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Dynamic processes (physical, chemical and biological) challenge our ability to quan- tify and manage the ecological risk of chemical contaminants in estuarine environments. Sele- nium (Se) bioavailability (defined by bioaccumulation), stable isotopes and molar carbon-to- nitrogen ratios in the benthic clam Potamocorbula amurensis, an important food source for predators, were determined monthly for 17 yr in northern San Francisco Bay. Se concentrations in the clams ranged from a low of 2 to a high of 22 µg g �1 over space and time. Little of that variability was stochastic, however. Statistical analyses and preliminary hydrodynamic modeling showed that a constant mid-estuarine input of Se, which was dispersed up- and down-estuary by tidal cur- rents, explained the general spatial patterns in accumulated Se among stations. Regression of Se bioavailability against river inflows suggested that processes driven by inflows were the primary driver of seasonal variability. River inflow also appeared to explain interannual variability but within the range of Se enrichment established at each station by source inputs. Evaluation of risks from Se contamination in estuaries requires the consideration of spatial and temporal variability on multiple scales and of the processes that drive that variability.

Coastal rivers represent a significant pathway for the delivery of natural and anthropogenic sediment-associated chemical constituents to the Atlantic, Pacific and Gulf of Mexico coasts of the conterminous USA. This study entails an accounting segment using published average annual suspended sediment fluxes with published sediment-associated chemical constituent concentrations for (1) baseline, (2) land-use distributions, (3) population density, and (4) worldwide means to estimate concentrations/annual fluxes for trace/major elements and total phosphorus, total organic and inorganic carbon, total nitrogen, and sulphur, for 131 coastal river basins. In addition, it entails a sampling and subsequent chemical analysis segment that provides a level of ‘ground truth’ for the calculated values, as well as generating baselines for sediment-associated concentrations/fluxes against which future changes can be evaluated. Currently, between 260 and 270 Mt of suspended sediment are discharged annually from the conterminous USA; about 69% is discharged from Gulf rivers (n = 36), about 24% from Pacific rivers (n = 42), and about 7% from Atlantic rivers (n = 54). Elevated sediment-associated chemical concentrations relative to baseline levels occur in the reverse order of sediment discharges: Atlantic rivers (49%) > Pacific rivers (40%) > Gulf rivers (23%). Elevated trace element concentrations (e.g. Cu, Hg, Pb, Zn) frequently occur in association with present/former industrial areas and/or urban centres, particularly along the northeast Atlantic coast. Elevated carbon and nutrient concentrations occur along both the Atlantic and Gulf coasts but are dominated by rivers in the urban northeast and by southeastern and Gulf coast (Florida) ‘blackwater’ streams. Elevated Ca, Mg, K, and Na distributions tend to reflect local petrology, whereas elevated Ti, S, Fe, and Al concentrations are ubiquitous, possibly because they have substantial natural as well as anthropogenic sources. Almost all the elevated sediment-associated chemical concentrations found in conterminous US coastal rivers are lower than worldwide averages. Copyright © 2012 John Wiley & Sons, Ltd.

Surface sediments in the Spokane River Basin are enriched in Pb, Zn, As, Cd, Sb, and Hg relative to local background levels. Maximum enrichment occurs in the Upper Spokane River in close proximity to Lake Coeur d9Alene. On average, enrichment decreases downstream. Subsurface sediments also are enriched in Pb, Zn, As, Cd, Sb, and Hg relative to background levels. Enrichment began between 1900 and 1920 in the middle of the basin; this is contemporaneous with similar findings in Lake Coeur d9Alene (the upstream source of the Spokane River), as well as the completion of Long Lake Dam (1913). In the most downstream part of the basin, enrichment began between 1930 and 1940. This temporal shift may reflect the latter9s greater distance from the Coeur d9Alene River Basin, the presumptive source of the enriched trace elements, but is more likely the result of the completion of Grand Coulee Dam (1934–1941) which backed up the Spokane River, and elevated water levels by about 30 m in the most downstream part of the basin.

