIONAL APPARATUS Cylinder, graduated, 50-mL, glass...each Flask, volumetric, Class A, 100 ml...each Pipet, volumetric, Class A, 50 ml...each Thermometer, -10 to 110 C...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 70

71 (0 to 5.00 mg/l) :

72 72

73 Sampling and Storage Collect samples in acid-cleaned glass or plastic containers. Adjust the ph to 2 or less with nitric acid (about 2 ml per liter). Store preserved samples up to six months at room temperature. Before analysis, adjust the ph to 4 to 6 with 8 N potassium hydroxide. Do not exceed ph 6, as copper may precipitate. Correct the test result for volume additions; see Correction for Volume Additions in Section 1 for more information. If only dissolved copper is to be determined, filter the sample before acid addition using the labware listed under Optional Apparatus. Accuracy Check Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a Copper Voluette Ampule Standard, 75 mg/l as Cu. c) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of standard, respectively, to the mixing cylinders. Stopper and mix thoroughly. d) For analysis with AccuVac Ampuls, transfer the solutions to dry, clean 50-mL beakers to fill the ampules. For analysis with powder pillows, transfer only 10 ml of the solution to 10-mL sample cells. e) Analyze each sample as described in the procedure. The copper concentration should increase about 0.3 mg/l for each 0.1 ml of standard added. f) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method Prepare a 1.00 mg/l copper standard by pipetting 1.00 ml of Copper Standard Solution, 100 mg/l as Cu, into 100-mL volumetric flask. Dilute to volume with deionized water and mix well. Prepare this solution daily. Using this solution as the sample, perform the copper procedure as described above. Method Performance Precision In a single laboratory, using a standard solution of 2.25 mg/l Cu and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of ±0.02 mg/l Cu. In a single laboratory, using a standard solution of 2.25 mg/l Cu and two representative lots of AccuVac Ampuls with the instrument, a single operator obtained a standard deviation of ±0.02 mg/l Cu. 73

74 () CuVer /pkg , ml, w/cap /pkg () CuVer 2 AccuVac /pkg , 50 ml each OPTIONAL REAGENTS Copper Standard Solution, 100 mg/l ml Copper Standard Solution, Voluette Ampule, 75 mg/l Cu, 10 ml...16/pkg CuVer 2 Reagent Powder Pillows...100/pkg Formaldehyde, 37%, ACS ml* MDB Free Copper Reagent Powder Pillows...100/pkg Hydrochloric Acid Solution, 6.0 N ml Hydrosulfite Reagent Powder Pillows...100/pkg Nitric Acid, ACS ml Nitric Acid Solution, 1: ml Potassium Chloride Solution, saturated...50 ml SCDB Potassium Hydroxide Standard Solution, 8.0 N ml* MDB Sodium Hydroxide Standard Solution, 5.0 N ml* MDB Water, deionized... 4 L OPTIONAL APPARATUS Description Unit Cat. No. AccuVac Snapper Kit...each Ampule Breaker Kit...each Cylinder, graduated, mixing, 25 ml...each Cylinder, graduated, polypropylene, 25 ml...each Cylinder, graduated, 100 ml...each Filter Paper, folded, 12.5 cm...100/pkg Filter Pump...each Flask, volumetric, 100 ml...each Funnel, polypropylene, 65 mm...each Hot Plate, 4" diameter, 120 V...each Hot Plate, 4" diameter, 240 V...each ph Indicator Paper, 1 to 11 ph...5 rolls/pkg ph Meter, EC10, portable...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet, volumetric, Class A, 1.00 ml...each Pipet Filler, safety bulb...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 74

75 μ μg/l, CuZERO 75

76 0.0 μg/l Cu μ 60 mg/l 10 mg/l mg/l 90,000 mg/l Cr mg/l 100 mg/l mg/l Fe2+ 6 mg/l 3mg/L mg/l 140 mg/l 3 mg/l 11mg/L 60mg/L mg/l mg/l 9mg/L EDTA PH 76

77 Sampling and Storage Collect samples in acid-washed plastic bottles. To preserve, adjust the ph to 2 or less with nitric acid (about 5 ml per liter). Store preserved samples up to six months at room temperature. Before testing, adjust the ph of the sample to between 2 and 6. If the sample is too acidic, adjust the ph with 5.0 N Sodium Hydroxide Standard Solution. Correct test results for volume additions; see Correction for Volume Additions in Section 1 for more information. Accuracy Check Standard Additions Method a) Fill six (3 pairs) 25-mL graduated mixing cylinders with 25 ml of sample. Properly mark each pair of cylinders as sample and blank. b) Using a TenSette Pipet, add 0.1 ml of Copper Standard Solution, 10.0 mg/l Cu, to two of the cylinders. Add 0.2 ml of standard to two more of the cylinders. Add 0.3 ml of standard to the other two cylinders, making a total of six samples (2 for each volume of standard). c) Analyze the samples as described above. The copper concentration reading should increase by 40 μg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method To assure the accuracy of the test, prepare a 100 μg/l copper standard: a) Pipet 1.00 ml of Copper Standard Solution, 10.0 mg/l Cu, into a 100-mL volumetric flask. b) Dilute to volume with copper-free, reagent-grade water. c) Use this standard in place of the sample in the procedure. The reading should be 100 μg/l Cu. d) Prepare this solution daily. Method Performance Precision In a single laboratory, using a standard solution of 100 μg/l copper and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 3.4 μg/l copper. Estimated Detection Limit The estimated detection limit for program 22 is 5.4 μg/l Cu. For more information on the estimated detection limit, see Section 1. Summary of Method The porphyrin method is very sensitive to trace amounts of free copper. Due to the sensitivity of the method, a masking agent is used to prepare a blank for each sample. The method is free from most interferences and does not require any sample extraction or preconcentration. Interferences from other metals are eliminated by the copper 77

78 masking reagent. The porphyrin indicator forms an intense, yellow-colored complex proportional to any free copper present in the sample. Total copper may be determined if a digestion is performed prior to analysis., 10-mL (100 tests) : (1) , (2) , (2) , (1) /pkg /pkg /pkg l, ml, w/ caps /pkg OPTIONAL REAGENTS Copper Standard Solution, 10 mg/l Cu ml MDB Hydrochloric Acid Solution, 1:1 (6 N) ml Nitric Acid, ACS ml Nitric Acid Solution, 1: ml Sodium Hydroxide Standard Solution, 5 N... 1 L Water, deionized... 4 L OPTIONAL APPARATUS Beaker, 100 ml...each Cylinder, mixing, graduated, 25 ml...each Flask, volumetric, Class A, 100 ml...each Hot Plate, 7 x 7 inches, 120 V...each Hot Plate, 7 x 7 inches, 240 V...each ph Paper, 1 to 11 ph units...5 rolls/pkg ph Meter, sension 1, portable...each Pipet, Mohr, 5 ml...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for /pkg Pipet, volumetric, 1.0 ml, Class A...each Pipet Filler, safety bulb...each Watch Glass, Pyrex, 100 ml...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 78

79 - 79

80 80

81 CyaniVer a)2.5n 25mL ph 7 9 b) c) d) 25mLa e) c 4 a)2.5n 25mL ph 7 9 b) c) d) 25mLa e)c f) 4 1mg/L4 CyaniVer 3 HexaVer20 mg/l 5 mg/l14 Sampling and Storage Collect samples in glass or plastic bottles and analyze as soon as possible. The presence of oxidizing agents, sulfides and fatty acids can cause cyanide loss during sample storage. Samples containing these substances must be pretreated as described in the following procedures before preservation with sodium hydroxide. If the sample contains sulfide and is not pretreated, it must be analyzed within 24 hours. Preserve the sample by adding 4.0 ml of 5.0 N Sodium Hydroxide Standard Solution to each liter (or quart) of sample, using a glass serological pipet and pipet filler. Check the sample ph. Four ml of sodium hydroxide are usually enough to raise the ph of most water and wastewater samples to 12. Add more 5.0 N sodium hydroxide if necessary. Store the samples at 4 C (39 F) or less. Samples preserved in this manner can be stored for 14 days. 81

82 Before testing, samples preserved with 5.0 N sodium hydroxide or samples that are highly alkaline due to chlorination treatment processes or distillation procedures should be adjusted to approximately ph 7 with 2.5 N Hydrochloric Acid Standard Solution. If significant amounts of preservative are used, correct for the volume added; see Correction for Volume Additions in Section 1 for more information. Oxidizing Agents Oxidizing agents such as chlorine decompose cyanides during storage. To test for their presence and eliminate their effect, pretreat the sample as follows: a) Take a 25-mL portion of the sample and add one drop of m-nitrophenol Indicator Solution, 10 g/l. Swirl to mix. b) Add 2.5 N Hydrochloric Acid Standard Solution drop-wise until the color changes from yellow to colorless. Swirl the sample thoroughly after the addition of each drop. c) Add two drops of Potassium Iodide Solution, 30 g/l, and two drops of Starch Indicator Solution, to the sample. Swirl to mix. The solution will turn blue if oxidizing agents are present. d) If Step c suggests the presence of oxidizing agents, add two level 1-g measuring spoonfuls of ascorbic acid per liter of sample. e) Withdraw a 25-mL portion of sample treated with ascorbic acid and repeat Steps a to c. If the sample turns blue, repeat Steps d and e. f) If the 25-mL sample remains colorless, adjust the remaining sample to ph 12 for storage with 5 N Sodium Hydroxide Standard Solution (usually 4 ml/l). g) Perform the procedure given under Interferences, Reducing Agents, to eliminate the effect of excess ascorbic acid, before following the cyanide procedure. Sulfides Sulfides quickly convert cyanide to thiocyanate (SCN). To test for the presence of sulfide and eliminate its effect, pretreat the sample as follows: a) Place a drop of sample on a disc of hydrogen sulfide test paper that has been wetted with ph 4 Buffer Solution. b) If the test paper darkens, add a 1-g measuring spoon of lead acetate to the sample. Repeat Step a. c) If the test paper continues to turn dark, keep adding lead acetate until the sample tests negative for sulfide. d) Filter the black lead sulfide precipitate using the apparatus listed under Optional Apparatus. Preserve the sample for storage with 5 N Sodium Hydroxide Standard Solution or neutralize to a ph of 7 for analysis. Fatty Acids Caution perform this operation in a hood as quickly as possible. When distilled, fatty acids will pass over with cyanide and form soaps under the alkaline conditions of the absorber. If the presence of fatty acid is suspected, do not preserve samples with sodium hydroxide until the following pretreatment is performed. The effect of fatty acids can be minimized as follows: a) Acidify 500 ml of sample to ph 6 or 7 with Acetic Acid Solution. 82

83 b) Pour the sample into a 1000-mL separatory funnel and add 50 ml of hexane. c) Stopper the funnel and shake for one minute. Allow the layers to separate. d) Drain off the sample (lower) layer into a 600-mL beaker. If the sample is to be stored, add 5 N Sodium Hydroxide Standard Solution to raise the ph to above 12. Accuracy Check Standard Solution Method Caution Cyanides and their solutions, and the hydrogen cyanide liberated by acids, are very poisonous. Both the solutions and the gas can be absorbed through the skin. Prepare a 100 mg/l cyanide stock solution weekly by dissolving grams of sodium cyanide in deionized water and diluting to 1000 ml. Immediately before use, prepare a 0.10 mg/l cyanide working solution by diluting 1.00 ml of the 100 mg/l stock solution to 1000 ml using deionized water. Use this prepared standard in place of sample in Step 3. Results should be 0.10 mg/l CN-. Method Performance Precision In a single laboratory, using a standard solution of 0.19 mg/l CN- and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of ±0.017 mg/l CN-. Estimated Detection Limit (EDL) The estimated detection limit for program 23 is mg/l CN. For more information on the estimated detection limit, see Section 1. Acid Distillation For USEPA reporting purposes, samples must be distilled. All samples should be treated by acid distillation except when experience has shown that there is no difference in results obtained with or without distillation. With most compounds, a one-hour reflux is adequate. If thiocyanate is present in the original sample, a distillation step is absolutely necessary as thiocyanate causes a positive interference. High concentrations of thiocyanate can yield a substantial quantity of sulfide in the distillate. The rotten egg smell of hydrogen sulfide will accompany the distillate when sulfide is present. The sulfide must be removed from the distillate prior to testing. If cyanide is not present, the amount of thiocyanate can be determined. The sample is not distilled and the final reading is multiplied by 2.2. The result is mg/l thiocyanate. The distillate can be tested and treated for sulfide after the last step of the distillation procedure by using the following lead acetate treatment procedure. 83

84 a) Place a drop of the distillate (already diluted to 250 ml) on a disc of hydrogen sulfide test paper that has been wetted with ph 4.0 Buffer Solution. b) If the test paper darkens, add 2.5 N Hydrochloric Acid Standard Solution drop-wise to the distillate until a neutral ph is obtained. c) Add a 1-g measuring spoon of lead acetate to the distillate and mix. Repeat Step a. d) If the test paper continues to turn dark, keep adding lead acetate until the distillate tests negative for sulfide. e) Filter the black lead sulfide precipitate through filter paper and funnel. This sample should now be neutralized to ph 7 and analyzed for cyanide without delay. Distillation Procedures A detailed procedure for the distillation of cyanide samples is included with the Hach Distillation Apparatus. Three detailed procedures, Free Cyanides, Cyanides Amenable to Chlorination, and Total Cyanides, are included with the four- and ten-position Midi-Dist Distillation System. See the Optional Apparatus listing. Summary of Method The pyridine-pyrazolone method gives an intense blue color with free cyanide. A sample distillation is required to determine cyanide from transition and heavy metal cyanide complexes. (100 Tests), 10 ml : (1) , (1) , (1) CyaniVer /pkg CyaniVer /pkg CyaniVer /pkg , , w/cap /pkg OPTIONAL REAGENTS Description Unit Cat. No. Acetic Acid Solution, 10% ml Ascorbic Acid g Bromine Water ml Buffer Solution, ph ml Hexanes, ACS... 4 L HexaVer Chelating Reagent Powder Pillows...100/pkg Hydrochloric Acid Standard Solution, 2.5 N ml MDB Lead Acetate, trihydrate, ACS g

85 Magnesium Chloride Solution... 1 L m-nitrophenol Indicator ml MDB Potassium Iodide Solution, 30 g/l ml MDB Sodium Arsenite Solution, APHA ml MDB Sodium Cyanide, ACS...28 g Sodium Hydroxide Standard Solution, 0.25 N... 1 L Sodium Hydroxide Standard Solution, 5.0 N... 1 L Starch Indicator Solution ml MDB Sulfuric Acid Standard Solution, 19.2 N ml Water, deionized... 4 L OPTIONAL APPARATUS Description Unit Cat. No. Beaker, glass, 600 ml...each Bottle, wash, 500 ml...each Cylinder, graduated, 50 ml...each Cylinder, graduated, 250 ml...each Distillation Apparatus, cyanide accessories...each Distillation Apparatus, general purpose accessories...each OPTIONAL APPARATUS, continued Description Unit Cat. No. Distillation Apparatus Heater and Support Apparatus, 115 Vac, 60 Hz... each Distillation Apparatus Heater and Support Apparatus, 230 Vac, 50 Hz... each Dropper, plastic... each Filter Paper, folded, 12.5 cm /pkg Flask, volumetric, Class A, 1000 ml... each Flask, volumetric, Class A, 250 ml... each Funnel, poly, 65 mm... each Funnel, separatory, 500 ml... each Hydrogen Sulfide Test Papers /pkg Midi-Dist Distillation System, 4-position... each Midi-Dist Distillation System, 10-position... each ph Meter, sension 1, portable... each Pipet, volumetric, Class A, 1.00 ml... each Pipet Filler, safety bulb... each Scoop, double ended... each Spoon, measuring, 1.0 g... each Support Ring, 4 inch... each Support Stand... each Thermometer, -10 to 110 C... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 85

86

87 Sampling and Storage Collect samples in clean plastic or glass bottles. Samples must be analyzed within 24 hours. Accuracy Check Standard Solution Method a) Dissolve gram of cyanuric acid in 1000 ml of deionized water to make a 1000 mg/l solution. It takes several hours for the cyanuric acid to dissolve. This solution is stable for several weeks. b) Dilute 2.00 ml of the 1000 mg/l solution to 100 ml with deionized water to make a 20 mg/l solution. Prepare fresh daily. c) Testing the 20 mg/l solution should give test results of about 20 mg/l cyanuric acid. Method Performance Precision In a single laboratory, using a standard solution of 25.0 mg/l cyanuric acid and two lots of reagent with the instrument, a single operator obtained a standard deviation of ±1.2 mg/l cyanuric acid. 87

88 Estimated Detection Limit The estimated detection limit for program 24 is 7.0 mg/l cyanuric acid. For more information on the estimated detection limit, see Section 1. Summary of Method The test for cyanuric acid uses the turbidimetric method. Cyanuric Acid 2 Reagent precipitates any cyanuric acid present and holds it in suspension. The amount of turbidity caused by the suspended particles is directly proportional to the amount of cyanuric acid present. Due to the nature of the precipitation reaction, low levels of cyanuric acid (less than 7 mg/l) are not detected by this method /pkg , ml, w/cap /pkg OPTIONAL REAGENTS Cyanuric Acid...25 g Water, deionized... 4 L OPTIONAL APPARATUS Balance, Analytical, 115 V, Scientech, Model SA each Balance, Analytical, 230 V, Scientech, Model SA each Filter Paper, folded 12.5 cm...100/pkg Flask, volumetric, Class A, 100 ml...each Flask, volumetric, Class A, 1000 ml...each Funnel, poly, 65 mm...each Pipet, volumetric, Class A, 2.00 ml...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 88

89 μ8140 μ 89

90 μ μ Sampling and Storage Most oxygen scavengers will react quickly with atmospheric oxygen. Collect samples in acid-rinsed plastic or glass containers, allowing the sample to overflow. Cap the container so there is no head space above the sample. Rinse each sample cell several times with sample, then carefully fill to the fill mark. Analyze the sample immediately. Other Oxygen Scavengers To determine other oxygen scavengers, perform the test as directed above, then multiply the DEHA result by the appropriate factor below: 90

91 Method Performance Precision In a single laboratory, using a standard solution of 242 μg/l DEHA and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of ±6.2 μg/l DEHA. Estimated Detection Limit The estimated detection limit for program 25 is 9 μg/l DEHA. For more information on the estimated detection limit, see Section 1. Summary of Method Diethylhydroxylamine (DEHA) or other oxygen scavengers present in the sample react with ferric iron in DEHA Reagent 2 Solution to produce ferrous iron in an amount equivalent to the DEHA concentration. This solution then reacts with DEHA 1 Reagent, which forms a purple color with ferrous iron. The color is proportional to the concentration of oxygen scavenger in the sample. Using this procedure other oxygen scavengers can be determined by multiplying the DEHA results by the appropriate multiplier. (100 tests) : (2) , (1) /pkg ml ml ml... 4 L ,, 0.5 and 1.0-mL /pkg , ml, w/ cap /pkg OPTIONAL REAGENTS Hydrochloric Acid, 1:1 (6 N) ml OPTIONAL APPARATUS Bottle, wash, 250-mL... each Cylinder, graduated, polypropylene, 25 ml... each ph Paper, 1 to 11 ph units... 5 rolls/pkg Thermometer, -10 to 110 C... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 91

92 8029 SPADNS Method μ 92

93 93

94 Sampling and Storage Collect samples in plastic bottles. Samples may be stored up to 28 days. Accuracy Check Standard Solution Method A variety of standard solutions covering the entire range of the test are available from Hach. Use these in place of sample to verify technique. Minor variations between lots of reagent become measurable above 1.5 mg/l. While results in this region are usable for most purposes, better accuracy may be obtained by diluting a fresh sample 1:1 with deionized water and retesting. Multiply the result by 2. Standard Adjust To adjust the calibration curve using the reading obtained with a 1.80-mg/L Standard Solution, press SETUP and use the arrow keys to scroll to the STD setup option. Press ENTER to activate the option. Then enter 1.80 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Standard Curve Adjustment in Section 1 for more information. Method Performance Precision In a single laboratory, using standard solutions of 1.00 mg/l fluoride and two lots of SPADNS Reagent with the instrument, a single operator obtained standard deviations of ±0.035 mg/l fluoride. In a single laboratory, using standard solutions of 1.00 mg/l fluoride and two lots of SPADNS AccuVac Reagent with the instrument, a single operator obtained standard deviations of ±0.040 mg/l fluoride. Estimated Detection Limit (EDL) The EDL for programs 27 and 28 is 0.05 mg/l F-. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Summary of Method The SPADNS Method for fluoride determination involves the reaction of fluoride with a red zirconium-dye solution. The fluoride combines with part of the zirconium to form 94

95 a colorless complex, thus bleaching the red color in an amount proportional to the fluoride concentration. Seawater and wastewater samples require distillation. See Optional Apparatus for Distillation Apparatus listing. Pollution Prevention and Waste Management SPADNS Reagent contains sodium arsenite. Final solutions will contain sodium arsenite (D004) in sufficient concentration to be regulated as hazardous waste for Federal RCRA. See Section 3 for more information on disposal of these materials. () SPADNS... 4 ml ml ml... 4 L () , Class A, ml , Class A, 2.00 ml , ml w/ cap /pkg , -10 to 110 C ( ACCUVAC ) SPADNS /pkg L ( ACCUVAC ), 50 ml OPTIONAL REAGENTS Fluoride Standard Solution, 0.2 mg/l F ml Fluoride Standard Solution, 0.4 mg/l F ml Fluoride Standard Solution, 0.5 mg/l F ml Fluoride Standard Solution, 0.6 mg/l F ml Fluoride Standard Solution, 0.8 mg/l F ml Fluoride Standard Solution, 1.0 mg/l F ml Fluoride Standard Solution, 1.0 mg/l F ml Fluoride Standard Solution, 1.2 mg/l F ml Fluoride Standard Solution, 1.4 mg/l F ml Fluoride Standard Solution, 1.5 mg/l F ml Fluoride Standard Solution, 1.6 mg/l F ml Fluoride Standard Solution, 1.8 mg/l F ml Fluoride Standard Solution, 2.0 mg/l F ml Silver Sulfate, ACS g Sodium Arsenite Solution ml MDB StillVer Distillation Solution ml

96 OPTIONAL APPARATUS AccuVac Snapper Kit... each Cylinder, graduated, 100 ml... each Cylinder, graduated, 250 ml... each Distillation Heater and Support Apparatus Set, 115 V, 50/60 Hz... each Distillation Heater and Support Apparatus Set, 230 V, 50/60 Hz... each Distillation Apparatus General Purpose Accessories... each ph Meter, sension 1, portable... each Pipet, TenSette, 1.0 to 10.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Stopper... 6/pkg For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 96

97 ; CLG 97

98 mg/l CaCO3 (3+) 0.25 mg/l (2+) 0.75 mg/l EDTA, 0.2 mg/l CaCO3 EDTA EGTA (2+) 1.4 mg/l (3+) 2.0 mg/l (2+) 0.20 mg/l (2+) mg/l 98

99 Sampling and Storage Collect samples in acid-washed plastic bottles. Adjust the sample ph to 2 or less with nitric acid (about 5 ml per liter). Preserved samples can be stored up to six months. Adjust the sample ph to between 3 and 8 with 5.0 N Sodium Hydroxide Standard Solution just before analysis. Correct the test results for volume additions; see Correction for Volume Additions in Section 1 for more information. Accuracy Check Using a 2.00 mg/l (as CaCO3) standard solution as sample, perform the hardness procedure described above. The results should be 2.00 mg/l calcium (as CaCO3). Method Performance Precision In a single laboratory using a standard solution of 2.00 mg/l Mg as CaCO3 and 1.88 mg/l Ca as CaCO3 with the instrument, a single operator obtained a standard deviation of ± 0.09 mg/l Mg as CaCO3 and ± 0.08 mg/l Ca as CaCO3. Estimated Detection Limit The estimated detection limit for program 30 is 0.13 mg/l magnesium hardness and 0.08 mg/l calcium hardness. For more information on the estimated detection limit, see Section 1. Summary of Method The colorimetric method for measuring hardness supplements the conventional titrimetric method because it can measure very low levels of calcium and magnesium. Also some interfering metals (those listed above) in the titrimetric method are inconsequential in the colorimetric method when diluting the sample to bring it within the range of this test. The indicator dye, calmagite, forms a purplish-blue color in a strongly alkaline solution and changes to red when it reacts with free calcium or magnesium. Calcium is chelated with EGTA to destroy any red color due to calcium and then the sample is chelated with EDTA to destroy the red color due to both calcium and magnesium. Measuring the red color in the different stages of chelation gives results as the calcium and magnesium hardness concentrations. 99

100 (100 Tests) : (1) , (1) , (1) , (1) ml ml MDB ml ml MDB EDTA, 1 M ml EGTA ml , 100-mL , 0.5 and 1.0 ml /pkg , ml, w/cap /pkg OPTIONAL REAGENTS Calcium Standard Solution, 2.0 mg/l as CaCO ml Nitric Acid, ACS ml Nitric Acid Solution, 1: ml Sodium Hydroxide Standard Solution 5.0 N ml MDB OPTIONAL APPARATUS ph Meter, sension 1, portable...each Thermometer, -10 to 110 C...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 100

