Determination of butyltins in harbour sediment and water by aqueous phase ethylation GC-ICP-MS and hydride generation GC-AAS

Sediment and water samples have been collected between 1992 and 1995 for evaluating butyltin contamination in two marinas from the coastal area in The Netherlands, two years after the ban of TBT. Sediments extracts were analysed by capillary gas chromatography-inductively coupled plasma-mass spectrometry. Sediment concentrations for TBT showed no trend of decrease between 1992 and 1995 and were extremely high in the marina secluded from tidal action; 17.5 +/- 8.0 microg g(-1) and much lower for the marina with tidal action; 0.117 +/- 0.073 microg g(-1). High ratios between TBT and DBT in the sediments indicate that degradation mechanisms in the sediments are of minor importance. Dissolved butyltin compounds were analysed in water by means of gas chromatography-atomic absorption spectrometry. Water concentrations of TBT showed no clear trend of decrease between 1992 and 1995 and were high in the marina secluded from tidal action; 139 +/- 166 ng litre(-1) but much lower for the marina with tidal action; 48 +/- 98 ng litre(-1). An active degradation mechanism during summer periods was indicated by low (<1) TBT/DBT ratios in the water phase of the marina secluded from tidal action.     

Measurement and analysis of the relationship between ammonia, acid gases, and fine particles in eastern North Carolina

An annular denuder system, which consisted of a cyclone separator; two diffusion denuders coated with sodium carbonate and citric acid, respectively; and a filter pack consisting of Teflon and nylon filters in series, was used to measure acid gases, ammonia (NH3), and fine particles in the atmosphere from April 1998 to March 1999 in eastern North Carolina (i.e., an NH3-rich environment). The sodium carbonate denuders yielded average acid gas concentrations of 0.23 microg/m3 hydrochloric acid (standard deviation [SD] +/- 0.2 microg/m3); 1.14 microg/m3 nitric acid (SD +/- 0.81 microg/m3), and 1.61 microg/m3 sulfuric acid (SD +/- 1.58 microg/m3). The citric acid denuders yielded an average concentration of 17.89 microg/m3 NH3 (SD +/- 15.03 microg/m3). The filters yielded average fine aerosol concentrations of 1.64 microg/m3 ammonium (NH4+; SD +/- 1.26 microg/m3); 0.26 microg/m3 chloride (SD +/- 0.69 microg/m3), 1.92 microg/m3 nitrate (SD +/- 1.09 microg/m3), and 3.18 microg/m3 sulfate (SO4(2-); SD +/- 3.12 microg/m3). From seasonal variation, the measured particulates (NH4+, SO4(2-), and nitrate) showed larger peak concentrations during summer, suggesting that the gas-to-particle conversion was efficient during summer. The aerosol fraction in this study area indicated the domination of ammonium sulfate particles because of the local abundance of NH3, and the long-range transport of SO4(2-) based on back trajectory analysis. Relative humidity effects on gas-to-particle conversion processes were analyzed by particulate NH4+ concentration originally formed from the neutralization processes with the secondary pollutants in the atmosphere.     

Strontium isotopic compositions of dissolved and suspended loads from the main channel of the Yangtze River

The concentrations of Sr and (87)Sr/(86)Sr isotopic ratios have been measured in the dissolved loads from the main channel of the Yangtze River. The result shows that the Yangtze River mainstream water has considerably higher Sr concentration (202-330 microg kg(-1)) and slightly lower (87)Sr/(86)Sr ratio (0.7098-0.7108) than the global average runoff values of dissolved Sr (78 microg kg(-1)) and (87)Sr/(86)Sr ratio (0.7119). The (87)Sr/(86)Sr values of 0.7098-0.7108 in river waters result from the intense weathering of carbonate and evaporate rocks that enriched in the Yangtze River drainage basin. The calculated result based on the end-member mixing model shows that about 91% of total dissolved Sr are derived from the weathering of carbonate and evaporate rocks and the other 9% derived from the weathering of silicate rock. The Yangtze River transports about 1.86 x1 0(11)g yr(-1) (2.12 x 10(9)mol yr(-1)) of dissolved Sr annually to the East China Sea, with an average (87)Sr/(86)Sr of 0.7108. The calculated "(87)Sr(excess) flux" of the Yangtze River is about 2.12 x 10(7)mol yr(-1), indicating the important impact on seawater Sr isotope evolution. The measured (87)Sr/(86)Sr ratios of suspended particulate matters in the Yangtze River water ranging from 0.7178 to 0.7252, are about 0.015 higher than that of corresponding dissolved loads, reflecting more important contribution of silicate particles in suspended particulate matters and preferential dissolution of carbonate rocks during basin weathering.     

