U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
PB-259 946
HANDBOOK FOR SAMPLING AND SAMPLE PRESERVATION OF
WATER AND WASTEWATER
ENVIREX INC, MILWAUKEE, Wis ENVIRONMENTAL SCIENCES Div
PREPARED FOR
ENVIRONMENTAL MONITORING AND SUPPORT LAB, CINCINNATI, OHIO
SEPTEMBER 1976
-------
TECHNICAL REPORT DATA
us&tictivM on Hi? reverse before completing)
\. REPORT NO.
3.
3. RECIPIENT'S ACCESSION NO.
PB-259 946
. TITUS AND SUBTITLE
HANDBOOK FOR SAMPLING AND SAMPLE PRESERVATION
OF WATER AND WASTEWATER
5. REPORT DATE
September 1976 (Issuing date)
6. PERFORMING ORGANIZATION CODE
7. AUTMOR(S)
J, H. Moser
K. R. Huibregtse
8. PERFORMING ORGANIZATION REPORT NO
0. PERFORMING ORO 'VNISATIQN NAME AND ADDRESS
Envirex, Inc., A Rexnord Company
Environmental Sciences Division
5103 West Beloit Road
Milwaukee, WI 53201
HO. PROGRAM ELEMENT NO.
1HD 621
HI). GONTRACT/GRANT NO.
Contract No. 68-03-2075
3. SPONSORING AGENCY WAME AND ADDRESS
Environmental Monitoring and Support Laboratory
Office of Research ®nd Development
UoSo Environmental Protection Agency
Cincinnati, OH 45268
H3. TYPE OF REPORT AND PERIOD COVERED
Contract - 6/28/74 to 6/1/76
D4. SPONSORING AGENCY CODE
EPA-ORD
!O.QUPPkQ(W(ENVAe)V NOTES
This research program was initiated with the overall objective of providing
guidelines for sampling and sample preservation of waters and wastewaters.
Information obtained from a review of the literature and the results of a
survey of field practices provides the basis for guidelines in general sampling
techniques, automatic samplers„flow measuring devices, a statistical approach
to sampling, preservation of physical, chemical, biological and radiological
parameters, and sampling procedures for waters emanating from municipal, indus-
trial, and agriculture sources. Sampling procedures for surface waters and
sludges are also included.
This report is not an official EPA manual. Rather, it is a research report
which is but one of a series being used as an input to develop EPA Manuals and
Guidelines.
This report was submitted in fullfillment of Contract No. 68-03-2075 by
Envirex, Inc., A Rexnord Company, under the sponsorship of the U.S. Environmental
Protection Agency. The report covers the period of June 28, 1974 to June 1, 1976.
KEV WORDS AND DOCUMENT ANALYSIS
t>. IDENTIFIERS/OPEN ENDED TERMS |c. COSATlField/GfOUp
Sampling*, Water*, Waste*, Samplers*,
Statistics*, Flow Measurement*,
Surveys*, Preservatives*.
Sampling of Surface
Waters, Agriculture,
Municipalities, Industries
and Sludges.
>0. 0ISTRIQUTION STATEMENT
Release to Public
US. SECURITY CLASS (ThisReport) |2J, NO. OP>A6ES
Unclassified
ae.
Unclassified
POP« aaae-?
-------
PORTIONS OF THIS REPORT ARE NOT LEGIBLE.
HOWEVER, IT IS THE BEST REPRODUCTION
AVAILABLE FROM THE COPY SENT TO NTIS
l-fl
-------
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL MONITORING series.
This series describes research conducted to develop new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations. It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161
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EPA-600A-76-049
September 1976
HANDBOOK FOR
SAMPLING AND SAMPLE PRESERVATION
OF WATER AND WASTEWATER
by
K. R. Huibregtse and J. H. Moser
Envirex Inc., A Rexnord Company
Environmental Sciences Division
Milwaukee, Wisconsin 53201
Contract No. 68-03-2075
Project Officer
Edward L. Berg
Quality Assurance Branch
Environmental Monitoring .and Support Laboratory
Cincinnati, Ohio 45268
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 1»5268
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DISCLAIMER
This report has been reviewed by the Environmental Monitoring and Support
Laboratory and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the U.S. Environmental
Protection Agency, nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.
ii
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FOREWORD
Environmental measurements are required to determine the quality of
ambient waters and the character of waste effluents. The Environmental
Monitoring and Support Laboratory~Cincinnati engages in the following activi=
Develops and evaluates techniques to measure the presence and concen=
tratlon of physical; chemical, and radiological pollutants in water,
bottom sediments, and solid waste.
Investigates methods for the concentration, recovery and indentifica-
tion of viruses, bacteria, and other microbiological organisms in
water. Conducts studies to determine the responses of aquatic
organisms in water.
Conducts an Agency-wide quality assurance program to assure standard-
isation and quality control of systems for monitoring water and
Standardised procedures for analyses of quality control become academic
if samples are not representative of their original environment or if changes
of constituent concentrations occur between time of sampling and analysis.
This handbook presents techniques for sampling and sample preservation to help
alleviate these problems. Procedures have been standardized as much as
possible throughout this document. However, sampling techniques could not be
predetermined for all situations, so the use of statistical procedures to
establish location and frequency of sampling, number of samples, and param-
eters to be analyzed is recommended when other guidelines do not exist.
Sample preservation methods and holding times are included for the 71 param-
eters listed for the NPDES program and selected biological species. Special
handling or sampling techniques are also included for the individual constitu-
ents. Personnel establishing a sampling program should find sufficient
information to determine the best techniques to apply. The justification for
the recommended practices in this handbook are included in a research report
that surveyed current field practices and available literature on sampling and
sample preservation techniques. Further information can be obtained from this
document entitled "Development of Guidelines for Sampling and Sample Preserva-
tion of Water and Wastewater."
This report is not an official EPA manual. Rather, it is a research
report that is but one of a series being used as an input to develop EPA
Manuals and Guidelines,
Dwight G. Ballinger
Director
Environmental Monitoring & Support
Laboratory-Cincinnati
i i i
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ABSTRACT
This research program was initiated with the overall objective of provid-
ing guidelines for sampling and sample preservation of waters and wastewaters.
Information obtained from a review of the literature and the results of a
survey of field practices provides the basis for guidelines in general sampling
techniques, automatic samplers, flow measuring devices, a statistical approach
to sampling, preservation of physical, chemical, biological and radiological
parameters, and sampling procedures for waters emanating from municipal,
industrial, and agriculture sources. Sampling procedures for surface waters
and sludges are also included.
This report is not an official EPA manual. Rather, it is a research
report that is one of a series being used as an imput to develop EPA Manuals
and Guidelines.
This report was submitted in fulfillment of Contract No. 68-03-2075 by
Envirex, Inc., A Rexnord Company, under the sponsorship of the U.S. Environ-
mental Protection Agency. The report covers the period of June 28, 1974 to
June 1, 1976, and work was completed as of August 1, 1976.
IV
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CONTENTS
PAGE
Foreword 111
Abstract iv
Figures ix
Tables xiv
Acknowledgments xvl 1
1. Introduction 1
2. General Considerations For Sampling 3
2.1 Objectives of Sampling Programs 3
2.2 Type of Sample 4
2.3 Automatic Samplers 10
2.4 Flow Measurement with Sampling 18
2.5 Practical Features of Sampling 37
2.6 References 39
3. General Considerations of Sampling Preservation
and Handl i ng 41
3.1 Universal Preservation 41
3.2 Sample Identification 42
3.3 Chain of Custody 43
3.4 Container Type and Cleaning 53
3.5 Holding Time 57
3.6 Volume of Sample 57
3.7 Reference 58
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CONTENTS (Continued)
PAGE
4. The Statistical Approach to Sampling 61
4.1 Basic Statistics and Statistical Relationships. 61
4.2 Determination of Number of Samples 78
4.3 Determi nati on of Sampl i ng Frequency .. 84
4.4 Determination of Parameters to Analyze 92
4.5 In-Plant Sampling and Network Monitoring 102
4.6 References 119
5. Sampling Municipal Wastewaters 123
5.1 Background. 12f3
5.2 Objectives of Sampling Programs 123
5.3 Frequency of Sampling 123
5.4 Location of Sampling Points 124
5.5 Number of Samples 129
5.6 Parameters to Measure 129
5.7 Type of Sample 130
5.8 Method of Sampling 130
5.9 Automati c Sampl ers 130
5.10 Volume of Sample and Container Type 131
5.11 Preservation and Handling the Samples 131
5.12 Flow Measurement 131
5.13 References 131
6. Sampling Industrial Wastewaters 133
6.1 Background 133
6.2 Objectives of Sampling Programs 133
6.3 Frequency of Sampling 134
6.4 Location of Sampling Points 135
6.5 Number of Samples 135
6.6 Parameters to measure 137
6.7 Type of Sample 137
6.8 Method of Sampling 140
6.9 Automatic Samplers 142
6.10 Volume of Sample and Container Type 143
6.11 Preservation and Handling of Samples 143
6.12 Flow Measurement 143
6.13 References 144
7. Sampling Surface Waters and Bottom Sediments 145
7.1 Background 145
7.2 Objectives of the Study 145
7.3 Parameters to Analyze 145
V I
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CONTENTS (Continued)
PAGE
7.4 Location of Sampling Points... 146
7.5 Number of Samples 150
7.6 Frequency of Sampling 153
7.7 Method of Sampling 153
7.8 Types of Samples 153
7.9 Volume of Sample and Container Type 161
7.10 Preservation and Handling of Sample 161
7.11 Flow Measurement 161
7.12 References 161
8. Sampling Agricultural Discharges 169
8.1 Background 169
8.2 Objectives 169
8.3 Frequency of Sampling 169
8.4 Location of Sampling Points 170
8.5 Number of Samples 170
8.6 Parameters to Analyze 170
8.7 Type of Sample.... 171
8.8 Method of Sampling. 171
8.9 Volume of Sample and Container Type 174
8.10 Flow Measurement 174
8.11 References 174
9 Sampling Sludges 177
9.1 Background 177
9.2 Objectives of Sampling Programs 177
9.3 Parameters to Analyze 178
9.4 Location of Sampling Points 178
9.5 Frequency of Sampling 180
9.6 Number of Samples 181
9.7 Type of Sample 181
9.8 Method of Sampling 181
9.9 Volume of Sample and Container Type 181
9.10 Preservation and Handling of Samples 181
9.11 Flow Measurement 181
9.12 References 182
10. Sample Preservation and Handling by Parameter Group.. 183
10.1 Introduction 183
10.2 Methods for Nutrients Parameter Group 183
10.3 Methods for Demand Parameter Group 194
vii
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CONTENTS (Continued)
PA&
10.4 Methods for Metals Parameter Group 202
10.5 Methods for Physical/Mineral Parameter Group. 207
10.6 Methods for Pesticides/Herbicides Parameter
Group 220
10.7 Methods for Biological Group 229
10.8 Methods for Radioactive Parameter Group 232
10.9 References 242
11 Collecting and Handling Microbiological Samples 247
11.1 Background 247
11.2 Common Analyses 247
11.3 Sample Bottle Preparation 249
11.4 Sample Collection 250
11.5 Sample Preservation and Handling 252
11.6 References 254
Index 255
V I I
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FIGURES
NUMBER PAGE
2.1 Volume and Time of Discrete Sample Collection for
Four Periodic Compositing Methods 6
2.2 Example of Flow Proportional Sample Installation... 17
2.3 Flow Measurement Devices for Filled Pipe Under
Pressure 21
2.4 Techniques for Pipes Discharging to the Atmosphere 22
2.5 Sharp Crested Weir 26
2.6 Flow Rates In gallons per minute for 60° and 900
V-Notch Weirs 27
2.7 Nomograph for Capacity of Rectangular Weirs 28
2.8 Nomograph to Determine Fee Flow Through 3-Inch to
8-ft Parshall Flumes 31
2.9 Parshall Flume 32
3.1 Chain of Custody Record Tag... 44
3.2 Gummed Seal for Sample Bottles 45
3.3 Bottle Sample Tag Used by NFIC - Denver 46
3.4 Example of a Field Log Sheet 48
3.5 Chain of Custody Record Form 49
3.6 Sample Transmittal Form 51
4.1 Statistical Components of a Water Quality Record.. 62
4.2 Gaussian or Normal Distribution 66
-------
FIGURES (Continued)
NUMBER
4.3
4.4
4.5
4.6
4.7
4.8
4.9
Pearson Type 111 Probability Distribution and Density
Graphical Method for Determining Probability Distribu-
tion
Histogram and Probability Curve for Larger Number of
Samples
Determination of the Number of Samples Based on the
Requi red Accuracy of Extreme Val ues
Determination of the Number of Samples Based on the
Requi red Accuracy of the Mean
Various Power Spectra for Variable X(t)..
Determination of Sampling Frequency
PAGE
68
74
76
82
85
86
88
4.10 Time Record of TOC of Municipal Wastewater, Racine,
Wi sconsi n 90
4.11 Power Spectrum of TOC Concentration of Municipal
Wastewater at Racine, Wisconsin 90
4.12 Power Spectrum of Chemical Plant Discharge, Case 1.... 91
4.13 Power Spectrum of Chemical Plant Discharge, Case 2 92
4.14 Relationship of TOC-BOD Concentrations of a Municipal
Wastewater 96
4.15 Segmentation of a Wastewater System 103
4.16 An Industrial Water/Wastewater System 106
4.17 Linear Graph Representation of an Industrial Water/
Wastewater System 107
4.18 Estimation of Variability and Correlation in Segments. 109
4.19 Correlogram for Segments 116
4.20 Spectral Analysis Computer Program 121
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FIGURES (Continued)
NUMBER PAGE
6.1 Factors of Plant Operation to be Considered in the
Design of the Sampling Program 136
7.1 Example of the Transect Sampling Scheme 148
7.2 Example of Grid Sampling Scheme ; 149
7.3 Use of Spatial Gradient Technique for Maximum Spacing
of Sampling Stations 150
7.4 Water Bottles 160
7.5 Bottom Grab Samplers 162
7.6 Core Samplers 164
7.7 Nets and Related Samplers 165
7.8 Periphyton, Samplers 167
7.9 Macroinvertebrate Sampler... ,. 168
8.1 View of Field Installation 172
8.2 View of Field Installation 173
!
8.3 Schematic of Water Level Recorder and Sampler Arrange-
ment 174
9.1 Recommended Minimum Sampling Programs for Municipal
Wastewater SI udge Treatment Processes 179
10.1 Recommended Preservation and Handling Methods-TKNJ...-. 187
10.2 Recommended Preservation and Handling Methods-NH3 190
10.3 Recommended Preservation and Handling Methods-N03 191
10.4 Recommended Preservation and Handling Methods-N02 192
10.5 Recommended Preservation and Handling Methods N02/N03. 193
XI
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FIGURES (Continued)
NUMBER PAGE
10.6 Recommended Preservation and Handling Methods-Ortho
Phosphate 193
10.7 Recommended Preservation and Handling Methods-Total
Phosphate 195
/?
10.8 Recommended Preservation and Handling Methods-BOD 198
10.9 Recommended Preservation and Handling Methods-COD 199
10.10 Recommended Preservation and Handling Methods-TOC 200
10.11 Recommended Preservation and Handling Methods-DO 201
10.12 Recommended Preservation and Handling Methods-As and B. 204
10.13 Recommended Preservation and Handling Methods-Ca, K,
Na and Cr VI 205
10.14 Recommended Preservation and Handling Methods-Hg and Ag 206
10.15 Recommended Preservation and Handling Methods-Metals... 208
10.16 Recommended Preservation and Handling Methods-Br" and
Cl 212
10.17 Recommended Preservation and Handling Methods-CN" and F" 213
10.18 Recommended Preservation and Handling Methods-SO." and
S" ..7 215
10.19 Recommended Preservation and Handling Methods-SO," and
Acidity T 216
10.20 Recommended Preservation and Handling Methods-Alkalin-
ity and G12 Res 217
10.21 Recommended Preservation and Handling Methods-Color
and Hardness 218
10.22 Recommended Preservation and Handling Methods-Oil and
Grease and pH 221
XI I
-------
FIGURES (Continued)
NUMBER PAGE
10.23 Recommended Preservation and Handling Methods-Phenolics
and Sp cond 222
10.24 Recommended Preservation and Handling Methods-Surfactant
and Turbidity ..' 223
10.25 Recommended Preservation and Handling Methods-Total
and Volatile Solids 224
10.26 Recommended Preservation and Handling Methods-SS and
TDS 225
10.27 Recommended Preservation and Handling Methods-Pesticides
and PCS's 228
10.28 Recommended Preservation and Handling Methods-
Benzidine 240
10.29 Recommended Preservation and Handling Methods-
Radioactive 241
11.1 Recommended Preservation and Handling Methods-
Microbiological Parameters 253
XI I
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TABLES
NUMBER PAGE
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
3.1
3.2
4.1
4.2
4.3
4.4
4.5
4.6
4.7
Time of Collection and Volume of Samples for
the Four Compositing Methods
Advantages and Disadvantages of Methods of Compositing
Manual Preparation of Volume Variable Composite4. ......
Automatic Samplers and Their Features
Flow Measurement 1n Pressure Pipes
Advantages and Disadvantages of Flumes and Weirs
Advantages and Disadvantages of Secondary Devices
Relative Comparison of Primary and Secondary Open
Channel Flow Measurement Devices
Comparison and Glass and Plastic Containers
Comparison of Cap Liners.
Areas Under Standardized Normal Density Function
Percentage Points of Chi-Square Distribution —
Percentage Points of Student Distribution
Computational Table for Graphical Normal or Pearson
Type 111 Distribution Determination
K Values for Positive Skew Coefficients
K Values for Negative Skew Coefficients
Sampling Priorities of Parameters for a Typical
Wastewater
5
7
9
11
19
33
34
35
54
55
67
69
71
73
79
80
94
XIV
-------
TABLES (Continued)'
NUMBER
4.8
4.9
4.10
4.11
4.12
Values of Correlation Coefficient p, for Two Levels
of Significance
Correlation Matrix of Coefficient, pxyp
xy
Wastewater Loads to Nodes
>
Coefficient of Variation in Branches
Determination of the Sampling Priorities of Segments...
PAGE
99
101
113
114
115
5.1 Process Testing Guide • 125
5.2 Recommended Minimum Sampling Programs for Municipal
Wastewater Treatment Processes * 127
6.1 NPDES Effluent Limitation Parameters by Industry 138
6.2 Types of Composites for Different Discharges 140
6.3 The Advantages and Disadvantages of Manual and Automa-
tic Sampling 141
6.4 Comparison of Requirements and Features of Automatic
and Manual Methods 142
7.1 Common Analyses for Surface Water and Sediment Sampling 146
7.2 Model State Water Monitoring Program Guidelines for
Biological Monitoring 154
7.3 Comparison of Water Samplers 155
7.4 Comparison of Bottom Grabs 156
7.5 Compari son of Cori ng Devi ces 157
7.6 Comparison of Net Sampling Devices 158
7.7 Comparison of Substrate Samplers 159
10.1 Parameter Group Classifications 184
XV
-------
TABLES (Continued)
NUMBER PAGE
10.2 Partial Listing of Commercial Mercury Reprocessors 188
10.3 Atomic Absorption Concentration Ranges with Convention
Atom1zat1on 203
10.4 Persistence of Pesticides Compounds in River Mater 227
10.5 Parameters of Biological Communities Most Commonly
Analyzed for Monitoring Purposes 231
10.6 Comparison of Chemical Preservatives for Biological
Parameters 233
10.7 Recommended Preservation and Handling Methods-BentMc
Macro Invertebrates 234
10.8 Recommended Preservation and Handling Methods-Fish 235
10.9 Recommended Preservation and Handling Methods-Macro-
phytes and Macroalgae 236
10.10 Recommended Preservation and Handling Methods-Periphy-
ton , 237
10.11 Recommended Preservation and Handling Methods-
Phytoplankton 238
10.12 Recommended Preservation and Handling Methods-
Zooplankton 239
xv i
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ACKNOWLEDGMENTS
This study required Input from an extensive number of Individuals and
organizations. Gratitude 1s extended particularly to those parties
who cooperated in responding to the questionnaire on sampling and
sample preservation practices. This Includes the EPA Regional Offices,
National Field Investigation Centers* and National Environmental
Research Centers as well as other government agencies and private
sources. /
Special acknowledgment 1s given to the staff of the Quality Assurance
Branch, Environmental Monitoring and Support Laboratory-Cincinnati, Ohio.
In particular, the direction and support of Mr. Edward L. Berg, Project
Officer, 1s appreciated. Finally, thanks are extended to all the staff
members of the Environmental Sciences Division—technical, administrative
and clerical—who participated 1n this project and contributed to Its
success. In addition to the two principal authors, the following technical
staff members contributed significantly to this report: D. H. Brady,
M. 0. Clark, D. A. Gruber, C. A. Hansen, R. A. Osantowski, R. E.
Wullschleger, A. E. Sanonl, and V. Novotny of Marquette University.
xv i i
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CHAPTER I
INTRODUCTION
Obtaining representative samples and then maintaining the Integrity of
the constituents is an integral part of any monitoring or enforcement
program. Standardization of the analytical techniques has been
established to a high degree but the result of analysis is only as good
as the sampling and the sample preservation. The purpose of this hand-
book Is to present the best techniques currently available for sampling
and sample preservation. The recommendations were developed from an
extensive research report (1) which included a literature review and
survey of current laboratory and field practices. The handbook will
allow the personnel to determine the most effective procedures for
their specific applications.
In sampling, the objective is to remove a small portion of an
environment that is representative of the entire body. It Is then
obvious that Improper sampling will give erroneous results. Once the
sample Is taken, the constituents of the sample must stay in the same
condition as when the sample was collected. The length of time that
these materials will remain stable Is related to the preservation
method. Effective sample preservation will allow a sample's constituents
to be preserved for longer periods of time.
The sampling technique is affected by the type of water or wastewater
to be sampled. Therefore the following areas are addressed in this
handbook:
I. Municipal wastewaters k. Agricultural runoff
2. Industrial wastewaters 5« Wastewater sludges
3. Surface waters and sediments
General Information on automatic samplers and flow monitoring is also
included.
Statistical methods have been presented in this handbook and will be
used to determine the following aspects of sampling programs:
1. Number of samples 3* Location of sampling
2. Frequency of sampling k. Parameters to measure
-------
Preservation methods are related to the parameters to be analyzed so,
In thts handbook, these techniques are classified by parameter. The
(71) parameters specified for the NPDES permit program in the Federal
Register, of October 16, 1973* and selected biological parameters are
included.
-------
CHAPTER 2
GENERAL CONSIDERATIONS FOR SAMPLING
There are certein areas of sampling which apply to all types of waters
and wastewaters Including:
1. Objectives of Sampling Programs
2. Type of Sample
3. Automatic Samplers
k. Flow Measurement with Sampling
5. Practical Features of Sampling
2.1 OBJECTIVES OF SAMPLING PROGRAMS
The objectives of a program directly affect all aspects of sampling and
the analyses performed on the sample. Therefore, determination of
objectives Is the first decision when establishing a sampling program.
2.1.1 Regulatory Objectives
Sampling and subsequent analyses are often performed to meet the require-
ments of state, federal or local regulatory agencies. The self-monitorIng
Is then enforced by agencies to assure compliance with the regulations.
An example Is the National Pollutant Discharge Elimination System (NPDES)
which issues a permit to discharge to surface waters.
Often the details of sampling including,number of samples, frequency,
parameters to analyze and location are specified in the permit. However,
other Important details such as type of composite are not included.
Compliance with regulatory objectives means that any previously
specified standards be followed.
2.1.2 Research Objectives
To evaluate the effectiveness of research projects, sampling must be done
at the Influent and effluent to a certain process. The program of
sampling may be simple or complex depending on the project. Standard
sampling techniques using the best available technology are critical for
establishing comparable and valid data.
-------
2.1.3 Process Control Objectives
Standardization of inplant sampling for process control is necessary for
comparable data or regulatory compliance. The determination of efficiency
of a unit process, whether treatment or production, is a process control
objective.
2.2 TYPE OP SAMPLE
2.2.1 Grab Samples
A grab sample is defined as a single sample taken at a point in time. It
can be taken using a pump, scoop, vacuum, or other suitable device. The
use of a pump over a short time period Cfifteen minutes or less) often is
convenient. The collection of a grab sample is appropiate when it is
desired to:
1. Characterize water quality at a particular time /
2. Provide information about minimum and maximum
3. Allow collection of variable sample volume
2.2.2 Composite Samples
A composite sample is defined as a sample formed by mixing discrete samples
taken at periodic points in time or a continuous portion of the flow. A
sequential composite is defined as a series of short period grab samples
each of which is held in an individual container, then composited to cover
a longer time period. Six methods are used for forming composites:
Method No. Sampling mode
Compositing principle
1
2
Continuous
Continuous
Periodic
Periodic
Periodic
Periodic
Constant sample pumping rate
Sample pumping rate proportional to
stream flow
Constant sample volume, constant
time interval between samples
Constant sample volume, time inter-
val between samples proportional to
stream flow
Constant time interval between
samples, sample volume proportional
to total stream flow since last
sample
Constant time interval between
samples, sample volume proportional
to stream flow at time of sampling
-------
Compositing on the basis of flow is necessary because this procedure will
provide a representative mass loading of the discharge on a receiving
water for the period sampled.
To Illustrate the differences between the periodic composite samples,
the following example Is given.
Example - It is desired to determine the average characteristics of
an industrial discharge over an 8 hour working day. The flow varies
as shown In Figure 2.1. Approximately 4 liters (1.1 gal.) of a
composite sample are needed by the laboratory for analyses.
Assuming eight samples are collected over the day, the time of
collection and volume of each sample used for the composite are
shown in Figure 2.1 and given In Table 2.1 for the four types of
periodic compositing methods.
Table 2.1. TIME OF COLLECTION AND VOLUME
OF SAMPLES FOR THE FOUR COMPOSITING METHODS
Sample
No.
1
2
3
4
S
6
7
8
Time of sampling, hr
composite method no.
3
1.0
2.0
3.0
4.0
5-0
6.0
7.0
8.0
4
• 1.8
2.7
3.4
4.0
4.6
5.3
6.2
8.0
5
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
6
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
Volume of sample, ml
composite method no.
3
500
500
500
500
500
500
500
500
4
500
500
500
500
500
500
500
500
5
160
420
660
760
760
660
420
160
6
302
560
735
795
735
560
302
0
In methods1 3, 5, and 6, there is a constant time interval between sampling
periods. In method 4, the Interval Is variable and dependent on the time
needed for a given volume of flow to pass. A sample Is therefore taken
each time 1,250 1 (330 gal.) passes.
2.2.3 Selection of Sample Type
Use grab samples when (1,2,3)
1. The stream does not flow continuously (i.e. batch dump).
2. The water or waste characteristics are relatively constant
(i.e. sludge).
-------
o
te.
Method 3
Q-5,000 sin vt/8
Method 5
«/» o
O "~
Ul
§
1.0 2.0 3-0 4.0 5.0 6.0 7.0
TIME, HOUR OF WORK DAY (t)
i. Method k
8.0
1.0 2.0 3.0^.0 5.0 6.0 7.0 8.0
Method 6
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Figure 2.1. Volume and time of discrete sample collection for
four periodic compositing methods
-------
3. The parameters to be analyzed are likely to change (i.e.
dissolved gases, residual chlorine, soluble sulflde, oil
and grease, microbiological parameters, etc.).
4. The maximum or variability is to be determined.
5. The history of water quality is to be established based on
relatively short time intervals.
Use composite samples when
1. Determining average waste concentrations.
2. To calculate mass/unit time loading.
2.2.k Selection of Composite Type
Choice of composite type Is dependent on the program and the advantages
and disadvantages of each is given In Table 2.2.
Table 2.2 ADVANTAGES AND DISADVANTAGES OF METHODS OF COMPOSITING
ComposItInfl method
Advantages
Disadvantages
Continuous
1. Constant sample Minimal manual effort;
pumping rate requires no flow
measurement
2. Sample pumping
rate propor-
tional to
stream flow
Most representative
especially for highly
variable flows; minimal
manual effort.
3. Constant sample Minimal instrumentation
volume, constant and manual effort;
time Interval requires no flow
between samples measurement
Requires large sample
capacity, or small pump
which may clog; may lack
representativeness
especially for highly
variable flows; requires
power.
Requires accurate flow
measurement/recording
equipment; requires large
sample volume; or small
pump which may clog;
requires variable
pumping capacity; requires
power.
May lack representative-
ness especially for highly
variable flows
-------
Table 2.2. (continued). ADVANTAGES AND
DISADVANTAGES OF METHODS OF COMPOSITING
Compositing method Advantages Disadvantages
k. Constant sample Minimum manual effort Requires accurate flow
volume, time measurement/recording
Interval between equipment
samples propor-
tional to stream
flow
5. Constant time Minimal tnstrumenta- Manual compositing from
Interval between tion flow chart
samples, sample
volume propor-
tional to total
stream flow since
last sample
6. Constant time Minimal instrumenta- Manual compositing from
interval between tlon flow chart
sample, sample
volume propor-
tional to total
stream flow at
time of sampling
2.2.5 Method of Compositing
The preparation of the flow rated composite is performed in various ways.
Table 2.3 summarizes the techniques necessary for preparing composites
from time constant, volume variable samples.
When using a volume constant, time proportional compositing method,
previous flow records should be used to determine an appropriate
flow volume increment so a representative sample is obtained without
overrunning the bottle capacity or supply.
-------
Table 2.3 MANUAL PREPARATION OF VOLUME VARIABLE COMPOSITE
Typa
Preparation
Equation
Time const/volume
prop, to flow sine*
last sample
Determine volume
since last sample
by integration
• V
F c
v •
discrete sample vol.
composite vol. (known)
Time const, volume
prop.to instanta-
neous flow rate
Fs • flow volume since
last sample
(integration)
' /
F • total flow volume
(estimated)
Note flow rate at ax
each time of discrete
sample collection
bx + ex
a,b,c » flow rates when
samples taken (noted)
x • volume sample/unit
flow (desired)
VG • composite volume
(known)
V. • discrete sample vol.
(desired)
V£ • composite volume
(known)
n • no. of discrete samples
-------
2.3 AUTOMATIC SAMPLERS
2.3.1 Background
Use of automatic samplers has been increasing to implement the NPDES
self-mon'torlng requirements. The following advantages are apparent ('():
I. Eliminates inevitable errors due to the human element in
manual sampling.
2. Reduces to a minimum costly personnel requirements.
3. Eliminates a routine task which can devolve into an irksome chore.
k. Provides the capability for more frequent sampling than Is
practical for manual sampling. /*
There are many commercial samplers (see Table 2.4). However, no. single
automatic sampling device is ideally suited for all situations. For
each application these variables should be considered (5):
I. Variation of water or wastewater characteristics with time.
2. Variation of flow rate with time.
3. Specific gravity and concentrations of suspended sol ids.
l». Presence of floating materials.
The following list of functional subsystems is intended to aid in the
proper selection and use of an automatic sampler.
2.3.2 Criteria for Evaluating Sampler Subsystems
2.3.2.I Intake Device -
I. Causes minimum obstruction of sewer or channel to minimize
chances of fouling or dar.ianc.
2. Is capable of drat/ing a sample representative of entire stream
flow (including surface, middle and bottom layers) (6). Use
of multiple intakes may be warranted (5).
3. Is resistant to plugging by providing coarse screening if
large materials such as rags, sticks, and stones are
present (5). However, smaller suspended solids should not
be excluded by the intake.
10
-------
Table 2.4. AUTOMATIC SAMPLERS AND THEIR FEATURES
Ability to sarple
Refrigeration "
Sampler
BIF
Brallsford DC-F
Brallsford CV-F
BVS PP-IOO
BVS SE-a.00
BVS SE-600
Chicago "Tru-Test"
Hydro-Numatlc
Infllco
ISCO 1391
Lakeside T-2
Hark land 1301*
Markland 101*
Harkland 102*
Harkland 10AT*
N-Con Surveyor
N-Con Scout
N-Con Sentry
N-Con Trebler
Method of sample transport
Dipper
Positive displacement pump
Vacuum pump
Pneumatic ejection
Submersible pump
Hone provided - solenoid
valve diversion from
sample line6
Dipper from sample chamber
provided by customer
Centrifugal pump
Dipper from sample chamber
provided by customer
Peristaltic pump
Dipper
Pneumatic ejection
Pneumatic ejection
Pneumatic ejection
Pneumatic ejection
Centrifugal pump
Peristaltic pump
Peristaltic pump
Dipper
orovlded
yes
no
no
yes
yes
yes
r«*
no
yes
Ice cavity*
yes
no
yes
yes
yes
no
no
no
yes
Ability to
Freeiln^"
no
no
no
yes
yes
yes
no
yes
no
no
no
yes
yes
yes
yes
no
no
no
no
withstand
Immersion
no
no
no
no
no
no
no
no
no
yes
no
no
no
no
no
no
no
no
no
Floatables
no
no
no
yes
no
.
b
yes
some
no
no
no
po
0
no
no
some
Coarse
bottom
sediments
no
no
ho
no
no
.
b
no
some
no
no
no
po
0
no
no
some
Self-
cleaning
features
none
continuous
flow
backflush
air purge
continuous
continuous
flow
continuous
continuous
flow
continuous
flow
backflush
none
none
none
air purge
none
gravity drain
backflush
backflush
none
a. Representativeness of sample questioned In References.
b. Depends on how
c. Continuous flow
user arranges sampler Intake.
sample line provided by user.
d. Refrigeration provided only for stationary sampler.
housing with Ice In ) hours (10).
-------
Table 2.4 (continued). AUTOMATIC SAMPLERS AND THEIR FEATURES
Refrigeration
Sampler Method of sample transport provided
N-Con Sentinel Dipper from sample chamber
provide! by customer yes
Phlpps * Bird Dipper no
Protech CC-125 Pneumatic ejection yes
Proteeh K-I25FP* Pneumatic ejection •
Protech CO-ISO* Pneumatic ejection
-------
Table 2.4 (continued). AUTOMATIC SAMPLERS AND THEIR FEATURES
VA>
Sampler
Sonford HG-**
THI
THI Mark $•
AVCO»
Springfield
Milk River
Envlrogenlcs
Rohrer 1
«•» too
Pavta-Dyrne
Reimord
Colston
Rohrer II
Near
Freenan
Mtthod of *eaple Transport
Saaple tube which fills
by gravity
Pneuaatlc ejection
Evacuated bottles
Peristaltic poop
Dipper froa saaple cheaber
provided with continuous
flow by screwrotor poap
Submerged puap
Hschanlcal - gravity
Dlaphraga puap
Evacuated bottle froa saaple
cheaber provided with
continuous flow •
Screw puap
Positive displacement puap
Serco NW-3 saaples froa •
fluae provided with
continuous flow
Dlephraga puap
Piston In tube
None provided - solenoid
valve diversion froa
saaple llnec
Refrigeration
provided
Ice cavity*
no
no
no
yes
yes
no
no
yes
yes
no
no
no
no
no
Ability to
Freezing
no
yes
no
no
no
—
y»<
yot
no
no
no
no
yes
no
yes
withstand
laaerslon
no
no
no
no .
no
—
yes
no
no
no
no
no
no
no
no
Coarse
bottoa
Floatables sedlaents
no no
no no
no no
soaa no
soaa soaa
_ _
r r
kk
•
no no
b b
P"°
^
yes no
b b
Self-
cleanlng
features
none
none
none
none
continuous
flow
~
na
continuous
flow
continuous
flow
continuous
MOM
backflush
none for
SERCO par
continuous
Mow
.•••».•*
continuous
MOH
e. Representativeness of saaple questioned In Reference S.
b. Depends on ho>
« user arranges saapler Intake.
c. Continuous flow saeple line provided by user.
d. Refrigeration
provided only for stationary see
pier.. „
_.O . iO_ .
-------
4. Is firmly secured or anchored at permanent Installations.
2.3.2.2 Sample Transport-*
I, Sample Hn« minimum size ts 0.6 cm OA In.) internal diameter (5).
2. Sample must not contact metals during transport.
3.. Sample line must be transparent and flexible, and made of an
inert material such as Tygon*. If trace quantities are to be
measured, a method of testing for tube contamination Is needed (8).
k. Purging of the sample line should be done between sample
collections. A clean water purge Is effective (5) but not
feasible Inmost Instances. A complete air purge ts sufficient
for non-permanent or winter operation. A final alternate is
a sample purge prior to collection.
2.3.2.3 Sample Collection - The sample collection device should meet
the soeciftc application does not require It.
I. Capable of lifting « sample a vertical distance (head) of
6.1 m (20 ft) (7).
2. Capable of maintaining a line velocity of 0.6 to 3*0 m/sec
(2-10 ft/sec) for vertical transport (7).
; 3. Sample volume independent of distance of vertical lift (head).
The Importance of line velocity and isoktnetlc conditions depends on the
concentration and density of the nonf llterable suspended solids in the
water and • the program requirements for accuracy of suspended solids
determinations and any other parameters affected by suspended solid*
concentrations. (See Chapter 5 for guidelines.) If the program requires
maintaining Isoklnetlc conditions, dial adjustment of the Intake velocity
should be Included as a criterion.
2.3.2.fr Power and Controls - The following features should be available:
11. Capability for both AC and DC operation.
2. Battery life for 2 to 3 days of reliable hourly sampling
without recharging (7).
3. Battery weight of less than 9 kg (20 Ib) and sealed so no
leakage occurs.
k. Solid state logic and printed circuit boards.
-------
S. Timing and control systems are contained In a water-proof
compartment and protected from humidity. Timer should use
solid state logic and a crystal controlled oscillator.
6. Controls to allow both flow-proportional sampling (directly
linked to a flow meter) and periodic sampling at an adjustable
Interval from 10 minutes to k hours (7).
7. Capability of multiplexing, I.e., drawing more than one
sample Into a discrete sample bottle to allow a small composite
over a short Interval (7). Also capability for filling more
than one bottle with the same aliquot for addition of
different preservatives.
2.3.2.5 Sample Storage •
I. Capability of discrete sample collection with provision for
single composite container.
2. Minimum discrete sample container volume of 500 ml (0.13 gal.)
and a minimum composite container capacity of 9.5 I (2.5 gal.)
3. Sampler capacity of at least 2k discrete samples.
*t. Containers of conventional polyethylene or
borosiUcate glass, and of wide mouth construction.
5- Capability for cooling samples by refrigeration or a space for
packing ice.
6. Insulation available if the sampler is to be used during freezing
conditions.
2.3.2.6 General Desirable Features -
I. Water tight casing to withstand total immersion and high
humidity.
2. Vandal-proof casing with provisions for locking.
3. A secure harness or mounting device if sampler is placed in
a sewer.
4. Explosion-proof manufacture.
5. Sizing to fit In a standard manhole without disassembly.
15
-------
6. Compact and portable for one-man installation.
7. Overall construction, including casing, of materials resistant
to corrosion (plastics, fiberglass, stainless steel).
2.3.3 Installation and Use
M* •••••B«ki»MtaMMMMHtartMMBMB«BM**MV*aB«aMI«MiMMBi^MaK*MMM
2.3.3.I General Consideration - Well-designed equipment will give good
results only when properly maintained (see Figure 2.2).
I. When a sampler is installed in a manhole, secure it either
in the manhole (e.g. to a rung) above the high water line or
outside of the manhole (e.g. to an above ground stake by means
of a rope).
2. Place the intake tubing vertically or at such a slope to
ensure gravity drainage of the tubing between samples,
avoiding loops or dips in the line.
3. Clean sample bottles, tubing and any portion of the sampler which
contacts the sample between setups. Whatever methods of
cleaning are used, all parts of the sampler which come in
contact with the sample should be given a final rinse with
tap water and with distil led water. A distilled water rinse
may not be necessary between setups on the same waste stream.
4. Inspect the intake after each use, and clean if necessary.
Care should be used in placing the intake(s) to assure a
representative suspended solids sample. The velocity of flow
should at all times be sufficient to prevent deposition of
solids. When a single intake is to be used in a channel, place
it at six-tenths depth (point of average velocity) (9, 20). For
wide or deep channels where stratification exists, set up a
sampling grid as described in Section l.k.2.
5. Maintain electrical and mechanical parts according to the
manufacturer's instructions. The desiccant should be replaced
as needed. If a wet-cell lead-acid battery is used, any
acid spilled should be neutralized and cleaned up.
6. Position the intake in the stream facing upstream. It should
be secured by a rope at all times with no drag placed on
the inlet tubing.
7. After the installation is complete, collect a trial sample to
assure proper operation and sample collection. The sampler must
give replicate samples of equal volume throughout the flow
range. If the sampler imposes a reduced pressure on a
waste stream containing suspended solids, run the first part of
the sample to waste.
-------
Signal from Flow
Monitor
Intake
Peristaltic Tubing
Pump
Flow
Monitor
Air Bubble
Tube
Intake
Automatic
Sampler
Figure 2.2. Example of flow proportional sampler installation
-------
2.?.3.2 W1nter OperatIon - For outdoor use In freezing temperatures
"special precautions should be used to insure reliable sample collection
and to prevent the collected sample(s) from freezing.
I. Place the sampler below the freezing level or in an insulated
box. ^'r
2. When AC Is available, use a light bulb or heating tape to
warm sampler. The following arrangement was found satisfactory
between -18 and -12°C (0 and 10°F)(ll):
...wrap short (k or 6 ft thermostatically protected 38°F)
heat tape around the sample bottle and the intake lines
on the AC samplers. Over the heat tape on the intake
loosely wrap a large plastic bag (airline trash bags,
10 mil, GSA 18105-808-9631). A large plastic bag
should also be placed over the sampler as loosely as
possible.
3. Be certain to place the line vertically or at such a slope to
ensure gravity drainage back to the source. Even with a back-
purge system some liquid will remain In the line unless gravity
drainage is provided. If an excess length of tubing exists,
this excess should be collected and placed in the water.
2.4 FLOW MEASUREMENT WITH SAMPLING
Flow measurement can be divided Into four categories:
1. Flow In completely filled pipes under pressure.
2. Flow from pipes discharging to the atmosphere.
3* Flow In an open channel or sewer.
4. Miscellaneous flow measurement
This section will give an overview of flow measurement. Other manuals
should be consulted for more information (12, 13, 14, 15).
2.4.1 Flow in Completely Filled Pipes Under Pressure
There are nine common types of flow measurement methods. Table 2.5
discusses the Information required to apply each one, and Figure 2.3
gives a visual example of some typical designs.
18
-------
Table 2.5. FLOW MEASUREMENT IN PRESSURE PIPES
VJ3
Type
Orifice
Vcnturl
Flow Nozzle
PI tot Tuba
Magnetic
FlouMter
Ultrasonic
FloMoetar
Elbow Meters
Eauatlon
Q - CAK AT
Q • CAK ^T
Q - CAK «fT
d. - dlaaeter at
* outlet end of
nozzle
»e - C *5gH
0.-V.A
*• " * 'center
Direct Voltage
Readout
Direct Readout
c^m
value Accuracy
0.61 to 0.71 l-tt (18)
-i •— •_ jt
eepenes on Oj*.
0.98 l-tt (18)
.98 - .99 l-2«
Good
C • correction
factor deter- Good
•Ined by cal 1-
bratlon
It at 3 to 30 fps
Better at Higher
velocities (13)
.Good In Certain
Instances
0.98 t tt Coed (hydraulics)
If Turbulent
Advantages
Inexpensive, Easy to
Install. Reliable
Low Pressure loss.
No Interference froa
Solids
Low Maintenance. In-
stallable In Pipe
Flanges, Less if than
Orifice. Moderate sus-
pended Solids Allowed
Good In Large Pipes.
