[Show abstract][Hide abstract] ABSTRACT: Reconstructions of 250 years historical inputs of two distinct types of black carbon (soot/graphitic black carbon (GBC) and char-BC) were conducted on sediment cores from two basins of the Puget Sound, WA. Signatures of polycyclic aromatic hydrocarbons (PAHs) were also used to support the historical reconstructions of BC to this system. Down-core maxima in GBC and combustion-derived PAHs occurred in the 1940s in the cores from the Puget Sound Main Basin, whereas in Hood Canal such peak was observed in the 1970s, showing basin-specific differences in inputs of combustion byproducts. This system showed relatively higher inputs from softwood combustion than the northeastern U.S. The historical variations in char-BC concentrations were consistent with shifts in climate indices, suggesting an influence of climate oscillations on wildfire events. Environmental loading of combustion byproducts thus appears as a complex function of urbanization, fuel usage, combustion technology, environmental policies, and climate conditions.
[Show abstract][Hide abstract] ABSTRACT: Metal concentrations in sediment and two species of freshwater fish (lake trout [Salvelinus namaycush], and grayling [Thymallus arcticus]) were examined in four Arctic lakes in Alaska. Concentrations of several metals were naturally high in the sediment relative to uncontaminated lakes in other Arctic regions and more temperate locations. For example, concentrations of Hg and Ni were 175 ng/g and 250 ng/g dry weight, respectively, in Feniak Lake surface sediment. If any anthropogenic enrichment has occurred, it is not distinguishable from background variability based on surface sediment to down core comparisons. With the exception of Hg, the site rank order of metal concentrations (Cu, Cd, Ni, Pb, and Zn) in sediment and freshwater fish tissue among lakes is not consistent. This suggests that a number of physical, chemical, and physiological parameters mediate metal bioavailability and uptake in these systems. Maximum concentrations of most metals in fish from this study are equal to or higher than those collected from remote Arctic lakes and rivers in Canada, Finland, and Russia. Muscle Hg concentrations in excess of 1 μg/g wet weight were observed in lake trout from Feniak Lake, which has no identified Hg source other than naturally Hg-enriched sediments. Fish diet seems to influence some heavy metal burdens, as evidenced by the higher concentrations of some metals in lake trout compared to grayling, and differences among lakes for lake trout. Cadmium, Cu, and Zn burdens were higher in lakes where snails were consumed by trout compared to lakes without snails.
[Show abstract][Hide abstract] ABSTRACT: Urban centers are major sources of combustion-derived particulate matter (e.g. black carbon (BC), polycyclic aromatic hydrocarbons (PAH), anhydrosugars) and volatile organic compounds to the atmosphere. Evidence is mounting that atmospheric emissions from combustion sources remain major contributors to air pollution of urban systems. For example, recent historical reconstructions of depositional fluxes for pyrogenic PAHs close to urban systems have shown an unanticipated reversal in the trends of decreasing emissions initiated during the mid-20th Century. Here we compare a series of historical reconstructions of combustion emission in urban and rural airsheds over the last century using sedimentary records. A complex suite of combustion proxies (BC, PAHs, anhydrosugars, stable lead concentrations and isotope signatures) assisted in elucidating major changes in the type of atmospheric aerosols originating from specific processes (i.e. biomass burning vs. fossil fuel combustion) or fuel sources (wood vs. coal vs. oil). In all studied locations, coal continues to be a major source of combustion-derived aerosols since the early 20th Century. Recently, however, oil and biomass combustion have become substantial additional sources of atmospheric contamination. In the Puget Sound basin, along the Pacific Northwest region of the U.S., rural locations not impacted by direct point sources of contamination have helped assess the influence of catalytic converters on concentrations of oil-derived PAH and lead inputs since the early 1970s. Although atmospheric deposition of lead has continued to drop since the introduction of catalytic converters and ban on leaded gasoline, PAH inputs have "rebounded" in the last decade. A similar steady and recent rise in PAH accumulations in urban systems has been ascribed to continued urban sprawl and increasing vehicular traffic. In the U.S., automotive emissions, whether from gasoline or diesel combustion, are becoming a major source of combustion-derived PM and BC to the atmosphere and have started to replace coal as the major source in some surficial reservoirs. This increased urban influence of gasoline and diesel combustion on BC emissions was also observed in Europe both from model estimates as well as from measured fluxes in recent lake sediments.