Temporal variability in particle-associated pesticide exposure in a temporarily open estuary, Western Cape, South Africa

This study assesses the risk of current-use pesticides in a temporarily open estuary in South Africa by developing probabilistic risk estimates. Particle-associated pesticides (chlorpyrifos, prothiofos, cypermethrin, fenvalerate, endosulfan and p,p-DDE) and physicochemical parameters (salinity, temperature, flow, and total organic content (TOC)) were measured in the Lourens River estuary (Western Cape) twice a month over a period of two years and equilibrium partitioning theory was applied to calculate concentrations of pesticides in the water. The 90th percentile concentrations of pesticides associated to suspended particles and the calculated concentrations in water were 34.0microg kg(-1) and 0.15microg l(-1) for prothiofos, 19.6microg kg(-1) and 0.45microg l(-1) for chlorpyrifos and 18.6microg kg(-1) and 0.16microg l(-1) for endosulfan. Highest average concentrations were found around the summer season due to higher application rates and as a result of the low flow during this season. Species sensitivity distribution indicated a 1.5-2.8 times higher toxicity (hazardous concentration HC5) for marine organisms compared to freshwater organisms. The calculated concentrations in the water exceeded all threshold values suggested by international water guidelines. Chlorpyrifos and endosulfan posed the highest acute risk to the Lourens River estuary. No sufficient toxicity data and threshold values were found for prothiofos.     

Composition and distribution of polycyclic aromatic hydrocarbons in the surface sediments from the Susquehanna River

Polycyclic aromatic hydrocarbon (PAH) concentrations in 34 surface sediments along the Susquehanna River were investigated in 2000. The total concentrations of PAHs in the surface sediments of Lake Clarke, Lake Aldred, the upper Conowingo Reservoir, and the lower Conowingo Reservoir were 3.3+/-1.5 microg g-1 (n=9), 1.6+/-1.3 microg g-1 (n=4), 9.8+/-5.5 microg g-1 (n=7), and 4.0+/-1.2 microg g-1 (n=14), respectively. These represent the first comprehensive measurement of PAHs in Susquehanna River surface sediments. Overall, total PAH concentrations were relatively lower in Lake Aldred, which is more shallow and sloped, and significantly higher in the upper Conowingo Reservoir. The sediment PAH levels were related to river flow rates, which are indirectly correlated with the particle size of the surface sediments. Total PAH levels in all the studied sites were below the effects range median (ERM) of 44.8 microg g-1 with 38% (13 of the 34 sampling sites) exceeding the effects range low (ERL) of 4.02 microg g-1. Principal component analysis indicated that variations in the PAH compound patterns of each reservoir decreased from upstream to downstream, indicating that the surface sediments were mixed along the Susquehanna River. The PAH patterns in the lower Conowingo Reservoir sediments were a combination of those upstream sources. Source analysis using isomer ratios as indicators suggested that PAHs in the Susquehanna River surface sediment are derived from the combustion of fossil fuels such as coal and gasoline with coal as the major source of contaminants.     