Less Expensive
No Head Loss. No
Solids Problem
No Solids Problem
No Foul Ing. Pressure
Loss. Mlntalzed
Disadvantages
Large Head Loss. Solids
Interference, Less ac-
curate et high velocity
More Expensive. Requires
•ore roe*
High Velocity, No Burrs
In Line
Point Measure Only.
Sot Ids P luggage a
Problen
Expensive, Can Ba Fouled
By Grease. Permanent
Air Bubbles Interference
Difficult to Calibrate
Linear Pipe
Dlaneters
Uostrea*
5-25
Diameters
(U)
STaieter,
(13)
10 Pipe
Oleaster
(12)
15 Diameters
to SO
(13)
-------
Table 2.5 (Continued). UNIT DESCRIPTION
Q - flow (cfs) (x 0.0283 • cu m/sec)
A -throat ftrea (ft2)
H - H. - H. differential head In (ft. of water)
H. • pressure head at center of pipe
at Inlet (ft. of water)
H, • pressure head at throat (ft. of water)
V 3 . t g • gravity constant.
, . (jl) (32.2 ft./sec2)
di
d - throat diameter (ft.)
d. • diameter of inlet pipe (ft.)
I • radius of curvature of center line (ft.)
D • pipe diameter (ft.)
V • velocity (ft./sec) (x 0.305 • m/sec)
20
-------
Turbine Meter
L
J
'^
V
f)
II
Pi tot Meter
Figure 2.3* Flow measurement devices - filled pipe under pressure (12)
-------
to
California Pipe Method
>fe
»/
»
^ o —
o—.
Horizontal Pipe Flow
_L
k 1
J 1
F
. X_ ,.
^\\\\
t
Y
J_L
Weir Flow Jet Flow
Vertical Open-End Pipe Discharge From Open-End Pipe
Figure 2.4. Techniques for pipes discharging to *he atmosphere (12)
-------
2.k.2 Flow from Pipes Discharging to the^Atmosphere
The common techniques for measuring the flow from open ended pipes
elthe full or partially full are listed below. Figure 2.k indicates
the systems described.
2.k.2.\ Flowing Full -
I. Orifice (12) Q = CAK fKUnits as before
2. Flow nozzle (|2) Q " CAK / H Units as before
3. Vertical open end pipe (12)
a. Weir flow Q - 8.80 D1'20 H1'2k
b. Jet flow Q - 5.81* D2>025H°'53
to
Q - flow, cfs (cu m/sec » cfs * 0.0283)
where D • internal pipe diameter, ft
H a distance from pipe outlet to top of
crest, ft
1. Rotating element meters
a. Propeller meters (Ott, Sparling)
where Q » f/k
f - pulse frequency
k « flow coefficient
b. Cup type meters
5. Orifice (Danaides) bucket (16)
6. Horizontal or sloped nnen end (12)
AX
Q - 0.008
Q » flow, cfs (cu m/sec « cfs x 0.0283)
A - cross sectional area (ft2)
X » distance from end to where Y measured (in.)
Y « vertical top measured at X (in.)
1.JK2.2 Pipes Flow Partially Full -
I. Horizontal or sloped open ended (See Reference 12 for correction
factor, Table *4.3)
0. - corr. factor Q'°°8 AX
rr
23
-------
2. California Pipe Method (12) Q - TV
i
T • 8.69 (I - 4):M8
W . d2-*8
d -pipe diameter (ft)
a • distance from top of pipe to flow (ft)
Q • cfs (cu m/sec « cfs x 0.0283)
3. Open Flow Nozzles - Various types are available (Kennison
and parabolic flume). The manufacture):
' should be consulted.
2.4.3 Flow Measurement In Open Channels or Sewers
Methods available can be divided as follows:
I. Velocity methods
2. Level measurement methods
3. Miscellaneous techniques
2.4.3.1 VeJoc i ty Method; - These techniques can be applted when the- cross
sectibnaT area can- be- determined and when the flow variability Is low.
I. Measurement with velocity Indicating Instruments/.
a. Current meters - To apply a current meter, use the
following procedures (18, 19):
1) Wace meter facing, upstream as close to vertical as
possible.
2) Take measurements at equal distances across the
channel. Total flow Is sum of the parts.
3) Take single measurement at depth of approximately 60%
below the surface. This method is used for shallow
waters where the two point method Is not applicable.
4) Take double measurements at 20* and 80* below the
surface and average. This technique is used for
depths greater than two feet.
5) Other methods include: six-tenths depth method,
vertical velocity curve method, subsurface method,.
Integration methods, three point type. For details see
reference 16.
-------
b. PI tot tuba - Us* the same aquation as bafora. Taka
measurements at equa -distant points across a flow stream.
It Is difficult to obtain accurate measurements at low
velocities with this equipment (17) •
2. Measurement of time of passage
a. Dye Injection - Add, a water soluble dye or tracer to the
water and measure the time from the Instant It Is dropped
to the point of either maximum color Intensity or highest
measurable concentration (20). Materials commonly used
are dtsodlum fluoreseln dye and lithium chloride salts.
For more accuracy, several measurements should be taken
and the results averaged.
b. Floats - Drop a float Into the water and measure the time
needed for It to travel a known distance. This establishes
surface velocity which Is multiplied by a coefficient of
0.85 to 0.95 depending on the depth of water, the velocity
and the nature of the stream or canal bed (7). Therefore
this coefficient Is difficult to accurately establish and
this float technique should be .used only as a flow rate
approximation.
2.4.3.2 Level Measurement Methods - Level measurement Is a technique
which allows the determination of flow by creating an obstruction and
then measuring the height of backed up water. The primary devices,
weirs and flumes create the obstruction and the secondary devices
measure the water level.
1. Primary devices
a. Weirs - A weir is a dam over which the water flows. The
most common type is a sharp crested weir of which
there are three varieties: 1) rectangular, 2) Clpollett!
and 3) triangular or V-notch.
The common form of the weir equation is:
Q • C L H or wet r velocity head correction
Q - CL (H+L)3/2 - h3/2
h - velocity head in feet
;Q • flow, cfs (cu m/sec • cfs x 0.0283)
L • effective width of the weir In ft
25
-------
H - head, ft
C •• coefficient dependent upon type of weir
where C • 3.33 rectangular
C • 3.367 Cipollett!
C - 2.*»9 for V notch weir
A typical sharp crested weir is shown in Figure 2.5.
Point To Measure
I Depth. H
I
Straight • At Least 4 H
Inlet Run
Approx. 2"
Figure 2.5 Sharp crested weir (12)
The approximate flow determines the type of weir to
use. A rectangular weir should be used for flows
greater than 2 cfs. V-notch weirs are used for flows
of less than 1.0 cfs (1.7 cu m/mln) and can be used
In the range of 1.0 to 10.0 cfs (1.7 to 17 cu m/min)
(20). The Clpolletti weir is accurate in the same
range as the rectangular weir and is often used in
irrigation ditches. The flow equation is modified by
changes in the C value and L value by the different
weirs. Nomographs for rectangular and triangular weirs
are Included to simplify application of these formulas.
However, with the availability of hand calculators,
the more accurate calculations should be used when
possible (see Figure 2.6 and 2.7).
26
-------
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Figure 2.6. Flow rates In gallons per minute for
60° and 90° V-notch wetrs (i2)
27
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b. For Installation of weirs, the following criteria
should be met (20):
1) The upstream face of the bulkhead should be smooth
and in a vertical plane perpendicular to the axis
of the channel.
2) The upstream face of the weir plate should be
smooth, straight, and flush with the upstream
face of the bulkhead.
3) The entire crest should be a level, plane surface
which forms a sharp, right-angled edge where it
intersects the upstream face. The thickness of
the crest, measured in the direction of flow,
should be between 0.03 and 0.08 inch (about 1 to
2 mm). Both side edges of rectangular weirs should
be truly vertical and of the same thickness as
the crest.
k) The upstream corners of the notch must be sharp.
They should be machined or filed perpendicular to
the upstream face, free of burrs or scratches, and
not smoothed off with abrasive cloth or paper.
Knife edges should be avoided because they are
difficult to maintain.
5) The downstream edges of the notch should be
relieved by chamfering if the plate is thicker than
the prescribed crest width. This chamfer should
be at an angle of J»5° or more to the surface of the
crest.
6) The distance of the crest from the bottom of the
approach channel (weir pool) should preferably
be not less than twice the depth of water above
the crest and in no case less than 1 foot.
7) The distance from the sides of the weir to the
sides of approach channel should preferably be
no less than twice the depth of water above the
crest and never less than 1 foot.
8) The overflow sheet (nappe) should touch only the
upstream edges of the crest and sides.
9) Air should circulate freely both under and on the
sides of the nappe.
29
-------
10) The measurement of head on the weir should be
taken as the difference in elevation between the
crest and the water surface at a point upstream
from the weir a distance of four times the
maximum head on the crest.
II) The cross-sectional area of the approach channel
should be at least 8 times that of the overflow
sheet at the crest for a distance upstream from
15 to 20 times the depth of the sheet.
12) If the weir pool is smaller than defined by the
above criteria, the velocity of approach may be
too high and the staff gage reading too low.
c. Flumes - Flumes are more expensive and more difficult to
install than weirs but they allow the measurement of
wide ranges of flows with little headloss.
1) Parshall Flume - This is commonly used to measure
sewer flow using the following equation:
Q • J»W Hn
Q • discharge, cfs (cu m/sec • cfs x 0.0283)
W - throat width, ft
H • head of water above level flow
n - 1522 w°-026
A nomograph Is Included to simplify the calculation
(Figure 2.8). Figure 2.9 shows a schematic of a
Parshall flume.
30
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Q:1/m!n (cfs)
H:m ,(ft) VSTILLING WEUSX
Figure 2.9. Parshall flume
2) Palmer-Bowlu? Flumes - These flumes are shorter,
fit flush with the bottom of a sewer and are more
conveniently Installed as fiberglass Inserts. TQ
calculate flow the following equation is used:
s.
9 b
A d
c c
2b T
2 2
AC • area at critical depth, m (ft )
de » critical depth, m (ft)
Vc » critical velocity, m/sec (fps)
b • width of flume, m (ft)
Q • discharge, m/sec (cfs)
0
g • gravitational constant 9.8 m/sec'
(32.2 ft/sec2)
32
-------
For Installation of flumes, use the same procedures
as used for installation of weirs.
d. Submergence - The effect of submergence is to cause large
Inaccuracies In the flow measurement. The submergence
is defined as the ratio of backwater level to crest
level. Weirs cannot be used when submerged, however,
correction factors can be applied to flumes at
submergence up to 70$ (21).
2. Choice of primary device - The advantages and disadvantages
or weirs and ftunes are listed In Table 2.6. If feasible a
flume is preferable because of the greater accuracy.
Table 2.6. ADVANTAGES AND DISADVANTAGES
OF FLUMES AND WEIRS
Advantages
Disadvantages
Weirs:
Inexpensive
Easily shop fabricated
Easily obtained
Difficult to prevent leaks
High headloss created
Must achieve free discharge,
proper approach velocity,
proper level to head ratio
for accurate measurement
Solids accumulation in front of weir
Flumes;
Self-cleaning
Low headloss
Greater range of accuracy
Dual "piggy-back", flumes
available to extend flow
range
Large size
Difficult to fit
High cost of flumes
Difficult to shop fabricate
3. Secondary Devices - There are six types of devices which
measure the head or liquid level upstream of the primary
devices:
33
-------
a. Hook or staff gauge
b. Differential pressure measurement
c. Surface float
d. Dipper (level sensing probe
e. Ultrasonic
f. Wire weight from overhead structures
4. Choice of secondary devices-Table 2.7 compares the advantages and
disadvantages of the level measuring devices.
Table 2.7 ADVANTAGES AND DISADVANTAGES OP SECONDARY DEVIES
Device Advantages Disadvantages
Hook gauge or Common, accurate Manual only, stilling
stage board well may be needed
Differential Pressure Measurement
a. Pressure bulb No compressed air Can clog openings,
source, can be di- expensive
rectly linked to
sampler
b. Bubbler tube Self-cleaning, less Need compressed air or
expensive; reliable other air source; can't
stand much abuse
Surface float Inexpensive, In-stream float catches
reliable debris
Dipper Quite reliable, Oil and grease will
easy to operate foul probe, expensive,
possible sensor loss
Ultrasonic No electrical or Air bubbles may cause
mechanical contact echo rebounding
In addition to above considerations, the following must
be considered:
1. Is flow-proportional sampling to be done?
2. Is a manual or automatic composite desired?
(i.e., is the flow monitor separate or
attached' to the sampler)
3. Is a record of flow needed?
A summary of the advantages and disadvantages for both the primary and
secondary types of devices is included in Table 2.8.
-------
Table 2.8 RELATIVE COMPARISON OF PRIMARY AND SECONDARY OPEN CHANNEL
FLOW MEASUREMENT DEVICES (a)
VJl
Primary
devices
Secondary devices
Channel char's
Characteristic
Suitable for continuous
measurement
Capability for sending
signal to sample (flow-
proportional sampling)
Need for stilling well
Low initial cost
Easy to install
Hight accuracy of measurement
Low maintenance (incl. cleaning)
Suitable for high solids
wastewater
Low susceptibility to fouling
(rags, debris, grease)
Wide flow range
Low headless
Low auxiliary requirements
(manpower, compressed air,
AC power)
(a) na = not applicable
= no or not suitable
+ = yes or suitable
only (Manning
formula
+
na
na
3
na
1
3
3
3
3
3
na
1
2
3
Hook gauge, Differential
Weir Flume stage board
+ +
na na
na na
2 1
2 1
2 3
1 3
2 3
1 3
2 3
1 3
na na
= fair,
= good ,
-
-
+
3
3
2
3
3
3
+
+
1
frequently a problem
sometimes a problem
= excellent, seldom or never
pressure
+
+
-
2
2
3
2
3
2
+
+
2
a problem
Float Ultra-
Device Dipper sonic
+ + +
+ + +
+ -
3 1 1
1 2 2
3 33
2 33
2 23
1 1 3
+ + +
+ + +
3 3 1
-------
2.*t.3 Miscellaneous Flow Measurement
2.4.3.1 Frlet ton Formula • Measurement of surface slope and channel
velocity and depth can be used to roughly estimate flow (13). The
Manning formula Is commonly used for estimating a flow:,
V - K486 R2/3 S1/2
V • avg. velocity, fps (m/sec • fps x 0.3048)
n • coefficient of roughness
» . . ,, ., s* i cross-sectional areaN
R - hydraulic radius, ft ( wetted perimeter }
S • slope of energy grade 1Ine
2.4.3.2 Tracer Techniques - Tracers of radioactive materials can be
used In two ways: I) Two Point Method, and 2) Total-Count Method.
However, both techniques require an experienced operator, permits, and
equipment not commonly available to sampling crews (12).
2.4.3.3 Salt Dilution Method • In this technique a known amount of
salt Is added to a stream and then the dilution Is determined after It
has traveled downstream (20).
C1 ' C2
Q • stream discharge
C • natural concentration instream
o
C. • tracer concentration
C, • final concentration
q • injection rate
2.4.3.4 Water Meters - An estimate of the flow can be obtained from
water meter readings when an Instantaneous flow rate is not critical.
This technique Is used in a confined area, such as the industrial plant.
A material balance is made of the Incoming and outgoing flow as a check
or Initial estimate of the flow rate (13).
2.4.3.5 Measuring Level Change In Tank - In some Instances the level
change in a tank can be used to estimate flow. To accomplish this, the
volume of the tank as related to depth must be established; then the
flow Is allowed to enter and the level change with time recorded.
-------
2.4.3.6 Pump Rates • When other methods are not available for flow
measurement, and a pump is used in the system, the operating character-
istics of the pump can be used to estimate flow. One method is to
record the pumping time and the pump capacity at discharge pressure and
then refer to manufacturers head curves for the total flow (25).
Another technique is to establish the pump's horsepower and determine
the capacity from the manufacturers curves. However, these techniques
should be used only for estimates of flows.
2.k.3.7 Calibrated Vessel - Another technique useful for free falling
water Is to capture a known volume of water over a recorded time Interval.
The flow rate is then established for a specific time. More than one
measurement Is necessary to allow accurate estimates.
l.k.k Flow Recording Equipment Errors (Reference 7)
Sources of measurement error with recording equipment are common to
both weirs and flumes and include:
I. Stilling well in wrong location with respect to weir or flume area.
2. Trash or debris in stilling well and conduit between flume and
welt plugged.
3. Float dirty, punctured, not vertical and rubbing against side
of stilling well. Slack in float cable.
k. Wrong recorder multiplier and chart paper. Pen not Inked and
not giving responsive trace. Recorder does not zero. An error
in calibration of 1.5 cm (0.6 in.) can cause an error In rate
measurement ranging from several hundred percent at low depths
on small weirs and twenty to thirty percent for moderate depths
In flumes With throat widths under 30.5 cm (12 In.)
2.5 PRACTICAL FEATURES OF SAMPLING
Follow these procedures when collecting water samples (3, 22, 23, 24):
I. Obtain from the principal investigator written and specific
instructions on sampling procedure.
37
-------
2. Check all sampling equipment prior to use to ensure good
operating conditions and cleanliness.
3. Check all sample bottles to avoid contamination.
4. Clean sampler intake tubing by flushing with hot water and then
rinsing. If organic or other contamination remains, replace
tubing and flush to remove organics. Clean bottles as indicated
in 3.4. If this cannot be done, rinse at least twice with water
to be sampled.
To obtain representative samples, follow these guidelines.
1. Take sample where wastewater is well mixed (e.g. near a Parshall
flume or at a point of hydraulic turbulence such as downstream of
a hydraulic jump). Weirs tend to enhance the settling of solids
upstream and accumulate floating solids and oil downstream, there-
fore such locations should be avoided as a sample source. For
low level turbulence, mechanical or air mixing should be used
to induce turbulence except when dissolved gases or volatile
materials are being sampled.
2. Take sample at 0.6 depth in a Chanel or where velocity or
mixing is sufficient to prevent solids deposition.
3. Place mouth of collecting container below the water surface
to avoid an excess of floating material.
4. Do not include large nonhomogeneous particles in the sample
(e.g. leaves in a surface water sample, rags in a municipal
influent sample).
5. Collect sufficient volume to allow duplicate analyses and
quality assurance testing (split or spiked samples). The
basic required volume is a summation of that required for
the parameters of interest as given in Chapter 10.
6. Maintain an up-to-date log book which notes possible
interferences, environmental conditions and problem areas.
7. Follow additional guidelines for manual sampling:
a. Sample facing upstream to avoid contamination.
b. Force sampling vessel through the entire cross
section of the stream whenever possible.
c. Drop an inverted bucket and jerk line just before
impact with the water surface.
d. Be certain that the sampler closes at the proper time
before sampling with a depth sampler. If a doubt exists,
discard sample and resample.
38
-------
8. Composite samples according to the converted flow rate as
opposed to the raw measurement produced by the secondary
device such as the head above a weir. The mathematical
relationship between flow rate and the measurement produced
by secondary devices are nonlinear functions and considerable
error, especially for highly variable flows, will result from
compositing samples based on the raw measurement (10).
2.6 REFERENCES
I. Wanderer, W. C., Jr. Water Pollution Control Federation Highlights.
Vol. 10, D-l, March 1973.
2. Tarazl, 0. S., et al. Comparison of Wastewater Sampling Techniques.
JWPCF. 42j708, May 1970.
3. Associated Water and Air Resources Engineers Inc. Handbook for
Industrial Wastewater Monitoring. U.S. EPA Technology Transfer.
pp. 7-1 to 7*48, August 1973*
4. Black, H. H. Procedures for Sampling and Measuring Industrial
Wastes. Sewage and Industrial Wastes. 24:45-65, January 1952.
5. Shelley, P. E., and G. A. Klrkpatrfck. An Assessment of Automatic
Sewer Flow Samplers. Hydrospace-Challenger Inc. EPA-R2-73-261.
Office of Research and Monitoring, June 1973* p. 233•
6. Rabosky, J. G., and D. L. torafdo. Gauging and Sampling Industrial
Wastewaters. Chemical Engineering. 80:111-120, January 1973.
7. Harris, D. J., and W. J. Keffer. Wastewater Sampling and Flow
Measurement Techniques. U.S. EPA Region VII. EPA 907/9-74-005.
June (974, p. 130.
8. Junk, G. A., N. J. Svec, R. D. Vick, and M. J. Avery. Contamination
of Water by Synthetic Polymer Tubes. Environmental Science and
Technology. £ (13):1100-1106, December 1974.
9. Metcalf and Eddy Inc. Wastewater Engineering: Collection, Treatment,
Disposal. New York, McGraw-Hill Book Company, 1972, p. 710.
10. Shay, J. B. A Simplified Method to Relate Average Head to Total
Flow. Water and Sewage Works, pp. 69-71, August 31, 1972.
11. U.S. EPA Inter-Office Memo from W. J. Keffer to G. L. FIsk,
March 13, 1973.
12. American Petroleum Institute. Manual on Disposal of Refinery Wastes.
Volume on Liquid Wastes, pp. 4-1 to 4-26, 1969.
39
-------
13. Associated Water and Air Resources Engineers Inc. Handbook for
Industrial Wastewater Monitoring. U.S. EPA Technology Transfer.
pp. 7-1 to 7-48, August 1973.
14. King. H. W. Handbook of Hydraulics. 4th Edition, Mc-Graw-HlH, 1954.
15. Streeter. V. L. Fluid Mechanics. New York, McGraw-Hill, 1966. p. 700.
16. Shelley, P.E. and G. A. Klrkpatrick. Sewer Flow Measurement -
A State-of-the-Art Assessment. U.S. EPA, EPA-600/2-75'027.
November 1975, 424 p.
17. Perry, R. H. and C. H. Chllton. Chemical Engineers' Handbook.
5th Edition, New York, McGraw-Hill, 1974. pp. 5-7.
18. Buchanan, T. J., and W. P. Somers, Discharge Measurements at
Gauging Station. Washington, D.C. U.S.G.S., Techniques of Water
Resources Inv., Book 3, Chapter A8, 1969. p. 65.
19. Smoot, G. F. and C. F. Novak. Calibration and Maintenance of
Vertical-Axis Type Current Meters. Washington, D.C., U.S.G.S.
Techniques of Water Resoruces Inv., Book C. Chapter B2, 1968, p. 15.
20. Water Measurement Manual. U.S. Bureau of Reclamation. U.S.
Government Printing Office, Washington, D.C. 1967. p. 16.
21. Envlrex Inc., Environmental Sciences Division. Recommended
Procedures for the Conduct of Storm Generated Discharge.
Rough Draft Report. EPA Contract No. 68-03-0335, Office of Research
and Development, p. 348.
22. APHA, AWWA, and WPCF. Standard Methods for the Examination of
Water and Wastewater, 13th Edition, New York, APHA, 1971. p. 874.
23. ASTM Annual Book of Standards. Part 23, Atmospheric Analysis, 1972.
24. Atwood, R. C. A Manual on Water Sample Collection and Handling
Techniques. Rough Draft Report for U.S. EPA Region 1, Surveillance
and Analysis Division. April 1974.
25. Forester, R. and D. Overland. Portable Device to Measure
Industrial Wastewater Flow. Jour. WPCF.46: 777-778, April 1974.
-------
CHAPTER 3
GENERAL CONSIDERATIONS OF
SAMPLE PRESERVATION AND HANDLING
Immediate analysis at the site of sampling will preclude the need for
sample preservation; however, this procedure Is not practical in most
situations. Therefore, sample preservation and other related aspects
of sample handling should be established to maintain the sample in its
Initial state until analysis. The following terms are used in this
discussion:
I. Preservation Method (Technique) - special handling of
the sample between time of sampling and analysis to
maintain the Integrity of constituents.
2. Preservative - chemical added to a sample to maintain
Integrity.
3. Holding Time - time between collection of the first
sample portion and analysis.
Some aspects of sampling are not dependent upon analysis or water type.
These are discussed in the following categories:
1. Universal Preservative A. Container Type and Cleaning
2. Sample Identification 5. Holding Times
3. Chain of Custody 6. Volume of Sample
3.1 UNIVERSAL PRESERVATION
No single preservative has been found which maintains the integrity of
all parameters in a sample.
3.1.1. ChemlcaI Add 11 ton
The most convenient preservative Is a chemical which can be added to a
sample bottle prior to sampling and Immediately disperses when the
41
-------
.sample Is added, stabilizing all parameters for long periods of time.
1 However, due to the biological nature of some tests (specifically BOD)
and the fact that chemical composition can be affected by chemical
addition (for example, adding nitric acid and analyzing for nitrate),
there presently Is no chemical available to preserve all parameters.
3.1.2 Freezing
Freezing has been the subject of many preservation studies (1-22).
It Is felt by some that freezing would be a method for increasing the
holding time and allowing collection of a single sample for all analyses.
However, the^resIdue solids components (flltrable and nonftltrable) of
the sample change with freezing and thawing (23). Therefore, return to
equilibrium and then high speed homogenl.zatlon Is necessary before any
analysis can be run. This technique may be acceptable for certain
analyses but not as a general preservation technique.
3.1 »3 Refrigeration
Refrigeration (or icing) has also been studies with various results
(10, 11, 13-15, 24-29). This Is a common technique used In field work
and has no detrimental effect on sample composition. Although It does
not maintain complete integrity for all parameters, It.does not
interfere with any of the analytical methods.
3.2 SAMPLE IDENTIFICATION
3.2.1 Sample Number
Assign each sample container a unique number for identification In &he
field and laboratory. The identification number should have as few
digits as possible to discourage abbreviation. The following guidelines
should facilitate proper identification:
1. Use preprinted rolls of peel back labels assigned from
the laboratory to a sampIIng .crew.
2. For relatively small numbers of samples use sequential
numbering .and affix a label to each bottle. When the same
sample is placed In two or more containers, assign two
or more numbers ,to that 'sample. For large numbers of
samples such as encountered In river, lake, or estuary
sampling, use a five digit number, the first two numbers
Indicating the week of the year. When a sample Is split into
two or more parts, use one sample number and apply a color
coded label to each sample which indicates the type of
preservative added. Therefore, once the type of preservative
has been Indicated, the general group of parameters to be
analyzed on that sample is established. For example, a blue
-------
label Indicates that nitric acid has been added, therefore,
the analyst could obtain an aliquot from this sample for metal
analysis.
3. Note the data and preservative on the label.
k. Note additional Information In the field notebook.
3.3 CHAIN OF CUSTODY (30)
3.3.1 General
As In any other litigation, the Government must be able to demonstrate
the reliability of its evidence In pollution cases by proving the chain
of possession and custody of any samples which are offered for evidence
or which form the basts of analytical test results introduced Into
evidence In any water pollution case. It Is Imperative that each EPA
Regional Office and Laboratory prepare written procedures to be followed
whenever evidence samples are collected, transferred, stored, analyzed,
or destroyed. The primary objective of these procedures Is to create an
accurate written record which can be used to trace the possession of the
sample from the moment of its collection through Its introduction into
evidence. A sample is in custody if it Is:
I. In actual physical possession, or
2. In view, after being In physical possession, or
3. In physical possession and locked up so that no one
could tamper with it.
Two procedures are included rotative to the transfer of custody of samples
(31): 0 the transfer of Individual samples and 2) the bulk transfer
of a group of samples. Both procedures will be discussed where appropriate
in the following material. If not otherwise stated, the procedures are
the same.
3.3.2 Rules for Sample Collection
1. Handle the samples as little as possible.
2. Obtain samples using the guidelines in this handbook.
3. Individual semples — Attach a Chain of Custody Record bottle tag
(see Figure 3.1) used in the transfer of individual samples
to the sample container at the time the sample Is collected.
The tag should contain information on sample number, date,
time taken, source of sample (including type of sample and
name of firm), analyses required, name of person taking sample
and witnesses. The tag should be signed, time recorded and
-------
(FRONT SIDE)
o
, CHAIN OF CUSTODY RECORD
ENVIRONMENTAL PROTECTION AGENCY
National Field Investigations Center-Denver
Denver Federal Center
Denver. Cntararia 8Q23C
Sample No. 1 Time Taken (hrs Date
Source of Sample
Sample Collector
Wltness(es)
Taken
'reservattve
Remarks: (Analyses Requires, Sample Type, etc.)
(BACK SIDE)
r
o
..
1 hereby certify (tat 1 received (hit unpU and dl«po»ed of It •• fated below:
*.
etc
Si!
r
deceived from
Xspositlon of Sample
Date Received
Signature
Time Received
1 hereby certify that 1 received thlt twpU «nd dltpottd of It »t rated below:
s;
ffo
r
deceived from
Xspositlon of Sample
Date Received
Signature
1 hereby certify thtt 1 obtained thlt twple end dltoatchtd It
t-
O
e t
SI
S.I
Ml/
3
tot* Obtained r
Date Dispatched
Sent to
Ime Obtained
Time Received
at ihoMi betoHt
Source
Tim Dispatched Method of Shipment
Signature
Figure 3.1 Chain of custody record tag
-------
dated by the person taking the sample. The sample container
may then be sealed with a preprinted, gummed sea) containing
the Agency's designation, date and signature of the person
taking the sample (see Figure 3.2). The seal should cover the
string or wire tie of the Chain of Custody bottle tag so that
the tag cannot be removed and the container cannot be opened
without breaking the seal. The tags and seals must be filled
out legibly in ballpoint (waterproof ink).
U.S. ENVIRONMENTAL PROTECTION AGENCY
lAM'LI «• .
SICNATuRf
MINT NAMI «•• TITLI ( I't'tcro' . tmttnr , ncumcitf in. )
1
•
Figure 3.2. Gummed seal for sample bottles
Bulk or Group Samples - Attach a sample tag as shown in
Figure 3.3 to the sample bottle. The gummed label seal Is no
longer necessary. Sample transfer Is accomplished In groups
using a group sample chain of custody record as described
later (Figure 3.6).
Record field measurements and other pertinent Information In a
bound field notebook or log. Sufficient information must
be Included to refresh the memory of sampling personnel In
the event that a witness Is required at an enforcement
proceeding. A separate set of field notebooks should be
maintained for each survey and stored In a safe place where
they can be protected and accounted for at all times.
Establish a field data record format to minimize field entries
or possible omissions. The following Information should be
Included:
date
time
survey name
type of samples taken
volume of each sample
type of analyses
sample numbers
sample location
field measurements
such as:
temperature
conductivity
DO
PH
flow
other pertinent Information
-------
o
EPA, NATIONAL FIELD INVESTIGATIONS CENTER, DENVER
Station No. 1
Station Location
_ BOD
Solids .
___ COD ._
_ __ Nutrient*
Date ITIme (Sequence No.
— Grab
__ Comp.
Metals
OII&Greasi
D.O.
Other
Samp) ers : -
\
Remarks/Preservative:
FRONT
O
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL FIELD INVESTIGATIONS CENTER - DENVER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
BACK
Figure 3.3 Bottle sample tag used by NFIC - Denver (30
-------
The entries should be signed by the person taking the
sample and errors crossed out with one line and
Initialed. Assign a survey coordinator or designated
representative the responsibility for preparing and
retaining field notebooks during and after the survey
(see Figure 3.M.
5. Watch the sample carefully during the time it
Is collected and dispatched to a receiving
laboratory or turned over to an assigned custodian.
The person taking the sample is responsible for
the care and custody of the sample and must assure
that each container is in his physical possession or
view at all times or is stored in a locked place
where no one can tamper with it.
6. Take color slides or photographs of the outfall
sample location and any visible water pollution.
Document in writing on the back pf the photo the
following information: signature of the photographer,
time, date and site location. Photographs of this
nature, which may be used as evidence, should be
handled according to the established Chain of Custody
procedures to prevent alteration.
3.3'3 Transfer of Custody and Shipment
The following procedures should be followed when samples are transferred
or shipped.
1. a. Individual Samples
When transferring possession of individual samples, the
transferree must sign and record the date and time on the
Chain of Custody Record Tag (see Figure 3.1). Record custody
samples for each individual sample when transfers are made
to a field sample custodian. To reduce the number of custody
cards, reduce the number of custodians In the chain of possession.
b. Bulk or Group Samples
When transferring possession of a group of samples, the Chain
of Custody Record Form (see Figure 3.5) Is used that allows
the transfer of custody of the samples to the laboratory In
groups. The transfer of custody of individual samples by
signing bottle tags is not used. If a portion of the samples
Identified on the record form is to be transferred, the
-------
FIELD DATA RECORD
00
STATION
SAMPLE
MM8ER
DATE OF
COUECTIOS
TIKE (HRSJ
StMPU
lull
SAHPU
ItCtntl n in.
f«
TEMPERATURE
OTHER PARAMETERS
Figure 3.4 An example of a field log sheet
-------
SURVET
fUgg
MM
Mloqvl.h.dbyr:,,,^
tebnquftStd by: n*~~»>
•*****»-.
KelinquUht d by: "»ll 1
Cm
r^T
"
•"
MO.
MO
NO or .
IIOUMU
Received by: (tymmi
Received by: rvtww*/
Received by: t*r»»ni
teceived by Mobile loborotory (or field
onolym: i«,-«—i
Time
Received for laboratory by:
Method o» Shiptn.nl:
Dote/Time
. Dale/Time
Dote/lime
Dole/Tim*
Date/Time
CMllribw«r CoorJi«M>io> FwU Fil«
Figure 3-5. Chain of custody record form
-------
Individual samples are noted in the column with the signature
of the person relinquishing them. The field laboratory person
receiving the samples acknowledges receipt by signing in the
appropriate column.
2. The field custodian or person taking the sample, If a custodian
has not been assigned, Is responsible for properly packaging
and dispatching samples to the appropriate laboratory for
analysts. This responsibility Includes properly filling out,
dating and signing the "dispatch of sample" portion of the Chain
of Custody Record tag (See Figure 3.1) used for single sample
transfer.
3. Package samples properly to avoid breakage. The
shipping containers should be padlocked for shipment
to the receiving laboratory. Preprinted gummed seals
may be utilized to seal the package so that tampering
can be detected (see Figure 3.2).
k. In the case of the transfer of individual samples,
all packages should be accompanied by a Sample
Transmlttal Form identifying the contents (see
Figure 3*6). The original of the completed form
end one copy should accompany the shipment, one
copy should be delivered directly to the laboratory
and to data management, and a copy should be retained
by the survey coordinator. When bulk transfer of a
group of samples is used, all packages should be
accompanied by the Chain of Custody Record (see
Figure 3.5) showing identification of the contents.
5. if samples are delivered to the laboratory when
appropriate personnel are not there to receive them,
the samples must be locked in a designated area within
the laboratory so that no one can tamper with them.
The person who received and locked the samples must
be the one who later delivers custody to the appropriate
custodian.
3.3.*» laboratory Custody Procedures
Chain of Custody procedures are also necessary in the laboratory from
the time of sample receipt to the time it is discarded. The following
procedures should be used in the laboratory.
50
-------
TO: (Laboratory Name and Address)
FROM: (Field Custodian or Field Sampler)
Sample No. Lab Number pseon Analysis Required
To be completed in Field:
Prepared by: . Oate:_
(Signature)
Field Notebook No. Ttme:_
To be Completed by Laboratory:
Received by: Date:_
(Signature)
Time:
Distribution: Original & I copy - Accompany shipment
I copy - Hail Directly to Laboratory
I copy - Hail to .Data Management
I copy - Survey Coordinator Field Files
Figure 3-6 Sample Transmittal Form
-------
1. The laboratory should designate two full-time
employees: one as a sample custodian and the
second as an alternate. In addition, the
laboratory should designate a clean, dry, isolated
room that can be securely locked from the outside
as a "Sample Storage Security Area". The sample
custodian must maintain a permanent log book in
which he records, for each sample, date and time
received, source of sample, sample number, how
transmitted to laboratory, and the number assigned
to each sample by the laboratory. A standardized
format should be established for log book entries.
2. Samples should be handled by the minimum
possible number of persons.
3. In the case of the transfer of individual samples,
all the Incoming samples should be received only
by the custodian, who shall Indicate receipt by
signing the accompanying Sample Transmittal Form
(see Figure 3-6) and who shall retain the signed
forms as permanent records. When bulk transfer
of a group of samples is used, the custodian should
sign the Chain of Custody Record sheet (see Figure
3.5), and also retain the sheet as a permanent
record.
k. Immediately upon receipt, the custodian should
affix a number to the attached tag, record the
required information in the log book and preserve
the sample according to the recommendations in
Chapter 10 if this has not been done already.
Store the sample in a locked sample room. This
room should be unlocked only when the analyst
removes or replaces samples.
5. The custodian only should distribute samples to
appropriate laboratory personnel performing
analyses. The custodian should enter in.the log
the laboratory sample number, time, and date and
the signature of the person to whom the samples
were given.
6. If a gummed label seal was used on the individual
sample container, laboratory personnel should
examine the seal on the container prior to opening.
They should be prepared to testify that their
examination of the sample container Indicated that
it had not been tampered with or opened.
-------
7. The analyst must record In his log book the name of
the person from whom the sample was received, whether
it was sealed, Identifying information describing the
sample (by origin and sample identification number),
the procedures performed and the results of the testing.
He should sign and date his notes and retain them as a
permanent laboratory record. Laboratory'personnel
should be prepared to justify any deviations from
standard procedures during cross-examination. In the
event that the person who performed me tests is
not available as a live witness at the time of
trial, the government may be able to introduce
the notes In evidence under the Federal Business
Records Act or the Federal Rules of Evidence law.
8. Laboratory personnel are responsible for the care
and custody of the sample once it is handed over to
them and should be prepared to testify that the
sample was in their possession and view or securely
locked up at all times from the moment it was
received from the custodian until the tests were
run.
9. Once the sample testing is completed, the unused
portion of the sample, together with all Identifying
tags and seals, should be returned to the custodian
who will make appropriate entries in his log. The
returned tagged sample should be retained in the
sample room until It is required for trial. Other
testing documentation also should be turned over
to the custodian.
10. Samples, tags, and laboratory records of tests
should be destroyed only upon the order of the
laboratory director, in consultation with previously
designated regulatory officials.
3.i» CONTAINER TYPE AND CLEANING
A variety of factors affect the choice of containers and cap material.
These include resistance to breakage, size, weight, interference with
constituents, cost and availability. There are also various procedures
for cleaning and preparing bottles depending upon the analyses to be
performed on the sample.
53
-------
3.A.1 Container Material
The two major types of container materials are plastic and glass (32).
Glass:
I. Ktmax or Pyrex brand
(boroslllcate)
2. Vycor
3. Corning
k. Ray-Sorbor Low-Actinic
5. Corex
Plastic:
I. Conventional polyethylene
2. Linear polyethylene
3. Polypropylene
k. Polycarbonate
5. Rigid polyvinyl chloride
6. Teflon
All these materials have various advantages and disadvantages. Kimax
or Pyrex brand boroslltcate glass is inert to most materials and is
recommended where glass containers are used. Conventional polyethylene
Is to be used when plastic is acceptable because of reasonable cost and
less adsorption of metal Ions (33). The specific situation will determine
the use of glass or plastic. However, use glass containers if pesticides
or oil and grease are to be analyzed. Table 3«1 summarizes the
advantages and disadvantages of these materials.
Table 3-1. COMPARISON OF GLASS AND
PLASTIC CONTAINERS
BorosiUcate Glass Conventional Polyethylene
Interference with
sample
Weight
Resistance to
breakage
Cleaning
Sterillzable
Space
Inert to all con-
stituents except
strong alkali
Heavy
Very fragile
Easy to clean
Yes
All constituents except
pesticides and oil and
grease
Light
Durable
Some difficulty in
removing adsorbed components
In some instances
Takes up considerable Substantial space savings
space during extended field studies
-------
3.*t.2 Container Caps
There are two main types of plastic container caps: polyethylene and
bakelite with liners. Use polyethylene caps (ease of cleaning) except
If these caps do not fit tightly to the container or if pesticides or
oil and grease analyses are to be performed. Teflon liners should be
used for pesticides and oil and grease samples. There are three liner
types available and the advantages/disadvantages are listed in Table 3.2.
Liner Type
Wax coated paper
Neoprene
Teflon
Table 3.2 COMPARISON OF
Advantages
Generally applicable
to al1 samples
Inexpensive
Same as wax
coated paper
Applicable for all
analyses
Minimizes container/
sample interaction
Mandatory for pesti-
cide analyses
CAP LINERS
Disadvantages
Must be inspected
prior to each use
because of deter-
ioration
Cannot use with
organ Ics
Same as wax coated
paper
High Cost.
3.**.3 Container Structure
Use a wide mouth container in most instances. This structure will permit
easy sample removal. It is also easily cleaned, quickly dried, and can
be stored inverted. Use a narrow neck bottle when interaction with the
cap liner or outside environment is to be minimized. Use a cleaned
solvent container for pesticide sample collection (3*0.
3.*t.*< Disposable Containers
Use disposable containers when the cost of cleaning is high. These
containers should be precleaned and sterile. The most commonly used
disposable container of this type is the molded polyethylene cubitainer
55
-------
shipped nested and sterile to the buyer. However, since their cubic
shape and flexible sides make them almost impossible to thoroughly clean,
use these containers only once.
3. A. 5 Container Washing
The following procedure should be followed to wash containers and caps:
1. Wash containers and caps with a non-phosphate
detergent and scrub strongly with a brush (if
possible wash 1 iners and caps separately).
2. Rinse with tap water, then distilled water.
3. Invert to drain dry.
k. Visually inspect for any contamination prior to
storage.
5. If the container requires additional cleaning,
rinse with a chromic acid solution (35 ml of
saturated sodium dichromate solution in
1 liter of sulfuric acid - this solution can
be reused). Then rinse with tap water and
distilled water and dry as indicated above.
3.^.6 Container Preparation
For certain parameters, a special cleaning procedure Is needed to avoid
adsorption or contamination due to interaction with container walls.
These procedures are outlined below.
1
1. Acid Rinse: If metals are to be analyzed, rinse
the container with a solution of one part nitric
acid to four parts water then with distilled water.
If phosphorus Is to be analyzed, rinse the container
with a solution of one part hydrochloric acid to one
part water followed by distilled water.
2. Solvent Rinse: If oil and grease or pesticides are
to be analyzed, rinse the sample container with hexane,
then acetone, and distilled water. The container should
have been previously cleaned with chromic acid solution
as described in Section $.k.$. Treat the container
caps similarly.
56
-------
Sterilization: For microbiological analyses,
sterilize the container and its stopper/cap by
autoclaving at 121 C for 15 minutes or by dry
heat at 180 C for two hours. Heat-sensitive
plastic bottles may be sterilized with ethylene
oxide at low temperatures. Wrap bottles in kraft
paper or cover with aluminum foil before sterili-
zation to protect against contamination. See
Standard Methods for details (33). An acceptable
alternative for emergency or field use is
sterilization of containers by boiling in water
for 15 minutes.
3.$ HOLDING TIME
Holding times are specific to the analysis. However, when a series of
analyses are to be done on the same sample, the parameters with the
shortest holding time are to be analyzed first followed by the
elatlvely stable parameters.
3.6 VOLUME OF SAMPLE
The volume of sample is dependent on the type and number of parameters,
the type of instrumentation used for analyses (e.g. Technicon auto-
analyzer), and expected concentrations of parameters in the wastewater.
To determine the total sample volume, list all the parameters to be
analyzed and tne required volume as given in Chapter 10. Add the
Individual volumes to obtain the total sample volume required, then
additional volumes as needed for split samples or for analytical quality
control. It must be remembered that for many parameters required volumes
of relatively clean surface water are greater than those of most
wastewaters.
A minimum one liter sample is recommended when grab samples are
analyzed and 3.785 L (1 gal.) is necessary if more than one analysis
is to be performed on a single sample. An air space at the top of the
container Is recommended so the sample can be well mixed before aliquots
are removed.
