oEPA
United States
Environmental Protection
Agency
Environmental Research
Laboratory
Athens GA 30605
EPA-600/3-78-064
July 1978
Research and Development
Inorganic Species
in Water:
Ecological
Significance
and Analytical Needs
A Literature Review
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic, terrestrial, and atmospheric environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/3-78-064
July 1978
INORGANIC SPECIES IN WATER:
ECOLOGICAL SIGNIFICANCE AND ANALYTICAL NEEDS
(A Literature Review)
by
Thomas B« Hoover
Analytical Chemistry Branch
Environmental Research Laboratory
Athens, Georgia 30605
ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
ATHENS, GEORGIA 30605
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DISCLAIMER
This report has been reviewed by the Environmental Research
Laboratory, U.S. Environmental Protection Agency, Athens,
Georgia, and approved for publication. Mention of trade names
or commercial products does not constitute endorsement or
recommendation for use.
11
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FOREWORD
Nearly every phase of environmental protection depends on a
capability to identify and measure chemical pollutants in the
environment. The Analytical Chemistry Branch of the Athens
Environmental Research Laboratory develops techniques for
identifying and measuring chemical pollutants in water and soil.
This report summarizes recent literature on the ecological
significance of chemical forms of elements, as opposed to total
elemental composition, in the aquatic environment. It includes
research into the toxicology, transport, transformation, and
distribution of inorganic species and the analytical methods
that have been used for their determination. This report will
acquaint researchers and administrators with the current
application of knowledge about speciation and with the needs for
improved analytical techniques.
David W. Duttweiler
Director
Environmental Research Laboratory
Athens, Georgia
111
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ABSTRACT
Representative studies of the environmental significance of
inorganic species (as opposed to total element content) in water
are reviewed with particular emphasis on the effects of chemical
forms on human health and on plant and animal life. Primary
attention is given to recent U.S. Government reports and
conference proceedings. The roles of valence state, ionization,
complexation, and adsorption in the transport and cycling of
elements are considered along with factors affecting the
distribution of elements and species in freshwater streams and
impoundments, in estuaries, and in the sea.
Information on the chronic effects on human health of trace
inorganic pollutants in water is almost entirely limited to
total elements because of an inability to distinguish among
forms on an element. The elements of greatest concern with
respect to the toxicity of different species, however, are
arsenic, chromium, lead, mercury, and selenium. In the
toxicology of aquatic biota, there is a rapidly growing
appreciation that both acute and chronic effects are strongly
related to chemical species.
The movement of inorganic species in the aquatic
environment is strongly influenced by adsorption on both mineral
and organic particulates. Adsorption is highly dependent on the
chemical species of the pollutant.
No broadly applicable analytical techniques of adequate
sensitivity are available for elemental speciation. This
deficiency in analytical ability prevents the evaluation of
research on toxicology and on transport of these chemical forms.
IV
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CONTENTS
Foreword iii
Abstract iy
Acknowledgments vii
1. Introduction 1
2. Conclusions 3
3. Recommendations 4
4. Biological Effects 5
Enzyme Systems 5
Bacteria and Phytoplankton 6
Algae 7
Daphnids and Molluscs 9
Fish 10
Mammals 17
Interactions of Toxicants 18
5. Human Health Effects 21
Acute Versus Chronic Effects 21
Cardiovascular Disease 22
Elements of Concern 22
6. Environmental Transport and Transformations 28
Interaction of Water and Solids 28
Biogeochemical Cycling 33
Distribution of Elements and Species 36
7. Analytical Methodology 40
Equilibrium Calculations 41
Direct Species Determination 42
Separation Techniques 48
8. References 51
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LIST OF ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
AAS
AF
ALA-D
ASV
DPP
EDTA
GOT
ISE
LC5Q-96 hr
LSV
MATC
NTA
atomic absorption spectroscopy
application factor
delta-aminolevulinic acid dehydratase
anodic stripping voltammetry
differential pulse polarography
ethylene diamine tetraacetic acid
glutamic oxalacetic transaminase
ion-selective electrode
lethal concentration (to 50% of population in
96-hour exposure)
linear sweep voltammetry
maximum allowable toxic concentration
nitrilotriacetic acid
SYMBOLS
Ag
Al
AS
B
Ba
Ca
Cd
Co
Cu
Cr
dL
Fe
Hg
K
L
Mg
Mn
silver
aluminum
arsenic
boron
barium
calcium
cadmium
cobalt
copper
chromium
deciliter
— iron
ym
mercury
potassium
liter
magnesium
manganese
microgram
micrometer
Mo
Na
ng .
NH,.
Ni4
P
Pb
PH
ppb
ppm
Ru
S
Se
Sn
Tl
Zn
molybdenum
sodium
nanogram
ammonium
nickel
phosphorus
lead
hydrogen ion
activity
part per billion
part per million
ruthenium
sulfur
selenium
tin
thallium
— zinc
VI
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ACKNOWLEDGMENT
This review has drawn heavily on an earlier literature
search made by Dr. W. R. Seitz, to whom the author is indebted.
R. W. Andrew, W. J. Blaedel, D. S. Brown, G. F. Craun, and N. L.
Wolfe have made cogent and constructive comments on the report
as a whole or on particular sections. Their interest and help
is appreciated.
VII
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SECTION 1
INTRODUCTION
Despite a growing recognition that the chemical forms of
elements in the aqueous environment have a critical effect on
the toxicity of pollutants to aquatic biota and on the transport
and recycling of inorganic pollutants, regulatory standards
necessarily are based largely on total-element concentrations
because of a lack of adequate analytical methodology for
individual species. This deficiency in analytical ability is
probably even more serious in the evaluation of research on
toxicology and on transport, and in the evaluation of models in
either of those areas.
The toxicology, distribution, and analytical chemistry of
heavy metals in the aquatic environment was the subject of an
international symposium (270), and the relation of speciation to
aquatic toxicology was considered in another symposium (15), but
the broader ecological aspects of inorganic speciation have not
been summarized.
This literature review is intended to provide researchers
and administrators with a coordinated assessment of the
significance of inorganic speciation in natural waters and,
secondarily, to provide direction for a program to develop
elemental analytical methodology to meet EPA's research and
standards-setting needs.
Excluded from this review are organic species except as
complexants for metal ions. The nutrient species of phosphorus
are included only as they interact with other inorganic forms.
Only a very small sampling of the literature on radionuclides
has been included.
The review is far from comprehensive. Few secondary
references have been obtained and many sources have been
examined only in abstract form. In all such cases, the source
of the abstract is indicated in the bibliography. Particular
emphasis was given to coverage of U.S. Government reports, which
might be less readily available than formal scientific journals.
To this end, three computer searches of technical information
files were utilized. The author accepts responsibility for any
deficiencies in coverage but believes that a broad enough
sampling has been obtained to meet his objectives.
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A conscious effort was made to limit the coverage to
references dealing specifically with chemical species, as
opposed to total element concentrations. The operational
definition of a species, however, depends upon the analytical
method used to determine it. In many cases the dominant, stable
form (free ion for example) was assumed even when a total-
element analysis was used.
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SECTION 2
CONCLUSIONS
Information on the chronic effects of trace inorganic
pollutants in water on human health is almost entirely limited
to total elements because of an inability to distinguish among
forms of an element. Speciation affects the distribution and
availability of elements in water supplies, and toxic synergism
or antagonism among elements suggests chemical interactions
dependent on species.
In the toxicology of aquatic biota, especially fish, there
is a rapidly growing appreciation that both acute and chronic
effects are strongly related to the chemical species of the
toxicant. For heavy metals, it appears in most cases that the
free atomic ion is the only, or most, toxic form.
The transport, transformation, and distribution of
inorganic pollutants in the aquatic environment is strongly
influenced by adsorption on both mineral and organic
particulates. Adsorption, which may be either physical or
chemical in nature, is highly dependent on the chemical species
of the pollutant.
Although many fewer inorganic species, than organic, are
significant in water, the inorganic forms are not biodegradable
and some, if not all, seem subject to perpetual cycles of
transformation that require constant surveillance from the
public health point of view.
No broadly applicable analytical techniques of adequate
sensitivity are available for elemental speciation.
Consequently, in most studies of the effects of speciation, the
inorganic species have been defined operationally by the methods
at hand for their determination.
The elements of greatest concern with respect to known or
suspected toxicity are different species of arsenic, chromium,
lead, mercury, and selenium.
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SECTION 3
RECOMMENDATIONS
The chemical species involved, and its effects, should be
identified so far as practicable in toxicological and
epidemiological studies. The interactions of toxic pollutants,
both organic and inorganic, require more study.
Improved analytical methods are needed for surface species
on sediment particles. Such a capability would aid both
equilibrium and kinetic studies of adsorption.
New and more sensitive ion selective electrodes should be
developed. Most crystal-membrane electrodes have practical
detection limits much greater than those dictated by the
solubility of the crystal but the reasons for the difference are
not clear.
The analytical applications of ion exchange should be
extended in two areas:
• Concentration of ionic species, especially as a means
of extending the detection limits of ion-selective
electrodes, and
• Chromatography of ions as a means of separating and
identifying several species in a sample.
4
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SECTION 4
BIOIiOGICAL EFFECTS
The effects of trace elements, both as the total element
and its specific chemical forms, can be studied systematically
using plants and lower animals as experimental subjects. It is
hoped that the information thus obtained can be extrapolated to
the corresponding effects on human health although such attempts
must be made with great caution. This Section deals with the
effects of chemical species on biota, starting at the
subcellular level and advancing into broad classes of plants and
animals in order of increasing complexity. Annual reviews in
the Journal of the Water Pollution Control Federation (288)
provide comprehensive and up-to-date literature surveys of the
effects of trace elements on aquatic biota, although material
relating specifically to speciation forms only a minor part.
The Leland et al. review is particularly noteworthy for a
summary on bioaccumulation of trace elements.
ENZYME SYSTEMS
The toxicity of inorganic pollutants is closely related to
their effects on essential enzyme systems. A toxic metal ion
may replace the essential metal characteristic of a particular
enzyme and act, as Schroeder put it (413), "like a key that fits
a lock but does not turn." Elements that act this way are
usually heavier than the replaced element and in the same, or
neighboring, groups of the Periodic Table. Alternatively, the
toxic element may form tight bonds with the normally labile
linkages of protein ligands. The availability of ions to act in
either of these ways may be mediated by non-biological or
foreign ligands that form insoluble or stable complexes. If
such ligands tie up essential ions, they may lead to deficiency
diseases or, if they tie up toxic ions, they may have a
protective or antidotal effect. The effects of pollutants on
enzymes, analytical applications of enzymes, and biological
indicators of pollution have been covered in two bibliographies
(208,482). A broader coverage of the biological effects of
metals in aquatic environments is provided by the bibliographies
of Eisler and Wapner (148,149).
The toxicity of a series of metal ions to aquatic organisms
(425) and the inhibition of urease by metal ions (232,427) have
both been correlated inversely with the solubility of the metal
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sulfides, suggesting that binding to protein sulfhydryl groups
is the mode of biological action of the metals. The morphology
of fish blood cells was altered by Cd and Cu in the water and
this effect was proposed as a biological assay technique (117).
The effects of Pb(II), Cu(II), Hg(II), Zn(II), and Cd(II) on
isolated cell mitochondria have been summarized (67). The
extreme toxicity of Cu(II) to mitochondria suggests that living
organisms have a protective mechanism that restricts access of
Cu inside the cell, but that the mechanism is less effective
toward the other heavy metals.
Studies with rat brain tissue indicated that the specific
toxic effects of Pb and alkyl derivatives of Hg and Sn could not
be defined in terms of a single enzyme, any one subcellular
compartment such as the mitochondrion, or even one function of
the tissue, but depended on the metabolic organization of the
whole tissue (84). Allantoinase was inhibited by 10~6 M
divalent cations of Hg, Cu, Zn, Pfc, and Cd, but its activity was
enhanced (10-20X) by 2.5 x 10~8 M concentrations of the same
ions (73).
BACTERIA AND PHYTOPLANKTON
The toxicity of heavy metals to bacteria has practical
significance in the biological treatment of sewage. Bench tests
showed that Cd (II), Cu(II) , Ni (II), Zn (II) , and Cr(VI) inhibited
the digestion of raw domestic sewage; addition of these ions to
the influent to an oxidation pond at concentrations up to 6 ppm
had no deleterious effect, however, presumably because most of
the metals were precipitated by the moderate alkalinity (pH 8)
(336). A systematic study of the effects of Na+, NH4+, K+,
Ca2+, and Mg2+ ions in anaerobic waste treatment revealed both
antagonistic and synergistic interations although most of these
ions were tolerated at concentrations less than 0. 1 M (273).
The chelating agent ethylenediamine tetraacetic acid (EDTA) was
reported to reduce the toxicity of Cu(II), Hg(II), Ni(II),
Cd(II), Zn(II), and Pb(II) in the activated sludge process but
was not effective with Ag(I), Co (II), Cr(III), or Cr(VI) (402).
At low total concentrations of Ca, EDTA inhibited the growth of
ammonia-oxidizing bacteria in activated sludge, although the
complexant reduced the toxicity of Cu (298). The self-
purification of river water polluted with sewage was inhibited
by 0.1 ppm Cu(II) or 1 ppm Pb(II) (251).
Bacteria that were relatively resistant to Hg compounds
were isolated from Chesapeake Bay sediment and were able to
metabolize HgCl2 or phenylmercuric acetate to elemental Hg
(109). Zinc, at 50 ppb, was somewhat more toxic than 10 ppb
Cu(II) to a natural population of heterotrophic bacteria (6) and
the effects of the combined metals were additive. In the same
study, an excess of L-cysteine did not protect the bacteria from
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the toxic effects of 100 ppb Hg(II) nor did albumin protect from
0.05 ppm Ag(I).