The oxidation states of arsenic in well-water from a chronic arsenicism area of northern Mexico

Aquifers in the Región Lagunera in northern Mexico are heavily contaminated with arsenic. The range of total arsenic concentrations in 128 water samples analyzed was 0.008 to 0.624 mg litre(-1), and concentrations greater than 0.05 mg litre(-1) were found in 50% of them. Approximately 400 000 people living in rural areas were exposed to high As concentrations. Most of the As was in inorganic form and pentavalent arsenic [As(V)] was the predominant species in 93% of the samples. In 36% of the samples, however, variable percentages (20-50) of trivalent As [As(III)] were found. Organic arsenicals were present in very small amounts. Since As(III) is several times more toxic than As(V), we suggest that periodic studies be performed on the As(III)/As(V) ratio in wells whose total As concentrations are above 0.05 mg litre(-1), in combination with epidemiological studies to evaluate possible differences in health effects produced by different As species.     

Water quality of the Guadiamar River after the Aznalcóllar spill (SW Spain)

In April 1998, a spill of 6 hm3 of pyritic mud and acidic water was released into the Guadiamar River due to the rupture of the Aznalcóllar tailings dam. Before the spill, the river was already strongly affected by acid mine drainage (AMD). In this study, the water quality of the Guadiamar River is analysed from a periodic sampling started after the spill. Previous data of the water quality have also been obtained. A recovery of the water quality is observed from 2002 on. The distribution of arsenic is opposed to that of the rest of metals, with the lowest concentrations to the north, due to the adsorption and/or coprecipitation on ferric oxyhydroxides. In the southern area, when pH values are close to 8, arsenic desorption occurs. There is a seasonal pattern of the trace metal content evolution, different in the northern and southern zones of the river. In the northern area the highest polluting levels occur in summer, due to a lower dilution of the mining leachates. In the southern area, the highest metal levels occur during the winter, since during the summer metals remain held by surface sorption processes in the hyporheic zone of the river.     

Environmental fate and bioavailability of wood preservatives in freshwater sediments near an old sawmill site.

Impacts of an old contaminated sawmill site located in Eastern Finland were studied, with emphasis on transportation and bioaccumulation of wood preservatives in the surrounding water system. To assess the transportation of chlorophenols and chromated copper arsenate (CCA) from the sawmill to the nearby lake, the concentrations of these compounds in selected sediment samples were analyzed. To assess the contribution of a pulp mill further upstream, the concentration of extractable organic halogens (EOX) was analyzed. Bioaccumulation of wood preservatives from sediments was examined using Lumbriculus variegatus as test organism. In sediments collected from the sawmill area, concentrations of chlorophenols, arsenic, chromium and copper were high. In the surrounding area the concentrations of these compounds were slightly elevated at some sampling points but were mostly within the natural range of variation. Thus, it can be concluded that transportation of wood preservatives from the sawmill area to its surroundings is fairly low. However, 60 microg/l of arsenic and 50 microg/l of copper were found in water taken from a brook that runs through a landfill area of the sawmill to the nearby river, and the concentration of arsenic in the surface sediment at one sampling point in the lake was slightly elevated. The total amount of organohalogens in sediment was higher in the river and the lake than in the sawmill area. Of all the wood preservatives studied, only arsenic was found to bioaccumulate in present conditions, reaching a tissue concentration of 362 microg/g dw in organisms exposed for 28 days to sediment from the brook. High concentration of arsenic in oligochaeta tissue was related to high concentration of arsenic in the pore water.     

Contamination by selected chlorinated pesticides in surface waters in Hanoi, Vietnam

