United States
Environmental Protection
Agency
Environmental Research
Laboratory
Narragansett Rl 02882
Research and Development
EPA-600/S3-81-050  Mar. 1982
Project Summary
Nearshore  Marine  Trace
Metal  Geochemistry
Michael L Bender
  This publication summarizes a
number of studies aimed at under-
standing several aspects of the near-
shore geochemistry of trace metals
which give information on conse-
quences of trace metal pollution
attending nearshore waste disposal.
  The studies included the distribution
of dissolved and particulate trace
metals in the Hudson  River Estuary;
pore water nutrient, carbon and metal
geochemistry in Narragansett Bay;
trace metal adsorption in Narragansett
Bay sediments; and benthic fluxes of
transition metals out of Narragansett
Bay sediments.
  The key findings are that dissolved
Mn, Ni, Cu, Cd and Zn tend to remain
dissolved during passage through an
estuary; that reducible metals (Mn and
Fe) are released at rapid rates from
reducing estuarine sediments; and
that other divalent cations forming
insoluble sulfides are sequestered in
reducing nearshore sediment pore
waters.
  This Project Summary was devel-
oped by EPA's Environmental Research
Laboratory, Narragansett, ft/, to an-
nounce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).

Introduction
  The disposal of wastes at a nearshore
site may affect the environment by
introducing heavy metals (among other
pollutants) at subtoxic and toxic levels.
Since  certain wastes (notably sewage
plant  effluent, sewage sludge, and
dredge spoils) have high metal concen-
trations, pollution of the affected envi-
ronment is likely, and it is important to
assess the impact of this pollution on
the ecosystem. There are three steps to
such an assessment: determining the
fate of a pollutant metal, determining
which metal  species (i.e.,  free ionic,
organically bound, particulate, etc.)
have deleterious biological effects, and
determining the deleterious effects of
different metal concentrations.
  This study has been concerned with
understanding the fate of manganese,
iron, nickel, copper, cadmium  and zinc
in the estuarine and nearshore envi-
ronment.  In particular, three central
issues have been addressed: 1) how
these metals  are partitioned between
the dissolved and particulate phases, 2)
to what extent they are removed from
the water column into sediments, in the
nearshore environments, and 3) under
what conditions these metals are re-
leased from sediments.
  A related problem was also addressed.
Benthic nutrient regeneration is a major
source of nutrients to nearshore waters.
The dumping of polluted solids into
these waters may, by impacting the
benthic community, decrease the benthic
fluxes of nutrients and lower the fertility
of the overlying waters.  The study
results give insights into the question of
whether nearshore dumping is likely to
be a problem in this respect.

Conclusions
  Estuarine conditions vary greatly as a
function of season, fertility (i.e., bloom
vs. non-bloom conditions), and river
runoff. There are also major variations

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    from one estuary to another. Hence
    caution must be used in extrapolating
    results from this study of two estuaries,
    concentrating on summer conditions, to
    other seasons and systems.
     The results reveal  that about half of
    the dissolved copper, and more than
    half of  the dissolved nickel, cadmium
    and zinc, entering the Hudson River at
    the harbor remain in the dissolved form
    until removed from the estuary by
    advection (water flow). Thus it is clear
    that adsorption, salting  out, and other
    processes do not purify the water of
    these elements. They remain largely
    dissolved, presumably the state most
    toxic to organisms. On the other hand,
    the mass balance could not be done well
    enough to rule out the possibility that up
    to half of the dissolved nickel, cadmium,
    and zinc entering the Hudson accumu-
    lates in sediments. In the case of copper,
    data show that about this fraction is
    removed from solution into sediments.
    Manganese is apparently slowly removed
    from nearshore waters by oxidation
    onto particulates. Where estuarine
    residence times are  on  the order of a
    month  and temperatures are warm,
    most of the dissolved manganese will be
    removed into sediments.
      The benthic flux of iron, manganese,
    nickel, copper and cadmium  out of
    anoxic nearshore sediments is consistent
    with the relative solubility of these
    metals in oxic and anoxic environments.
    Apparently as a result of  insoluble
    sulfide formation, nickel, copper and
    cadmium have low pore water concen-
    trations and are released at low rates to
    the overlying  waters. Manganese and
        iron have high concentrations in anoxic
        pore waters. They are rapidly released,
        although iron, which is very quickly
        oxidized in bottom water, shows a low
        net flux. These  results suggest that
        release of nickel, copper, cadmium and
        other metals from dumped dredge spoils
        can be minimized by disposal of spoils
        under low energy, high productivity
        waters.
          Nutrient benthic fluxes at  highly
        polluted and relatively clean Narra-
        gansett Bay sites are similar, indicating
        that pollution does not inhibit benthic
        bacterial decomposition and nutrient
        regeneration.

        Recommendations
          With regard to  preventing toxic metal
        release, the best type of nearshore
        environment for dumping dredge spoils
        and metal rich wastes are low energy
        environments underlying productive
waters. The low energy will obviate
sediment dispersal,  and the  high
productivity will supply biogenic debris
and insure maintenance of a reducing
environment in which most heavy metals
are sequestered within sediments. Pol-
luted sediments are likely to be at least
as highly reducing as clean  sediments
at a potential dump site. Thus a site
where  sediments are currently anoxic
very near the interface (certainly within
the top centimeter) would appear  to be
suitable for dumping.
  The conclusions are  based on very
limited sampling and must be tested by
more field work on pore water chemistry
and metal benthic fluxes.
  The effect of pollutants on benthic
nutrient regeneration has not been
adequately considered. While these
results do not indicate that this is a
problem, the possibility should be  eval-
uated by more extensive work.
          Michael L Bender is with the Graduate School of Oceanography, University of
            Rhode  Island, Kingston, Rl 02881.
          Earl Davey is the EPA Project Officer (see below).
          The complete report, entitled "Nearshore Marine Trace Metal Geochemistry,"
            {Order No. PB 82-109 372; Cost: $11.00, subject to change) will be available
            only from:
                  National Technical Information Service
                  5285 Port Royal Road
                  Springfield, VA 22161
                   Telephone: 703-487-4650
          The EPA  Project Officer can be contacted at:
                  Environmental Research Laboratory
                   U.S.  Environmental Protection Agency
                  South Ferry Road
                  Narragansett, Rl 02882
                                                                             -tf U S GOVERNMENT PRINTING OFFICE, 1982 - 559-017/0703
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Environmental Protection
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Information
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