PB86-121357
Determination of Ciiio?. inated Hydrocarbons in
Industrial and Municipal Wastewaters
IT Enviroscience, Inc., Knoxville, TN
Prepared for
Environmental Monitoring and Support Lab.
Cincinnati, OH
Oct 85
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
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EPA/600/4-85/069
October 1985
PB86-121357
DETERMINATION OF CHLORINATED HYDROCARBONS IN
INDUSTRIAL AND MUNICIPAL WASTEWATERS
By
J. R. Florance, J. R. Hall, M. Khare, S. M. Maggio, J. C. Mitchell,
R. A. Solomon, J. R. SoloRio, D. L. Strother, and M. N. Wass
IT Enviroscience
Knoxville, Tennessee 37923
Contract No. 68-03-2625
Project Officer
James J. Lichtenberg
Physical and Chemical Methods Branch
Environmental Monitoring and Support Laboratory
Cincinnati, Ohio 45268
Environmental Monitoring and Support Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
REPRODUCED BY
NATIONAL TECHNICAL
INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
SPRINGFIELD, VA. 22161
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA/600/4-85/069
2.
3. RECIPIENT'S ACCESSION NO.
PBS b 1 ?
7 7K
4. TITLE AND SUBTITLE
Determination of Chlorinated Hydrocarbons in
Industrial and Municipal Wastewaters
5. REPORT DATE
October 1985
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
J. R. Florance, J. R. Hall, M. Khare, S. M. Maggio,
J. C. Mitchell, R. A. Solomon, J.R. SoloRio, D. L. Stro
8. PERFORMING ORGANIZATION REPORT NO.
bher,
9. PERFORMING ORGANIZATION NAME AND ADDRESS
IT Enviroscience
Knoxville, Tennessee 37923
^ fj.
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-2625
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Monitoring and Support Laboratory
U. S. Environmental Protection Agency
26 W. St. Clair Street
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
1977/1984
14. SPONSORING AGENCY CODE
EPA 600/6
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The objective of this report is to present the data and the research
carried out to develop an analytical test procedure for the analysis of
specific organic toxic substances in effluent wastewaters. The procedure is
for the analysis of nine of the 114 priority or toxic pollutants identified by
the EPA as Category 3 — Chlorinated Hydrocarbons.
The procedure consists of several steps, including extraction,
concentration, clean up, and quantification by gas chromatography with
electron-capture detection and flame-ionization.
The report describes the work done leading to selection of the procedures
and includes data and information on a literature search, sample preservation
procedures, elution of the compounds on various gas chromatographic columns,
several solvent extraction efficiencies versus pH, stability of compounds in
water-soluble solvents, sample extract clean up procedures, and application of
the procedures on effluent wastewaters.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
18. DISTRIBUTION STATEMENT
Distribute to Public
19. SECURITY CLASS (This Report!
Unclassified
21. NO. OF PAGES
93
20. SECURITY CLASS (Thispage)
Unclassified
EPA Form 2220-1 (R»». 4-77) PREVIOUS EDITION is OBSOLETE
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
11
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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:
o Develop and evaluate methods to measure the presence and
concentration of physical, chemical and radiological pol-
lutants in water, wastewater, bottom sediments, and solid
waste.
o Investigate methods for the concentration, recovery, and
identification of viruses, bacteria and other microbiological
organisms in water; and, to determine the responses of aquatic
organisms to water quality.
o Develop and operate an Agency-wide quality assurance program
to assure standardization and quality control of systems for
monitoring water and wastewater.
o Develop and operate a computerized system for instrument auto-
mation leading to improved data collection, analysis, and
quality control.
Under authority of Sections 304(h) and 501(a) of the Federal Water Pollution
.Control Act of 1972 and the Clean Water Act of 1977, the Environmental
Protection Agency is required to promulgate guidelines establishing test
procedures for the analysis of pollutants. This report represents the
state-of-the-art for the measurement of chlorinated hydrocarbons in
industrial wastewaters.
Robert L. Booth, Director
Environmental Monitoring and Support
Laboratory - Cincinnati
iii
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ABSTRACT
The objective of this report is to present the data and the research
carried out to develop an analytical test procedure for the analysis of spe-
cific organic toxic substances in effluent wastewaters. The procedure is
for the analysis of nine of the 114 priority or toxic pollutants identified
by the EPA as Category 3 — Chlorinated Hydrocarbons.
The procedure consists of several steps, including extraction, con-
centration, clean up, and quantification by gas chromatography with
electron-capture detection and flame-ionization.
The report describes the work done leading to selection of the proce-
dures and includes data and information on a literature search, sample pre-
servation procedures, elution of the compounds on varius gas chromatographic
columns, several solvent extraction efficiencies versus pH, stability of
compounds in water-soluble solvents, sample extract clean up procedures, and
application of thesprocedures on effluent wastewaters.
The report was submitted in fulfillment of Contract No. 68-03-2625 by IT
Enviroscience under the sponsorship of the U.S. Environmental Protection
Agency. This report covers the period November 1977 to March 1979, and work
was completed as of March 1979.
iv
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CONTENTS
Disclaimer ii
Foreword iii
Abstract iv
Figures vi
Tables vii
Abbreviations and Symbols viii
Acknowledgements ix
1. Introduction 1
2. Conclusions and Recommendations 2
3. Results of Literature Search 4
4. Chlorinated Hydrocarbons 8
Materials and Methods of Preparation 9
Experimental 10
5. Supplemental Seven Day Preservation Study - Category 3 34
Introduction 34
Experimental 34
Discussion 34
6. Development of Method Detection Limits 36
Introduction 36
Experimental 36
Discussion 38
Conclusions and Recommendations 44
7. References 45
Appendices
A. Chlorinated Hydrocarbons: Analytical Method 612 67
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FIGURES
Number Page
1. Gas Chromatogram of Chlorinated Hydrocarbons 12
2. Gas Chromatogram of Chlorinated Hydrocarbons 13
3. Gas Chromatogram of Wastewater (15-C1-05-44) Extract 29
After Clean Up
4. Gas Chromatogram of Spiked Wastewater (15-C1-05-44) 30
Extract After Clean Up
5. Gas Chromatogram of Wastewater (15-C1-05-44) Extract 31
After Clean Up
6. Gas Chromatogram of Spiked Wastewater (15-C1-05-44) 31
Extract After Clean Up
A-l. Gas Chromatogram of Chlorinated Hydrocarbons 75
A-2. Gas Chromatogram of Chlorinated Hydrocarbons 76
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TABLES
Number . Page
1. Abstracts 4
2. Periodical List 5
3. Citations Found in Literature for Chlorinated Hydrocarbons 6
4. GC Columns Evaluated for Category 3 by EC 11
5. GC Retention Times, Analysis Temperatures and Detection 11
Limits for Category 3 by EC
6. GC Conditions for Category 3 by EC 14
7. Response and Linearity for Category 3 by FID 15
8. Response and Linearity for Category 3 by ECO 16
9. Solutions Needed for Preparation of pH Buffers 2, 7, and 10 17
10. Summary of Extraction Efficiencies and Percent Standard 18
Deviation of Category 3
11. Summary of Category 3 Extraction Efficiencies at Two 19
Concentrations
12. Average Percent Loss Due to Preservation 21
13. Average Percent Loss at Two Concentrations Due to 22
Preservation at pH-2 Without Cl2
14. Average Percent Change of Category 3 in 2-Propanol 23
15. Average Percent Change of Category 3 in 2-Butanone 23
16. Average Percent Change of Hexachlorocyclopentadiene in 24
2-Propanol and 2-Butanone
17. Average Percent Change of Hexachlorocyclopentadiene in 25
Dichloromethane
18. Average Percent Recovery of Category 3 after Florisil 26
Clean Up
19. Average Percent Recovery of Category 3 after Alumina 26
Clean Up
20. Results from Analysis of Wastewater Application Samples 28
21. Method Accuracy Expressed as Percent Recovery Based on 28
Spiked, Distilled, Deionized Water
22. Method Precision Expressed as Concentration (pg/L) 32
Based on Spiked, Distilled, Deionized Water
23. Method Accuracy Expressed as Percent Recovery Based 32
on a Spiked, Industrial, Wastewater Sample (Plastic's
Industry, 15-C1-05-44)
24. Method Precision Expressed as Concentration (yg/L) Based 33
on a Spiked, Wastewater Sample (Plastic's Industry,
15-C1-05-44)
25. Seven Day Preservation Study of Chlorinated Hydro- 35
carbons in Wastewater
vii
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TABLES (Continued)
Number - Page
26. MDL of Chlorinated Hydrocarbons in Interference-Free 37
Water
27. Concentration of Chlorinated Hydrocarbons in Water 38
28. Analytical Curve Data for 1,3-Dichlorobenzene, 39
1,4-Dichlorobenzene, and Hexachloroethane in Inter-
ference-Free Water
29. Analytical Curve Data for 1,2-Dichlorobenzene, Hexa- 40
chlorobutadiene, and 1,2,4-Trichlorobenzene in
Interference-Free Water
30. Analytical Curve Data for 2-Chloronaphthalene and 41
Hexachlorobenzene in Interference-Free Water
31. MDL of Chlorinated Hydrocarbons in Wastewater Code- - 42
COD-B
32. MDL of Chlorinated Hydrocarbons in Wastewater Code- 43
DCA-A
A-l. Gas Chromatography of Chlorinated Hydrocarbons 68
vm
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LIST OF ABBREVIATIONS
DMCS Dimethylchlorosilane
ODCB Orthodichlorobenzene
MDCB Metadichlorobenzene
PDCB Paradichlorobenzene
HCE Hexachloroethane
HCBD Hexachlorobutadiene
TCB 1,2,4-Trichlorobenzene
HCCPO Hexachlorocyclopentadiene
2-CN 2-Chloronaphthalene
ttCB Hexachlorobenzene
IX
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ACKNOWLEDGMENTS
The careful and critical evaluation of IT Enviroscience's work with
helpful suggestions by the EPA Project Officer, James J. Lichtenberg, and
the EPA Project Coordinator, James Longbottom, is sincerely appreciated and
was beneficial to the project.
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SECTION 1
INTRODUCTION
The Federal Water Pollution Control Act Amendments of 1972 (PL 92-500)
and more recently the Amendments of 1977 (PL 95-217) require in Section
304(h) that the Administrator of the U.S. Environmental Protection Agency
promulgate guidelines establishing test procedures for the analysis of the
priority pollutants, which are separated into 12 categories. This report
covers the research activity required in the method development for
Category 3 « Chlorinated Hydrocarbons.
The nine compounds in Category 3 ~ Chlorinated Hydrocarbons are hexa-
chloroethane, hexachlorobutadiene, hexachlorocyclopentadiene, 1,2-dichloro-
benzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene-j 1,2,4-trichlorobenzene,
hexachlorobenzene, and 2-chloronaphthalene.
The study includes a literature search from 1960 through 1978, sample
preservation studies, evaluation of solvents for liquid-liquid extraction,
stability studies of the compounds in water-miscible solvents, and eval-
uation of sample and extract clean up procedures.
The gas chromatographic characteristics data of the category compounds
are presented and include information on retention times with various gas
chromatography columns at different temperatures, responses to both
electron-capture and flame ionization detectors, linearity curves and chemi-
cal data for all compounds, and calculated and practical minimum detectable
levels.
Based on the information gathered in the research program, methods were
proposed for Category 3. These proposed methods were then used to develop
data on overall compound recoveries in spiked distilled water and wastewater
effluent samples.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
CONCLUSIONS
The results of the experiments performed indicate that the samples are
best preserved when the pH is adjusted to 2 and when they are dechlorinated
with sodium thiosulfate, exposed to a minimum amount of light (UV), and
stored and shipped at a temperature of 4°C. These procedures should be
implemented as soon as possible after the samples have been collected. Even
under these conditions, however, storage for seven days at low levels
(<10 ug/L) led to losses ranging from 22 to 76%, whereas at the higher level
(200 to 300 ug/L) losses were only from 2 to 18 percent.
Extraction of the samples with dichloromethane should be carried out at
a pH of 2 to give the maximum extraction efficiency. Data on spiked
distilled water show that the extraction efficiencies at the ug/L level or
less are lower (10 to 20%) than at concentration levels one to two orders of
magnitude higher.
The concentrated solvent-substituted extract is then analyzed on a 1.8 m
by 2 mm I.D. glass column packed with mixed phases of 1.5% OV-1 and
1.5% OV-225 on 80/100 mesh Gas-Chrom Q at two isothermal conditions, 75°C
and 165°C. All nine compounds are resolved by this column, and the minimum
resolution of 0.7 occurs between the meta- and paradichlorobenzene isomers.
