EPA 600/4 77-012
February 1977
Environmental Monitoring Series
                        EPA METHOD  STUDY 8,  TOTAL
                                     MERCURY  IN WATER
                                 Environmental Monitoring and Support Laboratory
                                         Office of Research and Development
                                        U.S. Environmental Protection Agency

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interlace in related fields.
The nine series are.

      1.  Environmental Health Effects Research
      2.  Environmental Protection Technology
      3.  Ecological Research
      4.  Environmental Monitoring
      5.  Socioeconomic Environmental Studies
      6.  Scientific and Technical Assessment Reports (STAR)
      7.  Interagency Energy-Environment Research and Development
      8.  "Special" Reports
      9.  Miscellaneous Reports

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-600/4-77-012
                                                    February 1977
                     EPA METHOD STUDY 8,

                   TOTAL MERCURY I N WATER
                            by

        John Winter, Paul Britton,  Harold Clements
Environmental Monitoring and Support Laboratory-Cincinnati

                     and Robert Kroner
                  Cincinnati, Ohio  45268
    Prepared in part under EPA Purchase Order 5-03-4294
                      Project Officer

                        John Winter
      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   45268

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                                 DISCLAIMER
     This report has been reviewed by the Environmental Monitoring and
Support Laboratory-Cincinnati, U.S. Environmental Protection Agency, and
approved for publication.  Mention of trade names or commercial products
does not 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 conducts research to:

     0  Develop and evaluate technique to measure the presence and
        concentration of physical, chemical, and radiological pollut-
        ants in water, wastewater, bottom sediments, and solid wastes.

     0  Investigate methods for the concentration, recovery, and
        identification of viruses, bacteria, and other microorganisms
        in water.  Conduct studies to determine the responses of
        aquatic organisms to water quality.

     0  Conduct an Agency-wide quality assurance program to assure
        standardization and quality control of systems for monitoring
        water and wastewater.

     This publication of the Environmental Monitoring and Support Laboratory,
Cincinnati, entitled:  EPA Method Study 8^, Total Mercury in Water reports
the results of a joint ASTM/EPA study of a cold vapor technique for  total
mercury in water, prior to acceptance by both organizations.  Federal agencies,
states, municipalities, universities, private laboratories, and industry
should find this evaluative study of a selected method of analysis for
mercury of vital importance in their efforts in monitoring and controlling
mercury pollution in the environment.
                                       Dwight G. Ballinger
                                       Director, EMSL -  Cincinnati
                                     iii

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                                 ABSTRACT
     The Office of Research and Development, EPA, coordinates the col-
lection of water quality data to determine compliance with water quality
standards, to provide information for planning of water resources develop-
ment, to determine the effectiveness of pollution abatement procedures,
and to assist in research activities.  In a large measure the success of
the pollution control program rests upon the reliability of the information
provided by the data collection activities.

     The Environmental Monitoring and Support Laboratory (EMSL) in
Cincinnati, Ohio, is responsible for insuring the reliability of physical,
chemical, biological, and microbiological data generated in the water
programs of EPA.  Within EMSL, the Quality Assurance Branch (QAB) conducts
interlaboratory studies for method evaluation and laboratory accreditation
programs, provides quality control samples, and develops quality control
guidelines for water quality laboratories.

     This report describes one study in the series conducted by the
Quality Assurance Branch.  It was completed in part by Mr. Robert C.
Kroner under EPA Purchase Order 5-03-4294.
                                    iv

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                                 CONTENTS
FOREWORD	  ill

ABSTRACT	   iv

FIGURES	   vi

TABLES	  vii

ACKNOWLEDGMENTS	viii

PARTICIPATING LABORATORIES	   ix

     INTRODUCTION	    1

     SUMMARY	    2

     DESCRIPTION OF STUDY

          Test Design	    3
          Preparation of Samples	    A
          Analysis and Reporting	    5
          Distribution of Samples	    5

     RESULTS	    6

     TREATMENT OF DATA

          Rejection of Outliers	  11
          Basic Data Summaries	  11
          Statistical Summaries	  28
          Single-Analyst Precision	  28
          Statements of Method Precision	  28
          Statements of Method Accuracy	  33
          Two-Sample (Youden) Charts	  33

     DISCUSSION AND CONCLUSIONS	  45

REFERENCES	  46

APPENDICES

     Proposed Standard Method of Test for Total Mercury in Water...  47

          (Al)  Disposal of Mercury Containing Wastes	  57

GLOSSARY OF TERMS	  60

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                                   FIGURES



Number                                                                 Page






   1    Method precision for analyses in distilled water	  31






   2    Method precision for analyses in natural water	  32






   3    Method accuracy for analyses in distilled water	  35






   4    Method accuracy for analyses in natural water	  36






  5-12  Youden Plots of retained data by ampul pair	  37
                                     vi

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                                    TABLES




Number




   1      True Values for Total Mercury
   2      Raw data from analyses in distilled water .....................   7






   3      Raw data from analyses in natural water .......................   9






  4-12    Data summaries by ampul for analyses in distilled water .......  12






 12-19    Data summaries by ampul for analyses in natural water .........  20






 20-21    Statistical summary ...........................................  29
                                      vii

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                               ACKNOWLEDGMENTS
     The authors gratefully acknowledge the hard work and cooperation of
the staff of the Quality Assurance Branch, EMSL, who assisted in the
study.  They especially want to acknowledge the excellent typing and
formatting skills of Ms. Betty Smith and M. Mary Doyle and the technical
assistance and guidance of Mr. Elmo C. Julian, formerly Physics and
Chemistry Branch, EMSL, who modified some of the statistical and
graphical programs used in this study.

     The staff also wishes to thank Mr. Thomas Bennett, Mercury Task
Group Chairman Committee D-19.05 of ASTM and Mr. John Kopp, Chief of the
Physical and Chemical Methods Branch of EMSL, for their cooperation and
assistance in this study.
                                   viii

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      PARTICIPATING LABORATORIES

           EPA LABORATORIES
Analytical Quality Control Laboratory
Cincinnati, OH  45202

Annapolis Field Office
Annapolis, MD  21401

Environmental Protection Agency
Kansas City, MO  64108

Environmental Protection Agency
Alameda, CA  94501

Environmental Protection Agency
Charlottesville, VA  22901

Houston Facility
Houston, TX  77036

Illinois District Office
Chicago, IL  60609

Indiana District Office
Evansville, IN  47711

National Field Investigation Center
Cincinnati, OH  45268

National Water Quality Laboratory
Duluth, KN  55804

Pacific Northwest Environmental Research Laboratory
Corvallis,  OR  97330

Southeast  Environmental Research Laboratory
Athens, GA 30601

Water  Supply Research Laboratory
Cincinnati, OH  45268

Wheeling Field Office
Wheeling,  WV  26005
                   ix

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                           PARTICIPATING LABORATORIES

                             NON-EPA LABORATORIES
Alaska Dept. of
Environmental Conservation
Juneau, AK  99801

Allied Chemical Corp.
Brunswick, GA  31520

Allied Chemical Corp.
Riegelwood, NC  28456
Allied Chemical Corp.
Buffalo, NY  14240

Allied Chemical Corp.
Morristown, NJ  07960
Allied Chemical Corp.
Solvay, NY  13209
American Electric Power Service
Huntington, WV  25710

Arkansas Dept. of Pollution
Control & Ecology
Little Rock, AR  72209

Atlantic Richfield Company
Harvey, IL  60426

B. F. Goodrich Chemical Co.
Calvert City, KY  42029

Brandt Associates, Inc.
Newark, DE  19711
Bunker Hill Company
Kellogg, ID  82827

California Div. of Mines & Geology
San Francisco, CA  94111
Charlton Lab. Unit of MEI
Portland, OR  97207
Chicago Bureau of Water
Chicago, IL  60611

Cities Service Oil Company
Refinery Lab
Lake Charles, LA  70601

Coca Cola Company
Atlanta, CA  30318

Commonwealth of Kentucky
Dept. of Health
Frankfort, KY  40601

Commonwealth of Massachusetts
Lawrence Experiment Station
Lawrence, MA  01843

Commonwealth Laboratory, Inc.
Richmond, VA  23223

Diamond Shamrock Chemical Co.
Mobile, AL  36614
Dow Chemical
Palquemine, LA  70764

Edna Wood Labs., Inc.
Houston, TX  77021

Environment Canada
Canada Centre for Inland Waters
Burlington, Ontario, Canada

Federal Paper Board Co., Inc.
Riegelwood, NC  28456

Froehling & Robertson
Richmond, VA  23261

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                          PARTICIPATING LABORATORIES

                             NON-EPA LABORATORIES
                                  (Continued)
General Testing Labs., Inc.
Kansas City, MO  64108

Georgia Dept. of Natural Resources
Atlanta, GA  30334

Gulf Research & Development Co.
Pittsburgh, PA  15230
Holston Defense Corp.
Kingsport, TN  37662

Huntington Alloys
Huntington, WV  25720

Hydro Research Labs.
Pontiac, MI  48058

Illinois Environ. Protection Agcy.
Carbondale, IL  62901

Illinois Environ. Protection Agcy.
Champaign, IL  61820

Indiana State Board of Health
Indianapolis, IN  46206

Industrial Testing Labs
St. Louis, MO  63104
Interstate Sanitation Commission
New York, NY  10019
Kern-Tech Laboratory
Baton Rouge, LA  70818

Koppers Company, Inc.
Monroeville, PA  15146
Los Angeles Dept. of Water & Power
Los Angeles, CA  90051

Louisiana State Dept. of Health
New Orleans, LA  70160

Maine Dept. of Environmental
Improvement Commission
Augusta, ME  04330

Maryland Dept. of Health
Baltimore, MD  21218

Maryland Water Resources Admin.
Annapolis, MD  21401

Michigan Dept. of Public Health
Lansing, MI  48914

Ministry of the Environment
Rexdale, Ontario, Canada

Montana Bureau of Mines & Geology
Butte, MT  59701

Moutrey & Associates, Inc.
Tulsa, OK  74145

National Institute of Occupational
Safety & Health
Cincinnati, OH  45202

North Carolina Dept. of Health
& Economic Resources
Raleigh, NC  27611

NUS Corporation
Pittsburgh, PA  15205

Oilwell Research, Inc.
Long Beach, CA  90831
                                    xi

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                          PARTICIPATING LABORATORIES

                             NON-EPA LABORATORIES
                                  (Continued)
Olin Corporation
Mclntosh, AL  36553

Olin Corporation
Pisgah Forest, NC  28768

Pennsylvania Dept. of Environ.
Resources
Erie, PA  16505

Pennwalt Corporation
King of Prussia, PA  19406
Pennwalt Corporation
Calvert City, KY  42029
Philadelphia Water Dept.
Philadelphia, PA  19136
Ralston Purina Company
St. Louis, MO  63188

St. Louis Testing Labs.
St. Louis, MO  63103

Seattle Metro Water Quality Lab
Seattle, WA  98119

Serco Laboratories
Minneapolis, MN  55406

South Dakota School of Mines
& Technology
Rapid City, SD  57701

Stewart Labs., Inc.
Knoxville, TN  37921

Tenco Hydro/Aerosciences
Countryside, IL  60525
Tennessee Dept. of Public Health
Nashville, TN  37319

Tennessee Valley Authority
Chattanooga, TN  37401

Texas State Dept. of Health
Austin, TX  78756
U.S. Air Force
Environmental Health Lab
Kelly AFB, TX  78241

U.S. Dept. of the Army
Corps of Engineers
Cincinnati, OH  45201

U.S. Geological Survey
Analytical Methods Research, WRD
Denver, CO  80225

U.S. Geological Survey
Harrisburg, PA  17108

University of Maine
Orono, ME  04473

Utah Environmental Laboratory
Port Hardy, B.C., Canada

Utah State Dept. of Social Services
Salt Lake City, UT  84113

Ute Research Laboratories
Fort Duchesne, UT  84026
Vermont Dept. of Water Resources
Monpelier, VT  05602

Washington State University
College of Engineering
Pullman, WA  99163
                                    xii

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                          PARTICIPATING LABORATORIES

                            NON-EPA LABORATORIES
                                 (Continued)
West Coast Technical Services, Inc.
San Gabriel, CA  91776

West Virginia Dept. of Health
Environmental Health Services Lab
South Charleston, WV  25303

West Virginia Dept. of Natural
Resources
Charleston, WV  25303

West Virginia Dept. of Natural
Resources
Elkins, WV  26241
Westinghouse Corporation
Pittsburgh, PA  15235

Westinghouse Corporation
Madison, PA  15663
Westinghouse Corporation
Elmira, NY  14900
Wilson & Company
Salina, KS  68401
                                    xiii

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                                 INTRODUCTION
     The various analytical laboratories of the U.S. Environmental
Protection Agency gather water quality data to provide information on
water resources, to assist research activites, and to evaluate pollution
abatement activities.  The success of these pollution control activities
depends upon the reliability of the data provided by the laboratories,
particularly when legal action is involved.

     The Environmental Monitoring and Support Laboratory-Cincinnati
(EMSL, formerly Methods Development and Quality Assurance Research Labora-
tory) of EPA was established to conduct EPA's quality assurance program
for the water laboratories and to assist EPA laboratories in the choice
of methods for physical, chemical, biological and microbiological analyses.
The quality assurance program of EMSL is designed to maximize the reliability
and legal defensibility of all water quality information collected by EPA
laboratories.  The responsibility for these activities of EMSL is assigned
to the Quality Assurance Branch (QAB).  This study is one of the QAB
activities.

     Prior to this method evaluation study, the research chemists of EMSL,
assisted by other chemists in EPA, had proposed a method of measurement
for total mercury in natural water and wastewaters.  The method developed
after considerable study included an acid-permanganate-persulfate digestion
at 95°C for two hours followed by reduction and measurement of mercury in
the vapor phase at 253.7 nm.

     Since EPA chemists are participating members of the D-19 Committee
on Water of the American Society for Testing and Materials, the same
method was proposed to the D-19 Committee for use in the Annual Book of
ASTM Standards, Part 31, Water.  It was logical therefore to propose a
joint EPA/ASTM study for mercury in water.  This report describes the
study and provides statements of precision and accuracy for the method.

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                                    SUMMARY
     The Quality Assurance Branch of the Environmental Monitoring and
Support Laboratory conducted a joint EPA/ASTM interlaboratory study on
the cold vapor technique for mercury in natural waters.