A hydrocarbon-oxidizing yeast, Rhodoturula rubra, that has
very low phosphate requirements, was studied (86). Under
phosphate-limited conditions, arsenate at 10~7 to 10~e M was
taken up competitively with phosphate, and Cu(II) was toxic at
10~6 M. Excess phosphate or trace amounts of Mn(II) protected
against the effects of Cu and the authors concluded that Mn
impurity in the phosphate was the effective agent. Iron is an
essential nutrient that may be limiting in marine or fresh water
environments. Marine phytoplankton may require soluble organo-
complexes of Fe for chlorophyll production (125), and EDTA has
been used to make Fe nutritionally available to algae in
autoclaved seawater (290). The addition of either Fe or
nitrilotriacetic acid (NTA) temporarily increased phytoplankton
photosynthesis in a mesotrophic lake but impeded the process in
a eutrophic lake (80). Presumably the additives by
precipitation-adsorption of the Fe or chelation of the NTA,
removed soluble metals ions from a toxic to nutritional level in
the mesotrophic lake, or to a deficiency level in the eutrophic
lake.
ALGAE
The major concern has been to find chemicals that can
control undesired algal blooms without harmful effects on other
aquatic life. Algae have been a convenient form of plant life
for investigating toxic effects of metal ions (368).
Copper
Copper is a widely used and effective agent for controlling
algal blooms in fresh water. Laboratory studies using cupric
ion-selective electrodes have shown that it is the free Cu(II)
that is effective (445). Trace amounts are essential and
concentrations below 40 ppb were limiting, whereas free Cu(II)
concentrations greater than 300 ppb were toxic. In these
studies, the availability of Cu was regulated by complexation
with EDTA, which had to be used in amounts insufficient to
complex all Mg (II). Thus, a competition between Cu(II) and
Mg (II) may be involved in the physiological action of Cu in
algae. Calcium also reduced the toxicity of Cu to phytoplankton
and algae (465). In natural waters, the availability of Cu may
be regulated by organic complexants naturally present (335,465)
or introduced with sewage effluent (38). During normal growth
the blue-green alga, Anabaena CYclindrica, produced an
extracellular polypeptide that ccmplexed Cu(II), Zn(II),
Fe(III), and phosphate. This may be a natural protective
mechanism of the plant against Cu (172). In a highly eutrophic
lake, the addition of 1/200th the amount of Cu usually used for
control inhibited nitrogen fixation by blue-green algae. It was
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concluded that the natural chelation capacity of the lake was
already saturated by indigenous Cu (227). Free Cu(II) at the
usual concentration of total Cu in seawater is very toxic to
algae; therefore, much of the natural Cu must be complexed
(347). The same authors report that ocean upwelling is toxic
until chelators are added, indicating that free Cu(II) is more
abundant in deep waters.
Silver
Mixtures of Ag and Cu ions were investigated for algal
control (508). The combinations were more toxic to one species
than the equivalent concentration of Cu, but were less toxic to
another algal species. Silver was also more toxic to fish. At
0.15 ppm in Mediterranean seawater, Ag(I) was much more toxic
than a similar concentration of either Cu-(II) , Zn(II) , or Hg(II)
and appeared to act synergistically with Cu(ZI) (454).
The effect of heavy metal ions on photosynthetic production
of oxygen by Chlamydomonas reinhardii leads to the following
decreasing order of toxicity: methylmercuric ion > Pb(II) ,
Cd(II) > Cu(II), Hg(II), Tl(I) > Ba(II) (no effect) (360). Both
HgCl2 and GH3HgCl inhibited the biosynthesis of lipids in fresh
water algae (3 17). In a study of algal growth rates, HgCl2 was
more toxic than (CH3)2 Hg (201). Chelation with EDTA reduced
the toxicity of both Cu and Hg, but the addition of enough EDTA
to complex all the mercury depleted the medium of essential
trace nutrients (448).
Selenium
Studies with two species of blue-green algae showed
appreciable species difference, but selenite was more toxic to
both than selenate (274). This conclusion with respect to blue-
green algae was supported in another study (368) that found, in
addition, that the growth of diatoms and single-celled algae was
stimulated by 1 to 10 ppm selenite. Up to 40 ppm of selenite-
was tolerated, but all concentrations of selenate were toxic to
the single-celled species. Selenium (form not specified)
reversed the inhibition of Hg to the growth of Phaeodactvlum
tricornutum (202).
Lead
Fixation of carbon dioxide by marine algae was reduced 50%
in three species by adding 15 to 18 ppm of Pb; however, 5 ppm Pb
caused 5Q% reduction in one species that had a high surface-to-
volume ratio (307). The concentrations refer to added Pb, not
necessarily to the free Pb(II) in the medium. Another study
(506) found that 10 ppm Pb (II) stopped photosynthesis after 24
8
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hours and that 0.1 ppm reduced photosynthesis and respiration by
25 to 50% after 2 to 3 days. Apparently, the Pb penetrated the
organisms slowly.
Other Metals
Patrick et al. (368) studied the effects of chemical forms
of trace metals on many algal species with the aim of promoting
the growth of diatoms and single-celled algae at the expense of
blue-green and filamentous algae. (The marked difference
between selenite and selenate with respect to the algal forms
has been noted above.) Vanadium, probably as vanadyl ion, was
not toxic at concentrations up to 5 ppm, but the growth of
diatoms versus filamentous algae was favored at very low levels
(less than 20 ppb). Similarly, low levels of Cr(VI) (40 to 50
ppb) favored the diatoms, but at 400 ppb blue-green algae
completely displaced the diatoms. A shift from diatom to blue-
green predominance occurred as borate concentrations approached
1 ppm. Diatom growth was inhibited by 10 ppb Ni(II) , but some
blue-green species were tolerant to 1 ppm.
DAPHNIDS AND MOLLUSCS
Simple aquatic animals are convenient for testing toxicity
in the laboratory and field. Ciliated protozoa (57) and fresh
water mussels (306), for example, were used as biological
indicators of heavy metal pollution. The toxicity of a long
series of metal ions to daphnids was correlated with the
negative logarithm of the solubility products of the metal
sulfides (46). Heavy metals were divided into two groups
according to whether their sulfates were more or less toxic to
daphnia than the chlorides (88,89). Artificial water hardness,
produced by CaCl2 or MgSO4, decreased the toxicity of Ni(II) ,
Co (II), and Cd(II) to daphnia and fish (474).
In a study of Tabata and Nishikawa (475), complexation with
EDTA or thiosulfate reduced the toxicity of Cu(II) to daphnia.
A more detailed study by Andrew et al. (14) concluded that the
toxicity of Cu to daphnia was directly related to the
equilibrium concentration of free or hydrated ion rather than to
soluble or total Cu. Cadmium behaved similarly, although it was
less completely complexed by NTA; the toxicity of mercury, which
was principally in the hydroxide form, was little affected by
added NTA or EDTA (188). Similarly, a seawater extract of
marine sediments, containing natural chelating agents, reduced
the toxicity of Cu to a copepod (292). The citrate complex of
Cu, however, was accumulated in aquatic animals (475) and was
appreciably more toxic to worms, crabs, and prawns than chromate
(384). Insoluble Cr(OH)3 was ingested with marine sediment by a
polychaete worm and excreted, whereas soluble chromate ion
accumulated to 12 times the concentration in water in a 19-day
period (102).
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The biological fate of Ru species was studied with the
radio tracer 1o*Ru. Particulate forms were preferentially
concentrated by algae, sponges, and ascidians (as compared to
soluble forms) (10). A cationic chloro complex was concentrated
by clams appreciably more than the neutral or anionic chloro
complexes (240). The chloro complexes were accumulated faster
by mussels than the NO-NO3 complexes (253,254).
FISH
Fish, an important economic resource for food and
recreation, are particularly susceptible to aquatic pollution.
The effects of pollution have been reviewed with respect to
freshwater fish (77) and marine animals (496). Some of these
effects have been proposed as biological indicators of water
quality (48,49,90,301).
The acute effects in fish of high concentrations of
different heavy metal ions are generally similar, causing
secretion of heavy mucus on the gills and leading to suffocation
(95). At somewhat lower concentrations, the ions have different
degrees of toxicity and there is considerable interest in
extrapolating from a concentration that is lethal to 50% of the
population over a 96-hour exposure (LCso-96 hr) to the maximum
allowable toxic concentration (MATC) that can be tolerated over
the normal lifetime of the animal. The ratio of the latter to
the former, called the Application Factor (AF), was expected to
be a measure of toxicity nearly independent of the test animal
(339). Differences between AF for Cu in hard and soft water
(389), and in water containing sewage treatment effluent (76),
suggested that the AF should be based on soluble, rather than
total, Cu.
The toxicity of heavy metal ions to fish has been related
to the inhibition of specific enzyme systems: carbonic anhydrase
(104), allantoinase and ornithine aminotransferase (73), and
lactic dehydrogenase and glutamic oxalacetic transaminase (GOT)
(103). The inhibition of GOT was most sensitive to Ag(I), and
Hg(II) and was correlated with the solubilities of the metal
sulfides (103). The activity of allantoinase was enhanced by
low concentrations (^ 10~* M) of Cu(II), Hg(II), Zn(II), and
Cd(II) but inhibited by higher concentrations (73) .
Chen and Selleck (101) based a mathematical model of the
toxic response of fish on the hypothesis of a first-order
biological toxic mechanism opposed by a de-toxifying reaction in
the organism that is also first-order after an induction period.
The critical or threshold concentration of pollutant is the
level at which the opposing rates are equal. They studied the
effects of Zn(II) and CN~, individually and combined, on guppies
and demonstrated a distinct antagonistic effect between the
toxicants. The opposing effects of anion and cation suggest a
10
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chemical combination. In Figure 1a the same data are plotted on
a mole-fraction basis. The complexes, Zn(CN)+ and Zn(CN)2 are
included in Figures 1b and 1c, respectively, in addition to Zn2 +
and Cn~. The linearity of response is improved somewhat by
inclusion of the complexes, but there is no clear choice between
the two additional forms. Both complexes appear more toxic, on
a molar basis, than the free ions, but are less toxic on a
weight basis. This treatment has been applied by Andrew (13),
as well. The kinetics of the uptake and elimination of
methylmercury by fish has also been evaluated (209). A somewhat
more sophisticated model for multiple toxicants was presented by
Anderson and Weber (11).
Elements
Copper-
Because of the wide usage of Cu salts for controlling
undesirable aquatic plants, there is great interest in the
effects of Cu on fish. Acute toxicity (LC50-24 hr) varied from
1.5 to 11.6 ppm for different Hudson River (NY) fish (385). In
this study, the decreasing order of toxicity of ions was Cu(II)
> Zn(II) > Ni(II). The LCso-96 hr to fathead minnows in a
natural stream was 0.6 to 1.0 ppm, based on the soluble Cu
concentration, which was appreciably less than the total added
Cu (76). The MATC of Cu for the same fish species in soft water
was between 10 and 18 ppb, based on growth, survival, and
spawning (339). The MATC, as estimated from 30- to 60-day
observation of eggs and fry in soft water, gave values of 5 to 8
ppb for brook trout, and 12 to 21 ppb for channel catfish and
walleye pike (403). The order of toxicity in this study was
Cu(II) ^ Cd(II) > Pb(II) > Cr(VT). Some fish species responded
visibly to these tolerable levels (10 to 20 ppb) of Cu (260):
goldfish tended to orient toward the source of a concentration
gradient, whereas suckers showed an avoidance reaction.
The toxicity of Cu has generally been observed to be lower
in hard water than in soft (339,403,462). This difference has
been explained by precipitation by carbonate—the insoluble
forms of Cu being relatively non-toxic. Similarly, alkalinity
appears to be a controlling factor in reducing toxicity based on
total Cu (462). LCso values for minnows in natural water of
variable quality were correlated with PO4 (13,184) . Soluble
complexes of Cu also appear to be relatively non-toxic to fish.
EDTA (348,475) and NTA (458) reduced the toxicity of Cu, and
carp grew well in ten times the LCSO of total Cu when
thiosulfate was added (348) . Atlantic salmon tolerated higher
levels of Cu in the presence of humic acid, a natural complexant
(516). In a study of toxic interactions of some industrial
waste components, no interaction between Cu(II) and acetic acid,
acetaldehyde, or acetone was found through LC50-96 hr studies of
bluegills (92). The toxicity of Cu to minnows was directly
related to the activity of Cu(II), as measured by an ion-
11
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.9 1.0
Figure 1
Critical Threshold Concentrations of Zinc-Cyanide
Species vs. Mole Fraction of Zinc.
12
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selective electrode (13). Thus, ICSO in two different types of
water had the same value in terms of Cu2* (% 7 x 10~8 M) but
differed four-fold in total Cu concentration (12). Soluble
organic or inorganic complexes of Cu were non-toxic (13). An
analysis of the forms of Cu in natural water indicated that less
than 25% of the total was likely to be uncomplexed at prevalent
conditions of bicarbonate and pH (462).
The combined effect of toxicants is important because
natural conditions are rarely limited to one pollutant. Several
workers have observed than Zn has a synergistic effect with Cu
(147,295), the combination being as much as 2 to 5 times as
toxic as a simple additive effect (456,459). No synergism was
found in another study (91), however. Anionic detergents have
also been noted as being somewhat synergistic with Cu (94) .
