Release and phase partitioning of metals from anoxic estuarine sediments during periods of simulated resuspension

Periodically, marine sediments are subjected to physical processes which resuspend them into the water column, releasing previously sequestered metals. The role of resuspension energy and duration on release and subsequent redistribution of sediment bound metals was measured experimentally using a particle entrainment simulator. Two metal contaminated anoxic sediments with different physical and chemical characteristics were resuspended for 12 h at energies of 2 and 5 dynes cm(-2). Samples were taken at specified intervals, and the water column pH, Eh and dissolved oxygen levels were monitored continuously. Over time, metal concentrations increased in the particulate (nonfilterable > or = 1 microm) and filterable (< 1 microm) phases of the overlying water. In general, metal enrichment followed the Irving-Williams order of complex stability. Overall, the sediment's chemical and physical composition were major factors in determining the amount of metal released, more so than the level of resuspension energy applied. These results provide insight into how physical and chemical processes interact during sediment resuspension to release sediment bound metals and control their phase distribution in the water column.     

Assessment of heavy metals remobilization by fractionation: comparison of leaching tests applied to roadside sediments

The pollution emitted by traffic activities and road maintenance is an area of great interest as contaminants can be transported to roadside sediments and pose a risk to environmental and human health. In the presentwork, deposited pollution in roadside sediments has been assessed by sampling along a highly traveled highway in Barcelona and the surrounding area. The available amounts of the heavy metals was determined by applying different leaching tests and calculating the concentration enrichment ratio (CER) and the environmental concentration guideline values (ECG). To gain information on the heavy metals (HMs) fractionation, the sequential extraction scheme (SES), established by the Standard Measurement and Testing (SM&T), was implemented, and the results were compared with those obtained by single leaching tests. An anthropogenic enhancement of certain metals was observed after considering both the CER and ECG values. However, if only ECG values were considered, an overestimation of the anthropogenically enhanced pollutants was obtained due to disregarding geochemical and particle size variability. CER values provide a more realistic assessment by determining different levels of anthropogenic impact. Thus, CER values suggest a minimum anthropogenic apportion for metals such as Cd, Cr, and Ni, whereas different situations from significant to extreme anthropogenic contribution were observed for Zn, Pb, and Cu. These results have been complemented by other leaching tests that minimize the time-consuming environmental evaluation. In this study, HCI extraction produces suitable results for a quick screening since they correlate well with the corresponding SES: Cu(r2 = 0.798), Pb(r2 = 0.958) and Zn(r2 = 0.901). Mild extractants have been observed to be limited to highly polluted samples due to their low leaching power. The information obtained following this procedure helps to identify hazardous areas that need a remedial strategy.     

Critical evaluation of desorption phenomena of heavy metals from natural sediments

In natural sediments, the majority of heavy metal ions are generally associated with the solid phase. To become bioavailable, the metal ions must desorb from the solid. Numerous studies of heavy metals in sediments have suggested that sorption and desorption exhibit hysteresis (i.e., the two processes are not reversible), while other studies have suggested that desorption hysteresis does not exist. In this study, sorption/desorption hysteresis of lead (Pb) and cadmium (Cd) was evaluated over the following range of conditions: (i) desorption induced by replacing the supernatant liquid with contaminant-free electrolyte solution; (ii) desorption induced by lowering the solution pH with mineral acid; and (iii) desorption induced by sequestration with EDTA. Given the importance of dissolved organic and inorganic ligands in regulating heavy metal behavior in nature sediments, sorption/desorption experiments were conducted on both untreated and prewashed sediments. Prewashing treatment increases the sorption potential of Cd but not Pb. Desorption hysteresis is observed in both the untreated and the prewashed sediments using the replaced supernatant method, and the desorption hysteresis appears to increase with aging time. Hysteresis is not observed when desorption is initiated by lowering the solution pH. A large fraction of the sorbed heavy metal ions can be easily desorbed by EDTA; between 0.04 and 1.2 mmol/kg Cd and Pb ions are resistant to desorption.     