This resolution between all the dichlorobenzenes and hexachloroethane,
however, is quite variable with concentration; that is, high ug/L levels of
hexachloroethane may make detection difficult at the ug/L level of .para- and
orthodichlorobenzene.
The original gas chromatographic packing was prepared by mixing equal
volumes of 1.5% OV-1 on Gas-Chrom Q and 1.5% OV-225 on Gas-Chrom Q.
Problems were encountered in preparing reproducible lots of the packing. It
was subsequently discovered that a blended gas chromatographic column
packing of 1.5% OV-1 and 2.25% OV-225 on Supelcoport gave identical results
and performance to the orginal mixed phase packing yet was reproducible from
lot to lot. Therefore, the blended packing has been recommended for the
analyses of the chlorinated hydrocarbons.
The category compounds' responses were linear by GC/FID over the con-
centration ranges of 10 to 1000 mg/L injected and by GC/EC over the range of
1 to 10,000 ug/L injected.
Evaluation of the solvent stability in 2-propanol and 2-butanone indi-
cates the latter solvent to be superior in promoting stability, since the
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concentration of all the Category-3 compounds except hexachlorocyclopen-
tadiene remained within an average of ±7% after a 90 day storage period at
room temperature in the presence of light. Hexachlorocyclopentadiene proved
to be highly unstable in both solvents, with significant decomposition
occurring in as little as 10 days. In a separate study with hexachloro-
cyclopentadiene alone in the two solvents, the results were similar to those
of the initial study. Shorter but similar studies with methanol and acetone
as the solvent also showed decomposition. Stability of hexachlqrocyclopen-
tadiene in dichloromethane sealed in ampules and screw cap vials was tested
for 45 days. Again, decomposition occurred between 10 to 30 days but was
most severe in the sealed ampules.
The Florisil column clean up procedure is rapid, keeps all category
compounds in one eluant, and allows separation for more polar halogenated
extracted components that may interfere with the analysis. The clean up
allows elimination of many late eluting components that slow down analysis
turnaround time.
Three treated industrial effluent samples and a municipal primary
effluent sample were analyzed by the complete method. Two of the industrial
effluents showed no Category-3 compounds. The municipal wastewater showed
five of the compounds at less than 20 yg/L and the remaining industrial
wastewater showed seven of the nine compounds at 0.4 to 120 yg/L. The
method may be applicable to a wide variety of wastewater effluents, but con-
firmation by a secondary technique, previous sample knowledge, or gas
chromatography/mass spectrometry will be required at times.
The accuracy of the method based on spiked solutions of distilled
deionized water expressed as percent of recovery varied from 65% for hexa-
chlorobenzene to 91% for 2-chloronapthalene at the low yg/L level. The
method precision, based on spiking the worst sample evaluated, had a single
operator coefficient of variation that ranged from 15% for p-dichlorobenzene
to 52% for hexachlorobenzene.
RECOMMENDATIONS
In future studies a more effective research schedule for a method de-
velopment project of this type should allow for the development of sample
clean up techniques before extraction and preservation studies are begun.
Such a schedule would allow application of the clean up procedure to the
extraction and preservation studies, particularly the latter, whereas the
formation of many additional compounds hampered both the quantification and
precision of these studies.
Studies should be performed on the stability of hexachlorocyclopen-
tadiene in water, since it lacks stability in the presence of UV light in
several other polar solvents.
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SECTION 3
RESULTS OF LITERATURE SEARCH
The literature review was made to determine the state of the art of ana-
lytical instrumentation and techniques utilized in the trace analysis of the
nine chlorinated hydrocarbons that had been specified by the EPA. The
resources of the University of Tennessee Science Library, the Oak Ridge
National Laboratory Central Research Library, and IT Enviroscience's own
facilities were used for this literature review.
The abstracts listed in Table 1 were searched from the years 1960 to
1979 for key words or subjects including methods of analysis for each of the
two categories of compounds, sample collection and preservation methods,
concentration techniques, clean up procedures, derivatization techniques and
applications of chromatography.
TABLE 1. ABSTRACTS
Analytical Abstracts
Aquatic Sciences Abstracts*
Chemical Abstracts, 1960-1972
Chemical Abstracts Condensates, 1976-1977*
CASIA, 1972-1976*
NTIS*
Pollution Abstracts
Recon Files*
*Computer searches.
Several abstracts were manually searched, but five were searched by com-
puter programs utilizing the key words or subjects mentioned in the last
paragraph, along with the topic compound's registry numbers. CASIA is the
computer program that searched Chemical Abstracts from 1972 to 1976. More
recently, abstracted articles were found when the Chemical Abstracts
Condensate program was run. The Recon File is a data bank of key articles
that have been compiled by the Oak Ridge National Laboratory Central
Research Library for its employees and is available publicly through the
University of Tennessee Library.
Table 2 lists the periodicals most often cited by the abstracts. In
addition to articles that appeared in these periodicals, numerous books,
governmental publications, and minutes of symposia and meetings were cited.
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TABLE 2. PERIODICAL LIST
Analyst
Analytical Chemical Acta
Analytical Biochemistry
Analytical Chemistry
Analytical Letters
Bulletin of Environmental Contamination and Toxicology
Environmental Pollution
Environmental Research
Environmental Science and Technology
International Journal of Air and Water Pollution
Journal of Agricultural and Food Chemistry
Journal of American Waterworks Association
Journal of the Association of Official Agricultural Chemists
Journal of the Association of Official Analytical Chemists
Journal of Chromatography
Journal of Chromatographic Science
Journal of Environmental Science and Health
Journal of Industrial Hygiene and Toxicology
Journal of Water Pollution Control Federation
TAPPI
Vom Wasser
Water, Air and Soil Pollution
Water and Sewage Works
Water Pollution Control
Water Research
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Copies of the most pertinent articles were obtained and will be kept on file
by IT Enviroscience throughout the lifetime of this project. A complete
reference of pertinent publications is given in Section 6.
Table 3 is a summary of the results of the literature search for the
analysis of chlorinated hydrocarbons. While the main interest was in
finding articles dealing with any or all of the nine topic compounds,
articles that dealt with compounds of a similar nature and whose analyses
might have been applicable to any of the topic compounds were also cited.
Therefore, while only 97 references were found that dealt directly with the
analysis of one or more of the nine compounds, an additional 182 were found
for similar chlorinated compounds.
TABLE 3. CITATIONS FOUND IN LITERATURE FOR CHLORINATED HYDROCARBONS
Total citations
Sampling and preservation
Preservation techniques
Concentration by liquid-liquid extraction
-Extraction solvents
Concentration by carbon/Tenax adsorption
Concentration by macroreticular resins *
Clean up
Techniques
Analysis by GC
GC substrates
Head space analysis
Purge/sparge technique
Analysis by LC
182a
15a
6
51a
30
16a
19a
25a
4
88a
64
9a
lla
6a
(97)b
(0)b
u
(25)b
(5)b
(H)b
(7)b
U
(72)b
(6)b
(3)b
(Db
aFirst number refers to the number of citations found for the general
class of chlorinated compounds.
bThe number in parenthesis refers to the number of citations in which
at least one of the topic compounds appears.
Sampling was most often mentioned in government publications, although a
few articles printed in public periodicals did address themselves to this
item. Two examples are cited in references 57 and 271. Most articles did
stress the importance of specially cleaned sampling bottles and avoidance of
contamination during the analysis for chlorinated hydrocarbons.(79)
Four preservation techniques, other than refrigeration, were published,
but the two most often reported were the additions of ascorbic acid or
potassium ferrocyanide to the water samples.(152, 189) Both chemicals,
which are reducing agents, are added to eliminate residual chlorine, which
can react with organic material in the water to generate erroneously high
levels of chlorinated hydrocarbons.
The most commonly reported method of concentrating the chlorinated
hydrocarbons in water was liquid-liquid extraction, which may or may not be
6
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followed by distillation or evaporation of the extracting solvent. Thirty
solvents were reported, but the most commonly used ones were diethyl ether,
petroleum ether, hexane, and benzene.(181, 185, 189) Alternate con-
centration techniques mentioned were carbon adsorption followed by solvent
elution or recovery of the chlorinated hydrocarbons on macroreticular resins
such as XAD-2 followed by solvent elution. (87, 153) The chlorinated hydro-
carbons have also been concentrated by head-space sampling techniques, purge
and trap (or VOA), or spray evaporation techniques.(18, 41, 57, 188)
Clean up procedures in which column chromatography with silica gel,
Florisil, or alumina was used were reported.(15, 27, 274) Thin-layer chro-
matography has been mentioned as a clean up tool for some chlorinated hydro-
carbons, but recoveries generally are low.(16, 143) As an alternative, back
extraction or the extraction solvent sometimes was sufficient to clean the
sample, although the technique was never claimed to be a clean up procedure.
Particular notice was taken during the literature survey for conditions
of gas chromatographic analysis for trace quantities of chlorinated hydro-
carbons in water. A large number of GC substrates, many obscure, were
reported. Five did stand out due to their frequent use: DC-200; QF-1 with
DC-200; SE-30; OV-225; and Bentone 34 with OV-101.(4, 17, 66, 106, 143)
Both flame ionization and electron-capture detectors were reported in use,
with the latter being more sensitive for higher chlorinated compounds.(4)
The limits of detection, however, were dependent on concentration factors,
as well as on the type of detector used.
Thin-layer chromatography and liquid chromatography were also used for
the analyses of some of the chlorinated hydrocarbons.(115, 205, 215)
Generally, the level of detection was the mg/L level for these analytical
methods. With special techniques and detectors, the level of detection can
be lowered, but the former are not usually available to all laboratories.
Little was found in the literature about the stability of the nine
chlorinated hydrocarbons in organic sol vents.(112) More was mentioned about
their instability under UV light.
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SECTION 4
CHLORINATED HYDROCARBONS
The EPA has designated 114 organic compounds in 12 categories as
priority pollutants. The purpose of this study was to develop an unexotic
test procedure to quantify in wastewater the effluents of the nine chlori-
nated hydrocarbons in Category 3: jn-dichlorobenzene, £-dichlorobenzene,
hexachloroethane, jv-dichlorobenzene, hexachlorobutadiene, 1,2,4-trichloro-
benzene, hexachlorocyclopentadiene, 2-chloronapthalene, and hexachloro-
benzene.
The technical objectives of this project included the determination of a
sample preservation scheme to minimize compound loss, the derivation of an
efficient.extraction technique for recovering and concentrating the com-
pounds from water, the establishment of a reliable and linear gas chroma-
tographic method applicable to all nine compounds, the determination of the
stability of the compound when dissolved in water-miscible solvents, the
development of a suitable sample clean up procedure, the application of the
final analytical method with a clean up procedure to industrial wastewater
samples, and the utilization of spiked aliquots of the wastewater samples
taken through the complete method to gather accuracy and precision data.
The resulting method in EPA format is found in Appendix A.
Experimental results indicated that samples were best preserved when
buffered to a pH of 2, dechlorinated with sodium thiosulfate, exposed to a
minimum amount of light (UV), and stored and shipped at a temperature of
4°C. These procedures should be performed or implemented as soon as
possible after the sample is collected. Since acid-preserved samples cannot
be shipped by air, the EPA has recommended that the sample be adjusted to a
pH of 6 or 8 for shipping purposes. However, IT Enviroscience still recom-
mends that the extraction step in the EPA approved method be performed at a
pH of 2 with dichloromethane (MeC^)- The recommendation was based on the
premise that the best extraction efficiency data were gathered at this pH
value.
Analysis of the concentrated, solvent-substituted extract was performed
on a 1.8 m long by 2 mm I.D. glass column packed with 1.5% OV-1 and 1.5%
OV-225 on 80/100 mesh Gas Chrom Q at two isothermal conditions, 75 and
160°C. All nine compounds' responses were quite linear, both by GC/FID at
concentrations of 10 to 1000 mg/L and by GC/EC over the 1 to 10,000 ug/L
range.
Evaluation of the stability of Category 3 -- Chlorinated Hydrocarbons in
2-propanol and 2-butanone indicated the latter solvent to be superior in
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promoting stability. The concentrations of all the Category-3 compounds
except hexachlorocyclopentadiene (HCCPD) remained within ±7% after a 90 day
storage period at room temperature in the presence of light. Hexachloro-
cyclopentadiene proved to be highly unstable in both solvents, with signifi-
cant decomposition occurring in as little as 10 days. A 45 day stability
study of the chlorinated hydrocarbons in dichloromethane indicated a 67%
decomposition rate in flame sealed ampules and a 33% decomposition in 20 mL
scintillation vials. Therefore, standards containing HCCPD should be pre-
pared fresh as needed and be refrigerated in the dark to maximize unstable
standard life. The method further recommends that all Category-3 standards
stored under normal lighting conditions be used within 60 days, as the con-
centration of j>-dichlorobenzene begins to decrease rapidly after that.