A detailed study was made of the long-term chronic effects
of Cu pollution of a natural stream (184). Laboratory tests
were made simultaneously using the same water. The laboratory
results underestimated the ecological effects over a 5-year
period, however, because the avoidance reaction of the fish
caused them to select less suitable spawning sites, resulting in
lower reproduction.
Cadmium-
The chronic toxicity of Cd to fathead minnows apparently
was somewhat less than that of Cu (MATC 40 to 60 ppb) (375) but
very similar to Cu in other fish species: 4 to 8 ppb to
flagfish (455,456) and brooktrout (403), and 10 to 25 ppb for
channel catfish and walleye pike (403). The Application Factor
tentatively derived for Cd was much smaller than that for Cu
(375) because of the accumulation of Cd in the test animals on
long-term exposure. Water hardness decreased the acute toxicity
of Cd to several fish species (474) and decreased the chronic
effects on walleye pike (403). In one study of a mixture of Cd
with Zn and Cu in hard water, the acute toxicity was appreciably
greater than would be expected from simple additive effects
(147).
Zinc-
The acute toxicity of Zn to native fish species of the
Hudson River was measured (385). In flow tests, Zn was more
toxic at pH 8 than at pH 6, in contrast to static measurements
(337). The speciation of Zn has been discussed in relation to
toxicity to fish (364). In chronic studies, the MATC was
estimated at 600 ppb for Atlantic salmon (457), less than 250
ppb for bluegills (93), less than 160 ppb for fathead minnows
(74), and less than 50 ppb for flagfish (456). Water hardness
(337) and NTA (458) reduced the toxicity of Zn. Calcium (91)
and, to a greater extent, Mg (515) reduced the toxicity of
Zn(II), as did CN- (92,101). In one study, Zn(II) and Cu(II)
13
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were markedly synergistic (457) , but this effect was not
observed in another study (91) .
High concentrations of Zn(II), like Cu(II), attack the
epithelial cells of the gills (296). Lloyd suggested that the
critical level is that at which the blood can no longer carry
the excess Zn away from the site of attack and that this occurs
at only twice the normal concentration of Zn in the gill tissue.
The effect of Ca (II) and Mg(II) on the toxicity of Zn(II) has
been interpreted as a competition for binding to active sites on
an enzyme (515). Taking glycine as a model compound, the order
of metal binding strengths is Cu(II) > Zn(II) > Mg(II) > Ca(II) .
Thus, Zn (II) and Mg(II) may be competitive, but Cu(II) is too
strong and Ca(II) is too weak to have much effect. The gonad
cells of rainbow trout were selectively damaged by Zn(II) (382) ,
concentrations of Zn (II) inhibited spawning in bluegills that
showed no other physiological effect (93).
Mercury-
The LCso-48 hr toxicity of Hg(II) to stickleback was 1.7
ppm (325). In contrast, Shaw and Lowrance (426) found 20 ppb
for the LCso-24 hr value for the guppy and, further, found
approximately the same toxicity for Cu(II). Although the latter
report shows a consistent order of toxicity (Ag (I) > Hg(II)
Cu(II) > Cd(II) > Zn(II) > Pb(II) > Ni(II)), the lethal
concentrations were much lower than found by modern bioassay
procedures. Chronic exposure of brook trout to CH3HgCl over
three generations indicated a MATC of less than 1 ppb although
there was some indication of acquired tolerance. Mercury
accumulated markedly in the tissues at exposure levels that
produced no direct toxic effects (326). EDTA greatly reduced
the toxicity of Hg(II) (348). Trout removed from an
oligotrophic Michigan lake contained more than twice the Hg
concentration of fish from a eutrophic lake (138). It was
concluded that adsorption of Hg on organic particulates removed
the metal ion from the food chain. The toxicity to pike of
CH3Hg+ (LCSO-30 day) was not significantly different when
administered as the soluble nitrate or as a protein complex
(329). No difference in toxicity to minnows was found between
the various inorganic chloro complexes: HgCl2, HgCl3~, or
HgCl42- (250).
High concentrations of Hg(II) do not seem to attack the
gills in the same manner as Cu(II) or Zn(II) (296). Both HgCl2
and CH3HgCl were rapidly absorbed through the gills, expecially
CH3HgCl, which was bound to red cells (in vitro) (353).
Electron micrographs of the gills of trout exposed to HgCl2 and
to CH3HgCl showed mercury only for the inorganic exposure (354).
Methyl mercury may have been lost during the specimen
preparation or it may have been carried away by the blood
stream. In a study of the effects of 49 compounds on two
enzymes in fish blood, GOT was particularly sensitive to
14
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inhibition by Ag(I) and Hg (II) (103). Selenite, at close to its
own toxic level, reduced the mortality of chubs exposed to
acutely toxic levels of mercury (258).
Other Metals-
Aluminum—Suspended Al(OH)3 had lower acute toxicity, but
greater chronic toxicity than soluble Al(III) (156). The forms
were varied by changing the pH but 50 ppb total Al had no effect
at a pH of 7 or greater.
Arsenic—Arsenite was more toxic than arsenate to trout
eggs but was rapidly converted to arsenate in aerobic water
(119).
Beryllium—The acute toxicity of BeSO4 to guppies was 100
times greater in soft water than hard (441). The LCso-96 hr was
lower than the 24-hr value, suggesting a slow or cumulative
effect.
Boron—Metaborate was nearly ten times as toxic to young
coho salmon in seawater as in fresh water (483).
Chromium—The toxicity of Cr(VI) to eggs and fry of seven
fish species appeared to be correlated with length of exposure
(403). The estimated MATC for 100 days exposure (150 to 300
ppb) agreed with that observed for 8 to 22 months exposure of
brook and rainbow trout (42). The LC50-96 hr values were found
for these species (42) and for minnows and goldfish (2).
Chronic exposure to Cr(VI) apparently induced some tolerance,
and it was suggested that Cr(VI) was less toxic than its
bi©reduction products (83) .
Lead—Lead(II) was about twice as toxic as cr(VI) under
similar chronic test conditions (403) andr like Cr, Pb showed an
effect that increased with time of exposure. Acute toxicity,
when based on total Pb, was markedly reduced by water hardness
(129), but Application Factors based on free Pb(II) were
consistent between hard and soft, water (128,223) .
Manganese—Ordinarily insoluble in oxygenated water, Mn can
be dissolved from sediments by the oxygen-deficient hypolimnetic
water of deep lakes or impoundments. The toxicity of Mn(II) was
apparently lethal to trout at 1 to 2 ppm but was controlled by
additions of Ca(II) (235).
Nickel—The MATC of Ni2+ to fathead minnows was 380 ppb
(greater~than for Cu(II), Cd(II), or Zn(II) (374). The toxicity
was reduced by addition of CaCl2 or MgSO« (474). The toxicity
of nickel cyanide apparently was due almost entirely to the
equilibrium concentration of HCN. On the other hand, silver
cyanide gave heavy metal symptoms, probably due to Ag(CN)2~
(142).
15
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Silver—The MATC of Ag+ to rainbow trout (0.07 to 0.13 ppb)
was determined by using Agl to provide controlled low
concentrations (127).
Anions—The anions of As, B, and Cr have been discussed
above. Molecular HCN was more toxic than CN- to fish (142).
The MATC of HCN for fathead minnow was 13 to 20 ppb (293), and 5
to 11 ppb for brook trout (263). In a study of a series of
copper cyanide complexes, the toxicity increased with the
proportion of cyanide, but all were hazardous (294).
Hydrogen cyanide was more toxic at low temperatures and a
limit of 5 ppb was not completely harmless to salmonid fish
although most warm water species could tolerate 25 ppb
(141,263). Some metal-cyanide complexes (Cu(CN)2- and Ag(CN)2~)
were major toxicants per se and entered the fish blood, whereas
the less toxic Ni (CN)4z- accumulated in the gills (69).
Chlorine--The effects of residual chlorine on aquatic life
have been reviewed (75). Although free chlorine (OC1-) may be
somewhat more toxic and act faster than the chloroamines, there
was not a great difference in toxicity between the forms of
residual chlorine. A limit of 3 ppb residual chlorine was
recommended.
Sulfur species--Molecular H2S was much more toxic than HS~,
and S«- had completely negligible effects at pH < 11 (70,357).
The toxicity varied greatly with water temperature and with age
and species of fish, but 2 ppb H2S was recommended as generally
safe, except in spawning areas, where the concentration should
not exceed 1 ppb (444). Natural H2S levels can easily exceed
these limits, especially in anoxic waters close to organic
sediments (37). Although H2S is readily oxidized by dissolved
oxygen, treatment with hydrogen peroxide or permanganate has
been suggested as a control measure (235).
The bisulfite ion (HSO3-) was 14 times as toxic as SO32- to
goldfish and 5 times as toxic to guppies (401). The
concentration of molecular SO2 was not significant at lethal
levels of the ions.
Nitrogen species-
Unionized NH3 (or NH4OH) has long been recognized as being
much more toxic to fish than the NH4+ ion in equilibrium with
it, and a maximum concentration of 0.02 ppm NH3 was recommended
for fresh water aquatic wild life (342). Acute (LCso-96 hr)
levels for striped bass and stickleback were about 2 ppm at 23°C
in both fresh water and seawater (211). Nitrite (NO2-) also is
highly toxic, causing methemoglobinemia in fish. Chloride ion
had a marked protective effect against nitrite toxicity to coho
salmon, however, apparently competing with NO2- for uptake
through the gills (371).
16
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MAMMALS
The toxicity of metals and their compounds to mammals,
including humans, was reviewed in a recent book (302). The
point is made that the dose-response relationship rarely shows
toxic effects over the entire exposure range. Rather, most
substances stimulate growth at trace levels but become toxic at
sufficiently large doses. Toxicity is closely related to the
electronic configuration of the atom, with elements and valence
states in the most stable configuration being least toxic.
Those cations that form "soft" acids tend to be most toxic
because they form strong complexes with the soft bases of the
biological system. An attempt was made in the review to
associate carcinogenicity with increasing electronegativity of
the element, but there appeared to be numerous exceptions.
Schroeder (413) has made an extensive study of the effects
of trace elements in water on the health of rats and mice over
several generations. He took elaborate precautions to provide
clean air and surroundings and to see that the diet contained
minimal amounts of the trace elements. In general, he found
that valence state has little effect on toxicity because
mammals, in most cases, have the ability to oxidize or reduce an
element to a form that can either be utilized or eliminated. On
the other hand, he stated that the natural valence state of an
element is generally the least toxic form. He made specific
comparisons of chemical species of selected elements.
Chromic ion, at 5 ppm in water, was an essential nutrient
for both mice and rats. It promoted growth, protected against
the toxic effects of Pb and Cd, increased life-span and
longevity, and lowered serum levels of glucose and cholesterol.
Chromate ion at the same level (5 ppm) had a negative effect on
the growth rate of mice (but not rats) and slightly increased
the incidence of tumors in mice.
Selenite, at 3 ppm, was highly toxic to rats, reducing
growth rate, increasing the incidence of fatty liver, and
consistently reducing survival. In contrast, selenate showed
none of these effects and greatly increased longevity in rats
and mice. Extraordinarily long lives of certain individuals
were highly correlated with the selenate diet; however, these
aged rats had a high incidence of malignant tumors. In another
study, Se (II) apparently induced a high incidence of liver
tumors in aged rats (345). It is not clear whether selenate
induced the cancers or, by prolonging life, allowed unidentified
carcinogens to take effect.
Methylmercury, at 1 ppm, markedly increased the growth of
mice but reduced fertility and viability of offspring.
17
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When all parameters were compared in both rats and mice,
only three elements were consistently toxic: selenite, cd, and
Pb. Lead, and to a lesser extent cd, reduced plasma levels of
Zn in rats if the diet was deficient in Cu, but nutritionally
adequate or excess amounts of Zn, Cu, or Fe protected against Pb
toxicity (372). In vitro studies with rat brain tissue showed
that Pb(II) and CH3Hg+ interfered with metabolic activity
similarly at levels below those producing overt toxicity in
humans (84). Methylmercury interfered specifically with the
conversion of glucose to carbon dioxide. In the same study,
alkyltin compounds produced different but equally toxic effects
as Pb and Hg. Triethyltin was more potent than dimethyl- or
dibutyltin.
Another of Schroeder's generalizations is that the least
abundant elements in seawater are the most toxic to mammals
because protective mechanisms have not been as well developed in
the evolutionary scheme as for the more abundant elements.
Figure 2 compares elemental abundances in seawater with the
concentrations found in the raw and finished water supplies of
U.S. cities. The latter data (265,477) are averages of
analytical results, unweighted by volume, and do not include
samples in which the element was not detected. Consequently,
the values shown tend to be higher than the true average
concentrations. Most of the elements less abundant than Al in
seawater were found at higher concentrations in drinking water.
Data on the toxic effects of compounds containing these elements
to mammals and humans have been summarized in exhaustive
bibliographies (130,342,343,344). Murthy and Petering (340)
found serum cholesterol levels in rats inversely related to
dietary, and to serum, Cu levels tut unrelated to dietary Zn.
High levels of Ca in the diet of rats increased the excretion of
heavy metals, providing some protection against the toxicity of
Cd and Pb (168), and the simultaneous administration of Zn
protected hamsters from the teratogenic effects of Cd (162).
INTERACTIONS OF TOXICANTS
As noted in the cited examples, the combined effects of
toxicants are not additive. Although the mechanisms of
synergism or antagonism are obscure and need further study
(276), some types of interaction are readily understandable.