101 μ8141 p- (N2H4) HydraVer 2 0 μg/l N2H4 101

102 μg/l mL 3 10 mg/l20mg/l 10 mg/l Sampling and Storage Collect samples in glass or plastic containers. Fill the containers completely and cap them tightly. Avoid excessive agitation or exposure to air. Samples must be analyzed immediately after collection and cannot be preserved for later analysis. Accuracy Check Standard Solution Method To assure the accuracy of the test, prepare the following solutions: a) Prepare a 25 mg/l hydrazine stock solution by dissolving g of hydrazine sulfate in 1000 ml of oxygen-free deionized water. Use Class A glassware. Prepare this stock solution daily. b) Prepare a 100 μg/l hydrazine working solution by diluting 4.00 ml of the 25 mg/l stock solution to 1000 ml with deionized oxygen-free water. Prepare just before analysis. c) Use the working solution in place of the sample in Step 4. The result should be 100 μg/l hydrazine. Method Performance Precision In a single laboratory using a standard solution of 250 μg/l hydrazine (N2H4) and two representative lots of reagent with the instrument, a single operator obtained a standard 102

103 deviation of ±9 μg/l hydrazine. In a single laboratory using a standard solution of 250 μg/l hydrazine (N2H4) and two lots of AccuVac Ampuls with the instrument, a single operator obtained a standard deviation of ±3 μg/l hydrazine. Estimated Detection Limit The estimated detection limit for program 31 is 16 μg/l N2H4, and the estimated detection limit for program 32 is 10 μg/l N2H4. For more information on the estimated detection limit, see Section 1. Summary of Method Hydrazine reacts with the p-dimethylaminobenzaldehyde from the HydraVer 2 Reagent to form a yellow color which is proportional to the hydrazine concentration. () HydraVer ml ml* MDB ml... 4 L () 25 ml , 20- and 25 ml, w/ caps /pkg ( AccuVac) AccuVac /pkg ml... 4 L ( AccuVac), 50 L OPTIONAL REAGENTS Hydrazine Sulfate, ACS g OPTIONAL APPARATUS AccuVac Snapper Kit...each Balance, AccuLab PocketPro, portable...each Cylinder, graduated, mixing, 25 ml...each Flask, volumetric, 100 ml, Class A...each Flask, volumetric, 1000 ml, Class A...each Pipet, serological, 1 ml...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet, volumetric, Class A, 1.00 ml...each Pipet, volumetric, Class A, 4.00 ml...each Pipet Filler, safety bulb...each Thermometer, -10 to 110 C...each Weighing Boat, 67/46 mm, 8.9 cm sq /pkg For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 103

104 0 mg/l Fe 104

105 Sampling and Storage Ferrous iron must be analyzed immediately and cannot be stored. Analyze samples as soon as possible to prevent oxidation of ferrous iron to ferric iron, which is not measured. Accuracy Check Standard Solution Method Prepare a ferrous iron stock solution (100 mg/l Fe2+) by dissolving grams of ferrous ammonium sulfate, hexahydrate, in deionized water. Dilute to 1 liter. Prepare immediately before use. Dilute 1.00 ml of this solution to 100 ml with deionized water to make a 1.00 mg/l standard solution. Prepare immediately before use. Run the test using the 1.00 mg/l Fe2+ Standard Solution by following either the powder pillow or AccuVac procedure. Results should be between 0.90 mg/l and 1.10 mg/l Fe2+. Method Performance Precision In a single laboratory using an iron standard solution of 2.00 mg/l Fe2+ and two representative lots of powder pillow reagents with the instrument, a single operator obtained a standard deviation of ±0.017 mg/l Fe2+. In a single laboratory using a standard solution of 2.00 mg/l Fe2+ and two representative lots of AccuVac ampuls with the instrument, a single operator obtained a standard deviation of ±0.009 mg/l Fe2+. Estimated Detection Limit The estimated detection limit for program 33 (powder pillows and AccuVac Ampuls) is 0.03 mg/l Fe. For more information on the estimated detection limit, see Section

106 Summary of Method The 1,10-phenanthroline indicator in Ferrous Iron Reagent reacts with ferrous iron in the sample to form an orange color in proportion to the iron concentration. Ferric iron does not react. The ferric iron (Fe3+) concentration can be determined by subtracting the ferrous iron concentration from the results of a total iron test. () /pkg , ml, w/ cap /pkg ( ACCUVAC ) AccuVac /pkg , 50 ml OPTIONAL REAGENTS Ferrous Ammonium Sulfate, hexahydrate, ACS g Water, deionized... 4 L OPTIONAL APPARATUS AccuVac Snapper Kit...each Balance, analytical, 115 V...each Balance, analytical, 230 V...each Clippers, for opening powder pillows...each Flask, volumetric, 100 ml, Class A...each Flask, volumetric, 1000 ml, Class A...each Pipet, volumetric, Class A, 1.00 ml...each Pipet Filler, safety bulb...each Weighing Boat, 67/46 mm, 8.9 cm square...500/pkg For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 106

107 107

108 108

109 Sampling and Storage Collect samples in acid-cleaned glass or plastic containers. No acid addition is necessary if analyzing the sample immediately. To preserve samples, adjust the ph to 2 or less with nitric acid (about 2 ml per liter). Preserved samples may be stored up to six months at room temperature. Adjust the ph to between 3 and 5 with 5.0 N Sodium Hydroxide Standard Solution before analysis. Correct the test result for volume additions; see Correcting for Volume Additions in Section 1 for more information. If only dissolved iron is to be determined, filter the sample before adding the acid. Accuracy Check Standard Additions Method a) Snap the neck off a 50 mg/l Iron PourRite Ampule Standard Solution. b) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of standard, respectively, to three 25-mL samples and mix thoroughly. c) For analysis using AccuVac Ampuls, transfer solutions to dry, clean 50-mL beakers to facilitate filling of the ampuls. For analysis with powder pillows, transfer only 10 ml of solution to the 10-mL sample cells. d) Analyze each standard addition sample as described above. The iron concentration should increase 0.2 mg/l for each 0.1 ml of standard added. e) If these increases do not occur, see Standard Additions in Section 1 for troubleshooting information. Standard Solution Method Prepare a 1.0-mg/L iron standard by diluting 1.00 ml of Iron Standard Solution, 100 mg/l Fe, to 100 ml with deionized water. Or, dilute 1.00 ml of an Iron PourRite Ampule Standard Solution (50 mg/l) to 50 ml in a volumetric flask. Prepare this solution daily. Run the test following the procedure for powder pillows or AccuVac Ampuls. Results should be between 0.90 mg/l and 1.10 mg/l Fe. Method Performance Precision In a single laboratory, using a standard solution of 2.00 mg/l Fe and two representative lots of powder pillow reagents with the instrument, a single operator obtained a standard deviation of ±0.017 mg/l. In a single laboratory, using a standard solution of 2.00 mg/l Fe and two representative lots of AccuVac ampuls with the instrument, a single operator obtained a standard eviation of ±0.009 mg/l Fe. Estimated Detection Limit (EDL) The EDL for program 33 is 0.03 mg/l Fe. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Summary of Method FerroVer Iron Reagent reacts with all soluble iron and most insoluble forms of iron in the sample to produce soluble ferrous iron. This reacts with 1,10-phenanthroline indicator in the reagent to form an orange color in proportion to the iron concentration. 109

110 () FerroVer /pkg , ml, with screw cap /pkg REQUIRED REAGENTS & APPARATUS (Using AccuVac Ampuls) FerroVer AccuVac /pkg , 50 ml OPTIONAL REAGENTS Description Unit Cat. No. Ammonium Hydroxide, ACS ml Hydrochloric Acid Standard Solution, 6 N ml Hydrochloric Acid, ACS ml Iron Standard Solution, 100 mg/l ml Iron PourRite Ampule Standard, 50 mg/l... 20/pkg Nitric Acid, ACS ml Nitric Acid Solution, 1: ml RoVer Rust Remover g Sodium Hydroxide Standard Solution, 5.0 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS AccuVac Snapper Kit... each Ampule Breaker, PourRite Ampules... each Clippers, Shears 71/4 "... each Cylinder, graduated, poly, 25 ml... each Cylinder, graduated, poly, 100 ml... each Digesdahl Digestion Apparatus, 115 V... each Digesdahl Digestion Apparatus, 230 V... each Filter Discs, glass, 47 mm /pkg Filter Holder, membrane... each Filter Pump... each Flask, Erlenmeyer, 250 ml... each Flask, filtering, 500 ml... each OPTIONAL APPARATUS (continued) Description Unit Cat. No. Flask, volumetric, Class A, 50 ml...each Flask, volumetric, Class A, 100 ml...each Hot Plate, 4" diameter, 120 VAC...each Hot Plate, 4" diameter, 240 VAC...each ph Meter, sension 1, portable...each ph Indicator Paper, 1 to 11 ph...each Pipet Filler, safety bulb...each Pipet, serological, 2 ml...each Pipet, serological, 5 ml...each

111 Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet, volumetric, Class A, 1.00 ml...each Spoon, measuring, 0.1 g...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 111

112 0 mg/l Fe 112

113 (EDTA) g/l FerroVer TPTZTPTZ 4FerroZine 24 C (75 F)5 25mL2 1) 25-mL25 ml 2) 125-mL 3) FerroZine 4) 5) ) 25-mL 7) 25mL 8) 9) 92 4FerroZine 24 C (75 F)5 25mL2 113

114 Sampling and Storage Collect samples in acid-washed glass or plastic bottles. To preserve samples, adjust the sample ph to 2 or less with nitric acid (about 2 ml per liter). Samples preserved in this manner can be stored up to six months at room temperature. If only dissolved iron is to be reported, filter sample immediately after collection and before the addition of nitric acid. Before testing, adjust the sample ph to 3 5 with ammonium hydroxide, ACS. Do not exceed ph 5 as iron may precipitate. Correct test results for volume additions; see Correction for Volume Additions in Section 1 for more detailed information. Accuracy Check Standard Additions Method a) Snap the neck off an Iron Voluette Ampule Standard, 25 mg/l Fe. b) Use the TenSette Pipet to add 0.1 ml of standard to the prepared sample measured in Step 10. c) Swirl to mix and allow another five-minute reaction period, then measure the iron concentration as in Step 10. d) Add two additional 0.1-mL standard increments, taking a concentration reading after allowing the five-minute reaction period for each increment. e) Each 0.1 ml of standard added should cause a 0.1 mg/l increase in the concentration reading. f) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method Prepare a 0.4 mg/l iron working solution as follows: a) Pipet 1.00 ml of Iron Standard Solution, 100 mg/l Fe, into a 250-mL volumetric flask. b) Dilute to volume with deionized water. This solution should be prepared daily. Analyze the working solution according to the above procedure. Method Performance Precision In a single laboratory, using a standard solution of 0.80 mg/l iron and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of ±0.004 mg/l iron. Estimated Detection Limit The estimated detection limit for program 37 is mg/l Fe. For more information on the estimated detection limit, see Section 1. Summary of Method The FerroZine Iron Reagent forms a purple colored complex with trace amounts of iron in samples that are buffered to a ph of 3.5. This method is applicable for determining trace levels of iron in chemical reagents and glycols and can be used to analyze samples containing magnetite (black iron oxide) or ferrites after treatment as described in Interferences. 114

115 () FerroZine /pkg , , w/cap /pkg OPTIONAL REAGENTS Ammonium Hydroxide, ACS ml Hydrochloric Acid Solution, 1:1 (6N) ml FerroZine Iron Reagent Solution ml Iron Standard Solution, 100 mg/l Fe ml Iron Standard Solution, Voluette Ampule, 25 mg/l Fe, 10 ml...16/pkg Nitric Acid, ACS ml Nitric Acid Solution, 1: ml Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker Kit...each Clippers, shears, 7¼-inch...each Cylinder, graduated, 25 ml...each Dropper, calibrated, 0.5-mL & 1.0-mL mark...6/pkg Flask, erlenmeyer, 125 ml...each Flask, volumetric, 250 ml, Class A...each Hot plate, 3 ½" diameter, 120 V...each Hot plate, 3 ½" diameter, 240 V...each ph Indicator Paper, 1 to 11 ph...5 rolls/pkg Pipet, serological, 2 ml...each ph Meter, EC10, portable...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet, volumetric, 1.00 ml, Class A...each Thermometer, -10 to 110 C...each Water Bath, with sample cell rack...each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 115

116 116

117 0.00 mg/l Fe ph34 1.0N 1.0NpH35 Sampling and Storage Collect samples in acid-cleaned plastic or glass bottles. If prompt analysis is impossible, preserve the sample by adjusting to ph 2 or less with hydrochloric acid (about 2 ml per liter). Preserved samples may be stored up to six months at room temperature. If reporting only dissolved iron, filter the sample immediately after collection and before adding the acid. Before analysis, adjust the sample ph to between 3 and 4 with 5.0 N Sodium Hydroxide Standard Solution. Do not exceed ph 5 as iron may precipitate. Correct the test result for volume; see Correction for Volume Additions in Section 1. Accuracy Check Standard Additions Method a) Snap the top off an Iron PourRite Ampule Standard Solution, 25 mg/l Fe. b) Use the TenSette Pipet to add 0.2, 0.4 and 0.6 ml of standard to three 50-mL samples. Swirl gently to mix. c) Analyze each sample as described above. The iron concentration should increase by 0.1 mg/l for each 0.2 ml of standard added. d) If these increases do not occur, see Standard Additions in Section 1 for more Information. 117

118 Standard Solution Method Prepare a 0.4 mg/l iron working solution as follows: a) Pipet 1.00 ml of Iron Standard Solution, 100 mg/l Fe, into a 250-mL volumetric flask. b) Dilute to volume with deionized water. Prepare this solution daily. Analyze this working solution according to the above procedure. Results should be between 0.36 and 0.44 mg/l Fe. Method Performance Precision In a single laboratory, using a standard solution of 1.00 mg/l Fe and two representative lots of reagents with the instrument, a single operator obtained a standard deviation of À0.006 mg/l Fe. Estimated Detection Limit The estimated detection limit for program 38 is 0.03 mg/l Fe. For more information on the estimated detection limit, see Section 1. Summary of Method FerroMo Iron Reagent 1 contains a reducing agent combined with a masking agent. The masking agent eliminates interference from high levels of molybdate. The reducing agent converts precipitated or suspended iron (rust) to the ferrous state. FerroMo Iron Reagent 2 contains the indicator combined with a buffering agent. The indicator reacts with the ferrous iron in the sample, buffered between ph 3-4, resulting in a deep blue-purple color. FerroMo (100 tests) : (4) , (2) FerroMo /pkg FerroMo /pkg , 50 ml , ml, w/cap /pkg OPTIONAL REAGENTS Hydrochloric Acid Solution, 6.0 N (1:1) ml Hydrochloric Acid, ACS ml Iron Standard Solution, 100 mg/l Fe ml Iron Standard Solution, PourRite Ampule, 118

119 25 mg/l Fe, 2 ml... 20/pkg Sodium Hydroxide Standard Solution, 1.0 N ml MDB Sodium Hydroxide Standard Solution, 5.0 N ml MDB Sulfuric Acid Standard Solution, 1.0 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker Kit... each Flask, volumetric, Class A, 250 ml... each ph Indicator Paper, 1 to 11 ph... 5 rolls/pkg ph Meter, Sension.1, portable... each Pipet Filler, safety bulb... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for Pipet... 50/pkg Pipet, volumetric, Class A, 1.00 ml... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 119

120 TPTZ 0.00 mg/l Fe 120

121 121

122 Sampling and Storage Collect samples in acid-washed glass or plastic bottles. Adjust the sample ph to 2 or less with nitric acid (about 2 ml per liter). Store samples preserved in this manner up to six months at room temperature. If reporting only dissolved iron, filter sample immediately after collection and before addition of nitric acid. Before testing, adjust the ph of the stored sample to between 3 and 4 with 5.0 N Sodium Hydroxide Standard Solution. Do not exceed ph 5 as iron may precipitate. Correct the test result for volume additions; see Correction for Volume Additions in Section 1. Accuracy Check Standard Additions Method (Powder Pillows) a) Snap the neck off a PourRite Iron Ampule Standard, 25 mg/l Fe. b) Use the TenSette Pipet to add 0.1 ml of standard to the prepared sample measured in Step 10. Swirl to mix. c) Measure the iron concentration as in Step 10. The measurement does not require the three-minute waiting period. d) Add two additional 0.1-mL aliquots of standard, measuring the concentration after each addition. The iron concentration should increase by 0.25 mg/l for each 0.1-mL addition of standard. e) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Additions Method (AccuVac Ampuls) a) Use a graduated cylinder to measure 25.0 ml of sample into each of three 50-mL beakers. b) Snap the neck off an Iron Ampule Standard, 25 mg/l Fe. c) Using a TenSette Pipet, add 0.1, 0.2 and 0.3 ml of standard, respectively, to the 50-mL beakers. Swirl to mix. d) Fill a TPTZ AccuVac Ampul from each beaker. e) Measure the concentration of each ampul according to the procedure. The iron concentration should increase by 0.1 mg/l for each 0.1 ml addition of standard. f) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method Prepare a 0.4 mg/l iron working solution as follows: a) Using Class A glassware, pipet 1.00 ml of Iron Standard Solution, 100 mg/l Fe, into a 250-mL volumetric flask. b) Dilute to volume with deionized water. Stopper and invert repeatedly to mix. Prepare this solution daily. 122

123 Method Performance Precision In a single laboratory using a standard solution of 1.00 mg/l Fe and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of À0.017 mg/l Fe. In a single laboratory using a standard solution of 1.00 mg/l Fe and one representative lot of AccuVac Ampuls with the instrument, a single operator obtained a standard deviation of À0.022 mg/l Fe. Estimated Detection Limit The estimated detection limit for program 39 is 0.04 mg/l Fe. For more information on the estimated detection limit, see Section 1. Summary of Method The TPTZ Iron Reagent forms a deep blue-purple color with ferrous iron. The indicator is combined with a reducing agent which converts precipitated or suspended iron, such as rust, to the ferrous state. The amount of ferric iron present can be determined as the difference between the results of a ferrous iron test and the concentration of total iron. () TPTZ /pkg , ml, w/cap /pkg ( ACCUVAC ) TPTZ AccuVac /pkg , 50 ml , ml, w/cap /pkg OPTIONAL REAGENTS Hydrochloric Acid Solution, 1:1, 6.0 N ml Iron Standard Solution, 100 mg/l Fe ml Iron Standard Solution, PourRite Ampule, 25 mg/l Fe, 2 ml... 20/pkg Nitric Acid, ACS ml Nitric Acid Solution, 1: ml RoVer Rust Remover g Sodium Hydroxide Standard Solution, 1.0 N ml MDB Sodium Hydroxide Standard Solution, 5.0 N ml MDB Sulfuric Acid Standard Solution ml MDB Water, deionized... 4 L

124 mg/l Mn 124

125 g/l Sampling and Storage Collect samples in acid-washed plastic bottles. Manganese may be lost by adsorption to glass container walls. Adjust the ph to less than 2 with nitric acid (about 2 ml per liter). Preserved samples may be stored up to six months at room temperature. Adjust the ph to 4 to 5 with 5.0 N sodium hydroxide before analysis. Do not exceed ph 5, as manganese may be lost as a precipitate. Correct the test result for volume additions; see Correction for Volume Additions in Section 1 for more information. If only dissolved Mn is to be determined, filter before acid addition. Accuracy Check Standard Additions Method a) Snap the neck off a Manganese Voluette Ampule Standard Solution, 250 mg/l Mn. b) Use the TenSette Pipet to add 0.1, 0.2 and 0.3 ml of standard, respectively, to the three 25-mL water samples. Swirl to mix. 125

126 c) Transfer only 10 ml of each solution to the 10-mL sample cells. d) Analyze each standard addition sample as described in the procedure. The manganese concentration should increase 1.0 mg/l for each 0.1 ml of standard added. e) If these increases do not occur, see Standard Additions in Section 1 for troubleshooting information. Standard Solution Method Prepare a 5.0 mg/l manganese standard solution by pipetting (use a TenSette or Class A volumetric pipet) 5.00 ml of Manganese Standard Solution, 1000 mg/l Mn, into a 1000-mL volumetric flask. Dilute to the mark with deionized water. Or, prepare this standard by diluting 1.00 ml of a High Range Manganese Standard Voluette Ampule, 250 mg/l, to 50 ml. Prepare these solutions daily. Use these solutions as the sample in the procedure. Method Performance Precision In a single laboratory, using a standard solution of mg/l Mn and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 0.18 mg/l Mn. Estimated Detection Limit The estimated detection limit for program 41 is 0.12 mg/l Mn. For more information on the estimated detection limit, see Section 1. Summary of Method Manganese in the sample is oxidized to the purple permanganate state by sodium periodate, after buffering the sample with citrate. The purple color is directly proportional to the manganese concentration. (100 tests) 10 ml : (1) , (1) () /pkg /pkg , ml, w/cap /pkg

127 OPTIONAL REAGENTS Hydrochloric Acid, 6 N ml Manganese Standard Solution, 1000 mg/l Mn ml Manganese Standard Solution, Voluette ampule, High Range, 250 mg/l Mn, 10 ml... 16/pkg Nitric Acid, ACS ml Nitric Acid Solution 1: ml Sodium Hydroxide Solution, 5.0 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker Kit... each Flask, Erlenmeyer, 250 ml... each Flask, volumetric, Class A, 50 ml... each Flask, volumetric, Class A, 100 ml... each Flask, volumetric, Class A, 1000 ml... each ph Indicator Paper, 1 to 11 ph... 5 rolls/pkg ph Meter, sension.1, portable... each Pipet, serological, 5 ml... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet, TenSette, 1.0 to 10.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Pipet Tips, for TenSette Pipet... 50/pkg Pipet, volumetric, Class A, 5.00 ml... each Pipet, volumetric, Class A, 1.00 ml... each Pipet Filler, safety bulb... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 127

128

129 0 mg/l Mn g/l Sampling and Storage Collect samples in a clean glass or plastic container. Adjust the ph to 2 or less with nitric acid (about 2 ml per liter). Preserved samples can be stored up to six months at room temperature. Adjust the ph to with 5.0 N sodium hydroxide before analysis. Correct the test result for volume additions; see Correction for Volume Additions in Section

130 Accuracy Check Standard Additions Method Note: Volume accuracy is very important when performing standard additions with 10-mL volumes. The fill mark on the 10-mL sample cell is not intended to measure standard addition volumes. a) Fill three 10-mL graduated mixing cylinders with 10.0 ml of sample. b) Snap the neck off a Manganese Voluette Ampule Standard, 10 mg/l Mn. c) Use the TenSette Pipet to add 0.1 ml, 0.2 ml and 0.3 ml of standard, respectively, to the three mixing cylinders. Stopper and mix each thoroughly. d) Analyze each sample as described in the procedure. The manganese concentration should increase 0.1 mg/l for each 0.1 ml of standard added. e) If these increases do not occur, see Standard Additions in Section 1 for more information. Note: An alternative to the above procedure is to pipet 10.0 ml of sample into dry sample cells before performing standard additions. A volumetric pipet or a TenSette Pipet can be used to deliver the sample volume. Standard Solution Method Prepare a 0.5 mg/l manganese standard solution as follows: a) Pipet 5.00 ml of Manganese Standard Solution, 1000 mg/l Mn, into a 1000-mL volumetric flask. b) Dilute to the mark with deionized water. Prepare this solution daily. c) Pipet ml of the solution from Step b into a 100-mL volumetric flask. d) Dilute to the mark with deionized water. This second dilution is equivalent to 0.5 mg/l Mn. Method Performance Precision In a single laboratory using a standard solution of 0.5 mg/l Mn and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of À0.013 mg/l Mn. Estimated Detection Limit The estimated detection limit for program 43 is mg/l Mn. For more information on the estimated detection limit, see Section 1. Waste Management The alkaline cyanide solution contains cyanide. Cyanide solutions should be collected for disposal as reactive (D003) waste. Store all cyanide solutions in a caustic solution with ph >11 to prevent release of hydrogen cyanide gas. In case of a spill, clean up the area as outlined below: 1. Use a fume hood or self-contained breathing apparatus. 2. While stirring, add the waste to a beaker containing a strong solution of sodium hydroxide and calcium hypochlorite or sodium hypochlorite (household bleach). 3. Maintain a strong excess of hydroxide and hypochlorite. Let the solution stand for 24 hours. 4. Flush the solution down the drain with a large excess of water. 130

