Hach DR2010 User manual

49300-22

DR/2010

SPECTROPHOTOMETER

PROCEDURES MANUAL

jnb/dk 10/00 rev2

TABLE OF CONTENTS

INTRODUCTION .............................................................................................................. 11

Sample Procedure Explained .................................................................................................. 13

SECTION I CHEMICAL ANALYSIS INFORMATION......................................... 17

Abbreviations .......................................................................................................................... 17

Converting Chemical Species ................................................................................................. 18

Hardness Conversion ........................................................................................................... 19

Dissolved Oxygen................................................................................................................ 20

Sample Collection, Preservation and Storage ...................................................................... 22

Collecting Water Samples ................................................................................................ 25

Acid Washing Bottles....................................................................................................... 25

Correcting for Volume Additions ........................................................................................ 26

Boiling Aids ......................................................................................................................... 26

Sample Filtration.................................................................................................................. 27

Temperature Considerations ................................................................................................ 29

Sample Dilution Techniques................................................................................................ 29

Sample Dilution and Interfering Substances .................................................................... 30

Using Pipets and Graduated Cylinders ................................................................................ 31

Using the TenSette Pipet...................................................................................................... 32

Operating the TenSette Pipet............................................................................................ 32

Mixing Water Samples ........................................................................................................ 33

Using Sample Cells.............................................................................................................. 35

Orientation of Sample Cells.............................................................................................. 35

Care of Hach 1-inch Sample Cells.................................................................................... 35

Cleaning Sample Cells...................................................................................................... 35

Sample Cell Matching ...................................................................................................... 36

Volume Measurement Accuracy ...................................................................................... 37

Using AccuVac Ampuls ...................................................................................................... 37

Using Reagent Powder Pillows............................................................................................ 38

Using PermaChem Pillows .................................................................................................. 39

Using the Pour-Thru Cell..................................................................................................... 39

Reagent and Standard Stability............................................................................................ 40

Interferences............................................................................................................................ 41

pH Interference .................................................................................................................... 41

Accuracy and Precision........................................................................................................... 42

Standard Additions............................................................................................................... 43

TABLE OF CONTENTS, continued

Method Performance............................................................................................................... 50

Estimated Detection Limit................................................................................................... 50

Precision .............................................................................................................................. 53

Estimating Precision......................................................................................................... 53

Selecting the Best Wavelength ............................................................................................... 54

Adapting HACH Procedures to Other Spectrophotometers................................................... 57

Preparing a Calibration Curve............................................................................................. 57

%T Versus Concentration Calibration ............................................................................. 57

Absorbance Versus Concentration Calibration ................................................................ 59

USEPA Approved and Accepted Definitions ......................................................................... 60

SECTION II SAMPLE PRETREATMENT ............................................................... 61

Digestion................................................................................................................................. 61

EPA Mild Digestion with Hot Plate for Metals Analysis Only........................................... 61

EPA Vigorous Digestion with Hot Plate for Metals Analysis Only ................................... 62

General Digesdahl Digestion (Not USEPA accepted) ........................................................ 63

Distillation .............................................................................................................................. 63

SECTION III WASTE MANAGEMENT AND SAFETY........................................ 65

Waste Management................................................................................................................. 65

Waste Minimization ............................................................................................................ 65

Regulatory Overview........................................................................................................... 65

Hazardous Waste Definition................................................................................................ 66

Characteristic Hazardous Waste Codes ............................................................................... 67

How to Determine if Waste is Hazardous ........................................................................... 67

Examples of Hazardous Waste............................................................................................ 68

Hazardous Waste Disposal.................................................................................................. 68

Management of Specific Wastes ......................................................................................... 69

Special Considerations for Cyanide Containing Materials .............................................. 69

Resources............................................................................................................................. 70

Material Safety Data Sheets.................................................................................................... 71

How to Obtain an MSDS..................................................................................................... 71

Sections of an MSDS........................................................................................................... 72

TABLE OF CONTENTS, continued

Safety....................................................................................................................................... 74

Material Safety Data Sheet .................................................................................................. 74

Reading Labels Carefully .................................................................................................... 74

Protective Equipment........................................................................................................... 75

First Aid Equipment and Supplies ....................................................................................... 75

General Safety Rules............................................................................................................ 75

OSHA Chemical Hygiene Plan............................................................................................ 76

SECTION IV PROCEDURES ........................................................................................ 77

ALUMINUM, Aluminon Method........................................................................................... 79

ALUMINUM, Eriochrome Cyanine R Method...................................................................... 87

ARSENIC, Silver Diethyldithiocarbamate Method ................................................................ 95

BARIUM, Turbidimetric Method ......................................................................................... 103

BENZOTRIAZOLE, UV Photolysis Method ....................................................................... 111

BORON, Carmine Method.................................................................................................... 117

BORON, Low Range, Azomethine-H Method .................................................................... 121

BROMINE, DPD Method..................................................................................................... 129

CADMIUM, Dithizone Method............................................................................................ 137

CHLORIDE, Mercuric Thiocyanate Method........................................................................ 145

CHLORINE, FREE, DPD Method ....................................................................................... 149

CHLORINE, FREE, DPD Rapid Liquid Method ................................................................ 157

CHLORINE, FREE, HIGH RANGE, DPD Method............................................................. 163

CHLORINE, FREE, DPD Test ‘N Tube™ Method ............................................................. 169

CHLORINE, TOTAL, Ultra Low Range, DPD Method ...................................................... 175

CHLORINE, TOTAL, Ultra Low Range, DPD Method ..................................................... 183

CHLORINE, TOTAL, DPD Method .................................................................................... 191

CHLORINE, TOTAL, DPD Rapid Liquid Method ............................................................. 199

CHLORINE, TOTAL, HIGH RANGE, DPD Method ........................................................ 205

CHLORINE, TOTAL, DPD Test ‘N Tube™ Method.......................................................... 211