Fifteen insecticides, which were banned in Vietnam in the period from 1990 to 1998, were chosen for the investigation of surface water samples in Hanoi and its surroundings. The investigation was focused on an area of approximately 30 by 20 km. Thirty water samples, in total were analysed: 11 samples from the Red river, seven from the Duong river, four from various lakes (West lake, Thuyen Quang, Bay Mau, Ba Mau), six from irrigation canals and two samples from wells. The procedure was repeated in November 1998 and in August 1999. The results showed that the contamination of the banned pesticides was highest in the rivers and then in the irrigation canals, followed by the lakes and wells. These pesticides could hardly be determined in just two drinking water samples (wells) and their concentrations rarely exceeded detection limits (0.05-0.25 ng l(-1)). The mean concentrations of sigmaHCHs (alpha, beta, gamma, delta-HCH) and sigmaDDTs (2,4'-, 4,4'-DDE; 2,4'-, 4,4'-DDD; 2,4'-, 4,4'-DDT) in the rivers were 17.2 +/- 71.8 and 43.7 +/- 79.9 ng l(-1) in the dry season (DS, November 1998), 29.3 +/- 117 and 56.1 +/- 65.6 ng l(-1) in the rainy season (RS, August 1999), respectively. However, the highest concentration of DDTs detected in a river sample (DS): 0.324 microg l(-1) was much lower than their allowable limit of concentration in surface waters, which is accorded with Criteria of Vietnam (1995) (DDTs < 10 microg l(-1)). Moreover, endrin, heptachlor, aldrin were also detected in most of water samples with considerable mean concentrations in rivers: 25.3 +/- 40.5, 17.4 +/- 23.8, 11.0 +/- 9.02 ng l(-1) in the DS and 18.5 +/- 23.2, 19.3 +/- 29.0, 12.8 +/- 8.44 ng l(-1) in the RS, respectively. Heptachlor epoxide (isomer A) and dieldrin were detected in some water samples with lowest concentrations.     

Total and inorganic arsenic in Antarctic macroalgae

The Antarctic region offers unparalleled possibilities of investigating the natural distribution of metals and metalloids, such as arsenic. Total and inorganic As were analysed in nine species of Antarctic macroalgae collected during the 2002 summer season in the Potter Cove area at Jubany-Dallmann Station (South Shetland Islands, Argentinian Base). Total As was determined by inductively coupled plasma-optical emission spectrometry after microwave-assisted acid digestion. Inorganic As was determined by acid digestion, solvent extraction, flow injection-hydride generation-atomic absorption spectrometry. Total As ranged from 5.8 microg g(-1) dry weight (dw) (Myriogramme sp.) to 152 microg g(-1)dw (Himantothallus grandifolius). Total As concentrations were higher in Phaeophytes (mean+/-SD: 71+/-44 microg g(-1)dw) than in Rhodophytes (mean+/-SD: 15+/-11 microg g(-1)dw). Inorganic As ranged from 0.12 microg g(-1) (Myriogramme sp.) to 0.84 microg g(-1)dw (Phaeurus antarcticus). The percentage of inorganic As with respect to total As was 0.7 for Phaeophytes, but almost 4 times higher for Rhodophytes (2.6). The work discusses possible causes for the presence of As in marine organisms in that pristine environment.     

Distribution patterns of nitrobenzenes and polychlorinated biphenyls in water, suspended particulate matter and sediment from mid- and down-stream of the Yellow River (China)

Samples of water, suspended particulate matter (SPM) and sediment were collected from mid- and down-stream of the Yellow River. The distribution and concentration of 10 nitroaromatic compounds and polychlorinated biphenyls (PCBs) were extensively studied. The total concentration of 10 nitrobenzenes (SigmaNBs) varied from 0.269 to 9.052 microg l(-1) in water, from 2.916 to 164.4 microg kg(-1) dry weight in SPM, and from 0.954 to 14.72 microg kg(-1) dry weight in sediment. PCBs associated with the sediments, measured as the summed responses of Aroclor 1242, 1248, 1254, 1260 (in comparison to those of a standard 1:1:1:1 mixture), were found to be in the range of non-detectable to 5.98 microg kg(-1). In the samples collected, various PCB congeners showed similar distribution characteristics with congeners containing 3-5 chlorine atoms accounting for more than 96.4% of total PCB. In most of the samples, PCB concentrations occurred in the order: TetraCB > TriCB > PentaCB. Levels of SigmaNBs in the Yellow River were relatively low in comparison with values reported from other river and marine systems, and PCB levels were comparatively low. Relative to the PCBs, SigmaNBs showed significantly more difference among the various stations, presumably due to the influence of different pollution sources. No obvious correlation was observed between the pollutant concentrations and either the TOC or the grain size of the sediments.     

