Mercury Speciation in the Water of Minamata Bay, Japan

The speciation of mercury (Hg) in Minamata Bay (Japan) was studied over a 2-year period (2006?C2008). Concentrations of dissolved total Hg, dissolved methylmercury (MeHg), particulate total Hg, and suspended solids were 0.43?±?0.14 ng/l (mean?±?standard deviation), 0.10?±?0.06 ng/l, 3.04?±?2.96 ng/l, and 5.94?±?2.10 mg/l, respectively. Correlations between concentrations of particulate total Hg and suspended solids at four depths (surface: 0 m; mid-depth: ?6 m, ?10 m; and bottom +1 m layer) were only significant in the bottom +1 m layer. The mean dissolved MeHg concentration and the ratio of dissolved MeHg to dissolved total Hg were considerably higher in summer compared to other seasons. The data suggest that bottom sediment was not the sole source of MeHg, and that MeHg may be produced in the water column by the conversion of divalent Hg eluted from resuspended bottom sediment. The correlation between seawater characteristics such as salinity, temperature, dissolved oxygen (DO), and dissolved MeHg concentration indicates that Hg methylation could be influenced by the heterotrophic activity of microorganisms in the seawater. In particular, inverse correlations were observed between DO, salinity, and MeHg concentration. However, dissolved MeHg concentrations did not correlate with seawater characteristics such as pH or chlorophyll-a.     

Application of ionic liquids for the extraction and passive sampling of endocrine-disrupting chemicals from sediments

Purpose

The aim of this study was to assess the applicability of ionic liquids (ILs) in the extraction of organic contaminants from sediments and in passive sampling as a receiving phase material.

Materials and methods

Solutions of two water-soluble ionic liquids (WSILs)—1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIm]BF₄) and N-butyl-3-methyl pyridinium tetrafluoroborate ([BMPy]BF₄)—were used for the extraction of endocrine-disrupting chemicals (EDCs), including bisphenol A (BPA), 17β-estradiol (E2), and nonylphenol (NP), from different sediments. Furthermore, a hydrophobic IL (1-hexadecyl-3-methyl imidazolium hexafluorophosphate) was filled in a polyethylene (PE) membrane tubing to build an IL-PE passive sampler for sediment pore water. Uptake kinetics were studied by exposing samplers to sediments artificially contaminated by EDCs and identified by exposing samplers to field-contaminated sediments.

Results and discussion

EDCs were efficiently extracted by WSIL solutions from the two artificially contaminated sediments, with maximum extraction efficiencies of 84.2–104.6 % by the [BMIm]BF₄ solution and 74.9–103.7 % by the [BMPy]BF₄ solution. However, WSIL solutions are not suitable for EDC extraction from sediment with very low organic carbon contents. EDCs in sediment pore water can be efficiently taken up by the IL-PE sampler, with uptake rate constants of 2.08?×?10^?2?l?g^?1?day^?1 (BPA), 5.74?×?10^?2?l?g^?1?day^?1 (E2), and 2.10 l?g^?1?day^?1(NP).

Conclusion

BPA, E2, and NP can be extracted efficiently by IL water solution from most of the artificially and field-contaminated sediments used in this study. The IL ([HDMIm]PF₆)-PE passive sampler can be used to monitor EDCs in the pore water of sediments. A good match between the calculated and measured concentrations of BPA and E2 in pore water of field-contaminated sediments was observed.     