The minimum volume of discrete samples intended for later compositing
is 400 ml (0.11 gal.). The final makeup volume of the composite should
be approximately 3*8 L (1 gal.).
57
-------
3.7 REFERENCES
1. Collier, A. W., and K. T. Marvin, Stabilization of the Phosphate
Ratio of Sea Water by Freezing, U.S. Government Printing Office,
Washington, 71-76, 1953.
2. May, B. Z., Stabilization of the Carbohydrate Content of Sea Water
Samples, Limnology and Oceanography. £: 342-343, I960.
3. Heron, J., Determination of Phosphate In Water After Storage In
Polyethylene, Limnology and Oceanography. £: 316-J21, I960.
4. Procter, R. R., Stabilization of the Nitrite Content of Sea Water
By Freezing, Limnology and Oceanography. £: 479-480, 1962.
5. Fogarty, W. J., and M.E., Reeder, BOD Data Retrieval Through Frozen
Storage, Public Works. 88-90, March 1964.
6. Morgan, F., PE, and E. F., Clarke, Preserving Domestic Waste
Samples by Freezing, Public Works. 73-75, Nev. 1964.
7. Marvin, K. T. andR. R. Procter, Stabilizing the Ammonia - Nitrogen
Content of Estuarine and Coastal Waters by Freezing, Limnology and
Oceanography. H>: 288-289, 1965.
8. Zanonl, A. E., Use of Frozen Wastewater As A Test Substrate,
Public Works, 72-75, November, 1965.
9. Tyler, L. P. and E. C. Margrave, Preserving Sewage Seed for BOD
Analysis, Water and Sewage Works. ]2\ 181-184, May, 1965-
JO. Agardy, F. J. and M. L. Klado, Effects of Refrigerated Storage on
the Characteristics of Wastes, Industrial Waste Conference (21st)
Purdue University, 1966.
11. Fitzgerald, G. P., and S. L. Faust, Effect on Water Sample
Preservation Methods on the Release of Phosphorus From Algae,
Limnology and Oceanography. J2.-332-334, 1967-
12. Gllmartln, M., Changes In Inorganic Phosphate Concentration Occurring
During Seawater Sample Storage, Limnology and Oceanography, J_2:
325-328, 1967.
13. Jenkins, D., The Differentration, Analysis and Preservation of
Nitrogen and Phosphorus Forms in Natural Waters, Advances in
Chemistry Series 73, American Chemical Society, Washington, D.C.,
265-279, 1968.
58
-------
14. Hegl,.V. H. R., and E. Fischer, Preservation for Chemical Analysis
of Household, and Community Sewage and Industrial Effluent.
15. Thayer, G. W., Comparison of Two Storage Methods for the Analysis
of Nitrogen and Phosphorus Fractions In Estuarine Water,
Chesapeake Science, U_: (3) 155-158, September, 1970.
16. Burton, J. D, and T. M. , Leatherland, The Reactivity of Dissolved
Silica In Some Natural Waters, Limnology and Oceanography.
: 473-476, 1970.
17. Hagar, S. W., Atlas, E. L., Gordon, L. L., Hantyla, A. W., and
P.K., Park, A Comparison at Sea of Manual and Autoanalyzer Analysis
of Phosphate, Nitrate and Silicate, Limnology and Oceanography,
17J 431-437, »972.
18. Phllbert, F. J., The Effect of Sample Preservation by Freezing
Prior to Chemical Analysis of Great Lakes Water, Proc 16th
Conf., Great Lakes Res. 282-293, 1973-
19. Degobbls, D., On the Storage of Sea Water Samples for Ammonia
Determination, Limnology and Oceanography, 18; 146-150,
January, 1970.
20. Burton, J. D., Problems in the Analysis of Phosphorus Compounds,
Water Research, Great Britain, 7_: 291-307, 1973.
21. Harms, L. L., Dornbush, J. N., and J. R. Anderson, Physical and
Chemical Quality of Agricultural Land Runoff, Journal WPCF.
4£: 2460-2470, November, 1974.
22. Dorsey, N. E., Properties of Ordinary Water Substance, Relnhold
Publishing Corp., New York, 1940, pp. 665.
23- Waksman, S. A., and C. L. Carey, Decomposition of Organic Matter
In Sea Water by Bacteria, Journal of Bacteriology. 29: 531-543,
1935. —
24. Phillips, G. E., and W. D., Hatfield, Preservation of Sewage Samples,
Water Works and Sewerage Journal . 88; June 1941
25> Moore, E. W. , Long Time Biochemical Oxygen Demands at Low Temperature,
Sewage Works Journal . ^3 (3): 561-577, May, 1941.
26. Ettlnger, M. 6., Schott, S., and C. C., Ruchhoft, Preservation of
Phenol Content In Polluted River Water Samples Previous to Analysis,
Journal - AWWA. 299-302, March, 1943.
59
-------
27. Brezonlk, P. L., and G. F., Lee, Preservation of Water Samples For
Inorganic Nitrogen Analysis with Mercuric Chloride, Air and Water
Pollution (Great Britain), JIO: 549-553, 1966.
28. Loehr, R. C., and 8. Bergeron, Preservation of Wastewater Samples
Prior to Analysis, Water Research (Great Britain) J.: 557-586, 1967.
29. Brown, £., Skougstad, M. W., and H. J. Fishman, Methods for
Collection and Analysis of Water Samples for Dissolved Minerals
and Gases, U.S. Dept. of the Interior, Washington, D. C., pp.
160, 1970.
30. In Press: Microbiological Methods for Monitoring the Environment/
Water and Wastewater, February, 1976.
31. Wills, C. G., Compliance Monitoring Procedures, U.S. Environmental
Protection Agency, National Field Investigations Center - Denver,
197*, pp. 29-37.
32. Struempler, A. W., Adsorption Characteristics of Silver, Lead,
Cadmium, Zinc, and Nickel on Borostllcate Glass, Polyethylene
and Polypropylene Container Surfaces, Analytical Chemistry, 45
(13) 2251-2254, November, 1972.
33. APHA, AWWA, WPCF, Standard Methods for the Examination of Water
and Wastewater, 13th Edition, Washington, D. C., 1971.
34. Thompson, J. F., EPA Manual of Analytical Methods, Primate and
Pesticide Effects Laboratory, Perrtne Florida, November, 1972,
Section 2 page 2.
60
-------
CHAPTER **
STATISTICAL APPROACH TO SAMPLING
For every sampling program four factors must be established:
1. Number of samples
2. Sampling frequency
3. Parameters to be measured
k, Locatlon(s) of sampling
These variables are usually established In varying degrees by the
discharge permit requirements which may or may not be scientifically
sound. In those cases where a new program is being initiated or where
the permit requirements need review, statistical methods and scientific
Judgment should be used to establish the best procedures.
it.I BASIC STATISTICS AND STATISTICAL RELATIONSHIPS
Data representing a physical phenomenon are broadly classified as
continuous or discrete and deterministic (those described by an explicit
mathematical relationship or formula) or nondeterministlc (random). Due
to the nature of water quality changes and the complexity of the pro*
cesses affecting the water or wastewater characteristics, there is no
way to predict an exact value for a datum at a future instant In time.
Such data are random in character and are conveniently described In
terms of probability statements and statistical averages rather than by
explicit equations. However, long-term changes in water quality tend
to have a functional character with random fluctuation components.
Statistical evaluation techniques provide a tool to detect and quantify
both the deterministic (functional) and the nondetermfnistlc (random)
components of a water or wastewater quality record. Figure 4.1 shows
the components of the record.
61
-------
WATER QUALITY
RECORD
DETERMINISTIC
LONG TERN
VARIATIONS
PERIODIC
VARIATIONS
NON-PERIODIC
TREND CHANCES
RANDOM
COMPONENT
STATIONARY
NON-STATIONARY
Figure 4.1 Statistical components of a water quality record
Statistical Parameters - Definitions
.1.1 Mean - The average of all values X, on a time record.
continuous distribution (population or true mean):
U •- A-/T
x T 0
dt
discrete distribution (sample mean):
x "IT
N
I "subscript denoting location of the variables X on the
record
X • estimation of the mean
N • number of discrete samples
T • time length of record
ux- true mean
t - time
62
-------
.2 Variance - A measure of the spread of the data about the mean X.
continuous distribution (population or true variance):
' *)2dt
discrete distribution (sample variance):
M MM
I ' N I
V.I.1.3 Standard Deviation - The square root of the variance having
the same dimension as the variable X. Therefore, It Is more convenient
to express the spread of data by the standard deviation than by the
variance.
o » / 2 - population or true standard deviation
x
Sy « /. 2 - sample standard deviation
X 5
Variance of the Mean - The characteristic which describes the
error of the estimate of the mean since the estimate will vary from the
true or population mean due to a limited number of data points.
w~
63
-------
frj.1.5 Standard Deviation of the Mean - Another expression of the
error of the estimate of the mean; the square root of the variance of
the mean.
s--sx
bx ~
/N
4.1.1.6 Relative Error of the Standard Deviation - The relative range
or difference between the upper and lower limits of the confidence
Interval of the standard deviation.
Q
s!
/ '
/2
X
N-l;
1-0/2
/ I
V
N-l; o/2
fi • range of difference between the upper and lower
Umlts of the confidence Interval of the standard
deviation ,
X « chl-square statistic •
o • level of significance
A.K1.7 Spectral Analysis - A technique for analyzing the recurrence
Intervals of variance in an existing data record. The power spectrum
Is plotted versus frequency to reveal all significant harmonic and
random variations In the signal.
Tx (f) • power spectrum function « / R (u) exp (-J2irfu) du
1 T
Rx (u) " a"tocovarlance function - I/ x (t) • (tfu) du
o
where p - lag time f « frequency
t - time j .- /~H~"
T - time length of the record
-------
k.\.\..8 NyquI a11 Frequency - A rule which states that the frequency of
sampling should be at least twice the highest or maximum frequency
f - 2 f
sampling max
Example: A data record shows a maximum 24-hour frequency
of variation. Then, the sampling frequency should be at
least 2 times the 24 hour dominant frequency, or at least
once every 12 hours.
4.1.1.9 Coefficient of Variation - The coefficient of variation provides
a relative measure of the variation or dispersion of a distribution.
Coefficient of variation • CV - —
X
4.1.1.10 Coefficient of Skewness - The coefficient of skewness provides
a relative measure of the degree of asymmetry of a distribution.
Coefficient of skewness
(N-l) (N-2) S*
4.1.2 Probability Density Functions (1)
A. 1.2.1 Gaussian or Normal Distribution - The most widely used
distribution for describing the vartabl I Ity of sample values, x.,
around the mean, X.
X . (X'V2 i z 22
Prob [X(t)
-------
These values are tabulated In Table 4.1. For this distribution, 68.3*
of all values will be within the Interval X + ISX, 95.41 within the
Interval X + 2SX and 99.7% within the Interval X + 3SX as Figure 4.2
shows.
»-
r* !i
"x *'»« * ™x ~™
\. M-» .1
, 95.W
99. n
lx *<
«.
Figure 4.2. Gaussian or normal distribution
It can be seen that this distribution Is defined from -• to +*•,
therefore:
Prob [x(t) < Xj - 1.0 - Prob [x(t) > X]
4.1.2.2 Pearson Type HI Probability Distribution - This distribution
Is defined f rom 0 toN+» and is therefore applicable to water quality
situations, since negative values do not exist.
Prob [x(t) IX] - / Y0 exp {-yx] • H +
Y , Y • coefficients
d • distance between mode and origin as
shown in Figure 4.3
66
-------
Table 4.1. AREAS UNDER STANDARDIZED NORMAL DENSITY
FUNCTION (2)
Vtluoofa-
<•
«,
ao
0.1
OJ
OJ
a4
0.5
0.6
0.7
04
0.9
1.0
I.I
1.2
u
1.4
U
l.<
I.T
IJ
1.9
2.0
2.1
2.2
2.1
14
2.5
2.6
2.7
2.1
2.9
0.00
0.5000
0.4602
0.4207
0.1121
0.3446
O.JOI5
0.274)
0.2420
0.2119
0.1141
O.I5S7
O.IJ57
0.1151
0.0)68
0.0808
0.0661
0.0548
0.0446
0.0)59
0.0217
0.022S
0.0179
0.0139
0.0107
0.008 JO
0.00621
0.00406
0.00)47
0.00256
0.00117
0.01
0.4960
0.4562
0.4168
0.1783
0.1409
0.1050
0.2709
0.21S9
0.2090
0.1814
0.1562
0.13)5
0.11)1
0.0951
0.079)
0.0655
0.05)7
0.04)6
0.0)51
0.0281
0.0222
0.0174
0.01)6
0.0104
0.00798
0.00604
0.0015)
O.OOJ36
0.00248
0.00181
0.02
0.4920
0.4522
0.4129
0.1745
0.»72
0.1015
0.2676
0.2)58
0.2061
0.1788
0.15)9
0.1)14
0.1 112
0.09)4
0.0778
0.0643
0.0526
0.0427
0.0X4
0.0274
0.0217
0.0170
0.01)2
0.0102
0.00776
0.005S7
0.00440
0.00)26
0.00240
0.00175
0.0)
6.4380
0.448)
0.4090
O.)707
0.3)36
0.2981
0.264)
0.2)27
0.2033
0.1762
0.1515
0.1292
0.1W3
0.0918
0.0764
0.06)0
0.0516
0.0418
0.0336
0.0268
0.0212
0.0166
0.0129
O.OW90
0.00755
0.00570
0.00427
O.C03I7
0.002J3
0.00169
0.04
0.4840
0.4443
0.4052
0.3669
0.3)00
0.294S
0.2611
0.2J96
0.2005
0.1736
0.1492
0.1271
0.1075
0.0901
0.0749
0.0618
0.0505
0.0409
0.0)29
0.0262
0.0207
0.0162
0.0125
0.00964
0.00734
0.00554
O.OMI5
O.IV3U7
0.002:6
. 0.00164
0.05
0.4801
0.4404
0.40!)
0.36)2
0.3264
0.2912
0.2578
0.2266
0.1977
0.1711
0.1469
0.1251
0.1056
0.0885
0.0735
0.0606
0.0495
0.0401
0.0)22
0.0256
0.0202
0.0158
0.0122
0.009)9
0.00714
0.005)9
0.00402
O.U0298
0.002 19
0.00159
0.06
0.4761
0.4)64
0.3974
0.3594
0.3228
0.2877
0.2546
0.2236
0.1949
0.1685
0.1446
0.12)0
0.10)8
0.0869
0.0721
0.0594
0.0485
0.0392
0.0314
0.0250
0.0197
0.0154
0.01 19
0.00914
0.00695
0.0052)
0.00391
0.00289
0.00:12
0.00154
0.07
0.4721
0.4)25
0.3936
0.3557
0.3192
0.2813
0.2514
0.2206
0.1922
0.1660
0.1423
0.1210
0.1020
0.0453
0.0708
0.0532
0.0475
0.0)84
0.0)07
0.0244
0.0192
0.0150
0.0116
0.008S9
0.00676
0.00508
0.00379
o.w:so
O.C*i:05
0.00149
0.08
0.4681
0.42S6
0.3897
03520
0.3IS6
0.2SIO
0.248)
0.2177
0.1894
0.16)5
0.1401
0.1190
0.1003
0.0838
0.0694
0.0571
0.0465
0.0375
0.0)01
0.0239
0.0188
0.0146
0.0113
0.00866
0.00657
000494
0.00368
0.00272
O.OOIW
0.00144
0.09
0.4641
0.4247
0.3859
0.3431
0.3121
O.I7T6
0.2451
0.2148
0.1867
0.1611
0.1379
0.1170
0.0985
0.0323
0.06S1
0.0559
0.0455
0.0)67
0.0:94
0.0233
0.01 S3
0.014)
0.0110
0.003-12
0.00039
O.CO480
0.00357
O.OO:M
0,001 <> 3
0.00139
67
-------
II
i
FREQUENCY CURVES
DATA
CURVE A 9 • 0.8
CV. • O.I
cumt • « • o.J
CV. - 0.*
OUMTIOH CURVES
OM
TOTAL FREQUENCY
CURVES
0.)
O.S 0.7 ••» 1.1 M '-5
VARIABU X, IN TERMS OF HEAN
Figure *».3. Pearson Type Ml probability
distribution and density
fr.1.2.3 Logarithmic Distributions - In certain situations, log-normal
or log-Pearson Type III Distributions, where logarithms of the value
X( are evaluated Instead of the arithmetic values, may give a better
data fit.
VI..2.V Chi Square Distribution - This function is the probability
distribution or a random variable:
«2 -
Zi.
E3 - Zn
a series of n independent random variables
each of which has a normal distribution with
zero mean and unit variance. The values of
the function is tabulated in Table 4.2.
68
-------
Table 4.2. PERCENTAGE POINTS OF CHI-SQUARE DISTRIBUTION (2)
V»lue of *;.. $uch that Probfct.' > £.] - a
/
*~N
xl.
ii •«
a
II
1
2
J
4
S
c
7
S
»
10
It
12
)}
14
15
16
17
IS
19
20
21
22
21
24
25
26
27
28
29
30
40
60
120
0.995
0.000039
0.0100
0.0717
0.207
0.412
0.676
0.989
1.34
1.73
2.16
2.60
1.07
3.57
4.07
4.6Q
5.14
5.70
6.26
6.84
7.43
8.03
8.44
9.26
9.89
10.52
11.16
11.81
12.46
11.12
11.79
20.71
15.51
81.85
0.990
0.975
0.00016 0.00048
0.0201
0.115
0.297
0.554
0.872
1.24
1.65
2.09
2.56
3.05
1.57
4.11
4.66
5.21
5.81
6.41
7.01
7.63
8.26
8.90
9.54
10.20
10.86
11.52
12.20
12.88
1156
14.26
14.95
22.16
37.48
86.92
Fotn > l?0. jj., w«| 1 -
djiujbuiion. L
0.0506
0.216
0.434
0.831
1.24
1.6V
2.18
2.70
3.25
3.82
4.40
5.01
5.61
6.26
6.91
7.56
8.21
8.91
9.59
10.28
10.98
11.69
12.40
13.12
13.84
14.57
15.11
16.05
16.79
24.41
40.48
91.58
B + VS
0.950
0.0039
0.103
0.352
0.711
1.15
1.64
2.17
2.73
3.33
3.94
4.57
5.23
5.89
6.57
7.26
7.96
8.67
9.39
10.12
10.85
11.59
12.14
13.09
11.85
14.61
15.38
16.15
16.93
17.71
18.49
26.51
43.19
93.70
1*
where
0.900
00158
0.211
0.584
1.06
1.61
2.20
2.81
3.49
4.17
4.87
5.58
6.30
7.04
7.79
8.55
9.31
10.08
10.86
11.65
12.44
13.24
14.04
14.85
15.66
16.47
17.29
18.11
18.94
19.77
20.60
29.05
46.46
100.62
0.10
2.71
4.61
6.25
7.78
9.24
10.64
12.02
13.36
14.68
15.99
17.28
18.55
19.81
21.06
22.31
23.54
24.77
25.99
27.20
28.41
29.62
30.81
32.01
31.20
34.38
35.56
36.74
37.92
.39.09
40.26
51.81
74.40
140.23
0.05
3.84
5.99
7.81
9.49
11.07
12.59
14.07
15.51
16.92
18.31
19.68
21.03
22.36
23.68
23.00
26.30
27.59
28.87
30.14
31.41
32.67
31.92
35.17
36.42
37.65
38.88
40.11
41.34
42.56
41.77
55.76
79.08
146.57
0.025
5.02
7.38
9.35
11.14
12.81
14.45
16.01
17.53
19.02,
20.48
21.92
23.34
24.74
26.12
27.49
28.85
30.19
31.53
32.85
34.17
15.48
16.78
18.08
19.36
40.65
41.92
43.19
44.46
45.72
46.98
59.14
81.10
152.21
0.010
6.63
9.21
11.34
13.28
15.09
16.81
18.48
20.09
21.67
21.21
24.71
26.22
27.69
29.14
J0.58
12.00
13.41
34.81
36.19
37.57
38.93
40.29
41.64
42,93
44.31
45.64
46.96
48.28
49.59
50.89
61.69
88.33
158.95
0.005
7.88
10.60
12.84
14.86
16.75
18.55
20.28
21.96
21.59
25.19
26.76
28.30
29.82
31.32
32.80
34.27
35.72
37.16
38.58
40.00
41.40
42.80
44.18
45.56
46.91
4J.2V
49.64
50.'99
52.14
53.67
66.77
91.95
161.65
i, is (he desired percentage point for i standardized normal
-------
4.J.2.5 Student t Distribution * This is a probability distribution
of a random variable:
t - -*--
n
1 * random variable with normal distribution; with zero mean and
unit variance
y » a variable with a Chi Square Distribution
n • number of degrees of freedom of the variable t . Values of
. this distribution are tabulated in Table 4.3. n
VJUa.fe Determination of the Tvoc of Distribution - To apply statistics,
the type of distribution must be determined. There are both graphical
and numerical techniques to accomplish this (3).
1, Graphical Procedure for Small Number of Samples (N<30).
$tep I. Arrange the data in increasing order of magnitude
{•Ml lest first, largest last) and assign a ranking number
{«») to each value based on Its order of magnitude (Table k. k
column 3).
St.ijr2. Calculate the percent probability for each value
usi ig one of the following two equations:
100
P - re-4 loo
where
p * probability (percent) of being less than
or equal to the chosen value
m - assigned number based on order of magnitude
n » total number of samples
St«P 3» Hot each value versus its corresponding percent
probability on probability paper (or tog probability
paper If data is log normally distributed).
70
-------
Table A.3. PERCENTAGE POINTS OF STUDENT t DISTRIBUTION (2)
Value of /M such that Probfc, > /„;,! - «
^Mi
^
Ew^*""*1*1 * a
<*•
a
H
1
2
3
4
5
6
7
8
9
JO
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
40
60
120
0.10
3.078
1.886
1.638
1.S33
1.476
1.440
1.415
1.397
1.383
1.372
1.363
1.356
1.350
1.345
1.341
1.337
1.333
1.330
1.328
1.325
1.323
1.321
1.319
1.318
1.316
1.315
1.314
1.313
1.311
1.310
1.303
1.296
1.289
0.050
0.02S
6.314 12.706
2.920
2.353
2.132
2.015
1.943
1.895
1.860
1.833
1.812
1.796
1.782
1.771
1.761
1.753
1.746
1.740
1.734
1.729
1.725
1.721
1.717
1.714
1.711
1.708
1.706
1.703
1.701
1.699
1.697
1.684
1.671
1.658
4.303
3.182
2.776
2.571
2.447
2.365
2.306
2.262
2.228
2.201
2.179
2.160
2.145
2.131
2.120
2.110
2.101
2.093
2.086
2.080
2.074
2.069
2.064
2.060
2.056
2.052
2.048
2.045
2.042
2.021
2.000
1.980
0.010
31.821
6.965
4.541
3.747
3.365
3.143
2.998
2.896
2.821
2.764
2.718
2.681
2.650
2.624
2.602
2.583
2.567
2.552
2.539
2.528
2.518
2.508
2.500
2.492
2.485
2.479
2.473
2.467
2.462
2.457
2.423
2.390
2.358
0.005
63.657
9.925
5.841
4.604
4.032
3.707
3.499
3.355
3.250
3.169
3.106
3.055
3.012
2.977
2.947
2.921
2.898
2.878
2.861
2.845
2.831
2.819
2.807
2.797
2.787
2.779
2.771
2.763
2.756
2.750
2.704
2.660
2.617
« - 0.995, 0.990, 0.')75, 0.950, and 0.900 follow
from /„;,-, «= -/,;.
71
-------
An example of a data treatment is shown on Table k.k and Figure k.k. If
the data had a perfectly normal distribution, a straight line approxi-
mation would be obtained. In this case, the difference between the
values at 84.13 and 15.87 percent probability would equal twice the
standard deviation. If the data on both ends of the probability
distribution tend to have a skew, a skewed distribution is more
appropriate.
Example - A wastewater stream was surveyed for ten weeks of a
year and the maximum daily concentrations of each week were
recorded as shown In Table k.k. The weeks of the survey were
chosen randomly. Estimate the maximum daily concentration which
would have a chance of being exceeded only once per year.
Since the sample size from which the maximum dally concentrations
ware taken is one week, the probability of a concentration being
exceeded once during a year becomes
a * 1/52 weeks • 0.019& 2 percent
Then the probability of the concentration being less than or
equal to the maximum Is
p (X < X$] • l-o - 98 percent
The computational procedure is shown in Table *».*t and the probabilistic
plot Is presented in Figure 't.4. From the graph the value Xs which has
the percent probability of being exceeded only 1 week per year (2
percent) Is 67-5 mg/1.
2. Graphical Procedure for Large Number of Samples (N>30).
For a large number of values It Is convenient to rearrange the data in
groups with the same range or Intervals, e.g.. 100-109 mg/1, 110-119
mg/1, 120-129 mg/1, etc., and to determine the number of values within
each interval. The plot of the frequency of occurrence vs. the
magnitude of the parameter is called a "histogram". The plot of the
72
-------
WO
Table k.k. COMPUTATIONAL TABLE FOR GRAPHICAL
NORMAL OR PEARSON TYPE III DISTRIBUTION DETERMINATION
Week of
the year
3
7
12
18
22
29
31
36
37
49
X,
Maximum daily
Concentration,
mg/1
52
33
41
59
37
32
47
38
57
45
Increasing
order of
magnitude, m
8
2
5
10
3
1
7
4
Q
6
Plotting
position,
72-73
13.18
45.45
90.91
27-27
9.09
63.66
36.36
81.82
54.55
X2
2704
1089
1681
3481
1369
1024
2209
1444
3269
2025
t
140603
35937
68921
205379
50653
32768
103823
54872
185193
9H25
EX.
20275
969279
-------
I
75
70
65
60
55
50
o
0 35
30
25
20
X$ * 67.5
2S * 55 - 33 * 22
*£ 11 mg/1
98
u
0.01 O.T 1 2 5 10 20 30 kn 60 86 90 95
PROBABILITY OF X BEING LESS THAN OR EQUAL TO GIVEN VALUE, PERCENT
99-9
Figure k.k. Graphical method for determining probability distribution
-------
total number of cases being less than or equal to a given boundary value
will yield the cumulative frequency distribution curve. Again, with the
upper boundary approaching +», the plotting position could be
determined from the formula
where m • number of cases with the same magnitude or lower.
Example - A wastewater stream was sampled each week for a period
of one year and maximum daily concentrations were recorded as
follows"
Concentration, Frequency of.
m
ma/1 Occurrence, fj m » £f.| p • rjy * |0°
28-28.9
30-30.9
31-31.9
32-22.9
33-33.9
34-34.9
35-35.9
36-36.9
37-37.9
39-30.9
1
2
7
10
14
8
5
3
I
1
1
3
10
20
34
-------
o
•z.
c
o
44
42
40
38
32
30
23
26
24
22
20
j
5=L
HISTOGRAM
c
h-
o
o
0 5 10 15
FREQUENCY OF OCCURRENCE
:= 32.
2'!
22L
20—
0.01
CUMULATIVE PROBABILITY DISTRIBUTION
0.1 1 2 5 10 20 40 60 80 95 99 99.9
PROBABILITY OF X BEING LESS THAN OR EQUAL TO A GIVEN VALUE
Figure 4.5. Histogram and probability distribution curve for larger number of s.ampjes
-------
The Pearson Type Ml distribution -Ires the use of natural data or
the logarithmic values of the na\ • data to compute the mean, standard
deviation, and skew coefficient or .,ie distribution. If logarithmic
data Is used, the method is called the log - Pearson Type III method
(M.
The skew coefficient reveals the degree to which the distribution Is
asymetrical. A skew coefficient of zero indicates a symmetrical
distribution of values. A normal distribution has a zero coefficient
of skewness. A positive coefficient indicates that values above the
mean tend to lie further from the mean than those below the mean.
Sparr and Hann (5) recommended the following relation between the co-
efficient of skewness and type of the best probability distribution.
Best Fitting
Skew Coefficient.Igl Probability Distribution
<0.5 normal
0.9-1.6 Pearson Type III
>1.7 log - normal
The method for obtaining the probability distribution using the Pearson
Type III curve involves calculation of the skew coefficient and can be
illustrated using the data given in Table 4.4.
1. Compute the mean
2. Compute the standard deviation
S • ' EX2 - (EX)2/N - ' 20275 - *dl27im =5.59
N - I 10-1
77
-------
3. Compute the coefficient of skewness
N2IX3 - 3NEXEX2 + 2(IX)3
N(N-I) (N-2) S3
9699279) '(3x1 0x44 1x20275)+ (2x44 I3)
10(10-1) (10-2) x 9-593
" 0.35
For a: skew coefficient of 0.35. the best fitting distribution is the
normal.
The value Xs having a percent chance of being exceeded only once (weekly
average) per year (a • 1/52 - 0.02) can be calculated from the equation
X$ - X + kS
with k taken from Table 4.5 for g - 0.35 and a - 2*. For g • 0.35* k
must be extrapolated between 2.211 and 2.261:
- 2.236
Then X$ - 44.0 + 2.236 x 9.59 • 65.4 mg/1
4.2 DETERMINATION OF NUMBER OF SAMPLES (6)
The number of samples necessary to reasonably characterize a water or
jtfastewater Is determined after collecting some background data on the
'concentration and variance of the parameters under consideration.
These values can be estimated; however, estimation will decrease the
confidence In the results. Two techniques can be used to calculate
the number of samples, one based on the allowed sample variability,
the other on the accuracy of the sample mean. Each will give a
desired value of N with the largest value to be chosen for application.
4.2.1 Determining Sample Size from a Constraint on the Variability
To apply this method the following Information is needed:
78
-------
Table
K VALUES FOR POSITIVE SKEW COEFFICIENTS (7)
Skew
Coefficient
<8>
3.0
2.9
2.8
2.7
2.6
2.5
2.4
2.3
2.2
2.1
2.0
1.9
1.8
1.7
1.6
1.5
1.4
•1.3
1.2
1.1.
1.0
.9
.8
.7
.6
.5
.4
.3
.2
.1
0
99
-0.667
-0.690
-0.714
-0.740
-0.769
-0.799
-0.832
-0.867
-0.905
-0.946
-0.990
-1.037
-1.087
-1.140
-1.197
-1.256
-1.318
-1.383
-1.449
-1.518
-1.588
-1.660
-1.733
-1.806
-1.880
-1.955
-2.029
-2.104
-2.178
-2.252
•2.326
95
-0.665
-0.688
-0.711
-0.736
-0.762
-0.790
-0.819
-0.850
-0.882
-0.914
-0.949
-0.984
-1.020
-1.056
-1.093
-1.131
-1.168
-1.206
-1.243
-1.280
-1.317
-1.353
-1.388
-1.423
-1.458
-1.491
-1.524
-1.555
-1.586
-1.616
-1.645
90
-0.660
-0.681
-0.702
-0.724
-0.747
-0.771
-0.795
-O.819
-0.844
-0.869
-0.895
-0.920
-0.945
-0.970
-0.994
-1.018
-1.041
-1.064
-1.086
-1.107
-1.128
-1.147
-1.166
-1.183
-1.200
-1.216
-1.231
-1.245
-1.258
•1.270
-1.282
80
-0.636
-0.651
-0.666
-0.681
-0.696
-0.711
-0.725
-0.739
-0.752
-0.765
-0.777
-0.788
-0.799
-0.808
-0.817
-0.825
-0.832
-0.838
-0.844
-0.848
-0.852
-0.854
-0.856
-0.857
-0.857
-0.856
-0.855
-0.853
-0.850
-0.846
•0.842
Percent Chance a
50
-0.396
-0.39C
-0.384
-0.376
-0.368
-0.360
-0.351
-0.341
-0.330
-0.319
-0.307
-0.294
-0.282
-0.268
-0.254
-0.240
-0.225
-0.210
-0.195
-0.180
-0.164
-0.148
-0.132
-0.116
-0.099
-0.083
-0.066
-0.050
-0.033
•0.017
0
20
0.420
0.440
0.460
0.479
0.499
0.518
0.537
0.555
0.574
0.592
0.609
0.627
0.643
0.660
0.675
0.690
0.705
0.719
0.732
0.745
0.758
0.769
0.780
0.790
0.800
0.808
0.816
0.824
0.830
0.836
0.842
10
1.180
1.195
1.210
1.224
1.238
1.250
1.262
1.274
1.284
1.294
1.302
1.310
1.318
1.324
1.329
1.333
1.337
1.339
1.340
1.341
1.340
1.339
1.336
1.333
1.328
1.323
1.317
1.309
1.301
1.292
1.282
4
2.278
2.277
2.275
2.272
2.267
2.262
2.256
2.248
2.240
2.230
2.219
2.207
2.193
2.179
2.163
2.146
2.128
2.108
2.087
2.066
2.043
2.018
1.993
1.967
1.939
1.910
1.880
1.849
1.818
1.785
1.751
2
3.152
3.134
3.114
3.093
3.071
3.048
3.023
2.997
2.970
2.942
2.912
2.881
2.848
2.815
2.780
2.743
2.706
2.666
2.626
2.585
2.542
2.498
2.453
2.407
2.359
2.311
2.261
2.211
2.159
2.107
2.054
1
4.051
4.013
3.973
3.932
3.889
3.845
3.800
3.753
3.705
3.656
3.605
3.553
3.499
3.444
3.388
3.330
3.271
3.211
3.149
3.087
3.022
2.957
2.891
2.824
2.755
2.686
2.615
2.544
2.472
2.400
2.326
0.5
4.970
4.909
4.847
4.783
4.718
4.652
4.584
4.515
4.444
4.372
4.298
4.223
4.147
4.069
3.990
3.910
3.828
3.745
3.661
3.575
3.439
3.401
3.312
3.223
3.132
3.041
2.949
2.856
2.763
2.670
2.576
-------
Table 4.6. K VA|.U|S FDR NEQATJYE SKEW COEFFICIENTS (7)
oo
o
Skew
Coefficient
0
- .1
- .2
- .3
- .4
- .5
- .6
- .7
- .8
- .9
-1.0
-l.l
-1.2
-1.3
-1.4
-1.5
-1.6
-1.7
-1.8
-1.9
-2.0
-2.1
-2.2
-2.3
-2.4
-2.5
-2.6
-2.7
-2.8
-2.9
-3.0
99
-2.326
-2.400
-2.472
-2.544
-2.615
-2.686
^2.755
-2.824
-2.891
-2.957
-3.022
-3.087
-3.149
-3.211
-3.271
-3.330
-3.388
-3.444
-3.499
-3.553
-3.605
-3.656
-3.705
-3.753
-3.800
-3.845
-3.889
-3.932
-3.973
-4.013
-4.051
95
-1.645
-1.673
-1.700
-1.726
-1.750
-1.774
-1.797
-1.819
-1.839
-1.858
-1.877
-1.894
-1.910
-1.925
-1.938
-1.951
-1.962
-1.972
-1.981
-1.989
-1.996
-2.001
-2.006
-2.009
-2.011
-2.012
-2.013
-2.012
-2.010
-2.007
-2.003
90
-1.282
-1.292
-1.301
-1.309
-1.317*
-1.323
-1.328
-1.333
-1.336
-1.339
-1.340
-1.341
-1.340
-1.339
-1.-337
-1.333
-1.329
-1.324
-1.318
-1.310
-1.302
-1.294
-1.284
-1.274
-1.262
-1.250
-1.238
-1.224
-1.210
-1.195
-1.180
80
-0.842
-0.836
-0.830
-0.824
-0.816
-0.808
-0.800
-0.790
-0.780
-0.769
-0.758
-0.745
rO.732
-0.719
-0.705
-0.690
rO.675
-0.660
-0.643
-0.627
-0.609
-0.592
-0.574
-0.555
-0.537
-0.518
-0.499
-0.479
-0.460
-0.440
-0.420
Percent Chance
50
0
0.017
0.033
0.050
6.066
0.083
0.099
0.116
0.132
0.148
0.164
0.180
0.195
0.210
0.225
0.240
0.254
0.268
0.282
0.294
0.307
0.319
0.330
0.341
0.351
0.360
0.368
0.376
0.384
0.390
0.396
20
0.842
0.846
0.850
0.853
0.855
0.856
0.857
0.857
6.856
0.854
0.852
0.848
0.844
0.838
0.832
0.825
0.817
0.808
0.799
0.788
0.777
0.765
0.752
0.739
0.725
0.711
0.696
0.68,1
0.666
0.651
0.636
10
1.282
1.270
1.258
1.245
1.231
1.216
1.200
1.183
1.166
1.147
1.128
1.107
1.086
1.064
1.041
1.018
0.994
0.970
0.945
0.920
0.895
0.869
0.844
0.819
0.795
0.771
0.747
0.724
0.702
0.681
0.660
4
1.751
1.716
1.68Q
1.643
1.606
1.567
1.528
1.488
1.448
1.407
1.366
1.324
1.282
1.240
1.198
1.157
1.116
1.075
1.035
0.996
0.959
0.923
0.888
0.855
0.823
0.793
0.764
0.738
0.712
0.683
0.666
2
2.054
2.000
1.945
1.890
1.834
1.777
1.720
1.663
.606
.549
.492
.435
.379
1.324
1.270
1.217
1.166
1.116
1.069
1.023
0.980
0.939
0.900
0.864
0.830
0.798
0.768
0.740
0.714
0.689
0.666
I
2. 326
2.252
2.178
2.104
2.029
1.955
1.880
1.806
1.733
1.660
1.588
1.518
1.449
1.383
1.318
1.256
1.197
1.140
1.087
1.037
0.990
0.946
0.905
0.867
0.832
0.799
0.769
0.740
0.714
0.690
0.667
O.J
2T576
2.432
2.338
2.294
2.231
2.108
2.016
1.926
1.837
1.749
1.664
1.581
1.501
1.424
1.351
1.232
1.216
1.155
1.097
1.044
0.995
0.949
O.S07
0.869
0.833
0.800
0.769
0.741
0.714
0.690
0.667
-------
1. Allowable error of the standard deviation (or the difference
from its true value) -S
2. Confidence level required - (I-a)
Therefore, for this situation, one is estimating that the value of a
certain variable will occur within a specific interval. A normal
distribution of the data around the mean is assumed. The data should
be checked for normality by plotting on probability graph paper.
Example - Determine the number of samples required from a
wastewater monitoring program such that the estimated
standard deviation will be within 25% of its true value
(t 12.51 of estimated value) at a confidence level of 98*.
a - I - 0.98 " 0.02 n
S" " °'25
n
From Figure 4.6, the value of S » 0.25 is found on the Y (vertical)
axis and a horizontal line is followed until the 98% confidence
(corresponds to o - 0.02) curve is met. . Then a vertical line is
dropped to the X (horizontal) azis to find the number of samples.
In this case N • 180 samples.
4.2.2. Determining Sample Size from a Constraint on the Mean Value
To apply this method, the following information is required:
I. Confidence level required - (I -a)
2. Coefficient of variation of the source to be
sampled - CV
3. Allowable accuracy of the average from the true
mean of the source.
A double iteration procedure should be used especially if the number of
samples is found to be small (N < 30).
The applicable equation is:
where: CV » ^ " coefficient of variation
X
-------
10.0
• • (
HH--<
5.0
••—<
• «M
.2
1.0
0.5
at*
0,25
0.1
0.05
0.01
rW-
rf-
\
£
T^ i i. i i m _
GRAPHICAL SOLUTION TO EQUATION
| -rffT
"
X
n
50 100
N-1; l-a/2 N-l; «/2
)f
;E
N • 180
500 1000
S*pU Slat.
Figure V.6. Determination of the number of samples based
on the required accuracy .of extreme values
82
-------
S • standard deviation
X • mean
0 • allowed deviation of the average value from the true
mean In percent
o/2 • probabtistic variable of normal distribution at a
confidence level I - o .
Estimations of CV, Sx, X can be used. For this calculation a normal
distribution is assumed.
Example - For a wastewater stream with an average daily concentra-
tion, J • |20 mg/l BOD, with a standard deviation, Sx » 32 mg/l,
determine the number of daily samples which would provide accuracy
of the daily averages within 5%.
6 - 5*
CV-^-nf -0-27
A
At 35% confidence interval Z • 1.96 (From Table 4.1).
/CV -
. N - ( e/
•• \
Q.27 • I.
Step I. N - e/too " - 0^5
• 110 samples
Step 2. Using N - 110, find ta/2>|M from Table
'(0.025J09) -1'983
2
rCV * t
N -[
•115 samples
83
-------
This problem can also be solved graphically. In Figure V.7 the number
of samples, N has been related to the parameter, B/(IOO x CV).
6
100 x CV TOO x 0.27
0.185
This value, 0.185, Is found on the Y- axis and a horizontal line Is
followed until the 95* confidence (corresponds to o • 0.05) curve is
met. Then a vertical line is dropped to the X axis to find the number
of samples. In this case M • 115 samples.
If both the accuracy of the standard deviation and the accuracy of the
mean are used as criteria, choose the larger number of samples from the
two calculations.
i
For the example, N • 180 and N: • 115; therefore, N « 180 samples
would be chosen.
4.3 DETERMINATION OF SAMPLING FREQUENCY
The various techniques for determining sampling frequency have been
evaluated and the method of spectral analysis has been chosen as the
most applicable. Although it requires the use of a computer, spectral
analysis should be applied whenever possible because of accuracy and
simplicity in final interpretation (8, 9, 10).
4.3.1 Definition
Spectral analysis - The power spectra describes the general frequency
composition of data in terms of the spectral density of its mean square
value and is a plot of this spectral density function versus frequency.
With this procedure, the distribution of the variance with frequency
can be seen. Power spectra for k variations of X(t) are shown in
Figure 4.8.
The relatively uniform and broad spectrum as is seen on Figure 4.8a Is
typical for randomly fluctuating records. If the signal is composed of
two harmonics with the frequency fi » 1 , • i as illustrated in
' T,, and f2 T2
Figure 4.8-d, the peaks will appear at frequencies f] and f2« As can be
seen the resultant power spectrum is basically the summation of the
power spectrum for a sine wave and random noise. Although the power
spectral density of a sine wave is infinitely large at the frequency of
the sine wave and zero at all other frequencies (see Figure 4,8-a), the
integral of the power spectrum over any frequency range that includes
the numerical frequency has a finite value equal to. the mean square
value of the sine wave, where ^ 1$ the amplitude of the sine wave.
-------
o
8
GRAPHICAL SOLUTION TO EQUATION
2
1000
Sample Size, N
Figure k.7. Determination of the number of samples based
on the required accuracy of the mean
85
-------
CO
o
>
4J
in
V.
tn
O
«
C.
V
o
TO
u
a) Periodic Determtn!sties
• W,»
l/t.
-life
I
b) Random: Wideband
Frequency
l/2At
^^ c) Random: Narrow Bartd
d) Raridbfti: Harrnohle
1/2At
Fre'quency
Figure 4.8. Various power/spectra for variable
-------
Since the variance of a sine wave equals S2 » X2/2 and the delta
m
function representing the variance of the sine wave is located at the
frequency of the sine wave, f1, then S2 „ / (f}) df or S2 .; f+df p df.
This means that the area under the power spectrum curve corresponds to
the variance of the signal. If another sine wave with frequency f + df
was superimposed on the basic frequency, the total variance of the signal
would be S2 - / (f,) df + /(f2) df. If the signal was composited from a
large number of sine waves then the total variance would become
S2 » / crdf
o
where fc is the maximal frequency detected on the signal.
Finally, the power spectra for "narrow band" random variation is ter-
minated at a frequency f0 » I < f max • ~e. As seen In Figure *».8-c,
the power spectrum at the enaTis peaked similarly to that of a sine
wave but It is continuous for frequencies f2 < fQ. Again the area under
the curve should equal the variance Sx2 |f the record has zero mean,
otherwise It should equal S 2 + u 2.
