Chemical speciation of polycyclic aromatic hydrocarbons in sediments: Partitioning and extraction of humic substances

The primary objective of this study was to examine the chemical speciation of polycyclic aromatic hydrocarbons (PAHs) found in sediments endowed with different characteristics. To achieve this purpose and because the nature of the sediments influences the distribution of PAHs, we have analyzed four different types of sediments. To study the role of organic matter in the sequestration of PAHs, we fractionated humic substances into humic acids and humin-mineral fractions. After their separation and purification, the humic components were examined for their sorptive reactivity by extracting them with organic solvents; these extracts were subsequently subjected to GC/MS analysis. Our results show that PAHs are distributed between labile and sequestered fractions in sediments. A slower uptake of PAHs occurs when the sequestered fraction is formed, and this process can be prolonged and may be influenced by the characteristics if the sediment. Our study suggests that organic contaminants are available in muddy sediments for a longer period of time than in sandy sediments.     

An overview of toxicant identification in sediments and dredged materials

The identification of toxicants affecting aquatic benthic systems is critical to sound assessment and management of our nation's waterways. Identification of toxicants can be useful in designing effective sediment remediation plans and reasonable options for sediment disposal. Knowledge of which contaminants affect benthic systems allows managers to link pollution to specific dischargers and prevent further release of toxicant(s). In addition, identification of major causes of toxicity in sediments may guide programs such as those developing environmental sediment guidelines and registering pesticides, while knowledge of the causes of toxicity which drive ecological changes such as shifts in benthic community structure would be useful in performing ecological risk assessments. To this end, the US Environmental Protection Agency has developed tools (toxicity identification and evaluation (TIE) methods) that allow investigators to characterize and identify chemicals causing acute toxicity in sediments and dredged materials. To date, most sediment TIEs have been performed on interstitial waters. Preliminary evidence from the use of interstitial water TIEs reveals certain patterns in causes of sediment toxicity. First, among all sediments tested, there is no one predominant cause of toxicity; metals, organics, and ammonia play approximately equal roles in causing toxicity. Second, within a single sediment there are multiple causes of toxicity detected; not just one chemical class is active. Third, the role of ammonia is very prominent in these interstitial waters. Finally, if sediments are divided into marine or freshwater, TIEs perforMed on interstitial waters from freshwater sediments indicate a variety of toxicants in fairly equal proportions, while TIEs performed on interstitial waters from marine sediments have identified only ammonia and organics as toxicants, with metals playing a minor role. Preliminary evidence from whole sediment TIEs indicates that organic compounds play a major role in the toxicity of marine sediments, with almost no evidence for either metal or ammonia toxicity. However, interpretation of these results may be skewed because only a small number of interstitial water (n = 13) and whole sediment (n = 5) TIEs have been completed. These trends may change as more data are collected.     

水丝蚓(Tubificid worms)扰动对磷在湖泊沉积物-水界面迁移的影响

为探讨水丝蚓(Tubificid worms)扰动对磷在湖泊沉积物-水界面间迁移的影响,选取太湖梅梁湾与大浦口两富营养化湖区为研究对象,通过室内培养实验,利用Rhizon间隙水采样器等技术,研究了水丝蚓扰动对太湖沉积物-水界面理化性质及溶解活性磷(SRP)在界面通量的影响.结果表明水丝蚓扰动能够增大表层沉积物含水率、氧化还原电位,减小间隙水中Fe2+浓度.水丝蚓没有显著改变梅梁湾间隙水中SRP浓度,同时促进了梅梁湾沉积物中SRP向上覆水的释放;但水丝蚓显著减小了大浦口间隙水中SRP浓度,并抑制了大浦口沉积物中SRP向上覆水的释放.水丝蚓扰动对磷在沉积物-水界面间迁移的不同影响可能是由沉积物中Fe2+含量差异较大造成的.     

Distribution and ecological relevance of fine sediments in organic-enriched lagoons: the case study of the Cabras lagoon (Sardinia, Italy)

