Methylmercury levels and bioaccumulation in the aquatic food web of a highly mercury-contaminated reservoir

The low Ebro River basin (NE Spain) represents a particular case of chronic and long-term mercury pollution due to the presence of an industrial waste (up to 436 μg/g of Hg) coming from a chlor-alkali plant Albeit high total mercury (THg) levels have been previously described in several aquatic species from the surveyed area, methylmercury (MeHg) values in fish individuals have never been reported. Accordingly, in order to investigate bioaccumulation patterns at different levels of the aquatic food web of such polluted area, crayfish and various fish species, were analysed for THg and MeHg content. At the hot spot, THg mean values of crayfish muscle tissue and hepatopancreas were 10 and 15 times, respectively, greater than the local background level. Higher mean THg concentrations were detected in piscivorous (THg=0.848 ± 0.476 μg/g wet weight (ww); MeHg=0.672 ± 0.364 μg/g ww) than in non-piscivorous fish (THg=0.305 ± 0.163 μg/g ww; MeHg=0.278 ± 0.239 μg/g ww). Although these results indicated that THg in fish increased significantly with increasing trophic position, the percentage of the methylated form of Hg was not strongly influenced by differences in relative trophic position. This is an important finding, since the fraction of THg as MeHg in the top fish predator was unexpectedly lower than for other species of the aquatic food chain. Moreover, mean THg concentrations in piscivorous fish exceed the maximum level recommended for human consumption. From our findings, it is clear that for this specific polluted system, speciation becomes almost mandatory when risk assessment is based on MeHg, since single measurements of THg are inadequate and could lead to an over- or under-estimation of contamination levels.     

Use of native mosses as biomonitors of heavy metals and nitrogen deposition in the surroundings of two steel works

A biomonitoring survey using the moss species Hypnum cupressiforme Hedw. was conducted in the surroundings of two steel plants located in the North of Spain. Levels of V, Cr, Ni, Cu, Zn, As, Cd, Hg, Pb and N were determined. Very high concentrations in the areas of study were detected when compared to nearby unaffected regions. Similar trends were observed for all the elements in the differently orientated transects, showing an appreciable influence of the NW prevailing winds of the region in the dispersion of pollutants, as well as a clear decreasing gradient in the concentrations of metals in mosses within a distance of 1500 meters from the facilities. A differentiation between the elements emitted by the chimney as result of the industrial activity (V, Cr, Ni, Cu and As) and those with a high presence in steel slag deposits (Zn, Cd, Hg and Pb) was observed. The range of contamination was also established by means of the Contamination Factor, indicating a category 4 out of 6 categories, which shows the high levels reported in the areas of study. A different dynamic was registered for nitrogen regarding the rest of the heavy metals analysed except for Hg, probably due to the elevated volatility and mobility of both elements, as well as their high persistence in the atmosphere.     

Pilot survey of a broad range of priority pollutants in sediment and fish from the Ebro river basin (NE Spain)

Priority organic pollutants were investigated in sediments and fish collected along the Ebro river basin (NE Spain) to evaluate their occurrence, transport and bioavailability. Sediments were collected in 18 sites and two species of fish were captured in nine sites according to the availability in each area. The sampling sites covered industrial, urban and agricultural areas. Four methods were used to detect 20 organochlorine compounds (OCs), 8 polycyclic aromatic hydrocarbons, 3 organotin compounds, 2 alkylphenols and 40 polybrominated diphenyl ethers (PBDEs) from purified extracts. The contamination pattern was site specific and no downstream increase in concentration of pollutants was observed but rather a generalized low level diffuse pollution. Target compounds were detected in sediments at 0.01 to 2331 microg/kg dry weight, and only OCs and PBDEs were accumulated in benthopelagic fish. Toxicological assessment was performed according to predicted environmental levels and revealed sites where adverse effects could occur.     

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L(-1) (as Sn), marine sediment ranged from 4 to 12 microg kg(-1) (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 microg kg(-1) (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters.     

Distribution of polycyclic aromatic hydrocarbons (PAHs) and tributyltin (TBT) in Barcelona harbour sediments and their impact on benthic communities

Sediments have long been recognised as a sink for many contaminants like polycyclic aromatic hydrocarbons (PAHs) and tributyltin (TBT), which by virtue of their nature can strongly adsorb onto sediments affecting the benthic community inhabiting them. Using geographical information systems, this study reports and combines the results of several already existing studies along Barcelona harbour in order to assess the potential ecological impacts of these contaminants on the benthos of the harbour ecosystem. Chemical analysis indicated low to moderate contents of PAHs and high contents of TBT in sediments in Barcelona harbour. Comparison against existing sediment quality guidelines (SQGs) indicated that acutely toxic effects would not be expected for PAHs but for TBT, which represents a serious environmental threat for the benthic community. Benthos surveys revealed a deterioration of the benthic community throughout the harbour, especially in the inner port.     

Fate of cationic surfactants in the marine environment, I. Bioconcentration of long-chain alkylnitriles and trialkylamines

Long-chain alkylnitriles (C_nH_2n+1CN, where n=13, 15, 17) (LANs) and long-chain-trialkylamines (NC_mH_2m+1C_nH_2n+1C_jH_2j+1, where m,n = 1, 14, 16, 18 and j= 14, 16, 18) (TAMs) were identified for the first time in biota samples at concentrations ranging from 9–574 ng g⁻¹ and from 157 to 825 (fresh wt. basis), respectively. In addition, the simultaneous occurrence in the aquatic environment of LANs and TAMs were also reported for the first time. The Kb values of both, LANs and TAMs varyied according to the different species but their were comparable to those found for PAHs.     

