Physico-chemical and toxicological characterization of the historic estuarine sediments: a multidisciplinary approach

The accumulation rates, the geochronology of metals and PAH contamination, and the Microtox toxicity are studied in five sediment cores (50 cm length) covering different areas of the Santander Bay, Northern Spain. Chronology given by (210)Pb and (137)Cs reveals significant differences in accumulation rates between sites (0.2-1.1 cm/year), as well as a variable degree of anthropogenic enrichment factors for Fe, Mn, Cu, Pb, Zn, Ni (from 1 to 15) and concentrations of summation Sigma 16PAHs (from 0.01 to 23.84 mg/kg dw) in sediments over the last 90 years. The results indicate the increasing contamination pressure from industrial and urban activities along the Bay. No toxic results from the Microtox test are obtained either with pore water or with normalised sediment aqueous extracts (European Norm EN 12457), suggesting low water solubility and low availability of contaminants in the studied sediments. However, the EC50 values from the Microtox Basic Solid Phase Test (BSPT) ranged from 0.03% to 2.35%, showing vertical toxicity profiles in accordance with metal and PAHs behaviour. The correlation degrees of Microtox BSPT toxicity to chemical concentration in sediment profiles are widely variable showing a high site-dependent toxicity. The oligochaete Limnodrilus hoffmeisteri has been used as a chronic bioassay over surface sediments of two of the studied sites, showing results coherent with the Microtox BSPT acute test results. Global results of the present work provide regional geochemical baselines for metals and PAHs and toxicological data now make it possible to obtain a preliminary quality assessment of the Santander Bay sediment profiles.     

Correlation of field-measured toxicity with chemical concentration and pollutant availability.

Direct field toxicity tests were performed in two Louisiana waterways, Bayous Trepagnier and St. John, on sediments containing organic/heavy metal mixtures. Our approach involved bioluminescent bacterial toxicity assays (using DeltaTox, which qualitatively identifies polluted areas, and Microtox, which quantifies toxicity). Samples were more completely analyzed in our laboratory using inductively coupled plasma atomic emission spectroscopy (ICP-AES) and gas chromatography/mass spectrometry (GC/MS). Results indicate that lead is the primary toxic metal at the sites examined, though concentrations of metals fluctuate due to spatial variation and the dynamic nature of the waterways. Polycyclic aromatic hydrocarbons (PAHs) are the most abundant group of organics measured and appear to contribute to the overall toxic response. DeltaTox located toxic hotspots where there was an average light loss of 53-100%. Toxicity results from both assays agree but are well correlated with concentration measurements only for certain sediment fractions. Overall, the DeltaTox/Microtox approach appears to be rapid and cost effective for on-site hotspot identification, and may increase understanding of hazards associated with heavy metal and organic contaminants in these waterways.     

Organic carbon changes in the surface sediments of the Venice lagoon

The concentrations of total, inorganic and organic carbon in the surface sediment of the central part of the Venice lagoon (31-55 stations) during the month of June in 1987, 1993 and 1998 were recorded. In two stations: San Giuliano and Lido, samples were collected on a monthly basis for 1 year also in different periods. On an average, by considering the whole central lagoon, inorganic carbon (IC) and total carbon (TC) did not show significant changes. In contrast organic carbon (OC) had alternating trends showing a decrease from 1987 to 1993, due to the almost complete disappearance of huge macroalgal biomasses, and a marked increase from 1993 to 1998, because of the high sediment disturbance caused by the catching of the clam Tapes philippinarum Adams & Reeve which had colonised the sediment free of macrophytes. The carbon changes monitored in the two stations studied on a seasonal basis during different years not only confirmed such results, but also enhanced the effects of fishing activities at Lido station and those depending on the disappearance of macroalgae at S. Giuliano. Moreover, this paper underlines the importance of seagrass beds. In fact in the areas colonised by those plants the percentage of fine sediments and organic matter is on the increase, while erosive processes are contrasted.     