131 Summary of Method The PAN method is a highly sensitive and rapid procedure for detecting low levels of manganese. An ascorbic acid reagent is used initially to reduce all oxidized forms of manganese to Mn2+. An alkaline-cyanide reagent is added to mask any potential interferences. PAN Indicator is then added to combine with the Mn2+ to form an orange-colored complex. (100 tests) 10 ml : (2) , (2) , (2) , (1) ml SCDB /pkg PAN 0.1% ml SCDB ml... 4 L REQUIRED APPARATUS 25 ml ml, w/cap /pkg OPTIONAL REAGENTS Hydrochloric Acid Solution, 1:1 (6 N) ml Manganese Standard Solution, 1000 mg/l Mn ml Manganese Standard Sol n, PourRite Ampule, 20 mg/l Mn, 2 ml...20/pkg Nitric Acid Solution, 1: ml Rochelle Salt Solution...29 ml DB Sodium Hydroxide Solution, 50% ml Nitric Acid, ACS ml OPTIONAL APPARATUS Ampule Breaker, PourRite Ampule...each Beaker, glass, 1000 ml...each Cylinder, graduated, mixing, 10 ml...each Dropper, plastic, calibrated, 1.0 ml...20/pkg Flask, volumetric, Class A, 1000 ml...each Flask, volumetric, Class A, 100 ml...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet, volumetric, Class A, 10.0 ml...each Pipet, volumetric, Class A, 5.0 ml...each Pipet Filler, safety bulb...each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 131

132

133 0 mg/l Mo6 g/l Sampling and Storage Collect samples in clean plastic bottles. Adjust the ph to 2 or less with nitric acid (about 2 ml per liter). Preserved samples can be stored up to 6 months at room temperature. Adjust the ph to 7 with 5.0 N sodium hydroxide before analysis. Correct the test result for volume additions; see Volume Additions (Section 1) for more information. Accuracy Check Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a Molybdenum Voluette Ampule Standard Solution, 500 mg/l Mo

134 c) Use the TenSette Pipet to add 0.1, 0.2 and 0.3 ml of standard, respectively, to the three mixing cylinders. Stopper each and mix thoroughly. d) For analysis with AccuVac Ampuls, transfer solutions to dry, clean 50-mL beakers. For analysis with powder pillows, transfer only 10 ml of solution to the sample cells. e) Analyze each standard addition sample as described in the procedure. The molybdenum concentration reading should increase 2.0 mg/l for each 0.1 ml of standard added. f) If these increases do not occur, see Standard Additions in Section 1 for troubleshooting information. Standard Solution Method To assure the accuracy of the test, use a Molybdenum Standard Solution, 10.0 mg/l Mo6+. Follow the procedure for powder pillows or AccuVac Ampuls. Results should be between 9.0 and 11.0 mg/l Mo6+. Standard Adjust To adjust the calibration curve using the reading obtained with the 10.0-mg/L standard solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 10.0 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Section 1, Standard Curve Adjustment for more information. Method Performance Precision In a single laboratory using a standard solution of 20.0 mg/l Mo6+ and two representative lots of powder pillows with the instrument, a single operator obtained a standard deviation of À0.3 mg/l Mo6+. In a single laboratory using a standard solution of 20.0 mg/l Mo6+ and two representative lots of AccuVac Ampuls with the instrument, a single operator obtained a standard deviation of À0.1 mg/l Mo6+. Estimated Detection Limit The estimated detection limit for program 44 is 0.2 mg/l Mo6+. For more information on the estimated detection limit, see Section 1. Summary of Method Powder Pillows MolyVer 1 and 2 Reagents are added to buffer and condition the sample. MolyVer 1 contains a buffer to control the ph in addition to a chelating agent to mask interferences. MolyVer 3 provides the mercaptoacetic acid, which reacts with molybdate molybdenum to form a yellow color proportional to the molybdenum concentration. AccuVac Ampuls The CDTA Solution masks metal interferences. The MolyVer 6 reagent provides the mercaptoacetic acid, which reacts with molybdate molybdenum to form a yellow color proportional to the molybdenum concentration. 134

135 (), 10 ml (100 tests) : (1) , (1) , (1) , (1) MolyVer /pkg MolyVer /pkg MolyVer /pkg ( ACCUVAC ) MolyVer 6AccuVac (25 tests) : (1) , (1) CDTA 0.4M ml SCDB MolyVer 6 AccuVac /pkg () , ml, w/cap /pkg ( ACCUVAC ), 50 ml ml, w/cap /pkg OPTIONAL REAGENTS Molybdenum Standard Solution, 10 mg/l Mo ml Molybdenum Standard Solution, Voluette Ampule, 500 mg/l Mo6+, 10 ml... 16/pkg Nitric Acid, ACS ml Sodium Hydroxide Standard Solution, 5.0 N ml MDB Sulfamic Acid Powder Pillows /pkg Water, deionized... 4 L OPTIONAL APPARATUS AccuVac Snapper Kit... each Ampule Breaker Kit... each Cylinder, graduated, mixing, 25 ml... each Filter Paper, folded, 12.5 cm /pkg Flask, Erlenmeyer, 250 ml... each Funnel, poly, 65 mm... each Pipet, serological, 5 ml... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 135

136

137 0 mg/l Mo6 g/l 137

138 HEDP30g/L HEDP 30mg/L Sampling and Storage Collect samples in glass or plastic bottles. Accuracy Check Standard Addition Method a) Add 25 ml of sample to three 25-mL mixing cylinders. b) Snap the neck off a Molybdenum PourRite Ampule Standard Solution, 75 mg/l Mo6+. c) Use the TenSette Pipet to add 0.1, 0.2 and 0.3 ml of standard, respectively, to three 25-mL samples. Mix thoroughly. d) Analyze 20 ml of each spiked sample as described in the procedure. The molybdenum concentration reading should increase by 0.3 mg/l for each 0.1 ml addition of standard. e) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method Prepare a 2.0-mg/L molybdenum standard solution by pipetting 10 ml of a 10-mg/L Molybdenum Standard Solution into a 50-mL graduated mixing cylinder. Dilute to the mark with deionized water and mix thoroughly. Analyze 20 ml of this solution according to the procedure. 138

139 Method Performance Precision In a single laboratory using standard solutions of 2.00 mg/l Mo6+ and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of À0.009 mg/l Mo6+. Estimated Detection Limit The estimated detection limit for program 47 is 0.07 mg/l Mo6+. For more information on the estimated detection limit, see Section 1. Summary of Method The ternary complex method for molybdenum determination is a method in which molybdate molybdenum reacts with an indicator and sensitizing agent to give a stable blue complex. t, 20 ml (100 tests) : (1) , (1) , (1) /pkg ml ml MDB , 25 ml , ml, w/cap /pkg OPTIONAL REAGENTS Hydrochloric Acid Solution, 1:1, 6.0 N ml Molybdenum Standard Solution, PourRite Ampule 75 mg/l Mo6+, 2 ml...20/pkg Molybdenum Standard Solution, 10 mg/l Mo ml Sodium Hydroxide Standard Solution, 1.0 N ml MDB Water, deionized...4 L OPTIONAL APPARATUS Cylinder, mixing, graduated, 50 ml...each Filter Paper, folded, 12.5 cm...100/pkg Funnel, poly, 65 mm...each ph Paper, 1-11 ph units...5 rolls/pkg Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet, volumetric, ml, Class A...each Pipet Filler, safety bulb...each PourRite Ampule Breaker...each For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving you. 139

140 140

141 141

142 Sampling and Storage Collect samples in acid-washed plastic bottles. Adjust the sample ph to 2 or less with nitric acid (about 5 ml per liter). Preserved samples can be stored up to six months at room temperature. Adjust the sample ph to between 3 and 8 with 5.0 N Sodium Hydroxide Standard Solution just before analysis. Do not exceed ph 8 as this may cause some loss of nickel as a precipitate. Correct test results for volume additions, see Correcting for Volume Additions, (Section 1) for more information. Accuracy Check Standard Solution Method Prepare a 0.5 mg/l nickel standard solution by diluting 10.0 ml of a 5 mg/l working stock solution to 100 ml in a 100-mL volumetric flask. The working stock solution should be prepared daily by diluting 5.00 ml of Nickel Standard Solution, 1000 mg/l as Ni, to 1000 ml with deionized water. Or, using the TenSette Pipet, add 0.2 ml of a Nickel Voluette Ampule Standard Solution, 300 mg/l Ni, into a 100-mL volumetric flask. Dilute to volume with deionized water. This is a 0.6 mg/l standard solution. Method Performance Precision In a single laboratory using a standard solution of 0.50 mg/l nickel and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of À0.008 mg/l nickel. Estimated Detection Limit The estimated detection limit for program 48 is mg/l Ni. For more information on the estimated detection limit, see Section 1. Summary of Method After buffering the sample and masking any Fe3+ with pyrophosphate, the nickel is reacted with 1-(2-Pyridylazo)-2-Naphthol indicator. The indicator forms complexes with most metals present. After color development, EDTA is added to destroy all metal-pan complexes except nickel and cobalt., 25 ml (100 tests) : (2) , (4) , (2) EDTA /pkg /pkg P.A.N., 0.3%... 2 ml ml MDB , , w/caps /pkg ml... 4 L

143 , , 25 ml OPTIONAL REAGENTS Nickel Standard Solution, 1000 mg/l Ni ml Nickel Standard Solution, Voluette Ampule, 300 mg/l Ni, 10 ml... 16/pkg Nitric Acid, ACS ml Nitric Acid Solution, 1: ml Sodium Hydroxide Standard Solution, 5.0 N ml MDB OPTIONAL APPARATUS Ampule Breaker Kit... each Flask, volumetric, Class A, 100 ml... each Flask, volumetric, Class A, 1000 ml... each ph Paper, 1 to 11 ph units... 5 rolls/pkg ph Meter, EC10, portable... each Pipet, serological, 1 ml... each Pipet, serological, 5 ml... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Pipet, volumetric, Class A, 5.0 ml... each Pipet, volumetric, Class A, 10.0 ml... each Pipet Filler, safety bulb... each Thermometer, -10 to 110 ãc... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 143

144 144

145

146 Sampling and Storage Collect samples in clean plastic or glass bottles. Store at 4 C (39 F) or lower if the sample is to be analyzed within 24 to 48 hours. Warm to room temperature before running the test. For longer storage periods, adjust sample ph to 2 or less with sulfuric acid, ACS (about 2 ml per liter). Sample refrigeration is still required. Before testing the stored sample, warm to room temperature and neutralize with 5.0 N Sodium Hydroxide Standard Solution. Do not use mercury compounds as preservatives. Correct the test result for volume additions; see Correction for Volume Additions (Section 1) for more information. Accuracy Check Standard Additions Method a) Fill three 25-mL mixing cylinders with 25 ml of sample. b) Snap the neck off a Nitrate Nitrogen Ampule Standard, 500 mg/l nitrate nitrogen. c) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of Nitrate Nitrogen Standard Solution to the three samples. Stopper and mix thoroughly. d) For AccuVac analysis, transfer the solutions to clean, dry 50-mL beakers. For analysis with powder pillows, transfer only 10 ml of solution to clean, dry sample cells. e) Analyze each sample as described above. The nitrate nitrogen (NO3 --N) concentration should increase 2.0 mg/l for each 0.1 ml of standard added. f) If these increases do not occur, see Standard Additions (Section 1) for more information. Standard Solution Method Use a Hach Nitrate-Nitrogen Standard Solution, 10.0 mg/l NO3-N, listed under Optional Reagents as the sample and perform the procedure as described above. Standard Adjust To adjust the calibration curve using the reading obtained with the 10.0-mg/L standard solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 10.0 to edit the standard concentration to match that of the standard used. Press ENTER to complete the curve adjustment. See Section 1, Standard Curve Adjustment for more information. If you are using a reagent blank correction, the blank correction should be entered before the Standard Adjust value is entered. Method Performance Precision In a single laboratory using standard solutions of 25.0 mg/l nitrate nitrogen (NO3 --N) and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of +0.3 mg/l nitrate nitrogen for program #50 and ±1.7 mg/l nitrate nitrogen for program #

147 Estimated Detection Limit The estimated detection limit for program 50 is 0.5 mg/l NO3 -N and 0.8 mg/l NO3 -N for program 51. For more information on the estimated detection limit, see Section 1. Summary Of Method Cadmium metal reduces nitrates present in the sample to nitrite. The nitrite ion reacts in an acidic medium with sulfanilic acid to form an intermediate diazonium salt which couples to gentisic acid to form an amber-colored product. Pollution Prevention and Waste Management NitraVer 5 contains cadmium metal. Both samples and reagent blanks will contain cadmium (D006) at a concentration regulated as hazardous wastes by the Federal RCRA. Do not pour these solutions down the drain. See Section 3 for more information on proper disposal of these materials. () NitraVer /pkg , ml, w/cap /pkg ( ACCUVAC ) NitraVer /pkg , 50 ml each /pkg OPTIONAL REAGENTS Bromine Water 30 g/l ml* Nitrate Nitrogen Standard Solution, 10.0 mg/l as (NO3--N) ml Nitrate Nitrogen Standard Solution, 1000 mg/l as (NO3--N) ml Nitrate Nitrogen Standard Solution, PourRite ampule, 500 mg/l as NO3--N, 2 ml...20/pkg Phenol Solution ml Sodium Hydroxide Standard Solution, 5.0 N ml* Sulfuric Acid, ACS ml* Water, deionized...4 L OPTIONAL APPARATUS AccuVac Snapper Kit... each Cylinder, graduated, mixing, 25 ml... each Dropper, for 29-mL bottle... each ph Indicator Paper, 1 to 11 ph... 5 rolls/pkg ph Meter, sension 1, portable... each Pipet Filler, safety bulb... each Pipet, serological, 2 ml... each Pipet, TenSette, 0.1 to 1.0 ml... each

148 Pipet Tips, for TenSette Pipet... 50/pkg PourRite Ampule Breaker... each Thermometer, -10 to 110 C... each For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. Contact the Hach office or distributor serving you. 148

149 NitraVer 5 NO3-N (NO3) 5:00 TIMER 2 149

150 0 mg/l NO3-N NO3-N (or NO3) g/l

151 Sampling and Storage Collect samples in clean plastic or glass bottles. Store at 4 C (39 F) or lower if the sample is to be analyzed within 24 to 48 hours. Warm to room temperature before running the test. For longer storage periods, adjust sample ph to 2 or less with sulfuric acid, ACS (about 2 ml per liter). Sample refrigeration is still required. Before testing the stored sample, warm to room temperature and neutralize with 5.0 N Sodium Hydroxide Standard Solution. Do not use mercury compounds as preservatives. Correct the test result for volume additions; see Correction for Volume Additions, (Section 1) for more information. Accuracy Check Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a Nitrate Nitrogen Ampule Standard Solution, 100 mg/l NO3-N. c) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of the standard to the three samples. Stopper and mix well. d) For analysis with AccuVac Ampuls, transfer the solutions to dry, clean 50 ml beakers. For analysis with powder pillows, transfer only 10 ml of the solution to dry, clean sample cells. e) Analyze each sample as described above. The nitrate nitrogen (NO3-N) concentration should increase 0.4 mg/l for each 0.1 ml of standard added. f) If these increases do not occur, see Standard Additions (Section 1) for more information. Standard Solution Method A 1.0 mg/l Nitrate Nitrogen Standard Solution is available from Hach. Use this standard in place of sample in the above procedure. Standard Adjust To adjust the calibration curve using the reading obtained with the 1.00-mg/L standard solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 1.0 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Section 1, Standard Curve Adjustment for more information. Method Performance Precision In a single laboratory using a standard solution of 3.0 mg/l nitrate nitrogen (NO3--N) and two representative lots of powder pillows with the instrument, a single operator obtained a standard deviation of +0.2 mg/l nitrate nitrogen. In a single laboratory using a standard solution of 3.0 mg/l NO3-N and two representative lots of AccuVac Ampuls with the instrument, a single operator obtained a standard deviation of +0.1 mg/l nitrate nitrogen. 151

152 Estimated Detection Limit The estimated detection limit for programs 53 and 54 is 0.2 mg/l NO3-N. For more information on the estimated detection limit, see Section 1. Summary of Method Cadmium metal reduces nitrates present in the sample to nitrite. The nitrite ion reacts in an acidic medium with sulfanilic acid to form an intermediate diazonium salt which couples to gentisic acid to form an amber-colored product. Pollution Prevention and Waste Management NitraVer 5 contains cadmium metal. Both samples and reagent blanks will contain cadmium (D006) at a concentration regulated as hazardous waste by the Federal RCRA. Do not pour these solutions down the drain. See Section 3 for more information on proper disposal of these materials. () NitraVer /pkg , ml, w/cap /pkg ( ACCUVAC ) NitraVer /pkg , 50 ml each /pkg OPTIONAL REAGENTS Bromine Water 30 g/l ml* Nitrate Nitrogen Standard Solution, 1.0 mg/l as NO3-N ml Nitrate Nitrogen Standard Solution, 100 mg/l as NO3-N ml Nitrate Nitrogen Standard Solution, PourRite Ampule, 100 mg/l as NO3-N, 2 ml... 20/pkg Phenol Solution, 30 g/l...29 ml Sodium Hydroxide Standard Solution, 5.0 N ml SCDB* Sulfuric Acid, ACS ml* Water, deionized... 4 L OPTIONAL APPARATUS AccuVac Snapper Kit... each Cylinder, graduated, mixing, 25 ml... each Dropper, for 1-oz bottle... each ph Paper, 1 to 11 ph units... 5 rolls/pkg ph Meter, sension 1, portable... each Pipet Filler, safety bulb... each Pipet, serological, 2 ml... each Pipet, TenSette, 0.1 to 1.0 ml... each

153 Pipet Tips, for TenSette Pipet... 50/pkg PourRite Ampule Breaker... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 153

154 NO3-N (NO3) 154

155 15:00 TIMER 3 0 mg/l NO3-N NO3-N (or NO3) g/l 155

156 Sampling and Storage Collect samples in clean plastic or glass bottles. Store at 4 C (39 F) or lower if the sample is to be analyzed within 24 to 48 hours. Warm to room temperature before running the test. For longer storage periods, adjust sample ph to 2 or less with sulfuric acid, ACS (about 2 ml per liter). Sample refrigeration is still required. Before testing the stored sample, warm to room temperature and neutralize with 5.0 N Sodium Hydroxide Standard Solution. Do not use mercury compounds as preservatives. Correct the test result for volume additions; see Correction for Volume Additions (Section 1) for more information. Accuracy Check Standard additions Method a) Fill three 25-mL graduated mixing cylinders with 15 ml of sample. b) Snap the neck off a Nitrate Nitrogen Ampule Standard Solution, 12.0 mg/l NO3-N. c) Using the TenSette Pipet, add 0.1, 0.2, and 0.3 ml of the standard to the three samples. Stopper and mix well. d) Analyze each sample as described above. The nitrate nitrogen concentration should increase 0.08 mg/l for each 0.1 ml of standard added. e) If these increases do not occur, see Standard Additions (Section 1) for more information. 156

157 Standard Solution Method Prepare a 0.20 mg/l nitrate nitrogen standard by diluting 2.00 ml of a 10.0 mg/l Nitrate Nitrogen Standard Solution to ml with deionized water. Use this standard in place of sample in Step 3. Standard Adjust To adjust the calibration curve using the reading obtained with the 0.20-mg/L standard solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 0.20 to edit the standard concentration to match that of the standard used. Press ENTER to complete the curve adjustment. If you are using a reagent blank correction, the blank correction should be entered before the Standard Adjust feature is entered. See Section 1, Standard Curve Adjustment for more information. Method Performance Precision In a single laboratory using a standard solution of 0.25 mg/l nitrate nitrogen (NO3-N) and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of mg/l nitrate nitrogen. Estimated Detection Limit The estimated detection limit for program 55 is 0.01 mg/l NO3-N. For more information on the estimated detection limit, see Section 1. Summary of Method Cadmium metal reduces nitrates present in the sample to nitrite. The nitrite ion reacts in an acidic medium with sulfanilic acid to form an intermediate diazonium salt which couples to chromotropic acid to form a pink-colored product. Pollution Prevention and Waste Management NitaVer 6 contains cadmium metal. Both samples and reagent blanks will contain cadmium (D006) at a concentration regulated as hazardous wastes by the Federal RCRA. Do not pour these solutions down the drain. See Section 3 for more information on proper disposal of these materials. (100 tests) : (1) , (1) NitriVer /pkg NitraVer /pkg ml ml, w/ cap /pkg

158 OPTIONAL REAGENTS Description Unit Cat. No. Bromine Water, 30 g/l...29 ml* Nitrate Nitrogen Standard Solution, 10.0 mg/l as NO3--N ml Nitrate Nitrogen Standard Solution, Voluette ampule, 12 mg/l as NO3--N, 2 ml... 20/pkg Phenol Solution, 30 g/l...29 ml Pretreatment Kit, contains: (1) , (1) each Sodium Hydroxide Standard Solution, 5.0 N ml* SCDB Sulfuric Acid, ACS ml* Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker, PourRite Ampules... each Dropper, for 29-mL bottle... each Flask, volumetric, Class A, 100 ml... each ph Indicator Paper, 1 to 11 ph... 5-roll/pkg ph Meter, sension 1, portable... each Pipet, serological, 2 ml... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Pipet, volumetric, Class A, 2.00 ml... each Pipet Filler, safety bulb... each Thermometer, -10 to 110 C... each Nitrate at these levels can be determined directly using the Nitrate Ion Selective Electrode (Cat. No ). For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 158

159 NO3-N 159

160 0.0 mg/l NO3-N 1 mg/l 1000 mg/l 12 mg/l100mg/l 400mg10mL 160

161 Sampling and Storage Collect samples in clean plastic or glass bottles. Store at 4 C (39 F) or lower if the sample is to be analyzed within 24 to 48 hours. Warm to room temperature before running the test. For longer storage periods (up to 14 days), adjust sample ph to 2 or less with sulfuric acid, ACS (about 2 ml per liter). Sample refrigeration is still required. Before testing the stored sample, warm to room temperature and neutralize with 5.0 N Sodium Hydroxide Standard Solution. Do not use mercury compounds as preservatives. Correct the test result for volume additions; see Correction for Volume Additions in Section 1 for more information. Accuracy Check Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a fresh High Range Nitrate Nitrogen Voluette Ampule Standard, 500 mg/l NO3-N. c) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of standard to the three mixing cylinders, respectively. Mix each thoroughly. d) Analyze each sample as described in the procedure; use a 1-mL aliquot of the spiked sample in each test. The nitrogen concentration should increase 2.0 mg/l for each 0.1 ml of standard added. e) If these increases do not occur, see Standard Additions (Section 1) for more information. Standard Solution Method To test accuracy, prepare a 20.0 mg/l nitrate nitrogen standard solution by pipetting 2.00 ml of a High Range Nitrate Nitrogen Voluette Ampule Standard Solution, 500 mg/l NO3--N, into a 50 ml Class A volumetric flask. Dilute to the line with deionized water. Substitute this standard for the sample and perform the test as described in the procedure. Method Performance Precision In a single laboratory, using a standard solution of 25.0 mg/l nitrate nitrogen (NO3-N) and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of ± 0.5 mg/l NO3-N. Estimated Detection Limit The estimated detection limit for program 57 is 0.3 mg/l NO3-N. For more information on the estimated detection limit, see Section 1. Summary of Method Nitrate in the sample reacts with chromotropic acid under strongly acidic conditions to yield a yellow product with a maximum absorbance at 410 nm. 161

162 NitraVer Test N Tube (50 tests) : (1) , (1) , *(50) Nitrate /pkg... * NitraVer B /pkg COD TenSette, 0.1 to 1.0 ml Pipet Tips, for TenSette Pipet... varies... 50/pkg OPTIONAL REAGENTS Nitrate-Nitrogen Standard Solution, Voluette Ampules, 500 mg/l N... 16/pkg Sodium Hydroxide Standard Solution, 5.0 N...50 ml Sulfuric Acid, ACS, concentrated ml Urea, ACS g Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker Kit... each Cylinder, graduated, mixing, 25-mL (3 required)... each Flask, volumetric, Class A, 50 ml... each ph Paper, 1 to 11 ph units... 5 rolls/pkg Pipet, volumetric, Class A, 2 ml... each Spoon, measuring, 0.5 g... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 162

163 163

164 Sampling and Storage Collect samples in clean plastic or glass bottles. If prompt analysis is impossible, store at 4 ãc (39 ãf) or lower if the sample is to be analyzed within 48 hours. Warm to room temperature before running the test. Do not use acid preservatives. Remove suspended solids by filtration. Accuracy Check Standard Solution Method Dissolve grams of fresh sodium nitrite and dilute to 1000 ml with deionized water to prepare a 100 mg/l nitrite standard solution. Prepare this solution daily. Alternatively, make a dilution of a fresh Hach Nitrite Standard Solution, 821 mg/l NO2 (250 mg/l NO2-N) using Class A glassware. Dilute 10mL of this standard to 100 ml with deionized water to give an 82 mg/l nitrite standard. Prepare this solution just before use. Using this solution as the sample, perform the nitrite procedure as described above. Method Performance Precision In a single laboratory using a standard solution of 123 mg/l nitrite and two representative lots of reagents with the instrument, a single operator obtained a standard deviation of +1 mg/l nitrite. Estimated Detection Limit The estimated detection limit for program 59 is 2 mg/l NO2. For moreinformation on the estimated detection limit, see Section