MATERIALS AND METHODS OF PREPARATION
Chemicals
The ^-dichlorobenzene, nv-dichlorobenzene, 1,2,4-trichlorobenzene, and
hexachloroethane were obtained from Eastman Kodak Company; the hexachloro-
cyclopentadiene, 2-chloronaphthalene, hexachlorobutadiene, and hexachloro-
benzene from Tridom Chemicals; the _p_-dichlorobenzene from Aldrich; and the
Aldrin from All tech Associates. Hydrochloric acid, potassium chloride,
potassium dibasic phosphate, sodium hydroxide, boric acid, sodium bicar-
bonate, sodium sulfate, Florisil (grade 923; 60-100 mesh), alumina, sulfuric
acid, and sodium thiosulfate were ACS reagent grade and were obtained from
Fisher Scientific. Burdick and Jackson HPLC distilled in glass grade
hexane, dichloromethane, and petroleum ether were purchased from Bodman
Chemical and used without redistillation. Gas chromatographic column
packings were obtained from Supelco, Inc. Prepurified nitrogen and 95%
argon/5% methane were obtained from the Linde division of Union Carbide.
Water Purification
It was of the utmost importance that the water in these experiments be
of a very high purity, so a high quality purification system was used.
Distilled ionized water was prepared by filtering tap water through a
Carborundum Company tube filtration unit, followed by elution through a
Barnstead D8904 organic removal column, a Barnstead D8901 high-capacity ion
exchange column, and finally a Barnstead D8902 ultrapure ion exchange
column. The effluent water was then distilled in a Corning megapure
distillation unit, which was modified to prevent any surfaces other than
Teflon and glass from contacting the water. All the plumbing and storage
containers throughout the system were made of Teflon or glass.
Gas Chromatography Column Preparation
Glass wool treated with dimethylchlorosilane (DMCS) was placed in the
detector end'of a coiled glass column, which was then attached by flexible
tubing to a water aspiration vacuum source. The desired packing material
was then added to the other end of the column while suction was applied.
After the column was filled, a vibrator was used in conjunction with the
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suction to provide a uniformly packed column. Additional packing material
was added, as before, if the previous treatment had reduced the volume of
the packing material. Another piece of glass wool was inserted in the
injector end of the column, with quarter-inch Swagelok fittings with
Supeltex M-l ferrules added to the columns and attached to the injector of
the gas chromatography (M-2 Vespel ferrules may "freeze" onto the chroma-
tograph fittings leading to column breakage). The columns were conditioned
at ambient temperature for 30 minutes followed by a l°C/minute temperature
program up to 210°C and held there overnight.
Apparatus
Kuderna-Danish evaporators were prepared by Lab Glass, Vineland, New
Jersey. Glass chromatography columns were obtained from Supelco, Inc. The
remaining glassware used in the study was ordered from Fisher Scientific and
modified to meet experimental specifications. Gas chromatographic deter-
minations were performed on an HP 5713A gas chromatograph equipped with a
63Ni electron-capture detector and an HP 5720A gas chromatograph equipped
with a flame ionization detector. Chromatograms were recorded on either an
HP 3380A or an HP 3380S recording integrator.
EXPERIMENTAL
This section describes the significant accomplishments and problems
associated with the analytical methodology for the nine Category-3 chlori-
nated hydrocarbons.
Gas Chromatography
A gas chromatography/electron capture method was developed to provide
separation of the nine Category-3 chlorinated hydrocarbons. Table 4 lists
the GC columns evaluated for the analysis of the Category-3 compounds, of
which five were found to be unsuitable. The most frequent problem was the
inability of the column to separate the three dichlorobenzene isomers, espe-
cially the meta- and para-isomers. Column No. 5, the bentone/OV-101 column,
gave an excellent separation of the dichlorobenzenes, but at the column tem-
perature limit would not elute hexachlorobenzene in a reasonable time
period.
The column that provided the best separation was No. 6, 1.8 m long X
2.0 mm ID glass with 1.5% OV-1 and 1.5% OV-225 on 80/100 Gas Chrom Q. The
separation at two packed isothermal conditions is displayed in Figs. 1 and
2. The analysis temperature, retention time, and minimum detection level
(MDL), calculated in an aqueous 1-liter sample and theoretical with model
conditions, for each compound are listed in Table 5. Table 6 lists the GC
conditions for the analysis of the chlorinated hydrocarbon data in Table 5.
The calculated MDL is defined as the component concentration whose output
signal is 10 times the base line noise.
10
-------
TABLE 4. GC COLUMNS EVALUATED FOR CATEGORY 3 BY EC
GC Column No.
1
2
3
4
5
6
Packing
OV-210 + OV-1
DC-200
OV-1
OV-225
Bentone 34 +
OV-101
OV-225 + OV-1
Description
1:1 blend of 3% OV-1 and 3% OV-210 on
80/100 mesh AW-DMCS Chrom G; 1.8 m X
2.0 mm ID glass
5% on 80/100 Chrom W-HP; 1.2 mm X 2.0 mm
ID glass
10% on 80/100 Gas Chrom Q;1.8mmX2.0mm
ID glass
3% on 80/100 Gas Chrom Q; 1.8 m X 2.0 mm
ID glass
5% Bentone 34 and 10% OV-101 on 100/120
Supelcoport 3 m X 2.0 mm glass
1.5% OV-225 and 1.5% OV-1 on 80/100 Gas
Chrom Q; 1.8 m X 2.0 mm ID glass
TABLE 5. GC RETENTION TIMES, ANALYSIS TEMPERATURES AND
'DETECTION LIMITS FOR CATEGORY 3 BY EC
Compounds
MDCB
PDCB
HCE
ODCB
HCBD
TCB
HCCPD
2-CN
HCB
Analysis
Temperature
(°c)
75
75
75
75
75
75
160
160
160
Retention
Time
(min.)
5.30
5.80
6.50
7.20
15.10
16.70
1.60
2.20
11.30
Aqueous Practical MDL
MDL Concentration in H?0
(ug/L)a (yg/L)b (yg/L)c
9.0
18.4
0.4
12.2
1.2
5.8
0.8
15.0
0.6
0.009
0.018
0.0004
0.012
0.001
0.006
0.001
0.015
0.001
0.9
1.8
0.04
1.2
0.1
0.5
0.1
1.5
0.1
Calculated MDL in ug/L (1 \L injection of standard).
Calculated based on sample concentration of 1 liter to 1 ml (1 yL injec-
tion).
cPractical MDL based on IT Enviroscience experience.
11
-------
COLUMN: 1.5% OV-2.25% OV-225 on Supelcoport
TEMPERATURE: 75°
DETECTOR: Electron Capture
B
A. 1,3-DICHLOROBENZENE
B. 1,4-DICHLORCBENZENE
C. HEXACHLORCETHANE
D. 1,2-DICKLORCBENZZN2
2. HEXACHLOR03UTADIZNE
?. 1,2,4-TRICHLOROBEJIZZ:ii
5 10 _ 15
RETENTION TIME-MINUTES
20
Figure 1. Gas Chromatogram of Chlorinated Hydrocarbons
12
-------
:CL'J>ttI: 1.5% OV-1- 2.25% OV-225 on Sucel'-oport:
:EM?ERAT'J?.£ : 15 5 'C
DETZCTCR: Elecrron Capture
B
A. HEXACHLORCCYCLOPENTADIZNZ
3. 2-CHLCRONAPHTHALZNE
C. HEXACHLOROBENZZ2JE
15
RETENTION TIME-MINUTES
Figure 2. Gas Chromatogram of Chlorinated Hydrocarbons
13
-------
TABLE 6. GC CONDITIONS FOR CATEGORY 3 BY EC
Electron Capture Detector Temperature, °C 300
Injector Temperature, °C 250
Oven Temperature, °C . 75 and 160
Carrier Gas 5% Methane/95%
Argon
Carrier Gas Flow Rate, cc/mi'n 30
Duplicated parameters on a 3 m long column did not improve component
separation, but merely increased the analysis time.
During the experiments, five OV-l/OV-225 columns were used, with no
significant differences in the results observed between the columns. The
one major problem encountered was the short one month column service life
when the column was conditioned at temperatures in excess of 220°C.
Response and Linearity
The data on the response and linearity of the compounds at con-
centrations varying by three orders of magnitude for a flame ionization
detector and four orders of magnitude for an electron-capture detector are
presented in tabular form in Tables 7 and 8.
All Category-3 compounds were quite linear over the 10- to 1000-mg/L
range by the FID detector with 2 uL injections. The EC detector was also
evaluated for linearity by injection of 1 \L of a standard with the con-
centrations of the Category-3 compounds ranging from the approximate minimum
detection level (MDL), 0.4 to 339 ug/L, to relatively high levels of 1 to
80 mg/L, depending on the compound. All the category compounds except
hexachloroethane and hexachlorobutadiene were linear over the higher con-
centration, but the area response/unit concentration yields were lower than
those at the lower concentrations. The other two compounds were linear, but
the high concentration standards yielded a greater area response/unit con-
centration.
Resolution
The resolution of the peaks were calculated by the equation
R = 2d/(Wi + W2), (1)
where d = the distance between the two peaks' maxima and W = the width of
the respective triangulated peaks' base-line. The resolution of the two
most adjacent peaks, nv-dichlorobenzene and £-dichlorobenzene, was 0.70. A
value of 1.0 indicated that the peaks had been completely (98%) resolved.
Extraction Studies
The nine chlorinated hydrocarbons were extracted from water at a pH of
2, 7, and 10 with two different solvents. Before the extraction, the water
14
-------
TABLE 7. RESPONSE AND LINEARITY TOR:CATEGORY:3:BY:FID
Compound
MDCB
PDCB
HCE
ODCB
HCBD
Concentration
mg/1
13
129
1290
12
119
1190
9
89
890
13
131
1310
17
168
1680
Average Area
Response
mvsec
10.5
152
1687
12.9
183
1855
13.4
148
1223
19.2
252
2502
15.4
180
1826
Compound
TCB
HCCPD*
2-CN*
HCB*
ALDRIN*
Concentration
mg/1
15
145
1450
49
486
4860
14
141
1410
15
149
1490
28
279
2790
Average Area
Response
mvsec
28.7
386
4043
48.4
594
5779
32.1
345
3272
11.8
118
1134
31.6
353
3521
Column - 1.8m long X 2mm ID glass packed with 1.5% OV-1/1.5% OV-225 on 80/100 mesh Gas chrom Q
with nitrogen carrier gas at 30 mL/min flow rate. Column temperature is 75°C except where *
indicates 160°C. Sample injection size is 2 pL.
-------
TABLE 8. RESPONSE AND:LINEARITY FOR CATEGORY 3 BY ECD
Compound
MDCB
PDCB
HCE
ODCB
HCBD
Concentration
(yg/L)
6.2
31
310
3,100
30,090
16.6
83
830
8,300
83,200
0.4
2
20
200
2,000
12.4
62
620
6,200
62,400
0.6
. 3
30
300
3,300
Average Area
(mm2 X attn.)
37.2
166.6
1,468
9,702.4
76,595.2
66.5
241.7
2,016
13,708.8
104,550.4
77.6
214
2,449.6
37,222.4
419,020.8
74.6
250.8
2,584
17,228.8
148,377.6
58.8
238.6
2,903.2
43,686.4
469,708.8
Average Ht.
(mm X Attn)
13.8
60.5
534.4
3,737.6
31,232
18
73.3
672
4.672
39,424
20.8
70.3
942.4
14,310.4
142,131.2
20.3
76
728
5,120
44,339.2
10
36.3
492
7,577.6
71,168
Concentration
Compound (yg/L)
TCB 5.2
26
260
2,600
26,10
HCCPD* 1
10
100
1,000
2-CN* 39
390
3,900
39,000
HCB* 1.5
15
150
1,500
ALDRIN* 3
30
300
3,000
Average Area
(mm2 X Attn)
128.2
571.7
6,263.2
48,358.4
433,664
36.5
613.6
7,648
80,742.4
128.8
994.4
7,750.4
57,907.2
231.2
2,537.6
30,240
232,140.8
1,070.3
5,648.8
42,214.4
490,086.4
Average Ht.
(mm X Attn)
17.8
77.3
798.4
6,246.4
54,579.2-
40.5
682.4
8,499.2
89,753.6
80.5
686.4
5,536
1,369.6
82.5
890.4
10,080
74,905.6
139
748
6,208
64,792
Column - 1.8m long X 2mm ID glass packed with 1.5% OV-1/1.5% OV-225 on 80/100 mesh gas chrom Q with 5%
methane /95% argon carrier gas at 30mL/min flow rate. Column temperature is 75°C except where
* indicated 160°C. Sample injection size is 1 yL.