Sediment and carbon accumulation in a small tidal basin: Yuehu,Shandong Peninsula,China

A small sedimentary basin (the Yuehu lagoon), located at the eastern tip of Shandong Peninsula, China, was selected to study its filling by sediment and the vertical flux of particulate organic carbon in response to natural/anthropogenic processes. Surficial and short core sediment samples were collected and analyzed to obtain data sets of grain size, organic carbon content, deposition rates and vertical fluxes of sediment and organic carbon. The analytical results show that the lagoon is covered mainly with fine-grained sediments with high deposition rate and particulate organic carbon content being found from the central part of the mud deposit. The sediment balance of the lagoon indicates high denudation rates of the catchment basin, which may be related to soil erosion in response to farming and land use pattern changes. Furthermore, preliminary analysis of the organic carbon fluxes of the Yuehu lagoon and other embayments of the region shows that these coastal systems make an important contribution to the regional shallow sea carbon burial.     

Novel approach for assessing heavy metal pollution and ecotoxicological status of rivers by means of passive sampling methods

In order to study the pollution of fluvial ecosystems, it is necessary to analyze not only the levels of chemical contaminants in water, but also those accumulated in the sediment matrix, as well as to assess its ecotoxicological status. Eleven Catalan (Spain) river sections (one sampling point per river) located near urban and industrial areas were sampled during winter of 2009. Water pollutants were collected by using passive samplers as Diffusive Gradient in Thin-Films (DGTs) and Semi-Permeable Membrane Devices (SPMDs). Point water samples were also collected. The concentrations of potentially toxic elements (PTE) in water, filtered water, DGTs and sediment samples were analyzed. Aqueous and organic solvent extracts of sediments samples and organic extracts of SPMDs were performed to assess acute toxicity to Vibrio fischeri by Microtox(?), and chronic toxicity to the green alga Pseudokirschneriella subcapitata. Microtox(?) test was also performed with DGT extracts. The results show that metals content of Catalan river waters are below the freshwater screening US EPA benchmarks, excepting some industrial areas (for Hg, Pb, and Zn). In contrast, sediments levels of some rivers were far above freshwater sediment screening US EPA benchmarks (for Zn, As, Cr, Pb, Ni, Hg, and Mn), particularly in the most industrialized areas. A good correlation was found between toxicity values of extracts (from sediments and DGTs) and PTE levels in sediments. The current results support the suitability of using combined point and passive sampling methods for assessing the chemical and ecotoxicological status of aqueous environments.     

Distribution of some trace metals and their fluxes in the Genesee River,NY

Total and particulate metal concentrations, measured during intensive synoptic studies of the Genesee River, NY, correlated with suspended-sediment concentration and river discharge. Dissolved metal concentrations, on the other hand, showed little systematic variation over the length of the river. Metal and sediment fluxes for two elevated-discharged periods peaked at a midbasin sampling site. For most metals at most sampling sties particulate materials comprised over one-half of the total material. Comparison of particulate material metal concentrations, normalized to the measured suspended-sediment concentrations had with basinwide average values shows that sites having low suspended-sediment concentrations had high particulate material metal contents relative to the basin averages, while sites with high suspended-sediment concentration had low metal contents. These results are consistent with a metal transport mechanism in the Genesee River involving (1) a nearly constant dissolved component, (2) a fine acid-soluble component, and (3) a coarse component that is effectively a neutral diluent in the sediment. Chemical factors, such as sediment organic content, also appear to affect metal transport in the Genesee River.     

An integrated approach to the toxicity assessment of Irish marine sediments: validation of established marine bioassays for the monitoring of Irish marine sediments

