Hach DR2010 User manual

49300-22

DR/2010

SPECTROPHOTOMETER

PROCEDURES MANUAL

© Hach Company, 1996–2000. All rights reserved. Printed in the U.S.A.	ap/dk 12/99 7ed
	jnb/dk 10/00 rev2

2

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

3

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

4

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

5

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

6

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

7

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

8

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

9

10

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.

11

INTRODUCTION, continued

Hach Company Trademarks

	AccuGrow®	H2O University™
	AccuVac®	H2OU™
	AccuVer™	Hach Logo®
	AccuVial™	Hach One®
	Add-A-Test™	Hach Oval®
	AgriTrak™	Hach.com™
	AluVer®	HachLink™
	AmVer™	Hawkeye The Hach Guy™
	APA 6000™	HexaVer®
	AquaChek™	HgEx™
	AquaTrend®	HydraVer®
	BariVer®	ICE-PIC™
	BODTrak™	IncuTrol®
	BoroTrace™	Just Add Water™
	BoroVer®	LeadTrak®
	C. Moore Green™	M-ColiBlue24®
	CA 610™	ManVer®
	CalVer®	MolyVer®
	ChromaVer®	Mug-O-Meter®
	ColorQuik®	NetSketcher™
	CoolTrak®	NitraVer®
	CuVer®	NitriVer®
	CyaniVer®	NTrak®
	Digesdahl®	OASIS™
	DithiVer®	On Site Analysis.
	Dr. F. Fluent™	Results You Can TrustSM
		OptiQuant™
	Dr. H. Tueau™
		OriFlow™
	DR/Check™
		OxyVer™
	EC 310™
		PathoScreen™
	FerroMo®
		PbEx®
	FerroVer®
		PermaChem®
	FerroZine®
		PhosVer®
	FilterTrak™ 660
		Pocket Colorimeter™
	Formula 2533™
		Pocket Pal™
	Formula 2589™
		Pocket Turbidimeter™
	Gelex®

Pond In Pillow™

PourRite®

PrepTab™

ProNetic™

Pump Colorimeter™

QuanTab®

Rapid Liquid™

RapidSilver™ Ratio™ RoVer® sension™

Simply AccurateSM

SINGLET™

SofChek™

SoilSYS™

SP 510™

Specê

StablCal®

StannaVer®

SteriChek™

StillVer®

SulfaVer®

Surface Scatter®

TanniVer®

TenSette®

Test ‘N Tube™

TestYES!SM

TitraStir®

TitraVer®

ToxTrak™

UniVer®

VIScreen™

Voluette®

WasteAway™

ZincoVer®

12

Sample Procedure Explained

13

Sample Procedure Explained, continued

14

Sample Procedure Explained, continued

15

16

SECTION I CHEMICAL ANALYSIS INFORMATION

Abbreviations

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

	Abbrev-	Definition	Abbrev-	Definition
	iation		iation
	°C	degree(s) Celsius (Centigrade)	HR	high range
	°F	degree(s) Fahrenheit	kg/ha	kilograms per hectare
	ACS	American Chemical Society reagent	l or L	Liter. Volume equal to one cubic
		grade purity		decimeter (dm3)
		Standard Methods for the Examination of	lbs/Ac	pounds per acre
		Water and Wastewater, published jointly by
			LR	low range
		the American Public Health Association
			MDL	Method detection limit
		(APHA), the American Water Works
	APHA	Association (AWWA), and the Water	MDB	marked dropping bottle
		Environment Federation (WEF). Order from
	Standard		mg/L	milligrams per liter (ppm)
		Hach requesting Cat. No. 22708-00 or from
	Methods
		the Publication Office of the American Public	µg/L	micrograms per liter (ppb)
		Health Association. This book is the
				(milliliter)-approximately the same as a
		standard reference work for water analysis.
			ml or mL	cubic centimeter (cc) or 1/1000 of a liter.
		Many procedures contained in this manual
				Also known as a “cc”.
		are based on Standard Methods.
	AV	AccuVac	MR	medium range
	Bicn	bicinchoninate	NIPDWR	National Interim Primary Drinking
				Water Regulations
	CFR	Code of Federal Regulations	NPDES	National Pollutant Discharge
				Elimination System
	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™
		Formazin Attenuation Units. Turbidity unit
	FAU	of measure based on a Formazin stock	SCDB	self-contained dropping bottle
		suspension.
	FM	FerroMo®	TNT	Test ‘N Tube™
	FV	FerroVer®	TPH	Total petroleum hydrocarbons
	FZ	FerroZine®	TPTZ	(2,4,6-Tri-(2-Pyridyl)-1,3,5-Triazine)
	g	grams	ULR	Ultra low range
	gr/gal	grains per gallon (1 gr/gal = 17.12 mg/L)	USEPA	United States Environmental
				Protection Agency

17

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 CONC.