In organic-enriched sedimentary systems, like many Mediterranean coastal lagoons, a detailed analysis of sediment grain size composition and partitioning within the muds is crucial to investigate sedimentological trends related to both hydrodynamic energy and basin morphology. In these systems, sediment dynamics are particularly important because the partitioning and transport of fine sediments can strongly influence the redistribution and accumulation of large amounts of organic matter, and consequently the distribution of benthic assemblages and the trophic status and functioning of a lagoon. Nevertheless, studies on benthic-sediment relationships have been based mainly on a rather coarse analysis of sediment grain size features. In muddy systems, however, this approach may impede a proper evaluation of the relationships and effects of the distribution of fine sediment and organic matter on the biotic benthic components. Here we show that the distribution of sedimentary organic matter (OM) and total organic carbon (TOC) in the Cabras lagoon (Sardinia, Italy) can be explained (i.e., predicted) as a function of a nonlinear increase in the amount of the cohesive fraction of sediments (< or = 8 microm grain size particles) and that this fraction strongly influences the structure, composition and distribution of macrobenthic assemblages. Even in such a homogeneously muddy system, characterized by "naturally" occurring impoverished communities, impaired benthic assemblages were found at < or = 8 microm, OM, TOC contents of about 77%, 11% and 3.5%, respectively. A review of studies conducted in Mediterranean coastal lagoons highlighted a lack of direct integrated analysis of sediment features and the biotic components. We suggest that, especially in organic-enriched coastal lagoons, monitoring programs should primarily investigate and consider the cohesive fraction of sediments in order to allow a better assessment of benthic-sediment relationships and ecological quality of the system.     

Spatio-temporal changes of marine macrobenthic community in sub-tropical waters upon recovery from eutrophication. I. Sediment quality and community structure

A two-year study was conducted in the vicinity of a harbour in sub-tropical Hong Kong, to examine the progress of improvement in sediment quality and recovery of macrobenthic community upon cessation of organic pollution caused by sewage discharge. Median sediment particle diameter (Mdphi) and levels of total organic carbon (TOC), total Kjeldahl nitrogen (TKN), ammonia-nitrogen (NH(3)-N) and total phosphorus (TP), as well as macrobenthic species composition and abundance were determined bi-monthly at three inside-harbour and two outside-harbour locations. At the two inside-harbour locations, significantly higher levels of TOC, TKN, NH(3)-N and TP in sediments were observed than the outside-harbour locations. However, no significant temporal change of nutrient levels was detected at all sampling locations during the two-year study, except a significant decrease in TKN and NH(3)-N levels at one outside-harbour location and a decline in NH(3)-N content at another outside-harbour location. Spatially, the highest in mean total species number, individual number, species diversity H' and lowest evenness J was found at one outside-harbour location, whereas the other four locations had relatively similar values. H' was negatively correlated with TOC, TKN, NH(3)-N and TP content in sediments while J was positively correlated with MDphi. Across the study period, the patterns of macrobenthic community were significantly different among all samplings and that the spatial difference of benthic community was best correlated with MDphi, TOC, TKN and water depth. A weak sign of recovery in macrobenthic community structure was detected at inside-harbour locations, with replacement of opportunistic by ubiquitous species over the two-year study. The slow recovery of macrobenthic community was related to sediment characteristics. Results of a larval settlement bioassay using the polychaete Capitella sp. I also demonstrated that the inside-harbour sediments were still unfavourable for colonization and larval settlement of species sensitive to pollution. The slow biodegradation of the organic pollutants and continuous presence of heavy metals in the sediment may hinder settlement and colonization of benthic animals. However, increases of H' and J were observed in a longer time scale when comparing the present data with those obtained four years ago. This suggested that a detectable recovery of benthic community in the harbour may take at least three years and a complete recovery may even take longer duration.     

An environmental assessment of the Charleston Ocean Dredged Material Disposal Site and surrounding areas after partial completion of the Charleston Harbor Deepening Project

A project to deepen shipping and entrance channels in Charleston Harbor was conducted from 1999 to 2002. This generated approximately 22 million cubic yards of sediment for offshore disposal. Assessments of biological and physical conditions in the Charleston Ocean Dredged Material Disposal Site and surrounding areas were conducted prior to deepening (1993-94), and partway through the disposal period (2000). Results from the 2000 survey are presented and compared to the baseline survey. The study area was composed of the disposal zone and surrounding areas and divided into 20 one square mile strata. Within each stratum, benthic grab samples were collected from ten random sites for analysis of sediment composition and contaminants and macrobenthic assemblages. No contaminant levels were above effects range low levels. Results revealed that sediments in the western strata had significantly higher silt/clay content in the 2000 survey when compared to baseline sediments, while sediments east of the disposal zone were similar to baseline. Analyses were performed on a subset of the benthic data that compared baseline to 2000 conditions in western and eastern strata. The benthic communities in western strata were altered following disposal operations. The benthic community east of the disposal area was not different from baseline conditions. These alterations in the benthic community were attributed to changes in bottom habitat characteristics rather than pollution effects.     