Effect of Environmental Factors on Estrogenic Compounds Adsorption by MIP

In this study, the effects of environmental factors, including humic acid (HA), pH, ionic strength, and the coexistence of competing estrogenic compounds, on the adsorption of four typical estrogenic compounds, estrone (E1), 17β-estradiol (E2), 17α-ethinylestradiol (EE2), and bisphenol A (BPA), were studied by molecularly imprinted polymer (MIP). The adsorption capacities of MIP for E2 were 116.3, 118.5, 127.0, and 109.0 µmol/g at HA concentrations of 0, 5, 15, and 20 mg/L in total organic carbon, respectively, while the corresponding adsorption capacities of nontemplate imprinted polymer (NIP) for E2 were 98.1, 109.4, 113.8, and 98.0 µmol/g. This implied that no significant trend could be found with the increasing HA concentrations. Furthermore, the selective adsorption capacity, represented by the difference in adsorption capacities between MIP and NIP, was not affected significantly. Similar observations were noted for E1, EE2, and BPA in the presence of HA. Ionic strength did not exert a considerable influence on the adsorption capacities of MIP and NIP for E1, E2, and BPA. However, at 0 mM of NaCl, EE2 adsorption capacities of MIP and NIP were 124.7 and 111.7 µmol/g, respectively, while the corresponding adsorption capacities were 144.7 and 138.2 µmol/g at 10 mM of NaCl due to the increased hydrophobic interactions. Nevertheless, the selective adsorption capacity was not significantly affected by the range of ionic strength tested in this study. The study demonstrated that there was no significant effect of pH on the adsorption capacity of both MIP and NIP from pH 3.1 to 9 and that no considerable effect of pH on selective adsorption capacity of MIP could be established. However, the adsorption capacities of MIP and NIP for E2 at pH 9 were 95.1 and 82.9 µmol/g, while at pH 11, the adsorption capacities were 12.1 and 5.9 µmol/g correspondingly. This means that adsorption capacity and selective adsorption capacity were influenced significantly due to the ionization of target compounds. A similar trend was observed for E1, EE2, and BPA. The study on the effect of the coexistence of competing estrogenic compounds demonstrated that selective adsorption capacities of MIP can be influenced. Differences between MIP and NIP for E1, E1, EE2, and BPA under competing conditions were 8.8, 6.8, 10.2, and 4.2 µmol/g, respectively, while the corresponding differences were 12.6, 18.2, 13.0, and 9.8 µmol/g, respectively, when adsorbed individually.     

Dissolution and spatial distribution of resin acids and retene in sediments contaminated by pulp and paper industry

Purpose

Wood extractives in sediments originating from the wood industry may interfere with benthic biota in aquatic environments. The research area was the Äänekoski watercourse in Central Finland, which has been affected by the chemical wood industry for over a century. The goal was to determine the dissolution potency of resin acids (RAs) and their derivative, retene, in the sediment, and their current vertical and spatial stratification to assess the load due to potential erosion.

Materials and methods

Sediments were collected from two upstream reference sites and three lake-like basins, located as far as 33 km downstream from the mills. The dissolution potency was studied by two different agitation times and temperatures from sediment-water (1+4 v/v) elutriates. The vertical distribution of extractives was determined from the uppermost 20 cm of sediment. Using spatial interpolation, the distribution of extractives was estimated from two upper sediment layers (0–2 and 2–5 cm) downstream from the source. According to the interpolation, the total amount of dehydroabietic (DHAA) and isopimaric acids (IPA) were calculated as kg/ha in the whole sediment area.

Results and discussion

The total concentration of RAs in the surface sediment reached up to 168 µg/g dw, and they were found to desorb to water up to 77 µg/l. The concentrations of retene were low both in the sediment (<51 µg/g dw) and elutriate (<0.53 µg/l). Spatial interpolation showed that the highest calculated amounts of the most abundant RAs were in Kuhnamo basin, in the sediment layer 2–5 cm; the estimated amount of DHAA and IPA were approximately 440 and 85 kg/ha, respectively.

Conclusions

Disturbances may change the exposure situation, causing desorption of sediment-associated compounds in levels that may be harmful to aquatic animals. The amount of desorption varies depending on the concentration of contaminants in sediment, the nature of disturbance, and the sediment organic carbon content. Low retene concentrations can be explained by oxic conditions and low abundance of RAs in the sediments.

     