Antagonism between ions of opposite charge naturally
suggests chemical combination. An example is the effect of
Zn(II) and CN~ on fish (101) described above. Similarly, the
toxicity of cyanide complexes of Cu (295) and Ag (142) depended
on the dissociative equilibrium. Selenite in the diet protected
rats against the toxic effects of Ag(II) or CH3Hg* added to
their drinking water (180). Selenium (form not specified but
probably selenite) reversed the inhibition of Hg(II) to the
18
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pC 0
O Raw and finished drinking wafer
41 Seawater
4
*
+
_o
o
a
c
o
c
o
u
8
12
O O
O
o
t+°° *0o°000o '•
4-
* 4. ^ O
j^K)!— * ^- ^ o
+
•f-
Sr B F P Ba Al Fe Mo Zn As Cu Mn Ni V Sn Sb Se Cd Co Cr Ag Pb Bi Be
Figure 2. Elemental Concentrations in Seawater and in Drinking Water,
-------
growth of algae (202), and dietary Se protected quail from the
toxic effects of methylmercury (179).
Antagonism between ions of the same charge and similar
chemical properties may result from competition for the same
enzyme system. The protective action of Mg(II) against Zn(II)
with respect to fish (515) has been cited above. Calcium and Zn
may interact similarly (91), and Zn is reported to counteract
the effects of Cd in animals (162) . Selenium and As, probably
both as anions, are antagonistic (342) and mutual antidotes.
Each stimulates secretion of the other in bile of mammals (289) .
Forms of Se appear to be antagonistic to many heavy metals,
including Hg(II) and Cd(366) , but the mechanism may be different
in each case (391).
Synergism of toxicants might be rationalized as a concerted
attack on separate enzyme systems of the organism. On a
molecular level, the production of different enzymes in the same
organism appears to be interrelated (2U2); an attack on one
enzyme may disable another apart from specific damage to the
second by another toxicant. Synergism with the toxicit.y of
Cu(II) to fish has been noted for Ag(I) (45U) , Cd(II) (459) , and
Zn(II) (295,457,U59) .
In a kinetic approach to modeling multiple toxicants,
Anderson and Weber (11) developed distinctions between additive
and independent responses. Toxicants that had the same response
curve (probably acting by the same mechanism) could be treated
as a single substance at the total concentration and were called
additive; independent toxicants had different response curves
unaffected by other constituents. In a test with guppies,
Cu(II) and Ni(II) were additive and Zn(II) was independent.
20
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SECTION 5
HUMAN HEALTH EFFECTS
ACUTE VERSUS CHRONIC EFFECTS
Although the acute toxicity of such species as
methylmercury (137) in food, chromate in ambient air (342), or
cadmium ion in food and drinking water (342) has been forcefully
demonstrated following accidental or industrial exposures to
unusually high concentrations, the long term effects of trace
levels of inorganic species can only be inferred from animal
experiments or epidemiclogical data. The synergistic and
antagonistic interactions among trace elements, both as
essential nutrients and as toxicants to human health, are
complex and little understood (321). The need for water quality
data, including chemical species information, for drinking water
as supplied to the consumer and for water supplies was
recognized in a National Academy of Sciences (NAS) Workshop
(20)t as a first step in developing epidemiological
correlations. A recent report from the NAS (314) thoroughly
reviewed the toxicological data and significance of 22 trace
elements in drinking water, recommended permissible limits of
concentration, and presented the rationale for such limits.
Although recommended limits were for the total elemental
concentration, in most cases the stable valence ion could be
assumed. The possible role of suspended particulates as
carriers of trace elements in drinking water was considered, but
not enough information was available to assess the significance
of undissolved forms. For the present, it is considered
appropriate to base drinking water standards on total elemental
concentrations for the following reasons:
• The total concentration of an element provides a safety
factor, because it includes all species.
• Adequate analytical methodology is not available to
characterize drinking water by the inorganic species.
• Epidemiological correlations are based on total
elemental concentrations because of the available
analytical data.
• Drinking water provides only a small fraction of the
total dietary intake of most elements.
21
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• Mammals appear to be quite efficient at interconverting
valence states of many elements, so that there is
little difference in chronic toxicity of the species.
• For most of the elements of concern, only one species
is prevalent in water.
CARDIOVASCULAR EFFECTS
An inverse correlation between human cardiovascular disease
and water hardness has been widely noted and reviewed
(114,344,502). Although several theories of a cause-and-effect
relationship have been advanced, none is generally accepted.
Because drinking water supplies less than 15% of the normal
intake of any of the elements considered as specific causative
agents, the form of the element in water, as opposed to food,
would seem to be significant if there is indeed a causal
relationship between water factors and health.
ELEMENTS OF CONCERN
Arsenic
Although the acute toxicity of As compounds is well known,
the levels ordinarily found in public water supplies are not
associated with any adverse health effects (342). The
recommended limit of 0.1 ppm in drinking water was intended to
provide less than 2Q% of the normal dietary intake. Inorganic
As (III) appears to be the most toxic form, whereas As(V) is the
prevalent form in oxygenated waters (342). Arsenite [As(III)]
can be methylated in the environment by bacteria to
methylarsinic acid, to dimethylarsinic acid, and to dimethyl-
and trimethylarsine (504). In addition, a variety of synthetic
organic arsenicals are distributed in the environment as
pesticides, which can be transported into water supplies. The
toxicity of various As compounds is extremely variable (344) . A
clear epidemiological dose-response relationship between As in
drinking water and incidence of skin cancer has been observed,
however (237). A thorough and recent review of the health
effects of As compounds (344) concludes that the interim
drinking water standard of 50 pg/L may not provide an adequate
margin of safety and that improvement of speciation techniques
for analysis is needed.
Chromium
Chromium is an essential nutrient involved in the
metabolism of glucose (422). Only two valence states are
ordinarily encountered and the higher [Cr(VI)] is much more
toxic than Cr(III). The EPA interim standard for drinking water
(490) of 0.05 ppm Cr is based on the carcinogenicity of inhaled
chromate dusts (342). Although cancers were induced in rats by
22
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the injection of Ca, Zn, or Cr(III) chromates, none were induced
by Ba, Pb, or Na chromates or by chromic acetate. The
International Agency for Research on Cancer concluded that there
is no evidence of hazard to humans from non-occupational
exposure to Cr (237). Schroeder (413) found Cr(III) to be an
essential trace element for rats and mice that regulates
carbohydrate metabolism, lowers serum cholesterol levels, and
protects against toxic effects of Pb and cd. From these
studies, he infers that atherosclerosis and diabetes mellitus
may be Cr deficiency diseases in humans.
Within the normal hydrogen ion activity (pH) range of
surface and drinking waters, cr(III) is hydrolyzed to its very
insoluble hydroxide and is rarely found as a soluble species.
Also, inorganic Cr(III) is poorly absorbed from the digestive
tract and rapidly disappears from the blood stream after
injection (328). In controlled studies (139), less than 3% of
an orally administered dose was absorbed by insulin-dependent
diabetics. Interconversion between Cr(VI), the stable valence
state in oxygenated waters, and Cr (III) can take place under
natural conditions (412) and ingested Cr(VI) can be reduced by
ascorbic acid taken orally as much as an hour or two later
(422). The anionic Cr(VI) penetrates cell membranes more
readily than Cr(III) and may bind to erythrocyte globin without
undergoing reduction (237) .
The NAS review (344) concludes that improved analytical
methods are needed for distinguishing the valence states of Cr,
especially in animal and plant tissue, and recommends that
consideration be given to basing the drinking water standard on
the hexavalent form.
Cadmium* Leadr Zinc
Cadmium, lead, and zinc occur in water as divalent ions or
complexes of the ions with inorganic or organic ligands. The
health effects of the soluble species, however, are considered
equivalent to those of the total element. Speciation may be
most significant in its effect on the availability of the
element in drinking water (20). Surveys of public water
distribution systems in Denver (28), Seattle (121), and four
locations in eastern U.S. (468) showed that soft, corrosive
waters may pick up Cd, Cu, Pb, and Zn between the treatment
plant and the home tap. Zinc and Cd were presumed to come from
galvanized pipe, and Pb from solder joints in new copper
plumbing (121). In older eastern cities, lead plumbing may be a
source of Pb in drinking water (114). New copper plumbing
contributed soluble Cu only during the first two months of use
(28).
23
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Cadmium-
Found only at trace levels in natural surface waters, Cd is
a cumulative poison and all sources of exposure need to be
watched carefully. The total normal human intake has been
estimated at 150 to 400 fig/day (140,228), with a daily
accumulation of 3 jig (140) . Only about 3 pg/day is supplied in
drinking water (20). A survey (145) of dry-weather flows at 720
water supply sites in the United States serving at least 100,000
people showed 4X that exceeded the EPA limit of 10 ppb for
drinking water, with a maximum of 130 ppb Cd. The levels
appeared to be related to population density. In other work,
the sources and significance of cadmium pollution were reviewed
by McCaull (324).
Lead-
Human exposure to Pb is probably closer to a critical toxic
level than for any other element. Schroeder states that, "no
person living today in industrialized societies ... is free of
the recondite toxicological effects of lead."(413) This
statement is based on the observation that human blood levels of
Pb inactivate the enzyme 6-aminolevulinic acid dehydratase (ALA.-
D) (222) and on the reduction of life span and reproduction of
rats fed 25 ppm Pb in their water (413). Lead inactivates ALA-D
to a much greater extent than Hg, Cu, or Cd, so the mechanism
does not seem to be simple thiol binding (166). Zinc is
antagonistic to Pb and the chelation therapy of Pb poisoning
that uses Ca-EDTA may lead to Zn deficiency.
Environmental and toxic effects of Pb pollution have been
reviewed (428,451). A recent EPA criteria document (492)
reviewed thoroughly the health and ecological effects, exposure
assesment, and analysis of lead, with particular emphasis on
air-borne forms. Lead(II), like Hg(II), binds strongly to
sulfhydryl groups of proteins and enzymes and interferes with
metabolic processes. It replaces Ca in the bone but can be
released under conditions of active Ca metabolism (79). At
sufficiently high concentrations, Pb has been associated with at
least 25 physiological effects (132). Clinical anemia in
children was associated with blood Pb levels greater than 40
pg/dL, central nervous system disorders at 50 pg/dL, and
encephalopathy symptoms at 80 pg/dL (492). Unlike most heavy
metals, Pb crosses the placenta and blood lead levels in newborn
children were closely correlated with those of the mothers
(492).
Although drinking water ordinarily supplies less than one-
tenth the Pb obtained from dietary sources (344), it is
important to control all inputs. Equilibrium calculations
indicate that soluble Pb should not exceed drinking water
standards in surface waters having moderate carbonate alkalinity
24
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(219). This conclusion was supported by a survey of raw
drinking water supplies (145). As delivered at the tap,
however, Pb concentrations are more variable and frequently
higher. A survey of 969 community water supplies in 1969 showed
that 14 samples, on the average, exceeded the 0.05 ppm limit for
Pb (323). A survey of Seattle and Boston, where soft, corrosive
water was supplied, showed clear evidence of Pb contributed by
the plumbing (114).
A NAS review (344) concluded that the interim standard of
0.05 ppm Pb does not provide a sufficient margin of safety,
especially for fetuses and young children. Conventional water
treatment procedures (either iron or alum coagulation, or lime
softening) were effective in removing Pb from water supplies
(491).
Zinc-
An essential trace nutrient, Zn is relatively non-toxic.
Drinking water provides a negligible fraction of the normal
dietary intake (344). The interim drinking water standard of 5
ppm is based primarily on taste preference (342). In a survey
of water as delivered to homes in Seattle, 10X exceeded the
standard, evidently because of corrosion of galvanized piping
(20). Zinc supplied in water was reported to be carcinogenic in
rats and teratogenic in rats and hamsters (302). On the other
hand, the NAS review (344) found no evidence of carcinogenicity,
mutagenicity, or teratogenicity.
The major significance of Zn, with respect to speciation,
is its interaction with other trace elements. It is clearly
antagonistic to Cd and Pb, both with respect to the toxic
effects of the latter elements (166,344,372,422) and to Cd
carcinogenicity. Cancer deaths in 28 countries were positively
correlated with estimated dietary Zn intake and also regionally,
within the United States, with blood Zn levels in healthy
subjects (411). The effect was interpreted as antagonism to Se.
Little is known about the mechanisms of nutritional interations
of elements, but it is not implausible that the chemical forms
are critical. Two general approaches may be mentioned: (1)
competition on a mass-action basis for active enzyme sites by
ions of similar charge, size, and electronic structure (515) and
(2) chemical reaction with an antagonist to produce a form that
is insoluble or otherwise unavailable (391). A study by the NAS
(343) placed highest research priority on the study of the
interactions between Zn and Cd and their relation to
cardiovascular disease.
Mercury
Since the recognition in the 1950*s in Japan and Sweden of
the extreme toxicity of methylmercury compounds and the
25
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subsequent discovery (216,505) that methylmercury is formed
biologically in significant amounts under natural conditions,
the environmental impact of Hg has been thoroughly reviewed
(137,173,267,269,369). The dialkylmercury compounds,
particularly dimethylmercury, are volatile, contributing to the
natural cycling of the element, and lipotropic, rapidly passing
through cell membranes and becoming incorporated in living
organisms. Methylmercuric ion and inorganic cations of Hg are
strongly bound to the sulfhydryl groups of proteins and this
appears to be the site of their physiological action (160).
This implies that any compound or complex of Hg with a smaller
formation constant than that of the mercury-protein bond (about
1016) (36) will be toxic. Mercury rapidly accumulates in the
aquatic food chain (137). Although mammals can excrete Hg quite
efficiently, methylmercury is stated to cause permanent brain
damage (413).
