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Analysis
of
Trace Organics
in the
Aquatic Environment
Editors
B. K. Afghan, Ph.D.
Chief
Water Quality National Laboratory
Canada Centre for Inland Waters
Burlington, Ontario, Canada
Alfred S. Y. Chau, M.Sc.

Chief
Quality Assurance Program
National Water Research Institute
First published 1989 by CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite
300 Boca Raton, FL 33487-2742
Reissued 2018 by CRC Press
© 1989 by Taylor & Francis

CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
This book contains information obtained from authentic and highly regarded sources. Reasonable
efforts have been made to publish reliable data and information, but the author and publisher cannot
assume responsibility for the validity of all materials or the consequences of their use. The authors and
publishers have attempted to trace the copyright holders of all material reproduced in this publication
and apologize to copyright holders if permission to publish in this form has not been obtained. If any
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future reprint.
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ISBN 13: 978-1-138-50562-9 (hbk)

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PREFACE
The importance of environment assessment pollution control to protect and upgrade en
vironmental quality, has led to the necessity and demand in the study and monitoring of the
pollutants in the aquatic environment. All research and surveillance activities to assess the
quality of the environment depend upon the availability of analytical data, since scientific
conclusions and political decisions on environmental issues are based on their interpretation.
Questionable data result in questionable conclusions.
One of the key elements of effective quality assurance to ensure reliable data generation
is the availability of reliable analytical methods and their appropriate application. Many
books have been published which cover measurement techniques for chemical constituents.
The present book is part of a multi-volume work which is designed to provide, in a single
source, theories and important analytical techniques and methodologies necessary for un
derstanding and determining the trace organic contaminants in various compartments of the
aquatic environment.
The first three volumes dealt with the analysis of pesticide residues and their toxic deg
radation products in the aquatic environment. This final volume covers the toxaphene,
organometallic compounds, humic acids, and related substances and industrial chemicals
such as PCBs, phenols, chlorinated dioxins, and volatile organics.
The book is intended to serve as a general reference for university and college students
as well as a practical reference for environmental chemists and technologists. It provides
sufficient theoretical and practical detail to ensure that a reader would be able to determine
trace constituents in an accurate manner. Each chapter covers practical applications of
techniques, and provides state-of-the-art methodologies in current use with special reference
to sampling, concentration, cleanup, quantitative and confirmatory analysis, etc. The detail
provided is such that it should not be necessary to refer to other protocols or manuals to set
up a particular method.
The authors of the chapters have attempted to emphasize the practical aspects, and with
the amount of information provided, it should be possible to make critical comparisons of
the available methods in order to satisfy specific needs.
The authors would like to acknowledge the assistance and support provided by Mrs. T.
Searle, Miss M. Srdanovic, and Miss M. Miscione for typing various chapters and coor
dinating the material as well as maintaining a close liaison with CRC Press.
B. K. Afghan
Alfred S. Y. Chau
THE EDITORS
B. K. Afghan, Ph.D. is presently the Chief, National Water Quality Laboratory of the
Water Quality Branch at the Canada Centre for Inland Waters in Burlington, Ontario. He
has completed a career of nearly 25 years of active research and service in analytical
chemistry.
Dr. Afghan has conducted independent research for over 20 years and has also directed
research activities related to analytical chemistry, radiochemistry, and application of electron
microscopy to biological studies.
He has published and/or co-authored over 50 technical papers and reports. The work has
included the development of new and/or improved methods for analysis of inorganic and
organic trace constituents in environmental samples. The techniques utilized included po-
larographic and related electroanalytical techniques, spectrophotometry, spectrofluorometry,
and luminescence, high pressure liquid chromatography, gas chromatography, and gas chro-
matography/mass spectrometry. He has also written chapters for books and has co-edited
books and symposium proceedings.
Dr. Afghan has contributed significantly to the promotion of analytical chemistry and
international cooperation in scientific matters. He has served as a member and/or chairperson
of various working groups devoted to standardization of chemical and biochemical water
quality parameters. He has served in an official capacity to professional societies such as
the Chemical Institute of Canada, the American Society for Testing and Materials, and the
International Standards Organization.
Dr. Afghan has lectured widely in Canada, the U.S., Europe, and Australia on advances
in analytical chemistry.
Alfred S. Y. Chau, M.Sc., is Chief, Quality Assurance Program at the Research and
Application Branch National Water Research Institute, Canada Centre for Inland Waters.
He obtained his B.Sc. degree from the University of British Columbia in 1961 and his M.Sc.
degree from Carleton University, Ottawa, Ontario, Canada.
From 1965 to 1970 he held the position of pesticide analyst in the Department of Agriculture.
At the Department of the Environment he was Head of the Organic Laboratories Section
and then Head of the Special Services Section. He has held his current position since 1987.
Mr. Chau was the General Referee and is a member of the Association of Official
Analytical Chemists, a Fellow of the Chemical Institute of Canada, a Life Fellow of the
International Association, U.K., and Fellow of the American Biographical Institute, and is
currently on the Advisory Board, National Division of the American Biographical Institute,
Chairman of several binational and multiagency quality assurance committees and a member
of the Canadian Advisory Committee on Quality Assurance Management, and International
Standards Organizations. Mr. Chau is listed in 23 international books of recognition including
Who's Who in the World, Who's Who in America, Personalities of America, International
Who's Who of Contemporary Achievement, and International Who's Who of Intellectuals.
He has published over 100 scientific papers in the areas of analytical methodologies, research,
and development of certified reference materials for organic and inorganic contaminants in
lake sediments.
Further, Alfred Chau is well known as an accomplished nature artist having work admitted
to regional and national juried exhibitions such as the Ontario Society for Artists Touring
Exhibition (Collectors’ Choice Awards, 1981), Ontario Jury Exhibition, 1985; Etobicoke
Civic Centre Art Competition (CCAC Award, 1984), World Wildlife Fund Art Auction,
1982, Canada Nature Art National Tour 1982-84. His works are in many private and
permanent collections including the Dofasco Canadian Art Collection, Hiram-Walker Art
Collection, the Beckett Collection, and IBM.
CONTRIBUTORS
B. K. Afghan, Ph.D. Iling-Biu Lee, Ph.D.

Chief Research Scientist
National Water Quality Laboratory National Water Research Institute
Canada Centre for Inland Waters Environment Canada
Environment Canada Burlington, Ontario, Canada
R. M. Baxter, Ph.D. Barry G. Oliver, Ph.D.
Research Scientist Research Scientist
Environmental Contaminants Division Canada Centre for Inland
National Water Research Institute Waters
Burlington, Ontario, Canada National Water Research Institute
John M. Carrón, B.Sc.
National Water Quality Laboratory
Francis I. Onuska, Ph.D.
Scientist
Environment Canada
Research and Applications Branch
National Water Research Institute
Alfred S. Y. Chau, M.Sc. Burlington, Ontario, Canada
Chief
Quality Assurance and Methods Section James F. Ryan, Chemical Technology
National Water Research Institute Diploma
Canada Centre for Inland Waters Research Technologist
Burlington, Ontario, Canada Canada Centre for Inland Waters
Y. K. Chau, Ph.D. Environment Canada
Research Scientist National Water Research Institute
National Water Research Institute Burlington, Ontario, Canada
David B. Sergeant, B.Sc. (Hons)
Ultratrace Laboratory
Ray E. Clement, Ph.D. Department of Fisheries and Oceans
Senior Scientist Bayfield Institute
Drinking Water Organics Section Great Lakes Laboratory for Fisheries and
Laboratory Services Branch Aquatic Sciences
Ontario Ministry of the Burlington, Ontario, Canada
Environment
Rexdale, Ontario, Canada Helle M. Tosine, B.Sc.
Manager
Jagmohan Kohli, Ph.D.
Drinking Water Organics Section
Chemist Ministry of the Environment
National Water Quality Laboratory
Rexdale, Ontario, Canada
Environment Canada
Burlington, Ontario, Canada Paul T. S. Wong, Ph.D.
Research Scientist
John Lawrence, Ph.D. Great Lakes Laboratory for Fisheries and
Director Aquatic Sciences
Research and Applications Branch Canada Centre for Inland
National Water Research Institute Waters
Burlington, Ontario, Canada Burlington, Ontario, Canada
TABLE OF CONTENTS
Chapter 1
Analysis of Volatile Halogenated and Purgeable Organics.................................................. 1
Barry G. Oliver
Chapter 2
Polychlorinated Biphenyls....................................................................................................31
Barry G. Oliver, R. M. Baxter, and Hing-Biu Lee
Chapter 3
Analysis of Toxaphene in Environmental Samples............................................................69
David B. Sergeant and Francis I. Onuska
Chapter 4
Environmental Aspects and Analysis of Phenols in the Aquatic Environment.............. 119
John M. Carron and B. K. Afghan
Chapter 5
Analysis of Chlorinated Dibenzo-p-Dioxins and Dibenzofurans in the Environment__ 151
Ray E. Clement and Helle M. Tosine
Chapter 6
Analysis of Polycyclic Aromatic Hydrocarbons in Environmental Samples................... 205
Francis I. Onuska
Chapter 7
Phthalate Esters in the Aquatic Environment................................................................... 243
Jagmohan Kohli, James F. Ryan, and B. K. Afghan
Chapter 8
Organometallic Compounds in the Aquatic Environment................................................ 283
Y. K. Chau and Paul T. S. Wong
Chapter 9
Humic Acid and Related Substances in the Environment................................................ 313
John Lawrence
Index....................................................................................................................................339
1
Chapter 1
ANALYSIS OF VOLATILE HALOGENATED AND PURGEABLE ORGANICS
Barry G. Oliver
TABLE OF CONTENTS
I. Introduction................................................................................................................... 2
A. Production and Uses......................................................................................... 2
B. Environmental Distribution............................................................................... 2
1. Ambient Water, Sediments, and Biota............................................... 2
2. Drinking W ater.................................................................................... 5
C. Health Effects................................................................................................... 5
1. Toxicity................................................................................................. 5
2. Carcinogenic and Mutagenic Responses ............................................7
3. Epidemiologic Studies and Risk Factor Calculations........................ 7
4. Exposure Routes and Doses................................................................. 7
II. General Analysis Procedures........................................................................................8

A. Sampling and SamplePreservation...................................................................8
B. Extraction, Concentration, and Cleanup......................................................... 8
1. Sediments and F ish ................................................................................8
2. Resin Adsorption................................................................................. 9
3. Direct Aqueous Injection...................................................................10
4. Liquid-Liquid Extraction.................................................................... 10
5. Static Headspace................................................................................. 11
6. Purge and T ra p ...................................................................................12
7. Closed-Loop Stripping........................................................................12
C. Separation........................................................................................................ 15
1. Packed Column Gas Chromatography.................................................15
2. Capillary Column Gas Chromatography .......................................... 16
D. Detection..........................................................................................................16
E. Calibration...................................................................................................... 18
III. Recommended Methods.............................................................................................. 19

A. LLE/ECD Method........................................................................................... 19
B. B&T/ELCD Method.........................................................................................20
C. Confirmation...................................................................................................21
D. Future Directions............................................................................................ 21
References...............................................................................................................................22
2 Analysis of Trace Organics in the Aquatic Environment
I. INTRODUCTION
A. Production and Uses