Seasonal, spatial and inter-annual variations of trace metals in mussels from the Adriatic sea: a regional gradient for arsenic and implications for monitoring the impact of off-shore activities

Mussels are widely used as bioindicator organisms for monitoring chemical pollutants including trace metals. These elements are natural constituents in the marine environment and their basal concentrations in the organisms can be influenced by several environmental and biological factors. The aim of this work was to extend our knowledge on the natural variability of trace metals in mussels tissues, focusing on seasonal and inter-annual fluctuations in a coastal reference site of the Adriatic coast (Portonovo); a total of 39 samplings were performed during 5 years, providing an extended data-set for tissue levels of As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn. Concentrations of trace metals in mussels tissues revealed marked seasonal fluctuations with significant differences between various sampling years. Such fluctuations appeared mostly related to phytoplanctonic blooms and especially to reproductive cycle which exhibited a certain inter-annual shift of the gametogenesis period. Lower concentrations were measured in summer months for the majority of elements while a different seasonal cycle was observed for arsenic, not correlated with gonadic development, neither with other elements. Chemical speciation of arsenic was characterized to distinguish compounds of natural origin from those potentially reflecting an anthropogenic impact. Arsenobetaine and arsenocholine were always the predominant forms (up to 85% of total arsenic), while a significant increase of dimethylarsine and trimethylarsine oxide in spring (24% of total arsenic) might reflect the effect of phytoplanctonic bloom on both geochemistry and trophic transfer of this element. A significant inter-annual variability was observed for both the seasonal cycle and the range of values measured for all the elements, with particularly marked differences for arsenic, ranging from less than 10 to more than 40 microg/g in summer periods of different years. Data obtained on reference mussels were used to assess the impact of 41 off-shore platforms distributed along 5 nautical districts in the Northern and Central Adriatic Sea. Organisms sampled on these structures from 2001 to 2005 exhibited a certain enrichment of cadmium and zinc, probably associated to the use of anodic electrodes. Marked annual and geographical variations were measured for concentrations of arsenic in mussels of different platforms. However, the comparison with results of Portonovo, allowed to exclude the anthropogenic impact of exploitation activities and revealed a natural regional gradient of arsenic levels in mussels tissues associated to the changing influence of the Po river runoff on seawater salinity. In particular the higher concentrations measured in organisms sampled from platforms in the Central compared to Northern Adriatic confirmed a significant relationship between salinity and arsenic bioaccumulation, consistent with a role of arsenobetaine as an acquired osmolyte for mussels. The overall results confirmed the importance of natural variability when assessing the potential impact of anthropogenic activities.     

Using trace element concentrations in Corbicula fluminea to identify potential sources of contamination in an urban river

We used the biomonitor, Corbicula fluminea, to investigate the contributions of trace elements associated with different point sources and land uses in a large river. Trace elements were analyzed in tissues of clams collected from 15 tributary streams draining five land use or point source types: agriculture, forest, urban, coal-fired power plant (CFPP), and wastewater (WWTP). Clams from forested catchments had elevated Hg concentrations, and concentrations of arsenic and selenium were highest (5.0+/-0.2 and 13.6+/-0.9 microg g(-1) dry mass (DM), respectively) in clams from CFPP sites. Cadmium concentrations were significantly higher in clams from urban and CFPP sites (4.1+/-0.2 and 3.6+/-0.9 microg g(-1) DM, respectively). Non-metric multidimensional scaling (NMS) of tissue concentrations in clams clustered at CFPP and forest/agriculture sites at opposite ends of the ordination space, and the distribution of sites was driven by Cu, Zn, Cd, and Hg.     

Short-term effects of metals on the filtration rate of the zebra mussel Dreissena polymorpha

In order to study the short-term ecotoxicity of metals to the freshwater mussel Dreissena polymorpha, the effects of Cu, Zn and Cd on the filtration rate of this mussel were determined in laboratory experiments. Filtration rate was chosen as the endpoint, because it is a sensitive sublethal parameter compared to mortality and it is an important parameter given the ecological role D. polymorpha fulfills. The filtration rate was calculated from the decrease in algal concentration, fed to mussels in aquaria, containing different metal concentrations. The EC50 for Cu (41 microg litre(-1)) was lower than for Cd (388 microg litre(-1)) and Zn (1350 microg litre(-1)). The NOEC(accumulation) for the essential metal Zn was higher than for the essential metal Cu. Cadmium, a non-essential metal, was accumulated at all elevated water concentrations, so the NOEC(accumulation) was the concentration in the control water (<0.2 microg litre(-1)). All (no) effect concentrations found in this study were above the quality criteria set for metal concentrations in Dutch surface water, suggesting that the zebra mussel is sufficiently protected by these quality criteria.     