     The method evaluated in this study is that described by Kopp, Long-
bottom, and Lobring (1) which requires a vigorous digestion with acid
permanganate, potassium persulfate and heat (95°C) to effect complete
oxidation of organically bound mercury prior to reduction and measurement
by absorption at 253.7 nm.

     Sample concentrates were prepared at similar, but slightly different,
concentrations of mercury.  An aliquot of each concentrate was added to
distilled water and natural water samples at concentrations of 0.2-10 ug
of mercury/liter.  One mercury measurement was made on the natural water
as background and one measurement each on the distilled water and natural
water samples with the added increment.  Recoveries from the natural
water samples were calculated by difference.  Recoveries for all concen-
trations were compared and significant statistical measures such as
standard deviation, mean recovery, etc., were calculated.  The following
equations provide the precision and accuracy which may be expected in
routine work:

     Distilled Water;

          Precision    S  =  0.2454 + 0.2922 X

                       Sr =  0.3117 + 0.0718 X

          Accuracy

             Mean Recovery, X  =  0.2028 + 0.9517 (cone)

     Natural Water;

          Precision    S  =  0.1661 + 0.3647 X

                       Sr =  0.0465 + 0.1379 X

          Accuracy

             Mean Recovery, X  =  0.1373 + 0.9508 (cone)

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                             DESCRIPTION OF STUDY
     The study design was based on Youden's original plan (2) for collab-
orative evaluation of precision and accuracy for analytical methods.
According to Youden's design, samples are analyzed in pairs, and each
sample of a pair has a slightly different concentration of the constituent.
The analyst is directed to do a single analysis and report one value for
each sample, as if for a normal routine sample.

     In this study, samples were prepared as concentrates in sealed glass
ampuls and presented to the analyst with complete instructions.  The
analyst was required to add an aliquot of each concentrate to a volume of
distilled water and to a volume of natural water of any kind.  Analysis
in distilled water evaluates the proficiency of the analyst to use  the
method on a sample free of interferences; analysis in natural water
(rivers, lakes, estuaries) is intended to reveal interferences in the
method.  Four pairs of samples were used.  One pair contained mercury
near the minimum detectable limit of 0.2 yg/liter; a second pair contained
mercury at an intermediate level of 0.5-0.6 vg/liter level and the  latter
pairs contained mercury at levels of 3-10 yg/liter.

Test Design

     A summary of the test design, using Youden's non-replicate  technique
for x and y samples is given below:

     1)   Eight samples, prepared as stable concentrates  in  sealed  glass
          ampuls, were presented to the analyst as unknowns.

     2)   When the analyst was ready to start  the analysis,  the  ampuls
          were opened and an aliquot diluted to volume  in distilled water
          and in a natural water according to  instructions.

     3)   Four levels of mercury concentration (four pairs  of  samples)
          were analyzed  to cover the levels observed in natural  waters.

     A)   Each sample was analyzed once only.

     5)   Natural water  samples were analyzed  with  and  without added
          increment and  the  added  level determined  by difference.

     Recoveries from distilled water and natural waters were compared.
Precision and accuracy were  calculated and interferences  were observed.

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Preparation of Samples

     Sample concentrates were prepared by dissolving precisely-weighed
amounts of reagent grade chemicals in high purity water* to produce
accurate concentrations of organic and inorganic mercury.  Each sample
contained the same ratio of inorganic to organic mercury (42%:58%) as
mercuric chloride and methyl mercury chloride, respectively.  The concen-
trates were preserved with 0.15% redistilled nitric acid and checked by
repeated analysis for a period of three months prior to distribution.
These analyses served to confirm both the calculated concentrations and
sample stability.  Analyses of the samples by an outside laboratory also
confirmed the concentrations.

     When diluted to volume according to the instructions,  the samples
contained the following concentrations of mercury:

                                   TABLE 1

                        True Values for Total Mercury**
                Sample               Concentration of Mercury
                                               Vg/liter
1
2
3
4
5
6
7
8
0.21
0.27
0.51
0.60
3.4
4.1
8.8
9.6
  *  Prepared by passage of distilled water through a four-cartridge
      Millipore Super-Q system.

 **  The concentrations are the actual levels calculated and added.   They
      are not based on analysis,  the latter being used for verification
      only.

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Analysis and Reporting

     The distilled water - natural water spike technique was used in this
study.  Each analyst was instructed to dilute separate 5.0 ml aliquots
of each concentrate to one liter with distilled water and a natural or
wastewater of his choice.  To insure sample stability the analyst was
also instructed to add 1.5 ml of redistilled nitric acid per liter during
sample preparation.  Accurate measurement of mercury in distilled water
confirmed the analyst's ability to measure mercury in a sample free of
interferences.  A difference in the recovery of mercury from distilled
water as compared to the recovery of mercury from natural water indicated
the presence of interferences.
Distribution of Samples

     An invitational memorandum announced the study to each EPA Region in
September, 1972.  The study was also announced in EPA's Analytical Quality
Control Newsletter which is circulated to about 7,000 technical offices
of government and private agencies in the United States and Canada.

     One-hundred and one laboratories from EPA, other Federal, State and
local agencies, Canadian groups, universities and private industry responded
and participated.  After a pre-selected cutoff date, beyond which no
further requests were answered, samples were packed and shipped.

     Each collaborator was sent 1) a set of eight ampuls, 2) instructions
for sample preparation, 3) a copy of the analytical procedure to be used,
and 4) duplicate report sheets.  Participants were allowed fifty days to
complete the analyses and report the data.  All data returned within the
prescribed time were included in this report; data reported later that
the cutoff date were omitted.

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                                    RESULTS
     Tables 2 and 3 present all raw data received, identified by labora-
tory and analyst codes.

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                                     TABLE 2
           Raw Data  from Analyses  for Total Mercury Increment
                              In  Distilled  Water
              AMPUL    AMPUL     AMPUL    AMPUL    AMPUL    AMPUL
                1        2       3        I.        5        6

INCREMENT, UG/L   0.21     0.27     0.51     0.60     3.4      "i. 1
                                                           AMPUL
                                                            7
                                                                   AMPUL
                                                                         9.6
LAB
NO.
ANALYST
  NO.
101
105
106
110
112
117
122
12J
124
125
137
11(2
li»5
US
152
157
169
180
180
180
182
181*
185
190
195
201*
212
230
233
233
253
259
261
2E2
267
311
324
329
352
356
T74
i|22
1)36
437
14 41
l»i)2
1(1(5
1(1(6
447
1(1(8
4?2
457
It67
1(68
U71
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
3
1
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
3
0
0
1
0
0
0
0
0
0
0
0
0

0
0
0
0
.10
.1(0
.50
.07
.61
.37
.21
.20
.50
.00
.10
.22
.1(0
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.1(3
.38
.10
.20
.21
.21)
.15
.20
.23
.20
.30
.58
.11
.22
.80
.1)8
.20
.20
.1)0
.50
.1)3
.80
.60
.OOR
.50
.20
.00
.46
.1)0
.50
.11)
.35
.1)1)
.1)0
.11
.20

.90
.29
.55
.30
0

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.50
.21
.31)
.31
.31
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.36
.00
.10
.27
.30
.65
.29
.35
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.30
.32
.1)1)
.17
.20
.29
.20
.30
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.27
.80
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.00
. 60R
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.30
.95
.50
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.16
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.50
.19
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.90
.26
.70
.20
0
0
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7
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.60
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.52
.56
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.58
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.50
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.75
.53
.58
.30
.50
.55
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.38
.38
.52
.1)0
.10
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.35
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.00
.05
.60
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.00
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.68
.80R
.l)OR
.28R
.30
.50
.53
.98
.50
.32
.25
.1)5
.56
.70
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.80R
.71)
.1)8
.30
0
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.61)
.60
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.60
.SI
.81
.57
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.83
.00
.22
.56
.80
.81
.67
.60
.50
.60
.61)
.70
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.61
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.60
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.60
.00
.95
.20
.56
.40R
.20
.61)
.90R
.60
.28
.30
.50
.29
.91)
.70
.52
.26
.60
.57
.80
.1)5
.1(5
.50
.OOR
.i)6R
.75
.50
3.80
3.80
J.50
2.00
3.10

3.20
4.20
4.1(0
1.1)8
1.60
3.10
3.20
3.30
3.60
3.1)0
5.70
5.1U
3.1)3
3.50
3.50
3.10
5.10
5.20
6.30
3.80
5.1)0
5.30
4.70
4.85
4.1(0
3.10
3.20
5.30
2.10
120. OOR
3.20
2.28
l).00
1.20
4.91
i(.87
5.50
2.1)5
l.UO
5.20
5.50
5.90
2.1)0
1.50
2.80
28. OOR
2.75
5.20
2.00
l).30
4.50
It. 50
2.50
4.30

4.20
4.80
5.10
1.25
4.40
3.50
3.50
3.80
4.10
4.20
4.20
4.27
4.70
4.40
4.30
3.70
3.73
4.10
7.70
4.38
4.20
4.10
5.60
4.95
6.00
3.60
3.80
4.00
2.60
148. OOR
3.40
5.56
4.20
0.90
5.86
5.89
4.50
3.10
1.65
4.00
4.30
4.30
4.10
2.10
3.40
30. OOR
3.21
3.80
2.90
8.
9.
10.
6.
8.

8.
9.
9.
3.
4.
7.
9.
8.
9.
8.
8.
10.
10.
5.
9.
8.
7.
8.
13.
6.
8.
9.
10.
10.
11.
7.
9.
8.
4.
328.
8.
4.
7.
2.
10.
11.
9.
7.
3.
9.
9.
9.
7.

7.
63.
6.
8.
6.
35
30
00
00
70

70
40
60
30
40
80
00
00
30
50
20
00
00
00
10
20
43
50
20
80
60
00
60
05
00
40
40
40
20
OOR
00
56
50
00
99
88
50
50
35
00
00
30
90

30
OOR
85
30
20
9.60
9.60
11.00
6.20
9.70

9.00
10.00
11.00
4.25
4.80
8.30
9.2&
7.60'
9.90
9.30
8.90
13.30
13.25
10.00
10.00
9.00
7.89
8.90
13.50
8.48
9.10
9.20
10.80
9.95
10.00
8.10
8.40
9.10
4.60
382. OOR
9.10
10.40
7.70
2.30
11.85
12.80
10.00
7.30
3.59
9.80
9.50
9.80
7.20
4.80
7.50
68. OOR
8.80
9.00
8.80
R • REJECTED

-------
                                     TABLE 2
                                   (Continued)
           Raw Data from Analyses  for Total Mercury  Increment
                              In Distilled  Water
              AMPUL     AMPUL    AMPUL    AMPUL    AMPUL    AMPUL
               1       2       3        4        5        6

INCREMENT, UG/L   0.21      0.27     0.51     0.60     3.4      4 . 1
AWPUL
  7
AfPUL
  8
         9.6
LAB   ANALYST
NO.    NO.
472 1
475 1
478 1
1)81 1
U86 1
1489 1
492 1
496
500
502
503
504
508
509
510
511
512
513
51U
515 1
516 1
517 1
518 1
519 1
520 1
521 1
522 1
523 1
52l» 1
525 1
526 1
527 1
528 1
529 1
530 1
531 1
532 1
533 1
534 1
535 1
0.
0.
0.
0.
0.
0.
0.
0.
0.

1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
1.
0.
0.
0.
0.
0.
0.
0.

0.
1.

0.
3.
12.
0.
4.
05
20
80
50
32
20
60
26
83

00
15
52
60
35
75
23
50
43
33
20
00
20
00
37
41
41
20
80
45
20

40
00

00
75R
10R
23
10R
0.
0.
0.
0.
0.
0.
0,
0,
0.

0.
0.
0.
0.
0.
0.
0.

0.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
5.
14.
0.
4.
71
30
30
45
36
17
58
32
63

90
15
40
70
25
80
28

79
30
20
91
20
00
25
41
16
30
BO
50
30
26
40
50
20
84
OOR
30R
04
80R
1.
0.
1.
0.
0.
0.
1.
0.
1.
0.
1.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.

0.
0.
0.
1.
1.
0.
0.
1.
1.
0.
3.
7.
0.
0.
5.
37
50
20
82
52
34
10
58
20
65
00
40
80
60
65
90
54
48
28
58
20
36
40
00

65
61
50
10
10
35
41
20
00
45
92R
OOR
65
OU
70R
0
0
0
0
0
0
1
0
1
1
0
0
1
1
0
1
0
0
0
0
0
0
0
1

0
0
0
0
1
0
0
0
2
0
1
7
0
D
3
.34
.50
.60
.92
.62
.51
.14
.70
.20
.20
.95
.70
.20
.80
.65
.00
.65
.52
.20
.54
.1(0
.18
.50
.00

.98
.69
.60
.80
.10
.35
.52
.30
.50
.35
.39
.OOR
.88
.03
.00
D
3
It
3
3
ti
3
3
4

3
3
it
3
3
3
3
3
3
3
3
2
3
4
3
3
3
3
3
L
3
2
3
6
1
23
11
3
0
4
67
50
20
08
50
00
10
50
20

45
36
10
10
40
00
50
50
20
30
30
00
00
00
80
50
81
50
60
70
80
60
20
25
90
10R
30
30
20
80
1.11
U.I4"
4.60
5.08
4.20
5.90
3.70
4.10
5.40

3.90
4.22
4.60
3.30

3.80
4.10
4.10
3.90
It. 10
4.50
3.60
4.00
5.00
4.53
4.60
4.29
4.20
4. 50
5.20
4.00
3.30
7.50
8.00
10.60
5.40
16.30R
6.70
0.20
3.30
3
8
9
10
9
13
6
8
12

7
8
11
7

8
8
9
9
9
10
6
8
9
11
e
10
9
10
9
8
7
3
12

36
20
9
0
10
.U
.80
.40
.75
.00
.00
.00
.30
.00

.00
.56
.60
.70

.10
.70
.00
.30
.10
.00
.30
.60
.00
.00
.40
.51
.10
.20
.20
.00
.20
.60
.00

.40R
.00
.80
.55
.00
1
10
10
11
9
13
9
9
14

S
S
12
7

S
9
9
9
9
12
7
11
10
13
8
11
10
11
9
8
8
u
15
5
18
25
9
0
10
.18
.00
.40
.05
.90
.00
.60
.00
.00