CHLORINE DIOXIDE, LR, Chlorophenol Red Method..................................................... 217

CHLORINE DIOXIDE, HR, Direct Reading Method.......................................................... 221

CHLORINE DIOXIDE, DPD Method.................................................................................. 223

TABLE OF CONTENTS, continued

CHROMIUM, HEXAVALENT, 1,5-Diphenylcarbohydrazide Method.............................. 233

CHROMIUM, TOTAL, Alkaline Hypobromite Oxidation Method ................................... 239

COBALT, 1-(2-Pyridylazo)-2-Naphthol (PAN) Method ..................................................... 245

COLOR, NCASI 253, Platinum-Cobalt Method.................................................................. 249

COLOR, TRUE AND APPARENT, APHA Platinum-Cobalt Standard Method ............... 253

COPPER, Bicinchoninate Method........................................................................................ 257

COPPER, Porphyrin Method................................................................................................ 265

COPPER, AUTOCATALYTIC, Colorimetric Method........................................................ 271

CYANIDE, Pyridine-Pyrazalone Method ............................................................................ 277

CYANURIC ACID, Turbidimetric Method......................................................................... 287

FLUORIDE, SPADNS Method............................................................................................ 291

FORMALDEHYDE, MBTH Method .................................................................................. 299

HARDNESS, Calcium and Magnesium; Calmagite Colorimetric Method.......................... 303

HARDNESS, TOTAL, Ultra Low Range, Calcium and Magnesium Chlorophosphonazo

Colorimetric Method ......................................................................................................... 309

HARDNESS, TOTAL, Ultra Low Range, Calcium and Magnesium; Chlorophosphonazo

Rapid Liquid Method ........................................................................................................ 313

HYDRAZINE, p-Dimethylaminobenzaldehyde Method ..................................................... 319

IODINE, DPD Method ......................................................................................................... 325

IRON, FerroZine Method ..................................................................................................... 333

IRON, FerroZine Rapid Liquid Method............................................................................... 339

IRON, FERROUS, 1,10 Phenanthroline Method................................................................. 345

IRON, TOTAL, FerroMo™ Method.................................................................................... 349

IRON, TOTAL, FerroVer Method ....................................................................................... 353

IRON, TOTAL, TPTZ Method............................................................................................. 361

LEAD, Dithizone Method..................................................................................................... 369

LEAD, LeadTrak™ Fast Column Extraction Method.......................................................... 377

MANGANESE, HR, Periodate Oxidation Method .............................................................. 387

MANGANESE, LR, PAN Method....................................................................................... 391

MERCURY, Cold Vapor Mercury Concentration Method.................................................. 397

MOLYBDENUM, MOLYBDATE, HR, Mercaptoacetic Acid Method.............................. 413

MOLYBDENUM, MOLYBDATE, LR, Ternary Complex Method ................................... 421

TABLE OF CONTENTS, continued

NICKEL, 1-(2 Pyridylazo)-2-Naphthol (PAN) Method ....................................................... 427

NICKEL, Heptoxime Method............................................................................................... 433

NICKEL, AUTOCATALYTIC, Photometric Method ......................................................... 439

NITRATE, LR, Cadmium Reduction Method...................................................................... 443

NITRATE, MR, Cadmium Reduction Method..................................................................... 449

NITRATE, HR, Cadmium Reduction Method...................................................................... 457

NITRATE, HR, Chromotropic Acid Method, Test ‘N Tube™ ............................................ 465

NITRITE, LR, Diazotization Method ................................................................................... 471

NITRITE, LR, Diazotization, NED Rapid Liquid Method................................................... 477

NITRITE, LR, Test ‘N Tube, Diazotization (Chromotropic Acid) Method......................... 483

NITRITE, HR, Ferrous Sulfate Method................................................................................ 487

NITROGEN, TOTAL, HR, Test ’N Tube™, TNT Persulfate Digestion Method................ 491

NITROGEN, AMMONIA, Nessler Method......................................................................... 499

NITROGEN, AMMONIA, Salicylate Method ..................................................................... 505

NITROGEN, AMMONIA, High Range, Test ’N Tube, Salicylate Method......................... 511

NITROGEN, AMMONIA, Low Range Test ‘N Tube, Salicylate Method .......................... 517

NITROGEN, MONOCHLORAMINE and FREE AMMONIA, Salicylate Method............ 523

NITROGEN, TOTAL, Test ’N Tube, TNT Persulfate Digestion Method ........................... 531

NITROGEN, TOTAL KJELDAHL, Nessler Method .......................................................... 539

NITROGEN, TOTAL INORGANIC, Test ‘N Tube, Titanium Trichloride Reduction ....... 549

ORGANIC CARBON, TOTAL, Low Range, Direct Method.............................................. 557

ORGANIC CARBON, TOTAL, High Range, Direct Method ............................................. 565

ORGANIC MATTER, Dichromate Method......................................................................... 573

OXYGEN, DISSOLVED, LR, Indigo Carmine Method...................................................... 579

OXYGEN, DISSOLVED, HR, HRDO Method ................................................................... 583

OXYGEN, DISSOLVED, SHR, Super High Range Method............................................... 587

OXYGEN DEMAND, CHEMICAL, Reactor Digestion Method........................................ 591

Colorimetric Determination, 0 to 150 mg/L COD ............................................................. 593

Colorimetric Determination, 0 to 1,500 and 0 to 15,000 mg/L COD................................ 595

OXYGEN DEMAND, CHEMICAL (COD), Dichromate Reflux Method .......................... 601

Colorimetric Determination............................................................................................... 603

Buret Titration.................................................................................................................... 605

OXYGEN DEMAND, CHEMICAL, Manganese III Digestion Method ............................. 611

TABLE OF CONTENTS, continued

OXYGEN DEMAND, CHEMICAL, Manganese III Digestion Method............................. 615

OXYGEN SCAVENGERS, Iron Reduction Method for Oxygen Scavengers .................... 623

OZONE, Indigo Method....................................................................................................... 627