Photochemical source of metals for sediments

A mass budget study of major in-lake Al fluxes, palaeolimnological data on a >10,000 year old sediment record, and in situ photochemical experiments performed at Plesné Lake (Czech Republic) suggest that photochemical liberation of organically bound aluminum (Al) and iron (Fe) by solar radiation is a significant natural source of their ionic species for lakes and subsequent oxyhydroxides for sediments. The results show that photochemically induced transformation of dissolved Al and Fe to solid oxyhydroxides deposited to Plesné Lake sediment dominated (91 and 73%, respectively) their sedimentary flux throughout the preindustrial era, since soil formation initiated in the catchment. The following sequence of processes occurs: (i) soil organic acids dissolve and bind metals and export them from terrestrial to aquatic systems. (ii) Photochemical decomposition of organic-metal complexes liberates a significant portion (approximately 50% in Pleseé Lake) of organically bound Al and Fe as inorganic ions. (iii) The liberated ionic Al and Fe hydrolyze, precipitate as oxyhydroxide particles, and settle. We hypothesise that the same Al and Fe transporting process occurs in other lakes and coastal marine areas and is ecologically important because Al and Fe oxyhydroxides can bind trace metals and phosphorus.     

Beryllium-7 as a tracer of short-term sediment deposition and resuspension in the Fox River, Wisconsin

Short-term (approximately monthly) sediment deposition and resuspension rates of surficial bed sediments in two PCB-laden impoundments on the Fox River, WI, were determined in the summer and fall of 1998 using 7Be, a naturally occurring radioisotope produced in the atmosphere. Decay-corrected activities and inventories of 7Be were measured in bed sediment and in suspended particles. Beryllium-7 activities generally decreased with depth in the top 5-10 cm of sediments and ranged from undetectable to approximately 0.9 pCi cm(-3). Inventories of 7Be, calculated from the sum of activities from all depths, ranged from 0.87 to 3.74 pCi cm(-2), and the values covaried between sites likely reflecting a common atmospheric input signal. Activities of 7Be did not correlate directly with rainfall. Partitioning the 7Be flux into "new" and "residual" components indicated that net deposition was occurring most of the time during the summer. Net erosion, however, was observed at the upstream site from the final collection in the fall. This erosion event was estimated to have removed 0.10 g (cm of sediment)(-2), corresponding to approximately 0.5 cm of sediment depth, and approximately 6-10 kg of polychlorinated biphenyls (PCBs) over the whole deposit. Short-term accumulation rates were up to approximately 130 times higher than the long-term rates calculated from 137Cs profiles, suggesting an extremely dynamic sediment transport environment, even within an impounded river system.     

Enrichment of heavy metals in sediment resulting from soil erosion on agricultural fields

Heavy metal pollution of soil and water is often associated with industry, but in this paper we demonstrate that water erosion on agricultural soil which has received only agrochemicals has enriched sediment metal concentrations to toxic levels which breach many accepted standards for soils and sediments. Eight 0.1 ha erosion plots with different cultivation treatments were monitored over a 6 year period for surface runoff, soil loss, and Cr, Cu, Pb, and Ni concentrations. Mean concentrations of these heavy metals were up to 3.98 times higher in the sediment than in the parent soil and in some erosion events the sediment had 13.5 times the concentration of metals in the soil. All the sediment heavy metal concentrations were significantly correlated (p < 0.01) with the clay and silt sized fractions of the sediment and with carbon content. The erosion was a highly selective process enriching the detached material in silt, clay, and organic carbon. This was particularly true in smaller erosion events. Sediment metal concentrations tended to follow the shape of runoff hydrographs, although the pattern changed from storm to storm.     

