Assessment of ecological risk from bioaccumulation of PCDD/Fs and dioxin-like PCBs in a coastal lagoon

The ecological risk posed by dioxin-like PCBs and PCDD/Fs congeners mixtures in five organisms representative of the food web of the lagoon of Venice (Italy) was estimated by applying the US-EPA [US-EPA. Guidelines for Ecological Risk Assessment. EPA/630/R-95/002F. Final Report. U.S. Environmental Protection Agency, Washington, DC; 1998.] procedure. Experimental concentrations of dioxin-like PCBs and PCDD/Fs in sediments, water, and organisms in six lagoon zones were used to define the spatial distribution of the pollutant homolog patterns. The Principal Component Analysis of homolog patterns in biota permitted to remark the difference between PCDD/Fs and dioxin-like PCBs bioaccumulation. Dioxin-like PCBs were found almost unaltered in all selected organisms, while PCDD/Fs homologs underwent an enrichment of low chlorinated furans in fish. The ecological risk for the dioxin-like PCBs and PCDD/Fs was estimated in the selected lagoon zones according to the Hazard Quotient approach by comparing the biota experimental concentrations in TEQ with an Internal No Effect Concentration of the 2,3,7,8-TCDD, estimated from both Ambient Quality Criteria and literature toxicity data. A high potential risk was found for benthic biota (i.e. clam and crab) and for mussel, while a negligible risk was estimated for fish. Moreover, the ecological risk resulted higher in the central part of the lagoon, and lower in the northern lagoon. Finally, the comparison between the TEQ concentrations of each homolog in biota and the estimated ecological risk highlighted that the risk was determined essentially by lower chlorinated PCDD/Fs (i.e. pentachloro and hexachloro PCDD/Fs), and by pentachloro-PCBs. These compounds should be regarded as homologs of concern and preferentially investigated in environmental monitoring of sediment, water, and biota.     

Fate of Irgarol 1051, diuron and their main metabolites in two UK marine systems after restrictions in antifouling paints

Two major antifouling biocides used worldwide, Irgarol 1051 and diuron, and their degradation products in Shoreham Harbour and Brighton Marina, UK were studied during 2003-2004. The highest concentrations of Irgarol 1051 were 136 and 102 ng L(-1) in water and 40 and 49 ng g(-1) dry weight in sediments for Shoreham Harbour and Brighton Marina, respectively. As the degradation product of Irgarol 1051, M1 was also widespread, with the highest concentration of 59 ng L(-1) in water and 23 ng g(-1) in sediments in Shoreham Harbour, and 37 ng L(-1) in water and 5.6 ng g(-1) in sediments in Brighton Marina. The target compounds showed enhanced concentrations during the boating season (May-July), when boats were being re-painted (January-February), and where the density of pleasure crafts was high. Overall, the concentration of Irgarol 1051 decreased significantly from late 2000 to early 2004, indicating the effectiveness of controlling its concentrations in the marine environment following restricted use. Diuron was only detected in 14% of water samples, and mostly absent from sediment samples.     

Dietary PBDE intake: a market-basket study in Belgium

A food market-basket, representative for the general Belgian population, containing various meat, fish and dairy food products, was assembled and analysed for its polybrominated diphenyl ether (PBDE) content. Additionally, fast food samples were also investigated. Based on the measured PBDE levels, an average daily dietary intake estimate of PBDEs was calculated. Of all foods analysed, fish had the highest average sum of PBDE levels (BDEs 28, 47, 99, 100, 153, 154, and 183; 460 pg/g ww), followed by dairy products and eggs (260 pg/g ww), fast food (86 pg/g ww) and meat products (70 pg/g ww). One fresh salmon filet had the highest total concentration of PBDEs (2360 pg/g ww), whereas levels in steak and chicken breast were the lowest of all foods analysed. BDE 209 was never found above LOQ in any food. PBDE intake calculations were based on the average daily food consumption in Belgium and were estimated between 23 and 48 ng/day of total PBDEs (lower and upper bound). This value is in accordance with what was previously reported for diets from geographical distinct areas, such as Canada, Finland, Spain, Sweden and the UK. Although it is only a minor constituent of the Belgian diet, fish is the major contributor to the total daily PBDE-intake (around 40%) due to the high PBDE levels in this type of food. Although low contaminated, meat products account for around 30% of the total dietary intake of PBDEs. Dairy products and eggs contribute to a lesser degree (less than 30%).     

