Natural and anthropogenic heavy metals in estuarine cohesive sediments: geochemistry and bioavailability

The geochemistry, mineralogy, and grain size distribution of several estuarine cohesive sediment samples from potentially human-influenced areas without such an influence were analyzed to determine the natural heavy metal content and evaluate its impact on the Bahía Blanca estuarine environment. The data were compared with different ranges of concentrations for heavy metals in marine sediments established by the NOAA Screening Quick Reference Tables in which values range from background levels to those considered toxic to the marine environment. Our total heavy metal contents were below the established hazardous levels in all the analyzed samples, even though the potentially human-influenced areas (harbors, industry, urban spread) showed the highest total concentration values as well as greater percentages of bioavailable compounds. This would imply a low and not extensive anthropogenic input into the environment. The relatively high proportions in which Cd, Pb, and Cr appear as bioavailable compounds at some sites not influenced by human activity suggest the presence of a natural source for these elements. This could be attributed to the weathering of naturally occurring volcanic minerals, indicating that special care must be taken when monitoring of sediment for anthropogenic activity is carried out within this environment. According to the results obtained, and in order to minimize the environmental impact caused by periodic water injection dredging, relocation of sewage outfalls from vessel mooring areas into open waters is strongly recommended.     

Dioxin-like compounds in sediments from the Daliao River Estuary of Bohai Sea: distribution and their influencing factors

The concentrations, compositional profiles, and potential ecological risk of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in sediments of the Daliao River Estuary were investigated. Total concentrations of PCDD/Fs, PCBs, and PCNs were in the range of 11.3-133.2 ng/kg dry weight (dw), 1 971-37 632 ng/kg dw and 33.1-284.4 ng/kg dw, respectively. The total TEQ values varied from 0.37 to 4.08 ng/kg dw, with the dominant contributions by PCDD/Fs, then by PCBs and PCNs. The spatial distributions of PCDD/Fs, PCBs and PCNs in the river estuary were much related to hydrodynamic conditions. The risk of contamination to the deeper sea was increased in the flood seasons. Moreover, our data confirmed that both organic matter in sediments and molecular properties of dioxin-like compounds were the factors which strongly influenced the partition behavior of these dioxin-like compounds between sediments and water phase in the estuarine zone.     

Historical records of organic pollutants in sediment cores

Analyses of sediment core samples are primary sources of historical pollution trends in aquatic systems. Determining organic compounds, such as POPs, in the dated sediments enables the estimation of their temporal concentration changes and the identification of the contaminant origin in local regions. Wars, large-scale fires, economical transitions, and bans on certain chemicals are reflected in the sediment organic compound concentrations. The high POP concentrations in surficial sediments suggest that these chemicals, even after being banned, remain in the environment. Furthermore, vertical profiles can help in understanding the sedimentation process and in estimating effective countermeasures against pollution. Moreover, studies published during the period 1991–2013 on PAHs, PCBs, OCPs, dioxins and dioxin-like compound concentrations in sediment core samples are reviewed.     

Dioxin-like compounds in HPLC-fractionated extracts of marine samples from the east and west coast of Sweden: Bioassay- and instrumentally-derived TCDD equivalents

Lipophilic extracts of sediment, settling particulate matter (SPM) and blue mussel (Mytilus edulis) samples, collected at coastal locations on the east and west coast of Sweden, were HPLC-separated into three fractions containing 1. monoaromatic/aliphatic, 2. diaromatic (e.g. polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDDs/Fs)), and 3. polyaromatic compounds (e.g. polycyclic aromatic hydrocarbons (PAHs)). The fractions were tested for dioxin-like effects using a sensitive bioassay, based on EROD-induction in cultured chicken embryo livers. The concentrations of PCDDs/Fs, PCBs and 15 PAHs in the samples were also determined. The polyaromatic fractions of the sediment samples were more potent as EROD-inducers than the diaromatic fractions. Only a small part of the EROD-induction caused by the polyaromatic fractions could be explained by the analysed PAHs in the samples, indicating presence of non-quantified polyaromatic EROD-inducing compounds in the samples. A greater pollution by EROD-inducing diaromatic and polyaromatic compounds on the east coast site than on the west coast site was seen. The filtration activities and faeces production of the mussels on the east coast experimental site increased the sedimentation of PCDDs/Fs, PCBs and PAHs. The described bioassay proved very useful in the assessment of dioxin-like compounds in both abiotic and biotic samples from the marine environment.     

