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DOI 10.1007/s00216-005-3228-y
R EV IE W
Received: 27 October 2004 / Revised: 2 March 2005 / Accepted: 24 March 2005 / Published online: 14 May 2005
Springer-Verlag 2005
Introduction
The analysis of industrial euents is required for two
primary purposes: environmental monitoring, and
monitoring for the loss of products, by-products and
raw materials from an industrial process.
Industrial euents are primarily derived from
chemical manufacturing and processing, textile manufacturing, electricity generation, and forest industries.
The nature of the constituents in the euents will be
determined by the raw materials used, the type of process employed and the eciency with which materials
are removed from the euent, either through recovery
processes or euent treatment.
A review with 12 references, entitled Euent analysis: Malaysian requirements was published in 1978 [1],
and another review with ten references called Methods
of nuclear power station euent analysis for application
to environmental monitoring and research was published in the same year [2]. Recently, others reviews have
been published concerning the analysis of euents [3, 4].
979
Turbidity is a measure of the light-scattering properties of colloidal and particulate material in the euent,
in contrast to the total suspended solids, which is a
gravimetric measure of the colloidal and particulate
material present. Turbidity is commonly measured using
a turbidimeter which itself consists of a nephelometer, in
which a light source illuminates the sample and scattered
light is detected using a photoelectric detector at right
angles to the incident light.
Acidity is a measure of the euents quantitative
capacity to react with a strong base to reach a designated
pH, while alkalinity is its acid neutralizing capacity.
Both are determined titrimetrically using specic indicators. Two reviews of pH measurements of euent
have been published, covering the use of pH-meters, pH
electrode care and maintenance, and so on [8, 9].
An eective sampling program for photo-processing
euents includes grab samples, which provide waste
characteristics at the time of sampling; composite, and
continuous sampling, which is useful when real-time
euent analysis is needed. Methods of ow measurement and their application have been discussed previously [10]. Three groups of characteristics are used to
evaluate euents: gross (pH, COD, BOD, total suspended and total dissolved solids), physical, and chemical species. Selection, sources, and types of sampling
equipment are discussed.
Chemical and physical properties are described for a
number of process streams and euents from a low-Btu
coal gasication pilot plant. Process streams include feed
coal, wet bottom ash, electrostatic precipitator tar, ash
pan water, process water, raw and cleaned gases, combined gases, and boiler stack gases. Wet ash was the
main source of inorganic species in the coal. The ash pan
water did not eectively leach inorganic or organic
components from the wet ash. Elemental analyses of gas
streams varied by as much as three orders of magnitude,
depending on location; the main elements in the combined gas stream were Cr, Pb, Ba, and Se, of which Cr
and Pb were the main elements in the stack gases. The
chemical components found in the tar, the main organic
by product, were typical of coal liquids. Organic components detected in the gas streams included alkylated 1ring and 2-ring aromatic hydrocarbons, aliphatic
hydrocarbons, and alkyl-phenols [11].
A review with eight references has been presented on
the scientic and technical aspects of wastewater from
the dyeing of cotton knitwear with vat dyes [12].
Euent treatment using hypochlorite-enriched seawater has the potential to decrease levels of toxins,
bacteria, BOD, COD, and organics to the acceptable
levels before it is discharged into deep oceans, rivers or
estuaries, which should help preserve the environment
and seas for future generations [13]. In addition to
euent treatment, the electrolytic generation of hypochlorite in the sea has vast potential to disinfect,
deodorize, and defoul deep-sea platforms, ship decks,
and oceanariums. The use of an ecient catalyst and
improved electrolysis systems, such as boron-doped
Metals analysis
The analysis of euents for metals is relevant to euents
from the chemical manufacturing, mining, metal manufacturing and the processing and electricity generation
industries. The specic metals and the form in which
they are present will be source-dependent. Metals may
be present in particulate matter as free metals, inorganic
metal salts or metal complexes, while they may be
present in soluble form as inorganic metal salts or metal
complexes. The analysis may be conducted at varying
degrees of complexity, beginning with total metal content, followed by lterable/non-lterable metals,
through to ionic and complexed forms of the metal. If
the sample is collected and acidied without rst being
ltered, then only the total metal content can be determined. Although the process of acidication may release
some metals bound to particulate matter, a digestion
procedure is necessary to release metals from particulates. Except for the case of mercury, such procedures
involve digesting the water sample with concentrated
acids or acid mixtures. The digested sample is made up
to a known volume with puried water prior to analysis
by atomic absorption spectrometry (AAS), inductively
coupled plasma atomic emission spectrometry (ICPAES), inductively coupled plasma-mass spectrometry
(ICP-MS) or electrochemical techniques [15].