.10
.34
. 50
.80

.20
.50
.00
.60
.60
.00
.50
.20
.00
.00
.80
.96
.00
.40
.70
.20
.00
.10
.75
.20
.60
.00
.30
.58
.00
   REJECTED

-------
                                     TABLE  3
             Raw Data from Analyses for  Total  Mercury Increment
                               in Natural Water
              AMPUL    AMPUL    AMPUL     AMPUL    AMPUL    AMPUL
                1        2        3       4        5        6

INCREMENT, UG/L   0.21     0.27     0.51      0.60     3.4      4. 1
                                                          AMPUL
                                                            7
                                                                        AMPUL
                                                                        9.6
LAB
NO.
ANALYST
  NO.
101
105
106
110
112
117
122
123
121.
125
137
142
1U5
148
152
157
169
1814
185
190
20U
212
230
233
233
253
259
261
262
267
311
324
329
352
356
37ii
422
1.36
1.1.1
1.1.2
It 43
1.1.6
447
448
1.52
457
1(68
471
472
475
478
481
486
489
492
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0. 15
0.20
0.50
0.07
0.30

0.10

0.30
1.00
0.10
0.22
0.40
0.30
0.29
0.35
0.10
0.20
0.23
0.22
0.20
0.32
0.14
0.80
0.48
0.20
0.20
0.00
0.30
0.44
0.80
2.20R
0.39
0.64
0.10
1.27
0.27
0.50
0.15
O.UO
0.56
0.40
0.26
0.50

0.90
0.49
0.20
0.08
0.20
1.20
0.48
0.30
0.10
C.44
0.30

0.50
0.21
0.3S

0.26
0.20
0.27
1.00
0.11
0.27

0.15
0.30
O.i5
0.20
0.23
0.31
0.26
0.20
0.16
0.19
0.80
0.49
0.20
0.21
0.80
0.20
0.61
1.00
7. 5 OR
0.10
0.59
0.50
1.05
0.40
0.50
0.15
0.42
0.32
0.50
0.24
0.20
0.40
1.10
1.00
0.10
0.65
0.20
0.80
0.53
0.35
0.16
0.46
0.64
0.60
0.50
0.35
0.42

1.06
0.20
0.57
1.00
0.11
0.50
0.50
0.22
0.55
0.60
0.40
0.46
0.51
0.47
0.37
0.35
0.40
1.00
1.05
0.70
0.45
0.20
0.40
O.E9
8. COR
4.20R
0.10
2.40
0.40
1.46
0.82
0.50
0.26
0.62
0.66
0.70
0.34
O.SO
0.50
4.00
0.28
0.20
1.44
O.JO
1.20
0.93
0.52
0.35
1.10
0.69
0.80
0.50
1.00
0.46

0.38
0.60
0.75
1.00
0.22
0.56

0.50
0.80
0.60
0.50
0.61
0.64
0.53
0.49
0.72
0.45
1.00
0.95
0.20
0.58
10.00R
0.60
0.66
8.70R
1.60
0.10
2.30
0.30
1.32
0.91
0.50
0.25
0.60
0.49
1.00
0.62

0.50
3.900
0.35
0.30
0.44
0.40
1.20
0.96
0.60
0.46
0.90
3.60
4.00
3.50
2.10
3.30
4.60
3.60
4.40
4.20
0.85
1.80
3.30
3.00
2.80
3.40
5.50
3.60
3.20
2.94
3.30
2.79
3.60
2.90
4.70
4.85
5.40
3.10
3.00
3.70
2.60
125. OOR
1.70
0.13
4.20
3.70
5.06
4.84

1.36
3.40
3.80
3.50
2.40
2.10
2.80
30. OOR
3.50
2.10
0.64
2.10
3.80
3.4S
3.50
4.00
3.20
4.30
5.00
4.00
2.50
4.40
5.00
4. 00
4.70
4.80
0.83
2.30
3.70

3.7(1
4.10
4.20
4.00
3.90
5.77
4.20
2.70
4.60
3.50
5.60
4.95
5.00
5.60
5.20
4.50
2.70
155. OOR
3.90
0.77
4.20
1.70

5.82

1.70
4.00
5.90
4.30
3.00
5.00
3.40
35. OOR
4.00
5.10
1.10
2.20
4.49
4.58
4.30
5.60
4.03
8.43
8.00
9.50
6.10
8 .40
10.30
8 .20
9.70
9.80
1.88
4.50
7.80
8.30
10.40
8.80
8.50
8.10
8.70
7.34
8.40
6.36
9.10
10.70
10.60
10.05
12.00
7.40
8.40
9.00
3.90
340. OOR
8.00
2.45
7.80
3.00

11.98

3.42
9.40
8.50
9.00
6.60

7.30
66. OOR
8.30
6.30
3.22
4.80
9.00
11.03
8.60
15.00
8.30
9.40
9.10
10.50
6.20
.9.20
12.80
8.70
9.70
11.00
1.98
5.00
8.30

8.30
9.60
9.50
9.00
9.20
7.80
8.80
6.72
9.50

10.80
9.95
10.00
8.10
7.80
10.00
4.00
379. OOR
8.50
3.35
8.00
4.10

13.27

3,52
10,00
9,50
12,00
6,20
3,80
7,50
72, OOR
9,40
9,00
1,18
5,10
10.00
11.98
9.80
14.00
9.00
R - REJECTED

-------
                                     TABLE 3
                                   (Continued)

            Raw Data from Analyses for Total Mercury Increment
                               in  Natural Water
              AMPUL    AMPUL    AMPUL    AMPUL    AMPUL    AMPUL    AMPUL    AMPUL
               123U5678

INCREMENT, UG/L   0.21     0.27     0.51     0.60     3.1*      I*. 1      8.8      9.6


LAB   ANALYST
NO.    NO.
<(96
500
503
501)
508
510
511
512
51k
515
516
517
518
519
520
521
522
523
52U
525
526
527
529
530
531
552
533
531.
535
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
0.
0.
0.

0.
0.

1.

3.
it.
1.
0.
k.
30
22
25
15
1(7
00
80
21*
i>0
30
22
00
20
00
18
03
16
20

45
20

00

35R
75R
80R
00
70R
0.31
0.00
0.65
0.80
0.35
0.25
1.20
0.28
0.40
0.33
0.1)14
0.78
0.40
1.00
0.32
0.00
0.06
0.25
1.00
0.50
0.30
0.2U
0.50
0.30
2.09R
5.75R
2.60R
0.07
3.80R
0.60
o.uo
1.10
0.60
0.95
0.1)0
l.liO
0.56
0. 50
0.56
0.77
0.1)0
0.1)0
1.00
0.65
0.20
0.32
0.50
1.1)0
1.10
O.iiO
0.1)1)
0.75
0.30
18.U3R
7.50R
1.70
0.01
14.30R
0.72
0.1.0
1.05
0.70
1.50

1.50
0.65
0.50
0.61)
0.73
0.16
0.50
1.00
1.10
0.1)0
0.35
0.60
1.20
1.30
0.50
0.55
1.00
0.30
2.66R
7.50R
1.70
0.00
I..20R
3.70
3.00
3.95
3.1)1
3.80
J.15
3.55
3.50
2.80
3.30
4.20
2.10
3.1.0
l).00
3.80
3.80
2.96
3.1)0
3.00
It. 60
2.50
2.80
5.00
7.20
18.86R
12.50
2.90
0.16
3.50
I.
tl
I.
ti
1)
3
1*
(1
l)
1)
1)
3
1.
1)
1)
It
3
1)
>.
5
3
3
6
21
19

2
0
3
.10
.10
.25
.22
.30
.73
.50
.00
.00
.10
.50
.10
.00
.00
.50
.80
.1.6
.10
.30
.20
.20
.50
.50
.DOR
.OOR

.1)0
.17
.90
8.50
12.00
9.1.5
7.76
11.20
8.10
8.35
8.50
8.90
9.10
11.00
6.50
8.60
9.00
11.00
8.20
7.21
8.90
13.80
9.00
6.80
7.50
15.75

28.00
21.30
13.00
0.53
7.20
9
17
9
a
11

10
9
9
9
11
7
11
9
12
8
7
9
10
9
7
8
1U
5
15
26
12
0
7
.20
.00
.05
.31.
.80

.70
.10
.60
.60
.00
.60
.80
.00
.00
.90
.96
.80
.70
.80
.30
.10
.50
.1)0
.1)0
.30
.60
.51)
.20
   REJECTED
                                     10

-------
                               TREATMENT OF DATA
Rejection of Outliers

     This study, done at low and fractional yg/liter levels, produced
some data which were orders of magnitude away from the true values.
These extraneous values had to be eliminated before beginning any data
evaluations.  If these were not removed, the deviations in the data would
indicate a misleadingly large standard deviation for the method.  To
prevent this from happening, those values which were further than four
standard deviations from the mean, as calculated from all data, were
discarded as outliers.  Assuming a normal distribution, there is a 99.994%
probability that the rejected data were properly discarded.

     After elimination of unreasonable data, it was necessary to remove
the remaining extreme values which had only a small chance of validity
and which would make a significant change in the precision and accuracy
values for the tested levels of mercury.  These abnormal values are a
part of the routine data in every interlaboratory study, resulting from
chemical, instrumental, and analyst error.  These outliers were rejected
by applying the two-tailed Student's t test to all values at a 99% proba-
bility level.  This gave a 99 to 1 assurance that the data rejected were
indeed true outliers and should be discarded.

     As the spread of valid data increases, fewer outliers are rejected
because of a large standard deviation in the denominator of the t test.
Similarly, when the spread of valid data is very small  the  t test is more
powerful and more of the outliers are detectable.  In either case, the
rejected values should be considered true outliers and  the analytical
conditions should be carefully reviewed for the cause of error.
Basic Data Summaries

     Complete data summaries are  given  in Tables  A  through  19.  Each
Table provides a statistical evaluation of  the data for a single  concen-
trate spiked into one  type of water.  With  the exception of  "N, ALL DATA"
and "MEAN, ALL", the statistical  parameters are based  on the data remaining
after the rejection of outliers  (retained data).

     In addition to the statistical measurements, all  data  are  ranked  in
ascending order and retained data are presented in  a histogram  using Vn
cell divisions.  Each  X in the histogram represents one analytical result
for 1-15 values/cell.   When more  than 15 values occur  per cell, only 15
X's are printed but the actual number of values included in the cell is
printed to the left.
                                    11

-------
                                       TABLE
                        Data Summary by Ampul, Analyses  for
                         Total Mercury in Distilled Water
AMPUL 1 INCREMENT « 0.21 UG/LITER ORGANIC * INORGANIC MERCURY
N.ALL DATA 91
TRUE VAL.  0.21
MEAN,ALL
MEANtRET.
MEDIAN
ACCURACY
 0.6515*
 0.41770
 0.38000
98.90502
RANGE           1.60000     COEF.  VAR.      0.6686*
VARIANCE        0.07800     SKEMNESS       1.38637
STD. OEV.       0.27929     NO.  OF CELLS   9
CONF. LIM.      ±0.55367 (95 PCT)
PCT RELATIV/E ERROR
       DATA IN ASCENDING ORDER
     0.00
     0.05
     0.07
     0.10
     0.10
     0.10
     0.11
     0.11
     0.1*
     0.15
     0.15
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.21
     0.21
     0.22
     0.22
     0.23
     0.23
     0.23
     0.2*
     0.28
     0.29
     0.30
     0.30
     0.32
     0.35
     0.35
     0.37
     0.37
     0.38
     0.38
     0.40
     0.40
     0.40
     0.40
     0.40
     0.40
     0.40
     0.41
     0.41
     0.43
     0.43
     0.43
     0.44
     0.45
     0.46
     0.48
     0.50
     0.50
     0.50
     0.50
     0.50
     0.50
     0.50
     0.52
     0.55
     0.58
      0.60
      0.60
      0.61
      0.75
      0.80
      0.80
      0.80
      0.80
      0.83
      0.90
      1.00
      1.00
      1.00
      1.00
      1.00
      1.00
      1.60
      3.00R
      3.75R
      4.10R
     12.10R
                          MIDPOINT   FREO.     HISTOGRAM
                               RETAINED DATA  ONLY
0.0889
0.2667
G.kkkk
0.6222
0.8000
0.9778
1.1556
1.3333
1.5111
11
29
28
 5
 6
 7
 0
 0
 1
xxxxxxxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxxxxxx
xxxxx
xxxxxx
xxxxxxx
R = REJECTED DATA
                                  12

-------
                                  TABLE 5
                  Data Summary by Ampul,  Analyses for
                    Total Mercury in Distilled Water
AMPUL 2 INCREMENT - 0.27 U3/LITFR  ORGANIC
                                            INORGANIC  MERCURY
N.ALL DATA 92
TRUE VAL.   0.27
MFAN.ALL    0.80728
«LDlAN
ACCURACY
          RAN3E
          VARIANCE
          STD.  DEV.
 0.44965  CONF.  LIM.
 0.33000
66.54010  °CT RELATIVE ERROR
           1.79999     COEF. VAR.     0.72238
           0.10551     SKEWNESS       2.02945
           0.32482     NO. OF CELLS   9
          +0.64026  (95 PCT)
       DATA IN ASCENDI^S ORDER
     0.04
     0.10
     0.15
     0. 16
     0. 16
     0.17
     0.17
     0. 19
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.21
     0.21
     0.23
     0.25
     0.25
     0.26
     0.26
     0.27
     0.27
     0.28
     0.29
     0.29
     0.30
     0.30
     0.30
     0.30
     0.30
     0.30
     0.30
     0.30
     0.30
     0.31
     0.31
     0.32
     0.32
     0.34
     0.35
     0.35
     0.35
     0.36
     0.36
     0.36
     0.40
     0.40
     0.40
     0.40
     0.40
     0.41
     0.44
     0.44
     0.45
     0.49
     0.50
     0.50
     0.50
     0.50
     0.50
     0.50
     0.58
     0.60
     0.63
 0.65
 0.70
 0.71
 0.79
 0.80
 0.80
 0.80
 0.80
 0.90
 0.90
 0.91
 0.95
 L.OO
 1.00
 1.00
 L.44
 1.70
 1.84
 4. SOP
 5.OOP
10.60R
U.30R
                          MIDPOINT   FREO.     HISTOGRAM
                               RETAINED  DATA  ONLY
O.lltOO
0.3liOO
0.5400
0.7400
0.9400
1.1400
1.3400
1.5400
1.7400
22
35
13
 8
 7
 0
 0
 1
 2
XXXXXXXXXXXXXXX
XXXXXXXXXXXXXXX
xxxxxxxxxxxxx
xxxxxxxx
xxxxxxx
X
XX
R = REJECTED DATA
                                  13