[Show abstract][Hide abstract] ABSTRACT: Integrating contaminated sediment clean up and restoration issues within the larger perspective of watershed management are especially critical in populated coastal and estuarine areas with multiple sources of stress from urbanization and development as well as sediment contaminated from historical sources. Sinclair Inlet and Dyes Inlet, located in the Puget Sound WA, have received historical inputs of contamination from military installations, industrial activities, municipal outfalls, and other nonpoint sources. As part of the record of decision to remediate contaminated sediments near the Puget Sound Naval Shipyard in Sinclair Inlet, sediments were dredged from contaminated areas, placed in an adjacent confined aquatic disposal pit, and covered with clean material dredged to deepen the navigational channel and turning basin. Other cleanup activities included restoring shoreline areas to minimize contaminated soil infiltration and improve shoreline habitat, and conducting a comprehensive cleaning, inspection, and repair of the Shipyard's storm water system. Concurrently, the City of Bremerton, also located in the Inlets, has made significant improvements to its combined sewer and storm water system, nearly eliminating combined sewer overflows and achieving a marked improvement in the water quality of the Inlets. Historical trends of contamination in the Inlets obtained from age-dated sediment cores show contamination levels peaking between 1940 and 1960 followed by an obvious decease in contaminant loads in the most recent deposits. During the interval between 1997-1978 and 2003 (following clean up activities) the sediments in Sinclair Inlet and Dyes Inlet changed significantly in texture by becoming, on average, nearly a full phi size coarser. Currently, models are being developed to simulate contaminant runoff and loading from the watershed and the fate and transport of contaminants in Sinclair and Dyes Inlets.
[Show abstract][Hide abstract] ABSTRACT: pca1 0.334 0.278 0.420 0.360 0.392 0.369 0.355 0.299 45.49% pca2 -0.003 -0.599 0.291 -0.434 -0.071 0.264 0.514 -0.169 12.57% pca3 0.061 0.051 -0.370 0.132 0.341 0.458 -0.044 -0.715 10.70% pca4 0.628 0.112 0.131 0.178 -0.425 -0.374 0.203 -0.428 9.82% pca5 -0.491 0.643 0.038 -0.168 -0.258 0.044 0.468 -0.171 8.58% pca6 -0.473 -0.349 0.135 0.736 -0.035 -0.193 0.180 -0.151 6.05% pca7 -0.039 0.045 0.062 -0.228 0.690 -0.633 0.192 -0.162 3.87% pca8 -0.152 0.109 0.749 -0.104 0.013 0.067 -0.528 -0.331 2.91% The final station locations selected based on this analysis are shown in the upper figure. Station 1 and 2 were selected as characteristic of the Port Orchard/Rich Passage region, an area of low metals and TOC with correspondingly low pca1 scores. Stations 3, 5 and 7 were chosen to represent potential source areas in Sinclair Inlet with high metals and high pca1 scores. Stations 4, 6 and 8 were chosen to be representative of central Sinclair Inlet with moderate metals levels and pca1 scores, and moderate to high TOC levels. Stations 9 and 10 were selected to represent Dyes Inlet, with station 9 reflecting moderate metals levels, and station 10 characterized by moderate to high metals and TOC. Flux Sampling: The flux sampling was carried out using two Navy developed flux chambers, BFSD1 and BFSD2 (see pho- tos at right; Chadwick et al., 1994). The chambers are similar in construction and function, but vary slightly in operation. In general, operations for BFSDs were in accordance with standard operating procedures (SOPs) documented in Chadwick and Stanley, 1993, and subsequent modifications adopted for CALEPA and described in Hampton and Chadwick, 2000. Flux sampling was conducted at the ten stations described above. At each site, a flux chamber was be deployed for a period of ~3 days during which a series of 10-12 samples were collected. At the end of the period, the chamber were retrieved, the samples processed and delivered to the analysis lab. During the field deployments is was determined that there was no ade- quate sediment substrate present at site 1. This site was dropped, and a replicate deployment at site 4 was substituted.
