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Environmental Measurements
William L. Budde
U.S. Environmental Protection Agency

I. Significance of Environmental Chemical


Determinations
II. Chemical Analysis Strategies
III. Development and Documentation
of Analytical Methods
IV. Characteristics of Analytes, Samples,
and Sampling Techniques
V. Processing of Samples before Determination
of the Analytes
VI. Chromatographic Analytical Methods
VII. Nonchromatographic Analytical Methods

GLOSSARY Analytical method The complete process used to deter-


mine an analyte or analytes in a sample. The analytical
Accuracy The degree of agreement between the mea- method documents all the individual steps in the pro-
sured concentration of a substance in a sample and the cess from sampling to reporting the results.
true value of the concentration in the sample. Analytical method attributes Measures of the quality,
Analysis The process of investigation of a sample of the reliability, and uncertainty of the determinations ob-
physical world to learn about its chemical components, tained with an analytical method. Typical analytical
composition, structure, or other physical or chemical method attributes are selectivity, sensitivity, detection
characteristics. Generally only samples are analyzed, limits, signal/noise, recovery, accuracy, bias, preci-
and individual elements, compounds, and ions are sep- sion, and validation. Analytical method attributes are
arated from one another, identified, measured, or de- sometimes called figures of merit.
termined. A pure compound or multi-element ion is Bias The systematic error in a measurement of the amount
analyzed only when it is investigated to determine its or concentration of an analyte in a sample.
components, composition, structure, or other physical Congeners Compounds or ions that are members of a se-
or chemical characteristics. ries of related substances that differ only by the number
Analyte A general term for any element, compound, or of hydrogens that have been substituted by the same
ion that is present in a sample or is targeted for deter- atom.
mination in a sample. Derivatives Compounds or ions that are produced by

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548 Environmental Measurements

chemical reactions of analytes. An analytically useful Signal/noise The ratio of analyte electronic or other mea-
derivative has physical or chemical properties that are surable signal to the mean background matrix signal.
not possessed by the analyte but that can be employed Technique A specific way of manipulating a sample or
to determine the analyte. substance or measuring a substance. One or more tech-
Detection limit The minimum quantity or concentration niques may be used within each procedure, and several
of an analyte that can be detected with an analytical procedures may be used within an analytical method.
method or technique. There are no generally accepted Validation The determination of the attributes, or figures
standard criteria for detection and detection limits often of merit, of an analytical method for one or more an-
depend on the sample matrix. Therefore, detection lim- alytes in one or more sample matrices by one or more
its must include the criteria for detection and the nature analysts in one or more analytical laboratories, and the
of the sample matrix. A technique with a higher analyte acceptance of the attributes as reasonable and useful
sensitivity does not always provide a lower detection by the users of the data. There are many levels of an-
limit because interfering sample matrix components alytical method validation ranging from the validation
may also be observed with higher sensitivities. of a method for a single analyte in a single matrix by
Determination The identification and the measurement a single analyst in a single laboratory to a multian-
of the concentration of an analyte in a sample. alyte, multimatrix, multianalyst, and multilaboratory
Isomers Two or more compounds or multielement ions validation.
that have the same elemental composition but different
structures.
Precision The degree of random variation in repetitive ENVIRONMENTAL CHEMICAL DETERMINA-
measurements of the concentration of an analyte in TIONS are the identifications and measurements of
a sample. Precision is usually measured by the stan- the concentrations of elements, compounds, or ions in
dard deviation or the relative standard deviation of the environmental samples. Air, water, soil, and sediment
measurements. are broad categories of environmental samples, and each
Procedure A specific part of an analytical method that of these can be divided into several subcategories—for
is concerned with one aspect of the method, for exam- example, ambient air, indoor air, and vapor emissions
ple, the liquid–liquid extraction of groups of similar from mobile or stationary combustion sources. Body
analytes from a water sample. fluids and tissue are often analyzed to determine human,
Qualitative analysis The process of just identifying the animal, and plant exposure to environmental chemicals.
analytes in a sample.
Quantitative analysis The process of both identifying
and measuring the concentrations of the analytes in a I. SIGNIFICANCE OF ENVIRONMENTAL
sample. CHEMICAL DETERMINATIONS
Recovery The amount of analyte measured a sample ma-
trix as a fraction of the amount of the same analyte that Accurate and precise identifications and measurements of
was added to the sample. If the analyte is present in the specific chemical substances in the environment are fun-
sample before the addition, the native amount is sub- damental to environmental research and protection pro-
tracted from the measured quantity before calculating grams. Determinations are required to understand natural
the recovery. background concentrations of chemicals in the environ-
Sample matrix The general nature of the sample and ment, the nature and extent of environmental pollution by
its components that can have a significant impact on anthropogenic chemicals, trends in concentrations of these
the performance of an analytical method. For exam- substances, the transport and fate of chemical substances,
ple, seawater and freshwater sample matrices are sig- and the causes of variations of concentrations in time and
nificantly different and this difference can impact the space. Accurate and precise determinations are also re-
performance of an analytical method. quired to assess human health and ecological risks caused
Selectivity A qualitative estimate of how well the analyte by exposure to natural and anthropogenic substances, es-
identification procedure is able to distinguish an analyte tablish air and water quality standards, develop pollution
in a sample from one or many similar analytes with control strategies, evaluate the effectiveness of pollution
similar, or even some of the same, physical or chemical prevention and treatment technologies, and monitor com-
properties. pliance with and the effectiveness of discharge and other
Sensitivity The electronic or other measurable signal pro- government regulations. These data are also needed to de-
duced by the analytical method or measurement tech- velop, calibrate, and verify mathematical models used to
nique per unit amount of analyte. predict the impact of changes in concentrations of specific
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Environmental Measurements 549

substances in the environment. Environmental chemical the time of the day of sampling; the frequency of sam-
determinations are also required to set priorities and make pling; the depth of sampling for water, soil, and sediment
cost estimates for the remediation of abandoned hazardous samples; the meteorological conditions and altitude for air
waste sites. sampling; and the need for replicate samples taken at the
In addition to specific chemical substances, a variety same time and place. For body fluids and tissue samples,
of other determinations are very important and are often a myriad of details must be considered including the num-
required for environmental research and protection pro- ber of persons contributing or the kinds of wildlife-related
grams. These include identifications and measurements of samples that must be collected. The plan should specify a
bacteria, viruses, protozoa, and minerals such as asbestos series of discrete samples, a composite sample from con-
fibers. Measurements of meteorological conditions, par- tributions at various intervals, or a continuous flow of sam-
ticulate matter in air by size, water turbidity, biological ple over a period of time. A sampling strategy that does not
oxygen demand, chemical oxygen demand, and radioac- provide appropriate and representative samples seriously
tivity are also very important. These and other similar jeopardizes the value of the chemical determinations.
determinations are beyond the scope of this article and the The sampling techniques and procedures define the type
reader should consult other reference books for informa- of sampling equipment, the containers used for the sam-
tion about these topics. ples, the procedures used to clean the sample contain-
ers and sampling equipment, the calibration of sampling
equipment, and sample compositing procedures if com-
II. CHEMICAL ANALYSIS STRATEGIES posite samples are required. Sample preservation must
ensure that the chemical composition of the sample at the
A wide variety of chemical analytical strategies are used time of analysis is the same as it was at the time and place
in environmental analysis programs. In order to develop of sampling, and is not the result of physical or chem-
an appropriate strategy for a specific program, the ob- ical changes caused by the conditions of shipment and
jectives of the program must be thoroughly defined and storage prior to chemical analysis. Significant research
understood by all participants. An analytical strategy for has been conducted to find sample containers that resist
the program can then be developed by selecting and com- adsorption or degradation of sample components. Sam-
bining the most appropriate analytical methods and other ples are often shipped and stored at low temperatures, and
key elements that will provide the results needed to fulfill treated with various chemical reagents, to retard microbi-
the objectives of the program. Some of the major issues ological degradation of the analytes or to prevent chemical
and strategies that must be considered in developing a spe- reactions that can change the composition of the sample.
cific strategy for an analysis program are described in this Appropriate sampling techniques and preservation pro-
section. cedures are required to provide valid samples and valid
chemical determinations.
A. Samples and Sampling Strategies
B. Determination of Total Elements
The goals of the environmental program will usually de-
or Total Related Substances
fine the specific types of samples that must be acquired
and analyzed—for example, ambient air, drinking water, A standard analysis strategy is the determination of the
ground water, soil, sediment, blood, sweat, urine, and tis- total amount of an element in a sample where the ele-
sue. The sampling strategy is a broad but detailed plan ment is present in several or more elemental forms, com-
for the acquisition of the samples needed for the project. pounds, ions, oxidation states, or physical phases. This
Sampling techniques and procedures are the actual physi- strategy was developed before chromatographic and other
cal processes used to acquire the samples. Sample preser- techniques were available to separate the individual sub-
vation protects the integrity and validity of the samples stances containing the element of interest. It is widely used
before, during, and after the actual sampling process. Sam- in environmental research and government regulatory pro-
pling strategies, techniques, and sample preservation are grams. However, the meaning of total is variable because
major factors contributing to the success or failure of en- some analytical methods do not include all the physical
vironmental chemical determinations. phases or chemical forms in the determination. The sam-
The sampling strategy defines in detail what, where, ple preparation procedures in individual analytical meth-
when, and how the environmental samples will be ac- ods define exactly which elemental forms, compounds,
quired. This plan should specify all details including the ions, oxidation states, and physical phases are included in
number of sampling stations for air, water, soil, sediment, a total measurement. A similar strategy is the determina-
or fish samples; the locations of the sampling stations; tion of the total amount or total concentration of a group
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550 Environmental Measurements