L
-------
was buffered by adding 50 ml concentrated buffer solution to 95 ml distilled
deionized water in a 2 liter separatory funnel. The concentration buffer
solutions used are listed in Table 9.
TABLE 9. SOLUTIONS NEEDED FOR PREPARATION OF pH BUFFERS 2, 7. and 10
pH Solution5
2 74.6 g, KC1 + 0.212 L, 1.0 N HC1
7 13.6 g, KH2P04 + 0.059 L, 1.0 N NaOH
10 62.2 g, NaHCOa + 0.35 L, 1.0 N NaOH
10 62.0 g, H3B03 + 0.88 L, 1 N NaOH
aUpon addition, dilute to 1 liter with distilled deionized water.
The pH-10 buffering scheme using 0.88 liter of 1 N^ NaOH and 62 grams of
H3B03 diluted to 1 liter with water proved to be unacceptable due to
impurities and salt formation in the solvent concentrates. The water
samples, after addition of appropriate buffer, were pre-extracted with
100 ml dichloromethane to minimize any remaining impurities in the water.
Each pre-extracted, buffered water sample was injected with 50 uL of a
standard containing approximately 2000 times the calculated MDL (see Table
10). •
A total of 24 samples were spiked, 8 at each pH level. Of the eight sam-
ples at each pH, four were extracted with dichloromethane, and four were
extracted with 15% dichloromethane—85% hexane by volume. Table 10 summarizes
the extraction efficiencies and percent standard deviation of these results.
The pH-2 and pH-10 dichloromethane extractions yielded the best overall
efficiencies, 76.6% and 71.3% respectively; however, the pH-2 extract con-
tained fewer GC/EC responsive impurities; therefore pH 2 was selected as the
extraction pH for this category of compounds.
The extraction data generated thus far were gathered from aqueous sam-
ples with individual component concentrations in the range of 0.2 to 3 ug/L.
Additional data were gathered from another pH-2 dichloromethane extraction,
utilizing aqueous component chlorinated hydrocarbon concentrations in the 2-
to 300 ug/L range. Table 11 summarizes the extraction efficiencies at the
two concentration levels. As seen in that table, the higher level extrac-
tion yielded an overall efficiency of 89.5%, a 12.9% increase over the lower
level extraction.' The standard deviations of the higher concentration
extractions were smaller, indicating that a more reproducible extraction
occurs at the higher levels.
17
-------
TABLE 10. SUMMARY OF EXTRACTION EFFICIENCIES AND
PERCENT STANDARD DEVIATION OF CATEGORY 3
I—«
00
Solvent
pH Type Bufferb
MDCB
PDCB
HCE
ODCB
HCBD
TCB
HCCPD
2-CN
cUpper number is percent recovery.
Blower Number is relative standard deviation.
Interference: results invalid.
HCB
2
2
7
7
10
10
A
B
A
B
A
B
1
1
2
2
3
4
Spike Concentration (yg/L)
74. 5C
7.0dt
77.3
4.3
54.8
5.4
52.6
27.1
84.4
7.0
68.8
6.6
0.88
95.7
9.8
85.4
7.6
68.4
17.4
62.1
15.1
146.66
2.1
88.3
12.9
2.58
82.7
8.3
81.9
1.9
52.4
10.2
53.0
23.2
80.2
13.7
75.6
11.3
0.021
119.3
24.0
89.1
1.9
79.4
31.3
69.2
6.5
273. 8e
2.1
95.8
28.9
1.3
76.4
7.3
80.0
2.5
53.7
11.0
48.0
33.0
91.8
10.2
67.7
14.9
0.06
82.4
7.3
85.7
4.9
63.6
8.6
55.7
23.0
93.0
8.6
72.6
11.3
0.52
36.5
18.8
44.2
8.4
46.7
10.3
45.7
31.8
49.8
21.3
81.0
11.4
0.17
70.2
13.7
76.6
5.6
70.3
4.3
69.7
21.5
80.2
9.8
60.0
8.5
1.62
72.0
18.5
69.0
9.2
85.5
8.3
75.9
17.7
90.8
16.4
85.7
6.7
0.04
aType A:
Type B:
bBuffer
Buffer
Buffer
Buffer
15%
Dichloromethane/85% Hexane
Dichloromethane
No. 1:
No. 2:
No. 3:
No. 4:
HC1/KC1
KH2POA/NaOH
H3B03/NaOH
NaHC04/NaOH
-------
The extraction of the higher concentration aqueous sample yielded an
average efficiency of 89.5%; there was relatively little interference as
less sample concentration was required, and therefore a less sensitive GC
attenuation setting could be used. The results also indicated the less
volatile compounds could be recovered with greater efficiency then the more
volatile ones. At this concentration level, the component extraction effi-
ciency increased with decreasing compound volatility, as would normally be
expected. Finally, the greatest improvement in efficiency was observed in
the least volatile compounds, hexachlorocyclopentadiene, 2-chlorophthalene,
and hexachlorobenzene.
TABLE 11. SUMMARY OF CATEGORY 3 EXTRACTION
EFFICIENCIES AT TWO-CONCENTRATIONS
Compound
MDCB
PDCB
HCE
ODCB
HCBD
TCB
HCCPD
2-CN
HCB
Aq. Cone.
(v9/L)
0.88
2.58
0.021
1.3
0.06
0.52
0.17
1.62
0.04
% Ext..Eff.
77.3
85.4
81.9
89.1
80.0
85.7
44.2
76.6
"69.0
Aq. Cone.
(pg/L)
88
258
2.1
130
6.0
52
17
162
4
% Ext. Eff.
84.6
86.7
87.1
88.1
99.9
91.3
90.2
93.1
96.0
19
-------
Preservation Studies
Twenty-four 1 liter samples were prepared by adding 50 ml of the
appropriate buffer to 950 ml distilled, deionized water. The buffered water
was pre-extracted with 100 ml of MeClo. the solvent decanted, and the water
placed in clean 1-liter bottles. Half the samples were spiked with 2 ml of
a solution containing 660 mg/L of Cl2 in water to yield samples with
1.2 mg/L of Cl2* All the samples were then spiked with 50 yL of a standard
containing approximately 2000 times the minimum detection level of each of
the nine chlorinated hydrocarbons. Half the samples were stored for seven
days at 4°C, and half were stored for seven days at ambient temperature
(23°C). All the samples were kept in the dark for the entire seven day
period.
As shown in Table 12, very low recoveries were obtained under all con-
ditions and many impurity peaks were seen on the chromatograms. The
impurity peaks prevented quantification of almost all the pH-7 samples and
all the pH-2 samples with 1.2 mg/L of Cl2- The very low concentrations,
0.02 to 2.6 yg/L, made efficient recoveries improbable at best. Therefore,
as in the extraction studies, pH-2 aqueous samples without Cl2 were prepared
at 100 times (2 ug/L to 260 ug/L) the level of the previous preservation
samples. The percent loss due to preservation was calculated by subtracting
thj percent recovery obtained from the preservation sample from the extrac-
tion efficiency of the higher concentration extraction (Table 13).
As seen in Table 13, much better recoveries were obtained from the
higher concentration study. At the higher concentration level, the percent
loss due to preservation, for samples stored at ambient temperature, ranged
from two to three times greater than when stored at 4°C. This information
emphasizes the importance of refrigerating samples during shipment and
storage.
An average 9.0% loss occurred in the samples stored at 4°C, which,
although acceptable, demonstrates the importance of analyzing samples soon
after they are taken. A longer term preservation study may be necessary in
order to determine whether long storage periods result in additional loss of
the chlorinated hydrocarbons.
The low level preservation study did determine that samples should be
treated with 70 mg of sodium thiosulfate per liter of wa'ter to remove free
Cl2 from the samples as soon as they are taken, as the sample with free Cl2
shows significantly larger and more numerous interference peaks when ana-
lyzed by GC/EC. Somewhat better recoveries were also obtained at pH 2 than
at pH 10 from the low level samples, indicating that samples should be
adjusted to pH 2 when they are taken.
Solvent Stability
Two standards with 2-propanol and 2-butanone as the solvents were pre-
pared that contained approximately 2000 times the MDL of each of the nine
chlorinated hydrocarbons. To each of the thirty 5 mL ampules was added 3 mL
20
-------
TABLE 12. AVERAGE PERCENT LOSS:DUE TO PRESERVATION:
pH
2
2
7
7
10
10
10
10
C19 Cone
(ing/L)
0
0
1.2
1.2
1.2
1.2
0
0
Temp
(°C)
Amb.
4
Amb.
4
Amb.
4
Amb.
4
*
Key
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
Spike Concentration
(yg/L)
MDCB
77.3
23.1
54.2
77.3
25.3
52.0
52.6
52.6
68.8
20.2
48.6
68.8
13.9
54.9
68.8
15.4
53.4
68.8
11.0
57.8
0.88
PDCB
85.4
26.9
58.5
85.4
30.7
54.7
62.1
62.1
88.3
22.3
66 '.0
88.3
15.3
73.0
88.3
16.3
72.0
88.3
10.3
78.0
2.58
HCE
81.9
11.3
70.6
81.9
10.8
71.1
53.0
53.0
75.6
31.1
44.5
75.6
25.0
50.6
75.6
26.4
49.2
75.6
21.8
53.8
0.021
ODCB
89.1
27.1
62.1
89.1
32.5
56.6
69.2
69.2
95.8
26.8
69.0
95.8
17.8
78.0
95.8
20.2
75.6
95.8
17.3
78.5
1.3
HCBD
80.0
2.5
77.5
80.0
3.8
76.2
48.0
48.0
67.7
26.0
41.7
67.7
23.0
44.7
67.7
24.6
43.1
67.7
15.7
52.0
0.06
TCB
85.7
20.7
65.0
85.7
27.0
58.7
55.7
55.7
72.6
24.8
47.8
72.6
19.3
53.3
72.6
16.1
56.5
72.6
7.3
65.3
0.052
HCCPD
44.2
7.5
36.7
44.2
10.9
33.3
45.7
22.7
23.0
45.7
7.4
38.3
81.0
14.5
66.5
81.0
5.0
76.0
81.0
9.5
71.5
81.0
2.7
78.3
0.17
2-CN HCB
76.6 69.0
32.9 66.6
43.7 2.4
76.6 69.0
40.1 46.6
36.5 22.4
69.7 75.9
51.1 34.3
18.6 41.6
69.7 75.9
50.6 34.1
19.1 41.8
60.0 85.7
41.4 46.5
18.6 39.2
60.0 85.7
36.4 22.1
23.6 63.6
60.0 85.7
21.8 38.6
38.2 47.1
60.0 85.7
10.4 16.7
49.6 69.0
1.62 0.04
*
A =
B =
C =
Percent
Recovery
Loss due
extraction efficiency
after seven days
to preservation
-------
TABLE 13. AVERAGE PERCENT LOSS AT TWO CONCENTRATIONS
DUE TO PRESERVATION AT pH^2:WITHOUT :C12
fo
ro
Rel. Cone. Temp
(yg/L) ( C)
1
100
4
Amb.
4
Amb.
Key*
A
B
C
A
B
C
A .
B
C
A
B
C
MDCB
77.5
25.3
52.0
77.3
23.1
54.2
84.6
78.6
6.0
84.6
69.5
15.1
PDCB
85.4
30.7
54.7
85.4
26.9
58.5
86.7
81.7
5.0
86.7
73.2
13.5
HCE
81.9
10.8
71.1
81.9
11.3
70.6
87.1
69.7
17.4
87.1
'54.9
32.2
ODCB
89.1
32.5
56.6
89.1
32.5
56.6
88.1
84.6
3.5
88.1
76.1
12.0
HCBD
80.0
3.8
76.2
80.0
2.5
77.5
88.8
71.3
17.5
88.8
46.5
42.3::
TCB
85.7
27.0
58.7
85.7
20.7
65.0
91.3
87.5
3.8
91.3
77.3
13.0
HCCPD
44.2
10.9
33.3
44.2
7.5
36.7
90.2
72.0
18.2
90.2
53.0
37.2
2-CN
76.6
40.1
36.5
76.6
32.9
43.7
93.1
90.8
2.3
93.1
84.4
8.7
HCB
69.0
46.6
22.4
69.0
66.6
2.4
96.0
88.4
7.6
96.0
67.1
28.9
*
Type A:
Type B:
Type C:
Percent
Recovery
Loss due
extraction efficiency
after seven days
to preservation
-------
TABLE 14. AVERAGE PERCENT CHANGE OF CATEGORY 3 IN-2-PROPANOL
Compound
MDCB
PDCB
HCE
ODCB
HCBD
TCB
HCCPD
2-CN
HCB
Day 0
+ 1.7
+ 1.0
0
0
+ 5.0
+ 3.9
-14.8
+ 4.0
- 0.8
Day 30
+ 4.5
+23.3*
+13.3
+13.8
+ 8.5
+19.4
-63.9
-15.5
+29.1
Day 60
-38.0*
- 1.4
-31.0
-17.8
-70.3*
+15.1
-72.6
+24.2
-46.5*
Day 90
- 2.7
- 1.1
-32.6
+ 6.6
-29.4
+ 6.3
-85.1
+7.2
-12.6
It
Variation in data possibly due to an error in standard preparation.