PALLADIUM, N,N'-Dimethyldithiooxamide Method ........................................................ 631

PCB IN SOIL, Immunoassay Method.................................................................................. 635

PHENOLS, 4-Aminoantipyrine Method .............................................................................. 645

PHOSPHONATES, Persulfate UV Oxidation Method........................................................ 651

PHOSPHORUS, REACTIVE, PhosVer 3 Method, Test ’N Tube Procedure ...................... 657

PHOSPHORUS, REACTIVE, (Also called Orthophosphate) Amino Acid Method ........... 663

PHOSPHORUS, REACTIVE, (Also called Orthophosphate) Molybdovanadate Method.. 669

PHOSPHORUS, REACTIVE, PhosVer 3 (Ascorbic Acid) Method.................................... 677

PHOSPHORUS, REACTIVE, LOW RANGE, Ascorbic Acid Rapid Liquid Method........ 685

PHOSPHORUS, REACTIVE, HIGH RANGE, Molybdovanadate Rapid Liquid Method . 691

PHOSPHORUS, REACTIVE, HR, Molybdovanadate Method, Test ’N Tube™ ............... 697

PHOSPHORUS, TOTAL, Acid Persulfate Digestion Method............................................. 703

PHOSPHORUS, TOTAL, PhosVer 3 with Acid Persulfate Digestion Test ‘N Tube.......... 707

PHOSPHORUS, TOTAL, HR, Molybdovanadate Method with Acid Persulfate Digestion,

Test ’N Tube™.................................................................................................................. 715

PHOSPHORUS, ACID HYDROLYZABLE, PhosVer3 with Acid Hydrolysis,................. 723

Test ’N Tube...................................................................................................................... 723

PHOSPHORUS, ACID HYDROLYZABLE, Hydrolysis to Orthophosphate Method........ 729

POLYACRYLIC ACID, Absorption-Colorimetric Method ................................................ 733

POTASSIUM, Tetraphenylborate Method........................................................................... 741

QUATERNARY AMMONIUM COMPOUNDS, Direct Binary Complex Method ........... 747

SELENIUM, Diaminobenzidine Method ............................................................................. 753

SILICA, HR, Silicomolybdate Method ................................................................................ 761

SILICA, LR, Heteropoly Blue Method ................................................................................ 767

SILICA, ULTRA LOW RANGE, Heteropoly Blue Method ............................................... 773

SILICA, ULR, Heteropoly Blue Rapid Liquid Method ....................................................... 779

SILVER, Colorimetric Method............................................................................................. 785

SODIUM CHROMATE, Direct Colorimetric Method ........................................................ 791

TABLE OF CONTENTS, continued

SULFATE, SulfaVer 4 Method ............................................................................................ 795

SULFIDE, Methylene Blue Method* ................................................................................... 803

SURFACTANTS, ANIONIC, Crystal Violet Method.......................................................... 807

SUSPENDED SOLIDS, Photometric Method...................................................................... 811

TANNIN AND LIGNIN, Tyrosine Method ......................................................................... 815

THM Plus™: Trihalomethanes, ........................................................................................... 819

TOXTRAK TOXICITY TEST, Colorimetric Method ......................................................... 829

TPH IN SOIL, Immunoassay Method................................................................................... 835

TPH IN WATER, Immunoassay Method ............................................................................. 845

TURBIDITY, Attenuated Radiation Method (direct reading) .............................................. 853

VOLATILE ACIDS, Esterification Method......................................................................... 857

ZINC, Zincon Method........................................................................................................... 861

SECTION V GENERAL INFORMATION ............................................................... 867

HOW TO ORDER............................................................................................................ 869

REPAIR SERVICE .......................................................................................................... 870

WARRANTY ..................................................................................................................... 871

INTRODUCTION

This manual is divided into five sections:

Section I Chemical Analysis Information

This section applies to all the procedures. It provides background information and reference/review material for the technician or chemist. Commonly used techniques are explained in detail.

Section II Sample Pretreatment

This section provides a brief overview of sample pretreatment and three digestion procedures. Two are USEPA digestions. The Hach Digesdahl method is also included.

Section III Waste Management and Safety

Section 3 includes information an waste management, regulations, waste disposal and resources on waste management. The Safety portion covers reading an MSDS and general safety guidelines.

Section IV Procedures

Section 4 contains step-by-step illustrated instructions for measuring over 120 parameters. The steps also include helpful notes. Each procedure contains information on sample collection, storage and preservation, accuracy checks, possible interferences, summary of method and a list of the reagents and apparatus necessary to run the test.

Section V Ordering Information

This section provides information needed for ordering, shipping, return of items and Hach trademarks.

Before attempting the analysis procedures the analyst should read the instrument manual to learn about the spectrophotometer’s features and operation.

INTRODUCTION, continued

Hach Company Trademarks

AccuGrow

AccuVac

AccuVer™

AccuVial™

Add-A-Test™

AgriTrak™

AluVer

AmVer™

APA 6000™

AquaChek™

AquaTrend

BariVer

BODTrak™

BoroTrace™

BoroVer

C. Moore Green™

CA 610™

CalVer

ChromaVer

ColorQuik

CoolTrak

CuVer

CyaniVer

Digesdahl

DithiVer

Dr. F. Fluent™

Dr. H. Tueau™

DR/Check™

EC 310™

FerroMo

FerroVer

FerroZine

FilterTrak™ 660

Formula 2533™

Formula 2589™

Gelex

H2O University™

H2OU™

Hach Logo

Hach One

Hach Oval

Hach.com™

HachLink™

Hawkeye The Hach Guy™

HexaVer

HgEx™

HydraVer

ICE-PIC™

IncuTrol

Just Add Water™

LeadTrak

M-ColiBlue24

ManVer

MolyVer

Mug-O-Meter

NetSketcher™

NitraVer

NitriVer

NTrak

OASIS™

On Site Analysis. Results You Can Trust

OptiQuant™

OriFlow™

OxyVer™

PathoScreen™

PbEx

PermaChem

PhosVer

Pocket Colorimeter™

Pocket Pal™

Pocket Turbidimeter™

Pond In Pillow™

ion

√

™

PourRite

PrepTab™

ProNetic™

Pump Colorimeter™

QuanTab

Rapid Liquid™

RapidSilver™

Ratio™

RoVer

sens

Simply Accurate

SINGLET™

SofChek™

SoilSYS™

SP 510™

Spec ™

StablCal

StannaVer

SteriChek™

StillVer

SulfaVer

Surface Scatter

TanniVer

TenSette

Test ‘N Tube™

TestYES!