X A
It should be noted that for any discrete sampling the maximum frequency
which can be resolved from the record is the Nyquist frequency; f max »
l/(2 At) where At is the sampling interval, and even the apparent effect
of this frequency will be confounded by the accumulated effects for all
larger frequencies.
4.3.2 Determination of the Sampling Frequency From Power Spectra
It is imperative that a good set of historical data be available for
analysis. This data should be taken at a frequency that is higher than
the expected harmonic variation component of the signal. For example,
if daily trends are to be analyzed, hourly samples may be taken. Then
the significance of any harmonic variability can be seen. In analyzing
the power spectra to determine sampling frequency, the sampling frequency
should be chosen just after the last significant peak on the power
spectra as shown in Figure 4.9.
In general, two "practical rules of thumb" are important when analyzing
times series data (11):
1. The data should cover a time period 10 times the longest period
of interest, e.g., 10 years of data if the annual period is of
interest.
2. The sampling interval (time between data points) should be less
than half the shortest period of interest. From hourly data, the
shortest period that can be evaluated.
87
-------
O
£
.
I
a) Narrow- - Ban* Random Signal
sampling
frequency
k.
o
I
I
b) Random - Harmonics
samplIng
Frequency
Figure 4.9. Determination of sampling frequency
-------
Is the effect of a two hour period. However, even the
affect of this period Is not clear because It includes
the effect of shorter periods. The shortest period
with • clearly defined effect would be the three hour
period.
For the narrow-band random signal, the frequency can be theoretically
anywhere below fQ. If harmonic components are present the frequency of
sampling should be higher than the highest significant harmonic
frequency multiplied by two. On Figure 4.9-b the sampling interval for
a random-harmonic signal would be
and the sampling frequency, f§, should be within the interval
2f2 < fx ' it ' '3
The following examples should clarify and further explain the power
spectra applications.
Example I - The wastewater influent for the city of Racine,
Wisconsin was sampled hourly in the summer of 197** and the TOC an-
alyzed. The record is shown in Figure 4.10. The average
calculated was 70.56 mg/1 and the variance was 1262.07 mg2/!2.
Determine the optimum sample frequency for this plant.
Spectral analysis is performed on the data and the spectrum is
plotted as shown in Figure *».! 1. A computer program to obtain
these results is included at the end of the chapter. It can be
seen that the power spectrum confirms the 2k hour variability as
shown In the cor re log ram. The finding Indicates that most of the
variability occurs within the frequency band 1A8 hr."1 to 1/16 hr.
with a strong peak at the frequency \/2k hr. . Almost 85
percent of the variance, SX2, js caused by these low frequency fluc-
tuations. There is also a less significant peak at the frequency
1/8 hr. . The rest of the record shows the effect of random
fluctuations.
The sampling frequency should be two times the frequency just after
the last significant variation or peak.
In this situation the last significant variation is at 1/16 hr.'1
(or I sample every 16 hours). Since this is the Nyquist frequency,
the sampling frequency should be twice as often or 2 x 1/16 hr.'1
• 1/8 hr. (one sample every 8 hours). This would reveal almost
100% of the wastewater variability over a sufficient length of time.
89
-------
100
too
mg/l
'Mon
Ttt"
Sat
Time
4.10. Tlnw record of TOC of municipal
it ftaclne, Wisconsin
-2
•4
1
j
frequency I/hour
figure k.}\. Power spectrum:of TOC concentratIon of municipal wastewater
at Racine, Wisconsin
90
-------
Example 2 - The spectra of wastewater variations typical for two types
of industrial discharges are presented in Figures 4.12 and 4.13.
Determine the optimum frequency for sampling.
On figure 4.12, a strong period occurs in the frequency band 1/16 hr
to 1/8 hr"' with a secondary peak in the frequency band 1/6 hr"' to
1/5 hr"'. This spectrum is typical for industrial plants working 24
hours, 7 days a week with three shifts a day. Note that almost no low
frequency or trend has been detected. Thus, the data seems to be
stationary. Therefore, the most feasible sampling program would be
twice the frequency just after the last significant peak. In this case
the last peak occurred from 1/6 hour"' to 1/5 hour"1 and the frequency
just beyond Is 1/4 hr"'. Therefore, the sampling frequency would be
2 x 1/4 hr"' or one sample every 2 hours.
0.25 0.10 0.1$
Frequency (I/hour)
0.20
0.25
Figure 4.12 Power spectrum of chemical plant discharge, Case 1
91
-------
Another chemical plant discharge, the spectrum of which Is shown In
Figure 4.13. shows a strong harmonic at the frequency 1/24 hr"', which
Is typical'for plants working mainly with one daily shift. There are
also a secondary peaks at frequencies 1/12 hr"' and 1/6 hr"'.
following the same theory, sampling could be scheduled at frequencies
of I sample per 12 hours. However, since the peak at 1/6 hr"' is
somewhat large, a more accurate program would require samples once
every 3 hours.,
I
i
0.05 0.10 0.15 0.20
Frequency (I/hour)
Figure 4.13 Power spectrum of chemical plant discharge, Case II
k.k DETERMINATION OF PARAMETERS TO ANALYZE
The decision regarding which parameters to analyze is critical since it
determines the value of sample, allowable holding time, preservation
method, etc. There are two statistical methods to resolve this
problem if prior regulations do not exist. The decision variable for
the first method ts the probability of exceeding a standard, and the
second is the correlation between parameters.
-------
4. 4. ] Probability of Exceeding a Standard
This technique requires I. Knowledge (or estlmates)of the mean - X
2. Knowledge (or estimates) of the standard
deviation - Sx
3« Value not to be exceeded - Xs
The probability of exceeding the standard is:
P (X > X$) - prob (Z > Za) - a
where
x - x
For a computed Za, the probability can be found In Table 4.1. Parameters
with the highest p(X 3> X$) have the highest priorities of sampling.
Example - The effluent standard for an Industry was determined
to be 100 mg/1 of Cl". A wastewater quality survey has
shown that the mean concentration of chlorides X, was
75 mg/1 and the standard deviation Sx, was 18 mg/1.
The probability of the standard being exceeded can be
computed as follows:
Determine Zg
° S 18
x
From Table 4.1 for Z • 1.39 the probability p (X > X ) Is
0.823 or 8.23 percent. s
Often an effluent standard will be specified for several
parameters. Then the parameters can be ranked in descending
order of their probability of being exceeded. The priority
of sampling will be In the same order. An example of how
this can be done In practice Is given in Table 4.7.
93
-------
Table 4.7. SAMPLING PRIORITIES OF PARAMETERS
FOR A TYPICAL WASTEWATER
Parameter
PH
TOC
COD
BOD
TKN
Phosphates
Conductivity
Total dissolved
solids
Suspended solids
Turbidity
Lead
Mercury
1 ron
Copper
Alkalinity
Acidity
Calcium
Hardness
Hagnes turn .
Total conforms
Fecal conforms
Chlorides
Water Quality Mean,.
itanrfacfU ^ x
6.5 - 8.0
None
70
30
5
1
None
500
30
20
5
5
10
7
None
None
None
None
None
too
10
200
7.8
31
60
20
3.5
0.5
320
491
28
19
3
2.5
7.8
0.8
-
-
-
-
-
81
5
156
Standard Z
.Dfivtatlon .S
0.4
7.9
11
8
1.5
0.2
80
125
5
3
1.0
1.5
1.9
0.15
-
'-
-
-
-
65
64
59
0.50
-
0.91
1.25
1.00
2.50
-
0.072
0.40
0.33
2.0
1.67
1.16
1.33
-
-
•>
-
-
0.29
1.25
0.90
p(x> xs)
0.308
0
0.181
0.125
0.158
0.006
0
0.472
0.34
0.37
0.0228
0.047
0.123
0.0918
0
0
0
0
0
0.386
0.125
0.184
Samp I Ing
PxJojrlty
5
16-22
7
9-10
8
15
16*22
1
4
3
14
13
11
12
16-22
16-22
16-22
16-22
16-22
2
9-10
6
-------
*>.*».2 Correlation Between Measured Parameters (12)
Another method Is to evaluate the closeness of correlation among the
water quality parameters of interest. It is known that a correlation
exists between many water quality parameters such as:
80 Cr and TOC
COO and TOC
Chlorides and Conductivity
Total dissolved solids and conductivity
Suspended solids and turbidity
Acidity, alkalinity and pH
Hardness, calcium and magnesium
Hardness, and alkalinity
The statistical relationship is not limited to chemical water quality
Indicators but It can also be extended to some biological and bacte-
riological parameters. If a strong correlation exists between two or
more parameters, the monitoring of one parameter may be discontinued or
monitored at a reduced frequency. In order to apply the technique,
the following must be available:
I. A data record for all parameters of interest.
2. A computer program for calculating correlation coefficients.
The relationship between two parameters x and y can be linear or non-
linear (such as logarithmic, exponential, etc.) If a non-linear
relationship seems to exist, attempt to linearize the relationship,
e . g . , by using logarithms of the values of x and y or some other
functional approximation. Then linear regression analysis provides the
linear functional relationship in the form:
Y • a + bx
Where a and b are the intercept and regression coefficient (slope),
respectfully, of the line of best fit. The coefficient of correlation,
PXy, will then be a measure of the closeness of the fit.
Figure k, 14 shows and example of the relationship of BOD to TOC for the
Racine, Wisconsin wastewater. In practice, the available data will be
limited to a sample of N pairs of observed values for x and y.
Only estimates of a and b can be determined based on this limited data.
the following equations can be used to obtain these estimates.
95
-------
•no
10
200
tng/1
fFlgure 4.\k. Relationship tcff TOC-BOD concentrations of
a mun!clpal wastewater
-------
a - Y - bX
b »
N
M U|
' '
- X) y,
N
t^l X' VI
JBI
- NXY
E (x, - X)2 E x2 - (Z x.)2 /N
i"l ' l»l ' M J
N = number of pairs of x. and y.
Y = mean of y 's
X " mean of x 's
The coefficient of correlation can be determined from the equation:
pxv
EM xjyj - NXY
1-1
2 2
Numerous computer package subroutines are available for the above
analysis.
The hypothesis that a relationship between x and y exists can be tested
at a given level of significance a (I - a - confidence that the
hypothesis holds). If the obtained | pxy | > PC wherc PC is the mlnimal
correlation coefficient from Table 4.8, the zero correlation hypothesis
(i.e., that there is no relationship) is rejected. For a perfect fit
I pxyj " 1.
97
-------
It ts convenient to arrange the results In a matrix as Is done In the
example (Table 4.9).
The pairs with high coefficients of correlation signifcantly greater
than the critical correlation coefficient are eligible for selective
elimination of one of the parameters of the pair or for reduction
of the frequency of the data acquisition. The decision on which
parameter should be eliminated will be based on cost of the data
acquisition and the priority of the parameter.
Example. A wastewater system was surveyed for an extended
per iod of time. As a result of the survey, 25 sets of wastewater
quality data was gathered. Each set contained data on pH, TOC,
COO, BOO, TKN, phosphorus, conductivity, total dissolved solids,
suspended solids, turbidity, lead, mercury, Iron, copper,
alkalinity, acidity, hardness, calcium, magnesium, coliform
bacteria, fecal coll form, and chlorides.
1. Determine the sampling priority of each parameter
2. Determine which parameter measurements can be eliminated
or reduced.
Determine the probability that the standard for each parameter
exceeded p(X > X ) • a. This will determine the sampling priority
of the parameter to be monitored. The priority is given by the
descending order of the magnitude of p(X > X ).
The correlation analysts of the above 22 parameters was performed
by a computer according to the previous equations. The analysis
provided the following Information:
Intercept, a
*y
Regression coefficient, b
xy
Correlation coefficient, p
xy
2
Theoretically, for all 22 parameters, 1/2(22 - 22) computations
would be required, but professional judgment will eliminate the
obviously uncorrelated pairs.
The critical correlation coefficient for N - 25 can be obtained
from Table 4.8.
98
-------
Table t).8. VALUES OF CORRELATION COEFFICIENT, p, FOR
TWO LEVELS OF SIGNIFICANCE (13)
uegrees of Freedom
n»N-1
l
10
11
12
13
14
IS
16
17
18
19
20
21
22
23
24
25
30
35
40
45
50
60
70
80
90
100
125
150
200
300
400
500
Percent Level
Five
0597
0550
0478
0411
0.754
0.707
0466
0.632
0.602
0.576
0353
0332
0314
0.497
0.482
0.468
0.456
0.444
0.433
0.423
0.413
0.404
0.396
0.388
0381
0.349
0325
0.304
0.288
0.273
0.250
0.232
0517
0.205
0.195
0.174
0.159
0.138
0.113
0.098
0.088
of Significance, a
One
IjOOO
0590
0559
0517
0474
0434
0.798
0.765
0.735
0.708
0.684
0.661
0.641
0.623
0.606
0.590
0375
0361
0349
0337
0326
0315
0305
0.496
0.487
0.449
0.418
0393
0372
0354
0325
0302
0.283
0267
0254
0.228
0208
0.181
0.148
0.128
O.US
99
-------
pcrit ' °'388 for
pcrlt " °**** for a " l*
The results of the analysts are shown in Table 4.9.
Sampling and analysis for total dissolved solids (TDS) has the
highest priority. However, due to the high correlation coefficient
betwenn TDS and conductivity, one of the analyses can be eliminated.
Total conforms have the second highest priority. But since the
correlation coefficient between total coll forms and fecal col I forms
is high, analyzing for fecal col(forms Is not necessary. There is
also high correlation in the group BOO, COD, and TOC, thus one or
two memebers can be eliminated or reduced. It can be also seen that
turbidity can replace analysis for suspended solids. One can also
eliminate at least one analysis from the group acidity, alkalinity,
and pH and from the group hardness, col(form and alkalinity. Metals
such as iron, lead, etc., have relatively low priority and at least
one or more parameters from this group can be reduced. Thus, the
following streamlined program could be proposed:
Parameter Prlor Ity of samp11ng
pH high
TOC or COD high
BOD reduced
TKN high
Phosphates reduced
Conductivity or TDS high
Suspended solids
or turbidity high
Lead reduced or not necessary
Mercury reduced or not necessary
Iron reduced
Copper reduced or not necessary
Alkalinity reduced
Hardness reduced
Total coliforms high
Fecal coliforms reduced or not necessary
Sampling for other parameters of the original 22 is not necessary.
100
-------
Table 4.9. CORRELATION MATRIX OF COEFFICIENT, p
Parameter pM
PH
TOC
COD
BODj
TKN
Phosp
Conduct
TOS
SS
Turb
Pb
Hg
Fe
Cu
Alk
A- t A
T CA! 1
Ffnt 1
CKlAr
0
0
0
0
0
0
0
0
0
0.18
0.1
0
0£
Of
0 - no
TOC
0.8
0.68
0
0
0.30
0.25
0.25
0.4
0
0
0
0
0*1
01 A
COO
0.63
0.15
0.18
0.41
0.35
0.40
0.51
0
0
0
0
0\c
A 10
engineering
BOO,
0.18
0.21
0.35
0.48
0.38
0.33
0
0
0
c
Olft
TKN
0.69
0.33
0.41
0.25
0.18
0
0
0
0
relevance;
P
•
0.17
0.20
0.75
0.68
0
0
0
0
Cond
0.91
0.10
0.18
0.28
0.41
0.30
0.38
Of\
A CO
TOS
«
0.18
0.59
0.31
• 23
0.39
0.25
0.41
• 15
• 35
Oejt
0*1
n QO
SS
—
0.
0.
0.
0.
0
89
18
25
58
31
assumed no relation.
T Pb Ho Fe Cu Alk Ac Ca Hard Ha TC FC Cl
--
0.15 -
.3' 0.70 "
0.61 0.18 0.2) —
0.25 0.69 0.59 0.41 --
0 0 0 0 0
-------
4.5 IN-PLANT SAMPLING AND NETWORK MONITORING
If the sampling location has not been predetermined, there are statistical
and other systematic methods of determining the location of sampling
points. However, these methods are only tools to aid sampling personnel
and do not replace the judgment and experience of the personnel.
4.5.1 Segmentation - Priority Technique
This technique can be applied to any large flowing network including an
Industrial plant collection system, a municipal sewerage system, or even
a watershed network. To apply this technique the following Information
must be known:
1. The mass flow rate of the parameter of interest,
2. The range of variation of the parameter Input
PJ • (QWJ Cwj> max ' (Qwj Cwj) mfn
3. The approximate frequency of the fluctuations, p..
1». Values for the coefficient of transformation
through each segment, B.g.
5. Values for the reduction in variation through
each segment, a...
4.5.1.1 Discussion of Methods - Segmentation of the system is done
first by Isolating the locations which modify the waste stream condition,
e.g., junctions of wastewater treatment units, overflows, stormwater
Inflow, sldestreams, lateral sewers, etc. An example of a municipal
wastewater system segmentation is shown in Figure l».15« The system has
16 segments, 12 inside the waste system, k on the receiving water body.
In an Ideal but unrealistic situation one can locate sampling stations
In all segments of the system. With limited economical resources, the
number of sampling points will, of course, be limited. Therefore, there
ts a necessity for a measure to establish priorities of sampling for .each
segment. The measure can be the cross-correlation coefficient between the
two segments. .If a. high correlation exists for the measured parameter
between two segments, one can rely on measurement of the parameter In
only one segment and sampling of the other segment is not necessary. Un-
like the large river monitoring systems, wastewater systems have at least
one fixed location of a monitoring point, such as the influent and/or
effluent of a treatment plant. Using the cross-correlation analysis be-
tween the monitored segment and other upstream and downstream segments
102
-------
Water
. c
S
Plant 1
Storm^
Water
2
)
/
3
S /
_ w — .
Plant 2
/•
k
N
O
5
K
Plant 3
c
6
\7 >
O V.
Intake L_j
Sanitary Waste
, o Q Treatment .. ( ,c
\ T^f } ri^nt f *\ '2 tfh '5
10 1
,6
Bypass I
11
Figure 4.15. Segmentation of a wastewater system
-------
it ts possible to determine segments with low correlation to the
monitored segment. A second consideration should be the worth of the
data measured at the segment. For example, If the magnitude of a'mea-
sured parameter and the magnitude of its variability is insignificant
when related to other segments, the segment will have a low priority
for monitoring.
First PriorIty Sampling Points - The location of at least one sampling
point Is strictly determined by the basic objectives of a monitoring
program, I.e., protection of the environment. This objective requires
that a sampling point be located just before a wastewater discharge to
a receiving water body. If the industry has several wastewater outfalls,
a sampling point should be located downstream from the last outfall. In
the case that the monitoring point is located in the receiving water
body, an upstream station to monitor the upstream water quality and
quantity ts necessary. This will allow the effect of the wastewater
discharge on the receiving water body to be clearly identified. If the
water intake for the Industry Is situated on the same water body, the up-
stream sampling point can be conveniently located at the water intake.
Second Priority Sampling Points - Other Important objectives of a sampling
program can be to monitor the quality of raw wastewater and to evaluate
the efficiency of a treatment process. Thus, a location for a second
priority sampling point would normally be at the Influent to a treatment
plant.
For small and middle size wastewater systems, sampling at the first
and second priority sampling points should be sufficient to meet most of
the'objectives and requirements established by regulatory agencies.
Third Priority Sampling Points - The location of additional sampling
points or sampling sites may be necessary for large wastewater systems
with many inputs. Their purpose is to provide additional information
or warning. In this case, the method of segmenting the wastewater
system and determining sampling priorities for each segment can Be of
use In establishing additional sampling points. Segmentation of a waste*
water system is accomplished by isolating the locations which substan-
tially modify the waste- stream conditions. These features include
junctions of wastewater streams, treatment units, wastewater overflow,
flow dividers, storm, and cooling water inflows, storage reservoirs,
etc. A method of segmentation Is outlined in the following paragraphs.
1. It Is recommended that a linear graph technique be
utilized to represent the wastewater system. Such
a linear graph would consist of nodes and junctions
and branches or lines. All wastewater inputs will
enter the system through the nodes and the nodes
will also separate the branches with different
characteristics. A branch is considered as a
segment with uniform geometric, hydraulic and
-------
transform characteristics. The following depicts
the classification of some typical elements of a
wastewater system.
Nodes • manholes, change of slope, change of
diameter of conduits, flow dividers,
junctions of sewers and channels, out-
falls, influent and effluent to treat-
ment steps, etc.
Branches - conduits, channels, treatment steps,
by-pass, adjacent receiving water
bodies, storage reservoirs, holding ponds,
etc.
For the industrial water/wastewater system of Figure
1».I6 a linear graph representation Is shown in
Figure k.}J.
2. In segregating the system, each node should be
uniquely numbered. Wastewater Input to each
node should be characterized by the range of
variation
PJ • (Q»J
which Is, basically, the range of waste loads to the
node j. The units of P. will be g/sec if the flow
Q Is expressed In or/sec and concentration, c in
mgVl ([g/sec] • [m3/sec] * [mg/1]). It might be
convenient also to know the approximate frequency
of fluctuations of the Input P.. A node table such
as Is shown on Table *». 10.should be prepared.
3. Each branch Is identified by a double identification
subscript A6 where A Is the number of the upstream
node and B is the number of the downstream node.
Coefficients of transformation, BA» and °AO should be
assigned for each branch. The coefficient of trans-
formation, B.p, describes roughly how the variability
of the wastewater is reduced in the segment. In most
cases, the coefficient of transformation, $._, can
be determined approximately from the geometry of, the
segment and treatment parameters. The coefficient,
a.* describes how the correlation Is reduced In the
segment. The following values of the coefficients
are recommended:
105
-------
I
I
I
I
t
PROCESS
I
PROCESS
2
SEDIMENTATION
AND
NEUTRALIZATION
PROCESS
3
HEAVV
METALS
REMOVAL
SANITARY
WASTE
SANITARY
WASTE
IHTACE
PROCESS
*
PROCESS
5
FLOTATION
AND TOXICITY
REMOVAL
EQUAL IZATIQt
AND
STORAGE
BIOLOGICAL
TREATMENT
PLANT
SLUDGE
HANDLING
SLUDGE
SOLIDS
EFFLUENT
MONITORING
Figure 4.16. An Industrial water/wastewater system
-------
o
•—i
oo
oo
SEGMENT -
SEVER OR
CHANNEL
SEGMENT - TREATMENT
PRIMARY SAMPLING SEGMENT
SECONDARY SAMPLING SEGME
Figure 4.17* Linear graph representation of an industrial water/wastewater system
-------
6AB ttAB
Short sewers and channels 1.0 1.0
Plug flow treatment steps, long „
sewers and channels with decay e 0.9-1.0
Completely mixed treatment steps I-E /100 0.85-0.95
with short detention time
(t « 1/f)
Completely mixed treatment steps I
with long detention time i/2(l+Kt)tf
(t » l/f)
Storage and equalization I
reservoirs and holding ponds
with no decay / 2tf / 2tf
AB • double identification subscript
K -decay coefficient In the segment
(base e), day"'
t • detention time In the segment, days
f « frequency of fluctuations of waste
inputs
E • treatment efficiency in percent
Determine approximate ranges of wastewater quality
variations for each segment. This can be done
approximately by starting at the most upstream nodes
containing wastewater inputs and moving downstream.
The variability will be modified by mixing downstream,
by the buffering capacity of segments, and by new
wastewater inputs (such as process discharges) in
downstream nodes.
Figure 4.18 Illustrates how this procedure is
accomplished. JK Is the most upstream node con-
taining a wastewater input and would therefore be the
starting point. The range of wastewater variability
will be:
where rJK is the wastewater quality variation range
in segment JK downstream from J. Above the downstream
node K the variation range becomes:
108
-------
Variability Range
"JK
rJK " rJK *
r* - rK
KL JK
rKL " rKL * 8KL
'KL
'KL
rLM-/TT
M L . K
rLM " rLM BLM
(PL,
'LM
"MM
Monitoring
Point
Figure A.18. Estimation of variability and correlation in segments
109
-------
At a node the variability range can be changed
by wastewater inputs to the node and by other
upstream branches entering the node. For a
case where more than one input enters a node.
the following relationship (Propagation, of
Errors) can be used to compute the variability
range:
Where A denotes the node under consideration,
B denotes a node Immediately downstream from A,
IA represents the upstream branches entering
node A, and Pt/\ represents the wastewater inputs
entering node A. In Figure A.17, the above
formula is used for node L.
The variability ranges for all segments In a net*
work can be computed using the relationships de-
scribed above and shown on Figure 4.18. it is
recommended that the variability range be checked
by known data from a survey or monitoring. The
above procedure should give adequate results
assuming that all inputs to the system are random
and uncorrelated to each other.
Determine the approximate correlation coefficient
for each segment's water quality variations related
to the variations in the monitored segment. The
correlation coefficient for the monitored segment,
PMN, Itself equals of course 1.0. Moving further
downstream or upstream the correlation coefficient
will decrease as the relation between the wastewater
fluctuations in the monitored segment and the segment
downstream or upstream diminishes. The change Of the
correlation coefficient can be roughly estimated as
fo11ows:
In a Branch; multiply the p by coefficient o
In a Node; multiply the correlation
coefficient by the ratio:
no
-------
where B is the node under consideration, AB Is the
branch located further away from the monitored seg-
ment, and BC is the branch located closest to the
monitored segment.
6. Additional sampling points should be located at
the segment where theoretically, the correlation
influence of the monitored point ends. Since the
correlation influence of both points extends both
downstream and upstream there will be an overlap
such that each sampling point will.have an area of
Influence to p • /p~~" where PC is the correlation
level on which the hypothesis of the existence of
a correlation between two water quality records Is
denied. Table 4.8 gives the values of the critical
coefficient of correlation, pc. If the number of
samples Is not'known, a value of pc « 0.25 - 0.30
will give a good estimate.
7. If there are several segments to be monitored,
i.e., one or more segments have a correlation level
less than the critical pc, the priority can be de-
termined according to the magnitude of the variability
range rjt for the segment ij. The segment with the
highest rjt will have the highest priority.
8. Once a new sampling location is established, the
procedure shall be repeated to find the next sampling
location.
9. This procedure should also be repeated for each important
parameter.
4.5.1.2 Example of Segmentation Technique
Determine the location of sampling points for the wastewater system
given In Figure 4.16. The analysis will be based on the COD information
representing the organic load to the system.
Step 1 - Divide the system into segments such as on the linear graph
representation in Figure 4.17*
II
-------
Step 2 - Locate a first priority sampling point (P) at the effluent
channel (segment 1-2). Locate second priority sampling points (S) at
the Influent to the treatment plant (segment 4-5) and in the receiving
water body (upstream and downstream from the waste discharge).
Step 3 - Estimate the variability range of the Inputs to the system
(Table 4.10)
Step 4 - Estimate the coefficients of variation ft and a for each seg-
ment (Table 4.11).
Step $ - Estimate the variation range in each segment. Proceed from
the most downstream and work upstream (Table 4.12 left portion).
Step 6 - Estimate the coefficient 6f correlation of wastewater vari-
ations In each segment as related to the nearest monitored segment,
I.e., to the segment 4-5. Proceed from the monitored segment (p - 1.0)
and work upstream (Table 4.12 right portion). Each segment is correlated
to the segment immediately downstream toward the monitoring point.
At this stage developing a correlograph (Figure 4.19) wilt aid In the
decision process In Step ?•
Step 7 * Once the correlation coefficients are estimated find those
where p < pc, with pe estimated to be 0.30. Based on this criterion
the priority for monitoring should be In segments 17-18, 16-17. 14-15,
13-14, 12-13, 16-19. However, when one segment is chosen for monitoring,
the upstream and downstream segments will usually have a high correlation
and, therefore, only one segment needs to be monitored. The second
criterion Is the magnitude of the variability, rjt, for the segments with
low correlation levels. Both the p and rji values should be examined for
these segments, the requirements and objectives of the program should be
considered, and then professional judgment must be excercised.
In this example segments 17-18, 16-17, and 16-19 are neighboring segments
with low correlation levels. Looking at the variability values, segment
16-19 has the highest value, indicating the greatest fluctuations in
wastewater quality. Therefore, of these three,segment 16-19 might have
the highest priority. Segments 14-15, 13-14, and 12-13 are also neighboring
segments with low correlation levels. Segment 13-14 has the greatest
variability and therefore would be chosen of the three. Since its
variability Is much higher than that for segment 16-19, it would have the
highest overall priority. At this stage correlation and variability
values can be recalculated to see If monitoring at these points would
satisfy the program requirements. If not, the procedure should be
repeated.
112
-------
Table 4.10. WASTEWATER LOADS TO NODES
CONSTITUENT: COD
Node
1
2
3
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Maximal Loading
p/sec
0
0
0
0
10
0
30.0
0
0
175
0
0
66.0
109
0
0
42
121.50
Minimal Loading
e/sec
0
0
0
0
1.2
0
6.0
0
0
100
0
0
17.0
21.0
0
0
23
93.0
pj
0
0
0
0
8.8
0
24.0
0
0
75
0
0
49.0
88.0
0
0
19
28.5
Fluctuations of maximum and minimum at most nodes - 1/8 hrs
113
-------
Table 4.11. COEFFICIENTS OF VARIATION IN BRANCHES
Branch
1-2
2-3
3'*
4-5
5-6
*-7
7-8
8-9
5-10
10-11
5-12
11-13
13-H
IV IS
7-16
16-17
17-18
16-19
Description
Effluent Channel
Activated Sludge Plant
Equalization Basin
Sewer
Sewer
Sewer
Sewer
Sewer
Neut ral 1 cat Jon PI ant
Sewer
Sewer
flotation Unit
Sewer
Sewer
Sewer
Sewer
'Chemical Coagulation
Sewer
$
1.0
O.I
0.2
1.0
1.0
1.0
1.0
1.0
0.9
1.0
1.0
0.5
1.0
1.0
1.0
1.0
0.7
1.0
•a
1.0
0.4
0.2
1.0
1.0
1.0
1.0
1.0
0.9
1.0
1.0
0.5
1.0
1.0
1.0
1.0
0.7
1.0
-------
Table k.\2. DETERMINATION OF THE SAMPLING PRIORITIES OF SEGMENTS
Segnent Upstreaa variation range DoMnstreaii variation range
t- (tr* » Ipl)°'S r. - r • 6
"u » " da
Correlation coefficient In the
at the dowistreaei node at tne opstreaej node
«•„.»,)_•. • • • •
Priority tar
tertiary •a«tt*rlnf
16-19 28.5
>7-«8 13.0
IJ-17 U.J
7-18 (Z8.52 » U.J*)°'$ - 3>.»5
19-11 75
9-10 75
8-9 «7.5
7-S (67.S2 *2*2)°-S-71.«»
6-7 <71.M* * J1.*5*)°'5 • 78.1*
5-6 (T8.2*2 * 8.82)0'5 - 78.73
14-15 88.0
13-1* (88? » W1)0'5 - 100.7Z
12-13 100.72
5-12 50.36
4-5 (78.7J2 + 50.362)0'5 - 96.U
28.5
13* 0.7 • 1J.3
13.3
31 -»5
75
75 • 0.9 • 67.5
67.5
71.64
78.24
78.73
88.0
100.72
100.72 * 0.5 • 50.J6
50.36
96.12
0.33 • 2S.SI/31.4S -0.30
0.14
0.33 • 13.3/31 -»S • O.I*
0.81 • 31. 45/78- »4 -0.33
0.63
0.70
0.81 *71.6*/78.2* -0.7$
0.82 * 78.24/78.73 • 0.81
1.0* 78.73/96.12 • 0.82
0.26 • 88/100.72 • 0.23
0.26
0.52
1.0 * 50.36/46.12 • 0.52
1.0
0.30
0.14, 0.7 • 0.10
0.14
0.33
0.63
0.7 • O.J - 0.«3
0.70
0.75
0.81
6.82
0.23
0.26
0.52 • 0.5 • 0.21
0.52
1.0
Tt
T3
Tl
Initial
•onItorIng
-------
S • Monitored segment
T,, T_, T. » First, second, third
* * priority segments
for monitoring
p *
p - O.I* p - 0.10
rt. * 13.3 r,j * 13-3
p - 0.75
r,, -71.6*
P - 0-81
.
p - 0.82
r,,- 78.73
IJ
p • 0.23
'IJ-88
p « 0.26
r - IQ0.72
p • 0.26
r., - 50.36
p • 0.52
r.t -0.52
e/ t v:
P - »•«
r - 96.«M[LJ
segment
Figure *.19. Correlograph for segments
-------
fr.5.2 Probability of Exceeding a Standard
In locating sampling points In a receiving water body the probability of
exceeding a receiving water standard should be considered. For all
conservative substances and all non -conservative substances except
oxygen and possibly temperature and nitrates, the critical section would
be located immediately downstream from the outfall. The section with the
maximum probability of violating the dissolved oxygen standard will be
further downstream near the "sag-point". The location of the critical
point can be approximately evaluated as follows
The probability that the dissolved oxygen standard will be exceeded is:
2
exp
where Z - DS " 5 (x)
and C « dissolved oxygen concentration
C$» dissolved oxygen standard
0 • oxygen deficit
D » maximal allowable oxygen deficit
D (x) • average oxygen deficit at distance x from the outfall
) ( x) • standard deviation of the deficit at the distance x
It can be seen that to find a maximal p(C < Cs) it Is sufficient to
find min Z or to find a location x where
D8 - D(x)
- min (Z)
The average dissolved oxygen can be computed from the equation
K.L if v ~^? TT 9 —
D(x).—LS (e ~K1 J - e U) + DQ e ZU
H7
-------
where L * average BOD discharge
K. * coefficient of deoxygenatlon
coefficient of reaeratlon
D - Initial oxygen deficit
.o
U » stream velocity
the standard deviation of the oxygen fluctuation can be related id
the fluctuation of the BOO discharge as follows (\k, 15, 16):
where
. X ~K X
( e t "e 1 U)
. •
$, • Standard deviation of the BOD discharge
o
Since D< ts a given constant the conditions satisfactory for flhdlnd x
with max p (D(x) > D$) is
The distance x^ can be found by plotting y*| vs. * for given
tLt ki artd u-
118
-------
4.6 REFERENCES
1. Potter, H. A., Theoretical Frequency Curves and Their Application
to Engineering Probferns, Trans. ASCE Paper, 1532, p. 142-173,
1924.
2. Owen, Donald, B., Handbook of Statistical Tables, Add I son-Wesley
Company, Reading, Mass.
3. Associated Water and Air Resources Enginbers, Inc. Handbook For
Industrial Wastewater Monitoring, U.S. EPA Technology Transfer,
7-1 to 7-8, August, 1973.
4. A Uniform Technique For Determining Flood Flow Frequencies,
Waslngton, D.C., Water Resources Council, Bulletin No. 15, 1967.
5. Sparr, T. M., and R. W., Hann, Variation of the Municipal Waste
Effluent Quality and The Implication for Monitoring, (Presented
at International Seminar and Exposition on Water Resources
Instrumentation, Chicago, June 4-6, 1974).
6. Montgomery, H. A. C., and I. C., Hart, The Design of Sampling
Programmes for Rivers and Effluents, Water Pollution Control
(London, England), 73_: 77-98, 1974.
7. Bendat, J. S., and A. G., Pterson, Random Data: Analysis and
Measurement Procedures, New York, Wiley - Interscience, 1971.
8. Drobny, N.L. Monitoring for Effective Environmental Management.
Proc. ASCE National Water Resources Engineering Meeting. Atlanta,
Georgia. January 24-28, 1972.
9. Gunnerson, C.G. Optimizing Sampling Intervals. Proc. IBM
Scientific Computing Symposium, Water and Air Resources Management.
White Plains, New York, 1968.
10. Sparr, T.M. and D.J. Schaezler. Spectral Analysis Techniques for
Evaluating Historical Water Quality Records. (Presented at Inter-
national Seminar and Exposition on Water Resources Instrumentation.
Chicago. June 4-6, 1974.
11. Wastler, T. A., Application of Spectral Analysts to Stream and
Estuary Field Studies, U.S. Dept. of Health, Education & Welfare,
Cincinnati, OhTo, p. 27, November 1963.
12. Kaesler, R.L., J.J. Cairns, and J.S. Grossman. Redundancy in Data
From Stream Surveys. Water Research. 8_: 637-642, August 1974.
13. Fisher, R.A. and F. Yates. Statistical Tables for Biological,
Agricultural and Medical Research. London, Oliver and Boyd, 1949.
19
-------
\k. Chamberlain, S. G.» C. V. Beckers, G. P. Grlmsrad, and R. D. Shu It,
Quantitative Methods for Preliminary Design of Water duality
Surveillance Systems, Water Resources Bulletin, 10: 199-219,
April
15. Thomann, R. V. , Variability of Waste Treatment Plant Performance.
Journal ASCI Sanitary Division. 9£: 819-837, January 1970.
1.6. Eckenf elder, W. W. , .Water dual tty Engineering for 'Practicing
Engineers, New York, Barnes and Noble, 1970.
120
-------
1.000 C- PROGRAM AUTO-STATISTICS
2.000 C *#**********************************
3.000 C COMPUTES AUTOCORRELATIONS AND AUTOSPECTRA
4.000 C *********************************************
5.000 DIMENSION X(lOOOr10)>XM<10)»VAR<10)»ACOV<150»10),W<10
6.000 PO)»SPEC<150»10)
7.000 READ<5»10> NSrN»MAXM,DELTA i
8.000 WRITE<6»70> NS»N>MAXM»D£LTA
9.000 70 FORMAT<3I5»F11.6>
10.000 C *********************************************************
11.000 C NS- NO OP X SERIES
12,000 C N = NO OF VALUES IN A SERIES
13.000 C MAXM= MAX LAGS NO
14.000 C DELTA * TIME INCREMENT
15.000 C ***********************************************
16.000 DO 60 I-lrN
17.000 READ(5»ll)
-------
0>
I
•rt
U.
50.000 C ***********************
51.000 C AUTOCORRELATION
52.000 C ***********************
53.000 MAXL-MAXM+1
54.000 DO 34 J-1?NS
55.000 DO 35 I«1»MAXL
56.000 ACOV=ACOV+X*X
66.000 28 CONTINUE
67.000 ACOV
71.000 WRITE<6»16)
72.000 DO 29 I=1,MAXL
73.000 DO 80 J=lfNS
74.000 W
75.000 80 CONTINUE
76.000 K=I-1
77.000 AD=K*DELTA
78.000 URITE<6fl7)ADr(UrJ»lrNS)
79,000 29 CONTINUE
80.000 IS FORHAK39H LAG TIME AUTOCORRELATIONS)
81.000 16 FORMAT(100(1H=))
82.000 17 FORMAT(F5.1»(10F13.2))
83.000 C ***************************************
84.000 C AUTOSPECTRUM
8S.OOO C *************************************
86,000 NF=2*MAXM
87.000 MAXL=MAXM-1
88.000 DO 43 J=lrNS
89.000 DO 40 K=lrMAXL
90.000 RK=K
91.000 W(K)=0.5*(l-fCOS(3.14157*RK/MAXM))
92.000 40 CONTINUE
93.000 NP=NF+1
94.000 DO 42 1=1>NP
95.000 IX=I-1
96.000 SPECdf J)=0.0
97.000 DO 41 K=lrMAXL
98.000 RK=K
99.000 KZ=K-H
100.000 SPECfACOV(KZ»J)*M
101.000 41 CONTINUE
102.000 SPEC(I.J)=2*DELTA*
107.000 DO 44 I=1»NP
108,000 IX=I-1
109,000 FREQ=IX/<2.0*DELTA*NF>
110.000 URITE(6r50) IX»FREQr(SPEC(I»J)»J=lrNS)
111.000 44 CONTINUE
112.000 18 FORMAT(41HLAG NO FREQUENCY AUTOSPECTRA)
113.000 19 FORMAT(100(1H=)>
114.000 50 FORMAT(I5>3X»F11.6r2X>UOF14.3»
115.000 STOP
116.000 END
122
-------
CHAPTER 5
SAMPLING MUNICIPAL WASTEWATERS
5.I BACKGROUND
Municipal wastewater consisting of the spent waters from a community is
treated by chemical, physical, or biological means prior to discharge to
surface waters. Three stages of treatment are commonly used at municipal
treatment plants (l): primary (screening, sedimentation), secondary
(activated sludge, trickling filter etc.), and tertiary (physical/chemical
treatment). The wastewater characteristics vary with the size and habits
of the community, the type of collection system (combined or separate),
the amount of infiltration, and the type of industrial discharges.
5.2 OBJECTIVES OF SAMPLING PROGRAMS
5.2.1 Regulatory
Sampling of municipal wastewaters is required by regulatory agencies for
the NPDES permit program (2). The location of sampling points, frequency,
sample type, etc. are specified in the permit.
$.2.2 Process Control
In addition, sampling is performed at municipal treatment plants for pro-
cess control purposes. This monitoring provides a check on the efficiency
of the process allowing the operator to make adjustments to optimize the
process efficiency.
5.2.3 Research
The special needs of a research project will dictate the sampling program.
Hence each project must be considered individually and no general guidelines
can be given.
5.3 FREQUENCY OF SAMPLING
5.3.1 Established by Regulation
Follow the frequency requirements indicated in the permit issued by the
regulatory agencies.
123
-------
5.3.2 Use of Statistics
Apply spectral analysis techniques (Section *».3.2) to establish the opti-
mum frequency. If the data required for this technique is not available:
1. Conduct a week-long survey collecting hourly samples. (Choose
a week of high industrial production).
2. Determine if any unusual industrial or community discharge
occurred during the sampling period (e.g. an extensive spill
or extremely heavy rainstorm) which may invalidate the data
and necessitate a repeated survey.
After data collection, the analysis of data should be performed as out-
lined previously.
5.3.3 Surveillance Purposes
A poll of EPA Surveillance and Analysis Labs indicated a general concurrence
that for normally variable domestic wastewaters a minimum of 8 evenly-
spaced grab samples collected over a 2k hour period, repeated for a
minimum of 3 weekdays, will result In a fair estimate of water chemistry
characteristics (3).
5.3.** Other Considerations
Follow interim sampling frequencies prior to the generation of data for
statistical analysis. Frequencies appear in Tables 5.1 and 5.2.
5.4 LOCATION Of SAMPLING POINTS
5.A.I Effluent Monitoring
Use effluent monitoring points established by regulatory permits.
Sample the effluent in a combined effluent pipe or mixing chamber and
avoid accumulated grease and oil. For BOD analysis, it is recommended
that samples be collected prior to the disinfection step because of
severe problems associated with the BOD test for disinfected effluents
When manually compositing effluent samples according to flow and when an
effluent flow measuring device Is not available, use the Influent flow
measurement without any correction for time lag. The error between the
Influent and effluent flow measurement Is Insignificant except In
those cases where large volumes of water are Impounded (such as in
reservoirs) as a result of Influent surges coupled with highly restrictive
effluent discharge (5).
-------
Table 5.1. PROCESS TESTING GUIDE (From 6)
PROCESS
TEST
FREQUENCY
Grit
RemoveI
Primary
Sedimentation
Activated
Trickling
Filter
Oxidation
Ponds
Final
Sedimentation
PRETREATMENT
Volatile Solids Dally
Total Solids Dally
Moisture Content Dally
PRIMARY TREATMENT
Settleable Solids Dally
pH Dally
Total Sulfldes Dally
Biochemical Oxygen Demand Weekly
Suspended Solids Weekly
Chemical Oxygen Demand Weekly
Dissolved Oxygen Weekly
Grease . Weekly
SECONDARY TREATMENT
Suspended Solids Dally
Dissolved Oxygen Dally
Volatile Suspended Solids Weekly
Turbidity Dally
Suspended Solids Daily
Dissolved Oxygen Dally
Dissolved Oxygen Dally
Total Sulfldes Dally
Total Organic Carbon Weekly
Total Phosphorus Weekly
Settleable Solids Dally
pH Da 11 y
Total Sulfides Dally
Biochemical Oxygen Demand Weekly
Suspended Solids Weekly
Chemical Oxygen Demand Weekly
Dissolved Oxygen Weekly
Turbidity Dally
MBAS Weekly
This Is a minimum sampling guide, and is subject to change with plant
site, complexity of operation, and problems encountered.
