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Anal Bioanal Chem (2005) 382: 978991

DOI 10.1007/s00216-005-3228-y

R EV IE W

F. Sanchez Rojas C. Bosch Ojeda

Effluent analysis in analytical chemistry: an overview

Received: 27 October 2004 / Revised: 2 March 2005 / Accepted: 24 March 2005 / Published online: 14 May 2005
 Springer-Verlag 2005

Abstract This review summarizes and discusses euent


analysis, focusing on the methods and techniques that
have been most frequently described in the literature
since 1975. The methods are classied into four main
categories: (1) physical and chemical properties; (2)
inorganic metals analysis; (3) inorganic non-metallic
analysis; (4) organic analysis.
Keywords Euent analysis Inorganic and organic
compounds Environmental monitoring

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].

F. Sanchez Rojas (&) C. Bosch Ojeda


Department of Analytical Chemistry, Faculty of Sciences,
University of Malaga, 29071 Malaga, Spain
E-mail: fsanchezr@uma.es
Tel.: +34-95-2131925
Fax: +34-95-2132000

In addition, the theory behind and the applications of


atomic-emission spectrometry and high performance liquid chromatography in the eld of water and euent
analysis have been treated in a book written by Boehnke
[5].
In the textile industry, many dierent processes are
used and almost all of them generate wastewater. The
euents resulting from these processes dier greatly in
composition, due to dierences in processes, fabrics used
and machinery. Textile wastewater is usually treated as a
mixed stream. For water and chemical reuse purposes,
however, it is preferable to keep process streams apart
and treat them separately [6]. This review provides an
overview of what is known about the wastewater of the
separate processes, and the method used to characterize
these streams.
Benfenati et al [7] reports the main results obtained
within the European Commission. The main objective
was the development and the evaluation of a protocol
for an integrated ecotoxicological/chemical assessment
of industrial liquid euents, using ecotoxicological assays and analytical methods.

Physical and chemical properties


Data on physical and chemical properties are relevant to
euents from all industrial sources and give a general
overview of the nature of the euent. Knowledge of
these parameters for any euent should be considered a
fundamental requirement.
Color may be taken to mean either true or apparent
color. Both may be important when describing an
industrial euent. Apparent color is determined without
removing any colloidal or suspended solid material,
while true color is determined after removing turbidity.
As some color may be removed in the separation process, the method used to remove the turbidity should be
stated when reporting the result. Visual comparison
methods or spectrophotometric methods can be used to
measure color.

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

diamond electrodes, could further enhance the economic


and eective use of bleached sea-water in the treatment
of wastewaters.
Euent samples collected from the sugar industry
were chemically evaluated for dierent parameters such
TSS, COD, and BOD [14]. A treatment process, mainly
physicochemical, has been developed to reduce the
harmful eects from the sugar mill euent.

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

streams, and feeds to and from sedimentation processes


[18].
Steel plant euents were analyzed by ame atomic
absorption spectroscopy (FAAS) [19]. Zn, Pb, Cd, Ni,
Cr, Mn, Fe, and Cu were determined in river water and
steel plant euents.
Results were given from a program of >60 tasks
involving the evaluation, development, testing, and eld
adaptation of measurement techniques for elemental
analysis and inorganic compound identication in process and euent streams [20]. Procedures for particulate
sampling at the inlet and outlet of ue gas desulfurization (FGD) systems were developed. Methods for
H2SO4 sampling in ue gas streams were developed
based on the controlled condensation of H2SO4vapor.
Two procedure manuals were written for reduced and
oxidized inorganic species. The reduced species manual
detailed gas chromatography (GC) and GC/MS procedures for identifying organometallic compounds as well
as homologous series. The oxidized species were identied using an integrated series of analytical methods. The
procedures developed, applied to samples from several
EPA programs, showed that the analytical scheme is
applicable to most solid samples from combustion
sources. Ion chromatography procedures were also
developed to analyze FGD system slurry streams. The
use of pH and chloride electrodes for controlling FGD
systems was investigated.
Table 1 shows a list of procedures used for the
determination of dierent metallic ions commonly
present in euents.
Membranes for Ca2+-selective electrodes were prepared by cross-linking a styrene-butadiene-styrene triblock copolymer with tri-10-undecenyl phosphate or
diallyl phenylphosphate followed by hydrolysis and
conditioning the resulting membranes to give pendant
Ca dialkyl phosphate exchange groups [25].
A multi-purpose dialyzer unit was designed and
incorporated into the conduits of a ow injection (FI)
system and employed for automated dilution and multicomponent determinations before detection by AAS.
The combined multipurpose dialyzer-FI-AAS system
was applied to the determination of copper in industrial
euent samples where there was a wide variation in
copper concentration levels. Both proposed multipurpose dialyzer-FI-AAS systems were suitable for handling the wide variety of concentration levels present in
industrial euent samples. The automated dialyzer
dilution system seemed to be ideally suited for the
determination of a single element in industrial euents
where the concentration of the element varied considerably in the samples. The method was further enhanced
with the removal of solid particles present in industrial
euents. These particles were of such a nature that they
continuously blocked the inlet path to the nebulizer of
the AAS detector. This multi-component determinationdialyzer system seemed to be ideally suited for the
simultaneous determination of elements, which is an
advantage for big laboratories where high throughput of

