RECOVERY: A Contaminated Sediment-Water Interaction Model

This paper describes the U.S. Army Corps of Engineers screening-level water quality model (RECOVERY version 3.0) for assessing long-term impacts of contaminated bottom sediments on surface waters. The model couples contaminant interaction between the water column and the bottom sediment, as well as between contaminated and clean bottom sediments. The analysis is intended primarily for organic contaminants with the assumption that the overlying water column is well mixed vertically. The contaminant is assumed to follow linear, reversible, equilibrium sorption and first-order decay kinetics. The system is physically represented as a well-mixed water column (i.e., zero-dimensional) underlain by a vertically-stratified sediment column (i.e., one-dimensional). The sediment is well-mixed horizontally but segmented vertically into a well-mixed surface (active) layer and deep sediment. The deep sediment is segmented into variably contaminated and clean sediment regions. Processes incorporated in the model are sorption, decay, volatilization, burial, resuspension, settling, bioturbation, and pore-water diffusion. The solution couples contaminant mass balance in the water column and in the mixed sediment layer along with diffusion in the deep sediment layers. The model was verified against laboratory and field data, as well as against an analytical solution for the water and mixed sediment layers. These comparisons indicate that the model can be used as an assessment tool for evaluating remediation alternatives for contaminated bottom sediments.     

The source and fate of sediment and mercury in the Tapajós River, Pará, Brazilian Amazon: Ground- and space-based evidence

We present results of mercury (Hg) in surface waters and soils and an analysis of satellite imagery from the Tapajós River basin, Brazilian Amazon, and the Reserva Garimpeira do Tapajós, the legal gold mining district of the basin. Hg bound to suspended sediment was roughly 600 and 200 times the concentration of dissolved Hg per litre of water, in impacted and pristine areas, respectively. Suspended sediments thus represent the major pathway of river-borne Hg. Median concentrations of Hg in suspended load from both impacted and pristine waters were 134 ppb, and 80% of samples were below 300ppb-in the range of naturally occurring surficial materials in the tropics. Regionally, riverine Hg fluxes were proportional to the concentration of total suspended solids. This shows that the dominant source of Hg is the sediment itself rather than anthropogenic mercury discharge from the small-scale mines. To independently test this conclusion, a mass balance was performed. A conservative calculation of the annual export of mercury (Hg) from the Creporí River (a minimum) was 1.6 tonnes for the year 1998-it could be significantly larger. This amount of Hg is difficult to account for by anthropogenic discharge alone, confirming that enhanced physical erosion caused by sluicing and dredging operations is the dominant source of Hg. We therefore conclude that gold mining operations are primarily responsible for elevated Hg concentrations. The dominant source of contamination is not, however, the loss of Hg in the gold amalgamation process. Rather, the disturbance and mobilization of large quantities of Hg-rich sediment and floodplain soil into the water column during mining operations is the source of contamination. These findings shift the focus of remediation and prevention efforts away from Hg control toward soil and sediment erosion control. The minimization or elimination of Hg losses in the mining process remains important for the health of local peoples and environments, but keeping basin soils and sediments in place would be a much more effective means of minimizing Hg fluxes to the region's rivers. To gain a spatial and historical perspective on the source and extent of emissions, satellite imagery was used. We were able to reconstruct historical mining activity, locate impacted areas, and estimate historical Hg fluxes with the imagery. To do so, the spectral characteristics of satellite images were calibrated to the concentration of suspended sediment in the rivers, which, in turn, is proportional to the Hg concentration. This analysis shows that mining-induced sediment plumes have been a dominant source of sediment to the Tapajós River system for decades. As well, the intensity and location of these emissions has varied through time. For example, sediment discharge from the Creporí River was greater in 1985 than in 1998; and the tributaries on the west bank of the Tapajós were actively being mined in 1985 but had been abandoned in 1998. This type of information should greatly assist in understanding original and ongoing sources of emissions, and in managing prevention and remediation efforts.     

沉水植物黑藻对沉积物有机、无机磷形态及潜在可交换性磷的影响

在室内模拟条件下研究了沉水植物黑藻对沉积物有机及无机磷形态及潜在可交换性磷的影响.结果表明:①黑藻可显著降低沉积物的有机质、阳离子代换量及总磷(p<0.05),对沉积物中的磷起到活化的作用.②黑藻对沉积物无机磷形态中的NaOH-P有极显著影响(p<0.01),对有机磷形态中的活性有机磷有一定影响(p<0.1),而对其他形态磷的影响没有达到显著水平.③有植物组沉积物的潜在可交换性磷的量增大了11.5%,而对照组沉积物的却减少了61.0%.两者变化的方向截然相反,而且变化的程度也存在较大差异.这说明黑藻的作用增大了沉积物中潜在可交换性磷的量.     

