Effects of Spatial and Temporal Variation of Acid-Volatile Sulfide on the Bioavailability of Copper and Zinc in Freshwater SedimentsEntry ID: usgs_brd_cerc_d_sulfides
Abstract: Variation in concentrations of acid-volatile sulfide (AVS) in sediments from
the upper Clark Fork River of Montana was associated with differences in
bioaccumulation of Cu and Zn and growth of larvae in the midge, Chironomus
tentans. Growth of midge larvae was significantly greater and bioaccumulation
of Cu was significantly less in surface sections (0-3 cm depth) of sediment
cores, which had ... greater concentrations of AVS and lesser ratios of
simultaneously extracted metals to AVS (SEM:AVS ratios) than in subsurface
sediments (6-9 cm). Concentrations of AVS were significantly less in sediments
incubated with oxic overlying water for 9 weeks than in the same sediments
incubated under anoxic conditions. Bioaccumulation of Cu differed
significantly between incubation treatments, corresponding to differences in
concentrations of AVS and SEM:AVS ratios, although midge growth did not.
Bioaccumulation of Zn did not differ significantly between depth strata of
sediment cores or between incubation treatments. When results from the two
sets of bioassays were combined, bioaccumulation of Cu and Zn, but not growth,
was significantly correlated with SEM:AVS ratios and other estimates of
bioavailable metal fractions in sediments. Growth of midge larvae was
significantly correlated with bioaccumulation of Zn, but not Cu, suggesting
that Zn was the greater contributor to the toxicity of these sediments.
Assessments of the toxicity of metal-contaminated freshwater sediments should
consider the effects of spatial and temporal variation in AVS concentrations on
The objective of this research was to evaluate whether spatial and temporal
variation in AVS concentrations and SEM:AVS ratios is associated with variation
in metal bioaccumulation and toxicity in freshwater sediments.
Sediments were collected in August 1993 from seven sites in the upper Clark
Fork River drainage of western Montana. Surface grab samples and sediment
cores were collected from two sites in the upper Clark Fork River, downstream
from the historic mining and smelting district, and four sites in Milltown
Reservoir (Milltown), including one riverine site at the upper end of the
reservoir, two sites in the main stem of the reservoir and one site in a
shallow backwater area. These six sites were selected to represent the range
of metal contamination and habitat types in the upper Clark Fork River and
Milltown Reservoir, based on the results of previous studies. Additional grab
samples were collected from Rock Creek, an uncontaminated tributary of the
Clark Fork, for use as a reference sediment in bioassays.
Sample containers, sampling gear, and laboratory apparatus were cleaned in the
laboratory with laboratory detergent, tap water, 10% HCl, and deionized water.
Sampling gear was acid washed in the field between sampling stations and rinsed
with site water. Surface grabs were collected with a polypropylene scoop (from
sites in the Clark Fork and Rock Creek) or with a petite Ponar dredge (from
sites in the Milltown Reservoir) and combined to produce 8-L composite samples.
Twelve core samples were collected from each of the six primary sites in 5 cm
diameter polybutyrate tubes. Cores were obtained from Clark Fork sites by
direct insertion of the core tubes into the sediment and from the deeper
Milltown sites with a manual core sampler with a polypropylene nosepiece, which
held the core tube inside a stainless steel core barrel (Wildco, Saginaw, MI,
USA). Cores were extruded in the field to obtain surface (0-3 cm) and deep
(6-9) cm) core sections. Sections from three cores were combined into each of
four composite samples for each site and depth. Sediment samples were placed
in polyethylene or polycarbonate containers, shipped on ice to the laboratory
within 24 h of collection, and stored at 4 degrees C. Sediments were
homogenized by stirring before samples were withdrawn.
Sediments from the six Clark Fork and Milltown sites were incubated in 30-cm X
15-cm glass aquaria equipped with polystyrene under-gravel platforms
(Wolverton's, Lansing, MI) covered with nylon mesh to allow water to
recirculate above and below the sediment layer. Two liters of sediment was
placed in thin (4 cm) layer on the platform of each aquarium, and 4L of
moderately hard reconstituted water (MHRW; hardness 90-100 mg/L as CaCO3, pH
7.8-8.2 ) was added. Water was lifted from below the sediment layer by gas
bubbled up through polystyrene gas-lift tubes in one corner of the platform and
passed back through another tube in the opposite corner of the platform. One
group of sediment samples, one from each site, received compressed room air
(the oxic treatment); and an identifical group (the anoxic treatment) received
nitrogen, with oxygen removed by an in-line oxygen trap (Baxter Scientific
Products, McGaw Park, IL). Aquaria were covered with plexiglas lids and sealed
with tape, except for small holes for the gas tubing inlet and for gas escape.
Aquaria were placed in water baths at 18 to 20 C in continuous darkness.