This paper describes the ecotoxicological evaluation of marine sediments from three sites around Ireland representative of a range of contaminant burdens. A comprehensive assessment of potential sediment toxicity requires the consideration of multiple exposure phases. In addition to the evaluation of multi-exposure phases the use of a battery of multi-trophic test species has been advocated by a number of researchers as testing of single or few organisms may not detect toxicants with a specific mode of action. The Microtox(R) solid phase test (SPT) and the 10-d acute amphipod test with Corophium volutator were used to assess whole sediment toxicity. Porewater and elutriates were assessed with the Microtox(R) acute test, the marine prasinophyte Tetraselmis suecica, and the marine copepod Tisbe battagliai. Solvent extracts were assayed with the Microtox(R) and T. battagliai acute tests. Alexandra Basin was identified as the most toxic site according to all tests, except the Microtox(R) SPT which identified the Dunmore East site as being more toxic. However, it was not possible to correlate the observed ecotoxicological effects with a specific and/or class of contaminants based on sediment chemistry alone. Therefore porewaters found to elicit significant toxicity (Dunmore East and Alexandra Basin) with the test battery were selected for further TIE assessment with T. battalgiai and the Microtox(R) system. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.     

The loading history of trace metals and nutrients in Altata-Ensenada del Pabellón,lagoon complex,northwestern Mexico

This paper summarizes the geochemical investigations about the origin and loading history of some trace metals (Ag, Cu and Zn) and nutrients (N and P) in the coastal lagoon complex of Altata-Ensenada del Pabellón, Mexico, by using the radioactive chronometers 210Pb and 228Th and the stable isotopes of C and N. The examination of sediment cores collected at different locations in the lagoon system identified a slight enrichment in metals and nutrients in some points, which was mainly associated to organic matter accumulation. Stable C and N isotope ratios revealed wastewater inputs to the lagoon system and the 210Pb geochronology showed that anthropogenic impact started 50 years ago, with the beginning of the agriculture development and the associated urban growth of the surrounding area. Several atypical 210Pb and 228Th/232Th profiles demonstrated that biological and physical disturbances are common phenomena in these environments, that frequently mask the pollution records; and therefore, considering that the contaminated sediments at some locations in the lagoon system are frequently resuspended and re-oxygenated, the pollutants will continue to be easily remobilized in the food chain.     

Geochemistry and bioavailability of metals in sediments from northern San Francisco Bay

In this study, metals (Be, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb and Hg) in the fine-grained fraction (<63 microm) from 12 sites at different locations in northern San Francisco Bay over a year period from March 2000 to March 2001 were analyzed after acid extraction. The results showed that metal concentrations in the sediments varied from site to site, whereas some of them were found elevated with respect to the sediment of Tomales Bay, CA, which has little contamination history, indicating an enrichment of the metals in the sediment samples analyzed. Sediment toxicity and bioaccumulation evaluation by a clam species, Macoma nasuta, exposed to the sediment samples collected from the six sampling sites was carried out. The results showed that the sediment samples tested significantly reduced clam survival. Toxicity of the sediments to the clam was, in part, related to elevated metal concentrations in the sediments. In order to examine geochemistry of the metals and to understand potential correlations between metal concentrations and geochemical matrix elements of the sediments, bioavailability and toxicity of the metals, detailed analysis of metal concentrations associated with total organic carbon and the Fe-oxy-hydroxides in the sediment samples was performed. The analysis showed that sediment geochemistry appeared to influence metal bioavailability and may have important impacts on the toxicity of these metals to the clam.     

Variations in bottom sediment nutrient and metal concentrations in the Genesee River watershed,New York

Variations in nutrient and metal concentrations of fluvial sediment may be due to varying combinations of natural and man-made factors: basin geology, surface erosion, riverbank erosion, industrial or other cultural contamination, the presence of minerals rich in trace elements (e.g. chromite), sediment ion-exchange capacity, sediment organic content, and the presence of metallic oxides. The data reported here were obtained in a study in New York State of sediment transport from the Genesee River watershed to Lake Ontario (6,500 km²; 2,400 sq.mi.). One hundred bottom sediment samples collected over a period of a year were chemically analyzed for aluminium, chromium, copper, iron, manganese, nickel, lead, zinc, total carbon, total organic carbon, total nitrogen, and phosphorus. The metal concentrations (arithmetic means ±S.D., in μg/g) were: Al, 6,660±2,620; Cr, 14±9; Cu, 18±7; Fe, 15,060±7,312; Mn, 424±212; Ni, 23±13; Pb, 40±67; and Zn, 69±37. For the major nutrients the results (mean ±1 S.D. in %) were: total carbon, 2.06 ± 1.68; total organic carbon, 1.37 ± 1.28; total nitrogen, 0.105 ± 0.098; and phosphorus, 0.0560 ± 0.014.     