			Table 1	Conversion Factors
To Convert From...			To...		Multiply By...	Conversion used in program #
mg/L Al			mg/L Al2O3		1.8895	9, 10
mg/L B			mg/L H3BO3		5.7	45
mg/L Ca-CaCO3			mg/L Ca		0.4004	220
mg/L CaCO3			mg/L Ca		0.4004	227
mg/L CaCO3			mg/L Mg		0.2428	227
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 Cr6+			mg/L CrO42-		2.231	90, 95
mg/L Cr6+			mg/L Na2CrO4		3.115	90, 95
mg/L Mg-CaCO3			mg/L Mg		0.2428	225
mg/L Mn			mg/L KMnO4		2.876	290, 295
mg/L Mn			mg/L MnO4-		2.165	290, 295
mg/L Mo6+			mg/L MoO42-		1.667	315, 320, 322
mg/L Mo6+			mg/L Na2MoO4		2.146	315, 320, 322
mg/L N			mg/L NH3		1.216	342, 343, 346, 347, 348
mg/L N			mg/L NO3-		4.427	346, 347, 348
mg/L Na	CrO	4	mg/L Cr6+		0.321	670
2
mg/L Na	CrO	4	mg/L CrO 2-		0.72	670
2			4
mg/L NH2Cl-N			mg/L Cl2		5.0623	386
mg/L NH2Cl-N			mg/L NH2Cl		3.6750	386
mg/L NH3-N			mg/L NH3		1.216	380, 385, 387
mg/L NH	-N		mg/L NH +		1.288	380, 385, 387
3			4
mg/L NO2-			mg/L NaNO2		1.5	373
mg/L NO2-			mg/L NO2--N		0.3045	373
mg/L NO2--N			mg/L NaNO2		4.926	345, 371, 375
µg/L NO2--N			µg/L NaNO2		4.926	376
mg/L NO2--N			mg/L NO2-		3.284	345, 371, 375
µg/L NO2--N			µg/L NO2-		3.284	376
mg/L NO3--N			mg/L NO3-		4.427	344, 351, 353, 355, 359, 361
mg/L PO43-			mg/L P		0.3261	480, 482, 485, 490, 492, 535
µg/L PO43-			µg/L P		0.3261	488
mg/L PO43-			mg/L P2O5		0.7473	480, 482, 485, 490, 492, 535
µg/L PO43-			µg/L P2O5		0.7473	488
mg/L SiO2			mg/L Si		0.4674	651, 656
µg/L SiO2			µg/L Si		0.4674	645

18

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 CaCO3 to German parts/100,000 CaO, multiply the value in mg/L x 0.056.

Table 2 Hardness Conversion Factors

			British	American	French	German
	Units of	mg/L	gr/gal		parts/	Parts/	meq/L1		lbs./cu ft
				gr/gal (US)				g/L CaO
	Measure	CaCO3	(Imperial)		100,000	100,000			CaCO3
				CaCO3
			CaCO3		CaCO3	CaO
	mg/L	1.0	0.07	0.058	0.1	0.056	0.02	5.6x10-4	6.23x10-5
	CaCO3
	English	14.3	1.0	0.83	1.43	0.83	0.286	8.0x10-3	8.9x10-4
	gr/gal
	CaCO3
	US gr/gal	17.1	1.2	1.0	1.72	0.96	0.343	9.66x10-3	1.07x10-3
	CaCO3
	Fr. p/	10.0	0.7	0.58	1.0	0.56	0.2	5.6x10-3	6.23x10-4
	100,000
	CaCO3
	Ger. p/	17.9	1.25	1.04	1.79	1.0	0.358	1x10-2	1.12x10-3
	100,000
	CaO
	meq/L	50.0	3.5	2.9	5.0	2.8	1.0	2.8x10-2	3.11x10-2
	g/L CaO	1790.0	125.0	104.2	179.0	100.0	35.8	1.0	0.112
	lbs./cu ft	16,100.0	1,123.0	935.0	1,610.0	900.0	321.0	9.0	1.0
	CaCO3

1‘epm/L, or ‘mval/L’

Note: 1 meq/L = 1N/1000

19

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
						mm
			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

20

SECTION I, continued

Table 3 Dissolved Oxygen Saturation in Water (continued)

					Pressure in Millimeters and Inches Hg
						mm
			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

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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.