-------
                                  TABLE 6
                   Data Summary  by Ampul,  Analyses  for
                    Total Mercury in Distilled Water
AMPUL 3 INCREMENT * 0.51  UG/LITFR  3RGANIC  «•  INORGANIC  MERCURY
N.ALL DATA 91*
TRUE VAL.  0.51
MEAN,ALL
MEAN,RET.
MEDIAE
ACCURACY
 1.02929
 0.65344
 0.52000
28.12685
RANGE
VARIANCE
STD. DEV.
CONF. LIM.
 2.25999
 0.14130
 0.37590
COEF. VAR.
SKEWNESS
NO. OF CELLS
0.57526
1.70852
9
+0.74937 (95 PCT)
PCT RELATIVE ERROR
       DATA IN ASCENDING ORDER
     0.04
     0.10
     0.20
     0.25
     0.27
     0.28
     3.30
     0.30
     0.32
     0.34
     0.35
     0.35
     0.35
     3.36
     0.38
     3.38
     0.38
     0.40
     0.40
     0.40
     0.40
     0.40
     0.41
     0.42
     0.45
     0.45
     0.45
     0.46
     0.4B
     3.48
     0.50
     0.50
     0.50
     0.50
     3.50
     0.50
     0.50
     0.50
     0.50
     0.50
     0.52
     0.52
     0.52
     0.52
     0.53
     0.53
     0.54
     0.55
     0.56
     0.56
     0.58
     0.58
     0.58
     0.58
     0.60
     0.60
     0.60
     0.61
     0.65
     0.65
     0.65
     0.65
     0.68
     0.70
     0.75
     0.82
     0.90
     0.98
     1.00
     1.00
      1.00
      1.00
      1.00
      1.00
      1.05
      1.10
      1.10
      1.10
      1.10
      1.20
      1.20
      1.20
      1.37
      1.53
      1.74
      1.80
      2.30
      3.80R
      3.92R
      5.40ft
      5.70R
      6.28R
      7.00R
      7.80R
 MIDPOINT  FREQ.     HISTOGRAM
      RETAINED DATA ONLY

   0.1656     6   XXXXXX
   O.U167    Ul   XXXXXXXXXXXXXXX
   0.6678    18   XXXXXXXXXXXXXXX
   0.9189     9   XXXXXXXXX
   1.1700     8   XXXXXXXX
   1.1*211     2   XX
   1.6722     1   X
   1.9233     1   X
   2.171*1*     1   X
    REJECTED  DATA
                                14

-------
                                  TABLE 7
                   Data Summary  by Ampul,  Analyses  for
                    Total Mercury in Distilled Water
41PUL 4 INCREMENT  =  0.60  UG/LITFR  DRGANIC  *•  INORGANIC MERCURY
N.ALL DATA 93
TRUt VAL.   0.60
MEAN,ALL    1.15289
MEAN,SET.    0.74386
MEDIAN      0.60000
     RANGE
     VARIANCE
     STO.  DEV.
     CONF.  LIM.
           2.97000
           0.21709
           0.46593
          +0.92354
            COfcF.  VAR.
            SKEWNESS
            NO.  OF CELLS
        195 PCT)
0.62637
2.34514
9
ACCURACY
           23.97704  PCT  RELATIVE  ERROR
       DATA IN ASCENDING  ORDER
     9.03
     3.18
     0.20
     0.20
     0.20
     0.22
     0.26
     0.30
     0.34
       35
       35
     0.40
     0.40
     0.45
     0.45
     0.45
     0.49
     0.50
     0.50
     0.50
     0.50
     0.50
     0.50
     0.50
     0.51
     0.51
     0.52
     3.52
     0.52
     0.53
     3.55
     0.55
     0.56
     0.56
     0.57
0.57
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.61
0.62
0.64
0.64
0.64
0.64
0.65
0.67
0.69
0.70
0.70
0.70
0.70
0.75
0.80
0.80
0.80
0.81
0.81
0.83
0.88
0.92
0.94
0.95
0.95
 0.98
 1.00
 1.00
 1.00
 1.00
 1.10
 1.14
 1.20
 1.20
 1.20
 1.28
 1.29
 1.39
 1.60
 1.80
 2.30
 2.50
 3.00
 4.OOP
 6.46R
 7.00R
 8.90R
15.UOR
MIDPOINT  FREO.     HISTOGRAM
     RETAINED DATA OMLY

  0.1950    11   XXXXXXXXXXX
  0.5250    U2   XXXXXXXXXXXXXXX
  0.8550    22   XXXXXXXXXXXXXXX
  1.1850     7   XXXXXXX
  1.5150     2   XX
  1.81*50     1   X
  2.1750     1   X
  2.5050     1   X
  2.8350     1   X
'< = REJECTED DATA
                                 15

-------
                                 TABLE 8
                  Data  Summary by  Ampul, Analyses for
                   Total  Mercury in Distilled Water
AMPUL 5 INCREMENT = 3.4 UG/LITE*  ORGANIC  »  INORGANIC  MERCJRY
N.ALL DATA 93
TRUE VAL.   3.40
MEAN,ALL    5.1309&
MEAN.3ET.    3.40088
MEDIAN      3.38000
     RANGE          11.10000     COEF. VAR.      0.37856
     VARIANCE        1.65755     SKEWNESS       2.31488
     STD. DEV.       1.28746     NO. OF CELLS   9
     CONF. LIM.    + 2.53740 (95 PCTI
ACCURACY
            0.02595  PCT RELATIVE  ERROR
       DATA IN ASCENDING  ORDER
     0.20
     0.67
     1.20
     1.40
     1.48
     1.50
     1.60
     1.90
     2.00
     2.00
     2.00
     2.10
     2.28
     2.40
     2.45
     2.60
     2.75
     2.80
     3.00
     3.00
     3.08
     3.10
     3.10
     3.10
     3.10
     3.10
     3.10
     3.10
     3.14
     3.20
     3.20
     3.20
     3.20
     3.20
     3.20
3.20
3.20
3.20
3.30
3.30
3.30
3.30
3.30
3.30
3.36
3.40
3.40
3.40
3.43
3.45
3.50
3.50
3.50
3.50
3.50
3.50
3.50
3.50
3.50
3.50
3.50
3.50
3.60
3.60
3.70
3.80
3.80
3.80
3.80
3.80
  3.81
  3.90
  4.00
  4.00
  4.00
  4.10
  4.20
  4.20
  4.20
  4.40
  4.40
  4.70
  4.70
  4.80
  4.85
  4.87
  4.91
  6.25
  6.30
 11.30
 23.10R
 28.00R
120.OOR
                     MIDPOINT  FRE3.    HISTOGRAM
                          RETAINED DATA ONLY
0.8167
 2.0500
 3.2833
 i».5167
 5.7500
 6.9833
 8.2167
 9.4500
10.6833
          12
          55
          16
           2
           0
           0
           0
           1
XXXX
XXXXXXXXXXXX
xxxxxxxxxxxxxxx
xxxxxxxxxxxxxxx
XX
   REJECTED DATA
                                  16

-------
                                   TABLE 9
                    Data Summary by Ampul, Analyses  for
                     Total Mercury in Distilled Water
AMPUL 6 INCREMENT * 4.1  UG/LITER  ORGANIC  *  INORGANIC  MERCURY
MtALL DATA 92
TRUE VAL.  4.10
^FAN.ALL    6.23096
MEAN,RET.   4.25785
MEDIAN      4.20000
     RAN3E           10.39999      COEF.  VAR.      0.33264
     VARIANCE        2.00610      SKEWNESS        0.83313
     STO.  DEV.        1.41636      NO.  OF CELLS    9
     CDNF.  LIM.     +  2.79163  (95  PCT)
ACCURACY
            3.85005  PCT RELATIVE  ERROR
       DATA IN ASCENDING ORDER
     0.20
     0.90
     1. 11
     1.25
     1.65
     2.10
     2.50
     2.60
     2.90
     3.10
     3.21
     3.30
     3.30
     3.40
     3.40
     3.50
     3.50
     3.60
     3.60
     3.70
     3.70
     3.73
     3.80
     3.80
     3.80
     3.80
     '3.80
     3.90
     3.90
     4.00
     4.00
     4.00
     4.00
     4.10
     4.10
4. 10
4. 10
4.10
4.10
4.10
4. 10
4.20
4.20
4.20
4.20
4.20
4.20
4.20
4.22
4.27
4.29
4.30
4.30
4.30
4.30
4.30
4.38
4.40
4.40
4.40
4.50
4.50
4.50
4.50
4.50
4.60
4.60
4.60
4.60
4.70
  4.80
  4.95
  5.00
  5.08
  5.10
  5.20
  5.40
  5.40
  5.56
  5.60
  5.86
  5.89
  5.90
  6.00
  6.70
  7.50
  7.70
  8.00
 10.60
 16.30R
 30.00R
11*8. OCR
                                     MIDPOINT   FREO.     HISTOGRAM
                                          RETAINED  DATA  ONLY
7778
9333
0889
 0.
 1.
 3.
 i»,
 S.itOOO
 6.5556
 7.7111
 8.8667
10.0222
 3
12
52
12
 2
 3
 0
 1
XXXX
XXX
xxxxxxxxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxxx
XX
XXX
    REJECTED DATA
                                  17

-------
                                  TABLE 10
                   Data Summary by Ampul, Analyses for
                    Total Mercury in  Distilled  Water
AMPUL 7 INCREMENT =  8.8  UG/LITE"  ORGANIC  +  INORGANIC  MERCURY
                                    19.45000      COfcF.  VAR.
                                     6.78160      SKEWNESS
                                     2.60415      NO.  OF  CELLS
                                   •f 5.13338  (95  PCT)
NiALL DATA
TRUE VAL.
MEANtALL
MCANfRET.
MEDIAE
90
8.80
12.91*298
8.47665
8.70000
RANGE
VARIANCE
STD. OEV.
CONF. LIM.

                                                 0.30721
                                                 0.23553
                                                 9
ACCURACY   -3.67439   PCT  RELATIVE  E*ROR
       DATA IN ASCENDING  OR-DFR
     0.55
     2.00
     3.14
     3.30
     3.35
     3.60
     4.20
     4.40
     4.56
     5.00
     6.00
     6.0C
     6.20
     6.30
     6.80
     6.85
     7.00
     7.20
     7.30
     7.40
     7.43
     7.50
     7.50
     7.70
     7.80
     7.90
     8.00
     8.00
     8*00
     8.10
     8.?0
     8.20
     8.30
     8.30
     a.35
 8.40
 8.40
 8.50
 8.50
 8.56
 8.60
 8.60
 8.70
 8.70
 8.70
 8.80
 9.00
 9.00
 9.00
 9.00
 9.00
 9.00
 9.00
 9.10
 9.10
 9.10
 9.20
 9.30
 9.30
 9.30
 9.30
 9.40
 9.40
 9.40
 9.50
 9.60
 9.80
10.00
10.00
10.00
 10.00
 10.00
 10.05
 10.20
 10.51
 10.60
 10.75
 10.99
 11.00
 11.00
 11.60
 11.88
 12.00
 12.00
 13.00
 13.20
 20.00
 36.40R
 63.00R
328.OOR
                      MIDPOINT   FREO.     HISTOGRAM
                           RETAINED  DATA  ONLY
 1.6306
 3.7917
 5.9528
 8.1139
10.2750
12.1*361
11*.5972
16.7583
18.9191*
 2
 7
 8
39
2l»
 6
 0
 0
 1
XX
xxxxxxx
xxxxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxxxxxx
xxxxxx
    REJECTED  DATA
                                   18

-------
                                TABLE  11
                   Data  Summary by  Ampul, Analyses  for
                    Total Mercury  in Distilled Water
A«PUL 8 INCREMENT =• 9.6 UG/LITER  ORGANIC  +  INORGANIC  MERCURY
NfALL DATA 92
THUS VAL.  9.60
MtAN.ALL   1U.06519
MEAN,SET.   9.37776
MFOIAN      9.30000
VARIANCE
STO. DEV.
C3NF.  LIM.
                     24.42000     COEF.  VAR.      0.34549
                     10.49769     SKEWNESS        0.93523
                      3.24001     NO.  OF CELLS    9
                    + 6.35042 (95 PCT)
ACCURACY
           -2.31498  PCT RELATIVE  ERROR
       DATA IN ASCENDING  ORDER
0.58
1. 18
2.30
3.59
4.10
4.25
4.60
4.80
4.80
5.20
6.20
7.20
7.30
       50
     7.50
     7.60
     7.70
     7.80
     7.89
     8.00
     8.10
     8.20
     8.20
     8.30
     8.34
     8.40
     8.48
     8. 80
     8.80
     8.80
     8.90
     8.90
     9.00
     9.00
     9.00
 9.00
 9.00
 9.10
 9.10
 9.10
 9. 10
 9.20
 9.20
 9.30
 9.30
 9.30
 9.50
 9.60
 9.60
 9.60
 9.60
 9.60
 9.70
 9.70
 9.80
 9.80
 9.90
 9.90
 S.95
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.40
10.40
     10.80
     11.00
     11.00
     11.03
     11.20
     11.40
     11.85
     11.96
     12.00
     12.50
     12.80
     13.00
     13.00
     13.25
     13.30
     13.50
     14.00
     15.75
     18.60
     25.00
     68.00R
    382.OOR
                                     MIDPOINT   FREQ.     HISTOGRAM
                                          RETAINED  DATA  ONLY
                                       1.9367
                                       U.6500
                                       7.3633
                                      10.0767
                                      12.7900
                                      15.5033
                                      18.2167
                                      20.9300
                                      23.61*33
 3
 7
17
1*9
11
 1
 1
 0
 1
XXX
xxxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxx
X
X
  =  REJECTED  DATA
                                    19