Simultaneous release of metals and sulfide in lacustrine sediment

A single DGT (diffusive gradient in thin films) probe that could measure metals and sulfide simultaneously and at the same location was deployed in the surface sediment of a productive lake (Esthwaite Water). It contained a layer of AgI that binds sulfide overlying a layer of chelating resin that binds metals. Analysis for sulfide in two dimensions showed local sources of sulfide, 1-5 mm in diameter, at 8-11 cm depth within the sediment. A transect of trace metals measured at 100-microm intervals through the largest sulfide "hot spot" demonstrated concomitant release of Fe, Mn, Cu, Ni, and Co. Substantial supersaturation with respect to metal sulfides was observed for Fe and Co at the site of metal generation, but at a distance of less than 1 mm, solution concentrations were consistent with equilibration with amorphous FeS and CoS phases. Simple mass balance calculations were consistent with Fe being supplied from reductive dissolution of its oxides and with sulfide being supplied from reduction of sulfate. The observed concentrations of Cu, Ni, Co, and Mn could be accounted for by their release from iron oxides without invoking Mn reduction. The metals are removed rapidly (approximately 1 min) at the edge of the hot spot. These first observations of the simultaneous release of trace metals and sulfide are consistent with the known removal of metals by formation of their insoluble sulfides if the in situ kinetics of metal sulfide formation is on this time scale. The coproduction of reduced Fe and S suggests that iron- and sulfate-reducing bacteria may exist together in the same localized zone of actively decomposing organic matter.     

Anaerobic degradation of linear alkylbenzene sulfonates in coastal marine sediments

This research shows for the first time the degradation of linear alkylbenzene sulfonates (LAS) under anaerobic conditions, together with the presence of metabolites and the identification of microorganisms involved in this process. This compound is the most widely used surfactant and its main environmental concern is related to its persistence in the absence of oxygen as LAS accumulates in anaerobic sediments and sewage sludges. Laboratory experiments performed with anoxic marine sediments spiked with 10-50 ppm of LAS demonstrated, however, that its degradation reached 79% in 165 days via the generation of sulfophenyl carboxylic acids (SPCs). Almost all of the added LAS (>99%) was found to be attached to the sediment while the less hydrophobic SPCs were predominant in solution, as their concentration increased progressively up to 3 ppm during the full course of the experiment. Average half-life for LAS has been estimated to be 90 days, although higher values should be expected when the LAS concentration exceeds 20 ppm, due to inhibition of the microbial community. Sulfate-reducing and methanogenic activities proved to be intense during the experiment. Several sulfate-reducing bacteria and firmicutes/clostridia have been identified as possible candidates for effecting this degradation. Our results imply that the persistence of LAS in anoxic compartments, such as marine sediments, should be reconsidered when evaluating its environmental risk.     

Trace metals in cut trough shell (Spisula subtruncata) from Belgian coastal waters

In the period 1985-1996 concentrations of mercury, cadmium, lead, copper, zinc and chromium in cut trough shell (Spisula subtruncata) sampled on 11 stations on the Belgian Continental Shelf were determined. On the whole, contents of trace metals showed a tendency to decrease. No significant differences in concentrations were found between the stations, except on one site for lead and chromium. Average concentrations (all stations) were (in mg/kg wet weight): 0.02 for mercury, 0.08 for cadmium, 0.38 for lead, 2.5 for copper, 12.7 for zinc and 0.47 for chromium. These values were well below legally authorized limits.     

辽宁沿海城市海鱼和贝类中重金属含量的测定及评价

经微波消解处理样品,采用石墨炉原子吸收光谱法(GFAAS)测定辽宁沿海城市常见海鱼和贝类中镉、铬、铜、铅、铁、锌六种元素的含量。其相对标准偏差(RSD)0.53%～4.01%,加标回收率90.0%～110.0%。结果表明:不同地区、不同鱼贝种类中重金属的分布存在差异,所检测鱼贝类中铬、铜、锌含量低于国家限量标准,部分样品中镉、铅含量超标,但低于暂定每周可耐受摄入量(PTWI)。因此辽宁沿海城市市售所检测的鱼贝类可食用,但仍有必要降低摄入量。     

Seven thousand years of records on the mining and utilization of metals from lake sediments in central China