TABLE 15. AVERAGE PERCENT CHANGE OF CATEGORY 3 IN 2-BUTANONE
Compound
MDCB
PDCB
HCE
ODCB
HCBD
TCB
HCCPD
2-CN
HCB
Day 0
- 3.5
- 3.3
-10.1
- 8.9
- 7.6
- 4.0
- 0.3
+ 0.3
- 0.8
Day 30
- 4.0
+14.0
+10.1
+11.1
+13.6
+ 6.7
-25.3
+16.4
+ 2.8
Day 60
+ 8.5
+ 2.4
+ 7.3
+ 2.8
+ 1.7
+ 3.4
-30.3
+ 2.4
-54.6*
Day 90
- 4.0
- 5.0
- 2.4
-17.3
- 6.8
- 4.9
-62.8
+ 4.3
+ 4.5
*
Variation in data possibly due to an error in standard preparation.
23
-------
of the 2-propanol standard; 30 other ampules were similarly filled with the
2-butanone standard. The ampules were then cooled to 4°C to minimize the
possibility of vapor ignition, flame sealed, placed in open test tube racks,
and stored on a bench top under normal laboratory lighting conditions
(fluorescence) for the duration of the study. Three ampules of each stan-
dard were opened immediately after they were flame sealed and were analyzed
versus the standards used to fill the ampules. On subsequent 30 day inter-
vals, up to 90 days, three ampules of each standard were opened and analyzed
versus a freshly prepared standard in the same solvent. Tables 14 and 15
summarize the solvent stability of the Category-3 chlorinated hydrocarbons.
Table 14 demonstrates that 2-propanol is unsuitable as a solvent for the
chlorinated hydrocarbons. The variability in the data cannot be due to
experimental technique, particularly in view of the significantly lower
level of variability found in the 2-butanone samples (Table 15). It is evi-
dent from a comparison of Tables 14 and 15 that 2-butanone is the superior
solvent for preparing and storing chlorinated hydrocarbon standards. All
component concentrations except two remained within ±7%.of the original con-
centrations after 90 days.
Hexachlorocyclopentadiene (HCCPD) concentrations decreased so rapidly in
both solvent systems that a separate stability study had to be made to
define the cause of its high decomposition rate.
Table 16 illustrates that the decomposition of HCCPO occurred even in
the absence of the other category compounds, indicating that the decom-
position is not affected by them. Since the HCCPD priority-pollutant stan-
dard was prepared and shipped in dichloromethane, an additional stability
study was performed that yielded a decomposition similar to that previously
noted. In this study the HCCPD stock solution in dichloromethane was stored
in ampules after being flame sealed and in 20 ml glass scintillation vials
having Teflon lined caps. The later storage scheme was incorporated as a
control related to HCCPD losses due to the flame sealing process. The
results are given in Table 17.
TABLE 16. AVERAGE PERCENT CHANGE OF HEXACHLOROCYCLO-
PENTADIENE IN 2-PROPANOL AND 2-BUTANONE
Day 0 3 10 36
2-Propanol +0.9 -9.8 -27.1 -63.4
2-Butanone +1.2 -5.6 -18.0 -23.6
24
-------
TABLE 17. AVERAGE PERCENT CHANGE OF
HEXACHLOROCYCLOPENTADIENE IN DICHLOROMETHANE
Day 0 3 10 30 45
Flame Sealed Ampul
Scintillation Vial
-2.48
0.00
-9.2
-2.2
-9.04
-13.83
-38.01
-10.66
-66.87
-23.92
The other significant concentration change occurred with ^-dichloro-
benzene, which, although essentially unchanged at day 60, decreased by 17.3%
by day 90. Subsequent analysis, versus a fresh standard, on day 150 yielded
a change of -30.3% which confirmed a decrease in concentration over time.
The results of this study indicated that except for hexachlorocyclopen-
tadiene a standard containing all the Category-3 compounds could be prepared
in 2-butanone and stored in the presence of fluorescent light at room tem-
perature for 60 days with a maximum change in any compound of less than nine
percent. Refrigeration of the standards would undoubtedly increase their
usable life. The change in hexachlorocyclopentadiene concentration
discussed above indicates that standards containing this compound should be
freshly prepared as needed.
Clean Up Studies
Initial clean up experiments involved the evaluation of both Florisil
and aluminia as possible vehicles for sample extract clean up.
Florisil clean up experiments were accomplished using columns prepared
by placing 12 grams of Florisil (activated at 130°C and corrected for 1 auric
acid value) into a 300 mm long X 10 mm ID chromatographic column. After the
Florisil was settled, with gentle tapping, approximately 1 gram of anhydrous
granular sodium sulfate was added to the top. The column was then pre-
eluted with 100 ml of petroleum ether after which a 10 ml aliquot of hexane,
containing the compounds of interest at approximately 1000 times the calcu-
lated MDL (Table 5), was quantitatively transferred into the column. The
column was then eluted using in order: 200 ml petroleum ether, 200 ml 6%
ethyl ether in petroleum ether, 200 mL 15% ethyl ether in petroleum ether,
200 ml 50% ethyl ether in petroleum ether, and 200 ml of ethyl ether. Each
of the eluates were collected and analyzed after being concentrated to 10 ml
using Kuderna-Danish evaporators. The major portion of each of the com-
pounds of interest were eluted in the single 200 ml petroleum ether eluate.
Recovery data are given in Table 18.
25
-------
TABLE 18. AVERAGE PERCENT RECOVERY OF
CATEGORY 3 AFTER FLORISIL CLEAN UP
First Fraction
(200 ml petroleum ether)
Compound Percent Recovery
MDCB 87
PDCB 89
HCE 85
ODCB 90
HCBD 89
TCB 94
HCCPD 100
2-CN 100
HCB 95
Aluminia clean up experiments were accomplished using columns prepared
by placing 12 grams of alumina (activated at 400°C) into a 300 mm long X
10 mm ID chromatographic column. After the alumina was settled with gentle
tapping, approximately 1 gram of anhydrous granular sodium sulfate was added
to the top. The column was then pre-eluted with 150 ml of pesticide grade
hexane after which a 10 mL aliquot of hexane, containing the compounds of
interest at approximately 1000 times the calculated MDL (Table 5), was quan-
titatively transferred into the column. The column was then eluted using
three successive 50 ml hexane eluates. The combined first two eluates'
(100 ml) recovery data are given in Table 19.
TABLE 19. AVERAGE PERCENT RECOVERY OF
CATEGORY 3 AFTER ALUMINA CLEAN UP
100 mL Hexane Fraction
Compound Percent Recovery
MDCB 101
PDCB 105
HCE 75
ODCB 88
HCBD 77
TCB 99
HCCPD 100
2-CN 92
HCB 93
The results of these experiments (Tables 18 and 19) indicated that the
recovery of the Category-3 chlorinated hydrocarbons is quite similar using
either Florisil or alumina columns.
26
-------
Florist! was selected as the separation vehicle for the wastewater
application because it is commonly used in most laboratories for the clean
up of pesticides and because all the components are eluted in a single
eluent of 200 ml of petroleum ether. Although not used in this study, alu-
mina stands as an acceptable alternative to Florisil.
Wastewater Application
In this section the practical use of the described methodology is
discussed as it relates to an environmental sample. Four Category-3
wastewater samples were analyzed by the methodology developed in this study.
Upon the initial analysis of the first wastewater sample, the need for a
clean up scheme was evident from the increased number of interferences indi-
cated. The four wastewater samples were analyzed to evaluate the method.
The background concentrations of the compounds of interest and the
wastewater sample descriptions are listed in Table 20.
In subsequent analyses, the precision and accuracy of the method were
developed based on a spiked distilled deionized water sample and a spiked
wastewater sample (Plastic's Industry, 15-C1-05-44) determined to be "worst
case" because it had the greatest number of interferences before clean up.
Both of these samples were analyzed after being carried through the complete
Florisil clean up scheme (Figs. 3 through 6). See analytical method,
Appendix A.
Accuracy was based on percent recovery determined from the analysis of
distilled deionized water and wastewater sample (Plastic's Industry,
15-C1-05-44) both of which were spiked with the compounds of interest.
These two samples were analyzed using triplicate extractions of each and
triplicate injections-of each extract. Both mean recoveries and mean con-
centrations along with standard deviation were calculated using the
critical-T analysis to discard outliers. The accuracy data and method pre-
cision determined from the analysis of the two samples are displayed in
Tables 21 through 24,
In conclusion, when applied to wastewater samples, the method was
demonstrated to be an acceptable reproducible and workable means by which
quantitative data for industrial and municipal effluents can be gathered.
27
-------
TABLE 20. RESULTS FROM ANALYSIS OF
WASTEWATER APPLICATION SAMPLES3
Sample Number*3
AC
B
C
D
MDCB
ND
26
8
ND
PDCB
ND
120
4
ND
HCE
ND
d
ND
ND
ODCB
ND
.76
13
ND
HCBD
ND
1.9
ND
ND
TCB
ND
1.0
2.5
ND
HCCPD
ND
0.99
0.30
ND
2-CN
ND
ND
ND
ND
HCB
ND
0.35
ND
ND
Concentration expressed in wg/L without correction for recovey data.
&A. "Effluent from a Plastics Industry Wastewater Treatment Plant,"
received from S. Bernotas, 8/24/78.
B. "Plastics Industry" (15-05-C1-44; Final Effluent Grab), received
from R. Libby, 9/05/78.
C. "Municipal Wastewater - Knoxville Third Creek Station."
D. "Final Effluent Grab - 12/12/78," received from Midwest Research
Institute, Houston, TX, 12/14/78.
canalysis performed after Florisil clean up.
dnot quantifiable (HCE peak not resolved from PDCB peak).
TABLE 21. METHOD ACCURACY EXPRESSED AS PERCENT
RECOVERY BASED ON SPIKED. DISTILLED. DEIONIZED WATER
Sample
1
2
3
X
s
Spike con-
centration
(ug/L)
MDCB
82
77
63
74
9.8
0.90
PDCB
72
72
70
71
1.1
2.6
HCE
75
75
75
75
0.0
0.04
ODCB
76
83
81
80
3.5
1.3
HCBD
72
73
61
69
3.6
0.06
TCB
96
89
78
88
6.7
0.52
HCCPD
60
60
57
59
9.1
0.12
2-CN
90
94
89
91
1.7
1.6
HCB
63
65
67
65
2.6
0.21
X.= Mean percent recovery
s = Standard deviation of percent mean recovery
28
-------
COLUMN: 1.5% OV-1+ 1.5% OV-225 On Gas Chrom Q
TEMPERATURE: 75°C
DETECTOR: Electron Capture
12
lo
Figure 3.
RETENTION TIME-MINUTES
Gas Chromatogram of Wastewater (15-C1-05-44) Extract
After Clean Up
29
-------
COLUMN: 1.5% OV-1+ 1.5% OV-225 On Gas Chrom Q
TEMPERATURE: 75°C
DETECTOR: Electron Capture
4 8 12
RETENTION TIME-MINUTES
16
20
Figure 4. Gas Chromatogram of Spiked Wastewater (15-C1-05-44) Extract
After Clean Up
30
-------
u>
I COLUMNi. 1.5% OV-1+ 1.5% OV-225 On Gas
Chrom Q
TEMPERATURE: 160 °C
DETECTOR: Electron Capture
COLUMN:
TEMPERATURE: 160"C
I DETECTORi Electron Capture
1.5* OV-1 + 1.0% OV-225
On Gas Chicun Q
4 B 12
RETENTION TIME-MINUTES
16
Figure 5. Gas Chromatogram of Wastewater
(15-C1-05-44) Extract After Clean Up
I 1 , ^ r~
0 4 8 12 K.
RETENTION TIME-MINUTES
Figure 6. Gas Chromatogram of Spiked
Wastewater (15-C1-05-44) Extract
After Clean Up
-------
TABLE 22. METHOD PRECISION EXPRESSED AS CONCENTRATION (yg/L)
BASED ON SPIKED, DISTILLED. DEIONIZED WATER
Sample MDCB
PDCB
HCE
ODCB HCBD TCB HCCPD 2-CN HCB
1
2
3a
x
x*
Sc
0.74
0.69
0.57
0.90
0.67
0.09
1.
1.
1.
2.
1.
0.