-------
                                    TABLE  12
                       Data Summary by Ampul,  Analyses for
                                 in Natural Water
AMPUL 1 INCREMENT = 0.21 UG/LITER ORGANIC + INORGANIC MERCURY
N.ALL DATA 78
TRUE VAL.  0.21
MEANtALL
MEAN,RET
MEDIAN
ACCURACY
 0.51*21*3
 0.34945
 0.27000
66.40551
RANGE
VARIANCE
STD. DEV.
CONF. L1M.
 1.27000
 0.07598
 0.27564
+0.54761
    COEF.  VAR.
    SKEWNESS
    NO.  OF CELLS
(95  PCT)
                                                     0.78879
                                                     1.44675
PCT RELATIVE ERROR
       DATA IN ASCENDING ORDER
     0.00
     0.00
     0.00
     0.00
     0.03
     0.07
     0.08
     0.10
     0.10
     0. 10
     0.10
     0.10
     0.14
     0.15
     0.15
     0.15
     0.16
     0.18
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     n.20
     0.22
     0.22
     0.22
     0.22
     0.23
     0.24
     0.25
     0.26
     0.27
     0.29
     0.30
     0.30
     0.30
     0.30
     0.30
     0.30
     0.30
     0.32
     0.35
     0.39
     0.40
     0.40
     0.40
     0.40
     0.44
     0.44
     0.45
     0.47
     0.48
     0.48
     0.49
     0.50
     0.50
     0.50
     0.56
     0.64
     0.80
     0.80
     0.80
     0.90
     1.00
     1.00
      1.00
      1.20
      1.27
      1.80R
      2.20R
      3.35R
      i*.70R
      U.75R
 MIDPOINT  FREQ.     HISTOGRAM
      RETAINED DATA ONLY

   0.079U    16     XXXXXXXXXXXXXXX
   0.2381    29     XXXXXXXXXXXXXXX
   0.3969    11     XXXXXXXXXXX
   0.5556     7     XXXXXXX
   0.711*1*     1     X
   0.8731     1*     XXXX
   1.0319     3     XXX
   1.1906     2     XX
R = REJECTED DATA
                                  20

-------
                                 TABLE 13
                    Data Summary  by Ampul,  Analyses  for
                              in Natural Water
AMPUL  2  I>JCRE*EMT = 0.27 UG/LITER DR&ANIC
                                            INORGANIC  MERCURY
N.ALL DATA 82         RAN3E
TRUE y/AL.   0.27      VARIANCE
    ,ALL    0.65390   STD.  DEV.
            0.41402   CONF.  LIM.
            0.32000
ACCURACY   53.34271   PC.T RELATIVE ERROR
                                     1.20000     COEF.  VAR.      0.67494
                                     0.0780S     SKEWNESS        1.06406
                                     0.27944     NO.  OF CELLS    9
                                   ±0.55477 (95  PCT)
       DATA IN ASCENOIMS ORUER
                                     MIDPOINT  FREO.     HISTOGRAM
                                          RETAINED DATA ONLY
     3.00
     0.00
     0.06
     0.07
     0.10
     0. 10
     0.11
     0.15
     0.15
     0.16
     0. 16
     0.19
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.20
     0.21
     0,21
     0.?3
     0.24
     0.24
     0.25
     0.25
     0.26
     0.26
     0.27
     0.27
     0.28
     0.30
     0.30
     0.30
     0.30
                0.30
                0.31
                0.31
                0.32
                0.32
                0.33
                0.35
                0.35
                0.35
                0.35
                0.40
                0.4C
                0.40
                0.40
                0.42
                0.44
                0.46
                0.49
                0.50
                0.50
                0.50
                0.50
                0.50
                0.50
                0.53
                0.59
                0.61
                0.65
                0.65
                0.78
                0.80
                0.80
                0.80
                0.80
                1.00
1.00
1.00
1.00
1.00
1.05
1.10
1.20
2.09R
2.60R
3.80R
5.75R
7.50R
0.0667     7    XXXXXXX
0.2000    21    XXXXXXXXXXXXXXX
0.3333    21    XXXXXXXXXXXXXXX
O.l»666    11    XXXXXXXXXXX
0.5999     U    XXXX
0.7332     5    XXXXX
0.8665     0
0.9998     6    XXXXXX
1.1331     2    XX
   * REJECTED  DATA
                                     21

-------
                                TABLE 14
                   Data Summary  by Ampul,  Analyses  for
                             in Natural Water
      3 l\CREMEMT = 0.51  UG/LITPR ORGANIC  «•  INORGANIC  MERCURY
N.ALL DATA 85
TRUE VAL.   0.51
MCAM.ALL
MEDIAN
ACCURACY
            1.11*505
            0.67384
            0.50500
                     RANGE
                     VARIANCE
                     STD.  DEV.
                     CDNF.  LIM.
           3.99000
           0.29254
           0.54087
          +1.08031
          COEF.  VAR.
          SKEWNESS
          NO. OF CELLS
      (95  PCT)
              0.80267
              3.32568
              9
           32.12645  PCT  RELATIVE  ERROR
       DATA IN ASCENDING  ORDER
     0.01
     0.10
     0.11
     0.20
     0.20
     0.20
     0.20
     0.22
     0.26
     0.28
     0.30
     0.30
     0.32
     0.34
     0.35
     0.35
     0.35
     0.37
     0.40
     0.40
     0.40
     0.40
     0.40
     0.40
     0.40
     0.40
     0.40
     0.42
     0.44
     0.45
     0.46
     0.47
     0.50
     0.50
     0.50
                0.50
                0.50
                0.50
                0.50
                0.51
                0.52
                0.55
                0.56
                0.56
                0.57
                0.60
                0.60
                0.60
                0.60
                0.62
                0.64
                0.65
                0.66
                0.69
                0.70
                0.70
                0.75
                0.77
                0.80
                0.82
                0.93
                0.95
                1.00
                I. 00
                1.00
                1.05
                1.06
                1.10
                1.10
                1.10
 1.20
 1.40
 1.40
 1.44
 1.46
 1.70
 2.40
 4.00
 4.20R
 4.30R
 7.50R
 8.00R
18.U8R
                                     MIDPOINT   FREU.     HISTOGRAM
                                          RETAINED  DATA  ONLY
0. 2317
0.6750
1.1183
1.5717
2.0050
2.1*1(83
2.8917
3.3350
3.7783
30
30
11
 5
 0
 1
 0
 0
 1
xxxxxxxxxxxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxx
xxxxx
    REJECTED  DATA
                                  22

-------
                                TABLE 15
                   Data  Summary  by Ampul, Analyses  for
                             in Natural Water
AMPUL 4 INCREMENT = 0.60 US/LITFR  ORGANIC  t  INORGANIC  MERCURY
M.ALL DATA 80
TRUE VAL.  0.60
Me AN,ALL
MEAN,RET.
MEDIAN
ACCURACY
 0.70864
 0.60000
18.10795
RANSE           2.30030     COEF.  VAR.      0.55003
VARIANCE        0.15192     SKEWNESS       1.32462
STD. DEV.       0.38977     NO.  OF CELLS   8
CONF. LIM.     +0.77421 (95 PCT)
PCT RELATIVE ERROR
       DATA IN ASCEMOIMS ORDER
     0.00
     0.10
     0.16
     0.20
     0.22
     0.25
     0.30
     3.30
     0.35
     3.35
     0.38
     0.40
     0.40
     0.40
     0.44
     0.45
     0.46
     0.46
     0.49
     0.49
     0.50
     0.50
     0.50
     0.50
     0.50
     0.50
     0.50
     3.50
     0.53
     3.55
     0.56
     0.58
     0.60
     0.60
     3.60
0.60
0.60
0.60
0.61
0.62
0.64
0.64
0.65
0.66
0.69
0.70
0.72
0.72
0.73
0,
       75
     0.80
     0.80
     O.BO
     0.90
     0.91
     0.95
     0.96
     1.00
      .00
      .00
      .00
      .00
      .00
     1.05
     1.10
     1.20
     1.20
     1.30
     1.32
     1.50
                1.50
                1.60
                1. 70
                2.30
                2.66P
                3.90R
                4.20R
                7.50R
                8.70R
               10.00R
                                     MIDPOINT  FREQ.     HISTOGRAM
                                          RETAINED DATA ONLY
                  0.11*38
                  O.U313
                  0.7188
                   .0063
                   .2938
                   .5813
                   .8688
                  2.1563
 6
25
22
12
xxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxxx
xxxx
xxxx
  = REJECTED DATA
                                  23

-------
                                 TABLE 16
                    Data Summary by Ampul, Analyses for
                              in Natural Water
AMPUL 5 INCREMENT = 3.4 US/LITER  ORGANIC  +  INORGANIC  MERCURY
NtALL DATA 83
T*UE VAL.  3.40
ME AM,ALL    5.38288
MCAN.RET.   3.41149
         RANGE          12.37000     COEF.  VAK.      0.43743
         VARI&NCE        2.22696     SKEWNESS        2.56669
         STD. DEV.        1.49230     NO.  OF CELLS    9
         CONF. LIM.     + 2.94313 195  PCT)
MEDIAN
ACCURACY
3.40500
0.33800  PCT RELATIVE ERROR
       DATA IN ASCENDING ORDER
     0.13
     0.16
     0.64
     0.85
     1.36
     1.70
     1.80
     2.10
     2.10
     2.10
     2.10
     2.10
     2.40
     2.50
     2.60
     2.79
     2.80
     2.80
     2.80
     2.80
     2.90
     2.90
     2.94
     2.96
     3.00
     3.00
     3.00
     3.00
     3.10
     3.15
     3.20
     3.20
     3.30
     3.30
     3.30
    3.30
    3.40
    3.40
    3.40
    3.40
    3.41
    3.48
    3.50
    3.50
    3.50
    3.50
    3.50
    3.50
    3.50
    3.55
    3.60
    3.60
    3.60
    3.60
    3.70
    3.70
    3.70
    3.80
    3.80
    3.80
    3.80
    3.80
    3.95
    4.00
    4.00
    4.00
    4.20
    4.20
    4.20
    4.40
  4.60
  4.60
  4.70
  4.84
  4.85
  5.00
  5.06
  5.40
  7.20
 12.50
 18.86R
 30.00R
125.OCR
                                     MIDPOINT   FREQ.     HISTOGRAM
                                          RETAINED  DATA  ONLY
 0.8172
 2.1916
 3.5661
 l».9l»05
 6.3150
 7.6891*
 9.0639
10.U383
11.8128
 5
15

-------
                                 TABLE 17
                    Data Summary by Ampul,  Analyses  for
                              in  Natural Water
      6  INCREMENT  *  4.1  KG/LITE*  ORGANIC
                                           INORGANIC MERCURY
N.ALL DATA
TRUE VAL.
MFAN.ALL
MF AN, RET.
MFDIAM
80
4.10
6.lilt311
3.80854
4.00000
RANGE
VARIANCE
STD. DEV.
CDNF. LIM.

                                     6.33000     COEF. VAR.     0.29282
                                     1.24377     SKEWNESS      -0.9S121
                                     1.11524     NO. OF CELLS   8
                                    +2.21445  (95 PCT)
ACCURACY
-7.10865  PCT RELATIVE  ERROR
       DftTA IN ASCENDING  ORDER
0.17
0.77
0.83
1.10
1.70
1.70
2.20
2.30

2.50
2.70
2.70
3.00
3.00
3.10
3.10
3.?0
3.20
3.30
     3.50
     3.60
     3.70
     3.70
     3.73
     3.77
     3.90
     3.90
     3.90
     3.90
     4.00
     4.00
     4.00
     4.00
4.00
4.00
4.00
4.00
4.00
4.00
4. 10
4.10
4.10
4.10
4.10
4.20
4.20
4.20
4.22
4.25
4.30
4.30
4.30
4.30
4.30
4.40
4.40
4.50
4.50
4.50
4.50
4.58
4.60
4.70
4.80
4.80
4.95
5.00
5.00
                           5.00
                           5.20
                           5.60
                           5.60
                           5.82
                           6.50
                          19.00R
                          21.00R
                          33.00R
                         153.OOR
                          MIDPOINT   FREQ.     HISTOGRAM
                               RETAINED  DATA  ONLY
0.5657
1.3569
2.U82
2-939U
3.7307
"*-5219
5.3132
                                       3     XXX
                                       3     XXX
                                       l»     XXXX
                                       9     XXXXXXXXX
                                      27     XXXXXXXXXXXXXXX
                                      21     XXXXXXXXXXXXXXX
                                       7     XXXXXXX
                                       2     XX
    REJECTED DATA
                                25

-------
                                 TABLE 18
                   Data Summary by Ampul,  Analyses for
                              in Natural  Water
AMPUL 7 INCREMENT = 8.8 UG/LITE"  ORGANIC «•  INORGANIC  MERCURY
N.ALL DATA 80
TRUE VAL.  8.80
MLAN.ALL   13.62260
MEAN,*ET.   8.76676
MEDIAN      8.50000
RANGE          27.47000     COEF. VAR.
VARIANCE       13.65052     SKEWNESS
STD. DEV.       3.69466     NO.  OF CELLS
CONF. LIW.    + 7.24153 (95 PCT)
                                                                2.00048
                                                                8
ACCURACY
           -0.37750  PCT RELATIVE E*ROR
       DATA IN ASCENDING ORDER
     0.53
     1.88
     2.45
     3.00
     3.22
     3.42
     3.90
     4.50
     4.80
     6.10
     6.30
     6.'3 6
     6.50
     6.60
     6.80
     7.20
     7.21
     7.30
     7.34
     7.40
     7.50
     7.76
     7.80
     7.80
     8.00
     8.00
     8.10
     8.10
     8.20
     8.20
     H.30
     8.30
     8.30
     8.35
     8.40
                8.40
                8.40
                8.43
                8.50
                8.50
                8.50
                8.50
                8.60
                8.60
                8.70
                8.80
                8.90
                8.90
                9.00
                9.00
                9.00
                9.00
                9.00
                9.10
                9. 10
                9.40
                9.45
                9.50
                9.70
                9.80
               10.05
               10.30
               10.40
               10.60
               10.70
               11.00
               11.00
               11.03
               11. ?0
               11.98
     12.00
     12.00
     13.00
     13.00
     13.80
     15.75
     21.30
     28.00
     66.00R
    3UO.OOR
MIDPOINT  FREQ.     HISTOGRAM
     RETAINED DATA ONLY