Careful studies of Hg concentrations in the Atlantic Ocean
showed great variations with depth and location (20 to 1300
ng/L) but the total amount in the sea is too great for human
activity to have had a significant influence (393). Numerous
studies in both fresh and salt water show that fish tend to
accumulate Hg in proportion to both the duration and the
intensity of exposure (316). Thus, many pelagic fish have
acquired Hg levels close to, or exceeding, the permissible limit
for human food.
A survey of 273 community water supplies for Hg showed only
12 with total Hg at or above 1 pg/L (199). There appears to be
no hazard from inorganic Hg in drinking water but, until it can
be demonstrated that effects on humans of methylmercury is
negligible, it was recommended that limits should be set as if
all Hg were in the most toxic form (3U4).
Nitrogen
The EPA interim limit of 10 ppm for nitrogen (as nitrate)
is based on the danger of methemoglobinemia to infants (342),
probably caused directly by nitrite. A survey of groundwater
supplies in rural Wisconsin (135) showed that 40X of the wells
exceeded this limit. Nitrate levels in surface waters in
Illinois were surveyed and highest concentrations were found in
areas of high agricultural production (207). Within a
watershed, highest levels occurred near the headwaters and
derived principally from inorganic fertilizers. Because so
little is known about the effect of nitrate on the general
population, this species should be monitored rather carefully.
selenium
Selenium is an essential nutrient similar to, but distinct
from. Vitamin E in its effects (416) . It is, however, also one
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of the most toxic natural elements on an atomic basis.
Approximately 0.05 ppm is needed in an individuals daily diet,
but 5 ppm is toxic (174) . The biological role of Se was
reviewed in a 1966 symposium (311) and its significance in water
supplies was thoroughly reviewed recently
Differing health effects depending on the form of the
element are particularly evident in the case of Se. In
foodstuffs, Se probably exists entirely in proteins in which Se
replaces S (460). Insoluble selenacious proteins from plants
and water-soluble inorganic Se compounds produced distinctly
different toxic symptoms in animals (304) . Elemental Se is
relatively non toxic but the oxidized forms, selenite [Se(IV) ]
and selenate [ Se (VI) ], are extremely toxic. Reports of the
relative toxicity of the latter valence states differ according
to the test animal and mode of administration. In oxygenated,
alkaline water the selenate ion is stable and soluble. In acid
waters, however, selenate is readily reduced to selenite, which
can precipitate with iron as the very insoluble basic ferric
selenite, Fe2 (OH) 4SeO3 (278), limiting the occurrence of Se in
water. An important route of elimination in mammals is by
methylation to volatile dimethyl selenide or dimethyldiselenide,
which are exhaled. These compounds, which do not appear to be
highly toxic (366), have been identified in the environment as
products of bacterial methylation (100).
Although specific animal diseases have long been associated
with a deficiency or excess of Se, there appear to be no long-
term systemic effects to humans that can be attributed to Se
(110,226). Selenium deficiency has been implicated, but
unconfirmed, in the Infant Sudden Death Syndrome; excess has
been associated with dental caries (343) .
Sodium selenite was effective in treating some infant cases
of kwashiorkor (primarily, a protein-deficiency disease) in Near
Eastern countries but the U.S. diet seems to provide
nutritionally adequate amounts of Se (226,422) . Although some
animal studies have associated Se with cancer (344) and
teratogenicity (302) , and recent epidemiological surveys found
an inverse correlation of cancer deaths with Se intake or blood
level (410), the International Agency for Research on Cancer
(237) concluded that, "the available data provide no suggestion
that selenium is carcinogenic in man, and the evidence for a
negative correlation between regional cancer death rates and
selenium is not convincing."
To properly assess the role of Se in human health there is
a critical need for improved analytical methods to determine
chemical forms and valence states (344,366) .
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SECTION 6
TRANSPORT AND TRANSFORMATIONS
The chemical elements comprising pollutants, of course, can
never be destroyed. Inorganic pollutants, much more than
organics, are subject to recycling under the influence of
natural or artificial processes. Because the harmful properties
of inorganic pollutants are often associated with a particular
element, such as a heavy metal, the chemical form in which the
element is found plays a crucial role in its distribution in the
environment and its ecological significance.
The physical and chemical mechanisms available for
controlling trace metals in water were reviewed by Leckie (283)
and were the subject on an EPA-sponsored conference (118). The
role of organic chelating agents in these processes (310) and
the effects of dissolved and suspended solids in fresh water
(453) were reviewed. Emphasis in the Sorensen et al. study of
dissolved solids was on major ions and on salinity as it affects
osmotic regulation, however, rather than on toxic effects of
trace species. In other work, Gupta and Chen (197) have
described a comprehensive analytical scheme for partitioning the
trace metals in nearshore marine sediments into seven fractions.
INTERACTION OF WATER AND SOLIDS
Leaching
The mineral content of surface and ground waters and
ultimately the sea is derived primarily from the weathering and
leaching of rocks and soils. The kinetics of dissolution of
mackinawite (FeS) were studied (365). The relation of soil
properties to the adsorption-desorption equilibria of certain
metal ions was studied (493). The roles of solubility,
complexation, and adsorption were discussed in another paper
(230) in which the kinetics and equilibria of adsorption of
metal ions were studied with respect to four homogeneous solids.
In a neutral or acid environment, adsorption was the dominant
process controlling the ionic content of the water.
Observations of the seepage of effluent water from a nuclear
reactor showed that particulate and cationic forms of the
radionuclides were strongly retained by the soil, but that
soluble nonionic and anionic forms were relatively mobile (394).
Factors affecting the mobility of major nutrient anions in soils
were identified (249).
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The role of aquatic sediments in the cycling and transport
of pollutants has been reviewed (271). Suspended sediments are
an important mode of movement of adsorbed ionic species, which
may later be remobilized by soluble complexants, change of pH,
or ionic strength (381). This leaching action led to
progressively less-contaminated sediments in the lower courses
of a delta (133). Molecular-size fractionation of organics in a
stagnating lake system suggested that metals were mobilized from
the sediments by low-molecular weight humic substances and then
transferred to colloidal particles (407). In this study, Zn was
associated with a 0 to 500 molecular weight fraction, whereas
Fe, Mn, and Mg were found chiefly in the 10,000 to 50,000
molecular weight fraction. Gel permeation chromatography was
used to study complexation equilibria of Cd(II) with organic
fractions from lake water (221). The organic coloring matter
from several lakes was monobasic, with a mean molecular weight
of about 320 (423). This material solubilized Fe increasingly
up to pH 10, principally by peptizing ferric hydroxide, although
there was some evidence of chelation. Cupric ion was relatively
more chelated that peptized.
Sanitary landfills are a potential source of ground water
pollution. Leachate from an abandoned landfill exceeded safe
levels of Fe, Cr, and Cu; Co and Ni concentrations were
borderline (107). six types of Hawaiian soils were compared for
their ability to remove pollutants from landfill leachate (105).
ion exchange was the principal mechanism for altering inorganic
concentrations. Montmorillonite was more effective than
kaolinite for removing lead from a municipal landfill leachate
(195). In a companion study, Pb, Cd, Zn, and Hg were
efficiently removed from the leachate by ion exchange on
montmorillonite clay (196).
Dredge spoils are another potential source of pollutants
through leaching, and a standard Elutriate Test is used to
assess the risk. In a study of factors in the test procedure,
only the oxygen content of the elutriate had a major effect on
the release of contaminants from the sediments (286). In the
case of some sediments that were classified as pollutants by the
Elutriate Test, only Mn was leached in significant amounts
(285). The test showed no release of Hg from a variety of
sediments that had been equilibrated with representative coastal
water concentrations of Hg (203). Dredging may release toxic
amounts of free sulfides, but there is little evidence regarding
heavy metals, which are strongly adsorbed on ferric oxides and
sulfides (442) .
Municipal sewage sludge is another potential source of
heavy metal pollution. A literature review failed to reveal any
information on the form of elements in the sludge and indicated
that the amounts of metal extracted by various procedures bore
no apparent relation to the total in the sludge (362). A study
29
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of the kinetics and equilibria of heavy metal accumulation on
activated sludge showed a relatively high capacity for Pb, Cd,
and Hg and much less for Ni and Cr (VI) (3U6) . In two sewage
sludges, Cu was more, and Cd less, readily extracted than Zn;
^^% and 37% of the extractable Cu in the respective samples was
in non-cationic forms (435) . The ocean disposal of municipal
sewage effluent has been a major contributor of metals to the
Southern California Bight (507). The metals were in particulate
form or associated with sludge particles. Disposal of sewage
sludge on strip-mine spoils, by raising the pH, may release
hazardous amounts of molybdate, which otherwise is immobilized
by adsorption on the acid spoils (275).
Complexation
The preceding section showed that complexation is one
important mechanism for removing metal ions from a solid phase
to a solution phase. This section deals with the sources and
characterization of significant organic complexants. The
interaction of organic chelators and trace metals with respect
to transport and transformation processes was reviewed by Siegel
(437) for marine aquatic systems and by Singer (439) for fresh
waters. "Humic and fulvic acids" are broad terms for classes of
organic complexants found in soils and natural waters. Their
role in controlling the availability of heavy metal ions has
been reviewed (243). Samples from the intracoastal waterway
from Charleston, SC, to Norfolk, VA, showed that the fractions
of soluble Fe, Cu, Pb, and Zn bound to humic substances were
highly variable but generally less than 5Q% (436). Benes et al.
(40) related the interaction of 18 elements with natural humic
material from a Norwegian lake to ionic charge and pH. The
chemical nature of fulvic and humic acids has been studied in
considerable detail (423).
Mercury forms very strong attachment to humic materials in
both fresh (406) and sea (469) water. In the analysis of sea
sediments for total Hg, the element was not completely released
at 500° C (267). Iron and Cu were solubilized by fresh water
humic acid primarily by peptizing the ferric hydroxide and
chelating the Cu ion (423). In seawater, also, humic acids were
effective in solubilizing Fe (373) . The complexation
equilibrium of Cu(II) with fulvic acid has been studied
(178,314). Voltammetric techniques, were used to characterize
complexes of Fe(II), Co(II), Pb(II), and cu(II) with organic
fractions from the Great Lakes (318) and to show that the Pb(Il)
fulvic acid complex is reversibly reduced at the electrode (82} .
Carbohydrates and amino acids are also naturally occurring
complexants. Metal complexation of carbohydrates was proposed
as an indicator of reducing conditions in sediments (331).
Seven free amino aqids were identified in pond water at
concentrations up to a few tenths ppm (518). The metal-
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complexing ability of sewage and sewage effluent (362) may be
related to ami no acids or carbohydrates although little has been
done by way of characterization. Two distinct molecular weight
fractions of sewage effluent were responsible for most of the
copper-complex ing capacity (38) . An equilibrium model for
sewage effluent discharged to seawater, under reducing
conditions, indicated that only Ni and Co would be appreciably
complexed by amino acids (332) .
The possible effects of synthetic complexants such as NTA
and EDTA has been considered. As little as 2 ppm NTA
solubilized Pb from some natural lake sediments (194). NTA, at
1 to 10 ppm, failed to release Cu from a lake sediment that
contained 250 ppm Cu (on a dry basis) (400) . EDTA was found in
domestic sewage effluent (British) at about 170 ppb (181). From
published stability constants, EDTA was expected to complex
trace metals to a greater extent than amino acids or humic acids
but without serious adverse effect.
Adsorption
Adsorption-desorption is an important process in the
transfer of metal ions between solid and solution phases. The
partition coefficients between river water and suspended
sediments were determined for six elements (19). Surface
analysis of river sediments indicated that Fe, Mn, Co, and Ni
were carried on suspended particles (185). A study of salt-
marsh estuaries in the southeastern United States showed that
the Fe and Mn content of the river was deposited almost
quantitatively in the estuary by settling of sediments and
flocculation of organics (501) . Increasing salinity in the
estuary displaced adsorbed Cd, Zn, and Mn, but not Hg. A survey
of Hg in the LeHave River (Nova Scotia) showed that soluble Hg
was rapidly discharged to bottom sediments downstream from the
municipal source, but the Hg associated with suspended particles
increased sharply with salinity in the estuarine zone (113).
The strong binding of Hg by marine sediments, noted above, is
probably a form of chemisorption rather than physical
adsorption. Significant differences between concentrations of
As, Cu, Hg, and Zn in surface and deep sediments from Lake
Superior were found when the analyses were based on the very
fine (less than 2 pm) fraction of the sediment (213) . Fine
particles have been noted as both source and sink for nutrients
and pollutants in the estuarine environment
The adsorption isotherms of Pb(II) (390) and of Zn(II)
(429) on soils have been measured. The equilibrium amount of
Pb(II) retained was substantially greater than the ion-exchange
capacity indicating that another mechanism was involved.
Although the data could be fit by either Freundlich or Langmuir-
type isotherms, the derived energy terms were not consistent
(452) . From the measured ion- exchange capacity of a synthetic
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clay it was estimated that 90% of the Pb in surface waters might
be adsorbed (218). It was difficult to extrapolate to natural
stream sediments. The negatively charged hydrous surfaces of
feldspar and similar minerals form active sites for the
adsorption of cations and account for the marked influence of pH
(361,367).
