EPA560/f 75003
A REVIEW OF
CONCENTRATION TECHNIQUES
FOR TRACE CHEMICALS
IN THE ENVIRONMENT
NOVEMBER 1975
OFFICE OF TOXIC SUBSTANCES
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
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EPA 560/7-75-002
A REVIEW OF CONCENTRATION TECHNIQUES
FOR TRACE CHEMICALS IN THE ENVIRONMENT
EPA CONTRACT No, 68-01-2925
EPA PROJECT OFFICER: VINCENT DECARLO
FOR
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF Toxic SUBSTANCES
WASHINGTON, D,C. 20460
NOVEMBER 1975
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This report has been reviewed by the Office of Toxic
Substances, EPA, and approved for publication. Approval
does not signify that the contents "necessarily reflect the
views and policies of the Environmental Protection Agency,
nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.
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ABSTRACT
The purpose of this report is to present a survey of
the methods which have been used for the concentration of
trace substances from the environment prior to analysis.
Methods for the preconcentration of organic and
inorganic (particularly heavy metal) compounds from water,
air and solids (soil and tissue) are discussed. The general
characteristics of each method are presented, and they are
discussed in terms of their applicability to a large-scale
monitoring effort.
The recent literature on the bioaccumulation of trace
substances has also been reviewed. While most bioaccumulation
is non-quantitative in nature, plant and animal studies may
serve as useful indicators of long-term contamination of
the environment.
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TABLE OF CONTENTS
PAGE
SECTION ONE
INTRODUCTION
1.0
1.1.
1.2
1.3 '
1.1
SECTION TWO
2.0
2.1
2.1.0
2.1.1
2.1.2
2.1.3
2.2
2.2.0
2.2.1
2.2.2
2.2.3
2.2.H
SECTION THREE
3.0
3.1
3.1.1
3.1.2
3-1.3
Accumulation Systems
Parameters Which Affect Accumulation
Criteria for Comparing Concentration
Techniques
Comments on Analytical Procedures
Format of the Report
ACCUMULATION FROM WATER
Introduction
Accumulation of Organic Compounds
Introduction
Extraction
Adsorption
Other Metho,ds
Accumulation of Inorganic Solutes From
Water
Introduction
Che lat ion/Extract ion
Ion Exchange
Coprecipitation and Cocrystallization
Head Space Analysis
ACCUMULATION OF TRACE ELEMENTS FROM
AIR
Introduction
Particulate Sampling
Filtration
Inertial Separation
Electrostatic Precipitation
1
2
3
H
6
8
9
9
11
17
29
31
31
34
40
46
51
173
175
179
189
199
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TABLE OP CONTENTS (CONT.)
PAGE
3.1.4
3.2
3.2.1
3.2.2
3-2.3
SECTION FOUR
4.0
4.1 •
4.2
4.3
SECTION FIVE
5.0
5.1
5.2
5.3
Thermal Precipitation
Gas Sampling
Absorption
Adsorption
Condensation
ACCUMULATION FROM SOLIDS
Introduction
Soils and Plants
Accumulation by Extraction
Headspace Analysis
BIOACCUMULATORS
General Discussion
Characteristics of Bioaccumulatpr
Systems
Bioaccumulator Methods
Presently Most Suitable Bioaccumulators
201
202
203
211
221
356
357
363
365
418
420
426
430
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LIST -OP TABLES
PAGE
SECTION ONE INTRODUCTION
SECTION TWO ACCUMULATION FROM WATER
2-1 Solvent Properties of Liquid 12
Chromatographic Interest
2-2 Compounds Tested for Retention on XAD-2 22
and XAD-7 Resins
2-3 Accumulation of Organic Substances from 54
Water by Compound
2-4 Accumulation of Organic Substances from 84
Water by Accumulator
2-5 Accumulation of Metal Ions from Water 121
SECTION THREE ACCUMULATION OF TRACE ELEMENTS. PROM AIR
3-1 Characteristics of Absorbers — 208
Approximate Range of Use
3-2 Accumulation of Inorganic Substances 227
from Air
3-3 Accumulation of Organic Substances from 236
Air by Compound
3-4 Accumulation of Organic Substances from 295
Air by Accumulator
SECTION FOUR ACCUMULATION FROM SOLIDS
4-1 Common and Chemical Names of 367
Organochlorine Pesticides
4-2 Common and Chemical Names of 368
Organophosphorus Insecticides
4-3 Common and Chemical Names of Carbamate, 369
Substituted Urea, Uracil, Benzonitrile,
Analides, Analines and Amide Pesticides
4-4 Common and Chemical Names of Triazine 370
and Dipyridinium Pesticides
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LIST OF TABLES (CONT.)
Bibliographic entries for all data referenced
in tables in Sections Two through Five are
presented at the end of each table or each
section in which the tables appear.
PAGE
4-5 Common and Chemical Names of Acidic 371
Pesticides
4-6 Common and Chemical Names of Some 371
Miscellaneous Pesticides
4-7 Inorganic Accumulation from Soil 372
4-8 Inorganic Accumulation from Plants 385
4-9 Organic Accumulation from Soil 391
4-10 Organic Accumulation from Plants 403
SECTION FIVE BIOACCUMULATORS
5-1
5-2
5-3
5-4
5-5
5-6
5-7
5-8
5-9
BIBLIOGRAPHIES
Prospecting by Plant Analysis
Plants That Have Been Used As
Indicators in Prospecting
Physiological and Morphological Changes
in Plants .Due to Metal Toxicities .
Bioaccumulation of Toxic Substances
from Air
Bioaccumulation of Toxic Substances
from Soil
Bioaccumulation of Substances from
Fresh Water
Bioaccumulation of 4 Toxic Substances
from Salt Water
Bioaccumulation of Toxic Substances
from Tissue
Bioaccumulation of Toxic Substances
from Fresh Water Culture
427
428
428
432
434
444
451
458
465
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LIST OP FIGURES
SECTION ONE
INTRODUCTION
PAGE
SECTION TWO
2-1
2-2
2-3
2-4
2-5
ACCUMULATION FROM WATER
Schematic Diagram of a Cell Used to
Collect Headspace Vapors from Solids
and Liquids
Tenax Injection Port
Chelation/Extraction by DQA and APDC
Selectivity Coefficients for Uni- and
Di-Valent Ions on DOWEX 50-X8 Ion
Exchange Resins
Cocrystallization by Thionalid,
2-mercaptobenzimidazole, and
5,7-Dibromo-8-Hydroxyquinoline
26
26
37
42
50
SECTION THREE ACCUMULATION OP TRACE ELEMENTS FROM
3-1
3-2
3-3
3-4
3-5
AIR
High Volume Air Sampler with Shelter 183
Common Cascade Impactor Designs 191
Andersen Air Sampler 194
Lundgren Impactor 195
Absorption Devices 205
SECTION FOUR ACCUMULATION FROM SOLIDS
SECTION FIVE BIOACCUMULATORS
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SECTION ONE INTRODUCTION
1.0 Accumulation Systems
Many toxic materials are present in environmental
media in concentrations (generally in the parts per
million to parts per trillion range) which are large
enough to have adverse effects on human health but too
small for direct detection and measurement. In such
cases a preliminary accumulation, or preconcentration
step is necessary before accurate quantitative analyses
can be made. Such preconcentrations can be carried out
using a wide variety of mechanical, chemical, and bio-
logical systems, which will be considered here under the
general title of accumulation systems.
This report summarizes current research into the
application of accumulation systems to the collection of
toxic chemicals from a number of environmental media,
including air, fresh and salt water, and soil. The sys-
tems considered exploit a wide variety of chemical,
physical, and biological principles, including mechanical
filtration (for the separation of dispersed particulate •
phases), chelation, ion exchange, solvent extraction,
adsorption, and active transport.
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1.1 Parameters Which Affect Accumulation
Accumulation systems can work on chemical, physical,
or biological principles. Where the accumulant exists
as a separate, dispersed phase within a particular medium,
a physical separation of phases will often suffice for its
concentration. An example of this is high-volume sampling
for particulate air pollutants. When the accumulant is
dissolved in or adsorbed onto the medium, however, some
kind of chemical separation is necessary. Chemical
separations include such processes as extraction, adsorp-
tion, and complex formation. In biological accumulation,
a living system processes the medium and incorporates
the chemical into its own structure.
The efficiency of accumulation can be determined by
the collection parameters which describe both the medium
and the concentration technique. Some of these parameters,
such as temperature and sample size are important for all
accumulation methods. Other parameters are only relevant
for selected systems. For an accumulation from aqueous
media the pH and ionic strength of the water are often
important. For the concentration of trace substances
from air, the sampling rate or pressure are important
parameters. Variation of any of these parameters may
be used to vary the types of compounds which are accumu-
lated by a given system.
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The method of concentration which is the most sensitive
to the widest variety of parameters is bioaccumulation.
Any factor which affects the growth and metabolic rate of
an organism (i.e. temperature, food supply, light) will
affect the rate of uptake of a trace element. This makes
it very difficult to obtain accurate quantitative information
on trace contaminants from biological systems, although they
can be excellent qualitative indicators of contamination.
1.2 Criteria for Comparing Concentration Techniques
For most samples containing a trace chemical in an
environmental medium more than one accumulation method can
be used to concentrate the sample for analysis. A number
of criteria are used to choose the best method, the most
important of which are:
1. Quality of Results
a) reproducibility of accumulation
b) stability of samples during collection or storage
c) ease of preventing extraneous results due to
impurities in the sampling system
d) range of useability (i.e. pH, temperature, salt
concentration, accumulant concentration)
e) concentration factor
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2. Costs
a) monitoring time requirements and sample sizes
b) adaptability for field monitoring
c) degree of technical ability needed for accurate
and reproducible, use of the accumulator system
d) ability to recover expensive reagents and
materials
3. Relationship to Subsequent Procedures
a) ease of interface with chosen method of
analysis
b) degree of specificity of collection
Point three relates to the means of analysis and the
additional processing that must be done to prepare the
concentrated sample for analyr-is. Since the ultimate
choice of an accumulation system should be made with the
analytical method in mind, an additional consideration is
the quality of the results obtainable from the chosen
method of analysis.
1.3 Comments on Analytical Procedures
Currently, the most widely used methods for the
quantitative analysis of environmental samples are gas-
liquid chromatography (GLC) for organic substances and
atomic absorption spectroscopy (AAS) for trace metals.
•-4-
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Advantages shared, by both methods include:
a) excellent interfacing with some accumulation
systems
b) mixtures can generally be analyzed without time
consuming pre-separations
c) high sensitivity and reproducibility of results
d) ease of operation
Infrared spectroscopy (IR) and nuclear magnetic
resonance spectroscopy (NMR) are not suitable for organic
trace analysis in most substances because of low sensitivity
and lack of selectivity. "Wet" analysis and colorimetric
analysis are sometimes used for inorganic trace analysis,
but these methods usually require tedious separations.
In certain cases, however, an effective interface can be
made between an accumulation method with high specificity
and a colorimetric assay.
New methods are emerging which combine the attractive
features of GLC and AAS with increased abilities for quali-
tative analysis. For organic samples, the combination of
gas chromatography with mass spectrometry (GC/MS) is very
effective for both identification and quantitative analysis
of the components of complex mixtures. Liquid-liquid
chromatography will undoubtedly soon emerge as an important
method for the separation and analysis of organic compounds,
particularly for water-soluble or non-volatile species.
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Similarly, the method of x-ray flourescence (XRF) is
capable of identifying and assaying mixtures of trace
metals. It is, moreover, a nondestructive technique which
is suitable for the direct analysis of particulate matter
on a filter. Other methods that are used to identify and
analyze inorganic samples include spark source mass
spectrometry, emission spectroscopy, and neutron activation
analysis. Cost is the most serious drawback to the use of
these newer methods. Equipment for XRF costs 5-6 times as
much as equipment for AAS; GC/MS can cost 20 times as much
as GLC.
1.4 Format of the Report
The discussion of accumulation systems in this report
has been organized by the medium from which the trace
element is accumulated: air, water, or a solid phase (soil
and tissue). Bioaccumulation has been treated separately
because, in this case, the parameters which affect the
accumulation are more dependent upon the technique and
species used than on the medium from which the accumulation
takes place.
Each section consists of a general description of
the concentration methods which are used for analysis
from the given medium. This includes a discussion of the
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physical or chemical basis for the method, along with a
description of the experimental techniques which are
currently being used.
A chart is included at the end of each section or sub-
section which lists the accumulation procedures which have
been found in the literature along with the chemicals which
were obtained and the analytical details. A complete biblio-
graphy of the relevant literature also follows each section
or subsection.
Section Two will discuss concentration techniques which
are used for the isolation of chemicals from aqueous
solutions. Organic and inorganic accumulants are treated
in separate subsections. Section Three describes accumu-
lation techniques for air samples. Its two major subsections
deal with gaseous materials and particulate matter. Section
Four treats accumulation from solid media such as soils and
living tissues. Bioaccumulation from all media is discussed
in Section Five. Biological analysis is a very important
part of any environmental program. Naturally occurring
systems serve as valuable indicators of long term problems
with toxic materials.
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SECTION TWO ACCUMULATION FROM WATER
2.0 Introduction
Aqueous systems contain a large number of elements and
compounds in trace quantities. These can enter a body of
water from the waste streams of factories or dwellings,
from run-off from the.soil, or from impurities picked up
by rainwater from the air. In order to concentrate such
substances for analysis they must first be separated from
the water and then from any other major constituents of the
system. With sea water, for example, this requires a
separation from the salt which is present in a concentration
of about 3%.
There are many problems with obtaining a "characteristic"
sample from an aqueous system since the concentrations of
trace chemicals can vary with the temperature and flow rate
of the water. The actual quantitative measurement of a
sample is fairly simple since the volume is insensitive to
most collection parameters. Usually a grab sample is taken
using a glass or polyethylene bottle. Otherwise,, water can
be passed through an adsorption column for the collection of
trace contaminants. The most important sampling parameters
are pH, ionic strength, and in some cases, temperature.
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In general, methods for the accumulation of trace
substances from aqueous systems do not vary significantly
between fresh and salt water, since the properties of the
accumulant are the primary consideration in choosing a
concentration technique. Therefore this section deals with
both media.
2.1 Accumulation of Organic Compounds
2.1.0 Introduction
Organic compounds can be roughly divided into two
classes based upon the water solubility of the neutral
molecules. The compounds which are of interest as pollutants
and toxicants are almost invariably among the lipophilic, or
non-water soluble organics. The possibility of toxic effects
of such compounds is increased by the fact that they may
easily be taken up by lipophilic tissues and accumulated in
animals. Such accumulation is much less likely for water-
soluble organic molecules which may remain in solution while
passing though the body. Water-soluble organics such as
humic acids, sugars, and proteins are non-volatile and
therefore are not amenable to measurement by gas chromato-
graphy, currently the most common technique for organic
separation and analysis. Methods for accumulating these
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water-soluble organic molecules usually involve isolation
and purification for a single desired substance. Because of
this lack of generality in accumulation methods as well as
the limited number of references to such compounds they will
be mentioned only briefly in this report.
Immediate polarity compounds such as glycols, phenols
and small organic acids can usually be separated from water
into an organic phase with the proper choice of pH and
extraction solvent. pH control is important since a
compound in an ionized form will tend to be much more water-
soluble. Very volatile organic compounds such as chloroform
or benzene also require care in their accumulation and -.
analysis to avoid loss by evaporation. A number of special
methods have been devised to measure these compounds.
As mentioned above, gas chromatography (GC) is currently
the method of choice for the separation of organic mixtures.
A flame-ionization detector is used for the analysis of
most organic compounds. Not only does this detector give
sub-nanogram sensitivity, it greatly simplifies sample
preparation since it is insensitive to air and water. The
electron-capture detector and micrometer are even more
sensitive for halogenated compounds than the flame detector.
The two methods which are most often used for the
accumulation of organic molecules from water are liquid-
liquid extraction and adsorption onto a lipophilic surface.
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Other methods, such as reverse osmosis and distillation,
will be discussed only briefly since they have been applied
only to a very limited extent.
2.1.1 Extraction
Extraction is probably the most widely-used method ••
for the accumulation of organic compounds from various en-
vironmental media. The accumulation of organic compound-s
from water by extraction with various solvents is dis- ,
cussed below. The variables involved include the nature
of the solvent, the ratio of solvent to water, the pH of
the water, and the ionic strength of the water.
The single most important parameter to consider when
selecting an organic solvent for extraction is its polarity,
It is convenient to measure polarity in terms of e ,•
a value derived from the use of the solvent in liquid
chromatography on alumina columns. Table 2-1 gives.the .
e° values for a large number of the most common solvents.
These values range from 0 for pentane (and even negative
values for fluoroalkanes) through about 1 for solvents
such as ethylene glycol. Inspection of this increasing
series of polarities shows that the more polar solvents
(above approximately e°=0.5) are water-soluble, whereas
those below e°=0.5 are not. In order to extract lipophilic
organic compounds from water one needs to select a water
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TABLE 2-1V
SOLVENT PROPERTIES OP LIQUID CHROMATOGRAPHIC INTEREST
SOLVENT e°(Al203)
Fluoroalkanes 0.25
n-Pentane 0.00
Isooctane 0.01
Petroleum ether 0.01
n-Decane 0.04
Cyclohexane 0.04
Cyclopentane 0.05
1-Pentene 0.08
Carbon disulfide 0.15
Carbon tetrachloride 0.18
Xylene 0.26
i-Propyl ether 0.28
Toluene 0.29
Chlorobenzene 0.30
Benzene 0.32
Ethyl bromide ' 0.37
Ethyl ether 0.38
Ethyl sulflde 0.3b
Chloroform 0.40
Methylene chloride 0.42
Methyl-i-butylketone 0.43
Tetrahydrofuran 0.45
Ethylerie dichloride 0.49
Methylethylketone 0.51
1-Nitropropane 0.53
Acetone 0.56
Dioxane 0.56
Ethyl acetate 0.58
Methyl acetate 0.60
Amyl alcohol 0.6l
Dimethyl sulfoxide 0.62
Anailine 0.62
Diethyl amine 0.63
Nitromethane 0.64
Acetonitrile 0.65
Pyridine 0.71
Butyl cellusolve 0.74
i-propanol, n-propanol 0.82
Ethanol 0.88
Methanol 0.95
Ethylene glycol 1.11
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insoluble extraction solvent, thus limiting the use of the
more polar solvents. The exact selection of a solvent from
among this nonpolar, water-immiscible group depends on the
range of organic compounds which is to be accumulated from
the water. Pentane, for example, is ideal for extracting
alkanes, but not very efficient for extracting fatty acids.
Methylene chloride, on the other hand, is particularly
effective for a wide range of solutes. It will efficiently
extract alkanes and fatty acids, for example. Other more
aromatic solvents may be suitable for extracting polycyclic
aromatic hydrocarbons from water.
Although the more polar extraction solvents cannot
be used for direct extraction of water, they are particular-
ly important for fractionating extracts obtained with non-
polar solvents. For example, certain pesticide analyses
are based on an initial extraction with methylene chloride.
This methylene'chloride extract is in turn extracted with
a more polar solvent such as acetonitrile in order to re-
move the more polar components from the methylene chloride
extract. This type of dual extraction can have wide ap-
plicability and excellent specificity when dealing with
a known class of solutes.
A review of the literature indicates that methylene
chloride has been used for the accumulation of organic
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compounds from the Charles River in Boston; that pentane
has been used for the accumulation of dissolved organic
p
material in sea water; and that benzene has been effec-
tively used for the accumulation of organochlorine and
•3
organophosphate insecticides from lake waters.
The second important parameter, the solvent-to-
water volume ratio, can be selected from considerations
such as the known solubility of the organic solvent in
water and the concentration effect to be achieved. With
most of the nonpolar solvents the use of about 50 to
100 milliliters of solvent per liter of water seems to be
suitable.
The pH of the water in an extraction influences the
chemical nature of the compounds which are extracted.
For example, to extract both neutral and acidic com-
pounds from water one would adjust the-pH to 1 or 2.
To extract both neutral and basic compounds, the pH would
be adjusted to 13 or 14. Extracts obtained under these
conditions .can frequently be further separated into neu-
tral and, for example, acidic components by another ex-
traction at suitable pH.
1. Kites, R.A., and Biemann, K., Science, 178: 158-69 (1972)
2. Blumer, M., in Proc. Symp. Organic Matter in Natural
Waters. Hood, D.W., ed., Univ. of Alaska, 1970.
3. Konrad, J.G., Pionke, H.B. and Chesters, G., Analyst.
94: 490-492 (1969).
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Ionic strength is a parameter which is seldom ad-
justed, although it is important for the efficient ex-
traction of material from fresh water. Solutions of
high ionic strength dissolve less organic solute than
solutions of low ionic strength. Therefore, when ex-
tracting fresh water, it is advisable to increase its
ionic, strength with, for example, sodium chloride before
proceeding with the extraction.
Large concentration factors can be achieved with sol-
vent extraction. The primary concentration factor is due
to the differential volume ratio of water to organic sol-
vent (a factor of 10 to 20). Subsequent concentrations
can be achieved by evaporating the organic solvent to a
very low volume. For example, if one liter of water is
extracted with 200 milliliters of methylene chloride and
then evaporated to 100 microliters, a concentration factor
4
of 10 is achieved. This concentration by evaporation
also places some constraints on the solvent selection.
Thus, if one wants to evaporate the solvent subsequent
to extraction, a volatile solvent must be selected. Again,
pentane and methylene chloride recommend themselves in
this regard.
The efficiency of solvent extraction is highly de-
pendent on the polarity of the solvent and the polarity
of the solute. For example, with nonpolar solvents and
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nonpolar solutes, extractions exceeding 90% in efficiency
are common. These values are normally achieved by repeti-
tive extractions with small volumes of solvents; three
extractions are usually sufficient. As the polarity of
the solute increases, the efficiency of extraction us-
ually decreases. For example, phenols can be extracted
with medium polarity solvents such as chloroform or ben-
zene (after the proper pH adjustment) with efficiencies
of 30 to 70 percent. Fatty acids can usually be extrac-
ted with medium polarity solvents such as methylene chlor-
ide to the extent of 75 to 90 percent.
As a method of accumulation, extraction has the ad-
vantage of being very straightforward and easy to carry
out. Grab samples of water are usually collected for this
procedure. Since only a few reagents are used, there
is little chance of sample contamination, and of
catalyzing reactions of the organic compounds. An
extraction is inconvenient to carry out in the field,
however. Therefore the necessity of transporting the
sample to a laboratory introduces the problem of sample
preservation. There is also a disadvantage in working
with solvents which are usually both toxic and flam-
mable. The disposal of such solvents could become a
problem in the field.
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If the extracting solvent is evaporated before
analysis, the most volatile organic compounds are lost.
This does not pose a great problem if a low-boiling sol-
vent such as methylene chloride is used and a careful
evaporation step is carred out (a Kuderna-Danish evap-
orator has been found most successful in this regard).
Extraction is very appropriate for accumulation from
small volumes of water (up to 4 liters), but it is in-
appropriate for very large samples. With this sample size
a G.C. with a flame-ionization detector can give analyses
on concentrations down'to a part per billion; larger samples
should only be needed for analyses in the part per trillion
range or when a less sensitive analytical technique is used.
2.1.2 Adsorption
Adsorption of organic compounds on lipophilic sur-
faces is another method for accumulating organic compounds
from both air and water. The pertinent operational para-
meters are the chemical nature of the adsorbent, factors
influencing the mass transfer between the fluid and the ad-
sorbent surface (such as particle diameter and fluid flow
rate), and the means of removing the materials of interest
from the adsorbent.
Most of the adsorbents used for environmental samples
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have lipophilic, that is, nonpolar surfaces. These ad-
sorbents include activated charcoal and a variety of
polymeric materials. The organic compounds which may be
accumulated on these adsorbents are usually of low to inter-
mediate polarity. Although some adsorbents have been used
in batch processes (i.e. 50 mg of activated carbon is
added to 100 cc of water and stirred), the usual procedure
is to pack a column with the adsorbent of choice and run
the aqueous sample through it. This is essentially a chroma-
tographic system in which the water (or air) acts as a
mobile phase to elute the adsorbed substances. Thus it
is usually the volume of water (or air) passing through
an adsorbent, rather than the amount of contaminant, which
determines the extent of an accumulation. Once the "break-
through" volume of a substrate (the volume at which it
starts to elute from the column) has been reached, its con-
centration in the column is not proportional to its con-
centration in the medium being measured. Thus it is desirable
to insure that the break-through volume of the earliest
eluting component of interest is not exceeded. This
factor may be controlled by changing the length of the
column used or the total volume of water which passes
through it.
When lipophilic adsorbents are used there is very
seldom any alteration of the aqueous sample-before adsorp-
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tion. For the collection of ionizable organics, how-
ever, it is often necessary to control the pH in the same
manner as for liquid-liquid extraction.
Once a compound has been adsorbed onto a solid sub-
strate, it must be desorbed in a form that can be used for
further analysis. . For gas chromatographic analysis this
requires a solution or gaseous state for the accumulant.
This is accomplished either by eluting the column with an
organic solvent or by heating the adsorbent to desorb the
desired substances. Heat desorption may be directly into
a G.C. or into a cold trap or other adsorbent column. In
choosing a resin as an accumulator, its ability to desorb
compounds under fairly mild conditions is just as im-
portant a consideration as its adsorptive capabilities.
In general, there is a molecular weight above which com-
pounds cannot be desorbed from a given adsorbent.
Until four years ago the most commonly used lipo-
philic absorbant was activated charcoal. This is a
material still favored by many workers within the En-
vironmental Protection Agency. A classic use of charcoal
involved the collection of water pollutants by passing
several hundred thousand gallons of river water through
4
large-scale carbon filters. These filters were then ex-
tracted with chloroform in a Soxhlet apparatus. Approxi-
4. Rosen, A.A., Skeel, R.T., and Ettinger, M.B., Journal
WPCF, 35: 777-782 (1963).
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mately 1600 grams of extract were obtained and subsequently
fractionated by large-scale chromatographic and distil-
lation techniques. Identification of the specific compounds
was carried out with infrared and ultraviolet spectrometry.
Materials such as naphthalene, tetralin, bis(chloroethyl)-
ether, diisobutyl carbinol, and phenylmethyl carbinol were
found in this river. More recently, using G.C. and G.C.-M.S.
analyses, hydrocarbons, chlorinated hydrocarbons, pesticides,
and many other organic compounds have been isolated from
5
water.
The use of activated carbon creates certain problems.
First, considerable variability is observed in collection
efficiency apparently due to variations in the moisture
content of the carbon. Second, it is well-known that acti-
vated carbon can act as a catalyst for oxidation and other
reactions, so that compounds which are adsorbed may be
chemically transformed before or during the desorption
step. A third problem is irreversible adsorption: some
compounds, particularly those of intermediate to high
polarity, can be irreversibly adsorbed? thus preventing
a measurement of their true abundance in the environment.
The current method of drying the carbon and extract-
ing the organics from it with either chloroform, benzene,
or tetralin introduce further limitations, since large
5. Kleopfer, R.D., Pairless, B.J., Environmental Science
& Technology, 6.: 1036 (19727!
-20-
-------
amounts of volatile compounds may be lost during both the
long drying period and the solvent concentration step.
Most of these problems with activated carbon have been
overcome by the use of a wide variety of polymeric adsor-
bents such as XAD, Porapak, Tenax, and Chromosorb 100.
These materials are all lipophilic. They accumulate non-
polar compounds with excellent efficiency and intermed-
iately polarity compounds with moderate efficiency.
Work by Burnham used macroreticular resins manu-
facutred by Rohm and Haas called XAD-2 and XAD-7 for the
adsorption of organic compounds from potable water. This
resin is a highly porous material (average pore size=9o8)
formed from polystyrene. In operation the resin was ground
to 100-150 mesh size and water was passed through it at
a flow rate of four bed-volumes per minute. The organic
compounds of interest were removed from the adsorbent by
elution with ethyl ether. Using this technique, compounds
such as acenapthalene, methylnapthalene, and methyl-
indene were found in well water from Ames, Iowa. These authors
also tested the efficiency of retention of various compounds
on these resins. Compounds such as ketones, esters, aro-
matic hydrocarbons and alkyl phenols were retained to 100%.
Phenol itself was retained to 45% and various sulfonic
acids were retained only to approximately 20%. (See Table 2-2)
6. Burnham, A.K., Calder, G.V., Fritz, J.S., Junk, G.A.,
Svec, H.J., and Willis, R., Analytical Chemistry,
44: 139-142 (1972).
-21-
-------
TABLE 2-2*
COMPOUNDS TESTED FOR RETENTION
ON XAD-2
Compound
Methyl isobutyl ketone
n-Hexanol
Ethyl butyrate
Benzene
Naphthalene
.Benzene .sulfonic acid
p-Tolu.ene sulfonic acid
Benzoic acid
Benzole acid (pH 3.2)
Phenylenediamine
2-Hydroxy-3-naphthoic acid
Phenol
Phenol
2 , 4-Dimet hylphenol
p-Nitrophenol
2-Methylphenol
4 , 6-Dinitro-2-aminophenol
Aniline
o-Cresol
AND XAD-7
RESINS
Resin Concentration,
(7) ppm
XAD-2
XAD-2
XAD-2
XAD-2
XAD-2
XAD-2
XAD-2
XAD-2
XAD-2
XAD-2
. XAD-2
XAD-2
XAD-7
XAD-2
XAD-2.
XAD-2
XAD-2
XAD-7
XAD-2
100
200
100
100
0.05
3.0
9.0
1.0.
1.0
0.9
0.6
0.4
0.4
0.4
0.2
0.3
0.4
4.0
0.3
Retention,
100
85
100
100
100
31
23
23
100
98
39
45
86
100
100
100
43
100
100
A. K. Burnham, G. V. Calder, J. S. Fritz, G. A. Junk, H. J.
Svee, and R. Willis, Anal. Chem. , 4_4: 140 (1972). (Used with
permission)
-22-
-------
They have since developed a detailed analytical procedure
7
for the use of these resins.
Other research using XAD resins has concentrated on
the use of these resins for the accumulation of organic com-
o
pounds from sea water. Riley and Taylor demonstrate that
alkyl carboxylic acids, various steroids, Vitamin B-12,
lindane, DDT, and methylene blue can be collected and re-
covered with efficiencies in excess of 95%- Humic acids
can also be collected, although the recovery is difficult
to determine due to the lack of characterization of these
materials.
Rohm and Haas have published a study of these resins,
particularly of XAD-4 which suggests that these resins
might be economically useful for the treatment of organic
9
wastes due to their strong adsorptive properties.
Numerous other chromatographic phases are used . .,'
for the accumulation of environmental compounds, primarily
for air analysis or for analysis of the head-space above
a liquid or solid sample. Head space analysis of a liquid
sample consists of blowing a stream of gas (helium, argon,
nitrogen or air) over or through the liquid in a container.
In the outlet of this container is placed a trap into which
7. Junk, G.A., et. al., J. Chrom., 99.: 7^5 (1974)..
8. Riley, J.P. and Taylor, D., Analytica Chimlca Acta, 46;
307-309 (1969).
9. Kennedy, D.C., Environmental Science & Technology, 7_:
138 (1973).
-23-
-------
the volatile compounds are carried by the gas stream (see
Fig. 2-1). When this trap consists of a cooled tube, the
operation is akin to a distillation. Usually a packed
column is used as the trapping agent, and the liquid may
be heated to increase the number of compounds volatilized
and collected. The analytical procedure followed is the
same as that used for air analysis by adsorption, and, as
for air samples, the rate and volume of gas collection as
well as the operating temperature are important parameters.
The method may be used for organic compounds with boiling
points up to 250°C.
Work by Zlatkis at the University of Houston on
the concentration and analysis of volatile trace organic
compounds in gases and biological fluids has centered
around the use of Tenax as a lipophilic adsorbent. The
organic compounds were removed from the adsorbent by re-
volatilization. In practice the adsorbent trap was
inserted into the gas chromatograph in front of the analy-
tical chromatographic column and heated, thus transfering
the trapped organic compounds to the analytical column
for direct analysis. Adsorbents such as Porapak and XAD-2
were not suitable for this sort of desorption because they
lacked thermal stability. In the case of Porapak, for
example, the devolatilization temperature was sufficient
10. Zlatkis, A., Lichtenstein, H.A., and Tishbee, A.,
Chromatographia,, 6_: 67-70 (1973)-
-24-
-------
to also decompose the adsorbent. Carbosieve, produced by
Supelco, proved even worse in this regard, since temp-
eratures of 400°C were needed to desorb organic compounds.
Such high temperatures caused decomposition of the adsor-
bent resulting in a considerable number of artifacts in
the resulting chromatographic analysis.
Tenax, on the other hand, can sustain relatively
high temperatures (350°C). This material, distributed by
Applied Science Laboratories in State College, Pennsyl-
vania, is a porous polymer of 2,6-diphenyl-p-phenylene
oxide, and it will trap a wide range of volatile organic
compounds with excellent efficiency. Traps consisted of
glass tubes (11 centimeters long by 10 millimeters O.D.)
containing 2 ml of Tenax packing and were constructed to
fit in the injector port of a Perkin-Elmer 3920 gas chrom-
atograph. (See Pig. 2-2). Aqueous samples were studied
by head space analyses in which the sample was heated to
100°C and stirred vigorously. The vaporized organic
compounds were then swept onto the Tenax trap as des-
cribed above. Sample collection with these systems was
rapid (an hour per sample), and the trapped samples could
be stored conveniently for at least a week. Zlatkis re-
ported several chromatograms of organic compounds trapped
from human urine, human breath, and the Houston atmosphere,
without any identification of most of the trapped compounds,
-25-
-------
Vacuum
I
Collection Column
Packed With Resin
Charcoal Trap
Gas
Liquid Sample
Figure 2-1. Schematic diagram of a cell used to collect
headspace vapors from solids and liquids.
(Used with permission)
Carrier
Gas
Oven
Injection
Port
Heater
Cap
Teflon
Body
Insulation
Glass Tube
7" Glass Wool
_/__ Tenax
/ Adsorbent
-1/16" Union
p
Figure 2-2. Tenax injection port.
(Used with permission)
Mieure
, J. P., J. Chrom. Sci. 11: 568 (1973).
2Zlatkis, A., J. Chrom. Sci. 12: 177 (197*0.
-26-
-------
Tenax is the most widely used resin for this type of
analysis although other adsorbents such as Chromosorb
and Porapak, which are used for air, can also be used for
head space analysis. The Environmental Protection Agency
is investigating the use of Tenax for head space analysis
in Cincinnati, and has applied it to the study of New Orleans
drinking water.
In summary, adsorption is probably the single most
valuable technique for the analysis of organic compounds
of intermediate to low polarity which are found in air,
water and, to some extent, solids. The primary limit-
ations of adsorption are in the occurence of artifacts
resulting from the decomposition of the organic adsorbent.
Most of these artifacts, however, can be avoided by the
proper cleaning of the adsorbent before use. XAD resins,
for example, can be cleaned of the residual monomer and
oligomer species by Soxhlet extraction for several hours
with acetonitrile followed by extraction with acetone and
12
methylene chloride. Other lipophilic adsorbents can be
cleaned in a similar manner. In most cases, where analysis
by devolatilization is used, suitable cleaning of the resin
can be achieved by heating the adsorbent in a stream of
helium or pure nitrogen for several hours at its maximum tol-
erable temperature.
11. U.S. Environmental Protection Agency, Draft Analytical
Report^—New Orleanis Water Supply ,~Nov. , 197^ •
12. Junk, G.A., et. al., J. Chrom. , 99.: 7^5 (1974).
-27-
-------
High concentration factors can be achieved by the
use of these lipophilic adsorbents as accumulators for
organic compounds. The final limitation on concentration
enhancement is due to the sample capacity of the adsor-
bent. The total volume of air or water which can be
passed through the lipophilic adsorbent sets a practical
limit to the concentration factor and fixes the duration
of sample collection. When samples are taken from a
polluted body of water, for example, considerable debris
is collected on the column, which eventually decreases
the flow through the column to impractical levels. In
general, concentration factors of 4 to 6 orders of mag-
nitude can easily be achieved using lipophilic adsorbents.
A great advantage in the use of adsorbents is that
the solid systems can easily be handled once a sample has
been collected in the field. Sealed collection columns
can often be stored for long periods of time prior to
analysis with no sample decomposition. This is not the
case, however, when there is enough adsorbed organic matter
TO
to support bacterial growth J (this has occurred on carbon
traps). Those systems which allow for direct heat desorp-
tion into the G.C. require very little manipulation and
the adsorbent is the only chemical in the system which
requires purification. This method of desorption does
13. Personnal communication: A.A. Rosen, National Field
Investigation Center, Cincinnati, December 1974
-28-
-------
have the disadvantage of total sample loss, if G.C.
conditions should fail to give a good separation. Ex-
traction methods require more manipulation, but result
in the ability to run a number of analyses on one field
sample. Unlike extraction, adsorption can accomodate
large volumes of water when necessary.
2.1.3 Other Methods
Freeze concentration is a method which has been
used for the accumulation of organic compounds from water
when the compounds of interest are not necessarily lipophilic
The water sample is frozen slowly, while being stirred,
allowing only pure water to be crystallized and leaving
all of the impurities in the remaining solution. The
choice of technique is critical in order to keep impur-
ities from becoming embedded in the ice as it forms.
This method leads to concentrations of only a factor of
10, however, before the recovery of organic molecules drops
14
off drastically. P.A. Kammerer, Jr. and G.F. Lee have
accumulated glucose, glycerine, phenylanine, and citric
acid with 88-100$ recovery; the average concentration
factor was only five in this procedure.
There does not appear to be any advantage to the use
of freeze concentration. There are much more efficient
Kammerer, P.A., Jr., Lee, G.F., Environmental Science
& Technology, 3.: 2?6 (1969T
-29-
-------
methods for the accumulation of lipophilic organic mole-
cules. While this form of concentration might be use-
ful for the analysis of water-soluble organic molecules
(perhaps by liquid-liquid chromatography) , for low-tem-
perature concentration freeze-drying would appear to be a
much more efficient method of removing water.
Reverse osmosis is another concentration method which
IS
is under investigation. This technique is expected to
yield concentration factors of 10 or 20. Since membranes
may be chosen with pores of varying sizes, this method of
collection may prove to be advantageous for a prelimi-
nary separation of organic molecules largely (but not tot-
ally) on the basis of molecular size. However, at the pre-
sent time this technique is not well developed.
Flocculation with FeCl~ and floatation using sur-
factants have also been used occasionally to concen-
trate organic compounds from water, but recoveries from
these processes are not quantitative
In the past fractional distillation of water was
used to separate compounds for further classification and
analysis. The use of the G.C. seems to have superceded this
method.
15. Deinzer, et. al., "Trace Organic Contaminants in
Drinking Water: Their Concentration by Reverse
Osmosis", presented before the Division of Environ-
mental Chemists ACS, Los Angeles, 1974.
16. Sridharan, N., Lee, G.P., Environmental Science &
Technology, £: 1030 (1972).
-30-
-------
2.2 Accumulation of Inorganic Solutes From Water
2.2.0 Introduction
The accumulation and subsequent analysis of the dis-
solved inorganic contents of waters are based on the chem-
ical properties of the solutes. This situation contrasts
with that of particulates found in air, where physical
properties (size distribution, density, mean diameter, etc.)
determine the means of accumulation.
Natural waters can be classed according to their total
content of dissolved solids:
* Sea water: ca. 3% dissolved solids by weight
* Fresh water: traces of dissolved solids
* Brine: more concentrated than sea water
* Brackish water: intermediate between sea
water and fresh water.
Most accumulator systems will work on any of these four
classes of water; therefore, no distinction will be made
among them in the following discussion, unless specifically
noted.
The solutes found in natural and in polluted waters
span the periodic table and have widely varying chemical
properties. Those occurring in the highest concentrations
are the ions of the common salts: Na+, Mg++, Ca++, Cl~,
-31-
-------
SOh , etc. and analyses can normally be performed
without preconcentration. Large concentrations of other
components are encountered occasionally, but they gener-
ally are found near their sources, such as the outfall from
an industrial plant. Because these components are usually
found in trace amounts, some degree of preconcentration
or accumulation is convenient} if not actually necessary,
as a prelude to quantitative analysis.
Among trace inorganics, those of particular interest
are the substances which are toxic to human and other life
forms. Their chemical properties range from alkali and
alkaline earth metals, such as Cs, Be, and Ba, to transi-
tion metals, such as Zn, Cd, Hg, and Pb, to metalloids,
such as As and Se. Because of the wide range in chemical
properties, no single accumulation system will quantitative-
ly collect all of them. Indeed, in some cases, a given
accumulator will not be capable of collecting all the
different complexes and oxidation states of a single ele-
ment present in a sample.
Since the concentration methods discussed below share "
the characteristic that some part of the system undergoes
a change of phase, it is useful to describe these systems
by the kind of phase change that occurs. The classifica-
tion to be used in this report is as follows:
-32-
-------
* Chelation/Extraction: A second liquid phase is
placed in contact with the aqueous system and
the accumulant is extracted into it. Formation
of a chelation complex is an essential aspect
of this type of system.
* Ion Exchange: A solid phase is placed in con-
tact with the aqueous system and the accumulant
is adsorbed onto it.
* Coprecipitation and Cocrystallization: A solid
phase is formed which incorporates the accum-
ulant .
* Headspace Analysis: The accumulant is chem-
ically converted (usually by reduction) to a
volatile species which is driven out of solution
and collected or directly analyzed.
* Flotation: A floating foam is formed which
incorporates the accumulant.
* Evaporation, Freeze Drying, and Freeze Con-
centration: The water is partially or totally
removed through a phase change. The accumu-
lants are left as solids or in a more concen-
trated solution.
• Electrolytic Reduction: The accumulants are
collected as metals on the anode of an
-33-
-------
electrolytic cell. (Subsequent analysis is
performed by anodic stripping voltammetry.)
The three most useful methods are Chelation/Extraction,
Ion Exchange, and Coprecipitation and Cocrystallization.
The fourth method, head space analysis, is limited to the
analysis of those elements which can be reduced to vola-
tile forms, such as Hg, As, and Se, but it is a good
method for these elements. The discussion which follows
will be limited to these four methods, since the others
have been put to relatively little use in the analysis of
environmental samples.
2.2.1 Chelation/Extraction
Solvent extraction, an accumulator method of major
importance for organic substrates, is not directly appli-
cable to metal ion accumlants since charged species are
generally not soluble in solvents which are immiscible with
water. However, most metals can be made to form stable
unchanged complexes with organic chelating agents. These
complexes can be extracted into an organic phase without
difficulty, given a proper choice of solvent and pH.
There are several important chemical equilibria that
govern chelation/extraction: The acid-base equilibria of
-34-
-------
the chelating agent, the formation equilibrium of the
chelate complex, and the distribution equilibrium of the
complex between the aqueous and organic solvents. For
example, the dissociations of 8-hydroxyquinoline are
(1)
and 2) basic:
OH
H20
+ OH
(2)
Hence the chemical form of 8-hydroxyquinoline, like all
chelating agents, depends on the pH. The basic require-
ments for a successful chelation-extraction procedure are
that a stable complex must be formed between the chelating
agent and the metal; the pH must allow the right number of
acidic or basic dissociations to yield a neutral complex;
and the distribution equilibrium:
Complex (aq) = Complex (org)
must favor extraction into the organic (org) phase. The
solvent must be capable of forming a two-phase system with
water, and the less water solubility it has, the better
-35-
-------
the extraction efficiency. In some chelation/extraction
systems, the chelating agent is placed in the aqueous phase
.prior to extraction, while in others the agent is introduced
in the organic phase, the complex forming during extraction.
Examples of chelating agents that have been used in
various chelation/extraction systems are 8-hydroxyquinoline,
acetyl acetone, diphenyl thiacarbazone (dithizone), and
ammonium pyrolidine dithiocarbamate (APDC). Metals col-
lected with these agents are shown in Figure 2-3. Like all
chelating agents, each of these possesses at least two
groups that can simultaneously form coordinate bonds to
metal ions. The extraction solvents include methylisobutyl
ketone (MIBK), ethyl propionate, chloroform and benzene.
The basic equipment for chelation/extraction is the
same as that used for organic solvent/solvent extraction,
and the procedure is similar. The use of chelating
agents and careful control of pH constitute the main
procedural differences.
Stability of the aqueous sample can be a problem for
some metals, for example' Ag and Hg. Immediate extraction
in the field is sufficient to stabilize them, but if the
water sample is to be taken to the laboratory, it should
be acidified in the field. This will prevent, for example,1^
17. P.K. West, P.W. West, and P.A. Iddings, Anal. Chem.
3_8, 1566 (1966), F.K. West, P.W. West, and F.A. Iddings,
Anal. Chim. Acta, 37, 112 (1967).
-36-
-------
Be
DQA
La
-Q
T1
DQ
APDC
Zn '
. Q
V
Q
APDC
Cr
(Vf )
D
APDC
Mo •
Q
APDC
W
Q .
.Mn
DQ
APDC
Fe
DQA
APDC
Co
DQA
APDC
Ni '
DQA
APDC
Pd
D
Pt
D
Cu
DQA
APDC
Ag
DQA
A?PC
Au
' D
Zn
DQA
APDC
Cd
DQA
APDC
*
Al
DQA
Sn •
Q '•
Pb
DQA
APDC
As
1PDC
Bi
APDC
Se
APDC
D = Dithizone
— P T-I v H T* r\ Y \T c\
A = Acetyl ace
DQA = Combinat
(Tri-lig
APDC - Ammoniu
Dithioc
• * Sachdev says
T.r-i -I-1-. nr\ A -? f
Figure 2-3: Chelation/Extraction .by DQA and APDC
with DQA if solution, aged 5-6
hrs. with MnO]j before extrac-
tion.
-------
the adsorption of Ag on the walls of the sample vessel.
Treatment with 5% HN03 + 0.05$ K2Cr07 is sufficient to
stabilize dilute Hg solutions.'^° However, since such acid-
ification increases the possibility of metal contamination,
it is advisable to perform the chelation/extraction in the
field shortly after the sample is collected, since the
organic solution of metal chelates is quite stable.
With a proper choice of chelating agents, most trace
metals can be accumulated by chelation/extraction procedures
Although some chelating agents are specific to only one
or two metals, others form complexes with a wide range of
elements. One especially useful system-1-^ combines three
agents (dithizone, 8-hydroxyquinoline, and acetyl acetone)
and quantitatively collects Al, Be, Cd, Co, Cu, Fe, Pb,
Ni, Ag, and Zn, all in one extraction at pH = 6. Other
documented systems account for at least an equivalent num-
ber of elements.
One major class of elements is not generally collected
by chelation/extraction procedures, namely the alkali and
alkaline earth metals. In addition, mercury is difficult
to handle because only some of its compounds can be easily
collected. However, other methods do exist for these
18. C. Feldman, Anal. Chem. 46, 99 (1974).
19. S. L. Sachdev and P. W. West, Envir. Sci. Tech. 4_,
749-51 (1970).
-38-
-------
elements, notably headspace analysis for mercury and
ion exchange for the alkali and alkaline earth metals.
The concentration factor attainable for a given solvent
is limited by its water solubility. For example, ethyl
propionate forms an approximately 3% aqueous solution by
volume. Thus the maximum concentration factor for a single
extraction is in the range of 10 to 50. Benzene, with a
water solubility of about 0.1% allows for concentration
factors up to 500. In any case, concentration factors much
in excess of 1,000 are probably inaccessible. Water samples
of more than 2 liters are difficult to handle in separ'atory
funnels, and the minimum volume of ortanic solvent is at
least 1-2 ml.
One major advantage of the chelation/extraction method
is that the organic extract is an ideal sample for atomic
adsorption spectroscopic analysis. In addition to providing
a concentration factor, the method also separates out the
interfering ions of the common salts (Na , Mg , Ca , Cl~),
and the organic solvent enhances the instrument sensitivity
by a factor of 2 or 3 over water. Another major advantage
is the simplicity of both equipment and procedure. A
technician using simple equipment can rapidly produce, from
a given water sample, a single extract that is suitable
for atomic absorption analysis of a broad range of elements.
-39-
-------
This is possible because elements do not usually inter-
fere with each other in atomic absorption spectroscopy .
2.2.2 Ion Exchange
The fundamental chemistry of ion exchange is shown
in Equation (1) :
bA+a + aB+b = bA+a + aB+b (1)
where A+a and B+ID represent ions in aqueous solution, and
A^a and Bpb represent ions bound to resin. The process of
ion exchange consists of one kind of ion, originally in
aqueous solution, displacing another ion from its binding
site on the resin. The result is that the first ion be-
comes bound to the resin while the second is released to
the solution.
If the ions are both univalent and if equilibrium is
established, the following equilibrium expression holds:
. K
[Bj]
where (A+) and (B+) are the concentrations of the ions in
solution and [At] and [Bi] are the activities of the ions
bound to the resin. It is convenient to tabulate a series
of equilibrium constants, K]_, ^...for a series of ions
.-40-
-------
A+, A+ .. all relative to a single ion B+. The conventional
standard for cationic exchange resins is H+, since such
resins are normally charged with strong acid before use.
Constants in such a series are known as selectivity co-
efficients, and a typical set is displayed in Figure 2-4.
In general, the larger the selectivity coefficient for a
given ion, the more strongly it is held by the resin, and
the ion with a larger coefficient will tend to displace
the ion with a smaller coefficient. However, given a high
enough concentration of even a low-valued ion like H+
(1.0), most ions will be displaced, hence the usefulness
of strong concentrated acid such as eluent.
Most ion exchange materials are manufactured in the
form of polymeric beads. For example, in the manufacture
of DOWEX resins, styrene and divinyl benzene are copoly-
merized to form a polystyrene type resin with a degree of
crosslinking governed by the amount of divinyl benzene in
the formulation. Ion exchange sites are then chemically
attached to the phenyl rings. According to the chemical
nature of the exchange site, the resin can be classed as:
* Strongly acidic (Sulfonic acid)
* Weakly acidic (Carboxylic acid)
* Strongly basic (Quarternary ammonium)
* Weakly basic (Ternary ammonium)
-------
H+
L.27
Li +
L.OO
Na+
L.98
K+
2.9C
Rb +
3.16
Cs +
3'. 2 5
Mg+H
3.29
Ca++
5.16
Sr+4
6,51
Ba+4
11.5
jo++
2.45
Co++
3.7^
AT-+ +
Ni
3-95
-, ++
3u
3.85
Ag+
8.51
Zn++
3-^7
p^++
Cd
3.88
Tl+
12. l\
Pb+4
9.91
NHj
2.55
(V)
I
Figure 2-4: Selectivity Coefficients for Uni- and Di-Valent Ions
on DOWEX 50-X8 Ion Exchange Resins
-------
• Chelating (Imino diacetic acid)
* Zwitterionic (Weak acid and weak base groups
on adjoining polymer strands).
Ion exchange resins are normally used chromatograph-
ically. The resin is held in a column, and the aqueous
solution is allowed to flow through the column at a slow
rate. Much higher collection efficiencies are attainable
with columns than can be achieved using batch methods,
since a column can be considered a series of "plates".
As the aqueous solution passes each plate equilibrium is
established, and some of the accumulant binds to the ion
exchange sites; the remainder passes to the next plate where
still more of the accumulant binds. Given enough plates,
collection efficiencies of 100% are possible. Batch methods
have been used because of their speed and ease of use, but
collection efficiencies are generally not as high as with
column methods.
When the entire aqueous sample has passed through the
column, and the accumulation is complete, the column is
washed with distilled water. Following this, the column
is usually eluted in order to remove the accumulant. The
eluant solution must contain an ion or combination of ions
which can effectively and efficiently displace the accum-
ulant, and in some cases it may also contain a chelating
-43-
-------
agent that will complex the accumulant to ease its removal
from the column.
As with other types of accumulator systems for inor-
. ganic solutes, control of pH is important in the use of ion
exchange. This is especially true for resins that are weakly
acidic, weaking basic, or chelating, and which are therefore
chemically quite sensitive to pH. A weakly acidic resin,
for example, has a relatively high affinity for protons.
The control of the pH of the eluant is even more important,
and the key to efficient separation of the components of
a mixture of ions. This is true whether the eluant is a
concentrated strong acid or a buffered chelating agent
such as EDTA.
The amount of resin and the length of the column are
also important. There must b.e enough binding sites for
the accumulants as well as enough plates for effective
collection. In addition, the flow rate must be low enough
so that near-equilibrium is attained at each plate.
Analytical applications of ion exchange are oriented
toward the separation of ions within a mixture. Although
much of the early work on ion exchange was performed as
part of the Manhattan Project, which demanded accurate
separations and analyses of mixtures of lanthanide and
actinide rare earths, its potential as an accumulation
-------
system Is high. The collection equilbrium (Equation 2)
favors the retention of ions at trace levels, making it
possible to pass large volumes of sample through an ion
exchange column and still have '100$ collection of the trace
metals. An ion exchange method has been used to concentrate
a 40 liter sample.20 It is then possible to use a .relatively
small amount of elua'nt to remove 100$ of the desired mater-
ial from the column. In this way concentration factors
of several thousand are attainable.
Ion exchange methods, in principle, can be used to
collect elements from all parts of the periodic table. •
This is made possible by the wide choice of resins and
eluting solutions. Strong acid resins such as DOWEX 50
can' collect nearly any cation, but they are optimum only
for the alkaline earths. Polyphosphate type materials are
favored for alkali metals, and chelating resins for trans-
ition and main group metals. For anibns, the basic, resins
are indicated. (This•includes the-anionic chloro com-
plexes of Zn, 'Cd, Bi, Au ('III) and Tl (III);)
One significant disadvantage in the use of ion -exchange
accumulators is the possibility of sample contamination.
This arises largely from the use of concentrated-, strong
20. T. Joyner, M. L. Healy, D. "Chakravarti, and T. Koyanagi,
Environ. Sci. Tech., 1, H17-2H (1967).
-45-
-------
mineral acids for the conditioning of columns and for
elution. Such acids often contain traces of heavy metals
which may interfere with accurate analysis.
Another disadvantage lies in the time necessary to
process a water sample. Typical flow rates are in the
range of milliliters per minute, and in the case of liter
size samples, this means hours per sample. On the other
hand, one person can run many samples at once since col-
umns can be set up with constant flow reservoirs.
2.2.3 Coprecipitation and Cocrystallization
One of the fundamental procedures in wet analytical
chemistry is precipitation of a solid containing the ion
or ions to be analyzed. The formation of analytically
useful precipitates, however, depends on the solubility
product of the solid being exceeded by at least several
orders of magnitude. Therefore direct precipitation,
in which the desired ion is a major component of the solid,
cannot be applied to materials found in solution in trace
amounts only.
However, solid formation is still useful as an accum-
ulation technique for trace analysis, if the major component
of the solid acts as a carrier which quantitatively col-
lects the desired trace ions. The process is known as
-46-
-------
copreclpitatlon if the carrier is a slightly soluble
inorganic base or salt. In general, the solid form of
the carrier has the same crystalline structure as the
solid form of the accumulant; all accumulants whose solid
form matches that of the carrier will be collected.
One commonly-used carrier for coprecipitation is Fe(OHK.
The formation of this carrier involves addition of ferric
ions to an aqueous sample, followed by strong base. The re-
sultant Pe(OH)-, precipitate collects the hydroxides of
the other transition metals.
The use of Fe(OH)o presents two problems: the iron that
is introduced may interfere with subsequent analysis, and
it also may contain its own traces of other metals which
will render the analysis invalid. Another coprecipitation
method, especially developed for sea water analyses, avoids
both problems: the addition of strong base generates a precip-
itate of Mg(OH)p from the natural magnesium ion content of
the sea; the hydroxides of Pb and six transition elements
are quantitatively collected, and the interference and
21
contamination problems of iron are avoided.
Another type of coprecipitation is involved in the
accumulation of radioactive ions from solution. With
radioactive barium, for example, BaCl~ is added,
21. T. Joyner, et al, op. cit.
-------
followed by H2SO^. The resulting precipitate of BaSO^ is
largely unradioactive, but it will contain essentially
all the radioactive barium and can be analyzed by radio-
??
assay.
When an organic chelating agent is used as a carrier,
the process is called cocrystaliization. A suitable
cocrystallization reagent is relatively insoluble in
water, and it forms complexes with the desired metal ions
that have even less water solubility than the reagent it-
self. Their chemical form is quite similar to that of
the agents used in chelation/extraction, and it is possible
that some chelating agents could be used for both types of
concentration.
In practice, the process begins with an aqueous sam-
ple. The chelating agent is added in an organic solvent
(such as acetone) that is miscible with water. The system
is then heated to remove the solvent, and as the solvent
is stripped off, crystals of the chelating agent form.
If the agent is well-chosen the crystals will contain
the desired metal ions as chelation complexes. Examples
of chelation agents used in this manner are 5,7-di-bromo-
8-hydroxyquinoline, thionalid and 2-mercaptobenzimidazole.
22. D. N. Kelkar and P. V. Joshi, Health Phys., 1J,
253-7 (1969).
-48-
-------
Elements collected by these agents are shown in Figure 2-5,
As an alternative method of crystal formation, a
water soluble chelating agent might be rendered insoluble
by the addition of ethanol to the system. In this manner
potassium rhodizonate can be used to accumulate Sr and Ba
from aqueous solution. 3
Cocrystallization has been tested on approximately
25-30 elements, mostly transition and main group metals.
Quantitative collections have been reported for most of
them. The alkali metals and the metalloids are not gen-
erally collected. As with other accumulators of metal
ions, pH is an important collection parameter.
Both coprecipitation and Cocrystallization yield
solids which can readily be taken up in solution for fur-
ther processing. Solids produced by Cocrystallization
can readily be taken up in an organic solvent, or directly
inserted into an AA spectrophotometer for analysis.
Coprecipitated hydroxides can be taken up in a small
amount of acid for further analysis, and at least one
investigator has treated such a solution by chelation/
•~)k
extraction. Very large concentration factors are
23- H. V. Weiss and M. G. Lai, Anal. Chem. , 32., 475-8
(I960)
24.. T. Joyner et al, op. cit.
-49-
-------
I
U1
o
I
Hf
T
Ta
TM
Cr
TB
W
T
Mn
TB
Fe
B
Ru
.T
Os
T
Co
TB
Ir
. T
Cu
B
Ag
TM
Au
TM
Zn
TB
Hg
TM
In
T
Tl
T
Sn
TM
T
M
B
= Th
-
= 5,
iona]
VIercc
7-Di-
l
Hydroxyquinoline
Figure 2-5: Cocrystallization by Thionalid, 2-Mercaptobenzimidazole,
and 5,7-Dibromo-8-Hydroxyquinoline
-------
possible, especially if the weight of the solid phase
is measured against the weight of the aqueous sample.
For either method, in addition to the equipment nor-
mally used for the collection of aqueous samples, either a
filtration setup or a setup for centrifugation and decan-
tation is needed. Filtration is necessary for large
samples; sea water samples of up to 100 liters have been
treated by Mg(OH)p coprecipitation.2^
As in the case of ion exchange, the process times may
be quite long (overnight in at least one case) but many
samples can be treated at once.
Both methods have been used in oceanographic work.
Both have the advantage of reducing a huge aqueous sample
of low stability to a small solid sample that is easily
handled and stable enough to be preserved until the ship
has returned to its home port.
2.2.4 Head Space Analysis
In head space analysis, an aqueous sample is treated
with reagents that convert the accumulants into volatile
chemical forms. The volatile species are swept from
solution by aeration (if necessary), cryogenically trapped
25. T. Joyner (telephone interview)
-51-
-------
(if necessary), and analyzed, usually by atomic absorption
spectroscopy.
Head space analysis is limited to a small portion of
the periodic table: Hg, As, Sb, Bi, and Se. It may be
possible to apply this method to such elements as Ge, Sn,
and Te in addition, but there seems little likelihood of
using it on any other large family of elements. It is
nonetheless a useful method since it is applicable to
elements which are difficult to accumulate by other methods.
The equipment is necessarily more complex for head space
analysis than for the other methods discussed above
Q /"
for accumulating trace metals from water. In a procedure^
for As, Sb, Bi, and Se, the gaseous hydrides are collected
in the ballon of a gas generator and subsequently released
into the burner of an atomic absorption spectrophotometer.
In the standard head space procedure2? for Hg, the solu-
tion is aerated to sweep out elemental Hg, and the air
stream is dried and then passed into a quartz-windowed
atomic absorption cell. A reaction flask, a drying flask,
a pump, and tubing complete the apparatus.
The chemistry of head space analysis for inorganic
26. P. J. Schmidt and J. L. Royer, Anal. Lett., 46,
489-92 (1974).
27. W. R. Hatch and W. L. Ott, Anal. Chem., 40, 2085 (1968)
-52-
-------
accumulants usually consists of reduction to the metal (Hg)
or the hydride (AsH^, SeH-, SbH.,, B1H-,). The reducing agent
for Hg is SnSOj, in hydroxylamine sulfate, sulfuric acid
and sodium chloride. For As, Se, Sb and Bi the reducing
agent is NaBHh added to the sample solution previously
acidified with 6M HC1. For both methods, with a sample
of 50 ml, detection limits of 1 ppb are attainable for
Se, Hg and Bi; for As and Sb the limit is 0.1 ppb.
If it is assumed that the accumulant is removed from
the aqueous solution into the same volume of vapor, a
concentration factor of about 1000 by weight is obtained,
based on the relative densities of water and air. For
aqueous concentrations in the ppb range this is sufficient.