A 268 cm section of sediment core from Liangzhi Lake in Hubei province in central China was used to assess the use and accumulation of metals in the lake in the past 7,000 years. The concentrations of trace metals, including Cu, Pb, Ni, and Zn, and major elements, Ca, Fe, and Mg, in a 14C- dated segment of sediment core were analyzed. Historical trends on the input of metals to Liangzhi Lake from around 5000 BC to the present were recorded in the sediments, representing about 7,000 years of history on the mining and utilization of metals in central China. The concentrations of Cu, Ni, Pb, and Zn increased gradually from about 3000 +/- 328 BC, indicating the start of the Bronze Age in ancient China. During the period 467 +/- 257 to 215 +/- 221 AD, there was a rapid increase in the concentrations of these metals in the sediments, indicating enormous inputs of these metals at that time. This era corresponded to China's Warring States Period (475- 221 BC) and the early Han Dynasty (206 BC-220 AD), during which copper and lead were extensively used in making bronze articles such as vessels, tools, and weapons. From 1880 +/- 35 AD to the early 1900s, there was also a significant increase in the concentrations of metals such as Cu, Ni, and Pb, which probably reflected the metal emissions and utilization during the early period of industrial development and weapon manufacture during the wars in China. The Pb isotopic analysis showed that the surface and subsurface sediments had lower 206Pb/207Pb and 208Pb/ 207Pb ratios than the deeper layers, reflecting the additional input of Pb from mining activities that took place during the Bronze Age era and in modern times. This study provides direct evidence of the environmental impact of the mining and utilization of metals in the last 7,000 years in one of the important regions of Chinese civilization.     

Potential remobilization of 137Cs, 60Co, 90Tc,and 90Sr from contaminated Mayak sediments in river and estuary environments

Following 50 years of nuclear production at Mayak PA, sediments in storage reservoirs are significantly contaminated. Dam failure or flooding could potentially transport large amounts of sediments, via rivers, to the Ob estuary and Kara Sea. The objectives of this work were to investigate fresh and seawater remobilization of 137Cs, 50Co, 99Tc, and 90Sr from contaminated Reservoir 10 sediments. Sediments were extracted sequentially using synthetic Techa freshwater, seawater, and chemical reagents with increasing dissolution powers. 137Cs and 90Sr freshwater distribution coefficients (apparent Kd) agreed quite well with published values; values for 99Tc were higher and values for 60Co were lower than expected. In seawater, mean apparent Kd values decreased by 94, 77, 48, and 73% (137Cs, 60Co, 99Tc, and 90Sr, respectively), indicating increased radionuclide mobility. Remobilization in seawater was 5, 15, 1, and 23% of total activities (i.e., releases of 165, 11, 0.3, and 170 kBq kg(-1) d.w.) for 137Cs, 60Co, 99Tc, and 90Sr, respectively. 137Cs and 99Tc were strongly bound to sediments (60% and 80%, respectively). 60Co and 90Sr were more mobile (70% reversibly bound). In conclusion, Mayak Reservoir sediments could potentially contaminate the Ob estuary due to remobilization of sediment-held radionuclides upon contact with seawater.     

Occurrence and specific congener profile of 40 polybrominated diphenyl ethers in river and coastal sediments from Portugal

Forty polybrominated diphenyl ethers (PBDEs), from mono- through hepta-brominated, were analyzed in river and coastal sediment samples of the eight main river basins of Portugal to investigate the occurrence, geographical distribution, and detailed congener profiles. Thirty-two sediment samples taken along the different rivers from inland to the open sea revealed an increase toward the river mouth with a total PBDE concentration of 20 ng/g-dw, and levels decreased to 0.5 ng/g-dw in coastal sediments. PBDEs were detected in all samples analyzed, indicating a diffuse source of pollution in the aquatic environments. Maximum levels were encountered in sediments collected close to urban and industrial areas. Of 40 congeners included in the analytical work, 17 congeners were detected in river sediments. BDE 47 was found in all samples analyzed whereas BDEs 100 and 99 were found in more than 26 out of 32 samples analyzed at concentrations from 0.03 to 10 ng/g-dw. This study is unique in showing the presence of previously nondescribed lower brominated PBDEs in riverine and marine sediments. BDEs 7, 11, 12+13, 15, 30, 32, 17, 25, 28+33, 49, 75, and 71 were identified in two to five samples with a median of 0.03-0.55 ng/g-dw. The analytical method developed consisted of the use of Soxhlet extraction with a novel cleanup method employing alumina cartridges and analysis by gas chromatography-mass spectrometry operated in negative chemical ionization mode.     