of closely related compounds or ions without specifying Some analytical methods have been developed for the
the relative or absolute concentrations of the individual determination of groups of closely related compounds or
substances. Closely related substances usually have some ions. The classic example is the measurement of com-
common physical or chemical properties, elemental com- bined phenolic materials colorimetrically after a reaction
position, or structure. that forms a red derivative with many phenols. However,
The broadest definition of, for example, total mercury different phenols form derivatives with somewhat differ-
(Hg) in a sample is the sum of the elemental Hg0 , the Hg in ent visible absorption spectra and various phenols have
all inorganic compounds of Hg1+ , the Hg in all inorganic different reactivities with the derivatizing reagent. There-
compounds of Hg2+ , and the Hg in all organic compounds fore this method is calibrated with pure phenol and the
in which Hg is bonded to C, O, N, S, or some other ele- measurement gives just an estimate of the total phenols
ment. All phases are included because some species may in the sample. For this reason this method is probably no
be present in the vapor phase (Hg0 ), some soluble in water, longer widely used and phenols are usually determined
and some insoluble in water or present in the particulate as individual compounds with other analytical methods.
phase of an air sample. More limited definitions of total Subgroups of complex mixtures of congeners are some-
are often used in analytical methods that separate physi- times measured together for convenience of interpreta-
cal phases or chemical forms that contain the element of tion or for government regulatory programs. These de-
interest. terminations give concentrations of, for example, total
If a water sample contains both soluble and insoluble tetrachlorobiphenyls and total pentachlorobiphenyls. Sim-
manganese compounds and ions, and it is filtered to sep- ilar determinations of chlorinated dibenzo- p-dioxins and
arate the dissolved and insoluble fractions, and the fil- chlorinated dibenzofurans at each level of chlorination are
trate and insoluble residue are analyzed separately, the specified in some analytical methods.
results can be expressed as total dissolved Mn and to-
tal suspended or insoluble Mn. Phosphorus (P) can be
C. Determination of Specific Substances
determined colorimetrically as the ortho-phosphate ion,
PO−34 , in aqueous samples after a reaction that forms an in- Before the development of efficient chromatographic sep-
tensely blue-colored derivative. However, polyphosphate aration techniques and selective and sensitive detectors,
ions and other ions and compounds containing P do not analytical methods for the determination of specific ana-
form this derivative. Total P in a sample can be determined lytes in environmental samples were very limited. These
with the same colorimetric procedure after acid hydrolysis methods depend on highly selective chemical reactions
and oxidation of all ions and compounds containing P to that are relatively rare and difficult to discover, or on very
PO−34 . In some elemental analyses the sample is treated selective physical measurements such as atomic absorp-
with reagents designed to make available for measurement tion or emission techniques for elemental analytes. There-
some fraction of an element or elements but not the total fore only a relatively few analytical methods for the most
amount. For example, a soil sample may be treated with common and amenable organic and inorganic compounds
water at pH 3 to simulate the leaching process of acid rain. or multielement ions were developed. It would have been
A total elemental analysis of the filtrate provides informa- essentially impossible, and enormously costly, to develop,
tion about just those elements solubilized by the mild acid test, document, and implement a large number of nonchro-
treatment. This can be called the determination of total matographic analytical methods for a wide range of often
mild acid leachable elements. similar organic and inorganic analytes.
The measurements of total organic carbon (TOC) and Vapor phase or gas chromatography (GC) and high per-
total organic halogen (TOX) in a sample are used to as- formance liquid chromatography (HPLC) provided capa-
sess many types of environmental samples. The analytical bilities for the separation of microgram (10−6 ) and smaller
methods for TOC employ procedures to physically sep- quantities of often similar individual substances in com-
arate the inorganic carbon—that is, carbonate, bicarbon- plex mixtures. A variety of GC and HPLC detectors were
ate, cyanide, and other inorganic substances containing developed, and depending on the detector, the separated
C—from the organic compounds and ions in the sam- substances could be determined with good to excellent
ple. The TOC is then measured by oxidation of the or- sensitivity and with fair to excellent reliability. It was soon
ganic compounds and ions to carbon dioxide, which is recognized that determinations of a broad range of specific
determined by one of several techniques. The analytical chemical substances was not only practical but also essen-
methods for TOX use procedures to separate inorganic tial to achieve the goals of many environmental research
halogen-containing ions from halogen-containing organic and protection programs.
compounds and then determine the total halogens in the Gas chromatographic techniques were first applied dur-
organic compounds. ing the 1960s to synthetic organic compounds and natural
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Environmental Measurements 551

products that are often complex mixtures of organic com- from the analytes during sampling or sample processing
pounds. The earliest applications of these techniques in by pH adjustments, chemical derivatization, evaporation
environmental research were GC-based determinations of of nontarget substances, or other techniques. Chromato-
petroleum hydrocarbons in polluted air and chlorinated graphic separation and detection techniques can be se-
hydrocarbon pesticides in several types of samples. An- lected to give the best practical resolution of analytes,
alytical chemists and environmental scientists concerned selective detection, and the lowest detection limits. The
about organic pesticides, industrial organic chemicals, and detector can be calibrated for quantitative analysis with
other organic compounds emphasized the development of standard solutions of the target analyte or analytes and the
analytical methods for the determination of specific or- analytical method tested, perfected, and validated using
ganic compounds. In contrast, the emphasis in elemental test sample matrices fortified with known concentrations
and inorganic analyses during the 1960–1980s was, with of the target analyte or analytes.
a few exceptions, on determinations of the total amounts The target analyte strategy is widely accepted, under-
or concentrations of specific elements in a sample without stood, and used in analytical chemistry, environmental re-
regard to the specific compounds or ions containing those search, environmental protection programs, and in many
elements. With the recognition that toxicity and other envi- other fields of investigation. It is used in most environmen-
ronmentally significant properties varied widely with the tal quality surveys and government regulatory compliance
specific compound or ion, inorganic analytical chemists monitoring programs. Many analytical methods for a va-
later focused on chromatographic separations of individ- riety of target analytes have been developed, tested, docu-
ual species. The term speciation came into use, mostly mented, and implemented. Cost estimates for analyses are
by inorganic chemists, to distinguish this type of analysis readily made and analytical costs are not difficult to con-
from the conventional determinations of the total amounts trol. The target analyte strategy is used in the vast majority
or concentrations of the elements in a sample. of chemical analyses reported in the scientific literature.
There are two general strategies for the determination of
specific organic or inorganic compounds and ions in envi-
2. The Broad Spectrum (BS) Strategy
ronmental samples. The target analyte strategy dominated
analytical chemistry before the development of chromato- The objective of the BS strategy is to discover the sub-
graphic separation techniques, and is by far the most com- stances present in the sample and to measure their con-
monly used with contemporary separation and detection centrations without a predetermined list of target analytes.
techniques. The broad spectrum strategy became feasible As a starting point the BS strategy may follow the general
with the development of high resolution chromatographic scheme of a target analytical method, but with minimum
separation techniques and spectroscopic detectors. sample processing to allow a broad variety of generally
similar substances to reach the chromatographic separa-
tion and the detector. Procedures to remove target analyte
1. Target Analyte (TA) Strategy
interferences are minimized or not used to avoid discard-
Target analytes are known substances with known chemi- ing interesting and potentially important components. If
cal, physical, and other properties. They are either known the sample is very complex, it is usually divided into frac-
or thought to be in samples, and they must be determined tions that are likely to contain components with similar
to meet the objectives of the environmental analysis pro- properties. Several or more different types of chromato-
gram. The TA strategy is the analysis of the sample with an graphic separations may be required for the various frac-
analytical method that is designed and optimized to deter- tions depending on the components of the sample and the
mine the target analyte or a group of similar and separated breadth of information desired. The chromatographic de-
target analytes. If the target analytes are a diverse group tectors are generally spectroscopic detectors that can pro-
with sufficiently different chemical and physical proper- vide information about the composition and structure of
ties, they are divided into subgroups according to their the sample components. This information is used to iden-
similar properties. Several optimized analytical methods tify known substances, unexpected substances, and even
and separate environmental samples are used to determine unknown substances. The most important and widely used
the analytes in the subgroups. detector for the broad spectrum strategy is the mass spec-
The TA strategy has many advantages that favor its trometer, but infrared, nuclear magnetic resonance, and
widespread application. Sample preparation procedures other spectroscopic techniques are sometimes used.
can be designed to separate the target analytes from the The identification of all or most substances in one or
sample matrix with maximum efficiency and to concen- more chromatograms, even with extensive spectroscopic
trate them in a suitable solvent for further chromato- data, can be a challenging and difficult process. The avail-
graphic separation. Some interferences can be separated able data may not be sufficient to even tentatively identify
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552 Environmental Measurements