Potential toxicity of resuspended particulate matter and sediments: Environmental samples from the Bay of Banyuls-sur-Mer and Thermaikos Gulf

This contribution attempts to determine whether, and to what degree, environmental samples of resuspended particulate matter and sediments exert a toxicological impact. Further, an attempt is made also to screen the toxic level of potentially hazardous sites, based upon established sediment toxicity criteria. Therefore, a rapid, cost-effective and highly sensitive biotest (bioluminescence assay, based upon marine bacteria) has been applied on: biological fluid extracts; bottom sediments; and sediment trap samples. Samples were taken either from the Bay of Banyuls-sur-Mer (northwestern Mediterranean, France) or Thermaikos Gulf (northeastern Mediterranean, Greece). Biological fluid extracts and sediment trap samples corresponded to periods of resuspension events, or preceding and following such events.The results have revealed that the sampling strategy and biotest implemented in this study might be a useful tool for screening the toxicity of resuspended matter and sediments. Resuspension events appear to be able to exert an influence on the chemical forms of the micro-pollutants; thus on their bioavailability and toxicity. Nevertheless, based upon chemical analysis combined with the bioassay, the toxic level of the sediment samples could be determined, with the level at potentially hazardous sites being characterised.     

Distribution of 137Cs in the Lena River estuary-Laptev Sea system.

Surface sediment samples in the Laptev Sea have average 137Cs content of 7.1 Bq kg(-1), a value intermediate between that of the western Kara Sea (23 Bq kg(-1) and the East Siberian Sea (4.2 Bq kg-'). Both surface sediment content and sediment inventory of 137Cs in the Laptev Sea sediments show significant variability, and the influence of a variety of environmental factors.137Cs concentrations in the Laptev Sea surface sediments range from 0.8 to 16 Bq kg(-1). There is a marked increase in 137Cs content of surface sediment samples collected near the Lena River delta, and a local enrichment in the 137Cs inventories at these sites is also evident. Fine-grained mixed-layer illite/ smectite rich sediments in the estuary provide effective adsorption sites to fix 137Cs, in spite of desorption processes associated with low salinities in estuarine mixing. The Lena River-Laptev Sea mixing zone is a major site of sea-ice production. River and shelf sediments are incorporated into sea-ice formed in this region (Holmes and Creager, 1974). The irregular 137Cs activity profiles of the Lena River estuary cores indicate disturbance or removal of 137Cs-laden sediments via sea-ice related processes. Lena River and Estuary sediments may have served as a secondary source (i.e. other than direct fallout) of 137Cs in sea-ice. North-east of the Lena River estuary, sediment contains a thin layer of 137Cs-bearing material over an erosion surface. The 137Cs-laden surface layer may be the result of transient deposition of estuarine sediments being delivered by sea-ice or spring floods.     

The stable aryl hydrocarbon receptor agonist potency of United Kingdom Continental Shelf (UKCS) offshore produced water effluents

The in vitro aryl hydrocarbon receptor (AhR) agonist potency of offshore produced water effluents, collected from the United Kingdom Continental Shelf, was determined using the dioxin responsive (DR)-chemically activated luciferase expression (CALUX) assay. Octadecylsilane (C18) solid phase extraction (SPE) extracts of produced water were exposed to DR-CALUX cells for 24 h in order to investigate the contribution in potency from compounds that are stable to metabolism by the CALUX cells during exposure. The stable AhR agonist potency determined over 24 h was highly variable and ranged from 1 to 430 ng TCDD TEQ_CALUX l⁻¹. These data reflect the highly variable composition of produced water discharges from different production fields. It is recommended that further work be performed to characterise the full range of stable dioxin like AhR agonists present in offshore produced water discharges using techniques such as bioassay-directed analysis.     