Interest in the presence of volatile halogenated compounds in water has been high for
several years because of the discovery of the ubiquitous presence of trihalomethanes, THMs,
in chlorinated drinking water in several countries.1'4 The THMs, chloroform, bromodichlo-
romethane, chlorodibromomethane, and bromoform, are formed from the reaction of chlorine
with naturally occurring organics such as fulvic acid,5'8 algae,9' 11 etc., during water disin
fection. There is also concern about other volatile halogenated compounds that are not water
chlorination byproducts such as tetrachloroethylene12 and carbon tetrachloride4 because they
have been found at high concentrations in some drinking waters from groundwater sources.
The purgeable halogenated compounds on the U.S. Environmental Protection Agency’s
priority pollutant list are shown in Table 1 together with some of their physical properties.13
In general the compounds have low boiling points (<200°C), high vapor pressures (^1
torr), low water solubilities, and fairly low octanol/water partition coefficients.
U.S. production figures for some of the compounds are shown in Table 2.14 It can be
seen that massive quantities of these materials are produced in the U.S. which is only a
fraction (1/2 to 1/5) of world production. Some of the compounds are used as chemical
intermediates, for example, 1,2-dichloroethane in the production of vinyl chloride which in
turn is used to produce polyvinyl chloride; chloroform and carbon tetrachloride in the
manufacture of fluorohydrocarbons. Many of the compounds are used as solvents in such
applications as paint, extraction or reaction media solvents, and in dry cleaning, vapor
degreasing, metal cleaning, and textile processing. Metal cleaning and dry cleaning are the
first and second largest solvent applications.14
The chlorinated hydrocarbons are produced by a variety of chlorination reactions involving
hydrocarbon feedstocks such as methane (natural gas), ethane, ethylene, propylene, and
propane.14 Chlorination of benzene in the presence of a catalyst such as ferric chloride is
used to produce the chlorinated benzenes. Industrial solvents are to a large extent recovered
and total production represents handling losses to the environment. On the other hand, the
quantity of chemical intermediates that enter the environment is only a small fraction of the
annual production. It should be noted that all THMs produced during water chlorination
(drinking or cooling water) will be lost to the environment.15 In addition to anthropogenic
sources, compounds such as CH3C1 and CH3Br are thought to have large natural sources
mainly in the oceans.16
B. Environmental Distribution
7. Ambient Water, Sediments, and Biota
The concentration of volatiles in ambient waters is usually quite low in the ng/L or ppt
range. Pearson and McConnell17 reported C2HC13, C2CL4, and CC14 concentrations in the
100 to 300 ng/1 range for Liverpool Bay, England seawater. Hammer et al.18 showed that
the CC13F concentration averaged 20 ng/1 in the Gulf of Maine, U.S. Kaiser and Valdmanis19
report concentrations from 11 to 76 ng/1 for CC12F2, CHC13, CC14, and C2HC13 in Lake Erie,
Canada. Concentrations of dichlorobenzenes ranged from 2 to 64 ng/1 for Lakes Huron and
Ontario, Canada.20 Somewhat higher concentrations in the |xg/l or ppb range are found in
wastewater effluents20,21 or in rivers close to outfalls.22,23,24
A mass balance study on Lake Zurich, Switzerland on the least volatile purgeable com
pound in Table 1, 1,4-dichlorobenzene, showed that the major environmental pathway of
this compound was volatilization to the atmosphere.25 Using laboratory studies, Dilling et
al.26 showed that the time required for 50% evaporation from water of many of the chemicals
in Table 1 was less than 1 h. Mesocosm experiments27 also showed that the major process
removing these compounds from water is volatilization. The removal of these purge-
Table 1
PURGEABLE HALOCARBONS IN THE U.S. ENVIRONMENTAL PROTECTION
AGENCY’S PRIORITY POLLUTANT LIST AND SOME OF THEIR PHYSICAL
PROPERTIES13
Boiling Point Vapor pressure

at 760 mm at 20°C Water solubility Log octanol/water
Chemical Formula (°C) (torr) at 20°C(mg/l) partition coefficient
Chloromethane CH3C1 -2 4 .2 3765 6450—7250 0.91

Bromomethane CH3Br 4.6 1420 900 1.1
Dichlorodifluoromethane CC12F2 -2 9 .6 4310 280 2.2
Vinyl chloride C2H3C1 -1 3 .4 2660 60 0.6
Chloroethane C2H5C1 12.3 1000 5740 1.5
Methylene chloride CH2C12 39.8 362 17000 1.3
Trichlorofluoromethane CC13F 23.8 667 1100 2.5
1.1- Dichloroethylene C2H2C12 37 591 400 1.5
1.1- Dichloroethane C2H4C12 57.3 180 5500 1.8
Trans- 1,2-dichloroethylene C2H2C12 47.5 200 600 1.5
Chloroform CHC13 61.7 151 8200 2.0
1.2- Dichloroethane C2H4C12 83.5 61 8690 1.5
1,1,1 -Trichloroethane C2H3C13 74.1 96 480-^400 2.2
Carbon tetrachloride CC14 76.5 90 785 2.6
Bromodichloromethane CHBrCl2 90 50 — 1.9
1.2- Dichloropropane C3H6CL2 96.8 42 2700 2.3
Trans-l,3-dichloropropene C3H4C12 112 25 2800 2.0
Trichloroethylene C2HC13 87 57.9 1100 2.3
Dibromochloromethane CHClBr2 120 15 — 2.1
1.1.2- Trichloroethane C2H3C13 133.8 19 4500 2.2
Cw-l,3-dichloropropene C3H4C12 104.3 25 2700 2.0
2-Chloroethylvinyl ether C4H70C1 108 26.8 15000 1.3
Bromoform CHBr3 149.5 10 3100 2.3
1.1.2.2- Tetrachloroethane C2H2C14 146.2 5 2900 2.6
Tetrachloroethy lene C2C14 121 14 150—200 2.9
Chlorobenzene C6H5C1 132 8.8 500 2.8
1.3- Dichlorobenzene C6H4C12 173 2.3 123 3.4
1.2- Dichlorobenzene C6H4C12 180.5 1.5 145 3.4
3
1.4- Dichlorobenzene C6H4C12 174 0.6 79 3.4

Table 2
U.S. PRODUCTION FOR SOME
VOLATILE CHLORINATED
HYDROCARBONS14
Thousands of metric tons

Compound 1970 1976
Vinyl chloride 1534 2289

1,1 -Dichloroethylene 54 70
1,2-Dichloroethane 3773 4773
Chloromethane 192 168
Methylene chloride 182 227
Chloroform 109 125
Carbon tetrachloride 459 385
1,1,1 -trichloroethane 166 234
Trichloroethy lene 274 127
Tetrachloroethy lene 320 304
Chlorobenzene — 163
1,2-Dichlorobenzene — 68
1,4-Dichlorobenzene
able compounds during wastewater treatment occurs mainly by volatilization; biodegradation

or adsorption to solids are minor processes.28 When effluents containing volatile chemicals
are discharged at depth (below the waterbody surface) or beneath an ice cover,29 volatilization
is restricted and the compounds make excellent tracers for industrial plumes in lakes22 and
in the ocean.30 Some exchange of these materials between water and the atmosphere does
occur,31 and some recycling takes place since measurable concentrations of these compounds
are found in rainwater.17 But the ultimate fate of these compounds appears to be destruction
in the troposphere by reaction with hydroxyl radicals or photodecomposition or reaction
with ozone in the stratosphere.32 The destruction in the stratospheric ozone layer by reactions
with freons and other halocarbons is still a matter of controversy.33,34
The concentrations of purgeable halocarbons in ambient lake and river sediments should
be low because partitioning onto solids is not a favored process for these chemicals.35,36
Sediments in Liverpool Bay were in the low (xg/Kg or ppb range for CC14, CHC13, C2C14,
and C2HC13.17 Great Lakes sediments20 and southern Californian coastal sediments21 con
tained similar concentrations (low ppb) for dichlorobenzenes. Exceptionally high sediment
perchloroethylene concentrations up to percent levels have been reported in the St. Clair
River, Canada, but this was due to direct spillage of the solvent into the river.37
Similarly, concentrations of these compounds in biota and fish should not be excessively
high because of their low octanol/water partition coefficients, Kows, and low bioconcentration
factors, BCFs. Mackay38 has fitted the equation, log BCF = log Kow -1 .3 2 , to a set of
literature data. From the Kow data in Table 1 (log Kow, 0.6 to 3.4), the maximum biocon
centration factor in fish for these compounds should be about 100. Values in good agreement
with this equation for bluegill sunfish39 and for rainbow trout40 have been measured in the
laboratory. Oliver and Niimi41 have reported somewhat higher BCFs, 270 to 420, for dich
lorobenzenes in rainbow trout exposed to environmental concentrations of these chemicals.
Since typical environmental water concentrations for these chemicals are in the low ppt
range, the maximum chemical concentrations in fish should be in the low ppb range. Field
studies have shown low ppb levels of dichlorobenzenes in lake trout from the Great
Lakes20 and in Dover sole from southern California.21 Similar low concentrations of CHC13,
CC14, C2HC13, and C2C14 have been found in various species of fish and other biota from
Liverpool Bay,17 from the U.S.,42 and from Norway.43 Biomagnification of these types of
5
chemicals does not occur because of the rapid establishment of equilibrium between fish
and water concentrations of the chemicals.17,41 Thus tissue residue levels are governed mainly
by the chemical concentration in the water and are not significantly influenced by the fish’s
food.41
2. Drinking Water
The contamination of drinking water with purgeable organics is a problem in many
countries. Table 3 shows the concentrations of trihalomethanes in several of these coun
tries.^2,3,44 47 Some limited data are available for other countries,4 but only fairly extensive
studies are included in the table. In general, all water that is disinfected with chlorine
contains THMs because of the reaction of chlorine with natural organic matter. Concentra
tions up to several hundred ppb have been observed in several locations (Table 3). Chlorinated
groundwaters contain somewhat lower THM concentrations than chlorinated surface waters
from the same region. Groundwaters usually have a much lower total organic carbon (TOC)
concentration than surface waters, so usually contain less THM precursor material.48 Also,
groundwaters are usually not as contaminated with bacteria as surface waters so they are
not as heavily chlorinated.
The concentration of THMs in water supplies has been related to TOC, chlorine dose,
pH, temperature, and bromide concentration — the higher the value for any of these pa
rameters the higher the yield.8,49'52 The presence of bromide in the water not only leads to
the formation of the brominated THMs but also has been shown to increase the total THM
yield.51,53 The bromide reacts with hypochlorous acid to yield hypobromous acid (Br— +
HOC1 —» HOBr + Cl —) which is a more efficient and faster reacting halogenating agent.
Several water supplies have reported quite high concentrations of brominated THMs.2,54
Chlorination of seawater yields almost exclusively CHBr355 because of the presence of high
bromide concentrations.
High concentrations of purgeable organics, which are not chlorination byproducts, have
been found in some drinking waters which use groundwater as the source. For example, in
Dubendorf, Switzerland, average tetrachloroethylene concentrations in the water supply in
one part of the city were 69 ppb.12 One well from which the city drew its water had average
C2C14 concentrations of 76 ppb.12 Similarly, C2C14 was found at concentrations up to 300
ppb in groundwater wells used by the city of Kalamazoo, Michigan for drinking water.56
Contamination from dry cleaning establishments were the cause of the above two problems.
In Nicaragua, CC14 concentrations of 1.1 ppb were found in a city’s water supply and tests
conducted on source wells close to an industrial park showed concentrations up to 2500 ppb
CC14.4 More and more contaminated groundwater aquifers in the vicinity of industrial dumps
are being discovered, especially in the southern U.S. where surface water supplies are in
short supply.57,58,59
Groundwater contamination is usually the result of improper disposal of industrial chem
icals. Most Cj and C2 chlorinated hydrocarbons have little affinity for soils34 so, when they
are dumped on the soil surface, their movement through the soil with water is only minimally
retarded.60,61,62 This mobility in the soil can result in the contamination of groundwater
aquifers.4,12,56 Most of these chemicals are highly resistant to biological degradation so they
pass through the soil unaltered.62
C. Health Effects
1. Toxicity
The toxicity of these chemical is low to moderate so direct toxic effects are not expected
at environmental concentrations.63 Occupational exposure to high concentrations or improper
use of these chemicals in confined spaces can lead to toxic responses.64
6
Table 3
TRIHALOMETHANE CONCENTRATIONS (|xg/l) IN WORLD DRINKING WATERS
Numberof CHC13 CHBrCl2_______________ CHBr2Cl______________ CHBr3

Location cities Range Median Range Median Range Median Range Median Ref.
U.S. 80 <0.1—311 21 <0.2— 116 6 <0.4— 100 1.2 <1.0-92 <1.0 2

Texas, U.S. 11 1.1— 14 2.5 NDa—53 0.3 ND— 173 ND ND-242 ND 44
(Ground waters)
Texas, U.S. 14 20—882 190 31—89 49 ND-125 11 ND-53 ND 44
(Surface water)
Canada 70 ND-83 9.0 ND-15 1.0 ND-6.5 ND ND-2.1 ND 3
Ontario, Canada 22 2— 121 22 ND-9 4.0 ND-5 ND NOT MEASURED 45
West Germany 39 0.1—52 2.5 ND-3.4 ND ND ND ND ND 46