all the components, especially if pure authentic samples spectroscopic detectors usually provide sufficient infor-
of suspected substances are not available in the laboratory. mation to make correct identifications of target analytes
Calibration of a broad spectrum method for quantitative even when some are not fully separated. Well tested and
analysis is delayed until the desired components are iden- documented analytical methods for 80–100 or more an-
tified. For these reasons, and the general preoccupation alytes in some types of samples are presently available.
with target analytes, the BS strategy is much less common Multianalyte methods significantly reduce the cost of an
than the target analyte strategy. analysis on a per analyte basis, and add support to the
The BS strategy is obviously important for the discov- already strong justification for high resolution chromato-
ery of unknown naturally occurring substances and an- graphic separations and spectroscopic detectors.
thropogenic chemicals in the environment. However, BS
strategies are more difficult than TA strategies to develop,
E. Remote Laboratory Analyses
document, and implement. Cost estimates for analyses are
and Field Analyses
uncertain because the number of substances found, iden-
tified, and measured is not known until after the samples Chemical analyses can be conducted in a laboratory re-
are analyzed. Therefore analytical costs are difficult to mote from the locations where the samples are taken or in
control. Because of the potential costs, the instrumenta- the field near the sampling sites (on-site). On-site analyses
tion requirements, the technical skills needed, and time can be conducted in a field laboratory, which may be a tem-
required, the BS strategy is not often employed especially porary building or a truck trailer, van, or recreational vehi-
by programs with limited objectives and budgets. A strat- cle equipped with utilities services and analytical equip-
egy sometimes used in environmental studies is to de- ment. Another type of field laboratory is within a materials
velop a target analyte method that can meet the objectives or fluids processing facility. Alternatively, field analyses
of the study and give some attention to other chromato- can be conducted with mobile or portable instrumentation
graphic peaks to identify potentially new or unexpected carried in a small van, sport utility vehicle, moved with a
substances. hand cart, or carried by a person. Each of these strategies
has some advantages and some disadvantages.
The remote laboratory has the advantages of provid-
D. Single Analyte and Multianalyte Methods
ing carefully controlled temperature, humidity, ventila-
Traditional analytical methods, which were generally de- tion, and background conditions with adequate space and
veloped prior to the widespread application of GC and utilities to support a large array of major analytical in-
HPLC techniques, were nearly always designed for a strumentation and a staff of skilled analytical chemists
single target analyte—for instance, the colorimetric de- and technicians working in a convenient, comfortable, and
termination of PO−3 4 . With the development of GC and safe environment. The major disadvantage is that environ-
HPLC separation techniques, the determination of sev- mental samples must be carefully preserved, shipped, and
eral or more similar compounds or ions in a sample was stored prior to analysis. Furthermore, the analytical results
feasible, and multianalyte analytical methods were devel- may not be available for several days or weeks because of
oped and documented. However, analytical chemists did the time required to transport the samples to the laboratory,
not generally attempt to include more than about 10–20 incorporate the analyses into work schedules, and service
target analytes in a method. This strategy was necessary the multiple clients of a remote laboratory.
because early GC and HPLC columns were not very ef- Field determinations have the major advantage of
ficient and most GC and HPLC detectors were either not greatly reducing the time between taking the samples
selective or had limited selectivity. Sample preparation and the availability of the analytical results. This may
procedures designed to reduce or eliminate interferences allow utilization of the results quickly, which can provide
continued to be very important. Analytical methods for significant cost savings in the field operations that
chlorinated hydrocarbon pesticides with a GC separation utilize the analytical information. For example, the rapid
and an electron capture detector require appropriate sam- availability of results from field determinations can
ple preparation. These multianalyte pesticide methods are be used to fine-tune a sampling strategy to obtain the
sometimes called multiresidue methods because the pes- most significant samples for detailed remote laboratory
ticides are residues in crops and other samples. analysis. Similarly, the results from field determinations
As more efficient high resolution chromatographic sep- can be used to direct the work of construction crews or
aration techniques were developed, and spectroscopic de- well drillers using heavy and costly equipment. Mobile or
tectors came into widespread use, the number of target portable instrumentation can provide rapid and low-cost
analytes in multianalyte methods was increased. The sep- results from a large number of samples taken over a broad
aration of most or all target analytes is often feasible and geographic area in a short period of time.
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The analytical methods that are feasible in the field may Standard chromatographic separation techniques are gen-
be significantly limited compared to what is feasible in a erally too slow for continuous measurements although
remote permanent laboratory. If a field laboratory is lo- GC separations, especially fast GC, are used for process
cated in a temporary building or a large truck trailer, and control.
adequate utilities and personnel are available, many of
the kinds of analytical methods that are routinely imple-
mented in a remote laboratory may be feasible in the field. G. Analytical Quality Assurance and Control
However, because of space and power limitations, a broad Analytical quality assurance (QA) is a broad program of
variety of instrumentation is usually not available, and the actions designed to ensure that the chemical determina-
number of different analytical methods that can be imple- tions are of known and acceptable quality. The QA pro-
mented is smaller than in a remote permanent laboratory. gram encompasses all aspects of the chemical analysis
Mobile or portable instrumentation is usually more lim- from the design of the sampling strategy to the documen-
ited, and generally sample analyses are less complete and tation of the results. Analytical quality control (QC) is the
detailed than in a field or remote laboratory. implementation of specific actions designed to control the
quality of the determinations at some defined level of ac-
F. Discrete Samples and ceptance. All physical measurements have some degree
Continuous Monitoring of variability and uncertainty, and the QA/QC program
should define the limits of these. The quality of analytical
Field analyses can be conducted with discrete or com- determinations is judged by the attributes, or figures of
posited samples similar to the samples used in a remote merit, previously defined, which include selectivity, sen-
laboratory or by continuous monitoring of substances in sitivity, detection limits, signal/noise, recovery, accuracy,
a flowing stream of gases or liquids. Continuous moni- bias, precision, and validation. These attributes are deter-
toring is required when the results are needed within a mined using a variety of special measurements and forti-
period of time that is shorter than the time required to fied samples (QA/QC samples) that are described in the
take and analyze conventional discrete samples. Continu- analytical method. The time relationship between the anal-
ous monitoring is often required to determine substances yses of the environmental samples and the determination
in a processing facility and provide rapid feedback of re- of the quality attributes is critical in estimating the quality
sults that are used in process control strategies. If con- of the environmental determinations.
tinuous determinations are made with sufficient speed to Published environmental chemical determinations are
permit changes in sampling or other strategies while the often used in ways that are not anticipated by the original
determinations are in progress, these are called real-time investigators. The determinations may be used by other
analyses. investigators to estimate human or ecological exposure,
Continuous environmental monitoring in the field is assess the level of industrial discharges, or to develop
needed when the substances present and their concen- environmental quality standards or discharge limitations.
trations are changing rapidly. Discrete samples taken at Therefore, the results of the QA/QC measurements, and
inappropriate times will give results that do not correctly their time relationships to the analysis of environmental
assess the variable conditions in the atmosphere or a flow- samples, should be permanently attached to the environ-
ing stream. Sample compositing may provide a better as- mental sample results. These QA/QC data should demon-
sessment, but continuous monitoring and integration of the strate that the environmental data were obtained under
determinations over time gives the best assessment. The controlled conditions that provide credibility to the re-
determination of the sources of fugitive emissions that sults. Other users of the data, sometimes years in the fu-
are rapidly dispersed in the atmosphere or in a flowing ture, should be able to assess the quality and applicability
water stream requires continuous and sometimes mobile of the information, and take into account the variability
continuous monitoring. The concentrations of air pollu- and uncertainty in the determinations.
tants such as CO, NOx , SO2 , and O3 , that vary widely
with sunlight, automobile traffic, wind speed, wind direc-
tion, and other meteorological conditions are monitored III. DEVELOPMENT AND
continuously. DOCUMENTATION OF
Sampling and analytical equipment used in processing ANALYTICAL METHODS
facilities and in the field have some of the same require-
ments. However, equipment used in a facility may have The complete development and documentation of an an-
fewer constraints in regard to size, weight, and power alytical method usually occurs over a period of several
requirements than mobile and portable field equipment. years or more. The germ of most new methods is often a
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554 Environmental Measurements