Growth of an amphipod and a bivalve in uncontaminated sediments: Implications for chronic toxicity assessments

This study assessed the sensitivity of the amphipod Chaetocorophium cf. lucasi, an inhabitant of New Zealand estuarine muddy sediments, and of the bivalve Macomona liliana, commonly found in New Zealand sandflats, to sediment particle-size distribution, total organic carbon, total organic nitrogen and water content. Growth and survival were evaluated after different test exposure times using laboratory-prepared natural sediment mixtures of sand and mud. The results suggest that amphipod survival was affected by the type of sand more than by the concentration of sand in the sediment samples. In samples with high survival rates, amphipod growth was impaired in sediments with higher sand proportions after a 10-day exposure, but after longer periods (28 or 30 days) there were no significant differences among treatments which had ≤76% sand. Bivalve survival and growth were not significantly affected by different natural sediment characteristics. Test duration for chronic toxicity tests with the bivalve M. liliana and the amphipod C. cf. lucasi should be at least 28 days for the detection of significant growth relative to the initial size.     

Utilisation of different carbon sources in a shallow estuary identified through stable isotope techniques

Organic carbon in estuarine sediments can have many different sources. Terrestrial, riverine, estuarine and marine C pools may all contribute to and influence the organic C (C_org) inventory of the estuarine sediments and the differing stable isotope signatures of the sources are reflected in the sediment's overall ¹³C content. Ecological interpretations of sedimentary isotope data may, however, be limited by the fact the total C_org inventory of a sediment may not be an accurate representation of the fraction that is labile and being actively turned over by the sedimentary community. To gain a better understanding of sedimentary C_org dynamics in estuaries and the relationship between the sedimentary C pool and the C_org undergoing mineralisation, we studied three components of an estuarine system: (1) the sedimentary C_org inventory on a transect from the mouth to the upper end of the estuary, (2) temporal changes of sedimentary C_org at one station throughout a year, and (3) the δ¹³C of respired CO₂ compared to the δ¹³C of available source material and sedimentary C_org in a novel application of methods developed for soil science. Our experiments demonstrated that material of marine origin dominated the studied estuary. At the time-series station, material of marine origin dominated the sedimentary C_org throughout the 1-yr study period. δ¹³C values of CO₂ released from the sediment differed significantly from the sedimentary C_org inventory at all study sites, but also clearly reflected differences between the main sections of the estuary. These results suggest that δ¹³C measurements of respired CO₂ are promising as a tool to advance our understanding of C cycling in estuaries, and highlight that the sedimentary C_org pool alone may not be a satisfactory indicator of OM utilisation in estuarine sediments.     

Comet assay for the detection of genotoxicity in blood cells of flounder (Paralichthys olivaceus) exposed to sediments and polycyclic aromatic hydrocarbons

To investigate the genotoxic effect of marine sediments on aquatic organism, sediment samples were collected from 13 sites along the coast of Gwangyang Bay (Korea). Concentrations of polycyclic aromatic hydrocarbons (PAHs) in sediments were determined and the relationship between exposure of flounder blood cells to sediment extracts and DNA single-strand breakage in the blood cells was examined using the comet assay. Levels of DNA damage were proportionally increased by exposure concentration and the highest sediment-associated DNA damage was observed at the station showing the highest PAHs contamination. DNA damage in blood cells exposed to five types of PAHs (benzo[a]pyrene, fluoranthene, anthracene, pyrene and phenanthrene) and in flounder (Paralichthys olivaceus) exposed to benzo[a]pyrene (BaP) for 0, 2 and 4 days were assessed by measuring comet tail length. The tail lengths of five PAHs-exposed groups at 50 and 100 ppb were significantly different from the non-exposed group, and the genotoxic effect of BaP correlated with both concentration and duration of exposure. Throughout the study, significant differences in DNA breakage were recorded between cells exposed to sediment extracts or PAHs and non-exposed control. This study demonstrated the comet assay as a successful tool in monitoring contamination of marine sediments and assessing genotoxicity of PAHs in marine organisms, either in vitro or in vivo.     