Belgium 9 ND-26 2.5 0.2—5.3 0.8 0.2—5.5 1.5 ND-2.7 0.7 47
(Ground waters)
Belgium 7 4.4— 106 49 2.4— 38 20 0.4— 13 5.8 ND-0.7 ND 47
(Surface waters)
a Not detected.
Analysis of Trace Organics in the Aquatic Environment
7
2. Carcinogenic and Mutagenic Responses

Reviews of the carcinogenic and mutagenic properties of these chemicals have been
compiled by Fishbein.65,68 Vinyl chloride has been clearly implicated in causing angiosarcoma
of the liver in occupationally exposed humans.65 Increased incidences of cancer of the
pancreas, lung, and brain also occur in occupationally exposed workers.65 In addition to
vinyl chloride, 1,1-dichloroethylene, trichloroethylene, tetrachloroethylene, chloroform, car
bon tetrachloride, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane have been shown to
cause cancer (mainly of the liver) in experimental animals.60,61 These compounds have also
been demonstrated to be mutagenic in several bacterial assays.65,66,69 Very little data on the
carcinogenic or mutagenic properties of the fluorocarbons and the chlorobenzenes is currently
available.68
3. Epidemiologic Studies and Risk Factor Calculations

Since the discovery of the ubiquitous presence of THMs in drinking water, several studies
have been conducted to see whether exposure to chlorinated drinking water (and the chlo
rination byproducts) poses an additional cancer risk.70'81 Because of the difficulties in the
design of epidemiological studies such as the presence of confounding factors, inaccurate
records of exposure levels, etc., these studies have not provided conclusive proof of the
association between chlorinated compounds in drinking water and increased cancer risk.82
But the evidence from these studies suggests the possibility of a causal relationship for rectal
cancer and, to a lesser extent, for bladder and colon cancer.92
Crouch et al.83 have attempted to calculate cancer risk factors for several U.S. drinking
waters using analytical data for specific organics plus carcinogenic potency data for these
organics from animal studies. The total cancer risk was assumed to be the sum of the risks
for the individual chemicals. A large portion of the total risk factor was found to be due to
the purgeable chlorinated organics because of their presence at reasonably high (pg/1) con
centrations. The major deficiency of the study was the uncertainties caused by lack of good
dose-cancer response data for the brominated trihalomethanes. The investigators concluded
that the consumption of certain U.S. drinking waters might pose moderately high risk.83
4. Exposure Routes and Doses

A person’s total daily intake of a chemical will be the sum of his water, air, and food
exposure. Volatile halogenated compounds have concentrations in the range jxg/1 for water
(—2 1 consumed/d), (xg/m3 for air, (—22 m3 consumed/d), and pg/kg for food (—2 kg
consumed/d).84 For a typical North American the daily intake of CHC13 is about 60 pg —
67% from water, 23% from air, and 10% from food.84 For CC14 the typical daily dose is
7.7 pg — 23% from water, 62% from air, and 15% from food.84 For people who consume
chlorinated drinking water, their main source of THM exposure will be from their drinking
water.84 If a groundwater is contaminated with, for example, tetrachloroethylene, the major
source of this compound will also be the drinking water.85
The exposure of rats to CHC13, CC14, and C2HC13 resulted in elevated serum and adipose
concentration of these chemicals.86 The rats quickly reached a steady state concentration
after which continued exposure did not lead to increases in tissue or serum concentrations.
Within three to six days after exposure was terminated, most of these halogenated compounds
had disappeared from the serum and adipose tissue.86 The analysis of blood from humans
exposed to chlorinated drinking water (chloroform concentration —100 |xg/l) showed that
they had higher serum CHC13 levels than a control group which used unchlorinated (CHC13
free) water.87 Serum CHC13 levels were about 12 |xg/l in the exposed group.87
From this information it is apparent that exposure to volatile halogenated compounds at
doses in the 100 pg/d range leads to chemical concentrations in the body in the pg/kg range.
A concentration of chemical at the 1 pg/kg level in the body corresponds roughly to 1000
molecules of chemical per cell.88 Whether or not long-term exposure to chemicals in this
concentration range can cause problems is presently a matter of controversy, but it would
seem prudent to reduce our exposure to these chemicals where possible. For example, several
methods have been proposed for reducing drinking water THMs: aeration after chlorination;
carbon adsorption; flocculation prior to chlorination for precursor removal; ozone, chlorine
dioxide, and chloramines as disinfection alternatives, etc.89'91 The World Health Organization
has established a drinking water guideline value of 30 jxg/1 for chloroform.92 The Environ
mental Protection Agency93 have set 100 (xg/1 total THMs as the maximum permissible
concentration in U.S. drinking waters. A less stringent standard of 350 |xg/l has been proposed
by the Department of Health and Welfare for Canada.94
II. GENERAL ANALYSIS PROCEDURES
A. Sampling and Sample Preservation

The collection of an appropriate representative sample is a vital part of performing an
environmental assessment of a chemical. For water, grab samples are most commonly used,
but the preferred method for sampling is to collect a composite sample which integrates the
effluent, stream, or river over a much longer time frame, e.g., days. Commercially available
composite samplers have been tested for volatiles and they collect the sample with minimal
losses.95 But the sample vessels in these devices are open so sample storage over hours or
days will lead to volatilization losses. Westrick and Cummins96 have designed a composite
sampler for effluents. The collection vessel in this devise is a modified 2-1 graduated cylinder
into which a Teflon® float is snugly fitted. A series of samples is introduced through an
inlet at the base of the cylinder using a switching valve, and the float moves upward as the
sample volume increases. The float seals the liquid surface inhibiting volatilization losses.
More recently Tig well et al.97 have combined a multichannel positive displacement Teflon®
and glass sampler with the cylinder-Teflon® float collection vessel above, to collect composite
samples for volatile organics analyses. Unfortunately these two composite samplers are not
currently commercially available.
Recently Blanchard and Hardy98 have proposed a new method to obtain time-weighted-
average concentration values for volatiles in water. The method is based on the permeation
of volatile organics through a silicon polycarbonate membrane and should prove very useful
with further development.
Bottles used for sample collection and storage should be filled to overflowing and sealed
with Teflon®-faced silicon rubber septa. Samples stored at room temperature in this way
were shown to be stable for at least 8 to 10 days.99 Partially filled bottles can be stored at
4°C for at least 2 days without significant losses.95 It is recommended that water samples
be stored with as little headspace as possible at ~4°C and be analyzed within 1 week.
Because these compounds have a low tendency for adsorption or bioconcentration the
most important compartment in the aquatic ecosystem will be the water phase.100 However,
if it is necessary to analyze sediments, fish, or other biota for purgeable organics, the samples
should be sealed in glass jars with aluminum- or Teflon®-lined caps and frozen on collection.
Amin and Narang101 have shown that sediment samples could be stored up to 90 days if
methanol was added at the time of collection. Untreated samples should be analyzed within
7 days of collection to minimize volatilization losses.
B. Extraction, Concentration, and Cleanup

1. Sediments and Fish
Very few methods have been tested for determination of volatile organics in sediments
and fish. As mentioned earlier, this is primarily because only a limited amount of partitioning
into these phases in the aquatic environment is expected. The methods that have been used
fall into two categories — headspace analysis and solvent extraction.
9
Speis102 has tested the purge-and-trap technique for sediments (purge-and-trap method
ology will be discussed later). A sediment slurry consisting of 15 g of sediment in 100 ml
of water is heated to 80°C and purged with helium (60 ml/min) for 4 min. Recoveries from
the Tenax trap for sediments spiked with chlorform, 1,1,1-trichloroethane, toluene, tetra-
chloroethylene, and chlorobenzene in the concentration range 7 to 200 |xg/kg were fairly
low, 24 to 52%, but were consistent over the concentration range examined. Minimum
detectable levels were about 0.1 |xg/kg. Michael et al.103 have described a similar purge-
and-trap procedure for volatiles in soils, sediments, and sludges, and reported recoveries
mainly in the 60 to 100% range. Michael et al.104 have used a similar procedure, for recovery
of volatiles from human biological samples. Their recoveries from spiked urine and blood
were higher and more consistent than Speis’ but their recoveries from spiked adipose tissues
(which should behave similarly to fish) varied from 13% for chlorobenzene to 80% for
methylene chloride.
Recently, Amin and Narange101 have described a closed-loop-stripping technique for
volatiles in sediments. The method uses a Porapak N cartridge for adsorption of the organics
and methanol for elution of the chemicals from the cartridge. Recoveries over 80% were
obtained for many volatile priority pollutants.
The best procedure developed to date for fish appears to be the solvent extraction procedure
of Ofstad et al.43 This procedure could also be used for sediments although they did not test
it for this purpose. The method consists of extracting 5 g of homogenized fish with a mixture
of 5 ml pentane and 20 ml isopropanol in a 100-ml glass-stoppered centrifuge flash. After
2 hr of shaking, enough water is added to the mixture to separate the isopropanol and to
bring the pentane layer into the narrow part of the flask. After the addition of a small amount
of Na2S 04 the flask is centrifuged to separated the phases completely. The pentane layer is
transferred to a glass-stoppered 10-ml centrifuge tube. The extract is cooled in ice, treated
with 3 ml of concentrated H2S 04 to remove the lipids, and centrifuged to separate the layers.
The pentane layer is then transferred to another centrifuge tube where it is washed with 3
ml of water and then centrifuged prior to gas chromatographic analysis.
Pearson and McConnell17 used direct pentane extraction for volatiles in sediments and
fish, but did not report recoveries. Ofsted’s procedure43 would appear to be preferable since
wet sediments and fish must be used for analysis, so the isopropanol in the solvent mixture
would tend to dissolve the water in the sample providing better contact between the solvent
and the sample.
Hiatt105 has reported a vacuum distillation procedure using capillary gas chromatography/
mass spectrometry for qualitative analysis of fish tissue for volatiles. The procedure is
complex and would appear to require further development and simplification to be useful
for quantitative analysis.
2. Resin Adsorption
XAD resins have been used for isolating and concentrating volatile organics from water
samples.106115 The most commonly used resins are XAD-2 and XAD-4. Various sizes of
columns have been used from 1.2 mm X 25 mm107 up to 2.3 cm X 10 cm108 and flow
rates through the columns are kept at ~5 to 10 times the column bed volume using nitrogen
or helium pressurized water reservoirs. Sized resins with finer mesh sizes (e.g., 100/120
Chromosorb 102 or 104) have been shown to give better recoveries (63 to 100%).109 In
general, a 100-fold concentration factor can be achieved using this technique for the THMs.109
Higher concentration factors are possible for chlorobenzenes using large water volumes,114
but breakthrough of more volatile compounds such as chloroform occurs under these con
ditions.108,109 Detection limits are generally in the low ppb range. Most investigators purify
the resin using sequential soxhlet extraction with methanol, acetonitrile, and diethylether,106
and store the resin under methanol until use. James et al.115 reported that the use of the
solvent series methanol-diethyl ether-water sample, instead of the commonly used series
methanol-water sample, reduced impurities arising from the XAD-2 resins. Although resin
adsorption is widely used in the analysis of medium and low volatility compounds, it has
never been widely adopted for volatiles because of breakthrough problems and because it
is less convenient than several other procedures.
3. Direct Aqueous Injection