Aluminum, Fe, and Mn play a significant role in the
distribution and transport of trace elements because, under
appropriate conditions of pH and oxidation state (Fe(III),
Mn (IV)), ions of these elements form hydrous oxide precipitates
that have large specific surface areas and strong adsorptive
capacities. This function has been discussed in terms of
controlling conditions, particle size, and effects of organic
ligands (210,245,247,284,406). The transformation of hydrous
aluminum (450) and ferric oxyhydroxide (282) precipitates to an
equilibrium crystalline mineral phase is extremely slow. Iron-
59 was a useful radio-tracer for following suspended sediments
in rivers (405). The precipitation of A13+ (229) and Fe3+
(165,257) with phosphate has been studied. Three forms of P in
surface sediments in Lake Erie sediments were identified: (1)
natural mineral apatite, (2) organic P, and (3) inorganic P
associated with amorphous hydrated ferric oxide (497). As
examples of the influence of these solid phases, the elementary
analysis of plankton from widely separated ocean areas suggested
that trace metals were transported by adsorption on fine (< 0.2
pm), Fe-rich particles trapped by the plankton (488). The As
content of the sediments of Lake Washington (WA) was strongly
correlated with Fe and Mn (115), as was the phosphate cycle in
Wisconsin lakes (33). The seasonal variation in the soluble and
particulate Fe transport to Lake Tahoe (NV) was recorded (152).
Organic particulates also sorb and transport, or
immobilize, metal ions. There probably is no clear distinction
in this case between chemisorption on the particulates and
complexation of the metals with surface ligands. This process
has been related to organic sediments in a stagnating lake
(407), to the association of Hg with suspended solids in sewage
treatment effluent (261), and to adsorption on bacterial cell
floes as a means of removing trace metals (143). The release of
trace metals on dilution of sewage sludge with seawater was
studied experimentally (395). Under aerobic conditions Cd, Cu,
Ni, Pb, and Zn were released to the greatest extent through
processes of oxidation, desorption, and complexation.
A study of the adsorption of Cu(II), Zn(II), Pb(II) , and
Cd (II) on four synthetic solids chosen to represent various soil
types concluded that adsorption is the most important process in
the soil-water system of a neutral or acid environment (230).
Similarly, Stumm and Bilinski (470) concluded, for natural
systems, that the dominant fraction of metal ions is associated
with particulate and colloidal material and that the strong
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effect of pH on adsorption results from its effect on
speciation. The variation with pH of adsorption of Cd, Cu, Pb,
and Zn on clays indicated that the least soluble species were
cationic hydroxy complexes, rather than the neutral hydroxides
(158). Organic ligands affected the hydrolytic equilibria but
did not necessarily reduce adsorption. The sorption and release
of trace metals from fly ash was investigated (480). The
alkalinity of the fly ash was related to its Fe/Ca ratio. The
movement of trace metals across the interface between seawater
and sediments has been discussed as a function of oxidizing or
reducing conditions (300).
Adsorption processes have been proposed for the removal of
metal ions in waste treatment. The addition of organic ligands
improved the surface potential for adsorption on carbon of
Cd(II) (231). Conversely, Fe coagulation improved the
adsorption of some organic complexants on carbon (495), and
Ca (II) improved the adsorption of viruses on sand, probably by
charge neutralization (244) .
BIOGEDCHEMICAL CYCLING
Mercury
The natural cycle of Hg, which has been studied more
extensively than that of any other heavy metal, has been
discussed in several reviews (137,157,183,267,469). The
principal features are indicated in Figure 3, which is derived
from many sources. The element and its compounds are relatively
volatile and a major release from the earth to oceans (393) and
atmosphere (267,269) is by evaporation and volcanic activity.
The major mercuric minerals are forms of HgS, which is extremely
insoluble and refractory. Weathering and erosion make the
mineral available to soil bacteria (137,173), which can
metabolize HgS to elemental Hg (5) or to organo-derivatives
(5,108,138). Dimethyl mercury is very volatile and escapes
directly from the soil or sediment. Methylmercuric ion, like
the simple mercuric ion, is strongly complexed to thiol groups
of protein-derived organics and undergoes exchange between
soluble and particulate complexes (36), indicated as MRHg-
Organic" in the figure. These ions and the elemental Hg also
experience strong physical adsorption to mineral particulates
("Partic." in the figure), and fallout with dust is a major
mechanism for the removal of Hg from the atmosphere (267). In
the aqueous phase, mercuric ion is the stable species under
usual conditions, and elemental Hg is oxidized (215). The
mercuric ion (represented as Hg(II)) is largely complexed with
inorganic ligands in aqueous solution (17,215). Bacteria and
other aquatic biota transform mercuric ion to the elemental form
(109,383) or to methylated species (108). Mercurous ion may be
an intermediate in several of these processes but it does not
seem to be a persistent or abundant, entity. Although industrial
33
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AIR
WAT ER
SOIL
Figure 3. Cycle of Mercury in the Environment.
(R represents the methyl group, primarily.)
34
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activity has created severe local disturbances in the cycle, it
has been completely insignificant on the global scale (267).
The possibility of biomethylation of elements other than
mercury was considered (404,504): As, Se, Te, and s were the
most probable candidates (see further below).
Iron
As has been indicated, the chief ecological significance of
Fe is in the formation of colloidal or fine amorphous particles
that have great adsorptive capacity for trace elements. In a
Lake Erie study (85), about 95% of the Fe was bound to inorganic
particles and was in equilibrium with the water; very little
Fe (II) appeared to be released from the lake bottom. The
particle size and aggregation of Fe with organics was a function
of circulation in a lake (3). The chemical mechanism of ion
adsorption on freshly formed ferric hydroxide precipitates is
poorly understood (472). The solubility of Fe species is
strongly dependent on pH, redox potential, and complexation
(217). Fe(III)-OH precipitates are very insoluble and only
slowly are transformed to stable crystalline forms (282). Over
a wide pH range, Fe(II) also forms basic phosphate precipitates
of indefinite stoichiometry (257). The solubility of Fe(II) in
hydroxyl-carbonate systems was redetermined because of errors in
classical thermodynamic data (440). Many organic compounds were
strongly complexed to Fe(II) and inhibited its oxidation
although oxygen was taken up by the system (479). Similarly,
the Fe(II)-Fe(III) couple was effective in oxidizing organic
matter, which was oxidized completely before the Fe(II) (248).
Iron is also an essential nutrient for phytoplankton and
apparently must be in a soluble, organo-complexed form to be
nutritionally available (290). The addition of EDTA was
effective in stabilizing the soluble Fe(II) content of seawater
against loss by adsorption on the walls of the container (291),
and natural complexation was proposed to control the adsorption
equilibrium in seawater. On the other hand, most Fe(II) was
present as uncomplexed Fe2* in anoxic bogwater (224).
Like Fe, Mn is significant for forming fine precipitates
that carry trace materials by adsorption. In oxygenated waters,
only negligible amounts of dissolved Mn are expected because of
the low solubility of Mn(IV) oxides. Nevertheless, Mn(II) was
reported in Kansas streams in approximate solubility equilibrium
with the divalent hydroxide or carbonate (18). In anoxic
sediments, Mn is resolubilized by reduction more readily than Fe
(136). Lake Erie sediments released Mn(II), which remained in
solution at less than 50% oxygen saturation (85). The reduction
process may be biological (378) or may represent direct reaction
with organic matter (236). Organic complexation may be a factor
35
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in solubilization (378) . in Arctic lakes,, Mn was largely
associated with organic ligands (32).
Selenium
The natural cycle of Se has been reviewed by Lakin (277).
Volcanic action releases Se principally in the atomic form,
which is oxidized to SeO2. Either elemental Se or selenite is
stable in water, depending on pH and oxidation potential. It is
precipitated principally as the very insoluble basic ferric
selenite. Biological methylation of Se in bottom sediments
yields at least three volatile compounds: (CH3)2Se, (CH3) 2Se2,
and one of unidentified composition (100). Bacterial ozidation
of CuSe to Se<> has been identified (485) .
Arsenic
The As cycle in natural waters was reviewed in broad terms
(161) and studied locally in Lake Washington (WA) (115). In
that location, the sediment levels of As were correlated with
the operation of a nearby copper smelter. The input to the lake
was approximately equally divided between atmospheric and
surface water sources. Two-thirds of the input was in the
arsenate form but 55% of the As in the sediment was arsenite,
with a few percent as dimethylarsinic acid. Arsenic was carried
to the sediments by association with Fe and Mn precipitates.
The methylation of As has also been observed in Florida soils
and surface waters (63). The chemical pathways for
biomethylation of As have been reported (111,322,504).
DISTRIBUTION OF ELEMENTS AND SPECIES
Closely related to the determination of the cycle of forms
of an element through the environment is the distribution of all
chemical species within any body of water. The principles
controlling the equilibria and kinetics of chemical and
biological transformations have been the subject of books (471),
chapters (283,334,470), and journal articles (39,398). The
sources, distribution, and effects of trace elements in the
aquatic environment were also the subject of a recent literature
review (287). In the following sections, chemical
characteristics are considered for major types of natural water
bodies.
Rivers and streams
Moving, fresh waters generally have relatively low
dissolved mineral content and moderate to high oxidation
potential. A major transport agent is suspended sediment,
either mineral or organic, which can carry trace elements by
adsorption or complexation.
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A nation-wide survey of surface waters serving municipal
supplies showed many instances of soluble heavy metal content
exceeding drinking water standards (265) . Although soluble Zn
frequently, and Cd occasionally, exceeded the standard, these
ions were generally well below the equilibrium solubility limits
for the stable solid phases (216) . On the other hand, Pb
concentrations, which rarely exceeded drinking water limits,
were close to the calculated solubility saturation in many
samples (219) . The percentage of total soluble elements in
Susquehanna River (NY) water that was exchangeable on Ca-Chelex
100 resin decreased in the order Cd > Pb > Zn > Cu (163) .
Similarly, anionic and cationic exchange properties of elements
in the Cape Fear basin (NC) were studied (430) . As expected,
Cr(VI) was almost completely anionic, but Cr(III) was mostly
particulate, with 37 to 49% distributed among anionic, cationic,
and soluble non-ionic forms.
River sediments are less contaminated with heavy metals
toward the mouth because of leaching or resuspension by organic
complexants (133). As a corollary, mountain streams high in
humic substances may have a high content of soluble metals
(494,498) . The upper reaches of the Susquehanna River, in fact,
had an unusually high fraction of soluble metals, although the
total loading was low, and the organic ligands were 94%
saturated with metals (150). The decrease in soluble metals
toward the mouth of the Cape Fear River was not accounted for by
dilution, but probably by chemical precipitation (430) . In
organic-rich river waters of Puerto Rico, only 44% of Cu and 75%
of Zn was organically complexed, probably because of competition
with Ca(II) (330). Calculation of the speciation of 2 ppm total
Cu in natural fresh water indicated very low levels for the free
ion (473) .
Heavy metal levels of Ottawa and Rideau River (Ontario)
sediments were correlated with surface area, suggesting an
adsorption mechanism, but the correlation was poor for Pb and
invalid for Hg (352) . Streams receiving mine drainage may have
high levels of dissolved metals because of the high acidity
resulting from the oxidation and hydrolysis of Fe(II) (380) .
lS§§ and Impoundments
The low flow velocity in lakes permits deposition of much
of the entering suspended solids. The sediment of an eutrophic
lake was a sink for Hg, Cd, Pb, and Tl (316) . The
solubilization of metals from the bottom sediments may be
mediated by organic complexation or by the usual large vertical
gradient of oxidation potential. Depending on depth and
latitude these bodies are subject to seasonal mixing or overturn
as a result of varying surface temperatures. Copper and Mn in
the Denver water supply were related to the overturn of the
reservoir (28) .
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A solubility equilibrium model for the Great Lakes (268)
indicated that the cold waters contained excess CO2 and were
unsaturated with respect to calcite, dolomite, and apatite,
although the warm waters were supersaturated with these
minerals. Another model for Cu, Ni, and Zn in Lake Michigan
(499) concluded that concentrations of Zn could be accounted for
by natural sources, whereas Cu and Ni were largely derived from
man-made pollution. A model was derived for the transport of
Zn, Pb, and Cd and their deposition in the sediments of a
reservoir (376). The transport of heavy metal cations in both
surface and groundwater was studied in the Perch Lake basin
northwest of Ottawa (29). The roles of Mn (136,378) and of Fe
(33) in the composition of lake sediments have been studied.
The cycling of Fe and Mn in Lake Erie (85) , of As in Lake
Washington (115), and of Mo in the Dillon Reservoir (CO) (68)
have been discussed.
The organic complexation of Cu, Pb, and Cd has been studied
in the Great Lakes (318). The speciation of 18 metals with 8
cations and 4 organic ligands was computed for the
concentrations found in Lake Superior (188). Seasonal
variations in the ionic Cu concentrations in a pond were related
to organic complexants (259) . The speciation of Cu("II) in Torch
Lake (MI), notoriously polluted by mining operations, was
investigated to account for the tolerance of algae and fish to
unusually high concentrations of soluble Cu (297). The
interaction of metals and organics has been investigated in
stagnating lakes and bogs of the Temperate Zone (224,377,407)
and in the Arctic region (31,32).
Estuaries and Bays
The large gradient of ionic strength as fresh waters merge
with the sea leads to flocculation of much of the organic burden
and precipitation of the heavy metals complexed or adsorbed
thereon (501). Some metals may be redissolved as chloride
complexes. The high organic content of bottom sediments and
poor circulation of water frequently leads to anoxic conditions
at the bottom of lagoons, with the biological production of
sulfide, which ties up heavy metals (484). In the New Bedford
(MA) harbor, Cu was associated with the very fine top sediment
(< 2 pm) and decreased in concentration exponentially from the
industrial source to the sea (464) . Selective leaching showed
that Cr was associated with a different sediment fraction than
Cu or Zn. The diurnal cycling between oxidizing and reducing
conditions on tidal flats has induced marked cycling of S and Fe
(37) . Salt marshes appear very effective at removing heavy
metal pollutants, at least until their capacity is exceeded
(434,500) . Metals whose distribution and chemistry in the
coastal environment have been studied include Hg
(113,134,500,501), Pb (134,434,484), Cd (501), Cu (134,484), Zn
(61,239), and Mn (193,484). The fate of trace elements was
38
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reviewed (159) and the requirements of a comprehensive model
were summarized (503). A surface complexation-adsorption model
successfully accounted for the removal of trace metals from the
aqueous phase in the Delaware Estuary (472).