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SECTION I, continued

Table 4 Required Containers, Preservation Techniques and Holding Times1

	Parameter No./Name	Container2	Preservation3,4			Maximum
						Holding Time5
Table 1A - Bacterial Tests
1-4. Coliform, fecal and total		P,G	Cool, 4°C, 0.008%, Na	S O	6	6 hours
			2	2	3
5. Fecal streptococci		P,G	Cool, 4°C, 0.008%, Na	S O	6	6 hours
			2	2	3
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, H2SO4 to pH<2			28 days
9. Biochemical oxygen demand		P, G	Cool, 4°C			48 hours
(BOD)
10.	Boron	P, PFTE or quartz	HNO3 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, H2SO4 to pH<2			28 days
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		P, G	Cool, 4°C, NaOH to pH>12, 0.6 g			14 days7
to chlorination			ascorbic acid6
25.	Fluoride	P	None required			28 days
27.	Hardness	P, G	HNO3 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, H2SO4 to pH<2			28 days
nitrogen
Metals8
18.	Chromium VI	P, G	Cool, 4°C			24 hours
35.	Mercury	P, G	HNO3 to pH<2			28 days
Metals, except boron, chromium VI
and mercury: 3, 5-8, 12, 13, 19, 20,		P, G	HNO3 to pH<2			6 months
22, 26, 29, 30, 32-34, 36, 37, 45,
47, 51, 52, 58-60, 62, 63, 70-72, 74,
759.
38.	Nitrate	P, G	Cool, 4°C			48 hours
39.	Nitrate-nitrite	P, G	Cool 4°C, H2SO4 to pH<2			28 days
40.	Nitrite	P, G	Cool, 4°C			48 hours
41.	Oil and grease	G	Cool, 4°C, HCl or H2SO4 to pH<2			28 days
42.	Organic Carbon	P, G	Cool, 4°C, HCl or H2SO4 or			28 days
			H3PO4 to pH<2
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, H2SO4 to pH<2			28 days

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SECTION I, continued

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

	Parameter No./Name	Container2	Preservation3,4	Maximum
				Holding Time5
49.	Phosphorus, elemental	G	Cool, 4°C	48 hours
50.	Phosphorus, total	P, G	Cool, 4°C, H2SO4 to pH<2	28 days
53.	Residue, total	P, G	Cool, 4°C	7 days
54.	Residue, filterable	P, G	Cool, 4°C	7 days
55.	Residue, Nonfilterable (TSS)	P, G	Cool, 4°C	7 days
56.	Residue, Settleable	P, G	Cool, 4°C	48 hours
57.	Residue, volatile	P, G	Cool, 4°C	7 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	P, G	Cool 4°C, add zinc acetate plus	7 days
			sodium hydroxide to pH>9
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

1This 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.

2Polyethylene (P) or glass (G).

3Sample 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.

4When 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 (HNO3) in water solutions at concentrations of 0.15% by weight or less (pH about 1.62 or greater); Sulfuric acid (H2SO4) in 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).

5Samples 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.

6Should only be used in the presence of residual chlorine.

7Maximum 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.

8Samples should be filtered immediately on-site before adding preservative for dissolved metals.

9Numbers refer to parameter number in 40 CFR, Part 136.3, Table 1B.

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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:

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.

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

25

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?

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

2. 1007

------------ = 1.007 = volume correction factor 1000

3.10.0 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 Aids

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.

26

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
OR
Pump, vacuum, portable, 115 V ..............................................................	each..............	14697-00
Pump, vacuum, portable, 230 V ..............................................................	each..............	14697-02

27

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.

28

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	mL deionized Water Used	Multiplication
Volume (mL)	to Bring the Volume to 25 mL	Factor
25.0	0.0	1
12.5	12.5	2
10.01	15.0	2.5
5.01	20.0	5
2.51	22.5	10
1.01	24.0	25
0.2501	24.75	100

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

29

SECTION I, continued

Table 6 Multiplication Factors for Diluting to 100 mL

Sample Volume (mL)	Multiplication Factor
1	100
2	50
5	20
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
----------25 = 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.

30