If additional accumulation is necessary, cryogenic trap-
ping of the vapors can provide the additional concentra-
tion factor.
This method is fairly simple to apply to the analysis
of environmental samples, at least after the apparatus
is set up and tested. Grab samples are collected in the
field and brought back to the laboratory, and assay by
head space analysis is rapid and routine enough to be
run by a technician.
-53-
-------
TABLE 2-3
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER BY COMPOUND
This table lists those organic compounds or classes
of compounds which have been concentrated from water using
one of the accumulation techniques which have been described,
The accumulator column lists either the solid adsorbent
or liquid extractant that was used for preconcentration.
The desorptlon or extraction medium in most cases is the
solvent or temperature which was used to remove the organic
compounds from a solid adsorbent.
-54-
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
Aeeuzulant
Alkanes and
Alkenes
, sym-Tetra-
chloroethane
sym-Tetra-
chloroethane
n-Hexadecane
sym-Tetra-
chloroethane
"bls-Chloro
isopropyl ether
n-Hexadecane '
sym-Tetra-
chloroethane
n-Hexadecane
s'ym-Tetra-
chlortfethane
CHC1,
Accunulator
XAD-2
XAD-1+8
XAD-H
XAD-2
XAD-7
Chromosorb 102
Desorptlon •
or
Extraction
Medium
Chloroform .
Extraction
Heat
Rat e .xTSan? 1 e
.S^ Voliune
22cc/min
5cc/min
Collection .
Parameters
Distilled water
Recovery .
and
Sensitivity
70?
90
11 '.
90
80
90
90
3
90
85-93
Associated
Analytical
Method
GC
Reference'
•
Webb (1975)
Mieure, Dietrich
(1973)
I
v_n
\j\
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Accurulant
BrClgCH
ClBrgCH
ci2ccci2
Br,CH
c2cig
.Alcohols and
amines
Hexyl
alcohol
2-Ethyl-
hexanol
2-Ootanol •
Decyl
alcohol
Doctecyl
alcohol
Accumulator
Activated •
Carbon
XAD-2 .
Desorption •.
or
Extraction
Medlua
CHC13
Ether
Sanpllng^/'^
Rat e ^/sarap 1 e
.s^ Volume
232
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
Accusslaat
Hexanol
Hexadecylamine
a-Terpineol
o-Terpineol
2-Ethylhexanol
a-Terpineol
2-Ethylhexanol
'a-Terpineol
2-Ethylhexanal
a-Terpineol
2-Ethylhexanol
Meth'anol
Accunulator
XAD-2
XAD-I+S
XAD-4
XAD-2
XAD-7
XAD-8
Chromosorb 102
Desorptlon •.
or
Extraction
Medium
Ether
Chloroform
Extraction ;
Heat .
Sampling^/^^
Rat e ^XSanp i e
*s^ . Volume
50cc/min
1501
SOccVmin
11
22oc/mln
5co/min
Collection .
Paraneters
pH=8
Distilled water
Recovery .
and
Sensitivity
85?
94
90
80
91
81
85
36
71
62
79
<5%
Associated
Analytical
Method
GC-MS
15? Carbowax
20M on
Chromosorh P
200° C
GC-FID
GC
Reference .
Burnham, et al.
(1972)
Junk, et al.
(1971)
Webb (1975)
Mieure, Diet rich
(1973)
-------
ACCUMULATION OF ORGANIC SUBSTANCES PROM WATER
iss'J=ulant
Ethers
, bis-Chloro
Isopropyl ether
Hexyl ether
bls-Chloro
isoprophyl
ether
bls-Chloro
Isopropyl ether
Bis(2-chloro-
Isopropyl)
ether
Bis(2-chloro-
Isopropyl)
ether
Acids
n-Heptanolc
acid
Accumulator
XAD-2
XAD-4+8
XAD-8
Activated
Carbon
XAD-1
Description -.
or
Extraction
Medium
Chloroform
Extraction .
Ether
Chloroform
Extraction
CHC1
2N NHjjOH
Samplinex^^
Rat e .X^anp'le
^r . Voluae
22cc/mln
50cc/mln
. 14
22cc/mln
23204
5cc/mln
Collection . -
Parameters
pH=3.2
neutral
Distilled Water
ippb
Seawater
pH=2
Recovery ,
and
Sensitivity
70
75
77
77
90
Associated
Analytical
Method
GC/MS
GC-PID
5* OV-l on
Chromosorb W
GC .
GC-MS
SE-30 on
Chromosorb W
l)Oe-210°C
ill
C-countlng
Rererenee -
Webb (1975)
Junk, et al.
(197$)
Webb (1975)
Kleopfer,
Falrless (1972)
Rlley, Taylor (1969)
CO
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Acca=alant
n-Heptadecanoic
.acid
l-Ketoglutarlc
acid
Octanolc Acid
Decanolc Acid
Palmitic Acid
Oleic Acid
Heptanoic Acid
Heptadecanoic
Acid
4-Ketoglutaric
Acid
Palmitic acid
Palmitic acid
Dehydroabletic
acid
Accumulator
XAD-l
/
XAD-4
XAD-l)
XAD-2
Desorptlon -.
or
Extraction
Medium
IN KOH
EtOH •
Ether
NH,,OH
NHjjOH
KOH
Chloroform
Extraction
Sampling/*^
Rat e .XSanple
• Volume
5cc/mln
50cc/mln
14
14
5cc/min
22cc/mln '
Collection .
Parameters
Seawater
pH=2
pH=7.6
.5% HC1 - H20
pH=2
pH=2
PH=7.6
Distilled water
Recovery .
and
Sensitivity
100
100
108
90
101
100
100
100
100
79
67
9<»
Associated
Analytical
Method
14
C-countlng
GC-FID
5% OV-l
Chromosorb W
1!)c
GC
Reference -
Rlley, Taylor (1969)
Junk, et al.
(1971)
Riley .Taylor
(1969)
Webb (1975)
I
VJI
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
Acsu=2l8at
Palmitic acid
Palmitic acid
Dehydroabietlc
acid
Dehydroabletic •
acid
Esters
Acetophenone
•Dlethyl
fumarate
Dibutyl
fumarate
Di-2-et'hyl
hexyl fumarate
Diethyl
malonate
Methyl
benzoate
Accumulator
XAD-7
XAD-8
XAD->7
XAD-8
XAD-2
XAD-2
1
Desorptlon -.
or
Extraction
Medium
Chloroform .
extraction
Ether
Sasipling^x^
Rate .x'Sar.ple
^^ • Voluae
22cc/min
50cc/min
1*
Collection .
Parameters
Distilled water
pH=8
pH=3.2
neutral
Recovery .
and
Sensitivity
16
90
90
92
86
92
8t
103
101
Associated
Analytical
Method
GC
*
GC-PID
5* OV-1 on
Chromosorb W
' Reference -
Webb (1975)
Junk, et al.
(WO
I
ON
o
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Assu=ulant
Methyl
. decanoate
Methyl
octanoate
Methyl
palmitate
Methyl
salicylate
Methyl
methacrylate
Ethyl
butyrate
Dl-2-ethyl
hexyl adipate
Ketones and
Aldehydes
2 6-Dimethyl
-ft-heptanone
' Accumulator
XAD-2
Extraction
with CH2C1^
XAD-2
Desorption •.
or
Extraction
Medium
Ether
Extraction c.
n-heptane
Ether
Sampllng^^
Rat e ^^Sanp le
^r • Volume
-SOcc/mln
li
2cc/mln
50cc
2320JI
SOcc/mln
V.
Collection .
Parameters
PH=3.2
neutral
Ippb
pH-8
Recovery .
and
Sensitivity
95$
98
70
96 •
35
100
93
Associated
Analytical
Method
GC-PID
5* OV-1 on
Chromosorb W
GC-MS
15? Carbowax
20M on
Chroraosorb P
200°C
GC-MS
.05% OV-17 or
glass beads
70»-250°C
GC-PID
5% OV-1 on
Chroraosorb W
' Reference
Junk, et al.
(19714)
Burnham, et al.
(1972)
Kites (1973)
Junk, et.al.
(1971)
I
ON
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Accuzulant
,2-Undecanone
Isophorone
Isophorone
Isophorone
Isophorone
Methyl isobutyl
ketone
Acetone
Unsubstltuted
Aromatlcs
.Naphthalene
Biphenyl
Fluorene
Anthracene
Acenaphthene
•
Accumulator
XAD-2
XAD-1
XAD-2
XAD-7
XAD-8 .
Chromosorb 102
XAD-2
Desorption -.
or
Extraction
Medium
Ether
Chloroform
Extraction
Heat .
Ether
r
Sar.pllne^/'^
Ra'te -Xaample
^^ . Volume
50cc/min
22cc/mln
5cc/mln
50cc/min'
14
Collection .
Parameters
pH=8
Distilled Water
pH=8
Recovery .
and
Sensitivity
921
86
76
1.6
47
100
21-42
98
101
81
83
92
Associated
Analytical
Kethod
GC-FID
5Z' ov-l on
Chromosorb W
GC
GC-FID
acid-washed
DMCS-treated
Chromosorb-W
5Z OV-1
Re^ereace ..
Junk, et al.
(1971)
Webb (1975)
Mieure and
Dietrich (1973)
Junk, et al.
(1974)
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
Acsasulant
Tetrahydro-
• naphthalene
Benzene
Naphthalene
Acenaphthylene
Indene
Acenaphthene •
2,2-Benzothio-
phene
'Naphthalene
2,3-Dihydro-
indene
sym-Tetra-
chloroethane
Indole
Benzothlazole
Quinollne
Benzoxazole
. Aecuaulator
XAD-2 •
,
Desorptlon •,
or
Extraction
Medium
Ether
Ether
Extraction
r
Sampling^^
Rat e .XSainple
^s • Volume
30-50cc/min
1
Collection .
Parameters
pH=8
PH=3
Iowa wellwater
pH=3.2
neutral
Recovery .
and
Sensitivity
62S
100
10.3 - 2ppb
18.8 - 8ppb
18.0 i 2ppb
1.7- 2ppb
15ppb
15ppb
I6ppb.
89S
100
81
92
Associated
Analytical
_ Method
GC-FID
acid-washed
DHCS-treated
Chromosorb W
5% OV-1
GC-MS
15? Carbowax
20M on
Chromosorb P
200° C
GC/MS
GC-FID
Kerersr.ee .
Junk, et al.
(1971)
Burnham, et al.
(1972)
Junk, et al.
(1971)
uo
1
-------
ACCUMULATION OF ORGANIC SUBSTANCES ?HOM WATER
Acsusalant
Naphthalene
Benzothlazole
Dibenzofuran.
Naphthalene
Benzothiazole
Dibenzofuran
Acenaphthene •
Naphthalene
Benzothlazole
Acenaphthene
Dibenzofuran
Naphthalene
Benzothlazole
Acenaphthene
Dibenzofuran
' Accumulator
XAD-4+8
XAD-l)
XAD-2
XAD-7
Desorption •.
or
Extraction
Medium
Chloroform
Extraction
-.
Sanpllng^/^
Rat e ^-'sample
^^ • Volume
22cc/mln
Collection .
Parameters
Distilled water
Recovery .
and
Sensitivity
90%
82
8H
80
82 '
82 .
81
79
71 •
99
93
61
HO
72
73
Associated
Analytical
Method
GC
' Hererar.ce
Webb (1975)
I
CTv
-tr
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
. .cc^lan.
Naphthalene
Benzothiazole '
Acenaphthene
Dibenzofuran
Benzene
pyridine
Anthracene
Perylene
Idene
Pyrene
Fluoranthene
3,1 Benzopyrene
Toluene
Biphenyl
Accumulator
XAD-8
Chromosorb 102
Tenax GC
Activated
Carbon
Extraction
with CH2C13
Desorptlon •.
or
Extraction
Medium
Chloroform
Extraction
Heat-
Ether .
Extraction
CHC13
Extraction c
n-heptane
Rat e ./•-'Sample
^^ • Volume
22cc/mln
5cc/min
34/hr
23204 '
2320i
Collection .
Parameters
Distilled water
pH 6.8-7.2
ipg/A standard
:lppb
Recovery .
ar.d
Sensitivity
.78* .
53
20
95
90
16-79
71-101
95-86
95-86
98
96
97
•'
16-79
Associated
Analytical
_ Method
GC
GC, Electron
capture, and
Phosphorus
detectors
GC-MS
SE-30 on
Chromosorb W
10e-210<>C
GC-MS
' Reference,
Webb (1975)
Mieure,
Dietrich(1973)
Leoni, Puccetti,
Grella (1975)
Kleopfer,
Fairless (1972)
Hltes (1973)
VJ1
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES PROM WATER
— «
Substltuted-
Non-polar
1-Me
naphthalene
2-Me
naphthalene
Ethyl benzene
Cumene
p-Cyroene
1-Methylnaph-
thalene
Isopropyl
Benzene
Ethyl Benzene
Benzyl
chloride
Accumulator
XAD-2
Desorptlon •.
or
Extraction
Medium
Ether
Ether
Extraction
Ether
Rat e ^Ssttsp 1 e
.S^ • Volume
30-50cc/min
lOOi
SOcc/mln
30-50cc/mln
50cc/min
50cc/mln
14
Collection .
Parameters
pH=8
pH=3
Iowa wellwater
Recovery .
and
Sensitivity
87-93S
'95
81
93
92
19.3 ± 2ppb
.1'- 2ppb
15ppb
882
Associated
Analytical
Method
-
GC-FID
acid-washed
DMCS-treated
ChromosorbW
GC/MS
GC-PID
'P.ereresce -
Junk, et al.
(1971)
Burnham, et al.
(1972)
Junk, et al.
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM WATER
Aec'^ulant
Chlorobenzene
lodobenzene
o-Dichloro-
benzene
m-Dichloro-
benzene
1,2,4,5-Tetra-
chlorobenzene
2,1-Dlchloro-
toluene
a-o-Dichloro-
toluene
m-Chlorotoluene
1,2,4-Tri-
chlorobenzene
2Methyl
naphthalene
2-Methyl
naphthalene
1-Methyl
naphthalene
2-Methyl
naphthalene
Accuaulator
XAD-2
XAD-lH-8
XAD-4
XAD-2
Desorptlon •.
or
Extraction
Medium
Ether
Chloroform
Extraction
Sar.pline^X^
Rat e -XSarep 1 e
^S^ • Voluae
50oc/mln
14
22cc/mln
Collection .
Parameters
pH=3.2
neutral
Distilled water.
Recovery .
and
Sensitivity
.90? .
81
88
93
74
71
96
80
99
77
77
77
75
Associated
Analytical
Method
GC-PID
GC
Reference. .
Junk, et al.
(1971)
Webb (1975)
I
CPi
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
Accusulant
1 Methyl
naphthalene
2 Methyl
naphthalene
1 Methyl
naphthalene
2 Methyl
naphthalene
1 Methyl
naphtha} fine
Xylene
Styrene
Ethylbenzene
Hexachloro-
benzene
Substituted-
Polar
Benzyl alcohol
Cinnanyl
alcohol
2-Phenoxy-
ethanol
Accumulator
XAD-2
XAD-7
XAD-8-
Activated
Carbon
-
XAD-2
Desorptlon -.
or
Extraction
Medium
Chloroform
Extraction
CHC1,
,
Ether
Sanpllng^/^
Rat e ^XSamp 1 e
^r • Volume
22cc/min
23204
30-50cc/mln
. U
Collection .
Paraseters
Distilled water
Ippb
pH=8
Recovery .
and
Sensitivity
76?
63
61
77
80
91
85
102
Associated
Analytical
Method
GC
GC-MS
SE-30 on
Chroraosorb W
tO°-210<>C
' P.ef erer.ce -
Webb (1975)
Kleopfer,
Fairless (1972)
I
oy
oo
i
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM WATER
Acsurulant
. Nitrobenzene
o-Nitro-
. toluene
w-Methyl-
anlllne
Phenylene
diamine
TNT
Aniline
o-Nitrptoluene
o-Nltrotoluene
o-Nitrotoluene
o-Nitrotoluene
o-Nitrotoluene
Accumulator
XAD-2
XAD-2
XAD-1+8
XAD-1.
XAD-2
XAD-7
XAD-8
Desorption •,
or
Extraction
Medium
Ether
Acetone
Toluene
KOH
Chloroform
Extraction
Sampllng^X*^
Ra't e ^/Sample
*s — • Volume
50cc/min
14
2 cc/min .
50cc
250cc/mln
5cc/mln
22cc/min
Collection .
Parameters
pH=3.2
neutral
pH=7.6
Distilled water
Recovery .
and
Sensitivity
.91* •
80
81
98
80
95
100 • :
83
83
82
61
77
Associated
Analytical
Method
GC-FID
GC-KS
15? Carbowax
20M on
Chromosorb P
200°C
LC-
C. g/Corasll
acetonitrlle
"C
GC
Reference .
• Junk, et al.
(197D
Burnham, et al.
(1972)
Walsh, Chalk.
Merritt, Jr.
(1973)
Rlley, Taylor
(1969)
Webb (1975)
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM 'WATER
— .
TNT
Phenols
Phenols
2,1-Dlmethyl
phenol
Phenol
P-Nitro
phenol
2-Methyl
phenol.
o-Cresol
l|,6-Dinitro-2-
amlno phenol
' Accumulator
Activated
carbon
XAD-1
XAD-2
Desorptlon •.
or
Extraction
Medium
Acetone
2N KOtt
Ether
'
Sampling '
Ra't e ^•''Sample
^X"^ ' Volume
2320)1
5cc/min
50cc/min
1504
Collection .
Paraseters
Ippb
pH=2-9
pH=8
Recovery .
and
Sensitivity
22?
0
(not accum)
100
15
100
100
100 .
1,3
Associated
Analytical
Method
LC-C18/
Corasil
Acetonitrile
H20
Photometric
GC-MS
15Z Carbowax
20M on
Chromosorb P
200°C
Reference -
Walsh, Chalk,
Merrltt, Jr.
(1973)
Riley , Taylor
(1969)
Burnham, et al.
(1972)
o
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Ascu=ulant
o-Cl phenol
Phenol
p-Cl phenol
o-Cresol
2,H,6-C1,
phenol J .
3,5 Xylenol
1-Naphthol
Phenol
Phenol
p-Cresol
Phenol
p-Cresol
. •
Accumulator
XAD-4
XAD-7
XAD-4+8
XAD-2
Desorptlon •.
or
Extraction
Medium
Ether
KOH
Chloroform
Extraction
i
Sampllng^x*^
Rat e .XSamp 1 e
. ^S^ • Volume
30-50cc/mln
14
5cc/mln
22cc/min
Collection .
Parameters
.5% HCL
pH=7.6
Distilled Water
Recovery .
and
Sensitivity
96?.
to
95
73
99
79
91
86
16
68
ID
41)
Associated
Analytical
Method
GC-FID
5% OV-17
ChromosorbW
GC-MS
1555 Carbowax
20 M on
ChromosorbP
200°C
GC
' Hererer.ee
Junk, et al.
(1971)
Burnham, et al.
(1972)
Webb' (1975)
I
—0
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Ascu=ulant
Pentachloro-
phenol
Phenol
p-Cresol
Phenol
p-Cresol
Pentachloro-
phenol
Phenol
m-Cresol
o-Ethyl
phenol
p -Ethyl
phenol
Phenol
o-Cresol
p-Cresol
Accumulator
XAD-2
XAD-7
XAD-8
Chromosorb 102
A-26 Anlon
Exchange Resin
Desorptlon •„
or
Extraction
Medium
Chloroform
Extraction
Heat
1M HC1 elutlon
followed by
CH2C12
extraction
Saraplinjix-^
Rat e ^XSamp 1 e
^s^ • Volune
22cc/min
5cc/min
10-15cc/min
Collection .
Paraseters
Distilled Water '
pH=12.0-12.5
Recovery .
and
Sensitivity
81*
19
33
29
17 • •
77 .
25-61
75
97
89
93-95
90-91
80-96,
Associated
Analytical
Method
GC
GC-OV-17
Rerereace
Webb (1975)
i
Mleure,
Dietrich
(1973
Chrlswell, et al.
(1975)
ro
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
Aesusalant
p-Chloro-
phenol
1-Chloro-3-
methyl phenol
2,'4,6-Tri-
chloro phenol.
Pentachloro-
phenol
3,5-Dimethyl-
phenol
2 Naphthol
Cresols
Dimethyl
phenols
Trimethyl
phenols
2,3,5,6-Tetra
methyl phenol
Chlorophenols
Dlchloro-
phenol
' Accumulator
A-26 Anion
.Exchange Resin
Activated
Carbon
Desorptlon -.
or
Extraction
Medium
4M HCl elution
followed by
CH2C12
extraction
CHC1
followed by
Florisil
column
Ra't e -x^oamp le
.S^ • Volume
10-15cc/min
23201
Collection .
Parameters
pH=12.0-12.5
Ippb
Recovery .
and
Sensitivity
95-100$
95-100
95-102
80-89
90-95
95
95^100
60-88
88-94 ;
90
80-82
86-100
Associated
Analytical
_ Method
GC-OV-17
GC-FID
10% Carbowax
2M on
Chromosorb W
210°-2'40eC
Rei~erer.ee
Chriswell, et al.
(1975)
; '• .;>
Elchelberger,
Dresser,
Lor.gbottom
(1970)
uo
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Accumulant
. Trichloro-
phenols
Phenol
1-Naphthol
2-Naphthol
o-Nltro-
phenol
Pentachloro-
phenol
Ketones and
. Aldehydes
Benzil
Acetophenone
Benzophenone
Benzil
Benzaldehyde.
Accumulator
Activated
Carbon
Extraction
with n-hexane/
Isopropanol
XAD-1
XAD-2
Desorptlon •.
or
Extraction
Medium
CHC13
followed by
Florlsil
column
Extraction c
h-heptane
Etner
Sampline/ —
Ra'te ^^Sanple
^s' • Volume
2320*
lOOcc
SOcc/mln
- 14
Collection .
Parameters
Ippb
2cc cone. HpSOn
pH=8
PH=3.2
neutral
Recovery .
and
Sensitivity
. 83-100?
101)
77
'111
102
91-97
92 '
93
' 97
101 '
Associated
Analytical
Method
GC-FID
1055 Carbowax
2M on
Chromosorb W
210°-2tO"C
GC-ECD
QF-1 on
Varaport
150°C
GC-FID
acid-washed
DMCS-treated
Chromosorb V
5% OV-1
Rerereace
Elchelberger,
Dresser,
Longbottora
(1970)
Rudllng (1970)
• Junk, et al.
(19711)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Acsu=ulant
'Salicyl-
aldehyde
Chlorohydroxy-
benzophenone
Ethers
Benzyl ether
Anisole
2-Methoxy-
naphthalene
Phenyl ether
Acids
Benzene
Sulfcnic
Acid
p-Toluene
Sulfonlc
Acid
Benzole
Benzole
Accumulator
XAD-2
Activated
carbon
XAD-2
Desorptlon •_
or
Extraction
Mediua
Ether
Acetone
Ether
*
Sampllngxx^
Rate ^/Sample
./^ . volume
50cc/min
li
23204
5-Occ/min
U
2cc/mln
50cc
Collection .
Parameters
pH=3.2
(neutral)
Ippb
PH=3.2
neutral
Distilled water
pH=3.2
(neutral)
Recovery .
and
Sensitivity
100%
99
87
97
91
31
23
100 . •
23
Associated
Analytical
.Method
GC-FID
acid-washed
DMCS-treated
Chromosorb W
GC-MS
SE-30 on
Chromosorb W
l40°-210"C
GC-FID
5t OV-1 on
Chromosorb W
GC or UV
Rererer.ee
Junk, et al.
(1971)
Kleopfer,
Fairless
(1972)
Junk, et al.
(1974)
Webb (1975)'
Burnham, et al.
(1972)
Ul
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Accumulant
. 2 Hydroxy-
naphtholc
Benzole
Esters
Benzyl acetate
Dime thoxy ethyl
phthalate
Dimethyl
phthalate
. Dlethyl
phthalate
Dlbutyl
phthalate
Di-2-ethyl-
hexyl phthal-
ate
2-Ethylhexyl
phthalate
2-Ehtylhexyl
phthalate
' Accumulator
XAD-2
-
XAD-7
Desorption •.
or
Extraction
Medium
Ether
Chloroform
Extraction
Sanpllng^^
Rat e -X^amp 1 e
^s — • Volume
50cc
50cc/mln
li
22cc/mln
Collection .
Parameters
pH=3.2
(neutral)
.5% HC1-H20
neutral
Distilled Water
Recovery .
and
Sensitivity
. 39!
107
100
91
63-91
92
90-101
88 :
33
22
Associated
Analytical
Method
GC or UV
GC-FID
5% OV-IM
Chromosorb W
GC
Reference
Burnham, et aL (1972)
Junk, et al.
(1971)
Webb (1975)
CTl
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Aeeu=ulant
, 2-Ethylhexyl
phthalate
2-Ethylhexyl
phthalate
Dlethyl
phthalate
Di-n-butyl
phthalate
Dl-octyl
phthalate
. Butyl
benzoate
Diisodecyl
phthalate
Accumulator
XAD-l) '
Extraction
with £H2C1,
Desorption •,
or
Extraction
Medium
Chloroform
. Extraction
Extraction c
n-heptane
'•
Sair.pllnex^
Rat e ^^Samp 1 e
^s^ . Volume
22cc/mln
2320JI
Collection .
Parameters
Distilled Water
Ippb
Recovery .
and
Sensitivity
. 11* .
13
•:
Associated
Analytical
_ Method
GC
GC-MS
.05% OV-17 or
glass beads
70°-250I>C
Reference
Webb (1975)
Kites (1973)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
«=«
Pesticides
Llndane
DDT
Endrln
Malathion
Atrazlne
Lindan
Aldrln
Dieldrln
DDT
DDE
Hexachloro-
benzene
Aldrin
Dieldrln
Heptachlor
Heptachlor
epoxlde
orChlordane
DDT
DDE
TDE
' Accumulator
XAD-1
XAD-2
XAD-2
Tenax GC
Desorption -.
or
Extraction
Medium
EtOH
Ether
• Ether
Ether
Rate ..X^air.ple
^/^ • Volume
5cc/raln
14
50cc/mln .
14
34/hr
Collection .
Parameters
pH=2
sea water
pH 6.8 - 7.2
lug/4 standard
Recovery .
and
Sensitivity
100$
100
75
100
83
95
HI
93
.96
81
71-91
1)2-92
94-97
88-102
96
99
91-109
60-96
93-96
Associated
Analytical
Method
11(C
GC
GC
GC
GC-FID
GC, Electron
Capture, and
Phosphorus
detectors
' Reference,
Riley, Taylor
(1969)
Junk, et al. (1971)
Junk, et al.(197t)
Leonl, Puccettl,
Grella (1975)
I
—J
co
I
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM WATER
Aceu=ulant
DCBP
BHC
Methoxychlor
Ronnel
Dursban
Dlazinon
Malathion
Parathion
Summithion
Llndane
Heptachlor
Aldrin
Heptachlor-
epoxide
Endrin
p,p'-DDE
Dieldrin
0,p'-DDT
P,P'-TDE
P,P '-DDT
PCB's
Lindane
Heptachlor
Aldrin
Accumulator
Tenax GC
Polyurethane
. ;
Polyurethane
Coated c"
SE-30
Desorptlon •.
or
Extraction
Medium
Ether
hexane
hexane
Sampling^^
Rat e ^XSanple
^s" . Volume
3l/hr
30-250l/rain
III.
30-250t/min
nt.
Collection .
Parameters
pH 6.8 - 7.2
1 Vg/l standard
Ippb
Ippb
Recovery .
and
Sensitivity
80-8W
•' 62-105
75
88-101
.89
80
71-104
90-112 .
108
55
50
15
68
78
' 80
73
68
80
8t
81
95
80
71
Associated
Analytical
Method
GC, Electron
Capture , and
Phosphorus
detectors
GC-ECD
3$ SE-30
'
' GC
GC-ECD
3* SE-30
' Reference .
Leonl, Puccettl,
Grella (1975)
Uthe, Reinke,
Gesser (1972)
Webb (1975)
Uthe, Reinke, .
Gesser (1972)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Accumulant
Heptachlor-
epoxlde
Endrin
p.p'-DDE
Dieldrln
o.p'-DDT
p.p'-TDE
p,p'-DDT
Llndane
Heptachlor
Aldrin
Heptachlor-
epoxlde
Endrin
P • P ' -DDE
Dieldrln
o.p'-DDT
P.P'-TDE
p.p '-DDT
Llndane
Heptachlor
Aldrin
Heptachlor-
epoxlde
Endrin
Accumulator
Polyurethane
Coated c
SE-30
Polyeurethane
Coated c"
DEG 5
Polyurethane
coated c
QF-1
Desorption -^
or
Extraction
Medium
hexane
hexane
hexane
Ra't e^x'Sample
.S^ • Volume
30-250 i/ml.n
•
30-250 Jl/mln
M
30-250 1/mln
Hi
Collection .
Parameters
.Ippb
IPPb
ippb
Recovery .
and
Sensitivity
95*
90
92
60
50
72 ' ,
50
100
87
73
an
-oy
95
88
51 '
• 17
71
31
100
87
o /
80
95
100
Associated
Analytical
Method
GC-ECD
3? SE-30
f
G-C-ECD
3% SE-30
G-C-ECD
3% SE-30
P.ererence
Uthe, Relnke,
Gesser (1972)
Uthe, Relnke,
Gesser (1972)
Uthe, Relnke,
Gesser (1972)
I
oo
o
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Accunmlant
P,P'-DDE
Dleldrln
o.p'-DDT
p , p ' -TDK
P , P ' -DDT
Lindane
Heptachlor
Aldrln
Heptachlor-:
epoxlde
Endrln
P,P'-DDE
Dleldrln
o.P'-DDT
p , p ' -TDE
P.P'-DDT
Lindane
Heptachlor
Aldrln
Heptachlor-
epoxide
Endrin
P.P'-DDE
Accunulator
Polyurethane
coated c
SE-30
-
Polyurethane
Coated c~
OV-25
Polyurethane
Coated c
OV-225-
Desorption •.
or
Extraction
Medium
hexane
.•
hexane
hexane
Rat e ^^ample
^S^ • Volume
30-250 i/mln
4i
30-250 i/mln
4*
30-250 i/min
Collection .
Parameters
Ippb
Ippb
Ippb
Recovery .
and
Sensitivity
96 %
73
72
87
69
.97
58
17
70
72
18
50
60
i,5
91
58
1)5
76
I U
74
72
Associated
Analytical
Method
G-C-ECD
3? SE-30
G-C-ECD
3$ SE-30
G-C-ECD
3* SE-30
' Reference -
Uthe, Reinke,
Gesser (1972)
Uthe, Reinke,
Gesser (1972)
Uthe, Reinke,
Gesser (1972)
I
oo
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
Dieldrln
o.p'-DDT
P,P'-TDE
P.P'-DDT .
DDT
Y-BHC
Heptachlor
Aldrin
Heptachlor
epoxide
Dieldrln
Endrln
Surfactants
Teepol
Hyamine 2839
Triton-X-100
Nonldet P80
Dyes
Rhodamine B
Methylene Blue
Accumulator
Polyurethane
coated c
OV-225
Humic Acid-
Fe colloids
Extraction
with benzene
XAD-1
XAD-1
Desorptlon •.
or
Extraction
Medium
hexane
"Extraction c~
n-heptrane
EtOH
EtOH
2N HN03
Sar.pllngrx —
Ra't e ^^Sanple
.S^ • Volume
30-250 4/mln
SOOcc
5cc/mln '
Collection .
Parameters
Ippb
p'H=2
pH=7.6
Recovery .
and
Sensitivity
50
15
80.5
x 15,000 cone
89
95
97
98
96
100
100
100
100
100 '
100
Associated.
Analytical
Kethod
G-C-ECD
3* SE-30
"c
GC
Photometric
Photometric
' Reference .
Uthe, Relnke,
Gesser (1972)
Poirrler, Bordelon,
Laseter (1972)
Konrad, Pionke,
Chesters (1969)
Rlley. Taylor
(196^5
Riley, Taylor
(1969)
I
CO
rv>
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
Accumulant
Other
Cholesterol
Pregnenalone
Vitamin B2
Vitamin B12
Accumulator
' XAD-l
*
Desorption -v
or
Extraction
Medium
EtOH
•
Samplinex^
Ra't e ^Xsamp le
^^ • Volume
5cc/min
Collection .
Parameters
pH=2
pH=2
pH=2
pH=2 :
Recovery .
and
Sensitivity
100?
100
100
' 100
Associated
Analytical
Method
Fluorimetric
14
C-countlng
Flour imetric
C-countlng
' Reference
Rlley, Taylor
(1969)
I
CO
(JO
I
-------
TABLE 2-4
ACCUMULATION OF 'ORGANIC 'SUBSTANCES PROM WATER BY ACCUMULATOR
This table lists those organic compounds or classes
of compounds which have b.een .concentrated from water using
one of the accumulation techniques which have been described.
The accumulator column lists either the solid adsorbent
or liquid extractant that was used for preconcentration.
The desorption or extraction medium in most cases is the
solvent or temperature which was used to remove the organic
compounds from a solid adsorbent.
-84-
-------
ACCUMULATION OF ORGANIC SUBSTANCES PROM WATER.
ARRANGED BY ACCUMULATOR
Accumulator
XAD-1
Accumulant
n-Heptanolc
acid
n-Heptadecanolc
acid
il-Ketoglutaric
acid
Cholesterol
Pregnenalone
Vitamin &2
Vitamin B12
Surfactants
Teepol
Hyamlne 2389
Triton-X-100
Nonidet P8.0
Dye's
Rhodaralne B •
Methylene Blue
Humlc Acids
Desorptlon
or
Extraction
Medium
2N NHjjOH
IN KOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH '
EtOH
2N HNO '
2N KOH
sS*^ Volume
5cc/mln
Collection
Parameters
Seawater
pH = "2
pH = 2
pH -.7.6
P.H = 2
pH - 2 ..
2
pH = 7.6
pH - 2
pH - 7.6
Recovery
and
Sensitivity
1002
100
100 •
,100
100 '
100
100
100
100
100
100 .
100
100
Associated
Analytical
Method
Hi
C-counting
Fluorimetrlc
C-counting
Fluorimetric
"57
Co counting
Photometric
Photometric
Reference
Riley, Taylor (1969)
I
oo
VJl
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PRCM WATER.
ARRANGED BY ACCUMULATOR
Accumulator
XAD-1
XAD-2
Accuaulant
Carbohydrates'
Amino acids
Phenols ,
Herbicides and
. Pesticides
Llndane
DDT -
Endrin
Malathion
Aromatlcs
1-Me
naphthalene
Benzll
Napthalene
2-Me
Napthalene
Blphenyl
Pluorene '
Anthracene
Acenaphthene
Desorption
or
Extraction
Median •
2N KOH
EtOH
Ether
^^^ Volume
5cc/min
5cc/mln .
U
30-50cc/mln
50cc/mln
1A .
Collection
Parameters
pH = 2 - 9
pH = 2
sea water
pH = 8
Recovery
and
Sensitivity
0'
(not accum)
100*
100
75
100
87-93
91-97
98
95
101
81
83
92
Associated
Analytical
Method
Photometric
C1*
ac-
GC
GC
GC-FID
acid-washed
DMCS-treated
Chroraosorb-W
5% OV-1
Reference
Rlley, Taylor
(1969)
Rlley Taylor
(1969}
Junk, et al.
(1971)
I
co
cr\
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
XAD-2
<
Accumulant
Hexanol
Phenols
2,l)-Dimethyl
phenol
Phenol
p-Nitro
phenol
2-Methyl
phenol
o-Cresol
H,6-Dlnitro-2-
amino phenol
Aldehydes & :
Ketones •&
Ethers
2,6-Dimethyl
-'(-heptanone
2-Undecanone
Acetophenone
Desorption
or
Extraction
Medium
Ether
Ether
Ether
Samplingxx'*x^
Ra^x-^Sample
^"^ Volume
50cc/mln
150i
50cc/min
1504
50cc/min
It
Collection
Parameters
»
•
Recovery
and
Sensitivity
85* •
100
15
100
100
100
43
93
88
92
Associated
Analytical
Method
GC-MS
15? Carbowax
20M on
Chromosorb P
200° C
GC-MS
155E Carbowax
20M on
Chromosorb P
200° C
GC-FID
5? OV-1 on
Chromosorb W
Reference
Burnham, et al.
(1972)
Burnham, et al.
(1972)
Junk, et al. Ugy'O
I
GO
-------
ACCUMULATION 0? ORGANIC SUBSTANCES PROM WATER
ARRANGED BX ACCUMULATOR
Accumulator
XAD-2
Accumulant
Aroraatlcs
Acenaphthylene
1-Methylnaph-
thalene
Indene
Acenaphthene
2,2-Benzothio-
phene
Isopropyl
Benzene
Ethyl Benzene
Naphthalene
2) 3-Dihydro-
Indene
Alkyl
Naphthalenes
bis-Chloro
isopropyl ether
sym-Tet;-a-
chloroethane • •
Desorption
or
Extraction
Medium
Ether
Extraction
Chloroform
Extraction
s*s Volume
50cc/mln
150*
. 22cc/min
Collection
Parameters
PH=3 " . .
Iowa wellwater
Distilled water
Recovery
and
Sensitivity
19. 3%- 2ppb
11.0 i.6ppb
18.8 i.Sppb
18.0 - 2ppb
1.7±.2PPb
.1 -.Ippb
15ppb
15ppb
!5ppb
15ppb
70'
61
Associated
Analytical
Method
GC/MS
Reference •
Burnham, et al. (1972)
Webb (1975)
I
oo
oo
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
XAD-2
Accumulant
n-Hexadecane
a-Terpineol
Naphthalene
o-Nltrotoluene
2-Methyl
naphthalene
1-Hethyl
naphthalene
Benzpthlazole
Phenol
p-Cresol
AcenaphtBene
Dibenzofuran'
2-Ethylhexar.ol
Isophorone
Pentachloro-
phenol
Palmitic acid
Dehydroablettc
acid
2-Ethylhexyl
phthalate
Desorption
or
Extraction
Medium
Chloroform
Extraction
Sampling^x*'^
Ra*2x*sample
^^^ Volume
22cc/min
t-
Collection
Parameters
Distilled water
Recovery
and
Sensitivity
90*
81
79
" 82
75
76
71
11
44
99
93
85
76
81
67
91
33
Associated
Analytical
Method
GC
Reference '
Webb (1975)
I
oo
-------
ACCUMULATION OF ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
..
XAD-2
•
Accuaulant
Benzene Sulfonic
acid
P-Toluene
Sulfonic acid
Benzole
Benzole (-3-)
2-Hydroxynaph-
tholc
Esters
Benzyl acetate
Dimethoxy ethyl
phthalate
Dimethyl
phthalate
Diethyl
phthalate
Dlbutyl '
phthalate
Dl-2-ethyl-
hexyl phthalate
Diethyl
fumarate
Dibutyl
fumarate
Di-2-ethyl- .
hexyl fumarate
Desorptlon
or
Extraction
Medium
Ether
Ether
-
\
Sampl ing^^*'^
^^sLple
*s^ Volume
2cc/min
50cc
••
5Dcc/mln
14
Collection
. Parameters
pH=3.2
neutral
•
Recovery
and
Sensitivity'
31?
• 23 ' •
100
23
39
100
94
63-91
92
90-101
88 .
86
92
81
Associated
Analytical
Method
GC or UV
GC-FID
5$ OV-1 on
Chromosorb W
Reference.
Burnham, et al.
(1972)
Junk, et al.
(197t)
I
vo
o
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
XAD-2
Accunulant
Diethyl
malonate
Methyl
benzoate
Methyl
decanoate
Methyl
octanoate
Methyl
pa Imitate
Methyl
sulicylate
Methyl . •.
methacrylate :
Ethyl
butyrate
Nitrogen
Compounds
Hexadecylamine
Nitrobenzene
Desorptlon
or
Extraction
Medium
Ether
Ether
Ether
Sampling^x*^*^
Rat^X^Sanple.
j»r Volume
50cc/min
1*
2cc/min
50cc
50cc/min
11
•
Collection
Parameters
Recovery
and
Sensitivity
103* .
101
95
98
70
96
-35
100
91
91
Associated
Analytical
Method
GC-FID
5% OV-1 on
Chromosorb W
GC-MS .
15$ Carbowax
20M on
Chromosorb P
200° C
GC-PID
Reference '
Junk, et al. (1971)
Burnham, et al.
(1972)
Junk, et al. (1971)
H
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
XAD-2
Accumulant
Indole
o-Nitro-
toluene
N-Methyl-
anillne
Benzothlazole
Qulnoline
Isoqulnoline
Benzpnltrile
Benzoxazole
Phenylene
dlamlne
TNT
Halogenated
Aromatic s
Benzyl
chloride
Desorptlon
or
Extraction
Medium
Ether
Ether
Acetone
Toluene
Ether
Sair.plinK^^^
Rate^x^ample
s**^ Volume
50cc/mln
11
2cc/min
50cc
250cc/mln
50cc/mln
It
Collection
Parameters
Recovery
and
Sensitivity
89* .
80
8H
100
81
83
88
92
98
30
95
88
Associated
Analytical
Method
GC-FID
GC-MS
15? Carbowax
20M on
Chromosorb P
200° C.
LC-
Cio/Corasll
acetonitrlle-
H20
GC-FID
Reference •
Junk, et al. (1971)
Burnham, et al.
(1972)
Walsh, Chalk,
Kerrltt, Jr. (1973)
Junk, et al. (1971)
ro
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
XAD-2
Accumulant
Chlorobenzene
lodobenzene
0-Dichloro-
benzene
m-Dichloro-
benzene
1,2,4,5-Tetra-
chlorobenzene
2,4-Dichloro-
toluene
a-o Dichloro-
toluene
r.-Chlor-otolxiene
1,2,1-Tri-
chlorobenzene
Herbicides &
Pesticides
Atrazine
Lindan
Aldrin
Dieldrin
DDT
Desorptlon
or
Extraction
Medium
Ether
Ether
Sampl InK^""'^
Rate^x-^ample
s* Volume
50cc/min
It
Collection
Parameters
Recovery
and
Sensitivity
902
81
88
93
7t
71
96
80
99
83
95
17
93
96
Associated
Analytical
Method
GC-FID
Reference
Junk, et al. (1971)
Junk, et al. (ig?1!)
I
VO
OJ
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
XAD-2
XAD-2
Accuraulant
Benzophenone
Benzil
Benzaldehyde-
Salicyl- '
aldehyde
Hexyl ether
Benzyl ether
Anisole
2-Methoxy-
naphthalene
Phenyl ether
Methyl iso-
butyl ketone
DDE
Acids
Octanolc
Decanoic
Palmitic
Olelc
Benzole
Desorptlon
or
Extraction
Medium
Ether
•
Ether
Ether
Ether
Sampling^*
^^ Volume
50cc/min
11
2cc/min
501
50cc/min
1*
Collection
Parameters
..5* HC1 - H20
Recovery
and
Sensitivity
93% .
97
101
100 .'
75
99
87
97
91
100 .
81
108
90
101
100
107
Associated
Analytical
Method
GC-FID
5$ OV-1 on
Chromosorb W
GC-MS
15$ Carbowax
2 OK on
Chromosorb P
200° C.
GC-FID
5$ OV-1M
Chromosorb W
Reference
Junk, et al. (1971*)
Burnham, et al. (1972)
Junk, et al. (1971)
Junk, et al. (197t)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
' •. ARRANGED 'BY ACCUMULATOR
Accumulator
XAD-l)
Accumulant
sym-Tetra-
chloroethane
bis-Chloro
isopropyl ether
a-Terpineol
Naphthalene
o-Nitrotoluene
2-Methyl
naphthalene
1-Methyl
naphthalene
Benzothiazole
Phenol
p-Cresol
Acenaphthane
Dlbenzofuran
2-Ethylhexanol
Isophorone
Pentachloro-
phenol
Palmitic acid
Desorption. •.
or
Extraction
Medium
Chloroform
Extraction
.-
i
Sanpllnex^
Rate ^-^Sample
^> — • Volume
22cc/min
-
Collection .
Parameters
Distilled water
Recovery .
and
Sensitivity
90J
80
80
• 80
83
77
77
' 82
38
69
81
82
91
86
8D
79
Associated
Analytical
Method
GC
Reference
Webb (1975)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
XAD-t
XAD-U
XAD-7
Accuir.ulant •
Dehydroabietic
acid
2-Ethylhexyl
phthalate
Phenols
o-Cl phenol
Phenol
p-Cl phenol'
o-Cresol
2,1,6-C1,
phenol
3,5 Xylenol
1-Naphthol
Acids
Heptanolc
Heptadecanoic
H-Ketoglutaric
Nitrogen
Compounds
Aniline
Phenols
Phenol
sym-Tetra-
chloroethane
n-Hexadecane
Desorption
or
Extraction
Medium
Chloroform
Extraction
Ether
NH,,OH
NHj,OH
KOH
Chloroform
Sampling^^^
Ra^>^Sample
^^ Volume
22cc/min
30-50cc/min
14 '
li
5cc/min
22cc/min
Collection
Parameters
Distilled Water
-
5« HCL
pH=2 ' • '
PH=2
pH=7.6
Distilled water
Recovery
and
Sensitivity
90$
11
11 '
7935
99
79 •
91
100
100
100
100
86
90
3
Associated
Analytical
Method
GC
^C
GC-MS
15$ Carbowax
20 M on
Chromosorb P
200° C.
GC
Reference •
Webb (1975)
Junk, et al. (197^)
Riley, Taylor (1969)
Burnham, et al.
(1972)
Webb (1975)
cr\
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER.
ARRANGED BY ACCUMULATOR.
Accumulator
XAD-7
XAD-8
Accunulant
a-Terpineol
Naphthalene
o-Nitrotoluene
-2-Methyl '
naphthalene
1-Methyl
naphthalene
Benzothlazole
Phenol
p-Cresol
Acenaphthene
Dibenzofuran
2-Ethylhexanol
Isophorone
Pentachloro-
phenol
Palmitic acid
Dehydroabletic
acid
2-Ethylhexyl
phthalate
sym-Tetra-
chloroethane
bis-Chloro
isopropyl ether
Desorption
or
Extraction
Medium •
Chloroform
Extraction
Chloroform
SamollnKx*'^
Rate^^alsple
^^ Voluxe
22cc/min
22cc/min
Collection
Parameters
Distilled water
Distilled water
Recovery
and • .
Sensitivity
362 . •
6V.
53
63
64
40
19
33
72
73
71 •
16
83
12
90
22
90
77
Associated
Analytical
Method.
GC
GC
Reference.
Webb (1975)
Webb (1975)
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER.
ARRANGED BY ACCUMULATOR.
Accumulator
XAD-8
Accunulant
a-Terplneol
Naphthalene
o-Nitrotoluene
2-Kethyl
naphthalene
1-Kethyl
naphthalene
Benzothlazole
Phenol
p-Cresol
Acenaphthene •
Dibenzofuran
2-E>thylhexanbl
Isophorone
Pentachloro-
phenol
Palmitic acid
Deny droabie tic
acid
2-Ethylhexyl
phthalate
Desorptlon
or
Extraction
Medium •
Chloroform
Extraction
San.plinK^^
Ra^^Sar.plc
^"^ Volume
22cc/mln-
Collection
Paraneter:
Distilled water
Recovery
ar.d
Sensitivity
62Z
78
77
77
.. 80
53
29
H7 ' '
20
95
. 79
H7
77
16
90
13
Associated
Analytical
Method
GC '
Reference •
Webb (1975)
co
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER.
ARRANGED 'BY ACCUMULATOR.
Accumulator
XAD- 4+6
•"""
.
•
Accumulant
sym-Tetra-
chloroethane
n-Kexadecane
o-Terpineol
Naphthalene
o-Nitrotoluene
2-Methyl
naphthalene
1-Methyl
naphthalene .
Benzothiazole
Phenol :
p«-Cresol
Acenaphthene
Dlbenzofuran
bis-Chloro
isoprophyl
ehter
Desorption
or
Extraction
Medium •
Chloroform
Extraction '
S — Volume
22cc/min
•
; Collection
Parameters
Distilled water
Recovery
and
Sensitivity
90* . .
11
80
80
83
77,
' 79 .
82
46
68
81
84
77
Associated
Analytical
Method
GC
Reference •
Webb (1975)
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER.
ARRANGED BY ACCUMULATOR
Accumulator
Chromosorb 102
Accumulant
Aromatics
Benzene
pyridlne
Phenols
Phenol
m-Cresol
o-Ethyl
phenol
p-Ethyl
phenol
Ketones
Methyl isobiityl
ketone
Acetone •
Halogenated
Aliphatics
CHC13
Alcohols
Met hano 1
Desorptlon
or
Extraction
Medium
Heat
^^ Volume
5cc/mln
Collection
Parameters
.
Recovery
and
Sensitivity
90%
16-79
25-61
75
97 .
89
100
21-42
85-93
<5«
Associated
Analytical
Method
GC
Reference
Kleure, Dietrich
(1973)
o
o
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER.
ARRANGED BY ACCUMULATOR
Accumulator
Tenax GC
Accumulant
Pesticides .
Hexachloro-
benzene
Aldrin
Dieldrln
Heptachlor ,
Heptachlor
epoxide
a-Chlorodene
DDT
DDE :
TDE
DCBP
BHC
Methoxychlor
Ronnel
Dursban
DIazinon '
Desorption
or
Extraction
Medium
Ether
Extraction
'
Sampllngx^x*'^
R£Ue^"SamPle
^^ Volume
34/hr
.
: Collection
?arameters
pK 6.8 - 7.2
lyg/i standard
Recovery
and
Sensitivity
71-91?
12-92
91-97
88-102
96
99
91-109
60-96
93-96
80-81
62-105
75
88-101
89
80
Associated
Analytical
Method
GC, Eleetror.
Capture, and
Phosphorus
detectors
Reference .
Leoni, Puccetti,
Grella (1975)
I
}-•
o
I—1
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
Tenax GC
A-26 Anlon
Exchange Resin
Accumulant
Malathion
Parathlon
Summlthion
Aromatlcs
Anthracene
Perylene
Ideno
Pyrene
Fluoranthene
3, 'I Benzopyrem
Phenol
a-Cresol
p-Cresol
Desorption
or
Extraction
Medium
Ether •' .
Extraction
1M HC1 elutior
followed by
CH-C12
extraction
Sampllnsxxx'X^
RaHx-^Sample
^^ Volume
. 34/hr
10-15cc/mln
•
Collection
Parameters
pH 6.8 - 7.2
• lyg/ l standard
pH 12.0 - 12.5
*
Recovery
and
Sensitivity
71-10UI
90-112
108
97-100
86-92
'95-86
98 .
96
97
93-95
90-94
80-96
Associated
Analytical
Method
GC, Electron
Capture, and
Phosphorus
detectors
TLC arid
Spectrophoto-
fluorlmetry
GC-DV-17
Reference •
Leonl, Puccetti, .
Grella (1975)
Chrlswell, 6t al.(1975)
o
ro
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRAN3ED BY ACCUMULATOR
Accumulator
A-26 Anlon
Exchange Resin
Accumulant
p-Chlorophenol
t-Chloro-3-
methyl phenol
2,4,6-Tri-
chloro phenol
Pentachloro-.
phenol
3,5-Dimethyl--
phenol
2 Naphthol
Desorptlon
or
Extraction
Medium
1M HCL elutlcn
followed by
CH2C12
extraction
Sampline^^"^
Ra<;VsamPle
i^^ Volume
10-15cc/mln
Collection
Parameters
pH 12.0 - 12.5
•
Recovery
and
Sensitivity
95-100?
95-100
95-102
80-89
90-95
95
Associated
Analytical
Method
GC-OV-17
_
Reference
Chriswell, et al. (1975)
I
H
O
UO
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
XAD-2
Accumulant •
Tetrahydro- •
naphthalene
Ethyl benzene
Cumene
p-Cymene
Benzene
naphthalene
Alcohols
Hexyl
2-Ethylhexanol
2-Octanol
Decyl
Dodecyl '
Benzyl
Clnnamyl
2-Phenoxy-
ethanol
Desorption
or
Extraction
Medium
Ether
Ether
Ether
Sampllng^^"^
Ra3^Sample
^"^ Volume
30-50cc/mln
2cc/mln
50 i
30-50cc/mln
1 I
Collection
Parameters
. pH=8
Recovery
and
Sensitivity
621
81
93
92
100
93
99
100
91
93
91
85
102
Associated
Analytical
Method
GC-FID
acid-washed
DMCS-treated
Chromosorb-W
5% OV-1
GC-MS
15J Carbowax
20M on
Chromosorb P
200° C
Reference .
Junk, et al. (19Tf)
Burnham, et al.
(1972)
Junk, et al. (1971) •
I
M
O
-f
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
Polyurethane
'.
Accumulant
Lindane
Heptachlor
Aldrin
Heptachlor-
epoxide
Endrin
p,p'-DDE
Dieldrin
o,p'-DOT
p.p'-TDE
p.p'-DDT
PCB ' S
Desorption
or
Extraction
Medium
hexane '
Sampllnc^x^^
Ra^^Sample
<*r Volume
30-250 i/min
• AO
Collection
Parameters
1 ppb
Recovery
and
Sensitivity
55%
50
45
68
78
80 .
73
68
80
84
84
Associated
Analytical
Method
G-C-ECD
3% SE-30 .
GC
Reference
Uthe , Reinke ,
Gesser (1972)
Webb (1975)
I
h-1
o
-------
ACCUMULATION OP OR3ANIC SUBSTANCES FROM WATER
ARRANGED 3Y ACCUMULATOR
Accumulator
Polyurethane
Coated c
DC-200
Accuculant
Lindane
Heptachlor
Aldrin
Heptachlor-
epoxide
. Endrin
P.P'-DDE ' .
Dieldrin
o , p ' -DDT
PjP'-TDE •
P.P'-DDT
Desorption
or
Extraction
Kedlun
hexane •
. —
Sampllnc^^^^
Rate^^^^
s^"^ Volume
30^-250 i/min
41. ....
Collection
Parameters
1 ppb
Recovery
and
Sensitivity
97%
92
92
100
100
99
100
93
100
98
Associated
Analytical
Method
G-C-ECD-
3% SE-30 .
'
Reference
Uthe , Reinke ,
& Gesser (1972)
•
I
M
O
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR.
Accumulator
Polyurethane
Coated c
SE-30
Accurculant
Lindane
Heptachlor
Aldrin
Heptachlor-
epoxide
Endrin
p , p ' -DDE ' .
Dieidrin
o.p'-DDT
p.p'-TDE
p.p'-DDT
Desorption
or
Extraction
Medium
hexanfe •
Sarr.plinf'x^'^
Ra>^Sa.-nple
^s^ Volume
30-250 t /mln
t 9
Collection
Parameters
1 ppb
Recovery
and
Sensitivity
95%
80
71
95
90
92 .
60
50 .
72
50
Associated
Analytical
Method
G-C-ECD
3% SE-30
Reference
Uthe,Reinke,
Gesser (1972)
I
M
O
-J
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED' BY ACCUMULATOR
Accumulator
Polyurethane
Coated c
DEC 5
Accunulant
Lindane
Heptachlor
Aldrin
Heptachlor-
epoxice
Endrin
p,p'-DDE ' .
Dieldrin
Ojp'-DDT
p.p'-TDE •
p.p'-DDT ' '
Desorption
or
Extraction
Medium
hexans ' •
Sampllr.e^^^
Ra^^Sa.TPle
^^ Volume
30-250 t/min
4Z
Collection
Parameters
1 ppb
Recovery
and
Sensitivity
100%
87
73
89
95
88 .
51
47 .
74
34
Associated
Analytical
Method
G-C-ECD
3% SE-30 .
•
_
Reference
Uthe, Rainke,
& Gesser (1972)
. ' . "
o
oo
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
Polyurethane
Coated c
QF-1
Accuiculant
Lindane
Heptachlor
Aldrin
Heptachlor-
epoxide
Endrin
p,p'-DDE
Oieldrin
0, p ' -DDT
p , p ' -IDE
p , p ' -DDT
Description
or
Extraction
Medina
hexane
Sarr.pline^^
^^-Sanple
^^ Volune
30-250 fc/nin
4i
Collection
Parameters
1 ppb
Recovery
and
Sensitivity
100%
87
80
95
100
96 .
73
72
87
69
Associated
Analytical
Method
G-C-ECD
3% SE-30
Reference •
Uthe, Rainke,
Gesser (1972)
I
M
O
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
Polyurethane
Coated c
QV-25
Accumulant
Lindane
Keptachlor
Aldrin
Heptachlor-
epoxice
Endrin
0VP'-DDE
Dieldrin
o , p ' -DDT
P , P ' -IDE •
P.P'-DDT ' '
Desorption
or
Extraction
Medium
hexane '
Sampling^^'^
Rate^xSanpie
^^ Volume
30-250 Jl/rain
'4 '£
Collection
Parameters
1 ppb
Recovery
and
Sensitivity
97%
58
47
77
70
72
48
50 .
60
45
Associated
Analytical
Method
G-C-ECD-
3% SE-30 .
Reference
Uthe, Reinke,
& Gesser (1972)
I
h-1
h-l
o
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATEH
ARRANGED BY ACCUMULATOR
Accumulator
Polyurethane
Coated c
OV-225
Accuttulant
Lindane
Heptachlor
Aldrin
Heptachlor-
epoxide
Endrin
p , p ' -DDE
' Dieldrin
o , p ' -DDT
p , p ' -TDE
p , p ' -DDT
Desorption
or
Extraction
Medium
hexane '
S amp 1 lv.%^^
Rata^Xsaap^
^^ Volume
30-250 i/mih
4 t
Collection
Parameters
1 ppb
Recovery
and
Sensitivity
91%
58
45
76
74
72 . :
44
50
64
45
Associated
Analytical
Method
G-C-ECD
3% SE-30 .
Reference •
Uthe, Reinke
& Gesser (1972)
.
H
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
Activated
Carbon
Accumulant
Aromatica
Toluene
Xylene
Styrene
Ethylbenzene
Phenols
Cresols
Dimethyl
phenols
Trlmethyl
phenols
2,3,5,6-Tetra-
methyl phenol
Chlorophenols
Dichloro-
phenols
Desorption
or
Extraction
Medium
CHC1,
CHC1,
followed by
Plorlsll .
column
Sampllngxx*x'^
Ra*>^Sample
^^ Volume
23204
Collection
Parameters
Recovery
and
Sensitivity
95-100?
60-88
88-91
90
80-92
86-100
Associated
Analytical
Method
GC-MS
SE-30 on
Chromosorb-W
JJO°-210° C
GC-FID
10? Carbowax
2K on
Chroraosorb W
210°-2liO° C
Reference
Kleopfer , Palrless
(1972)
Elchelberger, Dresses
Longbottom (1970)
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
Activated
carbon
Accumulant
Trlchloro-
phenols
Phenol
1-Naphthol
2-Naphthol
o-Nitro-
phenol
Ketones &
Ethers
Bis(2-chloro-
ethyl) ether
Bis(2-chloro-
isopropyl) •
ether
Chlorohydroxy-
benzophenone
Nitrogen
Compounds
TNT
Desorptlon
or
Extraction
Medium
CHC1,
followed by
Plorisil
column
CHC13
Acetone
Sampllne^*^
Ra^^Sampie
^**^ Volume
2320 t
Collection
Parameters
Recovery
and
Sensitivity
83-1002
101
77
111
102
22
Associated .
Analytical
Method
GC-FID
10$ Carbowax
2M on
Chromosorb W
210°-2tO°C
GC-MS
SE-30 on
Chromosorb W
l40°-210° C.
LC-C18/
Corasil
Acetonltrile-
H20
Reference .
Elchelberger,
Dresser, Longbottom
(1970)
Kleopfer, Palrless
(1972)
Walsh, Chalk,
Merritt, Jr. (1973)
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
Activated
Carbon
Accumulant
Halogenated
Allphatlcs
BrCljCH
ClBrgCH
Cl.CCCl-
2 2
c2ci6
Desorptlon
or
Extraction
Medium
CHClj
Rate ^^-.-r.-: ..
"^^ Sample
^"^ Volume
2320 i
3 days
Collection
Parameters
Recovery
and
Sensitivity
Associated
Analytical
Method
GC-MS
SE 30 on
Chromosorb W
1JO°-210° C
Reference '
Kleopfer, Palrless
(1972)
-t
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM WATER.
ARRANGED BY ACCUMULATOR
Accumulator
Activated
Carbon
Humic Acid-
Pe colloids
Extraction
with CH2C13
Accumulant
HaloKenated
Aromatic s
Hexachloro-
benzene
Herbicides &
Pesticides
DDT
Aromatica
Biphenyl
Esters
Diethyl
phthalate
Dl-n-butyl
phthalate
Di-2-ethyl-
hexyl adlpate
Desorption
or
Extraction
Medium
CHC13
Extraction *T
n-heptane
Sampline^^^
^^X^Sanple
^^ Volume
2320 I
Collection
Parameters
Recovery
and
Sensitivity
80.5
x 15,000 cone
16-79?
Associated
Analytical
Method
GC-MS
SE-30 on
Chromosorb W
40°-210° C
»C
GC-MS
GC-MS
.05? OV-17 on
glass beads
70°-250° C
Reference •
Kleopfer, Pairless
(1972)
"olrrler, Bordelon,
Laseter (1972)
Hites (1973)
Hites (1973)
Ul
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM WATER
ARRANGED BY ACCUMULATOR
Accumulator
Extraction
with CH2C12
Extraction
with n-hexane/
isopropanol
Extraction
with benzene.
