Paper No.
: 01-Fundamentals of Analytical Chemistry
Module :40- Environmental sampling and analysis
Principal Investigator: Dr.NutanKaushik, Senior Fellow
The Energy and Resouurces Institute (TERI), New Delhi
Co-Principal Investigator: Dr. Mohammad Amir, Professor of Pharm. Chemistry,
JamiaHamdard University, New Delhi
Paper Coordinator: Prof. Rajeev Jain, Professor of Chemistry, Jiwaji
University, Gwalior
Content Writer: Dr. Nimisha Jadon, Assistant Professor, Jiwaji University,
Gwalior
Content Reviwer: Prof. Rajeev Jain, Professor of Chemistry, Jiwaji
University, Gwalior
Analytical Chemistry Fundamentals of Analytical Chemistry
/ Instrumentation
Environmental smapling and analysis
Description of Module
Subject Name Analytical Chemistry / Instrumentation
Paper Name Fundamentals of Analytical Chemistry
Module Name/Title Environmental sampling and analysis
Module Id 40
Pre-requisites
Objectives
Keywords
Analytical Chemistry Fundamentals of Analytical Chemistry
/ Instrumentation
Environmental smapling and analysis
Paper: Fundamentals of Analytical Chemistry
Module: 40
Environmental Sampling and Analysis
Introduction
Environmental issues have received a great deal of interest in the recent times. Use of Analytical
techniques have made it easy to defineand control environmental pollution. Some of the techniques
employed to collect and analyze environmental samples have been described here.
Sampling
Sampling is the most crucial step in environmentalanalysis. Sampling errors often exceed
analytical procedural errors. According to a survey,analytical variance obtained was only 0.1
% of the total variance for geochemical samples, while the samplingvariance being 43% of
the total, with 53% attributable to the actual geochemicalvariance. For reliableinterpretation
of chemical analyses, the combined sampling and analyticalvariance should not exceed 20%
of the total variance.Sampling procedures for air, water, and solids will be addressed here.
Air Sampling
After the collection of appropriate samples,any number of standard measurement techniques
may be used.Air is made up primarily of N2, O2, and Ar, which comprise 99.9% of dry
air.Water vapor, minor and trace gaseouscomponents, aerosol and particulate species are also
present. Table 1 lists some gasesof environmental interest.
Table:1 Gaseous components of air
Compound Approximate Concentrations Relative measurement
(when present v/v)
CO 100 ppb to 20 ppm Electrochemical; GC
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
CO 345 ppm
2
CH 2 ppm
4
CFCl 200 ppt GC, electron capture
3
CF Cl 350 ppt GC, electron capture
2 2
Hydrocarbons 1 ppt to 1 ppb IR
NO 5 ppt to 1 ppb UV; chemiluminescence
NO 1 to 150 ppb Spectrophotometry;
2
chemiluminescence
NO 300 ppb IR; GC, electron capture
2
O 1 to 100 ppb UV; chemiluminescence
3
SO 1 to 100 ppb Flame photometric;
2
spectrophotometric
Factors considered in an analysis:
1. Sampling size:Volume of air sampled depends on minimumchemical concentration that
must be measured, sensitivity of measurement, and the information required.
2. Sampling rate:Sampling rates vary with sampling devices. Most sampling devices for
gaseous constituents have permissible flow rates of 0.003 to 0.03 m3/min. The collection
efficiency should be at least 75%.
3. SamplingDuration:Duration of sampling isdetermined by the information that is desired.
A sampling device capable of smooth operation at high flow rates is preferredfor short
sampling times.
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
4. Sample Storage:Air samples should be protected from heat and light. Care should be
taken that the testcomponent does not react with other components. Gaseoussamples are
sometimes collected by adsorption onto a solid.
A vacuum source, a means ofmeasuring the amount of air sampled, and a collector or
combination of collectors are required for sampling air.Some of the commonlyemployed
devices are described below:
1. Vacuum Sources:A vacuum is used to draw the sample through the collectiondevice.
Motor- or hand-driven vacuum pumps, aspirators, and automobile vacuumsare
generallyemployed.