A method for the separation and determination of
Fe3+, Al3+, Ca2+, K+, Na+, and some anions in ltrates and euents using a Dowex-50 column has been
described [16].
Anodic stripping voltammetry using a thin-lm Hg
electrode was used to determine total (free plus complexed) trace metal concentration in an aqueous sample
[17].
Various approaches to the chemical analysis of heavy
industry process materials and euents for trace element
constituents that might contribute to environmental
pollution are summarized. An assessment is given of the
capabilities and costs of nuclear methods, spark source
mass spectrometry, X-ray uorescence and electron and
ion microprobe spectrometry, atomic absorption spectrometry, absorption spectrophotometry, atomic emission spectroscopy, voltammetry (polarography), and
potentiometry (ion-selective electrodes) for determining
traces of Be, Cd, As, V, Mn, Ni, Sb, Cr, Zn, Cu, Pb, Se,
B, F, Li, Ag, Sn, Fe, Sr, Na, K, Ca, Si, Mg, U, and Th in
such matrices as y ash, coal, oil, ores, minerals, metals,
alloys, organometallics, incinerator particulates, slurry
980
981
Table 1 Summary of methods for metallic species determination
Elements
Reference
As
Cd
[21]
[22]
Cd
Cd
Ca
Co
Cu
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Hg
Hg
Mn
Pb
Ni
Pd
Pu
Pm-147
Sr-89; Sr-90
Tc-99
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[42]
[43]
[44]
[45]
[46]
982
Table 1 (Contd.)
Elements
Reference
Ti
[47]
Ti
Zn
Precious metals
acidication of the sample with glacial acetic acid, followed by its extraction into a small volume of toluene (at
a concentration factor of 100). The extract was then
analyzed by Zeeman graphite furnace electrothermal
atomic absorption spectrometry (ETAAS) with an
isobutyl methyl ketone solution of Pd as a modier [49].
During the conversion process of ammonium diuranate (ADU) to nuclear grade U dioxide in processing
plants, several liquid euents such as aqueous solutions
of nitrates of sodium and ammonium, together with
minute amounts of U, are generated. Three such euents which can be identied in a typical process plant
based on the ADU route are: (a) ammonium nitrate
euent from the precipitation stage of pure uranyl nitrate solutions; (b) NaNO3 euent generated after precipitating out uranyl nitrate rened cake; (c) storm drain
water collected from plant oor washings which require
treatment for reuse. The euents also contain Ca and
Mg at low levels. The complexity of the euent chemistry is the major challenge for many of the analytical
techniques, which require matrix removal prior to U
determination. The single column ion chromatography
method developed and described in this work for
determining trace quantities of U is an attractive one, as
it is simple, rapid, and sensitive and eliminates the need
for a prior matrix removal step. This method involves
dynamic separation and pre-concentration of U on a
low capacity resin-based cation exchange column and
subsequent detection by spectrophotometry at 520 nm
after post-column derivatization with 4-(2-pyridylazo)
resorcinol. The results from this method were compared
with those from instrumental neutron activation analysis
(INAA) and they were in good agreement. The INAA
method involves irradiation of the sample with thermal
neutrons in a nuclear reactor and then counting the
gamma rays emitted during the nuclear reaction using a
high purity Ge coaxial detector coupled to a multichannel analyzer. However, in INAA, for samples containing a high level of Na, prior removal of Na is
mandatory before irradiating the sample [51]. A method
[50]
[54]
[57]
[58]
[59]
983
984
Table 2 Summary of methods for determining inorganic non-metallic species
Species
Reference