Accunulant
Di-octyl
phthalates
Butyl
benzoate
Dllsodecyl
phthalate
Halogenated
Aromatics
Pentachloro-
phenol
Herbicides &
Pesticides
Y-BHC
Heptachlor
Aldrin
Heptachlor
epoxlde
Dleldrln
Endrin
Desorptlon
or
Extraction
Medium
Sampline^-^^
Ra^x^Sample
^>^ Volume
lOOcc
SOOcc
Collection
Parameters
2cc cone. HjSOjj
Recovery
and
Sensitivity
91?
89
95
97
98
96
Associated
Analytical
Method
GC-MS
.05* OV-17- on
glass bea-ds
70°-250°C
GC-ECD
QF-1 on
Varaport
150° c.
GC
Reference •
Kites (1973)
Rudling (1970)
Konrad, Plonke,
Chesters (1969)
c\
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM WATER
BIBLIOGRAPHY
Ahmed, S.M., Beasley, M.D., Efromson, A.C., and Kites,
Ronald A., "Sampling Errors in the Quantitation of
Petroleum in Boston Harbor Water." Analytical
Chemistry, _4j5: 1858-1860 (1974).
Allen, S.C., Pahl, R.H., and Mayhan, K.G., "Organic Desorption
From Carbon-1." Water Research, 5.: 3-18 (197D-
Baker, Robert A., "Microchemical Contaminants by Freeze
Concentration and Gas Chromatography." Journal WPCF, 37;
1164-1170 (1965).
Baker, Robert A., "Trace Organic Contaminant Concentration
by Freezing—I. Low Inorganic Aqueous Solutions."
Water Research, 1: 61-77 (1967).
Baker, Robert A., "Trace Organic Contaminant Concentration
by Freezing—II. Inorganic Aqueous Solutions."
Water Research, I: 97-113 (1967).
Baker,- Robert A. , "Trace Organic Contaminant Concentration
by Freezing—IV. Ionic Effects." Water Research, j£:
559-573 (1970).
Baker, Robert A., and Malo, Bernard A., "Phenolics by Aqueous-
Injection Gas Chromatography." Environmental Science &
Technology, I: 997-1007 (1967).
Earth, Edwin P., and Acheson, Nicholas H., "High-Molecular-
Weight Materials in Tap Water." Journal AWWA, 54: 959-
964 (1962).
Burnham, A.K., Calder, G.V., Fritz, J.S., Junk, G.A., Svec,
H.J., and Willis, R., "Identification and Estimation of
Neutral Organic Contaminants in Potable Water." Analytical
Chemistry, 44: 139-142 (1972).
Chriswell, Colin D., Chang, Richard C., and Fritz, James S.
"Chromatographic Determination of Phenols in Water."
Analytical Chemistry 4?: 1325 (1975).
-117-
-------
Deinzer, M., Melton, R., Mitchell, D., Kopfler, F., and
Coleman, E., "Trace Organic Contaminants In Drinking
Water; Their Concentration by Reverse Osmosis." Presented
before the Division of Environmental Chemistry, American
Chemical Society, Los Angeles, CA, March 31-April 4, 1974.
Eichelberger, James W., Dressman, Ronald C., and Longbottom,
James E., "Separation of Phenolic Compounds from Carbon
Chloroform Extract for Individual Chromatographic Iden-
tification and Measurement." Environmental Science &
Technology 4: 576-578 (1970).
Ettinger, M.B., "Proposed Toxicity Screening Procedure for
Use in Protecting Drinking-Water Quality." Journal
American Water Works Association 52.: 689-69** (I960).
Glaze, William H., Henderson, James E. IV, Bell, Johnny E.,
and Wheeler, Van A., "Analysis of Organic Materials in
Wastewater Effluents After Chlorination." Journal of
Chromatographic Science 11: 580-584 (1973).
Kites, Ronald A., "Analysis of Trace Organic Compounds in
New England Rivers." Journal of•Chromatographic Science
11: 570-574 (1973).
Kites, R.A. and Biemann, P., "Water Pollution: Organic Com-
pounds in the Charles River, Boston." Science 178: 158-
160 (1972).
Hurley, John T., "Pesticide Analysis in Water." Journal
AWWA 66_: 27-31 (1974).
Junk, G.A., Svec, H.J., Vick, R.D., and Avery, M.J., "Con-
tamination of Water by Synthetic Polymer Tubes."
Environmental Science and Technology 8: 1100 (1974).
Junk,. G.A., Richard, J.J., Grieser, M.D., Witiak, D. ,
Witiak, J.L., Arguello, M.D., Vick, R., Svec, H.J.,
Fritz, J.S., and Calder, G.V., "Use of Macroreticular
Resins in the Analysis of Water for Trace Organic Con-
taminants." Journal of Chromatography 99: 745-762 (1974).
Kammerer, Phil A. Jr., and Lee, G. Fred, "Freeze Concentra-
tion of Organic Compounds in Dilute Aqueous Solutions."
Environmental Science & Technology 3: 276-278 (1969).
Kennedy, David C., "Treatment of Effluent from Manufacture of
Chlorinated Pesticides with a Synthetic, Polymeric Adsor-
bent, Amberlite XAD-4." Environmental Science & Tech-
nology 7: 138-141 (1973).
-118-
-------
Kleopfer, Robert D. , and Pairless, Billy J., "Characteriza-
tion of Organic Components in a Municipal Water Supply."
Environmental Science & Technology' 6: 1036-1037 (1972).
Konrad, J.G., Pionke, H.B., and Cheaters, G., "An Improved
Method for Extraction of Organochlorine and Organophos-
phate Insecticides from Lake Waters." Analyst 9_4_: 490-
492 (1969).
Lee, E.G.H., and Walden, C.C., "A Rapid Method for the Esti-
mation of Trace Amounts of Kerosene in Effluents."
Water Research 4: 641-644 (1970).
Leoni, V., Puccetti, G., and Grella, A. "Preliminary Results
on the Use of Tenax for the Extraction of Pesticides and
Polynuclear Aromatic Hydrocarbons from Surface and
Drinking Waters for Analytical Purposes." Journal of
Chromatography 106: 119 (1975).
Mieure, J.P., and Dietrich, M.W., "Determination of Trace
Organics in Air and Water." Journal of Chromatographic
Science 11: 559-570 (1973).
Myrick, H. Nugent, and Ryckman, DeVere W., "Considerations
in the Isolation and Measurement of Organic Refractories
in Water." Journal AWWA 55: 783-796 (1963).
Poirrier, Michael A., Bordelon, Billy Ray, and Laester,
John L., "Adsorption and Concentration of Dissolved Car-
bon-14 DDT by Coloring Colloids in Surface Waters."
Environmental Science & Technology 12: 1033-1035 (1972).
Rambrow, Carl A., "Effect of Flow Rate on Carbon Filter Per-
formance." Journal AWWA 55.: 1037-1043 (1963).
Riley, J.P., and Taylor, D., "The Analytical Concentration
of Traces of Dissolved Organic Materials from Sea Water
With Amberlite XAD-1 Resin." Analytica Chimica Acta
i6: 307-309 (1969).
Rosen, A.A., Skeel, R.T., and Ettinger, M.B., "Relationship
of River Water Odor to Specific Organic Contaminants."
Journal WPCF 35: 777-782 (1963).
Rudling, Lars, "Determination of Pentachlorophenol in Organ-
ic Tissues and Water." Water Research 4: 533-537 (1970).
Semmens, Michael, and Gregory, John, "Selectivity of Strongly
Basic Anion Exchange Resins for Organic Anions." Environ-
mental Science & Technology 8: 834-9 (1974).
-119-
-------
Snoeyink, Vernon L., and Weber, Walter J. Jr., "The Surface
Chemistry of Active Carbon." Environmental' Science &
Technology 1: 228-234 (1967).
Sridharan, Nagalaxmi, and Lee, G. Fred, "Coprecipitation of
Organic Compounds from Lake Water by Iron Salts."
Environmental Science & Technology 12: 1031-1033 (1972).
Tardiff, R.G., and Deinzer, M., "Toxicity of Organic Com-
pounds in Drinking Water." Presented at the Fifteenth
Water Quality Conference, February 1973, University of
Illinois.
Uthe, J.F., Reinke, J. and Gesser, H. "Extraction of Organo-
chlorine Pesticides from Water by Porous Polyurethane
Coated and Selective Adsorbent." Env. Lett. 3_: 117
(1972).
Walsh, John T., Chalk, Ronald C., and Merritt, Charles Jr.,
"Application of Liquid Chromatography to Pollution
Abatement Studies of Munition Wastes." in Adv. Gas
Chrom. (ed. A. Zlatkis). p. 219 (1973).
Webb, Ronald G. "XAD Resins, Urethane Foams, Solvent Ex-
traction for Isolating Organic Water Pollutants."
EPA report (to be published).
-120-
-------
TABLE 2-5
ACCUMULATION OF METAL IONS FROM WATER
The following pages contain tables that function as
a guide to the accumulator literature. The entries are
arranged in alphabetical order by atomic symbol with each
entry referring to a specific accumulation procedure for
that metal.
Each entry contains the literature reference and
identifies the procedure by type of accumulator and
specific accumulator formulation (chelating agent and
solvent for chelation/extraction, resin type for ion
exchange, carrier for coprecipitation and cocrystallization,
and reducing agent for head space analysis).
Where available, the concentration factor, applicable
concentration, collection efficiency and optimum collection
pH are also given. The collection efficiency is stated in
terms of percent recovery and/or the standard deviation in
the percent recovery. Lists of abbreviations and references
are given at the end.
-121-
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Accumulator
Type
Chelation-,
extraction
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Chelation -
extraction
Chelation -
extraction
Chelation-
extraction
Ion exchange
Specific*
Accumulator
Formulation
APDC/
MIBK
DQA/
ethyl pro-
pionate
Dithizone
Oxine/
ethyl pro-
pionate
Oxine/
CHC13
APDC/
MIBK
Dithizone/
Ethyl pro-
prionate
Anionic resin
Concen-
tration
Factor
10
4 x 105
10
Applicable
Concen-
tration
.002-.25ppm
• 3 ppb
.002 ppm
Recovery
. 100
Collection
Parameters
pH = 2.8
pH = 6
pH = 6
PH = 7.2
pH = "2.0-2.5
pH = 7.5
Reference
Brown,
Skougstad,
Fishman (197C
Sachdev and
West (1970)
Take! chi, et
al. (1966)
Sachdev. and
West (1970)
Brooks (196^
Chao, Fishmar
and Ball
(1969)
Sachdev and
West (1969)
Chao, Fishmar
and Ball
f-\ n
I
* See list of Abbreviations at end of table,
-------
ACCUMULATION OP METAL IONS PROM WATER
Accumulant
. Ag •
Ag
Ag
Ag
Ag
Ag
Accumulator
Type
Ion exchange
Ion exchange
Chelation-
extractlon
Evaporation
Cocrystal-
lization
Cocrystal-
llzatlon
Specific*
Accumulator
Formulation
AG 1-X8 resin
Chitosan
DEDC/
CHC13
•
Thionalide
2-Mercapto-
benzimidazole
Concen-
tration
Factor
Applicable
Concen-
tration
.02-6.0 ppb
. 01 ppm
.05-100 ppt
%
Recovery
( + )
90-100
100
±11.7
100
99
Collection
Parameters
pH = 1
pH = 7.8
T = 120°C
pH = 3.5-7.0
pH =-1 - 5
Reference
Chao, Pishman
and Ball
(1969)
Muzzarelli, e
al . (1969,
1970)
Joyner et al.
(1967)
LeRoy and
Lincoln (1974
Lai and Weiss
(1962)
Weiss and Lai
(1963)
I
H
ro
LO
I
* See 11st of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS PROM WATER
Accumulant
Al-
Al
Al
Al
Al
Al
Al
Accumulator
Type
Chelat ion-
extraction
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Ion exchange
4
Specific*
Accumulator
Formulation
Oxine/
MIBK
PQA/
Ethyl pro-
pionate
Oxine/
Ethyl pro-
pionate
Trifluoro-
acetyl ace-
tone/
CHC13
Oxine/
CHC13
DQA/
benzene
CPG-8-HOQ
Concen-
tration
Factor
10
I* x 105
Applicable
Concen-
tration
.10-10.0 ppm
. 01 ppm
.009 ppm
270 ppb
%
Recovery
( + )
100
100
100
100 ±3
Collection
Parameters
pH = 8
pH = 6
pH = 6
pH = 7.2
pH = 5
pH = 4-9
Reference
Pishman
(1972) .
Sachdev and
West (1970)
Sachdev and
West (1970)
Joyner et al
(1967)
Brooks (1965)
Hsu and Pipes
(1972)
Sugawara,
Weetall, and
Schucker
U974)
I
H
IV)
J=r
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS PROM WATER
Accumulant
Al
Al
As
As
As
Accumulator
Type
Filtration
Evaporation
Chelation-
Extraction
Chelation-
Extraction
Chelation-
Extractlon
Specific*
Accumulator
Formulation
HA Millipore
filter; com-
plex with
f erron and
orthophenan-
throline
APDC/
MIBK
DDDC/
CHC13
AMTH/
butanol,
ethyl ace-
tone and
isoamyl
acetate
Concen-
tration
Factor
Applicable
Concen-
tration
.Olppm-.2ppt
1 ppm
.025 ppm
%
Recovery
( + )
±7.3
103±6
Collection
Parameters
T = 120°C
pH = 2 (six
hours UV
phot'ooxida-
tion)
pH = 0.6-1.2
Reference
Joyner (1964)
LeRoy and
Lincoln (1974
Mulford
(1966)
Tarn (1974)
Ramakrishna,
Robinson and
West (1969)
I
I-1
* See list of Abbreviations at end of table,
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
As
As
Au
Au
Au
Au
Au
Au
Accumulator
Type
Evaporation
Head space
analysis
Ion exchange
Ion exchange
Chelation-
extraction
Evaporation
Cocrystal-
lization
Cocrystal-
lization
Specific*
Accumulator
Formulation
Reduce with
NaBH/j
AG 1-X8 resir
Chitin
Dithizone/
CHClj
Thionalide
2-Mercapto-
benzimida-
zole
Concen-
tration
Factor
Applicable
Concen-
tration
.2-1.0 ppm
>0. 00015 ppb
.05 ppb
x 10 M
.000004 ppm
.02-1.0 ppm
.069 ppb
Recovery
±19-2
100
100
±11.7
98
99
Collection
Parameters
T = 120°C
pH = 1
for storage
pH = 6
1-5 hr.,
distilled
water
pH = 7.5
T = 120°C
pH = 0-7
pH = 1
Reference
LeRoy and
Lincoln (1974)
Fernandez
(1973)
Chao (1969)
Muzzarelli and
Tubertini
(1969)
Brooks (1965)
LeRoy and
Lincoln (1974)
Lai and
Weiss (1962)
Weiss and
Lai (1963)
I
M
ro
ON
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Ba-
Ba
Ba
Ba
Be
Be
Accumulator
Type
Chelation-
Extraction
Ion exchange
Ion exchange
Cocrystal-
lization
Chelation-
Extraction
Evaporation
Specific*
Accumulator
Formulation
HFA/
isoamyl ace-
tate
Dowex 50W-X8
resin
Dowex 50-X12
Ca form
Potassium
rhodizonate
DQA/
ethyl pro-
pionate
Concen-
tration
Factor
10
Applicable
Concen-
tration
5 ppb
I ppb
M
.002-. 10 ppn
.01-1. 0 ppm
Recovery
100
91±14
±0.86
99-100
100
±18.6
Collection
Parameters
1 mg/ml K+ to
control ion-
ization;
high pH
pH = 5-8
pH = 6
T = 120°C
Reference
Edelbeck and
West (1970)
Szabo and
Joensuu
(1967)
Andersen and
Hume (1968)
Weiss and
Lai (I960)
Sachdev and
West (1970)
LeRoy and ..
Lincoln
(1974)
I
ro
-j
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Bi
Bl
Bl
Bi
Ca
Ca
Ca
Accumulator
Type
Chelation-
Extraction
Ion exchange
Evaporation
Head space
analysis
Ion exchange
Ion exchange
Evaporation
Specific*
Accumulator
Formulation
APDC/
MIBK
Chelating
resin
Reduce with
NaBH/j
Chelex-100=
Dowex A-l
Dowex 50-X10
Concen-
tration
Factor
Applicable
Concen-
tration
.01-1.0 ppm
1' ppm
.01-500 ppm
%
Recovery
( + )
±12.4
•
-10.4
Collection
Parameters
pH = 2.8
T = 120°C
T = 120°C
Reference
Mulford
(1966)
Riley and
Taylor (1968)
LeRoy and
Lincoln (1974)
Pollock and
West (1973);
Schmidt and
Royer (1973);
Fernandez
(1973)
Blake, Bryant
and Waters
(1969)
Christova and
Kruschevska
(1966)
LeRoy and
Lincoln
(1974)
I
I-J
rv>
oo
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Cd
Cd
Cd
Cd
Cd
Cd
Accumulator
Type
Chelation-
Extraction
Chelation-
Extraction
Chelation-
Extraction
Ion exchange
Evaporation
« • '
Chelation-
Extraction
Specific*
Accumulator
Formulation
APDC/
MIBK
Dithizone
DQA/
ethyl pro-
pionate
Chelating
resins
Dithizone/
ethyl pro-
pionate
Concen-
tration
Factor .
10
10
Applicable
Concen-
tration
.001-. 1
.01-1.0 ppm
.001 ppm
%
Recovery
( + )
100
±12.5
Collection
Parameters
pH = 2.8
pH = 6
T = 120°C
pH = 7-5
Reference
Brown ,
Skougstad an
Fishman (197
Takeuchi,
Suzuki and
Yanagisawa
(1966)
Sachdev and
West (1970)
Riley and
Taylor (1968
Biechler
(1965)
LeRoy and
Lincoln
(1974)
Sachdev and
West (1969)
* See list of Abbreviations at end of table.
I
M
ro
MD
I
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Ce
Ce
Ce
Co
Co
Co
Accumulator
Type
Chelation-
Extraction
Chelation-
extractlon
Cocrystal-
lizatlon
Chelation-
Extractlon
Chelat^on-
Extraction
Chelation-
Extractlon
Specific*
Accumulator
Formulation
H(FHD)/
DBSO
Bis(2-ethyl
hexyl)-hy-
drogen phos-
phate/n-Hep-
tane
1-Nitroso-
2-naphthol
APDC/
MIBK
Diethyl/
Dithiocarba-
mate
Dithizone
Concen-
tration
Factor
Applicable
Concen-
tration
0.2-15 Ug
%
Recovery
( + )
99±2
>95
•
Collection
Parameters
pH = 5-5
pH = 7
pH = 2.8
Reference
Burgett and
Fritz (1973)
Joyner et al.
(1967)
Joyner et al.
(1967)
Brown,
Skougstad and
Fishman (1970)
Nix and
Goodwin (1970)
Sachdev and
West (1969)
uo
o
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS PROM WATER
Accumulant
Co
Co
Co
Co
Co
Co
Co
Accumulator
Type
Chelation-
Extraction
Chelation-
Extraction
Ion exchange
Chelation-
Extraction
Chelation-
Extraction
Ion exchange
Evaporation
Specific*
Accumulator
Formulation
Dithizone/
Ethyl prb-
pionate
DQA/
Ethyl pro-
pionate
Chitosan
APDC/
MIBK
Dithizone/
CCljj or
CHC13
Chelatlng
resin
Concen-
tration
Factor
10
10
Applicable
Concen-
tration
4 ppb
.004-. 20 ppm
.0104 yg
.5 ppb
.01-10. Oppm
Recovery
100
100.
• 100
±11.6
Collection
Parameters
pH = 7-5
pH = 6
pH = 7.8
from sea
water
pH = 7.5
-
T = 120°C
Reference
Sachdev and
West (1969)
Sachdev and
West (1970)
Muzzarelli,
Raith, and
Tubertini
(1970)
Joyner et al.
(1967)
Brooks (1965)
Riley and
Taylor (1968)
LeRoy and
Lincoln
(1974)
I
M
00
M
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Co
Co
Co
Co
Co
Co
Co
Co
Accumulator
Type
Cocrystal-
lization
Cocrystal-
lization
Cocrystal-
llzation
Coprecipita-
tion
Coprecipita-
tion
Ion exchange
Chelation-
Extraction
Chelation
Extraction
Specific*
Accumulator
Formulation
l-Nitroso-2-
naphthol
Thionalide
5,7-Dibromo-
8-Hydroxy
quinoline
KOH
Magnesium
hydroxide
CPG-8-HOQ
Dithizone/
acetone
HHFA and
TOPO/cyclo-
h#>xfln<=
Concen-
tration
Factor
Applicable
Concen-
tration
.025 ppm
.1-100 ppb
248 ppb
2 ppm
.2 ppt
*
Recovery
( + )
100
96
99
97+8
93
100±3
80±5
30-40
Collection
Parameters
pH = 1-9
pH = 10
pH = 8
pH = 6-7
From
Sea Water
pH * 5-7
pH = 2-8
PH = 4-9
Reference
Joyner et al.
(1967)
Lai and Weiss
(1962)
Riley and
Topping (1969
Joyner et al.
(1967)
Geetha and
Joseph (1968)
Sugawara,
Weetall, and
Schucker
(1974)
Matkovich and
Christian
(1974)
Mitchell and
Ganges (1974)
I
M
OO
ru
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS PROM WATER
Accumulant
Co
c°^
Co60
Cr
Cr
Cr (Vl)
Cr (VI)
Cr
Accumulator
Type
Chelation-
Extraction
Chelation-
Extraction
Chelation-
Extraction
Chelation-
Extraction
Chelation-
Extraction
Evaporation
Cocrystal-
lizatlon
Specific*
Accumulator
Formulation
DEDC/
MIBK
Sodium di-
ethyldithio-
carbamate/
benzene
Diethyl
dithiocarba-
mate
Add MnOjj-
Extract :
APDC/MIBK
Dithizone/
MIBK
Thionalide
Concen-
tration
Factor
Applicable
Concen-
tration
3 x lO-^g/
ml
.01-500 ppm
%
Recovery
( + )
100
99. 5*1. t
±9.8
100
Collection
Parameters
pH = 6
pH = 5-0-5.5
pH = 2.8
T = 120°C
pH = 10
Reference
Joyner et al.
(1967)
Motojima,
Kenji, BandOi
and Tamura
(1967)
Nix and
Goodwin (1970
Mulford (1966
Joyner et al.
(1967)
LeRoy and
Lincoln
(197*0
Lai and Weiss
(1962)
oo
UJ
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS PROM WATER
Accumulant
Cr (III)
Cr207=
Cs
Cs
Cs
Cs
Cs
Accumulator
Type
Cocrystal-
lizatlon
Chelation-
Extraction
Ion exchange
Ion exchange
Ion exchange
Ion exchange
Cocrystal-
lizatiqn
Specific*
Accumulator
Formulation
5,7-Dibromo-
8-Hydroxy-
quinoline
APDC/
MIBK
AMP crystals
APMW .
crystals
AMP
Chitosan
Ammonium
dipiecryl-
aminate
Concen-
tration
Factor
Applicable
Concen-
tration
• 5 ppb
5-50 ppm
.006 ppb
.1 ppb
%
Recovery
( + )
100
100
100
. 97*2
100
>98
Collection
Parameters
pH = 8
pH = 2.8
pH = 2
pH
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Cu
Cu
Cu
Cu
Cu
Accumulator
Type
Chelation-
Extractlon
Chelation-
Extraction
Che lat Ion-
Extract ion
Chelatlon-
Extractlon
Ion exchange
Specific*
Accumulator
Formulation
APDC/
MIBK
DQA/
Ethyl propi-
onate
Diethyldithic
carbamate
Dithizone/
Ethyl pro-
pionate
ChelatinK
resins
Concen-
tration
Factor
_
10
Applicable
Concen-
tration
•
2 ppb
%
Recovery
( + )
100
Collection
Parameters
pH = 2.8
pH = 6
pH = 7.5
Reference
Brown,
Skougstad, and
Fishman (1970)
Sachdev and
West (1970)
Takeuchi,
Suzuki, and
Yanagisawa
(1966)
Sachdev and
West (1969)
Riley and
Taylor: (1968);
Biechler
(1965)
Ul
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Cu
Cu
Cu
Cu
Accumulator
Type
Ion exchange
Ion exchange
Chelation-
extraction
- Chelation-
extraction
^
Specific*
Accumulator
Formulation
Lix-64
Chit in
DEDC/
MIBK
Dithizone/
CCl^ or CHC1,
DEDC/CClij or'
CHC13
2,2'-Diquino-
lyl neocupro-
ine/n-Hexanol-
Trifluqro-
acetyl acetone
/CHC13
8-Quinolinol
/CHC1-
APDC or Cup-
feron/MIBK
Concen-
tration
Factor
"
Applicable
Concen-
tration
1 x 10-%
%
Recovery
( + )
100
100
Collection
Parameters
pH >2
pH = 6 (1 hr
dist. water)
pH = 6
Reference
Cerrai and
Ghersini
(1969)
Muzzarelli and
Tubertini
(1969)
Joyner et al.
(1967)
Joyner et al.
(1967)
»
I
M
OJ
ON
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Accumulator
Type
Solvent
extraction
Evaporation
Coprecipita-
tion
Cocrystal-
lization
Ion exchange
Chelation-
Extraction
Chelation-
Extractlon
Specific*
Accumulator
Formulation
Dithizone
KOH
5,7-Dibromo-
8-Hydroxy
quinoline
CPG-8-HOQ
Dithizone/
acetone
HHFA and
_TOPO/c.YClo-
hexane
Concen-
tration
Factor
Applicable
Concen-
tration
.003 ppm
.01-500 ppm
5 ppb
39 ppb
5 ppm
.2 ppt
Recovery
100
±8.0
92-99
100
100±3
90±10
50
Collection
Parameters
pH = 7-5
T = 120°C
pH = 6-7
pH = 8
pH = 4-7
pH =- 1-8
pH = 4-6
Reference
Brooks (1965)
LeRoy and
Lincoln (1974)
Joyner et al .
(1967)
Riley and
Topping
(1969)
Sugawara,
Weetall, and
Schucker (1974)
Matkovich and
Christian
Mitchell and
Ganges (1974)
uo
—-a
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Eu
Eu
Pe
Pe
Fe
Accumulator
Type
Chelation-
Extraction
Chelation-
Extraction
Chelat ion-
Extraction
Chelation-
Extraction
Chelation-
Extract,ion
Specific*
Accumulator
Formulation
H(HFD)/
DBSO
HHPA and
TOPO/cyclo-
hexane "
APDC/
MIBK
Cupferron or
Oxine
Diethyl-
dithio-
carbamate
Concen-
tration
Factor
Applicable
Concen-
tration
0.2-15 PS
.002 M
%
Recovery
( + )
99-2
25-40
Collection
Parameters
pH = 5.5
pH =.1-5
pH = 2.5-3
Reference
Burgett and
Fritz (1973)
Mitchell and
Ganges (1974)
U.S. Environ-
mental Protec- ;
tion Agency
Takeuchi,
et al. (1?66)_
Platte (1968); ,
Nix and
Goodwin (1970) .
i
I
\->
Lx)
00
I
* See list of Abbreviations at end of table,
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Fe'
Fe
Fe
Fe •
Accumulator
Type
Ion exchange
Chelation-
extractlon
Chelation-
extraction
4
Filtration
Specific*
Accumulator
Formulation
Chelating
resins
DEDC/
MIBK
Diphenyl-
phenanthro-
line/Isobu-
tyl Alcohol
Cupferron/ '
MIBK
APDC or DEDC
CHClo
Trifluoro-
acetone/
OHC13
HA Millipore
filter
Concen-
tration
Factor
Applicable
Concen-
tration
%
Recovery
( + )
100
'
Collection
Parameters
pH = 6
Complex with
ferron and
orthophenan-
throline
Reference
Biechler
(1965);
Galle
(19715
Joyner et al.
(1967)
Joyner et al.
(1967)
'
Joyner (1964)
I
M
OJ
M3
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Fe
Fe
Fe
Fe (II)
Fe (II)
Fe (II)
Fe (III)
Accumulator
Type
Evaporation
Cocrystal-
lization
Coprecipita-
tion
Ion exchange
Chelation-
Extraction
Chelation
Extraction
Chelation-
Extraction
Specific*
Accumulator
Formulation
l-Nitroso-2-
napht.hol
KOH
Chitin
Dithizone/
Acetone
HHFA and
TOPO/ eye lo-
ne xane
DQA/
Ethyl
propionate
Concen-
tration
Factor
10
Applicable
Concen-
tration
.05-500 ppm
4 x -1(H»M
4 ppm
.004-. 40 ppm
Recovery
( + )
+ 10
99
100
100
100
70±5
100
Collection
Parameters
T = 120°C
pH =2-9
pH = 6-7
From
Sea Water
pH = 7, sea
water
pH = 0-5
pH = 4-5
pH = 6
Reference
LeRoy and
Lincoln (1971
Joyner et al.
(1967)
Joyner et al.
(1967)
Muzzarell
and Tubertin
(1969)
Matkovich am
Christian
(1974)
Mitchell and
Ganges (1974
Sachdev and
West (1970)
I
H
-t
O
I
« See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Fe (III)
Fe (III)
Fe (III)
Fe (III)
Ge
Hf
Hg
* See list
Accumulator
Type
Cocrystal-
lization
Ion exchange
Chelation-
Extraction
Chelation-
Extraction
Head space
Analysis
Cocrystal-
lization
Ion exchange
of Abbreviatic
Specific*
Accumulator
Formulation
5-7-Dibromo-
8-Hydroxy-
qulnoline
CPG-8-HOQ
Dithizone/
acetone
HHFA and
TOPO/cyclo-
hexane
Reduce, with
NaBHn
Thionalide
Chitosan
ns at end of t
Concen-
tration
Factor
able.
Applicable
Concen-
tration
5 ppb
41 ppb
4 ppm
.040 yg
%
Recovery
( + )
98-99
92±4
100
20-50
99
100 from
sea water
Collection
Parameters
pH = 8
pH = 4-5
pH = 0-5
pH = 1-4
pH = 10
pH =7.8
Reference
Riley and
Topping
(1969)
Sugawara,
Weetall, and
Schucker
(1974)
Matkovich and
Christian
(1974)
Mitchell and
Ganges (1974)
Pollock and
West; Schmidt
and Royer
(1973)
Lai and Weiss
(1962)
Muzzarelli,
Raith and
Tubertini
(1970)
Muzzarelli and
Tubertini
(1969)
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Hg
Hg
Hg
Hg
Hg
Hg
CH3Hg
Accumulator
Type
Ion exchange
Solvent
Extraction
Evaporation
Cocrystal-
lization
Cocrystal-
lization
Head space
analysis
*
Extraction
Specific*
Accumulator
Formulation
Diethylamino-
ethyl cellu-
lose, thio-
cyanate form
High-molecu-
lar-weight
amines (qua-
tenary)
Thionalide
2-Mercapto-
benzimidazole
Helium satur-
ated with
water vapor
Benzene
Concen-
tration
Factor
Applicable
Concen-
tration
100 yg
<1 .ng
.5-100 ppm
10 ng-10 yg
<1 Ug
%
Recovery
( + )
100
100
±24.6
98-100
99
100
90±4
Collection
Parameters
SCN
Cl cone.
Extracted
from brine
solutions
T = 120°C
pH = 3-5-7
pH = 1-5
TiClij in
H2SOi| to
reduce Hg
compounds
Reference
Kuroda,
Kiriyama and
Ishida (1968)
Moore (1972)
LeRoy and
Lincoln (197M)
Lai and Weiss
(1962)
Weiss and Lai
(1963)
April and
Hume (1970)
Bisogni and
Lawrence
(1971*)
-Cr
no
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Hg
In
In
Ir
Ir
K
Accumulator
Type .
Head space
analysis
Ion exchange
Cocrystal-
lization
Evaporation
Cocrystal-
lization
Evaporation
*
Specific*
Accumulator
Formulation
Reduce with
SnCl2
Chitosan
Thionalide
Thionalide
Concen-
tration
Factor
Applicable
Concen-
tration
>0.0001 ppm
2.6 yg
.07-2.0 ppm
1.-100. ppm
%
Recovery
( + )
100
98-100
±14.8
95
±19.8
Collection
Parameters
pH = 7.8
pH = 3.5-7
T = 120°C
pH = 10
T = 120°C
Reference
Hatch and Ott
(1968)
Muzzarelli,
Raith and
Tubertini
(1970)
Lai and Weiss
(1962)
LeRoy and
Lincoln (1972*)
Lai and Weiss
(1962)
LeRoy and
Lincoln (1971*)
I
M
-t
OJ
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
La
La
Lu
Mg
Mg
Mg
Accumulator
Type
Chelation-
Extractlon
Chelatior-
extraction
Chelation-
Extraction
Chelation-
Extractlon
Ion exchange
Evaporation
Specific*
Accumulator
Formulation
H(HFD)/
DBSO
Oxine/
CHC13
HHFA and.
TOPO/cyclo-
hexane
Eriochrome
black T/
Butyl Alco-
hol
Dowex. 50-X10
Concen-
tration
Factor
4 x 105
Applicable
Concen-
tration
0.2-15 Mg
.0003 ppm
.002 M
.01-20 ppm .
%
Recovery
( + )
99±2
100
20-60
+ 5
±13- 4
Collection
Parameters
pH = 5.5
PH = 7.2
. PH = 1-5
pH, cone . ,
time of
contact
T = 120° C
Reference
Burgett and
Fritz (1973)
Brooks (1965)
Mitchell and
Ganges (1974)
Zolotov and
Bagreev (1967)
Christ ova an
-------
ACCUMULATION OP METAL IONS PROM WATER
Accumulant
Mn •
Mn
Mn
Mn
Mn
Mn
Accumulator
Type
Chelation- •
Extraction
Ion exchange
Chelation-
Extraction
Chelation-
Extraction
Chelat ion-
Extract ion
Evaporation
Specific*
Accumulator
Formulation
APDC/
MIBK
Chelating
Resins
TTA/Acetone-
benzene
l-Nitroso-2-
naphthol/
CHC13
APDC/MIBK
Cupferron/
MIBK
APDC/CHC13
DEDC/
MIBK
Oxine/
CHC1,
Concen-
tration
Factor
4 x 105
Applicable
Concen-
tration
.002 ppm
.01-5 ppm
%
Recovery
( + )
9.9
100
±11.1
Collection
Parameters
pH = 6
immediate
analysis
.
pH = 6
pH = 7.2
T = 120°C
Reference
Brown ,
Skougstad and
Fishman (1970
Riley and
Taylor (1968)
Galle (1971)
Joyner et al.
(1967)
Joyner et al.
(1967)
Brooks (1965)
LeRoy and
Lincoln (1974
VJl
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS PROM WATER
Accumulant
Mn •
Mn
Mn
Mn
Mn
Mo
Mo
Accumulator
Type
Cocrystal-
lization
Cocrystal-
lization
Coprecipita-
tion
Chelation-
Extraction
Chelation-
Extraction
Chelation-
Extraction
Ion exchange
Specific*
Accumulator
Formulation
Thionalide
5,7-Dibromo-8
-Hydroxy-
quinoline
KOH
Dithizone/
Acetone
HHFA and
TOPO/cyclo-
hexane
Oxine/
MIBK
Dowex 1-X8,
SCN- or Cl-
form
Concen-
tration
Factor
\
Applicable'
Concen-
tration
5 PPb
2 ppm
.2 ppt
<10 ppb
Recovery
96
95
(pure water!
85
(sea water)
85±5
• 30
100
Collection
Parameters
pH = 10
pH = 8
pH = 6-7
From
Sea Water
pH =6-9
pH = 4-9
pH = 2-2.4
Reference
Lai and Weiss
(1962)
Riley and.
Topping
(1969)
Joyner et al.
(1967)
Matkovich and
Christian (IS
Mitchell and
Ganges (1974)
Chau and Lum-
Shue-Chan
(1969)
Kawabuchi
and Kuroda
(1969)
-t
cr\
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Mo
Mo
Mo
Mo
Mo
Mo
» See list
Accumulator
Type
Chelation-
Extraction
'Chelat ion-
Extraction
Evaporation
Cocrystal-
lization
Coprecipita-
tion
Ion exchange
of Abbreviatl
Specific*
Accumulator
Formulation
DEDC or APDC/
CHClo
8-Quinolinol/
APDC or
Dithiol/MIBK
a-Benzoinoxime/
CHClo
2-Amlno-4-
chlorobenzene-
thiol
hydrochloride/
CHC13
Oxine/
CHC13
a-Benzoinoxime
Fe(OH)3 .
CPG-8-HOQ
ons at end of ta
Concen-
tration
Factor
4 x 105
ble.
Applicable
Concen-
tration
.01 ppm
.02-20 ppm
12 ppb
212 ppb
Recovery
.1.00
. ±9.8
99-100
96.5
100±3
Collection
Parameters
pH = 7.2
T = 120°C
pH = 2-5
pH =4.0
pH = 2-5
Reference
Joyner et al.
(1967)
Brooks (1965)
LeRoy and
Lincoln (1974):
Joyner et al.
(1967)
Kim and Zeitlin
(1969)
Sugawara, Wee-
tall and
Schucker (1974)
I
M
-t
—J
I
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Na
Nd
Nl
Ni
Ni
Ni
Accumulator
Type
•Evaporation
Chelation-
Extraction
Chelatlon-
Extraction
Chelat ion-
Extraction
Chelation-
Extraction
Chelation-
Extraction
Specific*
Accumulator
Formulation
H(HFD)/
DBSO
APDC/
MIBK
Diethyldithio-
carbamate
Oxine
Dithizone
Concen-
tration
Factor
Applicable
Concen-
tration
.001-3-5 ppt
.2-15 yg
%
Recovery
( + )
il3.3
99+2
Collection
Parameters
. T = 120°C
pH = 5.5
pH = 2.8
Reference
LeRoy and
Lincoln (197J
Burgett and
Fritz (1973)
Brown,
Skougstad anc
Fishman (197
Takeuchi,
Suzuki and
Yanagisawa
(1966);
Nix and Goodi
(1970)
Takeuchi,
Suzuki and
Yanagisawa
(1966)
Takeuchi et
(1966);Sachd
Q TT\ H \Jd 0 4* f 1 Q
J=r
co
I
* See list of Abbreviations at end of table,
-------
ACCUMULATION OF METAL IONS PROM WATER
Accumulant
Ni
Ni
Ni
Ni
Ni
Ni
Accumulator
Type
Chelation-
Extraction
•Chelat ion-
Extract ion
Ion exchange
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Specific*
Accumulator
Formulation
furil
ct-dioximel/
CHC13
Dithizone/
Ethyl pro-
pionate
Chelating
Resins
DEDC/
MIBK
APDC or
Cupferron/
MIBK
Dithizone or
DEDC/CHC13
Dimethylgly-
oxi'ms/CHCl3
Oxine/
CHC13
Concen-
tration
Factor
10
10
4 x 105
Applicable-
Concen-
tration
•3-50 ppb
.004 ppm
.002 ppm
%
Recovery
( + )
99
99
100
Collection
Parameters
pH = 7.5
pH = 6
pH = 7.2
Reference
Wilson (1968)
Sachdev and
West (196'9)
Riley and
Taylor (1968)
Biechler (196
Galle (197D
Joyner et al.
(1967)
Joyner et al.
(1967)
Brooks (1965)
vo
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Nl
Ni
Ni
Ni
Ni
Os
Accumulator
Type
Evaporation
Coprecipita-
tion
Chelation-
Extraction
Ion exchange
Chelation-
Extraction
Cbcrystal-
lization
Specific*
Accumulator
Formulation
KOH
DQA/
Ethyl pro-
pionate
CPG-8-HOQ
Dithizone/
, Acetone
Thionalide
Concen-
tration
Factor
10
Applicable
Concen-
tration
.01 -50 ppm
.004-. 30 ppm
248 ppb
2 ppm
*
Recovery
( + )
±9-3
98
100±3
80
100
Collection
Parameters
T = 120°C
pH = 6-7
From
Sea Water
pH = 6
pH = 6-7
pH = 1-6
pH = 7-10
Reference
LeRoy and
Lincoln (197J
Joyner et al
(1967)
Sachdev and
West (1970)
Sugawara ,
Weetall and
Schucker
(197^)
Matkovich an
Christian
(1974)
Lai and Weis
(1962)
o
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
P
P
Pb
Pb
Pb
Accumulator
Type
Chelation--
Extraction
Evaporation
Chelation-
Extractlon
Chelation-
Extraction
Chelation-
Extractlon
Specific*
Accumulator
Formulation
AMTH/
iso-butyl
acetate
APDC/
MIBK
Diethyl di-
thiocarbamate
Dithizone or
Oxine
Concen-
tration
Factor
Applicable
Concen-
tration
. 01 ppm
1-100 ppm
%
Recovery
(+)
±5.9
Collection
Parameters
pH = 0.6-1.0
T = 120°C
pH = 2.8
Reference
Ramakrishna,
Robinson and
West (1969)
LeRoy and
Lincoln (1971
Brown ,
Skougstad anc
Fishman (197<
Takeuchi,
Suzuki and
Yanagisawa
(1966); Platt
(1968); Nix i
Goodwin (197C
Takeuchi,
Suzuki and
Yanagisawa
(1966)
I
Ul
M
I
« See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS PROM WATER
Accumulant
Pb
Pb
Pb
Pb
Pb
Accumulator
Type
Chelation-
Extraction
Ion exchange
Solvent
extraction
of PbI2
Chelat ion-
extraction
Chelation-
extraction
to
Specific*
Accumulator
Formulation
Dithizone/
Ethyl pro-
pionate
Chelating
Resins
KI/
MIPK
Oxine/
CHC13
Dithizone/
CHC13
Diethyl-
ammonium
diethyl-
dithio-carb-
amate/CHCl-
3
Nal, dithi-
zone/Iso-
propyl
methyl
Ketone
Concen-
tration
Factor
10
4 x 105
Applicable
Concen-
tration
.004 yg/ml
.013 ppm
.0001 ppm
%
Recovery
( + )
100
Collection
Parameters
pH = 7-5
EDTA added to
remove inter-
ferences
pH = 7-2
Reference
Sachdev and
West (1969.)
Riley and
Taylor (1968);
Biechler (1965
Galle (1971)
Chakrabarti,
Robinson and
West (1966)
Brooks (1965)
Joyner, et al.
(1967)
rv>
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Pb
Pb
Pb
Pb
Pd
Pd
Pd
Accumulator
Type
Evaporation
Coprecipita-
tion
Chelatlon-
Extractlon
Adsorption
Ion exchange
Chelation-
Extractibh
Evaporation
Specific*
Accumulator
Formulation
KOH
DQA/
ethyl propi-
onate
Anion-
Exchange
Membrane
Chitin
Chitosan
Dithizone/
CHC13
Concen-
tration
Factor
10
Applicable
Concen-
tration
.01-5-0 ppm
.005-. 6 yg/
ml
.1 ppb
t\ x 10-^ M
.02-1.0 ppm
Recovery
±IH
90-95
100
100
100
100
±9.8
Collection
Parameters
T = 120°C
pH = 6-7
From
Sea Water
pH = 6
Ca inter-
feres
pH = 6, 2hr,
dist. water
pH = 7
pH = 7-5
T = 120°C
Reference
LeRoy and
Lincoln (19.71*
Joyner, et al
(1967)
Sachdev and .
West (1970)
Lochmuller,
Galbraith, an
Walter (1971*)
Muzzareli an
Tuber tin!
(1969)
Brooks (1965)
LeRoy and
Lincoln (1972*
uo
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS PROM WATER
Accumulant
Pr •
Pt
Pt
Pu
Ra
Ra
Accumulator
Type
Chelation-.
Extraction
Chelation-
extraction
Evaporation
Cocrystal-
lization
Cocrystal-
lization
Coprecipita-
tion
Specific*
Accumulator
Formulation
H(HFD)/
DBSO
Dithizone/
CHC13
Potassium
rhodizonate
Potassium
rhodizonate
ZnS(Ag) scin-
tillation
powder/Ba
carrier
Concen-
tration
Factor
Applicable
Concen-
tration
.2-15 pg
.05-10 ppm
10"16 M
10-16 M
>1 pCi/1
Recovery
99+2
100
±12.3
100
100
68
Collection
Parameters
pH = 5-5
pH = 7.5
T = 120°C
pH = 7-8
pH = 5-7
pH = 3
T = 50°C
Reference
Burgett and
Fritz (1973)
Brooks (1965)
LeRoy and
Lincoln (1972*
Weiss and Lai
(I960)
Weiss and Lai
(I960)
Kelkar and
Joshi (1969)
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Rb '
Rb
Rb
Rh
Rn
Ru
Accumulator
Type
Ion exchange
.Ion exchange
Cocrystal-
lization
Evaporation
Coprecipita-
tion
•*
Ion exchange
Specific*
Accumulator
Formulation
AMP crystals
APMW crystals
Ammonium
dipicylamin-
ate
ZnS(Ag) scin-
tillation
powder/ Ba
carrier
Chitin and
Chitosan
Concen-
tration
Factor
Applicable-
Concen-
tration
5-50 ppm
.01-1 ppm
>1 pCi/1
1.3 ppb
%
Recovery
( + )
100
100
295
±7.4
68
100
Collection
Parameters
pE = 2
pH <7
-
pH = 2-8
T = 120°C
pH = 3
T = 50°C
pH = 3-1
HN03 added
Reference
Brooks (1965)
Krtil and
Krivy (1963)
Joyner, et al
(196?)
LeRoy and
Lincoln (1974
Kelkar and
Joshi (1969)
Muzzarelli
(1970)
Ul
U1
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Ru
Ru
Accumulator
Type
Cocrystal-
lization
Evaporation
Specific*
Accumulator
Formulation
Thionalide
Concen-
tration
Factor
Applicable
Concen-
tration
.01-5.0 ppm
%
Recovery
( + )
100
±12.8
Collection
Parameters
pH = 10
T = 120°C
Reference
Lai and Weiss
(1962)
LeRoy and
Lincoln (197J
ON
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Sb
Sb
Sb
Se
Se
Si
Si
Accumulator
Type
Ion exchange
Evaporation
Head space
analysis
Chelation-
extraction
Head space '
analysis
Chelation-
extraction
Evaporation
Specific*
Accumulator
Formulation
Chitosan
Reduce with
NaBH^
APDC/
MIBK
NaBH^ as
reducing
agent
AMTH and
citrate/MIBK
Concen-
tration
Factor
Applicable
Concen-
tration
.04-1.0 ppm
kO. 00015 ppm
0.01 ppm
.1-10 ppm.
%
Recovery
( + )
100
±11.1
±10.0
Collection
Parameters
pH 7.8,
from brine
T=120°C
pH=3-6
pH=0.6-1.2
T=120°C
Reference
Muzzarelli,
Raith, and
Tubertini
(1970)
LeRoy and
Lincoln
(197*0
Pollock and
West (1973);
Schmidt and
Royer (1973):
Fernandez
(1973)
Mulford
'(1966)
Fernandez
(1973)
Ramakrishna,
Robinson,
and West
(1969)
LeRoy and
T •» nn^~\ 1-1 t ^ n*7 1
I
1—t
U1
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Sm
Sn
Sn
Sn
Sn
Sn
Sr
Sr
Sr
Accumulator
Type
Chelation-
extraction
Chelation-
extraction
Evaporation
Cocrystal-
lization
Cocrystal-
llzation
Head space
analysis
Ion exchange
Ion exchange
Evaporation
Specific*
Accumulator
Formulation
H(FHD)/DBSO
Oxine/
CHC13
Thionalide
2-Mercapto-
benzimidazole
Reduce with
Dowex 50-X10
Dowex 50-X12
Ca form
Concen-
tration
Factor
4 x 105
Applicable
Concen-
tration
.02-15 vig
.003 ppm
.04-1.0 ppm
-0.0002 ppm
1 ppm
.08-3.0 ppm
Recovery
99±2
100
±9.2
96
100
±0.15
±8.8
Collection
Parameters
pH = 5.5
pH = 7.2
T = 120°C
pH = 10
pH = 5
0.2N HC1
T = 120°C
Reference
Burgett and
Fritz (1973)
Brooks (.1965
LeRoy and
Lincoln (197
Lai and Weis
(1962)
Weiss 'and La
(1963)
Fernandez
(1973)
Christova an
Kruschevska
(1966)
Andersen and
Hume (1968)
LeRoy and
Lincoln (197
00
I
» See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Sr
Ta
Ta
Te
Te
Ti
Ti
Accumulator
Type
Cocrystal-
lizatlon
Cocrystal-
lization
Cocrystal-
lization
Evaporation
Head space
analysis
Ion exchange
Evaporation
Specific*
Accumulator
Formulation
Potassium
rhodizonate
•Thionalide
2-Mercapto-
benzimidazole
Reduce with
NaBH^
CPG-8-HOQ
Concen-
tration
Factor
Applicable
Concen-
tration
-14 _i6
M
.1-50 ppm
17 ppb
.01-1.0 ppm
Recovery
CO
100
98
95-98
. ±13.7
95±3
±11.7
Collection
Parameters
pH = 5-7
pH = 3.5
pH = 1-5
T = 120°C
-
pH = 2-4
T = 120°C
Reference
Weiss and Lai
(I960)
Lai and Weiss
(1962)
Weiss and Lai
(1963)
LeRoy and
Lincoln (197^
Pollock and
West (1973);
Schmidt and
Royer (1973);
Fernandez
(1973)
Sugawara,
Weetall and
.Schucker
LeRoy and
Lincoln (1971
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Tl
Tl
Tl
233,
uo2
u
Accumulator
Type
Chelation-
extraction
Cocrystal-
lization
Chelation-
extraction
Ion exchange
Ion exchange
Cocrystal-
lization
Specific*
Accumulator
Formulation
Dithizone/
CHC1-
Thionalide
APDC/MIBK
Chitosan
Chitosan
l-Nitroso-2-
naphthol
Concen-
tration
Factor
Applicable
Concen-
tration
.01 ppb
.1 ppm
4 X 10"Sd
Recovery
100
100
94-97
100
>95
Collection
Parameters
pH = 7.5
pH = 10
pH = 3-10
pH = 5.5
(1-18 hour
shaking time)
pH = 7
pH = 7-8
Reference
Brooks (1965;
Lai and Weiss
(1962)
Mulford (196(
Muzzarelli,
Raith, and
Tuber tin!
(1970)
Muzzarelli
and
Tubertini
(1969)
Joyner et al
(1967)
I
H1
CTN
O
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
V
V
V
V
V
V
V(IV)
md V(V)
Accumulator
Type
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Evaporation
Chelation-
extractlon
Specific*
Accumulator
Formulation
Cupferron/
MIBK
Dichloro-
oxine
Phosphotung-
state/Iso-
butyl alcohol
DEDC/CHC1,
APDC/MIBK^
Oxine/
CHCL-
KCN, CyDTA,
and PAR/CHC1,
Cupferron/
MIBK.
Concen-
tration
Factor
l» X 105
Applicable
Concen-
tration
.002 ppra
.025 ppb
.05-50 ppm
% -
Recovery
( + )
100
±8 at 1 ppb
±8.3
Collection
Parameters
pH = 1
pH = 7.2
pH = 6.5
T = 120°C
pH = 3.8
Reference
Crump-Wiesner,
Feltz, and
Purdy (1971)
Chau and
Lum-Shue-Chan
(1970)
Joyner et al.
(1967)
Brooks (1965)
Nishimura,
Matsunaga,
Kudo and
Obara
LeRoy and
Lincoln (197*0
Crump-Wiesner
and Purdy
(1969)
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
V(V)
w
w
w
w
Zn
Zn
Zn
Accumulator
Type
Ion exchange
Ion exchange
Ion exchange
Chelation-
extraction
Cocrystal-
lization
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Specific*
Accumulator
Formulation
CPG-8-HOQ
CPG-8-HOQ
Dowex 1-X8
SCN-form
Oxine/
CHC1
Thionalide
Dithizone/
acetone
HHFA and
TOPO/
cyclohexane
DQA/ethyl
propionate
Concen-
tration
Factor
10
Applicable
Concen-
tration
200 ppb
250 ppb
.1" ppb
2 ppm
.0028 M
.001-.10ppm
%
Recovery
( + )
100±3
100±3
100
91
100
.10-25.
100
Collection
Parameters
pH = 4-7
pH = 2-4
PH = 3.5
pH = 6-9
pH = 3-6
pH = 6
Reference
Sugawara ,
Weetall and
Schucker (1974)
Sugawara,
Weetall and
Schucker (1974)
Kawabuchi
and Kuroda
(1969)
Joyner et al.
(1967)
Lai and Weiss
(1962)
Matkovich and
Christian
(1974)
Mitchell and
Ganges (1974)
Sachdev and
West (1970)
I
h-J
a\
rv>
i
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Zn
Zn
Zn
Zn
Zn
Zn
Accumulator
Type
Chelation-
extraction
Chelation-
extraction
Chelation-
extraction
Chelation- .
extraction
Ion exchange
Ion exchange
Specific*
Accumulator
Formulation
Dithizone/
ethyl pro-
pionate
APDC/MIBK
Diethyl di-
thio carbarn-
ate
Dithizone
Chelating
resins
Chitosan
Concen-
tration
Factor
10
Applicable
Concen-
tration
1 ppb
0.02 yg
%
Recovery
( + )
•
100
Collection
Parameters
pH = 7.5
pH = 2-6
-
pH = 7.8
Reference
Sachdev and
West (1969)
Mulford
(1966)"""
Platte (1968);
Nix and
Goodwin (1970)
Sachdev and
West (1969)
Riley and
Taylor (1968);
Biechler
(1965) ; Galle
(1961)
Muzzarelli,
Raith, and
Tubertinl
(1970)
oo
I
* See list of Abbreviations at end of table.
-------
ACCUMULATION OP METAL IONS FROM WATER
Accumulant
Zn
Zn
Zn
Zn
Zn
Zn
Zn
Accumulator
Type
Ion exchange
Chelation-
extractlon
Chelation-
extraction
Chelation-
extraction
Evaporation
Cocrystal-
lization
Cocrystal-
lizatlon
Cocrys£al-
lization
Specific*
Accumulator
Formulation
Chitin
DEDC/MIBK
Dithizone/
CHC13 or CCl^
APDC/CHCl^
Oxine /
CHC1
Oxine/
CHC1-
l-Nitroso-2-
naphthol
Thionalide
5,.7-Dibromo-
8-Hydroxy-
quinoline
Concen-
tration
Factor
H X 105'
Applicable
Concen-
tration
0.4 ppb
0.01 ppm
.01-2000ppm
5 ppb.
%
Recovery
( + )
100
101
100
±11.0
>95
98-100
100
Collection
Parameters
PH = 7
distilled
water
pH = 6
pH = 7.2
T = 120°C
pH = 7
pH = 7-10
pH = 8
Reference
Muzzarelli.
and Tubertini
(1969)
Joyner et al.
(1967)
Joyner et al.
(1967)
Brooks (1965)
LeRoy and
Lincoln (197*0
Joyner et al.
(1967)
Lai and Weiss
(1962)
Riley and
Topping (1969)
* See list of Abbreviations at end of table.
-------
ACCUMULATION OF METAL IONS FROM WATER
Accumulant
Zn
Zr
Zr
Zr
Accumulator
Type
Coprecipl-
tation
Ion exchang
Evaporation
Cocrystal-
lizatlon
it
Specific*
Accumulator
Formulation
KOH
CPG-8-HOQ
l-Nitroso-2-
naphthol
Concen-
tration
Factor
Applicable
Concen-
tration
135 ppb
.01-1.0 ppm
%
Recovery
( + )
96±7
100±5
±9.7
97
Collection
Parameters
pH = 6-7
From
Sea Water
pH = 4-6
T = 120°C
pH - 5
Reference
Joyner et al
(1967)
Sugawara,
Weetall, and
Schucker (19
LeRoy and
Lincoln (197
Joyner et al
(1967)
I
M
CT\
U1
I
* See list of Abbreviations at end of table.
-------
LIST OF ABBREVIATIONS USED IN TABLE 2-5
AMP
AMTH
APOC
APMW
CPG-8-HOQ
DBSO
DDDC
DEDC
DQA
HPA, HHPA
H(POD)
MIBK
MIPK
TOPO
TTA
Oxine
Dithizone
Ammonium molybdophosphate
Ammonium molybdate tetrahydrate
Ammonium pyrrolidine dithiocarbamate
Ammonium phosphomolybdatotungstate
Controlled Pore Glass with 8-Hydoxyquinoline as
immobilized chelate
Di-n-butylsulphoxide
Diethylammoniurn diethyldithiocarbamate
Sodium diethyldithiocarbamate
Dithizone, 8-Hydroxyquinoline, and acetyl acetone
Hexafluoroacetylacetone
1,1,1,2,2,6,6,7,7,7-decafluoro-3,5-heptanedione
Methyl isobutyl ketone
Methyl isopropyl ketone
Tri-n-octyl-phosphine oxide
2-Thenoyltrifluoracetone
8-Hydoxyquinoline
Diphenylthiocarbazone
-------
ACCUMULATION OF METAL IONS PROM WATER
BIBLIOGRAPHY
Andersen, Neil R., and Hume, David N. "Determination of
Barium and Strontium in Sea Water." Anal. Chim.
Acta, 40.: 207-220 (1968). ------
April, R. W. , and Hume, David. "Environmental Mercury:
Rapid Determination in Water at Nanogram Levels."
Sci., 170: 849-50 (1970).
Biechler, D. G. Anal. Chem. , ^7: 1054 (1965).
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SECTION THREE: ACCUMULATION OF TRACE ELEMENTS
FROM AIR
3.0 Introduction
The ambient atmosphere is. an aerosol composed of nitro-
gen and oxygen vith vapors, particulates and other gases
in trace amounts. In order to analyze for most of the
atmospheric gases, vapors and particulates, they must be
separated from the aerosol and concentrated. The condi-
tions for collection must be carefully controlled and
measured in order to relate the mass of the trace substance
accumulated to its concentration in the atmosphere. The
quantitative collection of substances is complicated by
the fact that the aerosol volume changes with variations
in temperature and pressure.
The problem of reliable and accurate sampling is
exacerbated by the dynamic nature of the atmosphere.
Changes in humidity, temperature, and windspeed can also
have significant effect on the collection efficiency of
sampling devices. If an aqueous solution is used to col-
lect the trace substance, change in this ambient temper-
ature can cause freezing or significant evaporation of
the solution, producing questionable results. The reli-
ability of the sampling technique is the most critical
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factor in determining the precision and accuracy of the
analytical results of a given measurement..
Organic, inorganic and organo-metallic substances are
found in trace gases of the atmosphere. The metallic
elements are primarily found in the atmospheric particu-
lates along with some inorganic salts such as silicates
and sulfates. A significant amount of organic particulates
is present in the atmosphere as a result of fossil fuel
combustion. The composition of these particulates can be
significantly altered by adsorption of organic gases and
vapors present in the atmosphere. The atmospheric par-
ticulates demonstrate a dichotomous distribution with a
separation size of approximately 2y. The larger particu-
lates generally emanate from mechanical sources such as
suspended soil particulates from fields, or particles
from rock-crushing for the production of cement. Si, Co,
Fe, Cr, and Mg are found primarily in the larger particles.
The smaller particulates originate principally from com-
bustion sources, heterogenous and photochemical reaction,
and condensation. The highest concentration of V, Mn,
Cu, Zn, and S are observed in these particulates. Because
these smaller particulates are readily inhaled, they are
most significant in determining the health hazard of
atmospheric particulates.
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The techniques for the accumulation of substances from
the atmospheric aerosol discussed in this report are based
on physical, chemical, aerodynamical and electrical prop-
erties. Some of the more important properties employed
in the collection of gases and particulates are absorptiv-
ity, solubility, adsorptivity, chemical reactivity,
polarity, mass, inertia, boiling point, and electrical
resistivity and conductivity. The methods of collection
described in the report are (1) absorption; (2) adsorption;
(3) condensation; (4) filtration; (5) sedimentation;
and (6) electrical precipitation. These methods are best
suited for the collection of different trace substances,
depending on their chemical and/or physical properties.
The efficiency of collection of a sampling system is
normally in the range of 90 to 100 percent.
In the next section, the various collection devices
for sampling trace substances in ambient air are described.
For each method, the sampling device should be designed
to minimize interference and contamination and to
maximize reliability, precision and accuracy.
3.1 Particulate Sampling
The atmospheric aerosol is composed of particles of
diverse physical and chemical composition. The particles
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that readily settle out of the atmosphere (greater than
50y) are referred to as dustfall or settlable particles.
Particles in the O.Oly to lOy range, which can remain in
the atmosphere for several weeks, are defined as suspen-
ded particles because these particles have a settling
velocity comparable to the velocity of air motion. The
particles of the size range O.Oly to O.ly that can act
as condensation sites for supersaturated vapor in the
atmosphere are known as Aitken nuclei.
The sources of particles in the atmosphere may be
industrial operations, transportation sources, natural
sources, or may be formed from chemical reactions in the
atmosphere involving natural or man-made gases.
Atmospheric particulates are generally classified by
their equivalent particle diameter based on their aero-
dynamic characteristics. This method of classification
of particles is necessary because of the aggregate nature
of atmospheric particles, and the attendant large varia-
tion in particle density and shape. The equivalent par-
ticle diameter is measured in microns in the range
10~^y to 50y. Most methods of collection of atmospheric
particulates are based on their aerodynamic or mass
• -
Methods of Air Sampling and Analysis, Intersocietv
Committee, American Public Health Association, Washington,
D.C. (1972)
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properties. No change in the momentum of the particle
should occur during sampling in order to get a represent-
ative sample of the aerosol. This type of sampling
(isokinetic) is not required for smaller particles because
they exhibit small inertial effects.