TitraStir

TitraVer

ToxTrak™

UniVer

VIScreen™

Voluette

WasteAway™

ZincoVer

Sample Procedure Explained

Sample Procedure Explained, continued

SECTION I CHEMICAL ANALYSIS INFORMATION

Abbreviations

The following abbreviations are used throughout the text of the procedure section:

Abbrev-

iation

°C degree(s) Celsius (Centigrade) HR high range

°F degree(s) Fahrenheit kg/ha kilograms per hectare

ACS

APHA Standard Methods

AV AccuVac MR medium range

Bicn bicinchoninate NIPDWR

CFR Code of Federal Regulations NPDES

conc concentrated P phosphorus

DB dropping bottle PCB Poly chlorinated biphenyl

EDL Estimated detection limit PV PhosVer

F&T free and total RL Rapid Liquid™

FAU

FM FerroMo

FV FerroVer

FZ FerroZine

gr/gal grains per gallon (1 gr/gal = 17.12 mg/L) USEPA

American Chemical Society reagent grade purity

Standard Methods for the Examination of Water and Wastewater, published jointly by

the American Public Health Association (APHA), the American Water Works Association (AWWA), and the Water Environment Federation (WEF). Order from Hach requesting Cat. No. 22708-00 or from the Publication Office of the American Public Health Association. This book is the standard reference work for water analysis. Many procedures contained in this manual are based on Standard Methods.

Formazin Attenuation Units. Turbidity unit of measure based on a Formazin stock suspension.

g grams ULR Ultra low range

Definition

Abbrev-

iation

l or L

lbs/Ac pounds per acre

LR low range

MDL Method detection limit

MDB marked dropping bottle

mg/L milligrams per liter (ppm)

µg/L micrograms per liter (ppb)

ml or mL

SCDB self-contained dropping bottle

TNT Te s t ‘N Tube™

TPH Total petroleum hydrocarbons

TPTZ (2,4,6-Tri-(2-Pyridyl)-1,3,5-Triazine)

Liter. Volume equal to one cubic decimeter (dm

(milliliter)-approximately the same as a cubic centimeter (cc) or 1/1000 of a liter. Also known as a “cc”.

National Interim Primary Drinking Water Regulations

National Pollutant Discharge Elimination System

United States Environmental Protection Agency

Definition

)

SECTION I, continued

Converting Chemical Species

Species conversion factors for many commonly used substances are preprogrammed into the DR/2010 (see Table 1). Conversions are method specific and are viewable after taking the reading by pressing

Table 1 Conversion Factors

To Convert From... To... Multiply By... Conversion used in program #

mg/L Al mg/L Al2O

mg/L B mg/L H

mg/L Ca-CaCO

mg/L CaCO

3BO3

mg/L Ca 0.4004 220

mg/L Ca 0.4004 227

mg/L Mg 0.2428 227

1.8895 9, 10

5.7 45

µg/L Carbo. µg/L Hydro. 1.92 182

µg/L Carbo. µg/L ISA 2.69 182

µg/L Carbo. µg/L MEKO 3.15 182

mg/L Cr

mg/L Mg-CaCO

mg/L CrO

mg/L Na2CrO

mg/L Mg 0.2428 225

mg/L Mn mg/L KMnO

mg/L Mn mg/L MnO

mg/L Mo

mg/L MoO

mg/L Na2MoO

mg/L N mg/L NH

mg/L N mg/L NO

mg/L Na

mg/L NH

mg/L NO

µg/L NO

mg/L NO

µg/L NO

mg/L NO

mg/L PO

µg/L PO

mg/L PO

µg/L PO

mg/L SiO

µg/L SiO

CrO

Cl-N mg/L Cl

Cl-N mg/L NH2Cl 3.6750 386

-N mg/L NH

-N mg/L NaNO

-N µg/L NaNO

-N mg/L NO

-N µg/L NO

-N mg/L NO

mg/L Cr

mg/L CrO

mg/L NaNO

mg/L NO

mg/L P 0.3261 480, 482, 485, 490, 492, 535

µg/L P 0.3261 488

mg/L P2O

µg/L P2O

mg/L Si 0.4674 651, 656

µg/L Si 0.4674 645

-N 0.3045 373

2.231 90, 95

3.115 90, 95

2.876 290, 295

2.165 290, 295

1.667 315, 320, 322

2.146 315, 320, 322

1.216 342, 343, 346, 347, 348

4.427 346, 347, 348

0.321 670

0.72 670

5.0623 386

1.216 380, 385, 387

1.288 380, 385, 387

1.5 373

4.926 345, 371, 375

4.926 376

3.284 345, 371, 375

3.284 376

4.427 344, 351, 353, 355, 359, 361

0.7473 480, 482, 485, 490, 492, 535

0.7473 488

CONC.

SECTION I, continued

Hardness Conversion

Table 2 lists the factors for converting one unit of measure for hardness to another unit of measure. For example, to convert mg/L CaCO parts/100,000 CaO, multiply the value in mg/L x 0.056.