analyses must be maintained. The scaling-down of


sample handling to a sample channelled to various
streams and detectors is a further advantage. A prerequisite of the multi-component determination dialyzer-FI-AAS system is, however, the number of atomic
absorption spectrophotometers required and this may be
a disadvantage of this system. The results obtained for
Cu(II) for both systems at a sampling rate of 120 samples per hour compared favorably with the standard
manual atomic absorption spectrometric method [27].
Methods for the determination of Hg in waters,
euents, soils, sediments and related materials by FAAS
have been summarized [36]. The paper contains a comparative table of methods as well as the following
additional methods: determination of Hg in raw, potable
and saline waters and euents by Br oxidation, gold
concentration and ameless AAS; determination of Hg
in suspended matter and sediments by aqua regia oxidation and ameless AAS; determination of Hg in waters and euents by ameless atomic uorescence
spectrometry; and determination of Hg in soils, sediments and related materials by permanganate oxidation
and ameless AAS.
The ENFORM is a computer-based information
system that addresses the material logistics, environmental releases, and economics of light water reactor
operation [41]. The most important system inputs consist of electricity energy generation requirements, details
of plant construction scheduling, unit costs, and environmental release factors. From these inputs, the ENFORM system computes the mass balances and
generates the environmental release information for
noxious chemistry and radionuclides from various fuel
cycle facilities. All code development subsequent to 1977
is summarized. Programming instructions are provided
for the modules that comprise the ENFORM system.
The ENGEN, a code that uses a generation schedule
specied by the user and isotopic data generated by
ORIGEN, was developed to produce a scenario-specic
database. Other codes (ENMAT, ENRAD, and so on)
were developed to use database information to estimate
radioactive and non-radioactive release information.
A straightforward technique involving sub-boiling
distillation has been developed for the purication of
river and euent water samples prior to the determination of tritium by liquid scintillation analysis. The
study evaluates the eciency of sub-boiling distillation
for decontaminating mixed beta/gamma emitters, which
could interfere with tritium determination. The technique eectively puries tritiated water in aqueous
samples, removing the major contaminating radioisotopes including Na-22, Mn-54, Co-60, Zn-65, Y-88 Cs137, and Eu-155. However, the technique requires less
analyst set-up and supervision time than conventional
distillation techniques and larger sample batches can
therefore be routinely analyzed [48].
Toluene-extractable organotin compounds in two
sewage euents and a complex, simulated euent were
determined at sub-ppb levels. The technique involves the

981
Table 1 Summary of methods for metallic species determination
Elements

Method and/or applications

Reference

As
Cd

In industrial euents, soil, and glass samples


Pre-concentration, extraction and spectrophotometric determination with high molecular
weight hydroxamic acids; in soil, plant, food, tobacco and industrial euents
Extraction at pH 6.5 by means of cryptand 221, a macrobicyclic polyether, with addition
of Rose Bengal as the counter-ion; Cd was stripped from the organic phase with
0.1 M H2SO4 and determined by AAS; in aerosols, marine sediments, and
industrial euents
Spectrophotometric with 4-(2-pyridylazo)naphthol in industrial euents, coal, and y ash,
with the use of hydroxyamidines as new extracting reagents
Electrode with polymeric membrane incorporating triallyl phosphate; in cocking
plant euent
Non-extractive and virtually specic quencho-uorimetric method based on the
instantaneous quenching action of cobalt upon the native uorescence of
4,7-diphenyl-1,10-phenanthroline; in environmental samples, and factory euents
Multipurpose dialyzer-FI-AAS system; in industrial euent samples where there is a
great variation in copper concentration levels
Sensitive spectrophotometric method: Cr(VI) forms chlorochromate anion in the presence
of acid and chloride ion. The formed anion is extracted in toluene as ion-pair with a
cationic dye-Rhodamine 6G
Analytical properties of 5,5-di-methyl-1,3-cyclohexanedione dithiosemicarbazone
monohydrochloride are described and used for the spectrophotometric determination
of total chromium in alloy steels and industrial euents
FI method based on the dynamic quenching of ruthenium uorescence
K ethyl xanthate was used for catalytic polarographic determination; in drinking water,
industrial euents and agricultural and ore samples
Solvent extraction of blue peroxy chromic acid by trioctylphosphine; in tannery euents
In drinking water, groundwater, and industrial wastewater euents using existing
ion chromatographic techniques
Solid-phase microextraction coupled with gas chromatography-ame photometric detection
Spectrophotometric method based on the extraction of its complex with
N-p-chlorophenylbenzohydroxamic acid into CHCl3; in drug samples and
simulated industrial waste euents
Methods for the determination of Hg in waters, euents, soils, sediments, and
related materials by FAAS
Solvent extractionseparation using criptand 221 in chloroform with erythrosine as
the counter ion. It was stripped from the organic phase with hydrochloric acid, and
was determined by AAS; in aerosols, sediments and euents
A similar method has been developed for the determination of Pb(II), using criptand 222B
in toluene and eosin as the counter ion
Spectrophotometric method using nickel complexes with hydrazine hydrate in the pH
range of 710 (kmax=585 nm), interference from foreign ions was studied along with
the analysis of Ni(II) in alloys and industrial euents
Spectrophotometric method; in the medium of 0.2 M HNO3 and in the presence of
emulsifying agent, Pd(II) forms a complex with p-dimethylaminobenzylidenerhodanine
(kmax=490 nm); in electroplating euent
Non-destructive assay by measuring the passive L X-rays following a-decay
Pm is co-precipitated with other lanthanide elements using an inactive Nd carrier. It is
then separated from other lanthanides and actinides by cation exchange chromatography
in a thiocyanate medium. Pm is then co-precipitated with Nd and determined by
liquid scintillation counting; in a wide variety of samples including environmental
material and power station liquid euent discharges
Sequential method in low-level liquid euents using beta counting. Ru-106 is oxidized
to volatile ruthenium tetroxide and allowed to react in situ with polyethylene powder;
Cs-137 is concentrated on ammonium phosphomolybdate and estimated as
tetraphenylborate; Sr-90 is co-precipitated as strontium sulfate and converted to
carbonate
Ion chromatography, non-radioactive strontium carrier and liquid scintillation spectroscopy
to individually quantify Sr-89 and Sr-90 in nuclear reactor euent. The equipment,
solutions, and operating conditions for the chromatographic separation of strontium
in aqueous solutions are identied. The beta spectra of Sr-90, Sr-89, and Y-90 are
obtained using liquid scintillation spectroscopy and the eects of quenching are shown
to be negligible. The positions of the liquid scintillation windows within the combined
beta spectra facilitating isotopic analysis of Sr-89 and Sr-90 are identied, followed
by a system of equations to quantify Sr-89 and Sr-90 within a sample
In gaseous and liquid euents from nuclear plants using a liquid scintillation counter