Effects of the closure of a major sewage outfall on sublittoral, soft sediment benthic communities

The present study examines the benthos within western inner Swansea Bay (Wales, UK), for the period before, during and immediately after the cessation of a major, sewage discharge from Mumbles Head. There have been significant improvements in seawater quality and changes in the species composition of the benthic communities following the cessation of the sewage discharge. There has been an increase in the diversity of deposit feeders, especially the amphipods, and a decrease in the diversity of the filter feeders, especially the polychaetes. Changes are not attributable either to sediment organic matter content or to gross changes in sediment type, but are related to the significant reduction in suspended particulate organic material and sewage contaminants discharged to the Bay. A recovery model has been proposed to describe how soft sediment benthic communities in a shallow, sublittoral, high tidal energy environment respond to the abrupt cessation of a major sewage discharge.     

Interactions between diatoms and fine sediment

Excessive mobilization and delivery of fine sediments to water bodies has detrimental impacts on those biotic elements used for waterbody status classification, including macroinvertebrates, fish and macrophytes. The relationship between fine sediment and diatoms is a reciprocal one, with diatoms influencing the production and retention of fine sediments, as well as being impacted by fine sediment derived from the catchment. Diatoms can increase the retention of fine sediments in benthic environments as a result of various mechanisms, including shear stress modification, surface adhesion and bed clogging. Enhanced retention of fines can have important implications for the transfer and fate of sediment‐associated nutrients and contaminants. Excessive fine sediment loadings impact diatom assemblages via shading, burial and scouring. Indirect impacts of increased fine sediment stress can result from changes in habitat availability, herbivory or predator changes, which cascade down the food chain. Indices based on the relative abundance of motile species have been proposed for using diatoms to assess waterbody status. However, disentangling the potential confounding impacts of alternative environmental stressors on these simplistic indices remains a significant challenge. Coupling sediment pressure models, capable of predicting the potential impact of mitigation, with meaningful diatom‐based indices, remains a challenge for catchment planning for sediment abatement and the attainment of improved, or protection of, ecological status. Existing targets for sediment management in river catchments are largely based on relationships between sediment stress and impacts on fish, but these thresholds have been widely criticized. There remains a need to develop generic modelling toolkits coupling sediment stress and impacts on a range of biological quality elements to support a weight‐of‐evidence approach. Copyright © 2012 John Wiley & Sons, Ltd.     

Effects of heavy metal contamination on the macrobenthic fauna in estuaries: the case of the Seine estuary

Heavy metal contamination levels are generally higher in estuaries than in the open sea. Some estuaries, the Seine estuary for example, have particularly high pollution levels of metals, yet continue to support a very high benthic biomass and remain quite productive. Measurements of sediment contamination are highly variable due to diverse chemical analysis methods, sediments origin and sources of contaminants found in the estuaries. Salinity appears to be the principal factor controlling contaminant distribution in the sediment and the overlying and/or interstitial waters; it also affects the bioavailability of contaminants in estuarine sediments. Of course, the response to contaminants varies greatly among species and assemblages. Trace metals explain only a small part of the variation in benthic community structure. Some species, such as the shrimp Crangon crangon, appears vulnerable to metal pollution, while other species, such as Scrobicularia plana, are able to tolerate quite high levels of cadmium in their tissue. This paper demonstrates the wide variability of benthic responses to contamination, which is probably due to the high spatio-temporal heterogeneity of the estuary. To reduce the problems due the heterogeneity and variability observed to date in the available results, it will be necessary to encourage integrated estuarine studies, in which sedimentologists, chemists, and biologists work together on the same campaigns at the same sites.     

Sediment‐water Fluxes of Nutrients and Dissolved Organic Carbon in Extensive Sea Cucumber Culture Ponds

Sediment samples were collected from three seawater aquaculture ponds, and soil characteristics, sediment oxygen consumption (SOC), dissolved organic carbon (DOC) and nutrient fluxes were measured using chamber incubations at laboratory. The three ponds were each representing a specific monoculture or polyculture model of sea cucumber. Total organic carbon (TOC) and total nitrogen (TN) contents in the dry sediment ranged from 0.14 to 0.26% and 0.022 to 0.037%, respectively. Total phosphorus (TP) contents in the sediment were more spatially and temporally variable. SOC ranged from 15.29 to 45.86 mmol m^–2 d^–1 and showed significant differences among the three ponds (p < 0.05). TOC, total carbon (TC) contents, and SOC of the sediment in the pond polycultured with jellyfish increased with culture time, indicating that jellyfish farming enhanced the accumulation of organic matter in the sediments to some extent. Sediment showed net nitrate and ammonium uptake in most ponds and months, and significant differences were found among months (p < 0.05). Dissolved inorganic phosphate (DIP) was released from the sediments in all ponds with low flux rates. DOC was released from the sediment in all ponds and ranged from 0.67 to 1.74 g DOC m^–2 d^–1. The results suggested that non‐artificial‐feeding sea cucumber culture ponds could not only yield valuable seafood products, but also effectively remove nutrients from the aquaculture systems and consequently alleviate nutrient loadings of the nearby coast.     