165 Interferences This test does not measure nitrates nor is it applicable to glycol based samples. Dilute glycol based samples and follow the Low Range Nitrite Procedure. Summary of Method The method uses ferrous sulfate in an acidic medium to reduce nitrite to nitrous oxide. Ferrous ions combine with the nitrous oxide to form a greenish-brown complex in direct proportion to the nitrite present. NitriVer /pkg , , w/ cap /pkg OPTIONAL REAGENTS Nitrite Standard Solution, 821 mg/l NO2 (250 mg/l NO2-N) ml Sodium Nitrite, ACS g Water, deionized... 4 L OPTIONAL APPARATUS Balance, analytical, 110 V...each Balance, analytical, 220 V...each Flask, volumetric, 1000 ml...each Flask, volumetric, 100 ml, Class A...each Pipet, volumetric, ml, Class A...each Pipet Filler, safety bulb...each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 165

166 (0 to mg/l NO2--N)

167 Sampling and Storage Collect samples in clean plastic or glass bottles. Store at 4 ãc (39 ãf) or lower and analyze within 48 hours. Warm to room temperature before running the test. Do not use acid preservatives. Remove the suspended solids by filtration. Accuracy Check Standard Solution Method Pipet 5.00 ml of a fresh 250 mg/l NO2-N standard into a ml volumetric flask. Dilute to the mark with deionized water. This makes a 5.00-mg/L intermediate standard. To prepare a mg/L NO2-N standard solution, dilute ml of the 5.00-mg/L intermediate standard to 500 ml in a volumetric flask. Prepare this solution immediately before use. Run the test using the mg/l NO2 -N standard in place of 167

168 the sample. Results should be between and mg/l NO2-N. Method Performance Precision In a single laboratory, using a standard solution of mg/l nitrite nitrogen and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of À0.001 mg/l NO2 N for the powder pillow method and À0.003 mg/l NO2 --N for the AccuVac method. Estimated Detection Limit The estimated detection limit for programs 60 and 62 is mg/l NO2-N. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Summary of Method Nitrite in the sample reacts with sulfanilic acid to form an intermediate diazonium salt. This couples with chromotropic acid to produce a pink colored complex directly proportional to the amount of nitrite present. NitriVer /pkg NitriVer 3 AccuVac /pkg , 50 ml (for AccuVac procedure) or, ml (powder pillow procedure) /pkg OPTIONAL REAGENTS Nitrite Standard Solution, 250 mg/l as NO2--N ml Water, deionized...4 L OPTIONAL APPARATUS Description Unit Cat. No. AccuVac Snapper Kit... each Flask, volumetric, 250 ml... each Flask, volumetric, 500 ml... each Pipet, serological, 10 ml... each Pipet, TenSette, 1 to 10 ml... each Pipet Tips for TenSette Pipet... 50/pkg Pipet, volumetric, Class A, 5.00 ml... each Pipet, volumetric, Class A, ml... each Pipet Filler, safety bulb... each Thermometer, -10 to 110 ãc... each For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving you. 168

169 NO3-N Test N Tube Test N Tube5 169

170 0.0 mg/l NO3-N 170

171 Sampling and Storage Collect samples in clean plastic or glass bottles. Store at 4 ãc (39 ãf) or lower and analyze within 48 hours. Warm to room temperature before running the test. Do not use acid preservatives. Remove suspended solids by filtration. Accuracy Check Standard Solution Method Pipet 5.00 ml of a fresh Hach standard, 250 mg/l as NO2 -N into a Class A 250-mL volumetric flask. Dilute to the line with deionized water to make a 5.00-mg/L intermediate standard. Pipet ml of the 5.0-mg/L intermediate standard into a Class A 500-mL volumetric flask. Dilute to the line with deionized water to make a mg/l NO2-N standard solution. Prepare immediately before use. Run the test using the mg/l NO2-N standard in place of the sample.results should be between and mg/l NO2 -N. Method Performance Precision In a single laboratory, using a standard solution of mg/l nitrite nitrogen and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of À0.004 mg/l NO2-N. Estimated Detection Limit The estimated detection limit for program 63 is mg/l NO2-N. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Summary of Method Nitrite in the sample reacts with sulfanilic acid to form an intermediate diazonium salt. This couples with chromotropic acid to produce a pink-colored complex directly proportional to the amount of nitrite present. NitriVer. 3 Test N Tube Set (50 tests) : (50) NitriVer. 3 Test N...*, 6 x 10 mm,6/pkg , for vials, 6/pkg , 100-mL COD/TNT , TenSette, 1 to 10 ml Pipet Tips for TenSette Pipet /pkg

172 OPTIONAL REAGENTS Nitrite Standard Solution, 250 mg/l as NO2--N ml Water, deionized...4 L OPTIONAL APPARATUS Flask, volumetric, 250 ml... each Flask, volumetric, 500 ml... each Pipet, volumetric, Class A, ml... each For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving you. 172

173

174 174

175 Sampling and Storage Collect samples in clean plastic or glass bottles. Most reliable results are obtained when samples are analyzed as soon as possible after collection. If chlorine is known to be present, the sample must be treated immediately with sodium thiosulfate. Add one drop of Sodium Thiosulfate Standard Solution, 0.1 N, for each 0.3 mg of chlorine present in a one liter sample. To preserve the sample, adjust the ph to 2 or less with concentrated sulfuric acid (about 2 ml per liter). Store samples at 4 ãc or less. Samples preserved in this manner can be stored up to 28 days. Just before testing the stored sample, warm to room temperature and neutralize with 5.0 N Sodium Hydroxide Standard Solution. Correct the test result for volume additions; see Correction for Volume Additions, in Section 1 for more detailed information. Accuracy Check Standard Additions Method a) Fill three 25-mL mixing cylinders with 20 ml of sample. b) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of Ammonium Nitrogen Standard, 10 mg/l as NH3-N to the three samples. Stopper the cylinders and mix well. c) Analyze a 10-mL portion of sample as described above. The ammonia nitrogen concentration should increase 0.05 mg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions (Section 1) for more information. Standard Solution Method Prepare a 0.40 mg/l ammonia nitrogen standard by diluting 4.00 ml of the Ammonia Nitrogen Standard Solution, 10 mg/l, to 100 ml with deionized water. Or, using the TenSette Pipet, prepare a 0.40 mg/l ammonia nitrogen standard by diluting 0.8 ml of a Ammonia Nitrogen Voluette Standard Solution, 50 mg/l as NH3-N, to 100 ml with deionized water. Method Performance Precision In a single laboratory using a standard solution of 0.40 mg/l ammonia nitrogen (NH3-N) and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of mg/l ammonia nitrogen. Estimated Detection Limit The estimated detection limit for program 64 is 0.02 mg/l NH3-N. For more information on the estimated detection limit, see Section 1. Summary of Method Ammonia compounds combine with chlorine to form monochloramine. Monochloramine reacts with salicylate to form 5-aminosalicylate. The 5-aminosalicylate is oxidized in the presence of a sodium nitroprusside catalyst to form a blue-colored compound. The blue color is masked by the yellow color from the excess reagent present to give a final greencolored solution. 175

176 () for 10-mL (100 tests) : (2) , (2) Ammonia Cyanurate /pkg Ammonia Salicylate /pkg , ml, w/ cap /pkg OPTIONAL REAGENTS Ammonia Nitrogen Standard Solution, 10 mg/l as NH3-N ml Ammonia Nitrogen, PourRite Ampules, 50 mg/l as NH3-N, 2 ml...20/pkg Cylinder, graduated, mixing, 25 ml...each Sodium Hydroxide Standard Solution, 1.0 N ml MDB Sodium Hydroxide Standard Solution, 5.0 N...50 ml SCDB Sodium Thiosulfate Standard Solution, 0.1 N ml MDB Sulfide Inhibitor Reagent Powder Pillows...100/pkg Sulfuric Acid, concentrated, ACS ml Sulfuric Acid Standard Solution, 1.0 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Cylinder, graduated, polypropylene, 500 ml...each Distillation Heater and Support Apparatus, 115 V...each Distillation Heater and Support Apparatus, 230 V...each Distillation Set, General Purpose...each Filter Paper, folded, 12.5 cm Flask, Erlenmeyer, polypropylene, 500 ml...each Flask, volumetric, Class A, 100 ml...each Funnel, poly, 65 mm...each ph Meter, sension.1, portable...each Pipet Filler, safety bulb...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet, volumetric, Class A, 2.0 ml...each PourRite Ampule Breaker Kit...each Thermometer, -10 to 110 ãc...each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 176

177 8075 mg/l, TKNZERO 177

178 178

179 179

180 Sampling and Storage Collect samples in a cleaned glass or plastic container. Adjust the ph to 2 or less with sulfuric acid (about 2 ml per liter) and cool to 4 ãc. Preserved samples can be stored up to 28 days. Accuracy Check Kjeldahl Nitrogen Standard Method This procedure checks digestion efficiency and indicates that amount of bound nitrogen that is freed during digestion. The methods and standards available to check digestion technique are found in the Accuracy Check section following the procedures in the Digesdahl Digestion Apparatus Instruction Manual. Using the digested Kjeldahl standard, perform the above TKN analysis on the colorimeter. The TKN value should come within about À3% of the value of the prepared Kjeldahl standard. Standard Solution Method (to check calibration accuracy only) Add one drop of TKN Indicator to each of two 25-mL graduated mixing cylinders. Fill one cylinder to the 20-mL mark with deionized water. Fill the other cylinder to the 20-mL mark with a 1.0 mg/l Ammonia Nitrogen Solution. Add 3 drops of Mineral Stabilizer to each cylinder. Invert several times to mix. Add 3 drops of Polyvinyl Alcohol Dispersing agent to each cylinder. Perform the TKN procedure as described in Steps 9 to 16. This display should show mg/l TKN. User Calibration For most accurate results, use a user-calibrated program. The Standard Adjust feature should not be used with a user-entered calibration; it will hinder performance. A one-time setup of a program for TKN is recommended for each new lot of reagents. A new calibration may be performed for each lot of Nessler Reagent by following these instructions: Standard Preparation Use the following standards to make a calibration curve. See Preparing a User-Entered Calibration Curve on page 49, for more information and instructions. Prepare standards representing concentrations of 20, 60, 80, 100, 140 and 160 mg/l NH3-N as follows: a) Using volumetric pipets, transfer 5.0, 15.0, 20.0, 25.0, 35.0, and 40.0 ml of 100 mg/l NH3-N standard solution into six separate 100-mL volumetric flasks. Dilute to volume with deionized water, stopper, and invert to mix. b) Begin at step 4 of the procedure using a 3-mL aliquot for the sample volume. Also prepare a blank solution by substituting a 3 ml aliquot of deionized water for sample in Step 4. Note: Standard solutions are prepared as if a 25-mL volume was used for the digestion. Actual concentrations prepared in Step 1 are 5, 15, 20, 25, 35, and 40 mg/l NH3-N. These represent original concentrations of 20, 60, 80, 100, 140, and 160 mg/l NH3-N, based on the 25 to 100 ml dilution in the digestion. User Entered Calibration Settings For TKN Program # = 101 to 105 Wavelength = 420 nm Resolution = 0 mg/l 180

181 Method Performance Precision In a single laboratory using a standard solution of 64 mg/l TKN and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of À1.0 mg/l TKN. Estimated Detection Limit The estimated detection limit for program 65 is 2 mg/l TKN. For more information on the estimated detection limit, see Section 1. Summary of Method Total Kjeldahl Nitrogen ± (also called crude protein) refers to the combination of ammonia and organic nitrogen. Organically-bound in the trinegative state, it is converted into ammonium salts by the action of sulfuric acid and hydrogen peroxide. The ammonia is then analyzed by a modified nessler method test. The Mineral Stabilizer complexes calcium and magnesium. The Polyvinyl Alcohol Dispersing Agent aids the color formation in the reaction of Nessler Reagent with ammonium ions. A yellow color forms, proportional to the ammonia concentration. Pollution Prevention And Waste Management Nessler reagent contains mercuric iodide. Both the sample and blank will contain mercury (D009) at concentrations regulated as a hazardous waste by the Federal RCRA. Do not pour these solutions down the drain. See Section 3 for more information on proper disposal of these materials : (1) , (1) , (1) , (1) , (1) , (1) , (1) , (1) , 50% ml ml ml SCDB Nesslers t... 2 ml ml Polyvinyl ml SCDB , 8.0 N ml MDB , 1.0 N ml SCDB , ACS... 6 ml ml TKN ml SCDB L Boiling Chips, g , 25 ml , TenSette, 0.1 to 1.0 ml , TenSette /pkg

182 , ml, w/ cap /pkg :, 115 V , 230 V OPTIONAL REAGENTS Ammonia Nitrogen Standard Solution, 1 mg/l NH3-N ml Ammonia Nitrogen Standard Solution, Voluette Ampule, 150 mg/l NH3-N, 10 ml... 16/pkg Ammonia Nitrogen Standard Solution, 100 mg/l NH3-N ml OPTIONAL APPARATUS Description Unit Cat. No. Ampule Breaker Kit...each Balance, AccuLab Pocket Pro...each Bottle, glass dispenser, 118 ml...each Bottle, plastic wash, 1000 ml...each Cylinder, graduated, 50 ml...each Flask, volumetric, 100 ml, Class A...each Mini Grinder, 120 V...each ph Paper, 1 to 11 ph units...5 rolls/pkg Pipet, volumetric, Class A, 0.50 ml...each Pipet, volumetric, Class A, 1.00 ml...each Pipet, volumetric, Class A, 2.00 ml...each Pipet, volumetric, Class A, 5.00 ml...each Pipet, volumetric, Class A, ml...each Pipet, volumetric, Class A, ml...each Pipet, volumetric, Class A, ml...each Pipet, volumetric, Class A, ml...each Safety Glasses...each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 182

183 NO3-N AmVer 183

184 0.00 mg/l NH3-N 184

185 Sampling and Storage Collect samples in clean plastic or glass bottles. Best results are obtained with immediate analysis. If chlorine is known to be present, add one drop of 0.1 N sodium thiosulfate for each 0.3 mg/l Cl2 in a one liter sample. Preserve the sample by reducing the ph to 2 or less with hydrochloric acid (at least 2 ml). Store at 4 C (39 F) or less. Preserved samples may be stored up to 28 days. Before analysis, warm samples to room temperature and neutralize with 5.0 N sodium hydroxide. Correct the test result for volume additions. See Correcting for Volume Additions on page 22 for more information. Accuracy Check Standard Additions Method a) Snap the neck off a Nitrogen, Ammonia Ampule Standard Solution, 50 mg/l NH3-N. b) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of standard to three 25 ml samples. Mix thoroughly. c) Analyze each sample as described above. The nitrogen concentration should increase 0.20 mg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions, Section 1, for more information. Standard Solution Method To check accuracy, use a 1.0 mg/l Nitrogen, Ammonia Standard Solution listed under Optional Reagents. Or, dilute 1 ml of solution from a 50 mg/l Ampule Standard for Nitrogen, Ammonia to 50 ml with deionized water using a 50-mL volumetric flask. Method Performance Precision In a single laboratory, using a standard solution of 1.0 mg/l ammonia nitrogen and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of mg/l NH3-N. Estimated Detection Limit The estimated detection limit for program 66 is 0.08 mg/l NH3-N. For more information on the estimated detection limit, see Section 1. Summary of Method Ammonia compounds combine with chlorine to form monochloramine. Monochloramine reacts with salicylate to form 5-aminosalicylate. The 5-aminosalicylate is oxidized in the presence of a sodium nitroprusside catalyst to form a blue-colored compound. The blue color is masked by the yellow color from the excess reagent present to give a final green-colored solution. Pollution Prevention And Waste Management The ammonia salicylate reagent contains sodium nitroferricyanide. Cyanide solutions are regulated as hazardous wastes by the Federal RCRA. Collect cyanide solutions for disposal as reactive (D001) waste. Be sure cyanide solutions are stored in a caustic solution with ph >11 to prevent release of hydrogen cyanide gas. See Section 3 for further information in proper disposal of these materials. 185

186 AmVer (25 tests) : (1) , (1) , (1) , *(50) AmVer Low Range Vials AmVer, Test N Tube /pkg... *, 5 ml sample /pkg Cyanurate Reagent Powder Pillows, 5 ml sample /pkg COD TenSette, 0-10 ml /pkg OPTIONAL REAGENTS Nitrogen, Ammonia Standard Solution, 1.0 mg/l NH3-N ml Nitrogen, Ammonia Standard Solution, 10 ml Voluette ampules, 50 mg/l NH3-N...16/pkg Nitrogen, Ammonia Standard Solution, 2 ml PourRite ampules, 50 mg/l NH3-N /pkg Hydrochloric Acid, ACS ml Sodium Hydroxide Standard Solution, 5.0 N...50 ml SCDB Sodium Hydroxide, N ml MDB Sodium Thiosulfate Standard Solution, 0.1 N ml MDB Sulfide Inhibitor Reagent Powder Pillows...100/pkg Sulfuric Acid, 1.00 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker Kit...each Cylinder, graduated, mixing, 25 ml, Class A...each Distillation Apparatus Set...each Heater and Support Apparatus (for distillation), 115 Vac...each Heater and Support Apparatus (for distillation), 230 Vac...each Filter Paper, folded...100/box Flask, Erlenmeyer, 500 ml...each Flask, volumetric, 50 ml, Class A...each Funnel, analytical (for filtering)...each Jack, laboratory (use with distillation apparatus)...each ph Indicator Paper, 1 to 11 ph...5 rolls/pkg Ampule Breaker Kit, PourRite...each Thermometer, -20 to 110 ãc...each Thermometer, -10 to 260 ãc...each For Technical Assistance, Price and Ordering 186

187 NO3-N AmVer 187

188 0.00 mg/l NH3-N 188

189 Sampling and Storage Collect samples in clean plastic or glass bottles. Best results are obtained with immediate analysis. If chlorine is known to be present, add one drop of 0.1 N sodium thiosulfate for each 0.3 mg/l Cl2 in a one liter sample. Preserve the sample by reducing the ph to 2 or less with hydrochloric acid (at least 2 ml). Store at 4 ãc (39 ãf) or less. Preserved samples may be stored up to 28 days. Before analysis, warm samples to room temperature and neutralize with 5.0 N sodium hydroxide. Correct the test result for volume additions. Accuracy Check Standard Additions Method a) Snap the top off an Ammonia PourRite Ampule Standard, 150 mg/l NH3-N. b) Use the TenSette Pipet to add 0.2, 0.4 and 0.6 ml of standard to three 25-mL samples. Swirl to mix. c) Analyze each sample as described above. The ammonia concentration should increase approximately 1.2 mg/l NH3-N for each 0.2 ml of standard added. d) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method To check accuracy, use a 10 or 50 mg/l Nitrogen, Ammonia Standard Solution or use a Nitrogen, Ammonia Voluette Ampule Standard, 50 mg/l. 189

190 Method Performance Precision In a single laboratory, using a standard solution of 50 mg/l ammonia nitrogen (NH3-N) and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of +5 mg/l NH3-N. Estimated Detection Limit The estimated detection limit for program 67 is 1 mg/l NH3-N. For more information on the estimated detection limit, see Section 1. Summary of Method Ammonia compounds combine with chlorine to form monochloramine. Monochloramine reacts with salicylate to form 5-aminosalicylate. The 5-aminosalicylate is oxidized in the presence of a sodium nitroprusside catalyst to form a blue-colored compound. The blue color is masked by the yellow color from the excess reagent present to give a green-colored solution. Safety Good safety habits and laboratory techniques should be used throughout the procedure. Consult the Material Safety Data Sheets for information specific to the reagents used. For additional information, refer to Section 3. Pollution Prevention And Waste Management The ammonia salicylate reagent contains sodium nitroferricyanide. Cyanide solutions are regulated as hazardous wastes by the Federal RCRA. Collect cyanide solutions for disposal as reactive (D001) waste. Be sure cyanide solutions are stored in a caustic solution with ph >11 to prevent release of hydrogen cyanide gas. See Section 3 for further information in proper disposal of these materials. AmVer., TNT (25 tests) : (1) , (1) , (1) , *(50) AmVer HR Vials AmVer. HR Test N Tube /pkg...* /pkg /pkg COD/TNT TenSette., 0-1 ml varies... 50/pkg

191 OPTIONAL REAGENTS Nitrogen, Ammonia Standard Solution, 50 mg/l NH3-N ml Nitrogen, Ammonia Standard Solution, 10 mg/l NH3-N ml Ammonia Standard Solution, PourRite. ampules, 150 mg/l NH3-N, 2 ml...20/pkg Hydrochloric Acid, ACS ml Sodium Hydroxide Standard Solution, 5.0 N ml Sodium Hydroxide Standard Solution, 1.0 N ml Sodium Thiosulfate Standard Solution, 0.1 N ml OPTIONAL REAGENTS (continued) Quantity Required Description Per Test Unit Cat. No. Sulfide Inhibitor Powder Pillows /pkg Sulfuric Acid, 1.00 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Cylinder, 25 ml, graduated, mixing... each Distillation Apparatus Set, general purpose... each Heater and Support Apparatus (for distillation), 115 VAC... each Heater and Support Apparatus (for distillation), 230 VAC... each Filter Paper, folded /pkg Flask, Erlenmeyer, 500 ml... each Funnel, analytical (for filtering)... each Jack, laboratory (use with distillation apparatus)... each ph Indicator Paper, 1 to 11 ph... 5 rolls/pkg PourRite. Ampule Breaker... each Sample Cell, ml, w/cap... 6/pkg For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 191

192 N 192

193 AmVer 15:00 TIMER mg/l N 193

194 194

195 Sampling And Storage Collect samples in clean plastic or glass bottles. Best results are obtained with immediate analysis. If chlorine is known to be present, add 1 drop of 0.1 N sodium thiosulfate for each 0.3 mg/l Cl2 in a 1 liter sample. Preserve the sample by reducing the ph to 2 or less with concentrated hydrochloric acid (at least 2 ml). Store at 4 C (39 F) or less. Preserved samples may be stored up to 28 days. Warm samples to room temperature and neutralize with 5 N Sodium Hydroxide before analysis. Correct the test result for volume additions; see Correcting for Volume Additions in Section 1. Accuracy Check Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a fresh High Range Nitrate Nitrogen PourRite Ampule Standard, 500 mg/l NO3 -N. c) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of standard, respectively, to 3 25-mL mixing cylinders. Mix thoroughly. d) Analyze each sample as described in the procedure; use a 1-mL aliquot of the prepared sample in Step 5. The nitrogen concentration should increase about 1.8 to 1.9 mg/l for each 0.1 ml of standard added. e) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method To check accuracy, use a 10.0 mg/l Nitrate Nitrogen Standard Solution listed under Optional Reagents. Alternatively, a 20.0 mg/l nitrate nitrogen standard can be prepared by diluting 2 ml of solution from a PourRite Ampule Standard for High Range Nitrate Nitrogen, 500 mg/l NO3 -N, to 50 ml with deionized water. Substitute this standard for the sample and perform the test as described. The recovery of the standards should be about 90-95%. Method Performance Precision/Accuracy The total inorganic nitrogen test provides an estimate of the total nitrite, nitrate, and ammonia nitrogen load in water or wastewater samples. This test is most applicable for monitoring an industrial process stream or a wastewater treatment stream where it is important to track the inorganic nitrogen load as it passes through the treatment process. The test exhibits different recoveries of each of the three nitrogen species, as summarized below. This test is not recommended for quantifying only one of the three species. In that case, use a specific procedure for each particular analyte. Ammonia Nitrogen In a single laboratory, using a standard solution of 20.0 mg/l NH3-N and 2 representative lots of reagent with the instrument, a single operator obtained a mean recovery of 21.3 mg/l with a standard deviation of À 0.77 mg/l N (replicate number = 7 per reagent lot). 195

196 Nitrate Nitrogen In a single laboratory, using a standard solution of 20.0 mg/l NO3-N and2 representative lots of reagent with the instrument, a single operator obtained a mean recovery of 18.9 mg/l with a standard deviation of À 0.55 mg/l N (replicate number = 7 per reagent lot). Nitrite Nitrogen In a single laboratory, using a standard solution of 20.0 mg/l NO2-N and 2 representative lots of reagent with the instrument, a single operator obtained a mean recovery of 14.6 mg/l with a standard deviation of À 0.77 mg/l N (replicate number = 7 per reagent lot). Estimated Detection Limit The estimated detection limit for program 68 is 0.7 mg/l N. For more information on the estimated detection limit, see Section 1. Summary of Method Titanium (III) ions reduce nitrate and nitrite to ammonia in a basic environment. After centrifugation to remove solids, the ammonia is combined with chlorine to form monochloramine. Monochloramine reacts with salicylate to form 5-aminosalicylate. The 5-aminosalicylate is oxidized in the presence of a sodium nitroprusside catalyst to form a blue-colored compound. The blue color is masked by the yellow color from the excess reagent present to give a final green-colored solution. REQUIRED REAGENTS (TiCl3 ) (25 tests) : (1) , (1) , *(50) TIN Pretreatment Diluent Vials AmVer. (25 tests) : (1) , (1) , (1) , *(50) AmVer. Diluent LR Vials /pkg... * /pkg ml...50 ml AmVer /pkg... * /pkg /pkg REQUIRED APPARATUS, 115V , 230V COD/TNT r TenSette., 0.1 to /pkg