Nicholson et al.116 were first to report the determination of THMs in water using the direct
aqueous injection (DAI) technique. The water sample (9 |jl1) is injected into a gas chro
matograph equipped with a packed column and a scandium tritide electron capture detector.
A comparison of the THM results from the DAI method with the purge-and-trap technique
showed it produced much higher results (up to a factor of two).116 This discrepancy was
thought to be due to the conversion of nonvolatile THM intermediates to THMs in the high
temperature gas chromatographic injector. The DAI method was studied further by Pfaender
et al.117 They used a 63Ni electron capture detector and found that injection of more than 1
|xl of water led to loss in detector sensitivity. Therefore, they implemented a bypass valve
to vent the water so that larger injection volumes (up to 10 (jlI) could be used. In agreement
with the earlier study, Pfaender et al.117 showed that the DAI technique produced higher
results than the purge-and-trap method. But, they showed that a value close to the true THM
could be obtained if the sample was reinjected after purging it for 30 min with purified
nitrogen, and subtracting this value from the THM value determined before purging.
The DAI method is simple, since it does not require any sample treatment, and it can
easily be automated with a GC autoinjector. Automation would be more difficult if it was
nonvolatile THM intermediates. The method detection limit is about 1 (xg/1 and repro
ducibility is in the 2 to 5% range. Provided that suitable GC separation can be achieved,
the method should work well for THMs and for chlorinated ethanes and ethylenes, but it
may be insufficiently sensitive for mono- and dichlorobenzenes. To date, its main use has
been for monitoring THM concentrations in drinking water.845118
4. Liquid-Liquid Extraction.
Extraction of volatile organics into a water immiscible organic solvent is one of the simplest
procedures for sample concentration. The organic contaminants tend to partition preferentially
into the organic solvent from the water. The equilibrium between the two phases can be
expressed mathematically by the Nemst distribution law:
K d = C s/c w (1)
where KD is the distribution coefficient and Cs and Cware the concentration of the chemicals
in the solvent and water, respectively. The extraction efficiency of the solvent can be
represented by the following equation:
100 Kp
( 2)
k d + v w/v s
where E is the percent extraction efficiency and Vs and Vw are the volumes of the solvent
and water. If the distribution coefficient of the chemical is known, it is possible to predict
the volume of solvent and the number of extractions required to achieve the desired recovery
efficiency using plots such as those developed by Robbins.119
The most common solvent used for liquid-liquid extraction (LLE) of volatile organics is
pentane,110 120 127 although hexane,128 hexane-diisopropylether 1:1,129 methylcyclohex-
ane,130131 and xylene,132 have also been used. The use of pentane (boiling point 36°C) is
11
preferred by most investigators because it elutes from the gas chromatographic column before
most of the volatile halogenated compounds being measured. Also, sufficiently pure pentane
is readily available commercially. However, problems associated with solvent losses, because
of its high volatility, and with bubble formation in the syringes of autoinjectors129 have
prompted some investigators to use less volatile solvents. In general, a sample to solvent
ratio of between 10 and 25 is employed since recoveries for most halogenated volatiles are
over 80% at these water/solvent ratios.120 123 Higher sample to solvent ratios up to 100 have
been used but the recovery efficiency can be as low as 20%.110,127 However, recoveries are
concentration independent and reproducible, so high sample/solvent ratios can be used if
lower detection limits are required.127 Solvent extracts are not usually concentrated to smaller
volumes by evaporation because of the volatility of the analytes.
Enhancement of LLE recoveries can be accomplished by adding electrolytes such as
Na2S04 to the aqueous solution. This salting-out effect has been used by Oliver133 for
dihaloacetonitriles which are poorly recovered by simple LLE.134
LLE can be performed by manual shaking of the sample plus solvent in a centrifuge tube
or volumetric flask for 2 to 3 min. A more efficient method, when many samples are
involved, is to extract the samples in septum-sealed vials on a mechanical or orbital shaker
for —15 min. In both cases a sample of the organic layer (top) is collected with a syringe
and injected into the gas chromatograph for analysis. The method has a precision of about
7 to 14% and gives detection limits in the range 0.1 to 1.0 jxg/1.126
Recently, Folgelquist et al.135 reported a completely automated segmented flow LLE
procedure for volatile halogenated compounds. The mechanized system, which extracts the
sample in a glass coil coated with a hydrophobic layer and separates the layers with the aid
of a hydrophobic membrane, is coupled on-line to a gas chromatographic on-column injector.
Using an EC detector and injection volumes of up to 130 |xl, concentrations down to the
pg/1 level in seawater have been determined.135
5. Static Headspace
The tendency of volatiles to partition into the headspace over aqueous solutions has been
used by some investigators as a method of concentration. An aqueous solution with some
headspace is equilibrated in a thermostat for 20 to 30 min and a sample of headspace gas
over the solution is withdrawn with a gas-tight syringe. This headspace sample is directly
injected onto the gas chromatograph for analysis. A summary of the theoretical aspects of
the technique have been given by Drozd and Novak,136 and by Vitenbert.137 The method
has been used by Kaiser and Oliver138 and by Helz and Hsu139 for halogenated hydrocarbons
using headspace injection volumes up to 1 ml on packed GC columns. For determinations
on capillary columns either a small injection volume (—20 |xl)140 or some type of precolumn
cryogenic trap141 must be used to prevent losses in column efficiency. Procedures for op
timization and enhancement of the concentration of volatiles in the headspace by changing
temperature, salt concentration, and pH have been discussed by Friant and Suffet.142 Elevated
temperature and salt concentrations increase the concentrations of volatiles in the headspace.
Automated systems for headspace gas chromatography have been developed143,144 which
improve the feasibility of the technique.
In general, detection limits in the 0.1 to 1 \x/\ range are attainable by the technique,138
but the reproducibility is not exceptional ( ± 10 to 20%). The procedure also requires a fairly
long equilibration time (—30 min) and is much less convenient than the LLE procedure.
The use of distillation145,146 and cryogenic trapping of headspace volatiles19,147 has been
used to enhance the sensitivity of the method to the ng/1 range. These methods may be
useful for broad surveys to pinpoint sources but, to date, the accuracy and reproducibility
of the procedures have not been adequately demonstrated.
6. Purge and Trap

The most common method used for quantification of volatile organics in water is the
purge-and-trap (P&T) technique first developed by Bellar and Lichtenberg.148 Briefly, the
organics are purged out of solution into the vapor phase with a stream of inert gas, the vapor
is swept through a sorption trap where the organics are trapped, and the trap is heated and
backflushed with an inert gas to desorb the organics onto a gas chromatographic column.
A block diagram of the purge and trap system is shown in Figure 1. Various shapes of
stripping vessels have been tested and it was concluded that the Bellar-Lichtenberg design
(Figure 1) performed the best.149
The sample (5 ml) is purged with helium at ambient temperature for 11 min at a flow
rate of 40 ml/min. The trap normally employed is 2,6-diphenylene oxide polymer — Tenax
(60/80 mesh) or a combination of Tenax (2/3) and silica gel, grade 15 (1/3) about 0.27 cm
ID and 25 cm long. The organics are desorbed from the trap by rapidly heating it to 180°C
and backflushing for 4 min with a helium flow of —20 ml/min. During this desorption phase
the packed GC column should be kept at —30°C to trap the volatiles at the head of the
column. If a capillary column is used a much lower desorption purge rate must be used (~1
to 2 ml/min) over a longer time, and some type of cryogenic trap must be used at the head
of the column to prevent serious peak broadening.
The P&T technique has been used extensively in drinking water surveys2,3,4 and detailed
reports discussing methodology and recovery studies on various volatile organics are avail
able.148157 Several articles have been written showing that the P&T technique compares
favorably with other volatile organic methodologies.158"160 The detection limit of the method
is in the low jxg/1 range and the reproducibility is good, ± 10%.154 The P&T system and
an automated system version are available commercially from Tekmar Company, Cincinnati,
OH; Envirochem Inc., Kemblesville, PA; and Chemical Data Systems, Oxford, PA.
Although some attempts have been made to lower the detection limit of the P&T method
by increasing sample volumes,161 in practice this leads to several difficulties. Larger sample
volumes require excessively long purge times162 and large purge gas volumes which could
lead to breakthrough of some of the more volatile compounds from the sorption trap. If a
combination of larger sample volume and higher purging temperature is used, more water
accumulates in the trap. This leads to difficulties in the subsequent gas chromatographic
analysis. For these reasons, there is not much flexibility available in sample volume, purging
time, or purging temperature.154 For routine monitoring of drinking water or wastewater the
P&T technique has proved to be excellent.
Pankow and Rosen163 have reported a whole column cryotrapping technique that can be
used with the P&T system. It is necessary to have a gas chromatograph with a cryogenic-
equipped oven so the capillary column can be cooled to —80°C. The PT device must provide
a trap-drying step which involves the passage of dry carrier gas through the trap at an above
ambient temperature (—40°C) for a period of about 2 min. This trap drying step prevents
column plugging due to ice formation and permits the injection of all the material in the
sample onto the capillary column. The method thus provides excellent sensitivity and good
chromatography.
7. Closed-Loop Stripping
The last commonly used procedure for volatiles is the closed-loop-stripping (CSA) pro
cedure developed by Grob et al.164-167 A block diagram of a recent CSA system is shown
in Figure 2.168 A 1-1 sample is thermostatted at the desired temperature (~40°C) and air is
pumped through the solution, then through a small 1.5-mg activated charcoal trap, and then
back to the pump in a closed circuit for a period of —2 hr. In principle, all the volatile
organics are purged out of the water and are adsorbed on the charcoal trap. After the stripping/
adsorption is completed, the carbon trap is removed from the apparatus and the organics
FIGURE 1. Block diagram of the purge and trap system. (From Test Methods. Methods for Organic Chemical Analysis of Municipal and Industrial Wastewater,
EPA-600/4-82-057, Environmental Protection Agency, Cincinnati, OH, 1982.)
13
(d) DESORBER
FIGURE 1 (continued)
(c) PURGING DEVICE
15
FIGURE 2. Block diagram of the closed-loop stripping system A, temperature monitor; B,

heater block insulation; C, aluminum heating block with cartridge heater; D, glass filter
holder with carbon filter; E and F, temperature controller (maintains 50°C); G, thermostatically
controlled water circulator for I (set at 95°C); H, foam insulation; I, glass condensing column;
J, 1-L sample bottle; K, thermostatically controlled water bath circulator (set at 40°C); L,
metal bellows air pump; M, 1/8-in stainless steel tubing. (From Coleman, W. E. et al.,
Environ. Sci. Technol., 17, 571, 1983. With permission.)
are stripped off the trap with ~8 pd of carbon disulfide (CS2). About 2 |xl of this CS2 extract
is then injected on the GC for analysis. Because all the volatile organics in 250 ml of water
are injected into the GC, this method provides a 50-fold enhancement in sensitivity over
the P&T method. Unfortunately, recoveries of the more volatile compounds such as CHC13
are low with CSA169 so this method cannot be used for their quantification. For compounds
in the volatility range between benzene and hexachlorobiphenyl, CSA recoveries are ex
cellent.168,169 Thus, the method is recommended for and has been successfully used for
medium volatility compounds.167171 It has also been applied for the analysis of taste and
odor producing compounds in drinking water.172 174 The method detection limit is in the low
ng/1 range and its reproducibility is about ± 9%*168 the CSA system is available commercially
from Brechbuhler AG, Schlieren, Switzerland and from Tekmar Company, Cincinnati, OH.
C. Separation
1. Packed Column Gas Chromatography
The dimensions of packed columns used for this analysis normally range from 2 to 3 m
in length and have from 2 to 5 mm inside diameters. A wide range of packing materials,
including various polar and nonpolar liquid phases bonded to supports and a variety of porous
polymers, have been used for separation of the volatile organics. When the sample is
introduced to the chromatograph as a discrete plug, as in the case of injection in a solvent
or in headspace gas, columns with low polarity liquid phases with fairly high percentage
loadings are usually used to obtain rapid separations. For example, the current recommended
column for the LLE procedure is 10% Squalane or Chromosorb W AW, 80/100 mesh, and
a commonly used column in headspace analysis is 10% OV-1 on Gas Chrom Q, 80% 100
mesh.138 These columns are generally operated isothermally at 67°C and 50°C, respectively.
Argon/methane at 25 ml/min is used as the carrier gas and the injection port temperature is
about 100°C. An added advantage of the Squalane column is that materials such as dihalo-
acetonitriles, which decompose on many other liquid phases, can also be quantified.
In the P&T method a significant amount of time (« 4 min) is required to desorb the
contaminants from the Tenax trap onto the GC column. Because of this slow injection
considerable peak broadening will occur unless the organics are trapped in a narrow band
at the front of the GC column. More polar columns such as 1% SP-1000 on Carbopak B,
60/80 mesh,150 158 0.2% Carbowax 1500 on Carbopak C, 80/100 mesh,158 and Porapak C150
are used in the P&T method. To provide a better chromatographic focus it is also acceptable
to pack a ~ 5 cm section at the front on the analytical column with packing having a higher
loading of liquid phase e.g., 3% SP-1000 or 3% Carbowax 1500.158 Generally, the column
temperature is kept low 45 to 60°C during the desorption phase of the P&T method and the
temperature of the column is programmed at rates between 6 and 8°C/min to 160 to 220°C
to elute the organics.
2. Capillary Column Gas Chromatography