[Show abstract][Hide abstract] ABSTRACT: This study evaluated the effect of hepatic methyl donor status on the ability of sodium arsenite (2.5, 5.0 and 10.0 mg/kg) administered by gavage once or on four consecutive days to induce DNA damage in male B6C3F1 mice. Maintenance on a choline-deficient (CD) diet prior to treatment resulted in mice with hepatic methyl donor deficiency (HMDD) and altered arsenical metabolism, as demonstrated by a decreased total urinary excretion of inorganic and organic arsenicals. The alkaline (pH > 13) Single Cell Gel (SCG) assay was used to evaluate for the induction of DNA damage (single strand breaks, alkali labile sites, DNA crosslinking) in blood leukocytes, liver parenchymal cells, and cells sampled from bladder, lung, and skin, while the bone marrow erythrocyte micronucleus (MN) assay was used to assess for the induction of chromosomal damage in bone marrow cells. Treatment with sodium arsenite once or four times induced a significant decrease in DNA migration (indicative of DNA crosslinking) in bladder and liver parenchymal cells of hepatic methyl donor sufficient (HMDS) mice, but in skin cells of HMDD mice. Both HMDD and HMDS mice exhibited a significant increase in the frequency of micronucleated polychromatic erythrocytes (MN-PCE) in bone marrow following four, but not following one, treatments. However, the positive response occurred at a lower dose for HMDS mice and, in these mice, bone marrow toxicity, as demonstrated by a significant reduction in the percentage of PCE, was present also. These results indicate that hepatic methyl donors deficiency significantly decreases the total urinary excretion of orally administered sodium arsenite and markedly modulates target organ arsenic-induced DNA damage, with an apparent shift from liver and bladder to skin.
Mutation Research/Fundamental and Molecular Mechanisms of Mutagenesis 07/1997; 386(3):315-34. · 3.90 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A limited survey conducted in the summer of 1989 indicted that concentrations of seven metals(As, Cd, Hg, Ni, Pb, Zn) in Norton Sound seawater are typical of coastal seawater. Of particular interest was Hg, which was determined to be in the range of 1 to 2 ng/L. Pacific Northwest Laboratory staff sampled seawater near Nome in June and September 1989. These seawater samples and sediment samples were analyzed for trace metals with the following objectives: to determine the concentrations of metals in surface and bottom water within 30 miles of Nome, to determine the concentrations of metals up-current and down-current of the BIMA gold dredge while the dredge was operating, to compare the U.S. Environmental Protection Agency (EPA) total recoverable digestion technique for the analysis of metals in seawater with other analytical-chemical methods, and to determine the concentrations of metals in sediment elutriates. In a related issue, few data were available on the levels of mercury and arsenic in Nome residents through 1988. To fill this data need, samples of hair collected from Nome women of child-bearing age were analyzed to determine the concentrations of mercury and arsenic. 13 refs., 1 fig. 12 tabs.
[Show abstract][Hide abstract] ABSTRACT: On December 23, 1988, the barge Nestucca was accidentally struck by its tow, a Souse Brothers Towing Company tug, releasing approximately 230,000 gallons of Bunker C fuel oil and fouling beaches from Grays Harbor north to Vancouver Island. Affected beaches in Washington included a 40-mile-long strip that has been recently added to Olympic National Park. The purpose of the monitoring program documented in this report was to determine the fate of spilled Bunker C fuel oil on selected Washington coastal beaches. We sought to determine (1) how much oil remained in intertidal and shallow subtidal habitats following clean-up and weathering, (2) to what extent intertidal and/or shallow subtidal biotic assemblages have been contaminated, and (3) how rapidly the oil has left the ecosystem. 45 refs., 18 figs., 8 tabs.
[Show abstract][Hide abstract] ABSTRACT: Studies were conducted to assess the fate and potential toxicity of brass powder deposited on water surfaces. Laboratory microcosms containing lake water were used to quantify the effects of surface dose, pH, alkalinity, microbiota, and sediment binding on the availability and subsequent toxicity of Cu and Zn from brass powder. Eight days after deposition on the water surface, high concentrations of Cu and Zn remained in the aquatic surface microlayer (upper 33 µm). The concentrations of total Cu and Zn in the subsurface bulkwater were reduced by the presence of bottom sediment but were little affected by biota. Toxicity of brass powder toDaphnia magna increased with increasing surface deposition (dose) and decreased with increasing water pH and alkalinity. Little or no toxicity occurred at brass powder surface doses of 50 and 1,000 mg/m2 for low- and high-alkalinity environments, respectively. Geochemical modeling suggested that toxicity resulted from concentrations of both Cu2+ and Zn2+ ions in solution.