197 OPTIONAL REAGENTS Hydrochloric Acid, ACS ml Nitrate Nitrogen Standard Solution, 10 mg/l NO3 --N ml Nitrate Nitrogen Standard Solution, PourRite Ampules, 500 mg/l NO3--N, 2 ml... 20/pkg Sodium Hydroxide Standard Solution, 5.0 N ml SCDB Sodium Thiosulfate Standard Solution, 0.1 N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Cylinder, graduated, mixing, 25 ml... each Flask, volumetric, Class A, 50.0 ml... each ph Indicator Paper, 1 to 11 ph... 5 rolls/pkg Pipet, volumetric, Class A, 2.0 ml... each PourRite Ampule Breaker... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 197

198 C N 02:00 Timer 2 198

199 05:00 Timer 3 199

200 10% >60ppm >1000 ppm mg/l) mg/l (3+) ppb ph 13 ph Hach chemists tested this chemistry on standard nitrogen solutions prepared from the following compounds and obtained 95% recovery:. Ammonium chloride. Ammonium sulfate. Ammonium acetate. Urea. Glycine Ammonium chloride or nicotinic-ptsa spikes in domestic influent, effluent and the ASTM standard specification for substitute wastewater (D ) also resulted in 95% recovery. Large amounts of nitrogen-free organic compounds in some samples may decrease digestion efficiency by consuming some of the persulfate reagent. Samples known to contain high levels of organics should be diluted and re-run to verify digestion efficiency. Sampling and Storage Collect samples in clean plastic or glass bottles. Best results are obtained with immediate analysis. Preserve the sample by reducing the ph to 2 or less with concentrated sulfuric acid (at least 2 ml). Store at 4 ãc (39 ãf) or less. Preserved samples may be stored up to 28 days. Warm samples to room temperature and neutralize with 5 N sodium hydroxide before analysis. Correct the test result for volume additions; see Correcting for Volume Additions in Section

201 Accuracy Check This method generally yields % recovery on organic nitrogen standards. For proof of accuracy Hach offers a set of three Primary Standards for Kjeldahl Nitrogen. 1. Prepare one or more of the following three solutions. Each preparation is for an equivalent 25 mg/l N standard. Use water that is free of all organic and nitrogen-containing species. a) Weigh g of Ammonium p-toluenesulfonate (PTSA). Dissolve in a 1000-mL volumetric flask with deionized water. Add deionized water to the 1000-mL mark. b) Weigh g of Glycine p-toluenesulfonate. Dissolve in a 1000-mL volumetric flask with deionized water. Add deionized water to the 1000-mL mark. c) Weigh g of Nicotinic p-toluenesulfonate. Dissolve in a 1000-mL volumetric flask with deionized water. Add deionized water to the 1000-mL mark. 2. Analyze each of these solutions using the test procedure above. Calculate the percent recovery for each using this formula: Hach analysts have found Ammonia-PTSA to be the most difficult to digest. Other compounds may yield different percent recoveries. Standard Solution Method Substitute 2 ml of a 20 mg/l ammonia nitrogen standard solution for the sample. To prepare a 20-mg/L standard, use a 20-mL Class A pipet to transfer 20 ml of a 100-mg/L Ammonia Nitrogen Standard (see Optional Reagents) to a 100-mL Class A volumetric flask. Dilute to the line with organic-free water. A single analyst should obtain less than 5% variation on replicates. Comparison of the user-obtained value with the standard concentration is an indication of test performance for this user. Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off an Ammonia Nitrogen Voluette Ampule Standard Solution, 160 mg/l as NH3-N. c) Use the TenSette Pipet to add 0.3 ml, 0.6 ml, and 0.9 ml of standard, respectively, to the three mixing cylinders. d) Stopper each cylinder and mix thoroughly. e) Add 2 ml of each prepared solution, respectively, to three TN Hydroxide Reagent Sample Digestion Vials. 201

202 f) Analyze each standard addition sample as described in the procedure. The nitrogen concentration should increase 2 mg/l for each 0.3 ml of standard added. g) If these increases do not occur, see Standard Additions in Section 1 for troubleshooting information. Blanks for Colorimetric Measurement The reagent blank may be used up to 7 days for measurements using the same lots of reagents. Store the reagent blank in the dark at room temperature (18-25 ãc). If a small amount of white floc appears prior to the end of one week, discard the reagent blank and prepare a new one. Method Performance Precision A Hach chemist analyzed two independent nutrient standards. The lowest average percent recovery was 95% with a standard deviation of À2%. In a single laboratory, using a standard solution of 15.0 mg/l N and two lots of reagent with the instrument, a single operator obtained a standard deviation of less than À0.5 mg/l N. For more information on Hach s precision statement, see Section 1. Estimated Detection Limit The estimated detection limit for program 58 is 2 mg/l N. For more information on the estimated detection limit, see Section 1. Summary of Method An alkaline persulfate digestion converts all forms of nitrogen to nitrate. Sodium metabisulfite is added after the digestion to eliminate halogen oxide interferences. Nitrate then reacts with chromotropic acid under strongly acidic conditions to form a yellow complex with an absorbance maximum near 420 nm. REQUIRED REAGENTS Description Cat. No. Test N Tube (100 vials) : TN Reagent C, *, 25/pkg TN*, 25/pkg TN () /pkg TN Reagent A, /pkg TN Reagent B, /pkg COD, 115/230 V, North American Plug COD, 230 V, European Plug COD/TNT TenSette, 0-10 ml

203 /pkg OPTIONAL REAGENTS Nitrogen, Ammonia, 100 mg/l NH3-N ml Nitrogen, Ammonia, Voluette Ampule, 160 mg/l NH3-N, 10 ml... 16/pkg Sulfuric Acid, ACS ml Primary Standards for Kjeldahl Nitrogen...set of Ammonium p-toluenesulfonate g Glycine p-toluenesulfonate g Nicotinic Acid p-toluenesulfonate g Sodium Hydroxide Standard Solution, 5.0 N...50 ml MDB Water, organic-free ml OPTIONAL APPARATUS Ampule Breaker Kit...each Balance, analytical, 115 VAC...each Balance, analytical, 230 VAC...each Cots, finger...2/pkg Cylinder, graduated, mixing, 25 ml (3 required)...each Flask, volumetric, Class A, 1000 ml (3 required)...each Flask, volumetric, Class A, 100 ml...each Pipet, volumetric, Class A, 20 ml...each ph Paper, 1 to 11 ph units...5 rolls/pkg

204 10.0 to mg/l N C 204

205 mg/l, NZERO 02:00 Timer 2 05:00 Timer 3 205

206 0 mg/l N 206

207 10% >240ppm >3000 ppm mg/l) mg/l (3+) ppb ph 13 ph Sampling and Storage Collect samples in clean plastic or glass bottles. Best results are obtained with immediate analysis. Preserve the sample by reducing the ph to 2 or less with concentrated sulfuric acid (at least 2 ml/l). Store at 4 ãc (39 ãf) or less. Preserved samples may be stored up to 28 days. Warm samples to room temperature and neutralize with 5 N sodium hydroxide before analysis. Correct the test result for volume additions; see Correcting for Volume Additions in Section 1. Accuracy Check This method generally yields % recovery on organic nitrogen standards. For proof of accuracy Hach offers a set of three Primary Standards for Kjeldahl Nitrogen. 1. Prepare one or more of the following three solutions. Each preparation is for an equivalent 120 mg/l N standard. Use water that is free of all organic and nitrogen-containing species. a) Weigh g of Ammonium p-toluenesulfonate (PTSA). Dissolve in a 1000-mL volumetric flask with deionized water. Add deionized water to the 1000-mL mark. b) Weigh g of Glycine p-toluenesulfonate. Dissolve in a 1000-mL volumetric flask with deionized water. Add deionized water to the 1000-mL mark. c) Weigh g of Nicotinic p-toluenesulfonate. Dissolve in a 1000-mL volumetric flask with deionized water. Add deionized water to the 1000-mL mark. 207

208 2. Analyze each of these solutions using the test procedure above. Calculate the percent recovery for each using this formula: Hach analysts have found Ammonia-PTSA to be the most difficult to digest. Other compounds may yield different percent recoveries. Standard Solution Method For proof of accuracy, substitute 0.5 ml of a 125 mg/l ammonia nitrogen standard solution for the sample in the procedure. To prepare a 125-mg/L standard, use a 25-mL Class A pipet to transfer ml of a 1000-mg/L Ammonia Nitrogen Standard (see OPTIONAL REAGENTS on page 370) to a 200-mL Class A volumetric flask. Dilute to the line with organic-free water. Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off an Ammonia Nitrogen Voluette. Ampule Standard Solution, 1000 mg/l as NH3-N. c) Use the TenSette. Pipet to add 0.1 ml, 0.2 ml, and 0.3 ml of standard, respectively, to the three mixing cylinders. d) Stopper each cylinder and mix thoroughly. e) Add 0.5 ml of each prepared solution, respectively, to three HR Total Nitrogen Hydroxide Digestion Vials. f) Analyze each standard addition sample as described in the procedure. The nitrogen concentration should increase 4 mg/l N for each 0.1 ml of standard added. g) If these increases do not occur, see Standard Additions in Section 1 for troubleshooting information. Blanks for Colorimetric Measurement The reagent blank may be used repeatedly for measurements using the same lots of reagents. Store the reagent blank in the dark at room temperature (18 C25 ãc) for a maximum of seven days. If a small amount of white floc appears prior to the end of one week, discard the reagent blank and prepare a new one. Method Performance Precision In a single laboratory, using a standard solution of 125 mg/l N and two lots of reagent with the instrument, a single operator obtained a standard deviation of less than 3 mg/l N. For more information on Hach s precision statement, see Section

209 Estimated Detection Limit The estimated detection limit for program 69 is 7 mg/l N. For more information on the estimated detection limit, see Section 1. Summary of Method An alkaline persulfate digestion converts all forms of nitrogen to nitrate. Sodium metabisulfite is added after the digestion to eliminate halogen oxide interferences. Nitrate then reacts with chromotropic acid under strongly acidic conditions to form a yellow complex with an absorbance maximum near 420 nm. REQUIRED REAGENTS Test N Tube HR (50 vials) : (1) , (1) , (1) , *(50) Hydroxide Digestion Vials, *(50) Acid Solution Vials HR /pkg... * () /pkg A, /pkg B, /pkg C, /pkg... * COD, 115/230 V, North American Plug COD, 230 V, European Plug COD TenSette, 0-10 ml /pkg OPTIONAL REAGENTS Nitrogen, Ammonia, 1000 mg/l NH3-N... 1 L Nitrogen, Ammonia, Voluette Ampule, 1000 mg/l NH3-N, 10 ml... 16/pkg Sulfuric Acid, ACS ml Primary Standards for Kjeldahl Nitrogen...set of Ammonium p-toluenesulfonate...25 g Glycine p-toluenesulfonate...25 g Nicotinic Acid p-toluenesulfonate...25 g Sodium Hydroxide Standard Solution, 5.0 N...50 ml MDB Water, organic-free ml

210 OPTIONAL APPARATUS Description Unit Cat. No. Ampule Breaker Kit...each Balance, analytical, 115 Vac...each Balance, analytical, 230 Vac...each Cots, finger... 2/pkg Cylinder, graduated, mixing, 25 ml each Flask, volumetric, Class A, 1000 ml each Flask, volumetric, Class A, 200 ml...each Pipet, volumetric, Class A, 25 ml each ph Paper, 1 to 11 ph units...5 rolls/pkg For Technical Assistance, Price and Ordering In the U.S.A. ªCall Out side the U.S.A ª Contact the Hach office or distributor serving you. Outside the U.S.A. ªContact the Hach office or distributor serving you. 210

211

212 212

213 0 mg/l C 213

214 600ml/L PH7 50NTU Sampling and Storage Collect samples in clean glass bottles. Rinse the sample bottle several times with the sample to be collected. Fill the bottle with minimum headspace before capping. Test samples as soon as possible. Acid preservation is not recommended. Homogenize samples containing solids to assure representative samples 214

215 Accuracy Check Standard Solutions Method a. Prepare a 1000 mg/l organic carbon stock standard by dissolving g dry primary standard Potassium Acid Phthalate in Organic-Free Reagent Water and dilute to 1000 ml. This stock standard is stable for about 1 month at room temperature. Alternatively, open one ampule of TOC Standard Solution (Cat. No ). b. Prepare a 10.0 mg/l C standard by transferring ml of the stock standard to a 1000-mL Class A volumetric flask. Dilute to volume using Organic-Free Reagent Water. Stopper and mix thoroughly. Prepare this standard fresh daily. Standard Additions Method a. Prepare a 150 mg/l C standard by transferring ml of 1000 mg/l C stock solution to a 100-mL Class A volumetric flask. Dilute to volume with organic-free water. Mix. b. Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of the 150 mg/l C standard to each of three Acid Digestion vials. c. Add the contents of one TOC Persulfate powder pillow to each vial. d. Add 3.0 ml of sample to each vial. Swirl to mix. e. Proceed with the procedure starting at step 8. f. The mg/l C concentration should increase by 5.0 mg/l for each 0.1 ml increment. Method Performance Precision In a single laboratory, using a standard solution of 9.0 mg/l C and one lot of reagents, a single operator obtained a standard deviation of À0.5 mg/l C. Estimated Detection Limit The estimated detection limit for Method is 0.3 mg/l C. Sensitivity At mid-range, the sensitivity, expressed as the concentration change per absorbance change, is 0.2 mg/l C. Summary of Method The total organic carbon (TOC) is determined by first sparging the sample under slightly acidic conditions to remove the inorganic carbon. In the outside vial, organic carbon in the sample is digested by persulfate and acid to form carbon dioxide. During digestion, the carbon dioxide diffuses into a ph indicator reagent in the inner ampule. The adsorption of carbon dioxide into the indicator forms carbonic acid. Carbonic acid changes the ph of the indicator solution which, in turn, changes the color. The amount of color change is related to the original amount of carbon present in the sample. 215

216 Test N Tube...50 vials : /pkg...* ml..25 ml , Low Range TOC /pkg...* TOC() /pkg...* ** ml.500 ml COD, 115/230 V ac (U.S.A. and Canada) COD, 115/230 V ac (Europe) ,10-mL , 50-mL TenSette., 0.1 to 1.0 ml TenSette., 1.0 to 10.0 ml , for TenSette. Pipet /pkg , for TenSette. Pipet /pkg Wipes, Disposable, Kimwipes /pkg OPTIONAL REAGENTS TOC Standard Solution (KHP Standard, 1000 mg/l C)... 5/pkg Potassium Acid Phthalate g Sulfuric Acid Reagent Solution, 5.25 N ml MDB OPTIONAL APPARATUS Analytical Balance...each Flask, volumetric, 1000-mL...each Flask, volumetric, 100-mL...each Pipet, Class A, mL...each Pipet, Class A, mL...each

217

218 218

219 0 mg/l C 219

220 600ml/L PH7 50NTU Sampling and Storage Collect samples in clean glass bottles. Rinse the sample bottle several times with the sample to be collected. Fill the bottle with minimum headspace before capping. Test samples as soon as possible. Acid preservation is not recommended. Homogenize samples containing solids to assure representative samples. 220

221 Accuracy Check Standard Solutions Method a. Prepare a 1000 mg/l organic carbon stock standard by dissolving g dry primary standard Potassium Acid Phthalate in Organic-Free Reagent Water and dilute to 1000 ml. This stock standard is stable for about 1 month at room temperature. Alternatively, open one ampule of TOC Standard Solution (Cat. No ). b. Prepare a 300 mg/l C standard by transferring ml of the stock standard to a 50-mL Class A volumetric flask. Dilute to volume using Organic-Free Reagent Water. Stopper and mix thoroughly. Prepare this standard fresh weekly. Standard Additions Method a. Prepare a 300 mg/l C standard by transferring ml of 1000 mg/l C stock solution to a 50-mL Class A volumetric flask. Dilute to volume with Organic-Free Water. Mix. b. Use the TenSette Pipet to add 0.1, 0.2, and 0.3 ml of the 300 mg/l C standard to each of three Acid Digestion vials. c. Add the contents of one TOC Persulfate powder pillow to each vial. d. Add 0.3 ml of sample to each vial. Swirl to mix. e. Proceed with the procedure starting at step 8. f. The mg/l C concentration should increase by 100 mg/l for each 0.1 ml increment. Method Performance Precision In a single laboratory, using a standard solution of 360 mg/l C and one lot of reagents, a single operator obtained a standard deviation of À8 mg/l C. Estimated Detection Limit Use Method Number to test TOC levels below 20 mg/l C. Sensitivity At mid-range, the sensitivity, expressed as the concentration change per absorbance change, is 6 mg/l C. Summary of Method The total organic carbon (TOC) is determined by first sparging the sample under slightly acidic conditions to remove the inorganic carbon. In the outside vial, organic carbon in the sample is digested by persulfate and acid to form carbon dioxide. During digestion, the carbon dioxide diffuses into a ph indicator reagent in the inner ampule. The adsorption of carbon dioxide into the indicator forms carbonic acid. Carbonic acid changes the ph of the indicator solution which, in turn, changes the color. The amount of color change is related to the original amount of carbon present in the sample. 221

222 Test N Tube...50 vials : /pkg...* ml..25 ml , Low Range TOC /pkg...* TOC() /pkg...* ** ml..500 ml COD, 115/230 V ac (U.S.A. and Canada) COD, 115/230 V ac (Europe) ,10-mL , 50-mL TenSette., 0.1 to 1.0 ml TenSette., 1.0 to 10.0 ml , for TenSette. Pipet /pkg , for TenSette. Pipet /pkg Wipes, Disposable, Kimwipes /pkg OPTIONAL REAGENTS TOC Standard Solution (KHP Standard, 1000 mg/l C)... 5/pkg Potassium Acid Phthalate g Sulfuric Acid Reagent Solution, 5.25 N ml MDB OPTIONAL APPARATUS Analytical Balance...each Flask, volumetric, 1000-mL...each Flask, volumetric, 100-mL...each Pipet, Class A, mL...each Pipet, Class A, mL...each

223 223

224 224

225 0 mg/l COD 225

226 226

227 0 mg/l COD 227

228 COD COD 2COD 0.50g COD 3 Cl (mg/l) Cl mg/l ,000 10,000 40,000 Cl- 0.5g HgSO4 mg/l Sampling and Storage Collect samples in glass bottles. Use plastic bottles only if they are known to be free of organic contamination. Test biologically active samples as soon as possible. Homogenize samples containing solids to assure representative samples. Samples treated with sulfuric acid to a ph of less than 2 (about 2 ml per liter) and refrigerated at 4 C can be stored up to 28 days. Correct results for volume additions; see Correction for Volume Additions (Section 1) for more information. Accuracy Check Standard Solution Method Check the accuracy of the 0 to 150 mg/l range with a 100 mg/l standard. Prepare by dissolving 85 mg of dried (120 C, overnight) potassium acid phthalate (KHP) in 1 liter of deionized water. Use 2.0 ml as the sample volume. The expected result will be 100 mg/l COD. As an alternative, dilute 10 ml of 1000-mg/L COD Standard Solution to 100 ml to make a 100-mg/L standard. Check the accuracy of the 0 to 1,500 mg/l range by using either a 300 mg/l or 1000 mg/l COD Standard Solution. Alternatively, prepare a 500 mg/l standard by dissolving 425 mg of dried (120 C, overnight) KHP. Dilute to 1 liter with deionized water. Use 2.0 ml of one of these solutions as the sample volume. Check the accuracy of the 0 to 15,000 mg/l range by using a 10,000 mg/l COD standard solution. Prepare the 10,000 mg/l solution by dissolving g of dried (120 C, overnight) KHP in 1 liter of deionized water. Use 0.2 ml of this solution as the sample volume; the expected result will be 10,000 mg/l COD. Method Performance Precision Program #16: In a single laboratory, using a standard solution of 100 mg/l COD and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 2 mg/l COD. Program #17: In a single laboratory, using a standard solution of 1000 mg/l COD and 228

229 two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 16 mg/l COD. For more information on Hach s precision statement, see Section 1. Estimated Detection Limit (EDL) The EDL for program 16 is 4 mg/l COD. The EDL for program 17 is 30 mg/l COD. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Blanks for Colorimetric Determination The blank may be used repeatedly for measurements using the same lot of vials. Store it in the dark. Monitor decomposition by measuring the absorbance at the appropriate wavelength (420 or 610 nm). Zero the instrument in the absorbance mode, using a vial containing 5 ml of deionized water and measure the absorbance of the blank. Record the value. Prepare a new blank when the absorbance has changed by about 0.01 absorbance units. Summary of Method The mg/l COD results are defined as the mg of O2 consumed per liter of sample under conditions of this procedure. In this procedure, the sample is heated for two hours with a strong oxidizing agent, potassium dichromate. Oxidizable organic compounds react, reducing the dichromate ion (Cr2O72-) to green chromic ion (Cr3+). When the mg/l colorimetric method is used, the amount of Cr6+ remaining is determined. When the 0-1,500 mg/l or 0-15,000 mg/l colorimetric method is used, the amount of Cr3+ produced is determined. The COD reagent also contains silver and mercury ions. Silver is a catalyst, and mercury is used to complex the chloride interference. Pollution Prevention and Waste Management Final samples will contain mercury (D009), silver (D011), and chromium (D007) at concentration levels regulated by the Federal RCRA. Please see Section 3 for further information on proper disposal of these materials. COD :, 0 to 150 mg/l COD... 1 to /pkg , 0 to 1,500 mg/l COD... 1 to /pkg Plus, 0 to 15,000 mg/l COD... 1 to /pkg L REQUIRED APPARATUS, 120 V, 14 speed COD, 115/230 V COD, 230 V, European-style plug COD/TNT

230 TenSette., 0.1 to 1.0 ml , for TenSette. Pipet /pkg Pipet, volumetric, Class A, 2.00 ml Pipet Filler, safety bulb to 2 racks OPTIONAL REAGENTS Description Unit Cat. No. COD Digestion Reagent Vials, 0 to 150 mg/l COD /pkg COD Digestion Reagent Vials, 0 to 1,500 mg/l COD /pkg COD Standard Solution, 300 mg/l ml COD Standard Solution, 1000 mg/l ml Mercuric Sulfate grams Potassium Acid Phthalate, ACS g Potassium Dichromate Standard Solution, 0.25 N ml* Sulfuric Acid, ACS ml* OPTIONAL APPARATUS Balance, analytical, 115 V... each Balance, analytical, 230 V... each Beaker, 250 ml... each Cylinder, graduated, 5 ml... each Electromagnetic Stirrer, 120 V, with electrode stand... each Electromagnetic Stirrer, 230 V, with electrode stand... each Flask, volumetric, Class A, 1000 ml... each Flask, volumetric, Class A, 100 ml... each ph Paper, 1 to 11 ph units... 5 rolls/pkg Pipet, serological, 5 ml... each Pipet Tips, for TenSette Pipet... 50/pkg* Pipet, volumetric, Class A, 10 ml... each Safety shield, for laboratory bench... each Spoon, measuring, 0.5 g... each Stir Bar, 22.2 x 4.76 mm (7/8" x 3/16")... each Stir Bar Retriever... each Timer... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 230

231 III COD 231

232 0 mg/l COD 232

233 Sampling and Storage Collect samples in clean glass bottles. Use plastic bottles only if they are known to be free of organic contamination. Test biologically active samples as soon as possible. Homogenize samples containing solids to assure representative samples. Samples treated with concentrated sulfuric acid to a ph of less than 2 (about 2 ml per liter) and refrigerated at 4 ãc may be stored up to 28 days. Correct results for volume additions; see Correcting for Volume Additions (Section 1) for more information. Accuracy Check Standard Solution Method Prepare an 800 mg/l COD standard solution by adding g of dried (103 ãc, overnight) potassium acid phthalate (KHP) to 1 liter of deionized water. Use 0.50 ml of this solution (0.60 ml for the chloride removal procedure) as the sample volume. The result should be 800 À26 mg/l COD. An 800 mg/l COD solution can also be purchased directly from Hach (see Optional Reagents). Method Performance (for Manganic III COD without the chloride removal procedure) Precision In a single laboratory, using a standard solution of 800 mg/l COD and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 23 mg/l COD. Estimated Detection Limit (EDL) The EDL for program 18 is 14 mg/l COD. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Summary of Method Chemical oxygen demand (COD) is defined as... a measure of the oxygen equivalent of the organic matter content of a sample that is susceptible to oxidation by a strong chemical oxidant ± (APHA Standard Methods, 19th ed., 1995). Trivalent manganese is a strong, noncarcinogenic chemical oxidant that changes quantitatively from purple to colorless when it reacts with organic matter. It typically oxidizes about 80% of the organic compounds. Studies have shown that the reactions are highly reproducible and test results correlate closely to Biochemical Oxygen Demand (BOD) values and hexavalent chromium COD tests. None of the oxygen demand tests provide 100% oxidation of all organic compounds.a calibration is provided which is based on the oxidation of Potassium Acid Phthalate (KHP). A different response may be seen in analyzingvarious wastewaters. The KHP calibration is adequate for mostapplications. The highest degree of accuracy is obtained when test resultsare correlated to a standard reference method such as BOD or one of thechromium COD methods. Special waste streams or classes will require aseparate calibration to obtain a direct mg/l COD reading or to generate a correction factor for the precalibrated KHP response. The sampledigestion time can be extended up to 4 hours for samples which are difficult to oxidize. 233