2. Metering Devices: Flow measurement devices are of two general types: thosewhich
measure rate and those which measure volume.
A rotameter is a rate-measuring device consisting of a spherical float withina tube having a
self-contained scale.
The dry-test meter and wet-test gas meter are volume-measuring devices.Dry-test gas meters
are helpfulin measuring large volumes.The wet-test meter is generally more accurate than the
dry-test meter for smallervolumes.
Air sampling pumps may be self-metering. The pump may be operated by a programmable
computer to setstart/stop times and for intermittent, repeated, or continuum sampling.The
sampling data can be transferred to thecomputer and stored for future use.
Calibration of gas-measuring devices is mandatory before and after use. A generalmethod
used is to measure volume of a liquid displacedby gas flowing through the meter. A saturator
prevents evaporation of part of the water from the carboy and is placed before the meter. The
water displacedfromthe carboy is weighed or its volume is measured. Accurate determination
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
of the gas volumeat standard conditions is possible by measuring the pressure witha
manometer in series and the temperature.
3. Devices used in sampling: The third component of the sampling train is the
collector,which may be of different types, depending on the particular application.Included
are filters, fritted-glass scrubbers, and impingers.
(a) Aerosol Components:Filtrationis the most commonly employed means of collecting
aerosol components. After collection on the filter, the contents of aerosol may be determined
by weighing, by chemical analysis, or by particle sizing. Fiber filters, granular filters, and
membrane filters are used frequently.
The impinger is a second type of collection device for aerosol constituents; this collects both
solid and liquid aerosols. In dry impingers, also called impactors,the aerosols impinge on a
surface exposed to the airstream. The cascade impactorconsists of a series of progressively
smaller size jetsimpinging at right angles on conventional microscope slides.
(b) Gaseous Components:Gases and vapors are collected by absorptionin a liquid, adsorption
on a solid surface, freezing or condensation, or filling anevacuated container. Once the
analytes are collected, they can be extracted from the sorbent, or thermally desorbed.
Solidphase micro extraction (SPME) can be employed for spot sampling of airby letting the
fiber equilibrate with the air. Headspace and purge-and-trap sampling can also be used.
Air sample bagsmade of Teflon or Tedlar are useful in sampling of gases and vapors in which
theanalyte concentration is well above the detection limits of the measuring system.
Analyzing air samples
By selecting an appropriate wavelength, a gasanalyzer can be made selective for a particular
gas;there are nondispersive-type IR and UV analyzers available based on filtersfor
wavelength isolation.
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
Some analytical procedures are described here for some important atmospheric
components.A highly selective and reliable method for the determination of nitrogen dioxide
in theenvironment involves absorption of the nitrogen dioxide in a solution of sulfanilicacid
containing an azo-dye- forming reagent.
Total oxides of nitrogen, excluding nitrous oxide, maybe determined in gaseous effluents
from combustion by collection of the gas samplein an evacuated flask containing an
oxidizing absorbent of hydrogen peroxidein dilute sulfuric acid. NO2 may be reacted, with
luminol in alkaline solution, to produce chemiluminescence with photon emission at 425 nm.
NO can be measured by UV absorption. Nitrous oxide, is the most abundant oxide of
nitrogen in the atmosphereand can be measured by IR absorption or gas chromatography with
electroncapture detection.Ozone can be measured by UV absorption. A monitor for SO2 is
based on flame photometric measurement, usinga fuel-rich air-hydrogen flame.Total
hydrocarbons in the air may be analyzed using infrared spectrophotometry.
The hydrocarbons absorb in the 3- to 4-µm region of the infraredspectrum using a 20-m
pathlength cell.
Other analyses performed include the detectionof acetylene, total aldehydes, ammonia,
formaldehyde, formic acid and total organicacids. Various aerosol fractions in the air are
commonly analyzed.