Distribution and Fate of Organotin Compounds in Japanese Coastal Waters

In order to elucidate the details of both the distribution and fate of organotin compounds (OTs) in the costal ecosystem, the concentrations of butyltin compounds (BTs) and phenyltin compounds (PTs) were determined in seawater, sediment and blue mussels Mytilus galloprovincialis collected in Maizuru Bay, Japan. The concentrations of tributyltin (TBT) in seawater, sediments and mussels ranged from 3.9 to 27 ng l^?1, from 1.2 to 19 ng g^?1 dry wt and from 0.77 to 11 ng g^?1 wet wt, respectively. Although the levels of TBT in seawater, sediments and mussels from Maizuru Bay were lower than those reported previously at other sites in Japan, the levels can still be toxic to susceptible organisms. Trace amounts of PTs were also found in seawater, sediment and mussel samples, indicating that there is a slight input of triphenyltin (TPT) into the seawater in the bay at present. The highest TBT concentration in seawater among all sites measured in the bay was found near a glass factory, and the lowest concentrations were observed at the center of the bay. The highest concentration of TBT in sediment was detected near a shipyard. In mussels, a high concentration of TBT was detected near a cement plant and timberyard. These results indicate that the major sources of contamination of OTs in the bay are considered to be from those facilities and ships. The proportion of TBT in seawater and mussels showed that, of total BTs, it was the predominant compound at most sites. These results suggested that there is a continuous input of TBT into the seawater and thereafter an accumulation of TBT in mussels due to their low metabolic capacity to degrade TBT. In sediment, the proportion of monobutyltin (MBT) was the highest of BTs at most sites. This could reflect a previous contamination by TBT used before the regulation of its usage in the bay.     

Distribution Coefficient and Adsorption–desorption Rates of di (2-ethylhexyl) Phthalate (DEHP) onto and from the Surface of Suspended Particles in Fresh Water

The commonly used plastic softener, di (2-ethylhexyl) phthalate (DEHP), also a known Endocrine Disrupting Compound, was found contaminated in various aquatic environments, including river water in Thailand. The data of adsorption kinetics from this study indicated that DEHP can adsorb onto pure bentonite and natural suspended sediment with average adsorption rate constants of 0.0056 and 0.0039 min^?1 respectively. The average distribution coefficients between suspended particles and water found in this study for pure bentonite and natural suspended sediment were 0.045 and 0.043 l g^?1 respectively. Although the studies were carried out in pH 4.0, 7.0 and 10.0, there were no obvious influences of pH on adsorption rates and distribution coefficients of DEHP onto both pure bentonite and natural suspended particles. The desorption rate was very small and was estimated to be less than 0.03 μg min^?1. The results indicated that suspended sediment could become a long term release of DEHP and facilitate the transport of DEHP mainly due to fast adsorption rate and relatively high adsorption capacity.     

A Survey of Organotin Compounds in the Northern Adriatic Sea

The extent of pollution with organotin compounds was investigated in water, sediment and bivalve mussels (Mytilus galloprovincialis) from the Northern Adriatic Sea. Butyl-, phenyl- and octyltin species were quantified after extraction and derivatisation by gas chromatography–mass spectrometry in a total of 99 samples from the period from 2000 to 2006. The accuracies of the analytical procedures were checked by spiking of unpolluted water samples and by the analysis of standard reference materials (harbour sediment PACS-2 and mussel tissue ERM-CE 477). Among organotin species analysed in samples butyltins were the predominant. Tributyltin was found to be present in the highest concentrations, suggesting its recent input into the marine environment. Butyltins were detected at all sites surveyed (sum of butyltins was up to 718 ng Sn L^?1, 3,552 ng Sn g^?1 d.w. and 9,991 ng Sn g^?1 d.w. in water, sediment and mussel samples, respectively), phenytins in much lower concentrations (up to 31 ng Sn L^?1, 326 ng Sn g^?1 d.w. and 442 ng Sn g^?1 d.w. in water, sediment and mussel samples) and to a much smaller extent, while octyltins were not detected at any location. The spatial distribution of tributyltin was closely related to boating, with the highest concentrations found in marinas (up to 586 ng Sn L^?1 for water samples, 1,995 ng Sn g^?1 d.w. for sediment and 6,434 ng Sn g^?1 d.w. for mussel samples). The temporal distribution clearly indicates a decrease of organotin pollution at all sites.     