[21]
[22]

Cd

Cd
Ca
Co
Cu
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Hg
Hg
Mn
Pb
Ni
Pd
Pu
Pm-147

Cs-137; Ru-106; Sr-90

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

Method and/or applications

Reference

Ti

Selective and sensitive method for extraction followed by spectrophotometric or


AAS determination using caeic acid and a liquid ion exchanger; pre-concentration,
separation and determination of titanium in steel, industrial euents and
environmental samples
Selective and sensitive extraction-spectrophotometric method; in industrial euents
Separation by extraction chromatography with tributyl phosphate; zinc is separated
from a variety of elements in binary and multi-component mixtures by exploiting
dierences in their extractability or stripping characteristics by dierent media;
in soil and euent
Automatic hydride generation system for the AAS; all determinations were
automatically and sequentially controlled by a computer
In metal industry euent and solid waste by ICP-AES after precipitation with
N,N-diphenylthiourea. The method was also used for analysis of process intermediates
in production control, and for the determination of many elements in solution with
concentrations varying from milligram to gram/liter levels
DC argon plasma source with echelon grating spectrometer; in industrial euents

[47]

Ti
Zn

As; Bi; Hg; Pb; Sb; Se; Sn


Pt; Pd; Rh; Ir; Ru; Ag; Au

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]

has been developed for the determination of the 238 U/235


U isotope abundance ratio in sequential extracts of
freshwater sediment from the vicinity of a uranium
enrichment plant by means of ICP-MS [52].
A method and apparatus for optical detecting the
composition of an euent stream from a vacuum-processing chamber is presented. A cell placed in the euent
stream from the vacuum-processing chamber creates a
glow discharge from the constituents in the euent
stream. An optical detector measures a particular
wavelength corresponding to the presence of a particular
species. In one version, the output from the optical
detector was used to determine the endpoint of a
chamber cleaning process [53].
The development of an optimized dehalogenation
process started with laboratory experiments on dierent
processes, such as OH or S2 and cementation. Precipitation with a low-concentration S2 solution was
found to be the most favorable process. A second stage
processing technique for wastewater from ue gas
scrubbers is described in which the water is mixed with
H2O2 and HNO3 in the rst stage. The residue is removed
via membrane lters; this way, the heavy metal ions
contained in the clear eluates can be determined by AAS
without interfering matrix eects. The residue is homogeneously dissolved by a combination of HNO3, HF and
HClO2. In the solutions obtained, heavy metals can be
analyzed by AAS without observable interferences [55].
The repetitive breakdown spark from a focused laser
beam was used to generate analytically useful emission
spectra for aerosols in air [56]. The application is simple;
a pulsed laser and optics, a spectrometer, and a method
to perform time resolution of the spark light. Time
resolution is essential because of the strong continuum
emission at early times. High temperatures in the spark
result in the vaporization of small particles, dissociation
of molecules, and excitation of atomic and ionic spectra.
The plasma acts as if it were in local thermodynamic
equilibrium, at least after 1 ls. Spectroscopic methods
were used to measure the time-resolved temperatures