Oceans
The outstanding feature of seawater is the remarkably
constant elemental composition in all oceans. This implies a
mixing time, (somewhat less than 1000 years (58)) appreciably
shorter than the times of major geological processes that
determine the ocean1s composition. Much effort has been given
to developing models to account for the composition of the sea
because these would shed light on the geological history of the
planet. Sillen (438) concluded from an equilibrium model that
the pH of the ocean, and hence its CO2 solubility, is determined
by the formation of silicate minerals. A comparison of
equilibrium solubility data for oxide and carbonate minerals in
seawater with sedimentation rates indicates that the sea is more
accurately represented by a steady-state model, rather than an
equilibrium model (408). Given the elemental composition of the
oceans, equilibrium species of the minor elements have been
calculated (146,189).
Refined analytical techniques have revealed significant
variations in concentrations of trace elements with depth and
location (393) and more attention is being given to the
determination of species. Copper in surface waters exists
chiefly as soluble organic complexes (7,347) although CuCO3 is
the major soluble inorganic form (389) and the deep waters
apparently have a relatively high concentration of free Cu2+
(347). Similarly, soluble, inorganic Zn in surface waters is
present chiefly as ZnCO3 or Zn(OH)2 (510,514).
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SECTION 7
ANALYTICAL METHODOLOGY
Ideally, analytical methods for inorganic species in water
should determine all the distinguishable forms without altering
the composition of the sample in the process of measurement.
This, clearly, is an extremely difficult goal because, for many
elements of interest, the total amount is at trace levels and
because many of the species of interest exist in labile
equilibrium that is subject to shifting with almost any
manipulation of the sample. Studies of the effects of
speciation have been based on analytical methods that were far
short of the "ideal". In fact, "species" are defined
operationally by the methods used to determine them, which may
be no more sophisticated than a distinction between "soluble"
and "insoluble" or "other" forms of an element.
Approaches to the solution of the analytical problem fall
into three categories, dicussed in the following sections:
• Calculation of thermodynamic equilibria. In this case,
the species are defined independently but their
concentrations in a real sample can only be inferred.
• Direct measurement of a physical or chemical property
associated with some portion of the total element in a
sample.
• Separation of the sample into fractions by physical or
chemical means, followed by total elemental analysis of
the fractions.
The problems, pitfalls, and special considerations involved
in the analysis of environmental water samples have been
reviewed (65,165,393), both with respect to trace concentrations
of elements and to particular species.
A recent review (34) deals with the sampling, preservation,
and concentration of environmental waters; another (144) is
concerned with the determination of trace concentrations of
elements and species in microsamples (< 1 jig) . Thorough and
recent literature reviews of analytical methods (167,431) deal
principally with "total element" methods but include direct
techniques for species. Florence and Batley (171) reviewed
40
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analytical methods for the forms of Cu, Pb, Cd, and Zn in
natural waters and proposed a speciation scheme.
EQUILIBRIUM CALCULATIONS
Thermodynamic methods, combined with equilibrium data for
such processes as solubility, complexation, or chemical
reaction, enable the calculation of the phases and species that
can coexist in equilibrium under specified restraints of
temperature, pressure, total concentration, etc. The
application of these techniques to environmental waters is
described in detail in such texts as that of Stumm and Morgan
(471) and the review by Kemp (256). Procedures for the
determination of stability constants have also been reviewed
(399). Because equilibrium constants are necessarily
experimentally derived, the methods, in effect, are a means of
extrapolating from laboratory conditions, in which the species
can be accurately identified and measured, to assumed field
conditions. The methods also permit the use of measurable
parameters of the field sample (temperature, pH, dissolved
oxygen, total elemental composition) to estimate the difficult-
to-measure species that can be present. The use of evaluated
thermodynamic data to calculate ionic equilibrium constants was
emphasized (461).
Mathematical models are useful only to the extent that they
successfully predict conditions in the real world. The
assumption of equilibrium is most often the major limitation of
thermodynamic models. More sophisticated calculations take into
account the rate at which key processes in the model proceed,
but suffer from a dearth of reliable kinetic data. All models
are simplifications, neglecting factors that are unknown or
assumed to be negligible, consequently, their validity must be
checked independently.
Among the environmental applications of thermodynamic
models, the U.S. Geological Survey papers on solubility
relationships are noteworthy. These include data for Hg (215),
Pb (219), Cd and Zn (216), Al (214), and Fe and Mn (217).
Hydrolytic equilibria of metal ions were reviewed
comprehensively by Baes and Mesmer (22). The inorganic and
metal-organic species in Lake superior were calculated for 18
metals and 12 ligands (188). The chemical speciation of Cu has
been calculated for a great variety of conditions and compared
to analytical determinations (22,313,389,473,513). The
speciation of elements in seawater has been calculated from
thermodynamic models (146,189,198). The significance of
kinetics in precipitation reactions has been treated (408,489)
and the problems in modeling complexation reactions were
discussed (151). The chemisorption of cations on ferric
hydroxide precipitates was successfully modeled (472). It has
been suggested (54) that calculation of metal-cyanide equilibria
41
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is the only way to estimate the species composition without
disturbing the equilibrium.
DIRECT SPECIES DETERMINATION
Electrochemical Methods
Potentiometry-
Measurement with ion-selective electrodes (ISE) is the only
practical potentiometric technique. The familiar and extremely
useful measurement of pH is included but ions other than
hydrogen are of more interest here. ISE measurement methods all
have the outstanding advantage of providing a rapid, fairly
direct, in situ measurement of a free ionic species without
altering the sample appreciably. They can also be used as
indicators in potentiometric titrations, in which case the
sample is changed. The term "free ion" may need some
definition. There is reason to believe that no bare, atomic
cation exists in water, all being solvated more or less strongly
with water molecules and possibly complexed with hydroxyl or
other very labile ligands. Nevertheless, there is no evidence
that any ionic species that gives an ISE response behaves
otherwise than as a "free" ion in biochemical or geochemical
processes. Some disadvantages and limitations are common to all
ISE methods:
• A properly functioning, reversible reference electrode
is needed. The potential difference is measured
between this electrode and the ISE.
• The measured potential is a function of the
thermodynamic activity of one or more substances
involved in the electrochemical cell reaction. To
relate the measurement to the activity of one ionic
species requires an extra-thermodynamic convention that
cannot be applied to calibration and measurement in
real systems without invoking assumptions or
appro ximati on s.
• To relate ionic activity to concentration requires
knowledge or control of the ionic strength of the
solution, information that may be difficult to obtain
in polluted or brackish water.
• The logarithmic response of an ISE to ionic activity
gives it an approximately constant relative error. At
higher concentrations, this tends to put ISE techniques
at a disadvantage with respect to other analytical
methods that have a nearly constant absolute error.
• All ISEs are more or less subject to interference from
other ions.
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• Only a few commercial ISEs have detection limits below
one part per million.
Applications of ISEs in environmental research have been
reviewed (279,312,392), as have more general applications
(266,356).
As endpoint indicators in potentiometric titrations, ISEs
have been used to determine ionization and stability constants
for use in equilibrium models. For example, the dissociation
constants of carbonic (327) and boric acids in seawater were
measured (206) and the speciation of Fe in seawater was studied
(87). The Fe(II) ISE was used to determine the stability
constant of FeHCO3+ (440). Attempts to measure complexation
constants and hydrolytic equilibria of methylmercury were
inconclusive (280,281)* Considerable structural information
about fulvic acid was obtained from potentiometric titration
(177).
The direct potentiometric measurement of ion activity has
been studied more extensively for Cu(II) than for any cation
other than H+. Conventional ISE techniques are suitable for
free Cu2* measurement at greater than about 50 ppb (446,463),
but special precautions are needed to obtain reliable
measurements at 10 ppb (447). These include polishing the
electrode surface (50), removing adsorbed Cu ions with acid (50)
or EDTA (12), using an antioxidant (12,447), avoiding light
(12,447), and providing steady flow rate past the electrode
(50,386). Reproducible measurements of 2 ppb Cu2* in seawater
were made with a non-Nernstian response (387). In this study
the electrode was leached with seawater until CuS was removed
from the surface of the electrode, which approached a Ag2S
electrode in response and gave mixed potentials to copper.
Laboratory measurements of Cu2* were extended to about 0.05 ppb
by following the rate of change of potential of an electrode
that had been carefully preconditioned (50). The response to
Cu2* of the chalcocite crystal was compared to that of the
synthetic sensing membrane (233) , and various commercial
electrodes were compared in buffered Cu(II) solutions (204).
Studies with the copper ISE have been used to determine the
toxicity of Cu2* to algae (445), to demonstrate that the free
ion is the species toxic to daphnia and minnows (13), to relate
Cu toxicity to salmon to humic acid levels (516), and to monitor
the Cu2* species in continuous-flow fish bioassay tests (313).
In a complete analytical scheme for the speciation of Cu
(462,463), the Cu ISE was used for the free ion. Direct
determination of Cu2* in seawater by ISE was considered more
reliable than extraction of the Cu diethyldithiocarbamate
complex (252). The Cu ISE was used for the indirect
determination of Fe(III) (176) and in the chelometric titration
of metals (355).
43
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Other ISE techniques that have been evaluated for
environmental use include the CN electrode (350,409) , which gave
a Nernstian response to greater than 0.25 ppm CN-. The nitrate
electrode was subject to some interferences that could not be
compensated (311). In another study, NO3- was determined by ISE
with an error of less than 2 ppm (334). The nitrate electrode
was applied successfully to sewage treatment effluents and
nitrification plant process streams (509). The Ca electrode was
used to measure adsorption of Ca2* on hydrous iron oxide (363);
phenolic compounds interfered. Measurements of Cd in soil
extracts by ISE and by atomic absorption spectrometry (AA) were
in close agreement for more than 50 ppb Cd (241). The
determination of Na and K in alpine streams was considered more
reliable by ISE than by AA because the electrodes did not
respond to suspended solids (386) . The complexation of Cu and
Pb with humic and fulvic acids in natural waters was studied
using ISEs (81).
Gas-sensing electrodes are discussed under Physical
Separations, because the distinctive feature is a semi-permeable
membrane that selectively passes gaseous species. The
potentiometric response then derives from ionic species in the
electrolyte filling solution.
Voltammetry-
Voltammetry refers to the measurement of current in an
electrochemical cell under controlled potential, and the
technique includes variations of polarography. Because of the
finite current, determined by the extent of faradaic reaction,
the cell is not at equilibrium, the concentration at the
electrode surface is usually not the same as in the bulk of the
sample, and the measured current often includes non-faradaic
components. Nevertheless, the procedures can yield useful
analytical data on species without altering the sample
significantly. Newer techniques such as pulse or square-wave
polarography substantially eliminate non-faradaic current
components so that the measurement is directly related to a
concentration of electroactive species. Under the usual
diffusion-limited conditions the maximum current is proportional
to the bulk concentration of the diffusing species that controls
the electrochemical reaction. These species are usually "free"
ions or labile complexes. The term "free" is used in the same
sense as with ISE. Complexes are designated "labile" or "non-
labile" qualitatively depending on whether they dissociate
rapidly enough to provide an equilibrium concentration of free
ions at the electrode surface during the period of measurement,
which may vary in the range of milliseconds to minutes.
Complexes can also be distinguished as "strong" or "weak"
depending on their stability constants. The smaller the
proportion of free reducible cations in equilibrium with the
complex, the more negative will be the potential at which the
reduction current reaches its maximum, or diffusion-limited,
44
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value, in accord with the Nernst relation. A scheme has been
proposed (359) to distinguish, at least qualitatively, among
free ions, strong and weak, labile and non-labile complexes
using current and potential measurements and titration with free
ions or ligands. A comprehensive scheme for the speciation of
trace metals in fresh water uses anodic stripping voltanunetry
(ASV) in combination with ion exchange and ultraviolet
destruction of organic ligands (170).
Despite the somewhat qualitative and subjective
interpretation of voltammetric data for complexes, the
techniques are extremely valuable for the determination of free
or labile forms because of a considerable degree of specificity
and high sensitivity. Linear sweep voltammetry (LSV) is a rapid
procedure with a detection limit of about 10~7 M (305).
Differential pulse polarography (DPP) has a detection limit of
about 10~8 M, whereas ASV, which involves electrochemical
preconcentration, can determine 10~9 M or less (9) , especially
in combination with LSV or DPP. Among the variations and newer
techniques that may prove advantageous are programmable
voltammetry (320), automated pulsed current voltammetry (220),
and semi-differential electroanalysis (120,191). Controlled-
potential deposition on graphite was used to separate ionic
species; the total metal deposited was then determined by X-ray
fluorescence (56) or by atomic absorption spectroscopy (35) .
The ASV technique, using thin mercury films supported on
solid electrodes, is favored for trace analysis because of its
great analytical sensitivity, but is has limitations. The
procedure is essentially limited to the ions of metals that form
amalgams, with a few exceptions (26,319). It is also subject to
intermetallic interferences (182). The significance of these
effects in the analysis of seawater has been studied in
considerable detail (64,417). All voltammetric methods at
mercury electrodes are subject to more or less interference
because of the adsorption of ligands or surface active materials
on the electrode, and this effect seems especially severe with
ASV (26,155,318). The specific interference of a wide variety
of natural and model organic compounds has been reported (66) .