Calibrating gas analyzers
Proper calibration of gas measuring devices is critical. Gas mixturesof known composition (if
they are not available commercially) should be prepared. This can be done staticallyby
successive addition of the gaseous constituents of interest to a cylinderand determining the
weight. Or standards are prepared dynamically by dilution of aconcentrated standard of a gas
or mixture of gases into a stream of a base gas, forexample, air or inert nitrogen. A stream of
mixed gases results, containing known concentrations of the test gases. The dilution is done
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
using either a permeationor diffusion tube. The test component, for example, NO or SO2,
from acontainer permeates through a membrane,or diffuses along a capillary. The permeation
or diffusion rate is governed by the vapor pressure of the compound, the temperature,the
membrane, and geometry. The rate is determined by determining theweight loss from the
container over a period of time.
Water sampling procedures
Potential sources of water pollutants include industries suchas the petroleum industry, the
iron and steel industry, the pulp and paper industry,the coal industry, the chemistry industry,
and the food industry, in addition to theprivate sources in the home and public and private
sewage disposal. Land runofferosion and mine wastes can be disastrous problems. There are
many different types of water matrices that are sampled and analyzed, including surface
waters (rivers, lakes, and runoff water), groundwater and springwater,potable (drinking)
water, estuarine waters, saline water, water from the atmosphere(rainwater, snow, fog, dew),
steam, and process waters. Sampling considerations will depend on the type of water sample.
In general samples may be obtained from faucet outlets, at different points in pipe systems,
from the surface of rivers and lake waters, and at different depths. Depth samplers are used to
collect samples from large bodies of water at a specific depth. These type of samplershave
some mechanism for removing a stopper after thesampler has been lowered to the desired
depth of a water body. Commercial samplers are availablefrom laboratory supply houses.
Samples to be shipped should haveatleast an air space of10 to 25 mL to allow room for
expansion.
Groundwater samples
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
Common devices for collecting samples include electric submersible pumps,
peristalticpumps, positive displacement bladder pumps, bailers and dialysis membranes. The
pump tubing, connected to the sampling tubing,should be medical-grade silicone rubber to
eliminate organic peroxides found in othergrades. Teflon connecting tubing should be used if
organics are to be determined. Bailers are employed for sampling small-diameter shallow
wells.
Teflon containers, while expensive,are generally employed for storage of samples with trace
analytes. Glass containers,particularly, should be washed with acid and perhaps stored filled
with EDTA solutionto minimize trace metal leaching by the sample.
On-site measurement or monitoring devices are required for many analyses. For example,
amperometric oxygen sensors are used todetermine immediate oxygen values and may be
immersed at different points and depthsto collect data of interest. Automatic samplers and
instruments are generally employed for regularor continuous monitoring and to gather desired
information. For example, a flow injection system can be controlled by a computer or timer,
to automatically take a sample at setintervals-perhaps through a filter sampler-and to inject
and measure it.
Analyzing water samples
Measurements done generally on collected samples are acidity or alkalinity,
biochemicaloxygen demand, carbon dioxide, chlorine, dissolved oxygen,
electricalconductivity, fluoride, particulate and dissolved matter, ammonia, phosphate,
nitrate,silica, sulfate, sulfite, sulfides, turbidity, various metal ions, bacteria,
microorganisms,and so forth.
Sampling of soil and sediments
Samples are generally obtained by dredging the bottom to obtain a grab sample,or dill core
samples are taken. Composite sediment samples are frequentlyemployed for determination.
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
Sediment samples may be segregated byparticle sizes by wet or dry sieving. They maybe air
dried, or heated to dry, dependingon the volatility of the analytes, followed by grinding to
help in extractionof analytes. Volatile analytes are extracted from wet samples.For trace
metal analysis, samples are usually dry ashed or wet digested.Surface soils are sampled for
recent spills. Stainless steeltools aregenerally used for sampling of organics and high-density
polyethylenefor inorganics. A soil punch is better for takingreproduciblesamples, by pushing
into the soil to the desired depth. Augers, either hand operated or powered, are
oftenemployed for sampling.