Sampels of sediment were removed from each aquarium periodically during the
incubation for analysis of acid-volatile sulfides (AVS), and the incubation was
terminated after 63 days. At the end of the incubation period, samples of
sediment were removed for sediment bioassays and analysis of metals, AVS, and
Sediment bioassays with larvae of the midge, Chironomus tentans, were conducted
with a static-renewal method. Bioassays with core sections were conducted
within 30 days of collection, and bioassays with incubated sediments were
started within 24 hours after the end of the incubations. Experimental designs
for the two sets of bioassays were similar: two treatment groups (core sections
or incubation treatment) were tested with sediments from all six sites, with
four replicates per group. Groups of four exposure chambers containing
sediments from the reference site (RC) were carried through both sets of
bioassays. Four replicate exposure chambers per site or treatment group were
placed in a 9-Liter all-glass aquarium. Exposure chambers were 300-ml glass
beakers with two 17-mm windows covered with stainless steel screen (250
micrometer mesh). Each aquarium received two water replacements per day from a
polyethylene head tank, with replacement of overlying water (MHRW) in the test
chambers facilitated by a drain tube with an intermittent siphon. Bioassays
with sediments from the oxic incubation (and one group of reference sediments)
received gentle aeration.
Cohorts of midge larvae for bioassays were startled from egg masses collected
on the same date and reared in the water used for bioassays (MHRW). Larvae of
uniform age (10-12 days after hatching) and uniform size (approximately 5 mm
long) were selected for bioassays. Midge larvae were added randomly to the
exposure chambers to a total of 10 larvae per test chamber. A suspension
containing 6 mg dry weight of flake fish food (Tetramin; Tetra-Werke, Berlin,
Germany) was added to each chamber daily during the 10 day exposure period. At
the end of the exposure, groups of exposure chambers were removed in random
order and the number of survivors for each chamber was recorded. Surviving
larvae from each chamber were transferred to 30 ml plastic cups that contained
dilution water and a small amount of acid-washed sand, fed a daily ration, and
set aside to allow clearance of gut contents. After 12 hours, larvae from each
cup were rinsed with ultrapure water, dried for 24 hours at 60 degrees, and
weighed to the nearest 0.01 mg.
Samples of midge larvae were prepared for metal analysis by digestion with high
purity reagents (J.T. Baker Instra-Analyzed or Ultrex) at 90 to 95 degrees C in
Teflon Centrifuge tubes. Concentrated nitric acid (1.5 ml at 70%) was added
for the first 24 hours of digestion, the sample cooled, a solution of 30%
hydrogen peroxide (1.0 ml) was added, and the digestion was resumed for an
additional 24 hours. Digested samples were diluted with ultrapure water to a
final volume of 10 ml and a final concentration of 10% (v/v) nitric acid.
Data Set Citation
Dataset Originator/Creator: John M. Besser, Christopher G. Ingersoll, and John P. Giesy
Dataset Title: Effects of Spatial and Temporal Variation of Acid-Volatile Sulfide on the Bioavailability of Copper and Zinc in Freshwater Sediments
Dataset Release Date: 1996
Dataset Release Place: Columbia, Missouri
Dataset Publisher: USGS, BRD, Columbia Environmental Research CenterOnline Resource: http://www.cerc.usgs.gov/clearinghouse/data/usgs_brd_cerc_d_cerc003...
Start Date: 1993-08-01Stop Date: 1993-08-01
Quality Precision and accuracy of analyses of metals and AVS were evaluated by
analyses of duplicate samples, standard reference materials, and matrix spikes.
The mean relative percent difference (RPD) for duplicate analyses of metals in
midge sample ws 9.2% for Cu and 5.7% for Zn. Mean recoveries of metals from a
standard reference ... tissue (SRM 1577a, bovine liver; National Institutes of
Standards and Technology, Gaithersburg, MD) were 80% for Cu and 105% for Zn.
Average RPDs were 12% for AVS analyses and 19% for SEM analyses. Recoveries of
sulfide spikes averaged 88% from spiked blanks and 71% from spiked sediments.
Recovery of Cu spikes from SEM extracts averaged 70% but was highly variable
(range 9-151%). A previous study of Clark Fork sediments also reported low and
variable recoveries of spikes of Cu and other metals in the SEM procedure.
Concentrations of Cu in SEM extracts in this study averaged only 15% of those
reported for the same sites in the previous study, which used a stronger
extractant (3 N vs. 1 N HCl), whereas concentrations of Zn averaged 87% of
those in the previous study. The difference in the recoveries of Cu and Zn is
consistent with the greater stability of Cu sulfides compared to Zn sulfides
and may indicate incomplete dissolution of amorphous C sulfides or sorption of
Cu to insoluble phases such as pyrites.
Access Constraints None
Use Constraints None
Data Set Progress
Role: TECHNICAL CONTACT
Phone: (573) 876-1818
Fax: (573) 876-1896
Email: John_Besser at usgs.gov
U.S. Geological Survey Biological Resources Division 4200 New Haven Road
Province or State: Missouri
Postal Code: 65201
John M. Besser, Christopher, G. Ingersoll and John P. Giesy. 1996.
Effects of Spatial and Temporal Variation of Acid-Volatile Sulfide
Environmental Toxicology and Chemistry, Vol. 15, No. 3
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Creation and Review Dates
DIF Creation Date: 2000-04-01
Last DIF Revision Date: 2017-08-23
Future DIF Review Date: 2001-04-01