Tracing anthropogenic contamination in the Pearl River estuarine and marine environment of South China Sea using sterols and other organic molecular markers

5beta-Coprostanol together with eight other sterols and unresolved complex mixtures (UCMs) were quantitatively investigated for surficial sediments and surface waters to assess the impacts of anthropogenic activities on the Pearl River estuarine and marine environment of South China Sea. The studied area extends from the Pearl River Estuary southward to the open sea. 5beta-Coprostanol concentrations ranged from trace amounts to 53 microgg(-1) TOC in surficial sediments. The highest levels and highest percentages of coprostanol were found in the Pearl River estuary, especially in the inner estuary and those sites close to the submarine outfalls of Hong Kong. For waters, only in estuarine samples was coprostanol quantitatively detected, ranging from 11 to 299 ngL(-1). Bimodal UCM "humps" were observed for most sediment samples, with concentrations ranging from 215 to 10,491 microg g(-1) TOC in sediments and from 2 to 26 mcirogL(-1) in waters, respectively. Progressive seaward declines in concentrations were found for both 5beta-coprostanol and UCM in surficial sediments. Trace or no 5beta-coprostanol was found in open-sea samples. Concentrations of coprostanol and UCM in surficial sediments are correlated. These results imply that there are obvious anthropogenic contaminations in the Pearl River estuary. The submarine outfalls in Hong Kong represent important sources of the sewage pollution to the Pearl River estuarine sediments evidenced by a combination of coprostanol concentration, diagnostic indices, sterol profiles and UCM. No obvious dispersion or transport of the sewage contamination occurred from the Pearl River estuary to the open South China Sea indicated by fecal sterol biomarkers.     

Cell bioassays for detection of aryl hydrocarbon (AhR) and estrogen receptor (ER) mediated activity in environmental samples

In vitro cell bioassays are useful techniques for the determination of receptor-mediated activities in environmental samples containing complex mixtures of contaminants. The cell bioassays determine contamination by pollutants that act through specific modes of action. This article presents strategies for the evaluation of aryl hydrocarbon receptor (hereafter referred as dioxin-like) or estrogen receptor mediated activities of potential endocrine disrupting compounds in complex environmental mixtures. Extracts from various types of environmental or food matrices can be tested by this technique to evaluate their 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents or estrogenic equivalents and to identify contaminated samples that need further investigation using resource-intensive instrumental analyses. Fractionation of sample extracts exhibiting significant activities, and subsequent reanalysis with the bioassays can identify important classes of contaminants that are responsible for the observed activity. Effect-directed chemical analysis is performed only for the active fractions to determine the responsible compounds. Potency-balance estimates of all major compounds contributing to the observed effects can be calculated to determine if all of the activity has been identified, and to assess the potential for interactions such as synergism or antagonism among contaminants present in the complex mixtures. The bioassay approach is an efficient (fast and cost effective) screening system to identify the samples of interest and to provide basic information for further analysis and risk evaluation.     

Changes in metal contamination levels in estuarine sediments around India – An assessment

This review is the first attempt to comprehend the changes in metal contamination levels in surface estuarine sediments with changing time around India. Contamination factor, geoaccumulation index, pollution load index, effects range low and effects range median analysis were used to evaluate the quality of the estuarine sediments (by using the available literature data). This study suggests that estuarine sediments from the east coast of India were comparatively less contaminated by metals than the west coast. Sediments from those estuaries were found to be more contaminated by metals on which major cities are located. An improvement in estuarine sediment quality (in terms of metal contamination) over time around India was noticed. This study provides managers and decision-makers of environmental protection agency with a better scientific understanding for decision-making in controlling metal pollution in estuarine sediments around India.     

Phosphorus forms and distribution in Zhejiang coastal sediment in the East China Sea

Surface and core sediment samples were collected from Zhejiang coastal waters of the East China Sea to study phosphorus（P） forms and understand the potential release of P as well as adsorption.The sediments were extracted sequentially to determine four phosphorus fractions,and non-sequentially for total phosphorus（TP）.The total concentration of phosphorus in the surface sediments ranged from 527.2 to 680.5 mg kg-1.Inorganic P was the major form and accounted for 84-94%of TP.Among the four forms,P-Detrital was dominant（58.6-73.2%）,followed by P-CDB（10.5-20.9%）,P-Organic（6.1-15.9%）,and P-CFA（5.9-16.3%）.The distribution pattern of TP in the surface sediments was similar to that of P-Detrital and P-Organic,but different from P-CDB and P-CFA.A relatively high level of phosphorus was observed in estuarine sediments,reflecting the influence from terrestrial input.Phosphorus in all forms in core sediments at each station decreased with depth.In addition,potentially bio-available phosphorus accounted for 20-34%of TP.     