In 1994, the NASQAN (National Stream Quality Accounting Network) programme was redesigned as a flux-based water-quality monitoring network for the Mississippi, Columbia, Colorado, and Rio Grande Basins. As the new programme represented a departure from the original, new sampling, processing, analytical, and data handling procedures had to be selected/developed to provide data on discharge, suspended sediment concentration, and the concentrations of suspended sediment and dissolved trace elements. Annual suspended sediment fluxes were estimated by summing daily instantaneous fluxes based on predicted suspended sediment concentrations derived from discharge-based log–log regression (rating-curve) models. The models were developed using both historical and current site-specific discharge and suspended sediment concentrations. Errors using this approach typically are less than ±10% for the 3-year reporting period; however, the magnitude of the errors increases substantially for temporal spans shorter than 1 year. Total, rather than total-recoverable, suspended sediment-associated trace element concentrations were determined by direct analysis of material dewatered from large-volume whole-water samples. Site-specific intra- and inter-annual suspended sediment-associated chemical variations were less (typically by no more than a factor of two) than those for either discharge or suspended sediment concentrations (usually more than 10-fold). The concentrations, hence the annual fluxes, for suspended sediment-associated phosphorus and organic carbon, determined by direct analyses, were higher than those determined using a more traditional paired, whole-water/filtered-water approach (by factors ranging from 1·5- to 10-fold). This may be important for such issues as eutrophication and coastal productivity. Filtered water-associated (dissolved) trace element concentrations were markedly lower than those determined during the historical NASQAN programme; many were below their respective detection limits. This resulted from the use of clean sampling, processing, and analytical protocols. Hence, the fluxes for filtered water-associated (dissolved) Ag, Pb, Co, V, Be, Sb, and Se, as well as the total (filtered water plus suspended sediment-associated) fluxes for these constituents, could not be estimated. Published in 2001 by John Wiley & Sons, Ltd.

Suspended sediment, sediment-associated, total trace element, phosphorus (P), and total organic carbon (TOC) fluxes were determined for the Mississippi, Columbia, Rio Grande, and Colorado Basins for the study period (the 1996, 1997, and 1998 water years) as part of the US Geological Survey's redesigned National Stream Quality Accounting Network (NASQAN) programme. The majority (≥70%) of Cu, Zn, Cr, Ni, Ba, P, As, Fe, Mn, and Al are transported in association with suspended sediment; Sr transport seems dominated by the dissolved phase, whereas the transport of Li and TOC seems to be divided equally between both phases. Average dissolved trace element levels are markedly lower than reported during the original NASQAN programme; this seems due to the use of ‘clean’ sampling, processing, and analytical techniques rather than to improvements in water quality. Partitioning between sediment and water for Ag, Pb, Cd, Cr, Co, V, Be, As, Sb, Hg, and Ti could not be estimated due to a lack of detectable dissolved concentrations in most samples. Elevated suspended sediment-associated Zn levels were detected in the Ohio River Basin and elevated Hg levels were detected in the Tennessee River, the former may affect the mainstem Mississippi River, whereas the latter probably do not. Sediment-associated concentrations of Ag, Cu, Pb, Zn, Cd, Cr, Co, Ba, Mo, Sb, Hg, and Fe are markedly elevated in the upper Columbia Basin, and appear to be detectable (Zn, Cd) as far downstream as the middle of the basin. These elevated concentrations seem to result from mining and/or mining-related activities. Consistently detectable concentrations of dissolved Se were found only in the Colorado River Basin. Calculated average annual suspended sediment fluxes at the mouths of the Mississippi and Rio Grande Basins were below, whereas those for the Columbia and Colorado Basins were above previously published annual values. Downstream suspended sediment-associated and total trace element fluxes increase in the Mississippi and Columbia Basins, whereas fluxes markedly decrease in the Colorado Basin. No consistent pattern in trace element fluxes was detected in the Rio Grande Basin. Published in 2001 by John Wiley & Sons, Ltd.