Patterns of mercury and methylmercury bioaccumulation in fish species downstream of a long-term mercury-contaminated site in the lower Ebro River (NE Spain)

Since the 19th century, large amounts of industrial waste were dumped in a reservoir adjacent to a chlor-alkali plant in the lower Ebro River (NE Spain). Previous toxicological analysis of carp populations inhabiting the surveyed area have shown that the highest biological impact attributable to mercury pollution occurred downstream of the discharge site. However, mercury speciation in fish from this polluted area has not been addressed yet. Thus, in the present study, piscivorous European catfish (Silurus glanis) and non-piscivorous common carp (Cyprinus carpio) were selected, to investigate the bioavailability and bioaccumulation capacities of both total mercury (THg) and methylmercury (MeHg) at the discharge site and downstream points. Multiple Correspondence Analysis (MCA) was applied to reduce the dimensionality of the data set, and Multiple Linear Regression (MLR) models were fitted in order to assess the relationship between both Hg species in fish and different variables of interest. Mercury levels in fish inhabiting the dam at the discharge site were found to be approximately 2-fold higher than those from an upstream site; while mercury pollution progressively increased downstream of the hot spot. In fact, both THg and MeHg levels at the farthest downstream point were 3 times greater than those close to the waste dump. This result clearly indicates downstream transport and increased mercury bioavailability as a function of distance downstream from the contamination source. A number of factors may affect both the downstream transport and increased Hg bioavailability associated with suspended particulate matter (SPM) and dissolved organic carbon (DOC).     

Evaluation of antibiotic mobility in soil associated with swine-slurry soil amendment under cropping conditions

Interest in identifying pools of antibacterial-resistance genes has grown over the last decade, with veterinary antibiotics (VAs) receiving particular attention. In this paper, a mesoscale study aimed at evaluating the vertical transport of common VAs—namely, fluoroquinolones, tetracyclines, sulfonamides, and lincosamides in agricultural soil subjected to drip irrigation—was performed under greenhouse conditions. Accordingly, leachates of cropped and uncropped soil, amended with swine-slurry leading to 19–38 μg kg^?1 (dry mass) antibiotics in the soil, were analyzed over the course of the productive cycle of a lettuce (42 days) with three sampling campaigns (N?=?24). High lincomycin (LCM) concentrations (30–39 μg L^?1) were detected in the leachates collected from the swine-slurry-amended soil. The highest LCM mass recovered in the leachates (30.1?±?1.63 %) was obtained from cropped experimental units. In addition, the LCM leaching constant and its leaching potential as obtained from the first-order model were higher in the leachates from the cropped experimental units. Lower concentrations of sulfadimethoxine were also detected in leachates and in soil. Enrofloxacin and oxytetracycline occurred only in soil, which is consistent with high soil interaction.     

Hair mercury levels in an urban population from southern Italy: fish consumption as a determinant of exposure

Mercury levels in hair of a general population, 237 adults aged between 35-45, in Naples, Italy, were assessed. The subjects were asked to fill in a questionnaire about age, gender, body weight, height, body mass index (BMI), fish consumption, number, surface and area of dental amalgam fillings. Total mercury (THg) concentrations in human hair ranged from 0.221 to 3.402 microg/g and the mean value for the subjects under study was 0.638 microg/g. Study participants were divided into three groups in accordance with fish consumption and dental amalgam: ANF (amalgam and no fish); NAF (no amalgam but with fish) and AAF (amalgam and fish). Significant differences in THg were found in the three groups (p<0.05). A multiple linear regression analysis showed a weak but significant correlation of THg content in hair with respect to gender and age, but almost no association was found between THg and dental fillings. Conversely, a strong correlation was obtained between THg and fish consumption regardless of the group evaluated. Finally, mercury levels in hair exceeded the levels corresponding to the EPA reference dose (RfD) of 0.1 microg Hg/kg body weight per day (1 microg Hg/g hair) in 6% of the population (4% men and 2% women). However, the THg limits in our subjects were not exceeded according to the WHO guidelines, which use a benchmark dose of 0.23 microg Hg/kg bw/day (14 microg Hg/g maternal hair).     

Occurrence and degradation of butyltins and wastewater marker compounds in sediments from Barcelona harbor, Spain

Contamination of Barcelona harbor sediments was assessed by the quantitative determination of butyltins (TBT, DBT and MBT) and surfactant intermediates, namely linear alkylbenzenes (LABs) and nonylphenols (NPs), as markers of urban and industrial wastewater contamination, respectively. Degradation indexes of TBT and LABs were calculated. Tributyltin predominated in the whole area over its degradation products, ranging from 98 to 4702 ng Sn/g. These elevated concentrations reveal a persistent historical contamination and a moderate degradation (BT(deg)). Moreover, the high LAB concentrations (1.2-53.1 microg/g) compared to the relatively low NP levels (3.8-72.0 ng/g) suggest a predominance of urban over industrial wastewater inputs, although a significant correlation (r(2) = 0.82, N = 12, P = 0.001) between LABs and NPs was found. Stormwater runoff and combined sewer overflows (CSO) were likely the most possible sources for both surfactant intermediates. The high degradation index values obtained for LABs could indicate an improvement in the wastewater management reducing its recent discharge into the Barcelona harbor area.