research project in which a determination is needed. Orga- articles and descriptions often contain detailed informa-
nizations that specialize in developing and manufacturing tion about required equipment, supplies, reagents, instru-
analytical instrumentation frequently play a major role in mentation, and personnel skills. The technical reports and
supporting the development of new analytical methods. draft method descriptions are often distributed informally
But instrumentation alone does not constitute an analyti- through personal contacts, scientific conferences, or the
cal method. The general acceptance and widespread use Internet.
of methods depends on many factors, including the needs
for research or environmental monitoring of various sub-
C. Methods Published by Standard-Setting
stances, the cost and complexity of instrumentation, the
Organizations
required laboratory or field skills, and especially govern-
ment regulations. There is a high degree of variability in Standard-setting organizations that publish analytical
the completeness, documentation, testing, and validation methods for environmental analyses include The Amer-
of published analytical methods. ican Society for Testing and Materials (ASTM), The
American Public Health Association (APHA), The
A. Research Methods American Water Works Association (AWWA), The Water
Environment Federation (WEF), The International Stan-
The basic concepts and fundamentals of most analytical
dards Organization (ISO), and the Association of Official
methods are usually first published in scientific journals—
Analytical Chemists (AOAC). These organizations
for example, The American Chemical Society publica-
assemble working committees of experts that consider
tions Analytical Chemistry, Environmental Science and
developed, widely used, and generally accepted analytical
Technology, and The Journal of The American Chemi-
methods for publication as standardized analytical meth-
cal Society. These descriptions are usually brief and often
ods. Requirements of individual organizations vary, and
merely summarize the techniques and procedures of the
these may include a description of the method in a specific
method. Research reported in scientific journal articles is
editorial format and the availability of multilaboratory
often focused on a detailed investigation of a narrow sub-
validation data for the proposed analytical method. Some
ject area, and new analytical techniques and procedures
of these organizations also sponsor or participate in
developed for the research are rarely tested in a broader
multilaboratory validation studies of proposed analytical
context. Analytical quality assurance and control are often
methods. When an analytical method is published by one
minimal or not described. Techniques and procedures de-
of these organizations, it usually has been thoroughly
scribed in scientific research journals are the beginnings
tested and used by many laboratories and analysts, and
of analytical methods, but they usually require consider-
is widely known and accepted by specialists in that
able development, modifications, and testing before they
type of determination. Published methods are reviewed
become widely accepted analytical methods.
periodically, updated as needed, and may eventually be
replaced by entirely new methods.
B. Methods in Development
Academic research groups, industrial laboratories, and
D. Methods Published or Referenced
government agencies interested in conducting environ-
in Government Agency Regulations
mental surveys or monitoring programs often adapt re-
search techniques and procedures to the broader needs of The U.S. Environmental Protection Agency (USEPA) and
the survey or program. During this stage considerable ex- other federal, state, and local government agencies in the
perimentation is underway to evaluate equipment, instru- United States may require chemical analyses to determine
mentation, chemical reagents, and other materials used compliance with air quality, water quality, liquid waste
in the method. The incipient method may be tested with discharge, solid waste disposal, and other environmen-
many potential analytes and sample matrices. Modifica- tal regulations. The analytical methods specified for these
tions are implemented to minimize or eliminate problems purposes may be methods in development, methods pub-
discovered during the development process. Techniques lished by standard-setting organizations, or new methods
and procedures are developed for identifications of ana- documented in the regulatory proposals. The USEPA has
lytes, calibration of instruments for quantitative analysis, promulgated two types of analytical methods. Some reg-
and analytical quality assurance and control. Methods in ulations, like some drinking water and waste water reg-
development may be described in a series of draft ver- ulations, require either analytical methods designated in
sions that are not usually formally published but may ap- the regulations or approved alternative test methods for
pear in bound or unbound technical reports. These meth- compliance monitoring. Other regulations—some USEPA
ods are described in more detail than in scientific journal solid waste regulations, for example—include or reference
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Environmental Measurements 555

analytical methods that are suggested or optional but allow of volatile substances range from below 0 to above 200◦ .
any other appropriate analytical methods. Some compounds with BPs at the upper end of this range
are surprisingly volatile. For example, nitrobenzene in
Fig. 1 has a BP of 211◦ but still has a VP of 0.245 Torr at
IV. CHARACTERISTICS OF ANALYTES, 25◦ . At normal room temperatures the distinctive odor of
SAMPLES, AND SAMPLING nitrobenzene vapor is readily detected by most people.
TECHNIQUES
B. Semivolatile Analytes
The physical and chemical properties of analytes and the
nature of the sample have a major impact on, and often Semivolatile analytes are usually defined as those hav-
limit, the sampling and other procedures and techniques ing VPs in the range of 0.1 to about 10−9 Torr, but this
that can be employed in an analytical method. Major issues range is approximate and some substances with VPs in
that must be considered when developing and analytical this range are considered volatiles or even nonvolatiles
method are the volatilities, thermal stabilities, photochem- (next section). For example, Hg0 has a VP of 2 × 10−3
ical stabilities, polarities, water solubilities, and chemical Torr at 25◦ , but is often considered a volatile analyte.
reactivities of the sample components or target analytes; Most semivolatile analytes have molecular weights in the
the physical state of the sample; and the nature of the sam- range of 100–500, but a MW in this range does not guar-
ple matrix. Analytes, whether organic or inorganic, can be antee that a compound is a semivolatile. However, since
broadly divided into three categories based partly on va- semivolatiles nearly always have higher MWs and con-
por pressure, or volatility, at ambient temperature and on tain more atoms than the volatiles, they have a signif-
some other physical and chemical properties. There are icantly larger number of isomers, congeners, and chi-
major differences in the procedures and techniques used ral forms. Semivolatiles are usually devoid of structural
to acquire and process condensed phase and vapor phase groups that are susceptible to thermal decomposition be-
samples. Sampling ground water requires expert selection low about 300◦ , or cause high polarity, or impart high
of procedures and techniques to avoid significant analyti- water solubility, or are very chemically reactive. Figure 2
cal errors. shows the structures, MWs, some melting points (MPs),
and VPs of four representative semivolatile compounds
of environmental interest. Both benzo[a]pyrene and 2,3,7,
A. Volatile Analytes 8-tetrachlorodibenzo- p-dioxin have VPs at the low end of
Volatile analytes are usually defined as those having va- the semivolatile range, but they have little or no polarity
por pressures (VPs) greater than about 0.1 Torr at 25◦ and and tend to behave like other semivolatiles with higher
an external pressure of 760 Torr [1 Torr = 1 mm of Hg VPs. The VPs of semivolatile compounds are generally
or 133 kilopascals (kPa)]. Figure 1 shows the structures, insufficient to give vapor concentrations at ambient tem-
molecular weights (MWs), boiling points (BPs), and VPs peratures that can be detected by a distinctive odor.
of three representative volatile compounds of environmen-
tal interest. Most volatile analytes have MWs below 200,
but a low MW does not guarantee that an analyte will
be volatile. Many substances have MWs below 200, but
they are not volatile because they are ionic or have po-
lar groups of atoms or engage in hydrogen bonding with
other molecules. Some compounds have high VPs—for
example, MTBE in Fig. 1—but reduced volatility in wa-
ter because of their high water solubilities. Boiling points

FIGURE 1 The structures, MWs, BPs, and VPs of three repre- FIGURE 2 The structures, MWs, some MPs, and VPs of four
sentative volatile compounds of environmental interest. representative semivolatile compounds of environmental interest.
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556 Environmental Measurements