234 COD, mg/l /pkg ml... 4 Kg L COD/TNT , 120 Vac, 14-speed , 118 ml /pkg , with inert Teflon liner, for mixing bottle... varies... 12/pkg COD, 115 V COD r, 230 V, European-style plug , extra fine point , for sample + acid TenSette., 0.1 to 1.0 ml TenSette., 1.0 to 10.0 ml , for TenSette. Pipet /pkg , for TenSette. Pipet /pkg OPTIONAL REAGENTS AND APPARATUS COD Standard Solution, 800 mg/l COD ml Potassium Acid Phthalate g Dispenser for sulfuric acid... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 234

235 TenSette C. 235

236 236

237 23. 0 mg/l COD 237

238 Sampling and Storage Collect samples in clean glass bottles. Use plastic bottles only if they are known to be free of organic contamination. Test biologically active samples as soon as possible. Homogenize samples containing solids to assure representative samples. Samples treated with concentrated sulfuric acid to a ph of less than 2 (about 2 ml per liter) and refrigerated at 4 ãc may be stored up to 28 days. Correct results for volume additions; see Correcting for Volume Additions (Section 1) for more information. Accuracy Check Standard Solution Method Prepare an 800 mg/l COD standard solution by adding g of dried (103 ãc, overnight) potassium acid phthalate (KHP) to 1 liter of deionized water. Use 0.50 ml of this solution (0.60 ml for the chloride removal procedure) as the sample volume. The result should be 800 À26 mg/l COD. An 800 mg/l COD solution can also be purchased directly from Hach (see Optional Reagents). 238

239 Method Performance (for Manganic III COD without the chloride removal procedure) Precision In a single laboratory, using a standard solution of 800 mg/l COD and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 23 mg/l COD. Estimated Detection Limit (EDL) The EDL for program 18 is 14 mg/l COD. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Summary of Method Chemical oxygen demand (COD) is defined as... a measure of the oxygen equivalent of the organic matter content of a sample that is susceptible to oxidation by a strong chemical oxidant ± (APHA Standard Methods, 19th ed., 1995). Trivalent manganese is a strong, noncarcinogenic chemical oxidant that changes quantitatively from purple to colorless when it reacts with organic matter. It typically oxidizes about 80% of the organic compounds. Studies have shown that the reactions are highly reproducible and test results correlate closely to Biochemical Oxygen Demand (BOD) values and hexavalent chromium COD tests. None of the oxygen demand tests provide 100% oxidation of all organic compounds. A calibration is provided which is based on the oxidation of Potassium Acid Phthalate (KHP). A different response may be seen in analyzing various wastewaters. The KHP calibration is adequate for most applications. The highest degree of accuracy is obtained when test results are correlated to a standard reference method such as BOD or one of the chromium COD methods. Special waste streams or classes will require a separate calibration to obtain a direct mg/l COD reading or to generate a correction factor for the precalibrated KHP response. The sample digestion time can be extended up to 4 hours for samples which are difficult to oxidize. (CRC) /pkg COD, mg/l /pkg ml...4 Kg L COD/TNT , 120 Vac, 14-speed , 118 ml /pkg , with inert Teflon liner, for mixing bottle... varies... 12/pkg COD, 115 V COD r, 230 V, European-style plug

240 , extra fine point , for sample + acid TenSette., 0.1 to 1.0 ml TenSette., 1.0 to 10.0 ml , for TenSette. Pipet /pkg , for TenSette. Pipet /pkg (VPD) , 115 V , 230V OPTIONAL REAGENTS AND APPARATUS COD Standard Solution, 800 mg/l COD ml Potassium Acid Phthalate g Dispenser for sulfuric acid...each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 240

241 241

242 0.0 mg/l O2 Cr3+ Cu2+ Fe2+ Mg2+ Mn2+ Ni2+ NO2 Sampling and Storage The main consideration in sampling with the High Range Dissolved Oxygen AccuVac Ampul is to prevent the sample from becoming contaminated with atmospheric oxygen. This is accomplished by capping the ampul with an ampul cap in the interval between breaking open the ampul and reading the absorbance. If the ampul is securely capped, it should be safe from contamination for several hours. The absorbance will decrease by approximately 3% during the first hour and will not change significantly afterwards. Sampling and sample handling are important considerations in obtaining meaningful results. The dissolved oxygen content of the water beingtested can be expected to change with depth, turbulence, temperature, sludge deposits, light, microbial action, mixing, travel time and other factors. A single dissolved oxygen test rarely reflects the accurate over-all condition of a body of water. Several samples taken at different times, locations and depths are recommended for most reliable results. Samples must be tested 242

243 immediately upon collection although only a small error results if the absorbance reading is taken several hours later. Accuracy Check The results of this procedure may be compared with the results of a titrimetric procedure (request lit. code number 8042) or dissolved oxygen meter (Cat. No ). Method Performance Precision In a single laboratory, using a standard solution of 8.0 mg/l O2 determined by the Winkler method and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of À0.41 mg/l O2. Estimated Detection Limit The estimated detection limit for program 70 is 0.10 mg/l O2. For more information on the estimated detection limit, see Section 1. Summary of Method The High Range Dissolved Oxygen AccuVac Ampul contains reagent vacuum sealed in a 12-mL ampul. When the AccuVac ampul is broken open in a sample containing dissolved oxygen, a yellow color forms, which turns purple as the oxygen reacts with the reagent. The color developed is proportional to the concentration of dissolved oxygen. AccuVac /pkg , 50 ml /pkg , ml, w/ cap /pkg OPTIONAL REAGENTS AND APPARATUS AccuVac Dissolved Oxygen Sampler... each AccuVac Snapper Kit... each AccuVac Drainer... each BOD bottle and stopper, 300 ml... each Dissolved Oxygen Meter, sension.6, Portable... each Dissolved Oxygen Reagent Set (Buret Method) tests Dissolved Oxygen Reagent Set (Digital Titrator Method) tests Dissolved oxygen may also be determined by titrimetric methods. Request Publication 8042 for additional information. For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 243

244 0 μg/l O2 μ 244

245 Sampling and Storage The main consideration in this procedure is to prevent contaminating the sample with atmospheric oxygen. Sampling from a stream of water that is hard plumbed to the sample source is ideal. Use a funnel to maintain a continual flow of sample and yet collect enough sample to immerse the ampul. It is important not to introduce air in place of the sample. Rubber tubing, if used, will introduce unacceptable amounts of oxygen into the sample unless the length of tubing is minimized and the flow rate is maximized. Flush the sampling system with sample for at least 5 minutes. Accuracy Check The reagent blank for this test can be checked by following these steps: a) Fill a 50-mL beaker with sample and add approximately 50 mg sodium hydrosulfite. b) Immerse the tip of a Low Range Dissolved Oxygen AccuVac Ampul in the sample and break the tip. Keep the tip immersed while the ampul fills completely. c) Determine the dissolved oxygen concentration according to the preceding procedure. The result should be 0 À1 Ìg/L. Method Performance Precision In a single laboratory, using a standard solution of 500 Ìg/L O2 and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 2 Ìg/L O2. For more information on Hach s precision statement, see Section 1. Estimated Detection Limit The estimated detection limit for program #71 is 10 Ìg/L O2. For more information on the estimated detection limit, see Section 1. Summary of Method When the vacuum-sealed AccuVac ampul is broken open in a sample containing dissolved oxygen, the yellow reagent solution turns blue. The blue color is proportional to the dissolved oxygen concentration. AccuVac /pkg , 50 ml , ml, w/cap /pkg OPTIONAL REAGENTS AND APPARATUS AccuVac Snapper Kit...each Sodium Hydrosulfite, technical grade g For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 245

246 246

247 Sampling The chief consideration when collecting a sample is to prevent the escape of ozone from the sample. The sample should be collected gently and analyzed immediately. Warming the sample or disturbing the sample by stirring or shaking will result in ozone loss. After collecting the sample, do not transfer it from one container to another unless absolutely necessary. Stability of Indigo Reagent Indigo is light-sensitive. Therefore, the AccuVac Ampuls should be kept in the dark at all times. However, the indigo solution decomposes slowly under room light after filling with sample. The blank ampul can be used for multiple measurements during the same day. Method Performance Precision In a single laboratory, using standard solutions of 0.15, 0.28 and 0.96 mg/l ozone for the low, mid and high range, respectively, and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 0.01, À0.02 and À0.02 mg/l O3 for the low, mid and high range tests, respectively. For more information on Hach s precision statement, see Section 1. Estimated Detection Limit The estimated detection limit for the programs #72, #73, and #74 is 0.02 mg/l O3. For more information on the estimated detection limit, see Section 1. Summary of Method The reagent formulation adjusts the sample ph to 2.5 after the ampul has filled. The indigo reagent reacts immediately and quantitatively with ozone. The blue color of indigo is bleached in proportion to the amount of ozone present in the sample. Other reagents in the formulation prevent chlorine interference. No transfer of sample is needed in the procedure. Therefore, ozone loss due to sampling is eliminated. 247

248 AccuVac : mg/l /pkg mg/l /pkg mg/l /pkg L , 50 ml OPTIONAL APPARATUS AccuVac Snapper Kit...each AccuVac Ampule sampler...each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 248

249 0 mg/l PH 249

250 Sampling and Storage Analyze samples immediately for best results. Accuracy Check Standard Solution Method Using a clear ph 7.0 buffer solution as the sample, perform the ph procedure as described above. Method Performance Precision In a single laboratory using a standard solution of ph 7.0 and two lots of reagent with the instrument, a single operator obtained a standard deviation of less than 0.1 ph units. Estimated Detection Limit The estimated detection limit for program 75 is a ph of 6.5. Standard Adjust To adjust the calibration curve using the reading obtained with the 7.0 buffer solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 7.0 to edit the standard concentration to match that of the standard used. See Section 1, Standard Curve Adjustment for more information. Press ENTER to complete the curve adjustment. 250

251 Summary of Method This method uses a sulfonphthalein indicator (Phenol Red) to determine ph colorimetrically. Phenol Red has a working range of ph 6.8 (yellow) to 8.2 (red)., 0.5 & 1.0 ml marks /pkg Phenol Red, spec grade ml...50 ml , ml, w/ cap /pkg OPTIONAL REAGENTS ph 7.0 Buffer Solution ml OPTIONAL APPARATUS Description Units Cat. No. Thermometer, -10 to 110 ãc... each For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving you. 251

252 PO4 252

253 PhosVer 3 2:00 TIMER 2 253

254 0.0 mg/l PO

255 5mL 5.00mL100 mg/l100 mg/l 10mL50mg/L, CDTA,,, EDTA,,, Diethanoldithiocarbamate, NTA ph 100 mg/l 10mg/L 1000mg/L 5000 mg/l 100 mg/l30 50 mg/l 200 mg/l 250 mg/l 15 mg/l 500 mg/l 10 mg/l Sampling and Storage Collect samples in clean plastic or glass bottles that have been cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use a commercial detergent. If prompt analysis is impossible, adjust the ph to 2 or less with about 2 ml of sulfuric acid, ACS, per liter of sample. Store at 4 ãc (39 ãf) or below. Preserved samples can be stored at least 24 hours. See Section 1 for more information on dilution factors, cleaning instructions, etc. Accuracy Check Ideally, a solution containing a known amount of the phosphonate product being used should be prepared. This will check the UV conversion of phosphonate to orthophosphate. Summary of Method This method is directly applicable to boiler and cooling tower samples. The procedure is based on a UV catalyzed oxidation of phosphonate to orthophosphate. Range may be as low as 0 to 2.5 mg/l or as high as 0 to 125 mg/l. Phosphonate is converted to orthophosphate during the UV digestion. Both the sample and the blank will develop color if orthophosphate is present in the sample. The increase in color in the sample is proportional to the phosphate produced in the digestion. 255

256 (100 tests) : (2) , (1) PhosVer /pkg () /pkg L , 50 ml , UV safety , 25 ml Pipet Filler, safety bulb , ml, w/cap /pkg , 115 V , 230 V OPTIONAL REAGENTS Hydrochloric Acid, 6.0 N (1:1) ml Sulfuric Acid, ACS ml OPTIONAL APPARATUS Cord Adapter, single to dual UV lamp...each ph Paper, 1 to 11 ph units...5 rolls/pkg Pipet, serological, 2 ml...each Pipet, TenSette, 1-10 ml...each Pipet Tips, for Tensette Pipet...50/pkg Pipet Tips, for Tensette Pipet /pkg Thermometer, -10 to 110 ãc...each UV Lamp, without power supply...each For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving you. 256

257 (0 to 45.0 mg/l) PO4 0.0 mg/l PO4 257

258 258

259 Sampling and Storage Collect samples in clean plastic or glass bottles that have been cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use a commercial detergent containing phosphate for cleaning glassware used in this test. Analyze samples immediately for best results. If prompt analysis is impossible, preserve samples by filtering immediately and storing at 4 ãc for up to 48 hours. Accuracy Check Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a Phosphate Voluette Ampule Standard Solution, 500 mg/l as PO4. c) Use the TenSette Pipet to add 0.1 ml, 0.2 ml and 0.3 ml of standard, respectively, to the three mixing cylinders. Stopper and invert to mix well. d) For analysis with AccuVac Ampuls, transfer the spiked samples to clean, dry 50-mL beakers to facilitate filling of the ampuls. For analysis with reagent solution, transfer the spiked samples to 25-mL sample cells. e) Analyze each sample as described in the procedure. Each 0.1-mL addition of standard should cause an increase of 2.0 mg/l PO4 3-. f) If these increases do not occur, see Standard Additions (Section 1) for more information. Standard Solution Method Obtain a Hach Phosphate Standard Solution, 10.0 mg/l as phosphate. Using this solution as the sample, perform the phosphate procedure as described above. Standard Adjust To adjust the calibration curve using the reading obtained with the 10.0 mg/l standard solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 10.0 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Standard Curve Adjustment, Section 1 for more information. Method Performance Precision In a single laboratory using a standard solution of 30.0 mg/l PO43-, two lots of reagent, and the instrument, a single operator obtained a standard deviation of À0.1 mg/l PO4 3- for the reagent solution method and a standard deviation of À0.2 for the AccuVac Ampul method. Estimated Detection Limit The estimated detection limit for program 77 is 0.3 mg/l PO4 3- and 0.4 mg/l PO4 3- for program 78. For more information on the estimated detection limit, see Section 1. Summary of Method In the molybdovanadate method, orthophosphate reacts with molybdate in an acid medium to produce a phosphomolybdate complex. In the presence of vanadium, yellow vanadomolybdophosphoric acid is formed. The intensity of the yellow color is proportional to the phosphate concentration. 259

260 () Molybdovanadate ml ml* MDB , ml, w/ cap /pkg ml... 4 L () Molybdovanadate /pkg , 50 ml ml... 4 L OPTIONAL REAGENTS Description Units Cat. No. Bromine Water, 30 g/l...29 ml* Hydrochloric Acid Solution, 1:1 (6.0 N) ml Phenol Solution, 30 g/l...29 ml Phosphate Standard Solution, 10.0 mg/l as PO ml Phosphate Standard Solution, Voluette Ampule, 500 mg/l as PO43-, 10 ml... 16/pkg Sodium Hydroxide Standard Solution, 5.0 N ml* MDB Sulfuric Acid, ACS ml* OPTIONAL APPARATUS AccuVac Snapper Kit... each Ampule Breaker Kit... each Cylinder, graduated, 25 ml... each Cylinder, graduated, mixing, 25-mL... each Dispenser, fixed volume, 1.0 ml Repipet Jr.... each Flask, erlenmeyer, 50 ml... each Flask, volumetric, Class A, 50 ml... each ph Paper, 1 to 11 ph units... 5 rolls/pkg ph Meter, Sension.1, portable... each Pipet, serological, 2.0 ml... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Thermometer, -10 to 110 ãc... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 260

261 ~ PO4 PhosVer mg/l PO4 261

262 200 mg/l, 100mg/L 10mg/L 300 mg/l 50mg/L 6 mg/l 125mL50mL mg/l ph Sampling and Storage Collect sample in plastic or glass bottles that have been cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use commercial detergents containing phosphate for cleaning glassware used in this test. Analyze samples immediately after collection for best results. If prompt analysis is impossible, preserve samples for up to 48 hours by filtering immediately and storing samples at 4 ãc. Warm to room temperature before testing. 262

263 Accuracy Check Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a Phosphate PourRite Ampule Standard Solution, 50 mg/l as PO4 c) Use the TenSette Pipet to add 0.1 ml, 0.2 ml, and 0.3 ml of standard, respectively, to the three mixing cylinders. Stopper each and mix thoroughly. d) For analysis with AccuVacs, transfer solutions to dry, clean 50 ml beakers to fill the AccuVac ampules. For analysis with powder pillows, transfer only 10 ml of solution to the sample cells. e) Analyze each standard addition sample as described in the procedure. The phosphate concentration should increase 0.2 mg/l PO43- for each 0.1 ml of standard added. f) If these increases do not occur, see Standard Additions in Section 1. Standard Solution Method Prepare a 2.0 mg/l PO43- standard solution by pipetting 4.0 ml of Phosphate Standard Solution, 50 mg/l as PO4 3-, into an acid-washed Class A 100-mL volumetric flask. Dilute to volume with deionized water. Stopper and invert to mix. Use this solution in place of the sample in the procedure to insure the accuracy of the test. The mg/l PO4 3- reading should be 2.00 mg/l. Method Performance Precision In a single laboratory using a standard solution of 1.00 mg/l PO43- and two lots of reagents with the instrument, a single operator obtained a standard deviation of À0.05 mg/l PO4 3- In a single laboratory using a standard solution of 1.00 mg/l PO43- and two representative lots of AccuVac ampuls with the instrument, a single operator obtained a standard deviation of À0.03 mg/l PO4 3-. Estimated Detection Limit (EDL) The EDL for program 79 is 0.05 mg/l PO4. For more information on the estimated detection limit, see Section 1. Summary of Method Orthophosphate reacts with molybdate in an acid medium to produce a Phosphomolybdate complex. Ascorbic acid then reduces the complex, giving an intense molybdenum blue color. () PhosVer 3 10 ml sample size /pkg , ml, w/cap /pkg () PhosVer 3 AccuVac /pkg , 50 ml

264 /pkg , ml, w/cap /pkg OPTIONAL REAGENTS Hydrochloric Acid Standard Solution, 6.0 N (1:1) ml Phosphate Pretreatment Powder Pillows... 50/pkg Phosphate Standard Solution, PourRite ampule, 50 mg/l as PO4 3-, 2 ml... 20/pkg Phosphate Standard Solution, Voluette Ampul, 50 mg/l, 10 ml... 16/pkg Sodium Hydroxide Standard Solution, 5.0 N ml* MDB Water, deionized...4 L OPTIONAL APPARATUS AccuVac Snapper Kit... each Ampule Breaker Kit for 10-ml ampules... each Aspirator, vacuum... each Cylinder, graduated, mixing, 25 ml, tall (3 required)... each Filter Holder, 47 mm, 300 ml, graduated... each Filter, membrane, 47 mm, 0.45 microns /pkg Flask, filtering, 500 ml... each Flask, volumetric, Class A, 100 ml... each ph Indicator Paper, 1 to 11 ph... 5 rolls/pkg ph Meter, Sension.1, portable... each Pipet, 2 ml serological... each Pipet, TenSette, 0.1 to 1.0 ml TenSette Pipet... each Pipet Tips, for /pkg Pipet Filler, safety bulb... each Pipet, volumetric, Class A, 4.00 ml... each PourRite Ampule Breaker Kit... each For Technical Assistance, Prices and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving you. 264

265 5 6 2ml 5N 3 25ml * = ++ * 265

266 Sampling and Storage Collect samples in plastic or glass bottles that have been acid-washed with 1:1 HCl and rinsed with deionized water. Do not use detergents containing phosphates for cleaning glassware used in this test. Analyze samples immediately after collection for best results. If prompt analysis is impossible, preserve samples up to 28 days by adjusting the ph to 2 or less with concentrated sulfuric acid (about 2 ml per liter) and storing at 4 ãc. Warm to room temperature before testing. Correct results for volume additions; see Volume Additions (Section 1) for more information. Interferences For turbid samples, use 50 ml of sample and double the reagent quantities. Use digested sample to zero the instrument in the reactive phosphorus procedure. This compensates for any color or turbidity destroyed by this procedure. For alkaline or highly buffered samples it may be necessary to add additional acid in Step 3 to drop the ph of the solution below 1. Summary of Method Phosphates present in organic and condensed inorganic forms (meta-, pyro- or other polyphosphates) must be converted to reactive orthophosphate before analysis. Pretreatment of the sample with acid and heat provides the conditions for hydrolysis of the condensed inorganic forms. Organic phosphates are converted to orthophosphate by heating with acid and persulfate. Organically bound phosphates are thus determined indirectly by subtracting the result of an acid hydrolyzable phosphorus test from the total phosphorus result. This procedure must be followed by one of the reactive phosphorus(orthophosphate) analysis methods for determination of the phosphorus content of the sample. If the ascorbic acid (PhosVer 3) method is used to measure the reactive phosphorus, this method is EPA approved for NPDES reporting. The following reagents and apparatus are required in addition to those required for the reactive phosphorus test /pkg , 5.0 N... 2 ml ml* MDB , 5.25 N... 2 ml ml* MDB , 25 ml , 50 ml , ml, w/caps /pkg OPTIONAL REAGENTS Hydrochloric Acid, 6 N ml

267 Sodium Hydroxide Solution, 5.0 N... 1 L Sulfuric Acid ml Water, deionized... 4 L OPTIONAL APPARATUS Description Unit Cat. No. Cylinder, graduated, 50 ml... each Flask, erlenmeyer, 125 ml... each Hot Plate, 4" diameter, 120 Vac... each Hot Plate, 4" diameter, 240 Vac... each Pads, cooling, 4 x 4" each ph Indicator Paper, 1 to 11 ph rolls/pkg ph Meter, Sension.1, portable each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 267

268 * = + 268

269 Sampling and Storage Analyze samples immediately after collection for best results. If prompt analysis is not possible, samples may be preserved up to 48 hours by cooling to 4 ãc (39 ãf). Warm to room temperature before testing. Summary of Method This procedure lists the necessary steps to convert condensed phosphate forms (meta-, pyro- or other polyphosphates) to reactive orthophosphate before analysis. The procedure uses acid and heat to hydrolyze the sample. Organic phosphates are not converted to orthophosphate by this process, but a very small fraction may be unavoidably included in the result. Thus, the acid hydrolyzable ± phosphate results are primarily a measure of inorganic phosphorus. This procedure must be followed by one of the reactive phosphorus (orthophosphate) analysis methods for determination of the phosphorous content of the sample. The following reagents and apparatus are required in addition to those required for the reactive phosphorus test., 5.0 N... 2 ml ml* MDB , 5.25 N... 2 ml ml* MDB , 25 ml , 50 ml OPTIONAL REAGENTS Hydrochloric Acid, 6 N ml Water, deionized... 4 L OPTIONAL APPARATUS Cylinder, graduated, 50 ml... each Flask, erlenmeyer, 125 ml... each Hot Plate, 4" diameter, 120 Vac... each Hot Plate, 4" diameter, 240 Vac... each Pad, cooling, 4" x 4"... each ph indicator Paper, 1 to 11 ph... 5 rolls/pkg ph Meter, sension.1, portable... each Thermometer, -10 to 110 ãc... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 269