Rapid methods in coke oven euents; samples analyzed were coke oven NH3 liquors and
corresponding synthetic solutions, with and without biological treatment
Sequential injection system for the automated in situ preparation of Azomethine-H and
on-line monitoring in water euents and fertilizer process streams
Separation and determination in waters, hydrometallurgical process solutions and euents
by ion-exclusion chromatography
Simple spectrophotometric method based on the reaction between
cyanide-formaldehyde-3-methyl-2-benzothiazolinone hydrazone and applied to
determine free and total cyanide in euent samples and in soil samples taken from a
treated cyanide dump
Spectrophotometric method based on conversion of pyridine to glutaconic aldehyde
by means of cyanogen bromide with subsequent condensation of the aldehyde with
6-amino-1-naphthol-3-sulfonic acid (J-acid); in industrial euents and biological samples
Extensive species- and concentration-dependent cyanide recovery studies were carried
out using a novel automated segmented FI-on-line UV digestion-amperometric (FI-UV)
method for determination of total cyanide in water and wastewater samples
Indirect method for the determination of free cyanide in industrial waste euent
samples by AAS
By either titrimetric, colorimetric, potentiometric, or IC techniques. Ion-selective electrodes
were used in the determination of F in environmental dusts, in the analysis of boiler
feed water, and for the determination of NH3 and CN in coke-oven euents
Automated on-line system in industrial euents and plating solutions based on the concept
of ow-injection analysis; samples with very high chloride content (up to 60 g/l) are
analyzed using an automated in-manifold double on-line dialysis technique.
The measurement is based on the red-colored iron thiocyanate complex
Method for the determination of Kjeldahl nitrogen that uses a block digester and a
low-toxicity Cu-Ti catalyst; in sewage euents, trade euents and sewage sludge
In soil extracts, liquid manure, stable manure, and plant euents, by a
potentiometric method using an NH3 gas sensitive electrode
Rapid photometric method designed for on-site measurement ammonia, in euent analysis
A new low-cost sensor that can measure ammonium and nitrate continuously in the
activated sludge process and do not require prior sample preparation, thus
simplifying operation signicantly in comparison to conventional analyzers
Using FIA with a coated tubular solid-state silver sulde ion-selective electrode
Indirect method in photographic waste euents using AAS; thiosulfate forms a stable
ion-association complex, [Pb (thiourea)6]2+ S2O23 in alkali medium which can be
extracted into n-butyl acetate-n-butanol mixture (2:1). The extract can be analyzed
directly for lead by ame AAS
[66]
BO2 ;
CO23
CN
CN
CN
CN
Halides
Cl
N
NH3
NH3
NH+
4 ; NO3
S2
S2O23
[67]
[68, 69]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81, 82]
[83]
[85]
[87]
[89]
quantication are thiocyanates and cyanates. Spectrophotometric and ion chromatographic techniques may
be used to determine all of these compounds once they
have been released from the sample matrix in the euent
[74].
Carbon dioxide may be determined either nomographically or titrimetrically. Chlorine and chlorine
dioxide may be present in euent as a result of disinfection processes, or due to their use as bleaching agents;
both may be determined by various titrimetric and colorimetric methods [79].
Nitrogen may be present in euents in various oxidation states, ranging from nitrate through nitrite to
ammonia and also as organic nitrogen. Organic nitrogen
and ammonia may be determined together analytically
as Kjeldahl nitrogen [80].