983

and electron densities. A simple one-dimensional


hydrodynamic model predicts the temperature. Beryllium in air at atmospheric pressure was detected at
0.7 lg/m3. Limits of detection for Na, P, As, and Hg in
air are also given.
On the other hand, it is now well known that the
toxicological and biological properties of most metals
depend upon their chemical form. Chemical speciation
analysis aims to determine the nature and concentrations of the compounds of an element present in a given
material. Trace elements may be present in aqueous
media in one of the following forms:
free metal ions surrounded by a layer of water molecules in the rst co-ordination sphere
inorganic complexes
organic complexes
in association with colloids and particulate materials
such as clays, iron oxides and organisms
The interactions between metals and the components
of the system are strongly inuenced by the specic form
of the element and also by the pH, salinity, temperature,
content of oxygen, biota, colloids and particulate matter
present in the system.
It is well recognized that speciation analysis consists
of at least three steps: sample preparation, separation of
dierent species and, nally, determination of the separated species. Several instrumental techniques have been
developed that allow selective detection of dierent
species at very low levels. Inductively coupled plasma
mass spectrometry is a relatively new technique that
allows the total concentrations of many elements to be
determined with the high sensitivity of mass spectrometry. It is well suited as a detector for inorganic and
organometallic species separated by HPLC.
In 1991, Bond [60] published a review with 69 references, entitled Instrumentation and procedures for
long-term automated monitoring of metal ions in
industrial euents by liquid chromatography with
electrochemical detection. Theoretical and practical
considerations relevant to the use and application of
inductively coupled plasma optical emission spectrometry (ICPOES) in the eld of environmental analysis are
also reviewed in [61]. Advantages and disadvantages of
ICPOES in relation to conventional techniques like
AAS, are detailed and discussed. Practical aspects of the
use and application of ICPOES are further described in
a series of case studies covering a range of sample types,
such as waters, wastewaters and euents, soils and solid
wastes. Each case study details sample preparation,
ICPOES method development, sample matrix proles,
interferences and overall performance and routine
analysis schedules. Recent developments and applications of ICPOES are also discussed.
Euent samples collected from some of the marble
industries were chemically evaluated for parameters like
TSS, TDS, BOD, COD, and metals like Cr, Fe, Zn, Pb,
Cu, and Ni [62].

Advantages and disadvantages of ICP emission


spectrometry compared to AAS, desirable features of an
ICP emission spectrometer, and common interferences
encountered in emission spectrometry are discussed [63].
A review and discussion of AAS in wastewater
analysis covers hollow cathode tubes, electrodeless discharge lamps, and common interferences in AAS
wastewater analysis [64].

Inorganic non-metallic analysis


Amongst the non-metals, cyanide is generally associated
with the mining, metal manufacturing and processing
industries. Nitrogen and phosphorus in their various
forms can be associated with chemical manufacturing
industries and any industry where biological wastewater
treatment is part of the process. Both of these elements
may become a source of nutrients once they enter
receiving waters. The form in which they exist also
determines the impact that they have.
A discussion, with 15 references [65], showed that S
compounds present in pulp mill euents have sucient
vapor pressure over the euents to be collected directly
in the air above and determined by gas chromatography
(GC). Table 2 shows a list of determination methods for
inorganic non-metallic species.
Although boron is a trace element in nature, occurring in only minute concentrations in natural systems, it
is one of the most important trace elements or micronutrients required by growing plants. Sources of
boron in the terrestrial environment are mainly soil
minerals and parent material, fertilizers, irrigation waters, sewage sludge, and euents, and coal combustion.
Fertilizers are one of the biggest industrial applications
of boron [67]. Four methods are discussed and compared for determining boron in waters, euents, sewage
and other materials in a review with ten references [70].
ICP-OES was used to determine B, C, H, I, P, S and
Si in organic compounds [71]. A comparison of this
method with previously-reported microwave techniques
showed that, while both approaches are sensitive
(detection limits in the low ng region), ICP-OES had
fewer complications and was less prone to interference
than the analogous microwave techniques. ICP-OES is
proposed for the simultaneous multi-element analysis of
gaseous euents from a gas chromatograph.
A dispersive interferometer IR instrument, eventually
intended to operate in situ, has been developed for stackeuent analysis [72], and an apparatus that performs
gas phase spectroscopy over two wavelength ranges for
the analysis of euent from a molten salt electrochemical cell is described. The cell is placed in a quartz tube
that is sealed at the top with a cap containing feed-thrust
for power, thermometry, and gas ow. A resistance
furnace brings the cell assembly to the desired temperature while the cap remains cooled by water. Inert gas
continually purges the cell headspace, carrying euent

984
Table 2 Summary of methods for determining inorganic non-metallic species
Species

Method and/or applications

Reference

MnO4 ; COD; NO2 ;


NO3 ; Cl ; SO24
B

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

from the electrolysis sequentially through two gas cells,


one in a Fourier transform IR (FT-IR) spectrometer and
one in a ber-optic-coupled UV-visible spectrometer.
Strong vibrational absorptions in the IR can easily
identify common euent components such as HCl, CO,
CO2, and H2O. Electronic bands can identify IR-inactive molecules of importance including Cl2 and O2. Since
the absorptivities of all of these species is known, gas
concentrations can determined without using standards.
Spectra from the electrolysis of molten MgCl2 are shown
and discussed [73].
Cyanide may be present in euents either as the
simple anion, or in metal complexes, which may be
soluble if alkali cyanides are also present. Metal cyanide
complexes have various degrees of dissociation and are
normally treated in industrial euents by chlorination
to cyanates. Analysis techniques therefore dierentiate
between total cyanide and cyanides amenable to chlorination. A further category of cyanides are those that
can be dissociated by weak acid to give free and
potentially dissociable forms of cyanide. Other
compounds related to cyanide that may also require