125
-------
Table 5.1. (Continued)
PROCESS TESTING GUIDE* (From 6)
PROCESS
TEST
FREQUENCY
ChiorInation
Thickening
Digestion
Centrlfuglng
Vacuum Filters
Incineration
Chemical
Coagulation t,
Flocculatlon
Activated
•Carbon
Recarbonation
Ammonia
Stripping
Filters
Mlfcroscreen
DISINFECTION
Chlorine Residual
MPN Coliform
SOLIDS HANDLING
Suspended Sol ids
Volatile Solids
Total Solids
Volatile Solids
pH
Gas Analysis
Alkalinity
Volatile Acid
Suspended Solids
Volatile Solids
Sludge Filterability
Suspended Solids
Volatile Solids
Ash Analysis
ADVANCED TREATMENT
Jar Test
Phosphorus Analysis
Apparent Density
COD
TOC
pH
Ammonia Nitrogen
pH
Suspended Sol Ids
Turbidity
Suspended Sol ids
Chemical Oxygen Demand
When
When
When
When
When
When
Dally
Weekly
Daily
Dally
Weekly
Weekly
Dally
Weekly
Weekly
Weekly
in Operation
in Operation
in Operation
in Operation
in Operation
in Operation
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Weekly
Dally
Dally
Daily
Weekly
This Is a minimum sampling guide, and is subject to change with plant
site, complexity of operation, and problems encountered.
126
-------
Table 5.2. RECOMMENDED MINIMUM SAMPLING PROGRAMS FOR MUNICIPAL
WSTEUATER TREATMENT PROCESSES (From 7)
^
T-p
PH
BOO
00
SS
•H,-.
TKH
NO.-II
P-T
Turb
TS
TVS
Set. S
SI. Vol.
COO
V. SS
Air Input
S
1
S'F*
C I/O
G I/O
C 2/W
G 3/W
C 3/W
C I/W
C I/W
C I/W
C 1/W
R
C 2/W
C 2/W
S
**
8
«.
_ TI
• •
1 1
•• E
t. k
e •.
C 2/W
e 3/w
G 2/W G I-3A
C2/W
G 3/W
C I/W
e j/w
& •
1 =
• _c
• — •
•i U •
3 £ *
G I/O
6 5/W G 3/W
C 2/W C 2/W
fr 5/W G I/O
C 5/W
C I/O
C I/O
C 1/0
C 3/W
kf
C 3/W
C 2/W C 2/W
R
|
1 C
1 !
G 1/W
G 1/W G 1/0
C 2/W
G I/W
C 3/W
C I/O
C 1/W
C 1/0
C I/O
Ho
G 3/W
G I/O
. | - |
ill!
• :- i i
z " y «
5 S - o
2 * - i
•J U Z ^
G I/O G 3/0
G I/O G 1/0 G 3/0 Ho
.• or Ho
C I/O
C 1/W
C 1/W
C 1/W
e 3/w
R
G 1-3/W C 1/W
G 3/0
S
•*
| e 2 g
S | 3 |
z s I " 5
5 > I 1 5
^ •* c 5 *~
G
Ho G
G Back- G 1/W G 2/W G
wash
G
G Back- G 1/0 G I/O G
wash
R
G 1/0 G 1/0 G
6
G 1/H G
C 3/W
•
J
•1
8
o
V
£
S
1/0
1/0
Diap
3/W
Owp
2/W
2/W
3/W
g
4*
u
3
i
•
^
5
s
Ha
G
G
G
G
G
S
•«
*
•
O
o
u
1
<
F
I/O
1/0
1/W
I/W
2/W
-------
Table 5.2 (continued). RECOMMENDED MINIMUM SAMPLING PROGRAMS FOR MUNICIPAL
WASTEWATER TREATMENT PROCESSES (Fran 7)
•V **
1 s
S* F2 S F
Micro Analysis
Ortho-P
Chlor. Resld.
Co II font
Fecal Coll.
Alk. e 2/W
Jar Test
Hardness
Sludge Vol.
Oil- S C 2/M
NBAS
"etal* e 2/M
Plant Flow R
1. S • type of staple
2. F • frequency
M Primary Clarification
n
M Activated Sludge
n
w Trickling Filter
*
G 2/W
C 3/W
G 3/0
G
C
D
W
N
R
Ho
» Aerated Pond
w
» Secondary Ponds
n
» . Secondary Clartfter
n
C I/O
c i/w
G 3/0
Grab
2* hour composite
Day
Week
Month
Record continuously
Monitor continuously
u
1
V
k
O
u
G I/O
ft
G I/W
G I/W
C 1/M
C I/W
o Chemical Treatment
n
C 3/W
c a/w
* Nitrogen Removal
q
" Two Stage Recarbon
n
» Filtration
e i/r
c i/w
G 3/W C 1/W
I 0
c • fi 8 c -
O k O — C *S *
< M < Wt <
G 2/W G 1/0
C 1/0
-------
5.^.2 In-Plant Locations
Apply the statistical technique outlined In Section 4.5.1 to determine
in-plant sampling locations. In addition to these locations, sample
all other unit processes periodically or when the variability of a
parameter adversely affects the efficiency of a unit process.
5.5 NUMBER OF SAMPLES
Use one or more of the following methods to determine the number of
samples:
I. Follow permit requirements by regulatory agencies.
2. Apply statistical methods in Section k.2 to the data from the
preliminary survey.
3. Use the frequency data to establish number of samples (e.g. I
sample every 6 hours will establish k samples per day).
5.6 PARAMETERS TO MEASURE
5.6.1 NPDES Requirements
Analyze all parameters as required for the NPDES permit system.
5.6.2 Other Parameters
Monitor the following parameters routinely, regardless of plant size. (8)
1. BOD 3. pH
2. Suspended Solids A. Flow
Secondary analyses include:
I. Fecal Col I form and Chlorine Residual 7. Phosphorus
2. Temperature 8. Dissolved Solids
3. Dissolved Oxygen 9. Alkalinity
*». Total Solids 10. Metals
5. Total Volatile Solids 11. COD
6. Nitrogen Series 12. Oil and Grease
Table 5.2 indicates the parameters to analyze for various unit processes.
Changes are allowed to compensate for specific plant conditions.
129
-------
5.7 TYPE OF SAMPLE
Use composite samples for alt overall monitoring (9) and grab
samples for checking individual unit processes. Use one
of the following types of composite samples to properly estimate
mass loading:
1. Continuous, volume proportional to flow
2. Periodic, volume constant, time proportional to flow since the
last sample.
Other composite types may be used If comparable results can be
demonstrated.
5.8 METHOD OF SAMPLING
Use automatic samplers whenever routine monitoring or process control
Is the objective. The Inaccuracies caused by untrained personnel .
collecting samples must be avoided (10). If manual grab samples are
necessary, allow only trained personnel who understand the Importance of
sampling to collect them.
5.9 AUTOMATIC SAMPLERS
Automatic samplers for municipal wastewaters must be capable of collecting
representative suspended solids samples throughout the collection and
treatment system. While sampler selection will depend on site conditions,
the following guidelines are suggested:
1. For sampling raw wastewater and primary effluent, use a sampler
having an intake velocity greater than 0.76 m/sec (2.5 ft/sec).
For sampling a final effluent with no visible solids, a sampler
having a lower intake velocity may be acceptable (3).
2. To determine the effectiveness of an automatic sampler to collect
suspended solids, statistically compare the suspended solids
values of the composite sample from the sampler with the mean
value of manual grab samples, with a minimum compositing period
of six hours and a maximum Individual sample frequency of one
hour (15). The acceptable ratio of sampler to manual grab
suspended solids values varies throughout the plant: influent
and primary effluent - 1.6-2.0; final effluent - 0.9-1.3 (3,11).
130
-------
5.10 VOLUME OF SAMPLE AND CONTAINER TYPE
For analyzing BOD, suspended solids and pH, collect a minimum volume of
2 I (0.6 gal.) (12). Use a separate sterilized container for coliform
analysis. Collect chlorine residual or oil and grease samples in a
glass container. Plastic is acceptable for the other recommended
analyses. Specific information by parameter type is given in Chapter 10.
5.11 PRESERVATION AND HANDLING THE SAMPLES
Follow the techniques Indicated In Chapter 10 to preserve the sample.
Composite samples should be iced during the compositing period.
5.12 FLOW MEASUREMENT
Establish a permanent flow measurement station at the influent to the
plant (after coarse screening) If none exists. Use a Parshall flume
and non-foul Ing secondary measurement device. Individual flow measurement
to unit processes can also be monitored for process control purposes.
As stated In Section 5.^.1, the flow rate of the effluent can In most
cases be considered identical to the influent flow with no time lag.
5.13 REFERENCES
1. Metcalf and Eddy, Inc. Wastewater Engineering. New York, McGraw-
Hill, 1972.
2. Federal Water Pollution Control Act, as amended 33 USC 1251 et req,
86 Stat. 816, P.L. 92-500.
3. Harris, D. J. and W. J. Keffer. Wastewater Sampling Methodologies
and Flow Measurement Techniques. EPA Report No. 907/9-74-005,
June 197*».
k. Henderson, F. M. Open Channel Flow. New York, MacMIIIan Co., 1966.
5. Barth, E. F. U.S. EPA Inter-office memo dated August 22, 1975.
6. URS Research Co., Environmental System Division, San Mateo CA94402.
Procedures for Evaluating Performance of Wastewater Treatment Plants.
Prepared for EPA Office of Water Programs. No. 68-01-0107.
7. Estimating Laboratory Needs for Municipal Wastewater Treatment
Facilities. EPA, Washington, D.C. No. 68-01-328. June 1973
p. A-l through A-29.
8. Water Pollution Control Federation Highlights. Vol. 12, H-1,
April 1975.
131
-------
9. Brown, L.C. Efficient Strategies for Sampling and Monitoring.
Paper presented at Intl. Seminar and Exposition on Water Resources
Instrumentation. Chicago, June 4-6, 1974.
10. Personal communication to Environmental Sciences Division, Envlrex
Inc. from Mr. Lawrence A. Ernest, Plant Superintendent, Metropolitan
Sewerage Commission, Milwaukee, Wl
II. NF1C-Denver. Comparison of Manual (Grab) and Vacuum Type Automatic
Sampling Techniques on an Individual and Composite Sample Basis.
EPA Report No. 330/1-74-001. September 1974.
12. American PublIc Health Association. Standard Methods for the
Examination of Water and Wastewater. 13th Edition, New York, 1971,
p. 874.
132
-------
CHAPTER 6
SAMPLING INDUSTRIAL WASTEWATERS
6.1 BACKGROUND
Industrial wastewaters vary In contamination, flow, frequency, and type
of discharge. This chapter presents general guidelines and considerations
so that effective sampling programs can be established for varied
situations.
6.2 OBJECTIVES OF SAMPLING PROGRAMS
6.2.1 Regulatory
The emphasis on industrial wastewater monitoring has increased with the
necessity to obtain a permit for discharging wastewater into navigable
waters (1). The permittee is required to compile and maintain records
of all monitoring activities as specified by the permit. Depending on
the nature of the discharge, the sampling frequency and parameters may
differ significantly.
6.2.2 Other Objectives
There are other reasons for industrial sampling as summarized by Black (2):
1. Determining quantities of polluttonal materials
discharged during a 2^-hour day and per unit
weight of product.
2. Locating major waste sources within the plant
to permit computing of constituent balances.
3. Exploring potential recovery from a given
department or unit process, considering pro-
cess modifications, and studying the economics
thereof.
133
-------
4. Defining factors Influencing character of
wastes from a given department or unit process.
5. Investigating and demonstrating variations In
character and concentration of combined wastes.
6. Establishing a sound basis for treatment of
residual wastes.
Therefore, an effective sampling program can not only meet regulatory
requirements but also reduce material losses and hazardous discharges
and determine system malfunctions.
6.3 FREQUENCY OF SAMPLING
6.3.1 Established by Regulation
Use permit requirements when compliance monitoring Is the objective.
If the sampling frequency is not specified by regulation, use the
statistical methods as discussed below.
6.3.2 Use of Statistics
Apply the statistics outlined in Section 4.3.2 to obtain frequency of
sampling whenever possible. Background data must be collected to
determine mean and variance. One of the following procedures can be
used to obtain this information (listed in order of preference) if it
has not been previously collected:
1. Conduct a week long preliminary survey consisting
of the hourly samples to characterize the system.
2. Conduct one .24-hour survey taking hourly samples
(as outlined in Section 2.4). Analyze individual
samples if batch dumps are suspected. Any weekly
pattern must be considered and samples taken on
the day of the greatest variation of the para-
meters of interest.
3. Obtain data from a plant with the same type of
industrial operation. However, where processes
differ, take samples to quantify the variation.
After data collection, use production figures to determine extreme
values, assuming a linear operating relationship (which is not always
the case).
134
-------
6.3.3 Other Considerations
Consider variable plant operations when determining frequency:
I. Seasonal operation
2. Less than 2k hour per day operation
3. Special times during the day, week or month set aside for cleanup
k. Any combination of the above*
When monitoring these types of operations, It Is necessary to sample
during normal working shifts in the season of productive operation.
Figure 6.1 gives procedures for the various situations.
6.4 LOCATION OF SAMPLING POINTS
6.4.1 Effluent Monitoring
Regulatory permits establish effluent monitoring points within a plant.
The permit may specify only the total plant discharge or a specific
discharge from a certain operation or operations. Consult permits for
these locations, or use those recommendations for obtaining representative
samples given in Section 2.5.
6.4.2 In-Plant Locations
In-plant sample locations are necessary if process control is the
objective. Use the statistical techniques outlined In Section 4.5.1
to establish the critical sampling locations within the plant. A
preliminary survey may be required to determine the variability of
the individual discharges. If a point of upset exists within the
plant, establishment of a sampling station or monitoring equipment at
that point will allow early detection.
Batch discharges may also require individual sampling stations to
establish their total impact on a discharge stream.
6.5 NUMBER OF SAMPLES
There are two ways to determine the number of samples:
1. Follow requirements from permit for regulatory monitoring.
2. Apply statistical methods (Section 4.2) to data from a
preliminary survey.
135
-------
Plant
Operation
Constant
2k hour per
day work
shift
Variable
Ho Individ-
ual cleanup
discharges
Year round
operation
Less than
2k hour day
Sample at all
times with
special empha-
sis on worse
than average
days
Specific
cleanup
time
Sample
during
working
shifts
Seasonal
Operation
Separate
postte over
cleanup
period
Sampling
during
operation
season
Figure 6.1.
Factors of plant operation to be considered In
the design of the sampling program
-------
6.6 PARAMETERS TO MEASURE
6.6.1 NPDES Requirements
Parameters required for measurement in NPDES permits are listed by
industry in Table 6.1 (3). These are the parameters commonly required
and are to be used as a minimum guideline where exact permit specifi-
cations do not exist.
J&.'..?. Other Parameters
Application of the techniques from Section 4.<» is a rational method of
establishing parameters to measure. However, If process control Is
desired, measure the critical constituent. For example, If a dis-
tillation tower is to be controlled, monitoring the organic carbon
content of the discharge stream may provide early Information of leaks
In the system.
6.7 TYPE OF SAMPLE
In any program, the type of sample, either composite or grab, must be
established. Permit restrictions will determine the type for effluent
monitoring but for in-plant surveys, both types should be considered
and the most appropriate chosen.
Collect grab samples In the following situations:
1. If a batch discharge is to be characterized.
2. If the flow is homogeneous and continuous with
relatively constant waste characteristics so a
grab sample is representative of the stream.
3« When the extremes of flow and quality character-
istics are needed (e.g., for design purposes).
4. When one Is sampling for a parameter which requires
that the entire sample be used for analysis with no
Interior transfers of containers (e.g., oil and grease).
5. When sampling for parameters which change character
rap1 Idly such as dissolved gases or those which cannot
be held for a long length of time before analysis
(e.g., bacteria counts, chlorine, dissolved oxygen
and sulfIde).
137
-------
Table 6.1. NPDES EFFLUENT LIMITATION PARAMETERS BY INDUSTRY
OO
Temperature Discharge*
Oils. Fats * Grease
Nitrite-Nitrogen
Nitrate-Nitrogen
Nitrogen (KJeldahl)
Phosphorus
Sulflte
Sulflde
Sulfate
Chloride
Chlorine
Fecal Coll fora Met.
Fluoride
Arsenic
•arlui
•oron
ChrovluBj
Cobalt
XX x
XX XXX X XXX X «
X X X X X X
X
XX X
X X
X X XX
X
X X X X X
XX X
X X X X X X X
X XXX X XXX
-------
Table 6.1 (Continued). NPDES EFFLUENT LIMITATION PARAMETERS BY INDUSTRY
! 1 . -,! 11 ,! £! . !i ; * I * ? 5 : _ ?
Lead
PH
Manganese
Hercury
Nlcket
Zinc
Phenols
PCB5
Aldrln
Dleldrin
Heptachlor
Color
COD
Cyanide
Iron
Surfactants
Alum I nun
Arsenic
Settleable Solids
iiPiniiUiSiiiniiiiiiiiiiiiniM-
X XX
X XX
X X
X X
XX XX
X XX XX
X X
X XXXXXX XXXX
XX X XX
X
X
X
X
X
-------
Collect or form composite samples in the following situations:
1. If the average characteristics of a flow
stream are to be established over a certain
period of time.
2. If performing individual analyses on all the
discrete portions of a composite does not give
sufficient information or merit the extra cost.
3- When the parameters to be measured are not
adversely affected by the time lag between
sampling and analyses.
If composite samples are to be taken, the specific type of composite must
be established. This is contingent upon economic factors and the type of
discharge (batch or continuous) to the sampling point. The restrictions
on common types of composites are listed in Table 6.2.
Table 6.2 TYPES OF COMPOSITES
FOR DIFFERENT DISCHARGES
Sample Type
Mostly
Continuous
Discharges
Batch (and
Continuous)
Discharges
Cost
1. Continuous-volume
proportional to Best
flow rate
2. Periodic-time pro-
portional to flow Better
since last sample
3. Periodic-time con-
stant volume constant Adequate
plus manual composite
Best
Adequate
Adequate only
with grab sam-
ples of batch
discharges
Highest
Medium
Lowest
6.8 METHOD OF SAMPLING
Choose manual or automatic sampling depending on how the advantages and
disadvantages of the methods apply to the specific sampling program
(Tables 6.3 and 6.4).
\kO
-------
Table 6.3. THE ADVANTAGES AND DISADVANTAGES OF
MANUAL AND AUTOMATIC SAMPLING
Type
Advantages
Disadvantages
Manual Low capital cost
Compensate for various
situations
Note unusual conditions
No maintenance
Can collect extra
samples In short
time when necessary
Automatic Consistent samples
Probability of decreased
varlabllity caused by
sample handI Ing
Minimal labor require-
ment for samp)Ing
Has capabllIty to
collect multiple
bottle samples for
visual estimate of
variabilIty & analysis
of Individual, bottles
Probability of Increased
varlabllIty due to
sample handI Ing
Inconsistency in collection
High cost of labor
Repetitious and monotonous
for personnel
Considerable maintenance
for batteries & cleaning;
susceptible to plugging
by sol ids
Restricted in size to the
general specifications
inflexibility
-------
Table 6.4. COMPARISON OF REQUIREMENTS AND
FEATURES OF AUTOMATIC AND MANUAL METHODS
Sampllnq Constituents Method of Choice
Automatic Manual
Length of Program:
Long X
Short X
Manpower Available:
2k hour operation (i.e.
shift worker available) X
Special provision needed
for work over 8 hours X
Availability of Automatic Sampler
Which Meets Program Needs:
Yes X
No X
Accessibility to Sampling Point:
Good X
Poor X
Number of Sampling Points:
Many X
6.9 AUTOMATIC SAMPLERS
If an automatic sampler Is to be used, the actual type of sampler Is
determined by the constituents in the wastewater. A list of samplers
Is indicated in Section 2.3*1 and the features and techniques for use of
automatic samplers are discussed in Section 2.3.2. To choose a sampler,
list the features needed for sampling the type of industrial wastewater.
If the variability of the wastewater Is not known or expected to be high,
a multiplex feature which takes more than one sample Into a single
bottle Is desirable. This would allow samples to be collected at short
time increments such as once every 10-15 minutes. Another possible
feature would be to fill more than one sample bottle at a time Interval.
\k2
-------
This multiple bottle technique would allow use of one bottle for the
composite and the other for possible discrete analysts. Once the needed
features have been established, the sampler which best matches these
features can be selected. Available samplers may need adaptation. It
Is Imperative that the stream be well mixed at the sampling point to
avoid problems when using automatic samplers In streams with a high
solids content.
6.10 VOLUME OF SAMPLE AND CONTAINER TYPE
The volume of sample to be taken Is determined by the number of analyses
to be performed on the sample. If this his not been determined, a grab
sample volume of 3.8 1 (I gal.) and an Individual composite volume of
0.4 I (0.11 gal.) should be taken. The container type Is also contingent
upon the analysis to be run. If there is any possibility of high
organic content in the sample, borosillcate glass must be used; otherwise
conventional polyethylene Is acceptable.
6.11 PRESERVATION AND HANDLING OF SAMPLES
This procedure is contingent upon the types of parameters to be
analyzed. Specific techniques are indicated by the parameter in
Chapter 10.
6.12 FLOW MEASUREMENT
6.12.1 Open Channel Flow
Open channel flow devices have been discussed in detail In Section 2.4.3
and should be used for effluent monitoring or determining the addition
of flow between two sewers.
6.12.2 Other Flow Measurement
Various methods of closed pipe or free discharge flow measurement may
be applicable for tn-ptant surveys. In-depth discussions of these
devices are available in the literature (4,5,6,7). These devices Include:
I. Flow nozzle 4. Magnetic meter
2. Orifice meter 5. Venturi meter
3. Pi tot tube 6. Elbow meter
More Information on these devices is Included in Section 2.4.
143
-------
6.13 REFERENCES
1. Federal Water Pollution Control Act, as amended 33 USC 1251 et seq.
86 Stat. 816, Public Law 92-500.
2. Black, H. H. Procedure for Sampling and Measuring Industrial Waters.
Sewage Ind. Wastes. 2*»:A5, January 1952.
3. N.F.I. C -Denver. Effluent Limitations Guidelines for Existing
Sources and Standards of Performance for New Sources for 28 Point
Source Categories. Denver, p. 122, August
*t. EPA Technology Transfer. Handbook for Monitoring Industrial
Wastewater, August 1973.
5. Bouveng, H. 0. Guide to Flow Measurement and Sampling with
Special Reference to Pulp and Paper Mill Wastewater Systems.
Pur and Appl . Chemistry. 19:267-290, 1969.
6. Chow, V. T. Handbook of Applied Hydrology. New York, McGraw-Hill,
7. Water Measurment Manual, Second Edition. Bureau of Reclamation,
U.S. Department of the Interior, Washington, D.C., 1967.
-------
CHAPTER 7
SAMPLING SURFACE WATERS AND BOTTOM SEDIMENTS
7.1 BACKGROUND
The sampling of rivers and streams, estuaries, lakes and oceans and
their associated bottom sediments are considered In this chapter.
Methods of sampling are directly affected by the objectives of the
study and parameters which are to be analyzed. Therefore, the decisions
regarding parameters must be made at the beginning of the study in order
to develop a rational sampling program.
7.2 OBJECTIVES OF THE STUDY
The main objectives of sampling surface waters and sediments are:
1. Evaluation of the standing crop, community structure, diversity,
productivity and stability of Indigenous aquatic organisms.
2. Evaluation of the quality and trophic state of a water system.
3. Determination of the effect of a specific discharge on a
certain water body.
7.3 PARAMETERS TO ANALYZE
Selection of parameters is dependent on the objectives and extent of the
program or study and must be performed prior to the development of the
sampling plan. Surface waters and sediments are commonly analyzed for the
chemical and biological parameters listed In Table 7.1.
-------
Tablo 7.1. COMMON ANALYSES FOR SURFACE
WATER AND SEDIMENT SAMPLINp
Chemical Biological
Dissolved Oxygen Fish
Phosphoto Bcnthlc Macro invertebrates
Nitrogen Series Periphyton
Alkalinity Phytoplankton
Silica Zooplankton
pH Macrophytos
Specific Conductance Macroalgae
Solldo (TDS, TS, TSS)
Organic Matter and Demand
Color
Turbidity
Peottc ides
Heavy Motels
7.*i LOCATION OF SAMPLING POINTS
Select the study site based on tho progrcm objectives, the parameters of
Interest, and tho sampling units. For oaemplo, the following guidelines
are suggested in tho EPA Kodcl Steto V.'otor Monitoring Program (1) for
selecting long-term biological trend monitoring stations:
I. At key locations In rater bodies which are of critical value
for sensitive uses such as domostlc voter supply, recreation,
propagation, end maintenance of fish and wildlife.
2. In major Impoundments nocr th'j mouths of major tributaries.
3» Near the mouths of rucjor r Ivors where they enter an estuary.
*». At locations in major v.-r.uor bodies potentially subject to inputs
of contaminants from areas of concentrated urban, industrial,
or agricultural use.
5. At key locations In vector bodies largely unaffected by man's
activities.
In order to avoid bias, use ono of the following random sampling plans to
determine scntpltng points within tho study site. Random sample selection
Is discussed in more detail in the EPA Biological Field and Laboratory
Methods Manual (2).
-------
7.A.I SlmpU Random Sampling
Us* a simple random sampling plan when there Is no reason to subdivide
the population from which the sample Is drawn. Then the sample Is drawn
such that every unit of the population has an equal chance of being
selected. First, number the universe or entire set of sampling units
from which the sample will be selected. This number Is N, Then from a
table of random numbers select as many random numbers, n, as there will
be sampling units selected for the sample. Select a starting point in
the table and read the numbers consecutively In any direction (across,
diagonal, down, up). The number of observations, n (sample size), must
be determined prior to sampling. For example, If n is a two-digit
number, select two-digit numbers Ignoring any number greater than n or
any number that has already been selected. These numbers will be the
numbers of the sampling units to be selected.
7.4.2 Stratified Random Sampling
Use a stratified random sampling plan if any knowledge of the expected
size or variation of the observations is available. To maximize
precision, construct the strata such that the observations are most alike
within strata and most different among strata, I.e., minimum variance
within strata and maximum variance among strata. Perhaps the most
profitable means of obtaining information for stratification is though
a prestudy reconnaissance (a pilot study). For information on conducting
a pilot study, consult the EPA Biological Methods Manual (2). Stratifi-
cation Is often based upon depth, bottom type, isotherms, or other
variables suspected of being correlated with the parameter of Interest.
Select as many strata as can be handled In the study. In practice,
however, gains in efficiency due to stratification usually become negli-
gible after only a few divisions unless the characteristic used as the
basis of stratification Is very highly correlated with the parameter
of Interest (2).
7.**.3 Systematic Random Sampling
Use a systematic random sampling plan to assure an adequate cross section
while maintaining relative ease of sampling. A common method of
systematic sampling Involves the use of a transect or grid. However,
choose a random starting point along the transect or grid to introduce
the randomness needed to guarantee freedom from bias and allow
statistical Inference.
7.4.4 Nonrandom Sampling
Use a nonrandom sampling plan If justified by the study flte, or parameters
of Interest, or the type of study being undertaken. For example, the
following sample locations might satisfy the program objectives:
-------
Parameter
SampI Ing Location
Fish
Benthtc macroinvertebrates
Portphyton
Phytoplankton
Zooptonkton
Mocrophytcs
Chomtcal
Shore)!ne sampltng
Right, left bank, midstream or
transect
Shore)Ine sampling
Transect or grid
Transect or grid
Shoreline sanpling or trancect
Transect or grid
J.k.k.y impact of Point Discharges - A transect sampling scheme may be
used to determine tha impact of a point discharge.
1. Piece linos transecting the receiving water at various angles
from tha discharge point.
2. Choose sampling Intervals randomly or uniformly or by the
methods described in Section 7.A.A.2.
3. Choose two remote control points to use as background.
<». Soe Figure 7.1 for example.
Control
oint
Point
Source
o /Control
Point
Figure 7*1 • Excmple of transect sampling scheme
A grid sempllng scheme may also be used but is not applicable to all
biological parameters. Grid placement must be contained in a similar
environment (e.g. all ripples or all pools) for a valid comparison.
I. Set up grids across and through the area to be sampled (i.e., in
both width and depth directions versus length) as required by the
program.
-------
2. The grid size Is dependent upon the degree of lateral and'
vertical mixing. If the amount of mixing Is unknown, then take
• larger number of samples across and through the stream than
would be otherwise desirable.
3. Choose the number of samples randomly, uniformly or using the
procedure In Section 7.'».'».2.
4. Choose a control point upstream of the grit system.
5. See Figure 7.2 for an Illustration of the grid method.
Figure 7.2. Example of grid sampling scheme
7.fr.fr.2 Spatial Gradient Technique - This technique may be used for the
rational selection of sampling station locations (3,k). It presupposes
the existence of historical data or some reasonable estimate of the
expected variability of the parameters to be monitored over the region
of interest, say, along the length of the river. This technique has
greater applicability for chemical than biological parameters.
I. Collect historical or comparable data to estimate the mean and
variance of the parameter of interest, Y.
2. Plot the maximum and minimum values of the parameter concentra-
tion versus distance along the river (Figure 7.3).
-------
I
Sample Station A
Point D
DISTANCE ALONG RIVER
Figure 7*3> Uso of cpaClol gradient technique for
monlmica ypcctng of sompltng stations
3. Calculate a slopo for both lines (G__.. and G , ).
"max ~ mln
4. Determlno the difference between the slopes, I.e.,
max
5. Dotermlne the maximum allowable error In the estimates of the
parcmotor value at Point B.
6.
A Y
max
max
max mln
7. Use this d to determine distance between points on a transect
or grid In a grid pattern.
7.5 NUMBER OF SAMPLES
The following Information Is summarized from the EPA Biological Methods
Manual (2).
150
-------
7.5.1 Simple Random Sampling
Use one of the following two methods depending on the decision variable.
1. Estimation of a Binomial Proportion - An estimate of the propor
tion of occurrence of the two categories must be available.
If the categories are presence and absence, let the probability
of observing a presence of P (0 < P < I ) and the probability of
observing an absence by Q (0 < Q < 1 , P + Q » 1). The second
type of Information which Is needed Is an acceptable magnitude
of error, d, In estimating P (and hence Q). With this Informa-
tion, together with the size, n, of the population, the formula
for n as an Initial approximation (n0), is:
a. For n > 30, use t « 2. This n ensures with a 0.95 proba-
bility that P Is within d of Its true value.
b. For n0 < 30 use a second calculation where t is obtained from
a table of "Student's t" with n -1 degrees of freedom.
If the calculation results In aft no, where
-§-< 0.05
no further calculation Is warranted. Use n as the sample
n ,
size. If -jj- * 0.05, make the following computation:
_
V1
J + J>
N
Estimation of a Population Mean for Measurement Data - In this
case an estimate of the variance, Sz, must be obtained from
some source, and a statement of the margin of error, d, must
be expressed in the same units as are the sample observations.
a. For n > 30, use: n •
o o
'
b. For nQ< 30, recalculate using t from the tables, and If
0.05, a further calculation is In order:
n
o
151
-------
After a sample of size, n, Is obtained from the population,
the basic sample statistics may be calculated. If the
sample size, n, is greater than 5 percent of the population
(5- > 0.05), a correction factor is used so that the
-
l
calculation for tho sample variance is:
(EX.)2
«2 0 N"n
3 °ir
7.5.2 Stratified Random Sampling
Conduct a pilot study or obtain from other sources reliable estimates of
tha variance within strata. If historical data has been collected, use
optimal allocation to determine the total number of samples.
y
N (
where t ° Student's t value (use 2 for estimate)
N,, ° number of sampling units in stratum k
3 variance of stratum k
s. ° /s. •=• standard deviation of stratum k
N ° total numbor of sampling units In all strata
d ° acceptable parcmotor error
If no data Is available, use proportional allocation to determine the total
number of samples:
I
.Nd2
j-
z^*t
i . k k
1 ~TT~
N d
Use the following equations to dotermlhe the number of samples to be
collected In each stratum, n. :
152
-------
nN. s.
Optimal allocation: n^ • ^ %
^ IN
nN
Proportional allocation: n. • -jj—
7.5*3 Systematic Random Sampling
Datarmlna the number of samples to be taken on the grid or transect using
the methods given In Section 7.M.2 or 7.5.1.
7.6 FREQUENCY OF SAMPLING
While the frequency of sampling will often be determined by the program,
use the Model State Water Monitoring Program (1) guidelines for guidance
In trend monitoring (Table 7.2).
7.7 METHOD OF SAMPLING
While compositing of Individual grab samples is permitted for most
chemical parameters, as a rule do not composite biological samples. For
biological parameters collect single grab samples In replicate. An
exception would be If a single grab sample does not contain a sufficient
number of the organisms to be counted or examined; then two or more grab
samples may be composited.
7.8 TYPES OF SAMPLERS
Choose the type of sampler that meets the needs of the sampling program
by considering the advantages and disadvantages, of the sampler type. In
general, equipment of simple construction Is preferred due to ease of
operation and maintenance plus lower expense. Advantages and disadvan-
tages of various water bottles are shown In Table 7.3 and Illustrated '
In Figure 7>^> This equipment Is useful for chemical, phytoplankton and
zooplankton sampling. Corers and bottom grabs (Tables 7.4 and 7.5 and
Figures 7*5 and 7.6) are useful for sediment sampling. Nets and substrate
samplers are covered In Tables 7.6 and 7.7 and Figures 7.7 and 7.8.
There are Inherent advantages of using a diver for sediment sampling.
The diver can ascertain what Is a representative sample in addition to
taking pictures and determining qualitatively the current velocity.
153
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Table 7.2. MODEL STATE WATER MONITORING PROGRAM GUIDELINES FOR BIOLOGICAL MONITORING (])
Community
Parameter
~ Collection & T~
Priority analysis method
Sampling frequency0
Plankton
Periphyton
Macrophyton
Macro!nver-
tebrate
Fish
Counts and Identification; 1
Chlorophyll a;
Blomass as ash-free weight
Counts and Identification; 1
Chlorophyll a; 2
Blomass as ash-free weight 2
Areal coverage; 2
Identification; 2
Biomass as ash-fres weight 2
Counts and identification 1
Blomass as ash-free weight 2
Flesh tainting; , 2
Toxic substances In tissue 2
Toxic substances in tissue 1
Counts and identification; 2
Biomass as wet weight; 2
Condition factor;
Flesh tainting 2
Age and growth 2
Grab samples
Artificial
substrates
As circumstances
prescribe
Artificial and
natural
substrates
Electroftshtng
or netting
Once each; in spring, summer
and fall
Minimally once annually
during periods of peak
perlphyton population
density and/or diversity.
Minimally once annually
during periods of peak
macrophyton population
density and/or diversity
Once annually during
periods of peak macro-
invertebrate population
density and/or diversity
Once annually during
spawning runs or other
times of peak fish
population density
and/or diversity
a Priority: 1) Minimum program; 2) Add as soon as capability can be developed.
b See EPA Biological Methods Manual. c. Keyed to dynamics of community.
d See Analysis of Pesticide Residues In Human and Environmental Samples, "USEPA, Perrlne Primate
Research Lab, Perrine, FL 32157 (1970)," & "Pesticide Analytical Manual," USDHEW, FHA, Wash, D.C.
-------
Table 7-3- COMPARISON OF WATER SAMPLERS
Device
Application
Container Type
Advantages
Disadvantages
Nansen Bottle Phytoplankton
Simple Bottle
Chemical
Bacteriological
\n
Kemnerer Bottle Chemical
Bacteriological
Zooplankton
Phytoplankton
Van Corn
Bottle
Pumps
Chemical
Bacteriological
Zooplankton
Phytoplankton
Chemical
Zooplankton
Phytoplankton
Teflon lined
Glass
PVC
Brass
Acrylic plastic
Nickel-pla.ted
brass
PVC
Vanes
Able to use In
series for deep
water
Easy to make
No cross contam-
ination, no pro-
blem with avoid-
ance, point
sample
No cross contam-
ination, point
sample, no avoid-
ance problem
Large volume,
samples a vertical
water column, con-
tinuous sample
Small volume
Cross contamin-
ation
Fixed capacity
from 0.^-16 1,
Fixed capacity
from 2-30 1.
Bulky, non repres-
entative
-------
Table ?.*». COMPARISON OF BOTTOM GRABS
Device
Advantages
Disadvantages
Ponar
Ekman
Tall Ekman
Peterson
Smith-Mcintyre
Hayward Orange
Peel
Dfver
Safe, easy to use, prevents escape of
material with end plates, reduces shock
wave, combines advantages of others,
preferred grab in most cases
Use in soft sediments and calm waters,
collects standard size sample
(quantitative), reduces shock wave
Does not lose sediment over top; use
in soft sedimants and calm water,
standard sample size, reduces shock wave
Quantitative samples in fine sediments,
good for hard bottoms and sturdy and
simple construction
Useful in bad weather, reduces premature
tripping, use in depths up to 1500 m
(3500 ft), flange on jaws reduced
material loss, screen reduces shock waves,
good in all sediment types
Easy to operate, commercially available
in various sizes, does not rust easily,
does not require messenger, good bottom
penetration, takes undistrubed sample
of top sediment
Can determine most representative
sampling point and current velocity
Can become burled In soft sediments
Not useful In rough water; not useful
if vegetation on bottom
Not useful in rough waters, others as
for Ekman
May lose sampled material, premature
tripping, not easy to close; does not
sample constant areas; limited sampling
capacity
Large, complicated and heavy, hazardous,
for samples to 7 cm depth only, shock
wave created
Difficult to determine sampling cover,
2 cables required, active washing
during sampling, jaws do not close
tightly, soft sediment fouls closing
mechanism
Requires costly equipment and
special training
-------
Table 7.5. COMPARISON OF CORING DEVICES
Device
Advantages
Disadvantages
VJ-I
Kajak or
K.B. Corer
Moore (Pfleger)
O'Connor
Elgmork's
Jenkins
fnequist
Ki rpicenko
Does not impede free flow of
water, no pressure wave, easily
applied to larcie area
Valve allows sample to be held
Can sample water with hard
bottoms
Sample easily removed, good in
soft muds, easy to collect, easy
to remove sample
Good in soft sediments and for
collecting an undisturbed
sediment-water interface sample.
Visual examination of benthjc
algal growth and rough estimates
of mixing near the interface after
storms can be made
Good in soft/medium sediments,
closing mechanism
Soft and hard bottoms, various
sizes, closes automatically
Careful handling necessary
to avoid sediment rejectionf not
in soft sediments
Not in deep water
Not in hard sediments
Complicated
Does not penetrate hard
bottom
Not for stony bottoms
-------
Table 7.6. COMPARISON OF NET SAMPLING DEVICES
Devices
Applicatton
Advantages
Dlsadvantaqes
Wisconsin Net
Zooplankton Efficient shape
Phytoplankton concentrates
sample
Closing Net Zooplankton
Samples one
stratum
QualItative
Clarke-Bumpus Zooplankton Quantitative
No point samplIng,
difficult to get
correct speed, clean
bottom only
Juday Plankton Zooplankton
Trap
No cross contamination Bulky and heavy,
bs twoen samp1es,
minimal avoidance,
large volume
calm rfater only,
clean bottom only,
primarily research
tool
158
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Table 7.7. COMPARISON OF SUBSTRATE SAMPLERS
Type of Substrate
Advantages
Disadvantages
vn
1. Artificial
Hester-Dendy
Ful1ner
EPA Basket Type
EPA Periphyton
Sampler
2. Natural
Any bottom or
sunken, material
Reduces compounding effects of substrate
differences, multiplate sampler
Higher precision than Hester-Dendy,
wider variety of organisms
Comparable data, limited extra
material for quick lab processing
Floats on surface, easily anchored,
glass slides exposed just below
surface
Indicate effects of pollution, gives
Indication of long term pollution
Long exposure time, difficult
to anchor, easily vandalized
Same as Hester-Oendy
No measure of pollution on
strata, only community formed
in sampling period.
May be damaged by craft;
easily vandalized
Possible lack of growth
-------
Brass Kemmerer Water Bottle
Figure 7.^ Water bottles
(Courtesy of Wildlife Supply Co.)
160
-------
Ekman Grab
Bonar Sampler (two sizes)
Figure 7.5. Bottom grab samplers
(Courtesy of Wildlife Supply Co.)
161
-------
\ \J
Figure 7.5
(Aberdeen) Grab
Bottom grabs
162
-------
Valve
Cylinder
Clamp
Nose of Sampler
Side View-Vertical Core Sampler
Elgmork's Core Sampler
Figure 7-6- Core samplers
-------
Clarke-Bumpus Sample*
Closing Net
o »
c „
5» |
$ «•
rt
O
I/I
01
2 3
» -o
IS
-------
Juday Plankton Trap
Wisconsin Net
Figure 7.7 (continued). Nets and related samplers
(Courtesy of Wildlife Supply Co.)
165
-------
Surface
w
Side V!©w
EPA Pariiphyeej} samplsr,
two ssyrofoam floatso
slides (30).
lex!glass frame supported by
holds eight glass microscope
Figure 7.8o P@p5phyton san^Sers.
166
-------
1
T
Side View
Hester-Dendy
Figure 7.9. Macro Invertebrate sampler
167
-------
7.9 VOLUME OF SAMPLE AND CONTAINER TYPE
The size of sample is dependent on the expected amount of the parameter
to be analyzed. The container type Is also dependent on parameter type.
Refer to Section 10.7 for specific information relative to the parameters
which are to be analyzed.
7.10 PRESERVATION AND HANDLING OF SAMPLES
Refer to Section 10.7 for specific information regarding preservation and
handling of samples relative to the parameters to be analyzed. There is
little or no published information on the preservation of bottom
sediment samples. Therefore, no specific techniques can be recommended
at this time.
7.11 FLOW MEASUREMENT
Flow measurement in rivers is accomplished by the combined use of a
current meter to measure the stream velocity and a stage recorder to
measure the surface elevation of the river. Consult USGS gaging stations
for additional or historic information. See Section 2.k for more details.
7.12 REFERENCES
1. National Water Monitoring Panel. Model State Water Monitoring Program.
U.S. EPA. Report No. EPA-MO/9/7^-002. U.S. EPA Office of Water
and Hazardous Materials. June 1975.
2. Weber, C. I., ed. 1973. Biological Field and Laboratory Methods for
Measuring the Quality of Surface Waters and Effluents. National
Environmental Research Center, Office of Research and Development,
U.S. EPA, Cincinnati, Ohio.
3. Hill, R. F. Planning and Design of a Narragansett Bay Synoptic
Water Quality Monitoring System. NEREUS Corp., 1970.
k. Drobny, N. L. Monitoring for Effective Environmental Management.
Proc, ASCE National Water Resources Engineering Meeting. Atlanta,
Georgia. January 2^-28, 1972.
168
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CHAPTER 8
SAMPLING AGRICULTURAL DISCHARGES
8.1 BACKGROUND
Agricultural discharges can be separated into two broad wastewater
categories: 1. concentrated animal waste or manure from a confined
feed lot; 2. runoff from an agricultural watershed. These two types
of wastewater differ mainly in the concentration of pollutants. Runoff
from fields, associated almost entirely with rainfall and snowmelt
events, is characteristically much less polluted, while feed lot runoff
is a highly concentrated point source. The values for constituents of
field runoff depend on the amount and intensity of rainfall or snowmelt,
land use,topography, soil type, use of manure or fertilizer, etc.