坦噶尼喀湖东北部入湖河流表层沉积物中磷的形态和分布特征

磷是坦噶尼喀湖生态系统中必不可少的营养元素,直接决定湖体初级生产力的高低,进而影响到周边居民对于动物蛋白的获取来源.为了解坦噶尼喀湖磷的外源输入,选择湖泊东北部的入湖河流,对表层沉积物(16个样点)中总磷(TP)和各形态磷含量及其分布特征进行分析,并探讨磷的形态分布特征与土地利用方式之间的相关关系.结果表明,入湖河流沉积物TP含量为73.05~239.94 mg/kg,平均含量为152.64±55.37 mg/kg,其中最高值出现在马拉加拉西河口.采用Psenner法对磷进行连续浸提并比较不同形态磷含量,由高及低依次为铁铝结合态磷(Fe/Al-P)钙结合态磷(CaP)有机磷(Org-P)残渣态磷(Res-P)弱吸附态磷(Labile-P).土地利用类型对TP及各形态磷含量影响较大,其中TP含量表现为河口湿地城镇附近林草地区,表明地表径流和人类活动会对TP含量产生影响,而对于不同形态磷含量,Laible-P、Fe/Al-P、Org-P含量均表现为河口湿地林草地城镇附近,Ca-P、Res-P含量均表现为城镇附近河口湿地林草地.分析沉积物理化性质与各磷形态之间的相关性,发现沉积物总氮(TN)、有机质和总有机碳与Fe/Al-P、LabileP和TP相关性较好,与Org-P、Ca-P和Res-P相关性较差,表明TN和有机质的输入,会伴随沉积物中磷含量的升高,其增量的赋存形态主要为氧化还原敏感态磷和Labile-P.沉积物粒径组成与各磷形态含量存在相关性,细粒径沉积物与各形态磷含量呈显著正相关,粗粒径沉积物与各形态磷呈显著负相关,表明细小颗粒更易吸附磷.     

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.     

Synergistic effects of diuron and sedimentation on photosynthesis and survival of crustose coralline algae

Effects of short-term exposure to sedimentation and diuron, separately and in combination, on the photophysiology and survival of crustose coralline algae (CCA) were examined in controlled time-course experiments, using pulse-amplitude modulation (PAM) chlorophyll fluorometry. These experiments indicated that the effects of sediments and diuron, when applied in isolation, were often reversible, with recovery time dependent upon sediment type and diuron concentration. Exposure to fine (<63 microm grain size), nutrient-rich estuarine sediments reduced effective quantum yields (Delta F/F(m')) of photosystem II in CCA species more than exposure to the same amount of fine (<63 microm grain size) calcareous sediments. Significant inhibition of photosynthesis (Delta F/F(m')) was also observed at diuron concentrations > or =2.9 microg L(-1). Fine estuarine sediments in combination with 0.79 microg L(-1) dissolved diuron, caused yields (Delta F/F(m')) to drop by 60% compared with controls after 24 h. The combined exposure to sediments and diuron also retarded recovery, thus Delta F/F(m') values were still only 60% of the controls after 9 days recovery in clean seawater. Mortality of CCA was observed in some fragments treated with combinations of sediment and diuron. Our results suggest that sediment deposition and exposure to diuron can negatively affect the photosynthetic activity of CCA, with sedimentation stress being significantly enhanced by the presence of trace concentrations of diuron.     

The mobility, partitioning and degradation of atrazine and simazine in the salt marsh environment

The transfer of the s-triazine herbicides onto a salt marsh and their subsequent behaviour and fate has been investigated in a series of laboratory-based experiments. The results indicate that atrazine and simazine enter the marsh system and undergo negligible adsorption onto suspended solids. Herbicide accumulation within the sediment compartment was thought to be due to other mechanisms such as partitioning into the surface microlayer, or association with sediment flocs. s-Triazine mobility within the sediment was dictated by compound and sediment type, reflecting greater mobility in the mud flat than the vegetated marsh sediment. The majority of the herbicides were, however, retained in the uppermost layers of the sediment profile indicating that salt marsh sediments act as a sink for these compounds. Although degradation rates in the sediment were relatively rapid, detectable levels of the parent compounds were still evident after 71 days, which implies that these compounds may persist in salt marsh sediments. The absence of degradation in the aqueous phase implies that adsorption to particulate matter is a prerequisite for the degradation of the s-triazine herbicides.     

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.