[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

that the analyzer is exposed to a sample stream that may


be dirty and/or corrosive. The problems involved with
analyzing incinerator euent are discussed in this work.
An installation and its performance are described for
NH3 determination by an IR analyzer in the euent of
an incinerator at a cyanuric acid manufacturing plant.
Nitrate and nitrite may be determined by IC, although colorimetric and continuous-ow analysis techniques may also be used [85].
A measurement of dissolved oxygen is needed to assay for BOD, but it may also be used in its own right.
Titrimetric analysis using either the Winkler method or
iodometric titration, or electrometric analysis using a
membrane electrode, may be used to determine dissolved
oxygen.
Analysis for phosphorus involves conversion of the
form of phosphorus present to dissolved orthophosphate, followed by determination of the orthophosphate
using either a colorimetric principle or IC. Silica may be
present, either in dissolved form or as colloidal material.
Gravimetric, colorimetric, and FAAS methods may be
used to determine silica.
Sulfur-based anions may be determined by IC, and
this technique is preferred when several species may need
to be determined simultaneously. However, these anions
also undergo specic colorimetric reactions, which form
the basis for either spectrophotometric analysis or
detection in automated analyzers such as continuousow analyzers [15].
S2O23 , SCN , SO24 , and SO3NH2 were determined
in desulfurization euent from coke oven gas by LC
using phthalic acid eluent. NH4SO3NH2, synthesized by
wet oxidation of the euent, was favorably determined
after removing Cu2+, Zn2+, and so on with a cationic
exchange resin [86].
Illustrative examples have been given of potentiometric ISEs and catalytic membrane amperometric
electrodes suitable for environmental analysis [88].
Methods have been given for the analysis of euent
from wastewater treatment. Cl , SO24 , HCO3 , CO23 ,
Na+, K+, Ca2+, and Mg2+ were determined in two
wastewater treatment euents. Two methods using the
key-diagram and the hexa-diagram were also reported
[90].

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

be the only option for the euent in order to meet the


international legislation on plant discharges. Any
extraction and separation technique may be used to
separate acetic acid from acrylic acid with a good
combination of selectivity, economy, and environmental
friendliness. A study demonstrates that a precursor of
advanced zirconia ceramics as well as practically pure
acetic acid can be obtained by the metal-organic precipitation process by using zirconium oxychloride to
treat the euent [92]. Short chain aliphatic acids are
important components of the dissolved organic matter
in silage euents. Although ion exclusion chromatography oers some advantages for the analysis of these
compounds, no attempt has yet been made to prove the
suitability of this method for silage euent analysis. In
order to gain experience in this eld, the separation
characteristics of a Dionex ion exclusion column have
been evaluated, the separation conditions have been
improved, and several sample clean-up methods have
been checked [93].
Residual organic compounds present in municipal
sewage treatment plant euents were analyzed using
high-resolution anion-exchange chromatography [94].
Using techniques such as UV spectroscopy, GC, and
MS, 56 organic compounds were identied in primary
euent and 13 organic compounds in secondary euent. Some of these constituents were quantied. Chromatographic procedures, coupled with radioactive tracer
chlorination, were applied to the analysis of chlorinated
primary and secondary euents. A detector system for
liquid chromatography based on cerate oxidimetry was
adapted as a rapid and sensitive continuous monitor for
measuring the COD of waters.
Two systems are presented for the automatic monitoring of the contents of an euent tank by high performance liquid chromatography (HPLC) under the
control of a computer program [97, 98].
Thermolysis or pyrolysis followed by mass spectrometry or gas chromatography/mass spectrometry
provides information on the identity, equivalency, and
structures of polymers and impurities [99]. The degradation mechanism of the polylactone from dimethylketene was determined and the euent gases from
nigrosine dyes were analyzed. Euents from chlorine
bleachers in a sulte and a sulfate paper plant were
investigated [100].
A method and apparatus are described for analyzing
high molecular weight organic substances by MS.
Samples can be solid or uid, including euents from
gas or liquid chromatographs. The sample is introduced,
for example by means of a transport band, to a vacuum
chamber, in which it is ionized by a focused laser beam.
The ions are then detected by a time-of-ight mass
spectrometer [101] and similar methods and apparatus
are also described for analyzing organic substances in
gas or liquid chromatograph euents by MS [102].
The ve fractions of non-volatile organic compounds
eluted after sorption from wastewater on Bondapak
C-18 were subjected to further liquid chromatography,