An alternate sampling method, called discrete sampling, is described for use with continuous on-line
composition analyzers [84]. This method usually involves transporting a discrete portion of material by a
carrier to an analyzer. This decreases the potential
exposure hazard to maintenance personnel and the time
985
Organic analysis
There is the potential for hundreds of thousands of organic compounds to be present in a range of dierent
industrial euents.
A review with 100 references entitled Analyses of
coke oven euents for polynuclear aromatic compounds was published in 1979 [91].
The euent contained low molecular weight carboxylic acids (acrylic and acetic acid), which show
strong resistance to biological and chemical oxidation,
and hence exhibited very high chemical oxygen demands
and total organic carbon levels. Incineration appeared to
986
treatment plants was studied. Water-polluting substances were enriched by solid-phase extraction, isolated,
and fractionated by thin-layer chromatography. By
subsequent biological detection with Bacillus subtilis,
Aspergillus niger and Chlorella vulgaris, the positions of
the toxic substances were veried. The spots were
scratched out and eluted, then the toxic substances were
analyzed by IR spectroscopy. The IR spectra of the
euents from the sewage treatment plants strongly
resembled those from adducts of ethylene oxide,
monoglycerides and diglycerides, adducts of ethylene
oxide and hydrogenated castor oil, amphoteric surfactants, and fatty alkoxylates. From the point of view of
preventive environmental protection, substances that are
used in large amounts should be completely biodegradable in sewage treatment plants under aerobic conditions
[110].
A method for identifying and quantifying components in an euent stream from an ammoxidation
reactor is patented. The apparatus comprises a microprocessor and a FT-IR spectrometer, wherein the
microprocessor is programmed to identify and quantify
each of the many components based upon the absorbance data and calibration data, the calibration data
being obtained from recovery run analyses and calibration analyses in the sample cell. The FT-IR spectrometer
has a sample cell through which a portion of the euent
stream ows, an IR source to emit IR radiation which
passes through the euent stream, an IR detector to
detect the transmitted IR radiation at the selected IR
wavelengths and to generate absorbance data due to
absorbance of the IR radiation by the components,
wherein each of the components absorbs IR radiation at
one or more of the IR wavelengths, and an output
apparatus to relay the absorbance data to the microprocessor [111].
An analytical scheme was developed to chemical
characterize the organic material in euents discharged
from kraft mills upon the producion of totally chlorinefree (TCF) bleached pulp. Besides determinations of
total organic carbon (TOC) and COD, the analytical
scheme includes highly selective analytical determinations of a number of low molecular weight organic
components. Phenolic compounds are determined as
their pentauorobenzoyl derivatives by GC/MS. Low
molecular weight aldehydes and ketones are determined
by aqueous-phase derivatization with o-pentauorobenzylhydroxylamine hydrochloride followed by GC/
MS analysis. Chelating agents, such as EDTA and
DTPA, are converted to their methyl esters by treatment
with boron triuoride in methanol and analyzed by GC.
The fatty and resin acids are analyzed as their methyl
esters by GC/MS. The sterols are determined by
extraction and silylation followed by GC/MS analysis.
The molecular size distribution of the organic euent
material is determined by using aqueous high-performance size exclusion chromatography. The distribution
between low molecular and high molecular weight
materials is studied by ultra-ltration and subsequent
987
988
Conclusions
Data pertaining to physical and chemical properties are
relevant when investigating euents from all industrial
sources and give a general overview of the nature of the
989
Table 3 Summary of methods for determining organic species
Species
Reference
4-Amino-azobenzene-4,5-disulfonic acid
Humic; lignin; phenolic matter
[95]
[96]
[118]
Non-polar phenolic;
organohalogenated compounds
Hydrocarbons
Formaldehyde
Methanol
Nonylphenol polyethyoxylates
Organic extracts
Sugars
Saccharides
Polychlorinated cymenes
and cymenenes
Xanthates
[100]
[122]
[124]
[125]
[126]
[127]
[128]
[129]
[130]
[136]
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