Little information is known about the chemical com-
position of the atmospheric aerosol. Sampled dustfall
particulates usually contain high levels of iron and
aluminum oxides, and calcium oxide. Suspended particles
are generally considered to consist of organic compounds,
metals and inorganic salts, such as sulfates, nitrates
and chlorides. The organic portion of the collected
particulates consists mostly of organic acids, alcohols,
and other water soluble organic acids and neutral com-
pounds .
The sampling techniques for atmospheric particulates
are based on sedimentation, filtration, aerodynamic
properties and precipitation. Sedimentation (the gravity
settling of particulates) is relied on for the accumula-
tion of the larger particulates. A wide range of
filtration methods is available for many sizes of par-
ticulates. Aerodynamic', sampling devices separate
particles by utilizing their size and density differences.
Examples of this technique are the cascade and Lundgren
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impactors. Precipitation of particles from the atmosphere
is accomplished by either thermal or electrical methods.
The collection efficiency of devices used to remove
particulates from the atmosphere may be determined by
their efficiency of removal of the total weight of par-
ticles or the particle count. Devices that exhibit high
efficiency for removal of the total mass of particles may
not efficiently remove the total number of particles.
The particulate sample may not accurately reflect
the composition of the atmospheric aerosol from which it
was sampled because the chemical and physical properties
of the particulates can be altered after collection by
condensation, adsorption, chemical reactions, and agglo-
meration. In the collection of sulfates by high volume
samplers, the relative humidity has a significant effect
on the determination of the total amount of sulfate in
the sample. Also, some organic particles may be lost
because they are volatile. New compounds may be formed
from reactions in the collected material during sampling
and storage. The size distribution of the particulates
can also be changed by fragmentation and agglomeration
during the sampling process.
-------
3.1-1 Filtration
As a method for the collection of suspended particu-
lates from the atmosphere, filtration permits great
flexibility in selection of the sampling rate, sampling
duration, and filter media. Filtration is a complex
process based on such phenomena as inertial impaction,
interception, diffusion, electrostatic attraction, grav-
imetric and adhesion forces, and reentrainment. The
collection efficiency of specific sized particles by a
medium is a function of particle size, porosity of medium,
face velocity, aerosol composition, load, pH of medium,
humidity and temperature. The total mass and particle
count efficiencies of a filter system must be determined
experimentally on the aerosol of interest.
The filter medium for atmospheric particulate sampling
is selected on the basis of its collection efficiency,
its inertness for reaction catalysis and the analytical
techniques to be performed. The two major types of fil-
ters employed for atmospheric sampling are fiber and
membrane filters. The fiber filters are prepared from
either glass or cellulose. Glass fiber filters are non-
hygroscopic and are generally used for gravimetric
analysis. Because glass fiber filters are not contaminated
with trace elements, they are usually selected when wet
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chemical analyses are to be performed on the sample.
The filter is almost 100? efficient for collecting the
total mass of suspended particulates at high velocity
sampling rates. Because of these characteristics, the
glass filter has been selected as the principle filter
medium in the high volume sampler used by the Environ-
mental Protection Agency to evaluate ambient air concen-
trations of suspended solids and many inorganic salts
and metals. But, because glass fibers will absorb sulfur
dioxide and promote its catalysis to sulfate, the Environ-
mental Protection Agency is evaluating other media for
sulfate aerosol determination. Although the cellulose
fiber filter has been shown to be inert in the conversion
of sulfur dioxide to sulfates, it has not replaced the
glass fiber filter because of its hygroscopic nature and
the presence of chemical contaminants. The collection ef-
ficiency of the cellulose filter dramatically changes
with variations of humidity. A wide range of collection
efficiencies for cellulose fiber filters has been
observed, depending on the manufacturer and the filter
type. Cellulose filters are not usually selected for
the filter medium if wet chemical analysis of particulates
is to be performed because the binders usually interfere
with the analysis. The use of either filter allows sam-
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pling at high volume flow rates with low pressure drops
because of their loose structure. These filters are
usually employed when collection of a large mass of the
aerosol is desired.
Membrane filters are thin (150y) with controlled
pore size and usually consist of a dry, stabilized cellu-
lose-ester-gel membrane. A wide range of sizes of membrane
filters with various pore diameters is available com-
mercially. Membrane filters are not affected by water,
saturated aliphatics, and aromatics, but they are dis-
solved by methanol, esters and ketones. The ash content
of the filter is barely traceable. The filter is thermally
stable within the temperature range of the atmosphere.
Membrane filters have been designed for aerosol assay at
-2 -1
flows of 0.05 to 5.0 liters cm min at 1 cm of mercury
differential pressure. Because the particulates are
trapped on the surface of the filter rather than in the
interstices, the method is amenable to x-ray diffraction
or fluorescence, and light microscopy techniques. This
kind of filter has demonstrated nearly 100$ mass removals
for particulates from 0.05 to lOy, and has been used for
collection of fine particulates from auto reactions and
chemical particles in the atmosphere. Because of its
relatively high resistance to flow, the filter is sel-
ected primarily for low volume flow sampling techniques.
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The high volume air sampler method is the most widely
used and accepted method for suspended particulate meas-
urement in the United States. The high volume sampler
uses fiber filters and can sample an aerosol at the rate
of 2.12 liters min , which permits the sampling of a
large volume of aerosol over a relatively short period
of time. An illustration of the high volume sampler is
shown in Figure 3-1• This sampler has many advantages,
being relatively inexpensive, rugged, and durable. With
a glass fiber filter it is well suited for high volume
flow sampling of particles in the 0.1 to 10y range. The
sampling method is capable of measuring wide ranges of
particle concentration. The instrument has demonstrated
a high level of precision, but it has been difficult to
determine its accuracy. A study was performed by EPA in
Texas in which twelve high volume samplers that simul-
taneously collected a synthetic atmosphere exhibited an
average error of 3-6$. Current research is being per-
formed to determine whether the anisokinetic sampling by
the high volume sampler introduces a significant error
in accuracy to the procedure. The high volume sampler
has been the predominant method for collecting atmospheric
particulates for chemical analysis, However, this
method is limited for size analysis, because it does
not provide for fractionization of composition sampled
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Figure 3-1: High Volume Air Sampler With
Shelter
-183-
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into an individual size and shape, or for the analysis
of specific fractions of particles collected.
A source of error in measuring the concentration of
the total suspended particulates by the high volume sample
is caused by the method of estimation of sample volume
flow rate. The sample volume flow rate is estimated by
arithmetically averaging the initial and final flow rates
for the sample period. Another source of error is the
influence of humidity on the sample weight. At a relative
humidity of 55%, a ^0% increase in the sample weight has
been observed compared to samples collected from dry air.
Also, above 70% relative humidity, particulates in the range
of O.OljJ to Ijj serve as nuclei for vapor condensation.
Other sources of error in high volume sampling can be
created by the volatilization of organic aerosols collected
on the filter and the change in the collection efficiency
of the filter with variations of volume flow rate.
Particles collected on fiber filters from the high
volume sampler are usually analyzed by atomic absorption
spectrophotometry and wet chemical methods which generally
require many hours of sample preparation. Cellulose
fiber filters and membrane filter samples have been
analyzed by x-ray diffraction and fluorescence.
-------
• J
Bonner, et al , who analyzed various cellulose fiber
filters from high volume samplers, estimated that the
accuracy of this sampling and analysis system is + 10$
and that its reproducibility is better than 5$. The
x-ray fluorescence technique offers the advantage of
being nondestructive, permitting further chemical analy-
sis by x-ray diffraction or microchemlcal methods.
Dittrich and Cothern analyzed a twenty-four hour sample,
collected on a glass fiber filter with a high volume
sampler for Ti, Fe, Cu, Zn, Pd, Cd and Sn using x-ray
fluorescence with a sensitivity limit of 0.1 microgram/
•3 i|
m of air. Mitsugi et al analyzed glass fiber filters
from low volume samplers which were operated for a month
at a sample volume rate of 20 &/min. The filter was
molded into briquets and assayed by x-ray fluorescence
for the elements of V, Mn, Ni, Cu, As, Br, Mo, Cd, Cr,
Sn, Sb and Pb. The detection limits observed were
o o
0.002 yg/nr for Mn, Ni, Cu, and As; 0.004 yg/m-1 for
Br, Mo, Cd and Sn; 0.006 yg/m^ for V and Pb; 0.009 yg/rrr
for Cr; and 0.013 yg/m0 for Sb. The polynuclear aromatic
2. Bonner, N. A., P. Bayun, and D. C. Camp. California
University, Livermore, California. Lawrence Radia-
tion Laboratory Report, Atomic Energy Commission
Contract # W-7405-ENG-M8.
3- Dittrick and Colthern. JAPCA 21: 716-719 (1971).
4. Mitsugi, Hidikatsu, Yoshihiro Nakagaua, and Nobuliro
Takata. Institute Hyogo Project Report 5: 1-6
(1973).
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hydrocarbons collected on glass fiber filters from high
volume samplers can be analyzed by benzene extraction
with subsequent spectrophotometric or GC analysis, or
by cyclohexane extraction followed with separation by
column chromotography and analysis by spectrophotometric
or microanalytic methods.
A new generation of samplers is currently being
developed by the Environmental Protection Agency. A
prototype dichotomous sample has been constructed which
divides the aerosol sample into two fractions at a
separation point of 2y diameter. The particles are
evenly distributed over the two membrane collecting fil-
ters. The filters are in cassettes in order to permit
rapid analysis by x-ray fluorescence. Thirty-six samples
can be analyzed by a small computer-controlled unit for
nineteen elements without requiring the operator's
attention, thus producing great savings in operations
cost for sample analysis.5 Because sulfur dioxide
absorbed on small particles causes the same physiolog-
ical response as the particulate sulfates, the analysis
5. Dzubay, T. C. and R. K. Stevens. Second Joint
Conference of Sensing of Environmental Pollutants,
Washington, D. C. December 10-12, 1973.
-186-
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for elemental sulfur by x-ray fluorescence of the small
particulates gives an excellent indication of the health
hazard of the sulfur compounds in the aerosol.
Other methods for analysis of atmospheric particulates
collected on filters are neutron activation analysis and
photon activation analysis. Neutron activation analysis
for trace elements of Cl, V, Mn, Cu, and Br has demon-
strated reproducibilities of greater than 10$.6 The rare
earth elements in atmospheric particulates collected by
a high volume sampler on Whatman 41 cellulose filters
were analyzed by Potts, et al.7 using neutron activation
analysis. The elements La, Ce, Nd and Sm were found in
the ppm range, whereas Eu, Gd, Tb, Yb and Lu were found
in the sub ppm range for three American midwestern cities.
Photon activation analysis has been used to measure as
many as nineteen elements in a particulate sample.."
Elements that are readily analyzed by photon activation
analysis to the submicrogram range include Pb, Ni, As,
Zn,. Sb, Br and I. The sensitivity of this method is
6. Heindryckx, R. and R. Dams. "Evaluation of Three Pro-
cedures for Neutron Activation Analysis of Elements in
the Atmospheric Aerosol using Short-Lived Isotopes."
Radiochem. , Radioanaly. Lett. , l6_:209-225, (1974).
7. Potts, Mark J., Charles W. Lee, and James R. Gadiux.
"Rare Earth Element." Env. Science Tech. 8_: 585-7 (1974).
8. Zoller, W.H. "Photon Activation Analysis." Second
Joint Sensing Environmental Pollution, Washington, B.C.,
December 10-12, 1973.
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intermediate between neutron activation and atomic
absorption. The destructive ring-oven technique can
also analyze atmospheric particles collected on Whatman 41
filter paper. Substances that are measured by this method
are Fe, Ni, Cu, and SO^9, Cd10 and Pb 1:L.
Another system employing filtration to collect atmos-
pheric particulates is the paper tape sampler. The tape
sampler collects particles on a narrow strip of paper and
evaluates the darkness or density of the soiled area by
its reflectance or transittance. This method has been
specified for continuous monitoring of fine particulates
12
by the American Society of Testing and Materials . The
paper tape can be impregnated with various chemicals in
order to determine the concentration of specific gases in
the air. Natusch, el. al. developed a method for collect-
ing hydrogen sulfide on paper tapes impregnated with silver
nitrate and determined the optical density of the metal
9. West, Philip W. and Sham L. Sachdev. "Air Pollution
Studies - The Ring Oven Technique." Journal of
Chemical Education., 4_6_:96-98, (1969).
10. Dharmarajan, V. and P. W. West. "Microdetermination
of Cadmium Airborne Particulates by Means of the
Ring-Oven Technique." Anal. Chim Acta 5J7: 469-72 (1971).
11. Jungreis, E. and P.W. West. "Microdetermination of
Lead by the Ring-Oven Technique Applicable to Air Pol-
lution Studies." Israel J. of Chem. 7_:4l3-l6 (1969).
12. Amer. Soc. of Testing and Materials. 1971 Annual Book
of ASTM Standards, Part 23, ASTM, Phil., PA, (19717"!
13. Natusch, D.F., J.R. Sewell & R.L. Tanner. "Determina-
tion of Hydrogen Sulfide in Air - Assessment of Impreg-
nated Paper Tape Methods." Anal. Chem. 46:410-15 (1974)
-188-
-------
sulfide formed. The sensitivity of this analytical
method is in the parts per billion range. Mac Leod and
1*1
Lee determined by anodic stripping voltametry the trace
elements of Cd, Pb, and Cu collected by paper tape samplers.
The analytical sensitivities of anodic stripping volta-
metry were sufficient to characterize diurnal variation
of the metals in samples collected in Chicago and Wash-
ington. The tape sampling method is not suited for air
evaluation based on volumetric or mass measurement, but
is used to determine the relative level of contaminant
concentration.
3-1.2 Inertial Separation
Atmospheric particles can be collected according to
size by utilizing their aerodynamic properties. Instru-
ments using this principle are usually called inertial
impactors or fractionators because they divide the aerosol
into fractions. The removal of particles is accomplished
when a stream of particle-laden air approaches a flat,
solid surface in its path. As the plate is approached,
the air velocity changes markedly, allowing the air to
flow around the plate. The particle, however, because of
its own inertia, will follow a separate path and will
MacLeod, Kathryn E. and R. E. Lee, Jr. "Selected Trace
Metal Determination of Spot Tape Samples by Anodic
Stripping Voltammetry." Anal. Chem. ^5:2380 (1973).
-189-
-------
usually impact on the surface of the plate. The collection
efficiency will vary with the air stream velocity and the
orientation of the plate.
Inertial impactors are classified as wet impingers or
dry impactors. Wet impingers collect particles in water
or some other liquid, but have such a low flow rate
(2.8l liters min"1) that they do not usually collect suf-
ficiently large particulate samples for trace substance
analysis. Dry impactors are usually in the "cascade"
configuration, which provides aerodynamic size separation
of particles by decreasing the size of the impaction jets
at successive stages (Figure 3-2). As the jet size is
increased, successively smaller mass particles obtain
sufficient velocity to impact on collection surfaces.
Common types of wet impingers used to collect gas
samples are the midget and the Greenburg-Smith impinger.
Wet impingers are efficient in the collection of particles
greater than approximately O.OOly diameter. The samp-
ling volume rate for Smith-Greenburg impingers is ap-
proximately 0. 028mVmin. , while the midget impinger is
around 2.8l liters/min. Samples collected in impingers
are generally analyzed by colorimetry, or any other
microchemical method, or by light or atomic absorption.
-190-
-------
Aerosol
Inlet
Impaction
Slides
Cleaned air
Outlet
Aerosol
Inlet
'Impact
Slide
Impaction
r. Slide
Cleaned air
Outlet
Figure 3-2. Common Cascade Impactor Designs
-191-
-------
Large Jet
Large
Particle
Aerosol
Inlet
Impaction
Slide
Small
Particle
Small
Jet
Small
Particle
Impaction
Slide
Figure 3-2 (cont'd): Common Cascade Impactor Designs
-192-
-------
A. S. Landry ^ has developed a method for the determin-
ation of atmospheric Pd and Cd, using wet impingers as
collection devices. Some other trace substances that
have been collected for analysis by wet impingement are
As16, Be1? and Asbestos18.
Two dry inertial separators currently used for air
sampling are the Andersen Sampler (Figure 3-3) and the
Lundgren Impactor (Figure 3-4). The Andersen Sampler
uses multiset impaction stages with progressively smaller
jet openings. Particles are collected on plates on each
stage, and size distribution is usually determined by
gravimetric analysis of each plate. The collection sur-
face for the Andersen Sampler may be glass or cellulose .
fiber filters, membrane filters of mylar, glass or tef-
lon. The Andersen Sampler can normally operate from
28.32 liter min metric units to greater than 0.85 m^
15- Landry, A.S. "The Simultaneous Determination of
Lead and Zinc in Atmospheric Samples". J. Ind. Hyg.
Toxic., 29.:l68-74 (1949).
16. Katz, Morris. Measurement of Air Pollutants, Guide
t£ the Selection of_ Methods, World Health Organiza-
tion, Geneva (1969).
17- Black, M. and R. E. Sievers. "Environmental Analysis
Problems Created by Unexpected Volatile Beryllium
Compounds in Various Samples." Analytical Chemistry
15:1773-1775 (1973).
18. Homes, S. "The Measurement of Asbestos Dust." Staub
Reinhaitung Luft, 33_:64-66 (1973)
-193-
-------
Vacuum
Pump
Jets
Stage
Collector
Jets-
Stage 2
Collector
Jets->
Stage 8-H
Collector
J
Stage 9
Filter
Figure 3-3: Andersen Air Sampler
-194-
-------
Aerosol Inlet
V\ \\X\\\N
First Stage
Nozzle
First Stage
Rotating
Drum
/ High
/ Efficiency
Filter
Figure 3-4: Lundgren Impactor
-195-
-------
min~l metric units and collect particles in the size
range of 0.^5 to lly with 95% collection efficiency. It
has been widely used for studies of atmospheric size dis-
tribution and for size distribution of specific aerosols
such as sulfates, lead compounds, and nitrates. A net-
work of ten Andersen Samplers, modified to operate at
0.14 m3 min"1 metric units has been used in the National
Air Sampling Network (NASN) .
Recently, a modified four-stage Andersen Sampler
has been developed which is a high volume sampling head.
q _")
The sampling head can sample at a rate of 0.57 m
metric units and fits directly onto the top of the
standard high volume sample unit. It sizes particles
from 1 . lp to 7y and above, and if a standard high volume
sampler filter is used as a back-up, particles in the
range 0.1 to l.ly are also collected. It was designed
to be readily adaptable to routine air sampling, and
field tests by EPA showed very satisfactory performance.
This instrument makes it possible to sample total sus-
pended particulates and particle size distribution at
the same time. EPA is using this sizing head in con-
nection with its current NASN operations.
-196-
-------
Fugas, et al. ° performed simultaneous tests on a
modified Andersen Sampler a.nd a high volume sampler.
The investigators found that significant amounts of par-
ticulates were lost by adhesion to the walls of the
Andersen Sampler. They observed losses of suspended
particles of (35%), Fe (15?), and Mg (16%). Only Pb
particles were not affected by wall losses. Roesler,
et al.20 noted that significant conversion of S02 to
sulfates occurred when the ambient aerosol was collected
by a six-stage Andersen impactor, as compared with a
high volume sampler. In six four-hour samples, the aver-
age sulfate concentration was two to three times as
large as the average concentration from the high volume
sampler. Because of these problems with artifact for-
mation and wall losses, modified Andersen samplers should
not be used for measuring the total suspended solids, Fe,
Mg, or sulfate concentrations of an atmospheric aerosol.
The same methods of analyzing particulate samples col-
lected by the Andersen Samplers can be performed as
19. Fugas, Mirka, J. Hrsak, and Dragica, Steiner-
Slereb. "Wall Losses With the Modified Andersen
Cascade Impactor." Inst. Natl. Rechn. Chim Appl.
Dixieme Colloq. Atmos. Polities., Proc. , Paris,
France, May 3-5, 1972.
20. Roesler, H., J.R. Stevenson and J.S. Nader. "Size
Distribution of Sulfate Aerosols in the Ambient
Air". JAPCA, 15:576-79 (1965).
-197-
-------
PI
described in Section 3.1.1. Dams, et al. evaluated
the material used on the collection surfaces of the An-
derson Samplers. They found mylar and teflon to be
unsatisfactory, but concluded that polyethylene is an
excellent collection surface for neutron activation
analysis.
The Lundgren Impactor uses rotating drums with mylar
filters or foil as collection surfaces. This impactor
increases the total collection surface area and permits
evaluation of changes in size distribution with time.
o _1
The impactor can operate from 0.014 to 0.14 m-1 min
with a normal sampling period of 24 hours. The impactor
will sample particles from 0.3 to lOy. The Lundgren
Impactor has never been widely used in routine sampling,
although its performance appears to be very comparable
to the modified Andersen Sampler for aerosol particle
size fractionation without the problems of sulfate arti-
fact formation and large losses due to collection of
•-) 2
particles on the walls. Blander, et al. used a Lundgren
21. Dams, R., K. A. Rahn, and J. W. Winchester. "Eval-
uation of Filter Materials and Impaction Surfaces
for Nondestructive Neutron Analysis of Aerosols".
Environ. Sci. Tech. 6^:441-448 (1972).
22. Blander, M., P.T. Cunningham, et al. "Chemistry of
Airborne Particulates." Chemical Eng. Div. Phys.
Inorganic Chem. Semiannual Rept. Jan.-June, 1973,
Argonne Nat'1. Laboratory, Argonne, IL (1973)-
-198-
-------
sampler to fractionate urban aerosol particles in order
to analyze for Pb, Br, Fe, and Zn. From x-ray fluorescence
and ion-microprobe mass analysis, the concentrations of
Pb and Br were observed to decrease with increasing par-
ticle size, while Fe and Zn concentrations showed the
opposite trend. In general, all analytical techniques
used in the analysis of filters can be used to assay the
particle distribution collected by the Lundgren sampler.
3.1-3 Electrostatic Precipitation
Electrostatic precipitators remove particles from
the air or from a gas stream by imparting an electrical
charge to the particles, causing them to move and adhere
to a grounded or oppositely charged collection surface.
This basic principle of operation is common to the dif-
ferent designs available. A high electrical potential
difference is applied between the discharge and collect-
ing electrodes.
A corona of charged gas ions is produced around the
discharging electrode. As particles flow around the
discharging electrode, they are charged by colliding
with the ions. The charged particles are then attracted
to the oppositely charged electrode, where they are neu-
tralized and collected. The collecting electrode is
-199-
-------
usually a tube or set of parallel plates surrounding the
discharge electrode, which is commonly -a platinum wire.
Conventional electrostatic precipitation is generally
selected when a relatively large sample collection is
desired for all suspended particulates particle sizes.
The electrostatic precipitator-offers two advantages
over filtration: the sampling efficiency is not influenced
by sampling rate, and the collected sample is in a readily
recoverable form. The sampling rate for the electro-
static precipitator ranges from 7 to 85 liter min , with
efficiencies near 100% for particulates ranging from
O.Oly to lOy. Frazer -> evaluated the collection effic-
iency of an electrostatic precipitator for the collection
of various particle sizes using electron microscope
screens. The minimum collection efficiency was found for
particles with a 2y diameter, with increased efficiencies
exhibited for larger and smaller particulates.
The precipitation force with an electrostatic pre-
cipitator is gentle, and sample alteration through
shattering of larger particulates is usually avoided.24
23. Frazer, D.A. "The Collection of Submicron Particles
by Electrostatic Precipitation." Am. Ind. Hyg. Quart.
11:75-79 (1956)
24. Williams, F.W. & E. Umstead. "Determination of Trace
Contaminants in Air by Concentrating on Porous Poly-
mer Beads." Anal. Chem. 40:2232-4 (1968).
-200-
-------
The collected samples can be analyzed for metals and in-
organics by the non-destructive analytical methods described
in the section on Filtration (Section 3.1.1). The micro-
chemical and other destructive methods for analyzing
organics can be performed on the samples directly, or
after other non-destructive analytical methods.
As particle samplers, electrostatic precipitators
are extremely precise, but are only accurate in collecting
particles with specific size, shape and electrical pro-
perties. Because of their high purchase and operating
cost and their unreliability under field conditions,
they are not often used for routine air sampling.
3.1.4 Thermal Precipitation
Thermal precipitation is based on the principle that
particles under the influence of a temperature gradient
will move towards a region of lower temperature. The
basic components of a thermal precipitation collector are
a hot wire suspended near a glass microscope slide. A
steep thermal gradient is created between the heated
wire and the unheated collecting surface, causing the
particles to be deposited on the glass slide.
Very low flow rates (10 or 20 cm min ) are pro-
vided by a vacuum pump or by water displacement. Sampling
-201-
-------
is virtually 100$ efficient for the particle size range
of 0.01 to lOy. Collection forces are gentle, so dis-
aggregation or shattering of particles do not occur.
High cost and very low flow rate make these instruments
impractical for routine ambient measurements. Currently,
their primary application is in the efficient collection
of particles for microscopic analysis.
3.2 Gas Sampling
The primary methods employed for concentrating trace
gases and vapors from the atmosphere are absorption, ad-
sorption, and condensation. In absorption, gases or
vapors are trapped by diffusing them into a liquid or
reacting them with a chemical absorbing agent into a
solution.. Absorption is generally used for sampling
gases from aerosols that can be prefiltered without
causing interferences.
Adsorption occurs when a gas is trapped by a solid
which holds the desired molecule with weak chemical bonds
or by electrostatic forces.
Condensation is a desirable method for collect-
ing non-reactive, insoluble gases and vapors, and non-
polar hydrocarbons. A major problem with condensation
is that a large amount of water vapor is generally col-
lected along with the trace gases. Because the gases
-202-
-------
or vapors are collected at low temperatures, reactions
between the collected substances are inhibited. The pre-
servation of the chemical composition of the sample by
condensation (cryogentic trapping) is an important ad-
vantage over the other methods for collecting gases and
vapors previously described.
3-2.1 Absorption
The absorbers conventionally used for air sampling
are those in which the gas samples bubble through a fixed
quantity of liquid. The most desirable type of collec-
tion system is chemisorption, in which gas or vapor
reacts with an absorbent in solution to form a non-
volatile product. In the chemisorption system, insoluble
products may be formed from the reaction of the collected
gas or vapor with the collecting reagent. In order to
insure that significant losses of the product do not
occur, special precautions must be taken.
Physical absorption, the other type of collection
system, is accomplished by absorbing the gas in a liquid
to form a solution with appreciable vapor pressure. Since
physical absorption is reversible, the vapor pressure
of the solution limits the amount of gas that can be
absorbed by the liquid. Therefore, strong chemical
-203-
-------
reactions are usually required in order to attain high
collection efficiencies. Low collection efficiencies are
usually obtained with physical absorption unless the gas
or vapor to be sampled has a high solubility in the liquid
and the ratio of gas to liquid volume is small. The ratio
of the volumes is minimized by decreasing the bubble size
and increasing the volume of collecting solution. In
physical absorption systems, the formation of binary or
tertiary mixtures in the absorbent solution can severely
limit the system's collection efficiency. These mixtures
can result in lowering of the boiling point of the collected
gas, resulting in its loss by evaporation. An attempt to
lower the vapor pressure of the collected gas or vapor by
refrigeration may cause loss of collection efficiency by
increasing the viscosity of the liquid.
Absorbers frequently employed for air sampling are:
(a) simple impingers; (b) fritted glass absorbers;
(c) spiral absorbers; and (d) packed towers. Examples of
these various types are illustrated in Figure 3-5.
No device will exhibit the same efficiency for all
gases under all conditions. Characteristic ranges of use
for some of the absorbers are displayed in Table 3-1.
The following are a few questions to consider in the sel-
ection of an absorption device for gas sampling systems:
-204-
-------
Figure 3-5: Absorption Devices
Simple Bubble Absorbers
American Public Health Association. Methods of Air
Sampling and Analysis, Washington, B.C. (1972)
-205-
-------
Figure 3-5 (cont'd): Absorption Devices
>
1
;
I
1
iA.''J .'. J a't.'IJ
e f
Bubbler Absorbers with Diffusers
h
-Bead-Packed Tower Absorbers
American Public Health Association. Methods of Air
Sampling and Analysis, Washington, B.C. (1972)
-206-
-------
Figure 3-5 (cont'd): Absorption Devices
i J
-Spiral Type Absorbers
American Public Health Association. Methods of Air
Sampling and Analysis, Washington, D.C.(1972)
-207-
-------
TABLE 3-1
CHARACTERISTICS OF ABSORBERS — APPROXIMATE RANGE OF USE
Type of Absorber
Absorbent Sample Rate,
Capacity, ml ml per mln.
Remarks
i
rv>
o
oo
I
Simple Bubbler
(Figure 3-5 a-d)
Bubbler With Diffuser
(Figure 3-5 e & f)
Spiral
(Figure 3-5 i & j)
Bead-packed Tower
(Figure 3-5 g & h)
5 to 100
1 to 100
10 to 100
5 to 50
5 to 3,000
500 to 100,000
40 to 500
500 to 2,000
Simple, non-plugging,
short gas-liquid con-
tact .
Easy to use, good gas
liquid contact,
subject to plugging.
Effective only at
low flow rates.
Efficient only at
low flow rates,
Resistance variable.
-------
1) At the desired sampling flow rate, will a
decrease in bubble size significantly
increase the collection efficiency of the
gas or vapor?
2) What amount of absorbing species is required
in order to collect the expected concentra-
tion of gas or vapor?
3) Will sufficient contact time of the gas
with the liquid exist to insure efficient
collection if the selected absorber is
used?
The particulates in the atmospheric aerosol may inter-
fere with the chemical analysis that follows absorption
sampling, and may cause clogging of the collection and meter
devices. If prefiltration is installed for the collection
of trace contaminants, any particles collected on the filter
should be analyzed in order to insure quantitative analysis
of sampled gas or vapor. The filter should also be non-
reactive and non-absorbing to the sampled gas or vapor.
Many dusts are highly absorbent, and often carry large
amounts of gaseous components in trace amounts on particles.
For the analysis of lead in the air, for example, absorp-
tion without prefiltration for alkyl lead can cause gross
overestimations of lead concentration because of the con-
-209-
-------
tribution of lead from inorganic particulates. The use of
a pretreatment — such as dehydrating agents to remove
moisture, soda lime for carbon dioxide, and liquid
scrubbing containing oxidizing agents — can result in
large systematic errors in analysis. The use of silica
based or anhydrous calcium sulfate granules for removal of
water or interfering substances may partially or completely
absorb the gas or vapor to be sampled as well.
Absorption is principally used for sampling inorganic
atmospheric gases that are soluble in an aqueous solution.
Because most absorption processes are accomplished by
chemisorption, and are analyzed by colorimetric and spec-
trophotometric techniques, the reagent is usually selected
on the basis of its efficiency in collecting the substances
of interest and its ability to limit the collection of
substances that would cause interferences or masking during
analysis. In most cases, the absorbent reagent will trap
a group of elements or compounds. The substance of in-
terest will be selected by using its chemical or physical
properties in the subsequent analytical technique. An
aqueous potassium iodide solution will accumulate halogens
such as Brp and do from the sampled air. The specific
element of analysis is then selected by precipitation dur-
ing sample preparation. Table 3-2 displays some of the
-210-
-------
specific reagents for chemisorption of a few inorganic
gases.
The major difficulties in using absorption for the
analysis of trace gases are the limited-volume sampling
rate, the susceptibility of the solutions to freezing and
evaporation, and the requirements for large amounts of
sample preparation for most analytic techniques. Because
the flow rates for most absorbers are in the range of a
few liters per minute, high gas collection efficiencies
are required in order to obtain reasonable sampling times.
3-2.2 Adsorption
Adsorption is largely a surface phenomenon. The amount
of absorbate collected in the process is dependent on the
total surface of adsorbent and the mass of the adsorbate.
Other factors that control efficiencies of adsorption are:
(1) nature of adsorbate and adsorbent; (2) geometric state
of the adsorbent; (3) temperature; (4) velocity of the air
stream; and (5) concentration of gas of interest and other
gas in the stream.
The adsorptive capacity of most columns is from 15 to
30 percent by weight. An adsorptive bed operates at high
efficiency until just before the capacity of the bed is
-211-
-------
reached. The adsorptive capacity of an adsorbent closely
parallels the critical temperature of the gas: gases with
critical temperatures below -50°C and boiling points below
-150°C are almost never adsorbed at normal temperature and
pressure. Compounds and gases with critical temperatures
between zero and 150°C are moderately adsorbable, and ad-
sorption is not quantitative at normal pressure and temp-
erature. The compounds and gases of low boiling point can
be adsorbed only if the adsorbent is refrigerated. Heavy
organic vapors (vapors with boiling points greater than
0°C) are easily adsorbed at normal temperature and pres-
sure by activated charcoal. Most heavy vapors demonstrate
increased adsorptivity with decreasing temperature.
Most common adsorbents are roughly granular in form,
and are supported in columns through which air is passed.
Those commonly used for air sampling are activated char-
coal, silica gel, activated alumina and other active earths
The electrically polar adsorbents, such as silicous oxides,
metallic oxides, and active earth compounds, attract polar
gases. Lipophilic polymeric resins may be used to concen-
trate many organic vapors.
Since the polarity of the adsorbed compounds or ele-
ments determines the strength of their binding on alumina
or silica gels, components with a higher polarity will
displace those with a lesser polarity. If the adsorption
-212-
-------
of benzene on silica gel is attempted in the presence of
phenol and acetic acid in the sampled air, the adsorbent
will act according to the principles of gas chromatography.
The benzene previously adsorbed on adsorptive beds will be
replaced by the phenol and acetic acid until the collection
process is completed. Under high humidity conditions the
polar adsorbent may be deactivated by saturation with water
vapor. Activated charcoal is usually selected for the
collection of non-polar gases and vapors from the atmosphere
since it exhibits this effect to only a limited degree.
On the other hand, recent studies utilizing gas chromato-
graphic techniques have shown that precautions must be taken
in the application of activated charcoal because charcoal
can act as a catalyst or oxidizing agent to some gases
and vapors adsorbed.
Methods employed for the desorption of the gases from
adsorptive beds are heating, while driving hot air or
super-heated steam through the bed, or eluting the adsor-
bates with a liquid solvent. Compounds desorbed from beds
by steam or hot air can be condensed and collected in oil
and aqueous fractions. The application of steam sometimes
presents difficulties for the desorption of organic com-
pounds because it can cause the compounds to hydrolyze,
resulting in a quantitative change in the yield of the
-213-
-------
accumulated substance. The elution of an adsorptive bed
by increasing vacuum may be used for fractionization.
The tenacity of the forces which provide for quantita-
tive extraction of the components from the air may cause
great difficulty when desorption of the collected compounds
is attempted. Mercury metal or volatile organic derivatives
are not desorbed quantitatively either by heating or by
elution with liquid reagents from silica gel. Activated
charcoal, when used for lead components, demonstrates the
same properties. Some non polar aromatic hydrocarbons are
irreversibly adsorbed in activated charcoal.
Organic molecules from the air can be readily adsorbed
on lipophilic solid supports either at ambient temperature
or with cooling (see Condensation - 3-2.3). The adsorp-
tion is due to the attraction between the lipophilic
adsorbent and the lipophilic adsorbate. The adsorbing
resin is usually packed into a tube through which an air
sample is drawn. This acts as a chromatography column with
air as the eluting mobile phase. As with all such systems,
an adsorbed compound will have a retention volume (of air
introduced into the column) above which it begins to elute
from the column. The size of the air sample which can be
used to accumulate a given substance is determined by this
volume, which depends upon the adsorbent, the column
-214-
-------
temperature and the air flow rate.
The adsorbents which have been used to collect organic
compounds from the air include many of the standard gas
chromatography supports. In addition to these, both activated
carbon and silica gel have been employed. These supports
vary widely in their ability to adsorb hydrocarbons, and
they are often chosen with characteristics which match the
GC column in which the analysis takes place. Heat desorp-
tion into the GC or a trap (usually packed with another
adsorbent and often cooled) is used almost universally,
although some investigators have used solvent extractions
to remove the concentrated organics from the adsorbing
column. The desorption step will often limit the types of
molecules which can be analyzed.
A major advantage of the lipophilic adsorbents is that
they do not retain water vapor from the air and they are not
affected by it. Silica gel has been used for analyses of
benzene and toluene, but the air must be dried by molecular
sieves before reaching the silica gel since moisture de-
activates the silica. Desorption of polar organics from
silica can be very difficult, making it a more limited
accumulating material than many of the other adsorbents
which are now in use.
^Activated carbon has been used for collection of air
-215-
-------
pil
pollutants. Grob and Grob in Zurich, Switzerland have
made use of small traps containing about 25 milligrams of
cigarette filter charcoal to collect pollutants from the
Zurich atmosphere. The organic compounds were subsequently
desorbed with carbon disulfide, a solvent selected for its
intermediate polarity and for its low response in a flame
ionization detector. Analysis of these extracts was per-
formed with very elegant high resolution capillary column
gas chromatography in combination with mass spectrometry.
The compounds identified included a variety of normal al-
kanes, a considerable number of alkyl benzenes, and some
alkyl substituted polycyclic aromatic hydrocarbons. All
of these compounds could be attributed to pollution of the
Zurich atmosphere by automobile exhaust.
The same authors also studied the collection efficiency
of their system by using two carbon filters in series. The
collection efficiency for compounds less volatile than do-
decane was approximately 90%- However, for more volatile
compounds the collection efficiency was 50% to 30%.
The Porapak series is another group of lipophilic ad-
sorbents which have been used for the accumulation o.f
Grob, K. and G. Grob. "Gas-Liquid Chromatographic-
Mass Spectrometric Investigation of Cg-CpQ Organic
Compounds in an Urban Atmosphere" . J_._ Cnromato-
graphy, Vol_._ 6_2: 1-13 (1971).
-216-
-------
organic compounds from both air and water. Work by Williams
25
and Umstead has demonstrated the applicability of Porapak
Q and S to the accumulation of small halogenated hydro-
carbons from the atmosphere. The Porapak beads were 80-
100 mesh packed in 6 foot by 1/4 inch stainless steel
columns. Accumulation of various freons and chlorinated
ethanes and ethylenes at a level of about one part per
million was demonstrated for calibration samples. Precis-
ions of about 10$ and recoveries in excess of 95% were ob-
tained with these techniques.
Another polymeric lipophilic adsorbent used in the
analysis of air is Chromosorb 102. This is a high surface
area, styrene-divinyl benzene copolymer which is very similar
to the Porapak series. Air flow rates of approximately 4
liters per minute over collection periods of several minutes
have given an analytical sensitivity of approximately lO"1^
grams per liter of air. Satisfactory blank analyses with
these materials were also carried out, indicating no con-
taminants in the resin.
Another lipophilic adsorbent of potential use is closely
related to gas chromatographic column packings; it consists
25. Williams, F.W. and E. Umstead. "Determination of
Trace Contaminants in Air by Concentrating on Porous
Polymer Beads". Anal. Chem. 40:2232-4 (1968).
-217-
-------
of support-bonded silicones such as stearic acid bonded to
o £
a silica by chemical ester bonds. W. A. Aue and Teli .
have shown that these materials can accumulate organic
compounds from polluted air with considerable effective-
ness. In operation, the solid adsorbent is packed in a
tube, air is pumped through it, the support is extracted
with pentane, and the pentane extract is evaporated and
analyzed by gas chromatography. The air samples analyzed
included auto exhaust and chlorinated hydrocarbons, but
these were laboratory studies and were not based on real
environmental problems. The authors discuss two limita-
tions of these materials. One is the occasional occurrence
of artifacts, and the second is the restriction of these
materials to collection of the less volatile components
of the atmosphere.
27
J. P. Mieure and M. W. Dietrich of the Monsanto
Chemical Company in St. Louis used lipophilic adsorbants
for the analysis of trace organic compounds in both air
and water. They recommend the use of porous polymer bead
columns of 4 to 6 inches in length, for which flow rates
26. W.A. Aue and P.M. Teli. "Sampling of Air Pollutants
with Support-Bonded Chromatographic Phases." J.
Chromatography , 6_2:15-2? (1971).
27. J.P. Mieure and W.B. Dietrich. "Determination of Trace
Organics in Air and Water". J_._ Chrom. Sci., II:559-
69 (1973).
-218-
-------
of 1/2 to 2 liters per minute can be achieved. These short
porous polymer bead columns were subsequently analyzed by
insertion into either the injection port of a gas chrom-
atograph or into the chromatographic oven directly
preceeding the analytical column. These authors have
used three lipophilic adsorbents:
' (1) Chromosorb 101, useful for acidic and
neutral components;
(2) Chromosorb 105, useful for low boiling
components; and
(3) Tenax GC, useful for basic, neutral and
high boiling components.
They recommend the use of these three columns in parallel
when attempting the analysis of an unknown air sample.
? R
Zlatkis has also found Tenax columns to be excellent
adsorbers of volatile organic compounds from air.
The use of solid supports for the adsorption of organic
molecules is even more advantageous for air analysis than
it is in the analysis of aqueous samples. For quantitative
results, the air volume which is pumped through the resin
must be accurately measured. The sample, once collected,
28. Zlatkis, A., Lichtenstein, H.A. and A. Tishbee.
Chromatographia, 6:67 (1973).
-219-
-------
can then be easily stored in the collection column until
analysis can be carried out. This form of storage is much
more convenient than the use of large bags for grab samples.
More tests are needed to determine the stability of
organic compounds from the air when they are adsorbed onto
resins for long periods of time. It has been found, however,
that very little sample loss occurs in sealed resin-filled
tubes when they are stored at low temperature.
The resins used for adsorption must be carefully cleaned
before they are used, but after collection there is very
little sample manipulation needed in order to analyze the
sample, thus minimizing the danger of contamination. Some
automatic sampling and analysis devices based upon the use
of a solid adsorbent have already been designed. For the
analysis of most lipophilic organic molecules from air, the
use of solid adsorbents appears to be preferable to cryogenic
trapping, the other alternative.
A current application of adsorption for air sampling
is the impregnation of filter materials of paper tape and
other samplers with adsorbing reagents. Atmospheric hy-
drogen sulfide has been collected with a filter containing
silver nitrate. Other compounds collected by this method
are boron hydrides, Cl , chromic acid, HF, and NH . The
sampling of mercury vapor by gold amalgamation has been
-220-
-------
29
developed by Bullock and Kalb for sampling source emis-
sions containing high concentrations of sulfur dioxide.
The adsorption of mercury onto silver wool has been eval-
uated for application for measuring ambient air concentrations
Q n ° 1
of mercury vapor.^ Scaringelli, et al.J have advanced
a method for determination of total mercury by adsorption
on activated charcoal with analysis by ultra-violet spec-
trophotometry.
3.2.3 Condensation
Cryogenic trapping is probably the most popular
method for accumulating volatile compounds from an aerosol.
The basic principle involved is the lowering of the temper-
ature far enough so that the desired accumulant is condensed
into a trap. Liquid air, liquid nitrogen and dry-ice in
acetone are usually employed for cooling the trap.
29. Bullock, C. and G. W. Kalb. The Determination of
Mercury in Stack Gases of High SO Content by the
Gold Amalgamation Technique. Tradet, Inc.,
Environmental Protection Agency, EPA #R2-73-153.
30. Long, S.J., et al. "Atomic Absorption Determination
of Elemental Mercury Collected from Ambient Air on
Silver Wool". 165th National Chemical Society Meet-
ing, Dallas, April 8-13, 1973-
31. Scaringelli, P.P., et al. "Determination of Total
Mercury in Air by Charcoal Adsorption and Ultraviolet
Spectrophotometry." 165th Nat'1. Amer. Chem. Soc.
Meeting, Dallas, April 8-13, 1973-
-221-
-------
The choice of cooling temperature depends upon the vola-
tility of the desired compound as well as the volatilities
of the major components of a given air sample.
A major difficulty with cryogenic trapping is the large
amount of water in most atmospheric samples (1 £ of air
at 25°C and 50% relative humidity contains 11 mg. of
water vapor). Accumulated organic trace compounds are thus
swamped by the volume of condensed water in the sample and
usually must be extracted from it with an organic solvent.
When liquid No or liquid air are used, COp, 0 , and some-
times Np condenses in the trap. This problem can be over-
come by lowering the pressure across the trap or by allowing
these gases to escape as the sample slowly warms. Water
vapor and CO can also be adsorbed before trapping with
molecular sieves and ascarite, respectively.
A second problem with cryogenic trapping involves the
formation of a micro-fog which passes through the trap in
the air stream and causes loss of a portion of the sample.
The use of packing materials in a trap or filters before
•30
the outlet reduces this problem, but Kaiser has found that
a 4 mm column of molecular sieves cooled with liquid- N? at
32. Kaiser, R.E. Anal. Chem., 45:965 (1973).
-222-
-------
a flow rate of 2£/hr. has a constant loss of about 10 ppb
of hydrocarbons. Kaiser has developed a temperature grad-
ient trap which cools the sample gradually, which he bel-
ieves has eliminated this problem for packed traps.
The types of traps used for the collection of organic
matter vary widely. The simplest are either thin metal
tubes, usually coiled, which run through a Dewar containing
the liquid N or stoppered tubes with air inlet and outlet
tubes. Often two or more of these '.ubes are used in series
to assure complete trapping of the volatile components.
Much of the current work involves the use of adsorbents in
the trap to further hinder the loss of organic volatiles.
Methane has been accumulated on carbon molecular sieves
00
at liquid nitrogen temperatureJJ while it passed through
an unpacked tube at the same temperature.34 A number of
different GC phases have been used in these traps, including
Carbowax, silica gel, molecular 'Sieves, Porapaks and
Chromosorbs.
Once the volatile constituents of the atmosphere have
been trapped, they must be made suitable for further
33. Kaiser, R.E. Anal. Chem. ^5:965 (1973).
34. Cooper, J.C., Birdseye, H.E. and R.J. Donnelly.
Environ. Sci. & Tech., 8:671 (1974).
-223-
-------
analysis. For organic molecules this almost invariably
means the use of a GC or GC/MS. The usual preparative
procedure is to extract the organic fraction from the water
that has been trapped with it, using an organic solvent such
as ether, chloroform or benzene. This solvent can then be
reduced in volume or used as is for injection into a GC.
This procedure can lead to the loss of water-soluble
organics such as oxygenated derivatives. If only the
volatile components are of interest, they may be distilled
from the water and heavier organics into another cold-trap
or directly into a GC. Most of the packed columns are
designed for simple heat desorption of the organic compounds
directly into a GC column or occasionally into another cold
trap. The development of the flame-ionization detector
(FID) has greatly facilitated this type of analysis because
of its relative insensitivity to water vapor, simplifying
the separation needed prior to analysis.
Two major difficulties with cryogenic trapping are the
clogging of lines with ice during sample collection and
its inconvenience as a field method for sampling. In most
studies, a bag sample is taken and the cryogenic trapping
is done in the laboratory. The use of low temperatures
has a great advantage, however, because it decreases the
possibility of reactions when the trapped pollutants become
-224-
-------
more concentrated. This usually means that samples can be
stored at low temperatures for periods of a few weeks
before an analysis is performed. For samples of high
volatility (i.e., methane), some form of cryogenic trapping
is absolutely necessary for accumulation.
-225-
-------
GLOSSARY OF TERMS
Aerosol: Finely divided solid or liquid particles sus-
pended in a gas. The term refers to a colloidal
system, with both a dispersed medium (particles)
and a dispersion medium (a gas). Includes
particles whqse sizes range from 50y to O.Oly
or less. (ly = 10~6 M.)
Atmospheric Aerosol: An aerosol whose dispersion medium
is air.
Particulate Size: For air pollution, the radius or dia-
meter of a spherical particle having the same
fall velocity with a density of 1 gm. cm~3.
The diameter is expressed in microns (y).
This definition is necessary because of -the
large variation of the density and shape of
atmospheric particles.
Total Suspended Particles: The term is used to describe
the actual measurement of suspended particles.
It is expressed as mass/volume of air sampled,
usually in ug/m^.
-226-
-------
TABLE 3-2
ACCUMULATION OF INORGANIC SUBSTANCES FROM AIR
The table has been prepared from a review of current
literature concerning sampling of inorganic substances
from air. Because much of the current literature collected
did not contain information about the specific methods of
accumulation of the substances, they were not included in
the table. Some of the original research for development
of sampling and analytical techniques was reviewed in order
to obtain an evaluation of the collection efficiency of
specific devices for the substances of interest.
Because surveys of the literature concerning the
analysis of mercury, ozone, nitrogen oxides and sulfur
oxides in air currently exist, the methods for concentrating
these substances have not been included in the table.
-227-
-------
ACCUMULATION OF INORGANIC SUBSTANCES FROM AIR
Accumulant
AsH3 (Arsine)
Boron Hydrides
(pentaborane,
decaborane)
Boron Hydrides
Br,
COC12 (Phosgene)
ci2
ci2
ci2
•TTC = trlphenylt
Accumulator
Type
Fritted tube
absorber
Continuous or
field model
analyzer
. Vlgreaux
bubbler
Midget
Impinger
Adsorption
Impinger
Midget
Impinger
Absorber
etrazollum chlo
Specific
Accumulator
Formulation
Silver diethy]
dithio carba-
mate (0.5?)
TTC* reagent
on paper or
tape
TTC in alka-
line solution
KI reagent
15* Kel-FlO on
Chromosorb T
or MS 5A
NaOH
KI reagent
Methyl orange
and HgSOjj
•ide
1
Samp line^*'^
Rat e^/Samp le
^*^ Volume
.0.5 4/min
1 ft/rain
0.5 Vmin
0.5 Z/min
0 . 5 * /min
Collection
Parameters
4 min sampling
time
1 hr sampling time
T » 20-*I00C
Recovery
and
Sensitivity
0 . 1 ppm
0 . 2 ppm
1 Vg
.1 ppm
Associated
Analytical
Method
Spectro-
photometry .
Reflectance
photometry
Spectro-
photometry
Spectro-
photometry
Colorimetry-
0-Tolidene
Spectro-
photometry
Reference
Saltzman (1961)
Kuhns , Porsyth, and
Mas! (1956)
Hill et al. (I960)
Saltzman (1961)
Basu, King and Lynn
(1972)
Katz (1969)
Saltzman (1961)
Katz (1969)
rv>
co
I
-------
ACCUMULATION OF INORGANIC SUBSTANCES FROM AIR
Accumulant
ci2
«2
ci2
cio2
CrO, (Chromic
3 Acid)
Fluorides
Accumulator
Type
Adsorption
Adsorption
Filtration
Midget
Implnger
Filtration
Implnger
Specific
Accumulator
Formulation
15$ Kel-FlO on
Chromosorb T,
Silica Gel, or
MS 5A
Modified Elin-
son Apparatus-
K boride-,
Na2CO.,- soaked
silica gel
with fluore-
sceine
Alkaline fil-
ter paper
KI reagent
Filter paper
impregnated
with 5-dl-
phenylcarba-
zlde reagent
NaOH and HgSO,,
S amp 1 inzx^x"^
Rate^X^Sample
^S" Volume
0.5 fc/min
600 mi.
hand pump
Collection
Parameters
Recovery
and
Sensitivity
99? at.lmg/m3
0.6 yg/m^
Associated
Analytical
Ket'nod
Alizarin
complexion
Spectro-
photometry
Colorlmetr'y
Alizarin lake
Reference
Basu, King and Lynn
(1972)
Ellnson et al.(1973)
Ito (1972)
Saltzman (1961)
Silverman and Ege
(1917)
Katz (1969)
I
INJ
rv>
M3
I
-------
ACCUMULATION OF INORGANIC SUBSTANCES FROM AIR
Accumulant
Fluorides
Fluorides
Fluorides
HCN
KCN
HCN
HC1
Accumulator
Type
Impinger
Fritted glass •
scrubber
Bubble or
implnger fol-
lowed by ion
exchange
Midget
Impinger
Fritted tube
Hi Vol Sampler
Midget
Impinger
Specific
Accumulator
Formulation
Titan ochromo
tropate
H20 or dilute
alkali
5% NaOH
5X NaOH
Glass fiber
filter impreg-
nated with
nickle ammo-
niate
0.01 N NaOH
^^ Volume
8 i/min
0.5 i/min
0.1 i/min
6 i/min
Collection
Parameters
10 rain sampling
Recovery
and
Sensitivity
.2 ppffi- in
solution
1002 1 ppb
100$ 0-10 ppb
100? 0.5 ug
Associated
Analytical
Method
Colorimetry
Spectro-
photometry-
Lanthanide-
Alizarin
complexan
reaction
Titration
Colorimetry
Colorimetry
Colorimetry
Titri.-netry
Reference
Katz (1969)
West, Lyles and
Miller (1970)
Nielsen and
Dangerfield (1955)
Saltzman (1961)
Saltzman (1961)
Tanaka et al.
(1973)
Saltzman (1961)
IV)
LO
O
I
-------
ACCUMULATION OP INORGANIC SUBSTANCES FROM AIR
Accumulant
HC1 and .Cl~
HP
HP
HP
H2S
H2S
Accumulator
Type
Midget
Implnger
Filtration
Silver tubes
Filled with
silver beads
Glass
impinger
Adsorption
Absorber
Specific
Accumulator
Formulation
Distilled
water
Alkaline
filter paper
NaCO- dried on
beads at 200°C
0.1 M NaOH
Modified Elin-
son Apparatus-
Zn acetate-
soaked marble
powder with
BaCl2
Alkaline
Cadmium hydrox
ide solution
Sampline^^
Rat e^^Samp le
^^^ Volu.-ne
2m3
66 l/min
1 4/min
Collection
Parameters
Recovery
and
Sensitivity
0.5 ppm
95? ,
2-500 ug/n^
Associated
Analytical
Method
Spectro-
p'r.ctorrietry ;
Nepheloraetry ;
Silver Ni-
trate titra-
tion
Alizarin
completion
Colorimetry
Reference
Katz (1969)
Ito (1972)
Buck and Stratmanr.
(1965)
Saltzman (1961)
Ellnson et al.
(1973)
American Chemical
Society (1973)
I
IV)
uo
h-1
I
-------
ACCUMULATION OF INORGANIC SUBSTANCES FROM AIR
Accumulant
H.SO,. (Sulfuric
2 q Acid)
K2S0l(
NH,
NH,
NH,
NH,
NH,
Accumulator
Type
Filtration
Absorber
Impinger
Impir.ger
Midget
Impinger
Filtration
Filtration
Specific
Accumulator
Formulation
Mineral Wool •
50$ ethanol
Dilute HgSOjj
H2S0;4
Boric Acid
Glass fiber
filter impreg-
nated with
sodium nitro-
prussiate
Glass fiber
filter soaked
in 2055 K2S°b
and dried
Sampline^^
Satex-^sample
^^^ Volume
30 i/min
1 i/min
1 fc/min
10 i/min
Collection
Parameters
Recovery
and
Sensitivity
80-10055.
95-5?
1 Ug
1-10 ppb
0.5-0.9 ppm
Associated
Analytical
Method
Nessleriza-
tion to form
color
Indophenol
analysis,
automatic
Indophenol
Analysis .
Technicon
auto-analyzer
Indophenol'
analysis
NHj, salts
analyzed by
pyridine py-
razolone
Reference
Billings, Kurker
and Silverman (1958)
Fudura et al. (1973)
Katz (1969)
Torii (1973)
Muramatsu et al.
(1973)
Chuone et al.
(197D
Kadowakl et al.
(1973)
I
ro
UJ
tv>
I
-------
ACCUMULATION OF INORGANIC SUBSTANCES FROM AIR
Accumulant
Os 0,
M -
PH, (Phosphine)
J
Pb and Zn
(simultaneously)
Pb and Zn
SiCljj
Accumulator
Type
Filtration
Adsorption
Greenburg-
Smlth Impinger
Electrostatic
precipitator
Adsorption
Specific
Accumulator
Formulation
Low-resistance
Whatman filter
paper
1% Mercuric
chloride in
0.1$ cresol
red in ethanol
5% HNO,
J
Kel-FlO on
Chromes orb T
SamplinE^^"^
Rat e -*^Sanip I e
^s^ Volume
75 H/hr
1 cfm
3 cfm
Collection
Parameters
2 hr sampling
35 min
12 min
Recovery
and
Sensitivity
0.06 ug
Associated
Analytical
Method
Colorimetry
Polarography
Polarography
Reference
HcLaughlin et al.
(1916)
Muthu and Kajurnder
(1973)
Landry (19^7)
Landry (19^7)
3asu, King and
Lynn (1972)
oo
I
-------
ACCUMULATION OF INORGANIC SUBSTANCES PROM AIR
BIBLIOGRAPHY
American Chemical Society. Instrumentation and Techniques
for Measurement of Air Pollution. New York: preprint
edition, 1973-
Basu, P. K.; King, C. J.; and Lynn, S. "A Three-Column,
Three Detector Gas Chromatographic Method for the Single
Sample Analysis of SiClj., Cl?, COClp, Ar, Np, Co, and
CO " J. Chromatographic Sci., 10: 479-80 (1972).
c. ——
Billings, C. E.; Kurker, Jr., C.; and Silverman, L. "Simul-
taneous Removal of Acid Gases, Mists, and Fumes with
Mineral Wool Filters." J . A . P . C . A . , 8_: 185-202 (1958).
Buck, M., and Stratmann, H. "Analytical Methods for Trace
Particulates." Brunnst-Chem. ^6:231 (1965).
Chuone, B. T.: Nanat, A.; and Zakartchenko, S. "Contribution
to the Measurement of Ammonia Concentration in Air
by the Indophenol Method Using Dry Supports." Proc.
Colloq. Int. Atmos. Polluees llth (Paris, FranceT:
p. 35-1 (1974).
Elinson, M. M.; Nosova, L. A.; and Ovchinnikov, I. M. "Method
and Apparatus for the Determination of Small Concen-
trations of Acid Gases." Zovodsk. Lab 3: 272-74 (1973).
Fudura, Masanori; Kanasaki, Teruo; Yamaoka, Shigeo; and
Oka, Michio. "Discussion of Sulfuric Acid Aerosol
Determination." J. Japan Soc. Air Pollution 8^:267 (1973).
Hill, W. H. et al. "Determination of Decaborane and Penta-
borane by Means of Triphenyltetrazolium Chloride."
Amer. Ind. Hyg. Assoc. J. 2JL: 231-38 (I960).
Ito, Shonosuke. "Methods and Tools for the Measurement of
Hydrogen Fluoride and Chlorine Gases." PPM (Japan)':
41-47 (1972).
Kadowaki, Suzushi; Koike , Kazumi; and Kojima, Ichiro.
"Determination of Micro Ammonium Salt in Air (II)--
Influence on the Method for Determination of Atmos-
pheric Ammonia (II)." J. Japan Soc. Air Pollution 8_:
270 (1973).
-234-
-------
Katz, M. Measurement of Air Pollutants, Guide to the
Selection of Methods. (1969).
Kuhns, L. J.; Forsyth, R. H.; and Masi, J. F. "Boron Hydride
Monitoring Devices Employing a Triphenyltetrazolium
Chloride Reagent." Anal. Chem., II: 1750-1752 (1956).
Landry, A. S. "The Simultaneous Determination of Lead and
Zinc in Atmospheric Samples." J. Ind. Hyg. Tox., 29 :
168-173 (19^7).
McLaughlin, A.I.G.; Milton, R.; and Perry, K. M. A. "Toxic
Manifestations of Osmium Tetroxide." Brit. J. Ind.
Med., 3_: 183-186 (1946) .
Muramatsu, Manabu; Seki, Akiko; Miyai, Shinkichi; and
Mori, Masaki. "Analysis of Gaseous Ammonia in Atmos-
phere by Ion-Active Electrode." J. Japa.n Soc. Air
Pollution 8: 262 (1973).
Muthu, M., and Majumder, J. K. "A Chromogenic Column for
Determining Phosphine in Air." Pestic. Sci., 4_: 707-
711 (1973).
Nielsen, J. P., and Dangerfield, A. D. "Use of Ion Exchange
Resins for Determination of Atmospheric Fluorides."
Arch. Ind. Health., 11: 61-65 (1955).
Saltzman, Bernard E. "Preparation and Analysis of Calibrated
Low Concentrations of Sixteen Toxic Gases." Anal. Chem.
33.: 1100 (1961).
Silverman, L., and Ege, Jr., J. F. "A Rapid Method for the
Determination of Chromic Acid Mist in Air." J. _Ind.
Hyg. Tox. , 29.: 136-186 (19^7).
Tanaka, Akemi; Hori, Mashiro; and Kobayashi, Yoshitaka;
"Studies on the Collection of Trace Concentration GJ.
Compounds in Air by High Volume Air Sampler." J.
Japan Soc. Air Pollution, 8_: 593 (1973).
Torii, Kinji. "Continuous Automatic Analysis of Ammonia
in Air." J. Japan Soc. Air Pollution, 8: 261 (1973).
West, P. W.; Lyles, G. R.; and Miller, J. L. "Spectrophoto-
metric Determination of Atmospheric Fluorides .lf
Environ. Sci. Technol., ±: 487-^91 (1970).
-235-
-------
TABLE 3-3
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR BY COMPOUND
This table lists those compounds which have been analyzed
in air samples along with the accumulation method which was
used.