87
87
82
6
85
03
0.
0.
0.
0.
0.
0.
030
034
033
04
032
002
0.99
1.09
1.06
1.30
1.05
0.05
0.043
0.044
0.037
0.06
0.041
0.004
0.50
0.50
0.41
0.52
0.47
0.05
0.12
0.12
0.11
0.12
0.12
0.006
1.44
1.50
1.42
1.6
1.45
0.04
0.13
0.13
0.13
0.21
0.13
0.0
x = Concentration of spike added to the 1 liter sample.
x = Mean concentration recovered.
CS = Standard deviation of the mean concentration.
Results based on triplicate injection of each sample.
TABLE 23. METHOD ACCURACY EXPRESSED AS PERCENT RECOVERY BASED ON A
SPIKED, INDUSTRIAL, WASTEWATER SAMPLE
PLASTIC'S INDUSTRY. 15-C1-05-44)
Sample
MDCB
PDCB
HCE ODCB HCBD TCB HCCPD 2-CN HCB
1
2
3
x
S
True con-
centration
(yg/L)
75
103
107
95
17
27
79
105
110
98
17
120
a 76
a 104
a 114
98
20
78
50
135
91
92
43
2.0
66
96
93
85 .
17
1.5
111
84
169b
97
19
1.2
62 73
45. 53.
131b 158b
53 63
12 14
1.6 0.55
x = Mean percent recovery.
S = Standard deviation of percent recovery.
aNot quantifiable (HCE peak not resolved from PDCB peak),
Rejected by critical T value test.
32
-------
TABLE 24. METHOD PRECISION EXPRESSED AS
CONCENTRATION (yg/L) BASED ON A SPIKED, WASTEWATER SAMPLE
(PLASTIC'S INDUSTRY, 15-C1-05-44)
Sample
1
. 2
3 a
C a
Cl
Cc
X
se
MDCB
20.
27.
28.
26.
0.
27.
25.
4.
20
85
95
11
90
01
67
8
PDCB
95.
126.
132.
117.
2.
120.
118.
20.
11
56
62
89
60
40
10
1
HCE
f
f
f
f
0.04
—
-
-
ODCB
59.25
80.94
88.30
76.22
1.30
77.52
76.16
15.1
HCBD
0.99
2.64
1.79
1.90
0.06
1.96
1.81
0.83
TCB
1.01
1.47
1.43
1.01
0.52
1.53
1.30
0.25
HCCPD
1.32
1.00
2.01
0.99
0.20
1.19
1.44
0.52
2-CN
0.99
0.72
2.09
ND
1.60
1.60
1.27
0.73
HCB
0.40
0.29
0.87
0.35
0.20
0.55
0.52
0.31
aC0 = Concentration of the unspiked sample in yg/L.
u £
C, = Concentration of the spike added to the sample in yg/L.
CC = Concentration of the spiked sample.
X = Mean concentration of spiked sample recovered.
eS = Mean standard deviation.
fNot quantifiable. (HCE peak not resolved from PDCB peak).
Results based on triplicate injection of each sample.
33
-------
SECTION 5
SUPPLEMENTAL SEVEN DAY PRESERVATION STUDY - CATEGORY 3
INTRODUCTION
In the development and application of this test procedure, IT
Enviroscience carried out preservation studies under different conditions
for the subject compounds in clean distilled water only. The purpose of
this brief study was to carry out a seven day preservation study of the sub-
ject compounds spiked into a real world wastewater following the preser-
vation techniques outlined in the resultant EPA Method 612 - Chlorinated
Hydrocarbons (Appendix A).
EXPERIMENTAL
The wastewater selected for use in this study was a fresh sample of
effluent wastewater from a Class B refinery producing gasoline, kerosene,
jet fuel, heating oil, heavy fuels, and LPG. The wastewater treatment
system consists of API oil/water separators, rapid sand filters, equaliza-
tion tank, rotating biological contactors, and final clarifiers. Total flow
from the plant is 3 to 4 MGD.
The pH of eight 1 liter samples was checked and found to be 6.5, which
is within the 6 to 8 range that samples should be adjusted to for preser-
vation, so no pH adjustment was necessary. Six of the eight sample bottles
were each spiked with the subject compounds at concentrations ranging from
13 to 300 ug/L.
The bottles were mixed for 15 minutes, and three of the spiked sample
bottles and one unspiked sample blank were analyzed following EPA
Method 612. The remaining bottles were refrigerated for seven days at 4°C
and then analyzed by the sample procedures. The results appear as Day 0 and
Day 7 in Table 25.
DISCUSSION
The results presented in Table 25 represent the mean values from three
spiked samples run on Day 0 and Day 7. The Day 0 recovery data are similar
to spiked wastewater recovery data presented in Section 4 of this report
with hexachloroethane and 1,2,4-trichlorobenzene having lower recoveries
than previously. The Day 7 data show that the maximum loss after seven days
was 52% for l,2,4trichlorobenzene and the minimum loss was 9% for hexach-
lorobutadiene. Overall, these losses are less than the previous data indi-
cated.
34
-------
TABLE 25. SEVEN DAY PRESERVATION3 STUDY OF CHLORINATED
HYDROCARBONS IN WASTEWATER
Mean Concentration
(ng/L)
Compound
MDCB
PDCB
HCE
ODCB
HCBD
TCB
2-CN
HCB
Spike Level
(yg/L)
204
288
12.8
298
31.2
188
268
14.9
Day 0
92.0 .
261
5.2
227
24.0
78.2
241
10.2
Day 7
57.8
192
3.0
167
21.8
37.0
163
6.2
Mean % Recovery
Day 0
45 '
91
41
76
77
42
90
69
Day 7
28
67
23
56
70
20
61
42
Preservation technique outlined in EPA Method 612.
Results based on triplicate sample analysis.
35
-------
SECTION 6
DEVELOPMENT OF METHOD DETECTION LIMITS
a
INTRODUCTION
A study was performed to determine method detection limits (MDL) for the
chlorinated hydrocarbons. Previous practice was to determine the detection
limits by either estimation or by calculation based on a specific con-
centration giving a signal equivalent to a specific signal/noise ratio. A
detection limit determined by these previously employed techniques may not
be achievable for the compounds of interest in either laboratory prepared
water or matrices encountered in environmental samples.
The EPA developed a method to determine the MDL, defined as the minimum
concentration of a substance that can be measured and reported with 99% con-
fidence that the value is greater than zero. Three sample matrices were
used in this study for the MDL determination. Based on the MDL, determined
in this study, analytical curves were established for each of the eight
chlorinated hydrocarbons in interference-free water.
EXPERIMENTAL
The MDL was determined for the chlorinated hydrocarbons in interference-
free water and two industrial wastewaters. Seven separate replicate spiked
samples were prepared for each of the three matrices. Spiking levels were
based on experience and instrumental limitations.
All dosed samples were analyzed by the test method developed during the
research program and described earlier in this report as well as in
Appendix A.
Based on the MDL in interference-free water, duplicate aliquots of
interference-free water were spiked at 4, 7, 10, 100, and"1000 times the
concentration level of the established MDL for each of the eight chlorinated
hydrocarbons. The results were used to establish analytical curves.
RESULTS
Method Detection Limits — Interference-Free Water
Table 26 lists data for the chlorinated hydrocarbons recovered from the
seven separate replicate spiked aliquots of interference-free water.
Included are the spike values, average recovered values, standard
deviations, MDL values, and ratios of spike to MDL values for each
chlorinated hydrocarbon.
36
-------
TABLE 26. MDL OF CHLORINATED HYDROCARBONS-IN-INTERFERENCE-FREE-PATER
CO
Sample No.
1 '
2
3
4
5
6
7
Method MDL Data
Spiked Value (yg/L)
Average Recovered
(pg/L) (n=7)
Standard Deviation /
MDL = 3.143 X
Standard Deviation
Ratio > Spike/MDL
MD'CB
5.76
7.03
6.32
6.57
6.49
6.37
6.29
6.34
6.40
.378
1.19
5
PDCB
5.33
6.75
5.90
6.19
6.08
6.01
5.82
6.06
6.01
.426
1.34
5
HCE
.024
.032
.035
.027
.047
.050
.036
.043
.027
.0097
.03
1
ODCE
6.75
7.56
7.20
7.50
7.32
7.25
7.17
6.26
7.20
.364
1.14
5 ..
HCBD
.016
.021
.036
.019
.040
.042
.036
.039
.030
.0112
.03
: : 1
TCB
.177
.180
.184
.157
.204
.206
.173
.198
.183
.017
.05
4
2-CN
3.23
3.74
3.23
3.68
4.00
3.77
3.36
3.88
3.57
.300
.94
4
HCB
.182
.216
.205
.210
.228
.208
.187
.206
.205
.016
.05
4
All concentrations are actual recovered values of yg/L based on water.
-------
The Analytical Curve — Interference-Free Water
Duplicates of five one-liter samples of deionized/distilled water were
each spiked with specific concentrations of the eight chlorinated hydrocar-
bons. These specific concentrations represented 4, 7, 10, 100, and 1000
times the MDL. The concentrations are listed in Table 27.
TABLE 27. CONCENTRATION OF CHLORINATED HYDROCARBONS IN WATER
Compound
4 X MDL
7 X MDL
10 X MDL 100 X MDL
Concentration units - ug/L
1000 X MDL
MDCB
PDCB
HCE
ODCB
HCBD
TCB
2-CN
HCB
4.78
5.35
0.12
0.59
0.14
0.22
3.75
0.20
8.36
9.37
0.21
8.04
0.24
0.39
6.57
0.35
11.9
13.4
0.30
11.5
0.34
0.56
9.38
0.50
119
134
2.99
115
3.41
5.60
93.8
5.04
1190
1340
29.9
1150
34.1
56.0
938
50.4
Some of the sample extracts, representing samples that were prepared at
4, 7, 10, 100, and 1000 times the MDL, had to be diluted before analysis,
because of the limited linear response range for electron capture detectors.
For this reason, the analytical curve data can only be displayed as con-
centration spiked versus concentration recovered. The data are summarized
in Tables 28-30.
Method Detection Limit - Industrial Wastewaters
The original spiking level in each of the two industrial wastewaters was
determined from a combination of the results obtained for the MDL in
interference-free water and the background analysis of the unspiked waste-
waters. Tables 31 and 32 list the actual recovery values from the seven
separate replicate spiked aliquots of industrial wastewater Codes COD-B and
DCA-A along with spike values, average recovered values, the standard
deviations, MDL values, and ratios of spike to MDL values.
DISCUSSION
The method detection limits determined for deionized/distilled water
compare favorably with these labeled "Practical MDL" reported in Table 5.
Excluding the set of data points representing 1000 X MDL, the analytical
curves for the chlorinated hydrocarbons in inteference-free water are
linear. The recovery of all eight chlorinated hydrocarbons was lower at the
concentration representing 1000 X the MDL. The reason for the low recovery
at this concentration is unknown. The linearity of the electron capture
38
-------
TABLE 28. ANALYTICAL CURVE DATA FOR 1,3-DICHLOROBENZENE,
1,4-DICHLOROBENZENE. AND HEXACHLOROETHANE:IN:INTERFERENCE-FREE WATER
1,3-Dichlorobenzene
Spi ke
yg/L
4.78
4.78
8.36
8.36
11.9
11.9
119
119
1190
1190
Recovered
yg/L
4.27
4.42
7.31
7.12
11.2
12.2
103
108
946
848
%
Recovery
89
92
87
85
94
102
86
90
79
71
1,
Spike
yg/L
5.35
5.35
9.37
9.37
13.4
13.4
134
134
1340
1340
4-Dichlorobenzene
Recovered
yg/L
4.86
4.96
8.28
8.26
11.5
14.2
121
126
1120
1020
%
Recovery
91
. 93
88
• 88
86
106
91
94
84
76 : ' : :
Hexachloroethane
Spike
yg/L
0.12
0.12
0.21
0.21
0.30
0.30
2.99
2.99
29.9
:29.9
Recovered
yg/L
.09
.10
.18
.18
.29
.32
2.46
2.62
19.8
16.0
%
Recovery
75
83
87
87
97
107
82
88
66
54
-------
TABLE 29. ANALYTICAL CURVE DATA FOR 1,2-DICHLOROBENZENE,
HEXACHLOROBUTADIENE. AND 1.2,4^TRICHLOROBENZENE IN:INTERFERENCE-FREE WATER
1 ,2-Dichlorobenzene
Spi ke
yg/L
4.59
4.59
8.04
8.04
11.5
11.5
115
115
1150
1150
Recovered
yg/L
4.38
4.54
7.31
7.69
14.6
14.5
112
119
1010
927
%
Recovery
95
99
97
103
127
126
97
103
88
81
Hexachlorobutadiene
Spike
yg/L
0.14
0.14
0.24
0.24
0.34
0.34
3.41
3.41
34.1
34.1
Recovered
yg/L
.09
.10
.19
.16
.33
.34
2.57
2.83
17.0
15.1
%
Recovery
68
73
77
69
96
100
75
83
50
44 :
1,2,
Spike
yg/L
0.22
0.22
0.39
0.39
0.56
0.56
5.60
5.60
56.0
:56.0
4-Trichlorobenzene
Recovered
yg/L
.22
.24
.36
.41
.55
.62
5.22
5.77
43.4
37.5
%
Recovery
97
107
92
106
98
111
93
103
77
67
-------
TABLE 30. ANALYTICAL CURVE DATA FOR
2-CHLORONAPHTHALENE AND:HEXACHLOROBENZENE IN INTERFERENCE^FREE WATER
2-Chl oronaphthal ene
Soike
ug/L
3.75
3.75
6.57
6.57
9.38
9.38
93.8
93.8
938
938
Recovered
P9/L
3.14
3.84
6.37
6.55
9.34
11.3
95.9
99.2
753
725
%
Recovery
84
102
97
100
100
121
102
106
80
77
Hexachlorbbeiizehe
Spike
yg/L
0.20
0.20
0.35
0.35
0.50
0.50
5.04
5.04
50.4
50.4
Recovered
ug/L
.17
.19
.35
.40
.49
.69
6:16
6.34
45.5
35.7
%
Recovery
83
94
98
114
97
136
122
126
90
71
-------
TABLE 31. MDL:OF CHLORINATED HYDROCARBONS:IN:WASTEWATER CODE-COD-B
ro
Sample No.