Table 2 Hardness Conversion Factors

Units of

Measure

mg/L

CaCO

English

British

gr/gal

(Imperial)

mg/L

CaCO

1.0 0.07 0.058 0.1 0.056 0.02 5.6x10

14.3 1.0 0.83 1.43 0.83 0.286 8.0x10

American

gr/gal (US)

CaCO

gr/gal

CaCO

US gr/gal

CaCO

Fr. p/

17.1 1.2 1.0 1.72 0.96 0.343 9.66x10

10.0 0.7 0.58 1.0 0.56 0.2 5.6x10

100,000

CaCO

Ger. p/

17.9 1.25 1.04 1.79 1.0 0.358 1x10

100,000

CaO

meq/L 50.0 3.5 2.9 5.0 2.8 1.0 2.8x10

g/L CaO 1790.0 125.0 104.2 179.0 100.0 35.8 1.0 0.112

lbs./cu ft

CaCO

16,100.0 1,123.0 935.0 1,610.0 900.0 321.0 9.0 1.0

1 ‘epm/L, or ‘mval/L’

Note: 1 meq/L = 1N/1000

French

parts/

100,000

CaCO

German

Parts/

100,000

CaO

meq/L

g/L CaO

to German

lbs./cu ft

-4

6.23x10

-3

1.07x10

-3

6.23x10

-2

1.12x10

-2

3.11x10

CaCO

8.9x10

-5

-4

-3

-4

-3

-2

SECTION I, continued

Dissolved Oxygen

Table 3 lists the mg/L dissolved oxygen in water at saturation for various temperatures and atmospheric pressures. The table was formulated in a laboratory using pure water. The values given are only approximations for estimating the oxygen content of a particular body of surface water.

Table 3 Dissolved Oxygen Saturation in Water

Pressure in Millimeters and Inches Hg

775 760 750 725 700 675 650 625

Temp inches

°F °C 30.51 29.92 29.53 28.45 27.56 26.57 25.59 24.61

32.0 0 14.9 14.6 14.4 13.9 13.5 12.9 12.5 12.0

33.8 1 14.5 14.2 14.1 13.6 13.1 12.6 12.2 11.7

35.6 2 14.1 13.9 13.7 13.2 12.9 12.3 11.8 11.4

37.4 3 13.8 13.5 13.3 12.9 12.4 12.0 11.5 11.1

39.2 4 13.4 13.2 13.0 12.5 12.1 11.7 11.2 10.8

41.0 5 13.1 12.8 12.6 12.2 11.8 11.4 10.9 10.5

42.8 6 12.7 12.5 12.3 11.9 11.5 11.1 10.7 10.3

44.6 7 12.4 12.2 12.0 11.6 11.2 10.8 10.4 10.0

46.4 8 12.1 11.9 11.7 11.3 10.9 10.5 10.1 9.8

48.2 9 11.8 11.6 11.5 11.1 10.7 10.3 9.9 9.5

50.0 10 11.6 11.3 11.2 10.8 10.4 10.1 9.7 9.3

51.8 11 11.3 11.1 10.9 10.6 10.2 9.8 9.5 9.1

53.6 12 11.1 10.8 10.7 10.3 10.0 9.6 9.2 8.9

55.4 13 10.8 10.6 10.5 10.1 9.8 9.4 9.1 8.7

57.2 14 10.6 10.4 10.2 9.9 9.5 9.2 8.9 8.5

59.0 15 10.4 10.2 10.0 9.7 9.3 9.0 8.7 8.3

60.8 16 10.1 9.9 9.8 9.5 9.1 8.8 8.5 8.1

62.6 17 9.9 9.7 9.6 9.3 9.0 8.6 8.3 8.0

64.4 18 9.7 9.5 9.4 9.1 8.8 8.4 8.1 7.8

66.2 19 9.5 9.3 9.2 8.9 8.6 8.3 8.0 7.6

68.0 20 9.3 9.2 9.1 8.7 8.4 8.1 7.8 7.5

69.8 21 9.2 9.0 8.9 8.6 8.3 8.0 7.7 7.4

71.6 22 9.0 8.8 8.7 8.4 8.1 7.8 7.5 7.2

73.4 23 8.8 8.7 8.5 8.2 8.0 7.7 7.4 7.1

75.2 24 8.7 8.5 8.4 8.1 7.8 7.5 7.2 7.0

77.0 25 8.5 8.4 8.3 8.0 7.7 7.4 7.1 6.8

78.8 26 8.4 8.2 8.1 7.8 7.6 7.3 7.0 6.7

80.6 27 8.2 8.1 8.0 7.7 7.4 7.1 6.9 6.6

SECTION I, continued

Table 3 Dissolved Oxygen Saturation in Water (continued)