TABLE I The Number of Possible Chlorinated Biphenyl, Chlorinated Dibenzo-p-Dioxin, and


Chlorinated Dibenzofuran Congeners and Isomers
Parent compound Total congeners Cl1 Cl2 Cl3 Cl4 Cl5 Cl6 Cl7 Cl8 Cl9 Cl10

Biphenyl 209 3 12 24 42 46 42 24 12 3 1
Dibenzo- p-dioxin 75 2 10 14 22 14 10 2 1
Dibenzofuran 135 4 16 28 38 28 16 4 1

The large number of potential congeners and iso- D. Condensed Phase Samples
mers of some semivolatile compounds is illustrated in
If only semivolatile and non-volatile components are of
Table I, which shows the numbers of possible chlorinated
interest, or the sample only contains these categories of
biphenyl, chlorinated dibenzo- p-dioxin, and chlorinated
analytes, sampling procedures for most condensed phase
dibenzofuran congeners and isomers. The total number
samples are not difficult and require only a few precau-
of chlorinated congeners of each parent compound is the
tions. These include the materials used for sample contain-
sum of the possible isomers at each level of chlorination.
ers, the cleaning of sample containers, and the preservation
Dibenzofuran has more possible chlorinated congeners
of the sample. Water samples for elemental analyses are
and isomers than chlorinated dibenzo- p-dioxin (Fig. 2)
treated with acid at the time of sampling, or well before
because it has just one ring oxygen and a less symmetrical
analysis, to reduce the pH to  2. This ensures the solu-
structure. If F, Br, I, CH3 , or any other uniform substituent
bility of metal-containing ions, which can precipitate or
replaces Cl, the same numbers of possible congeners and
adsorb on container walls at a pH  2. Glass containers
isomers would exist. If different atoms or groups of atoms
were mixed as substituents on these parent compounds,
a significantly larger number of different substances,
congeners, and isomers are possible.

C. Nonvolatile Analytes
All other compounds and essentially all ions are classified
as nonvolatile. Substances in this category have VPs lower
than about 10−9 Torr or have structural groups that are sus-
ceptible to thermal decomposition below about 300◦ , or
that cause high polarity, or that impart high water solubil-
ity, or that are very chemically reactive. Figure 3 shows the
structures, MWs, some MPs, and VPs of six representa-
tive compounds of environmental interest from this group.
All these examples except the herbicide glyphosate have
reported VPs in the semivolatile range, but they do not
behave like typical semivolatile compounds. Nitroglyc-
erine and N-nitrosodiphenylamine undergo thermal de-
composition at temperatures below well below 300◦ . The
pesticide carbofuran and the herbicide diuron are more
thermally stable, but they also tend to decompose below
300◦ and on hot surfaces. The polarities of the functional
groups of this class of compounds cause adsorption on
polar surfaces and dipole–dipole interactions with other
molecules. Nearly all carboxylic acids—for instance, the
herbicide 2,4-D in Fig. 3—are susceptible to decarboxyla-
tion at elevated temperatures and they interact with basic
substances or basic surfaces which reduces their volatility.
Similarly, basic substances like amines and some other ni-
trogen compounds interact with acids and acidic surfaces, FIGURE 3 The structures, MWs, some MPs, and VPs of six rep-
which reduces their volatility. resentative nonvolatile compounds of environmental interest.
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Environmental Measurements 557

are not used for elemental analysis samples because aque- down-hole samplers, pumps, tubing used with pumps, and
ous acid solutions can leach trace elements from glass. well casings can also impact the concentrations of analytes
Samples are taken in plastic containers that provide the in the sample. Considerable research has been conducted
added benefits of reduced weight compared to glass, little to evaluate the materials and techniques used to sample
or no breakage during handling and shipping, and single- groundwater, but uncertainties remain because there is no
use containers that can be disposed of at a plastic recy- satisfactory groundwater standard of reference for com-
cling facility. However, samples for the determination of parison of various techniques.
organic analytes are taken in glass containers to prevent Semivolatile analytes in vapor phase samples are of-
background contamination of the samples by organic com- ten associated with particulate matter or aerosols that are
pounds that can leach from plastic materials. These sam- collected on glass or quartz fiber filters in a flowing air
ples are often preserved by addition of acid to make the stream. However, some semivolatile analytes that have
sample pH  2 to retard microbiological degradation of higher VPs, for example, 3,3 ,5,5 -tetrachlorobiphenyl in
some analytes. Acid leaching of glass containers generally Fig. 2, can slowly vaporize from a particle trapped on
has no effect on the concentrations of organic analytes. a filter in the flowing air stream and will be lost unless
Condensed phase samples containing volatile analytes captured by an in-stream sampling device. Small glass or
require special techniques since the volatile components metal tubes containing polyurethane foam are often used
are elusive and can be readily lost during sampling and to capture vaporized semivolatile analytes. Other solid
sample processing. Water samples must be taken with little phase adsorbents, which are described in the next sec-
or no agitation of the sample and poured into the container tion, are also used to trap semivolatile analytes vaporized
so there is no air space, often called a headspace, between from particulate filters.
the top of the sample and the air tight seal of the container.
This prevents vaporization of volatile components into the
E. Vapor Phase Samples
headspace during shipment and storage, which reduces
the concentration in the aqueous phase. Aliquots of water There are two general approaches to sampling air, or va-
samples are removed from sample containers by inserting porous emissions from stationary (stack) and mobile (au-
a syringe needle through the inert airtight septum seal and tomobile, truck, etc.) sources, for the laboratory determi-
drawing water into a gas tight syringe. Solid samples, for nation of volatile analytes. Bulk vapor phase samples can
example soils and sediments, may also contain volatile be taken in the field in various containers and transported to
components trapped in pores or dissolved in associated a remote or field laboratory for analysis. Containers used
water and these components are easily lost during sample for bulk vapor phase samples include flexible polyvinyl
handling. Solid and semisolid samples are carefully and fluoride (Tedlar) bags, evacuated glass or metal reservoirs,
quickly placed in wide-mouth sample containers that are and thermally insulated cryogenic collection vessels. Al-
sealed in the field and not opened during any subsequent ternatively, the volatile analytes can be separated from the
processing of the sample. Volatile components are usually main components of air in the field and just the analytes
partitioned into water, organic solvents, or the vapor phase, and their collection devices transported to the laboratory.
and the extracts are analyzed using techniques developed The principal techniques used to separate volatile analytes
for liquid or vapor phase samples. Water or an organic from air in the field are cryogenic traps, impingers, and
solvent are added to the sample containers through inert solid phase adsorbents.
and airtight septum seals with a syringe.
Groundwater sampling is a significant challenge be-
1. Bulk Vapor Phase Samples
cause water must be lifted to the surface through a bore
hole from depths ranging from a few meters to 75 meters or Flexible plastic sample bags are generally limited to va-
more. The lifting process can disturb the equilibrium be- por phase samples that can be analyzed within a short
tween dissolved analytes and analytes associated with par- time after sample collection. This limitation is due to po-
ticulate matter and significantly change the temperature tential losses of analytes by surface adsorption and sur-
and pressure of the water sample. These factors can cause face chemical reactions. Transportation of inflated bags
changes concentrations of analytes and raise questions over long distances to a remote laboratory is cumbersome,
about the representativeness of the sample. Volatile com- and can result in total losses of samples due to punctures
ponents of groundwater samples are particularly suscepti- and other accidents. Plastic bags are used in some lab-
ble to losses caused by temperature and pressure changes oratory operations—for example, to collect automobile
and degassing of the sample. Several types of down-hole exhaust and vaporized fuel—and for samples that can be
water samplers are available and a several types of pumps conveniently transported to a laboratory.
are used to purge a well and lift a stream of ground wa- Evacuated stainless steel canisters are widely used col-
ter to the surface. The materials of construction of the lection devices for ambient air samples. Sample canisters
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558 Environmental Measurements