1
2
3
4
5
6
7
Method MDL Data
Spiked Value (yg/L)
Average Recovered
(yg/L) (n=7)
Standard Deviation
MDL = 3.143 X
Standard Deviation
Ratio = Spike/MDL
MDCB
7.26
11.85
11.13
11.03
10.71
11.73
12.26
11.94
10.85
1.67
5.26
2
PDCB
8.24
14.11
12.81
12.52
12.14
13.37
13.84
13.38
12.43
1.98
6.22
2
HCE
.166
.280
.277
.278
.275
.276
.298
.299
.207
.044
.138
2
ODCD
10.01
12.19
14.86
13.45
11.20
12.38
12.45
11.48
11.55
1.55
4.86
2
HCBD
.050
.208
.247
.221
.169
.145
.172
.341
.174
.064
.220
.:.... 2 .
TCB
.340
.618
.711
.527
.564
.591
.592
.560
.563
.114
.357
2
2-CN
7.29
8.55
9.39
7.79
9.17
8.57
8.54
9.38
8.47
.732
2.30
4
HCB
.314
.505
.602
.488
.488
.527
.532
.504
.494
.088
.278
2
All concentrations are actual recovered values of yg/L based on water.
-------
TABLE 32 . MDL . OF CHLORINATED HYDROCARBONS : IN .: WASTEWATER CODE-DCA-A
Sample No.
1
2
3
4
5
6
7
Method MDL Data
Spiked Value (yg/L)
Average Recovered
(yg/L) (n=7)
Standard Deviation
MDL = 3.143 X
Standard Deviation
Ratio- Spike/MDL :
MDCB
10.98
10.75
9.53
9.58
8.92
8.76
8.62
11.94
9.59
.946
2.97
4
PDCB
11.92
9.69
10.79
10.81
10.04
9.92
9.80
\
\
13.38
10.42
.799
2.51
5
HCE
.219
.170
.211
.203
.187
.189
.163
.299
.192
.021
.065
5
ODCB
11.47
9.80
10.24
11.58
10.92
9.00
9.18
11.48
10.31
1.05
3.29
4 .::
HCBD
.208
.157
.211
.132
.187
.171
.136
.341
.172
.032
.100
3
TCB
.566
.429
.459
.438
.433
.371
.401
.560
.443
.062
.193
3
2-CN
i — i
3
ft-
n>
-$
-*>
n>
-j
n>
3
o
CD
HH
3
-h
rt>
-1
n>
3
0
n>
HCB
.367
.374
.305
.464
.386
.341
.266
.504
.358
.063
.198
3
All concentrations are actual recovered values of yg/L based on water.
-------
detector was not the cause, since the extract, representing the sample set
prepared at 1000 X the MDL, was diluted to the same "as injected concentra-
tion" as the extract representing 100 X the MDL.
The method detection limits determined for industrial wastewater Code
COO-B were approximately five times greater than those found for
interference-free water. The MDLs in industrial wastewater Code DCA-A were
approximately two times greater than in deionized/distilled water. The mean
recoveries, for each of the chlorinated hydrocarbons, were higher in
industrial wastewater Code COD-B than in wastewater Code DCA-A. Even though
the spiking levels were the same in both industrial wastewaters, the average
standard deviation was greater in wastewater Code COD-B than in wastewater
Co'de DCA-A.
CONCLUSIONS AND RECOMMENDATIONS
The EPA method of determining the MDL appears to be satisfactory.
However, the analyst should develop MDL, recovery, and precision data on the
water type of concern.
The probability exists that in some cases MDLs lower than those deter-
mined in this study could be achieved. Some of the extraneous factors
affecting the MDL determination are:
1. Lack of baseline separation - related to single versus
multiple component solutions
2. "One of a kind" column
3. Peak broadening
4. Percent recovery
5. Analysis
Not all of the chlorinated hydrocarbons have baseline resolution from
each other, therefore for compounds such as 1,3-DCB, 1,4-DCB, HCE, 1,2-DCB,
HCBD, and 1,2,4-TCB a lower MDL might be achieved in a single component
solution rather than in a mixture as used during this study. The degree of
baseline spearation for these compounds in a mixture could vary from column
to column.
Compounds such as HCBD, TCB, and HCB have less instrumental sensitivity
due to peak broadening. If the analyst was only determining a single com-
pound such as TCB, and interferences allowed a greater GC column tem-
perature, a lower MDL probably could be achieved.
During this type of study an analyst could make an estimate for a MDL,
based on a signal to noise ratio only, and determine a MDL (3.143 X S) that
was derived from extracts representing a drastic reduction in the normal
percent recovery for that specific compound. This concentration level could
be below the method analytical curve break point without the analyst knowing
it during the MDL determination. This type of phenomenon could occur due to
a decrease in extraction efficiency, absorption, and other factors such as
adsorption.
44
-------
SECTION 7
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50
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APPENDIX A
CHLORINATED HYDROCARBONS: ANALYTICAL METHOD 612
1. Scope and Application
1.1 This method covers the determination of certain chlorinated
hydrocarbons. The following parameters may be determined by this
method:
Parameter STORET No.
Hexachlorocyclopentadiene 34386
Hexachlorobenzene 39700
Hexachlorobutadiene 34391
Hexachloroethane 34396
1,2-Dichlorobenzene ' 34536
1,2,4-Trichlorobenzene 34551
1,3-Dichlorobenzene 34566
1,4-Dichlorobenzene 34571
2-Chloronapthalene 34581
1.2 This method is applicable to the determination of these compounds
in municipal and industrial discharges. It is designed to be
used to meet the monitoring requirements of the National
Pollutant Discharge Elimination System (NPDES). As such, it pre-
supposes a high expectation of finding the specific compounds of
interest. If the user is attempting to screen samples for any or
all the compounds above, he must develop independent protocols
for the verification of identity.
1.3 The sensitivity of this method is usually dependent on the level
of interferences rather than instrumental limitations. The
limits of detection listed in Table A-l represent sensitivities
that can be achieved in wastewaters in the absence of inter-
ferences.
1.4 This method is recommended for use only by experienced residue
analysts or under the close supervision of such qualified per-
sons.
2. Summary of Method
2.1 A 1 liter sample of wastewater is extracted with methylene
chloride using separatory funnel techniques. The extract is
dried by passing through a sodium sulfate column and then
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TABLE A-l. GAS CHROMATOGRAPHY OF CHLORINATED HYDROCARBONS
Compound ;
1,3-Di chl orobenzene
1 , 4-Di chl orobenzene
Hexachloroethane
1,2-Dichlorobenzene
Hexachl orobutadi ene
1, 2, 4-Tri chl orobenzene
Hexachl orocycl opentadi ene
2-Chl oronaphthal ene
Hexachl orobenzene
Retention Time
(Minutes)
5.6
6.1
6.7
7.6
15.8
17.7
2.0*
3.65*
10.3*
Detection t
Limit (yg/L)
0.009
0.0018
0.001
0.012
0.001
0.006
0.001
0.015
0.001
Column conditions: Suplecoport 80/100 mesh coated with 1.5% OV-1/2.4%
OV-225 packed in a 1.8 m long X 2 MM ID glass column with 5% methane/95%
argon carrier gas at 30 mL/min flow rate. Column temperature is 75°C except
where * indicates 165°C. Under these conditions R.T. of Aldrin is 27.4
minutes at 165°C.
tDetection limit is calculated from-the minimum detectable CC response of
the electron capture detector being equal to five times the GC background
noise,.assuming a 10 mL final volume of the 1 liter sample extract, and
assuming a GC injection of 5 microliters.
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concentrated to a volume of 10 ml or less. Chromatographic con-
ditions are described which allow for the accurate measurement of
the compounds in the extract.
2.2 If Interferences are encountered or expected, the method provides
a selected general purpose clean up procedure to aid the analyst
in eliminating them.
3. Interferences
3.1 Solvents, reagents, glassware, and other sample processing hard-
ware may yield discrete artifacts and/or elevated baselines
causing misinterpretation of gas chromatograms. All of these
materials must be demonstrated to be free from interferences
under the conditions of the analysis by running method blanks.
Specific selection of reagents and purification of solvents by
distillation in all glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from source to source, depending on the diversity of the
industrial complex or municipality being sampled. While general
clean up techniques are provided as part of this method, unique
samples may require additional clean up approaches to achieve the
sensitivities stated in Table A-l.
4. Apparatus and Materials
4.1 Sampling equipment, for discrete or composite sampling.
4.1.1 Grab sample bottle - Amber glass, 1 liter or 1 quart
volume. French or Boston Round design is recommended.
The. container must be washed and rinsed with solvent
before use to minimize interferences.
4.1.2 Bottle caps - Threaded to screw on sample bottles. Caps
must be lined with Teflon. Foil may be substituted if
sample is not corrosive and foil is found to be inter-
ference free.
4.1.3 Compositing equipment - Automatic or manual compositing
system. Must incorporate glass sample containers for the
collection of a minimum of 250 ml. Sample containers
must be kept refrigerated during sampling. No tygon or
rubber tubing or fittings may be used in the system.
4.2 Separatory funnel - 2000 mL, with Teflon stopcock.
4.3 Drying column - 20 mm ID pyrex Chromatographic column with coarse
frit.
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4.4 Kuderna-Danish (K-D) Apparatus
4.4.1 Concentrator tube - 10 mL, graduated (Kontes
K-570050-1025 or equivalent). Calibration must be
checked. Ground glass stopper (size 19/22 joint) is used
to prevent evaporation of extracts.
4.4.2 Evaporative flask - 500 ml (Kontes K-47001-0500 or
equivalent). Attach to concentrator tube with springs.
(Kontes K-662750-0012).
4.4.3 Snyder column - three ball macro (Kontes K-503000-0121 or
equivalent).
4.4.4 Snyder column - two ball micro (Kontes K-569001-0219 or
equivalent).
4.4.5 Boiling chips - solvent extracted, approximately 10/40
mesh.
4.5 Water bath - Heated, with concentric ring cover, capable of tem-
perature control (±2°C). The bath should be used in a hood.
4.6 Gas chromatograph - Analytical system complete with gas chroma-
tograph suitable for on column injection and all required
accessories including electron capture detector, column supplies,
recorder, gasses, syringes. A data system for measuring peak
areas is recommended.
4.7 Chromatography column - 300 mm long X 10 mm ID with coarse
fritted disc at bottom and Teflon stopcock.
5. Reagents
5.1 Preservatives
5.1.1 Sodium hdroxide - (ACS) 10 N in distilled water.
5.1.2 Sulfuric acid - (ACS) Mix equal volumes of concentrated
with distilled water.
5.2 Methyl ene chloride, hexane and petroleum ether (boiling range 30
to 60°C) - Pesticide quality or equivalent.
5.3 Sodium sulfate - (ACS) Granular, anhydrous (purified by heating
at 400°C for 4 hr in a shallow tray).
5.4 Stock standards - Prepare stock standard solutions at a concen-
tration of 1.00 yg/yL by -dissolving 0.100 grams of assayed
reference material in pesticide quality hexane or other
appropriate solvent and diluting to volume in a 100 mL ground
70
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glass stoppered volumetric flask. The stock solution is trans-
ferred to ground glass stoppered reagent bottles, stored in a
refrigerator, and checked frequently for signs of degradation or
evaporation, especially just before preparing working standards
from them.