Although the separations of volatile organics on packed columns is generally quite good,
the use of capillary columns can improve separations and can lead to improved sensitivity
because of sharper peaks.120 A comparison of a packed vs. a capillary column chromatogram
for the THMs is shown in Figure 3.175 Special conditions must be used to attain good
separations on capillary columns, since the use of normal columns with film thicknesses of
0.1 to 0.25 |xm at normal operating temperature of 50° to 250°C would lead to very poor
separation of the volatile organics. First of all, columns with a thicker coating of liquid
phase 1 to 1.5 jx104123140 are required to increase the retention time of the volatile organics
in the column. Also cryogenic temperature programming of the gas chromatograph provides
a further increase in retention time for the volatile organics.147 Long capillary columns up
to 100 m in length125 and support coated open tubular columns (SCOT)104 have also been
used for volatiles.
The injection of analytes in a small volume of organic solvent or air yields an excellent
capillary chromatogram provided the conditions specified above are met. But, when the
P&T method is used some type of cryogenic focusing of the organics at the head of the
capillary column is required. Trussel et al.120 cooled the first loop of the capillary column
in liquid nitrogen to achieve the required focusing. The organics from the P&T Tenax trap
were desorbed with helium at a flow rate of 25 ml/min for 4 mn. Over this period and during
the analysis the column flow rate was 1 ml/min so only a fraction of the desorbed organics
were injected onto the capillary column. Trussel et al.120 observed no difficulties with this
procedure. Other investigators who have attempted to transfer to the capillary column a
much larger fraction of the organics (by desorbing at flow rates comparable to capillary
column flows) have run into difficulties with icing and plugging of the columns with traces
of water that are also desorbed from the Tenax trap. Special arrangements to overcome this
difficulty, using a section of wider bore capillary for cryogenic trapping prior to the analytical
column, have been reported by Kalman et al.176 and by Krost et al.177. As mentioned earlier
a trap-drying step can also be added to the P&T system to overcome this difficulty.163 With
the advent of gas chromatographs equipped with cryogenic ovens, whole column cryotrapping
can also be used.
D. Detection
The three most commonly used detector for volatile organics are the electron capture
detector (ECD), the electrolytic conductivity detector (ELCD), and the mass spectrometer
17
FIGURE 3. A comparison of a packed-column and

capillary-column chromatogram for the trihalomethanes
(CHC13, 100 |ig/l; CHBrCl2, 5 |xg/l; CHBr2 Cl, 4 (xg/1;
CHBr3, 2 p.g/1).
(MS). The ECD is usually used in the liquid-liquid extraction, the headspace, and the direct
aqueous injection methods. The ELCD is used almost exclusively with the P&T method.
The MS is used for all of the above methods as well as with the CSA technique. Both the
ECD and ELCD are halide sensitive detectors. The ECD has an excellent and large response
for compounds with three or more halide substituents but the sensitivity drops off exponen
tially for the di- and monohalo-substituted chemicals. The ELCD response is much lower
than the ECD response but is fairly uniform for all halosubstituted compounds regardless
of the number of halogens. These characteristics make the ELCD detector a better choice
than the ECD for the P&T method, where a fairly large quantity of material (all the organics
in the 5 ml sample) is injected into the GC.
The detection limits for the LLE/ECD, P&T/ELCD, and P&T/MS techniques are shown
in Table 4. The dramatic dropoff in sensitivity between tri- and di-substituted halogenated
compounds is apparent for the LLE/ECD method. A further reduction in sensitivity by a
factor of between 100 and 1000 is expected between di- and monohalosubstituted compounds.
This method would obviously not be the choice for compounds with few halogenated sub-
Table 4
METHOD DETECTION LIMITS (jtg/1) FOR
LLE/ECD, P&T/ELCD, AND P&T/MS178
Compound LLE/ECD* P&T/ELCDb P&T/MSb
Chloroform 0.5 0.05 0.1(83)c

1,1,1 -Trichloroethane 0.07 0.03 0.2(97)
Carbon tetrachloride 0.01 0.1 0.2(117)
1,2-Dichloroethane 9.0 0.03 0.2(62)
Trichloroethylene 0.09 0.1 0.2(95)
Bromodichloromethane 0.04 0.1 0.2(83)
Tetrachloroethylene 0.5 0.03 0.2(166)
Chlorodibromomethane 0.07 0.09 0.2(129)
Bromoform 0.2 0.2 0.5(173)
a Effective sample volume injected 0.04 ml.

b Effective sample volume injected 5 ml.
c Quantification mass, m/z.
stituents. A much lower fraction of the total organics in the sample is injected onto the GC
for the LLE procedure compared to the P&T method. In general, detection limits for all the
procedures in Table 4 are more than adequate for drinking water, since THMs are usually
present in the 1 to 100 (xg/l range2 and concentrations of concern for other compounds are
generally in the (xg/L range. If lower detection limits are required (as might be the case for
ambient waters) the headspace cryogenic trapping/ECD method of Comba and Kaiser147
could be used for the highly volatile compounds, and the CSA/MS procedure of Grob164
could be used for the medium volatility compounds.168 In both techniques the sensitivity
enhancement is achieved by injecting onto the GC the organics present in a larger portion
of the original sample 1 ml and 250 ml, respectively. If MS detection is used, enhanced
sensitivity could also be achieved using selective ion monitoring.179
The flame ionization detector26 128 178 180 has also been used for volatile organics even
though its sensitivity, particularly for halogenated compounds, is much lower than the halide-
specific detectors already discussed. It is useful for organics with few or no halogens. A
microwave emission detector has recently been applied to volatile organics and is reported
to have a good or better sensitivity than the ELCD and to offer element specific (bromine,
chlorine, iodine) responses.181182
E. Calibration
Calibration standards are prepared in methanol or other appropriate solvents by weighing.
(Ligon and Grade183 have proposed the use of the nonpurgeable polyethylene glycol) as a
carrier solvent for the P&T technique.) A few drops of the chemical are added to a previously
weighed flasks containing the solvent and the flask reweighed to obtain the concentration.
For halocarbons that boil below 30°C (bromomethane, chloroethane, chloromethane, di-
chlorodifluoromethane, trichlorofluoromethane, and vinyl chloride) a gas sampling syringe
containing the chemical is positioned just above the solvent in a preweighed solvent-con
taining flask and the chemicals slowly added. The heavier than air gas rapidly dissolves in
the solvent, and, after the addition is completed, the flask is reweighed to determine the
concentration. Samples of these individual concentrated standard solutions are pipetted into
a flask containing the appropriate solvent to obtain a mixed standard solution at fairly high
concentration, from which dilute standard solutions in the required concentration range can
be prepared. The diluted mixed standards, which are usually freshly prepared each working
day, are used to calibrate the instrumentation. Calibration must be carried out on a daily
19
basis and may even be required periodically throughout the day if detector responses are
prone to change. The concentration of chemicals in the samples being quantified must be
within the concentration range of the calibration standards.
Both the external standard (ES) and internal standard (IS) approaches have been used for
volatile organics. In the ES approach for the LLE procedure, a series of standards in pentane
(or other solvent being used) is prepared and calibration graphs for the gas chromatographic
procedure are derived for each compound to be quantified. The sample extracts are then run
using the same conditions. For the headspace or P&T techniques the external standards in
methanol or poly(ethylene glycol) are added directly to purified water at various concentra
tions and calibration graphs are obtained using the analytical protocols to be used for the
samples. For example, for the analysis of chloroform by the P&T method, varying amounts
of chloroform would be added to 5 ml of purified water in the P&T vessel, and each standard
would be carried through the entire procedure to construct the calibration graph.
In the IS procedure a compound or series of compounds having similar properties to the
analytes but not found in the sample are added to each sample or sample extract. These
internal standards must also be well separated from the study compounds on the gas chro
matograph. The comparative response factor (RF) of each analyte to the internal standard
is first measured:
RF - As Cls/Als Cs (3)
where As = response for the parameter to be measured als = response for IS, Cls =
concentration of Is, and Cs = concentration of parameter to be measured. After the RFs
for each compound have been determined the samples with added IS are run and the
concentration of chemicals are determined using the following equation:
Concentration (|xg/I) = As Cls/Als (RF) (4)
Some IS that have been used are dibromoethane,126 bromochloromethane, 2-bromo-l-chlo-