  2.2U69     7     XXXXXXX
  5.6807    12     XXXXXXXXXXXX
  9.1UI*    1(6     XXXXXXXXXXXXXXX
 12.5U82    10     XXXXXXXXXX
 15.9819     1     X
 19.U157     0
 22.8U91*     1     X
 26.2832     1     X
    REJECTED DATA
                                    26

-------
                                 TABLE  19
                    Data  Summary by  Ampul, Analyses for
                              in Natural Water
     RECOVERY OF INCREMENT FROM NATURAL WATER
AMPUL 8 INCREMENT * 9.6 UG/LITER ORGANIC * INORGANIC MERCURY
N.ALL DATA 79
TRUE VAL.  9.60
MEAN,ALL
MEAN,RET.
MEDIAN
1U.57516
 9.09660
 9.20000
RANGE          25.76000     COEF.  VAR.      0.39210
VARIANCE       12.722*6     SKEWNESS        1.11538
STD.  DEV.       3.56685     NO.  OF CELLS    8
CONF. LIM.     ± 6.99103 (95 PCT)
ACCURACY   -5.24370  PCT RELATIVE ERROR
       DATA IN ASCENDING ORDER
     1.18
     1.98
     3.35
     3.52
     3.80
     4.00
     4.10
     5.00
     5.10
     5.40
     6.20
     6.20
     6.72
     7.20
     7.30
     7.50
     7.60
     7.80
     7.80
     7.96
     8.00
     8.10
     8.10
     8.30
     8.30
     8.3*
     8.50
     8.70
     8.80
     8.90
     9.00
     9.00
     9.00
     9.00
     9.05
     9.10
     9.10
     9.20
     9.20
     9.20
     9.40
     9.40
     9.50
     9.50
     9.50
     9.60
     9.60
     9.60
     9.70
     9.80
     9.80
     9.80
     9.95
    10.00
    10.00
    10.00
    10.00
    10.50
    10.70
    10.70
    10.80
    11.00
    11.00
    11.80
    11.80
    11.98
    12.00
    12.00
    12.60
     12.80
     13.27
     14.00
     14.50
     15.40
     17.00
     26.30
     72.00R
    379.OOR
                                     MIDPOINT  FREQ.     HISTOGRAM
                                          RETAINED DATA ONLY
 2.1500
 5.3700
 8.5900
11.8100
15.0300
18.2500
21.1*700
2l».6900
 5
 9
kk
lit
 3
 1
 0
 1
XXXXX
xxxxxxxxx
xxxxxxxxxxxxxxx
xxxxxxxxxxxxxx
XXX
X
R - REJECTED DATA
                                    27

-------
Statistical Summaries

     A statistical summary is given in Tables 20 and 21 for each sample.
Most of the statistics have been selected from Tables 4 through 19 to
allow a convenient comparison of the effect that differences in concen-
tration level and background water had on the retained data.
Single-Analyst Precision

     In Tables 20 and 21, the standard deviations (S) indicate the dispersion
expected among values generated from a group of laboratories.  This
represents the broad error in any mass of data collected in a collaborative
study.  However, the measure of how well an individual analyst can expect
to perform in his own laboratory is another important measure of precision.
This single-analyst precision is measured here as the Sr value.  It was
defined by Youden (2) as
where

              n   =  the number of paired observations.

              D   =  the difference between observation for a sample
                       pair.

              D   =  the average value for D .

     Youden's Sr calculation permits a measure of precision without
duplication and hopefully avoids the well-intentioned manipulation of
data that can occur in a laboratory doing replicate determinations.


Statements of Method Precision

     Linear regressions were performed on the overall and single-analyst
precision estimates shown in Tables 20 and 21 for the cold vapor method
of determining mercury in distilled and natural waters.  Plots of these
regressions are shown in Figures 1 and 2.  Mathematical expressions of
the precision statements for mean recovery (X) from 0.2-10 yg/liter of
total mercury in distilled and natural waters are given as follows:

     Distilled Water:

          Overall precison  (S)  =  0.2454 + 0.2922 X

          Single-analyst precision  (Sr)  =  0.3117 + 0.0718 X
                                     28

-------
                       TABLE  20
                   STATISTICAL SUMMARY




Recovery of Total Mercury from Distilled and Natural Waters
STATISTICAL
PARAMETERS
True Value, yg/1
Mean Recovery, yg/1 (X)
Accuracy as %
Rel . Error
Standard Dev. , yg/1 (S)
Relative Dev. , %
Range, yg/1
Single-Analyst Standard
Dev., yg/1 (S )
Single-Analyst
Relative Dev. , %
DISTILLED WATER
SAMPLE 1 SAMPLE 2
.21 .27
.418 .450
98.9 66.5
.279 .325
66.9 72.2
1 . 60 1 . 80
0.19
44
NATURAL WATER
SAMPLE 1 SAMPLE 2
.21 .27
.349 .414
66.4 53.3
.276 .279
78.9 67.5
1.27 1.20
0.16
42
DISTILLED WATER
SAMPLE 3 SAMPLE 4
.51 .60
.653 .744
28.1 24.0
.376 .466
57.5 62.6
2.26 2.97
0.36
51
NATURAL WATER
SAMPLE 3 SAMPLE 4
.51 .60
.674 .709
32.1 18.1
.541 .390
80.3 55.5
3.99 2.30
0.16
23

-------
                                                                    TABLE  21
                                                               STATISTICAL SUMMARY
                                           Recovery of Total Mercury from Distilled and Natural Waters
U)
O
STATISTICAL
PARAMETERS
True Value, pg/1
Mean Recovery, ug/1 (X)
Accuracy as %
Rel. Error
Standard Dev. , ug/1 (S)
Relative Dev. , %
Range, ug/1
Single-Analyst Standard
Dev., ug/1 (Sr)
Single-Analyst
Relative Dev. , %
DISTILLED WATER
SAMPLE 5 SAMPLE 6
3.4 4.1
3.40 4.26
0.03 3.85
1.29 1.42
37.9 33.2
11.1 10.4
0.79
20
NATURAL WATER
SAMPLE 5 SAMPLE 6
3.4 4.1
3.41 3.81
0.34 -7.11
1.49 1.12
43.7 29.3
12.4 6.3
0.36
10
DISTILLED WATER
SAMPLE 7 SAMPLE 8
8.8 9.6
8.48 9.38
-3.7 -2.3
2.60 3.24
30.7 34.5
19.4 24.4
0.89
10
NATURAL WATER
SAMPLE 7 SAMPLE 8
8.8 9.6
8.77 9.10
-0.4 -5.2
3.69 3.57
42.1 39.2
27.5 25.8
1.39
16

-------
 Y AXIS
  •••4
l-l
Q) .|.
o
M

e
c
o
•H
CO
•H
O
<1)
                                   FIGURE 1



           Linear Regression Plot  of Precision  in Distilled Water
              The precision of this method  for  total mercury in

              distilled water samples, within the recovery range

              of 0.2-10 yg/liter, may be  expressed as follows:


                   S  =  0.2454 + 0.2922  X


                   Sr -  0.3117 + 0.0718  X
                                         ...-••••••'
         Mean Recovery (X), yg mercury/liter
                                     31

-------
 Y AXIS
  +4

                                                             •  S
M

-------
     Natural Water:

          Overall precision (S)   =  0.1661 + 0.3647 X

          Single-analyst precision (Sr)   =  0.0465 + 0.1379 X


Statements of Method Accuracy

     Linear regressions were performed on the mean recovery estimates
shown in Tables 20 and 21 for the cold vapor method of determining
mercury in distilled and natural waters.  Plots of these regressions are
shown in Figures 3 and 4.  Mathematical expressions of the mean recovery
for 0.2-10 yg/liter of total mercury in distilled and natural waters are
given as follows:

     Distilled Water;

          Mean Recovery, X - 0.2028 + 0.9517  (True Concentration)

     Natural Water:

          Mean Recovery, X = 0.1373 + 0.9508  (True Concentration)


Two-Sample  (Youden) Charts

     The retained data were plotted according  to  the method  of Youden and
are shown in Figures 5  through  12.  Two results for each  sample  pair were
used respectively as the x and  y  coordinates  to plot a  single point  for
each analyst.  The plot of points  for each  sample pair  shows the perform-
ance of the method for  that concentration level.

     If random errors were largely responsible for the  spread of results
around the  true values,  the data  on a plot  would  be equally  distributed
among the four quadrants  (+ +),  (- +),  (- -)  and  (+ -).   However,  if
systematic  error  influences the method  more,  the  values are  not  randomly
distributed but  are  grouped along a 45°  slope line in  the (- -)  and  (+ +)
quadrants.  This  occurs  because an analyst  tends  to  get either high  or
low results on both  samples in  a  pair,  forming an elliptical pattern on a
45° slope.  If an analyst  shows large  systematic  or  random error relative
to other  data, his plot points  will be  far  removed from the  general
cluster.  Extreme values  suggest  a procedure or  instrument out of control.
If the method of  analysis  is  inherently imprecise there will be  a general
scatter of  data  points  away  from the  45°  line.  A significant bias or
interference  in  the  method will cause the general grouping to be low (- -)
or high  (+  +).

     The  presence of a  number of  values greater  than the  true values
crowded the plots of points which were less than the true values.  In
order  to  present these  points more fairly,  scale units for the  plots were
selected  which would place the  true value at least one-third of  the


                                     33

-------
distance from the origin.  This arbitrary rule worked well on all data
plots, presenting a reasonable spread of data points over each chart and
providing an interpretablfe representation of method performance.  Data
which were extremely high are shown as greater than (>) values in the
upper right-hand corner of each plot.
                                    34

-------
 Y AXIS
o

M


I
  *
M

SI
O
o
0)


d "•2
                                 FIGURE  3



           Linear Regression Plot of Accuracy in Distilled Water
              Accuracy as the mean recovery of this method for

              total mercury in distilled water samples, within

              the true concentration range of 0.2-10 vg/liter,

              may be expressed as follows:



              Mean Recovery - 0.2028 + 0.9517 (True Concentration)
              2            4            6             8     X AXIS



         True Concentration,  yg of mercury/liter





                                     35

-------
                                   FIGURE 4



              Linear Regression Plot of Accuracy in Natural Water
                Accuracy as the mean recovery of this method for

                total mercury in natural water samples, within

                the true concentration range of 0.2-10 yg/liter,

                may be expressed as follows:


                Mean Recovery = 0.1373 + 0.9508 (True Concentration)
  Y AXIS
M
0)
3
o
)-l
01
o

60
01

o
o
0)
Pi

d
ca
0)
S
         	4	4	4-	4-	

              2           4            6           8   X AXIS



          True Concentration, yg of mercury/liter
                                      36

-------
                        FIGURE 5
Two Sample Chart for Recovery of Total Mercury, vg/liter
0-6
0-5.

0-4 .

0-3

0-2

0-1

0-0
0
xxxx (>0,6)
. . . vy . XXX


cu
u
3 x
(
X

X
X^^
^^ Y
' ^^v^ ^^
^^ ^^
\^^ ^
X


DISTILLED WATER -
X XX X
/\
x x x
xx x
x x x B
; x
x *\ x
o ^
x xx

X XX
X

X
SAMPLE 1
• O 0-1 0-2 0-3 0-4 0«5 0











-6
                               37

-------
                     FIGURE 6
Two Sample Chart for Recovery of Total Mercury, yg/liter
                                               XXXXX (>0,6)
                                               XXXXX


0-5 .


0-4 .

0-3.
i
t
0-2.

0-1 .
*
4
0-0
	 	 1 	 -1-

X

ru
LJ
i X
fl
X
X X
: x x
X
X >< x *
x x
x x
X
	 M 	 1 	 »-
NATURAL WATER
x
x x xx
X
X
X
X X
XX X
x x* X -
xx x
£ x
X
x x
xx
X

SAMPLE 1
•M 	 1 	 1 I 	
      0-1     0-2     0-3     0-4      0-5     0-6
                        38

-------
                      FIGURE 7
  Two Sample Chart for Recovery of Total Mercury, yg/liter
                                                 XXXXX (>1,2)
i-2

1-0 .

0-8

Q'B
0-4


0-2 .
0-0




T
LJ

X XX
X X
X X
X
X x xx
X
1 1 	 ,
DISTILLED WATER x
X
x xx
XX X
x x
X
xx x x x

xxx
/XX X
x x
<
<


X
SAMPLE 3
' 1 1 1
0-0     O-2     0-4     0-6     0-8      1-0      1-2
                            39

-------
                       FIGURE 8
Two Sample Chart for Recovery of Total Mercury, pg/liter
1-2

1-0 .

O-Q .

O-G
0-4.

0-2 .

0-0
O
xxxx (>1,2)
. . . . . xxx ...


X
-vr
Ld
S x
^
X>
x X X V
X *
V
X XX >
x xx
XXX
X X
X X
X
X
X
X

NATURAL WATER
X
X
XX X
x X
x x
X X
X3 x
' ^ x
X
X

X

SAMPLE 3











-O O-2 0-4 O-G O-8 1-0 1-2
                            40

-------
                         FIGURE 9
      Two Sample Chart for Recovery of Total Mercury, vg/liter
B-0
6-O
4-O
 2-0
 0-0
      ID
                      vx

                       ><
 x

x

 X
                             •+-H-
                                  DISTILLED WATER
                x  x  *
                               x x  x
                                X
                                XX
                                    SAMPLE 5
    O«O         2-O         4-0         G-O
                                          8-0
                              41

-------
                          FIGURE 10
       Two Sample Chart for Recovery of Total Mercury, vg/liter
8-0
6-0 ..
4-0.
2-G.
0-0
      ID
                                           +
                                  NATURAL WATER
                              x    x

                                  X
                              X   X X
                             x xx
                       * x
                       X*XX
                  v
                  8 X
                     XX
         X
     x    x
   0-0
                2-0
                                   SAMPLE 5
4-0
6-0
8-0
                             42

-------
                      FIGURE 11
   Two Sample Chart for Recovery of Total Mercury, yg/liter
                                                     x (>20)
20-0
16- Q

12- Q
8-0 .


4-0 .