Selection of bioindicators for monitoring marine environmental quality in the Bay of Fundy,Atlantic Canada

Distribution of metals, PAH's and PCB's in lobsters, mussels, and sediments were used to assess marine environmental quality of the Bay of Fundy. This study demonstrates that the lobster (Homarus americanus) is a better bioindicator for monitoring contaminants in the marine environment and has a greater capacity for the uptake and accumulation of contaminants than the mussel (Mytilus edulis) and sediments. A definite pattern in the spatial distribution of lobster Cu, Cd, and Ag was evident. The distribution of organic contaminants for both mussels and lobsters in the Bay of Fundy lacked a spatial trend, and organic contaminants were undetectable in sediments from all sites. The Gulf Watch Programme, which monitors chemicals in mussels in the Bay of Fundy, did not indicate a problem with high levels of Cu, Cd, and Zn in the ecosystem. Analytes below the detection limit, such as in mussels and sediments, increase the difficulties of chemical analysis and detection for environmental monitoring. Deficiencies of mussels in monitoring the Bay of Fundy were discussed.     

Ecotoxicity assessment of natural attenuation effects at a historical dumping site in the western Baltic Sea

During the late 1950s and early 1960s of the past century, industrial waste material highly enriched in various contaminants (heavy metals, PAHs) was dumped in the inner Mecklenburg Bay, western Baltic Sea. Large-scale shifts in the spatial distribution of heavy metals in surface sediments were mapped by geochemical monitoring in the mid-1980s and 12 years later in 1997. A further study in 2001 was designed to investigate the small-scale spatial distribution of contaminants inside, on top of, and around the historical dumping ground and to examine possible effects to benthic organisms (Arctica islandica, microbiological toxicity tests). The site is located within an area characterized by a discontinuous deposition of fine sediments, but net sedimentation rate of about 3mm/y led ultimately to a gradual coverage of the dumped material. During the first decades after the dumping, about half of the originally dumped material was already spread over the surrounding area as a result of sediment dynamics and re-suspension processes. Recent sediments of the historical dump site are still significantly enriched in heavy metals and PAHs. Microbiological toxicity test results were positive, though uptake of contaminants in mussels was found to deviate only slightly from that of a non-contaminated reference station due to a gradual dilution and decrease in bioavailability of the contaminants.     

Sediment disturbance off the Tagus Estuary, Western Portugal: chronic contamination, sewage outfall operation and runoff events

Sediment disturbance patterns in the coastal area off the Tagus Estuary (Portugal) have been assessed using a set of combined techniques. The potential sources of disturbance in the area include chronic contamination of the fine sediments originating from the estuary, a local input from a long-sea sewage outfall and occasional high runoff episodes following torrential rain. The Sediment Quality Triad approach, combining environmental chemistry (namely organic contaminants), macrofaunal benthic communities and laboratory sediment toxicity assays, was performed on sediment samples from 20 sites. The samples were collected before the outfall commenced operation and four years after commissioning, in order to evaluate the relative magnitudes of the three potential sources of disturbance. The sediment contamination created by the estuary was identified as the most important cause of reduced sediment quality, as disturbance in all three components of the Sediment Quality Triad were only found in a site located near the estuary.     

Non-steady state diagenetic record in eastern equatorial Atlantic sediments

The radiocarbon age profile of a sediment core from the eastern equatorial Atlantic shows a marked decrease in both clay and carbonate accumulation rates at the end of the last glacial period, with overall rates of 3.2 and 8.1 cm/kyr for the Holocene and late glacial respectively. The transition from glacial to postglacial conditions recorded in the sediments at 39 cm is above the visual Fe(II)/Fe(III) redox boundary at 48 cm which has been used in the past to identify the glacial section, and even further above the increase in preserved organic carbon content at 55 cm. It is concluded from the present organic carbon profile, and recent observations in this area and elsewhere, that organic diagenesis in these sediments is not steady state. Instead it is suggested that the uppermost glacial sediments lost carbon through oxic remineralisation at the change to postglacial conditions, and that this process is now continued with nitrate as the electron acceptor. These observations suggest that the double MnO_x solid phase peak which occurs in these and similar sediments is a direct consequence of an adjustment of the oxic layer depth following the decrease in carbon flux at the onset of the Holocene.     