Pressure in Millimeters and Inches Hg

775 760 750 725 700 675 650 625

Temp inches

°F °C 30.51 29.92 29.53 28.45 27.56 26.57 25.59 24.61

82.4 28 8.1 7.9 7.8 7.6 7.3 7.0 6.7 6.5

84.2 29 7.9 7.8 7.7 7.4 7.2 6.9 6.6 6.4

86.0 30 7.8 7.7 7.6 7.3 7.0 6.8 6.5 6.2

87.8 31 7.7 7.5 7.4 7.2 6.9 6.7 6.4 6.1

89.6 32 7.6 7.4 7.3 7.0 6.8 6.6 6.3 6.0

91.4 33 7.4 7.3 7.2 6.9 6.7 6.4 6.2 5.9

93.2 34 7.3 7.2 7.1 6.8 6.6 6.3 6.1 5.8

95.0 35 7.2 7.1 7.0 6.7 6.5 6.2 6.0 5.7

96.8 36 7.1 7.0 6.9 6.6 6.4 6.1 5.9 5.6

98.6 37 7.0 6.8 6.7 6.5 6.3 6.0 5.8 5.6

100.4 38 6.9 6.7 6.6 6.4 6.2 5.9 5.7 5.5

102.2 39 6.8 6.6 6.5 6.3 6.1 5.8 5.6 5.4

104.0 40 6.7 6.5 6.4 6.2 6.0 5.7 5.5 5.3

105.8 41 6.6 6.4 6.3 6.1 5.9 5.6 5.4 5.2

107.6 42 6.5 6.3 6.2 6.0 5.8 5.6 5.3 5.1

109.4 43 6.4 6.2 6.1 5.9 5.7 5.5 5.2 5.0

111.2 44 6.3 6.1 6.0 5.8 5.6 5.4 5.2 4.9

113.0 45 6.2 6.0 5.9 5.7 5.5 5.3 5.1 4.8

114.8 46 6.1 5.9 5.9 5.6 5.4 5.2 5.4 4.8

116.6 47 6.0 5.9 5.8 5.6 5.3 5.1 4.8 4.7

118.4 48 5.9 5.8 5.7 5.5 5.3 5.0 4.8 4.6

120.2 49 5.8 5.7 5.6 5.4 5.2 5.0 4.7 4.5

122.0 50 5.7 5.6 5.5 5.3 5.1 4.9 4.7 4.4

SECTION I, continued

Sample Collection, Preservation and Storage

Correct sampling and storage are critical for accurate testing. For greatest accuracy, thoroughly clean sampling devices and containers to prevent carryover from previous samples. Preserve the sample properly; each procedure has information about sample preservation.

• The least expensive containers are polypropylene or polyethylene.

• The best and most expensive containers are quartz or PTFE

(polytetrafluoroethylene, Teflon).

• Avoid soft glass containers for metals in the

microgram-per-liter range.

• Store samples for silver determination in light absorbing containers,

such as amber bottles.

Avoid contaminating the sample with metals from containers, distilled water or membrane filters. Thoroughly clean sample containers as described under Acid Washing Bottles.

Preservation slows the chemical and biological changes that continue after collection. These changes may change the amount of a chemical species available for analysis. Normally, analyze the samples as soon as possible after collection, especially when the analyte concentration is expected to be low. This also reduces the chance for error and minimizes labor.

Preservation methods include pH control, chemical addition, refrigeration and freezing. Table 4 gives the recommended preservation for various substances. It also includes suggested types of containers and the maximum recommended holding times for properly preserved samples.

Preserve aluminum, cadmium, chromium, cobalt, copper, iron, lead, nickel, potassium, silver and zinc samples for at least 24 hours by adding one Nitric Acid Solution Pillow 1:1 (Cat. No. 2540-98) per liter of sample. Check the pH with pH indicator paper or a pH meter to assure the pH is 2 or less. Add additional pillows if necessary. Adjust the sample pH prior to analysis by adding an equal number of Sodium Carbonate Anhydrous Powder Pillows (Cat. No. 179-98). Or raise the pH to 4.5 with Sodium Hydroxide Standard Solution, 1 N or 5 N.

SECTION I, continued

Table 4 Required Containers, Preservation Techniques and Holding Times

Parameter No./Name Container

Preservation

3,4

Maximum

Holding Time

Table 1A - Bacterial Tests

1-4. Coliform, fecal and total P,G Cool, 4°C, 0.008%, Na

5. Fecal streptococci P,G Cool, 4°C, 0.008%, Na

2S2O3

6 hours

Table 1B - Inorganic Tests

1. Acidity P, G Cool, 4°C 14 days

2. Alkalinity P, G Cool, 4°C 14 days

4. Ammonia P, G Cool, 4°C, H

9. Biochemical oxygen demand

P, G Cool, 4°C 48 hours

to pH<2 28 days

2SO4

(BOD)

10. Boron P, PFTE or quartz HNO

to pH<2 6 months

11. Bromide P, G None required 28 days

14. Biochemical oxygen demand,

P, G Cool, 4°C 48 hours

carbonaceous

15. Chemical oxygen demand P, G Cool, 4°C, H

to pH<2 28 days

2SO4

16. Chloride P, G None required 28 days

17. Chlorine, total residual P, G None required Analyze immediately

21. Color P, G Cool, 4°C 48 hours

23-24. Cyanide, total and amenable to chlorination

P, G Cool, 4°C, NaOH to pH>12, 0.6 g

ascorbic acid

14 days

25. Fluoride P None required 28 days

27. Hardness P, G HNO

to pH<2, H2SO4 to pH<2 6 months

28. Hydrogen ion (pH) P, G None required Analyze immediately

31, 43. Kjeldahl and organic

P, G Cool 4°C, H

to pH<2 28 days

2SO4

nitrogen

Metals

18. Chromium VI P, G Cool, 4°C 24 hours

35. Mercury P, G HNO

to pH<2 28 days

Metals, except boron, chromium VI and mercury: 3, 5-8, 12, 13, 19, 20, 22, 26, 29, 30, 32-34, 36, 37, 45, 47, 51, 52, 58-60, 62, 63, 70-72, 74,

P, G HNO

to pH<2 6 months

38. Nitrate P, G Cool, 4°C 48 hours

39. Nitrate-nitrite P, G Cool 4°C, H

to pH<2 28 days

2SO4

40. Nitrite P, G Cool, 4°C 48 hours

41. Oil and grease G Cool, 4°C, HCl or H

42. Organic Carbon

P, G Cool, 4°C, HCl or H

to pH<2

3PO4

to pH<2 28 days

2SO4

SO4 or

28 days

44. Orthophosphate P, G Filter immediately; Cool, 4°C 48 hours

46a. Oxygen, dissolved probe G Bottle and top None required Analyze immediately

46b. Oxygen, dissolved, Winkler Do Fix on site and store in dark 8 hours

48. Phenols G only Cool 4°C, H

to pH<2 28 days

2SO4

SECTION I, continued

Table 4 Required Containers, Preservation Techniques and Holding Times1 (continued)