ropropane, 1,4-dichlorobutane,150 and aaa-trifluorotoluene.151 The IS procedure should pro
vide more consistent data than the ES procedure but there is little, if any, literature information
comparing the two approaches.
III. RECOMMENDED METHODS
The LLE/ECD method is recommended for routine monitoring of drinking water for THMs
and for several other halogenated solvents such as trichloro- and tetrachloroethylene because
the method exhibits good sensitivity for these compounds, both the extraction and chro
matographic procedures are simple, and the method is easily automated. For general volatile
organics scanning of drinking water, wastewater, and ambient waters the P&T/ELCD method
is recommended. This method provides good sensitivity for a broader range of compounds,
is reasonably simple and can be partially automated. Detailed methods for sediments and
biota are not presented because the methods are still in the developmental stage, and because
the need for such methods (because of the low tendency of the compounds to partition into
these phases) has yet to be demonstrated.
A. LLE/ECD Method
Add 10 ml of glass-distilled pentane to the water sample in a Teflon®-lined septum-sealed
120 ml hypovial (actual volume 160 ml). This is accomplished by injecting the pentane into
the inverted bottle with a syringe, a second syringe needle (also piercing the septum) allows
10 ml of water sample to escape from the filled bottle as the pentane enters.121 Place the
samples on an orbital or wrist action shaker for 15 to 20 min. Sample the pentane (top)
layer with a syringe and inject on the gas chromatograph. Alternatively remove 1 to 2 ml
of the pentane layer with a syringe or pipet and place in an autosampler vial for autoinjection
onto the GC.
The primary gas chromatographic column used in this analysis is a glass, 2.74 m x 2
mm ID, column-packed with 10% Squalane on 80/100 mesh Chromosorb W AW. Chro
matographic conditions are: oven 68°C isothermal; injection port, 100°C; 63Ni ECD, 350°C;
argon:methane (90:10) carrier gas flow, 20 ml/min; injection volume, 2 |xl (syringe or
preferably autoinjector). A second more polar column of similar dimensions packed with a
phase such as 6% OV-11 and 4% SP-2100 on 100/120 supelcoport126 can be used for
qualitative confirmation. An integrator should be coupled to the GC output since peak areas
rather than peak heights are preferred.
Prepare standard solutions to the analytes in pentane to span the range of concentration
required. Run the samples using the same conditions. The chemical concentrations in the
sample are calculated by dividing the concentration in the sample extract, after correction
for the blank, by 15. Because at the solvent to sample ratio of 1:15 recoveries for volatile
organics are greater than 80%, losses due to incomplete recovery are usually neglected. The
precision of the method for concentrations in the low ppb range is about ± 10 to 15%.126
If the gas chromatographs in your laboratory have capillary capability or if you are in the
process of purchasing a gas chromatograph, you should seriously consider using capillary
rather than packed columns for volatile analyses. Capillary columns are expensive but
currently available bonded phases are extremely stable so columns can be used for at least
six months to a year. The primary column should be either OV1 or SE54 or equivalent
(1 |xm film thickness, 60 m length) with the more polar OV17 as the secondary confirmation
column. Split or splitless injection (2 |xl) could be used depending on sensitivity requirements
with helium as the carrier gas (linear velocity 20-30 cm/sec). An acceptable temperature
program would be: initial temperature 70°C (initial hold 10 min), 5°C/min to 200°C (final
hold 20 min).
When analyzing chloroform and less volatile compounds hexane should be substituted for
pentane as the extraction solvent, since there are fewer operational problems with this less
volatile solvent.128
B. P&T/ELCD Method
The P&T device consists of the sample purger, the trap, and the desorber (see Figure 1).
The trap consists of 7.7 cm lengths of Tenax, silica gel, and activated charcoal. If it is not
necessary to analyze the dichlorodifluromethane, the charcoal can be eliminated and the
Tenax polymer section lengthed to 15 cm. The desorber must be capable of heating the trap
from room temperature to 180°C in less than 30 sec to effect rapid desorption of the organics.
P&T devices are available commercially (see Section II.B.6) and detailed design parameters
have been published150 152 so no further discussion is required here.
Inject 5 ml of sample into the purging device with a syringe. Purge sample with helium
at 40 ml/min for 11 min. After purging, heat trap rapidly to 180°C while flushing with
helium at 25 ml/min in the reverse direction for 4 min. After desorption, initiate temperature
program on gas chromatograph. All lines between the trap and the GC must be heated to
80°C to prevent condensation.
The primary gas chromatographic column for this method is 2.44 m long x 2.7 mm I.D.
stainless steel or glass packed with 1% SP-1000 on Carbopak B (60/80 mesh). Chromato
graphic conditions are: oven initial temperature 45°C for 3 min, program at 8°C/min to
220°C, final hold 15 min; injection port 175°C; helium carrier flow rate 40 ml/min. The
secondary confirmatory column recommended has the same dimensions as the primary
21
column but contains n-octane coated-Porasil-C (100/120 mesh). The initial column temper
ature for this column is 50°C (3 min hold) then the column is programmed to 170°C at 6°C/
min and held for 4 min.150 An electrolytic solvent (2-propanol/water, 50/50, v/v) flow 0.12
ml/min, a hydrogen gas flow rate of 10 ml/min, and a furnace temperature of 820°C are
used for the Hall electrolytic conductivity detector.156
The P&T plus detection device is first calibrated by spiking 5 ml of prepurified and
prepurged distilled water with the chemicals of interest and carrying them through the entire
procedure or by using the internal standard approach as described in Section II.E. Blanks
must also be run. The samples are then analyzed by the same procedure. The precision of
the method is about 10 to 20% for concentrations in the low ppb range.
As previously recommended for the LLE method, capillary columns should be used if
practicable. For the P&T method, a P&T device with an additional adsorption-column drying
step and a gas chromatograph equipped with a cryogenic oven are also required if capillary
columns are used.
C. Confirmation
The gas chromatographic methods with halide-sensitive detectors cannot be used to un
ambiguously identify volatile organics. The certainty of the identification is improved if a
second column is used, but positive identification requires both qualitative and quantitative
detection with a mass spectrometer. Once a positive identification of a compound in a certain
vicinity has been established by MS, monitoring and surveillance activities can be carried
out using LLE/ECD or the P&T/ELCD methods with the occasional confirmation by GC/
MS. The coupling of the P&T device with a mass spectrometer for both qualitative and
quantitative analysis has been discussed in detail by Munch et al.178 They used the internal
standards fluorobenzene for aromatics and 2-bromo-l-chloropropane for aliphatics and report
good agreement with the P&T/ELCD method for specific samples. A comparative evaluation
of the GC/MS and the GC/electrochemical detector approach has been made by Brass.184
Although the capitol investment is high, the use of GC/MS must be considered a viable
method for routine analysis if a mass spectrometer is available and can be devoted to this
purpose. Although the cost per analysis is higher, the added certainty of the organic iden
tifications may make this a cost-effective procedure.
D. Future Directions
The methodology for volatile organics in water is reasonably well advanced, but the
methods for other matrices are only in the developmental stage. Although adsorption to
sediments and bioconcentration by biota in the aquatic environment may be of minor im
portance as pointed out earlier, methods for matrices such as soils are needed because
dumping on land can lead to groundwater contamination. Therefore, soil analysis methods
should aid in the identification of pollutant sources. Also there is a complete lack of inter
laboratory comparison studies for these compounds due to the difficulty in producing stable
aqueous solutions for round robin studies. Research into methods of preparing samples
suitable for such studies and actual interlaboratory comparisons are needed.
The improvement and increased automation of existing methodologies is also a future
requirement. Automation in both the sample extraction and in the data analysis are required
so that environmental agencies can keep up with increasing analytical demands with de
creasing manpower resources. The trend toward capillary column chromatography to improve
separations and quantitations is continuing. The direct coupling of capillary columns to mass
spectrometers185 improves the efficiency of sample transfer and also eliminates adsorption
and decomposition losses at the GC/MS interface. This may be particularly important for
labile compounds such as the dihaloacetonitriles. The development of mass selective detectors
may lead to improved sensitivities for volatile organics if selective ion monitoring is used
and will definitely lead to more certain compound identifications. These detectors are prob
ably already inexpensive enough to be devoted to volatile organic analysis.
REFERENCES
1. Rook, J. J., Formation of haloforms during the chlorination of natural waters, Water Treat. Exam., 23,
234, 1974.
2. Symons, J. M., Bellar, T. A., Carswell, J. K., DeMarco, J., Kropp, K. L., Robeck, G. G., Seeger,
D. R., Slocum, C. J., Smith, B. L., and Steven, A. A., National organics reconnaissance survey for
halogenated organics, J. Am. Water Works Assoc., 67, 634, 1975.
3. National Survey for Halomethanes in Drinking Water, Report No. 77-EH-9, Department Health and Welfare
Canada, Ottawa, Ontario, 1977.
4. Trussell, A. R., Cromer, J. L., Umphres, M. D., Kelley, P. E., and Moncur, J. G., Monitoring of
volatile halogenated organics: a survey of twelve drinking waters from various parts of the world, in Water
Chlorination: Environment Impact and Health Effects, Vol. 3, Jolley, R. L., Brungs, W. A., and Cumming,
R. B., Eds., Ann Arbor Science, Ann Arbor, MI, 1980, 39.
5. Rook, J. J., Chlorination reactions of fulvic acids in natural waters, Environ. Sci. Technol., 11, 478, 1977.
6. Steven, A. A., Slocum, C. J., Seeger, D. R., and Robeck, G. G., Chlorination of organics in drinking
water, J. Am. Water Works Assoc., 68, 615, 1976.
7. Oliver, B. G. and Lawrence, J., Haloforms in drinking water: a study of precursors and precursor removal,
J. Am. Water Works Assoc., 71, 161, 1979.
8. Peters, C. J., Young, R. J., and Perry, R., Factors influencing the formation of haloforms in the
chlorination of humic materials, Environ. Sci. Technol., 14, 1391, 1980.
9. Hoehn, R. C., Barnes, D. B., Thompson, B. C., Randall, C. W., Grizzard, T. J., and Shaffer,
P. T. B., Algae as sources of trihalomethane precursors, J. Am. Water Works Assoc., 72, 344, 1980.
10. Oliver, B. G. and Shindler, D. B., Trihalomethanes from the chlorination of aquatic algae, Environ. Sci.
Technol., 14, 1502, 1980.
11. Briley, K. F., Williams, R. F., Longley, K. E., and Sorber, C. A., Trihalomethane production from
algal precursors, in Water Chlorination: Environmental Impact and Health Effects, Vol. 3, Jolley, R. L.,
Brungs, W. A., and Cumming, R. B., Eds., Ann Arbor Science, Ann Arbor, MI, 1980, 117.
12. Giger, W. and Molnar-Kubica, E., Tetrachloroethylene in contaminated ground and drinking waters,
Bull. Environ. Contam. Toxicol., 19, 475, 1978.
13. Water-Related Environmental Fate of 129 Priority Pollutants, Report EPA-440/4-79-029b, U.S. Environ
mental Protection Agency, Cincinnati, OH, 1979.
14. Kirk Othmer Encyclopedia of Chemical Technology, Vol. 5, John Wiley & Sons, New York, 1979, 668.
15. Jolley, R. L., Pitt, W. W., Taylor, F. G., Hartmann, S. J., Jones, G., and Thompson, J. E., An
experimental assessment of halogenated organics in water from cooling towers and once-through systems,
in Water Chlorination: Environmental Impact and Health Effects, Vol. 2, Jolley, R. L., Gorchev, H., and
Hamilton, D. H., Eds., Ann Arbor Science, Ann Arbor, MI, 1978, 695.
16. Lovelock, J. E., Natural halocarbons in the air and in the sea, Nature, 256, 193, 1975.
17. Pearson, C. R. and McConnell, G., Chlorinated Cj and C2 hydrocarbons in the marine environment,
Proc. R. Soc. London Ser. B, 189, 305, 1975.
18. Hammer, P. M., Hayes, J. M., Jenkins, W. J., and Gagosian, R. B., Exploratory analyses of trich-
lorofluoromethane (F-11) in North Atlantic water columns, Geophys. Res. Lett., 5, 645, 1978.
19. Kaiser, K. L. E. and Valdmanis, I., Volatile chloro- and chlorofluorocarbons in Lake Erie — 1977 and
1978,7. Great Lakes Res., 5, 160, 1979.
20. Oliver, B. G. and Nicol, K. D., Chlorobenzenes in sediments, water, and selected fish from Lakes Superior,
Huron, Erie, and Ontario, Environ. Sci. Technol., 16, 532, 1982.
21. Young, D. R. and Heesen, T. C., DDT, PCB and chlorinated benzenes in the marine ecosystem off
southern California, in Water Chlorination: Environmental Impact and Health Effects, Vol. 2, Jolley,
R. L., Gorchev, H., and Hamilton, D. H., Eds., Ann Arbor Science, Ann Arbor, MI, 1978, 267.
22. Kaiser, K. L. E., Comba, M. E., and Huneault, H., Volatile halocarbon contaminants in the Niagara
River and in Lake Ontario, 7. Great Lakes Res., 9, 212, 1983.
23. Kaiser, K. L. E. and Comba, M. E., Volatile contaminants in the Welland River watershed, 7. Great
Lakes Res., 9, 274, 1983.
24. Correia, Y., Martens, G. J., Van Mensch, F. H., and Whim, B. P., The occurrence of trichloroethylene,
tetrachloroethylene and 1,1,1-trichloroethane in western Europe in air and water, Atmos. Environ., 11,
1113, 1977.
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Sometimes you will find the beak of a swimming bird telling a
different story. It will be a very strong beak, with notches along it. It is
a fish-eating swimmer. Its rough bill is to hold fast to the slippery fish.
Then, too, you may find webbed feet which have a new story to tell.
You may find a webbed foot, quite small, with a very long leg. The
web goes only part way to the toe nail. That bird could not swim. No.
He was a wading bird.
His long stilt-like legs held his body above the water, while he
watched for his fish food. The webs in his feet served, not to make
him a paddle-foot, but just to keep him from sinking in the soft sand
or mud. Or you may find the webs changed to broad flaps on each
toe.
Now turn to the hen. Is her beak made for digging in mud, under
water? No. Her short, strong beak is for picking up grain or insects
from the ground. Now see what feet she has to match this beak. She
has walking feet. Her feet are large and strong, with separate toes
and strong nails. How does she use her feet? She spends nearly all
her time scratching and digging in the ground. She scratches up the
earth with her toes. She finds insects, worms, larvæ, and such
things, to eat.
Once more look at a beak. Take the swallow’s short, wide, widely
opening beak. Watch the swallow as he flies. Now up, now down!
Now here, now there! He wheels, he makes a dash! He feeds upon
the wing. He eats insects. See that short, broad mouth, which opens
as wide as his whole head, and shows his big yellow throat. Is it not
just the thing for catching insects?
The swallow sweeps after the insect, and into that open throat it
goes! What story will this beak tell?
The story of a bird made for flying fast and far. The story of a bird
built to wheel and turn quickly. It must have large wings, a very light
body. As its head is so wide, it must be flat, or it will be too large.
This bird does not need to walk. Its food is in the air. Its legs and feet
will be very small. Its toes will be long, and made for holding or
clinging to trees or roofs. Its feathers must be close set; and its tail
be well shaped for a rudder.
Suppose some one shows you the foot of an ostrich. It is a huge
foot, with two great toes. You will say at once “that is a walking foot.”
It is not to be carried into the air. These great toes are not for
digging, but for walking or running.
Look at the soles of these toes. They are cushioned or padded thick.
That bird must live where the soil is soft, and these padded feet will
keep him from sinking. Yes, he lived on the desert sand. He is the
largest bird in the world. He can run faster than a horse. Such a bird
could not be lifted into the air on wings. He has short, stout wings,
which he flaps as he runs, and as they have large feathers on them,
they catch the air as sails do, and so help him along.
His bill is like a huge hen’s bill. He eats melons, grass, and grain.
These are some of the stories told by beaks and feet.
LESSON XXX.
TREE, GROUND, AND WATER BIRDS.
In old times they told fables of birds which had no feet, and lived
always on the wing. There are no such birds. All birds have feet, all
rest from flying. But the motion of flying is so beautiful and easy, that
it is no wonder that birds of strong flight are much upon the wing.
The eagle and hawk families are very swift of flight, and spend most
of their time mounting and wheeling. They are keen of sight, and
from great heights will see their prey, and swoop down upon it.
The swallow family seems never tired of flying. They feed upon the
wing. The tiny humming-birds move their wings so quickly, you
cannot see them. They hover with this motion while they drink honey
from flowers. They are very seldom seen resting.
Pigeons are among our swiftest birds. Have you noticed how thirsty
pigeons are? That is because they are very hot blooded. They need
much hot blood to warm up in their lungs the air which they drive
through their hollow bones. Thus they make a kind of balloon of their
bodies. The pigeon’s body helps to keep it up in the air.
Many of the birds that live much on the wing build their nests on or in
trees. I shall tell you a little of nests in another lesson. Now we will
speak of one or two tree-living birds.
The butcher bird, or shrike, is about the size of a robin. It is a pretty
bird, gray or brown in color. Its food is living things, as beetles, bees,
mice, and young birds. It has a very curious habit. It brings home
part of its food, and hangs it on a thorn near its nest.
The butcher bird chooses trees with thorns or sharp twigs, and
makes its nest among them. Then on the thorns, all about the nest, it
hangs insects and little animals. I saw one of these nests once,
about which hung a young bluebird, a beetle, three bees, and a big
AT THE POND.
spider.
I have thought it may hang up little dead animals partly as a trap for
big blue-bottle flies. For these flies cluster about the dead bodies,
and the shrike, keeping guard near his nest, picks them up at his
ease.
A much nicer bird, one which I wish lived in our country, is the bower
bird. This bird makes its nest in a tree, but fashions a little arbor for
itself, among the grasses. Into its grass palace it brings all the pretty
things it can find. Shells, bright stones, bits of cloth, glass, bones,
flowers, are all brought to its little play-house. Would you not love a
bird which had such pretty ways?
Of all the birds in our own land, none is more splendid than the
cardinal bird of the South. He has a crimson beak and plumes. His
song is very sweet. He is a brave bird, and very kind and polite to his
mate. It is very cruel to kill such a creature for its feathers.
In the North, we have the blue jay, nearly as fine a bird as the
cardinal. He has a jet-black collar, a bright coat of shaded blue, and
a white neck-tie. Indeed, he is a fine, gay, saucy, cheerful bird. But
he has a very naughty way of breaking up the nests of other birds,
and stealing their eggs.
The jay likes to have his home near the water, and when you go near
it, he comes out and scolds loudly.
But now we will turn from birds which make their homes in trees, and
look a little at birds that live on the ground. You will at once think of
the barn-yard fowls, and their many cousins.
Have you seen a barn-yard full of these birds? It is a fine sight.
There are the spotted guinea fowls with their fretful cry, and the great
peacocks spreading their splendid trains. There are the black, white,
yellow, spotted, red, and green-breasted cocks and hens, and there
are pheasants which seem to be dressed in rainbows.
Among these fowls the turkey struts, spreading his tail like a wheel,
and scraping the tips of his wings on the ground, as he walks high on
his toes. Far out in the Western woods, you may see the wild turkey,
which is nearly as fine a bird as a pheasant or a peacock.
Turkey hens are very good mothers. They seem very fond of their
little ones, and are always on the watch to guard them. By nature
they are shy birds, and like to run away, and hide their nests. One
will go off and hide a nest, and seem very proud to come back with a
train of fifteen or more little ones.
Grouse, partridges, and quails, are ground-living birds, related to our
common fowls. So are the pretty prairie-hens of the West. The quail
is a dear little bird. Sometimes in the winter, when the snow is deep,
and it cannot find food, it will come to the barn-yard or the door-step,
and feed with the fowls. Once, in the woods, I came softly to an
opening, and there were about twenty quails feeding on a bed of
squaw-berries. They ran about picking up berries and making happy
little sounds, like a band of children enjoying a holiday.
One day I was going through a pine-wood path, when a mother quail
and ten little ones ran across the roadway. She hid in the brush, and
began to call, “Come! Come! Come!” and from the other side of the
path, little squeaks replied, “Yes! Yes! Yes!”
Soon three more brown, fluffy balls ran across the road. Then out ran
the little brown mother in great distress. Her neck feathers stood out
in a collar. “Come! come! come!” she called. “Wee! wee! wee!” said a
little faint voice, and tumbling along the foot path, went one more
small bird. “Now she has them all,” I thought.
But still, out of the brush, the anxious mother cried, “Come! come!”
and at last, dropping into ruts, rolling in the dust, too new and weak
even to say, “Wee,” hardly able to keep on his legs, went the tiniest
little bird! He followed his mother’s voice, and slipped in among the
brush and pine needles.
When the little brown mother had all her brood, she made a sweet,
low, glad note in her hiding place. “O Mrs. Quail!” I cried; “can you
count? Can you count fifteen?” She never told me whether she could
or not. But she had counted fifteen that time, that was sure.
Now, let us take a peep at the birds which live mostly on the water;
you will think first of the great, solemn white swans. Then of the
snowy geese and of the parti-colored ducks. What splendid colors
ducks have!
If you live by the sea, you will often watch the gulls and gannets with
their wide white wings. All these birds build their nests in reeds and
grass along the bank, or in ledges of rock in a cliff.
One day I was sitting behind some rocks on a little island. All at once
I heard a hearty laugh. I rose up softly, and looked over the rocks.
There on the water sat, all alone, a water-fowl. I hid my head and
gave a loud “ha! ha! ha!”
Then the bird threw back his head, and gave a laugh with all its
might. It made me think of what my grandfather used to say to the
boys, if they were too loud in their mirth for his taste. “Do not laugh
like a loon,” he would say.
Is it news to you that a bird can laugh? The water-fowl and I laughed
at each other for a long time. Then I rose and stood in plain sight.
Down he went under the water, and I saw him no more. I wish you
would read a lovely poem written by the poet Bryant, about “The
Water-fowl.”
Once I was out on the sea in a boat. We saw lying on the water the
tail of a fish. We rowed near. Well! Here was a sight! A large duck,
called an alwife,[25] had tried to swallow a fish. But the fish was too
big for her throat. Having got part of it in, she could get the fish
neither in nor out. So she and the fish had both choked to death, and
were floating around in the water.
A very famous man once said, that he thought a gull must be the
most happy of birds. It can swim, fly, walk, almost equally well. It is at
home on earth, water, or air.
I have seen a bird called “The Diver.” It goes down under water for
its food. It uses its wings under water to swim with, and will stay
there a long time. Most ducks will dive, and come up a long way from
where they went down.
The water birds all have close, thick plumage. Most of the down
which we use, comes from the water birds of the far North. The down
not only keeps them warm, but keeps air in its meshes, and helps
them to float. It is like a cork jacket for them.
Water birds live chiefly on fish, crabs, and little water animals. But
many of them eat seeds and berries of plants growing along the
coast. They will readily pick up any kind of food thrown upon the
water. Gulls follow ships for days to get the scraps thrown overboard
by the sailors.
FOOTNOTES:
[25] Alwife is probably a short form of “Old Wife.” This duck is
often called the “Old Squaw” on the Cape Cod coast.
LESSON XXXI.
ON THE WING.
In the spring and summer, you go to field and garden, and you hear
and see many birds. As you walk about the woods, you may see a
dozen kinds of birds in a few minutes. There will go a yellow-bird,
looking like a canary. There, all splendid in black and gold, an oriole
is busy building his curious nest. There flies from the swamp a red-
wing blackbird. A big woodpecker drums on the nearest tree. A
bluebird with a russet breast sits singing on the top rail of a fence.
Sparrows, swallows, crows, are everywhere.
Out of the grass whirrs up a lark with his brown and yellow coat, and
black velvet collar. The thrush sings in a bush. The catbird, in the
shade, cheers his mate with a rich, mellow note, and then darts out
into the sunshine in his glossy drab dress.
But in late autumn, or in winter, you walk abroad, and where are all
the birds? A crow may sit, scolding, on a dead limb. A social robin
may flit down to your door. The velvet sparrows may be balls of
noise and feathers. But where are the other birds? Are they all
dead?
Oh, no! They have flown off to sunny lands, where they will have
mild weather, and food in plenty, and green trees. The birds migrate.
What is it to migrate? It is to go from one place to another a long way
off. They migrate as the season changes.
Let us take that pretty bird, the bobolink, as an example of a bird on
his travels. In the winter months he is feasting and singing in the
warm West India Islands. There he finds grubs, insects, and seeds in
plenty. He grows so fat, that they call him the butter-bird.
About the first of April, he finds Jamaica too hot for him, and flies
over to Georgia, or South Carolina. He settles in the rice-fields, and
ROBERT O’ LINCOLN.
eats so much rice that he is a great trouble to the planters. They call
him the rice-bird. But they are soon rid of him. About the middle of
May, the rice-bird, with hundreds of his relations, goes up to Virginia
and Pennsylvania.
At this time, he eats May-flies, caterpillars, and various insects. But
his taste for seeds continues, and he devours the young wheat and
barley at a great rate. The farmers name him the reed-bird. Many
reed-birds are shot, and sent to market.
In spite of the guns, the bobolink seems now in the gayest hour of
his life. He sings with all his might, and his black and white coat, with
its touches of yellow, is at its best.
But again he starts northward. He goes up to New York, and New
England, and appears in the orchards and wheat-fields, at the end of
May, or the first of June. There he is called, from his song, the
bobolink.
But Mr. and Mrs. Bobolink must now set themselves to the serious
business of making a nest, and rearing a family. They choose a good
nest place, and begin to build in a great hurry. Mrs. Bobolink is not
so gayly dressed as her mate. She is brown, with a little dull yellow
in her plumage.
Mr. Bobolink ends his wildest songs when the little birds come from
the shells. Their mouths are always wide open, crying for food. Mr.
Bobolink is very busy feeding his children. He flies back and forth all
day long, bringing insects to his nursery. The gay concerts are
ended.
At this time, too, Mr. Bobolink changes his clothes. He puts on a
working suit, with more brown in it. His gay plumes do not come
back until the next spring.
After the little ones learn to fly, in August, if it is hot, the whole family
may go to Canada, for a trip. But as soon as the cool September
mornings come, all the bobolinks think of the South. They gather in
great companies, and turn their heads toward the West Indies.
Now and then, they may rest for a few hours, or a warm day or so,
but they fly pretty steadily southward. When cold weather has come,
we see no more bobolinks. They are all busy eating and singing in
the sunny tropic lands.
I wish you would all read, and perhaps learn to recite a charming
poem called “Robert o’ Lincoln.” It was written, by the great poet
Bryant, about this little bird of many names, and many homes.
Now from the story of the bobolink, you see the manner of this
migration of birds. You see why birds migrate. It is to keep where
they find the food and the weather which they prefer. Its cause is the
change of the season. As the season changes the food changes.
Some birds move away because it is growing too hot where they are,
and they like cooler places. Again, there are birds which stay near us
in the winter, and fly North in the summer, almost to the land of
constant snow.
Those birds which breed in the cold polar regions often find a winter
home in the Northern States. But some birds which breed in the
coldest climates fly to hot countries for their winter of rest and play.
When birds come in the spring, and leave in the fall, they rear their
young where they make their summer home. We call them our
summer birds.
Our winter birds are those which come to us in the cold weather, do
not build nests near us, but fly away when the season grows warm.
While they stay near us, they take shelter at night in shrubs or
evergreen trees.
What we call birds of passage are birds that stop with us for only a
few days, as they are flying long distances, half round the world,
perhaps.
Then there are birds, as the robin, sparrow, thrush, which may stay
all the year round near one place. In the warm weather they build
nests, and rear their young. In cold weather, such birds are often
driven near houses and barns to get food.
Crows may stay all winter in one place if food is plenty. If they cannot
find enough to eat, they gather in great numbers, and fly to places
where they will get more food.
When I was a child, I read that swallows, cuckoos, corn-crakes, and
other birds, would lie torpid all winter. The book I read told me that
the birds would cluster in great masses, silent, nearly frozen, eating
nothing, and in the spring would wake up fresh and gay. That is not
at all true. They do not lie torpid. They fly away.
Birds gather in great numbers, with much noise and flurry, to get
ready for a trip. Crows, storks, cranes, swallows, and others, fly in
great flocks. By the sea-side you may hear a far-off cry and a rush of
wings, and looking up, you may see a flock of wild geese, or ducks,
on their journey, flying far out over the water.
When a vast flock moves in this way, they seem to have some few
wise old birds for guides, in advance, and some for guards on each
side of the band. Geese fly in a V-shaped line, for hours at a time.
When they need to stop for food, they break the V line and fly in
disorder. They seem to search the ground for a feeding place. A
cornfield suits them best, and they settle for a feast. If they cannot
find a cornfield they will try a swamp.
Hawks travel over half the world. The hawk, which summers on the
Scotch hills, may go to Egypt for winter, and perch on the pyramids.
The stork, which the little Dutch children in Holland feed and love,
may go to Africa for Christmas. The birds which you feed in July will
be singing in Hayti or Brazil in January.
What is very strange is, that birds will, year after year, come back to
the very place and nest that they left. The oriole, catbird, bluebird,
jay, titmouse, and others, will each summer return to the same vine
or tree, to build a new nest or repair the old one.
They come singing back, and we are glad to see them. But from their
songs we get no news of the fair tropic lands where they have been
happy amid rich fruits and flowers.
LESSON XXXII.
NEST BUILDING.
I think nothing about birds is more interesting than their way of
building their nests. In this lesson we will look at a few curious nest-
builders.
First, let me tell you that that largest of birds, the ostrich, builds no
nest. She puts her eggs in the sand. The sun-heat is all they need
during the day, and the father-bird cares for them at night. A few
birds lay their eggs in heaps of dead leaves, and let the leaves keep
them warm.
The cuckoo,[26] and the cow-bird[27] lay their eggs in the nest of
some other bird. They choose a bird smaller than themselves, and
put one egg in its nest. Then they go to another nest, and so on, until
their eggs are laid.
A few birds lay their eggs right on the earth, or sand, and make no
nest at all. But they sit on the eggs, and brood them. Most birds
make nice, careful nests. They seem to take pride in building good
homes.
A lady who has carefully studied the ways of birds, says that all birds
of a kind do not build equally good nests. For instance, some robins
build very strong, neat nests. Others build loose, untidy nests, which
will hardly hold the eggs.
This same lady says that birds, by practice, improve in nest building.
As a rule, she thinks the old birds, that have built for several years,
make better nests than robins building for their first brood. She says
she watched a robin, which had a home in her garden. That robin
improved in nest building, and built better and better each year.
Perhaps no bird builds a more firm, neat, and elegant nest, than that
ON THE TREE TOP.
smallest of all,—the humming-bird. This bird does not need a large