The accumulator is the system used for accumulation
(i.e. midget impinger) or, if a chemical is given, it refers
to an absorbent which was used in a column (i.e. Texax).
The desorption or extraction medium generally refers
to the method of taking materials from an absorbent resin
for analysis. Where collection was by absorption, however,
this column contains the name of the absorbing liquid.
All other information is given if it was included in
the original article.
-236-
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
Accurulant
cl - CH .
cl - C12
C2 - C6
c2 - c^,
c2 - c8
Accumulator
Carbon molecu-
lar sieves-lOcn
Porapak Q & S
Alumina
Molecular
sieves
Chromosorb P
deactivated wltl
di n-butyl
phthalate
Cryogenic trap
Cryogenic trap
Glass-wool
filter
Desorption •
or
Extraction
Medium
Temperature
gradient
<200«C
temp., gradient
n
120°C
heat with
hot water
distillation
ItcLb 6 ^^^^S&nplC
.S^ Volume
124/mln
H4
24/hr
1.54/hr
.52/min
(5 rain)
14
14/mln
2004
Collection
Parameters
-20° to liquid M2
temperature
gradient
-100°C
-20°C
-80°C
through drying agent
•IgClOjj or KCO,
llq. »2 77°K
liq. 62
(C02 removed with
as carl te)
Recovery .
and
Sensitivity
9^% at
.01 ppb
-100«
5 .
89-100$
Associated
Analytical
Method
GC-FID,
Carbon mole-
cular sieves
-20° -200-C
GC-FID
10$ DC 200 on
Supelcort Q
-60 - 150°C
GC-FID '
DC-200 on
Supelcort Q.
-60°- - 150°C
II
GC-FID
didecyl
phthalate on
Chromosorb' P
90°C
or • •
tri-m-tolyl
phosphate on
Chromosorb W
93° or 73°C
GC-FID
hexadecane or.
firebrick
Mass spectra
Reference •
Kaiser (1973)
Kaiser (1970)
Kaiser (19?0)
Williams (1965)
Feldsteln,
3alestrieri (1965)
Shepherd, et al.
(195D
I
rv>
uo
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Ascurulant
Cp - C,
£ \>
C2 ~ C5
^ J
C2 - C10
c xu
c2 - c
£ 3
c - c
C- J
c - ?
c.
C3 - C5
J J
c3 - c5
Accumulator '
Carbowax
Acid silica gel
#58
10$ Carbowax • •
1510 on gas
Chromosorb Z
Silica gel #15
12X molecular
sieves
Cryogenic trap
Layer trap
OV-17 on
Chromosorb G
silica gel, &
molecular sieve
5X & 13X
Porapak Q
Desorption
or
Extraction
Medium
room tempera-
ture
room tempera-
ture
room tempera-
ture
heat
heat
heat
heat
SamplinKx^
Ra t e .^"Samp 1 e
^^ Volume
77cc
90cc/mln
72cc
. lOOc'c
<100i
<_HQQ1.
<5Qt
Collection
Parameters
liq. N, 77°K
C.
liq. N-
C.
liq. H?
C.
21° - 24°C
11
liq. N 77°K
£.-
<24"Hg pressure •
21° - 24°C
ii
Recovery
and
Sensitivity
l-3000ppb
95*
95<
Associated
Analytical
Method
GC-FID
dibutyl
maleate
0°C
GC-FID
acid silica
gel 30°C
GC-FID
15% dibutyl
maleate or
acid Chromo-
sorb G
25°C
GC-FID
ii
total carbon
analyzer •
GC-FID
n
Reference
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
iceunul^t
c3-c5
C3 - C5
CU - C7
CU - C8
C1 - C15
C1 - C15
S - C5
c5-.c6 _
ci - cio
Accumulator
Chromosorb 103
Silica gel #58
10? Carbowax
151)0 on Gas
Chrom Z
Tenax GC
Dexsil 300 on.
Chromosorb W .
10? Carbowax
1510 on fire-
brick
Cryogenic trap
Cryogenic trap
Desorption
or
Extraction
Medium
room tempera-
ture
heat
hot water
heating
hot water
heating
room tempera-
ture
Sampl ing>^
Rat e^x-'sample
^/"^ Volume
C to liq. N'2
temp, gradient
liq: N2
liq. N2
liq. air
Recovery
and '
Sensitivity
95? .
>90%
.Ippb
99?
Associated
Analytical
Method
GC-FID
GC-FID
GC-FID
dibutyl
rr.aleate
acid silica
gel
30°C
GC-FID
-etched Hi
with Emulpho
30°' - 170°C
GC-FID
DC 200 on
Kieselguhr
-80° - 150°C
GC-FID
bs-2(methoxy
ethyl) adl-
pate
37°C
GC-FID
silicon on
firebrick
GC-
polyethyiene
glycol or
DC 550 sill-
cone
Reference
aellar, Sigsby
(unpublished)
• ii
Kopczynski, et al.
(1972)
Lorine'man , et al .
(197D
Bertsch, Chang,
Zlatkis (197D
Kaiser (1973)
Be liar, Brown,
Sigsby Jr. (1963)
Felcstein,
Balestrieri (1965)
Hughes , Hurn
(I960)
I
(V)
uo
-------
ACCUMULATION OF ORGANIC SUBSTANCES PROM AIR '
„„=,««
C6 - C20
c7 - cl4
C8 " C18
C9 - C18
alkanes •
C1-C3
Alkanes and
Alkenes
Isobutane
n-Butane
Butene-1
trans-Butene-2
cis-Butene-2
Accumulator
eigarette-filte
charcoal
Support-bonded
silicones
(Cl8H37S103/2)
on Chromosorb A
Graphitized •
carbon black
Tenax GC
10? sucrose
acetate on
Gas Chrom Z
Carbowax 15 kO
Desorption
• or
Extraction
Medium
extraction
with CS-
75°C *
extraction
with pentane
' ioo°c
100°C
heat-hot water
*3. & s ^^^^s&inp IG
's' Volume
2.5i/min
25n3
184/mln
2004
30-300cc/ir.in
Collection
Parameters
25° - 60°C
-55°C
Cincinnati Air
Liquid N2
Recovery
and
Sensitivity
Quantitative
6.0 ppb
<1.5
1.0
1.1
Associated
Analytical
Method
GC-MS
GC-FID
OV-101 on
Chromosorb V/
R.T. - 130°C
GC-FID
OV-101
Capillary
columns
GC-FID
5? Dexsll .
300 on
Chromosorb W
GC-FID
Porapak Q
160"C
GC-PID
Reference
Grob & Grob (1971)
Aue, Tell (1971)
Raymond, Guiochon
(1974)
Mleure, Dietrich
(1973)
Bellar, Sigsby, Jr.
(1907)
Bellar, Brown
Sigsby (1963)
-fr
O
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Aceusulant
Butadiene-1,3
Isobutylene
Isopentane
n-Pentane
3-Methyl-
butene-1
Petene-1
2-Methyl-
butane-2
cis-Pentene-2
Methane
Ethane
Ethylene
Acetylene
Propane
n-Butane
n-Pentane
n-Hexane
Accumulator
Carbowax 15^0
Chroraosorb 103
Desorption
or
Extraction
Medium
heat-hot water
heat
Sair.pling^X^
Rat e ^x^Sarap i e
^S^ Volume
30-300cc/mln
60-300cc/mln
<5*
20cc/min
Collection
Parameters
Cincinnati Air
Liquid N2
22"C
head-space
Recovery .
and
Sensitivity
1 . Oppb
<1.5
15.5
7.6
2.6
1.6
3-8
1.7
95?
retention
volume (1)
<10
<20
50
500
Associated
Analytical
Method
GC-FID
GC-FID
GC-FID
C101
Reference
Bellar, Brown, Sigsby
(1963)
Bellar, Sigsby
(Unpublished)
Bellar, .
Lichtenberg (197^)
I
IV)
-f
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Acc'i-ulant
Methane
Ethane
Acetylene
Propane
n-Butane
n-Pentane
n-Hexane
n-Dodecane
n-Tridecane
n-Hexadecane
n-Pentadecane
n-Nonane
n-Decane
Limonene
n-Pentane
2,3 Dimethyl
butane
n-Hexane
Methyl Cyclo-
pentane
n-Octane
2-Methyl
Octane
n-Undecane
Accumulator
Porapak
Porapak Q
Tenax GC
Desorption -
or
Extraction
Medium
heat
heat
heat
Sar.pllnex^
Rate ^-''Sample
^^ Volume
. <5l
20cc/mln
*
50-200cc/mln
Collection
Parameters
22°C
head-space
atmosphere In
Houston
Recovery .
and
Sensitivity
95!!
retention
volume (1)
<50
<100
<250
>500
1.3-15 ppb
1.6-1.1
0.0-5.7
Associated
Analytical
Method
•OC-FID
GC-FID
C101
GC-FIC
capillary
columns
Reference'
Bellar, Sigsby
(Unpublished)
Bellar, Lichtenberg
(197D
Bertsch, Chang,
Zlatkis (197D
IV)
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accu.-ulant
n-Hexane
n-Hexadecane
n-Heptadecane
n-Ootadecane
n-Nonadecane
n-Elcosane
Limonene
Isododecane
Isotridecane
n-Dcdecane
2-Methyl-
hexane
n-Heptane
Isooctane
n-Octane
Isononane
n-Nonane
Isodecane
n-Decane
Isoundecane
n-Undecane
Accumulator
Tenax GC
Cigarette
Filter
Charcoal
•
Desorption
or
Extraction
Medium
heat
extraction c~
CS2 72°
Sampling.-^
Rate ^-^Sarap 1 e
^S^ Volume
20cc/min
2.5 1/min
25m3
Collection
Parameters
head-space
Recovery .
and
Sensitivity
retention
volume (1)
>500
Associated
Analytical
Method
GC-PID
C101
GC-MS
Reference.
Bellar, Lichfcenberg
U97'0
Grob & Grob
(1971)
I
ro
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accuzulant
n-Tridecane
Isbtetrade-
cane
n-Tetradecane
n-Pentadecane
n-Pentadecane
n-Hexadecane
n-Keptadecane
n-Dodecane
Isotridecane
Isotetrade-.
cane
n-Decane
Isoundecane
Decahydrona-
phthalene
Isododecane
1-octene
n-Octane
1-nonene
Isonane
n-Nor.ane
Isodecane
Accumulator
Cigarette
Filter Carbon
Graphltized
Carbon Black
,
Desorption •
or
Extraction
Medium
extraction c~
CS2 72"
400°C
Sampling^/'
Rate .X^ample
.S^ Volume
.2.5 Jl/min
25m3
. 5 i /rain
200 S.
Collection
Parameters
Recovery .
and
Sensitivity
Associated
Analytical
Method
OC-MS
GC-FID
OV-101
capillary
column
-
Reference
Grob & Grob
(1971)
Raymond , Guiochon
(1971)
I
IV)
-Cr
-------
ACCUMULATION OF ORGANIC SCJBS7ANC2S FROM AIR
Ascusulant
Ethylene
Ethylene
Acteylene
Ethane
Ethane
Ethylene
Acetylene
Haloger.ated
Hexachloro-
butadiene
Accumulator
Silica Gel
12x Holecular
Sieves
Layer Trap
(7$ OV-17 on
chromosorb G
+ silica gel
+ 13x & 5A
molecular
sieves )
Scrubber
Hg(C101<)2 on
dlatomaceous
earth
Chromosorb 101
Desorption •
or
Extraction
Medium
100°C
heat
heat
hexane
Sampling/'^
Rat e ^XSample
.s — Volume
550cc/min
2500cc/min
200cc/min
<20i
<25t
i50^
3£/min
Collection
Parameters
o°c
-78°C
-78°C
22°C
22eC
Room temperature ;
must be dry
ar.bient temperature
up to 90°C
Recovery .
and
Sensitivity
>90?
(C.2p.pm)
1002
lOppb
95%
95%
88-lOOg
Associated
Analytical
Ketnod
color
reaction
GC-PID
GC-FID
GC-PID
GC-PID
OV-17
150°C
Reference
Stitt, Tominatsu
(1953)
Stitt, Tomirnatsu
(1953)
Hughes, Gordon
(1959)
Eellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
Mitsuo, Aoyaraa,
Yamaki (1971;)
Mann, et al.
(1971)
I
rv>
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Ace'^n:ulant
Methylene
chloride
Chloroform
CClj,
C2C1 H
Methylene-
chlorlde
Chloroform
1,1 Dichloro-
ethylene
C12FCCF2C1
CHC1,
CHjCCl
Chloro-
.ethylene
Accumulator
Chromosorb 103
Chromosorb P
deactivated
with di-n-butyl
phthalate
Porapak Q
Porapak Q
Desorption •
or
Extraction
Medium
heat
120°C
heat
on-column
adsorption
heat
Sair.pllRe^x^
Rat e .x'Sample
^>r Volume
20cc/min
•54/min
20cc/min
100cc-500cc
Collection
Parameters
head-space
-80-C dried with
MgCIO,, or KCO,
head-space
30°-50°C
Recovery .
and
Sensitivity
retention
volume (1)
500 •
500
-100$
retention
volume (1)
500
500
•
Associated
Analytical
Method
GC-FID
°im
101
GC-
didecyl
phthalate on
Chroir.osorb P
90°C "
GC-FID
C101
GC-
coulometric
detector
Reference
Bellar,
Lichtenberg (1971.')
Williams (1965)
Bellar,
Lichtenberg (1971)
Williams & Umstead
(1968)'
I
IV)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Ascuzulant
CC12F2
CC1,F
C12FCCC1F2
BrF2CCBrF2
CHjCClj
CHC1=CC12
cci2=cci2 .
CHC1
Tetrachloro-
ethylene
Methlene-
chloride
Chloroform
Accumulator
Porapak S
Porapak S
Tenax GC
Tenax GC
Desorption
or
Extraction
Medium
on-column
adsorption
heat
on column
concentration
heat
heat
Rat e ^X^arnp 1 e
.s^ Volume
100cc-500cc
lOOcc
50-200cc/mln
20cc/mln
Collection
Parameters
30°-50*C
SO'-SO'C
atmosphere in
Houston
head-space
Recovery .
and
Sensitivity
retention
volume (1)
500
500
Associated
Analytical
Method
GC-
coulometric
detector
GC-
coulometric
detector
GC-FID
capillary
columns
GC-FID
C101 •
Reference
Williams & Umstead
(1968)
-.
Williams & Urastead
(1968)
Bertsch, Chang,
Zlatkis (1971)
Bellar,
Lichtenberg (1971)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR "
Aceuzulant
CH2C12
CHC1
C1,CCH
ClgCCHCl
ci2ccci2
General
esters &
. ethers
Trichloro-
ehtylene
C2C1D
Tetrachloro-
ethylene
Trichloroethane
Accumulator
Tenax GC
Activated
carbon
Cigarette
filter
charcoal
Silica Gel
Desorption
or
Extraction
Medium
heat
heat
decane
cs2
extraction &
pc 70 op
COp [£ (s
cumine,
pyrldlne or
Et20
Rat e ^-^Samp 1 e
^^ Volume
20cc/min
13cfm
SOOcc/min
60i
2.5i/nin
2.5^in
Collection
Parameters
head-space
dry ice
Recovery .
and
Sensitivity
3-8 ppb
7-12
8-16
9-1)0
3-6
95-1002
90*
Associated
Analytical
Method
'GC-PID
C101
IR
GC-capillary
columns
GC-
SE-30 on
Chromosorb
110°C
GC-HS
GC-MS
Colorimetry
Reference '
Bellar,
Lichtenberg (WO
Turk, D'Angio (1962)
Herbol she liner ,
Funk, Drasche
(•1972)
Grob & Grob (1971)
Grob & Grob (1971)
Ogata, et al. (1973)
I
IV)
-Cr
OO
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM AIH
Accu.-ulant
Dlchloro-
methane
CClj,
C13C2H
Perfluoroiso-
butylene
Hexafluoro-
propene
CH Br
j
Acids
N-butyric acid
Isovaleric
acid
Alcohols
and Thiols
Methanethiol
2-propanethlol
Accumulator
1,2,3-tris
(2-cyanoethoxy)
propane on
Chromosorb W
Cryogenic Trap
Glass Wool
Filter
Midget
Impinger
Implnger
Filter paper
with 10% NaOH
.
Chromosorb P
deactivated
with dibutyl-
phthalate
Desorptlon
or
Extraction
Mediun
heat:
distillation
MeOH •
5% KOH in
EtOH
concentrated
HCl/hexane
120°C
Sampllng^-^
Rate .x^Sample
.s^ Volume
50cc/min
li/min
200i
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Acc'Aiulant
EtOH
Propanol
Methanol
Methanol
Ethanol
2-Propanol
Allyl Alcohol
2 Methyl
Pi-opane-2-ol
2-Methyl
Propanol
Propylene
Glycol
Triethylene
Glycol
Accumulator
Chromosorb P
deactivated
with di-n-butyl
phthalate
Porapak Q
Polyethylene
Glycol 100
1,2,3-tris
(2-cyanoethoxy)
propane on
Chromosorb W
1,2,3-tris
(2-cyanoethoxy)
propane on
Chromosorb W
Folln
aeration- tubes
Desorption
or
Extraction
Medium
120?C
heat
heat
water
Sampling^. —
Rate ./-^Sample
^*r Volume
.5l/»in
50cc/rain
SOcc/min
3001
20-304/min
Collection
Parameters
-80°C dried with
MgClO^ or KCO
•*
21°C
Recovery .
and
Sensitivity
-100?
70-80?
95-97?
Associated
Analytical
Method
f)C-
didecyl
phthalate on
Chromosorb P
90°C
GC-Porapak Q
160"C
GC-
Celite 515 +
Apiezon L
GC-FID
Porapak Q
GC-FID
Porapak Q
Colorlmetry
Reference'
Williams (1965)
Bellar, Sigsby
(1970)
Novak, Vasak,
Janak (1965)
Bellar, Sigsby
(1970)
Bellar, Sigsby
(1970)
Vise, Puck, Stral
(1967)
I
IV)
VJ1
o
I
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM AIR
Accu=ulant
Esters
EtOAc
Methyl
Acetate
Ethyl
acrylate
Methyl
methacrylate
Malelc
annhydride
Accumulator
Chromosorb P
deactivated
with dl-n-butyl
phthalate
1,2,3-tris .
(2-cyanoethoxy)
propane on
Chromosorb W
Kldget
impinger
Chromosorb 101!
20$ Trlcresyl
phosphate on
Chrom W(HP)
100/120
25J Didecyl
phthalate on
Chrom P
100/120
Oxyproplo-r
nltrlle/Poracll
C 80/100
Porapak Q
Desorptlon
or
Extraction
Medium
120°C
heat
KMnOjj/NaOH
(not removed)
Sa.-npllngxxx^
Rate^x^Sanple
^S^ Volume
.54/min
50cc/mln
300cc/mln
.25i/mir.
Collection
Parameters
-80°C dried with
MgCIO,, or KCO,
Recovery .
and
Sensitivity
-100?
m
80
20.
50
90
90
Associated
Analytical
Method
GC-
didecyl
phthalate on
Chroncsor'o ?
90°C
GC-FID
Porapak Q
Colorlraetry
GC-FID
Reference '
Williams (1965) .
Bellar, Slgsby
(1970)
Gisclard, Robinson,
Kuczo, Jr. (1958)
Pellizzari, et al.
(1975)
I
rv>
VJl
-------
ACCUMULATION CP ORGANIC SUBSTANCES FROM AIR
Accurulant
Malelo
annhydride
-
B-Propio-
lactone
Accumulator
20? Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Carbowax 400/
Poracil C
100/120
Chroir.osorb 101
Tenex GC
Activated
carbons
Chromo'sorb 101)
20$ Trlcresyl
phosohate on
Chrom W(KP)
100/120
252 Dldecyl
phthalate on
Chrom P
100/120
Oxypropio- •
nitrile/Poracil
C 80/100
Porapak Q
Desorption •
or
Extraction
Medium
(not removed)
(not removed)
Sar.pl inex"^
Rat e ^''Ifample
^s^ Volume
.25Jl/min
.251/min
Collection
Parameters
Recovery .
and
Sensitivity
90%
95
95
80 .
0-90
98
20
50
98
90 .
Associated
Analytical
Method
GC-FID
GC-PID
Reference •
Pellizzari, et al.
(1975)
Pellizzari, et al.
(1975)
I
rv>
ui
r\j
I
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM AIR
Aecusulant
B-Proplo-
lactone
Ketones and
Aldehydps
Acetone
Acroleln
Acetone
Butanone
Cyclohexanone
Accumulator
20% Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Carbowax 100/
Poracil C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
Chromosorb P
deactivated
with di-n-butyl
phthalate
Porapak Q
Silicone E301
on Celite 515
Desorption •
or
Extraction
Medium
(not removed)
120°C
120-C
Sampllng-Xx^
Ra't e ^x^Sample
^S^ Volume
. .25£/min
.5*/min
lOOcc/mln
<230cc
Collection
Parameters
-80°C dried with
MgClO^ or KC03
.5mm Hg
pressure drop
Recovery .
and
Sensitivity
90%
90
95
95.
90-95
-100.
Associated
Analytical
Method
"GC-PID'
GC-
didecyl
phthalate or.
Chro.T.osorij ?
90°C
GC-Porapak Q
160"C
GC-FID
Silicone E301
on celite
Reference.
Pelllzzari, et al.
(1975)
Williams (1965)
Bellar, Sigsby
(1970)
Cropper, Kamlnsky
(1963)
uo
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES ?HOM AIH
Accunulant
Ootenal
Acetone
Acetaldehyde
Acrolein
Propanal
. Acetone
2-Methylpro-
panal
Butanal
Methylethyl-
ketone
Methyl
Formate
Ethyl Formate
Methyl
Acrolein
Vinyl Methyl
Ketone
2,3-Butane-
dlone
Accumulator
Cigarette
Filter Charcoal
Polyethylene
Glycol bOQ
1,2,3-tris
(2-cyanoethoxy)
propane on
Chromosorb W
•
Desorptlon •
or
Extraction
Medium
extraction c"
CS2 72°
heat
Sampling./^
Rat e .XSamp le
^/^ Volume
2.5Vmin
25mi3
50cc/mln
Collection
Parameters
24eC
Recovery .
and
Sensitivity
•
Associated
Analytical
Method
GC-MS
GC-
Celite 515 +
Aplezon L
GC-FID
Porapak Q
Reference •
C-rob & Grob
(1971)
Novak, Vas£k,
Janak (1965)
Bellar, Sigsby
(1970)
-t
I
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM AIR
Aceuzulant
Cyclobutanone
Crotonalde-
hyde
2,2-Dimethyl
Butanal
Methyl Ethyl
Ketone
Accumulator
1,2,3-tris
( 2-cyanoethoxy )
propane on
Chromosorb W
Chromosorb 10^
20$ Tricresyl
phosphate on
Chrom W(HP)
100/120
25$ Dldecyl
phthalat'e on
Chrom P
100/120
Oxyproprio-
nitr-ile/Poraoil
C 80/100
Porapak Q
20? Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Carbowax kOO/
Poracil C
100/120
Desorptlon
or
Extraction
Medium
heat
(not removed)
•
Sampling^^^
Rate^X^ample
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Acsusulant
Methyl ethyl
ketone
Ethers and
Oxides
Ether
Propyl ether
bis(chloro-
raethyl) ether
bis-Chloro-
meth
Ethylene
Oxide
2,3-Butylene
Oxide
Isobutylene
Oxide
Accumulator
Chromosorb 101
Tenax GC
•Activated
carbons
Chromosorb P
deactivated
with di-n-butyl
phthalate
Porapak Q
Porapak Q
1,2,3-tris
(2-cyanoethoxy'
propane on
Chromosorb W
Desorption •
or
Extraction
Kediun
(not removed)
120«C
180°C
180° .
under vacuum
heat
Sampling^
Rate ^/Sample
^^ Volume
.251/min
5l/mln
151
1-51/mln
151 at .
1.51/min
50cc/nln
Collection
Parameters
-8o°C dried with
HgClO^ or KCO,
Recovery .
and
Sensitivity
95?
95
90-95
-100
100
Quantitative
to 201
Associated
Analytical
Method
GC-FID '
GC-
didecyl
phthalate on
Chromosorb ?
90°C
Mass spectra
Mass. spec.
GC-FID
Porapak Q
Reference-
Pellizzarl, et al .
(1975)
Williams (1965)
Collier (1972)
Collier (1972)
Bellar, Sigsby
(1970)
I
tv>
VJI
CT:
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
Accunulant
1,2-Butylene
Oxide
Tetrahydro-
furan
1,2 Dichloro-
ethyl ethyl
ether
Accumulator
1,2,3-trls
(2-cyanoethoxy;
propane on
Chromosorb W
Chromosorb lO'J
20$ Trlcresyl
phosphate on
Chrom W(H?)
100/120
25% Didecyl
phthalate on
Chrom P
100/120
Oxyproprio-
nitrile/Poracll
C 80/100
Porapak Q
20? Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Carbowax llOO/
Poracil C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
Desorption •
or
Extraction
Medium
heat
(not removed)
Sampling/''^
Rate .X'San'.ple
^s^ Voluae
50cc/min
.25i/min
Collection
Parameters
Recovery .
and
Sensitivity
98?
20
50
98
90
90
90
95
95
90-95
Associated
Analytical
Method
GC-FID
Porapak Q
GC-FID
Referer.ee-
Bellar, Sigsby
(1970)
Pelllzzarl, et al.
(1975)
I
ro
\j\
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accusularit
Styrene
epoxide
Accumulator
Chroraosorb 10*1
20? Tricesyl
phosphate on
Chrom W(HP)
100/120
25? Didecyl
phthalate on
Chrom P
100/120
Oxypropio-
iltrile/Poracll
C 80/100
Porapak Q
20? Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Carbowax i|00/
Poracll C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
Desorption •
or
Extraction
Medium
(not removed)
Sampling/^
Rat e ./Samp i e
.S^ Volume
.251/min
Collection
Parameters
Recovery .
and
Sensitivity
90?
20
80
96.
95
90
90
95
90
30-95
Associated
Analytical
Method
GC-FID
-.
Reference .
Pellizzari, et al.
(1975)
I
ro
vjn
oo
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Aceusulant
Butadiene
diepoxide
Accumulator
Chromosorb 101)
20$ Tricresyl
phosphate on
Chrom W(HP)
100/120
25% Dldecyl
phthalate on
Chrom P
100/120
Oxyproplo-
nitrile/Poracll
C 80/100
Porapak Q
202 Carbowax '
600 on Chromo-
sorb W(HP)
100/120 mesh
Carbowax 400/
Poracil C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
Desorption
or
Extraction
Medium
(not removed)
Sampling/^
Rat e ^x^Samp le
^f — Volume
.254/min
Collection
Parameters
Recovery .
and
Sensitivity
90?
20
80
96
95
90
90
95.
90
30-95
Associated
Analytical
Method
GC-FID
Reference •
Pellizzari, et al.
(1975)
IV)
\J\
VD
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
Ace-i=ulant
Propylene
oxide
Accumulator
Chromosorb 101!
20!! Tricresyl
phosphate on
Chrom W(KP)
100/120
25? Didecyl
phthalate on
Chror. ?
100/120
Oxypropio-
nitrlle/Poraci]
C 80/100
Porapak Q
20? Carbowax '
600 on Chrono-
sorb W(KP)
100/120 mesh
Carbowax 400/
Poracil C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
Desorption •
or
Extraction
Medium
(not removed)
Sanplinsx^
Rate -^Sample
^^ Volume
.25i/min
Collection
Parameters
Recovery .
and
Sensitivity
902
20
80
96
" 95 .
90
90
95
90
30-95
Associated
Analytical
Method
GC-FID
Reference'
Pellizzari, et al.
(1975)
a\
o
I
-------
ACCUMULATION CP ORGANIC SUBSTANCES -PROM AIR '
Accunulant
Bis-(2-chloro-
ethyl) ether
Accumulator
Chroiaosorb 101!
20? Tricresyl
. phosphate on
Chrom W(HP)
100/120
25J Didecyl
phthalate on
Chrom P
100/120
Oxypropio-
nitrlle/Poracll
C 80/100
Porapak Q
20$ Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Carbowax 1)00/
Poracil C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
Desorption
or
Extraction
Medium
(not removed)
Sampllng^^
Ra't e .x^samp 1 e
^s^ Volume
.25i/min
Collection
Parameters
Recovery .
and
Sensitivity
801
20
50
90.
90
90
95
95
80
0-90
Associated
Analytical
Method
GC-FID
,
Reference .
Pellizzari, et al.
(1975)
I
rv>
CTN
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Aecurulant
Bis-(chloro-
' methyl) ether
Accumulator
Chromosorb 101!
20? Trlcresyl
. phosphate on
Chrom W(HP)
ICO/120
25' Didecyl
phthalate on
Chro^i P
100/120
Oxypropio-
nitrile/Poracil
80/100
Porapak Q
20? Carbowax
£00 on Chrome-
sorb W(HP)
iao/120 mesh
Carbowax JlOO/
Poracil C
100/120
Chrorr.osorb 101
Tenax GC
Activated
carbons
Desorptlon
or
Extraction
Medium
(not removed)
Sampling^"^
Rate^x^sample
^S^ Volume
.251/min
Collection
Parameters
Recovery .
and
Sensitivity
801
20
50
90
" 90 • •
90
95
95
80
0-90 .
Associated
Analytical
Method
GC-FID
Reference •
Pellizzari, et al .
(1975)
rv>
I
-------
ACCUMULATION CP ORGANIC SUBSTANCES FROM AIR
Acc\i=ulant
Other
Aliphatlcs
Methyl nitrate
Ethyl nitrate
Butyronitrate
Methyl sulfide
Methyl
dlsulfide
Trimethyl
phosphate
Acetonltrile
Methyl nitrate
Acrylonitrile
Nltromethane
Propionitrile
Acrylonitrile
Cyclohexyl-
mine
Nitroglycerin
Ethylene
glycol
dinltrate
Accumulator
Chroinosorb P
deactlved
with di-n-
butyl
phthalate
Graphitized
carbon black
1,2,3-tris
( 2-cyanoethoxy )
propane on
Chromosorb W
Midget
Iniplnger.
Midget
Implngers with
Fritted Glass
Desorptlon
or
Extraction
Medium
120-C
heat
heat
KMnO^XNaOH
.01N HC1
95? EtOH
Sampling-/^
Rat e ^s*&&sx9 1 e
^S^ Volume
.5A/min
. <5 t
50cc/min
300cc/min
1.54/min
m/mln
Collection
Parameters
-80°C dried with
MgCIO,, or KC03
25o
Recovery .
and
Sensitivity
-100?
100
100
-100
Associated
Analytical
Method
GC-
didecyl
•phthalate on
Chronosorb ?
90°C
GC
GC-FID
Porapak Q
Colorimetry
Colorlmetry
Reference •
Williams (1965)
Raymond, Gulochon
(1975)
Bellar, Sigsby
(1970)
Gisclard, Robinson,
Kuczo, Jr. (1958.)
Watrous, Schultz
(1950)
Einert, et al.
(1963)
00
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accurulant
Dlchloro-
nitro-ethane
2-nltropro-
pane
. Methyl amlne
Ethyl methane
sulfonate
Accumulator
Impinger
Fritted glass
bubbler
Filter paper
with 9% oxalic
acid
Chrome-sorb 101)
20% Tricresyl
phosphate' on
Chron W(HP)
100/120
253 Didecyl
phthalate on
Chrom P
100/120
Oxyproorio-
nitrile/Poracll
C 80/100
Porapak Q
20* Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Desorption
or
Extraction
Medium
H2SOi)
cone. HpSO,.
silica gel
2-propanol
H20
concentrated
HCl/hexane
(not removed)
Sampling/^'
Rate ^X^ample
^^ Volume
.5£/min
2-6£/min
.25i/mln
Collection
Paraaetera
Recovery .
and
Sensitivity
95-98;-
100
99
75
50-100
<99
98$
20
50
98
90
90
Associated
Analytical
Method
Colorlmetry
GC
TMCBA on
Chromosorb V.'
139°C
GC-FID
Reference.
Jones, Riddick
(1952)
Vlles (I960)
Okita, et al.
(1973)
Pellizzari, et al.
(1975)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accurralant
Ethyl methane
sulfonate
N-Nitroso-
diethylamlne
Accumulator
Carbowax 'too/
Poracll C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
Chronosorb 101!
20$ Tricresyl
phosphate on
Chrojr. W(HP)
100/120
25f. Dldecyl
phthalate on
Chrom P
100/120
Oxyproprio-
nitrile/Poracll
C 80/100
Porapak .Q
201 Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Desorption
or
Extraction
Medium
(not removed)
(not removed)
Sampling^X^^
Rate .^Sample
^^^^ Volume
.254/min
.25Vmln
Collection
Parameters
Recovery .
and
Sensitivity
90?
95
95
90-95
Associated
Analytical
Method
' GC-FID
GC-FID
-.
Reference
Pellizzari, et al.
(1975)
Pellizzari, et al.
(1975)
I
ro
en
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accunulant
N-Nitroso-
diethylamine
Nitroiaethane
Accumulator
Carbowax !)00/
Poracil C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
N-Nltroso-
diethylamine
Chroraosorb Id1!
20? Tricresyl
phosphate on
Chrom W(HP)
100/120
25? Didecyl
phthalate on
Chrom P
100/120
Oxypropri'o-
nitrile/Poracll
C 80/100
Porapak Q
20% Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Desorptlon
or
Extraction
Medium
(not. removed)
• •
(not removed)
Sampllng^X^
Rat e .x'Sanple
^S^ Volume
.25Z/mln
.254/min
Collection
Parameters
Recovery .
and
Sensitivity
98Z
20
50
98
90
90
Associated
Analytical
Method
' GC-PID
GC-PID
Reference'
Pellizzari, et al.
(1975)
Pellizzari, et al.
(1975)
I
I\)
o-
c^
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accu=ulant
Nitromethane
Sulfolane
i
Accumulator
Carbowax l)00/
Poracil C
100/120
Chromosorb 101
Tenax GC
Activated
carbons
Chromosorb lot
20? Tricresyl
ohosphate on
Chrom W(HP)
100/120 .
25$ Didecyl
phthalate on
Chrom P
100/120
Oxypropio-
nitrile/Poracil
C 80/100 •
Porapak Q
201 Carbowax
600 on Chromo-
sorb W(KP)
100/120 mesh
Carbowax 400/
Poracil C
100/120
Desorption
or
Extraction
Medium
(not removed)
(not removed)
Sampline/'^
Rat e -Xaarap le
-^"^ Volume
. .254/rain
.254/min
Collection
Parameters
Recovery .
and
Sensitivity
90$
95
95
90-95
90
20
80
96
95
90.
90
Associated
Analytical
Method
' CC-FID
'GC-FID .
Reference .
Pelllzzari, et al.
(1975)
Pellizzarl, et al.
(1975) '
I
to
CTN
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accu=ulant
Sulfolane
1,3-Propane-
sultone
Accumulator
Chromsorb 101
Tenax GC
Activated
carbons
Chrome-sorb 104
20% Tricresyl
phosphate on
Chrom W(HP)
100/120
25% Didecyl
phythalate on
Chrom P
100/120
Oxyproprio-
nitrile/Poracil
C 80/100
Porapak Q
20? Carbowax
600 on Chromo-
sorb W(HP.)
100/120 mesh
Carbowax i)00/
Poracil C
100/120
Chromosorb 101
Desorption
or
Extraction
Medium
(not removed)
(not removed)
Sanpllng^^
Rat e .^Sample
^s* Volume
.25i/mln
.25^/min
Collection
Parameters
Recovery .
and
Sensitivity
95%
90
30-95
80
20
50
90
90
90
95
95
Associated
Analytical
Method
• GC-PID
GC-FID
Reference-
Pellizzari, et al.
(1975)
Pellizzari, et al.
(1975)
I
IV)
o>
CO
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accusulant
1,3-Propane-
sultone
General
Aromatlcs
C7 - C10
c?-c9
C8 - cii
C6 - C20
C8 - Ci8
Accumulator
Tenax GC
Activated
carbons
10$ Carbowax
15^0 on Gas
Chrom Z
Carbowax
Tenax GC
Cigarette
filter .'
charcoal
Graphitlzed
carbon black
Desorption •
or
Extraction
Medium
(not removed)
room
temperature
room
temperature
heat
cs2
1)00°C
Sampling^x**^
Rate^XSample
^^ Volume
. .25H/mln
lOOcc
77cc
2.5Vmln
25m3
. 5i/roin
2001
Collection
Parameters
.llq. N2 .
25° - 60°C
Recovery .
and
Sensitivity
80?
0-90%
l-50ppb
Associated
Analytical
Method
"GC-FID
GC-FID
bis(M-phenoxy
-phenoxy )
benzene &
apiezon
70°C
GC-FID
10? poly-
ethylene
glycol on
Gas Chron Z
GC-FID
Dexsil 300
on Chromo-
sorb W
GC-MS
GC-FID
OV-101
capillary
columns
Reference •
Pellizzarl, et al.
(1975)
Altshuller, et al.
(1971)
Kopczynski, et al.
(1972)
Mieure, Dietrich
(1973)
Grob & Grob (1971)
Raymond, Gulochon
(1974) '
I
rv>
en
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accuzulant
C6 - C10
Onsubstituted
Aromatics
Benzene
Naphthalene
Benzene
Napthalene
Benzene
Naphthalene'
Benzene
Accumulator
Silica Gel 58
Silica Gel 15
Glass beads
Chromosorb 103
Porapak Q ;
Glass Beads
Tenax GC
Tenax GC
Tenax GC
Desorptlon
or
Extraction
Medium
250'>C
heat
120°
heat
heat
heat
heat
heat
heat
Sampling^ —
Rat e .x^Sample
^r volume
<50
72cc .
20cc/mln
20cc/min
72cc
50-200cc/min
50-200cc/min
50-200cc/min
Collection
Parameters
21°-21°C
21e-2l°C
liq. N2
head-space
head-space
liquid N2
250-60°C
atmosphere in
• Houston
atmosphere in
Houston
Recovery .
and
Sensitivity
2-130ppb
retention
volume (1)
500
500
500
500
15ppb
>90*
1.3-15ppb
Associated
Analytical
Method
GC-FID
GC-FID
GC-FID
bis(m-phencxji
-phenoxy)
benzene with
aplezon 73°C
GC-FID
C101
GC-FID
rt
101
GC
GC-FID
Dexsil 300
on Chromo-
sorb W
GC-FID
capillary
columns
GC-FID
capillary
columns
Reference •
Bellar, Sigsby
(unpublished)
Lonneman, Bellar,
Altshuller (1968)
Lonneman, et al.
(WO .
Bellar,
Lichtenberg (1971)
Bellar,
Lichtenberg (1971)
Lonneman, Bellar,
Altshuller (1968)
Mleure, Dietrich
(1973) ;
Bertsch, Chang,
Zlatkis (1971)
Bertsch, Chang,
Zlatkis (1971)
o
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accurulant
Benzene
Benzene
Indene
Napthalene
Benzene
Pyridine
Benzene
Benzofuran
Naphthalene
Diphenyl
Fluorene
Benzothia-
zole
Biphenyl
Accumulator
Tenax GC
Silicone
elastomer
E-301 con
Celite 5^5
or
polythyene
glycol 400
Silicone E301 .
on Celite 545 '
Cigarette
filter charcoal
•
Desorptlon
or
Extraction
Medium
heat
120°C
cs2
extraction c~
CS_ 72°
Sampling./^
Rat e ./Samp 1 e
^r Volune
20cc/min
<29cc
<110cc
2.54/min
25ni3
Collection
Parameters
head-space
24°
•5mm Hg
pressure drop
Recovery .
and
Sensitivity
retention
volume (1)
>500
Associated
Analytical
Method
GC-FID
C101
GC-FID
75? Celite
545
25$ Apiezon L
GC-FID
Silicone E301
on cellte
and others
GC-MS
Reference '
Bellar,
Lichtenberg (1974)
Novak, Vasak,
Janak (1965)
Cropper, Kaminsky
(1963)
Grob & Grob (1971)
I
(X)
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accuzulant
Acenaphthene
Dlbenzofuran
Fluorene
Benzofuran
Benzene
Napthalene
Acenaphthene
Fluorene
Napthalene
Diphenyl
Indar.e
Indene
Benzene
Accumulator
Cigarette
filter
charcoal
Graphltlzed
Carbon Black
Silica Gel 58
Silica Gel 15
Acid Treated
Silica Gel
Silica Gel
Silica Gel
Desorptlon
or
Extraction
Medium
extraction c~
CS2 72"
loa°c
250 C
heat
isooctane
isopropanol
Sampling^^
Rat e ^^Sanp 1 e
^^ Volume
2.51/min
25m3
. 5fc/mln
200)1
<50
<_500
60cc/min
1.2-1.54/min
l-3*/rain
Collection
Paraaeters
21<>-2l4«C
21«-21<>C
dried with 5A
molecular sieves
Recovery .
and
Sensitivity
20ppm
80%
Associated
Analytical
Method
GC-MS
GC-FLD
OV-101
.capillary
column
GC-FID
GC-FID
formaldehyde
stain
UV
GC-FID
polypropylene
glycol on
diatomaceous
earth
Reference .
Grob & Grob (1971)
Raymond, Guiochon
(1974)
Bellar, Sigsby
(unpublished)
Hubbard, Silverman
(1950)
Maffett, Doherty,
Corapronl (1962)
Whitman, Johnston
(1964)
-------
ACCUKULATION OF ORGANIC SUBSTANCES FROM AIR
Accuzulant
Benzene
Benzene
Furan
Benzene
Accumulator
Silica Gel
1,2,3-tris
(2-cyanoethoxy)
propane on
Chromosorb W
Cyrogenic
Trap Glass
Wool Filter
Midget
Iraplnger
Layer Trap
(72 OV-17 on
chromosorb G
+ silica gel
+ 13x & 5A
molecular
sieves)
Glass Beads
'
Desorption •
or
Extraction
Medium
cyclohexane/
heptane
C-H-Cl-XC-F-Cl,
22 2 22 1
heat
distillation
isooctane
heat
120"
Sar.pllnex-^
Rat e .Xsamp 1 e
^^ Volume
l-3Vmin
SOcc/min
l£/min
200cc/min
£50 Ot
72cc
Collection
Parameters
dry air
sat . air
llq. 02
cool air before
sampling
21o_21,oc
liq. N-
Recovery .
and
Sensitivity
80-100?
30?
90-100?
• 2-130ppb
Associated
Analytical
Method
UV
GC-FID
Porapak Q
Mass spectra
• UV
GC-FID
GC-FID
bis(n-phenoxj
-phenoxy)
benzene v;ith
apiezon 73°C
Reference
Elklns, Pagnotto,
Comproni (1962)
Bellar, Sigsby
(1970)
Shepherd, et al.
(1951)
Andrews,' Peterson
Cl9f7)
Bellar, Sigsby
(Unpublished)
Lonneman, Bellar,
Altshuller (1968)
tV)
-J
00
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIH '
Accusulaat
Substituted
Nonpolar
Toluene
Xylene
Toluene
Xylenes
Styrene
Hexachloro^
benzene
Toluene
Chlorobenzene
o-Dichloroben
zene
1,2,4-Trir
Chlorobenzene
Toluene
Accumulator
10$ Carbowax
15^0 on gas
Chrom Z
Carbowax
Chroraosorb 101
Chromosorb 103
Porapak Q
Desorptlon •
or
Extraction
Medium
room
temperature
room
temperature
hexane
heat
heat
Sampling^ —
Rat e .^Sa.Tnp le
^S^ Volume
lOOcc
77cc
3A/mln
20cc/mln
20cc/mln
Collection
Parameters
liq. N2
head-space
head-space
Recovery .
and
Sensitivity
l-50ppb
88-100$
retention
volume (1)
500
500
500
500
retention
volume (1)
500
Associated
Analytical
Method
GC-FID
bis(M-phenoxy
-phenoxy)
benzene &
aplezon
70-0
GC-FID
10' poly-
ethylene
glycol on
Gas Chrom Z
GC-SCD
OV-17
15C°C
GC-FID
C101
-.
GC-FID
C101
Reference •
Altshuller, et al.
(1971)
Kopczynskl, et al.
(1972)
Mann, et al.
(1971)
Bellar
Lichtenberg (1971)
Bellar, Lichtenberg
(1971)
I
ro
-Cr
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM A±R
Aceuzulant
Toluene
Ethyl Benzene
p-Xylene
m-Xylene
o-Xylene
Isopropyl
Benzene
n-Propyl
Benzene
3,4 diethyl
Toluene
Mesitylene
t-Butyl
Benzene
sec-Butyl
Benzene
n-Butyl
Benzene
Toluene
. Accumulator
Glass Beads
•
Desorptlon
or
Extraction
Medium
heat .
Sarapling^^
Rate^x^Sample
^^ Volume
72cc
50-200cc/min
Collection
Parameters
liquid N2
Recovery .
and
Sensitivity
37 ppb
6
6
16
8
3
2
8
2
-
-
-
>90$.
Associated
Analytical
Method
GC
GC-FID
Etched Ml
with Eroul-
phor
3C0-170°C
Reference '
Lonneman, Eellar,
Altshaller (1963)
Eertsch, Chang,
Zlatkls (1971!)
01
I
-------
ACCUMULATION CF ORGANIC SUBSTANCES FROM AIR
Acc'x-ulant
Xylenes
1,2,4-Trl-
methyl-
benzene
o-Diethyl-
benzene
Methyl Propyl
benzene
Dlchloro-
benzene
Methylindane
Methylnaph-
thalene
Styrene
1,3,5-Tri-
methyl-
benzene
Accumulator
Tenax GC
Desorption
or
Extraction
Medium
heat
Sampling
Rate^ — Sample
.^ Volume
50-200cc/mln
50-200.cc/mln
Collection
Parameters
atmosphere In
Houston
•
Recovery .
and
Sensitivity
>90
.
Associated
Analytical
Method
GC-FIC
Etched Nl
with Emul-
phor
30°-170°C
GC-FID
capillary
columns
Reference '
Bertsch, Chang,
Zlatkls (197t) -
Bertsch, Chang,
Zlatkls (197*0
I
IV)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
jiccuzulant
Isobutyl Ben-
zene
o-Ethyl
toluene
Dimethyl-
ethyl-
benzene
Toluene
Ethyl Benzene
p-Xylene
m-Xylene
o-Xylene
m-ethyl
toluene
Toluene
Chlorobenzene
o-Dichloro-
benzene
1,2,1-Trl-
chlorobenzene
Accumulator
Tenax GC
Desorptlon •
or
Extraction
Medium
heat
S&nplinss^
Rate ^X'Samp 1 e
^^ Volume
50-200cc/raln
20cc/min
Collection
Parameters
atmosphere in
Houston
head-space
Recovery .
and
Sensitivity
0.3-9.7-
3-1-1.5
2. 1-3. 4
5.9-7.8
3.0-1.8
1.5-t.O
retention
volume (1)
500
500
500
500
Associated
Analytical
Method
GC-FID
capillary
columns
GC-PID
C101
Reference .
Bert sen, Chang,
Zlatkls (1971*) •
Bellar,
Llchtenberg (1971)
I
IV)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accuaulant
Acetophenone
Toluene
Xylenes
Toluene
Xylenes
Benzyl
chloride
Arorcatics
C6 - C20
Toluene
Methylindan
2-Methyl- '
naphthalene
Accumulator
Support-bonded
sllicones
Sillcones
Sillcone
elastomer
E-301 on
Celite 515
or
polyethylene
glycol 'tOO
Sillcone E301
on Celite 515
Cigarette-
filter
Charcoal
Desorptlon •
or
Extraction
Medium
extraction
with pentane
120-C
cs2
extraction c
CS2 72°
Saaiplinex^
Rate ^XSanple
^^ Volume
itt/min
<29cc
<77cc
<110cc
<_210cc
lOOcc/min
<500cc
2.54/min
25m3
2.51/min
25m3
Collection
. Parameters
filtered to 5u
21"
.5mm Hg
pressure drop
Recovery .
and
Sensitivity
•
Associated
Analytical
Method
GC-FID
OV-101 on
Chromosorb W
R.T. - 130°C
GC-FID
75$ Celite
5U5
25% Apiezon I
GC-FID
Silicone E30]
on cellte
and others
GC-FID
Silicone E30:
on Celite
GC-MS
Reference •
Aue, Teli (1971)
Novak, VasSk,
Jana> (1965)
Cropper, Kaminsky
(1963)
Grob & Grob (1971)
I
IV)
-~]
co
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIH
Accuculant
1-Methyl-
naphthalene
2,6-Dimethyl-
naphthalene
1,6-Dimethyl-
napthalene
1,8-Dimethyl-
naphthalene
Methyldi-
phenyl
m-Ethyl.-
toluene
1,3.5-Tri-
methylbenzene
o-Ethyl-
toluene
1,2,4-Tri-
methylbenzene
P-cymene
n-Butylben-
zene
Methylpropyl-
benzene
Accumulator
Cigarette
filter
Charcoal
,
Desorption
or
Extraction
Medium
extraction c
C32 72"
Sanpling^X''^
Rate ^x'sample
^s"^ Volume
2.5l/min
25m3
Collection
Parameters
Recovery .
and
Sensitivity
Associated
Analytical
Method
OC-MS
.
Reference •
Grob & Grob
(1971)
I
IV)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accu=ulant
sec-Butylben-
zene
1,2,3-Trl-
methyl-
benzene
Ethyldi-
methyl-
benzene
Toluene
Ethylbenzene
Xylene
m-xylene
o-xylene
n-Propyl-
benzene
Ethyl-toluem
Dichloro-
benzene
1,2,3,5- •
Tetraraethyl-
benzene
Methylindane
Accumulator
Cigarette
Filter Carbon
.
Desorptlon
or
Extraction
Medium
extraction c
CS2 72"
Sampling./'^
Rat e^^^ar.p le
^s*^ Volume
2.5i/mln
25m3
Collection .
Parameters
Recovery .
and
Sensitivity
Associated
Analytical
Method
GC-MS
Reference'
Grob & Grob
(1971)
*
I
[\J
oo
o
I
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM AIR
Accusulant
1,2,3,1-
Te'tramethyl-
benzene
1,2,1,5-
Tetraraethyl-
benzene
1,1-Dimethyl-
• naphthalene
2,3-Dimethyl-
naphthalene
Kexaraethyl-
benzene
Dlphenyl-
methane
Pentamethyl-
benzene
2-methylnaph-
thalene
1-methylnaph-
. thalene
n-Tetra- •
decar.e 2-ethyl-
naphthalene
1-Ethylnaph-
thalene
Accunulator
Graphltlzed
Carbon Black
•
Desorption
or
Extraction
Medium
itoo°c
Sampllnzx^
Rat e ^/aar.p le
^^ Volume
.5Vmin
2004
Collection
Parameters
Recovery .
and
Sensitivity
Associated
Analytical
Method
GC-FID
OV-101
capillary
column
Reference '
.
Raymond, Guiochon
(197D
I
(V)
oo
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM AIR
Accuralant
1,6-Dimethyl
naphthalene
sec-Butyl-
benzene
1,2,3-Tri-
methylbenzene
P-cymene
Diethylben-
zene
n-Butylben-
zene
Ethyldi-
methyl-
benzene
1,2,1,5-
Tetramethyl-
benzene
Toluene
Ethyl-
benzene
m-xylene
Styrene
o-Xylene •
Accumulator
Graphitized
Carbon Black
•
Desorptlon
or
Extraction
Medium
100 °C .-
Samplina/^
Rat e .Xoarap 1 e
^S^ Volume
. .54/min
Collection
Parameters
Recovery .
and
Sensitivity
Associated
Analytical
Method
ffC-FID '
OV-101
capillary
columns
Reference.
Raymond, Guiochon
(1971)
I
ro
oo
ro
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
.Aeeusulant
n-Propyl-
benzene
p -ethyl
toluene
1,3,5-Tri-
methylben-
zene
p-xylene
m-ethyl
toluene
PCB
(Aroclors
1212 or 1218)
PCB's
Toluene
Styrene
Ethyl benzene
Propyl ben-
zene
Isopropyl .
benzene
Accumulator
Graphitized
Carbon Black
Polyurethane
Foam
Silica Gel' 58
Silica Gel 15
Desorptlon
or
Extraction
Medium
loo c
pet. ether
250°C
heat
Sanipllng^^^
Rate^X'san'.ple
^s^ Volune
• . 54/mln
200Z
.'t-.Sm^min
12-3*1 hr
<50
£500
Collection
Parameters
5-20°C
21o_2i(oC
21°-2H°C
Recovery .
and
Sensitivity
>90*
•39ng/m3
96-992
Associated
Analytical
Method
GC-FID
OV-101
capillary
columns
GC-ECD
OV-17/OF-1
GC-FID
GC-FID
Reference
Raymond, Guiochbn
(1971)
•Bidleman, Olney
(197la)
Bidlenan, Olr.ey
(1971-0)
Bellar, Sigsby
(unpublished)
I
rv>
oo
OJ
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Aseusulant
Toluene
Toluene
Xylenes
Toluene
Xylene
Methyl
vinyl- '
pyridine
PBC's
Accumulator
Acid treated
Silica Gel
Silica Gel
Cryogenic
Trap Glass
Wool Filter
Impingers
Midget
Impinger
n-hexane
• •"
Desorptlon
or
Extraction
Medium
isooctane
distillation
KMnOjj/NaOH
•
Sampling/''*
Rat e ./Sample
^S^ Volume
60cc/mln
1.2-1.54/mlri
Ifc/mln
300cc/min
Collection
Parameters
dried with 5A
molecular sieves
liq. 0, '
C.
COp removed with
ascarlte
cooled prior to
collection
Recovery .
and
Sensitivity
20ppm
80*
•
Associated
Analytical
Method
formaldehyde
stain
GC-FID
polypropyl-
ene glycol
on diatoma-
ceoiis earth
Mass spectra
Colorlmetry
"
Reference
Hubbard, Sllverraan
(1950)
Whitman, Johnston
(196H)
i
Shepherd, et al.
(1951)
Bisclard, Robinson
'Kuczo, Jr. (1958)
Okuno, Tsujl
(1972)
I
IV)
oo
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
Accurulant
Toluene
Styrene
Ethyl
benzene
Propyl
benzene
Isopropyl
benzene
Toluene
Xylenes
Substituted
Polar
Phenols
Phenols
Acetophenone
Tolualdehyde
Kethyl
acetophenone
Benzal-
dehyde
Accumulator
Layer Trap
Layer Trap
(72 OV-17 on
. chromosorb G
•H silica gel
+ 13x & 5A
molecular
sieves)
Glass beads
Chromosorb 103
Porapak Q
Ten ax GP
Desorptlon
or
. Extraction
Medium
heat
120°
heat
heat
Sampling^^^
Rate jSsamp 1 e
^^ Volume
£5001
72cc
20cc/min
50-200cc/mln
Collection
Parameters
21«-21)<>C
llq. N2
head-space
Recovery .
and
Sensitivity
2-130ppb
retention
volume (1)
500
500
>.902
Associated
Analytical
Method
GC-PID
GC-PIC
bis(m-phen-
oxy-phyenoxy
Benzene with
apiezon 73°C
GC-FID
C101
GC-PID
etched Ni
with Emul-
phor
Reference
Bellar, Sigsby
(Unpublished) •
Lonneman, Bellar,
Altshuller (1968)
Lonneman, et al.
' (1971)
Bellar
Lichtenberg (197^)
Berts oh, Chang,
Zlatkls (1971*)
I
ro
oo
ui
I
-------
ACCUMULATION 07 ORGANIC SUBSTANCES FROM AIR
Accu=ulant
p-Tolual-
dehyde
m-Tolual-
dehyde
Acetophenone
o-Tolual-
dehyde
Phenols .
P-cresol
Benzaldehyde
Benzoyl
chloride
Aniline
Nitrobenzene
Benzaldehyde
Acetophenone
Benzaldehyde
t-Methylbenz-
aldehyde
Acounulator
Tenax GC
Tenax GC
Sllicone E301
on Celite 5^5
Cigarette--
Filter Charcoal
1
Desorption •
or
Extraction
Medium
heat
,
120 C
CS
t
extraction c
CS2 72'
Sampling
Rat e ./Samp 1 e
.s — Volume
50-200cc/min
lOOcc/min
230cc
2.5i/min
2.5i/rain
25m3
Collection .
Parameters
atmosphere -in •
Houston
25°-60°C
.5nun Hg
pressure drop
.
Recovery .
and
Sensitivity
Associated
Analytical
Method
GC-FID
capillary
columns
GC-FID
Dexsil 300
on Chromo-
sorb W
•GC-FID
SiliconeE301
on celite
GC-KS
Reference
Bertsch, Chang,
Zlatkis (197*0. •
Kieure, Dietrich
(1973)
Cropper-. Kaminsky
•(1963)
Grob &.'Grob (1971)
-
IV)
oo
a\
I
-------
ACCUMULATION CP ORGANIC SUBSTANCES FROM AIR '
Accu=ulant
Acetophenom
2-Methyl-
•benzalde-
hyde
Dimethyl-
benzalde-
hyde
Dimethyl-
phthalate
Phenol
Xylidine
2-aralno
pyridine
P-chloro
nitroben-
zene
Accumulator
Cigarette
Filter Carbon
Graphltlzed
Carbon Black
Acid Treated
Silica Gel
Midget
Itnpiriger
Sintered
glass
Bead-filled
tube
Desorption •
or
Extraction
Medium
extraction c
CS 72°
. 2
.
t
heat
isooctane
HO
C.
fuming
nitric acid
Sampllng^x^
Rate .x-'Sanole
^^ voluae
2.5i/min
nCmJ
fc JiU
1-21
60cc/min
200cc/min
l.SVmin
Collection .
Parameters
20"
cool air before
sampling
Recovery .
and
Sensitivity
87-104*
20ppm
90-100*
100J
Associated
Analytical
Method
G'C-MS
GC
Formaldehyde
stain
UV
Colorlmetry
Reference
Grob & Grob
(1971)
Raymond , Guiochon
(1975)
'Kubbard, Silverman
(1950)
Andrews, Peterson
(1971)
Watrous, Schulz
(1950).
I
ro
oo
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accu=ulant
Aniline
Bis-(2-
chloroethyl
ether
N-Nltroso-
diethylamlne •
Bls-(chloro-
methyl) .
ether
Maleic
anhydride
1,3-Propane-
sultone
Aniline
Bis-(2-
chloro-
etfiyljether
N-Nltroso-
diethylamine
Bis-(chloro-
methyl)
ether
Accumulator
Chromosorb
101)
20% Trlcresyl
phosphate on
Chrom W(HP)
100/120
Desorption
or
Extraction
Medium
(not removed)
Sanpling^^^
Rat e ^XSamp le
.^ Volume
.25)l/min
Collection .
Parameters
Recovery .
and
Sensitivity
80$
20$
Associated
Analytical
Kethod
GC-FID
Reference
Pelllzzarl, et al.
oo
oo
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
Accu=ulant
Maleic
anhydride
1,3-Propane
. sulfone
Aniline
Bls-(2-
chloroethyl
ether
N-Nitroso-
dlethylamlne "
Bls-(chloro
methyl) •
ether
Maleic
anhydride
1,3-Propane
sulfone
Aniline
Bis-(2-
chloro-
ethyl)
ether
Accumulator
20J Tricresyl
phosphate on
Chrom W(HP)
-100/120
25?Didecyl
phthalate on
Chrom P
100/120
Oxyproplo-
nltrile/Poracl]
C 80/100
Desorptlon •.
or
Extraction
Medium
(not removed)
(not removed)
Sanpling^x^
Rat e ^XSanple
.^ — Volume
.251/mln
.25i/mln
.
Collection .
Parameters
Recovery .
and
Sensitivity
20?
50
90.
.
Associated
Analytical
Method
GC-PID
GC-FID
.
Reference
Pelllzzari, et al.
Pellizzarl, et al.
'
. .
I
r\j
oo
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Aceu=ulant
N-NItroso-
dlethylamine •
Bis- (chloro
methyl)
ether
Maleic
anhydride.
1,3-Propane
sulfone
Aniline •
Bis-(2- •
chloro- •
ethyl)ether
N-Nltroso-
dlethylamine
Bis- (chloro
methyl)
ether
Maleio
anhydride
1,3-Propane
. sulfone
Accumulator
Oxyproplo1-
nitrile/Poraci]
.C 80/100
Porapak Q
Desorption •
or
Extraction
Medium
(not removed)
Sanipllngx^^
Rat e .s^sa-iKf 1 e
Voluxe
.25i/min
Collection .
Paraneters
Recovery .
and
Sensitivity
90!5 '
90$
Associated
Analytical
Method
GC-FID
Reference
Pellizzari, et al.
I
IV)
VD
O
I
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM AIR
Aceu=ulent
Aniline .
Bis-(2-
chloro-
ethyl)
ether
N-Nitroso-
diethylamine
Bis-(chloro
methyl)
ether
Maleic
anhydride
1,3-Propane
sulfone
Aniline
Bi-s-(2-
chloro-
ethyl)ether
N-Nitroso-
diethylamine
Accumulator
20$ Carbowax
600 on Chromo-
sorb W(HP)
. 100/200 'mesh
.
Carbowax ^OO/
Poracil C
100/120 .
Desorption •
or
Extraction
Medium
(not removed)
Sampllng^X^^
Ra't e ^^x^Samp 1 e
^^ Volume
.251/min
Collection .
Parameters
Recovery .
and
Sensitivity
90*
951
Associated
Analytical
Method
GC-FID
Reference
Pellizzari, et al •
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM AIR
Aceurulant
Bis-(chlorc
methyl)
ether
Maleic
.anhydride
1,3-Propane
sulfone
Aniline .