Parameter No./Name Container

49. Phosphorus, elemental G Cool, 4°C 48 hours

50. Phosphorus, total P, G Cool, 4°C, H

53. Residue, total P, G Cool, 4°C7 days

54. Residue, filterable P, G Cool, 4°C7 days

55. Residue, Nonfilterable (TSS) P, G Cool, 4°C7 days

56. Residue, Settleable P, G Cool, 4°C 48 hours

57. Residue, volatile P, G Cool, 4°C7 days

61. Silica P, PFTE or quartz Cool, 4°C 28 days

64. Specific conductance P, G Cool, 4°C 28 days

65. Sulfate P, G Cool, 4°C 28 days

66. Sulfide

67. Sulfite P, G none required Analyze immediately

68. Surfactants P, G Cool, 4°C 48 hours

69. Temperature P, G None required Analyze immediately

73. Turbidity P, G Cool, 4°C 48 hours

1 This table was adapted from Table II published in the Federal Register, July 1, 1997, 40 CFR, Part 136.3,

pages 26-27. Organic tests are not included. 2 Polyethylene (P) or glass (G). 3 Sample preservation should be performed immediately upon sample collection. For composite chemical samples

each aliquot should be preserved at the time of collection. When use of an automated sampler makes it impossible

to preserve each aliquot, then chemical samples may be preserved by maintaining at 4°C until compositing and

sample splitting is completed. 4 When any sample is to be shipped by common carrier or sent through United States Mails, it must comply with the

Department of Transportation Hazardous Material Regulations (49 CFR Part 172). The person offering such

material for transportation is responsible for ensuring such compliance. For the preservation requirements of Table

II, the Office of Hazardous Materials, Materials Transportation Bureau, Department of Transportation has

determined that the Hazardous Materials Regulations do not apply to the following materials: Hydrochloric acid

(HCl) in water solutions at concentrations of 0.04% by weight or less (pH about 1.96 or greater); Nitric acid (HNO

in water solutions at concentrations of 0.15% by weight or less (pH about 1.62 or greater); Sulfuric acid (H

water solutions at concentrations of 0.35% by weight or less (pH about 1.15 or greater); and Sodium hydroxide

(NaOH) in water solutions at concentrations of 0.080% by weight or less (pH about 12.30 or less). 5 Samples should be analyzed as soon as possible after collection. The times listed are the maximum times that

samples may be held before analysis and still be considered valid. Samples may be held for longer periods only if

the permitee, or monitoring laboratory, has data on file to show that the specific types of samples under study are

stable for the longer time, and has received a variance from the Regional Administer under §136.3(e). Some

samples may not be stable for the maximum time period given in the table. A permitee, or monitoring laboratory, is

obligated to hold the sample for a shorter time if knowledge exists to show that this is necessary to maintain sample

stability. See §136.3(e) for details. The term “analyze immediately” usually means within 15 minutes or less after

sample collection. 6 Should only be used in the presence of residual chlorine. 7 Maximum holding time is 24 hours when sulfide is present. Optionally all samples may be tested with lead acetate

paper before pH adjustments in order to determine if sulfide is present. If sulfide is present, it can be removed by the

addition of cadmium nitrate powder until a negative spot test is obtained. The sample is filtered and then NaOH is

added to pH 12. 8 Samples should be filtered immediately on-site before adding preservative for dissolved metals. 9 Numbers refer to parameter number in 40 CFR, Part 136.3, Table 1B.

P, G Cool 4°C, add zinc acetate plus

Preservation

sodium hydroxide to pH>9

3,4

to pH<2 28 days

2SO4

Maximum

Holding Time

7 days

2SO4

) in

)

SECTION I, continued

Collecting Water Samples

Obtain the best sample by careful collection. In general, collect samples near the center of the vessel or duct and below the surface. Use only clean containers (bottles, beakers). Rinse the container several times first with the water to be sampled.

Take samples as close as possible to the source of the supply. This lessens the influence the distribution system has on the sample. Let the water run long enough to flush the system. Fill sample containers slowly with a gentle stream to avoid turbulence and air bubbles. Collect water samples from wells after the pump has run long enough to deliver water representative of the ground water feeding the well.

It is hard to obtain a truly representative sample when collecting surface water samples. Obtain best results by testing several samples. Use samples taken at different times from several locations and depths. The results can be used to establish patterns for that particular body of water.

Generally, as little time as possible should elapse between collecting the sample and analyzing it.

Depending on the test, special precautions in handling the sample may be necessary. This prevents natural interferences such as organic growth or loss or gain of dissolved gases. Each procedure describes sample preservatives and storage techniques for samples that are held for testing.

Acid Washing Bottles

If a procedure suggests acid-washing, use the following procedure:

Use chromic acid or chromium-free substitutes to remove organic deposits from glass containers. Rinse containers thoroughly with water to remove traces of chromium.

a) Clean the glassware or plasticware with laboratory detergent

(phosphate-free detergent is recommended).

b) Rinse well with tap water.

c) Rinse with a 1:1 Hydrochloric Acid Solution or 1:1 Nitric Acid

Solution. The nitric acid rinse is important for testing for lead.

d) Rinse well with deionized water. Up to 12-15 rinses may be

necessary if chromium is being determined.

e) Air dry.

SECTION I, continued

Wash glassware for phosphate determinations with phosphate-free detergents and acid-wash with 1:1 HCl. Thoroughly rinse the glassware with deionized water. For ammonia and Kjeldahl nitrogen, rinse with ammonia-free water.

Correcting for Volume Additions

If you use a large volume of preservative, correct for the volume of preservative added. This accounts for dilution due to the acid added to preserve the sample and the base used to adjust the pH to the range of the procedure. This correction is made as follows:

1. Determine the volume of initial sample, the volume of acid and base

added, and the total final volume of the sample.

2. Divide the total volume by the initial volume.

3. Multiply the test result by this factor.

Example:

A one-liter sample was preserved with 2 mL of nitric acid. It was neutralized with 5 mL of 5 N sodium hydroxide. The result of the analysis procedure was 10.00 mg/L. What is the volume correction factor and correct result?