8.2 OBJECTIVES
There are two main objectives In sampling agricultural discharges:
1. Research - to study both field and feedlot runoff.
2. Regulatory - to monitor field or feedlot runoff or
effluent from feedlot runoff treatment.
8.3 FREQUENCY OF SAMPLING
8.3.1 Feedlot Discharge
8.J.1.1 Regulatory - Follow the sampling frequency given in the
discharge permit. Daily sampling is the maximum requirement In most
permits.
8.3.1.2 Other - Apply the spectral analysis techniques as outlined in
Section J».J». Collect preliminary data If not available by conducting
one of the following (in order of preference)
a. A one week survey collecting hourly grab samples where
the discharge is continuous.
169
-------
b. A 24-hour survey collecting hourly grab samples.
Calculate the mean and variances as indicated In Section 4.1 and apply
a computer program for spectral analysis (Section 4.3).
8.3.2 Field Runoff
Apply the statistical methods outlined In Section 4.3 If possible.
Collect preliminary data by sampling every 5 minutes for the duration
of sever* runoff events (1). Collect and analyze samples Individually
or composite them proportional to flow, depending on the objectives of
Jh! um'i r T"! °f th^/«rlabn'ty In the runoff occurs during
the initial part of the runoff hydrograph on the rising side of flow
crests, tampling Is the most critical at this time.
8.4 LOCATION OF SAMPLING POINTS
8.4.1 Feed 1ot D1scharge
Channel feedlot runoff to a central point by sloping or trenching if no
treatment is provided. If treatment is provided, sample effluent from
the treatment system.
0.4.2 Field Runoff
Select a site downstream of the runoff area at a point where runoff
collects into a channelized flow. Use the topography of the area to
locate this point. Choose a location with sufficient depth to cover
the sampler intake without excavation.
8.5 NUMBER OF SAMPLES
The number of samples for both feedlot discharge and field runoff are
calculated in the following manner:
1. Follow regulatory requirements
2. Apply the statistics in Section 4.2 after the mean and
variance are determined through a preliminary survey (see
Section 8.3).
8.6 PARAMETERS TO ANALYZE
8.6.1 Established by Regulation
Analyze all parameters required by discharge permits.
170
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8.6.2 No Requirements
Analyze the following parameters (2, 3, 4):
I. Nutrients (total phosphate and nitrogen series)
2. Demand
3. Physical/Mineral (total and suspended solids)
4. Microbiological (fecal coliform and fecal streptococci)
Other analyses such as metals or pesticides may be necessary depending
on the nature of the study.
8.7 TYPE OF SAMPLE
Do not collect a single grab sample due to the high variability of run-
off. Collect a series of samples for analysis, or form a composite
sample according to flow using one of three methods:
1. Constant sample volume, time between sampling periods
proportional to stream flow.
2. Sample volume proportional to total stream flow since
last sampling period; constant time between sampling
periods.
3. Sample volume proportional to instantaneous stream flow
rate; constant time between sampling periods.
Use method I whenever possible, since this technique will allow a
large number of samples to be taken at high flows. Choose a flow
volume increment that will not exceed the bottle supply. An automatic
samplerand integrated flow measurement device is necessary for this
type of sampling. Both methods 2 and 3 are acceptable also, but not
preferred.
8.8 METHOD OF SAMPLING
Collect samples either automatically or manually; analyze the discrete
samples separately or composite them proportional to flow. For
sampling field runoff, use an automatic system activated by runoff
through the flume. Typical samplinq/flow measurement stations are
shown in Figures 8.1 and 8.2. If feedlot runoff contains large parti-
culate matter (e.g., corn cobs), manual sampling will be necessary.
171
-------
H Flume
Automat ic
Sampler
Self-Start ing
Stage Recorder
Stil1inq Wei 1
Figure 8.1 View of field
installation (from 5)
-------
Motorized
Sampling Slot
.Self-Starting
Stage Recorder
—H Flume
Figure 8.2. View of field Installation (from 7)
-------
STRIP CHART
~L
-RECORDING PEN
FLOW
HYDROGRAPH
IZv.IEI
SOLENOID
Z SAMPLING
CONTACTS
SAMPLE
BOTTLE
T SAMPLE
V \t ^W"~"~^~"*
1 *
\
^- CLAMP
•
r
-FLOAT
^« 01 iM/^r-rr
Figure 8.3. Schematic of water level recorder
and sampler arrangement (from 5)
-------
8.9 VOLUME OF SAMPLE AND CONTAINER TYPE
Use multiple sample containers to provide the best preservation for
specific parameters. For example, if the parameters given in Section
8.6.2 (nutrients, demand, physical/mineral, microbiological) are to be
analyzed, three containers and three preservation techniques would be
required for each sample.
Container Parameter Group Technique
1 Nutrients Add H^SO. to pH 2 or 40-400
mg/l RgCT. and refrigerate
at 4®C Z
2 Demand Ice as soon as possible
Physical/Mineral after collection.
3 Microbiological Collect in sterile container
and ice as soon as possible.
8.10 FLOW MEASUREMENT
Select the flow measurement device based on the specific application and
the need for accuracy. A type H flume is advantageous because of its
wide range of accuracy (3.6). The measurement instrumentation should
include a continuously recording flow chart, with a pressure-sensitive
record preferred to ink. A schematic of a typical installation Is shown
in Figure 8.3. More detailed information on flow measurement is given
in Chapter 2.
8.11 REFERENCES
I. Miner, J.R., L.R. Bernard, L.R. Ftrva, G.H. Larson, and R.I. Upper.
Cattle Feedlot Runoff Nature and Behavior. Journal WPCF. 38:
834-8*7, October 1966. ~~
2. Humenlk, F.J. Swine Waste Characterization and Evaluation of
Animal Wa'ste Treatment Alternatives. Water Resources Research
lost., Univ. of North Carolina, Raleigh, N.C., June 1972. 152p.
3. Harms, L.L., J.N. Dornbush, and J.R. Andersen. Physical and
Chemical Quality of Agricultural Runoff. Journal WPCF. 46: 2460-
2470, November 1974. ~~
4. Robblns, J.W.D., D.W. Howells, and G.J. Kriz. Stream Pollution
from Animal Production Units. Journal WPCF. 44_: 1536-1544,
August 1972.
175
-------
5. Harms, L.L. South Dakota School of Mines and Technology. Rapid
City, South Dakota. Personal Communication to Environmental
Sciences Division. December 20, 197*»-
6. Madden, J.M. and J.N. Dornbush. Measurement of Runoff and Runoff
Carried Waste from Commercial Feedlots. Proc. Int. Symposium on
Livestock Wastes. Ohio State Univ., Columbus, Ohio. April 19-22,
1971- Wi-li7.
7. Leonard, R. A. USOA Southern Piedmont Conservation Research
Center. Watkinsville, Georgia. Personal Communication to
Environmental Sciences Division. July 17, 1975.
176
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CHAPTER 9
SAMPLING SLUDGES
9.I BACKGROUND
The quantity and composition of sludge varies with the characteristics
of the wastewater from which It Is concentrated and with the concentra-
tion process used. Some common types of sludge are:
I. Coarse screenings from bar racks
2. Grit
3. Scum from primary settling tanks
4. Primary settling tank sludge
5. Return and waste activated sludge
6. Flotation or gravity thickened sludge
?• Aerobic or anaerobic digester sludge
8. Drying bed sludge
9* Vacuum filter cake
10. Sludge press cake
II. Centrifuge sludge
12. Fine screening backwash water
13. Sand filter backwash water
14. Sludges from special treatment processes such as the treatment
of industrial wastes or combined sewer overflows.
Sludge sampling methods are usually confined to water and wastewater
plants, either municipal or industrial. The sampling programs
employed are concerned mainly with the following sludges: primary
settling tank sludge, return and waste activated sludge, thickened
sludge, digester sludge, and the resulting cakes produced by sludge
drying methods.
9.2 OBJECTIVES OF SAMPLING PROGRAMS
9.2.1 Process Control
Most sludges are measured for various process control reasons including
the following:
177
-------
1. Optimization of sludge drawoff procedure
2. Determination of the efficiency of a concentration process
3. Determination of the loadings to the process
k. Evaluation of feed material for subsequent sludge conditioning
techniques which may vary with changing feed characteristics
5. Control of the activated sludge process, i.e., the mixed
liquor suspended solids (MLSS) concentration
6. Control of blanket depths In clarifiers
7. Determination of sludge characteristics that may be
detrimental to digester processes
9.2.2 Research
Research projects require specific sampling techniques which are
determined by the program.
9.3 PARAMETERS TO ANALYZE
The parameters to analyse will depend on the objective of the process.
For example, analysis of total and suspended solids content of the
sludge is necessary to determine the efficiency of a sludge thickening
processes. A guide for parameters to analyze Is shown in Figure 9.1.
Additional parameters to analyze Include: heavy metals, pesticides,
and nutrients.
3.1* LOCATION OF SAMPLING FOB NTS
9.fr. 1
Piping - Collect samples directly from the piping through a
samp 1 1 ng cock ha v 5 ng a mUnomum l.D. of 3»8 cm (1.5 in.) (1).
9.^.1.2 Channels - Collect samples at the measuring weirs, or at
another point where the sludge is well mixed.
9.^.2 Batch Sludges
178
-------
Temperature
PH
BOD
SS
TS
TVS
Alkalinity
Volatile Acids
Settleable Solids
•1
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i
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i
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c
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a
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L. .
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I/O
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C
V
X
o
c
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Su
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I/O
I/O
I/H
§
»«
w
10
en
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*-
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tl
u
C
C
1
P
C
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u
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F
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i
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i
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i
Is
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S
S
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en
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9.fr.2.l Digesters - Collect samples from a mixed sink which is fed
th rough 1 ! nes a t tached at different levels in the digester. Be certain
to waste sludge accumulated in the lines prior to sampling (1).
9.4.2.2 Tanks - Mix tank thoroughly and collect samples. Or collect
samples at various depths and locations in the tank. Mix samples
together prior to analysis.
9.4.3 Specific "In Plant" Locations
The following locations are recommended for sludge sampling at waste-
water treatment plants:
I. Primary Sludge - Draw sludge from the settling tank hoppers
into a well or pit before pumping, mix well and then collect
a representative sample directly from this well. Alternately,
collect samples from openings in pipes near the sludge pumps
or from the pump itself (k) .
2. Activated Sludge - Collect samples at:
a. the pump suction well
b. the pump or adjacent piping
c. the point of discharge of the return sludge to
the primary effluent.
The sample point should be located in a region of good
agitation to insure suspension of solids (k) .
3. Digested Sludge - Collect samples at the point of the
discharge of the digester drawoff pipe to the drying beds
or the drying equipment (3).
k. Bed Dried Sludge - Collect equal-sized samples at several
points within the bed without including sand. Mix
thoroughly
5. Filtered Sludge - Collect equal size portions (possibly by
using a cookie cutter) at the filter discharge CO.
9.5 FREQUENCY OF SAMPLING
The extreme variability of sludges creates a need for frequent
sampling to achieve accurate results. Each composite sample should
be composed of at least 3 individually obtained samples (4). Sample
batch operations at the beginning, middle and end of a discharge, or
more frequently If high variability is suspected (A). Tapped lines
should also be sampled in three separate Intervals because of
variations in the sludge at the drawoff source (i.e., clarifier,
digester, etc.). Minimum frequencies for various sludge processes
180
-------
are included in Figure 9-1-
9.6 NUMBER OF SAMPLES
The number of samples is determined from the frequency and the
number to include in the composite. Refer to Figure 9.1 for minimum
guidelInes.
9.7 TYPE OF SAMPLE
Collect grab samples when analyzing an unstable sludge for a para-
meter which is affected by the instability, or when analysis is
required as soon as possible (e.g., sludge volume index test for
activated sludge samples).
Analysis of composite samples is recommended in all other situations
to reduce the effects of sludge variability. Use at least three
individual samples to form the composite. Wherever possible, collect
frequent discrete samples and composite according to flow rate (5).
9.8 METHOD OF SAMPLING
Automatic samplers are not commonly available for sludge sampling
due to the high fouling potential and solids content of the waste-
water. Use manual sampling techniques in most situations unless
special adaptations can be made.
9.9 VOLUME OF SAMPLE AND CONTAINER TYPE
Use a wide mouth container to sample sludges. The size and material
of container depends on the parameters to be analyzed. In general,
a clean borosilicate glass container is preferable to reduce the
possibility of adsorption of organics to the container wall; however,
polyethylene can be used. See Chapter 10 for more details.
9.10 PRESERVATION AND HANDLING OF SAMPLES
Preservation methods are discussed in Chapter 10. Be certain to
completely mix the sample after a preservative is added to disperse
the chemical and allow adequate preservation. Considerable mixing
or homogenization is required prior to aliquot removal to insure
representative portions are obtained. Further studies on the
preservation of sludges appear warranted.
9.11 FLOW MEASUREMENT
For flowing lines do not use flow measuring devices which will be
easily fouled by solids (e.g., orifice, venturi meter). Use a
permanently installed, self-cleaning or non-obstructive device
such as a magnetic flow meter.
181
-------
Batch sludge discharges are not easily quantified in terms of volume
discharged. Make estimates from pump capacity, the change In depth in
a tank or well and time of pumping or other appropriate methods.
9.12 REFERENCES
1. Joint Committee of American Society of Civil Engineers and Water
Pollution Control Federation. Sewage Treatment Plant Design -
WPCF Manual of Practice, No. 8, 196?.
2. Estimating Laboratory Ne«ds for Municipal Wastewater Treatment
Plants. USEPA, Office of Water Program Operations, Washington,
O.C., Report No. EPA-^30/9"7^-002. Operation and Maintenance
Program. June I973i pp. A-I to A-29.
3. Technical Practice Committee - Subcommittee on Operation of
Wastewater Treatment Plants. Operation of Wastewater Treatment
Plant - WPCF Manual of Practice No. 11, 1970.
J». New York State Department of Health. Manual of Instruction for
Sewage Treatment ?}&nt Operators, New York, N.Y., Health
Education Service, 308 p.
5. Technical Practice Committee - Subcommittee on Sludge Dewateri,ng.
Sludge Dewatering - WPCF Manual of Practice No. 20, 1969.
182
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CHAPTER 10
SAMPLE PRESERVATION AND HANDLING BY PARAMETER GROUP
10.1 INTRODUCTION
Sample preservation Is distinctive to each parameter so recommendations
have been divided Into Individual categories. The parameter groups In
Table 10.1 are covered In this chapter. Microbiological parameters are
covered In Chapter 11.
Certain precautions and considerations are necessary when applying these
recommendations:
1. An asterisk is used when insufficient information
is available for recommendations and the best
available technique has been included.
2. When a chemical preservative is added to sludge
or high solids concentration samples, extreme
agitation is necessary to disperse the chemical
preservative throughout the sample, if the
chemical preservative cannot be dispersed, the
alternate preservation method must be used.
3. Holding times are divided Into two sections to
reduce the problems arising when composite
samples are analyzed. The maximum compositing
Interval Is applicable in situations when a
chemical preservative is needed but is not
added until after the composite Is complete.
Whenever possible an alternate procedure using refrigeration only has
been Included with a shorter holding time. Use this approach when the
recommended preservative may interfere with some of the analysis.
10.2 METHODS FOR NUTRIENTS PARAMETER GROUP
10.2.1 Background
In terms of the materials necessary to support aquatic plant and animal
life "nutrients" is a broad term. However, for this report It should
183
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Table 10.1. PARAMETER GROUP CLASSIFICATIONS
CHEMICAL PARAMETER GROUPS
oo
.e-
Nutrients Demand
Kjeldah! Nitrogen 800
Ammonia Nitrlgen COD
Nitrate-Nitrogen TOC
Nitrite-Nitrogen DO
Ortho Phosphate
Total Phosphate
Metals
Arsenic
Boron
Chromium
Mercury
Sod i um
Antimony
Cobalt
Copper
Iron
Zinc
Manganese
Selenium
Thallium
T 1 tan i um
Physical/Mineral
Beryl 1 ium
Cakiutn
Magnes i um
Potassium
Aluminum
Barium
Cadmium
Lead
Nickel
Vanadium
Molybdenum
Silver
Tin
Acidity
Alkalinity
Bromide
Chloride
Chlorine
Color
Cyanide
Fluoride
Hardness
Oil and
Grease
PH
Phenols
Specific
Conductance
Sulfide
Sulfite
Sulfactants
Total Solids
Suspended
Solids
Volatile
Solids
Total Dissolved
Solids
Turbidity
Pesticides
and Others
DDT
Dieldrln
PCB's
Benzldlne
Algicldes
Radioactive Materials
Alpha
Beta
Radium
Biological
Bent hi c
Macro1nvertebrates
Fish
MacroaIgae
Macrophyton
Per Iphyton
Phytoplankton
Zooplankton
-------
be understood that the term refers to the common nitrogen and phosphorus
forms. Both nitrogen and phosphorus can be limiting factors in the growth
of aquatic life. Both nitrogen and phosphorus are present In large
quantities In many of the Inputs to surface waters such as wastewater
treatment plant effluent and agricultural runoff.
10.2.1.1 Nitrogen compounds - Nitrogen occurs in natural systems In as
many as seven valence states. Of these, four are of major Interest In
environmental applications: total Kjeldahl nitrogen, ammonia, nitrate
and nitrite. These compounds are readily interconverted by bacterial
action, and the ratios of concentrations can be used as an indication of
recent pollution. The total Kjeldahl nitrogen includes ammonia, poly-
peptides, amlno acids and other long chain organonltrogen compounds.
These organlcs can be changed Into ammonia plus other compounds by cer-
tain bacteria. The ammonia can then be converted to the nitrite state,
hydrogen Ions and water by other bacteria under aerobic conditions.
However, nitrite Is quite unstable and can be easily converted to the
nitrate form when oxygen Is present. The nitrate form is the completely
oxidized state of nitrogen and is used as a fertilizer. Nitrates are
also contributed from atmospheric nitrogen which Is changed to nitric
acid anhydride during electrical storms. This unstable form changes to
nitric acid upon contact with water. Usually nitrate Is present In
drinking water at levels of 10 mg/l or less. A limit of *»5 mg/1 has
been established since nitrate causes an illness in infants, known as
methemogloblnemla (1).
10.2.1.2 Phosphate compounds - Phosphate Is present In natural systems
In three forms:ortho, condensed, and organic phosphate. It has been
found to be a limiting factor in plant growth in concentrations of 10 pg/1
(I). The largest contribution of phosphates is now the phosphate based
detergents. However, in some Instances phosphate is added to a waste,
generally an industrial waste, to allow sufficient bacterial growth.
Because of its role in the eutrophication of lakes, the phosphorus concen-
tration in point discharges to such bodies of water Is being closely
monitored.
10.2.2 Recommended Preservation and Handling Methods
10.2.2.1 General - The use of mercuric chloride and sulfurlc acid
have been found to be effective In preserving most nutrient types (2,3,
A,5,6). Although the 1971 EPA Methods Manual among others (7) suggests
a dosage of kO mg/l mercuric chloride, studies by Krawczyk (6),
Hell wig (3) and Howe and Hoi ley (5) Indicated higher dosages were
necessary in polluted water. The adverse environmental effect of mercury
must be considered. If this toxic preservative is added in the field
there is a danger of environmental contamination; even lab disposal by
normal procedures can result In indirect contamination by dilute mercury
In water. Therefore, whenever other preservatives are available and
185
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adequate, they should be used and mercuric chloride avoided. When sul-
furlc acid is used as a preservative, reduce the pH of the sample to
1.5. Studies have shown that this level must be reached for effective
bacterial kills (8). TBS Prakasam showed that acid addition to pH 2
will still allow the ammonia content of a sample to increase indica-
ting that bacterial activity still existed (9). However, whenever
possible acid should be used in preference to mercury, although both
methods are acceptable. When mercury is used, samples must be
treated for mercury reclamation using the procedure in Section 10.2.2.2.
10.2.2.2 Mercury Reclamation - In order to use mercury salt solutions
as preservatives, the mercury solution must be cleaned prior to dis-
posal. The recommended procedure allows the collection of mercuric
chloride on an Amberlite IRA-400 resin. The system is then regenerated
and the collected regenerant sent to a mercury reprocessor. There are
several reprocessers available nationally some of whom are listed In
Table 10.2.
A summary of the procedure to be used follows (11):
1. Adjust the pH of highly acidic solutions to pH of 4-6 and
highly basic solutions to pH of 6-8. Solutions originally
In the range of 6-8 are not to be adjusted.
2. Settle sample 2k hours to allow precipitates to form and
settle.
3. Vacuum filter solutions through a large bench top Buchner
funnel (approximately 32 cm In diameter) using relatively
fast paper.
J». Add 5 mg/l sodjurn chloride solution to the filtrate to
form the HgCl^" complex an Ion. This amount of NaCl will
complex up to *tOO mg/l of Hg In solution.
5. Pass the treated solution through a glass column (3 1/2 in
10 x k In 00 x k ft high) containing a bed of the ion ex-
change resin IRA-AOO three feet deep topped off with a
bed of activated charcoal 6-8 In. deep at a rate of flow
of 500 ml/mln.
10.2.2.3 Total Kjeldahl Nitrogen - Use sulfurlc acid (preferred) -or
chloride (only if necessary) plus refrigeration to preserve samples for
Kjeldahl nitrogen analysis. Samples can be held up to 30 days (12)
when sulfuric acid is used and up to k2 days (13) with mercuric chlor-
ide. Clean borosilicate glass containers as indicated in Section 3.k
but no special preparation Is necessary. Ice the samples during the
compositing period and add the total chemical preservative prior to
sample collection or Immediately after the composite is formed. The
volume needed varies with the analytical method. If a macro Kjeldahl
digestion Is done, collect 500-800 mis of sample depending upon the
expected concentration, collect 20-100 mis if a Technicon or automated
186
-------
Parameter: Total Kleldahl Nitrogen (Primary)
Water or Wastewater: x Hunlclpai Wastexater x Agricultural Runoff
*. Industrial W«t*w*tar .» Sludge*
*._. Surface Water * Sediment*
Preservation Method: Preferred;
I: Preferred; add H->SQi tn pH !•«« »h>n l.r pint
refrigeration at*V»C, Option (not preferred): i»0 mg/l
HqCj? Plus refrigeration for'ocean, surface and mildly
polluted waters (TOC<20 mg/1) (6) or 400 mq/1 HgCl2 plui
M , u , .. T. ue waers mg or » mq q? pus
Maximum Holding Times refrigeration for highly polluted waters (TOO20 mg/1)
Grab Samples 30 days
Composite Samples 29 days Max. Compositing 2k hours
(After Composite Preparation)Period
Container Type: Glass or plastic
Volume: 500-800 mis (maxl analysis) or 20-100 mis (automated analysis)
Preparation Method: "Q"_a
Comments: Add preservative prior to sample collection/Ice during
compositing. Use fulfurlc acid whenever possible.
Parameter: Total KJeldahl Nitrogen (Alternate)
Water or Wastewater: x Municipal Wastewater x Agricultural Runoff
x Industrial Wastewater x Sludge *
x Surface Water x Sediment*
Preservation Method: Refrigeration at 4°C
Maximum Holding Times
Grab Samples 2fr hours
Composite Samples 6 hours* Max. Compositing 24 hours .
(After Composite Preparation)Period
Container Type: Glass or plastic
Volume: 500-800 mis
Preparation Method: none
Comments: ~~
Figure 10.1. Recommended preservation
and handling methods - TKN
187
-------
Table 10.2. PARTIAL LISTING OF
COMMERCIAL MERCURY REPROCESSORS (10)
Company '. Processing a
Bethlehem Apparatus Co., Inc. H
Front and Depot Streets
Hellertown, PA 18055
Phone: (215) 838-7034
Goldsmith Division, National Lead Co. M
111 North Wabash
Chicago, IL 60602
Phone: (312) 726-0232
MallJnckrodt Chemical Works M C 0
223 West Side Avenue
Jersey City, NJ 07303
Phone: (201) 432-2500
(Mr. Frank L. Mackey, Eastern Branch Plant Manager)
Quicksilver Products, Inc. M C
350 Brannan Street
San Francisco, CA 94)07
Phone: (A 15) 781-1988
(Miss Grace Emmans, Owner and President)
Sonoma Mines, Inc. C
P.O. Box 226
Guernevllle, CA 94556
Phone: (707) 869-2013
(Mr. C. 0. Reed, President)
Wood Ridge Chemical Corp. M C
Park Place East
Wood-Ridge, NJ 07075
Phone: (201) 939-4600
(Mr. E. L. Cadmus, Technical Director)
a
M - Supplies flasks for return of metallic mercury.
C • Will accept mercury sulfide for reprocessing.
0 • Will accept certain organic mercury chemicals.
Special approval must always be obtained before shipment Is made to
a reprocessor.
186
-------
Is to be used. Follow the sampling procedures outlined In
Section 2.5.
10.2.2.4 Ammonia Nitrogen - Use sulfurlc acid (preferred) or mercuric
chloride plus refrigeration to preserve ammonia samples. Avoid extended
exposure to the air (14,15) by keeping the container capped. The holding
time depends on the type of sample. If a raw sewage sample Is to be
analyzed, hold up to seven days and If other, less polluted samples are
Involved a holding time up to 30 days in acceptable when sulfurtc acid
Is the preservative (12). The maximum compositing period Is 24 hours
with Icing of the samples during this Interval. The preservative should
be added to the container prior to sample collection or immediately after
the composite is formed. Collect 500-800 mis of sample volume Into
glass or polyethylene bottles when macro analysis Is necessary. If the
TechnIcon or automatic analysis is used the required volume Is 20-100
mis. Clean the container as Indicated In Section 3.4; no special
precautions are necessary.
10.2.2.5 Nitrate Nitrogen* - Mercuric chloride plus refrigeration at 4°C
Is the only acceptable preservative since acid catalyzes the nitrite
to nitrate conversion (4). Referenced holding times vary from 18 to 100
days (3»5»6»16). Therefore an 18 day holding time is recommended until
further study Is done. Turbidity removal may be required prior to
analysis. Clean borosilicate glass or polyethylene containers as
Indicated In Section 3.4. Collect a 100-250 ml volume of sample follow-
ing the procedures outlined in Section 2.5.
10.2.2.6 Nitrite Nitrogen - Same as nitrate nitrogen but use 7 day
holding time.I
10.2.2.7 Total Nitrate/Nitrite Nitrogen - Preserve the total nitrite/
nitrate group by addition of sulfurlc acid when possible since Intercon-
verslon of the species Is not critical. Mercuric chloride can be used
but Is not preferred. Hold samples after preservation and refrigeration
at 4°C for up to 30 days (12). Collect a 100-250 ml volume of sample
Into borosilicate glass or polyethylene containers. No special
preparation Is required, but clean containers as Indicated In Section 3.4.
Collect samples as outlined In Section 2.5 with no special provisions.
10.2.2.8 Urtho Phosphate - Immediately after col lection,'fiIter samples
through washed 0.45 u membrane (17) filters Into an acid washed borosilicate
glass container (18). This procedure wiII reduce the conversion of
condensed phosphate to ortho phosphate by removing suspended and micro-
bial material which may catalyze the reaction (17). Do not add sulfuric
acid because this will hasten the hydrolysis of compounds (19, 20).
Refrigerate the samples at 4°C or lower and analyze immediately if possible
or within 48 hours. Do not collect automatic composite samples for ortho-
phosphate analysis because the sample cannot be immediately filtered and
the transfer of the sample may cause adsorbance to container walls to
be more critical. If unflltered samples are analyzed, then the data record
189
-------
Parameter:
Ammonia Nitrogen (Primary)
Water or Wastewater:
X
T
•MM
X
Municipal Wastewater
Industrial Wastewater
Surface Water
Agricultural Runoff
Sludge *
Sediment ••'••
Preservation Method: Preferred:
Add h^SOj, to pH less than 1.5 plus refrigeration
at 4°C. Option (not preferred): AO mg/1
HgClj plus refrigeration for ocean, surface
and mildly polluted waters (TOC<20 mg/l)(6) or
400 mg/1 HgCl2 plus refrigeration for highly
polluted waters (TOC>20 mp/l)
Maximum Holding Times
Grab Samples 7 days for strongly polluted water (Raw sewage)
.. .^ , , 30 days for mildly, polluted nater (Low biological activity)
Composite Samples 6.7g .A^ Max. Compositing ;4 hn.ir^
(After Composite Preparation) Period
(See grab restrictions)
Container Type: glass or Plastic . ;
Volume: 100-1000 mis for manual method or 20-100 mis for automated analysis
Preparation Method: None
Comments: Use H-.SO. v/henever possible/ice the sample during
compositing
Parameter:
Ammonia Nitrogen (Alternate)*
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
JK Municipal Wastewater
Jf Industrial Wastewater
l-»«^i»»
X Surface Water
•v^v«
Refrigeration at k°C
Agricultural Runoff
Sludge *
Sediment *
hours
Composite Samples 6 hours*
(After Composite Preparation)
Container Type: Class or Plastic
Vo I ume: ,___
Preparation Method:
Comments:
Max. Compositing
Period
2k hours
100-1000 mis (20-100 mis for automated analysis)
Ice sample durinq compositina
Figure 10.2 Recommended preservation and
handling methods-NH_
190
-------
Parameter: Nitrate Nitrogen (Primary)
Wittr or Wastewater:
J| Municipal Wastewater
* Industrial Wastewater
*•«»
x Surface Water
Agricultural Runoff
Sludge
Sediment
Preservation Method: Preferred:
Add
at
HoSOj, to pH less than 1.5 plus refrigeration
«.°C. Option (not preferred): 40 rog/1
HgCl2 plus refrigeration for ocean, surface
and mildly polluted Miters (TOC<20 mg/l)(6) or
WO mg/1 HgClj pi as refrigeration for highly
polluted waters (TOC>20 mg/l )
naxlmum Holding Times,
Crab Samples IB days ( 5)
Composite Samples 17 days ( 5)
(After Composite Preparation)
Max. Compositing
Period
hours
Container Typefllass or Plastic
Volume:
100-250 mis.
Preparation Method:
Comments:
Turbidity Removal
Acid catalyzes conversion of nitrite to nitrate (k )
Parameter: Nitrate Nltrogen (Alternate)
Water or Wastewater:
Preservation Method:
J<__ Municipal Wastewater X_
X Industrial Wastewater X
me^**^ •••^••m
X Surface Water X
MlB^B^ MMMWB
Refrtqerate at 4°C
Agricultural Runoff
Sludge*
Sediment*
2k hours
hours*
Maximum Holding Times
Grab Samples _____
Composite Samples ______^_^
(After Composite Preparation)
Container Type: Glass or Plastic
Volume:
Max. Compositing
Period
2
-------
Parameter:
Nitrite Nitrogen (Primary)
Water or Wastewater:
_X Municipal Wastewater
_X Industrial Wastewater
X Surface Water
Agricultural Runoff
Sludge *
Sediment-
Preservation Method: Preferred: Add H2SOj, to pH less than 1.5 plus refrigeration
at ¥>C. Option (not preferred): 40 tnq/1
HgCl2 plus refrigeration for ocean, surface
and mildly polluted waters (TOC<20 mg/l)(6) or
MOO mg/l HgCl2 plus refrigeration for highly
polluted waters (TOO20 mg/1)
Maximum Holding Times
Grab Samples
II days
Composite Samples 10 days
(After Composite Preparation)
Container Type: Class or Plastic
Volume: 100-250 mis
Max. Compositing
Period
21* hours
Preparation Method:
Comments:
Turbidity Removal
Acid catalyzes conversion of nitrite to nitrate
Parameter: Nitrite Nitrogen (Alternate)
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Crab Samples
_X Municipal Wastewater X
_X Industrial Wastewater X
X Surface Water X
• ••• i • «*^__
Refrigerate at b°C
Agricultural Runoff
Sludge*
Sediment*
2k hours
Composite Samples 6 hours*
(After Composite Preparation)
Container Type: Glass or Plasth
Volume:
Max. Compositing
Period
hours
100-250 mis
Preparation Method:
Comments:
Turbidity Removal
Figure 10.4. Recommended preservation
and handling method-NO™
192
-------
Parameter: Total Nitrite/Nitrate Mltrooen
Water or Vastewater: X Municipal Wastewatcr X Agricultural Runoff
X Industrial Wastcwater X Sludge*
X Surface Water X Sediment *
Preservation Method: Preferred: Add t^SOj, to pH less than 1.5 plus refrigeration
at ¥>C. Option (not preferred): AO mg/l
HgC)2 plus refrigeration 'for ocean, surface
and mildly polluted waters (TOC<20 mg/1) (6) or
1»00 mg/1 HgCtj plus refrigeration for highly
u . u ... T. polluted waters (TOC>20mg/l)
Maximum Holding Times ^ ^
Grab Samples _ 30 days (12) _
Composite Samples 29 days _ Max. Compositing M hours _
(After Composite Preparation) Period
Container Type: _ Glass or' Plastic _
Volume: _ - 100-250 mis _
Preparation Method: None __
Comments: Use H?SO([ whenever possible _
Figure 10.5. Recommended preservation and
handling methods-N02/NO-
tQrameter: OrthoPhosphate (Primary/No Alternate)*
Water or Wastewater: X Municipal Wastewater X Agricultural Runoff
X Industrial Wastewater X Sludge*
X Surface Water X Sediment *
preservation Method: Filter Immediately after sampllno through 0.
-------
must Indicate this fact. Acid wash borosllicate glass containers with
a hydrochloric acid mixture as indicated in Section 3>*t after the con-
tainer has been cleaned. Collect 50*250 ml of sample using the grab
sampling precautions listed in Section 2.5.
10.2.2.9 Total Phosphate - Add sulfuric acid (preferred) or mercuric
chlorlae to preserve samples for total phosphate analysis. Use
acid when only phosphate is analyzed or when it does not interfere
with other analyses. Use mercuric chloride when interference is
involved to reduce the rate of degradation In the sample (16). Samples
are stable and can be held indefinately (12, 16). Rinse borosilicate
glass or polyethylene containers with hydrochloric acid (see Section 3.*0
after cleaning. This procedure will remove detergent or other residual
phosphates (18). Collect 50-250 ml samples as composite or grab samples
following the recommendations in Section 2.5*
10.2.2.10 Preservation For All Nutrients - Collect two samples If all
nut rIen ts a re ana1yzed. Use one borosilicate glass or polyethylene
container which has been previously hydrochloric acid rinsed to collect
2550 ml of sample or 1000 mis if automated analysis of ammonia and TKN
is used. Follow grab or composite procedures indicated in Section 2.5-
Add mercuric chloride and refrigerate samples. These samples can be
held 7 to 30 days. This procedure will be sufficient for TKN, ammonia,
nitrate, nitrite and total phosphate. Collect a second sample of
approximately 250 ml, filter (0.^5 u membrane) Into a hydrochloric acid
rinsed borosilicate glass bottle and refrigerate at 4°C. Analyze this
sample for orthophosphate within A8 hours of sampling.
10.3 METHODS FOR DEMAND PARAMETER GROUP
10.3.1 Background
The uptake of oxygen is critical to many life forms. Since a suitable
amount of dissolved oxygen is needed for most aquatic life to exist,
the importance of demand cannot be minimized. Since dissolved oxygen
is inherently related to this overall measure, this parameter has also
been included in this section.
10.3.1.1 Biochemical Oxygen Demand (BOD) - One way of measuring the
impact of a discharge on a receiving stream is by analysis of biochemical
oxygen demand. This procedure is generally a bioassay technique which
measures the amount of oxygen used by organisms aerobically decomposing
organic material. In general, standard conditions are used to simulate
a biological environment. Samples are seeded with a varied culture of
microorganisms, diluted with nutrient rich water (in some cases), and
incubated in the dark at 20°C for 5 days. After this time the oxygen
concentration is again measured. The depletion is said to represent
70-80 percent of the total demand for a domestic waste. The oxygen used
191*
-------
Parameter: Total Phosphate (Primary)
Water or Wastewater:
X Municipal Wastewater
X Industrial Wastewater
• • ••
X Surface Water
Agricultural Runoff
Sludge *
Sediment *
Preservation Method: H?SOitto pH<1.5 plus refrigeration at 4 C or
AO to *<00 mg/1 HqCl2 plus refrigeration at A C
Maximum Holding Times
Grab Samples
Indefinite
(12 )
Composite Samples Indefinite
Max. Compositing
Period
2k hours
(After Composite Preparation)
Container Type: Class or Plastic/ Hydrochloric Acid Wash
Volume:
50-250 mis - depends on concentration
Preparation Method:
Comments:
None
Use acid whenever possible
Parameter: Total Phosphate (Alternate)
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Crab Samples
Municipal Wastewater
Industrial Wastewater
Surface Water
Refrigerated at fr°C
_X Agricultural Runoff
J Sludge*
X Sediment*
Indefinite
Indefinite
Composite Samples
(After Composite Preparation)
Glass or Plastic/ Hydrochloric Acid Wash
Max. Compositing
Period
24 hours
Container Type:
Volume:
50.-250 ml
Preparation Method:
Comments:
Figure 10.7. Recommended preservation and
handling methods-Total Phosphate
195
-------
Is theoretically related to the organic concentration by the following
equation.
Cn Ha °b Nc * (n * f - I • ? c) °r* n C02 + (f ' f c) H2° * cHN3
However, precision varies [up to 20% reproduclbi 1 Ity(l) ] according to
many factors including toxic substances, critical concentrations, initial
conditions, acclimation and others. Another disadvantage of the BOO
parameter is the length of time (at least 5 days) between sample collec-
tion and reporting of the test results.
10.3.1.2 Chemical Oxygen Demands (COD) - This test measures the total
amount of oxldizable matter under acidic oxidizing conditions. It Is
imperative that exactly the same procedure by followed for all analyses
because the extent of reaction Is time and temperature dependent. The
disadvantage of the COD parameter is that it may not be indicative of
the biochemical oxygen demand In an environment. Either materials are
oxidized In the COD test which are not biologically attacked or chemical
species such as sulfite create excessive oxygen depletions. This may
result in misrepresentation of the biochemical oxygen demand. However,
the test results can be obtained within three hours.
10.3.1.3 Total Organic Carbon (TOC) - The total organic carbon can be
related to the oxygen demand by the equation: C + Oj — ^ C0£. However,
compounds which contain oxygen are not adequately represented using
this formula and partial oxidation is not measured (i.e., acetaldehyde and
oxygen to acetic acid). The same problem exists for this test as for
COD, in that the actual biological effects on the environment are not
measured. However, this analysis can be done in minutes and Is adaptable
to on-line monitoring.
10.3.1..** Dissolved Oxygen (DO) - The basic objective of all the demand
tests is to determine the effect of a discharge on the dissolved oxygen
concentration of a receiving water. Often it is desirable to measure
or monitor the DO In the receiving water directly. All gases soluble
in water are affected by the ambient temperature and pressure and this
is also true for oxygen. As the temperature increases, the amount of
soluble oxygen decreases. Therefore, the worse conditions are apparent
on a hot day. Although the solubility of the oxygen in the atmosphere
varies from 7-13 mg/1, 8 mg/1 is generally considered the upper limit
for demand considerations because of the temperature and altitude dependence.
10.3-2 Recommended Preservation and Handling Methods
10.3.2. 1 General - Refrigeration is recommended when biological species
are involved while chemical addition can be used when chemical species
are considered. Dissolved gases can not be preserved, so in situ
analysis Is required.
196
-------
HeehofflieaS Oxygen Demand ° lee all samples for BOD analysis
©n aneTtransporto Reducing the temperature to the
...6toy* freezing 5s preferable (21). Generally See Is used.
samples within 2k tears of collection (22P23), Composite
held an additional & hours to allow for transportation of
site sample to tha laboratory. Be certain samples are
fleetSon (1) and transportation (23). Collect 1 to 2
into clean boro§llleate glass or polyethylene containers,
in Section 2,5 for sample collection.
10.3.2.3 Chemical Oxygen Demand - Add suIfuric acid to achieve a pH of
1.5 (8) and refrigerate the sample at *»°C. Hold the sample up to 7
days. Of aeld addition affects the stability of the sample refrigerate
and analyse within 2k hours (21, 22). This will alleviate the difficulty
of deoraylslfylng an oil and then resuspendlng It prior to analysis,
Homogenise samples with high solids content prior to aliquot removal.
Clean gla§g boroslllcate glass or polyethylene containers as outlined
in Section 3«4>» No special preparation is required. Sample following
In Section 2,5.
10.3.2.*} Total Organic Carbon = Treat the sample the same way as COO
(Seeti®n TO.3«2.3).Homogenlzatlon and ultrafine homogenization may be
required prior to analysis if high solids samples are to be analyzed.
This will allow removal of representative subsamptes and may aid the .
snalytiesl procedure.
10,3,2.5 Dissolved Oxygen ° Analyze DO in situ or on the site of
s©mplIng.Us® the membrane electrode probe calibrated for temperature
and altitude whenever possible to minimize Interference from pressure
and temperature changes and avoid the high alkalinity from the szide
teehnlquQ. Always use a stirring device with a probe to move water
past the mambrane. If the sample cannot be analyzed ijn situ use glass
BOD bottles to contain the sample and eliminate entrained air (1). If
transportation prior to analysis is mandatoryp fix sample with azide
reagantSo store at a temperature below that of the water body and analyze
immadiatoly upon arrival at the destination. Do not hold sample longer
than ^=8 hour's (1).
10.3.2.6. Recommended Methods for Entire Group - Take two samples when
possible and analyze one Immediately for DO or f?« with azide analysis
for later analysis. Split the second sample into 2 containers (either
polyethylene or borosllicate glass). Preserve one bottle, 600 mlsc with
sulfuric acid to pH less than 1.5 and Ice the second bottle, 2 liters,
for immediate transport. When the samples arrive at the laboratory, BOD
analysis should begin immediately and the pH of the second sample checked
to maintain the desired level.
197
-------
Par** ten
Biochemical Oxygen Demand (Primary)
Ot Wastewater:
JK^ Municipal Wastewater X_
JC__ Industrial Wastewater X_
X Surface Water X
Agricultural Runoff
Sludge *
Sediment *
Preservation Method: Icing at 0°-4°C (Do not freeze)
Maximum Holding Times
6rab Samples & hours
Composite Samples 6 hours
(After Composite Preparation)
Container Type: Class or Plastic
Volume: 1000-2000 mis
Max. Compositing
Period
hours
Preparation Method:
Comments:
Parameter: Biochemical Oxygen Demand (Alternate)
Water or Wastewater:
Preservation Method:
_X_ Municipal Wastewater
X Industrial Wastewater
••M^
X Surface Water
••*•»
Refrigeration at 4°C
X Agricultural Runoff
JK__ Sludge *
X Sediment *
Maximum Holding Times
Grab Samples 2
-------
Parameter:
Chemical Oxygen Demand (Primary)
Water or Wastewater:
Preservation Method:
x Municipal Wastewater * Agricultural Runoff
JJ Industrial Wastewater * Sludge*
Jjj Surface Water x Sediment *
H..SO. to ph less than 2 plus refrigerate
at 4°C
Maximum Holding Times
Grab Samples 7 days*
(can be longer If proven)
Composite Samples 6 days
(After Composite Preparation)
Container Type: Glass or Plastic
Volume:
Max. Compositing
Period
2k hours
100-500 ml
Preparation Method:
Comments:
Homogenize high solids samples
Parameter:
Chemical Oxygen Demand (Alternate)
Water or Wastewater:
Preservation Method:
_X Municipal Wastewater X
X Industrial Wastewater X
«•*•••«• ^^^Bfll
_£ Surface Water X
Reqrlqeratlon at 4 C
Agricultural Runoff
Sludge*
Sediment"
Maximum Holding Times
Grab Samples 2k hours
Composite Samples 6 hours*
(After Composite Preparation)
Glass or Plastic
Max. Compositing
Period
2*t hours
Container Type:
Volume: 100-500 mis .