986

characterized, and examined for toxic substances and


mutagens [103].
A procedure, which involved extraction of euents,
concentration of the extract, and derivatization of acidic
components for GC/MS analysis, was described for the
identication and quantication of low molecular
weight compounds, phenols, fatty acids, and resin acids
in pulp bleaching euents [104]. It was revealed that
several characteristics of the components made the
analysis inaccurate, and special care was needed in terms
of sample storage, solvent extraction, and concentration
of the extract in order to prevent the components from
undesirable changes and evaporation loss.
Extracts from ve tannery and leather nishing
industry discharges were studied by HPLC/MS using a
moving belt interface [105]. Twenty compounds were
identied including binaphthyl sulfone, which was a
major component of all discharges and which could not
be determined using GC successfully.
For the sensitive and selective analysis of HPLC
euents, a new detection system with resonance Raman
spectrometry was developed. A micro LC was coupled
with a laser Raman spectrometer by a quartz tube ow
cell. This cell, which can be directly connected with a
micro-column, is simply inserted into the capillary
holder in the sample compartment of the Raman spectrometer. Several derivatives of 4-dimethylaminoazobenzene (DAAB) eluted from a separation column were
detected continuously by measuring the intensity of
resonance Raman scattering at 1406 cm 1, since Raman
lines were observed for all compounds at about this
wavenumber. A chromatogram obtained by this method
was similar to the one obtained by UV detection.
Moreover, rapid identication of compounds possessing
almost the same retention time was possible by operation in a stop-and-go mode. The LC-Raman proved to
be a useful detection system with both high sensitivity
and excellent selectivity for colored compounds [106].
Wastewaters resulting from the production and
purication of 2,4,6-trinitrotoluene (TNT) were characterized. Nitro-aromatic compounds were identied
and quantied over a year-long sampling period. Sources of the identied compounds were predicted on the
basis of the operation of the manufacturing process
[107]. This work serves as the primary step in an evaluation program to assess the environmental impact of a
complex industrial discharge. Cluster analysis is used to
characterize the distribution of ether-extractable wastestream components resulting from the production and
purication of TNT [108]. This method is compared to
other methods of analysis in order to establish a representative mixture of components that can be used in
toxicological evaluations. Dinitrotoluene isomers were
determined in seawater and industrial euent by GC
with glass capillary columns and electron-capture
detection after extraction with C6H6. A 3,5-dinitrotoluene isomer was not found in industrial euent [109].
Owing to the alarmingly poor health of sh (Salmonidae) in many Swiss rivers, the euent of sewage

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

determination of TOC and COD in permeates and


concentrates. The analytical scheme developed has been
found to be very useful for characterizing whole mill
euents as well as bleach plant euents from TCFbleaching of softwood and hardwood pulps [112].
Direct analysis of oily water euents was investigated as a method of determining petroleum hydrocarbons in the discharge from primary oil production
facilities. A co-solvent, isopropanol, was chosen which
produced a clear, homogeneous solution when added to
oil-in-water euent. The clear solution was then analyzed directly for aromatic hydrocarbon content using
UV spectroscopy [113]. A direct aqueous supercritical
uid extraction (SFE) system was developed which can
be directly interfaced to an infrared spectrometer for
the determination of oil in water [114]. The technique is
designed to provide an environmentally clean, automated alternative to established IR methods for oil in
water analysis, which require the use of restricted organic solvents.
Resin acids are major sources of sh toxicity in many
Canadian softwood pulp mill euents. Therefore, their
accurate detection is an important factor in the evaluation of the environmental impact of these euents.
Among the various methods used to detect and quantify
resin acids, GC is usually the method of choice due to its
high resolution and accuracy. However, major disadvantages, such as tedious sample pre-treatment protocols and low sample output reduce the suitability of this
method for analyzing large numbers of samples in a
short period of time. A traditional GC method and an
immunochemical method were compared. In the GC
method, liquidliquid extraction was further evaluated
using four dierent solvents for their extraction eciency. An ELISA based on polyclonal antibodies was
developed for detecting dehydroabietic acid (DHA), one
of the most abundant resin acids found in softwood pulp
mill euent. Both GC and the direct ELISA were used
to quantify DHA in a spiked euent and the results
were compared. Since the immunoassay requires no pretreatment, only a small volume of sample, and results in
a larger sample output, this alternative method of resin
acid analysis shows promise [115]. In a review, the most
relevant analytical methods for determining resin acids
in process water euents from pulp and paper mills are
discussed [116].
Microactivity tests (MAT) are commonly used to
analyze feedstock and catalyst properties. Evaluation is
rapid and requires only small amounts of catalyst and
feedstock. However, until now, the small quantity of
recovered liquid euent did not allow for the complete
characterization of the whole euent. Only two chromatographic analyses could be made on a routine basis.
Improved techniques of separation have been built up to
characterize the whole euent and more specically the
heaviest cuts. Using an appropriate device requiring
small amount of whole euent, the method elaborates
fractions such as gasoline, light-cycle oil and bottom
cuts by facilitating molecular and structural analyses of