An in vitro/in vivo screening assay as a sensitive tool to assess endocrine disruptive activity in surface water

Adult male fathead minnow were exposed for 14 or 28-days under flow-through conditions to undiluted filtered water samples from the rivers Meuse and Rhine in the Netherlands. The experiment included two vessels per treatment each containing 10 fish and samples of five fish were taken after 14 and 28 days. Additional groups were exposed to 17alpha-ethinylestradiol (EE2) as a reference and untreated drinking water as a negative control. Major endpoints examined included induction of vitellogenin (VTG) synthesis, VTG mRNA activity, hepato- and gonadosomatic indices (HSI and GSI) and gonadal histology. No significant difference was recorded in body weight or mean GSI values between the various treatments. Only exposure to Meuse water resulted in significantly higher HSI means after 14 days. Histological examination showed no apparent effects on gonadal tissue except for eosinophilic blood plasma in fish exposed to Meuse water or EE2. After 14 and 28 days, elevated VTG and VTG mRNA levels were measured in most livers of the fish exposed to Meuse water, but not in the fish exposed to Rhine water. This was confirmed by measuring estrogenic responses in the in vitro ER CALUX assay. Induction of VTG synthesis proved to be the most sensitive endpoint in the Non Spawning Male Fish Assay for in vivo detection of bio-available estrogenic activity supplementary to a sensitive in vitro assay. The other endpoints examined varied too much and required a higher number of fish or replicates to achieve sufficient power for statistical testing making them less animal friendly.     

Presence, biotransformation and effects of sulfophenylcarboxylic acids in the benthic fish Solea senegalensis

The presence of linear alkylbenzene sulfonates (LAS) and their degradation intermediates, sulfophenylcarboxylic acids (SPCs), with concentrations up to 100 ppb has been found in surface waters taken from the estuary of the river Guadalete (Cádiz, SW of Spain). Higher concentrations were found at the sampling site located adjacent to the discharge outlet of a wastewater treatment plant (WWTP). The concentrations decreased downstream to a few ppb as a result of dilution, sorption, and degradation processes, which were taking place along the estuary. Once the presence of both xenobiotics was confirmed in the environment, an in vivo assay was conducted to study their biotransformation and effects in the benthic fish Solea senegalensis. A flow-through system was employed, consisting of an exposure phase (120 h) with environmental levels of the surfactant (200, 500 and 800 microg/L of 2?C(10)LAS), followed by a depuration stage (72 h). The generation of SPCs has been quantified during these phases in both water and fish, with LAS biotransformation shown in all cases. The antioxidant enzymes catalase (CAT), glutathione peroxidase (GPX), glutathione reductase (GR), the phase II enzyme glutathione S-transferase (GST), and the phase III acid and alkaline phosphatases (AcP, ALP) were also estimated and utilized as biomarkers.     

Impact of dredging in a shallow coastal lagoon: Microtox Basic Solid-Phase Test, trace metals and Corophium bioassay

The aim of this work was to measure survival of the amphipod Corophium insidiosum and luminescence inhibition in the marine bacterium Vibrio fisheri on surface sediment samples collected from a shallow coastal lagoon (Pialassa Baiona, northern Adriatic Italian coast) before execution of dredging operations to deepen the main inner channel of the lagoon and restore the water circulation. Trace metal (Cd, Cu, Cr, Hg, Ni, Pb) concentrations, grain size and organic carbon matter content as loss of ignition were also measured. Toxicity testing with V. fisheri was carried out according to the Microtox Basic Solid-Phase Test (BSPT) protocol. The preliminary outcomes of this work show that: (a) the investigated area can be categorised as moderately degraded; (b) there is no evident spatial pattern in sediment toxicity and trace metal concentrations; (c) Microtox responses are not biased by sediment characteristics such as silt, clay and organic matter content.     