Boiling Aids

Total Volume 1000 mL 2 mL 5 mL++ 1007 mL==

1007

------------- 1.007 volume correction factor==

1000

10.0 mg/L 1.007× 10.07 mg/L correct result==

Hach 1:1 Nitric Acid Pillows contain 2.5 mL of acid: correct for this volume. The addition of a Sodium Carbonate Power Pillow neutralizes the 1:1 Nitric Acid Pillow does not need to be corrected for.

Boiling is necessary in some procedures. Using a boiling aid such as boiling chips (Cat. no. 14835-31) reduces bumping. Bumping is caused by the sudden, almost explosive conversion of water to steam as it is heated. Avoid bumping; it may cause sample loss or injury.

Make sure the boiling aids will not contaminate the sample. Do not use boiling aids (except glass beads) more than once. Loosely covering the sample during boiling will prevent splashing, reduce the chances of contamination and minimize sample loss.

SECTION I, continued

Sample Filtration

Filtering separates particles from the aqueous sample. Filtration uses a medium, usually filter paper, to retain particles but pass solution. This is especially helpful when sample turbidity interferes with analysis. Two general methods of filtration are gravity and vacuum. Gravity filtration uses gravity to pull the sample though the filter paper. Vacuum filtration uses suction and gravity to move the sample through the filter. An aspirator or vacuum pump creates the suction. Vacuum filtration is faster than gravity filtration. Vacuum filter (see Figure 1) as follows:

1. Using tweezers, place a filter paper into the filter holder.

2. Place the filter holder assembly in the filtering flask. Wet the filter

with deionized water to ensure adhesion to the holder.

3. Position the funnel housing on the filter holder assembly.

4. While applying a vacuum to the filtering flask, transfer the sample to

the filtering apparatus.

5. Slowly release the vacuum from the filtering flask and transfer the

solution from the filter flask to another container.

Figure 1 Vacuum Filtration

REQUIRED APPARATUS FOR VACUUM FILTRATION

Description Unit Cat. No.

Filter Discs, glass 47 mm.................................................................. 100/pkg................2530-00

Filter Holder, membrane ......................................................................... each..............13529-00

Flask, filter, 500 mL ................................................................................ each..................546-49

Pump, vacuum, hand operated ................................................................each..............14283-00

Pump, vacuum, portable, 115 V ..............................................................each..............14697-00

Pump, vacuum, portable, 230 V ..............................................................each..............14697-02

SECTION I, continued

Many of the procedures in this manual use gravity filtration. The only labware required is filter paper, a conical funnel and a receiving flask. This labware is included under Optional Equipment and Supplies at the end of a procedure. Gravity filtration is better for retaining fine particles. For faster filtering, add solution until the filter paper cone is three-fourths filled. Never fill the cone completely. Gravity filter (see Figure 2) as follows:

1. Place a filter paper into the funnel.

2. Wet the filter with deionized water to ensure adhesion to the funnel.

3. Place the funnel into an erlenmeyer flask or graduated cylinder.

4. Pour the sample into the funnel.

Figure 2 Gravity Filtration

REQUIRED APPARATUS FOR GRAVITY FILTRATION

Description Unit Cat No.

Cylinder, graduated, 100 mL ...................................................................each ................. 508-42

Funnel, poly, 65 mm ................................................................................each ............... 1083-67

Filter Paper, 12.5 cm ................................................................................each ............... 1894-57

Flask, erlenmeyer, 125 mL ......................................................................each ................. 505-43

Testing for metals requires acid and heat to pretreat the sample. Since these conditions destroy filter paper, vacuum filtration with glass fiber filter discs is recommended. Also, glass filter discs, unlike paper, do not retain colored species.

SECTION I, continued

Temperature Considerations

For best results, most tests in this manual should be performed with sample temperatures between 20 °C (68 °F) and 25 °C (77 °F). If a test requires closer temperature control, notes in the procedure will indicate this.

Sample Dilution Techniques

Ten and 25 mL are the volumes used for most colorimetric tests. However, in some tests, the color developed in the sample may be too intense to be measured. Unexpected colors may develop in other tests. In both cases, dilute the sample to determine if interfering substances are present.

To dilute the sample easily, pipet the chosen sample portion into a clean graduated cylinder (or volumetric flask for more accurate work). Fill the cylinder (or flask) to the desired volume with deionized water. Mix well. Use the diluted sample when running the test.

To help with dilutions, Table 5 shows the amount of sample used, the amount of deionized water used to bring the volume up to 25 mL and the multiplication factor.

The concentration of the sample is equal to the diluted sample reading multiplied by the multiplication factor.

More accurate dilutions can be done with a pipet and a 100-mL volumetric flask (see Table 6 for more information). Pipet the sample and dilute to volume with deionized water. Swirl to mix.

Table 5 Sample Dilution Volumes

Sample

Volume (mL)

25.0 0.0 1

12.5 12.5 2

10.0

5.0

2.5

1.0

0.250

1 For sample sizes of 10 mL or less, use a pipet to measure the sample into the graduated

cylinder or volumetric flask.

mL deionized Water Used

to Bring the Volume to 25 mL

15.0 2.5

20.0 5

22.5 10

24.0 25

24.75 100

Multiplication

Factor

SECTION I, continued

Table 6 Multiplication Factors for Diluting to 100 mL

Sample Volume (mL) Multiplication Factor

1 100

250

520

10 10

25 4

50 2

Sample Dilution and Interfering Substances

Sample dilution may influence the level at which a substance may interfere. The effect of the interferences decreases as the dilution increases. In other words, higher levels of an interfering substance can be present in the original sample if it is diluted before analysis.

An Example:

Copper does not interfere at or below 100 mg/L for a 25.00 mL sample in a procedure. If the sample volume is diluted with an equal volume of water, what is the level at which copper will not interfere?

Total volume

------------- ----------------- ----------- Dilution factor= Sample volume

----------- 2=

12.5

Interference Level Dilution Factor× Interference level in sample=

100 2× 200=

The level at which copper will not interfere in the undiluted sample is at or below 200 mg/L.

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