Investigating soils retention ratios and modelling geochemical factors affecting heavy metals retention in soils in a tropical urban watershed

This study aimed at investigating the retention of Pb and Cd in soils and the geochemical factors influencing the adsorption of these pollutants. Soil samples were air-dried and ground to pass through a 2-mm sieve, and different soil extracts were prepared for chemical analysis (organic matter, cation exchange capacity and pH). Total Pb and Cd were extracted with diacid using digestion method and determined by atomic adsorption spectrophotometer (AAS) after filtration. Results revealed that the heavy metals retention ratio (RR) of the Rhodic ferralsol, Xanthic ferralsol and Mollic gleysol (2) were very high for Cd (>80 %) and was relatively low (generally < 60 %) for Pb. In contrast, RRs for the Plinthic gleysol and the Mollic gleysol (1) were relatively low (<60 %), regardless of the heavy metal concerned. Multiple regression equations indicated for Pb and Cd concentrations different linear relationships over simple linear regression, when pH, organic matter, clay percentage and cation exchange capacity (CEC) were used as independent variables. Results indicate that organic matter exerts major influences on the retention of Pb and Cd in soils, while CEC, clay content and pH have a minor influence in this process in the Ntem watershed. From these observations, the application of soil organic matter could be a solution in protecting shallow aquifers from heavy metal pollution and thus insuring that they are not a hazard to public health.     

Heavy metal anomalies in lagoon sediments related to intensive agriculture in Altata-Ensenada del Pabellón coastal system (SE Gulf of California)

Heavy metal concentrations were examined in surface sediments from 79 sites within the Altata-Ensenada del Pabellon lagoon system. Data were normalized to separate natural from anthropogenic factors using aluminum and lithium as conservative elements and following two different discriminating criteria. For the normalization process, the natural metal concentrations were assumed to vary consistently with aluminum and lithium, unless the metal contents were of human origin. Strong linear correlations (P < .001) were observed between the conservative elements and the metals measured. According to Szefer's normalizing criteria, about 90% of the polluted sites, for at least one metal, occurred near agricultural discharge drains. In accordance with the Muller [Umschau 79 (1979) 778.] scale, this lagoon system is subject to pollutant effects only with regard to Pb (moderately to strongly polluted). It was concluded that either Al and Li could be useful to normalize granulometric variability in heavy metal studies of these lagoon sediments, and that Summers' normalization criterion proved more rigorous than Szefer's for these types of sediments.     

Sediment integrative assessment of the Bay of Cádiz (Spain): An ecotoxicological and chemical approach

This study consisted of the sediment toxicity assessment of the Bay of Cádiz based on two endpoints: growth inhibition for Cylindrotheca closterium (benthic microalgae) and fecundity inhibition for Tisbe battagliai (harpacticoid copepod). A new methodology to eliminate (but not as storage technique) the autochthonous biota present in the sediment samples by immersing them in liquid nitrogen (? 196 °C) was also assessed. Sediment toxicity data showed different toxicity levels for both organisms. In general, T. battagliai was more sensitive; however a good correlation (r = 0.75; p  < 0.05) between sediment toxicity results for both species was found. Data in pore water (pH, redox potential, and toxicity for microalgae and copepod) and sediment (pH, redox potential, organic carbon, and metal concentrations) demonstrated that ultra-freezing did not alter sample characteristics; thus, this technique can be adopted as a pre-treatment in whole-sediment toxicity tests in order to avoid misleading results due to presence of autochthonous biota. Multivariate statistical analysis such as cluster and principal component analysis using chemical and ecotoxicological data were employed. Silt and organic matter percentage and lead concentration were found to be the factors that explain about 77% of sediment toxicity in the Bay of Cádiz. Assay methodology determined in this study for both assayed species is considered adequate to be used in sediment toxicity monitoring programs. Results obtained using both species show that the Bay of Cádiz can be considered a moderately polluted zone.     