nest, she is so tiny, and her eggs, usually only two, are like small
beans. The nest is made in the shape of a cup. It is built of soft
moss, or the downy seeds of plants. These are pressed and
moulded until they are almost like felt.
The nest is made quite thick. All over the outside, the bird fastens
bits of moss, or lichens. These are stuck on with a kind of glue, from
the bird’s mouth. This is done, not so much for beauty, as to conceal
the nest. When thus pasted over with moss, it looks like a knot or bit
of tree branch.
This tiny bird is very shy, and wishes to hide its nest. It is so
cunningly built, that even when close by it you are little likely to see
it.
The bird does not fly straight to, or from, this nest. That might lead
enemies there. Instead, it rises high, straight up into the air, and
when up out of sight, takes its direction as it chooses. When it comes
back, it pursues a similar plan. From far up in the air, above the nest,
it drops straight down, like a little fiery star, into its home.
The goldfinch is another bird which glues mosses on the outside of
its nest to hide it. While this is done rather for use than beauty, I think
most birds like to have a pretty home. I have seen birds weave bits
of colored wool, or silk, in and out the nest, plainly for the sake of the
color, and not for strength.
All the finch family line their nest with down or feathers. The wood-
wren, on the contrary, lines its nest always with hair, and never with
feathers. She goes far and wide to find soft hairs for this use.
I think an oriole’s nest is one of the most beautiful of bird-homes.
The mother-oriole makes the nest, and her mate brings her wool,
fine root-fibres, hairs and threads, which she uses. If he brings her a
bit which she does not like, she throws it away, and seems to think
him a bird of very little sense.
If Mrs. Oriole is not suited with her work, as it goes on, she tears it
down, and goes to work again. She wants it just right.
The nest is in the shape of a long pocket, and is sewed firmly to
some twigs on the end of a branch. It is very curious to see the
stitches which are taken in and out, with string, or long horse-hairs.
The nest is tied firmly to the tree, and is woven very firmly together. It
is lined with downy seeds. The entrance is small and near the top,
and the nest is larger at the bottom, where the young birds will lie.
The tailor-bird sews even better than the oriole. She takes a large
leaf, bends the edges against those of a leaf near, and carefully
sews them together, with bits of fibre for thread, while her bill is the
needle. When this leaf-purse is made, the cunning little mother fills it
half full of cotton-like down, from plants, and her home is made.
Sometimes she chooses a large leaf, and sews its edges together.
The object of these nests is to have them hung far out, where
snakes cannot get at the eggs or young. For you must know that
snakes are cruel enemies of birds.
The house-sparrow likes to build her nest under overhanging eaves.
If she builds where she has not a roof of that kind, she makes a roof
for herself, of straw.
Many birds, as the woodpecker, titmouse, and others, find a hole in a
tree, and put in a soft lining. This makes a very nice, safe home.
The golden-crested wren makes a most lovely nest of mosses,
woven firmly together with spiders’ webs and cobwebs. It is very
delicate and pretty.
Just the opposite of this is a magpie’s nest. That is a large platform
of coarse twigs, and over it a roof, quite as large, of twigs, while all
around it the magpie sets up a thorn fence. You would hardly think a
bird could build such a house.
Once I found the nest of the song thrush. It was large, and made of
grass, straw, and such things, all firmly plastered with mud. It was
nearly as smooth inside as a china bowl. I wondered that this little
bird could build such a large, heavy nest.
Many birds which live near the water build their nests among the tall
reeds. They will bind three or four reeds together, with the nest hung
between them.
No doubt you have often found the neat little round nest of the
bluebirds, or yellow-birds, nicely woven of hairs, and made smooth
and soft inside. Sometimes their soft, smooth nests are woven of
fine, soft fibres. It is wonderful how fine and clean they are, after the
little busy bird has made them ready for her home.
Many birds build in clefts of rocks, or under large overhanging stones
by the water-side. Their chief thought seems to be, to have the nest
safely hidden. Other birds build right on the ground. Have you never
found a lark’s nest, low among daisies, grass and buttercups?
Last summer I found two nests of the meadow pipit, or peewee.
They were built of dry grass in a hollow, shaded by some bramble-
berry bushes and big dandelions. I had one of these nests drawn for
the cover of this Reader. It was a very pretty bower, and the little
birds grew up safely.
Most birds build each one alone, but in Africa the weaver-bird lives in
colonies. The nests are built like very large wasps’ nests. Sometimes
one or two hundred birds will build in one place. They make a roof
for the nest.
I began by telling you of very little nests. I will end by telling you of a
very big nest. I saw the nest of a fishing eagle, in a great pine-tree.
The nest was built of large sticks. It was nearly as large as a half
barrel. The tree was dead. A tree always dies when an eagle builds
in it. This nest was more like a great rough platform than a nest. It
had a wall of sticks about it to keep the little eaglets from falling out
before their feathers grew.
FOOTNOTES:
[26] The cuckoo in England lays in the nests of other birds. The
American cuckoo does not.
[27] The cow-bird is also called the cow-bunting.
LESSON XXXIII.
THE BIRD AT HOME.
You have now seen the bird building a nest, and you have seen the
finished nest. Let us take a little look at the bird at home. Let us have
a peep at the family life of birds.
The mother-bird lays two, four, six, or more eggs in her nest. Each
kind of bird has its own kind of eggs. The wood-pigeon has a pure
white egg; the blackbird’s egg is a bluish green, with russet spots;
the cuckoo’s egg is of a yellowish tint with red and brown marks; the
kingfisher’s egg is yellow with orange spots; the robin’s egg is a
lovely greenish blue. Some eggs have purple spots, some are brown
with red spots.
Each bird knows its own eggs. Sometimes a lazy cow-bird puts her
eggs in the nest of a wren or bluebird, while that bird is away looking
for food. When the bird comes home, she knows at once the strange
egg in her nest. She scolds and cries. But, in the end, she takes care
of it.
When eggs are put into a nest in this way, it is the strange egg which
thrives. The cow-bird hatches before the eggs among which it lies.
Then the mother-bird at once begins to feed her adopted child, and
her own eggs are left and do not hatch.
The young cuckoo is so big and strong that it pushes its foster
brothers and sisters out of the nest, and lives there alone. The good
mother-bird, perhaps only a little sparrow, tires herself out bringing
insects for the wide-open beak of her big, greedy child.
The mother-bird is very patient all the long days, or weeks, while she
must sit brooding her eggs. If you go near her, she may fly off, or she
may cower close over her eggs, and look at you in a very timid way. I
am sure you will hurry past, and not terrify the dear little thing.