5.5 Florisil - PR grade (60/100 mesh): purchase activated at 1250°F
and store in the dark in glass containers with glass stoppers or
foil-lined screw caps. Before use, activate each batch at 130°C
in foil-covered glass containers.
6. Calibration
6.1 Prepare calibration standards that contain the compounds of
interest, either singly or mixed together. The standards should
be prepared at concentrations covering two or more orders of
magnitude that will completely bracket the working range of the
chromatographic system. If the sensitivity of the detection
system can be calculated from Table A-l as 100yg/L in the final
extract, for example, prepare standards at 10 ug/L, 50 ug/L,
100 ug/L» 500 yg/L, etc. so that injections of 1 to 5 uL of each
calibration standard will define the linearity of the detector in
the working range.
6.2 Assemble the necessary gas chromatographic apparatus and estab-
lish operating parameters equivalent to those indicated in
Table A-l. By injecting calibration standards, establish the
sensitivity limit of the detector and the linear range of the
analytical system for each compound.
6.3 The clean up procedure in Section 10 utilizes Florisil chroma-
tography. Florisil from different batches or sources may vary in
absorption capacity. To standardize the amount of Florisil that
is used, the use of lauric acid value (Mills, 1968) is suggested.
The referenced procedure determines the adsorption from hexane
solution of lauric acid (mg) per gram Florisil. The amount of
Florisil to be used for each column is calculated by dividing
this ratio by 110 and multiplying by 20 grams.
6.4 Before using any clean up procedure, the analyst must process a
series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the
reagents.
7. Quality Control
7.1 Before processing any samples the analyst should demonstrate,
through the analysis of a distilled water method blank, that all
glassware and reagents are free of interference. Each time a set
of samples is extracted or there is a change in reagents, a
method blank should be processed as a safeguard against chronic
laboratory contamination.
71
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7.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the
accuracy of the analysis. Where doubt exists over the iden-
tification of a peak on the chromatogram, confirmatory techniques
such as mass spectroscopy should be used.
8. Sample Collection. Preservation, and Handling
8.1 Grab samples must be collected in glass containers, leaving a
minimum headspace. Conventional sampling practices should be
followed, except that the bottle must not be prewashed with
sample before collection. Composite.samples should be collected
in refrigerated glass containers in accordance with the require-
ments of the program. Automatic sampling equipment must be free
of tygon and other potential sources of contamination.
8.2 The samples must be iced or refrigerated from the time of collec-
tion until extraction. Chemical preservatives should not be used
in the field unless more than 24 hours will elapse before deliv-
ery to the laboratory. If the samples will not be extracted
within 48 hours of collection, they should be adjusted to a pH
range of 6.0 to 8.0 with sodium hydroxide or sulfuric acid.
8.3 All samples should be extracted immediately and must be extracted
within 7 days and completely analyzed within 30 days after
collection.
9. Sample Extraction
9.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample
into a two liter separatory funnel. Check the pH of the sample
with wide range paper and adjust to within the range of 5 to 9
with sodium hydroxide or sulfuric acid.
9.2 Add 60 ml methylene chloride to the sample bottle, seal and shake
30 seconds to rinse the inner walls. Transfer the solvent into
the separatory funnel, and extract the sample by shaking the fun-
nel for two minutes with periodic venting to release vapor
pressure. Allow the organic layer to separate from the water
; phase for a minimum of ten minutes. If the emulsion interface
between layers is more than one-third the size of the solvent
layer, the analyst must employ mechanical techniques to complete
the phase separation. The optimum technique depends on the
sample, but may include stirring, filtration of the emulsion
through glass wool, or centrifugation. Collect the methylene
chloride extract in a 250 ml Erhlenmeyer flask.
9.3 Add a second 60 ml volume of methylene chloride to the sample
bottle and complete the extraction procedure a second time, com-
bining the extracts in the Erhlenmeyer flask.
72
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9.4 Perform a third extraction in the same manner. Pour the combined
extract through a drying column containng 3 to 4 inches of
anhydrous sodium sulfate, and collect it in a 500 ml Kuderna-
Danish (K-D) flask equipped with a 10 ml concentrator tube.
Rinse the Erhlenmeyer flask and column with 20 to 30 ml methylene
chloride to complete the quantitative transfer.
9.5 Add 1 to 2 clean boiling chips to the flask and attach a three
ball Snyder column. Prewet the Snyder column by adding about
1 mL methylene chloride to the top. Place the K-D apparatus on a
hot water bath (60 to 65°C) so that the concentrator tube is par-
tially immersed in the hot water and the~entire lower rounded
surface of the flask is bathed in vapor. Adjust the vertical
position of the apparatus and the water temperature as required
to complete the concentration in 15 to 20 minutes. At the proper
rate of distillation the balls of the column will actively
chatter but the chambers will not flood. When the apparent
volume of liquid reaches 1 to 2 ml, remove the K-D apparatus and
allow it to drain for at least 10 minutes while cooling. Note —
The dichlorobenzenes have a sufficiently high volatility that
significant losses may occur in concentration steps if care is
not exercised. It is important to maintain a constant gentle
evaporation rate and not to allow the liquid volume to fall below
1 to 2 ml before removing the K-D from the hot water bath.
9.6 Momentarily remove the Snyder column, add 50 ml hexane and a new
boiling chip and replace the column. Raise the temperature of
the water bath to 85 to 90°C. Concentrate the extract as in 9.5,
except use hexane to prewet the column. Remove the Snyder column
and rinse the flask and its lower joint into the concentrator
tube with 102 ml of hexane. A 5 ml syringe is recommended for
this operation. Stopper the concentrator tube and refrigerate if
further processing will not be performed immediately.
9.7 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000 ml gra-
duated cylinder. Record the sample volume to the nearest 5 ml.
9.8 Unless the sample is known to require clean up, proceed to analy-
sis by gas chromatography.
10. Clean up and Separation
10.1 Florisil Column Clean up for Chrlorinated Hydrocarbons.
10.1.1 Adjust the sample extract to 10 ml.
10.1.2 Place a 12 gram charge of activated Florisil (see 6.3) in
a 10 mm ID chromatography column. After settling the
Florisil by tapping the column, add a 1 to 2 cm layer of
anhydrous granular sodium sulfate to the top.
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10.1.3 Pre-elute the column, after cooling, with 100 ml of
petroleum ether. Discard the eluate and just before
exposure of the sulfate layer to air, quantitatively
transfer the sample extract into the column by decan-
tation and subsequent petroleum ether washings. Discard
the eluate. Just before exposure of the sodium sulfate
layer to the air, begin eluting the column with 200 ml
petroleum ether and collect the eluate in a 500 ml K-D
flask equipped with a 10 ml concentrator tube. This
fraction should contain all of the chlorinated
hydrocarbons.
10.1.4 Concentrate the fraction by K-D as in 9.5 except prewet
the column with hexane. When the apparatus is cool,
remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube with 1 to 2 ml
hexane. Analyze by gas chromatography.
11. Gas Chromatography
11.1. Table A-l summarizes some recommended gas chromatographic column
materials and operating conditions for the instrument. Included
in this table are estimated retention times and sentitivities
that should be achieved by this method. Examples of the separa-
tions achieved by this column are shown in Figs. A-l and A-2.
Calibrate the system daily with a minimum of three injections of
calibration standards.
11.2 Inject 2 to 5-pL of the sample extract using the solvent-flush
technique. Smaller (1.0 uL) volumes can be injected if automatic
devices are employed. Record the volume injected to the nearest
0.05 uL, and the resulting peak size, in area units.
11.3 If the peak area exceeds the linear range of the system, dilute
the extract and reanalyze.
11.4 If the peak area measurement is prevented by the presence of
interferences, further clean up is required.
12. Calculations
12.1 Determine the concentration of individual compounds according to
the formula:
(A) (B) (Vt)
Concentration, yg/L =
(Vi) (Vs)
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1.5% OV-1+ 1.5% OV-225 On Gas Chrom Q
TEMP E3ATUHE : 7 5 ° C
DETECTOR: Electron Capture
A.
B.
C.
D.
1,3-DICHLOROBENZENE
1,4-DICELOROBENZENE
HEXACHLOROETHANE
1,2-DICHLOROBENZENE
HEXACHLOROBUTADIENS
1,2,4-TRICHLOROBENZENE
5 _____ 10 15 20
RETENTION TIME-MINUTES
Figure A-l. Gas Chromatogram of Chlorinated Hydrocarbons
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COLUMN: 1.5% OV-1- 2.25% OV-225 on Supelcoport
TEMPERATURE: 165°C
DETECTOR: . . Electron Capture
A. HEXACHLOROCYCLOPSNTADIENE
3. 2-CHLORCNAPHTHALENE
C. HEXACHLOROBENZSNE
0 5 10 15
RETENTION TIME-MINUTES _.__
Figure A-2. Gas Chromatogram of Chlorinated Hydrocarbons
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Where: A = Calibration factor for chromatographic system, in
nanograms material per area unit
B = Peak size in injection of sample extract, in area units
V.,- = Volume of extract injected (u/L)
V-j. = Volume of total extract (uL)
Vs = Volume of water extracted (ml)
12.2 Report results in micrograms per liter without correction for
recovery data. When duplicate and spiked samples are analyzed,
all data obtained should be reported.
13. Accuracy and Precision
The U.S. EPA Environmental. Monitoring_and Suppqrt Laboratory -..
Cincinnati is in the process of conducting an interlaboratory method
study to determine the accuracy and precision of the test procedure.
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REFERENCES
Mills, P. A., Variation of Florisil Activity: Simple Method for
Measuring Absorbent Capacity and Its Use in Standardizing Florosil
Columns, Journal of the Association of Official Analytical Chemists.
29:51, 1968.
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GLOSSARY OF TERMS
The termino1og> and statistical measurements used in this study report
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.
~ ^tvno
R. E., % = Y true X 100
*true
F-tests A statistical test applied to the ratio of the squares of S and/or
S data to estinate whether the water types used in the study were statisti-
cally different than the distilled water data.
The following formulae (4) were used;-
F =
(S Distilled Water)?
(S Any Other Water Type)*
(S,, Distilled Hater)2
F = r
(Sr Any Other Water Type)2
To achieve a number greater than 1 the variances were reversed as needed.
The resultant values were compared to a standard one-sided 99.5% critical
value table (5) to determine deviation where:
f (degrees of freedom) = n -1
f (degrees of freedom = n' -1
n = number of data points to calculate the S or S in the
numerator; * r
n" = number of data points to calculate the S or S in the
denominator.
If the calculated F exceeds the theoretical value found in the table, the
data may be considered significantly different.
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Mean Recovery. The arithmetic mean of reported values; the average.
IX.
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.
— • I
Outlier. A datum point determined by applying an Extreme Studentized De-
viate T test at a selected probability level to be extreme in relationship
to the other data and therefore rejected.
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. = 'lOO -
Single-Analyst Relative Deviation. The ratio of the single-analyst 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 for a
single analyst to the size of numbers so that the deviations at different
mean values and between analysts can be compared.
S
Single-analyst R.D. = 100 —
X
Standard Deviation (S). The most widely used measure to describe the dis-
persion of a set of data. For normally distributed data, 7. +_ S will include
68%, and X +^ 2S will include about 95% of the data from a study.
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 nonreplicate study design.
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Sr =
Student's t-test. A statistical test performed to determine whether the
mean recoveries, X, for a particular water type when compared to distilled
water data were significantly different. The calculated t values were
compared to a standard two-tailed t distribution table (5); calculated
values exceeding the table values were considered significantly different.
When S values were found to be similar the following t-test was used:
7 _ 7
t = X Y
which will have student t's distribution with n + n - 2 degrees of freedom.
x y
Where:
X = the larger of the mean recoveries (water type or distilled
water);
Y = the smaller of the mean recoveries (water type or distilled
water);
n and n = the corresponding number of data points for X and ?;
S and S^ = the corresponding S , single-analyst standard devia-
y tions for X and ?.
When S values and were found to be significantly different the following
formulas were applied:
""''" )? - 7
t = X Y
Where the degrees of freedom were:
T test. The difference between a single observation (X ) and the
estimated population mean (X) expressed as a ratio over the
estimated population standard deviation (S). The value obtained
is compared with values from a table for the critical T distribu-
tion (3). If the calculated T value exceeds the theoretical
T value at a prescribed confidence level, the analyzed value is
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probably not from the same population as the rest of the data and
can be rejected.
Xn - X
Youden Pair. A set of two samples having slightly dissimilar concentrations
of the constituent of concern, based on Youden's nonreplicate analysis
technique.
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