each cut. The set of analyses requires only a very small


euent fraction sample [117].
To separate and classify the relative amounts of two
or more classes of hydrocarbon molecules in a sample
(for example, a diesel fuel containing aromatic hydrocarbons), an input stream comprising a mobile phase
and the sample is injected into a chromatographic column, and the euent stream is split into a rst euent
and a second euent. The mass of C in each of the
classes of hydrocarbons in the rst euent stream is then
determined, preferably using a ame ionization detector,
and the second euent stream is directed through a
variable restrictor, allowing the pressure and mass ow
rate to be independently controlled [119].
In a book entitled POHC (principal organic hazardous constituent) analysis methods for hazardous
waste incineration (Volume 1, Part 2), preliminary data
are given on determinations of hazardous substances in
hazardous waste incinerator euents, using GC/FID,
GC/MS, and HPLC/UV methods specically developed
for these hazardous compounds [120].
An arrangement for continuously monitoring and
determining chlorohydrocarbons in waste gas and
wastewater using ame-emission spectrometry is described [121], where a heating segment (for example, a
ame) is provided with a element (like a wire), made
from Cu or Cu oxide, which is positioned in the immediately vicinity. The chlorohydrocarbons are transferred
in a mixture with air to the heating element. A photodetector, sensitive to light emitted from the resulting Cu
halide, produces a signal corresponding to the intensity
of the emitted light. This arrangement is dependable and
cost-eective, and the disadvantage of having to perform conventional waste gas and wastewater processing
by means of active C can be avoided.
The inuents and euents of a municipal biological
wastewater treatment plant were examined for non-polar and polar organic compounds by GC/MS and
HPLC/MS, respectively. More than 90% of the nonpolar organics, but only 50% of the polar organic
wastewater compounds, were eliminated after biological
wastewater treatment processing. The chromatographic
separation of C-18 adsorbable polar organic compounds
was performed by HPLC using an analytical C-18 column. Detection was performed by UV-spectrometry and
mass spectrometry (LC/MS). For identication, collisionally-induced dissociation (CID) after soft thermospray-ionization (TSP) was used (LC/MS/MS). For
comparison, detection was also performed by owinjection analysis (FIA) using TSP-ionization and MSdetection, bypassing the analytical column, and identication was achieved with tandem MS detection (FIA/
MS/MS). No prior chromatographic separation was
necessary. Changes in the retention time and co-elution
eects induced by matrix compounds can be recognized
and compensated for by MS detection. Quantication
by LC/MS and FIA/MS using the standard addition
method leads to comparable results. The time required
for detection, identication, and quantication is 20-fold

988

to 30-fold more in the LC/MS-mode than in FIA-mode


[123].
An on-line process analytical system, developed and
placed in routine operation, gives a complete analysis of
cracking reactor output and then groups the peaks into a
26-component cracking pattern to match a pre-determined linear program. Approximately 200 components,
from H to C-20 hydrocarbons, are determined. The online analytical system is used to ne-tune pyrolysis
conditions for maximum protability [131].
Organic pollution of a liquid and/or gas medium is
determined by bringing this medium into contact with
ozone gas and measuring the amount of CO2 formed.
This simple and dependable method may be automated
and permits continuous measuring and detection of organic material (euent from a factory, a municipal
sewer, or the like) [132].
Volatile organic compounds in pulp mill euents
were trapped on Tenax resin, desorbed by heating and
analyzed by GC/MS [133]. The potential of GC with
microwave-induced plasma atomic emission detection
(CG/MIP/AED) as a complementary analytical technique in environmental screening analysis of aqueous
samples is studied [134]. New self-developed macros are
helpful tools for acquiring information on the elemental
compositions and concentrations of organic pollutants
analyzed by GC/MIP/AED. The concern over the
presence of micro-pollutants in the aquatic environment has caused a growing demand for methods of
identication of organic contaminants, which are
present at relatively low concentrations in water. In
environmental analysis, GC has long been used in
many standard target methods and for sample screening purposes. Since almost all pesticides and many of
the organic compounds in the US Environmental Protection Agency (EPA) priority pollutants list contain
heteroatoms, it is clear that element selectivity is a
desirable characteristic for environmental analysis. The
most common element-selective detectors, such as the
nitrogen-phosphorus detector (NPD) or the electroncapture detector (ECD), still detect several elements
and the element-to-carbon selectivity is sometimes
modest. The AED, on the other hand, can detect all
elements except helium separately. This denes it as the
most versatile selective detector. Regardless of the
selectivity of a detector, and the use of retention data
on two columns with dierent stationary phases, stateof-the-art conrmation of target compounds and the
identication of unknowns require a detector that
provides structural information. In this respect, MS,
which is sensitive, oers several complementary modes
of operation and is compatible with GC, which is the
technique of choice. The combined use of AED and
MS detection allows selective screening for compounds
containing specic elements and, subsequently, provisional identication. The applicability of GC-AED/MS
to screen for and identify heteroatom-containing compounds in a complex sample, in this case wastewater,
was studied [135].