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Revival: Analysis of Trace Organics in

the Aquatic Environment (1989) First

Investment in blood the true cost of Britain s Afghan

Advances in Energy and Built Environment Select

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Revival: Computer Chemistry (1989) First Edition

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Revival Safe Drinking Water 1985 the Impact of

Aquatic Fitness Professional Manual 7th Edition Aquatic

Alfred S. Y. Chau, M.Sc.

Reissued 2018 by CRC Press

© 1989 by Taylor & Francis

No claim to original U.S. Government works

A Library of Congress record exists under LC control number: 88037888

ISBN 13: 978-1-138-50562-9 (hbk)

B. K. Afghan, Ph.D. Iling-Biu Lee, Ph.D.

ANALYSIS OF VOLATILE HALOGENATED AND PURGEABLE ORGANICS

II. General Analysis Procedures........................................................................................8

III. Recommended Methods.............................................................................................. 19

A. Production and Uses

Boiling Point Vapor pressure

Chloromethane CH3C1 -2 4 .2 3765 6450—7250 0.91

1.4- Dichlorobenzene C6H4C12 174 0.6 79 3.4

Thousands of metric tons

Vinyl chloride 1534 2289

able compounds during wastewater treatment occurs mainly by volatilization; biodegradation

Numberof CHC13 CHBrCl2_______________ CHBr2Cl______________ CHBr3

U.S. 80 <0.1—311 21 <0.2— 116 6 <0.4— 100 1.2 <1.0-92 <1.0 2

West Germany 39 0.1—52 2.5 ND-3.4 ND ND ND ND ND 46

2. Carcinogenic and Mutagenic Responses

3. Epidemiologic Studies and Risk Factor Calculations

4. Exposure Routes and Doses

II. GENERAL ANALYSIS PROCEDURES

A. Sampling and Sample Preservation

B. Extraction, Concentration, and Cleanup

3. Direct Aqueous Injection

6. Purge and Trap

FIGURE 2. Block diagram of the closed-loop stripping system A, temperature monitor; B,

2. Capillary Column Gas Chromatography

FIGURE 3. A comparison of a packed-column and

Compound LLE/ECD* P&T/ELCDb P&T/MSb

Chloroform 0.5 0.05 0.1(83)c

a Effective sample volume injected 0.04 ml.

Concentration (|xg/I) = As Cls/Als (RF) (4)

Some IS that have been used are dibromoethane,126 bromochloromethane, 2-bromo-l-chlo-

III. RECOMMENDED METHODS

smallest of all,—the humming-bird. This bird does not need a large

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Numberof CHC13 CHBrCl2_ CHBr2Cl CHBr3