上海郊区小城镇街道灰尘理化性质及重金属时空分布特征

为了解上海郊区不同类型小城镇街道灰尘的基本理化性质和重金属的时空分布特征,分别于2003年7月（夏季）和2004年4月（春季）在枫泾镇、松江新城和朱家角镇采集街道灰尘样品共计90个,分析了样品的pH、粒度、有机质和重金属的含量。结果表明：3个小城镇街道灰尘的理化性质和重金属时空分布特征具有较好的一致性,pH值为841~1137,呈碱性;有机质的平均含量为3413 g/kg;粒度主要呈单峰和双峰分布特征,粒径平均值为1736 μm,以砂粒为主。各重金属的平均含量均高于上海市土壤环境背景值。Cr和Ni含量夏季高于春季,但区域分异不显著。城镇中心区域和镇级公路Cd、Cu、Pb和Zn含量明显大于乡村。Cr Ni,Cu Pb Zn,Fe Mn之间具有极显著的相关性,有机质是街道灰尘重金属的重要载体     

Screening ecological risk assessment for the benthic community in the Venice lagoon (Italy)

According to the risk hypothesis: the sediment as source of potential risk for the benthic community, an Ecological Risk Assessment (ERA) based on the quotient method was undertaken. The exposure of the benthic community to different classes of pollutants (metals, chlorinated organic compounds and polynuclear aromatic hydrocarbons) was inferred by estimating the pollutant stocks in the top 15-cm sediment of the whole Venice lagoon, after application of geostatistic techniques. The risk was calculated by comparing the sediment exposure profiles with the ecotoxicological benchmarks for benthic organisms. Kriging based maps of the spatial distribution of the estimated risk for the benthic community over the whole lagoon were obtained. The highest risk, found in the areas nearest to the sources of contamination (e.g., the industrial district of Porto Marghera and the river mouths), was posed by mercury (40% of the sampling stations showed exposure levels higher than the Probable Effect Level), arsenic and nickel (75% of the sampling stations exceeded the Threshold Effect Level).     

Sediment accumulation rate and radiological characterisation of the sediment of Palmones River estuary (southern of Spain)

Chemical analyses and radioecological methods were combined in order to estimate the sediment accumulation rate in the upper 20 cm depth of the Palmones River estuary. Organic matter, total carbon, C:N and (137)Cs vertical profiles showed changes at 13 cm depth. These changes could be associated with the decrease in river input since 1987 when a dam situated in the upper part of the estuary started to store water. Using 1987 as reference to date the sediment, accumulation rate was 1.2 cm yr(-1). As alternative method, two layer model of (210)Pb(xs) vertical distribution showed a sedimentation rate of 0.7 cm yr(-1) with a surface mixing layer of 7 cm thickness. The high ammonium, potassium and sodium content in pore water and the strong correlation between (137)Cs activities and organic matter in dry sediment suggests that (137)Cs (the only anthropogenic product detected) is mainly accumulated in the estuary associated with the particulate organic material from the catchment area.     

The importance of physico-chemical parameters on the speciation of natural radionuclides in riverine ecosystems

External gamma radiation levels were measured in the catchment areas of the Sharavathi River and the dose rates in air were found to be in the range 26.0-61.0 nGy h⁻¹. Soil and sediment samples of the riverine environment were analysed for natural radionuclides such as ²²⁶Ra, ²³²Th and ⁴⁰K using a NaI(Tl) gamma spectrometer. The activity concentration of ²¹⁰Pb and ²¹⁰Po in soil and sediment samples was determined by radiochemical separation techniques. Evaluation of the activity concentration of radionuclides with grain size revealed an increase in the activity of ²²⁶Ra, ²³²Th and ⁴⁰K towards fine grain size. The activity concentrations for all isotopes in all samples were not significantly correlated with pH. However, the activity of ²¹⁰Po and ²¹⁰Pb in sediment showed a moderate positive correlation with organic matter content and a good correlation with clay content of sediment.     