Geochemical signature of contaminated sediment remobilization revealed by spatially resolved X-ray microanalysis of annual rings of Salix nigra

An X-ray microprobe was used to determine the concentration and distribution of Ni, U, and other metals within annual rings of willows (Salix nigra L.) from a former de facto radiological settling basin (Steed Pond; SP) and a depositional environment downstream (Tims Branch; TB) on the Savannah River Site (SRS). Geochemical and historical information about both areas are well documented. Following spillway breaches at SP in 1984 and the early 1990s, TB is inundated with contaminated sediments during storms. Bulk elemental composition of tree cores was determined using ICP-OES. Synchrotron X-rayfluorescence (SXRF) analysis showed that the metal contents of SP and TB cores were an order of magnitude higher than those from a reference site. TB cores were enriched with Ni in 1984 and 1991, corresponding with SP spillway breaches (containing 790 mg kg(-1) Ni in 1991). Cores from SP exhibited an extremely high Ni peak in 1996, approximately 5000 mg kg(-1), even though contaminant levels at SP did not change. The geochemical signature of contaminants recorded in TB annual rings reflected the significant sediment remobilization events consistent with the detailed history of the site, and at concentrations relative to their proximity to the source term. However, physiological processes occurring within impacted trees strongly influence the chronological accuracy of dendroanalysis and must be investigated further.     

Method for testing the aquatic toxicity of sediment extracts for use in identifying organic toxicants in sediments

Biologically directed fractionation techniques are a fundamental tool for identifying the cause of toxicity in environmental samples, but few are available for studying mixtures of organic chemicals in aquatic sediments. This paper describes a method for extracting organic chemicals from sediments and then re-introducing them into water column toxicity tests in a way that mimics, at least in part, the partitioning processes that govern bioavailability in sediment. This involves transferring solvent extracts of sediment into triolein and then placing the mixture inside low-density polyethylene dialysis tubing in a configuration similar to semipermeable membrane devices (SPMDs) used for environmental monitoring. For four model compounds, SPMDs were shown to effectively maintain water column exposure in static systems for 10-14 d, with partition coefficients similar to K(OW). Toxicity tests indicated that the SPMDs were compatible with four of five freshwater organisms tested and could be used to measure both lethal and sublethal end points. An example application showed good correspondence between organism responses in intactsediment and extracts in SPMDsfor both field-collected and spiked sediments. The SPMD-based method offers a simple, flexible test design, amenable to several different test organisms, and the ability to work with complex mixtures of contaminants while maintaining partitioning behavior similar to that within intact sediments.     

Broad dissemination of plasmid-mediated quinolone resistance genes in sediments of two urban coastal wetlands

Contamination of soil and water with antibiotic-resistant bacteria may create reservoirs of antibiotic resistance genes that have the potential to negatively impact future public health through horizontal gene transfer. The plasmid-mediated quinolone resistance genes qnrA, qnrB, qnrS, qepA, and aac(6')-Ib-cr were detected by PCR amplification of metagenomic DNA from surface sediments of the Tijuana River Estuary, a sewage-impacted coastal wetland along the U.S.-Mexico border; sediments of Famosa Slough, a nearby urban wetland that is largely unaffected by sewage, contained only qnrB, qnrS, and qepA. The number of PCR-positive sites and replicates increased in both wetlands after rainfall. Real-time quantitative PCR revealed a significant increase (p < 0.0005) in qnrA abundance (copies per gram sediment or per 16S rDNA copy) in Tijuana River Estuary sediments immediately following rainfall, but no significant change was measured at Famosa Slough (p > 0.1). Nucleotide sequences of cloned qnrA amplicons were all affiliated with qnrA genes found on plasmids of clinical isolates with one exception that was most similar to the chromosomal qnrA gene found in Shewanella algae. Our results suggest that urban wetlands may become reservoirs of antibiotic resistance genes, particularly where wastewater is improperly managed.