Bis-(2-
chloro-
ethyl) ether
. N-Nitroso-
dlethylamine
Bis-(ohloro
methyl)
ether
Ma'lelc
anhydride
1,3-Propane
sulfone
' Aniline
'Accumulator
Carbowax l)00/
Poraoil C
100/120
Chrowosorb
101
Tenax GC
Desorptlon •.
or
Extraction
Medium
(not removed)
Sampling ^
Rat e ^*S§a.wp 1 e
^ • Volu.T.e
•.25t/min
Collection .
Parameters
Recovery .
and
Sensitivity
95%
95
80
Associated.
Analytical
Method
GC-FID
Reference
Pelllzzari, et al.
I
rv>
vo
ro
-------
ACCUMULATION OF ORGANIC SUBSTANCES ?HOM AIS '
Accusulant
Bis-(2-
chloro-
ethyl)
ether
N-Nltroso-
diethylamine
Bis-(chlorc
methyl)
ether
Malelc
anhydride
l,3-Propan«
sultone
Aniline
Bis-(2-
chloro-
ethyl)
ether
N-Nitroso-
diethylaraine
Bis-(chlorc
methyl)
ether
Accumulator
Tenax GC
Activated
carbons
Desorption •
or
Extraction
Medium
(not removed)
Sarr.pllnex^
Ra't e ^x^Sample
^s^ Volu-ne
.25^/min
Collection .
Parameters
Recovery .
and
Sensitivity
8oj!
0-90%
Associated
Analytical
Method
GC-FID
Reference
Pellizzarl, et al.
I
rv>
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR '
Accurulant
Maleic
• anhydride .
1,3- Propane
sulfone
Pesticides
Lindane
Keptachlor
Aldrin
Dieldrin
Heptachlo'r
expoxide
P , P ' -DDT
o,p'-DDT
Chlordane
Lindane
Aldrin
Dieldrin
DDT
Accuaulator
Activated
carbons
Silicones
Support-bond-
ed silicones
'Polyurethane
Foam
Impingers
Poiyetby-lene-
Coated Silica
Desorption •
or
Extraction
Medium
(not removed)
pet. ether
ethylene
glycol
Saapling^x^
Rat e ^XsajBp 1 e
^S^ Voluae
.25£/min
184/min
.1-.8m3/min
. 5nr/min
1 . 5m3/hr
Collection .
Parameters
cooled prior
to collection
Recovery .
and
Sensitivity
0-90*
.009-.009ng/m3
.008-.037ng/m3
. 005-0. 25ng/m3
poor
100J
Associated
Analytical
Method
GC-FID
GC
OV-101 on .
'Chromosorb W
R.T.-130°C
GC-ECD
OV-17/QF-1
Titration
Reference-
PellizzarJ , et al.
Aue, Tell -(1971)
Bldleman, Olney
(197la)
Herzel, Lahmann
(1973.)
I
(V!
-------
TABLE 3-4
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR BY ACCUMULATOR
This table lists those compounds which have be.en analyzed
in air samples along with the accumulation method which
was used.
The accumulator is the system used for accumulation
(i.e. midget impinger) or, if a chemical is given, it refers
to an adsorbent which was used in a column (i.e. Texax).
The desorption or extraction medium generally refers
to the method of taking materials from an adsorbent resin
for analysis. Where collection was by adsorption, however,
this column contains the name of the adsorbing liquid.
All other information is given if it was included in
the original article.
-295-
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Carbowax
Car bo wax
10X Carbowax
' 1540 on Gas •••
: Chrom Z
1 OX Carbowax
1540 on Gas
Chrpm Z
10 J Carbowax
! 1540 on fire-
j brick
1
• \0t Carbowax
; 1510 on Gas
• Chrom Z
Accumulant
Allphatlcs
c2-c5
C2 - C10
C4 " C8
CK - C5
Aromatlcs
C7 - C10
Toluenes
Xylenes
Alkyl benzene
Desorptlon
or
Extraction
Medium
room
temperature
room
temperature
room
temperature
hot water
heating
room
temperature
Sampling ^s^
Rate ^^
^S^ Sample
s^ Volume
77cc
lOOcc
90cc
lOOcc/min
UOcc/mln
(f mln. )
lOOcc
Collection
Parameters
llq. N2 ?7°K
liq. N2
liq. N2
llq. N2
liq. N2
Recovery
and
Sensitivity
1-3000 ppb
.1
1-50
Associated
Analytical
Method
GC-FID
dibutyl
maleate
0°C
GC-FID
15? dibutyl
maleate or
acid Chromo-
sorb G
25°C
GC-FID
dibutyl
maleate
acid silica
gel
30°C
GC-FID
bs-2(methoxy-
ethyl) adi-
pate
37°C
GC-FID
bis(in-phenoxy
-phenoxy)
benzene &
apiezon
70°C
Reference.
Kopczynski, et al.
(1972)
Altshuller, et al.
(1971)
Kopczynski, et al.
(1972)
Lonneman, et al.
(1974)
Bellar, Brown,
Sigsby, Jr. (1963)
Altshuller, et al.
(1971)
cr\
\
-------
ACCUKULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Carbowax
1510
f
Carbowax
Accunulant
Isobutane
n-Butane
Butene-1
trans-Butene-2
cis-Butene-2
Butadiene-1,3
Isobutylene
Isopentane
n-Pentane
3-Methyl-
butene-1
Pentene-1
2-Methyl
butene-2
cls-Pentene-2
C7 - C9
1 J
Toluene
Xylenes
Alkyl benzenes
Styrene
Desorption
or
Extraction
Medium •
heat-hot water
room
temperature
^^ Volume
30-300cc/rain
60-300cc/mln
77cc
Collection
Parameters
Atmosphere in
Cincinnati
Liquid N2
s
Recovery
and
Sensitivity
6.0 ppb
< 1-5
1.0
1.1
1.0
< 1.5
15-5
7.6
2.6
1.6
3-8
1.7
Associated
Analytical
Method
GC-FID
GC-FID
10% poly-
ethylene
glycol on
Gas Chron Z
Reference
Be liar, Brown,
Sigsby (1963)
Kopczynskl, et al.
(1972)
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM AIR
Accumulator
20$ Carbowax
600 on Chromo-
sorb W(HP)
100/120 mesh
Accumulant
Ethyl methane
sulfonate
3-Propiolacton<
w-Nitroso-
diethylamlne
1,2 Dichloro-
ethyl' ethyl
ether
Nitromethane
Methyl ethyl
ketone
Styrene epoxlde
ff-Nitroso-
diethylaraine
Butadiene
diepoxide
Glycidaldehyde
Sulfolane
Propylene
oxide
Desorption
or
Extraction
Medium
(not removed)
Sampllng^X^
Sat e -X'Samp 1 e
./^ Volume
.25fc/mln
t
Collection
Parameters
Recovery
and
Sensitivity
")
(
\ 9055
I
J
^
/ 90*
\
J
Associated
Analytical
Method
GC-FID
Reference
Pelllzzarl, et al.
(1975)
I
(V>
MD
CD
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
20% Carbowax
600 on Chromo-
sorb K(HP)
100/120 mesh
Accumulant
Aniline
Bis-(2-chloro-
ethyl) ether
w-Nitroso-
diethylamine
Bis-(chloro-
' methyl) ether
Maleic
anhydride
1,3-Propane-
sultone
Desorption
or
Extraction
Medium
'(not removed)
Sampline,^^
Rate -x^Bample
.s*^ Volume
.25i/mln
Collection
Parameters
Recovery
and
Sensitivity
]
V
> 90%
I
\
\
J
_^
Associated
Analytical
Method
GC-FID
Reference
Pellizzari, et al.
(1975)
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Carbowax 400/
Poracil C
100/120
Accumulant
Aniline
Sis-(2-chloro-
ethyl) ether
w-Hitroso-
diethylamine
Bls-(chloro-
nethyl) ether
Malelc
anhydride
1,3-Propane-
sultone
Desorption
or
Extraction
Medium
(not removed)
Sampling^ —
Rat e .xx'Samp le
^^ Volume
.25*/min
Collection
Parameters
Recovery
and
Sensitivity
-N
/
I
> 95?
f
\
J
• ~
Associated
Analytical
Method
OC-PID
Reference
Pellizzarl, et al.
(1975)
I
uo
o
o
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Carbowax '100/
Poracll C
100/120
Accumulant
Ethyl methane
sulfonate
. B-Propiolacton<
w-Nitroso-
diethylamine
1,2 Dichloro-
ethyl'ethvl
ether
Nltromethane
Methyl ethyl
ketone
Styrene epoxide
N-Nitroso-
diethylamine
Butadiene
diepoxlde
Olycldaldehyde
Sulfolane
Propylene
oxide
Desorptlon
or
Extraction
Medium
(not removed)
Sampling^/'"
Rate^x^Sample
^^ Volume
.25*/nin
Collection
Parameters
Recovery
and
Sensitivity
]
\ 90?
\
J
~]
> 99*
\
J
Associated
Analytical
Method
GC-PID
Reference
Pellizzarl, et al.
(1975)
I
o
M
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Chromosorb
101
Accumulant
Ethyl methane
sulfonate
.B-Propiolactom
w-Nitrosc-
diethylamine
1,2 Dichloro-
ethyl ethyl
ether
Nitromethane
Methyl ethyl
ketone
Styrene epoxlde
w-Nitroso-
diethylamine
Butadiene
dlepoxlde
Glycidaldehyde
Sulfolane
Propylene
oxide
Desorption
or
Extraction
Medium
(not removed)
tete -x^Sample
.S*^ Volume
.25Vnin '
' Collection
Parameters
*
Recovery
and
Sensitivity
95%
^
•
> 95?
'
J -
Associated
Analytical
Method
GC-PID
Reference
Pellizzarl, et al.
(1975)
I
L/O
O
rv>
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Chromosorb
101
.
Chromosorb 101
.
Chromosorb 102
Accumulant
Aniline
Bis-(2-chloro-
ethyl) ether
w-Nitroso-
diethylamine
Bls-(chloro-
methyl) ether
Maleic
anhydride
1,3-Propane-
sultone
Acidic and
neutral com-
pounds
Hexachloro-
butadiene
Hexachloro-
benzene
Organlcs
(bp>60°C)
Desorptlon
or
Extraction
Medium
(not removed)
heat
hexane
120°C
Sampling/^
Rat e .^Sample
^^^ Volume
•25i/min
.5-24/mln
3i/min
U/mln
104
• '
Collection
Parameters
ambient temperature
up to 90°C
2 psl pressure drop
Recovery
and
Sensitivity
")
/
/
(
> 955!
(
\
\
J
88-100*
>95X
.1 PPb
Associated
Analytical
Method
GC-FID
GC-FID
GC-ECD
OV-17
150°C
GC-FID
Carbowax 20N
60-180°C
Reference
Pellizzari, et al.
(1975)
Mieure, Dietrich
(1973)
Mann, et al.
(1371)
Dravnieks, et al.
(1971)
I
OJ
o
LO
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Chromosorb 103
Accuaulant
Low-boiling
compounds
Methane
Ethane
Ethylene
Acetylene
Propane
n-Butane
n-Pentane
n-Hexane
Benzene
Toluene
Methylene
chloride
Chloroform
Phenols
Napththylene
Chlorobenzene
o-Dichloro-
benzene
l,2,lJ-Trichloro-
benzene
aliphatlcs
Desorptlon
or
Extraction
Medium
heat
heat
heat
heat
heat
S amp 1 \.n.z^^
Rate-"Sanple
s^ Volume
.5-2£/min
<5i
<5i
<5l
20cc/rain
*10i
Collection
. Parameters
ambient temperature
up to 90°C
22°C
22°C
22°C
head-space
22°C
Recovery
and
Sensitivity
95?
retention
volume (t)
<10'
<20
50
500
500
500
500
500
500
500
500
500
500
95*
Associated
Analytical
Method
GC-FID
GC-FID
GC-FID
A
GC-FID
GC-FID
C.101
GC-FID '
Reference
Nieure, Dietrich
(1973)
Bellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
Bellar,
Llchtenberg (197*))
.
Bellar, Sigsby
(Unpublished)
I
UJ
o
-fr
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Chromosorb
101
Accumulant
Ethyl methane
sulfonate
,B-Propiolacton<
w-Nltroso-
diethylamine
1,2 Dichloro-
eth.vl ethyl
ether
Nitromethane
Kethyl ethyl
ketone
Styrene epoxlde
w-Nltroso-
dlethylaraine
Butadiene
diepoxide
Glycldaldehyde
Sulfolane
Propylene
oxide
Desorption
or
Extraction
Medium
(not removed)
• '
Sarnplinex^
Rat e .X"Samp 1 e
^^ Volume
.25H/min
Collection
Parameters
•
Recovery
and
Sensitivity
~)
/
> 98*
\ '
J •
")
...
>90!5
( '
•'
J
Associated
Analytical
Method
GC-FID
Reference
Pelllzzari, et al.
(1975)
.
I
U)
o
vn
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Chromosorb
ion
Chronosorb P
deactivated
with di-
n-butyl
phthalate
Accumulant
Aniline
Bls-(2-chloro-
ethyl) ether
N-Nitroso-
diethylamine
31s-(chloro- •
methyl) ether
Maleic
anhydride
1,3-Propane-
sultone
Methanethlol
2-propanethlol
C-, - Cc
2 6
aliphatics
Desorption
or
Extraction
Medium
(not removed)
120°C
-
Sampling/''^
Rat e -^Sample
jS"^ Volume
.25 i/nin
. 5«./min
. •
Collection
Parameters
-80°C dried with
MgCIO,, or KCO,
Recovery
and
Sensitivity
• 80?
-100
-100
Associated
Analytical
Method
GC-FID
GC-
.dldecyl-
phthalate on
Chromosorb P
90°C
GC-FID
cidecyl-
phthalate or.
Chromosorb P
90°C
or
tri-m-tolyl
phosphate on
Chromosorb W
93° or 73°C
Reference
Pellizzari, et al.
(1975)
Williams (1965)
Williams (1965)
I
LO
O
-------
ACCUMULATION OP OIWAMIC SUBSTANCES PRCM AIR
Accumulator
. Chromosorb P
deactivated
with di-
n-butyl
phthalate
Dexsll
Dexsil 300 on
Chromosorb W
Porapaks
Porapak Q 4 S
Accuaulant
EtOH
Acetone
EtOAc
Ether
C^-Cjj aldehydes
Propyl ether
Acrolein
Methyl nitrate
Ethyl nitrate
Butyronitrate
cci,,
Methyl sulflde
Methyl
dlsulfide
c, - c15
aliphatic s
•
Cl - C12
allphatics
Desorption
or
Extraction
Medina •
120°C
heat
,s^ Voluze
. 54/mln
2l/hr.
Collection
?araneters
-80°C dried with
MgClO,. or KCO,
i j
-1140°C to liq. N,
temp, gradient
-100°C
Recovery
and
Sensitivity
-100S
Associated
Analytical
Method
GC-
didecyl-
phthalate on
Chromosorb P
90°C
GC-FID
DC 200 on
Kieselguhr
-80°-150°C
GC-PID
10% DC 200 on
Supelcort Q
-60°-150°C
i
1 :
Reference i .
i :
Williams (1965)
Kaiser (1973)
Xaiser (1970)
I
OJ
o
-0
I
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM .AIR
Accumulator
, Porapak Q
Porapaks
Porapak Q
j
3
0
Accuaulant
Methane
Ethane
Acetylene
n f\
"3 C5
aliphatios
bis(chloro-
methyl) ether
Acetone
Propanol
Butanone
Cl - C3
chlorinated &
fluorinated
alkanes and
alkenes
Propane
n-Butane
n-Pentane
n-Hexane
Benzene
Toluene
Desorption
cr
Extraction
Medium
heat
heat
heat
180°C
heat
Sampline^^^
Rate ^^7,---,..
^*r Sample
^"^ Volur.e
<5i
<5*
<504
15*
1.54/min
1.7*
20cc/mln
Collection
Paraneters
22°C
22°C
22°C
head-space
Recovery
and
Sensitivity
95*
95
100
Quantitative
retention
volume (i)
<50
<100
<250
>500
500
500
Associated
Analytical
Method
GC-FID
GC-FID
GC-FID
Mass spectra
GC-Porapak Q
160°C
GC-ECD
Porapak
100°-166°C
GC-FID
C101
, !
Reference • !
i i
Bellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
Collier (1972)
Bellar, Sigsby
(1970)
Williams, Umstead
(1968)
Bellar, Lichtenberg
(1970)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accusulant
Porapak Q
Accumulator
Methylene-
chloride
Chloroform
Phenols
Naphthalene
1,1 Dichloro-
ethylene
C12FCCF2C1
CHC13
CH3CC1,
Chloro-
ethylene
bis-Chloro-
methyl ether
Desorption •
or
Extraction
Medium
heat
on-column
adsorption
heat
180°
under vacuum
Sampllng.x'^
Rat e -x-'Sa.inp i e
.S^ Volume
20cc/min
100-SOOcc
151 at
1.54/min
Collection
Parameters
head-space
aO'-SO'C
Recovery .
and
Sensitivity
retention
volume (i)
500 .
500
500
500
Quantitative
to 20 S.
Associated
Analytical
Method
GC-FID
C101
GC-
coulometric
detector
Mass Spec.
Reference
Bellar, Lichtenberg
(1974)
Williams, Umstead
(1968)
Collier (1972)
I
uo
o
vo
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Porapak Q
Accumulant
Ethyl methane
sulfonate
S-Propiolactone
w-Kitroso-
diethylamine •
1,2 Dichloro-
'ethvl' ethyl
ether
NItromethane
Methyl ethyl
ketone
Styrene epoxide
w-Nitroso-
diethylamine
Butadiene
diepoxide
Glycidaldehyde
Sulfolane
Propylene
oxide
Desorptlon
or
Extraction
Medium
(not removed)
Sampllng^x^
lat e .^Samp 1 e
^S^ Volume
.25A/mln
'
Collection
Parameters
•
Recovery
and
Sensitivity
•)
\ 90%
'
}
95%'.
Associated
Analytical
Method
GC-FID
.
Reference
Pelllzzarl, et al.
(1975)
I
UJ
t-1
o
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Porapak Q
Porapak S
Accumulant
Aniline
Bls-(2-chloro-
. ethyl) ether
N-Hltroso-
dlethylamlne
3is-(chloro-
methyl) ether
Maleic
anhydride
1,3-Propane-
sultone
CC123F2 .
CH2=CC12
C12FCCC1F2
BrF2CCBrF2
CHC1,
CHjCCl,
CHC1=CC12
cci2=cci2
Desorptlon
or
Extraction
Medium
(not removed)
on-column
adsorption
heat
-
Ssjnplinjj ^^^^
Rstc ^^^^oflnipls
^S — Volume
.25,/min
100cc-500cc
lOOcc
Collection
Parameters
300-500C
Recovery
and
Sensitivity
' 9°Z
Associated
Analytical
Method
GC-FID
GC-
coulometric
detector
Reference
Pelllzzarl, et al.
(1975)
Williams, Unistead
(1968)
I
U3
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM:AIR
Accumulator
Glass Beads
•
•
Accuaulant
Benzene
Toluene
Ethyl Benzene
p-Xylene
m-Xylene
o-Xylene
Isopropyl
Benzene
n-Propyl
Benzene
3,1 Ethyl
Toluene
Mesitylene
t-Butyl
Benzene
sec-Butyl
Benzene
n-Butyl
Benzene
Desorption
or
Extraction
Medium •
heat
S arr.p 1 in S^**
s^^ Volume
72cc '
Collection
Parameters
liquid N2
Recovery
and
Sensitivity
15 ppb
37
6
6
16
8
3
2
8
2
_
-
-
Associated
Analytical
Method
GC
Reference
Lonneman, Bellar,
Altshuller (1968))
•
I
uo
M
rv>
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM AIR
Accumulator
Tenax GC
'
•
Aocunulant
Volatile
organic s
Basic, neutral
and high- .
boiling com-
pounds
C4 ~ C15
^ •*• J
aliphatics
C9 " C18
alkanes
Aromatlcs
C8 - cll
Alkyl benzenes
Naphthalene
Toluene
Naphthalene
Xylenes
Alkyl. benzenes
Desorption
or
Extraction
Medium •
300°c
heat
heat
San-ollng^-^'^
Rat>^Sar.ple
^^ Volume
.5-2i/mln
.5-2i/mln
50-200cc/mln
50-200cc/mln
Collection
Parameters
Ambient temperature
up to 90°C
25°. - 60°C
25° - 60°C
Recovery
and
Sensitivity
>90$
>90t
Associated
Analytical
.Method
GC-FID
etched Ni
with Emul-
phor
30°-170°C
GC-FID
GC-FID
etched Ni
with Emul-
phor
30°-170°C
GC-FID
5% Dexsil
300 on
Chromosorb W
• GC-FID
Dexsil 300
on Chromo-
sorb W
GC-FID
Etched Ni
with Emul-
phor
30°-170°C
Reference
Zlatkis,
Llchtensteln,
Tishbee (1973)
Mieure, Dietrich .
(1973)
Bertsch, Chang,
Zlatkis (1974)
Mieure, Dietrich
(1973)
Mieure, Dietrich
(1973)
Bertsch, Chang,
Zlatkis (1974)
I
UJ
M
UJ
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Tenax GC
•
•
Accuaulant
Oxygenated
Compounds
Acetohenone
Tolualdehyde
Methyl
acetophenone
1,2,4-Trimethyl
benzene
o-Diethylben-
zene
n-Dodecane
Methyl Propyl-
benzene
Dichlorobenzene
n-Tridecane
Benzaldehyde
Methylindane
p-Tolualdehyde
m-Tolualdehyde
Acetophenone
o-Talualdehyde
Naphthalene
Methylnaph-
thalene
n-Hexadecane
n-Pentadecane
Desorption
or
Extraction
Medium •
heat
x.
Saraolinc.x^'^
Ra^^1ar:ple
s^ Volume
50-200cc/min
Collection
Parameters
Atmosphere in
Houston
«.
Recovery
and
Sensitivity
>90*
Associated
Analytical
Method
GC-FID
etched Ni
with Emul-
phor
GC-FID
capillary
columns
•
Reference
t
Bertsch, Chang,
Ziatkis (197t)
>
•
•
I
OJ
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Tenax GC
Accumulant
Ethyl methane
sulfonate
.B-Proplolactom
tf-Hitroso-
diethylamine
1,2 Dlchloro-
ethyl' ethyl
ether
Nitromethane
Methyl ethyl
ketone
Styrene epoxlde
w-Nitroso-
dlethylamine
Butadiene
diepoxide
Glycldaldehyde
Sulfolane
Propylene
oxide
Desorption
or
Extraction
Medium
(not removed)
Sanpllng>^
Rate ^Xsair.ple
.s^ Volume
.25Vnln
Collection
Parameters
Recovery
and
Sensitivity
~) •
\ 95?
\
J
—v
^
\ 90%
\
J
Associated
Analytical
Method
GC-PID
Reference
Pellizzarl, et al.
(1975)
I
UJ
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Tenax GC
Accuiaulant
Aniline
3is-(2-chloro-
ethyl) ether
w-Nitroso-
diethylamlne
3is-(chloro-
methyl) ether
Maleic
anhydride
1,3-Propane-
sultone
Styrene
1,3,5-Trimethyl
benzene
Isobutyl
Benzene
1-Methyl,
2-Ethyl
Benzene
Dimethylethyl-
benzene
Desorption
or
Extraction
Medium
(not removed)
heat
Sanpllng-x^
Rat e ^x*Samp 1 e
^S^ Volume
.25Vmin
50-200cc/mir.
Collection
Parameters
atmosphere in
Houston
Recovery
and
Sensitivity
"j
> 80*
\
.J
Associated
Analytical
Method
GC-FID
GC-FID
capillary
columns
Reference
Pellizzari, et al.
(1975)
.
Bertsch, Chang,
Zlatkis (1974)
I
UJ
M
cr\
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Tenax GC
.
Acoumulant .
Benzene
n-Nonane
Toluene
n-Decane
Ethyl Benzene
p-Xylene
m-Xylene
o-Xylene
m-Methylethyl
benzene
Limonene . '
n-Pentane
2 , 3 Dimethyl '
butane
ri-Hexane
Methyl Cyclo-
pentane
n-Octane
2-Methyl
octane
CHC13 .
Tetrachloro-
ethylene
n-Undecane
Desorptlon
or
Extraction -
Medium
heat
•
Sampling .s^
Rate .s'
^^ Sample
^ Volume
50-200cc/min
.•
Collection
Parameters
atmosphere in
Houston
Recovery
and
Sensitivity
1.3-15 ppb
1.6-4.4
0.3-9.7'
1.0-2.7
3.1-4.5
2.1-3.4
5.9-7.8
3.0-4.8
1.5-4.0
0.0-5.7
Associated
Analytical
Method
GC-FID
capillary*
columns
Reference
Bertsch, Chang,
Zl'atkis (1974)
I
uo
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accuaulator
Tenax GC
Accumulant
n-Hexane
Benzene
Toluene
Methylene-
chloride
Chloroform
Chlorobenzene
o-Dichloro-
benzene
1,2,4-Tri-
chlorobenzene
CH,C1.
2 2
CHCl,-
3
C1,CCH.
3 3
Cl.CCHCl
2
ci2ccci2
Desorption
or
Extraction
Medium
heat
heat
Sampling ^S^
Rate ~s^
./^ Sample
^S^ Volume
20cc/min
20cc/min
Collection
Parameters
head-space
head-space
Recovery
and
Sensitivity
retention
volume (I)
>500
500
500
500
500
500
500
500
3-8 ppb
7-12
8-16
9-40
3-6
Associated
Analytical
Method
GC-FID
'"lOl
GC-FID
C101
Reference
Bellar,
Lichtenberg (1974)
•
Bellar,
Lichtenberg (1974b)
I
OJ
h-'
co
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Tenax GC
Silicones
Support-bonded
silicones
(Cl8H37S103/2)
on Chromp-
sorb A
Support-bonded
silicones
Accumulant
Phenols
P-cresbls
Alcohols
Ke tones
Phthalate
esters
c7 - cl4
aliphatics
Acetophenone
Llndane
Heptachlor
Aldrin
Dleldrin
Heptachlor
epoxlde
Desorptlon
or
Extraction
Medium
extraction
with pentane
extraction
with pentane
Sampling .s''
Rate ~^^
-S^ Sample
^S^ Volume
I8i/min
U/min
I8t/mln
Collection
Parameters
25° - 60°C
filtered to 5u
Recovery
and
Sensitivity
Quantitative
Associated
Analytical
Method
GC-FID
Dexsil 300 on
Chromosorb W
GC-FID
OV-101 on
Chromosorb W
R.T. - 130°C
GC-FID
OV-101 on
Chromosorb W
R.T. - 130°C
GC-
OV-101 on
Chromosorb W
R.T. - 130°C
Reference
Kieure, Dietrich
(1973)
Aue, Tell (1S7D
Aue, Tell (1971)
Aue, Tell (1971)
I
UJ
M
MD
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Slllcones
Sillcone
elastomer
E-301 on
Cellte 515
or
polyethylene
glyool "lOO
Sillcone E301
on Celite 5^5
Accumulant
C6 - C10
Benzene
Toluene
Xylenes
Alkyl
benzenes
Indene
Naphthalene
Benzene
Toluene
Pyridine
Xylenes
Cyclohexanone
Benzaldehyde
Benzoyl
chloride
-------
ACCUMULATION CF ORGANIC SUBSTANCES FROM AIR
Accumulator
Sllicor.es
Sllicone E301
on Celite 515
SE-52 on
Chromosorb W
or
Charcoal
Activated
Carbon
Accumulant
Benzyl chloride
Benzotri-
chloride
Benzal chloride
C1-C2
chlorinated
alkanes and
alkenes
Alkanes and
alkenes
General
aromatic s
General
esters &
ethers
Trichloro-
ethylene
Desorptlon
or
Extraction
Medium
120°C
heat
heat
heat desorp-
tlon into
liquid Ng trap
heat
decane
Sampling ^^
Rate ^S
.s^ Sample
^^ Volume
lOOcc/min
50cc/mln
lOi/mln
13cfm
13cfm
500cc/min
601
Collection
Parameters
,5mm Hg
pressure drop
dry Ice
Recovery
and
Sensitivity
60-100?
80-100
95-100
Associated
Analytical
Method
GC-FID '
Silicone E301
on Celite
GC-ECD
. SE-52 on
Chromosorb W
IR and GC-
capillary
columns
IR
GC-caplllary
columns
GC-
SE-30 on
Chromosorb
110°C
Reference
Cropper, Katninsky
(1963)
Murray, Riley
(1973)
Turk, D'Angio (1962)
Turk, D'Angld (1962)
Herbolsheimer,
Funk, Drasche
(1972)
I
LO
IV)
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Activated
carbons
Accumulant
Ethyl methane
sulfonate
B-Propiolactone
N-Nitroso-
diethylaroine
1,2 Dichlbro-
ethvl' ethvl
ether
Nitronethane
Methyl ethyl
ketone
Styrene epoxlde
w-Hitroso-
diethylamine
Butadiene
diepoxide
Glycidaldehyde
Sulfolane
Propylene
oxide
Desorptlon
or
Extraction
Medium
(not removed)
Sampling^^
Rate^x^Sample
^^ Volume
.254/nin
Collection
Parameters
Recovery
and
Sensitivity
~]
> 90-95?
\ '
J •
^)
-
^30-952
\
J
Associated
Analytical
Method
GC-FID •
Reference
Pellizzari, et al.
(197^)
I
UJ
(V)
fY>
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Activated
carbons
Accumulant
Aniline
Bis-(2-chloro-
., ethyl) ether
w-Nitroso-
diethylaraine'
Bis-(chloro-
'methyl) ether
Maleic
anhydride
1,3-Propane-
sultone
Desorption '
or
Extraction
Medium
(not removed)
Sampllng^x^
Rate -x^Bample
^s^ Volume
.254/mln
Collection
Parameters
Recovery
and
Sensitivity
0-9055 ;
Associated
Analytical
.Method
GC-FID
Reference
Pelllzzari, et al.
(1975)
-,
- .
I
00
IV)
uo
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Cigarette-
filter
Charcoal
.
Accumulant '
C6 " C20
allphatlcs"
Aromatic s
C6 ~ C20
Toluene
Benzene
Benzofuran
Methylindan
Naphthalene
Alkyl benzenes
Dlphenyl
Pluorene
Alkyl
naphthalenes
Others
Benzaldehydes
Acetophenone
C,Q alcohols
Desorption
or
Extraction
Medium
extraction
with CS,
75°C *
cs2
cs2
Sampling ^^
Rate ~s^
^S"^ Sample
^^ Volume
2.5*/mln
25m3
2.5*/mln.
25m3
2.5i/min
Collection
Parameters
Recovery
and
Sensitivity
Associated
Analytical
Method
GC-MS
GC-MS
GC-MS
Reference
Grob & Grob (1971)
Grob 4 Grob (1971)
Grob & Grob (197D
I
LO
[NJ
-------
ACCUMULATION OF ORGANIC SUBSTANCES PROM AIR
Accumulator
Cigarette
Filter Charcoal
Accumu-lant
2-Methylnaph-
.- thalene :
h-Hexadecane
1-Methylnaph-
. thalene
Benzothiazole
h-Heptadecane
Diphenyl
2,6-Dimethyl-
naph thalene
1., 6-Dimethyl-
naphthalehe :
1,8-Dimethyl-
naphthalene
n-Octadecane
Methyldiphenyl
Acenaphthene
n-Nonadecane
Dibenzofuran
Fluorene
n-Eicosane
Benzaldehyde
Benzofuran
Desorptlon
or
Extraction
Medium
extraction c
CS2 72"
Sampling .^
Rate ~s"
^X^^SamPle
^s"^ Volume
2. Si/rain
25 m3
Collection
Parameters
•
'•
Recovery
and
Sensitivity
Associated
Analytical
Method
GC-MS
'
Reference
Grob & Grob
(1971)
•
I
OJ
ro
ui
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Cigarette
Filter Charcoal
Accuaulant
l-Ethyl-3- ' •
methylbenzene
Limonene
1,3,5-Tri-
methylbenzene
Isododecane
l-Ethyl-2-
nethylbenzene
1,2,4-Tri-
me thy Ibenzene
Octenal
l-Isopropyl-4-
«ie thy Ibenzene
n-Buty Ibenzene
Propylmethyl-
benze'ne
sec-Buty Iben-
zene
1,2,3-Tri-
me thy Ibenzene
Isotridecane
n-Oodecane
Ethyldimethyl-
_ benzene
Desorption
or
Extraction
Medlua
extraction c
CS-
72"
Sampling ^s —
Rate ^/^
^r Sample
^/^ Volume
2.5£/nin
25 m3
•
•
Collection
Parameters
•
V
Recovery
and
Sensitivity
Associated
Analytical
. Method
GC-MS
'
. •
Reference
Grob & Grob
(1971)
-
I
U)
ro
cr\
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
• AccuEUlator
Cigarette-
Filter Char-
coal
•
Accuaulant
2-Methylhexane
n-Heptane
Isooctane
Benzene
n-Octane ' '
Isononane
n-Nonane
Toluene , •
Isodecane
Tetrachloro-
ethylene -
n-Decane
Ethylbenzene
1,4-Dimethyl-
benzene
Isoundecane
1,3-Diraethyl-
benzene
1,2-Dimethyl-
benzene
n-Propylbenzene
n'-Undecane
l-Ethyl-4-methyi
benzene
Desorption
or
Extraction
Kediun
extraction c"
CS,
i 72oc
/
•
Sarnpllng ^^
Rate ~s"^
^X*1^32-111?!6
^S^ Volume
2.5*/rain
25 m3
Collection
Parameters
.
Recovery
ar.d
Sensitivity
Associated
Analytical
. Kethod
GC-MS
'
. •
Reference
Grob & Grob
(1971)
I
uo
ro
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM AIR
Accumulator
Cigarette
Filter Carbon
)
)
D
Accumulant
Dichlqrobenzene
1,2,3,5-Tetra-
methylbenzene
n-Tridecane
Methylindane
1,2,3,4-Tetra-
oethylbenzene
Isotetradecane
1,2,4,5-Tetra-
methyl benzene
4-Methylbenzal-
dehyde
3-Methylbenzal-
dehyde
n-Tetradecane
Acetophenone
2-Methylbenzal-
dehyde
Naphthalene
n-Pentadeca'ne
Dime thy Ibenzal-
dehyde
Desorption
or
Extraction
Medium
extraction c
CS2 72"
-•
• «
Sampling .s^
Rate ~s^
^ — Sample
^s Volume
2 . 5l/min
25 m3
.
Collection
Parameters
V
• •-
Recovery
and
Sensitivity
Associated
Analytical
. Method
GC-MS
"'
Reference
Grob & Grob
(1971)
I
uo
ro
CO
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM AIR
Accumulator'
Graphitized
Carbon Black
•
Graphitized
Carbon Black
• Accuaulant
1-4-Dimethyl-
haphthalene
2-3-Dimethyl-
naphthalene
Hexamethyl-
benzene
Acenaphthene
n-Pentadecane
Diphenylme thane
n-Hexadecane
Fluorene
n-Heptadecane
n-Octadecane
Dimethyl-
phthalate
Trims thyl
phosphate
Naphthalene
n-Dodecane
Isotridecane
Tridecene
Pentamethyl-
benzene .
2-Methylnaph- •
thalene
1-methylnaph-
thaler,e
Isotetradecane
Diphenyl
Desorption
or
Extraction
Medium •
400°C
heat
400«C
Sampllne^^'^
Ratex^araple
s^ Volun-.e
.5i/nin
200 t
t -
1-2 £
<5 it
.5 t/min
200 i
Collection
Parameters
20°
25°
Recovery
and
Sensitivity
87-104%
100%
[
Associated
Analytical
Method
GC-FID
OV-101
capillary
column
f
GC
GC-FID
OV-101
capillary
columns
.
1;
Reference j j
1 i
Raymond, Guiochon
(1974)
,
Raymond , Guiochon
(19751
I
uo
rv>
M3
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM'AIR
Accumulator
. Graphitized
Carbon Black
•
Accusmlaht
n-Te trade cane
2-ethylnaph-
thalene
1-Ethylnaph-
thalene
1,6-dimethyl-
naphthalene •
sec-Butylben-
zene
n-Decane
1,2,3-Tri-
methylbenzene
p-cymene
Indane
Isoundecane
Indene
Diethylbenzene
n-Butylbenzene
Ethyldimethyl-
benzene
Decahydronaph-
thalene
n-Undecane
1,2,1,5-Tetra-
methylbenzene
Isododecane
Desorptlon
or
Extraction
Medium
ilOO'C
Sampllng^x'^
RatexX^an!ple
s^ Volume
-54/rain
200 I
Collection
. Parameters
-
Recovery
and
Sensitivity
Associated
Analytical
Method
GC-FID
OV-101
capillary
columns
Reference
Raymond, Guiochon
(197t)
I
00
LO
O
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM'AIR
Accumulator
Graphltized
- Carbon Black
•
Accioulant
allphatlcs
Aromatic s •
Toluene
Alkyl benzenes
Styrene
1-octene
n-octane
Ethylbenzene
1-nonene
m-xylene
Isonane
o-Xylene
n-Nonane
Isodecane
n-Propyl-
benzene
P-ethyl
toluene
1,3,5-Tri-
raethylbenzene
p-xylene
m-ethyl
toluene
Desorption
or
Extraction
Mediua
llOO'C
Sampling^--''
^"^ Volume
•54/mln
2001
Collection
Parameters
-
Recovery
ar.d
Sensitivity
Associated
Analytical
Method
GC-FID
OV-101
capillary
columns
Eeferer.ce
Raymond, Guiochon
(1971)
•
I
oo
uo
M
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM Ala
Accumulator
Polyurethane
Foam
Alumina
-
Silica Gel
Accunulant
PCS
(Aroclors 1212
or 1218)
p,p'-DDT
0,P'-DDT
Chlqrdane •
PCB's
c2-c .
c. L.C.
aliphatlcs
Propane
n-Butane
n-Pentane
n-Hexane
Benzene
Toluene
Desorption
or
Extraction
Medium •
pet. ether
<100°C
temp, gradient
heat
Scunolincr ^^^^
,S^ Volume
.1-.8 m3/min
.5 m /min
12-31 hr
1.5Jl/hr
20cc/min
Collection
Parameters
5-20°C
-20°C
head-space
.
Recovery
and
Sensitivity
>90% •
• 3-9ng/m
.009-.090ng/ra3
.008-.037ng/m3
. 005-0. 25ng/m3
96-99?
retention
volume (J.)
>50
>500
500
500
500
500
Associated
Analytical
Method
GC-ECD
OV-17/QF-1
GC-FID
DC-200 on
Supelcort Q.
-60°-150°C
GC-FID
C101
Reference
Eidleman, Olney
(197la)
Bldleman, Olney
(197lb)
Kaiser (1970)
Bellar,
Lichtenberg (1971)
I
OJ
OJ
ro
I
-------
ACCUMULATION 0? ORGANIC SUBSTANCES FROM AIR
Accumulator •
Silica Gel
Silica Gel
Silica Gel 58
Acid Silica
Gel 58
Silica Gel 15
Silica Gel 58
Silica Gel 58
Silica Gel 15
Accumulant
Aliphatics
Ethylene
Ethylene •
Acetylene
Acetylene
c2 - c5
c2'- c5
c3-c5
Arc-mat Ic s
C6. ~ C10
Benzene
Toluene
Styrene
Ethyl benzene
Propyl benzene
Isopropyl
benzene
Desorptlon
or
Extraction
Medium
100°C
100°C
250°C
room temp.
heat
250°C
.heat
Samollng .s*
Rate ~s^
^S^ Sample
^^ Volume
550cc/mln
2500cc/mln
200cc/mln
*25l
90cc/min
72cc
*100i
<25*
S50
*500 .
Collection
Parameters
0°C
-78°C
-78°C
22°C
llq. N2
210-21°C
21°-2')0C
2i°-2l°C
21°-24°C
Recovery
and
Sensitivity
>90% '
(.C2ppra)
100?
lOppb
Associated
Analytical
Method
color
. reaction
GC-FID
GC-FID
acid silica
gel 30°C
GC-FID
GC-FID
GC-FID
GC-FID
Reference
Stltt, Tomlmatsu
(1953)
Stltt, Tomlmatsu
(1953)
Hughes, Gordon
(1959)
Bellar, Sigsby
(Unpublished)
Lonneman, et al.
(1971)
Bellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
I
U)
OJ
OJ
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Silica Gel
Acid Treated
Silica Gel
Silica Gel
Acoumulant
Aromatlcs
C6 - C10
Benzene
Toluene
Phenol
Benzene
Toluene
Benzene
Toluene
Xylenes
Benzene
Halogenated
Aliohatlc
Trichlorethane
C2C13H
Desorption
or
Extraction
Medium
isooctane
isopropanol
cyclohexane/
heptane
cumene , pyrl-
dlne or EtgO
Sampling .S^
Rate ^s^
^^ Sample
^S*^ Volume
60cc/min
1.2-1.5*/nln
1-34/mln
l-3*/mln _
•Collection
Parameters
dried with 5A
molecular sieves
dry air
sat. air
dry ice
Recovery
and
Sensitivity
20ppm
80%
80-100
30
90
Associated
Analytical
Method
formaldehyde
stain
UV
G.C-FID
polypropylene
glycol on
diatomaceous
earth
UV
Colorimetry
Reference
Hubbard, Silverman
(1950)
Maffett, Doherty,
Monkman (1956)
Whitman, Johnston
(196*.)
Elklns, Pagnotto,
Comproni (1962)
Ogata, et al.
(1973)
I
uo
UJ
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Molecular
Sieves
Carbon
Molecular
Sieves - 10cm
12x Molecular
Sieves
13x Molecular
Sieves
Molecular
Sieves
12x Molecular
Sieves
Polyethylene
Glycol
Polyethylene
Glycol 400
Polyethylene
Glycol 'lOO on
Stainless
Steel Nets
Accumulant
Allphatlcs
cl - C4
Ethane
Ethylene
C2 - C6
c2-c5
Methanol
Acetone
Insecticides
Desorptlon
or
Extraction
Medium
Temperature '
gradient
<200°C ._;
heat
moo°c
temperature
gradient
heat
benzene
Sampling ^^
Rate 's^
^^ Sample
^ — Volume
124/min
H*
<20i
lOW/mln
(10 min)
Collection
Parameters
-20° to liquid N,
temperature
gradient
22°C
21°-21°C
21°C
Recovery
and
Sensitivity
$k% at
.01 ppb
95%
2ppb
Associated
Analytical
Method
GC-FID
Carbon
molecular
sieves
-20°-200°C
.GC-FID
GC-FID
Porapak Q
70°C
GC-FID
DC-200 on
Supelcort Q
-60°-150°C
GC-FID
GC-
Cellte 5^5 +
Aplezon L
GC
Reference
Kaiser (1973)
Bellar, Slgsby
(Unpublished)
Harbourn, McCambley,
Trollope (1973)
Kaiser (1970)
Bellar, Sigsby
(Unpublished)
Novak, Vasak,
Janak (1965)
Beyermann, Eckrich
(1971 & 1973)
I
uo
oo
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
25$ Didecyl
phthalate on.
Chrom P
100/120
Accuraulant
Ethyl methane
sulfonate
B-Propiolactom
w-Nitroso-
diethylamine
1,2 Dlchloro-
ethvl' ethyl
ether
Nitromethane
Kethyl ethyl
ketone
Styrene epoxide
»-Nltroso-
dlethylamine
Butadiene
diepoxide
Glycldaldehyde
Sulfolane
Propylene
oxide
Desorption
or
Extraction
Medium
(not removed)
Sampllng^x^
tete.s^Sa.mp'le
^*r Volume
.25fc/min
Collection
Parameters
Recovery
and
Sensitivity
•)
> 502
\ , '
J .
~)
-.
} 80%
(
\ '
J '
Associated
Analytical
Method
GC-FID '
Reference
Pellizzari, et al.
(1975)
U)
OJ
cr\
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
25% Dldecyl
phthalate on
Chrora P
100/120
Oxypropio-
nltrile/Poracll
C 80/100
Accumulant
Aniline
Bis-(2-chloro-
. ethyl) ether
w-Nitroso--
diethylamine
Bls-(chloro-
methyl) ether
Malelc
anhydride
1,3-Propane-
sultone
Ethyl methane
sulfonate
. 8-Proplolactonf
w-Nltroso-
diethylaalne
1,2 Dlchloro-
ethyl' ethyl
ether . '
Nitromethane
Methyl ethyl
ketone
Desorptlon
or
Extraction
Medium
(not removed)
(not removed)
Sampling-X^
Rate^/Sample
^^^ Volume
.254/mln
.25Jl/min
• '
Collection
Parameters
Recovery
and
Sensitivity
50%
7
/ 98$
\
J
Associated
Analytical
Method •
GC-FID
GC-FID
Reference
Pellizzari, et al.
(1975)
I
OJ
-------
ACCUMULATION OP ORuANIG SUBSTANCES FROM AIR
Accumulator
Ox'ypropioni- •
trlle/Poracil
C 80/100
Accunulant
Styrene epoxide
w-Nitroso-
diethylainine
Butadiene
dlepoxlde
Glycldaldehyde
Sulfolane
Propylene
oxide
Aniline
Bis-(2-chloro-
ethyl) ether
N-Nitroso-
diethylamine
3is-(chloro-
methyl) ether
Maleic
anhydride '
1,3-Propane-
sultone
Desorptlon
or
Extraction
Medium
(not removed)
SaEpllng^-'''^
aa^Xsasple
s^ Voluae
.25£/min
'
Collection
Parameters
Recovery
and
Sensitivity
} :
\ 96%
\
)
^
/
f 90?
\
Associated
Analytical
Method
GC-PID
'
Reference
Pelllzaari, et al.
(1975)
I
uo
oo
00
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
20$ Tricresyl
phosphate on
Chrom W(HP)
100/120
Accuraulant
Ethyl methane
sulfonate
B-Propiolactom
w-tlitroso-
diethylamine
1,2 Dichloro-
ethyl" ethyl
ether •
Nitroniethane
Methyl ethyl
ketone
Styrene epoxide
«-l!itroso-
dlethylamlne
Butadiene
dlepoxlde
Glycldaldehyde
Sulfolane
Propylene
oxide
Desorptlon
or
Extraction
Medium
(not removed)
Sampling>x^
Rate .s'sa.mv 1 e
^^ Volume
.251/mln
Collection
Parameters
Recovery
and
Sensitivity
|
\ 20%
\ '
) .
^v .
/ .
\ 20?
(
\
Associated
Analytical
Method
GC-FID
Reference
Pellizzarl, et al.
(1975)
I
OJ
oo
VO
I
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
20? Tricresyi
phosphate on
Chrom W(HP)
100/120
Accumulant
Aniline
Bis-(2-chloro-
ethyl) ether
tf-Nitroso-
diethylamine
Bis-(chloro-
methyl) ether
Malelc
anhydride
1,3-Propane-
sultone
Desorptlon
or
Extraction
Medium
(not removed)
Sampllng^''^
Rate .s^Sa.mp'ie
.^^ Volume
.25i/mln
Collection
Parameters
Recovery
and
Sensitivity
•"]
I
> 20?
>
\
\
\
/
Associated
Analytical
Method
GC-FID
Reference
Pellizzari, et al.
(1975)
I
oo
-t
o
I
-------
ACCUMULATION OP.ORGANIC SUBSTANCES FROM AIR
Accumulator
1,2,3-tris
( 2-cyanoethoxy ) -
propane on
Chromosorb W
Accumulant
Methanol
Acetaldehyde
Acrolein
Propanal
Acetone
2-Methylpro-
panal
Butanal . '
Methylethyl-
ketone
Benzene
Ethylene Ox-ide
Methyl Formate
Ethanol
Propylene
Oxide
Acetonitrile
Furan
Dichlorome thane
Methyl Nitrate
Ethyl Formate
Acrylonitrile
2-Propanol
Methyl Acetate
Desorption
or
Extraction
Kediun
heat
Sampling ^^
Rate ^s"^
^s^ Sample
^s^ Volume
50cc/min
Collection
Parameters
Recovery
and
Sensitivity •
Associated
Analytical
. Method
GC-FID
Porapak Q
Reference •
Bellar, Sigsby
(1970)
I
uo
-------
ACCUMULATION OP ORGANIC SUBSTANCES PROM AIR
Accumulator
1,2,3-tris
(2-cyanoethoxy)
propane on
Chromosorb W
•
Acou.-nulant
Nitrome thane
Allyl Alcohol
2,3-Butylene
Oxide
Methyl
Acrolein
Isobutylene
Oxide
Propionitrile
2-Methyl Furan
1,2-Butylene
Oxide
2-Methyl
Propane-2-ol
Tetrahydro-
furan
Vinyl Methyl
Ketone
2 , 3-Butanedione
Cyclobutanone
Crotonaldehyde
2/2-Dimethyl
Butanal
2-Methyl
Propanol
Desorption
or
Extraction
Medina
heat
Sampling .S^
Rate ^^
^'"'sample
^^ Volume
50cc/min
!
Collection
Parameters
Recovery
and
Sensitivity
Associated
Analytical
. Method
GC-FID
Porapak Q
'
Referer.ee
Bellar, Sigsby
(1970)
I
uo
.t
ro
I
-------
ACCUMULATION OK ORGANIC SUBSTANCES PROM AIR
Accumulator
1,2,3-trls
(2 cyanoethoxy
Propane
1,2,3-trls
(2 cyanoethoxy
Propane on
Chromosorb W
Cryogenic
Trap
Cryogenic Trap
Cryogenic Trap
Glass-wool
Filter
Cryogenic Trap
Acoumulant
General
Aromatic s
CP
•a *"ii
j • "
Alcohols,
esters, alde-
hydes, oxides,
ketones
Allphatics
C - C
2 4
C2-C8
c; - 7
C - C
5 6
Desorption
or
Extraction
Medium
heat
heat with
hot water
distillation
hot water
. heating
Sampling .s^
Rate ^s^
^^ Sample
^s^ Volume
50cc/min
50cc/mln
*
lt
U/min
2004
14
Collection
Parameters
llq. K, 77° K
C.
liq. 02
(C02 removed with
ascarlte)
liq. N2 77°K
£24" Hg pressure
liq. N,
^ 2
Recovery
and
Sensitivity
89-100?
95
99
Associated
Analytical
Method
GC-PID
Porapak Q
160°C
. GC-
Porapak Q
160°C
GC-PID
hexadecane on
firebrick
10°C
Mass spectra
total carbon
analyzer
GC-FID
silicon on
firebrick
Reference
Bellar, Sigsby
(1970)
Bellar, Sigsby
(1970)
Feldstein,
Balestrieri (1965)
Shepherd, et -al.
(1951)
Cooper, Birdseye,
Donnelly (1971))
Feldstein,
Balestrieri (1965)
00
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Cryogsnle
Trap
Cryogenic
Trap
Cryogenic
Trap Glass
Wool Filter
Cryogenic
Trap
Cryogenic Trap
Glass Wool
Filter
Impingers
Midget
Impinger
Accumulant '
Aliphatics
C6 - C10
Others
Benzene
Toluene
Xylene
Alcohols
Aldehydes
Ke tones
Epoxides
C13C2H
Benzene
Xylidine
Desorptlon
or
Extraction
Medium
room temp.
distillation
room temp.
distillation
isooctane
Sampling ^^
Rate —
^S^ Sample
^S^ Volume
SOOcc
U/min
SOOcc
U/min
2001
200cc/min
.Collection
Parameters
liq. air
liq. 02
C0~ removed with
ascarite
liquid air
liquid 02 '
C02 removed with
ascarite
cool air before
sampling
Recovery
and
Sensitivity
90-100*
Associated
Analytical
Method
GC-
polyethylene
glycol or
DC 550 sill-
cone
Mass spectra
GC-TC
polyethylene
glycol 100
Mass spectra
UV
Reference
Hughes, Hurn
(I960)
Sheoherd, et al.
(1951)
Hughes, Hurn
(I960)
Shepherd, et-al.
(195D
Andrews, Peterson
(1917)
I
LO
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Implngers
Midget
Implnger
Midget
Impingers
with Fritted
Glass
Midget
Impinger
Implnger
Accumulant '
Ethyl acrylate
Methyl
methacrylate
Acrylonitrile
Methyl vinyl
Pyridlne
Cyclohexyl-
amine
Nitroglycerln
Ethylene glyool
dinitrate
Perfluoroiso-
butylene
Hexafluoro-
propene
R-C=CF2
Nitroparaffins
Dichloro-nltro-
ethane
CHjBr
PBC.' s
Desorption
or
Extraction
KediuQ
KMnO^/NaOH
.01N HC1
95? EtOH
MeOH
H2SO
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Impir.gers
Impingers
Polyethylene-
Coated Silica
Layer Trap
Layer Trap
(71 OV-17 on
chromosorb G
+• silica gel
+ 13x & 5A
molecular
sieves)
Accumulant
Lindane
Aldrlri
Dieldrln .
DDT
Aliphatics
Ethane
Ethylene
c3-c5
Aromatlcs
Benzene
Toluene
Styrene
Ethyl benzene
Propyl benzene
Isopropyl
benzene
Desorption
or
Extraction
Medium
ethylene
glycol
heat
heat
heat
heat
Sampling ^^
Rate ~^^
^ Sample
^^ Volume
1.5 ra3/hr
<25i
£50£
^1)004
^500i
Collection
Parameters
~-
22°C
21o_2jjoc
21°-2'J0C
Recovery
and
Sensitivity
poor
100?
95%
Associated
Analytical
Method
GC-FID
GC-FID
GC-FID
Reference
Herzel, Lahmann
(1973)
Bellar, Sigsby
(Unpublished)
Eellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
Bellar, Sigsby
(Unpublished)
I
LO
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Scrubbers
Scrubber
HgfClO^Jp or
on diato-
maceous earth
Scrubber
Hg(C10,,)2 on
diatomaceous
earth
Scrubber
Hg(C104)2 or
HjSO^-HgSOj, on
diatomaceous
earth
Others
Sintered glass
absorber
Sintered glass
Accumulant .
paraffins
acetylene
general
aromatic s
aromatic
Isocyanates
2-amino
pyridine
Desorptlon
or
Extraction
Medium
DMF/HC1
H20
Sampling .s
Rate 's^
^^ Sample
^S*^ Volume
ll/mln
Collection
Parameters
Room temperature
must be dry
Recovery
and
Sensitivity
100*
100*
Associated
Analytical
Method
OC-FID
Colorimetry
Colorlmetry
Reference
Mitsuo, Aoyama,
Yamaki (197f)
Meddle, Radford,
Wood (1969)
Watrous, Schulz
(1950)
I
OJ
-------
ACCUMULATION OP ORGANIC SUBSTANCES FROM AIR
Accumulator
Others
Bubbler
Fritted glass
bubbler
Bubbler with
glass beads
Glass beads
Bead-filled
tube
Accumulant
aromatic
isocyanates
nitroalkanes
2-nitro-
propane
organic
R-C=S com-
pounds
C6 - C10
benzene
alkyl
benzenes
toluene
xylenes
p-chloro ,
nitrobenzene
Desorption
or
Extraction
Medium
.1NHC1/HOAC
cone. HjSOjj
silica gel
2-propanol
u n
K20
EtOK with
diethylanine
120'
fuming nitric
acid
Sampling —
Rate ^S^
.*r Sample
^ — Volume
2 ftVhr
.5Vmin
500cc/hr
72oc
1.5/l/min
Collection
Parameters
llq. N2
Recovery
and
Sensitivity
952
100
. 99
75
50-100
2 tubes
2-130 ppb
100%
Associated
Analytical
Method
Colorlmetry
Colorlmetry
Colorinetry
'
GC-FID
bis(m-phenoxy
-phenoxy)
benzene wish
apiezon 73*C
Colorlraetry
Reference
Marcali (1957)
Jones (1963)
• -
Viles (19fO)
Lonr.ecan, Bellar,
Altshuller (1968)
Lonnen-.an, et al.
(1971)
Watrous, Schulz
(1950)
CO
I
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
Accumulator
Others
Folln aeration
tubes
Filter paper
with' 10$ NaOH
Filter paper
with 9J oxalic
.• acid
lOt sucrose
acetate on
Gas Chrom Z
Accumulant
Propylene
Glycol
Triethylene
Glycol
N-butyrlc acid
Isovaleric acid
methyl amlne
trimethyl
amlno
C - C
1 3
alcohols
esters
epoxldes
aldehydes
Desorption
or
Extraction
Medium
Water
concentrated
HCl/hexane
100°C
Sampling ^s^
Rate ^^
.S^ Sample
^s^ Volume
3001
20-30i/mln
2-64/mln
Collection
Parameters
-55"C
Recovery
and
Sensitivity
70-80$
95-97 -
2 tubes
<99
Associated
Analytical
Method
Colorimetry
GC
TMCBA on
Chromosorb V
139°C
GC-FID
Porapak Q
160°C
Reference
VJlse, Puck, Stral
(1967)
Okita, et al.
(1973)
Bellar, Sigsby
(1970)
I
OJ
-------
ACCUMULATION OF ORGANIC SUBSTANCES FROM AIR
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Beyermann, K., and Eckrich, W. "Differentiation of the
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Gisclard, J.B.; Robinson, D.B.; and Kuczo, P.J. Jr. "A Rapid
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Jones, Lawrence R. "The Determination of 2-Nitropropane in
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Kaiser, R.E. "Ultratrace Analysis of Volatile Substances
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-352-
-------
Kopczynski, Stanley L.; Lonneman, William A.; Sutterf ield,
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-354-
-------
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-355-
-------
SECTION FOUR ACCUMULATION PROM SOLIDS
4.0 Introduction
The accumulation of toxic substances from solids is a
broad and ill-defined topic covering such diverse solids
as soil, plant and animal tissue, sediment, and particulate
matter in the air. In an effort to narrow the scope of
study for this section, the solids chosen for detailed
analysis are soils and plant tissue. These two areas were
not chosen to imply that they are in any way more impor-
tant than any other solid but, rather, they were chosen
to be illustrative of all solids. The main accumulator
systems applicable to solids are solvent extraction, head
space analysis and biological accumulation. Biological
accumulation is considered elsewhere (Section Five) in
this report.
The method of toxic substance retention (ion exchange,
incorporation, etc.), type of medium (organic vs. inor-
ganic), and composition of the solid are all factors that
must be considered in choosing an extractant for a par-
ticular solid. For instance, before extractions from
animal tissues can be performed, it is necessary to
-356-
-------
separate the lipids from the other tissue constituents.
In contrast to this, many plant tissues are simply dry
ashed before extraction.
Soils and Plants
The soil is a dynamic chemical-biological system
composed of a complex matrix of inorganic matter that holds
animal material, water and gases. The complexity of the
soil medium can be ascertained by looking at the wide range
of characteristics of its constituents. For instance, the
inorganic matrix is composed of material ranging in size
from meters to millimicrons, a difference of 9 orders of
magnitude or more. Likewise the organic matter in the
soil varies from large tree roots to viruses.
In reality the soil acts as an accumulator for many
of the end products of today's society. In recent years
the soil has served as a receptor for municipal waste-
water, applied by spray irrigation and, when used in this
manner, the soil filters out most of the water's impuri-
ties. The soil also accumulates many of the materials
which fall on its surface, whether they are dusts from
a smoke stack or atmospheric gases dissolved in the rain-
water which falls on the earth's surface.
-357-
-------
A clear understanding of the mechanisms by which these .
added materials are held in the soil is necessary to pro-
pose accumulation techniques. These retention mechanisms
can be broken down into the following six areas:
1) Surface filtration
2) Ion exchange
3) Plant uptake
*J) Chemical immobilization
5) Clay entrapment, and
6) Microorganism activities.
These six retention mechanisms will be examined indivi-
dually in order to illustrate some of the problems which
will be encountered in applying accumulator techniques
to remove soil "pollutants".
Surface filtration occurs when a "pollutant" is too
large to infiltrate through the soil pores. If the compound
is organic in nature, the soil microorganisms will decompose
it into smaller particles until it can be incorporated into
the soil. If the "pollutant" is inorganic in nature, it
will remain on the surface unaffected. Whether it is organic
or inorganic in nature, it is susceptible to surface runoff
forces as long as it remains on the soil surface.
-358-
-------
Ion exchange is simply the reversible process by which
cations and anions are exchanged between solid and liquid
phases. The general mode of ion transfer in the soil is
that of cation exchange, with the organic colloids and
clay minerals being the primary exchange sites. Since
the clay minerals and organic colloids are generally
negatively charged, they attract positively charged ions,
thus neutralizing the system. The numerous cations which
soil colloids have adsorbed to their exchange sites are
held in varying degrees of tenacity, depending upon their
charges and their hydrated and unhydrated radii. As a
rule ions with a valence of 2 or 3 are held more tightly
than are monovalent cations. Also, the greater the de-
gree to which the ion is hydrated, the less tightly it
is held.
There are several pertinent points to consider when
selecting a solvent to extract a pollutant from the soil.
First, the cation exchange phenomenon is pH dependent,
the lower the pH the more H ions are on the exchange
sites and the fewer sites that are available for exchange.
Second, heavy metals of high valence with low hydration
will be held more tightly on the exchange sites than will
monovalent ions. Finally, in most soils, anion exchange
is very limited, so that most added anions will not be
held in the soil by the exchange mechanism.