have smooth and inert internal surfaces and few or no impinger compared to some bulk air sampling techniques
active sites that adsorb volatile analytes or catalyze chem- is that hundreds of liters of air can be drawn through the
ical reactions. The 1–6 L canisters are easily transported to device over a period of several hours. Sampling trains with
a remote or a field laboratory. Canisters are leak tested and multiple collection devices in series are used to collect dif-
cleaned in the laboratory prior to use, evacuated to about ferent fractions of a vapor phase sample. Components of
5 × 10−2 Torr or less, and transported to the sampling site sampling trains can include particulate filters of several
where samples are taken by opening the sampling valve. types and sizes, particle-size separation devices, multiple
Composite samples can be taken over time and/or space, impingers, and solid phase adsorbents.
and an in-line pump can be used to pressurize the container Solid phase adsorbents are simple and inexpensive
with either additional sample air or pure air if sample di- devices used to separate volatile analytes from the
lution is required. Pressurized samples are useful when principal components of air in the field. A porus solid
longer term composite samples are taken or when larger phase adsorbent is placed in a glass or metal tube that is
samples are needed to lower detection limits. taken to the field where air is drawn through the adsorbent
Condensation of an entire air sample with liquid ni- to trap the analytes. The adsorbent tube is then sealed
trogen or liquid helium has been used for many studies. and returned to the laboratory for analysis. Many types
However, this technique is expensive to implement and re- of solid phase adsorbents are used including alumina,
quires specialized portable equipment for handling cryo- activated carbons of various types, charcoal, graphitized
genic fluids in the field. carbon black (Carbopack B and C), carbon molecular
sieves, GC packing materials such as Chromosorb 101
and 102, ethylvinylbenzene–divinylbenzene copolymer
2. Separated Analytes
(Porapak Q), styrene–ethylvinylbenzene–divinylbenzene
Cold trapping is used to separate volatile analytes from terpolymer (Porapak P), silica gel, 2,6-diphenyl- p-
the main components of air in the field. Air is drawn by a phenyleneoxide (Tenax-GC), styrene–divinylbenzene
pump through an inert, often nickel, metal tube immersed copolymers (XAD-1, XAD-2, and XAD-4), and acrylic
in a fluid at a very low temperature as, for instance, −150◦ . ester polymers (XAD-7 and XAD-8). Adsorbent trapping
The tube may be packed with some inert material such as is applicable to a wide variety of nonpolar and some polar
Pyrex glass beads, and the temperature is sufficient to con- volatile analytes.
dense most analytes but insufficient to condense oxygen Some adsorbents do not bind analytes strongly, which
or nitrogen. Plugging of the condensation tube with ice or is an advantage for subsequent processing, but may re-
other solids can be a major problem when sampling large sult in the gradual release of some volatile analytes during
volumes of humid air. This problem is addressed by the long vapor sampling periods. Long sampling periods are
employment of air dryers that trap moisture but allow the often required—for example with ambient air—because
nonpolar volatile analytes to pass into the cold stage of of generally lower analyte concentrations compared to
the trapping system. However, the more polar and water- vapor phase samples from stationary or mobile sources
soluble analytes are also removed by efficient air dry- of air pollutants. Breakthrough of the more volatile po-
ing systems. Another potential problem is that some ana- lar and nonpolar analytes from the adsorbent is controlled
lytes may react during subsequent processing with trapped by placing additional adsorbents in the tube or additional
ozone, nitrogen oxides, or other substances present in the sampling tubes in a sampling train. Analytes adsorbed on
air. A practical limitation of the cold trapping technique is solid phase materials may also react with substances in
the requirement for liquid nitrogen or liquid argon in the the air as, for instance, with nitrogen oxides and ozone,
field during extended sampling periods. to produce products not in the original sample. Long air
Impingers are used to extract various substances from sampling times also risk oxidation of some adsorbents
vapor phase samples. An impinger is a closed glass or and the production of background substances and other
metal vessel with an inlet tube that extends to near the bot- artifacts. These potential problems are usually evaluated
tom of a liquid and an outlet tube well above the surface during analytical method development and controlled by
of the liquid. The impinger may contain various aqueous using appropriate quality control procedures
or nonaqueous liquids including solutions of derivatizing
agents. Vapor is drawn by a pump into the inlet tube and
bubbled through the liquid, which dissolves soluble an- V. PROCESSING OF SAMPLES BEFORE
alytes or the analytes react with reagents in solution to DETERMINATION OF THE ANALYTES
form soluble compounds. The liquid may also condense
various substances, including water vapor, and collect fine Some processing of samples before the determination of
particulate material that passes through a coarse filter or the analytes is often required to achieve optimum analyti-
another separation device. A important advantage of an cal method performance. Sample processing also defines
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Environmental Measurements 559

exactly what elemental forms, compounds, ions, oxidation for example an industrial wastewater or a soil from a haz-
states, and physical phases are included in the determina- ardous waste land fill, fractionation of the solvent extract
tion of specific substances or in the total amount of an before determination of the analytes is usually required.
element or a group of related substances in a sample. The Fractionation is often accomplished with open column
degree of sample processing that is either appropriate or liquid chromatography or preparatory scale high perfor-
needed depends on a variety of considerations including mance liquid chromatography (Section VIA2). The deter-
mination of total elements in particulate matter collected
r The chemical analysis strategy, that is, a total, target on air filters, in most water samples, or in solids requires
analyte, or broad spectrum determination an acid digestion of the sample to ensure that the elements
r The physical phases of the sample that are included in are in water-soluble chemical forms for the measurement.
the determination The vigor of the digestion also determines the recovery of
r Whether the samples will be analyzed in a remote or a the elements from sediment and other insoluble material.
field laboratory or with laboratory, mobile, or portable Invariably, the analytical method developer is required
instrumentation to make compromises between the amount and complex-
r The complexity of the sample matrix ity of the sample processing and the separating power,
r The number of target analytes selectivity, and other attributes of the chromatographic or
r The diversity of properties of the target analytes nonchromatographic determination. These compromises
r The nature and concentrations of analyte interferences are often strongly influenced by the projected cost and
r The detection limits required time required for various method options and by the de-
r The efficiency of the chromatographic separation used sired quality, detail, and reliability of the results. Major
in the analytical method issues usually are the availability of laboratory or field
r The selectivity of the chromatographic detector or the equipment and instrumentation, the experience and skill
nonchromatographic measurement technique of the staff in using the equipment, and other laboratory or
r The willingness to risk severe contamination of a GC field infrastructure required to complete the analyses of the
or HPLC column, or some other critical instrument samples. Most research and standard analytical methods
component, by a concentrated or high background contain many compromises that may not be clearly de-
environmental sample fined in the method description, but should be understood
by the user.
Some sample matrices, such as ambient air or drinking
water, are analyzed without sample processing with some
analytical methods. Volatile compounds in ambient air VI. CHROMATOGRAPHIC
collected in canisters or volatile compounds trapped from ANALYTICAL METHODS
ambient air on solid phase adsorbents are determined di-
rectly (Section VIA1). Similarly, the total concentrations Nearly all contemporary analytical methods designed for
of some elements in low turbidity drinking or surface water specific compounds or ions in environmental samples em-
amples preserved at a pH < 2 can be determined without ploy some type of chromatographic separation. Gas chro-
further sample processing (Section VIIA). Common inor- matography is the dominant technique for the separation
ganic anions, like Cl− , Br− , NO− 3 , etc., are determined in of volatile and semivolatile analytes (Figs. 1 and 2 and
surface, ground, drinking, and some other water samples Table I). Reverse phase high performance liquid chro-
without sample processing. However, many sample ma- matography is used for the separation of nonionic ana-
trices and analytical methods require at least some, and lytes that are thermally unstable, nonvolatile, or reactive
sometimes considerable, sample processing prior to the and not amenable to GC (Fig. 3). High performance ion
determination of the analytes. exchange chromatography and capillary electrophoresis
Semivolatile organic analytes trapped on air filters or are used for the separation of ionic substances. Analytes,
on solid phase adsorbents or in water, soil, and other solid either fully or partially separated, are sensed by in-line
samples are extracted with an organic solvent, or a solvent chromatographic detectors that produce electronic signals
mixture, and the extracts are concentrated by evaporation that are usually converted into digital form and stored in
of the solvent before the determination of the analytes. computer data systems. The computer systems, which are
Solid samples are often extracted with the classical Soxh- used with nearly all contemporary chemical analytical in-
let apparatus or with a variety of other techniques includ- strumentation, typically have software to control the op-
ing several that use organic solvents at elevated temper- eration of the instrument, acquire and store raw data, and
atures and pressures. If a sample is highly concentrated, reduce the data to more usable analytical information.
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560 Environmental Measurements