Bioaccumulation of cadmium by the freshwater isopod Asellus aquaticus (L.) from aqueous and dietary sources

Experiments were conducted to determine the kinetics and relative importance of aqueous and dietary uptake of cadmium by the freshwater isopod Asellus aquaticus (L.). Test animals were exposed during 30 days to aqueous Cd in a continuous flow system (exposure levels: 0.2 - 10 microg litre(-1)) and kept on a diet of previously contaminated Elodea sp. (range of Cd concentrations: 2-350 microg g(-1), dry weight). Preceding semi-static experiments on dosage-control of the dietary factor revealed a rapid uptake of Cd by Elodea, with relatively high concentration factors (CF), which ranged from 4.8 to 5.5 (dry weight log (CF) after 16 days). For Asellus uptake from water appeared to be the predominant route. Highly significant bioconcentration of cadmium from water was observed in the animals, even at exposure levels below 1.0 microg litre(-1). In the various treatments, direct uptake from water accounted for 50-98% of the body burdens after 30 days exposure. The experimental results were described with a first order one-compartment bioaccumulation model. Model parameter estimates (mean +/- standard error) were obtained for rate constant of uptake (560 +/- 110 day(-1)), rate constant of elimination (0.032 +/- 0.017 day(-1)) and assimilation efficiency of Cd uptake from food (1.1 +/- 0.7%). The (dry weight) bioconcentration factor (BCF) and bioaccumulation factor (BAF) for extrapolated steady state conditions were estimated at 18 000 (BCF) and 0.08 (BAF). Experiments conducted at two different pH levels (5.9 versus 7.6) revealed no significant effects of pH on the uptake of aqueous Cd by the isopods. The results are discussed in relation to their potential significance to the field situation.     

Environmental tritium of the Danube basin in Yugoslavia

An overview of environmental distribution of tritium in the Danube basin in Yugoslavia during the period 1976-1990 is presented. Temporal and regional variations of environmental tritium in the Danube along its flow (1425-847 km from the confluence) and its tributaries (the Sava, the Tisa, the Velika Morava and the Timok) at various locations, as well as in alluvial groundwaters, are given. In Belgrade, monthly values of tritium in rainfall ranged from 1.1 to 18.3 Bq litre(-1), with a maximum in the late spring and early summer months. The half-life for decline in concentration was estimated as 8.3+/-1.0 years. The total amount of tritium deposited in the first 6 months during 1976-90 was 35% larger than in the second 6 months for the same period. Seasonal variations were noticeable in rivers and groundwaters, but these were greatly attenuated and smoothed for the latter. Tritium content in the monthly composite samples from the river in the Belgrade region varied between 2.5 and 18.2 Bq litre(-1) for the Danube and from 1.5 to 16.8 Bq litre(-1) for the Sava. The yearly mean values along the Danube and its tributaries ranged from 2.4 to 15.9 Bq litre(-1) with individual measurements 1.0-30.2 Bq litre(-1). The half-lives were between 6.9+/-1.7 for the Velika Morava and 9.4+/-0.9 for the Danube. Groundwaters, particularly ones in the Ranney wells, followed changes of tritium content in the rivers with a time lag from a few days to a month. During the period of observation, tritium content decreased in alluvial waters with half-lives from 9.9+/-1.6 (Belgrade area) to 7.3+/-1.8 (the Velika Morava).     