-359-
-------
Most plant nutrition occurs through the plant's
extensive root system. For root uptake to occur, the
nutrients must be In the Ionic form. The ionizatlon of
nutrients is accomplished by the soil microorganisms,
by chemical reactions caused by the root, or is spontan-
eous in nature. In many cases the root is "blind" to
the ionic species which is being taken into the plant.
In this manner the plant acts as an accumulator by ab-
sorbing the most readily accessible ions from the soil
solution. Once inside the plant, the ions may be pre-
ferentially translocated from one site in the plant to
another, depending on the plant's metabolism, state of
development, and species.
Chemical immobilization can occur in the soil when
two or more ions coprecipitate out of the soil solution.
This is the process, by which soil minerals are formed.
When this occurs the precipitate will follow well defined
solubility rules. For example, HgSe (tiemannite) is
insoluble in water but soluble in aqua regia. A knowledge
of mineral and toxic substance solubility is necessary to
differentiate between an extraction solvent which will
selectively accumulate ions which are relatively free to
enter the soil solution from those which are bound up in
soil minerals.
-360-
-------
Clay entrapment can occur in instances when there are
expanding clay minerals of the montmorillonite type and
anions of the correct radii present. The entrapment occurs
when the clay is dehydrated and the ions lose their hulls
of oriented water molecules. Ions whose diameters allow
them to fit well into the lattice "holes" are then entrapped
in the clay micelle. Some anions which are affected by
this mechanism are K+, NH4+, Rb+, Cs+, Ba+23 Sr+2 and Li+.
Once these ions are taken into the clay micelle they are
not easily released by most soil reactions.
Microorganisms affect the availability of ions in
many ways. In general, microbial affects can be delineated
into the following six general areas:
1) release of inorganic ions during the decomposition
of organic materials
2) removal of inorganic ions from solution and the
disappearance of the available form of the element
to satisfy the nutrient demands of the microflora
(immobilization)
-361-
-------
3) utilization of inorganic ions as energy sources,
resulting in an oxidation
4) reduction of an oxidized state of the element
in the absence of adequate Cu.
5) Indirect transformations resulting from the ac-
tivities or the products of microorganisms
(i.e., changes in pH or alterations in the par-
tial pressure of Op by microbial respiration
causing oxidation state changes)
6) change in the total quantity of an element in
the soil by fixation, assimilation, or gas
formation.
Due to the extreme heterogeneity of the soil matrix,
it is essential that an adequate sampling technique be
derived so that the actual extraction is representative
of the soil chemical composition. Interpretation of the
extraction technique should also consider the possibility
that some elements which are immobile in soil solutions,
and therefore will not enter into the environment, will
become quite mobile in the extractant. An example of
this is the breakdown of minerals and release of ions
by acid extraction.
A compendium of the literature relating to the ac-
cumulation of toxic substances from soils and plant
-362-
-------
tissues is presented in Tables 4-7 through 4-10. The material
is broken down into four areas — accumulation of both organic
and inorganic material from both plant tissue and from
soil.
2 Accumulation by Extraction
In general, the extraction of inorganic material from
soils is accomplished by leaching the soil with the salt
of an acid or a chelating compound. This technique re-
places the available ions from the soil exchange sites.
Frequently ammonium acetate, sodium chloride or EDTA are
used for this purpose. If a total digestion of soil
inorganic matter is required, a strong acid - either
HpSOj, or HClOh - is used, and the soil is frequently
refluxed. The effectiveness of the accumulation process
generally depends on the soil pH, soil texture, amount
of extractant applied, and the organic content of the
soil.
Inorganic nutrients are generally extracted from
plant tissue after the tissue has undergone some pre-
treatment such as macerization or dry ashing. The most
frequently used extractants are acetonitrile and strong
acids. Likewise, the accumulation of organic matter
-363-
-------
from plant tissue generally follows the pretreatment of
the sample.
The choice of extractant for organic accumulations
is much more varied due to the diverse nature of the
organic constituents. In Tables 4-9 and 4-10 the or-
ganic material is differentiated into nine areas.
While these nine areas are specifically all sub-
divisions of pesticide analyses, in the more general sense
they are representative of all organic matter in the soil.
Most soil and plant analyses for organic matter have been
performed to determine the fate and metabolic pathways
of applied pesticides. Since the chemical nature of
pesticides is closely related to many toxic substances
of interest, the extraction of these toxic lipophilic
substances from soil will parallel the pesticide ex-
tractions. This can be verified by comparison of pest-
icide and toxic substance extractions from both air and
water. The following list shows the grouping and possible
extractants for each area:
1. Qrganochlorine pesticides - hexane: acetone
2. Organophosphorus pesticides - acetone or
acetone: isopropanol
3. Acidic pesticides - KC1 or ethyl ether
4. Triazine pesticides - chloroform or acetonitrile
-364-
-------
or methanol: H-O
5. Carbamate pesticides - polar: nonpolar solvent
mixtures
6. Uracil pesticides - NaOH
7. Anilide and aniline pesticides - benzene or
acetone
8. Benzonitrlle and amide pesticides - benzene:
isopropanol
9. Dipyridinium pesticides - strong acids
The choice of extractant is dependent on the type
of organic matter desired, the moisture content of the
sample, the pH of the sample, and the equilibration
time required for sampling.
3 Headspace Analysis
Headspace analysis of soil samples can be accomplished
by heating samples to 70°C, thus causing the volatili-
zation of the various hydrocarbon species which are
present. The vapors are then swept into a Tenax trap
by a stream of purified nitrogen, and the trap is sub-
sequently analyzed by devolatilization into a gas
chromatographic column, as described in the section on
the accumulation of organic matter from water (Section
2.1).
-365-
-------
Compounds with volatilities less than octadecane
and pyrene can be quantitatively analyzed under these
conditions. The advantages of this headspace analysis
technique for solid samples, as compared with extraction
analysis, are a minimization of contamination, an in-
crease in analysis speed, and the potential for auto-
mation.
-366-
-------
TABLE 4-1
COMMON AND CHEMICAL NAMES OP ORGANOCHLORINE PESTICIDES
Common Name
Aldrin
Aroclors
a-, B-, 6-and y-BHC
Chlordane
p,p'-DDE
p,p'-DDT
p,p'-DDT
Dieldrin
Fndosulfan
Endrin
Heptachlor
Heptachlor epoxide
p,p'-methoxychlor
TDE (ODD)
Toxaphene
Chemical Name
l,2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-
hexahydro-1,4-endo-exo-5,8-dimethano-
naphthalene
Polychlorinated biphenyls
a-, Q-, 8- and y-isomers of 1,2,3,4,5,6-
hexachlorocyclohexane
l3233,4,5,6,7,8-octachloro-253,3a34,737a-
hexahydro-4,7-methanoindane
l,l-dichloro-2,2-bis-(p-chlorophenyl) ethene
1,1,l-trichloro-2,2-bis-(o-chlorophenyl) ethane
l,l,l-trichloro-2,2-bis-(p-chlorophenyl)- ethane
1,2,3,4,10,10-hexachlor0-6,7-epoxy-1,4,
4a,5,6,7,8,8a-octahydro-l,4-endo-exo-5,8-
dimethanonaphthalene
6,7,8,9,10,10-hexachloro-l,5,5a,6,9,9a-
hexahydro-6,9-methano-2,4,3-benzodioxathiepin
3-oxlde
l,2,3,4,10,10-hexachloro-6,7,-epoxy-l,4,4a,
5,6,7,8,8a-octahydro-l,4-endo-endo-5,8-
dlmethanonaphthalene
l,4,5,6,7,8,8-heptachloro-3a,4,7,7a-
tetrahydro-4,7-methanoindene
1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-
tetrahydro-2,3-epoxy-4,7-methanoindene
1,1,l-trichloro-2,2-bls-(p-methoxyphenyl)
ethane
l,l-dlchloro-2,2-bls-(p-chlorophenyl) ethane
Chlorinated'camphene containing 67 to 69%
chlorine
-367-
-------
TABLE 4-2
COMMON AND CHEMICAL NAMES OF ORGANOPHOSPHORUS INSECTICIDES
Common Name
Disulfoton
Dursban
Dyfonate
Hinosan
Kitazin P
Methidathion
Mevinphos
Phorate
POA (phoratoxon)
PSO
PS02
POASO
POAS02
Zinophos
Chemical Name
0,0-diethyl S-[2-(ethylthio)ethyl]
phosphorodithioate
0,0-diethy1-0-3,5,6-trichloro-2-pyridyl
phosphorothioate
0-ethyl S-phenyl ethylphosphonodithioate
0-ethyl S,S-diphenyl phosphorodithioate
0 ,0-diisopropyl S-benzyl phosophorothioate
0,0-dimethyl S-(N-formyl-N-methylcarbo-
myI/methyl) phosphorodithioate
Mixture of isomers of methyl-3-hydoxycro-
tonate? dimethylphosphate
0,0-diethyl S-(ethylthiomethyl)
phosphorodithioate
Oxygen analog of phorate
Sulfoxide analog of phorate
Sulfone analog of phorate
Oxygen analog of the sulfoxide of phorate
Oxygen analog of the sulfone of phorate
0,0-diethyl 0-2-pyrazinyl phosphorothioate
-368-
-------
TABLE 4-
COMMON AND CHEMICAL NAMES OF CARBAMATE. SUBSTITUTED UREA.
URACIL, BENZONITRILE, ANILIDES, ANILINES AND AMIDE PESTICIDES
Common Name Chemical Name
CARBAMATES
Aldicarb 2-methyl-2(methylthio)propionaldehyde
0-(methylcarbamoyl)oxime
Carbofuran 2,3 j-dihydro-2,2-dimethyl-7-benzofuranyl-
methylcarbamate
Chlorpropham (CIPC) Isopropyl N-(3-chlorophenyl) carbamate
Propham (IPC) Isopropyl N-phenylcarbamate
Triallate S-2,3,3-trichloroallyl N,N-diisopropyl-
thiolcarbamate
URACILS
Bromacil 5-bromo-3-sec-butyl-6-methyluracil
Terbacil 3-tert-butyl-5-chloro-6-methyluracil
ANI.LIDES and ANILINES
Alachlor 2-chloro-2',6'-diethyl-N-(methoxymethyl)
acetanilide
DCA 3,4-dichloroaniline
DCNA 2,6-dichloro-4-nitroaniline
Propanil 3 34-dichloropropionanilide
TCAB 3,3',^,4'-tetrachloroazobenzine
BENZONITRILES and AMIDES
Dichlobenil 2,6-dichlorobenzonitrile
2,6-DCBA 2,6-dichlorobenzoic acid
KERB N-(l,l-dimethylpropynyl)-3,5-dichloro-
benzamide
-369-
-------
TABLE 4-
COMMON AND CHEMICAL NAMES OP TRIAZINE AND DIPYRIDINIUM PESTICIDES
Common Name Chemical Name
TRIAZINES
Atrazine 2-chloro-4-ethylamino-6-isopropylamino-
s_-triazine
Hydroxyatrazine 2-hydroxy-i*-ethylamino-6-isopropylamino-
s_-triazine
Prometryne 2,4-bis(isopropylamino)-6-methylmercapto-
s_-triazine
Propazine 2-chloro-il, 6-bis ( isopropylamino)-s_-triazine
DIPYRIDINIUM PESTICIDES
Paraquat l,l'-dimethyl-M,4'-dipyridinium salt
usually dichloride or dimethylsulfate
-370-
-------
TABLE 4-5
COMMON AND CHEMICAL NAMES OF ACIDIC PESTICIDES
Common Name Chemical Name
2,4-D 2,4-dichlorophenoxyacetic acid
Picloram 4-amino-3,5, 6-trichloropicolinic acid
2j4,5-T 2,4j5-trichlorophenoxyacetic acid
TABLE 4-6
COMMON AND •CHEMICAL 'NAMES OF 'SOME MISCELLANEOUS PESTICIDES
Common Name ' Chemical' Name
Amitrole 3-aminc—S^triazole
Oryzemate 3-allyloxy-l,2-benzisothiazole 1,1-dioxide
Trif luralin a,a,a-*trif luoro-2,6-dinitro-N-N-dipropyl-
p-toluidine
-371-
-------
TABLE 4-7
INORGANIC ACCUMULATION FROM SOIL
-372-
-------
INORGANIC ACCUMULATION PROM SOIL
Accumulant
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
As
Extractant
CaCl2
NaCl
KC1
NH,,OAc
HC1
Dithionate-
Citrate-
Bicarbonate
Ammonium
Oxalate
Na,P2Oy
H20 •
H20
NH^P
HC1
Special
Procedures
Pressure plate
Head space
analysis
Interferences
Time, pH
pH
PH
pH
pH .'
pH, Fe, POjj
pH, Fe, P0,j
pH, Fe, PO,,
PH
PH
Comments
Available Al
Available Al
Available Al
Available Al
Available Al
Total Al
Amorphous inorganic
and organic Al
Organic complexed
Al
From shale and
spoil material •
Concentration
(ppm)
.7-38.9
.7-700
2.0-586
28.8-1,122
.45-11.9
0.5
0.1
0.6
0.5-29,700
0.1-0.6
105.0-H500
3.3-15.3
% Recovery
92-100
98-101
92-100
93-106
Reference
Hoyt & Nyborg (197D
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
McKeague et al. (1971);
Arshad et al. (1972)
McKeague et al. (1971);
Arshad et al. (1972)
McKeague et al. (1971);
Arshad et al. (1972)
Massey & Barnhisel (1972)
Bradford et al. (1971)
Tandon (1970)
Melton et al. (1973)
I
uo
-
-------
INORGANIC ACCUMULATION FROM SOIL
Accumulant
Ba
B
B
Ca
Ca
Cd'
Co
Co
•DPTA » I
Extractant
H20
H20 •
hot HgO
H20
H20
HC1
H.O
DPTA»-Sodiuro
Acetate-CaClp
ilethylene trlam
Special
Procedures
Special
apparatus
Pressure plate
Shake
Lne pentaacetic
Interferences
Time dependent
PH
pH, 0/R '
icid
Comments
Prom shale and
spoil material
Extractable only.
A reference to
which the amount
of ions absorbed
by plant is related
Water soluble only
Labile pool
nutrients
Concentration
(ppm)
1.0-2. 4
2.0
o. y-'t.i
1.0-930
0.5
.01-. If)
0.5
it Recovery
Reference
Bradford et al.(1971)
Bradford et al. (1971)
John (1973)
Bradford et al. (1971)
Massey 4 Barnhisel (1972)
Lagerwerff (1971)
Bradford et al. (1971)
Lopez 4 Graham (1970)
I
UJ
-<]
-fc-
I
-------
INORGANIC ACCUMULATION PROM SOIL
Accumulant
Co
Cr
Cu
Cu
Cu
Cu'
Cu
Cu
Cu
Cu
Extract ant
NaOAc
H20
H20
DPTA
DPTA-Sodium
Acetate-CaCl2
NaOAc
HC1
Ammonium
Acetate
Ammonium
oxalate
Citric acid
Special
Procedures
Shake
Interferences
PH
pH, 0/R
PH
time, pH,
organic matter
phosphorus
time, pH,
organic matter
phosphorus
time, pH.
organic matter
phosphorus
time
Comments
Available
nutrients
Water soluble only
Water soluble, only
Available Cu
Labile pool
nutrients
Available
nutrients
Parent material,
exchangeable Cu
and Zn
Parent material,
exchangeable Cu
and Zn
Parent material,
exchangeable Cu
and Zn
Parent material,
exchangeable Cu
and Zn
Concentration
(ppm)
0.2
0. 01-. 017
0'.01-.20
0.2-3.2
0.5
0.1
1.6
0.5
2.6
0.7
% Recovery
Reference
Lopez 4 Graham (1972)
Bradford et al. (1971)
Bradford et al. (1971)
Pollett & Lindsay (1971)
Lopez & Graham (1970)
Lopez & Graham (1972)
Maclas (1973)
Maclas (1973)
Macias (1973)
Mac las (1973)
I
UJ
-o
Ul
I
-------
INORGANIC ACCUMULATION PROM SOIL
Accumulant
Cu
Cu
Cu
Cu
Cu
Pe
Fe
Fe
Fe
Fe
Fe
*EDTA » e
Extractant
EDTA»
DTPA
H20
KC1
H20
Dithionite-
cltrate-
bi carbonate
Ammonium
oxalate
Ha,,P207
H20
DPTA
CaCl2
;hylenediamlne t
Special
Procedures
Pressure plate
Shake
etraacetic acid
Interferences
PH
PH
Comments
Available
nutrients
Available
nutrients
Does not reflect
uptake by plant
Does not reflect
uptake by plant
From shale and
spoil material
Total Fe
Amorphous , Inorgan-
ic, and organic Fe
Organic complexed
Fe
Water soluble only
Available Fe
Nutrients avail-
able for plant .
growth
Concentration
(ppm)
0.2-9.7
0.2-9.7
0.5
0.01-.8
1.7-168.3
0.1
% Recovery
.
Reference
Haq and Miller (1972)
Kaq and Miller (1972)
Roth et al. (1971)
Roth et al. (1971)
Massey & Barnhlsel (1972)
McKeague et al. (197D
McKeague et al. (1971 ) '
McKeague et al. (1971)
Bradford et al. (1971)
Follett & Lindsay (1971)
Lopez & Graham (1970)
cr\
I
-------
INORGANIC ACCUMULATION PROM SOIL
Accumulant
Fe
Fe
Fe
Fe
Fe. •
Fe
Hg
Hg
Hg .
Extractant
DPTA-S odium
Acetate-CaCl2
NaCl, Sodium
citrate, ' :
Citric acid,
Sodium dlthi-
onite
HC1
NaOAc
EDHA-NaNO,
H20
H20
BaCl2
We2 '
Special
Procedures
Shake
Chelate
Pressure plate
Interferences
pH, 0/R
Organic matter
PH
Time , organic
matter
PH
pH, Cl~
Comments
Labile pool
nutrients
Removes free Fe anc
Mn02 from clay
Available Fe .
Varying importance
of total nutrient
level and pH
Available
nutrients
Labile Fe
From shale and
spoil material
Water soluble only
Hg (II)
Total Hg
Concentration
(ppm)
0.5
1.7
1.0
0.5
.0002-. 019
0.7
3.2-168
% Recovery
97-102.5
Reference
Lopez & Graham (1970)
Anderson & Jeanne (1970)
Sorenson et al. (1971)
Lopez & Graham (1972)
Johnson & Young (1973)
Massey & Barnhlsel (1972)
Bradford et al. (1971)
Hahne & Kroontje (1973)
Melton et al. (1971)
I
OJ
-------
INORGANIC ACCUMULATION FROM SOIL
Accunmlant
K
K
Li
Mg
Mg
Mn .
Mn
Mn
Mn
Mn
Extractant
H20
H20
H20
H20
H20
H20
H20
NaOAc
CaCl- solution
DPTA-Sodium
Acetate-CaCl2
Special
Procedures
Pressure plate
Pressure plate
Pressure plate
Shake
Shake
Interferences
pH
PH
PH
pH
PH
PH
pH, 0/R
Comments
From shale and
spoil material
Water soluble only
Water soluble only
Water soluble only
From shale and
spoil material
From shale and
spoil material
Available
nutrients
Nutrients avail-
able for plant
growth
Labile pool
nutrients
Concentration
(ppm)
0.5
0.7-128
0.03-1.08
O.t-'lOO
0.5
0.5
0.2
0.2
0.1
0.5
% Recovery
'
Reference
Massey & Barnhisel (1972)
Bradford et al. (1971)
Bradford et al. (1971)
Bradford et al. (1971)
Massey & Barnhisel (1972)
Massey & Barnhisel (1972)
Gupta (1972)
Lopez & Graham (1972)
Lopez & Graham (1970)
Lopez & Graham (1970)
OO
I
-------
INORGANIC ACCUMULATION PROM SOIL
Acoumulant
Mn
Mn
Mn
. ' 'Mn..'
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Extractant
NaCl, Sodium
citrate,
Citric acid,
Sodium
dithionlte
HC1
KC1
NH^OAc
Hydroquinone-
NH^OAc
CaCl2
HOAc
H3PO,,
HC1
DPTA
EDTA
DPTA
Special
Procedures
Interferences
Organic matter
PH
Comments
Removes free Iron
and Mn02 from clay
Available Mn.
Varying importance
of total nutrient
level, pH
Exchangeable pH
dep.
Exchangeable
Reducible
Soluble
Soluble-plant avail
able Mn
Soluble
.Soluble
Available Mn
Avaiable
nutrients
Available
nutrients
Concentration
(ppm)
2.6-99.1
1.6-111.9
2.7-266.9
3.0-68.5
5.1-78.1
12.9-112.8
0.2-31.7
3.9-111.6
1.1-10.0
1.6-10.0
% Recovery
Reference
Anderson & Jenne (1970)
Sorenson et al. (1971)
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
Hoyt & Nyborg (1971)
Follett & Lindsay (1971)
Haq and Miller (1972)
Haq and Miller (1972)
I
00
-4
vo
I
-------
INORGANIC ACCUMULATION FROM SOIL
• Accumulant
Mn
Mo
Mo
Na
Na
Ni
Ni
Ni
Ni
P
P
Extractant
H20
H20
H20: Dowex
(1-X1) resin:
NaCl
H20
H20
H20
H20
H20
KC1
NaHCO,
HC10,,
Special
Procedures
Pressure plate
Pressure plate
Heat
Interferences
pH
PH
PH
Comments
Water soluble only
Water soluble only
From shale and
spoil material
Water soluble only
Water soluble only
From shale and
spoil material
Does not reflect
uptake by plant
Does not reflect
uptake by plant
Total P
Concentration
(ppm)
0.01-.95
0.01-22.0
0.2
0.5
0.9-19,200
0.01-0.09
0.5
7.5
123
% Recovery
Reference
Bradford et al.(1971)
Bradford et al. (1971)
Bhella & Dawson (1972)
Massey & Barnhisel (1972)
Bradford et al. (1971)
Bradford et al. (1971)
Massey & Barnhisel (1972)
Roth et al. (1971)
Roth et al. (1971)
Carter et al. (1972)
Sommers & Nelson (1972)
I
UJ
oo
o
I
-------
INORGANIC ACCUMULATION PROM SOIL
Accumulant
P
Pb
Pb
S
S
Si
Sr
Sr
Tl
Extractant
Sodium
arsenate
HC1
H20
CaCl2 solution
KHjPO^
solution
H20
NH,,C1
H20
H20
Special
Procedures
Interferences
POjjVpH,
temperature
PH
Comments
Extractable only.
A reference to
which the amount of
ions absorbed by
plant is related.
Water soluble only
Soluble SOjj
Absorbed SO^
Water soluble only
Does not remove
nonexchangeable Sr
Water soluble only
Water soluble only
Concentration
(ppn)
0.01-.30
0.2-21.0
0.1-10.1
0.1
% Recovery
Reference
Barrow (1974)
Lagerwerff (1971)
Bradford et al. (1971)
Cowling & Jones (1970)
Cowling & Jones (1970)
Bradford et al. (1971)
Juo & Barber (1970)
Bradford et al. (1971)
Bradford et al. (1971)
I
00
oo
h-'
I
-------
INORGANIC ACCUMULATION FROM SOIL
Accumulant
V
Zn
Zn
Zn
Zn
Zn
Zn
Zn
Zn
Zn
Zn
Zn
•TEA = Ti
Extractant
H20
H20 '
H20
CaCl2 solution
CaCl2
DPTA-CaCl2
DPTA-TEA«CaCTl2
DPTA-Sodium
Acetate-CaCl2
DPTA
DPTA'
DPTA
EDTA
iethanolamine
Special
Procedures
Pressure plate
Shake
Shake
Interferences
PH
pH
pH, clay con-
tent , organic
matter
PK
pH, clay con-
tent , organic
matter
pH, 0/R
Soil texture
Comments
Water soluble only
Water Soluble only
From shale and
spoil material
Nutrients available
for plant growth
Available nutrients
Labile pool
nutrients
Available nutrients
Available Zn
Available nutrients
Concentration
(ppm)
0.01-1.20
0.01-.10
0.5
0.1
0.2
O.H
1.1
0.5
0.3
0.2-9.7
0.6-9.0
0.2-9.7
% Recovery
Reference
Bradford et al.(1971)
Bradford et al. (1971)
Massey & Barnhisel (1972)
Lopez & Graham (1970)
John (1972)
Lopez & Graham (1972)
John. (1972)
Lopez 4 Graham (1970)
Alley et al. (1972);
Brown et al. (1971)
Haq and Miller (197?)
Follett & Lindsay (1971)
Haq and Miller (1972)
I
UJ
oo
rv>
I
-------
INORGANIC ACCUMULATION PROM SOIL
Accumulant
Zn
Zn
Zn
Zn
Zn
Zn '
Zn
Zn
Zn
Zn
Zn
*EDDHA =
Extractant
EDTA
EDDHA*
HC1
HC1
HC1
HC1
HCl-H2S0l)
HC1-H2SO,,%
HCl-HgSO,,
HNOo-HP-HClOj,-
MgCl2
Ethylene diamin
Special
Procedures
s di(0-hydroxyph
Interferences
Soil texture
Soil texture
time, phos-
phorus, organ-
ic matter
Organic matter
content
pH, clay con-
tent, organic
matter
Soil texture
pH, clay con-
tent, organic
matter
anyl acetic aci
Comments
Available nutrients
Parent material.
Exchangeable Cu and
Zn
Extractable only.
A reference to
which the amount of
ions absorbed by
plant Is related.
Available Zn.
Varying importance
of total nutrient
level and pH
Available nutrients
Total zinc
I)'
Concentration
(ppra)
0.2 .
2.0-7.5
0.5
<). 2
2.8
0.6
0. Q-b.k
1.6
1.6
% Recovery
• Reference
Alley et al. (1972);
Brown et al. (1971)
Haq and Miller (1972)
Alley et al. (1972)
Brown et al. (1971)
Macias (1973)
Lagerwerff (1971)
Sorenson et al. (1971)
John (1972)
Alley et al. (1972)
Haq and Miller (1972)
John (1972)
John (1972)
I
uo
oo
00
I
-------
INORGANIC ACCUMULATION PROM SOIL
Accumulant
Zn
Zn
Zn
Zn
Zn
Zn
Extractant
NHjjOAc
NH^OAc
•
NH^OAc
Ammonium
oxalate
Citric Acid
NaOAc
•
Special
Procedures
Interferences
pH, type of
clay
pH, clay con-
tent , organic
matter
Time, pH,
organic matter
phosphorus
Time, pH,
organic matter
phosphorus .
Time
pH, clay con-
tent, organic
matter
Comments
Available Zn
Parent material.
Exchangeable Cu and
Zn
Parent material.
Exchangeable Cu and
Zn
Parent material.
Exchangeable Cu and
Zn
Concentration
(ppm)
2.0
•
1.2
5.3
4.2
0.96
% Recovery
-
Reference
Reddy & Perkins (197^)
John (1972)
Maclas (1973)
Maclas (1973)
Macias (1973)
John (1972)
I
uo
oo
-t
I
-------
TABLE 4-8
INORGANIC ACCUMULATION FROM PLANTS
-385-
-------
INORGANIC ACCUMULATION FROM PLANTS
Accumulant
Al
Al
As
As
B
Ca
Cd
Cl
Co
Cu
Extractant
HC1
HC1
HNO~: H^SOj,:
H20: NHj,
Oxalate
HN03; H2S0l,
Ca(OH)2:
HC1
H2S01)-HN03
Na2C03
H20: HC10,,,
HF
HC1
Special
Procedures
Dry ash first
Ignite sample
first
Dry after
Ca(OH). addi-
tion
Ignite sample
first
Ignition
Oven dry :
grind: ash dry
first
Dry ash first
Medium
Plant tissue
Plants
Plants, food
Food
Plants
Plants
Food
Plants
Plants
Citrus roots
Comments
Concentration
28 ppm
10 ppm
% Recovery
Reference
Hoyt and Nyborg (1971)
AOAC 1 (1970)
AOAC 1,2 (1970)
AOAC 2 (1970)
AOAC 1 (1970)
AOAC 1 (1970)
AOAC 2 (1970)
AOAC 1 (1970)
AOAC 1 (1970)
Brams and Flskell
(1971)
I
UJ
oo
cr\
I
-------
INORGANIC ACCUMULATION FROM PLANTS
Accuraulant
Cu
Cu
Cu
Cu
Cu
Fe •
Fe
Fl
Hg
Hg
Extractant
H2S0l,-HN03
H»03
NH,. Citrate:
NH?OH: Dithi-
zone in CCl^
HN03: HC1
H20: HN03:
HC10,,
HC1
HNO,
Ca(OH)2
HN03
HN03: HN03-
H2SOjj
Special
Procedures
Dry ash first
Dry ash first
Ignite sample
first .
Dry ash first
Dry after
Ca(OH), addi-
tion
Medium
Food
Grass
Plants .
Alfalfa plant
Alfalfa plant
Plants
Grass
Food
Plants and
food
Food
Comments
pH dependent
Total Cu determin-
ed
No pretreatment
necessary
pH dependent
Total Hg
Special apparatus
Concentration
8 ppm
9 .ppm
0.01 ppb
% Recovery
96-100
95-102
Reference
AOAC 2 (1970)
Bonn and Aba-Husayn
(1971)
AOAC 1 (1970)
Baker (1971)
Baker (1971)
AOAC 1 (1970)
Bonn and Aba-Husayn
(1971)
AOAC 2 (1970)
Hoover, Helton, and
Howard (1971)
AOAC 2 (1970)
I
UJ
oo
-
-------
INORGANIC ACCUMULATION FROM PLANTS
Accumulant
K
Mg
Mn
Hn
Mn
Mn •
Mn
Mo
Mo
Na
Extractant
HjSO,,: HC1
HC1
MgO-H20: HC1
HN03
HC1
HNOji HC10,,:
HC1
HC1
HNOj: HClOj,
HC10,, '
HjSO^HCl
Special
Procedures
Ignite sample
first
Dry ash after
MgO-H20
Dry ash first
Dry ash first
Ignite sample
first
Medium
Plants
Plants
Barley,
Rape, Alfalfa
Grass
Wheat, alfal-
fa, corn,
sorghum
Wheat, alfal-
fa, corn,
sorghum
Plants
Plants
Clover
Plants
Comments
pH dependent
Requires extra
attention
pH dependent
Concentration
'1(7-1658 ppm
.1 ppm
.1 ppm
0.6 ppm
% Recovery
87.0-103.5
Reference
AOAC 1 (1970)
AOAC 1 (1970)
Hoyt and Nyborg (1971)
Bohn and Aba-Husayn
(1971)
Smith and Schrenk
(1972)
Smith and Schrenk
(1972)
AOAC 1 (1970)
AOAC 1 (1970)
Bhella and Dawson
(1972) .
AOAC 1 (1970)
I
uo
oo
oo
I
-------
INORGANIC ACCUMULATION PROM PLANTS
Accumulant
. P
Pb
Pb
S
Sb
Se •
Se
Sn
Zn
Zn
Extractant
HC1
KC1 •
HNO,: HC10,,.
Na2CO,: H20:
HN03: H2SO,,
H^-HNO,
HgO fixative:
HN03: HgSO,,
HC1
HN03: HClOj,:
HC1
Special
Procedures
Ignite sample
first
Dry ash first
Fusion
Grind sample
first
Ignite sample
first
Medium
Plants
Food
Corn and
alfalfa plants
Plants
Food
Plants
Food
Food
Plants .
Wheat, alfal-
fa, corn,
sorghum
Comments
Requires extra
attention
Concentration
12 ppm
.03 ppm
% Recovery
Reference.
AOAC. 1 (1970)
AOAC 2 (1970)
Lagerwerff, Armiger,
and Specht (1973)
AOAC 1 (1970)
AOAC 2 (1970)
AOAC 1 (1970)
AOAC 2 (1970)
AOAC 2 (1970)
AOAC 1 (1970)
Smith and Schrenk
(1972)
I
OJ
CO
\o
I
-------
INORGANIC ACCUMULATION FROM PLANTS
Accumulant
Zn
Zn
Zn
Zn
Extractant
HC1
HCIQ1'"230^
HNO,
j
uwr\ • UPT n
nNU^: nClUj,
•
Special
Procedures
Dry ash first
Dry ash first
Medium
Wheat, alfal-
fa, corn,
sorghum
Food
Grass
Corn and oat
grain
Comments
pH dependent
Concentration
.03 ppm
10. 't ppm
'
% Recovery
«9. 5-106. 5
Reference •
Smith and Schrenk
(1972)
AOAC 2 (1970)
Bohn and Aba-Husayn
(1971)
John (1972)
•
I
oo
VD
o
I
-------
TABLE 4-
ORGANIC ACCUMULATION FROM SOIL
-391-
-------
ORGANIC ACCUMULATION FROM SOIL
Accumulant
ACIDIC PESTICIDES.
2,4-D
PICLORAM
PICLORAM
PICLORAM
2,1,5-T
ANILIDE . & ANILINE P
ALACHLOR
DCA
DCA
DCNA
Extractant
H^O,,, HgO, ETHYL
ETHER
KC1 -. KOH
ACETONE - HgPO,,
ACETONE - WATER
HC1
H20
ETHYL ETKER
5STICIDES -
BENZENE
ACETONE
ETHYL ALCOHOL
HC1: ACETONE:
GLYCOL
Special
Procedures
Tumbling
Shaking
Stirring
Stirring
Shaking
Shaking
Blending
Shaking
Shaking
Comments
- '
18 hours equili-
brium
-
-
- -
-
-
Sterilize 1-66 '
days
Concentration
.013 to 1.3 ppm
-
-
.025 to .1 ppm
(V)
I
-------
ORGANIC ACCUMULATION FROM SOIL
Accunulant
PROPANIL
PROPANIL
PROPANIL
TCAB
TCAB
TCAB
BEHZONITRILE AND AM
DICHLOBENIL
DICHLOBENIL
2,6-DCBA
KERB
Extractant
ACETONE
ETHANOL
ACETONE: BENZENE
ACETONE
ACETONE: BENZENE
ETHANOL
IDE PESTICIDES
ETHANOL
BENZENE:
ISOPROPANOL
ETHANOL
METHANOL
Special
Procedures
Blending
Shaking
Blending
Blending
Blending
. Shaking
Boiling
• Shaking
Boiling
Soxhlet
Comments
-
-
-
-
. -
-
0.5-12 month
equilibrium .
-
1-6 month
equilibrium
34 day equili-
brium
Concentration
-
100 ppm
-
-
-
.05 ppm
2.0 ppm
.07-. 08 ppm
2.0 ppm
20 ppm
% Recovery
>90
97-108
90
>90
98
-
90
81-105 .
• 90
38-100
Reference
Chisaka and Kearney
(1970)
Burge (1973)
Kearney, et al.
(1970)
Chisaka and Kearney
(1970)
Kearney, et al.
(1970)
Burge (1973)
Verloop and Nimmo
(1970)
Skroch, et al.
(1971)
Verloop and Nlmmo
(1970)
Yih, et al.(1970)
I
UJ
MD
UJ
I
-------
ORGANIC ACCUMULATION FROM SOIL
Accunulant
KERB
CARBAMATE PESTICIDE
ALDICARB
CARBOFURAN
3-KETO
CARBOFURAN
3-HYDROXYCARBO-
FURAN
CIPC
EPTC
IPC
Extractant
H2SO,| - METHANOL
3
ACETONE: METHANOL
AND CHLOROFORM:
ACETONITRILE
HC1
HC1
HC1
ETHANOL
ISOOCTANE
ETHANOL
Special
Procedures
-
Shaking • .
Re fluxing
Refluxing
Refluxing
Shaking
Steam distill
Shaking
Comments
-
0,1,7 day
equilibrium
-
-
-
-
1 day equilibrium
—
Concentration
.01 ppm
20 ppm
0.2-100 ppm
0.1-10 ppm
0.2-100 ppm
100 ppm
-
100 ppm
% Recovery
-
85-100
71-115
76-98
72-119 '
92-100
>90
91-100
Reference
Adler, et al.
(1972)
Bull, et al.
(1970)
Butler and
McDonough (1971)
Butler and
McDonough (1971)
Butler and
McDonough (197D
Surge and
Gross (1972)
Smith and
Fitzpatrlck (1971)
Burge and Gross
(1972)
I
UJ
^o
J=r
I
-------
ORGANIC ACCUMULATION FROM SOIL
Accumulant
TRIALLATE
TRIALLATE
DIPYRIDINIUM PESTIC
PARAQUAT
MISCELLANEOUS PESTI
AMITROLE
TRIFLURALIN
TRIFLURALIN
TRIFLURALIN
TRIFLURALIN'
ORGANOCHLORINE FES'!
ALDRIN
ALDRIN-DIELDRIN
Extractant
BENZENE: ISOPROPA-
NOL
BENZENE: ISOPROPA-
NOL
IDES
H2S0l)
CIDES
NH^OH: GLYCOL
HEXANE: ACETONE
BENZENE: ISOPRO-
PANOL
METHANOL
METHANOL
ICIDES
HEXANE: ACETONE
HEXANE: ACETONE
Special
Procedures
Shaking
Shaking
Ref luxing .
Shaking
Sonified
Shaking
Tumbling
Tumbling
Shaking
Shaking
Comments
1 day equilibrium
-
1 to 17 day
equilibrium
-
1 day equilibrium
2 day equilibrium
0-7 day equilibrium
-
Concentration
-
-
-
2.0 ppm
0 . 1 ppm
0.1 to 1.0 ppm
0.1 to 2.5 ppm
6.0 ppn
.05-.! ppm
.005 to .015
% Recovery
95
>90
>80
68-97
—
89-99
61-71
81-95
90-100
38-81
Reference
Smith (1971)
Smith and
Fitzpatrick (1971)
Earnest (1971)
Grove and Chough
(1971)
Parr and Smith
(1973)
Smith (1972)
Harrison and
Anderson (1970)
Harrison and
Anderson (1970)
Saha and Sumner
(1971)
McCaskill, et al.
(1970)
I
U)
MD
\~n
I
-------
ORGANIC ACCUMULATION PROM SOIL
Accumulant
ALDRIN-DIELDRIN
ALDRIN-DIELDRIN
ALDRIN, DIELDRIN
HEPTACHLOR,
HEPTACHLOR EPOX-
IDE
AROCHLOR
Y-3HC
Y-BHC
T-3HC
Y-BHC
CHLORDANE
CHLORDANE
CHLORDANE '..
Extractant
HEXANE: ISOPRO-
PANOL
ACETONITRILE
HEXANE
ACETONE: PETROLEUM
ETHER
HEXANE: ACETONE
HEXANE: ACETONE
HEXANE: ACETONE
ACETONE
ACETONE
WATER: HEXANE-
ACETONE
WATER: HEXANE-
2-PROPANOL
Special
Procedures
Tumbling
Blending
Grinding
Soxhlet
Shaking ' •
Soxhlet
Soxhlet
' Polytron
Polytron
Shaker
Shaker
Comments
-
-
' -
1) day equilibrium
1.5 hour equilibrium
1M days
1 month equili-
brium
-
. -
™
Concentration
-
-•
0.1-0.') ppm
-
,001 ppm
50 ppm
9-10 ppm
2.0 ppm
2.0 ppm
=1 ppm
1 ppm
% Recovery
88-102
90-95
90-105
>80
87-92
79-10<4
90-99
91-99 •
93
-
—
Reference
Onsager, et al.
(1970)
Lichtenstein (1970)
Grussendorf (1970)
Duke, et al. (1970)
Browraan (1971)
Adams and Li
(197D
Guenzi and Beard
(1970)
Johnsen and Starr
(1972)
Johnsen and Starr
(1972)
Saha (1971)
Saha (1971)
I
oo
vo
a\
I
-------
ORGANIC ACCUMULATION FROM SOIL
Accumulant
CHLORDANE
CHLORDAHE
•
a-,Y-CHLORDANE
HEPTACHLOR
HEPTACHLOR EPOX-
IDE
P,P'-DDE
P,P'-DDE;
o,P'-DDT;
p,p'-DDT
P,P'-DDE;
o,p'-DDT; '
P,.P'-DDT
P,P'-DDE;
o,p'-DDT;
P,P'-DDT
P,P'-DDE;
o,P'-DDT;
P,P'-DDT
p,p'-DDT
o,p'-DDT
Extractant
WATER: METHANOL
WATER: BENZENE-
METHANOL
BENZENE: ACETONE
HEXANE: ACETONE
ACETONE
HEXANE: ACETONE
HEXANE: ISOPRO-
PANOL
HEXANE: ACETONE
HEXANE: ACETONE
HEXANE: ACETONE
Special
Procedures
Shaker
Shaker
Shaking
Shaking
Polytron
Shaking
Tumbling
Shaking
Shaking
Shaking
Comments
-
_
_
8 day equilibrium
1 month equili-
brium
_
_
_
it day equilibrium
8 day equilibrium
Concentration
1 ppm .
1 ppm
0 . 1 ppm
0.32 ppra
2 ppm
.005-. 015 ppm
_
.05 - .1 ppm
0.1 - 0.2 ppm
0.43 ppm
% Recovery
-
_
85-91
84-99
92-105
38-81 .
88-102
90-100
88-112
77-111
Reference
Saha (1971)
Sana (1971)
Dorough, et al.
(1972)
Browman (1971)
Johnsen and Starr
(1972)
McCaskill, et al.
(1970)
Onsager, et al.
(1970)
Saha and Sumner
(1971)
Browman (1971)
Browman (1971)
I
UJ
-------
• ORGANIC ACCUMULATION FROM SOIL
Accunulant
fc,p'-DDT
p ,p '-TDK
p-p'-DDT
P-p'-DDT
p - p'-DDT '
P-p'-DDT
DIELDRIN
DIELDRIN
DIELDRIN .
DIELDRIN
DIELDRIN,
HEPTACHLOR
EPOXIDE
Y- and 6 ENDO-
SULFAN
Extractant
HEXANE: ISOPRO-
PANOL
BENZENE: ISOPRO-
PANOL
HEXANE: ACETONE
HEXANE: ACETONE:
CHjCOONa
HEXANE: ACETONE
HEXANE: ISOPRO-
PANOL
ACETONE
ACETONE
HEXANE: ACETONE
ACETONE
PETROLEUM: ETHER
Special
Procedures
Soxhlet
Shaking
Soxhlet
Shaking
Soxhlet
Soxhlet
Polytron
Polytron
Shaking.
Ultrasound
Heat
Comments
31 days
-
30 day equili-
brium
-
It day equili-
brium
-
1 month equili-
brium
-
t day equilibrium
-
Concentration
1.2 ppm
.-
-
-
10.0 ppm
-
2.0 ppm
0.2 ppm
.Ot-.08 ppm
1-2 ppm
0.2-0.3 ppm
% Recovery
87-102
90
70-102
93
95-100
92-95
92-105 '
96±2.2
87-91
92-99
87-89
Reference
Burge (1971)
Swoboda, et al.
(1971)
Peterson, et al.
(1971)
Willis, et al.
(1971)
Guenzi and Beard
(1970)
Caro and Taylor
(1971)
Johnsen and Starr
(1972)
Johnsen and Starr
(1972)
Browman (1971)
Johnsen and Starr
(1972)
Greve and Wit
(197.1) •
co
I
-------
ORGANIC ACCUMULATION FROM SOIL
Accunulant
ENDRIN
HEPTACHLOR
HEPTACHLOR
HEPTACHLOR
EPOXIDE
HEPTACHLOR
EPOXIDE
HEPTACHLOR
EPOXIDE-
HEPTACHLOR
METHOXYCHLOR
METHOXYCHLOR
TDE
p,p'-TDE
Extractant
HEXANE: ISOPRO-
PANOL
PENTANE:' ACETONE
HEXANE: ACETONE
HEXANE: ACETONE
ACETONE
ACETONITRILE .. .
HEXANE: ACETONE
ACETONE
HEXANE: ACETONE
HEXANE: ACETONE
Special
Procedures
Shaking
Tumbling
Shaking .
Shaking
Polytron
Blending
Shaking
Polytron
Shaking
Shaking
Comments
1.5-2 day equili-
brium
-
8 day equilibrium
8 day equilibrium
1 month equili-
brium
-
8 day equilibrium
8 day equilibrium
-
8 day equilibrium
Concentration
- .
.-
0.13 ppm
0.27 ppm
2.0 ppra
-
2.6 ppm
2.0 ppm
.05-0.1 ppm
0.6 'ppm
% Recovery
97-99
92-98
-
87-123
91-99
90-95
11-97
93±1
90-100
89-108
Reference
Saha and Sumner
(1971)
McCaskill, et al.
(1970)
Browman (1971)
Browman (1971)
Johnsen and Starr
(19.72)
Lichtenstein (1970)
Browman (1971)
Johnsen and Starr
(1972)
Saha and Sumner
(197D
Erowman (1971)
I
OJ
^O
VD
I
-------
ORGANIC ACCUMULATION FROM SOIL
Accumulant .
TOXAPHENE
TOXAPHENE
MIXTURE OF 11
ORGANOCHLOHINE
PESTICIDES
ORGANOPHOSPHORUS PE
DISULFOTON
DURSBAN
DYFONATE
METHIDATHION
MEVINPHOS
PHORATE
Extractant
BENZENE: ISOPRO-
PANOL
HEXANE: ACETONE
HEXANE: ISOPRO- .
PANOL
3TICIDES
ACETONE: WATER
ACETONE
HEXANE OR CHLORO-
FORM
ACETONE: .CaCl2
HEXANE: NagSOjj
HEXANE: NajSO^
Special
Procedures
Shaking
Soxhlet
Shaking
Blending
Tumbling
Shaking
Shaking
Shaking
Shaking
Comments
-
-
-
-
-
-
-
-
-
Concentration
-
-
'
-
0.1 ppm
-
10 ppm
100 ppm
100 ppm
$ Recovery
90
88±2.9
6l±10
85-92
110
86-83
97-9«
91
98
Reference
Swoboda, et al.
(1971)
Veith and Lee
(197D
Hannon, et al.
(1970)
Mer.zer, et al.
(1972)
Dusch, et al.
(1970)
Kilgemanl and
Terriere (1971ab)
Getzin (1970)
Burns (1971)
Burns (1971)
o
o
I
-------
ORGANIC ACCUMULATION FROM SOIL
Accumulant
PHORATE
PHORATE, POA,
PSO
PS02, POASO,
POAS02
ZINOPHOS
TRIAZINE PESTICIDES
ATRAZINE
ATRAZINE
ATRAZINE
HYDROXYATRAZINE
PROKETRYNE
Extractant
ACETONE: WATER
HEXANE: ACETONE
HEXANE: ACETONE
HEXANE
METHANOL
ACETONITRILE:
WATER
ACETONITRILE:
WATER .
HC1: ACETONITRILE:
WATER
TOLUENE
Special
Procedures
Blending
Shaking
Shaking
Soxhlet
Soxhlet
. Blending
Refluxing
-
Shaking
Comments
-
-
-
- •
1 hour mix
21 hour equili-
brium
-
3 day equilibrium
_
Concentration
-
_-
-
-
8.0 ppm
.05-1 ppm
.05-2 ppm
-
_
% Recovery
85-92
91-96 '
61-77
86-91
95
71-89 .
80-111
89.5 1.5
75-80
Reference
Menzer, et al.
(1972)
Getzin and Shanks
(1970)
Getzin and Shanks
(1970)
Kiigemani and
Terriere (1971ab)
Zimdahi, et al.
(1970)
Ott, et al.
(197D
Mattscn, et al.
(1970)
Hance and Chesters
(1970)
Walker and
Crawford (1970)
I
-t
o
M
I
-------
ORGANIC ACCUMULATION PROM SOIL
Accumulant
PROPAZINE
URACILS
BROMOCIL
TERBACIL
TERBACIL
NON- PESTICIDES
POLYCYCLIC
AROMATIC
HYDROCARBONS
Extractant
TOULENE
OIL NaOH
DIL NaOH
ETHYL ACETATE
METHANOL: BENZENE
•
Special
Procedures
-
Shaking, .
blending
Shaking,
. blending
Shaking
Soxhlet
Comments
-
-
_
_
Concentration
- .
80 ppm
8 ppm
0.i|-o.45 ppm
-vS-3600 ppb
% Recovery
75-80
. 8?
87
80-112
39-88
Reference
Walker and
Crawford (1970)
Zlmdahl, et al.
(1970)
Zimdahl, et al.
(1970)
Skroch, et al.
(1971)
Glger and Blumer
(•1971)
I
-f
O
-------
TABLE 4-10
ORGANIC ACCUMULATION PROM PLANTS
-U03-
-------
ORGANIC ACCUMULATION FROM PLANTS
Accuraulant
BENZONITRILE PE
KERB
MISCELLANEOUS P
ORYZEMATE
ORGANOCHLORINE
CYCLODIENE
PESTICIDE
RESIDUES
ORGANO-
CHLORINE
PESTICIDE
RESIDUES
ORGANO-
CHLORINE
PESTICIDE
RESIDUES
Extractant
5TICIDES
H2S0l)-
METHAHOL
iSTICIDES
ACETONITRILE:
n-HEXANE
'ESTICIDES
HEXANE-ACE-
TONE-MENTHA-
NOL-H20
ACETONITRILE
H20-
ACETONITrflLE
Special
Procedures
homogenize
first
filtration
SOXHELET
chopped and
mixed first
chopped and
mixed first
Medium
CROPS
RICE PLANT
SOYBEAN PLANTS
KALE, COLLARDS
AND POTATO
KALE, COLLARDS.
AND POTATO
Comments
-
-
2-ENDRIN and
2-HEPTACHLOR
RESIDUES
7 PESTICIDES and
RESIDUES
7 PESTICIDES and
RESIDUE. FOR
DEHYDRATED SAMPLE
Concentration
.01 ppm
/
-
0.2-20 ppm
% Recovery
-
-
-
56-107
96-108
Reference
Adler, et al.
(1972) ' '
Uchiyama, et al.
(1973)
Nash and Beall
(1971)
Burke, et al.
(1971)
Burke, et al.
(1971)
I
_Cr
O
-Cr
I
-------
ORGANIC ACCUMULATION FROM PLANTS
Accumulant
ORGANO-
CHLORINE •
PESTICIDE
RESIDUES
ORGANOPHOSPHORU5
HINOSAN
HINOSAN
KITAZIN P
KITAZIN P
ORGANO-
PHOSPHOROUS
PESTICIDE
RESIDUE
ORGANO-
PHOSPHOROUS
PESTICIDE
RESIDUES
Extract ant
ETHYL ETHER-
HEXANE-
NajSO,,
> PESTICIDES
ACETONITRILE
WATER- TOLUENE
ACETONITRILE
ACETONITRILE:
H20-TOLUENE
ACETONITRILE
ACETONITRILE
Special
Procedures
grind sample
first
macerate and
homogenize
first
pulverize
first
macerate and
homogenize
first
-
chop and-
blend first
chop and
mix first
Medium
WHEAT
RICE PLANT
RICE GRAIN
RICE PLANT
RICE GRAIN
CROPS AND
FRUITS
KALE, COLLARDS
AND POTATO
Comments
17 PESTICIDES and
RESIDUES
RAPID TECHNIQUE
-
-
-
-
11 PESTICIDES and
RESIDUES
t PESTICIDES and
RESIDUES
Concentration
.01 ppm
-
-
-
-
.02 ppm
8-16.3 ppm
% Recovery
82-95
-
-
-
-
81-116.
88-107
Reference •
Levl, et al.
(1972)
Ueyama, et al.
(1973)
Ueyama, et al.
(1973)
Yamamoto, et al.
(1973)
Yamamoto, et al.
(1973)
'Storherr, Ott, and
Watts (1971)
Burke, et al.
(1971)
I
-Cr
O
I
-------
ORGANIC ACCUMULATION FROM PLANTS
Accuiaulant
ORGANO-
PHOSPHOROUS
PESTICIDE
RESIDUES
MISCELLANEOUS NC
CH-I
3
Extractant
ETHYL ACETATE-
Na?SO,
c. **
JH-PESTICIDES
METHANOL .
•
Special
Procedures
Ice bath
Ice cold
Medium
FOOD AND '
CROPS
SORGHUM AND
RICE PLANT
AND GRAIN
Comments
_
Concentration
6.7 ppm
% Recovery
75.3-100
Reference '
AOAC 3 (1970)
Rangaswamy, et al.
(1972)
•
I
-Cr
O
I
-------
ACCUMULATION PROM SOLIDS
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-413-
-------
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of Aldrin, Dieldrin, Chlordane, and DDT in Soil and
Sugarbeets." J. Econ. Entomol., 6_3_: 1143-1146 (1970).
Ott, D. E.; Formica, G.; Liebig, G. P., Jr.; Eberle, D. 0.;
and Gunther, F. A. "Mechanize Extraction and Cleanup
of Atrazine Residues in Soil Prior to Gas Chromato-
graphic Analysis." J. Ass. Offic. Anal. Chem., 54:
1338-1396 (1971).
-414-
-------
Parr, J. P., and Smith, S. "Degradation of Trifluralin
Under Laboratory Conditions and Soil Anaerobiosis."
Soil Sci.q 115: 55-57 (1973).
Peterson, J. R.; Adams, R. S., Jr.; and Cutkomp, L. K.
"Soil Properties Influencing DDT Bioactivity."
Soil Sci. Soc. Amer.. Proc., 35.: 72-77 (1971)..
Rangaswamy, J. R.; Majumder, S. K.; and Poornima, P.
"Colorimetric Method for Estimation of Methyl Iodide
Residues on Jowar (Sorghum) and Rice." J. of the
AOAC, 5_5_: 800-801 (1972).
Reddy, M. R., and Perkins, H. P. "Fixation of Zinc by Clay
Minerals." Soil Sci. Soc. Amer. Proc., 38: 229-234
(1974).
Roth, J. A.; Wallihan, E. F.; and Sharpless, R. G.
"Uptake by Oats and Soybeans of Copper and Nickel
Added to a Peat Soil." Soil Sci., 112: 338-342 (1971).
Saha, J. G. "Comparison of Several Methods for Extracting
Chlordane Residues from Soil." J. of the AOAC, 54:
170-174 (1971).
Saha, J. G., and Sumner, A. K. "Organochlorine Insecticide
Residues in Soil From Vegetable Farms in Saskatchewan."
Pesticides Monitoring J., 5_: 28-31 (197D.
Schuman, G. E.; Stanley, M. A.; and Knudsen, D. "Automated
Total Nitrogen Analysis of Soil and Plant Samples."
Soil Sci. Soc. Amer. Proc., 371: 480-481 (1973).
Skroch, W. A.; Sheets, T. J.; and Smith, J. W. "Herbicide
Effectiveness, Soil Residues, and Phytotoxicity to
Peach Trees." Weed. Sci., 19.: 257-260 (1971).
Smith, A. E. "Disappearance of Triallate From Field Soils."
Weed. Sci., 19_: 536-537 (1971).
Smith, A. E. "Persistence of Trifulralin in Small Field
Plots as Analyzed by a Rapid Gas Chromatographic Method."
J. Agr. Food Chem., 20: 829-831 (1972).
-415-
-------
Smith, A. E., and Fitzpatrick, A. "The Loss of Five
Thiolcarbamate Herbicides in Nonsterile Soils and
Their Stability in Acidic and Basic Solutions."
J. Agr. Food Chem., 18.: 720-722 (1970).
Smith, D. L., and Schrenk, W. G. "Application of Atomic
Absorption Spectroscopy to Plant Analysis. I. Comparison
of Zinc and Manganese Analysis with Official AOAC
Colorimetric Methods." J. of the AOAC, 55.: 669-675
(1972).
Smith, K. A.; Bremner, J. M.; and Tabatabai, M. A. "Sorption
of Gaseous Atmospheric Pollutants by Soils." Soil Sci.,
116; 313-319 (1973).
Sommers, L. E., and Nelson, D. W. "Determination of Total
Phosphorus in Soils: A Rapid Perchloric Acid Digestion
Procedure." 3_6_: 902-904 (1972).
Sorenson, R. C.; Oelsligle, D. D.; and Knudsen, D. "Extrac-
tion of Zn, Pe, and Mn from Soils with 0.IN Hydrochloric
Acid as Affected by Soil Properties, Solution: Soil
Ratio, and Length of Extraction Period." Soil Sci. ,
111: 352-359 (197D.
Storherr, R. W.; Ott, P.; and Watts, R. R. "A General
Method for Organophosphorus Pesticide Residues in
Nonfatty Foods." J. of the AOAC, 54.: 513-516 (1971).
Swoboda, A. R.; Thomas, G. W.; Cady, P. B.; Baird, R. W.,
and Knisel, W. G. "Distribution of DDT and Toxaphene
in Houston Black Clay on Three Watersheds." Environ.
Sci. Technol., 5_: 141-145 (197D-
Tandon, H. S. "Fluoride-Extractable Aluminum in Soils:
2. As An Index of Phosphate Retention by Soils." Soil
Sci., 109: 13-18 (1970).
Uchiyama, M.; Abe, H.; Sato, R.; Shimura, M., and Watanabe,
T. "Fate of 3-A11 Yloxy-1, 2-Benzisothiazole 1, 1-
Dioxide (Oryzemate) in Rice Plants." Agr. Blol. Chem.,
37: 737-7^5 (1973).
Ueyama, I.; Uesugi, Y.; Tomizawa, C., and Murai, T. "Metabolic
Pate of 0-Ethyl S, S-Diphenyl Phosphorodithiolate (Hinosan)
in Rice Plant." Agr. Biol. Chem., 37.: 1543-1551 (1973).
-416-
-------
Ulrich, B., and Khanna, P. K. "Desorption and Dissolution
of Salts From Soils as a Function of Soil: Water Ratio."
Soil Sci., 114: 250-253 (1972).
Veith, G. E., and Lee, G. F. "Water Chemistry of Toxaphene—
Role of Lake Sediments." Environ. Sci. Technol., _5_:
230-234 (197D.
Verkoop, A., and Nimmo, W. B. "Metabolism of Dichocobenil
in Sandy Soil." Weed. Res., 10_: 67-70 (1970).
Walker, A., and Crawford, D. V. "Diffusion Coefficients for
Two Triazine Herbicides in Six Soils." Weed. Res., 10:
126-132 (1970).
Walsh, G. E.; Miller, C. W.; and Heitmuller, P. T. "Uptake
and Effects of Dichlobenil in a Small Pond." Bull. Environ,
Contain. Toxicol., 6_: 279-288 (197D.
Willis, G. H.; Parr, J. F.; and Smith, S. "Volatilization of
Soil Applied DDT and ODD From Flooded and Non-Flooded
Plots." Pesticides Monitoring J., 4_: 204-208 (1971).
Woodham, D. W.; Mitchell, W. G.; Loftis, C. D., and Collier,
C. W. "An Improved Gas Chromatographic Method for the
Analysis of 2,4-D Free Acid in Soil." J. Agr. Food Chem.,
19: 186-188 (1971).
Yamamoto, H.; Tomizawa, C.; Uesugi, Y., and Murai, T.
"Absorption, Translocation and Metabolism of 0,0-Diiso-
propyl S-Benzyl Phosphorothiolate (Kitazin P) in Rice
Plant." Agr. Biol. Chem., 37_: 1553-1561 (1973).
Yih, R. Y.] Swithenbank, C., and McRae, D. H. "Transforma-
tions of the Herbicide N-(l,l-dimethylpropynyl)-3,5-
dichlorobenzamide in Soil." Weed. Sci., 18.: 604-608
(1970).
Zimdahl, R. L., and Freed, U. H.; Montgomery, M. L., and
Furtick, W. R. "The Degradation of Triazine and Uracil
Herbicides in Soil." Weed. Res., 10: 18-26 (1970).
-417-
-------
SECTION FIVE BIOACCUMULATORS
5-0 General Discussion
Radioactive isotopes, heavy metals, and organic com-
pounds (including chlorinated organics) are all accumulated
in food chains. Particular plant and animal species will
selectively accumulate one or more of these substances.
Due to the biochemistry of particular organisms, individual
species will be able to selectively resist accumulation of
substances, which are not required by particular cells for
metabolism. The availability of other accumulated sub-
stances in high concentrations may limit the accumulation
of a given compound.
A survey of the recent literature of biological accumu-
lation was performed in order to determine whether any
plant or animal species are satisfactory accumulators of
chemical compounds and ions for quantitative analysis.
This literature search included the available literature
on the following types of bioaccumulation:
1. biogeochemical techniques
2. microbial accumulation
3- radioisotope accumulation
4. accumulation of trace metals by animals and plants
-418-
-------
5- accumulation of pesticides by animals and plants
6. plants as indicators of chemical equilibria and
air and water pollution.
The bioaccumulator literature falls generally into
two categories: laboratory experimental studies and field
studies. Laboratory studies allow a given organism
to grow in a medium while maintaining precise control
over ambient concentrations of the accumulant being
studied. At predetermined time periods after the onset
of the experiment the amounts accumulated by the organism
are analytically measured, allowing measurement of ac-
cumulation factors on a time horizon. Graphical rela-
tionships and regression functions can be calculated for
accumulation factor vs. time and accumulation factor vs.
ambient concentration.
Field studies are most useful in identifying the
suitability of particular species as indicators of ambient
concentrations of metals and ions. Field studies yield
quantitative data on the distribution of plant species
and on the accumulated levels of metals, compounds, and
ions in plants and animal organs, but do not allow a pre-
sentation of quantitative data on lengths of exposure
time or on ambient concentration levels.