Adsorption effects have been turned to advantage, however, by
using the capacitive current to study the adsorption of fulvic
acid and its interaction with Pb (82). This application was
more a research tool than a practical analytical method for
environmental samples, however. Organics strongly adsorbed on
pyrolytic carbon electrodes were determined directly by DPP
(72). Fast Fourier Transform of faradaic admittance was
suggested as a method for monitoring ASV techniques for abnormal
quasi-reversibility or surfactant interferences (415). ASV and
direct DPP measurements were combined to demonstrate that
adsorption was not a serious interference in measurements of
carbonate and glycine complexation (8,155). Studies of the
competition of Ca and Cu for the ligands NTA and EDTA by DPP
45
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indicated that concentrations of complexes were not uniform
throughout the cell (466) . ASV analysis of very thin layers of
solution eliminated the need for stirring and deaeration and
used small samples (131) .
A significant application of voltammetric methods is in the
determination of stability constants for use in equilibrium
models. These measurements can be made under controlled
conditions that avoid interferences. The competitive
interactions between trace metals and alkaline earths for
ligands was studied (358). The stability constants of Pb, Cu,
Cd, and Zn with hydroxyl and carbonate (47), and of Zn (OH) 2 (60)
were determined. The complexation of Cd with EDTA in seawater
was studied (308) and ASV was used to monitor Cu species in a
flow bioassay system (313). In natural water samples, several
workers have distinguished between free and labile ions, on one
hand, and the total elemental forms by adjustment of pH
(9,98,511,512).
The role of electroanalytical techniques for trace element
speciation was discussed in general terms (96), and the
speciation of Cu (349) and Zn (514) in seawater were studied. A
polarographic method for distinguishing Fe(II) and Fe(III) in
mine water was developed (476) as were conditions for the direct
determination of CH3Hg+ in water (212). Se(IV) was determined
at 4 ppb after ion-exchange separation (16) . Organic As
compounds were determined by DPP (45) and NO3- was determined by
polarographic reduction at a Cu-Cd thin-film electrode (55) .
The organic complexation of Cu, Pb, and Cd in Great Lakes
samples was reported (318). The organic complexing capacity of
natural waters and effluents has been determined by titration
with Cu(II) by using ASV as the analytical method
(38,97,99,106,433,449). Co(III) was preferred as a titrant
because it formed, with most ligands, stabile complexes that did
not interfere in the subsequent determination of excess metal
(200). An analytical procedure for trace levels of CN- in
natural waters and sewage was based on complexation with Cu and
polarographic determination of the excess (27). Coulometric
determinations of dissolved oxygen (262) and residual chlorine
(315) have been applied to environmental samples.
Spectrometric Methods
Many ions can be determined quite specifically and
sensitively by forming colored complexes with organic reagents.
The color-forming reaction may disturb labile equilibria in the
sample, however, and some care is needed to relate the
measurement to the species in the sample. Errors in the
diethyldithiocarbamate determination of Cu in natural waters
were discussed (252). Colorimetric methods were listed in a
review paper on the determination of anions in water (279). An
automated colorimetric procedure for CN species (molecular HCN,
free CN-, and weak complexes) was developed (255). A
46
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colorimetric determination of Cu (CN) 2 was included in a complete
analytical scheme for Cu speciation (463) , and a spectrometric
method has been published (396) for trace levels of Fe(II) in
fresh and saline water. lonization constants of NH4 + , H2S, HCN,
HSCN, phenol, and several mercaptans were determined
spectrophotometrically (487) .
Laser Raman spectroscopy is a direct, but not highly
sensitive, method for1 characterizing several ions in water.
Detection limits of 25, 50, 50, and 100 ppm were found,
respectively, for nitrate, phosphate, sulfate, and carbonate
(24) .
Biological Methods
The effects of inorganic species on biological systems were
discussed in Section 4. Many of these effects, especially with
enzymes, form the basis of very sensitive and specific
analytical schemes, which have been reviewed (486) . A
bibliography on biological indicators of environmental quality
gives additional applications (482). Immobilized nitrate
reductase formed the basis of a sensitive continuous flow method
for NO3— by providing very specific reduction of that species
(421) and an automated continuous monitor for anti-
cholinesterase agents showed a specific response to 10 ppm of
(190).
Living organisms provide sensitive indications of
pollutants but are generally less specific than enzymes. The
role of bioassays has been reviewed (338) . Bacteria were used
to monitor a group of heavy metals at 2 to 3 ppm in industrial
effluent (59) and the response of algae to copper was used to
titrate organic chelators in seawater to 10-7 M (122,123).
Other Methods
The composition of particles and solid surfaces can be
resolved by various electron and X-ray methods. High resolution
X-ray spectrometry can distinguish valence states of some
elements and was used to determine the ratio of 32- to SO42~ in
air parti culates (187) . Electron spectroscopy is the only
technique that can give the oxidation state of surface elements
at the ultra-trace level (144) . Scanning electron microscopy in
the x-ray imaging mode, combined with X-ray diffraction, showed
that cadmium in contaminated marsh sediments was associated with
calcium in mixed carbonate crystals (234) . Photoelectron
spectroscopy showed the distribution of cobalt species adsorbed
on alumina (478) .
Electron spin resonance identified Mn(Il) species in water
at 10~* M and indicated that manganese was approximately in
solubility equilibrium with Mn(OH)2, but far from oxidation-
reduction equilibrium (18) .
47
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Nitrite ion was determined by enthalpimetry of its reaction
with sulfamic acid (205) . The procedure required only a small
sample (2 ml) , had a detection limit about 70 ppb, and was free
of interferences.
Kinetic and catalytic reactions are capable of great
sensitivity and considerable specificity but seem to have been
little applied to environmental analysis (65).
Chemiluminescence methods can determine Cu(II), Co (II) , Ni(II),
Cr(III), Fe(II), or Mn(II) at 10~« to 10-i» M (419). The
technique found Cr(III) at 1 to 10 ppb in natural waters (420)
and was used to determine total Fe (reduced to Fe(II) for
analysis) in a variety of samples (418).
Isotope- and radio-tracer techniques are useful for
following the distribution of an element among phases, or
species because minute amounts of the tracer can be positively
identified by atomic mass or radiation. The technique has been
recommended for studying the speciation of trace levels of Cd
(379) and for following silt in rivers and reservoirs (405).
The technique was used to check the efficiency of dialytic
separations (30) and to show that Hg-humic complexes exchanged
with fresh Hg(II) but not with other ions (469). There was
negligible exchange between CH3Hg+ and Hg2+ in river water
(272). Radio tracer methods have shown that marine systems
slowly attain equilibrium with sediments (116) or with EDTA
(175). Several workers have reported that radio-Zn was not
distributed in biological species in the same manner as the
stable isotope (43,78), possibly because the radio-isotope was
not applied in the same chemical form as the natural element
(299).
SEPARATION TECHNIQUES
Physical
Many speciation studies are restricted to a distinction
between soluble or filtrable form, as determined by passage
through a 0.45-jim membrane, versus total element
(38,124,290,424). Some efforts have been made to define the
size of very fine particles more closely—in the case of
colloidal ferric hydroxide, by filtration through 0.2- and 0.1-
pm membrane (423), or 0.05 pm membranes (87). Pores nominally
0.025 fjm in diameter passed some forms of Pb less toxic than
free Pb2 + (126). Molecular sieves (318) or gel permeation
chromatography (221,318,377) have been used to fractionate
organic complexes or ligands into molecular weight classes.
Natural complexes of Co, Cu, Mn, and Zn did not pass through a
dialysis membrane (30). Dialyzed inorganic solutions of Pb and
Cd had the same total elemental composition as the original
preparation, which was greater than the ionic form shown by DPP
and also greater than the theoretical solubility limit (126).
48
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Dialysis and centrifugation were used in another study of the
hydrolytic speciation of Cd in dilute solutions (41) .
The determination of unionized dissolved species in water,
particularly gases, is needed because of their effects on
aquatic life. Elemental S was determined by adsorption on XAD-2
resin, elution and concentration into cyclohexane, followed by
gas chromatography (388). Two basic techniques have been used
to remove molecular gases from solution for analysis. Sparging
the sample with an inert gas is a direct method that works well
for those gases having favorable distribution coefficients.
When the molecular species is in equilibrium with ionic forms,
it is important to remove only a small fraction of the dissolved
gas to avoid displacing the equilibrium and this requirement
limits the sensitivity. Accurate analytical procedures were
developed for HCN (69) and for H2S (71). Conflicting reports
were given as to whether spargeable H2S in sewage effluents was
in equilibrium with sulfide ion, determined by the methylene
blue colorimetric procedure (71,225).
The other major technique used to sample dissolved gases is
diffusion across an air gap or through a semipermeable membrane.
This procedure has been widely applied because it is rapid and
removes only a small amount of gas for analysis. Oxygen,
nitrogen, and carbon dioxide were sampled through a silastic
membrane and determined by gas chromatography (264). The major
application, however, is in gas-sensing electrodes in which the
diffused gas establishes an ionic equilibrium in the absorbing
electrolyte and is sensed by an appropriate ISE and reference
electrode. The principles and construction of these devices
have been described (169,397) and methods of calculating
theoretical detection limits were given (23). Probes for CO2
(432), NH3 (351,481), and H2S (225) were evaluated. The design
of probes for SO2, HCN, NO2, and C12 were given (397). The
semipermeable membrane approach was used to sample HCN for
colorimetric determination with a Technicon Autoanalyzer (154),
and for sampling dissolved 02 for coulometric determination
(262).
Chemical
Chemical separations, even more than physical, entail the
risk of disturbing the distribution of species unless the
separation process is much faster than the competing
transformations. Solvent extraction of organic complexes, such
as the diethyldithiocarbamate complex of Cu (259), is a familiar
technique for concentrating trace elements for subsequent
photometric or AAS determination. Concentration techniques,
including solvent extraction, have been thoroughly reviewed
(153). Although these methods are intended primarily for total
trace elements, some may be adaptable to ionic species. stable
natural complexes of Hg were separated by solvent extraction
49
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(267). Extraction of sewage sludge with acetic acid gave a
measure of available metals somewhat different than the total
elemental analysis (44). selective acid leaching of sediments
gave an indication of adsorbed elements distinct from the
substrate mineral (309). Extraction and leaching techniques
were developed to partition the trace metals in sediments into
characteristic groups (3,197).
Ion exchange chromatography permits the separation of ionic
species or complexes (25,40,467). A fairly general procedure
has been developed for the chromatography of the ions of strong
electrolytes (443). Mercury species (25) and Ca and Mg (21)
were separated and concentrated by ion exchange chromatography.
Ion-exchangeable forms were distinguished from total dissolved
metals (163) and anionic and cationic species were separately
concentrated in the field on ion exchangers (430). Ion
exchangers were also used as collecting agents to preconcentrate
several ions without separating them (1,124,370,517). Ion
exchange (186) and ultraviolet radiation (192) were used to
decompose complex cyanides in the determination of total CN.
In principle, ion exchange membranes can be used to
concentrate all ions of the same charge type in a sample by the
same factor (51,53). Coupled with an ion-specific detector this
technique should greatly extend capabilities for trace analysis
and speciation. Applied to the determination of NO3-, the
method was inconveniently slow, gave enrichment factors of less
than 10, and was subject to several interferences (303).
Commercial cation exchange membranes were unsatisfactory for the
enrichment of Cu2* in one trial (52), but gave more favorable
results in another (112).
Differences in chemical reactivity can also be used to
separate species. In an analytical scheme for the speciation of
arsenic, varying pH of reduction and differing volatility of the
products allowed six organic and inorganic forms to be
determined in the same apparatus (62).
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NTIS - National Technical Information Service, U.S.
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99
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA-600/3-78-064
3. RECIPIENT'S ACCESSIOWNO.
4. TITLE AND SUBTITLE
Inorganic Species in Water: Ecological Significance
and Analytical Needs (A Literature Review)
5. REPORT DATE
July 1978 issuing date
6. PERFORMING ORGANIZATION CODE
'. AUTHOR(S)
Thomas B. Hoover
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORG "\NIZATION NAME AND ADDRESS
Environmental Research Laboratory--Athens , GA
Office of Research and Development
U.S. Environmental Protection Agency
Athens, Georgia 30605
10. PROGRAM ELEMENT NO.
1BD713
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Same as above
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/01
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Representative studies of the environmental significance of inorganic species
(as opposed to total-element content) in water are reviewed. The effects of chemical
forms on human health and on plant and animal life, and the roles of valence state,
ionization, complexation, and adsorption in the transport and cycling of elements are
considered along with factors affecting the distribution of elements and species in
freshwater streams and impoundments, in estuaries, and in the sea.
Information on the chronic effects on human health of trace inorganic pollutants
in water is almost entirely limited to total elements because of an inability to
distinguish among forms of an element. The elements of greatest concern with respect
to the toxicity of different species are arsenic, chromium, lead, mercury, and
selenium. In the toxicology of aquatic biota, there is a rapidly growing appreciation
that both acute and chronic effects are strongly related to chemical species.
The movement of inorganic pollutants in the aquatic environment is strongly
influenced by adsorption of particular species on both mineral and organic particulate
No broadly applicable analytical techniques of adequate sensitivity are available
for elemental speciation. This deficiency in analytical ability prevents the
evaluation of research on toxicology and on transport of these chemical forms.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a.
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Inorganic chemistry, Chemical analysis,
Chemical composition, Water pollution,
Contaminants,Ions, Toxicity
Chemical species
Health effects
Distribution
99A
99D
68D
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21, NO. OF PAGES
108
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
100
. S. GOVERNMENT PRINTING OFFICE: 1978-757-140/1448 Region No. 5-11
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