Characteristics of organic matter in PM2.5 in Shanghai

Solvent extractable organic compounds (SEOC), organic carbon, elemental carbon and water soluble organic carbon (WSOC) in PM(2.5) samples collected in Shanghai, China in 2002 and 2003 were measured to determine the composition and sources of the organic matter in atmospheric aerosols. Distinct seasonal variations were detected with higher concentrations of organic matter in winter. The concentration of total carbon of about 20 microg m(-3) in winter was about three times the summer value. About 30% of the total carbon was water soluble. Unresolved complex mixture (UCM) and fatty acids were the most abundant components quantified in SEOC, similar to other Chinese cities previously studied. High ratio of UCM to n-alkanes (U:R) and the composition of triterpanes indicated that engine exhaust was a major source of the airborne organic matter. Emissions from coal burning had more impact in the rural areas, according to the U:R value and PAHs composition. Chemical mass balance (CMB) modeling shows that about half of the organic carbon was from engine exhaust and about 15% was from coal burning. No clear spatial variation in the concentration of the organic matter was found between urban and rural areas. Our results showed that due to the rapid urbanization and relocation of industrial plants from urban areas to rural areas in the past 20 years, air pollution in rural areas is becoming a serious problem in Shanghai and the Yangtze River delta.     

Existence of nonpoint source of perfluorinated compounds and their loads in the Tsurumi River basin, Japan

Products containing perfluorinated compounds (PFCs) have been widely used during the last 50 years. As a result, worldwide environmental pollution by PFCs has been reported. The sources of PFC pollution in the aquatic environment have been poorly understood. In this study, river water and sewage treatment plant (STP) effluent were sampled along the stretch of the Tsurumi River and also at a fixed station in the river. The concentrations of perfluorooctanesulfonate (PFOS), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were measured. With an increase in river flow rate, it was observed that the PFC concentrations in the river water at fixed station were remained the same or increased for PFOS (179.9+/-34.4-179.6+/-69.5 ng l(-1)), PFHxA (5.5+/-0.8-9.0+/-2.6 ng l(-1)), PFHpA (3.1+/-0.3-4.4+/-1.0 ng l(-1)), and PFOA (15.9+/-0.3-13.4+/-2.5 ng l(-1)) whereas the concentration of PFNA (38.0+/-3.3-15.4+/-3.0 ng l(-1)) and PFDA (3.9+/-0.3-2.1+/-0.3 ng l(-1)) were decreased. On the other hand, the loads of every PFC increased with an increase in river flow rate. The loads of PFCs in rain runoff were estimated to be 2-11 times greater than those in STP effluents that are discharged into the river. These results indicate the existence of a PFC nonpoint source (NPS) and its impact to the total PFC load of river is significant.     

Levels of methylmercury and controlling factors in surface sediments of the Carson River system, Nevada

Spatial and temporal distribution of methylmercury (MeHg) was determined in surficial sediments collected from a river-reservoir system impacted by Hg-contaminated mine wastes. Despite the fact that total mercury concentrations (HgT) in surface sediments of the Carson River system were in the microg.g(-1) range, levels of MeHg varied from about 2 to 28 ngHg.g(-1) dry weight, representing less than 3% of Hg(T). Concentrations of MeHg were well correlated with both the biotic (r=0.95) and abiotic activity (r=0.85) of the sediment, determined as the ability of each compartment to specifically reduce an alternative electron acceptor. However, the positive relationship between the two measured activities suggests that the abiotic activity may be due to reductant substances produced by micro-organisms. When sediments collected from the Carson River were used in laboratory assays for the determination of potential rates of MeHg production, the addition of inorganic Hg (added as HgCl2) resulted in increased rates of methylation when the spike concentration was lower or equal to 15.3 microg.g(-1) dry weight. This trend was reversed for spike concentration of inorganic Hg above 15.3 microg.g(-1). The reduction of methylation rate was associated with an inhibition of microbial activity. These observations suggest that seasonal inputs into the river of significant amounts of inorganic Hg eroded from mill tailings during winter and spring flooding events could have an inhibiting effect on Hg-methylating micro-organisms. This observation could explain the low [MeHg]/[HgT] ratios previously documented in waters of the Carson River system.     

The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.