In order to assess the utility of bioaccumulators in
the accumulation and monitoring of substances present in
-1*19-
-------
the ppb and ppt range, chemical and biological accumulating
systems which accumulate the same molecules or ions in the
same media were compared. Concentration factors and
accuracy of concentration were compared. The only bio-
accumulators of potential importance for quantitative
studies are listed in section 5.3.
5-1 Characteristics of Bioaccumulator Systems
Organisms accumulate chemical substances in three
ways. Some substances are taken up actively by cellular
biochemical transport processes; this is the familiar
process of active transport. In this process, termed
active transport, organisms expend energy in order to
maintain certain substances at high concentrations in the
cell. Generally, substances concentrated in active trans-
port are trace metals and compounds which are important
to the cell metabolism. These include S, Fe, and P.
Other substances are accumulated by absorption onto
tissue or through cell walls. A characteristic of accumu-
lation by this mechanism is that accumulation factors and
accumulation time will be similar for both live and
dead tissue. Absorption and the speed of concentration
-420-
-------
will be greater in dead tissue for those organisms whose
biochemical mechanisms actively exclude the compounds or
ions being absorbed. Pesticides and other organics are
accumulated by this mechanism.
A third method of concentration is that of food chain
concentration. Chemical substances whiah are consumed
during metabolism will not be concentrated along a food
chain; however, compounds and ions which are not employed
in metabolism will be concentrated by the higher members
of a food chain, which eat producers and first level pre-
dators with low concentrations of non-metabolized sub-
stances in their systems.
Since biochemical mechanisms are generally molecule-
specific and enzyme-specific, it is not surprising that
each biological accumulator is selective as to the sub-
stances which are accumulated. While chemical accumulator
systems will generally accumulate a class of compounds
with similar chemical behavior (i.e., one accumulator
system may accumulate As, Sb, and Bi; another may accu-
mulate Ga, In, and Ft; and another may accumulate Ti,
(II) and Va (III)), in general biological accumulators
will be more selective. A particular organism may accu-
mulate Pb but not Sn or may accumulate P and not Sb.
-421-
-------
Biological accumulators are not selective, however, for
substances passively absorbed. In accumulation of chlori-
nated organics, for example, one organism may accumulate
a wide range of chlorinated organics such as DDT, ODD,
DDE, aldrin and dieldrin.
Bioaccumulator species generally exhibit variability
in the ability of individuals of the species to accumu-
late a substance. This generally makes organisms unsa-
tisfactory for quantitative analytical work, especially
when compared to chemical or physical accumulation systems ,
It can be confidently predicted that 73% of a particular
organic compound will be recovered by using a carbon
filter. For a biological accumulator such confidence is
not generally justified. Accumulation factors vary with
the following:
1. temperature variations
2. pH variations
3- age of organism
4. daily oscillations (endogenous rhythms)
5. seasonal and growth period oscillations
6. latitudinal day length variations
7- variations due to location of sample leaf on
plants
-------
8. variations due to the ambient concentration level
9. variations due to the part of the body samples
(such as digestive system, gills, bones)
10. variations due to different soil mostures and
different precipitation levels.
The bioaccumulation changes encountered for different
environmental conditions make the use of biological accumu-
lators for analytical work impossible. For example,
Cearley (1973) found that the southern naiad (Najas
quadulepensis) accumulated cadmium with an accumulation
factor varying from 6,000 to 40,000. The factor of accumu-
lation varied with the ambient concentration of the cadmium
ions. There is no simple functional relationship relating
concentration of cadmium in the sourthn naiad to ambient
2
concentrations. Wilkes and Weiss (1971) found that
dragonfly nymphs (Tetragonuria) accumulate DDT with an
accumulation factor varying from 250 to 2,700. The
accumulation factor changes with the length of exposure time,
Thus, the accumulator system can be used for analytical
assessment of ambient concentration only if the time of
exposure is accurately known.
1. Cearley, J.E. and R.L. Coleman, "Cadmium Toxicity
and Accumulation in Southern Naiad," Bull, of Environ-
mental Contamination and Toxicology, £: 100-101 (19737.
2. Wilkes, F.G. and C.M. Weiss, "The Accumulation of DDT
by the Dragonfly Numph, Tetragoneuria," Trans. Amer.
Fish. Soc., (No. 2), (1971).
-423-
-------
Organisms such as bacteria, plankton, yeasts, and
other microorganisms are generally more useful for
analytical accumulation than are higher organsims such
as fungi, invertebrates, vascular plants, and higher
animals. More advanced organisms contain many organized
biochemical systems and biological subsystems. Microbial
organisms display a much simpler biological organization
and are regulated by a limited number of chemical systems.
It is therefore possible to characterize analytically
the relationship between accumulation factors and ambient
concentrations of chemicals, and to specify constraints
within which the microbial systems must be grown to
achieve analytical accumulation.
More highly organized biological systems are
characterized by complex biochemical systems and organs
that permit them to adapt to adverse conditions; they
can become specialized for survival in hostile niches
and in adverse environments to which microbial systems
are not specifically adapted. Therefore, species
distribution of organisms such as vascular plants,
insects, and animals can indicate differences in environ-
-424-
-------
mental constraints and can serve as indicators of the
chemical concentrations found in different environ-
mental media.
For example, trees, bushes, and understory plants
serve as excellent indicators of mineral concentrations
in the ground water. The presence of plants which are
particularly adapted'to' assimilating high concentrations
of particular ions, or which are adapted to resisting the
effects of particular ions, is useful in locating ore
deposits. Certain species grow while others are absent
in the vicinity of aluminum ore deposits. Chemical
extraction and analysis of ions present in plant tissues
is used to further verify the presence of an ore deposit.
Tissue analyses of certain plants can be used to
characterize ground water chemistry without direct
sampling of the ground water. Some of the plant species
are particularly useful because of their deep root systems.
These plants accumulate dissolved substances from sub-
surface soil and ground water which is filtered through
rock formations, allowing the convenient monitoring of
ground water at depths which can only be directly measured
by the use of expensive and time-consuming drilling
technologies.
-------
5.2 Bioaccumulator Methods
The accumulation of particles from air takes place
through respiration or by absorption onto surface tissue.
Only a few organisms have been successfully used as indica-
tors of particulate levels in the air. There has been no
successful quantitative study of the relationship•of particle
concentrations in tissue as indicators of the concentrations
in the air. Human blood levels of cadmium and lead have been
employed as indicators of dangerous levels of these compounds
for industrial workers who are exposed to those metals in the
factory air. Plants such as Spanish moss and rice have been
used as indicators of the aerial dispersion of compounds.
The growth distribution of lichens has been used as an
indicator of air particulate levels.
A wide spectrum of plants, which have been used as
accumulation systems for measuring substances in 'the soil,
is recorded in the literature. Many plants accumulate
pesticides and provide a monitor on the pesticide concentra-
tions residing in the food chain. Others accumulate metals
such as nickel, copper, aluminum, and tungsten. These
accumulators, as summarized in the accompanying tables, are
plants which serve as indicators of metal concentrations in
the soil.
3. See Tables 5-1 to 5-3. Cannon, H.L., Science, 132:
591 (I960).
-426-
-------
TABLE 5-1
PROSPECTING BY PLANT ANALYSIS
Locality
Australia
Canada
British Columbia
British Columbia
British Columbia
British Columbia
British Columbia
British Columbia
British Columbia
British Columbia
British Columbia
Eastern Canada
Quebec
Cornwall. Wales
Cornwall, Wales
Cuba
Esterel (Pyrenees)
Far East
Finland
Finland
Germany
Greece
Japan
Nigeria
Norway
Sweden
Sweden
Sweden
Sweden
Sweden
United States
Arizona
Arizona
Arizona
Calif., Nevada
Idaho
Missouri
New Mexico
New York
New York
Pennsylvania
Pennsylvania
Tennessee
Utah
Utah
U.S.S.R.
U.S.S.R.
U.S.S.R.
U.S.S.R.
U.S.S.R.
U.S.S.R.
U.S.S.R.
U.S.S.R.
U.S.S.R.
Metal
sought
U
Cu,Zn
Cu
Zn
Zn
Mn
Au
Ag
Ni
Mo
Cu
Cu.Zn
Cu
\V
Sn
Ni
U
As
Ni
Cu
Ni
Cr
U
Pb-Zn
Cu
V
Pb, Zn
Pb-Ag
Mo
W
U
Cu
Cu
Ba
Zn, Pb,
Cu
Zn
U
Zn
Pb, Zn
Pb-Zn
Zn
Mn
U
U
Cu, Mo
Cu, Fe
B
Ni
Co
Cu
Cr
I'h
Mo
Element
used
U ,
Cu.Zn
Cu/Zn
Zn
Zn
Mn
Au
Ag
Ni
Mo
Cu /Zn
Cu/Zn
Cu
W
Sn
Ni
U
Fe
Ni
Cu
Ni
Cr
U
Pb
Cu
V
Pb, Zn,
Cu
Pb-Ag
Mo
W
Alpha
count
Cu
Cu
Ba
Zn, Pb,
Cu
Zn
U
Zn
Zn
Pb,
Cu/Zn
Zn
Ni
U
U
Mo
Fc
B
Ni/Cu
Co
Ni/Cu
Cr
Ph
Mo
Plant sampled
Xaiithosteuni paratloxus
Birch
Sagebrush, juniper
Silver birch
Alder
Hemlock
Horsetails, trees
Horsetails, trees
Fir, cedar
Balsam
Pine, fir
Alder, maple, birch, willow
Balsam twigs
Heather
Heather
Vegetation
Vegetation
Grass
Birch
Vegetation
Birch, spruce, pine
Vegetation
Cypress, pine
Savannah trees
Birch, willow
Birch, pine
Birch, pine
Tree cover
Tree cover
Tree cover __;
... >*•
Oak
Oak, mcsquite
Cresotc bush, oak
Fir, manzanita
Fir, pine, spruce
Oak
Juniper, pine
Willow ,
Birch, maple, hemlock
Birch
Vegetation
Oak
Juniper
Juniper, pinyon
Legumes
Birch, fir
I'hrcatophytes
Grasses, herbs
Grasses, herbs
Grasses, larch
Grass
Vegetation
Vegetation
. Results*
Good correlation
Good correlation
Good correlation
Good correlation
Good correlation
Good correlation
Good correlation
No correlation
Good correlation
Good correlation
Good correlation
Used in prospecting
Anomalies discovered
Anomalies discovered
Anomalies discovered
Good correlation
Good correlation
Veins defined
Good correlation
Correlations at low
concentrations, not
at high
Good correlation
Good correlation
Good correlation
Good correlation
Too erratic to be use-
ful
V-shalc discovered "
Good correlation
No correlation
No correlation
No correlation
Good correlation
Good correlation
Good correlation
Good correlation
Good correlation Zn,
Pb, poor correla-
tion Cu
Good correlation
Anomalies discovered
Defined Zn area
Good correlation
Good correlation
Good correlation
Good correlation
Anomalies discovered
Anomalies discovered
Two niiijor Cu discov-
eries
Outlined Cu ore
Good correlation
Good correlation
Good correlation
New Cu discoveries
Good correlation
Good correlation
Good correlation
Reference
(57)
(58)
(37)
(34)
(59)
(34)
(60)
(60)
(61)
(34)
(38)
(62)
(35)
(4)
(4)
(63)
(64)
(3)
(6)
(36)
(65)
(8)
(66)
(42)
(7)
(4)
(8)
(8)
(8)
(5)
(67)
(68)
(69)
(70)
(50)
(71)
(72)
(26)
(73)
(39)
(74)
(75)
(31)
(76)
(77)
(78)
(79)
(12)
(SO)
(12)
(12)
(12)
(12)
* "Correlation" Minifies correlation butxvccn plant content ,iml soil content over known mineralization.
Source: H.L. Cannon, "Botantical Prospecting for
Ore Deposits," Science 132 (I960), p. 595. (Used
with permission)
-427-
-------
PLANTS THAT
Universal (U) c .,
orlocnl(L) Famlly
L
L
L
L
L
L
U
L
U
L
U
U
L
L
L
L
L
L
L
L
U
U
U
U
U
V
Gooscfoot
Goosefoot
Lily
Gooscfoot
Gooscfoot
Plumbago
Pink
Pink-
Mint
Mint
Mint
Moss
Poppy
Plumbago
Buckwheat
Loasa
Birch
Guttiferae
Grass
Morning-glory
Legume
Legume
Legume
Sunflower
Sunflower
Mustard
Table 5-2
HAVE BEEN USED AS INDICATORS
IN PROSPECTING
Genus and species
Bitumen
Anabasis salsa
Sal.iota spp.
Alliiiiii sp.
Boron
Salsola nitraria
Carotin ceratoides
Liinoniunt siiffriiticosum
Copper
Gypsophila patrini
Polycarpea spirostylis
Acrorephalins roberti
Elsholl:la liairhowensls
Ociininn Itomblei
Merceya laiifo/ia
Esclischoltzia mexicana
Armeria maritima
Gypsum
Eriogonunt inflatum
Mentzelia spp.
Iron
Betula sp.
Clnsia rosea
Lead
Erianthus giganteiis
Phosphorus
Convolvulus altliacoifles
Selenium
Astragalus bisulcaliis
Astragalus racemosus
Astragalus pectinatns
Oonnpsis spp.
Aster vennstiis
Stanleva spp.
Common
name
Saltwort
Onion
Saltwort
Winter fat
Staticc
Karum
Pink
Elsholtzia
Basil
Copper moss
Calif, poppy
Thrift
Desert trumpet
Blazing star
Birch
Copey clusia
Bcardgrass
Bindweed
Poison vetch
Poison vetch
Poison vetch
Goldenwced
Woody aster
Princcsplume
Locality
Caspian Sea
Caspian Sea
California
U.S.S.R.
U.S.S.R.
U.S.S.R.
U.S.S.R.
Australia
Katanga
China
Rhodesia
Sweden and
Montana
Arizona
Scotland
Western U.S.
Western U.S.
Germany
Venezuela
Tennessee
Spain
Western U.S.
Western U.S.
Western U.S.
Western U.S.
Western U.S.
Western U.S.
Reference
(20)
(20)
(44)
(24) .
(24)
(24)
03)
(45)
(16)
(15)
(17)
(14)
(46)
(47)
(18)
(18)
(48)
(49)
(50)
(48)
(51)
(51)
(51)
(51)
(51)
(51)
Selenium and Uranium
U
L
L
L
U
L
Legume
Legume
Legume
Buckwheat
Violet
Saxifrage
Astragalus pattersoni
Astragalus preussi
Astragalus sp.
Silver
Eriegonum oval/folium
Zinc
Viola calamineria (hitea)
Philadelphia sp.
Poison vetch
Poison vetch
Garbancillo
Eriogonuni
Zinc violet
Mock orange
Western U.S.
Western U.S.
Andes
Montana
Belgium and
Germany
Washington
(18)
(18)
(19)
(47) .
(52)
(53)
Source: See Table 5-3.
Table 5-3
PHYSIOLOGICAL AND MORPHOLOGICAL CHANGES IN PLANTS
DUE TO METALTOXICITIES
Element
Effect
Reference
Aluminum
Boron
Chromium
Cobalt
Copper
Iron
Manganese
Molybdenum
Nickel
Uranium
Zinc
Stubby roots, leaf scorch, mottling (54)
Dark foliage; marginal scorch of older leaves at high concentrations: (54)
stunted, deformed, shortened inlcrnodes; creeping forms: heavy
pubescence; increased gall production (24)
Yellow leaves with green veins (31)
White dead patches on leaves ' (30)
Dead patches on lower leaves from tips; purple stems, chlorotic leaves (55)
with green veins, stunted roots, creeping sterile forms in some species (16)
Stunted tops, thickened roots; cell division disturbed in algae, resulting (55)
cells greatly enlarged (56)
Chlorotic leaves, stem and petiole lesions, curling and dead areas on
Icuf margins, distortion of laminae . • (54)
Stunting, yellow-orange coloration . (55)
White dead patches on leaves, apctalous sterile forms (30)
Abnormal number of chromosomes in nuclei; (28)
unusually shaped fruits: (32)
sterile upetulous forms, stalked leaf rosette (31)
Chiorolic loaves wiih green veins, white dwarfed forms; (31)
dead areas on leaf tips; roots sumted (55)
Source: H.L. Cannon, "Botantical Prospecting for
Ore Deposits," Science 132 (I960), p. 593. (Used
with permission)
-428-
-------
Vascular plants, fish and Invertebrates accumulate
many substances from fresh water. Transition metals,
SI 7^
radioactive isotopes such as Cr^ and Se , pesticides,
are all mentioned in the literature as substances which
are accumulated by plants and fish. Plants provide accurate
monitoring when employed as monitors of long-term ambient
concentrations because of their slow growth rate. Pish and
invertebrates generally have widely varying concentration
factors depending upon which parts of the body are measured.
Fungi, bacteria, yeast, algae, and invertebrates such
as daphnia, are accumulators which have been studied under
laboratory conditions. A functional relationship between
organism concentration and ambient concentration can often
be determined for these species. Accumulation usually
requires 8 to 90 hours, and in some cases organisms can
accumulate ions in the ppb range.
Mollusks, polychaete worms, and algae are all mentioned
in the literature as accumulators of substances from salt
water. Transition metals such as Cd, Cu, Mn, Fe, Hg, Pb ,
radioactive transition metals such as Co-3 , Co , Cr^ ,
K , Fe^^, Mn , Mg-^, and pesticides such as DDT, DDE, ODD,
Dieldrin, Parathion and toxaphene are all accumulated.
-429-
-------
The concentration factors achieved by mollusks vary
widely with the season, the biological process involved
(for example, the unique accumulation rate during the
spawning season) and with the section of the body analyzed.
For example, the gonads of Militus edulus accumulate Co
with a concentration factor of ten, while the stomach
Cft
accumulates Co with a concentration factor of 1,000,
and the bones and gills in concentrations of 100 over the
ambient level. Accumulation by mussels requires a time
period of approximately one to two months, and it is not
therefore a good laboratory system for water sampling.
Mammals act as food chain accumulators from tissues
of fish, plants, insects, animal invertebrates, and other
vertebrates. Few experimental determinations of accumulant
concentration factors for food chains are recorded in the
literature. Thus, analysis of the metal, radioactive metal,
and pesticide content of mammal tissues can at present only
be used as rough indicators of the occurrence of toxic
substances within a food chain.
5.3 Presently Most Suitable Bioaccumulators
Three recommendations can be made for further study
of bioaccumulators:
1) Yeast, fungi, and several, microbial systems
including bacteria are the accumulation systems
-430-
-------
which give the most accurate quantitative
indication of environmental contamination levels.
In particular, yeast accumulation from water
follows a direct functional relationship between
ambient and tissue concentration.
2) Aquatic organisms accumulate selenium from fresh
water organisms such as algae, daphnia, and
other microinvertebrates. Selenium is present
in forms such as seleno-methionine and selinite.
The importance of these bio-accumulators is that •
selenium is difficult to accumulate using physical-
chemical systems.
3) Most other bioaccumulator systems are useful as
indicators of pollution levels rather than for
the analysis of environmental levels of toxic
substances. This includes the use of mollusks
as indicators of metals, mammals as indicators
of pesticides and radioactive isotopes, and plants
as indicators of metal deposits.
-------
TABLE 5-4
BIOACCUMULATION OF TOXIC SUBSTANCES FROM.AIR
-432-
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM AIR
I
-t
U)
UJ
I
ACCOSULAflT
Cd .
Cd
Pb
Pb
0-ethyl S,S-
Dlphenyl-
Phosphorodl-
thlolate
? (Hinosan)
ACCUMULATOR I MEDIA
Human blood
Human urine
Tillandsia
usneoides
(Spanish Moss)
Human blood
Rice Plants
Air
Air
Air
Air ••
Air
ACCUMULATION
FACTOR
Indicator, no
quantitative re-
lationship
Indicator, no
quantitative re-
lationship
Indicator
Indicator
(.001-. 003 ?)
APPLICABLE | ACCURACY i
CONCENTRATION « CONFIDENCE
Unknown
1)0 ppm (?)
Unknown
Unknown
Indicator
Indicator
Laboratory
results dif-
fered from
field re-
sults
TIME REG..
FOR ACCUM.
Unknown
Unknown
Unknown
Unknown
1 weeks
REFERENCE
CerniJc (WO
Cernlk (1971)
Martinez,
Nathany, and
Dharmara.1 an
(1971)
McNeil and
Plasnikdg?1*)
Takase, Tan,
Ishlzuko
(1973)
-------
TABLE 5-5
BIOACCUMULATION OP TOXIC SUBSTANCES PROM SOIL
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROhi SOIL
I
-t
OJ
Ul
I
.ACaiKULAfJT
Cl
Kg
Ni
Ni
Ni
Hi
P32
ACCUMULATOR
Citrus seedling
tissue
Milfoil, wormwood,
other plants
Eucalyptus
lesoveffi
Eucalyptus
salvbris
Malalevca
shethlana
Hybanthus
floribundis
(Spruce needles)
Plcera excelsa
MEDIA
Soil
Soil
Soil
Soil
Soil.
Soil
Soil
ACCUMULATION
FACTOR
Cl~ uptake de-
pends on root
surface area and
is independent
of Cl~ concen-
tration
30-100
85
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Cl" uptake,
independent
of .high Cl~
concentra-
tion
Unknown
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
TIME REQ.
FOR ACCUM.
(?)
Unknown
4 weeks
dependent
on season
REFERENCE
Attman (1972)
Bol'shakov,
K'yakora,
Plushko, and
Sheherbakov
(1969)
Cole (1973)
Cole (1973)
Cole (1973)
Cole (1973)
Gagnalre
(1962)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES PHOH SOIL
I
J=-
00
a\
I
ACCUKULAST
P32
P32
P32
P32
Pb
ACCUMULATOR
(Spruce wood)
Picea excelsa
Acer campestrls
(Hedge maple)
Populus nigra
(Black poplar)
Thuja
(Arbor Vltae)
•
Spartina alterni-
flora
MEDIA
Soil
Soil
Soil
Soil
Soil
ACCUMULATION
FACTOR
135
Wood 35
Shoots 170
Unclear
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
Unclear
TIME P.EQ.
FOR ACCUM.
4 weeks de-
pendent on
season
*l weeks de-
pendent on
season
4 weeks de-
pendent on
season
I) weeks de-
pendent on
season
Months (?)
REFERENCE
Gagnalre
(1962)
Gagnalre
(1962)
Gagnaire
(1962)
Gagnaire
(1962)
Banus (1971)
-------
BIOACCUHULATION OF TOXIC SUBSTANCES FROM SOIL
I
-t
00
-<1
I
ACCUHULANT
Sr90
Sr90
Sr90
Sr90
Sr90
ACCUMULATOR
(Spruce needles)
Picea excelsa.
(Spruce wood)
Plcea excelsa
Acer campestris
(Hedge maple)
Populus nlgra
(Black Poplar)
•-
Thuja
(Arbor Vitae)
MEDIA
Soil
Soil
Soil
Soil
Soil
ACCUMULATION
FACTOR
85
135
Wood 85
Shoots 170
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
Accumulation
varies with
season, -chem-
ical compo-
sition of
soil
Accumulation
varies with
season, chem-
ical compo-
sition of
soil
TIME REQ.
FOR ACCUK.
*) weeks de-
pendent on
season
*) weeks de-
pendent on
season
4 weeks de-
pendent on
season
b weeks de-
pendent on
season
l| weeks de-
pendent on
season
REFERENCE
Gagnaire
(1962)
Gagnaire
(1962)
Gagnaire
(1962)
Gagnaire
(1962)
Gagnaire
(1962)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM SOIL
I
-C-
UJ
oo
I
ACCUMULANT
w
DDT
DDT
ACCUMULATOR
Nathofagus
menziesll
(Sliver Beech)
Aphanonyces
euteldes
Fusarium solanl
*
-
MEDIA
Soil
Soil
Soil
ACCUMULATION
FACTOR
22.2-79.5
1.8
1.8
APPLICABLE
CONCENTRATION
.9 - 270 ppm
291 ppb
291 ppb
ACCURACY &
CONFIDENCE
Good func-
tional rela-
tionship be-
tween accumu-
lation and
concentration
in soil.
Linear rela-
tionship for
beech seed-
ling leaves
Concentration
factor varies
with plant
density in
soil and witt
soil moisture
content, and
pH
Concentration
factor varies
with plant
density in
soil and with
soil moisture
content, and
PH
TIME REQ.
FOR ACCOM.
8 weeks
21 hours
21 hours
REFERENCE
Quin, Brooks,
and Reay
Q972)
Ko and
Lockwood
(1963)
Ko and
Lockwood
(1968)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES PROM SOIL
I
-Cr
OJ
vo
I
ACCUMULANT
DDT
DDT
DDT
DDT
ACCUMULATOR
Pythlum utimum
Rhizoctona solanl
*
Streptonyces albus
Streptonyoes
aureofaciems
MEDIA
Soil
Soil
Soil
'
Soil'
ACCUMULATION
FACTOR
1.8
1.8
1.8
1.8
APPLICABLE
CONCENTRATION
294 ppb
294 ppb
29U ppb
291 ppb
ACCURACY &
CONFIDENCE
Concentration
factor varies
with plant
density in
soil and with
soil moisture
content, and
pH
Concentration
factor varies
with plant
density in
soil and with
soil moisture
content, and
pH
Concentration
factor varies
with plant
density in
soil and with
soil moisture
content, and
pH
Concentration
factor varies
with plant
density in
soil and with
soil moisture
content & pH
TIME REQ.
FOR ACCUK.
24 hours
24 hours
2U hours
24 hours
REFERENCE
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES PROM SOIL
I
-Cr
-t
O
I
ACCUKULAOT
DDT
DDT
Dleldrin
Cl
cl^ijjL
JrJTj-'0
cl'r*Tr
Cl »
Dieldrin
Dieldrin
ACCUMULATOR
Streptonyces
griseus
Streptonyces
viridochromogenes
Cotton plants
Aphanomyces
euteiches
Fusarium solanl
MEDIA
Soil
Soil
Soil
Soil
Soil
ACCUMULATION
FACTOR
1.8
1.8
(80?) (leaves)
2.1
2.H
APPLICABLE
COf!CE^^TRATION
291 ppb
291 ppb
250 ppb
250 ppb .
ACCURACY &
CONFIDENCE
Concentration'
factor varies
with plant
density in
soil and with
soil moisture
content and
?H
Concentration
factor varies
with plant
density in
soil and with
soil moisture
content and
pK
Unknown
Varies with
density of
plant growth,
soil moisture:
and pH
Varies with
density of
plant growth,
soil moisture;
and pH
TIME REQ.
FOR ACCUM.
24 hours
24 hours
21 days
2*1 hours
24 hours
REFERENCE
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Kavadia (1972)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
-------
- BIOACCUMULATIGN OF TOXIC SUBSTANCES FROM SOIL.
I
-Cr
-Cr
ACCUMULAHT
Dieldrln
Dleldrln
Dieldrln
Dleldrln
Dieldrln
ACCUMULATOR
Pythium ultlmum
Rhlzoctonla solanl
Streptomyces albus
Streptoniyces
aureofaciens
Streptomyces
grlseus
MEDIA
Soil
Soil
Soil
Soil
Soil
ACCUMULATION
FACTOR
2.1
2.1
2.1)
2.1
2.1
APPLICABLE
CONCENTRATION
250 ppb
250 ppb
250 ppb
250 ppb
250 ppb
ACCURACY &
CONFIDENCE
Varies with
density of
plant growth,
soil moisture
content and
PH
Varies with
density of
plant growth,
soil moisture
content, and
?K
Varies with
density of
plant growth,
soil moisture
content, and
PH
Varies with
density of
plant growth,
soil moisture
content , and
PH
Varies with
density of
plant growth,
soil moisture
content & pK
TIME REQ.
FOR AC CUM.
21 hours
21 hours
21 hours
21 hours
21 hours
REFERENCE
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
LOCkW°fld968>
-------
BIOACCUMULATION OP TOXIC SUBSTANCES FROM SOIL
ro
I
ACCUMULAfJT
Dleldrin
N-1-papthyl-
phtalamlc
acid
(Naptalan)
PCNB
(pentachlo-
ronitroben-
zene)
PCNB
(pentachlc—
ronitroben-
zene)
PCNB
(pentachlo-
ronltroben-
zene)
ACCUMULATOR
Streptomyces
vlridochromogenes
Phaseoleus vulgar is
(Bean plants)
Aphanomyces
euteiches
Pusarium soiani
Pythlum ultimum
MEDIA
Soil
Soil
Soil
Soil
Soil
ACCUMULATION
FACTOR
2.1
7
7
7
APPLICABLE
CONCENTRATION
250 ppb
250 ppb
250' ppb
250 ppb
ACCURACY t
CONFIDENCE
Varies with
density of
plant growth,
soil mois-
ture content,
and pH
Varies with
concentration
of plant
growth, soil
moisture con-
tent, and pH
Varies with
concentration
of plant
growth, soil
moisture con-
tent, and pH
Varies with
concentration
of plant
growth, soil
moisture con-
tent, and pH •
TIME REQ.
FOR ACCUM.
24 hours
21 hours
21 hours
21 hours
REFERENCE
Ko and
Lockwood
(1968)
Devlin and
Yakllch(1972)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM SOIL
00
I
ACCUMULANT
PCNB
(pentachlo-
robenzene)
PCNB
(pentachlo-
robenzene)
PCNB
(pentachlo-
robenzene)
PCNB
(pentachlo-
robenzene)
PCNB
(pentachlo-
robenzene)
ACCUMULATOR
Rhlzoctonla solanl
Streptomyces albus
Streptomyces
aureofaciens
Streptomyces
griseus
•
Streptomyces
viri dochromogene s
MEDIA
Soil
Soil
Soil
Soil
Soil
ACCUMULATION
FACTOR
7
7
7
7
7
APPLICABLE
CONCENTRATION
250 ppb
250 ppb
250 ppb
250 ppb
250
ACCURACY 4
CONFIDENCE
Varies with
concentration
of plant
growth, soil
moisture con-
tent, and pH
Varies with
concentration
of plant
growth, soil
moisture con-
tent, and pH
Varies with
concentration
of plant
growth, soil
moisture con-
tent , and pH
Varies with
concentration
of plant -
growth, soil
moisture con-
tent, and pH
Varies with
concentration
of plant
growth, soil
moisture con-
tent, and oH
TIME REQ.
FOR AC CUM.
24 hours
24 hours
24 hours
24 hours
24 hours
REFERENCE
Ko snd
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
Lockwood
(1968)
Ko and
Lockwood
C1968)
-------
TABLE 5-6
BIOACCUMULATORS OF TOXIC SUBSTANCES PROM FRESH WATER
-------
BIOACCUMULATION OP TOXIC SUBSTANCES FROM FRESH WATER
I
-Cr
-t
Ul
I
ACCUMULAHT
Cd
Cr51
Cu
Cu
Pb
ACCUMULATOR
Najas quadulepensls
Spreng
(Southern Naiad)
Anguilla anguilla
Ictalurus nebulosus
(Brown bullhead)
Lymnaea stagnatls
Lolium perenne
(Rye grass)
,
MEDIA
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
(may also
accumulate
from soil)
ACCUMULATION I APPLICABLE
FACTOR § CONCENTRATION
6000-40000
not>2
203-240 roots
124-266 shoots
375-1500 ppb
ACCURACY &
CONFIDENCE
Accumulation
factor may
be second
order func-
tion of am-
bient concen-
tration
not >60%
se= .3 ppm
shoots
.04 ppm
roots
under labor-
atory condi-
tions. Con-
centration
factor
varies with
medium con-
centration
TIME REQ.
FOR ACCOM.
11 - 21 days
20 days
30 days
4 hours
21 days
REFERENCE
Cearley (1973)
Descamps
(1973)
Brungs ,
Leonard.
McKim U973)
Spronk,
Tilders,
(1973)
Jones,
Clement.
Hopper (1973)
-------
BIOACCUMULATION OP TOXIC SUBSTANCES FROM FRESH WATER
ACCUHULAHT
Se"
[from seleno-
raethionine.
CMjWajCljOKH^KOSvl}
Se (from
selenlte)
Se (from
selenite)
Se (from
seienlte )
Zn
. Zn
Zn
ACCUMULATOR
Scenelesmua
dimorphus
(algae)
Daphnla pulex
Daphla magna
Cyclops serrulatls
Lepomis macrochlrus
(Blueglll sunflsh)
Phaeodactylum
trlcornutum
Neocosmospora '
vaslnfeoa
(fungi)
MEDIA
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
'culture
ACCUMULATION
FACTOR
<.25 gill
<.l bone
5.6 (PH 6.5)
APPLICABLE
CONCENTRATION
.8 ppb
.8 ppb
.8 ppb
.8 ppb
1.6 ppm
ACCURACY &
CONFIDENCE
±50%
Concentration
factors are
accurate if
pH, tempera-
ture, and
metabolic con-
ditions are
held constant
TIME REQ.
FOR ACCUK.
24 hours
24 hours
24 hours
24 hours
96 hours
60 minutes
REFERENCE
Sandholm,
Oksan
Pesonen
(1973)
Sandholm,
Oksan
Pesonen(i973)
Sandholm, *
Oksan
Pesonen(l973)
Sandholn,
Oksan
Pesonen(l973)
Cairns et al.
(1971)
Davies (1972)
Paton and
Budd (1972)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM FRESH WATER
I
-t
-t
—J
I
ACCUKULANT
Zn6*
DDT
DDT
DDT
i
9
DDT
ACCUMULATOR
Dunaliella
tertiolecta
(algae)
Tetragonurla
(Dragonfly nymphs)
Daphnia Magna
G ambus ia affinls
Fish
MEDIA
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
ACCUMULATION
FACTOR
Unknown
250-2700
(varies func-
tionally)
16000-23000
.88
1870
APPLICABLE
CONCENTRATION
600 ppb
3,5-20 ppb
. 11 ppm
.002 ppm
ACCURACY &
CONFIDENCE
Accumulation
varies with
temperature
and light
Concentration
factor varies
with plant
density in
soil and with
soil moisture
content, and
PH
Accumulation
factor varies
with back-
ground con-
ce. trat- ,,m
Accumulation
varies with
temperature
Unknown
TIMS REQ.
FOR ACCUM.
1 hours
.5-6 days
26 hours
Unknown
REFERENCE
Parry and
Uayward
(1973)
Wllkes and
Weiss (1971)
Crosby and
Tucker (1971)
Murphy and
Murphy (1971)
Vrochlnskii
(197D
-------
BIOACCUMULATION OF TOXIC SUBSTANCES PROM FRESH WATER
I
-t
-t
co
I
ACCUMULANT
Dlchlobenil
Dichlobenil
Dlchlobenil
Dlchlobenil
Dichlobenil
<*-hexachlo-
rocxclohexr .
ane- Slei
cxCX
"-hexachlo-
rocyclohex-
ane
ACCUMULATOR
Potamogeton
Poecilla labiplnna
Gambusia afflnis
Orthemis
Plankton
Chlorella
pyrenoidosa
(algae)
Daphnia Magna
MEDIA
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
ACCUMULATION
FACTOR
1.3
1.2
6.6
• 1.6
2.9
200
60
(350)
APPLICABLE
CONCENTRATION
1 ppra
1 ppm
1 ppm
1 ppm
1 ppm
(153-267) vari-
ance
(11,. 05 ppm)
(.8 ppm)
ACCURACY &
CONFIDENCE
Unknown, time
of measurement
critical
Unknown, time
of measurement
critical
Unknown, time
of measurement
critical
Unknown, time
of measurement
critical
Unknown, time
of measurement
critical
(153-267)
variance
±20*
±20*
TIKE REQ.
FOR ACCL'H.
2 days
2 days
2 days
2 days
2 days
15 minutes
3 hours
(1/8 hours)
REFERENCE
Walsh, Miller,
Heitmuller
(1971)
Walsh, Killer,
Heitmuller
(1971)
Walsh, Miller,
Heltmuller
(1971)
Walsh, Miller,
Heitmuller
(1971)
Walsh, Miller,
Heitmuller
(1971)
Canton and
Greve (1971)
Canton and
Greve (1971)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM FRESH WATER
I
J=-
-t
VO
I
ACCUMULAHT
"-hexachlo-
rocyclohex-
ane
HgCH3
HgCH3
HgCH3
HgCH3
E
|
ACCUMULATOR
Leloistes
reticulatus
("guppy")
Lepomis
macrochirus
(Blueglll)
Salmo gardner
(Rainbow trout)
Hemibarbus barbus
(Japanese Barbel)
Trlblodon
haleonesis
(Dace)
MEDIA
Fresh water
Fresh- -water
Fresh water
Fresh water
Fresh water
ACCUMULATION
FACTOR
110
250
<270
1171 gill
106.5 liver
35.0 stomach
57.9 intestine
111.2 heart
331.8 kidney
8.7 muscle
297.1 blood
. -v-100,000
•v.100,000
APPLICABLE
CONCENTRATION
(.01, .05 ppm)
(.8 ppm)
.275 PPb
<1 ppm
<1 ppm
ACCURACY &
CONFIDENCE
. ±20*
No
Unknown
Unknown
Unknown
TIME REQ.
FOR ACCUM.
3 hours
18 hours
100 hours
21 hours
Unknown
Unknown
REFERENCE
Canton and
Greve (197D
Burrows and
Krenkel (1973)
Olson,
Bergman,
and Fronuji
TCakizawa,
Kosaka,
Sugai,
Sasagawa,
Sekiguchi,
Mlnagua(1972)
Taklzawa,
Kosaka,
Sugal ,
Sasagawa,
Sekiguchi,
Minagua(1972)
-------
BIQACCUMULATION OF SUBSTANCES FROM FRESH WATER
v_n
o
I
ACCUMULANT
HgCl2
+ +
(Hg++)
HgCl2
, ++ i
(Hg++)
HgCl2
++
(Hg++)
ACCUMULATOR
Carasslus auratus
(goldfish)
Salmo gardnerl
(Rainbow trout)
Chorella
(Algae)
MEDIA
Fresh water
Fresh water
Fresh water
ACCUMULATION
FACTOR
32-250
102.1 gill
9.U liver
8.5 stomach
4*1.5 Intestine
9.k heart
16.8 kidney
.58 muscle
55-92 blood
Unknown
APPLICABLE
CONCENTRATION
Range 1 ppb-
100 ppb
.275 PPb
Unknown
ACCURACY &
CONFIDENCE
.Accumulation
factor dif-
ferent for
different am-
bient concen-
trations:
Unknown
"Varies with
concentration
of algae and
temperature.
There is less
accumulation
at lower tem-
perature and
higher algae
density
TIME.REQ.
FOR ACCUM.
8l hours
2*1 hours
Varies with
algae con-
centration
and temper-
ature, 20
minutes and
longer •
REFERENCE
McKone,
Young,
Bradie, and
Lisle (1971)
Olson,
Bergman,
and Fromm
(1973)
Shieh
and Barber
(1973)
-------
TABLE 5-7
BIOACCUMULATION OF FOUR (4) TOXIC SUBSTANCES
FROM SALT WATER
-451-
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM SALT WATER
ro
I
ACCUMULAirT
Cd
. c°
Cs37
• Cu
Cu
•Co60
ACCUMULATOR
Mytilus
galloprovinclalls
Mytilus edulis
(Mussel)
Mytilus edulis
(Mussel)
Nereis
diverslcolor
(Polychaete worm)
Mytilus . .
galloprovinclalls .
(Mussel)
Fucus inflatus
(Brown angae)
MEDIA
Salt water
Salt water
Salt water
Salt water
Salt water
Salt water
ACCUMULATION B APPLICABLE
FACTOR | CONCENTRATION
•\,80
95 gill
1000 stomach
10 gonad
100 bone
-<1
.38-. 68
172
100-510
50 ppb
(?)
(for -v-50 ppb)
55 ppb
ACCURACY &
CONFIDSNCE
Unknown
Varies with
environmen-
tal gradi-
ents
Unknown
Variable
accumulating
factor
Unknown
Accumulation
factor varies
with age,
temperature,
season.
Measures are
±8?
TIME REQ.
FOR ACCOM.
1-8 days
21 days
21 hours
Unknown
(weeks?)
8 days
Growth
season
REFERENCE
Hajari,
Petronlo
(1973)
Pentreath
(1973)
Lee,
Saverheloen,
Benson (1972)
Bryan arid
Huiajnez'stone
(1971)
Maj ori ,
Petronlo(i973)
Buyanov and
Boyko (1972)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM SALT WATER
v_n
UJ
I
ACCUMULANT
Co60-
.Co60
Qo60
Co60
ACCUMULATOR
Fucus serratus
Fucus vesiculosus
Mytilusedulls
Tapes Japonlca
MEDIA
Salt water
Salt water
Salt water
Salt water
ACCUMULATION
FACTOR
100-510
310-5700
12 mantle
10 gills
15 adductor
muscle
330 liver
1500 byssus
72 gonad
20 viscera
6H all soft
parts
36 shell
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Accumulation
factor varies
with age,
temperature,
season.
Measures are
±81
Accumulation
factor varies
with age,
temperature,
season.
Measures are
±8?
Agrees with
other similar
experimental-
ly calculated
concentration
factors
Unknown
TIME REQ.
FOR ACCUM.
Growth
season
Growth
season
40-80 days
( 1)0-80 days)
(?)
REFERENCE
Buyanov and
Boyko (1972)
Buyanov and
Boyko (1972)
ShimiEu,
Kajlhara,
Suyama, and
Hlyama (197D
Xameda,
Shlmizu,
Hlyama (1968)
-------
BIOACCUMULATION OP TOXIC SUBSTANCES FROM SALT WATER
ACC'JMULAKT
Hg
K*°
Mn
Fe
ACCUMULATOR
Angullla angullla
(Eel)
Fucus inflatus
(Brown algae)
Kereis diversicolor
(Polychaete worm)
Neresls diversi-
color
(Polychaete worm)
Mytilus edulls
(Mussel)
MEDIA
Salt water
Salt water
Salt water
Salt water
Salt water
ACCUMULATION
FACTOR
8 days at . 2ppm:
157 gills
51.5 kidneys
62.5 spleens
16.0 brains
18.0 livers
16-11
.01-. 16
.01-106
950 gill
5000 stomach
100 gonad
100 bone
APPLICABLE
CONCENTRATION
1.23 ppb
ACCURACY &
CONFIDENCE
Unknown
±8J and accu-
mulation
factor varies
with age,
season, and
temperature
Variable
accumulation
factor
Variable
accumulation
factor .
Varies with
environmen-
tal gradi-
ents
TIME REQ.
FOR ACCUM.
Gills: 5 hrs
Rest of or-
gans: up to
8 days
Growing
season
Unknown
(weeks?)
Unknown
(weeks?)
21 days
REFERENCE
Bouquegneau
(1973)
Buyanov and
Boyko (1972)
Bryan and
Hummerstone
(197D
Bryan and
Hummers; one
(1971)
Pentreath
(1973)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM SALT WATER '
I
-t
VJ1
\J1
I
ACCUMULANT
V-
Pb
Pb
Zn
Zn65
ACCUMULATOR
Mytilus edulis
(Mussel)
Nereis dlverslcolor
(Polychaete worm)
Mytilus
galloprovlncialis
(Mussel)
Nereis diverslcolor
(Polychaete worm)
Mytilus edulis
(Mussel)
Mytilus edulis
(Mussel)
MEDIA
Salt water
Salt water
Salt water
Salt water
Salt water
Salt water
ACCUMULATION
FACTOR
200 gill
200 stomach
70 gonad
60 bone
.01-. 13
3.91-1080 ..
.09-1.78
260 gill
160 stomach
100 gonad
30 bone
100 shell
APPLICABLE
CONCENTRATION
1.66 ppb
5-100 ppb
25.6 ppb
ACCURACY &
.CONFIDENCE
Varies with
environmental
gradients
Variable ac-
cumulation
factor
Accumulation
proportionate
to concentra-
tion in water
Variable ac-
cumulation
factor
Varies with
environmen-
tal gradients
Agrees with
other experi-
mental work
done by same
experimenters
TIME REQ.
FOR ACCUM.
21 days
Unknown
Unknown
Unknown
21 days
10-80 days
REFERENCE
Pentreath
(1973)
Bryan and
Hummerstone
(1971)
Majorl and
Petronio
(1973)
Bryan and
Hummerstone
(197D
Pentreath
(1973)
Kameda ,
Shimizu,
Hiyama (1968)
-------
BIOACCUMULATION OP TOXIC SUBSTANCES FROM SALT WATER
I
-t
vn
O\
I
ACCUMULAKT
Zn65
Zn'5
ODD
(DDT)
DDE
(DDT)
DDT
ACCUMULATOR
Tapes Japonlca
Pucus splralls
(Brown seaweed)
Crassostrea
vlrginiea
(Oysters)
Crassostrea
virginlca
(Oysters) •
Crassostrea
vlrglnica
(Oysters)
MEDIUM
Salt water
Salt water
Salt water
Salt water
Salt water
ACCUMULATION
FACTOR
50 shell
Unknown
280-980
21,000-31,000
45,000-69,000
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Agrees with
other experi-
mental work
done by same
experimenters
Unknown
Variable and
also varies
with time,
season, and
biological
function
Varies with
time, season,
and biologi-
cal function
Time depen-
dent on sea-
son and bio-
logical
function
TIME REQ.
FOR ACCUM.
40-80 days
Unknown
24 weeks
24 weeks
24 weeks
REFERENCE
Kameda,
Shimizu,
Hiyama (1968)
VanWeers(1973)
Lowe,
Wilson,
Rick, and
Wilson (197D
Lowe,
Wilson,
Rick, and
Wilson (1971)
Lowe,
Wilson,
Rick, and
Wilson (1971)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM SALT WATER
I
-Cr
Ul
-J
I
ACCUMULANT
Dieldrin
Parathion
Toxaphene
ACCUMULATOR
Rangia cuneata
(Mollusc)
Crassostrea
vlrginlca
(Oysters)
Crassostrea
virginioa
(Oysters)
•
MEDIUM
Salt water
Salt water
Salt water
•
ACCUMULATION
FACTOR
850-2000
21)0-360
23,000-30,000
APPLICABLE
CONCENTRATION
.8 ppb
ACCURACY &
CONFIDENCE
Varies with
season
Varies with
time, season,
and biologi-
cal function
(i.e. spawn-
ing)
Varies with
time, season,
and biologi-
cal function
(i.e. spawn-
ing)
TIME REQ.
FOR AC CUM.
72 hours
2U weeks
24 weeks
. REFERENCE
Petrocelli,
Hanks , and
Anderson(1973)
Lowe,
Wilson,
Rick, and
Wilson (1971)
Lowe ,
Wilson,
Rick, and
Wilson (197D
-------
TABLE 5-8
BIOACCUMULATION OF TOXIC SUBSTANCES FROM TISSUE
(THAT IS, POOD CHAIN ACCUMULATION)
-458-
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM TISSUE
I
-t
VJ1
M3
I
ACCUMULAKT
Cd
Cd
Co60
Co60
Co60
' Co60
CO60
\ Co60
Cs13?
ACCUMULATOR
Halichoerus grypus
(Seal)
Phoca vltullna
(Seal)
Ondatra zlbethicus
(Muskrat )
Peromyscus leucopus
(White footed
mouse)
Peromyscus nuttalll
(Golden mouse)
Slgmodon hispldus
(Cotton rat )
Microtus pinetorum
(Pine mouse)
Syvllagus
florldanus
(Cotton tail
rabbit )
Ondatra zlbethicus
(Muskrat)
MEDIUM
Tissue
(fish)
Tissue
(fish)
Tissue
Tissue
Tissue
Tissue
Tissue
Tissue
Tissue
ACCUMULATION
FACTOR
Unknown
(Indicator)
Unknown
(Indicator)
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Varies with
age
Varies with
age
TIME REQ.
FOR ACCUM.
Unknown
Unknown
REFERENCE
Heppleston
and French
(1973)
Heppleston
and French
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kave and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES PROM TISSUE
o
I
ACCUMULANT
C8137
Cs137
Cs137
Cs137
Cu
Cu
Hg
Hg
ACCUMULATOR
Peromyscus leucopus
(White footed.
mouse)
Peromyscus nuttalll
(Golden mouse)
Slgmodon hlspldus
(Cotton rat)
Microtus pinetorum
(Pine mouse)
Syvllagus
floridanus
(Cotton tall
rabbit)
Phoca vlbulina
(Seal)
Hallchoerus grypus
(Seal)
Chickens
Phoca vlbulina
(Seal)
MEDIUM
Tissue
Tissue
Tissue
Tissue
Tissue
Tissue
(fish)
Tissue
(fish)
Tissue .
(fishneat)
Tissue
(fish)
ACCUMULATION
FACTOR
'Unknown
(Indicator)
Unknown
(Indicator)
<1 in tissue
and eggs
Unknown
(Indicator)
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Varies with
age
Varies wtih
age
Unknown
Varies with
age
TIKE REQ.
FOR ACCUM.
Unknown
Unknown
<1 day
Unknown
REFERENCE
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Heppleston
and French
(1973)
Heppleston
and French
(1973)
Campbell, L.D.
et al. (1973)
Heppleston
and French
(1973)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM TISSUE
ACCUMULANT
Hg '
Pb
Pb
Ru106
Ru106
Ru106
Ru106
Ru106
Ru106
ACCUMULATOR
Hallcchoerus grypus
(Seal)
Hallohoerus grypus
(Seal)
Phoca vibullna
• (Seal)
Ondatra zibethious
(Muskrat )
Peromyscus leucopus
(White footed
mouse)
Perorayscus nuttalli
(Golden mouse)
Siginodon hlspidus
(Cotton rat)
Microtus pinetorum
(Pine mouse)
Syvllagus
floridanus
(Cotton tail
rabbit)
MEDIUM
Tissue
(fish)
Tissue
(fish)
Tissue
(fish)
Tissue
Tissue
Tissue
Tissue
Tissue
Tissue
ACCUMULATION
FACTOR
Unknown
(Indicator)
Unknown
(Indicator)
Unknown
(Indicator)
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Varies with
age
Varies with
age
Varies with
age
TIKE REQ.
FOR ACCUM.
Unknown
Unknown
Unknown
REFERENCE
Heppleston
and French
(1973)
Heppleston
and French
(1973)
Heppleston
and French
(1973)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM TISSUE
cr\
ro
I
ACCUMULANT
se75
from selen-
Ite
Sr90
Sr90
Sr90
Sr90
Sr90
.Sr90
Zn
Zn
ACCUMULATOR
Punt las arulios
Ondatra zlbethlcus
(Muskrat)
Peromyscus leucopus
(White footed
mouse )
Peromyscus nuttalli
(Golden mouse)
Signed on hlspidus
(Cotton rat)
Mlcrotus pinetorum
(Pine mouse)
Syvilagus
floridanus
(Cotton tail
rabbit )
Halichoerus grypus
(Seal)
Phoca vibullna
(Seal)
MEDIUM
Tissue
Tissue
Tissue
Tissue
Tissue
Tissue
Tissue
Tissue
(fish)
Tissue
(fish)
ACCUMULATION
FACTOR
Unknown
(Indicator)
Unknown
(Indicator)
APPLICABLE
CONCENTRATION
ACCURACY &
CONFIDENCE
Varies with
age
Varies with
age
TIMS REQ.
FOR ACCUM.
2k hour
Unknown
Unknown
REFERENCE
Sandholm,
Oksan,
Personen
(1973)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Heppleston
and French
(1973)
Heppleston
and French
(1973)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM TISSUE
oo
I
ACCUMULAIIT
Zn65
Zn'3
Zn65
Zn65
Zn65
Zn
DDD
(DDT)
DDT
ACCUMULATOR
Ondatra zibethicus
(Muskrat)
Peromyscus leucopus
(White footed
mouse)
Peromyscus nuttalli
(Golden mouse)
Slgmodon hispldus
(Cotton rat)
Microtus pinetorum
(Pine mouse)
Syvilagus
floridanus
(Cotton tall
rabbit)
Mink adipose tissue
Mink adipose tissue
MEDIA
Tissue
Tissue
Tissue
Tissue
Tissue
Tissue
Tissues,
animal and
plant
Tissues,
animal and
plant
ACCUMULATION
FACTOR
2.16
3.95
APPLICABLE
CONCENTRATION
,
ACCURACY &
CONFIDENCE
±2.18$ devia-
tion. No date
on efficiency
of mechanism
±2.75$ devia-
tion. No date
on efficiencj
of mechanism
TIME REQ.
FOR ACCUM.
<1 weeks
<4 weeks
REFERENCE
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962
Kaye and
Dunaway (1962)
Kaye and
Dunaway (1962)
Aulerlch et al.
(1972)
Aulerich et al.
(1972)
-------
BIOACCUHULATION OF TOXIC SUBSTANCES FROM TISSUE
I
0%
-t-
I
ACCUMULAHT
Dieldrin
«-hexachlo-
rocyclohex-
ane
ACCUMULATOR
Mink adipose tissue
Leblstes retlculatus
•
MEDIUM
Tissues,
animal and
plant
Tissue
(daphnla)
ACCUMULATION
FACTOR
8.14
3-1
APPLICABLE
CONCENTRATION
1 weeks
ACCURACY &
CONFIDENCE
±.71? devia-
tion for cit-
ted experi-
ment, no data
on efficiency
of mechanism
±35*
TIME REQ.
FOR ACCUM.
<1 weeks
21 hours
REFERENCE
Aulerich et
al. (1972)
Canton and
Greve (1971)
-------
TABLE 5-9
BIOACCUMULATION OF TOXIC SUBSTANCES FROM FRESH WATER
CULTURE (THAT IS, ACCUMULATION FROM AGAR AND NUTRIENT MEDIA)
-465-
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM FRESH WATEH CULTURE
I
-Cr
ACCUMULANT
DDT
DDT
,
DDT
DDT
DDT
ACCUMULATOR
Mueor raraannlanus
Glomerelbo
cingulata
Trichoderaia viride :
Streptomyotes
lavendulae \
Streptomyctes
grlseus
*
MEDIUM
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
ACCUMULATION
FACTOR
Unknown
Unknown
Unknown
-
• Unknown
Unknown
APPLICABLE
CONCENTRATION
.1-1 ppra
.1-1 ppm.
.1-1 ppm
.1-1 ppm
.1-1 ppm
ACCURACY &
CONFIDENCE
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
TIME REQ.
FOR ACCUK.
21 hours
21 hours •
21 hours
21 hours
21 hours
REFERENCE
Chacko and
Lockwood(1967)
Chacko and
Lockwood(1967)
Chacko and
Lockwood(196?)
Chacko and
Lockwood(1967)
Chacko and
Lockwoo
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM FRESK WATER CULTURE
I
-t
ON
-J
I
ACCUMULANT
DDT .
DDT
DDT
DDT
DDT
DDT
ACCUMULATOR
Streptomyctes
venezuelae
Bacillus subtllus
Serratla marcesoens
Agrobacterlum
tumefaclens
Anacystls nidulans
Scenedesmus obliquus
MEDIUM
Fresh water
culture
(may also
accumulate
In soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
Fresh water
ACCUMULATION
FACTOR
Unknown
Unknown
Unknown
Unknown
819 ± 232
626 ± 131
APPLICABLE
CONCENTRATION
.1-1 ppm
.1-1 ppm
.1-1 ppm
.1-1 ppm
1 ppm
1 ppm
ACCURACY &
CONFIDENCE
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
As noted
under labora-
tory condit-
ions
As noted
under labora-
tory condit-
ions
TIME REQ.
FOR ACCUK.
21 hours
21 hours
21 hours
21 hours
7 days
7 days
REFERENCE
Chacko and
Lockwood(i967)
Chacko and
Loekwood(1967)
Chacko and
Lockwood(1967)
Chacko and
Lockwood(1967)
Gregory,
Reed, and
Priester(i969)
Gregory ,
Reed, and
Prlester(i969)
-------
BIOACCUMULATIOH OF TOXIC SUBSTANCES FROM FRESH WATER CULTURE
I
-t
CT\
oo
I
ACCUMULANT
DDT
DDT
DDT
Dieldrin
Dieldrin
Dieldrin
ACCUMULATOR
Euglena gracills
Parameclum busarla
Parameclum
multlmicronutleatum
Mueor ramannianus
Glomereila clngulata
Trichodema vlride
MEDIUM
Fresh water
Fresh water
Fresh water
Fresh water
(may also
accumulate
In soil)
Fresh water
(may also
accumulate
in soil)
Fresh water
culture.
(may also
accumulate
in soil)
ACCUMULATION
FACTOR
99 * 22
264 ± 21
961 ± 16
. Unknown
Unknown
Unknown
APPLICABLE
CONCENTRATION
1 ppm
1 ppm
1 ppm
.1-1 ppm
.1-1 ppm
.1-1 ppm
ACCURACY &
CONFIDENCE
As noted
under labora-
tory condit-
ions
As noted
under labora-
tory condit-
ions
As noted
under labora^
tory condit-
ions
Accumulation
factor varies
with pK
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
TIME REQ.
FOR ACCUM.
7 days
7 days
7 days
2k hours
2*1 hours
24 hours
REFERENCE
Gregory,
Reed, and
Prlester(1969)
Gregory,
Reed, and
Priester(1969)
Gregory,
Reed, and
Prlester(1969)
Chacko and
Lockwood(1967)
Chacko and
Lockwood(1967)
Chacko and
Lockwood(ig67)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM FRESH WATER CULTURE
ACCUMULAHT
Dieldrln
Dieldrin
Dieldrln
Dieldrin
Dieldrln
ACCUMULATOR
Streptomyctes
lavendulae
Streptomyctes
griseus
Streptomyctes
venezuelae
Bacillus subtilus
Serratla marcescens
MEDIUM
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
Fresh water
culture
(may also
accumulate
in soil)
ACCUMULATION
FACTOR
Unknown
Unknown
Unknown
Unknown
Unknown
APPLICABLE
CONCENTRATION
.1-1 ppm
.1-1 ppm
.1-1 ppm
.1-1 ppm
.1-1 ppm
ACCURACY &
CONFIDENCE
Accumulation
factor
varies with
pH
Accumulation
factor
varies with
pH
Accumulation
factor varies
with pH
Accumulation
factor varies
with pH
dccumulatlon
Factor varies
•;ith pH
TIME REQ.
FOR ACCUM.
2k hours
24 hours
24 hours
2 4 hours
24 hours
REFERENCE
Chacko and
Lockwood(1967)
Chacko and
Lockwood(1967)
Chacko and
Lockwood(ig67)
Chacko and
Lockwood(1967)
Chacko and
Lockwood(1967)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM FRESH WATER CULTURE
O
I
ACCUMULANT ] ACCUMULATOR
I
Dleldrin
Par at hi on
Par at hi on
Parathlon
Parathlon
Parathlon
Agrobacterium
tumefaclens •.
Anacystis nidulans
Scenedesmus obllquus
Euglena gracills
Paramecium busaria
Paramecium
mult imlcronutleat urn
MEDIUM
Fresh water
culture
(may also
accumulate
In soil)
Fresh water
Fresh water
Fresh water
Fresh water
Fresh water
ACCUMULATION
FACTOR
Unknown
50 ± 3 ppm
72 ± 7 PPia
62 ± 2 ppm
94 ± 2 ppm
116 ± 2 ppm
APPLICABLE
CONCENTRATION
.1-1 ppm
1 ppm
1 ppm
1 ppm
1 ppm
1 ppm
ACCURACY &
CONFIDENCE
Accumulation
factor varies
with pH
As noted
under labora-
tory condit-
ions
As noted
under labora-
tory condit-
ions
As noted
under labora-
tory condit-
ions
As noted
under labora-
tory condit-
ions
As noted
under labora-
tory condit-
ions
TIME REQ.
FOR ACCOM.
21) hours
7 days
7 days
7 days
7 days
7 days
REFERENCE
Chacko and
Lockwood(1967)
Gregory,
Reed, and
Prlester(i969)
Gregory,
Reed, and
Priester(i969)
Gregory,
Reed, and
?rlester(1969)
Gregory,
Reed, and
Prlester(1969)
Gregory,
Reed, and
Prlester(1969)
-------
BIOACCUMULATION OF TOXIC SUBSTANCES FROM FRESH WATER CULTURE
ACCUMULATE
Mn •
ACCUMULATOR
Bacillus subtilis
W23
MEDIUM
Fresh water
ACCUMULATION
FACTOR
-
APPLICABLE
CONCENTRATION
55 ppm
ACCURACY &
CONFIDENCE
Complex
active trans-
port mechan-
ism
TIME REQ.
FOR ACCUM.
2 ninutes-
*l hours
REFEREUCE
Fisher,
Buxbaum,
Toth,
Eisenstadt,
Silver (1973)
-------
BIOACCUMULATORS
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I twrlMiOMi. iini ohi U/A i «
(I'lcasc rrihl iHuructions on t/ic reverse before completing)
1. HLPOH I' NO. . \y.
EPA 560/7-75-002 !
4. TITLE AND SI.M.ITITLI:
A Review of Concentration Techniques for
Trace Chemicals in the Environment
7. AUTHORIS)
Energy Resources Co. Inc.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Energy Resources Co. Inc.
185 Alewife Brook Parkway
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12. SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
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3. RECIPIENT'S ACCESSION-NO.
5. REPORT PATE November, 1975
Date of Approval
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8. PERFORMING ORGANIZATION REPORT NO.
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Cnterim Report 7/74-2/75
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15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report contains a discussion of the techniques which
are currently available for the concentration of trace pollutants
prior to their analysis. Methods for the accumulation of metals
and organic compounds from air, water, and solids are covered as
well as a review of recent literature on bioaccumulation. Each
section includes tables in which concentration methods, and the
accumulated materials are listed along with the pertinent
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