Macroinvertebrate community response to acid mine drainage in rivers of the High Andes (Bolivia)

Several High Andes Rivers are characterized by inorganic water pollution known as acid mine drainage (AMD). The aim of this study was to assess the relationship between metal concentrations in the sediments and the macroinvertebrate communities in two river basins affected by AMD. In general, the taxon diversity of the macroinvertebrate community at the family level was low. The concentrations of Cd, Cu, Zn, Pb and Ni at mining sites were higher than at unpolluted sites. The pH of the water was alkaline (7.0-8.5) in unpolluted sites, whereas it dropped to very low values (<3) at mining sites. Redundancy Analysis (RDA) showed that pH was the best predictor of macroinvertebrate community richness. The number of macroinvertebrate families decreased gradually with increasing acidity, both in pools and riffles, though it is suggested that riffle communities were more affected because they are in closer contact with the acid water.     

Tidal salt marsh sediment in California, USA: part 3. Current and historic toxicity potential of contaminants and their bioaccumulation

To assess potential health risks to benthic organisms from exposure to toxic contaminants, sediment chemistry data from five salt marshes along the coast of California were compared with threshold effects levels (TELs) and probable effects levels (PELs). As an integrated estimate of toxicity potential of multiple contaminants, mean PEL quotients (mPELQs) were used to categorize sampling stations into three groups: high (>0.5), medium (0.1–0.5) and low (<0.1). In all sediments from Stege Marsh located in San Francisco Bay, at least one contaminant exceeded PELs by up to 18-fold and mPELQs were higher than 0.7. Mean PELQs in two core sediments from eastern Stege Marsh ranged from 0.7 to 2.1, indicating that benthic organisms in Stege Marsh may have been adversely affected for several decades. To investigate bioavailability and bioaccumulation of contaminants in sediments, longjaw mudsuckers (Gillichthys mirabilis) were transplanted to six Stege Marsh stations for 60 days. Body burdens of organic contaminants clearly showed that they were readily available for benthic organisms. Measured concentrations of organic contaminants in mudsuckers were similar to estimated levels computed using a theoretical bioaccumulation potential model. Levels of PCBs and arsenic in mudsuckers were higher than screening values set as guidelines for the protection of humans and levels of PCBs and DDTs were higher than criteria for wildlife. The results of this study indicate that the levels of contaminants in Stege Marsh sediments may not fully support the well-being of benthic organisms and also may provoke adverse effects on fish-eating animals and humans through trophic transfer.     

Fate and Transport Modeling of Potential Pathogens: The Contribution From Sediments1

Abstract: Escherichia coli was used as a bacterial tracer for the development, calibration, and validation of a watershed scale fate and transport model to be extended to a suite of reference pathogens (Cryptosporidium, Giardia, Campylobacter, E. coli O157:H7). E. coli densities in water and sediments from the Blackstone River Watershed, Massachusetts, were measured at three sites for a total of five wet weather events and three dry weather events covering three seasons. The confirmed E. coli strains were identified by ribotyping for tracking the sources of E. coli and for determining the association of downstream E. coli isolates with isolates from upstream sediments. A large number of downstream samples were associated with upstream sediment sources of E. coli. E. coli densities ranged from 71 to 6,401 MPN/100 ml in water samples and from 2 to 335 MPN/g in sediments. Pearson correlation analysis revealed significant correlations between E. coli and total coliforms in water (r = 0.777, p < 0.01) and sediments (r = 0.728, p < 0.01). In addition, E. coli concentrations in water were weakly correlated with sediment particle size and sediment concentrations (r = 0.298, p < 0.01). A hydrologic model, WATFLOOD/SPL9, was used to predict the temporal and spatial variation of E. coli in the Blackstone River. The rapid rise of stream E. coli densities was more accurately predicted by the model with the inclusion of sediment resuspension, thus demonstrating the importance of the process.     