Homogenize high solids samples
Preparation Method:
Comments: Method used If acidification disturbs the stability of the
sample
Figure )0.9. Recommended preservation and
handling methods - COD
199
-------
Parameter:
Total Orqanic Carbon (Primary)*
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
Municipal Wastewater x Agricultural Runoff
Industrial Wastewater X Sludge*
' Surface Water x Sediment *
SO to pH less than 1.5 plus refrigeration at
7 days
Composite Samples 6 days
(After Composite Preparation)
Container Type: Glass or Plastic
Volume:
Max. Compos11 i ng
Period
2k hours
50 mis
Preparation Method:
Comments:
Homoqenitatlon of high solids samples
Parameter:
Total Organic Carbon (Alternate)*
Water or Wastewater:
Preservation Method:
Maximum Holdjng Times
Crab Samples
Municipal Wastewater
Industrial Wastewater
X Surface Water
Refrigeration at A°C
2k hours
Agricultural Runoff
Sludge*
Sediment *
Composite Samples 6 hours*
(After Composite Preparation)'*"
Container Type: Glass or Plastic
Volume: 50
Max. Compositing
Period
2k hours
Homooanlzatlon of hi oh solids samples
Preparation Method:
Comments: Use alternate when sample contains appreciable amounts of
emulslfled oiI
Figure 10.10. Recommended preservation and
handling methods-TOC
200
-------
Parameter: Dissolved Oxygen (Primary)
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
X Hun Ic1 pa 1 Wastewater
X Industrial Wastewater
•••^^•M
X Surface Water
•^••^•w
None
Agricultural Runoff
Sludge
Sediment
In situ
Composite Samples Jot recommended
(After Composite Preparation)
Container Type: Glass - BOD Bottle
Volume: 300 ml
Max. Compositing
Period
Preparation Method: ^
Comments:
Do not use electrode on samples with sulfur compounds or
on solids
Parameter: Dissolved Oxyqen (Alternate)
Water or Wastewater: X Municipal Wastewater X Agricultural Runoff
X Industrial Wastewater X Sludge*
X Surface Water X Sediment*
Preservation Method: Fix uslno Method fr.5.I or k.5.2 p 5 greater than
I97fr EPA Manual and store at temperature lower than
Maximum Holding Times sampling temperature.
Crab Samples fr-8 hours
Composite Samples Not recommended
(After Composite Preparation)
Max. Compositing —
Period
Container Type:
Volume:
Glass BOD Bottle/Water seal
300 ml
Preparation Method: -- __
Comments: Not used for: raw sewage, biolooical flees, high solids samples.
oxidizing constituents, color-interferences
Figure 10.11. Recommended preservation and
handling methods - DO
201
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10.<» METHODS FOR METALS PARAMETER GROUP
IO.fr.1 Background
Metals analyses have been greatly simplified by the acceptance of atomic
absorption as the major analytical tool. Since metals are often found
in very low concentrations, this analytical method is appropriate
because of Its high sensitivity (see Table 10.3). The metals listed are
Included In this portion of the report with the addition of boron which
is not analyzed using atomic absorption.
J0.fr.2 Recommended Preservation and Handling Methods
10.^.2.1 Arsenic - Handle arsenic sample without consideration of the
analytical technique to use. Collect samples as Indicated In Section 2.5
Into borosllicate glass or polyethylene bottles previously nitric acid
rinsed (see Section 3.*t). Collect 100-200 ml and preserve with nitric
acid to pH less than 2 to reduce adsorption of Ions to the container
sides. Store sample a maximum of 6 months but a shorter time Is desirable.
10,4.2.2 Boron • Collect 50-100 mis of sample Into nitric acid rinsed
po1 yethyVene~contaIners (borosiltcate containers cannot be used).
Refrigerate at *»°C and hold samples up to 6 months.
10.^.2.3 Calcium, Potassium and Sodium,- Collect samples of all water or
wastewater type and preserve with nitric acid to pH less than 2. The
analytical technique does not affect the preservation method. Use nitric
acid rinsed polyethylene or borostlicate glass containers (see Section 3.A)
and collect 100-250 ml per metal. Hold samples a maximum of 6 months.
10.A.2.1* Chromium \M - Analysis for this unstable metal form should begin
immediately (}).FTthis is not possible, refrigerate the sample and
analyze within 2** hours. Ice composite samples over the maximum composite
interval of 2k hours and analyze within 6 hours of composite preparation.
Report total time between collection and analysis with the results if It
exceeds the maximum recommended. Unscratched polyethylene or borosllicate
glass containers are required since chromium VI Is easily adsorbed to
Container walls. Acid rinse containers with nitric acid before sample
collection. A 100-200 ml volume Is sufficient for analysts.
10.A.2.5 Mercury - Preserve samples by adding 5% nitric acid V/V and
0.05* V/V potassium dlschromate (26). Nitric acid rinse (see Section 3.J»)
borosllicate glass or polyethylene bottles. Mercury Is much less
stable than other metals, so hold samples up to 30 days (12). Only
manual grab or manual composite samples are acceptable for mercury
analysis due to possible losses of volatile mercury ion. Collect sample
(200-300 mis) and preserve Immediately. Check nitric acid prior to
use for trace mercury content and correct the final result for volume
change.
202
-------
Table 10.3. ATOMIC ABSORPTION CONCENTRATION RANGES WITH
CONVENTIONAL ATOMIZATION (25)
Metal
Aluminum
Antimony
Arsenic*
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury ••
Molybdenum
Nickel
Potassium
Selenium*
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
Zinc
Detection
Limit
mg/l
0.1
0.2
0.002
0.03
0.005
0.002
0.003
0.02
0.03
0.01
0.02
0.05
0.0005
0.01
0.0002
0.1
0.02
0.005
0.002
0.01
0.002
0.1
0.8
0.3
0.2
0.005
Sensitivity
mg/l
1
0.5
-
0.4
0.025
0.025
0.08
0.1
0.2
0.1
0.12
0.5
0.007
0.05
-
0.3
0.15
0.04
-
0.06
0.015
0.5
4
2
0.8
0.02
Optimum
Concentration
Range
mg/I
5
1
0.002 -
1
0.05
0.05
0.2
0.2
0.5
0.2
0.3
1
0.02
0.1
0.0002 -
0.5
0.3
0.1
0.002 -
0.1
0.03
1
10
5
1
0.05
100
40
0.02
20
2
2
20
10
10
10
10
20
2
10
0.01
20
10
2
0.02
4
1
20
200
100
100
2
•Gaseous hydride method.
•*Cold vapor technique.
203
-------
Parana ter:
Arsenic
Water or Wastewater:
Preservation Method:
X
MM*
X
••«•<
X
Municipal Wastewater
Industrial Wastewater
Surface Water
HNO. addition to pH < 2
_X Agricultural Runoff
X ^ SludgeA
X Sediment A
Maximum Holding Times
Grab Samples 6 months
Composite Samples
6 months
(After Composite Preparation)
Container Type:
Volume: 100-200 mis
Max. Compositing
Period
2k hours
PI as 11c or Glass/HNO, Rinse
Preparation Method:
Comments:
Parameter:
Boron
Water or Wastewater:
X Municipal Wastewater
X Industrial Wastev/ater
••^M«V
X Surface Water
_X Agricultural Runoff
_X Sludqe *
x Sediment *
Preservation Method: Refrigeration at
Maximum Holding Times
Grab Samp.lfcs 6 months
Composite Samples 6 months
(After Composite Preparation)
Max. Compositing - no maximum -
Period
Container Type:
Volume: 50-100 mis
Plastic only/HMO, Rinse
Preparation Method:
Comments:
None
Figure 10.12. Recommended Preservation and
handling methods-As § B
201*
-------
Parameter:
Catcturn, Potassium and Sodium
Water or Wastewater:
Preservation Method:
_X Municipal Wastewater
X Industrial Wastewater
•••^B*
X Surface Water
_X Agricultural Runoff
X Sludge *
Sediment
HNO. addition to pH less than 2
Maximum Holding Times
Grab Samples 6 months
Composite Samples 6 months
(After Composite Preparation)
Container Type: 100-250 mis
Volume:
Preparation Method:
Comments:
Max. Compositing
Period
2k hours
Parameter:
Chromium VI
Water or Wastcwater:
_X Municipal Wastewater
X Industrial Wastcwater
X Surface Water
_X Agricultural Runoff
X Sludqe*
" *
X Sediment
Preservation Method: Refrigeration at 4 C
Maximum Holding Times
Grab Samples 2A hours
Composite Samples 12 hours
Max. Composition
Period
(After Composite Preparation)
Container Type: Plastic or glass (not scratched)/HNO, Rinse
Volume:
2 A hours
100-200 mis
Preparation Method:
Comments:
Remove solids by centrifuge
Figure 10.13. Recommended preservation and
handling methods-Ca, K, Na, Cr VI
205
-------
Parameter:
Mercury
Water or Wastewater:
_X Municipal Wastewater X
X Industrial Wastewater X
^•••MB ^HM^HI
X Surface Water X
Agricultural Runoff
SIudge *
Sediment *
Preservation Method: 5% v/v HNOr addition plus 0.05% Cr,0,*
Maximum Holding Times
Grab Samples
30 days (12)
Composite Samples Manual, only 30 jayMax. Compositing
(After Composite Preparation)Period
Plastic or Glass/UNO Rinse
Container Type:
Volume:
200-300
Preparation Method:
Comments:
None
* Correction for volume chanoe plus analysis of acid
for mercury impurities required
Parameter:
Silver
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
_X Municipal Wastewater X
X Industrial Wastewater X
•^•••••B •i^HH^MI
X Surface Water X
_MM •! I "M
HNO, addition to pH less than 2
Agricultural Runoff
Sludge *
Sediment *
30 days
Composite Samples 30 days
(After Composite Preparation)
Container Type: Pnlygt-hyleng/ HMO Rinse
3
Volume:
Max. Compositing
Period
hours
200-IPO
Preparation Method:
Comments:
None
Figure 10.14. Recommended preservation and
handling methods-Hg, Ag
206
-------
1Q.*t.2.6 SIIver - Keep samples for stiver analysis In nitric acid rinsed
polyethylene containers and store in the dark. Add nitric acid to pH
less than 2 to reduce adsorption. Hold samples up to 30 days (27)
maximum. Collect a sample volume of 200-300 ml following the procedures
In Section 2.5-
10.A.2.7 Other Metals - Take samples for metal analysis In nitric acid
washed boroslltcate glass or polyethylene containers (28). Collect a
volume of 200-500 ml (depending on precision required) using the pro-
cedures outlined in Section 2.5. Preserve samples by addition of nitric
acid to pH 2 (27). They are stable up to 6 months with preservation. To
preserve dissolved parameters, filter sample through 0.45 V filter
paper and add nitric acid to pH less than 2. The filtrate is then
stable up to 6 months. These techniques for total metals apply to (25):
Aluminum Iron Thallium
Antimony Lead Tin
Barium Magnesium Titanium
Bery111 urn Manganese Vanad'um
Cadmium Molybdenum Zinc
Chromium (Total) Nickel
Cobalt Selenium
Copper Silver
10.4.2.8 Preservation Methods for All Metals . - Take one 200 ml sample
into a nitric acid washed*polyethylene bottle. Analyze for chromium VI
Immediately and place a boron aliquot in separate plastic container.
Acidify the remainder with nitric acid to pH 2 and refrigerate up to 6
months. Manually collect the mercury sample and preserve Immediately in
a separate container with potassium dichromate. '
10.5 METHODS FOR PHYSICAL/MINERAL PARAMETER GROUP
10.5.1 Background
The physical and mineral group encompasses a wide range of parameters.
To simplify this section, these constituents have been subdivided into
anions and other parameters. This subdivision is given below:
An ions Other
Bromide Conductivity pH
Chloride Alkalinity Acidity
Cyanide Chlorine , Hardness
Fluoride ON and Grease Phenols
Sulfate Surfactants Color
Sulflde Total Solids Suspended Solids
Sulflte Dissolved Solids Volatile Solids
Turbidity
207
-------
Parameter: All Others Total Metals
Water or Wastewater:
Preservation Method:
X Municipal Wastewater X
X Industrial Wastewater X
MMMBM *M«MM.
X Surface Water X
• ' »-
HNO addition to pH less than 2
Agricultural Runoff
Sludge *
Sediment
Maximum Holding Times
Grub Samples 6 months
Composite Samples 6 months
(After Composite Preparation)
Max. Compositing
Period
hours
Container Type:
Volume: 200-500 ml
Plastic or Glass/HNO, Rinse
3
None
Preparation Method:
Comments: Dissolved metal samples should be filtered immeldatelv on site
and then nitric acid addgd tp pH IMS than 2.
.Figure 10.15. Recommended preservation and
handling methods-Metals
208
-------
10.5.1.1 An Ions - These anions are diverse and found In wide ranges of
concentration across the country. Bromide Is generally contributed by
leaching from sea water but recently industrial discharges have released
this compound. However, the normal concentration remains less than I mg/1
Chloride, on the other hand, Is quite common >n all water supnlles.
Salt passes through the bodies of most organisms virtually unchanged.
In domestic wastewater this can add approximately 15 mg/1 Cl to the
waste stream. Chloride can add a salty taste to water in concentrations
greater than 250 mg/1. Fluoride was found to be an effective tooth decay
preventattve in low concentrations (1 mg/1). However, concentrations
greater than 10 mg/1 can be harmful. The addition of fluoride is care-
fully monitored so the disadvantages are not apparent.
Cyanide compounds are any material with a CN group attached. They can
be either simple or complex but are toxic If they solublllze In water.
If cyanides are present in water at concentrations as low as 0.1 mg/1,
they will adversely affect the biological activity of a natural water
body.
The three sulfur compounds, sulfate, sulflte and su\fide are Interrelated
through bacterial or oxidizing activity. Sulflte, S0«, is readily oxi-
dized to sulfate, SOr, under aerobic conditions and Is therefore very
unstable. Sulfate Is commonly found in waters and wastewaters but under
certain circumstances it can be converted to sulfide causing corrosion
and odor. The mechanism for these conversions is as follows:
anaerobic
SOj + organic materials *• S - + H.O + CO-
M bacteria * L
S - * 2H* ^=t H2S
The hydrogen sulfide gas is odorous and the hydrogen tons released with
the gas will accumulate in sewers causing crown corrosion. Therefore,
the concentrations of parameters In (his group are frequently monitored
10.5.1.2 Other Compound and Materials - More information Is found re-
garding the other physical and mineral parameters. However, the amount
of information available is dependent on the specific constituent.
Specific conductance or conductivity will give a general indication of
the ionic concentration of a solution. In most applications, conductance
can only be used as a monitoring parameter, rather than an actual indi-
cation of concentrations. On the other hand, pH measures the concen-
tration or activity of hydrogen ions. Most potable waters are slightly
basic due to the presence of carbonate or bicarbonate, but this may be
affected by other constituents. Alkalinity and acidity are related to
the buffering capacity of a water or wastewater. Acidity is the capacity
of a water or wastewater to donate protons. The corrosiveness of a water
209
-------
Increases at high acidity and there Is always some acidity In waters
with pH lower than 8.5. Alkalinity Is the capacity of water of
wastewater to neutralize acids or accept protons. The main contributors
to alkalinity are salts of weak acids or strong baste compounds. Both
acidity and alkalinity are related to the carbon dioxide - carbonate -
bicarbonate Interaction In a water system.
Hardness Is defined as the capacity of a water to precipitate soap.
This is, In most cases, equal to the sum of the calcium and magnesium
ion concentrations since other contributing constituents are usually
apparent In very low amounts. The amount of hardness is significant
from two standpoints. The second effect is the higher pipe scaling
occurrence when hard water Is used. The following Indicates the
relative degrees of hardness:
Hardness, mg/1 Classification
0-75 Soft
75-150 Moderately hard
150-300 Hard
300 and up Very hard
Color and turbidity can often be confused. However, the distinction
is that turbidity will affect the passage of light and is caused by
suspended matter in the water. It is the property that scatters light
and can be caused by any type of material, Inorganic to organic. True
color is the natural tint of the water after the suspended material
has been removed. Apparent color will indicate the turbidity also.
In most cases true color is that desired by an investigator. This can
be Imparted to a water through natural sources or certain industrial
discharges.
Chlorine residual Is measured on domestic water supplies or wastewaters
that have been discharged. The use of chlorine as a disinfectant Is
widespread and has been studied extensively. There are two mechanisms
for chlorine disinfection. One Is free chlorine which is defined as
chlorine, hypochlorous acid and hypochlorlte. The other mechanism Is
that of combined chlorine or chloramines. Both types should be included
when testing total residual chlorine.
Oil and grease are defined as any material which Is soluble in extractant.
This can Include long chain hydrocarbons, fatty acids, esters, oils and
other materials. Determination of representative oil and grease is
difficult because of Its low solubility and tendency to separate from
water. Therefore, collection of a representative sample Is complicated
by oil gathering on the surface of a water body.
210
-------
Phenols ©re used In the manufacture of plastics res8ns and dyes and ar
-------
Parameter: Bromide (Primary - no alternate)
Water or Wastewater:
PratervatI on Method:
X
••••M
X
•MM
X
Municipal Wastewater
Industrial Wastewater
»
Surface Water
Refrigeration at 4°C
^ Agricultural Runoff
J Sludge
X Sediment
Maximum Holding Times
Crab Samples 24 hours*
Composite Samples 24 hours *
(After Composite Preparation)
Max. Compositing
Period
24 hours *
Container Type:
Volume:
Preparation Method:
Comments:
Plastic or Glass
- SQQ nil
None
Parameter:
Chloride (Primary - no alternate)
Water or Wastewater: X Municipal Vastcwater X_
' X Industrial V/astev/ater X_
X Surface Water X_
Preservation Method: Refrigeration at 4°C
Agricultural Runoff
Sludge
Sediment
Maximum Holding Times
Grab Samples
days
Composite Samples
d*ys
(After Composite Preparation)
Container Type: Plastic or Glass
Volume: 50 - 200 mis
Max. Compositing
Period
48 hours
Preparation Method:
Comments:
None
Figure 10.16. Recommended preservation and
handline methods - Br 5 Cl
212
-------
Parameter:
Cyanide (Primary - no alt»rnai.»)
Water or Wastewater:
Preservation Method:
Haxlmun Holding Times
Grab Samples
Municipal Wastcwater y Agricultural Runoff
Industrial Wastewater x Sludge
_X Surface Water x Sediment
Na OH addition to pH 12 or greater plug
r ef r1g e ra t i on a t. A°C.
24 hours *
Composite Samples 6 hours *
(After Composite Preparation)
Max. Compositing 2 4 hours
Period
Container Type:
Volume:
Preparation Method:
Comments:
Plastic or Glass
500 - 1000 mis.
None
Sample before chlorine is added to the sample
Parameter:
Water or Wastewater:
Fluoride (Primary - no alternate^
Municipal Wastewater
Industrial Wastcwater
Surface Water
JC Agricultural Runoff
X Sludge
X Sediment
Preservation Method: Refrigeration at k C
Maximum Holding Times
Grab Samples
days
Composite Samples 12 days
(After Composite Preparation)
Container Type: Plastic Only
Volume:
300 - 5— mis
Preparation Method:
Comments:
None
Max. Compositing
Period
48 hours
Figure 10.17. Recommended preservation and
handling methpds ^ CM" § F-
213
-------
Immediately remove chlorine to avoid reduction of cyanide to carbon
dioxide and nitrogen gas. Collect 500-1000 ml following pro-
cedures outlined in Section 2.5.
10.5.2.k Fluoride * - Polyethylene containers only are allowed for fluoride
collection since fluoride is easily absorbed onto glass. Collect samples
of 300-500 mis and refrigerate at k C for up to 14 days.
10.5.2.5 Sulfate * - Refrigerate samples at 4°C for 7 days. Clean boro-
silicate glass or polyethylene containers using the procedures outlined
In Section 3-4. Collect a volume of 100-500 mis using the sampling
methods discussed In Section 2,5*
fide * - Add 2 ml/I of I normal zinc acetate to samples and
t 4"C. This will stabilize sulfide samples up to 7 days
10.5.2.6 Sul
although the compositing interval must be limited to 24 hours unless
the preservative Is present In the bottle. Clean borosilicate glass
or polyethylene as Indicated in Section 3.4 and collect 300-500 ml.
10.5.2.7 Sulflte * - Collect a full sample bottle and cap Immediately
to reduce contact with oxygen. Refrigerate samples at 4 C in either
polyethylene or borosilicate glass and analyze immediately or within
2k hours of sampling (grab) and 30 hours for composite (6 hour transport
time). Collect 200-500 mis.
lp.5.2.8 Acidity * - Refrigerate samples at 4°C and analyze grabs within
24 hours and composite samples within 48 hours. This short holding time
will reduce changes In the carbonate - bicarbonate balance. Collect
100 ml of sample into polyethylene or Lorosilicate glass containers.
10.5.2.9 Alkalinity * - Follow the same procedures as Section 10.5.2.8.
JO.5.2.10 Chlorine residual * - Analyze samples within |5 minutes of
collection or note the interval between sampling and analysis. Use
borosilicate glass containers only to avoid the loss of chlorine
residual through reduction of contaminants on the container walls,
and fill sample container to top to reduce changes in the chlorine
residual.
Avoid exposure to sunlight and excessive agitation of the sample.
Collect a volume of 200-500 mis. Do not use composites.
10.5.2.11 Color* - Refrigerate samples at 4°C for 2k hours (grab) or
18 hours for composites. The short holding time will reduce natural
changes In color. Collect a volume of 100-200 ml of sample Into clean
borosilicate glass containers to prevent the adsorption of colored
organlcs onto the container walls.
214
-------
Parameter: <;Mifa»0 (Primary - no alternate)
Water or Wastewater: X Municipal Wastewater j^ Agricultural P.ynoff
X Industrial V/astewater x Sludge
x Surface Water x Sediment
Preservation Method: - - - • l0-
Rofrlnorafinn at
-
Maximum Holding Tinies
Grab Samples
7 days
Composite Samples g dav«
composite bampies g days
(After Composite Preparation)
Container Type: Plastic or Glass
Volume:
Max. Compositing
Period
hours
100.- 5QQ ml (Depends on analytical method)
Preparation Method:
Comments: \
None
Parameter:
Sulfide (Primary - no alternate)*
Water or Wastawater:
Preservation Method:
jK Municipal Wastewater X Agricultural Runoff
_X Industrial Wastewater X Sludge
_X Surface Water X Sediment
Addition of 2 ml/1 1 molar zinc acetate plus
Refrigeration at A C
Maximum Holding Times
Grab Samples
7 days
Compos i te S nmpIcs
Composite anmpies ^ days
(After Composite Preparation)
Container Tvpe: Plastic or Glass
Volume:
Max. Compositing
Period
2k hours
tnn - 500 mis
Preparation Method:
Comments:
None
Figure 10.18. Recommended preservation and
handling methods - SOr and S=
215
-------
Parameter:
Sulflfo
fPrimary - no alternate)
Water or Uastewater:
Municipal Wasteviater
Industrial Wastewaten
Surface Water
Preservation Method: Refrigeration at *t C
Agricultural Runoff
Sludge
Sediment
Maximum Holding Times
Grab Samples
Immediate analysis (2k hours or _less)*
Composite Samples 6 hours maximum
(After Composite Preparation)
Max. Compositing
Period
Ik hours
Container Type:
Volume:
Preparation Method:
Comments:
Plastic or Glass
200 - 500 mis
None
Full sample and avoid contact with oxygen
Parameter:
Water or Wastcwatcr:
Preservation Method:
Maximum Molding Times
Grab Samples
Compos Ite S ampIes
Acidity (Primary - no alternate)*
_X Municipal Wastewater
_X Industrial Wastev/ater
X Surface Water
""" o *
l/or Inn at U C
Agricultural Runoff
S1udge
Sediment
2k hours
(After Composite Prep
Container Type:
Volume:
Preparation Method:
Comments:
onj
lastic or Glass
Max. Compositing
Period
2k hours;
inn mis
Figure 10.19. Recommended preservation and
handling methods-SOj1 and acidity
216
-------
Parameter:
Alkalinity (Primary - no alternate)*
Water or Wattewater:
Preservation Method:
Maximum Holding Times
Grab Samples
X Municipal Wastewater
x Industrial Wastewater
••»•*
* Surface Water
"»••••
Refrigeration at,fr&C
Agricultural Runoff
Sludge
Sediment
2k hours
Composite Samples
2'i hours
(After Composite Preparation)
Container Type: Plastic or Glass
Volume: 100 mis
Max. Compositing
Period
24 hours
Preparation Method:
Comments:
None
Parameter:
Chlorine Residual (Primary - no alternate)*
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
_X_ Municipal Wastewater X_
X Industrial Wastewater X
•MMMB •••••••
X Surface Water X
Agricultural Runoff
SIudge
Sediment
Immediate. analss Hess then K
Composite Samples not recommended Max. Compositing
(After Composite Preparation) Period
Container Type:
Volume:
Glass only
200 - 5QQml_s_
Preparation Method:
Comments:
Avoid exposure to sunlight or P.xresslvc
Figure 10.20. Recommended preservation and
handling methods - Alkalinity and C^ Res.
217
-------
Parameter:
Color (Primary - no alternate) ft
Water or Wastewater:
Preservation Method:
Maximum Holding Tims
Grab Samples
JC^ Municipal Wastcwater X
X Industrial Wastewater X
••»• .MMM
X Surface Water X
Refrigeration at k C
Agricultural P.unoff
S1udge
Sediment
2k hours
Composite Samples ?t hotir
(After Composite Preparation)
Max. Compositing
Period
hnur
Container Type:
Volume:
Preparation Method:
Comments:
Glass
100 - 200 mis
None
Both apparent and trua color ara arA
-------
10.5*2.12 Hardness* - Refrigerate samples at k C and analyze within
7 days. Collect 50-100 mis Into polyethylene or boroslltcate glass
containers. Follow this procedure when hardness Is specifically analyzed,
rather than a summation of metal tons.
» '*
10.5.2.13 Oil and Grease - Take sample Into a solvent rinsed boroslll-
cate glass container, add sulfurlc acid to pH less than 2 and
refrigerate at 4°C. Analyze the sample within 2k hours. Use a
Teflon cap liner on alt containers. Do not contact the sample with
any plastic surfaces other than Teflon because it will absorb
onto these other organic compounds. Collect a volume of 800 ml and
analyze the entire contents. Take only grab samples for oil and grease
analysis to avoid losses of the surface oil. A cylindrical sample
which takes a cross-section of the stream is one acceptable technique.
When this technique is not available, induce mixing with baffles, pumps,
etc. to create a homogeneous flow stream. Then take sample directly
Into a solvent rinsed container.
10.5.2.\k_ pH * - Analyze samples on site whenever possible. Other-
wise refrigerate samples at 4 C and analyze within 6 hours. After a
composite is formed, analyze pH within 3 hours. Collect 50-100 mis
for analysts in polyethylene or borosilicate glass containers. Keep
containers closed prior to analysis to avoid unnecessary changes in
the sample.
10.5.2.15 Phenolics * - Preserve samples for pheuol analysis by
addition of Ig^i CuSoi, plus H^PO^ to pH less than k and refrigerate at
AC (I). Various preservatives have been tested with copper sulfate
established as most effective (31)• However, elmination of the
possible precipitation of copper compounds at high pH, induced the
use of additional acid. Analyze grab samples within 2k hours of sampling
and composite samples within 2k hours of composite preparation.
Borosilicate glass bottles only are acceptable due to background
contamination or adsorption (32), especially at low concentrations.
Collect a volume of 300-1000 mis and remove oxidizing agents immedi-
ately by the addition of ferrous ammonium sulfate.
10.5.2.16 Spec I fie Conductance - Refrigerate samples at 4°C and
analyze within 48 hours to 7 days depending on the biological activity
of the sample. Use clean polyethylene containers (glass absorbs tons
readily) to collect 100-250 mis.
10.5.2.17 Surfactants - Refrigerate samples at 4°C and analyze within
2k to 48 hours. Acid rinse polyethylene or borostllcate glass con-
tainers with nitric acid (see Section 3.4) prior to sample collection
to remove residual detergents. Collect 500-1000 mis of sample
219
-------
10.5.2.18 Turbidity - Refrigerate samples at k C and store In the dark.
Analyze grab samples in 2k hours and composite samples In 48 hours. The
short holding time will reduce changes In turbidity as colloidal material
solublllzes. Use polyethylene or borostltcate glass containers to collect
100 mis of sample.
10.5.2.10 Total Solids - Refrigerate samples at 4° C and analyze samples
within 7 days of sampling (25). Either polyethylene or borosillcate glass
containers can be used to collect 100-250 mis of sample. Collect
samples using Isoklnetlc sampling with a vertically placed Intake to
obtain a cross-section of the stream.
10.5.2.20 Volatile Solids - Follow the same procedures used for Total
Solids in Section 10.5.2.19.
10.5.2.21 Suspended Solids - Collect 200-500 mis of sample using
isoklnetic procedures through a vertically placed intake when possible,
or sample only well mixed streams. Refrigerate samples at 4°C in clean
polyethylene or borostlicate glass containers. Hold samples up to 7
days, however, biologically active samples may require analysis sooner
to avoid changes In the sample from colloidal or other materials.
Results from questionnaires (33) regarding current practices indicated
that this may be needed for municipal wastewater influent, mixed liquor
from activated sludge plants, agricultural runoff, biological sludges or
other materials.
10.5.2.22 Total Dissolved Solids - Follow the procedures outlined for
Suspended Solids in Section 10.5.2.21.
10.5.2.23 Preservation for Physical/Mineral Group - At least two samples
must be taken into clean glass containers.A 1-liter sample should be
preserved with sulfurtc acid and refrigerated for analysts of oil and
grease. Collect a second 1-liter sample and then Immediately
separate the aliquots for cyanide, phenolIcs and sulfite and add the
appropriate chemical preservative. If transport time is greater than
15 minutes, analyze chlorine residual on site. If possible, in situ
analysis of pH Is recommended; otherwise measure pH of sample
Immediately upon receipt In the laboratory.
10.6 METHODS FOR PESTICIDES/HERBICIDES PARAMETER GROUP
10.6.1 Background
The use of pesticides to control diseases and increase food production
is one of the Important technical advances of the scientific community.
However, the detrimental effects due to the accumulation of pesticides in
fatty tissues of animals and plant waxes is causing environmental hazards
and concern among many people. This problem is complicated because many
220
-------
Parameter: Oil and Grease (Primary - no alternate)*
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
_X Municipal Wastewater X Agricultural Runoff
_X Industrial Wastewater X Sludge
J| Surface Water * Sediment
H.SO, addition to pH 2 plus refrigeration
at *>°C
2*» hours*
Composite Samples Not recommended Max. Compositing
(After Composite Preparation)Period
Container Type:
Volume:
Glass/Solvent Rinse/Teflon Ijner
800 mis
Preparation Method: None
Comments:
Analyze entire volume directly from the
sanple containers
Parameter:
pH (Primary - no alternate)*
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
_X Municipal Wastewater X
X Industrial Wastewater x
•••^•VM ^^•^•H
_X Surface Water x
Refrloeration at k°C
Agricultural Runoff
Sludge
Sediment
Immediate analysis (within 6 hours)
Composite Samples 3 hours
(After Composite Preparation)
Container Type: Plastic or Glass
Volume:
Max. Compositing
Period
hours
50-- 100 mis
Preparation Method:
Comments:
None
Samples bottle kept closed prior to analysis
Figure 10.22. Recommended preservation and
Handling methods - Oil and Grease and pH
221
-------
Parameter:
Ptwinlln—(Primary - no alternate),
Water or Uastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
x Municipal Wastewater X Agricultural Runoff
* Industrial Wastewater jX Sludge
X Surface Water jj Sediment
1 g/1 CuSO, .plus H,PO. to pH less than :
k plus refrigeration at kC
2k hours *
Composite Samples 2k hours *
(After Composite Preparation)
Max. Compositing
Period
hours
Container Type:
Volume:
Preparation Method:
Commonts:
Glass
500 - 1000 mis
None
Remove oxidizing agents Immediately by add 1hg
ferrous ammonium sulfate
Parameter: Specific Conductance (Primary - no alternate) *
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Crab Samples
X Municipal Wastewater
X Industrial Wastewater
MM>M«BM»
X Surface Water
at k°c
Agricultural Runoff
S1udgc
Sediment
2k hours *
Composite Samples 2(1 hours *
(After Composite Preparation)
Container Type:
Volume:
Plastic
100 - 250
Preparation Method:
Comments:
Max. Compositing
Period
2k hours
Figure 10.23. Recommended preservation and
handling methods - Phenolics and Sp. Cond.
222
-------
Parameter: Surfactants - (Primary - no alternate)*
Water or Vastewater:
PratervatI on Method:
Maximum Holding Times
Grab Samples
Municipal Wastewater X
Industrial Wastewater X
•^MMMi
Surface Water X
4>MM
Refrigeration at *>°C
Agricultural Runoff
Sludge
Sediment
2k hours *
Composite Samples Ik hours *
(After Composite Preparation)
Max. Compositing
Period
2k hours
Container Type:
Volume.:
Preparation Method:
Comments:
Glass or Plastic / HNO? Rinse
500 - 1000 mis
Uone
Parameter: _
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
Turbidity (Primary - no alternate)^
jj__ Municipal Wastewater JJ Agricultural Runoff
X Industrial Wastewater J< Sludge
JC Surface Water __* , Sediment
Refrigeration at *t°C (Store In dark)
2k hours
Composite Samples 7^ ^..r.
(After Composite Preparation/
Max. Compositing
Period
Container Type:
Volume:
Pt aal ¥ \f f\i* rt 11
100 mis
Preparation Method:
Comments < ,..
None
Uf\**.nf hnlrllnn tlm» Ayr
Figure 10.24. Recommended preservation and
handling methods - Surfactant and Turbidity
223
-------
Parameter: Total Solids (Primary - no alternate)*
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
X Municipal Wastewater
X Industrial Wastewater
^•^^—B
* ' Surface Water
••••MMBB
Refrigeration at ^C
_X Agricultural Runoff
_X Sludge
X Sediment
7 days
Composite Samples
(After Composite Preparation)
Container Type: _ Plastic or
Volume: _ 100 - 250 mis
Max. Compositing
Period
2*4 hours
Preparation Method:
Comments:
None
Parameter:
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
Volatile Solids (Primary - no alternate)*
X Municipal Wastewater x
X Industrial Wastewater X
•^—•••— H^^MB
X Surface Water X
•^^•1— V*«~
Refrigeration at 4°C
Agricultural Runoff
Sludge
Sediment
7 days
Composite Samples 6 days
(After Composite Preparation)
Container Type: P)astlc or Class
Volume:
Max. Compositing
Period
2k hours
100 - 250 mis
Preparation Method:
Comments:
Hone
Figure 10.25. Recommended preservation and
handling methods - Total and Volatile Solids
22k
-------
Parameter: Suspended Solids (Primary - no alternate)*
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
_X Municipal Wastewater
X Industrial Wastewater
MM«M»
X Surface Water
•»••••
Refriperatlon at k°C
_X Agricultural Runoff
JC Sludge
X Sediment
Up to 7 days*
Composite Samples up to 6 days*
(After Composite Preparation)
Container Type: Plastic or Glass
Volume:
Max. Compositing
.Period
200 - 500 mis
Preparation Method:
Comments:
*Blologically active samples should be
analyzed sooner
Parameter:
Total Dissolved Solids (Primary - no alternate)*
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
X Municipal Wastewater X
X Industrial Wastewater X
X Surface Water X
Refrigeration at A°C
Agricultural Runoff
Sludge
Sediment
48 hours* - 7 days
Composite Samples
VWHIfW^ I W ^BIH|Sl^a
(After Composite Preparation)
Container Type: Plastic or Glass
Volume: 200 - 500 mis
hours* - 6 day^ax. Compositing
!'Period
2't hours
Preparation Method:
Comments:
None
^Biologically active samples should be
analyzed sooner
Figure 10.26. Recommended preservation and
handling methods - SS and TDS
225
-------
types of pesticides resist degradation over long time periods and are not
easily destroyed. There are several kinds of pesticides including organo-
chlorine, organophosphorus and carbamate compounds. Of these types the
chlorinated hydrocarbons have the longest half life. Therefore, many
pesticide users have converted to less objectionable types of materials
In their present applications. However, the previous accumulation of
organochlorines still necessitates analysts for these compounds.
The short half life of the organophosphorus and carbamate problems is
beneficial to the environment but It complicates preservation techniques
If actual concentrations are to be measured. Table 10.4 shows the rate
of disappearance of these pesticides in non preserved river water. The
problem of disappearance is quite apparent.
PolychlorInated biphenyls (PCB's) are not pesticides, but they react
similarly and have the same type of persistence. Use of PCB's has been
widespread in the recent past as plasttcizers in polyvlnyl chloride,
In brake linings, in varnish and in many other applications. Therefore
the concentration of PCB's in the environmental remains significant.
10.6.2 Recommended Preservation and Handling Methods
10.6.2.1 General - Use glass containers specially prepared with a
solvent rinse as outlined In Section *t.5> Whenever possible use empty
solvent containers or similar bottles (3*0. This will reduce the
possibility of contamination. Line cap with teflon liner.
10.6.2.2 Chlorinated Hydrocarbons and PCB's - Collect liquid samples
Into solvent rinsed narrow mouth glass jars and cover with TeflonR
lined bakellte caps. A suitable bottle can be obtained by using an
empty solvent container (3M. Prepare the bottle by washing with a
chromic acid rinse and solvent rinse. Refrigerate the sample and extract
within one week. Collect grab samples following the procedures outlined
In Section 2.5. Collect sludges and sediments In wide mouth containers
for ease of handling. Freeze sludge or solids samples. These can be
stored up to two months. Volume is dependent on the precision required
and Instrumentation involved.
10.6.2.3 Alglcldes - Since there are many varieties of algfcldes on
the market, the following procedure should be followed:
I. Determine active agent in algicide.
2. Consult individual parameters and follow specific recommendations.
3. If active agent In unknown, follow procedures for Chlorinated
Hydrocarbons and PCB's (Section 10.6.2.2).
10.6.2.fr Benzldlne - Follow procedures outlined for Chlorinated
Hydrocarbons and PCB's (Section 10.6.2.2).
226
-------
Table 10.4. PERSISTENCE OF PESTICIDE COMPOUNDS IN RIVER
WATER (35)
Original compound found , %
Compound 0-tlme
Organochlorine compounds
BHC
Heptachlor
Aldrin
Heptachlor
epoxlde
Telodrin
Endosulfan
Dieldrin
DDE
DDT
DDD
Chlordane (tech.)
Endrin
Organophosphorus compounds
Parathlon
Methyl parathion
Ma lath I on
Ethion
Trlthlon
Fenthlon
Dlmethoate
Merphos
Merphos recov.
as Def
Azod r 1 n
Carbamate compounds
Sevln
Zectran
Matacil
Mesurol
Baygon
Monuron
Fenuron
100
100
100
100
100
100
too
100
100
100
100
100
100
80
100
100
90
100
100
0
100
100
90
100
100
90
100
80
80
1 wk
100
25
100
100
25
30
100
100
100
100
90
100
50
25
25
90
25
50
100
0
50
100
5
15
60
0
50
ko
60
2 wk
100
0
80
100
10
5
100
100
100
100
85
100
30
10
10
75
10
10
85
0
30
100
0
0
10
0
30
30
20
-------
Parameter: Chlorinated Hydrocarbon Pesticides and PCBs (primary)
Water or Wastewater: x Municipal Wastewater x Agricultural Runoff
* Industrial Wastewater _____ Sludge
* Surface Water _ Sediment
•retervatlon Method: Refrigerate at A°C
Maximum Holding Times
Grab Samples 1 week before extraction * _
Composite Samples NA _ Max. Compositing
(After Composite Preparation) Period
Container Type: Glass/ Teflon liner/ Soi ant Rinse ++
Volume: 1,000 - *ttOOO ml depends on instrument, concentrations
Preparation Method: None
Comments: _ + After extraction the holding time Is Indefinite
++ Cleaned and Empty Solvent Bottle Recommended
Parameter: Chlorinated Hydrocarbon Pesticides and PCBs (primary)
Water or Wastewater: Municipal Wastewater Agricultural Runoff
_____ Industrial Wastewater x Sludge
Surface Water x Sediment
Preservation Method: Freeze samples
Maximum Holding Times
Crab Samples 2 months - 6 months
Composite Samples - Max. Compositing ng
(After temposite Preparation)Period
Container Type: Glass/ Wldemouth/ Teflon liner/ Solvent.Rinse
Volume: Depends on C<
Preparation Method: None
Volume: Depends on Concentration expected / Approx TOO grams dry weight
_________sol Ids
Comments:
Figure 10.27. Recommended preservation and
handling methods - pesticides and PCB's
228
-------
Parameter:
BenzI dine
Water or Vastewater:
X Municipal Wastewater
X Industrial Wastewater
X Surface Water
_X Agricultural Runoff
_X Sludge
X Sediment
Preservation Method: Refrigeration at
Maximum Holding Times
Crab Samples
Composite Samples
1 week
Max. Compositing
Period
(After Composite Preparation)
Container Type: Glass/Narrow mouth/ Teflon liner/Solvent Rinse
VoIume: 1.000-A,OOP ml depends on concentration/instrument
Preparation Method:
Commen t s:
None
Figure 10.28. Recommended Preservation and
Handling Methods - Benzidine
229
-------
10.7 METHODS FOR THE BIOLOGICAL GROUP
10.7.1 Background
IQ.7.K1 General - There are various biological parameters and many
different analyses which can be performed on each species. Individual
study objectives must be consulted prior to selection of the parameter
and analysis which Is to be done.
10.7.1.2 Fish - Fish Investigations attract the most public attention
due to the visibility of the organism and the public appeal. Fish are
found In most natural waters and are used by man as a food supply and
recreational resource. In the aquatic community fish exist at the
peak of a food web and are indicative of the conditions of water quality.
10.7.1.3 Benthic Macro invertebrate - This group Is defined as those
organisms living on or near the bottom which are retained by a U.S.
standard #30 sieve. They occupy many stages of the food web and Include
herbivores, omnlvores, carnivores and decomposers. Their usefulness in
pollution studies is enhanced due to their limited mobility and comparably
long life spans. The lack of mobility and sensitivity to stress allows
their use for characteristics of recent pollution events.
I0.7»l«*> Perlphyton (Auwfuchs) - Perlphyton Include plants growing near
or attached to solid surfaces and the semi-sessile and free living forms
found within the attached mat. The periphyton community with the
plytoplankton community are some of the primary producers of organic
matter In the aquatic system. The community of periphyton become even
more critical to the ecosystem In shallow areas. The community composi-
tion, however, is quite variable and depends on various factors such as
water movement., depth, etc.
10.7.1.5 Phvtoplankton - Phytoplankton are those forms of plankton
which are able to carry on photosynthetic activities under proper
conditions. These Include chtorophyl1 bearing plants, primarily algae
and usually constitute the greatest portion of the plankton btomass.
The species composition of this community depends on many factors. One
important aspect is the dependence on nutrient type and concentration
which gives this community an Indirect measure of the concentrations of
these chemical parameters.