270 Test N tube PO4 TenSette 5 Test 'N Tube 0.00 mg/l PO4 270

271 PhosVer 3 PhosVer 3 271

272 , ph 200 mg/l 100mg/L 10mg/L 300 mg/l 50mg/L 6 mg/l 425mL50mL mg/l Sampling and Storage Collect samples in plastic or glass bottles that have been acid cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use commercial detergents containing phosphate for cleaning glassware used in this test. Analyze samples immediately after collection for best results. If prompt analysis is impossible, preserve samples for up to 48 hours by filtering immediately and storing at 4 ãc. Warm to room temperature before analyzing the sample. Accuracy Check Note: Clean glassware with 1:1 hydrochloric acid solution. Rinse again with deionized water. Do not use detergents containing phosphates to clean glassware. Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a Phosphate PourRite Ampule Standard, 50 mg/l as PO4 3-. c) Use the TenSette Pipet to add 0.1 ml, 0.2 ml and 0.3 ml, respectively, to the three 25-mL aliquots of sample prepared in step a. Mix well. d) Analyze each sample as described in the procedure; use 5.0 ml of the prepared standard additions for each test. The concentration should increase as follows: 0.2 mg/l, 0.4 mg/l, 0.6 mg/l PO4, respectively. e) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method To check accuracy, use a 1.0 mg/l Phosphate Standard Solution listed under Optional Reagents. Or, prepare a 1.0-mg/L PO4 3- standard by pipetting 2 ml of solution from a Phosphate Voluette Ampule Standard for Phosphate, 50 mg/l as PO4-, into an 272

273 acid-washed, Class A 100-mL volumetric flask. Dilute to the mark with deionized water. Substitute this standard for the sample and perform the procedure as described. Method Performance Precision In a single laboratory, using a standard solution of 5.00 mg/l PO4 3- and two lots of reagent with the instrument, a single operator obtained a standard deviation of À0.08 mg/l PO4 3-. Estimated Detection Limit (EDL) The EDL for program 82 is 0.07 mg/l PO43-. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Sample Disposal Information Final samples will contain molybdenum. In addition, final samples will have a ph less than 2 and are considered corrosive (D002) by the Federal RCRA. Summary of Method Orthophosphate reacts with molybdate in an acid medium to produce a phosphomolybdate complex. Ascorbic acid then reduces the complex, giving an intense molybdenum blue color. Test N Tube...50 tests : (1) , (50) * PhosVer /pkg Test N Tube /pkg... * COD/TNT TenSette, 1 to 10 ml , for TenSette Pipet /pkg OPTIONAL REAGENTS Bromine Water, 30 g/l ml Hydrochloric Acid Standard Solution, 6.0 N (1:1) ml Phenol Solution, 30 g/l ml Phosphate Standard Solution, 1 mg/l as PO ml Phosphate Standard Solution, Voluette ampule, 50 mg/l as PO43-,10mL...16/pkg Phosphate Standard Solution, PourRite ampule, 50 mg/l as PO43-, 2 ml...20/pkg

274 Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker, Pour Rite (2-mL ampule)... each Ampule Breaker Kit... each Aspirator, vacuum... each Cylinder, graduated, mixing, 25 ml (3 required)... each Dispenser, Repipet Jr., 2 ml... each Filter Holder, 47 mm, 300 ml, graduated... each Filter, membrane, 47 mm, 0.45 microns /pkg Flask, filtering, 500 ml... each Flask, volumetric, Class A, 100 ml... each ph Indicator Paper, 1 to 11 ph units... 5 rolls/pkg ph Meter, sension.1, portable... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for pkg Pipet Filler, Safety Bulb... each Pipet, volumetric, Class A, 5.00 ml... each Pipet, volumetric, Class A, 2.00 ml... each For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving you. 274

275 mg/l, PO4ZERO 275

276 PhosVer mg/l PO4 PhosVer 3 276

277 PhosVer 3 ph, 200 mg/l 100 mg/l 10 mg/l 100 mg/l 300 mg/l ph 50 mg/l 10 mg/l 90 mg/l 80 mg/l Sampling and Storage Collect samples in plastic or glass bottles that have been acid cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use commercial detergents containing phosphates for cleaning glassware used in this test. Analyze samples immediately after collection for best results. If prompt analysis is impossible, preserve the sample for up to 28 days by adjusting the ph to 2 or less with 277

278 concentrated sulfuric acid (about 2 ml per liter) and storing at 4 ãc. Neutralize and warm the sample to room temperature before analysis. Correct test results for volume additions; see Volume Additions in Section 1. Accuracy Check Note: Clean glasswarewith 1:1 hydrochloric acid solution. Rinse again with deionized water. Do not use detergents containing phosphates to clean glassware. Standard Additions Method a) Fill three 25 ml graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a Phosphate PourRite Ampule Standard, 50 mg/l as PO43-. c) Use the TenSette Pipet to add 0.1 ml, 0.2 ml and 0.3 ml, respectively, to the three 25-mL aliquots of sample prepared in step a. Mix well. d) Analyze each sample as described in the procedure using 5.0 ml of the prepared standard additions for each test. The concentration should increase 0.2 mg/l, 0.4 mg/l, and 0.6 mg/l PO4 3-, respectively. e) If these increases do not occur, see Standard Additions (Section 1). Standard Solution Method To check accuracy, use a 1.0 mg/l Phosphate Standard Solution (see Optional Reagents). Or, prepare a standard by pipetting 2 ml of solution a Voluette Ampule Standard for Phosphate Standard, 50 mg/l as PO4 3-, into an acid-cleaned Class A 100-mL volumetric flask. Dilute to the mark with deionized water. Substitute this standard for the sample and perform the procedure as described. The mg/l PO4 3- reading should be 1.0 mg/l. ORPrepare a 2.5 mg/l standard solution by pipetting 5 ml of a 50-mg/L Phosphate Voluette Ampule Standard into an acid-washed 100-mL Class A volumetric flask. Dilute to the mark with deionized water. Method Performance Precision In a single laboratory, using a standard solution of 3.00 mg/l PO43- and two lots of reagent with the instrument, a single operator obtained a standard deviation of À0.06 mg/l PO4 3-. Estimated Detection Limit The estimated detection limit for program 82 is 0.07 mg/l PO4 3-.For more information on the estimated detection limit, see Section 1. Sample Disposal Information Final samples will contain molybdenum. In addition, final samples will have a ph less than 2 and are considered corrosive (D002) by the Federal RCRA. Summary of Method Phosphates present in organic and condensed inorganic forms (meta-, pyro- or other polyphosphates) must be converted to reactive orthophosphate before analysis. Pretreatment of the sample with acid and heat provides the conditions for hydrolysis of the condensed inorganic forms. Organic phosphates are converted to orthophosphate by heating with acid and persulfate. Orthophosphate reacts with molybdate in an acid medium to produce a phosphomolybdate complex. Ascorbic acid then reduces the complex, giving an intense molybdenum blue color. 278

279 Test N Tube...50 tests : (1) , (1) , (1) , (1) , (50) * PhosVer /pkg /pkg , 1.54 N... 2 ml ml Test N Tube /pkg...* ml...4 liters COD, 115/230 Vac (U.S.A. and Canada) COD, 115/230 Vac (Europe) COD/TNT TenSette, 1 to 10 ml , for TenSette Pipet /pkg OPTIONAL REAGENTS Description Unit Cat. No. Total and Acid Hydrolyzable Test N Tube Reagent Set... each Hydrochloric Acid Standard Solution, 6.0 N (1:1) ml Phosphate Standard Solution, 1 mg/l as PO ml Phosphate Standard Solution, PourRite ampule, 50 mg/l as PO43-, 2 ml... 20/pkg Phosphate Standard Solution, Voluette ampule, 50 mg/l as PO43-, 10 ml... 16/pkg Sodium Hydroxide Standard Solution, 5.0 N...1 L Water, deionized... 4 L OPTIONAL APPARATUS Ampule Breaker Kit... each Ampule Breaker, PourRite ampules... each Cylinder, graduated, mixing, 25 ml (3 required)... each ph Indicator Paper, 1 to 11 ph units... 5 rolls/pkg ph Meter, Sension.1, portable... each Pipet Filler, safety bulb... each Pipet, volumetric, Class A, 5.00 ml... each Pipet, volumetric, Class A, 2.00 ml... each Pipet, TenSette, ml... each Pipet Tips, for TenSette Pipet... 50/pkg For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving 279

280 PhosVer 3 Test N Tube mg/l, PO4ZERO 280

281 PhosVer mg/l PO4 PhosVer PhosVer 3 281

282 200 mg/l 100 mg/l 10 mg/l 100 mg/l 300 mg/l ph, ph 50 mg/l 10 mg/l 90 mg/l 80 mg/l PhosVer 3 282

283 Sampling and Storage Collect samples in plastic or glass bottles that have been acid cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use commercial detergents containing phosphate for cleaning glassware used in this test. Analyze samples immediately after collection for best results. If prompt analysis is impossible, the sample may be preserved up to 48 hours by cooling to 4 ãc (39 ãf). Warm to room temperature before testing. Accuracy Check Note: Clean glassware with 1:1 hydrochloric acid solution. Rinse with deionized water. Do not use detergents containing phosphate to clean glassware. Standard Additions Method a) Fill three 25-mL graduated mixing cylinders with 25 ml of sample. b) Snap the neck off a Phosphate PourRite Ampule Standard, 50 mg/l as PO43-. c) Use the TenSette Pipet to add 0.1 ml, 0.2 ml and 0.3 ml, respectively, to the three 25-mL aliquots of sample prepared in step a. Mix well. d) Analyze each sample as described in the procedure. Use 5.0 ml of the prepared standard additions for each test; the concentration should increase as follows: 0.2 mg/l, 0.4 mg/l, and 0.6 mg/l PO43-, respectively. e) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method Obtain a 1.0 mg/l Phosphate Standard Solution listed under Optional Reagents. Or, this can be prepared by pipetting 2 ml of a Voluette Ampule Standard for Phosphate, 50 mg/l as PO4 3-, into an acid washed Class A 100-mL volumetric flask. Dilute to the mark with deionized water. Substitute this standard for the sample and perform the procedure as described. Method Performance Precision In a single laboratory, using a standard solution of 3.00 mg/l PO43- and two lots of reagent with the instrument, a single operator obtained a standard deviation of À0.06 mg/l PO43-. Estimated Detection Limit The estimated detection limit for program 82 is 0.07 mg/l PO43-. For more information on the estimated detection limit, see Section 1. Sample Disposal Information Final samples will contain molybdenum. In addition, final samples will have a ph less than 2 and are considered corrosive (D002) by the Federal RCRA. Summary of Method Phosphates present in organic and condensed inorganic forms (meta-, pyro- or other polyphosphates) must be converted to reactive orthophosphate before analysis. Pretreatment of the sample with acid and heat provides the conditions for hydrolysis of 283

284 the condensed inorganic forms. Organic phosphates are converted to orthophosphate by heating with acid and persulfate. Orthophosphate reacts with molybdate in an acid medium to produce a phosphomolybdate complex. Ascorbic acid then reduces the complex, giving an intense molybdenum blue color. REQUIRED REAGENTS Test N Tube tests : (1) , (1) , (1) , (1) , (50) PhosVer /pkg /pkg , 1.54 N... 2 ml ml Test N Tube /pkg...* mL REQUIRED APPARATUS COD, 115/230 Vac (U.S.A. and Canada) COD, 115/230 Vac (Europe) COD/TNT TenSette, 1 to 10 ml , for TenSette Pipet /pkg OPTIONAL REAGENTS Bromine Water, 30 g/l ml Hydrochloric Acid Standard Solution, 6.0 N (1:1) ml Phenol Solution, 30 g/l ml Phosphate Standard Solution, 1 mg/l as PO ml Phosphate Standard Solution, PourRite ampule, 50 mg/l as PO4 3-, 2 ml...20/pkg Phosphate Standard Solution, Voluette ampule, 50 mg/l as PO43-, 10 ml...16/pkg Sodium Hydroxide Standard Solution, N ml Sulfuric Acid Standard Solution, N... 1 L Water, deionized... 4 L

285 OPTIONAL APPARATUS Description Units Cat. No. Ampule Breaker Kit, Voluette...each Ampule Breaker, PourRite...each Cylinder, graduated, mixing, 25 ml (3 required)...each Flask, volumetric, Class A, 100 ml...each ph Indicator Paper, 1 to 11 ph units...5 rolls/pkg ph Meter, sension.1, portable...each Pipet, TenSette, ml...each Pipet Tips, for TenSette Pipet...50/pkg Pipet, volumetric, Class A, 5.00 ml...each Pipet, volumetric, Class A, 2.00 ml...each Pipet Filler, safety bulb...each For Technical Assistance, Price and Ordering In the U.S.A. call Outside the U.S.A. ªContact the Hach office or distributor serving you. 285

286 PO4 mg/l PO4 286

287 0.00 mg/l PO4 10,000 mg/l CaCO 3 150,000 mg/l Cl - 1 ml 10 N25mL pipet filler 40,000 mg/l CaCO g sulfamic 4 100,000 mg/l 5mg/L 125mL C 1mL 10 N 25mL pipet filler ph 287

288 Sampling and Storage Collect samples in clean plastic or glass bottles that have been cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use a commercial detergent containing phosphate for cleaning glassware used in this test. Analyze samples immediately for best results. If prompt analysis is not possible, preserve samples by filtering immediately and storing the sample at 4 ãc (39 ãf) for up to 48 hours. Accuracy Check Standard Additions Method a) Snap the neck off a Phosphate PourRite Ampule Standard Solution, 500 mg/l as PO43-. b) Use the TenSette Pipet to add 0.1 ml, 0.2 ml and 0.3 ml of standard, respectively, to three 25-mL samples. Mix well. c) Analyze each sample as described in the procedure. Each 0.1-mL addition of standard should cause an increase of 2.0 mg/l orthophosphate (PO43-). d) If these increases do not occur, see Standard Additions (Section 1)for more information. Standard Solution Method Prepare a 10.0-mg/L phosphate standard by pipetting 10.0 ml of a Phosphate Standard Solution, 50 mg/l as PO4 3- into a 50-mL volumetric flask. Dilute to volume with deionized water. Or, prepare a 10.0-mg/L PO43- standard solution by using the TenSette Pipet to add 1.00 ml of Phosphate PourRite Ampule Standard, 500 mg/l as PO43-, into a 50-mL volumetric flask. Dilute to volume with deionized water.substitute this standard for the sample and perform the test as described. The mg/l PO43- reading should be 10 mg/l. Method Performance Precision In a single laboratory using a standard solution of 15.0 mg/l PO43- and two lots of reagent with the instrument, a single operator obtained a standard deviation of À0.12 mg/l PO43-. Estimated Detection Limit The estimated detection limit for program 85 is 0.14 mg/l PO43-. For more information on the estimated detection limit, see Section 1. (100 Test) : (1) , (1) ml ml MDB* ml ml MDB* , ml, w/ cap /pkg

289 OPTIONAL REAGENTS Description Units Cat. No. Amino Acid Reagent Powder Pillow...100/pkg Bromine Water, 30 g/l ml Hydrochloric Acid Solution, 1:1 (6 N) ml Phenol Solution, 30 g/l ml Phosphate Standard Solution, 50 mg/l PO ml Phosphate Standard Solution, PourRite ampule, 500 mg/l PO43-, 2 ml...20/pkg Sodium Hydroxide Standard Solution, 5.0 N ml MDB Sulfamic Acid g Sulfuric Acid Standard Solution, 10 N... 1 L Water, deionized... 4 L OPTIONAL APPARATUS Description Unit Cat. No. Ampule Breaker Kit, PourRite... each Aspirator, vacuum... each Cylinder, graduated, 50 ml... each Cylinder, graduated, mixing, 25 ml... each Filter Holder, 47 mm, 300 ml, graduated... each Filter, membrane, 47 mm, 0.45 microns /pkg Flask, filtering, 500 ml... each Flask, erlenmeyer, 125 ml... each Flask, volumetric, Class A, 50 ml... each ph Indicator Paper, 1 to 11 ph... 5 rolls/pkg ph Meter, sension.1, portable... each Pipet, serological, 2.0 ml... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for TenSette Pipet... 50/pkg Pipet, volumetric, Class A, ml... each Pipet Filler, safety bulb... each Spoon, measuring, 0.05 g... each Thermometer, -10 to 110 ãc... each For Technical Assistance, Price and Ordering In the U.S.A. ªCall Outside the U.S.A. ªContact the Hach office or distributor serving you. 289

290 Test N Tube TenSette TenSette PO4 C 13 C C 2 290

291 0.00 mg/l PO4 291

292 100mg/L 100mg/L 550mL 6 71 ph 20 C) 25 C) 1000mg/L Sampling and Storage Collect samples in plastic or glass bottles that have been acid cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use commercial detergents containing phosphate for cleaning the glassware used in this test. For best results, analyze the samples immediately after collection. If prompt analysis is impossible, preserve the samples for up to 748 hours by filtering immediately and storing at 4 C. The sample should have a neutral (6 8) ph and be at room temperature before analysis. Accuracy Check Note: Clean glassware with 1:1 hydrochloric acid solution. Rinse again with deionized water. Do not use detergents containing phosphates to clean glassware. Standard Additions Method a. Fill three 10-mL graduated mixing cylinders with 10 ml of sample. b. Snap the neck off a Voluette Ampule of Phosphate Standard Solution, 500 mg/l as PO4 (Cat. No ). c. Use the TenSette Pipet to add 0.1 ml, 0.2 ml and 0.3 ml, respectively, to the three 10-mL aliquots of sample prepared in step a. Mix well. d. Analyze each sample from step c as described in the procedure; use 5.0 ml of the prepared sample for each test. The concentration should increase as follows: 5 mg/l, 10 mg/l, and 15 mg/l PO4, respectively. 292

293 e. If these increases do not occur, see Standard Additions in Section 1 of the DR/890 Procedures Manual for more information. Standard Solution Method To check accuracy, prepare an 80 mg/l PO4 standard by pipetting 8.0 ml of solution from a 10-mL Voluette Ampule of Phosphate Standard Solution, 500 mg/l as PO4, into an acid-cleaned 50-mL Class A volumetric flask. Fill to the line with deionized water. Substitute this standard for the sample and perform the procedure as described. Standard Adjust To adjust the calibration curve using the reading obtained with the 80 mg/ml PO4 standard solution, press the SETUP key and scroll, using the arrow keys, to the STO option. Press ENTER to activate the standard adjust option. Then enter 80.0 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Standard Curve Adjustment, Section 1 of the Procedures Manual for more information. Method Performance Precision In a single laboratory, using a standard solution of 80.0 mg/l PO4 and two lots of reagent with the instrument, a single operator obtained a standard deviation of ±3.0 mg/l PO4. Estimated Detection Limit (EDL) The EDL for program 86 is 7.0 mg/l PO4. For more information on derivation and use of Hach s estimated detection limit, see Section 1 of the DR/890 Procedures Manual. Sample Disposal Information Safety Final samples will contain molybdenum. In addition, final samples will have a ph less than 2 and are considered corrosive (D002) by the Federal RCRA. Consult the Material Safety Data Sheet for information specific to the reagent used. Good safety habits and laboratory techniques should be used throughout the procedure. Consult the Material Safety Data Sheet for information specific to the reagents used. Summary of Method Orthophosphate reacts with molybdate in an acid medium to produce a phosphomolybdate complex. In the presence of vanadium, yellow vanadomolybdophosphoric acid forms. The intensity of the yellow color is proportional to the phosphate concentration. Installing this Program on the DR/800 This procedure will add the current method as a new Hach program to your DR/ Turn the DR/800 on by pressing the ON key. 293

294 2. Press the SETUP key. 3. Press the down arrow key two times so that the prompt line shows USER. 4. Press the ENTER key. 5. Enter 8138, followed by ENTER. 6. Enter each of the numbers in the right column, each followed by ENTER. The line numbers in the left column relate to the line number on the display. At any time you may use the arrow keys to scroll back to review or change any number you have already entered. 294

295 Test N Tube vials : (50) Test N Tube *, (2) Test N Tube /pkg...* ml COD/TNT TenSette, 1 to 10 ml s, for TenSette Pipet /pkg OPTIONAL REAGENTS Bromine Water, 30 g/l...29 ml** Hydrochloric Acid Standard Solution, 6.0 N (1:1) ml Phenol Solution, 30 g/l...29 ml Phosphate Standard Solution, PourRite ampule, 500 mg/l as PO4, 2 ml... 20/pkg Phosphate Standard Solution, Voluette ampule, 500 mg/l as PO4, 10 ml... 16/pkg OPTIONAL APPARATUS Ampule Breaker Kit...each Aspirator, vacuum...each Cylinder, graduated, mixing, 10 ml, 3 required...each Filter Holder, 47 mm, 300 ml, graduated...each Filter, membrane, 47 mm, 0.45 microns...200/pkg Flask, filtering, 500 ml...each Flask, volumetric, Class A, 50-mL...each ph Indicator Paper, 1 to 11 ph units...5 rolls/pkg ph Meter, sension 1, portable...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for TenSette Pipet... 50/pkg Pipet Tips, for TenSette Pipet /pkg Pipet, volumetric, Class A, 5.00-mL...each Pipet, volumetric, Class A, 8.00-mL...each PourRite Ampule Breaker...each

296 10127 (0.0 to mg/l ) Test N Tube PO4 TenSette TenSette 296

297 Molybdovanadate 0.0 mg/l PO4 297

298 100mg/L 100mg/L 850mL ph 20 C) 25 C) 1000mg/L Sampling and Storage Collect samples in plastic or glass bottles that have been acid cleaned with 1:1 Hydrochloric Acid Solution and rinsed with deionized water. Do not use commercial detergents containing phosphates for cleaning the glassware used in this test. Analyze samples immediately after collection for best results. If prompt analysis is impossible, preserve the sample for up to 28 days by adjusting the ph to 2 or less with concentrated H2SO4 (about 2 ml per liter) and storing at 4 C. Warm the sample to room temperature and neutralize with 5.0 N NaOH before analysis. Correct test results for volume additions; see Volume Additions in Section 1of the DR/890 Procedures Manual. Accuracy Check Note: Clean glassware with 1:1 hydrochloric acid solution. Rinse again with deionized water. Do not use detergents containing phosphates to clean glassware. Standard Additions Method a. Fill each of three 10-mL graduated mixing cylinders with 10 ml of sample. b. Snap the neck off a 10-mL Voluette Ampule of Phosphate Standard Solution, 500 mg/l as PO4 (Cat. No ). 298

299 c. Use a TenSette Pipet to add 0.1 ml, 0.2 ml and 0.3 ml, respectively, to the three 10-mL aliquots of the water sample prepared in step a. Mix well. d. Analyze samples from step c as described in the procedure. Use 5.0 ml of the prepared sample for each test. The concentration should increase: 5 mg/l, 10 mg/l, and 15 mg/l PO4, respectively. e. If these increases do not occur, see Standard Additions (Section 1 of the DR/890 Procedures Manual) for more information. Standard Solution Method To check accuracy, prepare an 80 mg/l standard by pipetting 8.0 ml of solution from a 10-mL Voluette Ampule of Phosphate Standard Solution, 500 mg/l as PO4 into an acid-cleaned, Class A, 50-mL volumetric flask. Dilute to the mark with deionized water. Substitute this standard for the sample and perform the procedure as described. Standard Adjust To adjust the calibration curve using the reading obtained with the 80 mg/l PO4 standard solution, press the SETUP key and scroll, using the arrow keys, to the STO option. Press ENTER to activate the standard adjust option. Then enter 80.0 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Standard Curve Adjustment, Section 1 of the Procedures Manual for more information. Method Performance Safety Precision In a single laboratory, using a standard solution of 80.0 mg/l PO4 and two lots of reagent with the instrument, a single operator obtained a standard deviation of ±3.0 mg/l PO4 Estimated Detection Limit The estimated detection limit for program 87 is 7.0 mg/l PO4. For more information on the estimated detection limit, seesection 1 of the DR/890 Procedures Manual. Good safety habits and laboratory techniques should be used throughout the procedure. Consult the Material Safety Data Sheet for information specific to the reagents used. Sample Disposal Information The final samples will contain molybdenum. In addition, the final samples will have a ph less than 2 and are considered corrosive (D002) by the Federal RCRA. Consult the Material Safety Data Sheet for information specific to the reagent used. Summary of Method Phosphates present in organic and condensed inorganic forms (meta-, pyro- or other polyphosphates) must be converted to reactive orthophosphate before analysis. Pretreatment of the sample with acid and heat provides the conditions for hydrolysis of 299

300 the condensed inorganic forms. Organic phosphates are converted to orthophosphate by heating with acid and persulfate. Orthophosphate reacts with molybdate in an acid medium to produce a phosphomolybdate complex. In the presence of vanadium, yellow vanadomolybdophosphoric acid forms. The intensity of the yellow color is proportional to the phosphate concentration. Installing this Program on the DR/800 This procedure will add the current method as a new Hach program to your DR/ Turn the DR/800 on by pressing the ON key. 2. Press the SETUP key. 3. Press the down arrow key two times so that the prompt line shows USER. 4. Press the ENTER key. 5. Enter 8138, followed by ENTER. 6. Enter each of the numbers in the right column, each followed by ENTER. The line numbers in the left column relate to the line number on the display. At any time you may use the arrow keys to scroll back to review or change any number you have already entered. 300