The feasibility of decontamination of reduced saline sediments from copper using the electrokinetic process

The remediation of metal contamination in estuarine and reduced sediments is another challenge for the electrokinetic process. Problems result from the complex chemical composition of saline reduced sediments. In the experiments described here copper was added into saline reduced sediments to simulate the natural situation. Two constant voltages were applied across the electrokinetic cell to investigate the effect of an increase in potential difference on the electrokinetic process. Acetic acid at pH 6 and 4 was also added to the cathode in separate experiments to enhance copper removal. The results from this study showed that in the unenhanced experiments most of copper remained in the soil and was unaffected by the electrokinetic process. At the end of unenhanced electrokinetic experiments, the copper concentration was found only to be slightly changed in the anode region. Up to 21% of the copper was found precipitated near the anode when the applied voltage was 10V and this increased to 25% when the applied voltage was 7V. In the enhanced electrokinetic experiments up to 98% of copper was removed from section 1 and precipitated again in sections 2 and 3. This indicates that a significant amount copper removal from the saline sediments may be achieved by the enhanced electrokinetic process.     

Influence of variable chemical conditions on EDTA-enhanced transport of metal ions in mildly acidic groundwater

Adsorption of Ni and Pb on aquifer sediments from Cape Cod, Massachusetts, USA increased with increasing pH and metal-ion concentration. Adsorption could be described quantitatively using a semi-mechanistic surface complexation model (SCM), in which adsorption is described using chemical reactions between metal ions and adsorption sites. Equilibrium reactive transport simulations incorporating the SCMs, formation of metal-ion-EDTA complexes, and either Fe(III)-oxyhydroxide solubility or Zn desorption from sediments identified important factors responsible for trends observed during transport experiments conducted with EDTA complexes of Ni, Zn, and Pb in the Cape Cod aquifer. Dissociation of Pb-EDTA by Fe(III) is more favorable than Ni-EDTA because of differences in Ni- and Pb-adsorption to the sediments. Dissociation of Ni-EDTA becomes more favorable with decreasing Ni-EDTA concentration and decreasing pH. In contrast to Ni, Pb-EDTA can be dissociated by Zn desorbed from the aquifer sediments. Variability in adsorbed Zn concentrations has a large impact on Pb-EDTA dissociation.     

Bioavailability of sediment-associated and low-molecular-mass species of radionuclides/trace metals to the mussel Mytilus edulis

Sediments can act as a sink for contaminants in effluents from industrial and nuclear installations or when released from dumped waste. However, contaminated sediments may also act as a potential source of radionuclides and trace metals to the water phase due to remobilisation of metals as dissolved species and resuspension of particles. The marine mussel Mytilus edulis is a filter-feeding organism that via the gills is subjected to contaminants in dissolved form and from contaminants associated to suspended particles via the digestive system. In this paper the bioavailability of sediment-associated and seawater diluted Cs, Co, Cd and Zn radioactive tracers to the filtering bivalve M. edulis has been examined. The mussels were exposed to tracers diluted in ultrafiltered (<10 kDa) seawater (Low Molecular Mass form) or to tracers associated with sediment particles from the Stepovogo Fjord at Novaya Zemlya in short-term uptake experiments, followed by 1-month depuration experiments in flow-through tanks. A toxicokinetic model was fitted to the uptake and depuration data, and the obtained parameters were used to simulate the significance of the two uptake pathways at different suspended sediment loads and sediment-seawater distribution coefficients. The results of the model simulations, assuming steady state conditions, suggest that resuspended particles from contaminated sediments can be a highly significant pathway for mussels in the order ¹⁰⁹Cd ≌ ⁶⁵Zn < ¹³⁴Cs < ⁶⁰Co. The significance increases with higher suspended sediment load and with higher K_d. Furthermore, the experimental depuration data suggest that Cs is retained longer and Co, Cd and Zn shorter by the mussels when associated with ingested sediments, than if the metals are taken up from the low molecular mass (LMM) phase.     

贵州阿哈水库沉积物中重金属二次污染的趋势分析

通过对受矿山活动影响的贵州阿哈水库沉积物-水界面的模拟试验及实测分析,从水库水质安全角度讨论了沉积物中蓄积的重金属作为二次污染源的可能性。研究发现：在水体季节性缺氧期间,沉积物中部分重金属元素将大量释放到水体中,严重威胁水质安全。Fe,Mn的最大释放发生在水体缺氧事件的50小时内。而Co,Cu,Ni,Pb等元素总体释放量较小,并主要在10小时内达到最大释放。对比其他地区,阿哈水库中重金属元素具有更强的界面扩散作用。锰的扩散通量在季节上表现为：冬季＞秋季＞春夏季。而铁的扩散通量则为：春夏季＞秋季＞冬季。锰的界面扩散通量远大于铁的界面扩散通量,表明界面附近锰的循环极为剧烈且远强于铁。这对其他重金属元素的界面循环产生了重要影响。界面附近的铁、锰、硫循环对重金属迁移有着显著的控制作用。受到氧化还原条件的影响,重金属扩散通量在季节上变化较大。