A. Chromatographic Separation Techniques The term high performance is often used to distinguish
this technique from open-column liquid chromatography
1. Gas Chromatography
conducted at atmospheric pressure with gravity flow of
The basic components of a gas chromatograph are a car- the mobile phase. Columns vary in diameter from <1–
rier gas system, a column, a column oven, a sample injec- 5 mm ID, or larger, and from a few cm in length to 30 cm
tor, and a detector. Very pure helium is the near universal or more. Column packings consist mainly of silica parti-
carrier gas for environmental and many other analyses. cles, usually 3–10 µm in diameter, coated with low-bleed
Open tubular GC columns are constructed of fused sil- stationary phases of varying polarity chemically bonded
ica with low-bleed stationary phases of varying polarity to the silica surface. Organic polymers are also used as
chemically bonded to the silica surface. Columns are typ- stationary phases in analytical separations. Automated
ically 30–75 m in length and have inside diameters (ID) or manual syringe injections of aliquots of liquid sam-
in the range of about 0.25–0.75 mm. The column oven ples and known-volume sample loops are used for sample
is capable of precise temperature control and temperature injection.
programming at variable rates for variable times. The dominant HPLC technique is the reverse phase con-
Analytes are introduced into GC columns with several figuration in which a nonpolar or slightly polar station-
techniques. An aliquot of a relatively concentrated va- ary phase is used with a more polar mobile phase that is
por or air sample—for example, from a plastic bag or a often water, methanol, acetonitrile, or mixtures of these
canister—can be introduced into a short section of tubing solvents. The normal phase configuration, which was de-
of known volume, called a sample loop, and subsequently veloped before reverse phase, uses a more polar station-
purged with carrier gas into the GC column. Volatile an- ary phase and a nonpolar mobile phase, but it is not often
alytes in ambient air samples in a canister or trapped on used in contemporary HPLC. A vast array of organic com-
a solid phase adsorbent are usually concentrated and fo- pounds containing a variety of functional groups are re-
cused in a cryogenic trap or a secondary adsorbent trap, tained on nonpolar or slightly polar stationary phases, and
then thermally vaporized into the GC carrier gas stream. are sufficiently soluble in more polar mobile phases to give
However, in some analytical methods, volatiles trapped excellent separations. Analytes are retained on the column
on an absorbent are thermally desorbed directly into the by an equilibrium process in which the dissolved molecule
GC column. Aliquots of organic solvent extracts from var- is alternately associated with the stationary phase, through
ious aqueous and solid samples are usually injected with weak noncovalent bonding interactions, and the mobile
a syringe into the carrier gas stream in a heated injection phase where it is transported toward the detector.
port. Both manual and automated syringe injection sys- Isocratic elution is the use of a mobile phase that has
tems (autoinjectors) are used and the latter are generally a constant composition throughout the elution of analytes
very reliable, precise, and have the capacity to process from the column. Gradient elution is the gradual chang-
many samples unattended. ing of the mobile phase composition as the analytes elute
Mixtures of analytes are separated by repeated equili- from the column. Gradient elution is frequently used to
brations between the vapor state, where the analytes are enhance analyte resolution and shorten the time required
entrained in the flowing carrier gas toward the detector, for a separation. The pH of typical mobile phases can be
and the absorbed or dissolved state, where they are at- adjusted over a reasonable range to improve resolution and
tracted to the stationary phase on the wall of the column selectivity. Various buffer substances, salts, and ion pair
by generally weak molecular forces. Analytes that tend reagents can be used to control pH and ionic strength, and
to favor the absorbed state move more slowly through the to facilitate the separation of some analytes. Reverse phase
column to the detector than do analytes that favor the vapor HPLC is more complex than GC because of the number
state. Complete separations of a few nanograms (10−9 ) or of operational parameters including column dimensions,
less of each of 40–50 or more analytes in 30 min or less column packings, mobile phases, gradient elution, and var-
is not uncommon. ious mobile phase additives.

2. High Performance Liquid Chromatography 3. High Performance Ion Exchange


Chromatography
The basic components of a high performance liquid chro-
matograph are a high pressure mobile phase delivery sys- Ion exchange is another form of HPLC that uses a station-
tem, a metal column packed with fine particles containing ary phase consisting of a cross-linked synthetic organic
the stationary phase, a sample injector, and a detector. polymer, often called a resin, with —SO3 H or —NH2
A high pressure pump is used to force the mobile phase groups attached to phenyl or other aromatic rings on the
solvent or solvent mixture through the packed column. polymer backbone. Mobile phases are usually water or
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Environmental Measurements 561

water and a miscible organic solvent. In basic solution Nonselective detectors respond to most or all changes
the SO3 H groups of a cation exchange resin are ionized in the composition of the carrier gas or mobile phase, and
and consist of —SO− 3 groups and associated counterions, are capable of detecting nearly all entrained or dissolved
for instance, Na+ . Cationic analytes are retained on the analytes. The GC flame ionization and thermal conduc-
cation exchange column by displacing the resin counteri- tivity detectors and the HPLC refractive index detector
ons in an equilibrium process. The cationic analytes are are examples of nonselective detectors. Nonselective de-
subsequently eluted with a mobile phase containing a high tectors provide no direct information about the identity
concentration of counterions or counterions of a higher of the analytes except the time of arrival, the time of
charge, for example, Ca2+ . Isocratic and gradient elutions maximum concentration, and the time of return to pure
are used with gradients in both solvent composition and carrier gas or mobile phase. Thus the peak shape of the
counterion concentration. Mobile phase pH is a very im- analyte is usually well-defined, the measurement of peak
portant operational parameter that can have a significant area or height can be precise, but the information needed
impact on the retention or elution of various ionizable an- to identify the analyte that caused the change is weak.
alytes from a resin. Identifications are based on comparisons of measured re-
In an acid solution the amino groups of an anion ex- tention times of separated analytes with retention times
change resin are protonated and exist as —NH+ 3 groups of expected analytes measured under the same chromato-
and associated counterions, for instance, Cl− . Analyte an- graphic conditions. While measured retention times can
ions are retained on the column by displacing the resin be very precise, especially with fused silica capillary GC
counterions in an equilibrium process. The anion analytes columns and multiple internal standards, there is a high
are subsequently eluted with a higher concentration of probability of coelution of two or more analytes in most
counterions or some type of gradient elution. Anion ex- environmental samples. This is because the peak capac-
change chromatography is widely used for the separation ity of a chromatogram, which is the number of analytes
of inorganic anions and chelated metal anions in aque- that can be fully separated, is limited. For most environ-
ous samples. With some natural or industrial water sam- mental samples the peak capacity is much smaller than
ples that contain high concentrations of ions such as Na+ , the number of possible analytes that respond to a nons-
Ca2+ , Mg2+ , Cl− , and SO−4 , cation and anion analytes may elective detector. Therefore, there is a significant risk of
not be retained on the column, and this can result in poor misidentifications or a false positives.
analyte recoveries. Selective detectors respond to only certain classes of
analytes and they are often used in environmental chemi-
cal determinations. The electron capture, photoionization,
4. Other Chromatographic
electrolytic conductivity, and flame photometric GC de-
and Related Techniques
tectors are selective for limited groups of analytes. Se-
Supercritical fluid chromatography (SFC), capillary elec- lective HPLC detectors include electrochemical detectors
trophoresis (CE), and several related separation tech- and the single wavelength ultraviolet-visible (UV-VIS)
niques are occasionally used in environmental chemical absorption and fluorescence detectors. Preinjection or
determinations. The CE technique is very important in bio- postcolumn on-line chemical reactions are used to con-
chemistry and molecular biology because of the very high vert nonresponsive analytes into derivatives that respond
resolving power that can be achieved, the high speed of to a selective detector. The information produced by a
separations compared to HPLC, and its ability to separate selective detector about the nature of the analyte is im-
charged species such as proteins, peptides, and deoxyri- proved, compared to the nonselective detector, but still
bonucleic acid fragments. These techniques have con- is not strong because the most significant piece of infor-
siderable potential for environmental analyses and may mation obtained is the retention time. Although the range
emerge as very important techniques in the future. of potential analytes that respond to a selective detector is
much narrower than the range that responds to a nonselec-
B. Chromatography Detectors tive detector, multiple potential analytes still can have the
same retention time. The nature of the sample is a factor
On-line detectors for GC, HPLC, and other chromato- is considering whether multiple analytes could be present
graphic separation techniques are conveniently divided that may have the same retention time.
into three general classes: Spectroscopic detectors measure partial or complete
energy absorption, energy emission, or mass spectra in
r Nonselective detectors real time as analytes are separated on a chromatography
r Selective detectors column. Spectroscopic data provides the strongest evi-
r Spectroscopic detectors dence to support the identifications of analytes. However,
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562 Environmental Measurements