301 REQUIRED REAGENTS Test N Tube vials : (50) Test N Tube *, (2) , (1) (1) , (1) Molybdovanadate ml..25 ml /pkg , 1.54 N...2 ml ml Test N Tube /pkg... * ml COD, 115/230 Vac (U.S.A. and Canada) COD, 115/230 Vac (Europe) COD/TNT, DR/800 series , LDPE, 0.5 to 1.0 ml /pkg TenSette 1 to 10 ml , for TenSette Pipet /pkg each OPTIONAL REAGENTS Description Unit Cat. No. Hydrochloric Acid Standard Solution, 6.0 N (1:1) ml Phosphate Standard Solution, PourRite ampule, 500 mg/l as PO4, 2-mL... 20/pkg Phosphate Standard Solution, Voluette ampule, 500 mg/l as PO4, 10-mL... 16/pkg Sodium Hydroxide Standard Solution, 5.0 N...1 L Sulfuric Acid, ACS, concentrated ml OPTIONAL APPARATUS Ampule Breaker Kit...each Aspirator, vacuum...each Cylinder, graduated, mixing, 10 ml (3 required)...each Filter Holder, 47 mm, 300 ml, graduated...each Filter, membrane, 47 mm, 0.45 microns...200/pkg Flask, filtering, 500-mL...each Flask, volumetric, Class A, 50-mL...each ph Indicator Paper, 1 to 11 ph units...5 rolls/pkg ph Meter, sension 1, portable...each Pipet Filler, Safety Bulb...each Pipet, TenSette, 0.- to 1.0-mL...each Pipet Tips, for pkg

302 Pipet, volumetric, Class A, 8.00-mL...each Stopper, No. 7 one hole... 6/pkg Tubing, rubber feet

303 8186 (SiO2) SiO2 303

304 0 mg/l SiO2 304

305 50 mg/l PO460 mg/l PO4 2%75 mg/l PO4-11% Sampling and Storage Collect samples in clean plastic bottles. Analyze samples as soon as possible after collection. If prompt analysis is not possible, store samples for up to 28 days by cooling to 4 C (39 F) or below. Warm samples to room temperature before analysis. Accuracy Check Standard Additions Method a) Open a Low Range Silica Standard Solution Pillow, 50 mg/l SiO2. b) Using the TenSette Pipet, add 0.1, 0.2, and 0.3 ml of standard to three 10-mL samples. Mix thoroughly. c) Analyze each sample as described above. The silica concentration should increase 0.5 mg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Adjust To adjust the calibration curve using the reading obtained with the 1.00-mg/L Standard Solution (see Optional Reagents), press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 1.00 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Section 1, Standard Curve Adjustment for more information. 305

306 Method Performance Precision In a single laboratory, using standard solutions of 1.00 mg/l silica and two representative lots of reagent and a instrument, a single operator obtained a standard deviation of ±0.025 mg/l silica. Estimated Detection Limit (EDL) The estimated detection limit for program 90 is mg/l SiO2. For more information on the estimated detection limit, see Section 1. If testing for very low levels of silica, use the ultra-low range silica method on the Hach DR/2010 or DR/4000 Spectrophotometers. Reagent Preparation To prepare Amino Acid F Reagent Solution, dissolve 11.4 grams of Amino Acid F Reagent Powder in 100 ml of 1.0 N Sodium Hydroxide Solution. The solution is stable for at least one month if stored in a plastic bottle. Summary of Method Silica and phosphate in the sample react with molybdate ion under acidic conditions to form yellow silicomolybdic acid complexes and phosphomolybdic acid complexes. Acid reduces the yellow silicomolybdic acid to an intense blue color, which is proportional to the silica concentration., 10 ml sample (100 tests) : (1) , (1) (2) F /pkg /pkg Molybdate 3..., ml SCDB REQUIRED APPARATUS, ml, w/ cap /pkg OPTIONAL REAGENTS Silica Standard Solution, 1.00 mg/l SiO ml Silica Standard Solution Pillows, 20 mg/l as SiO2, 10 ml...16/pkg Sodium Bicarbonate, ACS g Sodium Hydroxide Standard Solution, N ml Sulfuric Acid Standard Solution, 1.0 N ml OPTIONAL APPARATUS Bottle, 118 ml, polyethylene, oblong...6/pkg Dropper, 0.5- & 1.0-mL marks...6/pkg Pipet, serologic, 2 ml, poly...each Pipet, TenSette, 0.1 to 1.0 ml...each

307 Pipet Tips, for Pipet...50/pkg Standard Methods for the Examination of Water and Wastewater...each Thermometer, - 10 to 110 C...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 307

308 8185 (SiO2) SiO2 2:00 Timer 2 308

309 0 mg/l SiO2 50 mg/l PO460 mg/l PO4 2%75 mg/l PO4-11% 309

310 Sampling and Storage Collect samples in clean plastic or glass bottles. Analyze samples as soon as possible after collection. Store samples up to 28 days at 4 C (39 F) or below. Warm samples to room temperature before analyzing. Accuracy Check Standard Additions Method a) Open a High Range Silica Standard Solution, 1000 mg/l SiO2. b) Use the TenSette Pipet to add 0.1 ml, 0.3 ml, and 0.5 ml of the standard to three 10-mL samples. Mix each thoroughly. c) Analyze each sample as described above. The silica concentration should increase 10.0 mg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method To check the accuracy of the method, use the Silica Standard Solutions, 25 and 50 mg/l as SiO2, listed under Optional Reagents. Analyze according to the above procedure using deionized water as the blank. Standard Adjust To adjust the calibration curve using the reading obtained with the 50.0 mg/l standard solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 50.0 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Section 1, Standard Curve Adjustment for more information. Method Performance Precision In a single laboratory, using a standard solution of 50.0 mg/l SiO2 and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 1.0 mg/l silica. Estimated Detection Limit The estimated detection limit for program 89 is 1.00 mg/l SiO2. For more information on the estimated detection limit, see Section 1. Summary of Method Silica and phosphate in the sample react with molybdate ion under acidic conditions to form yellow silicomolybdic acid complexes and phosphomolybdic acid complexes. Addition of citric acid destroys the phosphate complexes. Silica is then determined by measuring the remaining yellow color. 310

311 , 10 ml sample (100 tests) : (1) , (1) , (1) /pkg /pkg Molybdate..., ml SCDB , ml, w/ cap /pkg OPTIONAL REAGENTS Silica Standard Solution, 10 mg/l ml Silica Standard Solution, 25 mg/l ml Silica Standard Solution, 50 mg/l ml Silica Standard Solution, 1000 mg/l ml Sodium Bicarbonate, ACS g Sulfuric Acid Standard Solution, N ml MDB Water, deionized... 4 L OPTIONAL APPARATUS Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for Pipet... 50/pkg Standard Methods for the Examination of Water and Wastewater... each Thermometer, -10 to 110 C... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 311

312 10098 (SiO2) SiO2 312

313 2:00 Timer 2 0 mg/l SiO2 50 mg/l PO460 mg/l PO4 2%75 mg/l PO4-11% 313

314 Sampling and Storage Collect samples in clean plastic or glass bottles. Analyze samples as soon as possible after collection. Store samples up to 28 days at 4 C (39 F) or below. Warm samples to room temperature before analyzing. Accuracy Check Standard Additions Method a) Open a High Range Silica Standard Solution, 1000 mg/l SiO2. b) Use the TenSette Pipet to add 0.1 ml, 0.3 ml, and 0.5 ml of the standard to three 10-mL samples. Mix each thoroughly. c) Analyze each sample as described above. The silica concentration should increase 4 mg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method To prepare a 160-mg/L silica standard, pipet 40.0 ml of a 1000-mg/L Silica Standard Solution into a 250-mL volumetric flask. Dilute to the line with deionized water. Analyze according to the above procedure using deionized water as the blank. Standard Adjust To adjust the calibration curve using the reading obtained with the 160-mg/L standard solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 160. to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Section 1, Standard Curve Adjustment for more information. Method Performance Precision In a single laboratory, using a standard solution of mg/l SiO2 and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of 2.0 mg/l silica. Estimated Detection Limit The estimated detection limit for program 88 is 3.0 mg/l SiO2. For more information on the estimated detection limit, see Section 1. Summary of Method Silica and phosphate in the sample react with molybdate ion under acidic conditions to form yellow silicomolybdic acid complexes and phosphomolybdic acid complexes. Addition of citric acid destroys the phosphate complexes. Silica is then determined by measuring the remaining yellow color. 314

315 , 25-mL sample (100 tests) : (1) , (1) , (2) /pkg /pkg /pkg ml... 4 L ml, /pkg OPTIONAL REAGENTS Silica Standard Solution, 10 mg/l ml Silica Standard Solution, 25 mg/l ml Silica Standard Solution, 50 mg/l ml Silica Standard Solution, 1000 mg/l ml Sodium Bicarbonate, ACS g Sulfuric Acid Standard Solution, N ml MDB OPTIONAL APPARATUS Flask, volumetric, 250 ml, Class A...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for Pipet...50/pkg Pipet, volumetric, Class A, 100 ml...each Pipet Filler, safety bulb...each Standard Methods for the Examination of Water and Wastewater...each Thermometer, -10 to 110 C...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 315

316

317 20000mg/L CaCO mg/L 40000mg/L 500mg/L User- Entered Calibration There are various programs to determine sulfate, each with a different level of accuracy. Best results are obtained by performing a user-entered calibration with each new lot of reagent. Programs 91 and 92 can be run when a high degree of accuracy is not needed. Use of the Standard Adjust feature will improve performance when using programs 91 and 92. It should NOT be used with a user calibration, as it will hinder performance. Using Class A glassware, prepare standards of 10, 20, 30, 40, 50, 60, and 70 mg/l sulfate by pipetting 1, 2, 3, 4, 5, 6, and 7 ml of a 1000-mg/L sulfate standard into 100-mL volumetric flasks. Dilute to the mark with deionized water and mix well. Zero the instrument with water. The user-entered settings for sulfate are: Program number: #101 to 105 Wavelength: 520 nm Resolution: 0 mg/l See Creating User-Entered Program in the instrument manual for specific instructions on entering a user-entered program. Sampling and Storage Collect samples in clean plastic or glass bottles. Samples may be stored up to 28 days by cooling to 4 C (39 F) or lower. Warm to room temperature before analysis. 317

318 Accuracy Check Standard Additions Method- Powder Pillows a) Snap the neck off a Sulfate Standard PourRite Ampule,1000 mg/l SO4. b) Use a TenSette Pipet to add 0.1, 0.2 and 0.3 ml of standard to thethree 10-mL samples. Mix thoroughly. c) Analyze each sample as described above. The sulfate concentrationshould increase 10 mg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Additions Method- AccuVac Ampuls a) Snap the neck off a Sulfate Standard PourRite Ampule, 2500 mg/l SO4 b) Fill three 25- ml graduated cylinders with 25 ml of sample. Use a TenSette Pipet to add 0.1, 0.2 and 0.3 ml of standard to the three cylinders. Mix thoroughly. For AccuVac Ampuls, transfer to a 50-mL beaker. c) Analyze each sample as described above. The sulfate concentration should increase 10 mg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions in Section 1 for more information. Standard Solution Method Check the accuracy of the test by using the Sulfate Standard Solution, 50 mg/l, listed under Optional Reagents. Or, prepare this solution by pipetting 1.0 ml of a PourRite Ampule Standard for Sulfate (2500 mg/l) into a 50-mL volumetric flask. Dilute to volume with deionized water. The final concentration is 50 mg/l sulfate. Substitute this standard for the sample and proceed with the test as described in the procedure. Standard Adjust Standard adjust is recommended when using stored programs 91 or 92. It should not be used with a user-entered calibration. To adjust the calibration curve using the reading obtained with the 50-mg/L standard solution, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 50 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Section 1, Standard Curve Adjustment for more information. Method Performance Precision In a single laboratory, using a standard solution of 50 mg/l sulfate and two representative lots of powder pillows with the instrument, a single operator obtained a standard deviation of ±0.5 mg/l sulfate. In a single laboratory, using a standard solution of 50 mg/l sulfate and two representative lots of AccuVac Ampuls with the instrument, a single operator obtained a standard deviation of ±3 mg/l sulfate. Estimated Detection Limit (EDL) The EDL for program 91 is 4.9 mg/l SO4 and the EDL for program 92 is 3 mg/l SO4. 318

319 For more information on derivation and use of Hach s estimated detection limit, see Section 1. Summary of Method Sulfate ions in the sample react with barium in the SulfaVer 4 Sulfate Reagent to form insoluble barium sulfate. The amount of turbidity formed is proportional to the sulfate concentration. The SulfaVer 4 also contains a stabilizing agent to hold the precipitate in suspension. () SulfaVer /pkg , ml, w/ cap /pkg () SulfaVer 4 AccuVac /pkg , 50-mL OPTIONAL REAGENTS Sulfate Standard Solution, 50 mg/l ml Sulfate Standard Solution, 1000 mg/l ml Sulfate Standard Solution, PourRite Ampule, 2500 mg/l, 2 ml...20/pkg Sulfate Standard Solution, PourRite Ampule, 1000 mg/l, 2 ml...20/pkg Water, deionized... 4 L OPTIONAL APPARATUS AccuVac Snapper Kit...each Cylinder, graduated mixing, 25 ml...each Filter Paper, folded, 12.5 cm...100/pkg Flask, volumetric, 50 ml, Class A...each Funnel, poly, 65 mm...each Pipet, TenSette, 0.1 to 1.0 ml...each Pipet Tips, for Pipet...50/pkg Pipet, volumetric, 1.00 ml, Class A...each Pipet, volumetric, 2.00 ml, Class A...each Pipet, volumetric, 3.00 ml, Class A...each Pipet, volumetric, 4.00 ml, Class A...each Pipet, volumetric, 5.00 ml, Class A...each Pipet, volumetric, 6.00 ml, Class A...each Pipet, volumetric, 7.00 ml, Class A...each Pipet Filler, safety bulb...each PourRite Ampule Breaker...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 319

320 320

321 Sampling and Storage Collect samples in clean plastic or glass bottles. Fill completely and cap tightly. Avoid excessive agitation or prolonged exposure to air. Analyze samples immediately. Method Performance Precision In a single laboratory, using standard solutions of 0.73 mg/l sulfide and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of ± 0.02 mg/l sulfide. 321

322 Estimated Detection Limit (EDL) The EDL for program 93 is 0.01 mg/l S2-. For more information on derivation and use of Hach s estimated detection limit, see Section 1. Soluble Sulfides Determine soluble sulfides by centrifuging the sample in completely filled, capped tubes and analyzing the supernatant. Insoluble sulfides are then estimated by subtracting the soluble sulfide concentration from the total sulfide result. Summary of Method Hydrogen sulfide and acid-soluble metal sulfides react with N, N-dimethyl-p-phenylenediamine oxalate to form methylene blue. The intensity of the blue color is proportional to the sulfide concentration. High sulfide levels in oil field waters may be determined after dilution. Pollution Prevention and Waste Management Sulfide 2 Reagent contains potassium dichromate. The final solution will contain hexavalent chromium (D007) at a concentration regulated as a hazardous waste by Federal RCRA. See Section 3 for more information on proper disposal of these materials. (100 tests) : (2) , (2) ml ml MDB ml ml MDB ml... 4 L , 25 ml , Class A, ml Pipet Filler, safety bulb , ml, w/ cap /pkg OPTIONAL REAGENTS Description Units Cat. No. Bromine Water, 30 g/l...29 ml Phenol Solution, 30 g/l...29 ml Sodium Sulfide, hydrate g OPTIONAL APPARATUS Bottle, Wash, 250 ml... each Dropper, for 1 oz. bottle... each Flask, erlenmeyer, 50 ml... each Standard Methods for the Examination of Water and Wastewater... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 322

323 8028 LAS 323

324 0 mg/l LAS 324

325 Sampling and Storage Collect samples in clean plastic or glass bottles. Analyze samples as soon as possible, but they may be stored at least 24 hours by cooling to 4 C (39 F). Warm to room temperature before testing. Accuracy Check Standard Additions Method a) Snap the neck off a Detergent Voluette Ampule Standard Solution, 60 mg/l as LAS. b) Using the TenSette Pipet, add 0.1, 0.2, and 0.3 ml of standard to three 300-mL samples. Mix thoroughly. c) Analyze each as described above. The anionic surfactants reading should increase 0.02 mg/l for each 0.1 ml of standard added. d) If these increases do not occur, see Standard Additions (Section 1) for more information. Method Performance Precision In a single laboratory, using a standard solution of mg/l LAS, two lots of reagent, and the instrument, a single operator obtained a standard deviation of ±0.010 mg/l LAS as anionic surfactant. Estimated Detection Limit The estimated detection limit for program 26 is mg/l LAS. For more information on the estimated detection limit, see Section 1. Summary of Method Detergents, ABS (alkyl benzene sulfonate) or LAS (linear alkylate sulfonate) are determined by association with crystal violet dye and extraction of the ion-pair complex into benzene. Pollution Prevention and Waste Management Benzene (D018) solutions are regulated as hazardous waste by Federal RCRA. Do not pour these materials down the drain. Collect water saturated with benzene solutions for disposal with laboratory solvent wastes. See Section 3 for more information on proper disposal of these materials., ACS ml ml ml ml /pkg , 25 ml

326 , 50 ml ml , 500 ml Ring, support, 4 inch , ml, w/ cap /pkg Stand, support, 127 X 203 mm (5 X 8") OPTIONAL REAGENTS Acetone, ACS ml Detergent Standard Solution, Voluette ampule, 60 mg/l as LAS, 10 ml... 16/pkg OPTIONAL APPARATUS Ampule Breaker Kit... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for Pipet... 50/pkg Thermometer, -10 to 110 C... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 326

327 mg/l 327

328 Sampling and Storage Collect samples in clean plastic or glass bottles. Analyze samples as soon as possible after collection. The sample may be stored seven days by cooling to 4 C (39 F). Method Performance Precision In a single laboratory, using a standard solution of mg/l Suspended Solids with the instrument, a single operator obtained a standard deviation of 18.2 mg/l Suspended Solids. For more information on Hach s precision statement, see Section 1. Estimated Detection Limit The estimated detection limit for program 94 is 22.1 mg/l Suspended Solids. For more information on the estimated detection limit, see Section 1. Summary of Method This method of determining suspended solids is a simple, direct measurement which does not require the filtration or ignition and weighing steps that gravimetric procedures do. The USEPA specifies the gravimetric method for solids determinations, while this method is often used for checking in-plant processes. 328

329 , 600 ml, low form , 1.2 L, 120 V , 1.2 L, 240 V , 500 ml, , serologic, 25 ml OPTIONAL APPARATUS Stirring Rod, glass...3/pkg Wash Bottle, 250 ml...each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 329

330

331 Sampling and Storage Collect samples in clean plastic or glass bottles. Accuracy Check Standard Solution Method Prepare a 200-mg/L tannic acid standard solution by dissolving grams of tannic acid in deionized water and diluting to 1000 ml. Prepare this solution monthly. A 2.0 mg/l tannic acid standard is prepared by diluting ml of the stock solution to 1000 ml with deionized water. Prepare this standard daily. Method Performance Precision In a single laboratory, using standard solutions of 4.0 mg/l tannic acid and two representative lots of reagent with the instrument, a single operator obtained a standard deviation of ±0.1 mg/l tannic acid. Estimated Detection Limit The estimated detection limit for program 98 is 0.1 mg/l tannin and lignin. For more information on the estimated detection limit, see Section

332 Summary of Method This test measures all hydroxylated aromatic compounds, including tannin, lignin, phenol and cresol. This method produces a blue color proportional to the amount of these compounds present in the sample. Report results as total tannin and lignin expressed as mg/l tannic acid. (up to 100 tests) : (1) , (1) ml ml TanniVer ml ml ml... 4 L , volumetric, Class A, 5.0 ml , volumetric, Class A, 0.5 ml , mL, w/ cap /pkg OPTIONAL REAGENTS Formaldehyde ml Sodium Pyrophosphate, ACS...50 g Tannic Acid g OPTIONAL APPARATUS Description Unit Cat. No Balance, analytical, 115 V... each Balance, analytical, 230 V... each Cylinder, graduated, 25 ml... each Filter Paper, folded, 12.5 cm /pkg Flask, volumetric, 1000 ml... each Funnel, poly, 65 mm... each Pipet, TenSette, 0.1 to 1.0 ml... each Pipet Tips, for Pipet... 50/pkg Pipet, volumetric, Class A, ml... each Pipet, Filler, safety bulb... each Spoon, measuring, 0.2 g... each Weighing Boat, 67/47 mm /pkg For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 332

333 C, 1.0mL ( ); 333

334 1N ABS ToxTrak ToxTrak 334

335 2 5.0mL, 0.5mL ( ),, 1mL 10mL,, 0% 1/10, ,

336 ABS.. 336

337 Disposal of Test Cultures Dispose of active bacterial cultures by using one of these methods: 1. Autoclave used test containers at 121 C for 15 minutes at 15 pounds of pressure. Once the containers are sterile, pour the contents down the drain with running water. The reaction tubes may be washed and re-used. 2. Sterilize test containers by using a 1:10 dilution of commercial laundry bleach. Pour the test container contents and test containers into the bleach solution. Allow minutes of contact time with the bleach solution. Then pour the liquid down the drain and wash the reaction tubes for re-use. Summary of Method Resazurin is a redox-active dye, which changes from pink to blue when it is reduced. Bacterial respiration occurring in the sample reduces resazurin. If toxic substances are present, they inhibit the rate of resazurin reduction. The sample color is compared to a toxin-free control tube to determine how toxic the sample is to an indigenous culture or a culture of E. coli. A chemical accelerant reduces the reaction time of the procedure. ToxTrak (25 tests) : (1) , (1) , (1) , (2) , (2) ToxTrak /pkg ToxTrak ml SCDB /pkg /pkg ml COD/TNT , 1 ml /pkg , volumetric, 5.00 ml, Class A Test N /pkg OPTIONAL REAGENTS Culture Set: (incl. Bactrol Discs and Lauryl Tryptose Broth Tubes)...25 cultures Bactrol Discs, E. coli... 25/bottle Isopropanol ml Lauryl Tryptose Broth Tubes... 15/pkg

338 OPTIONAL APPARATUS Burner, Alcohol, 60 ml... each Burner, Bunsen... each Germicidal Cloth... 50/pkg Incubator, Dri Bath, 25 well, 120/230 V... each Incubator, Dri Bath, 25 well, 120/230 V, with European power cord... each Test Tube Rack... each Timer... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 338

339 FAU=1 NTU=1 FTU Formazin FAU 339

340 Sampling and Storage Collect samples in clean plastic or glass bottles. Analyze samples as soon as possible. Store samples up to 48 hours by cooling to 4 C (39 F). Analyze the sample at the same temperature as it was collected. Accuracy Check Standard Solution Method The stored program has been calibrated using formazin, the primary standard for turbidity. A 200 FAU formazin solution for checking the accuracy of the test can be prepared using the following procedure. 1. Pipet 5.00 ml of a 4000 NTU Formazin stock solution into a 100-mL volumetric flask. 2. Dilute to the mark with deionized water. Prepare this daily. Convenient stabilized turbidity stock solution (200 NTU StablCal Standard) is available from Hach. Standard Adjust To adjust the calibration curve using the reading obtained with the 200 FAU formazin standard, press the SETUP key and scroll (using the arrow keys) to the STD setup option. Press ENTER to activate the standard adjust option. Then enter 200 to edit the standard concentration to match that of the standard used. Press ENTER to complete the adjustment. See Section 1, Standard Curve Adjustment for more information. Method Precision Precision In a single laboratory, using a turbidity standard solution of 200 FAU with the instrument, a single operator obtained a standard deviation of ±2 FAU. Estimated Detection Limit The estimated detection limit for program 95 is 21 FAU. For more information on the estimated detection limit, see Section 1. Summary of Method This turbidity test measures an optical property of the sample which results from scattering and absorption of light by particles in the sample. The amount of turbidity measured depends on variables such as the size, shape, color, and refractive properties of the particles. This procedure is calibrated using formazin turbidity standards and the 340

341 readings are in terms of Formazin Attenuation Units (FAU). This test cannot be used for USEPA reporting purposes, but it may be used for daily in-plant monitoring. One FAU is equivalent to one Nephelometric Turbidity Unit (NTU) of Formazin. However, the optical method of measurement for FAU is very different than the NTU method (1 NTU = 1 FTU = 1 FAU when traced to formazin primary standards.), ml, w/cap /pkg Formazin, 4000 NTU ml ml DB StablCal Stabilized Turbidity Standard, 200 NTU ml L OPTIONAL APPARATUS Description Units Cat. No. Bath, ultrasonic... each Bottle, wash, 250 ml... each Flask, volumetric, Class A, 100 ml... each Flask, filter, 500 ml... each Filter Holder... each Filter Pump, aspirator... each Oiling cloth, for applying silicone oil... each Pipet Filler, safety bulb... each Pipet, volumetric, Class A, 5.0 ml... each Sample Degassing Kit... each Stopper, rubber, one-hole, No /pkg Tubing, rubber, 5/16 I.D feet Tweezers, plastic... each For Technical Assistance, Price and Ordering In the U.S.A. Call Outside the U.S.A. Contact the Hach office or distributor serving you. 341

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