O-O



CD
X
X
X '
X* $
x *xx
X
*«*
X
X
X
X
	 1 	 1 —
DISTILLED WATER
X

X
X x xX
Xxx X
xxx
xxX5x
X
gpx x
n ^V
X





SAMPLE 7
i 	 j — _ 	 1 	
0-0
4-0
8-0
12-O      16-0     20-0
                           43

-------
                               FIGURE 12
         Two Sample  Chart for Recovery of Total Mercury,  ng/liter
 20
                                                                xx (>20)


4-0
)-C

;-c




CD
U
Itf
I

1 x
3
X $
„*£


3


'X~
X
XX
xx
xXxX
X
X
X
NATURAL WATER
X
X
X
X
X X
< *
x x
\£\C v V
*'*\s^\ X\
f - 	 	 — 	
XX
X


•

SAMPLE 7
0-0 4-Q 8-0 12-0 16-0 20

-------
                          DISCUSSION AND CONCLUSIONS
     Throughout the 0.2-10 vg/liter concentration range tested, mercury
was detected and measured using the cold vapor procedure of Kopp (1).

     In describing method performance, it has been common to assume that
statistics such as mean recovery (X), standard deviation (S) and single-
analyst standard deviation (Sr) are:  1) constants which are independent
of the true concentration level or 2) uniform percentages of the true
concentration.  Tables 20 and 21 show that neither of these assumptions
is valid within the concentration range studied.  As a matter of fact,
for most studies, whenever the concentration range approaches the detection
limit these assumptions seem to be invalid.  An alternative is to assume
that some linear relationship exist between the statistics and the true
concentration level.  If this is true, then regression equations of the
form Y = aX + b will provide good predictions of the method statistics.
Please note that the earlier two assumptions are really special cases of
the linear assumption.

     In this study, the regression equation plots in Figures 1 through 4
fit the points well enough to justify a linear assumption and should,
therefore, prove useful for predicting the statistics of this method
within the 0.2-10 yg/liter range studied.

     Another interesting observation that can be made from Tables 20 and
21 and Figures 1 through 4 is that the type of background water did not
have any dramatic effect upon the method statistics.  This indicates that
the method is not sensitive to natural interferences.  However, since few
analysts used marine waters or industrial effluents, this conclusion is
limited to natural surface waters such as rivers and lakes.

     Visual interpretation of the Youden plots  (Figures 5-12)  leads to a
better understanding of the method precision and bias statistics in
Tables 20 and 21 and Figures 1 through 4.  First notice that the points
tend to approach the hypothetical 45 degree line as the concentration
level increases.  This indicates less relative influence attributable to
random error and thereby verifies the decreasing single-analyst relative
deviation.  Next, note that the points generally tend to form  a denser
cluster as the concentration level  increases.  This verifies the decreasing
relative deviation values presented  in Tables 20 and 21.  Also, note that
points away from the intersection of the true concentration lines tend  to
be high for the lower two concentration levels  (0.2-0.6 yg/liter) and low
for the higher two concentration levels  (3-10 yg/liter).  This verifies
the decreasing percent relative error values in Tables  20 and  21.
                                      45

-------
     In conclusion, the vigorous digestion procedure using permanganate,
persulfate and heat as specified in the method, successfully reduces the
organic mercury to a measurable form.

     The precision and accuracy of the method for distilled water and
natural water samples follows:

     Distilled Water;

          Precision    S  -  0.2454 + 0.2922 X

                       Sr -  0.3117 + 0.0718 X

          Accuracy

             Mean Recovery, X  •=  0.2028 + 0.9517 (cone)

     Natural Water;

          Precision    S  -  0.1661 + 0.3647 x"

                       Sr =  0.0465 + 0.1379 X

          Accuracy

             Mean Recovery, X  =  0.1373 + 0.9508 (cone)
                                  REFERENCES
     1.    Kopp,  J.  F.,  M.  C.  Longbottom and L.  B.  Lobring,  1972.   Cold
          Vapor  Method  for the Determination of Mercury,  J  A W W A,  Vol.
          64,  No.  1,  pp.  20-25.

     2.    Youden,  W.  J.,  1967.   Statistical Technique for Collaborative
          Tests, Association  of Official Analytical Chemists, Inc.,  Wash-
          ington,  D.C.
                                     46

-------
                                  APPENDIX

         Proposed Standard Method of Test for Total Mercury in Water (1)
1.
     1.1  This method describes a procedure for the determination of
total mercury in water in the range of 0.2-10.0 yg Hg/liter.   It consists
of a wet chemical oxidation which converts all mercury to the mercuric
ion; reduction of mercuric ions to metallic mercury, followed by a cold
vapor atomic absorption (AA) Analysis (2, 3).

     1.2  The method is applicable to fresh waters, saline waters, and
industrial and sewage effluents.

     1.3  Both organic and inorganic mercury compounds may be analyzed by
this procedure if they are first converted to mercuric ions.   Potassium
permanganate in acid solution oxidizes some organomercury compounds but
studies have shown that several methyl and phenyl mercury compounds are
only partially oxidized by this method.  However, using potassium persulfate
and potassium permanganate as oxidants, and a digestion temperature of 95
C, approximately 100% recovery of these compounds can be obtained (3, 4).

     1.4  The range of the method may be varied through instrument and/or
recorder expansion and by using a larger volume of sample.

     1.5  A method for the disposal of mercury containing wastes is also
presented (Appendix Al).
2.   Summary of Method

     2.1  The cold vapor AA procedure is a physical method based on the
absorption of ultraviolet radiation at a wavelength of 253.7 nm by mercury
vapor.  The mercury is reduced to the elemental state and aerated from
solution in either a closed recirculating system or an open one-pass
system.  The mercury vapor passes through a cell positioned in the light
path of an atomic absorption spectrophotometer.  Absorbance is measured
as a function of mercury concentration.
3.   Significance

     3.1  The cold vapor AA measurement portion of this method is applicable
to the analysis of materials other than water  (sediments, biological
materials, tissues, etc.) if, and only if, an  initial procedure for
digesting and oxidizing the sample is carried  out, insuring that the
mercury in the sample is converted to the mercuric ion, and is dissolved
in aqueous media (3, 6).
                                     47

-------
4.   Definitions
     4.1  For definitions of terms used in this method, refer to ASTM
Definitions D1129, Terms Relating to Water (7).
5.   Interference

     5.1  Possible interference from sulfide is eliminated by the addition
of potassium permanganate.  Concentrations as high as 20 mg/liter of
sulfide as sodium sulfide do not interfere with the recovery of added
inorganic mercury from distilled water (3).  •

     5.2  Copper has also been reported to interfere; however, copper
concentrations as high as 10 mg/liter had no effect on the recovery of
mercury from spiked samples (3).

     5.3  Sea waters, brines and industrial effluents high in chlorides
require additional permanganate (as much as 25 ml).  During the oxidation
step, chlorides are converted .to free chlorine which will also absorb
radiation at 253.7 nm.  Care must be taken to assure that free chlorine
is absent before the mercury is reduced and swept into the cell.  This
may be accomplished by using an excess of hydroxylamine sulfate reagent
(25 ml).  In addition, the dead air space in the reaction flask must be
purged before the addition of stannous sulfate.  Both inorganic and
organic mercury spikes have been quantitatively recovered from sea water
using this technique.

     5.4  Interference from certain volatile organic materials which will
absorb at this wavelength is also possible.  If this is expected, the
sample should be analyzed both by using the regular procedure and again
under oxidizing conditions only, that is, without the stannous sulfate.
The true mercury value can then be obtained by subtracting the two values.
6.   Apparatus

     6.1  See Figure 1 for the schematic of the closed recirculating
system and Figure 2 for the open one-pass system.

     6.2  Atomic Absorption Spectrophotometer - Any commercial atomic
absorption instrument is suitable if it has an open burner head area in
which to mount an absorption cell, and if it provides the sensitivity and
stability for the analyses.  Also instruments designed specifically for
the measurement of mercury using the cold vapor technique in the working
range specified are commercially available and may be substituted.

     6.3  Mercury Hollow Cathode Lamp

     6.4  Recorder - Any multi-range variable speed recorder that is
compatible with the UV detection system is suitable.
                                     48

-------
     6.5  Absorption Cell - See Figure 3 - The cell is constructed from
glass or plexiglass tubing 25.4 mm O.D.  x 114 mm (Note 1).   The ends are
ground perpendicular to the longitudinal axis and quartz window (25.4 mm
diameter x 1.6 mm thickness) are cemented in place.  Gas inlet and outlet
ports (6.4 mm diameter) are attached approximately 12 mm from each end.
The cell is strapped to a support and aligned in the light beam to give
maximum transmittance.

     Note 1 - An all glass absorption cell, 18 mm O.D. by 200 mm, with
       inlet 12 mm from the end, 18 mm O.D. outlet in the center, and
       with quartz windows has been found suitable.

     6.6  Air Pump - Any peristaltic pump, with electronic speed control,
capable of delivering 1 liter of air per minute may be used.   (Regulated
compressed air can be used in an open one-pass system).

     6.7  Flowmeter - Any flowmeter capable of measuring an air flow of 1
liter per minute is suitable.

     6.8  Aeration Tubing - A straight  glass  frit having a coarse porosity
is used in the reaction flask.  A clear  flexible vinyl plastic tubing
such as Tygon, is used for passage of the mercury vapor from  the reaction
flask to the absorption cell.

     6.9  Drying Tube - 150 mm  x 18 mm  diameter  tube  containing  20  grams
of magnesium perchlorate.  A small reading  lamp with  60w bulb may also be
used to prevent condensation of moisture inside  the cell.  The lamp is
positioned to shine on the  absorption cell  maintaining  the air temperature
in the  cell about  10  C above ambient.

     6.10 Reaction Flask  -  Either a  300 ml  B.O.D.  bottle or  250  ml
erlenmeyer flask fitted with a  rubber stopper may  be  used.
 7.    Reagents

      7.1  Purity of  Reagents  - Reagent grade chemicals,  or equivalent, as
 defined in ASTM Methods E 200, for Preparation,  Standardization, and
 Storage of Standard  Solutions for Chemical Analysis (7), shall be used in
 this test.

      7.2  Purity of  Water - Unless otherwise indicated,  references to
 water shall be understood to mean reagent water conforming to ASTM
 Specification D1193, for Reagent Water, Type I (7).

      7.3  Mercury Standard Solutions

      7.3.1  Mercury, Stock Standard Solution (1 ml « 1 mg Kg) - Dissolve
 0.1354 grams of mercuric chloride (HgCl2) in 75 ml of distilled water
 containing 10 ml of  concentrated nitric acid and dilute to 100 ml in a
 volumetric flask.
                                      49

-------
     7.3.2  Mercury, Intermediate Standard Solution (1 ml = 10 yg Hg) -
Add 10 ml of the stock mercury solution to distilled water containing 2
ml of concentrated nitric acid and dilute to 1 liter.  Prepare fresh
daily.

     7.3.3  Mercury Working Standard Solution (1 ml = 0.1 yg Hg) - Add 10
ml of the intermediate mercury standard to distilled water containing 2
ml of concentrated nitric acid and dilute to 1 liter.  Prepare fresh
daily.

     7.4  Nitric Acid (Sp gr 1.42) - Concentrated nitric acid (HNO-j) ,
reagent grade.

     Note 2 - If a high reagent blank is obtained, the reagent grade
       HN03 will have to be distilled or a spectro-grade acid will have
       to be used.

     7.5  Potassium Permanganate Solution (50 g/liter) - Dissolve 50
grams of potassium permanganate (KMnO^) in distilled water and dilute to
one liter.

     7.6  Potassium Persulfate Solution (50 g/liter) - Dissolve 50 grains
of potassium persulfate (K2S20g) in distilled water and dilute to one
liter.

     7.7  Sodium Chloride - Hydroxylamine Sulfate Solution (120 g/liter) -
Dissolve 120 grams of sodium chloride (NaCl) and 120 grams of hydroxylamine
sulfate [(NH2OH)2H2S04] in distilled water and dilute to one liter.

     7.8  Stannous Sulfate Solution (100 g/liter) - Dissolve 100 grams of
stannous sulfate (SnSO^) in distilled water containing 14 ml of concen-
trated sulfuric acid and dilute to one liter.  This mixture is a suspension
and should be stirred continously during use.

     7.9  Sulfuric Acid (Sp gr 1.84) - Concentrated sulfuric acid O^SO^) ,
reagent grade.


8.   Sampling

     8.1  Collect the samples in accordance with the applicable method of
American Society for Testing and Materials, as follows:

          D510 - Sampling Industrial Water (7)
          D860 - Sampling Water from Boilers (7)
          D1496 - Sampling Homogenous Industrial Waste Water (7)

     8.2  Samples should be collected in acid-washed glass or high density
polyethylene bottles.  Samples could be analyzed within 38 days if collected
in glass bottles, and within 13 days if collected in polyethylene bottles
(8).
                                     50

-------
     8.3  Samples should be preserved with concentrated nitric acid to a
pH of 2 or less immediately at the time of collection,  normally about 2
ml/liter.  If only dissolved mercury is to be determined, the sample
should be filtered through a 0.45 jj membrane filter using an all glass
filtering apparatus before acidification.
9.   Calibration

     9.1  Transfer 0, 1.0, 2.0, 5.0 and 10.0 ml aliquots of the working
mercury solution containing 0-1.0 yg of mercury to a series of reaction
flasks.  Add enough distilled water to each flask to make a total volume
of 100 ml.  Mix thoroughly and add 5 ml of concentrated sulfuric acid and
2.5 ml of nitric acid to each flask (Note 3).

     Add 15 ml of KMnO^ solution to each bottle and allow to stand at
least 15 minutes.  Add 8 ml of potassium persulfate to each flask and
heat for two hours in a water bath at 95 C.  Cool to room temperature and
add 6 ml of sodium chloride—hydroxylamine sulfate solution to reduce the
excess permanganate.  After waiting 30 seconds treat each flask individ-
ually by adding 5 ml of the stannous sulfate solution and immediately
attach the bottle to the aeration apparatus forming a closed system.
Continue as described under Procedure  (10.1).