The use of a metallothionein-like-proteins (MTLP) kinetic approach for metal bioavailability monitoring in dredged material

Ecotoxicological effects associated with contaminants present in dredged material from Spain were determined using a marine biotest based on the determination of metallothionein-like-protein concentrations (MTLPs) in the shore crab Carcinus maenas. Intermoult female C. maenas were exposed in the laboratory to sediments from three Spanish ports, Ría de Huelva (SW, Spain), La Coru?a (NW, Spain) and Bahía de Cádiz (SW, Spain) per replicate during 21 days. Hepatopancreas samples from crabs were taken for metallothioneins analysis on days 0, 7 and 21. Furthermore, chemical analysis was performed in the stations to determine the degree and nature of sediment contamination (Cr, Ni, Cu, Zn, Cd, Pb, Hg, As, PAHs and PCBs). A significant increase (p<0.05) in metallothionein concentration was observed over time in individuals exposed to sediment from the port Ría de Huelva characterized by high concentrations of metals. A toxicokinetic approach is proposed in this study related to the use of this biomarker in C. maenas to evaluate bioavailability associated with metals present in dredged material. As a first step, this toxicokinetic approach might reveal as a sensitive tool for evaluating bioavailability of contaminants present in dredged material.     

Distribution of organotin compounds in the bivalves of the Aegean Sea, Greece

Five bivalve species--Mytilus galloprovinciallis (Mediterranean mussels), Venus gallina (stripped venus), Modiola barbatus L. (bearded horse mussels), Pecten jacobeus (scallops) and Callista chione (hard clams)--were collected from seven areas in Aegean Sea, Greece, between August 2001 and January 2003 and analyzed for organotins (OTs). The concentrations (as geometric means) found were 17.1 ng g-1 for tributyltin (TBT), 18.8 ng g-1 for dibutytltin (DBT), 7.8 ng g-1 for monobutyltin (MBT) and 13.0 ng g-1 for triphenyltin (TPhT) (wet weight), which are at similar or lower levels than those reported worldwide. Studying OTs distribution between different bivalve species, lower concentrations were observed in mediterranean mussels, possibly due to their growth in water column (grown on sea net pens in mussel farms), in contrast to the free-ranging species, collected from fishing grounds. Concentrations of the OTs in the examined bivalves varied seasonally.     

Impacts of wastewater sludge amendments in restoring nitrogen cycle in p-nitrophenol contaminated soil

The possible impacts on nitrogen-cycle in a p-nitrophenol (PNP) polluted soil and the e ectiveness of wastewater sludge amendments in restoring nitrification potential and urease activity were evaluated by an incubation study. The results indicated that PNP at 250 mg/kg soil inhibited urease activity, nitrification potential, arginine ammonification rate and heterotrophic bacteria counts to some extents. After exposure to PNP, the nitrification potential of the tested soil was dramatically reduced to zero over a period of 30 days. Based on the findings, nitrification potential was postulated as a simple biochemical indicator for PNP pollution in soils. Nitrogen-cycling processes in soils responded positively to the applications of wastewater sludges. A sludge application rate of 200 tons/ha was su cient for successful biostimulation of these nitrogen processes. The microbial activities in sludge-amended, heavy PNP-polluted soils seemed to recover after 30–45 days, indicating the e ectiveness of sludge as a useful soil amendment.     

Transport and fate of mercury under different hydrologic regimes in polluted stream in mining area

Seepage from Hg mine wastes and calcines contains high concentrations of mercury (Hg). Hg pollution is a major environmental problem in areas with abandoned mercury mines and retorting units. This study evaluates factors, especially the hydrological and sedimentary variables, governing temporal and spatial variation in levels and state of mercury in streams impacted by Hg contaminated runo . Samples were taken during di erent flow regimes in theWanshan Hg mining area in Guizhou Province, China. In its headwaters the sampled streams/rivers pass by several mine wastes and calcines with high concentration of Hg. Seepage causes serious Hg contamination to the downstream area. Concentrations of Hg in water samples showed significant seasonal variations. Periods of higher flow showed high concentrations of total Hg (THg) in water due to more particles being re-suspended and transported. The concentrations of major anions (e.g., Cl??, F??, NO3?? and SO4 2??) were lower during higher flow due to dilution. Due to both sedimentation of particles and dilution from tributaries the concentration of THg decreased from 2100 ng/L to background levels (< 50 ng/L) within 10 km distance downstream. Sedimentation is the main reason for the fast decrease of the concentration, it accounts for 69% and 60% for higher flow and lower flow regimes respectively in the upper part of the stream. Speciation calculation of the dissolved Hg fraction (DHg) (using Visual MINTEQ) showed that Hg(OH)2 associated with dissolved organic matter is the main form of Hg in dissolved phase in surface waters in Wanshan (over 95%).