西苕溪干流水体、悬浮物和表层沉积物中营养盐分布特征与水质评价

了解不同介质的营养盐分布可以全面掌握河流的环境现状。为了调查西苕溪干流的营养盐分布特征和水质现状,沿着干流采集了11个点位的水体、悬浮物和表层沉积物样品,并对水体、悬浮物和表层沉积物中的营养盐特征进行了分析,拟为苕溪流域的水污染防治提供基础数据。研究表明:整个西苕溪干流,水体和沉积物中总氮(TN)和总磷(TP)浓度均存在丰水期明显高于枯水期的季节变化特征,水体中总氮的浓度均超出地表水环境质量Ⅴ类的标准,显示氮污染是西苕溪流域的特点。相关性分析结果表明,悬浮物中的TN和有机质(OM)呈极显著性正相关(r=0.974,p0.01);水体中的TN和悬浮物的各营养盐指标之间的相关性均达到了极显著水平,但沉积物营养盐指标与水体的TN和TP相关性不明显,显示沉积物并不能很好反映流域水质的现状。     

An integrated approach to the toxicity assessment of Irish marine sediments: application of porewater Toxicity Identification Evaluation (TIE) to Irish marine sediments

An integrated approach to the ecotoxicological assessment of Irish marine sediments was carried out between 2004 and 2007. Phase I Toxicity Identification Evaluation (TIE) of sediment porewaters from two sites on the east coast of Ireland were conducted. Initial Tier I screening of three Irish sites identified the need for TIE after significant toxicity was observed with Tisbe battagliai and the Microtox assay at two of the assayed sites (Alexandra Basin and Dunmore East). Porewaters classified as toxic were characterised using four manipulations, ethylenediaminetetraacetic acid (EDTA) chelation, sodium thiosulphate addition, C(18) Solid Phase Extraction (SPE) and Cation Exchange (CE) SPE. Prior to initial testing, and TIE manipulations, all porewater samples were frozen at -20 degrees C for several months until required. After initial Tier I testing Alexandra Basin porewater was classified as highly toxic by both assays while Dunmore East porewater only warranted a TIE with T. battagliai. Results of TIE manipulations for Alexandra Basin porewater and the Microtox Basic test were inconclusive. The toxicity of the porewater in this assay was significantly reduced after freezing. Three experimental episodes were conducted with one month between each for the Alexandra Basin porewater. After each month of freezing the baseline toxicity was further reduced in the Microtox assay, therefore it was not possible to draw accurate conclusions on the nature of the active contaminants in the sample. However, toxicity to T. battalgiai did not change after storage of the porewater. The C(18) and CE SPE decreased the toxicity of Alexandra Basin porewater to the copepod indicating that both organic and cationic compounds (e.g. metals) were active in the sample. Dunmore East porewater was assayed with T. battalgiai and again a combination of organic and inorganic compounds were found to be partly responsible for the observed toxicity (C(18), CE SPE and EDTA reduced toxicity). Results from these TIEs provide insight into the complexity of interpreting marine TIE data from porewater studies where mixtures of unknown substances are present.     

Reconstruction of historical trends of PCDD/Fs and PCBs in the Venice Lagoon, Italy

Historical trends of PCDD/Fs and PCBs from the year 1900 have been reconstructed for the Venice Lagoon area by using a fugacity-based dynamic multimedia model. A novel approach to estimate the inputs to the system was applied. Emissions to the lagoon were estimated by studying dated sediment cores taken from salt marshes located in the lagoon area. These cores have recently proven to be a suitable tool to reconstruct the temporal trends of atmospheric deposition of POPs. According to the model, concentrations of PCBs and PCDD/Fs in air and water reflect the trends of their production and usage, peaking during the 1960s. The peaks in the sediment were delayed by 5-40 years depending on the congener. Predicted concentrations are in good agreement with experimental results. The most important input parameters, identified by a sensitivity analysis, are the degradation constants, K(ow), the Henry's law constant, vapour pressure, active sediment depth, sediment resuspension, and deposition rates, and water residence time in the lagoon.