A xed bed catalytic micro-reactor, incorporating


repetitive injection GC/MS euent analysis is described
[137]. The micro-reactor temperature can be kept constant or varied to permit non-isothermal analyses such
as temperature-programmed desorption measurements.
The use of repetitive injection GC/MS to generate
structure-specic volatile product evolution proles is
described for 1-butene oligomerization and n-hexane
cracking reactions.
A systematic evaluation of iodoheptauoropropane
as a potential replacement for peruorocompound
chemistries in dielectric etch applications has been presented [138]. In the experiments discussed, 1-iodoheptauoropropane- and 2-iodoheptauoropropane-based
etch processes had been used in a via etch application in
an inductively coupled high d.c. plasma etch tool. Part I
of this article discusses the etch process behavior of
1-iodoheptauoropropane and 2-iodoheptauoropropane, while Part II examines lms deposited by the
1-iodo isomer. This article focuses on the composition of
the process euent stream, as characterized by FT-IR
spectroscopy. Data generated by both isomers of the
compound are presented and compared to those generated by conventional etch processes. Signicant reductions in global warming emissions (8085%) were
obtained relative to the conventional processes. The FTIR data were correlated with process and lm analytical
data presented in Parts I and II to generate better
understanding of key plasma mechanisms in iodouorocarbon etch environments.
Yield is an important measure of the selectivity and
protability of a pulp process. So far, yield estimations
have principally been limited to gravimetric measurements in the laboratory and the amount of raw material
utilized in the industry. Due to the time-consuming
procedure of estimating the yield in the laboratory and
the low accuracy associated with estimating the raw
material consumption during industrial production, it
would be of great use to be able to estimate the yield loss
during bleach plant euent analysis. In a study, yield
loss estimations for bleaching were derived via TOC
analysis of the euent [139].
Euents arising from the cellulose industry result in
dierent types of environmental impact, which can be
considered to be related with their solids content, organic charge, toxicity, and colour. Saez [140] analyzed
the incidence of the organic compounds produced by the
paper and paste industry, with regard to the toxicity and
anaerobic biodegradation of their euents, and reviewed the technologies available for their treatment.
Table 3 shows a list of other procedures available for
organic species determination.

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

Method and/or applications

Reference

4-Amino-azobenzene-4,5-disulfonic acid
Humic; lignin; phenolic matter

Reversed phase HPLC; and related products in industrial wastewater euents


UV analyzer for continuous absorbance measurements at 254 nm was
constructed; the UV analyzer with automatic turbidity compensation
was tested
Neutron activation analysis

[95]
[96]

HPLC; in environmental samples; the method employs an amine column


to separate mixtures of aromatics into groups of compounds with
similar spectrophotometric responses. A estimate of total aromatics is
then derived by comparing the response of each group with the response
of suitable reference compounds. Since the results must be expressed in terms
of these reference compounds, the method is semi-quantitative.
However, values derived for total aromatics in renery euents, extracts of
the mussel Mytilus edulis, and two petroleum oils agreed well with those
given by more cumbersome traditional methods
In raw sewage, primary euent, and primary sludge from municipal
wastewater treatment works. Extraction of the sample with cyclohexane
is followed by a two-step column chromatographic clean-up employing
aluminum oxide and silica gel, with nal determination by GC/MS
Reaction with 1,3,5-trihydroxybenzene in alkaline solution to produce an
orange-red dye with kmax=470 nm; spectrophotometric determination
of methanol in environmental samples (in air, distillery waste, polluted
river water, and coke oven euent) is described. Methanol is oxidized
to formaldehyde with acidic potassium permanganate and the
resulting formaldehyde is reacted with J-acid. The method has been
successfully applied to the determination of methanol in euents from
distilleries and polluted air [118]
Spectrophotometric in environmental samples; oxidation to formaldehyde
with acidic potassium permanganate and the resulting formaldehyde is
reacted with J-acid; in euents from distilleries and polluted air
Nonylphenol polyethyoxylates and their biodegradation products in
sewage sludge, which is eective, economical and applicable to HPLC
In water samples using GC-MS in full scan mode
Photometric determination in food and environmental samples; is based on
the reaction of 3,4-dimethylphenol with sugars in sulfuric acid to form a
red chromogen with kmax at 510 nm; the method requires neither sophisticated
instruments nor any hazardous reagents and is relatively free from
various interferences; in milk, molasses, and industrial euents
In wastewater from the brewing industry involving the coupling of
on-line micro-dialysis sampling with microbore high performance anion
exchange chromatography and integrated pulsed electrochemical detection.
Microdialysis and a trap column provided on-line sample clean-up that
enabled the detection of fructose, glucose and sucrose without any
further sample preparation
GC/LRMS/SIM in euents and sludge from three dierent mills and in
sh and mussels exposed to pulp mill euent
In hydrometallurgical process solutions and euents; applicable to
the xanthates commonly used in otation plants, i.e., xanthates of which
the length of the alkyl carbon chains is from 1 to 5. The xanthates are
separated according to chain length as well as structural isomerism, and
the separated species are then detected spectrophotometrically at a
wavelength of 305 nm

[118]

Non-polar phenolic;
organohalogenated compounds
Hydrocarbons

Polynuclear aromatic hydrocarbons

Formaldehyde

Methanol
Nonylphenol polyethyoxylates
Organic extracts
Sugars

Saccharides

Polychlorinated cymenes
and cymenenes
Xanthates

euent. Knowledge of these parameters for any euent


should be considered a fundamental requirement.
A wide variety of equipment and instrumentation,
ranging from standard laboratory glassware, bench-top
meters such as pH-meters and conductivity meters,
balances, spectrophotometers through to gas and liquid
chromatographs coupled with detectors such as mass
spectrometers are needed to analyze the wide range of
components present in industrial euents.
Further investigative eorts are necessary in various
areas of euent analysis: sources of euents, classes of

[100]

[122]

[124]

[125]
[126]
[127]
[128]

[129]

[130]
[136]

analytes, legislative requirements, and analytical


requirements (such as sampling protocols, quality control and instrumentation, and the techniques required to
isolate various classes of analytes for analysis).

References
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Malaysia Planters Conf, 1719 October 1977, Kuala Lumpur,
pp 83105

990
2. Dutton JWR, Harvey BR, Mitchell NT (1978) Methods of
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