The impact of reed-protecting structures on littoral zones

The impact of several types of reed-protecting structures on hydrodynamic conditions, sediment properties and littoral water quality were investigated. All types of embankment lead to a dissipation of wave energy. The embankment with fagots (type 1) shows a limited porosity in contrast to the other types examined. All kinds of embankment enhance the accumulation of organic matter at the land/water-interface. Hence, they protect littoral accumulation zones from erosion. The embankment with fagots causes changes in sediment properties at the seaward side of reed belts. The surface of mineral sediments is turned into a fine-grained mud, with a high content of organic matter. Accelerated sedimentary microbial processes (oxygen demand) are produced by increasing nutrient availability (carbon, nitrogen). As a result, the O₂-saturation of water bodies is significantly reduced. This is in contrast to the embankment with wooden partitions and palisades (type 2 and 3), which had no significant effects on sediment conditions and water quality. The consequences of changes in type 1-protected reed stands are discussed. Practical recommendations are given for the further use of reed-protecting structures.     

Trace contaminant concentrations in the Kara Sea and its adjacent rivers, Russia.

Trace organic (chlorinated pesticides, PCBs, PAHs and dioxins/furans) and trace metal concentrations were measured in surficial sediment and biological tissues (i.e., worms, crustaceans, bivalve molluscs, and fish livers) collected from the Russian Arctic. Total DDT, chlordane, PCB and PAH concentrations ranged from ND to 1.2, ND to <0.1, ND to 1.5 and <20-810 ng g(-1), respectively, in a suite of 40 surficial sediment samples from the Kara Sea and the adjacent Ob and Yenisey Rivers. High sedimentary concentrations of contaminants were found in the lower part of the Yenisey River below the salt wedge. Total dioxins/furans were analysed in a subset of 20 sediment samples and ranged from 1.4 to 410 pg g(-1). The highest trace organic contaminant concentrations were found in organisms, particularly fish livers. Concentrations as high as 89 ng g(-1) chlordane; 1010 ng g(-1) total DDTs; 460 ng g(-1) total PCBs; and 1110 ng g(-1) total PAH, were detected. A subset of 11 tissue samples was analysed for dioxins and furans with total concentrations ranging from 12 to 61 pg g(-1). Concentrations of many trace organic and metal contaminants in the Kara Sea appear to originate from riverine sources and atmospheric transport from more temperate areas. Most organic contaminant concentrations in sediments were low; however, contaminants are being concentrated in organisms and may pose a health hazard for inhabitants of coastal villages.     

太湖东部不同类型湖区底泥疏浚的生态效应

为研究底泥生态疏浚对太湖东部不同类型湖区水生生态系统的影响,2012年8月于东太湖养殖湖区和胥口湾草型湖区采集沉积物和生物样品,分析疏浚对底泥污染控制、水质改善以及各生物群落结构的影响.结果表明,底泥疏浚能有效去除表层沉积物中的营养物质,降低底泥重金属含量及其潜在生态风险,但底泥疏浚对不同类型湖区水质和生物群落结构的影响存在明显差别.在富营养化较严重的东太湖养殖湖区,底泥疏浚达到了一定的改善水质的效果,浮游植物密度、生物量均不同程度降低,且群落中蓝藻所占比例下降;水生植物和底栖动物群落也在较短时间内得到恢复;胥口湾草型湖区的底泥疏浚则破坏了原先良好的水生植物群落,造成湖区整体水质下降,各主要生物类群的恢复相对缓慢.     

Indicators of sediment and biotic mercury contamination in a southern New England estuary

Total mercury (Hg) and methylmercury (MeHg) were analyzed in near surface sediments (0-2 cm) and biota (zooplankton, macro-invertebrates, finfish) collected from Narragansett Bay (Rhode Island/Massachusetts, USA) and adjacent embayments and tidal rivers. Spatial patterns in sediment contamination were governed by the high affinity of Hg for total organic carbon (TOC). Sediment MeHg and percent MeHg were also inversely related to summer bottom water dissolved oxygen (DO) concentrations, presumably due to the increased activity of methylating bacteria. For biota, Hg accumulation was influenced by inter-specific habitat preferences and trophic structure, and sediments with high TOC and percent silt-clay composition limited mercury bioavailability. Moreover, hypoxic bottom water limited Hg bioaccumulation, which is possibly mediated by a reduction in biotic foraging, and thus, dietary uptake of mercury. Finally, most biota demonstrated a significant positive relationship between tissue and TOC-normalized sediment Hg, but relationships were much weaker or absent for sediment MeHg. These results have important implications for the utility of estuarine biota as subjects for mercury monitoring programs.