Archives of Environmental Contamination and Toxicology 10/1988; 17(5):575-81. · 2.01 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A current approach to evaluating the potential toxicity of metal pollutants (MP) in sediments requires using methods for estimating sorbed metals, amorphic Fe oxide, Mn oxides, and reactive particulate organic carbon (RPOC). Methods for estimating these variables are reevaluated and extraction conditions optimized. The hydroxylamine hydrochloride method, used to estimate the quantities of sorbed metals and amorphic Fe oxide and oxidic Mn adsorbents, was found to yield excellent recovery of MP spikes added at the beginning of the extraction, and adequate precision and selectivity for amorphic over crystalline Fe oxides. Hot KOH was tentatively selected over NH/sub 4/OH for estimating RPOC because of its greater convenience; correlations with laboratory sorption experiments will be required to provide an adequate basis for selection. Determination of both sorbed metals and RPOC are relatively insensitive to solid-to-extractant ratio. Metal pollutants and RPOC extraction are also relatively insensitive to normality of HCl and KOH, respectively. 10 refs., 2 figs.
[Show abstract][Hide abstract] ABSTRACT: From 1983 to 1985, Battelle/Marine Research Laboratory conducted reconnaissance-level field and laboratory studies to better characterize toxic contamination problems occurring in selected urban-industrialized bays (Bellingham Bay, Port Gardner - Everett Harbor, Fourmile Rock - Elliot Bay dump site vicinity, Sinclair Inlet) of Puget Sound. It was envisioned that this goal was best achieved by simultaneously determining levels of contamination in selected baseline or 'reference bays' (Samish Bay, Case Inlet, Dabob Bay, Sequim Bay). Two major tasks composed this effort. The first was conducted in 1983 and consisted of preliminary or screening surveys to collect and analyze sediment samples from 101 stations distributed in the four urban-industrialized bays (Figure 1), and at 80 stations distributed in the four baseline bays (Figure 2). The second task was undertaken in 1984 and involved detailed surveys and analyses of the same bays, but at a limited number of stations (32 in urban embayments, 16 in baseline bays). The stations to be resampled in 1984 were the ''cleanest'' of the clean and the ''dirtiest'' of the dirty as determined by the 1983 sediment chemical analyses, and within restrictions imposed by sediment type.
[Show abstract][Hide abstract] ABSTRACT: Many aquatic contaminants, because of low water solubility (hydrophobicity) or association with floatable particles, concentrate at the sea surface. Thirty-six samples of the sea-surface microlayer (SMIC), the upper 50 μm, were collected from sites in Puget Sound, Washington State. Sites included three urban bays, central Puget Sound, and a rural reference site. Exposure of floating fish eggs to approximately half of these samples resulted in sublethal and lethal toxic effects (Hardy et al., 1987c).Chemical analyses revealed high concentrations of contaminants in many of the samples. Major temporal and spatial differences in sea-surface chemistry occurred, but maximum (for all) and mean (for 1985) concentrations were aromatic hydrocarbons, 8030 (mean 132) μg liter−1: saturate hydrocarbons, 2060 μg liter−1: pesticides, 43·8 (mean 0·46) ng liter−1; PCBs, 3890 (mean 631) ng liter−1; and total metals, 4750 (mean 626) μg liter−1. Stepwise multivariate regression indicated that the percentage of fish eggs developing to normal live larvae decreased with increasing concentrations of a complex mixture of contaminants. Principal component analysis demonstrated that the major types of contaminants did not differ greatly in their statistical contribution to the toxicity, i.e. no single chemical was responsible for the observed toxicity.The chemical composition of the SMIC samples suggested that contamination originated from a variety of sources including atmospheric deposition, terrestrial runoff of fossil fuel combustion products, and sewage disposal.
[Show abstract][Hide abstract] ABSTRACT: The Marine Research Laboratory conducted studies during CY 1985 to evaluate the effects of sea-surface contamination on the reproductive success of a valued marine species. Microlayer and bulk water samples were collected from a rural bay, central Puget Sound, and three urban bays and analyzed for a number of metal and organic contaminants as well as for densities of neuston and plankton organisms. Fertilized neustonic eggs of sand sole (Psettichthys melanostictus) were exposed to the same microlayer samples during their first week of embryonic and larval development. Also, we evaluated the effects of microlayer extracts on the growth of trout cell cultures. Compared to rural sites, urban bays generally contained lower densities of neustonic flatfish eggs during the spawning season. Also, in contrast to the rural sites or the one central Puget Sound site, approximately half of the urban bay microlayer samples resulted in significant increases in embryo mortality (up to 100%), kyphosis (bent spine abnormalities) in hatched larvae, increased anaphase aberrations in developing embryos, and decreased trout cell growth. The toxic samples generally contained high concentrations of polycyclic aromatic and/or chlorinated hydrocarbons and/or potentially toxic metals. In some cases, concentrations of contaminants on the sea surface exceeded water-quality criteria by several orders of magnitude. Several samples of subsurface bulk water collected below highly contaminated surfaces showed no detectable contamination or toxicity.