depending on the spectroscopic technique, other method phase and also provides high selectivity, sensitivity, and
attributes such as sensitivity and peak area measurement the ability to correct for interferences when necessary.
accuracy may be reduced compared to some nonselec- Colorimetric and electrochemical techniques were used
tive and selective detectors. The mass spectrometer and more frequently for elemental determinations before the
Fourier transform infrared spectrometer are examples of development of the three major spectroscopic techniques.
spectroscopic detectors used on-line with GC and HPLC. Their use has decreased significantly because of inherent
The diode array detector, which can measure the UV-VIS limitations in selectivity, sensitivity, susceptibility to inter-
spectra of eluting analytes is a selective spectroscopic de- ferences, and the need for chemical processing to prepare
tector because only some analytes absorb in the UV-VIS light absorbing derivatives.
region of the spectrum. The mass spectrometer, which can
use a variety of ionization techniques, is probably the most
1. Atomic Absorption
widely used GC and HPLC detector for environmental
chemical determinations. All detectors respond, to some During the 1960s flame AAS became the dominant tech-
extent, to natural background substances in environmen- nique for determinations of the elements in low concen-
tal samples and sample extracts. Background chemical trations in water samples and aqueous extracts of other
noise is highest in the most contaminated environmen- samples. Aqueous sample aerosols are injected directly
tal samples and at the highest instrument sensitivities, but into the flame and precise determinations of many ele-
spectroscopic detectors are best equipped to distinguish ments can be made. However, instrument detection limits
chemical noise from environmental analytes. for some important elements, for example As, Cr, Pb, Sb,
Se, and Tl, in water and other matrices are >50 µg/L, and
often much greater, and AAS is limited to measuring one
VII. NONCHROMATOGRAPHIC element at a time. The high temperature graphite furnace
ANALYTICAL METHODS sample introduction system provided instrument detec-
tion limits of <5 µg/L for most elements, and allowed
Analytical methods that do not employ a chromatographic automation of sample processing, but was still limited to
separation of analytes are widely used for some envi- measuring one element at a time. Other AAS sample in-
ronmental determinations. These methods generally de- troduction techniques, especially chemical reduction and
pend on highly selective physical measurements or selec- elemental Hg vaporization (cold vapor) and conversion
tive chemical reactions. Atomic absorption spectrometry of As and Se to volatile hydrides, provided similarly low
(AAS), atomic emission spectrometry (AES), and mass detection limits. The graphite furnace and Hg cold vapor
spectrometry (MS) are most often used for determina- techniques are often referred to in the scientific literature
tions of the elements, but electrochemical and colorimet- as flameless AAS methods.
ric techniques are sometimes used. Derivatives of analytes,
sometimes called complexes, that strongly absorb in the
2. Atomic Emission
UV-VIS spectrum are employed in colorimetric methods
for the elements and some compounds and multielement Elemental analysis with AES had been practiced since
ions. Ozone, nitrogen oxides, and some other substances the mid-1930s using flames and arc or spark discharges
in air are determined by selective chemical reactions that to vaporize and atomize samples and excite the atoms
produce measurable light emission (chemiluminescence). for optical emission. The AES technique provided rapid
Fluorescence spectrometry is used in some methods, espe- simultaneous or sequential multielement determinations,
cially with fiber optics technology, for remote monitoring. but the flames and arc or spark discharges had significant
Immunoassays have been developed for a few analytes and limitations. Interferences from electrode and other sample
they are especially useful in field analyses. components were not uncommon, elemental measure-
ments were often imprecise, detection limits were not
sufficiently low, and liquid samples were difficult to
A. Elemental Analysis
analyze. The increasing demand for rapid, selective, and
Atomic emission and atomic absorption techniques are sensitive multielement determinations led to the devel-
highly selective because the number of elemental analytes opment of the inductively coupled plasma (ICP) sample
is small, and each has a unique atomic spectrum. Frequen- vaporization, atomization, and excitation source that met
cies are selected for measurements to maximize selectiv- the analytical requirements and gave new life to AES. The
ity and sensitivity, minimize interferences, and correct for ICP allowed the direct injection of aqueous aerosols into
interferences when necessary. Mass spectrometry mea- a 5500–8000 K argon ion plasma and elemental measure-
sures mass to charge ratios of elemental ions in the gas ments with minimal or no interferences from background
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Environmental Measurements 563

components or other analytes. Analytical methods clinical analyses, have been developed for a small number
utilizing ICP/AES are widely used for the determination of organic compounds—for instance, several triazine
of multiple elements in environmental samples. pesticides. However, many chemicals of environmental
interest have MWs and shapes that are too small and
similar for effective application of immunochemical
3. Mass Spectrometry
techniques.
The ICP technique also produces gas phase elemental ions The further development of nonchromatographic ana-
and the ICP was quickly adapted as an ion source for mass lytical methods based on these and other techniques has
spectrometry. This combination became one of the most been impeded by fundamental limitations in selectivity,
useful and important techniques for rapid multielement and sometimes sensitivity, for a wide variety of similar
analyses of gases, liquids, and solids. The argon ICP is substances—for example, those in Table I and Figs. 1–3.
a very efficient ion source that produces mainly singly The cost of developing, testing, and documenting a large
charged ions. It is estimated that 54 elements, all metals, number of specialized methods, often for just one or a few
are ionized with 90% or greater efficiency. Only C, H, N, analytes, is generally prohibitive compared to the cost of
a few electronegative elements, and the noble gases are chromatographic methods that allow the determination of
ionized with efficiencies less than 10%. A small number multiple generally similar analytes in an environmental
of elements—for example, As, B, Be, Hg, I, P, S, Se, and sample.
Te—have estimated ionization efficiencies in the 10–90%
range. Although Ar has a low ionization efficiency, it is
present in the ion source in great quantity and gives a SEE ALSO THE FOLLOWING ARTICLES
few significant ions at m/z 40 (Ar+. ) and m/z 80 (Ar+.2 ).
ANALYTICAL CHEMISTRY • ENVIRONMENTAL GEOCHEM-
Other background ions, such as m/z 41 (ArH+ ) and m/z
ISTRY • ENVIRONMENTAL OBSERVATION AND FORECAST-
56 (ArO+. ), are formed from sample components, usually
ING SYSTEMS • ENVIRONMENTAL TOXICOLOGY • GAS
water, and mineral acids that are used to ensure dissolu-
tion of some analytes. These ions obscure ions from some CHROMATOGRAPHY • LIQUID CHROMATOGRAPHY • POL-
LUTION, AIR • POLLUTION CONTROL • POLLUTION, EN-
elements, but techniques are available to circumvent most
VIRONMENTAL • SOIL AND GROUNDWATER POLLUTION •
of these interferences.
WATER POLLUTION

B. Organic and Inorganic


BIBLIOGRAPHY
Compounds and Ions
Colorimetric determinations are selective for specific “Annual Book of ASTM Standards, Section 11, Water and Environmen-
substances—for example, the PO−3 4 ion (Section IIB)—
tal Technology,” American Society for Testing and Materials, West
Conshohocken, PA.
because of selective color-forming chemical reactions
Bloemen, H. J. Th., and Burn, J., eds. (1993). “Chemistry and Analysis of
between reagents and target analytes. Several of these Volatile Organic Compounds in the Environment,” Blackie Academic
techniques continue to be important for the determination & Professional, London.
of a few inorganic anions. However, ion exchange Budde, W. L. (2001). “Analytical Mass Spectrometry: Strategies for En-
chromatographic techniques are increasingly used for vironmental and Related Applications,” Oxford University Press, New
determinations of multiple ions in environmental sam- York.
Clesceri, L. S., Greenberg, A. E., and Eaton, A. D., eds. (1998). “Standard
ples. Some electrochemical techniques, like ion selective Methods for the Examination of Water and Wastewater,” 20th ed.,
electrodes, are selective because the materials of con- American Public Health Association, Washington, DC.
struction, such as ion selective membranes, and operating Keith, L. H., ed. (1996). “Principles of Environmental Sampling,” 2nd
parameters are carefully chosen so the devices respond ed., American Chemical Society, Washington, DC.
only to specific analytes. Ion selective electrodes are Parker, L. V. (1994). “The effects of ground water sampling devices
on water quality: A literature review,” Ground Water Monitoring and
widely used for the determination of pH and a few other Remediation 14, 130–141.
inorganic ions, for example F− . Immunoassay methods, Schwarzenbach, R. P., Gschwend, P. M., and Imboden, D. M. (1993).
which are very widely used and enormously important in “Environmental Organic Chemistry,” Wiley, New York.