     Note 3 - Loss of mercury may occur at elevated temperatures.
       However, with the stated amounts of acid the temperature rise
       is only about 13 C.  (25-38 C) and no losses of mercury will
       occur  (3).
 10.   Procedure

      10.1 Transfer  100 ml  or  an  aliquot  diluted  to  100  ml  containing not
 more  than 1.0 yg  of mercury to a reaction  flask.  Add 5 ml of  sulfuric
 acid  and 2.5 ml of  nitric  acid mixing after  each addition  (Note 3,  9.1).
 Add 15  ml of potassium permanganate  solution to  each sample bottle.
 Shake and add additional portions of potassium permanganate solution
 until the purple  color persists  for  at least 15  minutes.  Add  8 ml  of
 potassium persulfate  to each  flask and heat  for  2 hours in a water  bath
 at  95 C.  Cool and  add 6 ml of sodium chloride-hydroxylamine sulfate to
 reduce  the  excess permanganate.   Wait 30 seconds and add 5 ml  of stannous
 sulfate to  each flask individually and immediately  attach  it to the
 aeration apparatus.  The circulating pump, which has previously been
 adjusted to a rate  of 1 liter per minute,  is allowed to run continuously.

      The absorbance will increase and reach  maximum within 30  seconds.
 As  soon as  the recorder pen levels off,  approximately 1 minute, open the
 by-pass valve and continue the aeration until the absorbance returns to
 its minimum value (Note 4).   Close the by-pass valve,  remove the stopper
 and  frit from the reaction flask and continue the aeration. Proceed with
 the  standards and construct a standard curve by  plotting peak  height
 versus  micrograms of  mercury.

                                      51

-------
     Note 4 - Because of the toxic nature of mercury vapor, precaution
must be take to avoid its inhalation.  Therefore, a by-pass has been
included in the system to either vent the mercury vapor into an exhaust
hood or pass the vapor through some absorbing media, such as:

     (a)  equal volumes of 0.1N KMnO^ and 10% t^SO^

     (b)  0.25% iodine in 3% KI solution
11.  Calculation

     11.1 Determine the peak height of the unknown from the chart and
read the mercury value from the standard curve.

     11.2 Calculate mercury concentration in sample by formula:

     yg Hg/liter       pg Hg     X        10°0	
                     in aliquot     volume of aliquot
12.  Precision and Accuracy

     12.1 A statement of precision and accuracy will be made available by
the:
          Quality Assurance Branch
          Environmental Monitoring and Support Laboratory,EPA
          Cineinnati,  Ohio
                                    52

-------
                             APPENDIX REFERENCES
1.   These methods are under the jurisdiction of ASTM Committee D-19 on
     Water.  Annual Book of ASTM Standards,  Part 31,  Water.   American
     Society for Testing and Materials,  Philadelphia, PA.

2.   Hatch, W.  R. and W. L. Ott, 1968.  Determination of Sub-Microgram
     Quantities of Mercury by Atomic Absorption Spectrophotometry, Anal.
     Chem. 4(3:2085.

3.   Kopp, J. F., M. C. Longbottom and L.  B. Lobring, 1972.   Cold Vapor
     Method for Determining Mercury, JAWWA 64:20.

4.   U.S. Environmental Protection Agency.  Mercury Recovery Study,
     Region IV Surveillance and Analysis Division, Athens, Georgia.
     (Not Published)

5.   Dean, Robert B., Robert T. Williams and Robert H. Wise, 1971.
     Disposal of Mercury Wastes from Water Laboratories, Environmental
     Science and Technology, 5^:1044.

6.   Uthe, J. F., F. A. J. Armstrong and M.  P.  Stainton, 1970.  Mercury
     Determination in Fish Samples by Wet Digestion and Flameless Atomic
     Absorption Spectrophotometry, Jour. Fisheries Research Board of
     Canada, 27:805.

7.   Appears in this publication.

8.   U.S. Environmental Protection Agency.  Mercury Perservation  Study,
     Region IV Surveillance and Analysis Division, Athens, Georgia.
     (Not Published)
                                      53

-------
          SCHEMATIC  ARRANGEMENT OF EQUIPMENT  FOR MERCURY MEASUREMENT
                          by  Cold  Vapor  AA Technique

                          Closed Recirculating System


                                   FIGURE  1
A - Reaction Flask
B - Drying Tube, filled with
C - Rotameter, 1 liter of air/minute
D - Absorption Cell with quartz windows
E - Air Pump, 1 liter of air/minute
F - Glass tube with fritted end
G - Hollow cathode mercury lamp
H - AA Detector
J - Gas washing bottle containing 0.25% iodine in a 3% potassium iodine solution
K - Recorder, any compatible model
                                      54

-------
        SCHEMATIC ARRANGEMENT OF EQUIPMENT FOR MERCURY MEASUREMENT

                        by Cold Vapor AA Technique

                           Open One-Pass System
                                 FIGURE 2
                                        A
         u
        V
         IE
A - Reaction Flask
B - Drying Tube, filled with MgC104
C - Rotameter, 1 liter of air/minute
D - Absorption Cell with quartz windows
E - Compressed Air, 1 liter of air/minute
F - Glass tube with fritted end
G - Hollow cathode mercury lamp
H - AA Detector
J - Vent to hood
K - Recorder, any compatible model
L - To vacuum through gas washing bottle contain 0.25% iodine in a 3%
     potassium iodine solution
                                     55

-------
                                 FIGURE 3
                                 10 -18 CM
                     CELL FOR  MERCURY MEASUREMENT

                        BY COLD VAPOR TECHNIQUE
     The length and  OD  of  the cell are not critical.   The body of  the cell
may be of any tubular material but the end windows must be of  quartz because
of the need for UV transparency.

     The length and  diameter of the inlet and outlet  tubes are not important,
but the position of  the side arms may be a factor in  eliminating recorder
noise.  There is some evidence that displacement of the air inlet  arm away
from the end of the  cell results in smoother readings.  A mild pressure in
the cell can be tolerated, but too much pressure may  cause the glued-on end
windows to pop off.

     Cells of this type may be purchased from various supply houses.
                                    56

-------
                                  APPENDIX

                 Al.  Disposal of Mercury Containing Wastes


Al.l Introduction

     Mercury salts are components of the wastes from the following
determinations:

          Chemical Oxygen Demand, D1252
          Ammonia in Water, D1426
          Chloride Ion in Industrial Water and Wastewater, D512
          Examination of Water Formed Deposits by Chemical Microscopy,
            D1245

Also, mercuric chloride is often used to preserve water samples for
nitrogen and phosphorus analysis.

     The safest way to retain mercury salts is as the sulfide at a high
pH.  Acidic solutions should be neutralized and combined with alkaline
wastes and water samples containing mercury preservatives.  To precipitate
mercury, a convenient source of the sulfide ion is sodium thiosulfate.
However, it should not be added to acidified wastes because of its rapid
decomposition to elemental sulfur.  The sulfur which precipitates in-
creases the volume of sludge which must be processed and stored.

     Mercury sulfide is insoluble and is stable to most reagents except
aqua regia and bromine.  Bacterial conversions to methyl mercury are pre-
vented by maintaining the pH above 10.


A1.2 Procedure

     Dilute all combined acidic wastes to about twice their original
volume.  Adjust the pH to greater than 7 by slowly adding sodium hydroxide
solution (40-50 percent, w/v) with stirring.  Combine this neutralized
waste and any pooled alkaline wastes with stirring.  At this point the
combined wastes should have a pH of 10 or higher; if not, add sodium
hydroxide until a pH of 10-11 has been obtained.

     While the combined alkaline wastes are still warm, stir in small
portions of sodium thiosulfate solution (40-50 percent, w/v) until no
further precipitation seems to occur.  Allow the precipitate to settle.

     Draw off a few milliliters of clear supernatant, make sure the pH
is still above 10, and then add an equal volume of sodium thiosulfate
solution.  If the supernatant still contains dissolved mercury, a pre-
cipitate will rapidly form, indicating that additional sodium thiosulfate
must be added to the waste slurry.
                                      57

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     After the precipitate has settled, decant or siphon off the clear
tested supernatant and discard it.  Wash the precipitate twice with
water containing a trace of NaOH, allow to settle, and discard both of
the clear washings.  Dry the washed precipitate first in air, then in an
oven at a temperature no higher than 110 C.

     Store the dry solids until a sufficient quantity has accumulated to
justify shipment to a commercial reprocessor:  (Table 1).

     Metallic mercury and waste organomercurials should be stored in
suitable air tight containers until a commercial reprocessor can be
contacted for specific shipping instructions:  (Table 1).
                                     58

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                              TABLE 1

                    Reprocessors of Mercury (a)
Bethlehem Apparatus Co., Inc.                                M
Front and Depot Streets
Hellertown, PA  18055
Phone:  (215) 838-703A

Goldsmith Division, National Lead Co.                        M
111 North Wabash
Chicago, IL  60602
Phone:  (312) 726-0232

Mallinckrodt Chemical Works                                  MCO
223 West Side Avenue
Jersey City, NJ  07303
Phone:  (201) 432-2500
(Mr. Frank L. Mackey, Western Branch Plant Manager)

Quicksilver Products, Inc.                                   MC
350 Brannan Street
San Francisco, CA  94107
Phone:  (415) 781-1988
(Miss Grace Emmans, Owner and President)

Sonoma Mines, Inc.                                           C
P.O. Box 226
Guerneville, CA  95446
Phone:  (707) 869-2013

Wood Ridge Chemical Corp.                                    MC
Park Place East
Wood-Ridge, NJ  07075
Phone:  (201) 939-4600
(Mr. E. L. Cadmus, Technical Director)

M = Supplies flask for  return of metallic mercury.
C = Will accept mercury sulfide for  reprocessing.
0 = Will accept certain organic mercury  chemicals.

Note a  - Special approval must always be obtained before shipment
         is made to a  reprocessor.
                                 59

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                               GLOSSARY OF TERMS
     The statistical measurements used in method study reports of the
Environmental Monitoring and Support Laboratory-Cincinnati are defined
as follows:

     Accuracy as % Relative Error (Bias) .  The signed difference between
       mean value and the true value, expressed as a percent of the true
       value.
                R.  E. ,  %  =  y -  X 100
                             Atrue

     Confidence Limit (95%) .   The range of values within which a single
       analysis will be included, 95% of the time.

                95% C.  L.  =  X  ±  1.96S

     Mean Recovery.   The arithmetic mean of reported values; the average.
     Median.   Middle value of all data ranked in ascending order.  If
       there are two middle values,  the mean of these values.

     n.   The number values (X^  reported for a sample.

     Range.   The difference between the lowest and highest values reported
       for a sample.

     Relative Deviation (Coefficient of Variation).  The ratio of_the
       standard deviation, S, of a set of numbers to their mean, X,
       expressed as percent.  It is an attempt to relate deviation
       (precision)  of a set of data to the size of the numbers so that
       deviations at different mean values can be compared.

                   R. D.  -  100 =
                                 X

     Skewness (k).   A pure number, positive or negative, which indicates
       the lack of symmetry in a distribution.  For example, "k is positive
       if the distribution tails to the right and negative if the distri-
       bution tails to the left.

                             Z(X, - X)3
                                    60

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Standard Deviation (S).  The most widely used measure to describe
  the dispersion of^ a set of data.  Normally, X ± S will include
  68 percent, and X ± 2S will include about 95 percent of the
  data from a study.
                            n - 1

Standard Deviation: Single Analyst  (Sr).  A measure of dispersion
  for data from a single analyst.   Calculated here using an
  equation developed by Youden based on his non-replicate study
  design.
 t  test.  The difference between a  single  observation  (Xn)  and the
   estimated population mean  (X) expressed as  a  ratio  over  the
   estimated population standard deviation (S) .   The value  obtained
   is  compared with  critical  values from a table for the Student's
   t distribution.   If the  calculated  t  value  exceeds  the theoretical
   t value  at a  prescribed  confidence  level,  the analyzed value is
   probably not  from the same population as the  rest of the data and
   can be rejected.
                                 61

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                                    TECHNICAL REPORT DATA
                             (Please react Instructions on the reverse before completing)
 1. REPORT NO.
   EPA-600/4-77-012
                                                             3. RECIPIENT'S ACCESSIOr+NO.
 4. TITLE ANDSUBTITLE
   EPA Method  Study 8,  Total Mercury  in Water
                                                            5. REPORT DATE
                                                             February 1977  issuing date
                                                            6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
   John Winter,  Paul Britton, Harold  Clements
   and Robert Kroner
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Environmental Monitoring and Support Laboratory-Cin,,(
  Office of Research and Development
  U.S. Environmental Protection Agency
  Cincinnati,  Ohio  45268
                                                             10. PROGRAM ELEMENT NO.

                                                             [   1HD621
                                                             11. CONTRACT/GRANT NO.

                                                                P.O. No. 5-03-4294
 12. SPONSORING AGENCY NAME AND ADDRESS
   Same as above.
                                                             13. TYPE OF REPORT AND PERIOD COVERED
                                                                Final     	
                                                            14. SPONSORING AGENCY CODE

                                                                 EPA/600/06
 15. SUPPLEMENTARY NOTES
   Prepared  in part under contract, P.O.  No. 5-03-4294 by Robert C. Kroner.
 16. ABSTRACT        "	~	
        The Environmental Monitoring  and Support Laboratory-Cincinnati of  EPA
   conducts EPA's  quality assurance program for the water laboratories and
   assists EPA  laboratories in the choice of methods for  physical, chemical,
   biological and  microbiological analyses.  The responsibility for quality
   assurance activities of EMSL is assigned to the Quality Assurance Branch
   (QAB).  This study,  one of the QAB activities, describes a joint EPA/ASTM
   evaluation study  of  a method of analysis for total mercury in natural water
   and wastewaters.   The method includes an acid-permanganate-persulfate digestion
   followed by  reduction and measurement of mercury in  the vapor phase at
   253.7 nm.  This report describes the study, its conclusions and provides
   statements of precision and accuracy.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                                                                          c. COSATI Field/Group
   Mercury Inorganic Compounds
   Mercury Organic Compounds
   Water Analysis
   Waste Disposal
   Industrial Wastes
                                              Method Validation Studies
                                              Statistical Evaluation
                                              Analysis  for ug/liter
                                               levels of  mercury
  07/B
  07/C
 8. DISTRIBUTION STATEMENT
   Release Unlimited
                                              19. SECURITY CLASS (ThisReport)
21. NO. OF PAGES
    76
                                               20. SECURITY CLASS (This page)
                                                                         22. PRICE
EPA Form 2220-1 (9-73)
                                              62    vV U.S. GOVtHMMEHT MIKTING OFFICE 1977-757-056/55'(9 Region No. 5-11

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