[Show abstract][Hide abstract] ABSTRACT: The sea-surface microlayer is an important interface between the atmosphere and ocean and a collection point for many anthropogenic materials including potentially toxic metals. We developed a glass plate sampler to collect the upper 30 to 55 micrometers of the sea surface. Samples of the microlayer and subsurface bulk water from an urban and rural bay were analysed for concentrations of Pb, Zn, Cu, Cd and Fe. Metal concentrations in both the microlayer and bulk water were generally 2 to 15 times greater in the urban than in the rural bay. Concentrations of metals in the microlayer of both bays averaged 6 to 65 times greater than those in the bulk water. In the urban bay, microlayer concentrations of Pb, Zn and Cu from 10 to > 100 μg 1−1 were common. Measured microlayer metals concentrations agree well with those predicted from atmospheric deposition rates using a previously derived empirical model developed from laboratory microcosm studies. Further work will be required to determine whether or not these high microlayer metal concentrations contain significant biologically available fractions which could impact fisheries recruitment of larval icthyoneuston.
Estuarine Coastal and Shelf Science 01/1985; · 2.32 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Deposition of atmospheric particles provides a major source of metals to the world's oceans. Before entering the water column these metals must pass through the sea-surface microlayer (upper 50 ..mu..m), a boundary with unique physical, chemical, and biological properties. A model, derived from laboratory microcosm studies, is used to predict the behavior of six metals under two conditions of biotic enrichment and wind mixing and three atmospheric deposition rates. Mean residence times of metals in the microlayer are 1.5-15 h. Maximum predicted enrichments (microlayer/water metals concentrations) are Pb > Cu > Zn > Ag > Ni > Mn. These predicted enrichments agree well with mean microlayer metal enrichments measured in the field.
Limnology and Oceanography - LIMNOL OCEANOGR. 01/1985; 30(1):93-101.
[Show abstract][Hide abstract] ABSTRACT: The effect of variations in pH, salinity, sulfide and dissolved organic carbon (DOC) concentrations on the speciation of dissolved Ag were calculated using the MINTEQ geochemical model. Molecular-weight-averaged conditional equilibrium constants for natural Ag-organic complexes were estimated from the equilibrium constants for specific metal-organic complexes and the concentration of the organic compounds, reported to be present in seawater, summed by principal functional group. These calculations show that the major Ag complexes in seawater are AgHS/sup 0/, for S(-II) concentrations above 0.01 ..mu..g L/sup -1/, AgCl/sup 0/, AgCl/sub 2//sup -/, AgCl/sub 3//sup -/ and AgCl/sub 4//sup 0/. If the AgCl/sup 0/ complex is the primary bioavailable or toxic chemical species as has been reported, the toxicity of silver will decrease significantly with increased S(-II) concentration, pH, and with decreased salinity. Organically complexed silver was calculated to represent
[Show abstract][Hide abstract] ABSTRACT: Trends in contaminant loading to the central basin of Puget Sound have been inferred from the chemical composition of age-dated sediment cores. During the last hundred years there have been dramatic changes in the quantity of specific heavy metals and organic compounds entering Puget Sound. The sedimentary history of several chemicals, including Pb, Hg, Ag, Cu, As and hydrocarbons, shows increased concentrations paralleling the urbanization of the Seattle-Tacoma area. Contaminant concentrations began to increase above background in the late 1800s and reached maximum concentrations usually in sediments deposited in 1945 to 1965. Synthetic organics such as PCB, DDT and CBD first appear in sediments deposited in the 1930s or later and reached a maximum in the 1960s. The presence of the subsurface maximum concentrations in the fine-grain deepwater sediments indicates the pollution control strategies have significantly improved the sediment quality of central Puget Sound.