During 1998/1999, surface and subsurface sediment samples were collected along the entire length of the Spokane River from its outlet at the northern end of Lake Coeur d'Alene (CDA), Idaho, to Lake Roosevelt on the Columbia River, Washington. The study was conducted to determine if the trace element enrichments observed in Lake CDA and on the floodplain and in the CDA River extend through the Spokane River Basin (SRB). As in Lake CDA, surface sediments in the SRB are enriched in Pb, Zn, As, Cd, Sb and Hg relative to local background levels. Pb, Cd and Zn are the most elevated, with maximum enrichment occurring in the upper Spokane River in close proximity to Lake CDA. On average, enrichment decreases downstream, apparently reflecting both increased distance from the inferred source (the CDA River Basin), as well as increased dilution by locally derived but unenriched materials. Only Cd and Zn display marked enrichment throughout the SRB. Pb, Zn and Cd seem to be associated mainly with an operationally defined iron oxide phase, whereas the majority of the As and Sb seem to be matrix-held. Subsurface sediments also are enriched in Pb, Zn, As, Cd, Sb and Hg relative to background levels. Based on 137Cs and excess 210Pb dating, trace element enrichment began in the middle part of the SRB (Long Lake) between 1900 and 1920. This is contemporaneous with similar enrichments observed in Lake CDA, as well as the completion of Long Lake Dam (1913). In the most downstream part of the basin (Spokane River Arm of Lake Roosevelt), enrichment began substantially later, between 1930 and 1940. The temporal difference in enrichment between Long Lake and the River Arm may reflect the latter's greater distance from the presumed source of the enrichment (the CDA River Basin); however, the difference is more likely the result of the completion of Grand Coulee Dam (1934–1941), which formed Lake Roosevelt, backed up the Spokane River, and increased water levels in the River Arm by about 30 m.

During 1989 and 1990 a series of 12 gravity cores, and 150 surface grab samples were collected in Lake Coeur d'Alene, Idaho to determine trace element concentrations, partitioning and surface and subsurface distribution patterns in the bed sediments of the lake. In addition, selected subsamples from one core were analyzed for 117 Cs activity to begin to establish a trace element geochemical history for the lake. The intent was to try and relate the trace element concentrations and distributions in the sediment column to past and present mining and mining related activities in the area. Substantial portions of the surface and near-surface sediments in Lake Coeur d'Alene are markedly enriched in Ag, As, Cd, Hg, Pb, Sb and Zn, and somewhat enriched in Cu, Fe and Mn. Surface distribution patterns, as well as variations in the thickness of the trace element-rich subsurface sediments, indicate that the source of much of this enriched material is the Coeur d'Alene River. The similarity between the trace element-rich surface and subsurface sediments with respect to: their location, their bulk chemistry, and their trace element partitioning indicate that the sources and/or concentrating mechanisms causing the trace element enrichment in the lake sediments probably have been the same throughout their depositional history. An estimated 75 million metric tons of trace element-rich sediments have been deposited on or in the lakebed. Based on a Mt. St. Helens' ash layer from the 1980 eruption, ages estimated from 137 Cs activity, and the presence of 80 discernible and presumably annual layers in a core collected near the Coeur d'Alene River delta, indicate that the deposition of trace element-rich sediments began, at least in the Coeur d'Alene River delta, some time between 1895 and 1910, dates consistent with the onset of mining and ore-processing activities that began in the area in the 1880's.