10.7.1.6 Macrophytes - This group Includes large plants, primarily
rooted, found In the aquatic ecosystem which can be seen without
magnification. These are present In three growth forms: free floating,
submerged and emergent. These plants cover large areas In shallow
water and may Interfere with navigation, migration and recreational uses
of a water body.
230
-------
10.7.K7 Zooplankton - This Is the portion of the plankton group made
up of free-floating animal populations. These species are found at all
depths of the water column and In both standing and flowing waters.
They have the ability of Independent movement and can alter their
position In the water column.
10.7.1.8 PossIble Analyses - Some common analysis techniques are briefly
discussed below.The parameters most commonly analyzed for monitoring
purposes are summarized In Table 10.5 (36).
1. Count and identification - A useful test to determine overall
the health of species in an ecosystem by providing data on
standing crop and community structure.
2. Weight/length - The growth rate of a community Is determined
and compared to previous studies to indicate a change In water
quality.
3. Flesh Tainting - A test of palatabllity to determine if sublethal
chemical doses have imparted an unpleasant taste to fish or
shellfish flesh.
**. Acetylene I Inesterase - An Indirect test of the previous effect
of organophosphate pesticides on the central nervous system
of fish in a water system.
5. Tissue Analysts - A qualitative or quantitative test of the
concentration or histologies I effects of various materials
Including metals and pesticides in flesh.
6. Stomach Contents - An analysis of this will Indicate the type
and amount of feeding done by an organism prior to collection.
7. Wet, Dry and Ashfree Weight - These tests are used to make
quantitative tests of the standing crop of a population.
8. Chlorophyll a - An estimate of the algal btomass is obtained
which roughly indicates the standing crop.
9. ATP Determinations - ATP tests measure the total viable plankton
biomass.
10. Diatom Species Proportional Count - This test Indicates the
health of a diatom community by comparing the results through
the use of a diversity Index.
231
-------
Table 10.5. PARAMETERS OF BIOLOGICAL COMMUNITIES MOST
COMMONLY ANALYZED FOR MONITORING PURPOSES (36)
Community
Parameter
Units
Plankton
Perlpbyton
Macrophyton
Fish
Counts
Chlorophyll a
Biomass (ash-free dry
weight)
Numbers/ml by genus and/or
species
mg/m*
mg/m*
Counts Numbers/mm*
Chlorophyll a mg/m1
Biomass (ash-free weight) mg/m*
Autotrophic index Ash-free weight (rng/m1)
Chlorophyll a (mg/m1)
Areal coverage Maps by species and specie*
associations
Biomass (ash-free weight) g/m'
Macroinvertebrate Counts
Biomass
Toxic substances
Toxic substances
Counts
Biomass (wet weight)
Condition
Grab — number/in*
Substrate — number/sampfo
g/m1
rag/kg
mg/kg
Number/unit of effort, expressed
as per shocker hour or per
100 feet of a 24-hour net set
Same as counts
K(TL) -
m grams
L* (length in mm)
232
-------
10.7.1.9 Preservatives - Various preservatives exist to maintain species
In the desI red conditions. The advantages and disadvantages of various
types are Indicated in Table 10.6 (37,38).
10.7.2 Recommended Preservation and Handling Methods
The recommended procedures have been Included in Tables 10.7~10.I2 (37,38).
Follow the methods given for specific parameter type and the desired
test method. Analysis of parameters sooner than the maximum holding
time Is advisable In most situations.
10.8 METHODS FOR RADIOACTIVE PARAMETER GROUP
10.8.1 Background
Radiation is not a biological or chemical parameter but rather a
physical property. As such, it Is not affected by temperature changes
or recombination Into different molecular species.
There are different types of radiation; those which are of general con-
cern are those which are capable of causing ionization, that Is, pro-
ducing ions by ejection of orbital electrons from the atoms of the
material through which they travel. Radiation can be divided into
parti cut ate radiation and electromagnetic radiation. For the purposes
of this chapter only two types of particulate radiation will be con-
sidered, beta and alpha particles, and one type of electromagnetic
radiation, gamma radiation.
The radioactive properties of radioactive waste materials do not lend
themselves to stabilization or removal by the various chemical, physical
or biological processes used to treat "normal" industrial wastewaters.
Radioactive waste treatment only alters the chemical state and the only
method which will render these materials "safe" is long-term storage.
For these reasons samples of water and/or wastewater for gross alpha
and gross beta determinations should be taken from areas suspected of
being contaminated with/these materials. Data from this type of
analysts will help to determine If a radioactive contaminant Is being
discharged, and whether or not that discharge is significant. Some of
the major pathways of Introduction of these materials Into the envir-
onment are as follows:
Nuclear Power Plants - Effluents from plant treatment operations
are routinely discharged. Monitoring programs at nuclear power
plants are regulated by the U.S. Nuclear Regulatory Commission
(NRC).
233
-------
Table 10.6. COMPARISON OF CHEMICAL
PRESERVATIVES FOR BIOLOGICAL PARAMETERS
Chemical
Advantage
Disadvantage
General Preservation
1. Formalin
(5-10* for-
maldehyde)
2. 70* ctHanoi
3.
Isopropyt
Oxyqutnoltne (2%
solution)(8-hydroxy-
qulnollne sulfate)
5. Merthlolate
solution
Additives
6. Glycerin (added
with I, 2 or 3)
7. Copper sulfate
8. Detergent
Stains
9. Lugols's solution
Kills species;
infinite holding
period
Objectionable odor,
can cause contraction
or deflaggelation
Needs neutralization
w/sodium tetraborate
Safer 6 easier for Can cause contractual
analyst to use; same reaction
advantages as formalin
Can cause contractual
reaction
Safer & easier for
analyst to use; can
be added as solid
in premeasured pack-
ets; same advantages
as formalin
Morphology & color Does not produce
of algae are retained; a sterile sample
distinguish between
zoo and phyto plankton
longer
Prevents tissues
from drying
Retains bluegreen
color of algae
Lowers surface ten-
sion to prevent clump-
ing or clinging to
container walls.
Stains other mater-
ial ; also toxic
Stains algae; aids
settlIng by releas-
ing gases
Samples stable only
one year
-------
Table 10.7. RECOMMENDED PRESERVATION AND HANDLING
METHODS - BENTHIC MACRO INVERTEBRATES
VI
Item
Preservation
Holding Time
Count and Identification
Wet Weight
Dry Weight
Ash-free Weight
Calorimetry
Radio Tracer Studies
Flesh Tainting
Tissue Analysis
70% Ethyl Alcohol
Refrigerate at k°
or Ice.
Refrigerat at *»°C
or Ice,
Container
1 Year
Immediate to 2k hours
Glass or Plastic
Glass or Plastic
Immediate to 2k hours Glass or Plastic
Filter and Refrigerate 6 Months
at li°C.
Refrigerate at 4°C or |mnediate to 2Z, hours
Ice. Once filtered,
store in desiccator
Freeze
Freeze
Freeze
1 Year
Indefinite
Indefinite
Glass or Plastic
Glass or Plastic
Glass or Plastic
Glass or Plastic
Glass or Plastic
-------
Table 10.8. RECOMMENDED PRESERVATION AHD HANDLING METHODS - FISH
Preservation
Holding Time
Container
Count/Identtfteation/
Weigh/Length
Flesh Tainting
AcetylcholInesterase
Tissue Analysts
Stomach Content
Formalin, add 3 gr. borax and
50 ml glycerin per liter*
None - analyze immediately
Clean then freeze
Freeze sample
Freeze sample
Remove stomach from fish and pre-
serve In \0% Formalin (as i\)
Indefinite (1 year) Borosilicate Glass or
(sooner Is better) Polyethylene
None
Indefinite
Indefinite
Indefinite
None
Borosilicate Glass or Poly?
ethylene
Aluminum Foi1
Aluminum Foil
Borosilicate Glass of Poly-
ethylene
Aluminum Foil
Indefinite (1 year) Glass or Plastic
(Prefer sooner)
Comments - * Change solution to alcohol after 1 week
-------
Table 10.9. RECOMMENDED PRESERVATION AND HANDLING METHODS - MACROPHYTES AND MACROALGAE
Preservation Method
Holding Time
Container
Count and Identification 5% formalin
1 year
Plastic or Glass
Wet Weight
Refrigeration at *» C or Icing lmmediate-24 hours Plastic or Glass
Dry Weight
Refrigeration at 4 C or icing lmnediate-24 hours Plastic or Glass
Ash-free Weight
Freeze
6 months
Plastic or Glass
Chlorophyll A
Freeze at -20
1 month Plastic or Glass
(keep out of 1ight,
acid)
-------
Table 10.10. RECOMMENDED PRESERVATION AND HANDLING METHODS - PERIPHYTON
Preservation
Holding time
Container
N)
OJ
CD
Count and identification
Diatom species proportional
count
Wet and dry weight
Ash-free weight
Chlorophyll Determination
ATP Determination
5% neutral formalin
neutral Formalin
Refrigerate at *»°C or
Ice (do not freeze)
Freeze at -20°C
Immediate extraction in
S0% aqueous acetone,
store at -20°C
Extract by boiling with
Trls Buffer and store
extract at -20°C
6 months
6 months
infinite
Immediate to
2k hours
6 months
I month (keep
out of 1Ight/
acid
6 months
Opague, glass
or plastic
Glass or
plastic
Glass or
plastic
Glass or
plastic
Glass or
plastic
Glass or
plastic
-------
Table 10.11. RECOMMENDED PRESERVATION AND HANDLING METHODS - PHYTOPLANKTON
Count and Identification
Wet weight
Dry weight
Ash-free weight
Chlorophyll A
Preservation
a. 5% neutral formal in
b. Merthlolate
Refrigerate at A°C or Ice
sample (do not freeze)
Refrigerate sample at A C
or Ice
Filter and Freeze at -20°C
Extract immediately or
filter and freeze in Desic-
Ho 1 d i ng T ? me
a. Indefinite
b. One year
Immediate to
2 A hours
Immediate to
24 hours
6 months
1 month (keep out
Container
Opague, Plastic
or Glass
Plastic or Glass
Plastic or Glass
Plastic or Glass
Plastic or Glass
Diatom species
Proportional count
Calorimetry
ATP Determination
cator -20°C
Formalin
Refrigerate at *»°C or ice
Once filtered, store in
desiccator
Extract by boiling with
Tris Buffer, freeze extract
at -20 C
of light/acid)
6 months - Inde-
f* * •_
mite
Immediate to
24 hours
6 months
Opague, Plastic
or Glas.s
Plastic or Glass
Plastic or Glass
-------
Table 10.12. RECOMMENDED PRESERVATION AND HANDLING METHODS - ZOOPLANKTON
Preservation
Holding Time
Container
5% Forma 11n or
Count and Identification Luqol's Solution plus
Wet weight
Dry weight
Calorimetry
ATP Determination
50% glycerin or 70% ethanol
pius 50% glycerin
Refrigerate at
(do not freeze)
C or Ice
Refrigerate-at 4 C or Ice
(do not freeze)
Refrigerate at 4°C or Ice
(do not freeze). Once fil-
tered, store in desiccator
Immediately extract by boiling
with TrIs Buffer, store extract
at -20°C
1 year
Immediate to
24 hours
Immediate to
24 hours
Immediate to
24 hours
6 months
Glass or Plastic
Glass or Plastic
Glass or Plastic
Glass or Plastic
Glass or Plastic
-------
Parameter: Radioactive Parameters
Water or Wastewater:
Preservation Method:
Maximum Holding Times
Grab Samples
Municipal Wastewater X
Industrial Wastewater X
^•MBB
Surface Water x
Agricultural Runoff
SIudge A
Sediment*
HMO, addition to final concentration of Ife
Depends on half life of radionuclide*
Composite Samples Same as above
(After Composite Preparation)
Container Type: Polyethylene or Teflon
Volume:
Max. Compositing
Period
Depends on expected concentration
Preparation Method:
Comments:
None
*Short lived radI onuclIdes should be analyzed immediately
Figure 10.29. Recommended preservation and
handling methods - Radioactive
241
-------
Hospitals - These institutions use radioactive materials for
various diagnostic and therapeutic procedures and small amounts
of wastes are generated some of which are discharged to sanitary
sewers. The discharges are regulated by the USNRC.
Processing of Uranium Ores - Installations which process uranium
ore produce considerable volumes of wastes which are high in
alpha emitters. This Industry Is also under the supervision
of the USNRC.
Fuel Element Processing - This industry reprocesses fuel elements
from nuclear power plants to recover unused fuel and to process
the waste materials created by the fission process. The wastes
produced by this process have extremely high levels of radiation
and fall under the scrutiny of the USNRC.
Research Laboratories - These facilities sometimes use radionuclIdes
for various techniques. Wastes may be discharged after being
treated, stored, diluted, etc. These?discharges are regulated
by the USNRC.
10.8.2 Recommended Preservation and Handling Methods
Collect samples as Indicated in Section 2.5. Collect a flow proportional
composite sample whenever possible (39). The volume collected will vary
with expected concentrations but a minimum of 1 liter should be obtained
H ,1»2). Acceptable sample containers are polypropylene, polyethylene
,43) or Teflon. Pretreat the sample container as follows
a. Fill the container with concentrated nitric acid and leave stand
for one day.
b. Rinse with detergent water.
c. Rinse twice with double distilled water.
Acidifv sample to a final concentration of \% acid using nitric acid
(kOtk\). Analyze short lived radionuclIdes as soon as possible. If the
species has a long half life, the holding time Is not critical.
10.9 REFERENCES
1. APHA, AWWA, WPCF, Standard Methods for the Examination of Water and
Wastewater, 13th Edition, Washington, D.C. American Public Health
Association, p. 369» 1972.
2. Hellwig, O.H.R., Preservation of Water Samples, International
Journal of Air and Water Pollution, (Great Britain) 1:215-228,
p. 1064.
-------
3. Hellwlg, D.H.R., Preservation of Wastewater Samples, Water Research
(Great Britain) J_:79-91, 1967.
k. Brezonlk, L. and G. F. Lee, Preservation of Water Samples for
Inorganic Nitrogen Analysis with Mercury (II) Chloride. International
Journal of Air and Water Pollution, (Great Britain) JjO:549-553, 1966.
5. Howe, L. H. Ill, and Hoi ley, C. W. , Comparisons of Mercury (II)
Chloride and Sulfurlc Acid as Preservatives for Nitrogen Forms In
Water Samples, Environmental Science and Technology. 3, 5:
, May, 1969.
6. Krawczyk, D. F., Preservation of Wastewater Samples for Forms of
Nitrogen and Phosporus, National Environmental Research Center.
US EPA. Corvalles, Oregon, 1975.
7. Environmental Protection Agency, Methods For Chemical Analysts of
Water and Wastes, 1971 , U.S. Government Printing Office, Washington
O.C., 1-4, 1971.
8. Zobell, C. E., and B. F. Brown, Studies on the Chemical Preservation
of Water Samples, Journal of Marine Research, 5_ (3): 178-182,
9. Prakasam, T.B.S., Effect of Various Preservation Techniques on the
Nitrogen Profile of Treated and Raw Poultry Waste, Draft Copy, 1975.
10. Dean, R. B., R. T. Williams, and R. H. Wise. Disposal of Mercury
Wastes from Water Laboratories. Environmental Science and
Technology: 5_ pp10M»-10*»5, 1971.
II. Memo Prepared by D. F. Krawczyk and P. Lefount for the Pacific
Northwest Environmental Research Laboratory, CorvalUs, Oregon.
November 29, 1973.
12. Memo-Preservation and Holding Times for Nutrient and Demand Para-
meters, From Dr. Mark Carter to Mr. Dwight Bellinger, October 9, 197*».
13. Memo-Stability of Samples Preserved with Mercury (11) Chloride,
To Region X Laboratory from Arnold Gahler, November 27, 1972.
14. Beckett, H.J. and A.L. Wilson. The Manual Determination of Ammonia
In Fresh Waters Using an Ammonia -Sensttttve Membrane Electrode.
Water Research (Great Britain), 8^333-3*0, 1971*.
15. Santiago, M. A., H. K. Soo and K. E. White. Sample Isolation
Chamber for Automated Ammonia Analysis. Ann Arbor, Michigan,
Great Lakes Research Division, p. 8.
-------
16. Jenkins, D., The Differentiation, Analysis, and Preservation of
Nitrogen and Phosphorus Forms in Natural Water, Advances In
Chemistry Series 73, American Chemical Society, Washington, D. C.,
1968.
17. Heron, J., Determination of Phosphate in Water After Storage In
Polyethylene, Limnology and Oceanography, 7j 316-321, 1972.
18. Shannon, J. E., and G. F. Lee , Hydrolysis of Condensed Phosphates
in Natural Waters, Internationa) Journal of Air and Water
Pollution, Great Britain, JjO: 735-756, 1966.
19. Van Wazer, J. R. Phosphorus and Its Compounds: Volume 1
Chemistry and Volume 11 Technology, Functions And Applications.
Intersclence Publishers, Inc. New York, 1966.
20* Sawyer, C. H., and P. L. McCarty, Chemistry for Sanitary Engineer,
New York, McGraw-Hill Book Company, 1967, p 518.
21. Loehr, R. C., and B. Bergeron, Preservation of Wastewater Samples
Prior to Analysis, Water Research, (Great Britain), 1: 577-586,
1967.
22. Agardy, F. J., and M. L. Kiado, Effects of Regrigerated Storage
on the Characteristics of Wastes, Industrial Waste Conference
(21st), Purdue University, Lafayette, Indiana, 1966, p. 226-233.
23. Phillips, G. E., and W. D. Hatfield, The Preservation of Sewage
Samples, Water Works and Sewerage, 88: June, 1941.
2k. Steener, P. G., M. J. Finkel, 0. H. Siegmund and B. H. Szafranski.
The Merck Index of Chemicals and Drugs. Merck and Co. Rahway,
N. J. I960.
25. Environmental Protection Agency, Methods For Chemical Analysis of
Water and Wastes, Office of Technology Transfer, Washington, D.C.
vl-xli, 1974.
26. Feldman, C., Preservation of Dilute Mercury Solutions, Analytical
Chemistry, 31: 99-102, July, 1974.
27. Streompler, A. W., Adsorption Characteristics of Silver, Lead,
Cadmium, Zinc, and Nickel on Borosflicate Glass, Polyethylene and
Polypropylene Container Surfaces, Analytical Chemistry, k$ (13):
2251-2254, November, 1973.
28. Clement, J. L., Preservation and Storage of Water Samples for
Trace Element Determinations, Department of Civil Engineering,
University of Illinois, Urbana, Illinois, 40p, June, 1972.
244
-------
29. Ludzack, F. J., W. A. Moore, and C. C. Ruchnoft. Determination of
Cyanides In Water and Waste Samples. Analytical Chemistry. 26:
1784-1792, November 1954.
30. Brown, C. W., P. F. Lynch, and M. AhmadJtan. Novel Method of
Sampling ON Spills and for Measuring Infrared Spectra of Oil
Samples. Analytical Chemistry. 1:183-184, January 1974.
31. Ettlnger, M. B., S. Schott, and C. C. Ruchoft. Preservation of
Phenol Content In Polluted River Water Samples Previous to Analysis.
Journal AWWA. 35:229*302, March 1943.
32. Afyhan, B. K., P. E. Betllveau, R. H. Larose, and J. F. Ryan.
An Improved Method for Determination of Trace Quantities of Phenols
In Natural Waters. Analytical Chemlea Acta (Netherlands). 71:
355-366, 1974.
33. Responses from Question on Sampling and Sample Preservation -
Current Practices, 1974. Region V, NERC Cincinnati, NERC Corvallls,
Cornwall University, Metropolitan Sanitary District, Chicago.
34. Thompson, J. F. EPA Manual of Analytical Methods, Primate and
Pesticide Effects Laboratory. Perrlne, Florida. November 1972.
35. Elchelberger, J. W. and J. J. Lichtenberg. Persistence of
Pesticides in River Water. Environmental Science and Technology.
5:541-544, June 1971.
36. National Water Monitoring Panel. Model State Water Monitoring
Program. US EPA Report No. EPA-440/9/74-002. US EPA Office of
Water and Hazardous Materials. June 1975.
37* Slack, K. V., R. C. Averett, P. E. Greeson, and R. G. Lipscomb.
Methods for Collection and Analysts of Aquatic Biological and
Microbiological Samples. Book 5. U.S. Dept. of the Interior,
Washington, D.C., 1973.
38. Weber, C. I., ed. Biological Field and Laboratory Methods.
National Environmental Research Center, Cincinnati, Ohio.
Report No. EPA-670/4-73-001, July 1973.
39. Robtnson, L. R. Monitoring Streams for Radioactive Wastes.
Water and Sewage Works. Reference No. 1965, pp R-152 to R-I60.
245
-------
1»0. Page, T., Battelle Pacific Northwest Laboratory, Rfchland,
Washington, Personal Communication to Environmental Sciences
Division, January, 1975-
k\. Baratta, P., U.S. Public Health Service, National Center for
Radiological Health, Boston, Massachusetts, Personal Communications
to Environmental Sciences Division, Janualy, 1975-
42. Kahn, B., and A. S. Goldln, Radiochemical Procedures For The
Identification of The More Hazardous Nuclides, Journal AWWA k$:
767-771, June, 1957.
43. Gruftewald, R., University of Wisconsin - Milwaukee, Milwauke,
Wisconsin, Personal Communication to Environmental Sciences
Division, January, 1975-
V». Bhogat, S. K., W. H. Funk, R. H. Fllby, and K. R. Shah, Trace
Element Ana-lysis of Environmental Samples by Neutron Activation
Method, Journal WPCF, *£: 24U-2423, December, 1971.
246
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CHAPTER It
COLLECTING AND HANDLING MICROBIOLOGICAL SAMPLES
11.1 BACKGROUND
The control of fecal contamination from warm-blooded animals Is a signifi-
cant factor In the maintenance of public health. Pathogenic organisms
which are normally present in municipal wastewaters can cause serious
diseases and other health problems In the water supply or in waters
used for recreational purposes.
Since monitoring plays such on Important role In the control of pathogens,
certain parameters have become recognized as indicators of the sanitary
quality of a stream or water supply. The parameters most frequently used
as indicators of pollution Include standard plate count, total coll form,
fecal col(form and fecal streptococci, as well as the pathogens themselves
(e.g. Salmonella).
11.2 COMMON ANALYSES
11.2.1 Standard Plate Count
The standard plate count method "enumerates only that portion of the
bacterial population that can grow under the conditions of the test, and
usually constitutes only a small fraction of all the bacteria present" (I).
The number of developing bacteria may vary greatly due to the influence
of Individual bacterial growth requirements. Some of these requirements
Include temperature, oxygen level, and nutrients present.
11.2.2 Conforms
The col(form group may be subdivided into the two following categories (2):
I. Collforms normally of fecal origin (primarily E. coll types).
2. Collforms usually associated with vegetation and soils (primarily
E. aerogenes and E_. cloacae) as well as intermediates, all of
which may occur in fecal matter but In smaller numbers than
E. coll.
-------
Standard Methods, 13th Edition (3) defines the col (form group as "all of
the aerobic and facultative anaerobic, gram-negative, nonspore-formlng,
rod shaped bacteria which ferment lactose with gas formation within *»8
hours at 35°C". The two analytical techniques recommended by EPA and
Standard Methods for the enumeration of coll forms are the multiple tube
and membrane filter methods (3,*»). The microbiological standards for
public water supplies and drinking waters are based solely on total
co II form numbers.
Since many of the col (form organism groups originate from sources other
than human and animal feces (5), water microbtologlsts distinguish the
fecal from the nonfecal conforms. The transition In recent years to the
fecal col (form analysis as an indication of bacterial pollution Is
Intended to provide a more accurate estimate of the sanitary quality of
the water involved.
11.2.3 Feca I Co II forms
Fecal coltform organisms are defines as those col (forms "that ferment
lactose with gas production within 2k hours at M.5°C i 0.2°C"(3).
Research has shown this organism to be a reliable Indicator of contamina-
tion of streams, municipal and Industrial discharges, and recreational
waters (6). No method Is presently available which distinguishes human
fecal collforms from those of other warm-blooded animals.
The analytical techniques for Identifying fecal col i forms in water are
the multiple-tube fermentation method and the membrane filter technique.
Both are described by Standard Methods, l?th Edition (3) and EPA's
manual
11.2.4 Fecal Streptococci
The role of fecal streptotoccl as Indicator organisms has recently been
given more attention. Fecal streptococcal determinations may become an
important asset In water pollution surveys on rivers and streams to
distinguish whether the source of the contamination is animal or human.
The EPA manual (k) proposes the following definition of fecal
streptococci :
Fecal streptococci include the serological groups, D, Q and the
virldans streptococci that are of sanitary significance and grow
on KF streptococcus and PSE media and In azlde destrose/EVA MPN
media at 35°C.
The EPA manual (k) and Standard Methods, 13th Edition (3) have listed
three methods of analysis: multiple tube technique (MPN), membrane filter
technique (MF), and a plate count procedure.
-------
11.2.5 Salmonella
Salmonella are a group of pathogenic microorganisms responsible for many
waterborne-dlsease outbreaks. The absence of Salmonella does not Indicate
the absence of other pathogenic organisms. Generally, a large volume of
sample Is required to Isolate this pathogen, as opposed to the relatively
small volume needed for col I form and fecal col(form analysis. Salmonella
have been Isolated In sewage and stormwater.
A state-of-the-art approach to Salmonella Identification Is presented In
Standard Methods (3) and In EPA's manual 00.
11.3 SAMPLE BOTTLE PREPARATION
Sample bottles must be resistant to sterilizing conditions and the solvent
action of water. Wide mouth screw cap or ground glass stoppered bottles,
or heat-resistant plastic bottles (preferably polypropylene) may be used
provided they can be sterilized without producing toxic materials. Screw
capped bottles must be equipped with neoprene rubber liners or other
materials that do not produce bactertostatlc or nutritive compounds upon
sterll I ration.
11.3.1 Selection and Cleansing of Bottles
Select bottles of sufficient capacity to provide a volume necessary for
all analyses, but not less than 100ml should be collected. Discard
bottles which have chips, cracks, and etched surfaces. Bottle closures
must be capable of creating a water-tight seal. Before use, thoroughly
clease bottles and closures with detergent and hot water, followed by a
hot water rinse to remove all traces of detergent. Then rinse three times
with a good quality distilled water. A test for the biological examination
of glassware where bacterlostltlc or inhibitory residues may be present
ts described In EPA's manual GO.
11.3.2 Use of Dechlorlnating and Chelat Ing Agents
Add a dechlorinatlng agent to the sample bottle when water and wastewater
samples containing residual chlorine are anticipated. Add sodium thto-
sulfate to the bottle before sterilization at a concentration of O.I ml
of a 10 percent solution for each 125 ml (k oz) sample volume
Add a chelatlng agent to the sample bottle when samples suspected of
containing >O.OI mg/l concentration of heavy metals such as copper, nickel,
zinc, etc. Add 0.3 ml of a 15 percent solution ethyl ene dlamine tetra-
acettc acid (EOTA) for each 125 ml (4 oz) sample volume prior to
sterilization (7,8).
-------
11.3.3 Wrapping of Bottles
Protect the tops and necks of ground glass stoppered bottles from
contarn1 nation by covering them before sterilization with aluminum foil
or kraft paper. Screw-cap closures do not require a cover.
II.3.*» Sterilization of Bottles (A)
Autoclave glass or heat-resistant polypropylene plastic bottles at 12I°C
for 15 minutes. Glassware may be alternately sterilized In a hot air
oven at 170°C for not less than one hour. Ethylene oxide gas steriliza-
tion Is acceptable for plastic containers that are not heat resistant.
Sample bottles sterilized by gas should be stored overnight before being
used to allow the last traces of gas to dissipate.
11.4 SAMPLE COLLECTION
These sampling and procedural methods are applicable for sampling potable
water, streams and rivers, recreational waters such as bathing beaches and
swimming pools, lakes and reservoirs, marine and estuartne waters,
shellfish harvesting waters, and domestic and Industrial waste discharges.
In no case should a composite sample be collected for bacteriological
examination. Data from Individual samples, even though averaged, show
a range of values. A composite sample will not display this range.
Individual results will give information about industrial process
variations. Also, one or more portions that make up a composite sample
may contain toxic or nutritive material and cause erroneous results.
Collect samples by hand or with special devices if depth samples are
required or If the sampling site is difficult to access such as bridges
or banks adjacent to surface waters.
I M.I Surface Sampling by Hand
Collect a grab sample directly into a sample bottle prepared as described
In Section 11.3. Locate and then carefully identify the sampling site
on a chain of custody tag, If this is required, a label, and a field log
sheet (see Section 3.3). Remove the bottle coverings and closure and
protect them from contamination. Avoid touching the inside of the
closure. Grasp the bottle securely at the base with one hand and plunge
the bottle mouth down Into the water to avoid Introducing surface scum.
Position the bottle towards the current flow and away from the hand of
the collector and the side of the sampling platform or boat. The sampling
depth should be 15 to 30 cm (6-12 In.) below the water surface. An
artificial current can be created, if the water body is static, by moving
the bottle horizontally in the direction It is pointed and away from the
sampler. Tip the bottle slightly upwards to allow air to exit and the
bottle to fill. After removal of the bottle from the stream, pour out
250
-------
a imall portion of the sample to allow an air space of 2.5*5 cm (1-2 tn.)
above each sample for proper mixing of the sample before analysis.
Tightly stopper and label the bottle.
II. k. 2 Surface Sampling by Weighted Bottle Frame (*0
When sampling from a bridge or other structure above a stream or body of
water, place the bottle in a weighted frame that holds the bottle
securely. Remove the cover and lower the device to the water. It is
preferable to use nylon rope which does not absorb water and will not rot
Face the bottle mouth upstream by swinging the sampling device first
downstream, and then allow It to drop Into the water, without slack in
the rope. Pull the sample device rapidly upstream and out of the water,
thus simulating the scooping motion of grab sampling. Take care not to
dislodge dirt or other material from the sampling platform that might
fall Into the open bottle.
ll.fr. 3 Depth Sampling
Additional devices may be needed for collection of death samples
from lakes, reservoirs, estuaries and the oceans. Lower the depth sampler
and/or container to the desired depth and open the device until full.
Then closeand return to the surface. Although depth measurements are
best made with a p re-marked steel cable, the sample depths can be
determined by premeasurlng and marking the nylon rope at intervals with
a non-smearing Ink, paint, or fingernail polish.
\}.k.k Potable Water Supplies (M
The sanitary quality of potable water supplies has been recently
established by the EPA Drinking Water Standards (9). These Standards
emphasize the Importance of a) collecting samples from properly distrib-
uted sampling sites, and b) repetitive sampling from single points. The
sampling program includes examination of water as It enters and flows
throughout the distribution system. For application of the Standards,
the frequency of sampling and the location of sampling points shall be
established Jointly by the utility, the Reporting Agency, and the
Certifying Authority. Additionally, the laboratory, the methods of
analyses, and the technical competence of personnel shall be approved
and Inspected by the Reporting Agency and the Certifying Authority.
(See J»OCFR,I4I, National Interim Primary Drinking Water Regulations)
11.4.5 Water Distribution System Sampling (*t)
Make certain the samples are not collected from spigots that teak or
from spigots that contain aeration devices or screens within the faucet.
For samples taken from direct water main connections, flush the spigot
for five minutes to clear the service line. For wells equipped with
hand or mechanical pumps, pump the water to waste for five minutes before
the sample Is collected. Remove the cap asepttcally from the sample bottle.
251
-------
Hold the sample bottle upright near the base while It Is being filled.
Avoid splashing at all times. Do not rinse the bottle with the sample,
but fill It directly to within 2.5-5 cm (1-2 In.) from the top. Replace
bottle closure and hood covering. Caution must be used to prevent
contaminating the sample with finger, gloves or other materials. If the
well does not have pumping machinery, collect the sample using a weighted
sterilized sample bottle. Care must be taken to avoid contaminating the
sample either with the surface scum from the water surface, or with dislodged
material from the sides of the well.
11. k. 6 Recreational Water Sampling
Collect samples daily during high use seasons— generally in the afternoon
(10). Collect the samples at the most commonly used locations (e.g.
bathing beach). Obtain samples of estuarine water at high tide, low tide
and ebb tide to obtain the cyclic water quality deterioration.
11.4.7 Domestic and Industrial Waste Discharges (A)
It Is often necessary to sample secondary and tertiary wastes from
municipal waste treatment plants and various industrial waste treatment
operations. In situations where the plant treatment efficiency varies
considerably, collect grab samples around the clock at selected Intervals
for a three to five day period. If It Is known that the process displays
little variation, fewer samples are needed. In no case should a composite
sample be collected for bacteriological examination. The NPOES has
established wastewater treatment plant effluent limits for all dischargers.
These are often based on maximum and mean values. A sufficient number
of samples must be collected to satisfy the permit and/or provide statis-
tically sound data and give a fair representation of the bacteriological
quality of the discharge. (See AOCFR136, Guidelines Establishing Test
Procedures for the Analysis of Pollutants.)
11.5 SAMPLE PRESERVATION AND HANDLING
The recommended preservation and handling methods are summarized In
Figure II. 1.
11.5.1 Preservation Techniques
Immediately after collection, place the sample container in crushed ice
or a refrigerator at A°C (3). When crushed ice is used, transport the
samples and Ice In an insulated waterproof container. Do not use dry
ice since it may freeze the sample.
II. 5. 2 Holding Times (3.*0
Hold the samples a maximum of 6 hours before analysis. If It Is necessary
to mail in samples, potable water samples can be held up to 30 hours
before analysis.
252
-------
Total coll form, fecal coll form, fecal streptococci,
Parameter: Salmonella, Shingella, and standard plate count
Water or Wastewater: -x Municipal Wastewater x Agricultural Runoff
x Industrial Wastewater _x Sludge
*_ Surface Water x Sediment
Preservation Method: Refrigeration at A°C or -2 Prying v«ter
Icing with crushed ice (do not freeze)
Maximum Holding Times
Grab Samples 6 hours with preservation. 30 hours with preservation for
ite
potaoie water
Composite Samples not reennm»nd»rf Max. Compositing
(After Composite Preparation) Period
Container Type: BorosMIcate glass; polyethylene, polyproovlene/sterMe/narrow mouth
Volume: 100-300 ml
Preparation Method: Sterilize containers
Comments: I. For chlorinated waters, add O.I ml lot sodium thlosulfate
for each 125 ml of sample prior to bottle sterilization.
2. For waters with >0.01 mg/1 heavy metals, add 0.3 ml 15% EDTA
for each 125ml of sample prior to bottle sterilization.
Figure U.I. Recommended preservation and
handling methods - microbiological parameters
253
-------
11.6 REFERENCES
1. Nobler, P. Removal of Pathogenic Microorganisms by Sewage Treatment
Processes. Sewage and Ind. Wastes. 31:1373-1382, December 1959.
2. Kobler, P. and H. F. Clark. Col (form Group and Fecal Cot (form
Organisms as Indicators of Pollution In Drinking Water. Journal
AWWA. 52:1577-1579, December I960.
3. APHA, AWWA, and WPCF. Standard Methods for the Examination of Water
and Wastdwater. 13th Edition. Washington, D.C., APHA, 1972, 369 P-
J». Bordner, R. H., J. A. Winter, and P. V. Scar pi no, ed. Microbiological
Methods for Monitoring the Environment. U.S. EPA, Environmental
Monitoring and Surveillance Laboratory, Cincinnati (In press).
5. Wolf, H. W. The Col (form Count as a Measure of Water Quality.
From Mitchell, R. Water Pollution Microbiology. New York, Wiley-
Inter science, 1972.
6. Geldrelch, E. E. Sanitary Significance of Fecal Col I forms in the
Environment. FWPCA Publication WP-20-3, 1966.
7. Shipe, E. L. and A. Fields. Comparison of the Molecular Filter
Technique with Agar Plate Counts for the Enumeration of E. Co 1 1
In Various Aqueous Concentrations of Zinc and Copper SulFate.
Appl. Micro. 2:382, 195**.
8. Snipe, E. L. and A. Fields. Chelation and a Method for Maintaining
the CoHform Index in Water Supplies. Public Health Reports.
, 1956.
9. EPA Drinking Water Standards. U.S. EPA, Washington, D.C. (in press).
10. Proceedings of the First Microbiology Seminar on Standardization of
Methods. U.S. EPA. San Francisco. January 1973. 203 P> Report
No. EPA-R4-73-022.
-------
INDEX
Agricultural Discharges, 169-176
Feedlot Discharges
Frequency, 169-170
Location, 170
Field Runoff
Frequency, 170
Location, 170
Biological Parameters
Common Parameters, 146
Common Analyses, 146
Preservation
Types'of Preservatives, 234
Methods, 235-240
Chain of Custody, 43-53
Current Meters,
Flow Nozzle, 19, 20, 22
Freezing Samples, 42
Frequency of Sampling
Method for Determining
Using Spectral Analysis, 84-92
Municipal Wastewatens, 125-128
Industrial Wastewaters, 134
Surface Waters/Bottom Sediments,
153, 154
Agricultural Discharges, 169, 170
Sludges, 180
Holding Time
General, 57, Chapter 10
Demand Parameters
Recommend Preservation, 196-201
Elbow Meters, 19
Flow Measurement
in Pipes, 18-24
in Open Channels or Sewers 24-33
Primary Devices, 25-33, 35
Municipal Wastewater, 143
Industrial Wastewater, 143
Surface Water/Bottom Sediment,
168
Agricultural Discharges, 175
Sludges, 181, 182
Icing, 252
Location of Sampling Points
Segmentation Technique, 102-116
Municipal
Effluent Monitoring, 124
In-Plant Locations, 129
Sludges, 178, 180
Industrial
Effluent Monitoring, 135
In-Plant Locations, 135
Surface Waters
Grid Method, 149
Transects, 148
Spatial Gradient Technique, 150
Agricultural Runoff, 170
255
-------
Location of Sampling Points (cont.)
Probability of Exceeding Standard,
117-118
Magnetic Flowmeter, 20
Manning Formula, 36
Mercury (11) Chloride
Use, 185-188
Metals
Recommended Preservation, 202-207
Microbiological Parameters
Common Types, 247-254
Bottle Cleansing, 249
Bottle Sterilization, 250
Recommended Preservation, 252,
253
Sample Collection, 250-252
Use of Chelatlng Agent, 249
Use of Dechlorinating Agent,
249
Nyqulst Frequency, 65
Number of Samples
Methods for Determining
Based on Variability, 78-81
Based on Mean Value, 81-84
Municipal Wastewater, 129
Industrial Wastewater, 135
Surface Waters/Bottom Sediments,
150-153
Agricultural Runoff, 170
Sludges, 181
Nutrients
Recommended Preservation,
194
011 and Grease
Preservation, 219-221
Sampling, 219
185-
Orlflce Meter, 21, 23
Palmer-Bowlus Flume, 32-33, 35
Parameters
Methods for Determining, 92-101
Correlation between Parameters,
95-101
Probability of Exceeding
Standard, 93-94
To Analyze
Municipal, 127-129
Sludges, 178, 179
Industrial, 137, 138, 139
Surface Waters, 146
Agricultural Discharges, 170, 171
Parshall Blume, 30-33, 35, 131
Pesticides/Herbicides
Recommended Preservation, 226-229
Physical/Mineral Parameters
Recommended Preservation, 211-225
Pltot Tube, 20, 22, 25
Preservation and Handling
Municipal Wastewaters, 129
Surface Waters/Bottom
Sediment, 168
Sludges, 181
Probability Distribution
Gaussian (Normal), 65-67
Pearson Type 111, 66
Logarithmic, 68
Chi-Square, 68, 69
Student t, 70, 71
Determination of Type, 70-78
Radioactive Parameters
Defined, 232
Sources, 232, 241, 242
Recommended Preservation, 241, 242
256
-------
Refrigeration, 42
Sample Containers
Cleaning, 56
Materials, 54, 55
Preparation, 56, 242, 249, 250
Sample Identification, 42, 43
Samplers
Automatic
Criteria for Selection, 10-16
Installation and Use, 16-18
For Municipal Wastewaters, 130
For Industrial Wastewaters,
142, 143
Biological
Water Samplers, 155
Bottom Grabs, 156
Coring Devices, 157
Nets and Related Devices, 158
Substrate Samplers, 154
Agricultural Discharge, 172-174
Samples
Type of:
Grab, 4
Composite, 4-9
Municipal, 130
. Industrial, 137, 140
Surface Waters/Bottom
Sediments, 153
Agricultural Discharges, 171
Sludges, 181
Sludges, Types, 177
Sampling, 177-182
Spectral Analysis
Definition, 64
Municipal Wastewater
Application, 129
Industrial Wastewater
Application, 134
Agricultural Runoff, 170
Method, 87-92
Ultrasonic Flowmeter, 20, 34, 35
Universal Preservative, 41, 42
Venturl Meter, 20, 22
Volumes of Samples
General, 57
Municipal Wastewater, 131
Industrial Wastewater, 143
Surface Water/Bottom Sediments,
168
Agricultural Discharges, 170
Sludges, 181
Weirs, 26-30, 33, 35
SamplIng Method
Automatic, 10-18
Manual, Guidelines,
37
Municipal, 123
Industrial, 133, 141
Surface Waters/Bottom
Sediments, 153
Agricultural Discharges,
Sludges, 181
171
257
-------
NTIS
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Passive Solar Heating and Cooling Conference and
Workshop Proceedings May 18-19,1976,
University of New Mexico, Albuquerque, New
Mexico
LA-6637-C/PSK 352 p PC$10.50/MF$3.00
Predicting the Performance of Solar Energy Systems
AD-A035 6087 PSK 45 p PC$4.00/MF$3.00
NIOSH Analysis Methods for Set J
PB-263 9597 PSK 128 p PC$6.00/MF$3.00
Rat-Plate Solar Collector Handbook: A Survey of
Principles, Technical Data and Evaluation Results
UCID-17086/PSK 96 p PC$5.00/MF$3.00
How to Order
When you Indtoate Ms m*iod of payment,
PIMM note It • purchase order It not aoconv
parted by payment, you wU be bMed an add-
ttonal 18.00 »HfttndD» charge. And plMM
Include the card expiration date when using
American Express.
Normal deSvsry time takee ftaee to five weeks.
tt to vital Hal you order by number or your order
wl be msnusJy Mad, (muring a (May. MDU can
opl tor gfterty ma» tor $3.00 outtlda North
American oonenent charge par Nam* Juat check
•ta priority mi box. H you'ra reefy praaaad tor
•ma. oal tta NTW Ruah Handing 8«rv(oa (703)
867-4700. for a $10.00 chargapar Nam. your
you can pk* up your ordar m tit
Information Center & Bookstore or at our
Springfield Operations Center within 24 hours for
a $6.00 per Item charge.
Vbu may also place your order by telephone or
If you have an NTIS Deposit Account or an
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The ordar desk number Is (703) 557-4060 and
the TELEX number Is 69-9405.
Thank you tor your Interest In NTIS, Wa ap-
predate your order*
METHOD OP PAYMENT
Charge my NTIS deposit account no.
Purchsse order no.
Check enclosed for!
Bill me. Add 16.00 per order and sign bekm (Not aveNable
outside North American continent.)
G Charge to my American Express Card account number
D
NAME.
ADORESS-
CTTY. STATE. ZIP.
Card expiration date
Signature.
O Priority mail requested
dp and mall to:
U.S. DBPAHTMINT OF COMMERCE
Sprtngllald, Va. 12161
(TOJ)M7-4a*0 TELIXSS-S409
Hem Number
Quai
Pa^Copy
ntny
(MF)
Unltprtoe*
Alprtoaaaub|ert to crwga. The prices Sub Total
sboveareao^rsteasof 3/31/78 AddMonal Charge
Foreign Prices on Request.
-r " Enter Grind Total
Total Price*
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