Sample Preparation for trace organics
The determination of trace organic compounds in environmental samples requiresgetting
them segregated from the sample matrix before measurement, and generallyinvolves
extraction of some sort. Some trace organics include aliphatic andaromatic hydrocarbons,
aldehydes, phenols, chlorinated solvents, polychlorinated biphenyls(PCBs), pesticides, and
phthalates and adipates (from the polymer industry).Water samples are conveniently
extracted by employing water-immiscible solvents in a separatory funnel. Polar solvents such
as ethylacetate or dimethylether are helpful in extraction of organic acids. Non polar solvents
such as hexane, n-heptane, cyclohexane, or dichloromethane are used in the extraction of
neutral lipids, for example, triglycerides,and other nonpolar constituents such as aliphatic
hydrocarbons and organopesticides.Solid-phase extraction is widelyemployed to separate and
pre-concentratetrace organics from water samples.
Moist samples such as soils are generally dried in a vacuum oven and then ground. Prior to
extraction, the samples are rehydrated by addition of an aqueous buffer,which helps the
transfer of analytes into a water-miscible extracting solvent such as acetone.The solid-solvent
mixture is stirred or shaken and then filtered or centrifuged to separate the matrix.Usually,
three extractions, employing small aliquots of solvent,are required forefficient quantitative
Analytical Chemistry Fundamentals of Analytical Chemistry
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extraction. Heating may also be done in some cases, orultrasonic energy (ultrasonic batchor
ultrasonic probe) can be used to improve efficiency.Continuous Soxhlet extraction is
generally used. Volatiles in soils and sediments may be sampled directly using headspace
analysis for gas chromatography.After obtaining the extracted and pre-concentrated organic
analytes, an additional cleanup is performed, for example, by running them through a
columnof adsorbent packing material such as silica or alumina. Then chromatographyis
generallyemployed for determination of test analytes. Pesticides are usually determined bygas
chromatography with electron capture detection or GC-MS. A nonpolar capillaryGC column
is employed for this purpose. Trace PCB and polycyclic aromatic hydrocarbon (PAH)
determinations can be done using HPLC with UV detection.
Contaminated land sites analysis
Determining the magnitude of pollution in contaminated land sites is one of the most
commonly faced environmental issues. Sampling is critical to make proper
evaluation.Obviously, samples will be taken to represent areas of the site wherecontamination
is expected, or where pollutants are expected to be transported.Surface soil samples, runoffin
nearby streams, rivers or lakes, sediments, and vegetation from surface aquaticsystems and at
the land site should be assessedwith great care.
Methods established by EPA
The Environmental Protection Agency has published hundreds of official methods
fordetermination of organic and inorganic constituents in air, drinking water,
wastewater,solid waste, pesticides and toxic substances. Laboratories may also develop new,
reliable and economic methods for analyzing contaminants,provided they meet certain
criteria. The EPA Environmental Monitoring ManagementCouncil (EMMC) has accepted use
of a performance-based measurementsystem (PBMS), which conveys "what" needs to be
done, but not prescriptively"how" to do it. The focus is on the result, rather than on the
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
method employed to achieve thatoutcome. An acceptable level of performance is defined for
a particular analysisusing criteria such as accuracy, precision, detection limits, specificity,
sensitivity,and robustness. If a laboratory can show that it meets the criteria, themethod
becomes an accepted one.
I. Do you know
1. Trace PCB and polycyclic aromatic hydrocarbon (PAH) determinations can be
done using HPLC with UV detection.
2. Depth samplers are used to collect samples from large bodies of water at
aspecific depth.
3. Nonpolar solvents such as hexane, n-heptane, cyclohexane,or dichloromethane
are used to extract neutral lipids.
4. Motor- or hand-driven vacuum pumps, aspirators, and automobile vacuums
are generallyemployed.
5. The EPA Environmental Monitoring ManagementCouncil (EMMC) has
accepted use of a performance-based measurementsystem (PBMS).
II. Interesting facts
1. A vacuum is used to draw the sample through the collection device.
2. In general samples may be obtained from faucet outlets, at different pointsin
pipe systems, from the surface of rivers and lake waters, and at different
depths.
3. A monitor for SO2 is based on flame photometric measurement, usinga fuel-
rich air-hydrogen flame.
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
4. Teflon connecting tubing should be used if organics are to be analyzed.Bailers
are useful for sampling small-diameter shallow wells.
5. Flow measurement devices are of two general types: those that measure rate
and those that measure volume.
Analytical Chemistry Fundamentals of Analytical Chemistry
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Environmental smapling and analysis