During the summer of 1990, 12 gravity cores were collected in Lake Coeur d'Alene, Idaho at various depths and in a variety of depositional environments. All core subsamples were analysed to determine the bulk sediment chemistry; selected subsamples were analysed for trace element partitioning and 137Cs activity. The purpose of these analyses was to determine the trace element concentrations and distributions in the sediment column and to try to establish a trace element geochemical history of the lake in relation to mining and mining-related discharge operations in the area. Substantial portions of the near-surface sediments in Lake Coeur d'Alene are markedly enriched in Ag, As, Cd, Hg, Pb, Sb and Zn, and slightly enriched in Cu, Fe and Mn. Variations in the thickness of the trace element-rich sediments, which range from more than 119 cm to as little as 17 cm, indicate that the source of much of this material is the Coeur d'Alene River. An estimated 75 million tonnes of trace element-rich sediments have been deposited on or in the lake bed. Estimated trace element masses in excess of those considered representative of background conditions range from a high of 468 000 tonnes of Pb to a low of 260 tonnes of Hg. The similarity between the trace element-rich surface and subsurface sediments with respect to their location, their bulk chemistry, their interelement relations and their trace element partitioning indicate that the sources and/or concentrating mechanisms causing the trace element enrichment in the lake sediments have probably been the same through-out their depositional history. Based on a Mt St Helens'ash layer from the 1980 eruption, ages estimated from 137Cs activity and the presence of 80 discernible and presumably annual layers in a core collected near the Coeur d'Alene River delta indicate that deposition rates for the trace element-rich sediments have ranges from 2.1 to 1.3 cm/year. These data also indicate that the deposition of trace element-rich sediments began, at least in the Coeur d'Alene River delta, some time between 1895 and 1910, dates consistent with the onset of mining and ore processing activities that began in the area in the 1880s.

Mining, milling, and processing wastes containing quantities of arsenopyrite were produced around Lead, South Dakota, from 1875 to 1977. Much of this material was discharged into Whitewood Creek, and from there portions of the waste were transported to the Belle Fourche River, thence to the Cheyenne River, and finally to the Missouri River. In 1958, the Missouri River was dammed at Pierre, forming Lake Oahe. Analyses of cores collected from the lake bottom showed the presence of arsenic-rich layers in the bed sediments; substantial portions of the arsenic are due to arsenopyrite in the 8–16 and 16–32 μm size fractions of the sediments. In addition, suspended-sediment samples collected from the Cheyenne River above Lake Oahe contain detectable quantities of arsenopyrite in the 8–16 and 16–32 μm fractions. Solid material collected from the banks and floodplains of the Belle Fourche River and Whitewood Creek contains reduced and oxidized phases. The reduced phases have arsenic maxima in the 16–32 and 32–63 μm size ranges. These fractions also contribute the most arsenic to the samples; the major source being arsenopyrite. The oxidized segments have arsenic maxima in the 63 μm size ranges. The 63 μm fractions contribute the most arsenic to the oxidized samples. This arsenic, despite the oxidized nature of the samples, is associated with arsenopyrite coated with thin iron oxide rinds. It has been calculated that 80% of the arsenic in these deposits is associated with sulfides (in the form of arsenopyrite), while 20% is associated with iron oxides. The arsenopyrite found in the banks and floodplains of Whitewood Creek and the Belle Fourche River are the likely source of the arsenopyrite found in the suspended sediments of the Cheyenne River and in the bed sediment of Lake Oahe.

Six cores, ranging in length from 1 to 2 m, were collected in the Cheyenne River arm of Lake Oahe, South Dakota, to investigate potential impacts from gold-mining operations around Lead, South Dakota. Sedimentation rates in the river arm appear to be event-dominated and rapid, on the order of 6–7 cm yr.−1. All the chemical concentrations in the core samples fall within the wide ranges previously reported for the Pierre Shale of Cretaceous age and with the exception of As, generally are similar to bed sediment levels in the Cheyenne River, Lake Oahe and Foster Bay. Based on the downcore distribution of Mn, it appears that reducing conditions exist in the sediment column of the river arm below 2–3 cm. The reducing conditions do not appear to be severe enough to produce differentiation of Fe and Mn throughout the sediment column in the river arm. Cross-correlations for high-level metal-bearing strata within the sediment column can be made for several strata and for several cores; however, cross-correlations for all the high-level metal-bearing strata are not feasible. As is the only element which appears enriched in the core samples compared to surface sediment levels. Well-crystallized arsenopyrite was found in high-As bearing strata from two cores and probably was transported in that form from reducing sediment-storage sites in the banks or floodplains of Whitewood Creek and the Belle Fourche River. It has not oxidized due to the reducing conditions in the sediment column of the Cheyenne River arm. Some As may also be transported in association with Fe- and Mn-oxides and -hydroxides, remobilized under the reducing conditions in the river arm, and then reprecipitated in authigenic sulfide phases. In either case, the As appears to be relatively immobile in the sediment column.