Diazinon Mitigation in Constructed Wetlands: Influence of Vegetation

In intensively cultivated areas, agriculture is a significant source of pesticides associated with storm runoff. When these pollutants enter aquatic receiving waters, they have potential to damage nearby aquatic ecosystems. Constructed wetlands are a best management practice (BMP) designed to help alleviate this potential problem. A constructed wetland system (180?×?30 m) comprised of a sediment retention basin and two treatment cells was used to determine fate and transport of a simulated storm runoff event containing the insecticide diazinon and suspended sediment. Wetland water, sediment, and plant samples were collected spatially and temporally over 55 d. Results indicated that 43% of the study’s measured diazinon mass was associated with plant material, while 23 and 34% were measured in sediment and water, respectively. Mean diazinon concentrations in water, sediment, and plants for the 55-d study were 18.1?±?4.5 μg/l, 26.0?±?8.0 μg/kg, and 97.8?±?10.7 μg/kg, respectively. Aqueous concentrations fluctuated in the wetlands between 51–86 μg/l for the first 4 h of the experiment; however, by 9 h, aqueous concentrations were approximately 16 μg/l. During the 55 d experiment, 0.3 m of rainfall contributed to fluctuations in diazinon concentrations. Results of this experiment can be used to model future design specifications for mitigation of diazinon and other pesticides.     

Occurrence of Sexual Hormones in Sediments of Mangrove in Brazil

The presence of sexual hormones (female estrogens) was assessed in sediments of a mangrove located in the urban region of southern Brazil. The estrogens are involved in human sexual reproduction. They act as the chemical messengers, and they are classified as natural and synthetic. The estrogens inputs in the environment are from treated and untreated sewage. The presence of estrogens in sewage is excretion from the female due to natural production and use of contraceptives (synthetic estrogens). With the indiscriminate release of sewage into the environment, estrogens can be found in rivers, lakes, and even in oceans. In this work, the presence of estrone (E1), 17-??-estradiol (E2), and 17-??-ethynilestradiol (EE2) in eight sedimentary stations in Itacorubi mangrove located on Santa Catarina Island, south Brazil, was investigated. Historically, the Itacorubi mangrove has been impacted by anthropogenic activities because the mangrove is inserted in the urban area of the Florianopolis. The estrogen EE2, used as contraceptive, had the highest concentration in mangrove sediment, 129.75?±?3.89 ng/g. E2 was also found, with its concentration ranging from 0.90?±?0.03 to 39.77?±?1.19 ng/g. Following the mechanism, under aerobic or anaerobic conditions, E2 will first be oxidized to E1, which is further oxidized to unknown metabolites and finally to CO₂ and water (mineralized). EE2 is oxidized to unknown metabolites and also finally mineralized. Theoretically, under anaerobic conditions, EE2 can be reduced to E1 even in environments such as mangrove which is essentially anaerobic.     

Analysis and Occurrence of Endocrine Disruptors in Brazilian Water by HPLC-Fluorescence Detection

A method for simultaneous analysis of bisphenol A (BPA) and 17α-ethinylestradiol (EE2) in water supply was developed using solid-phase extraction and high-performance liquid chromatography with fluorescence detection. The linearity was evaluated between 2.5 and 200 μg L^?1 (r> for the analytes. The limits of quantification were 1.5 and 2.1 ng L^?1 for BPA and EE2, respectively. The extraction was made with C18 cartridges, and recoveries obtained varied between 70 and 102 % for the strengthening of 5 μg L^?1. After the validation, the method was applied in the determination of pollutants in surface water and water supply of Sao Luis, Brazil, where BPA was found in two of the eight samples analyzed, with concentrations of 1.11 and 3.61 μg L^?1.     

Organotin Compounds in Sediments from the Göta älv Estuary

Concentrations of organotin compounds in sediments from four sites in the Göta älv estuary, SW Sweden, rangefrom 17 to 366 ng/g dw for tributyltin (TBT) and from1.5 to 71 ng/g dw for triphenyltin (TPT), similar toresults from other harbours and marinas and from an earlier study in the Göteborg Harbour, which is located in the estuary. Also dibutyltin, monobutyltin, diphenyltin and monophenyltin, the degradation products of TBT and TPT, werefound. TBT concentrations are the highest in the inner harbour and in the upper sediment layer of ca. 10 cm, indicating the risk for mobilisation of TBT bound in surface sediments in thefrequently disturbed harbour environment.     

Processes Controlling Trace-Metal Transport in Surface Water Contaminated by Acid-Mine Drainage in the Ducktown Mining District, Tennessee

Former mining activities lasting 140 years in the Ducktown Mining District, Tennessee, USA, has contaminated the streams draining the district with acid-mine drainage (AMD). North Potato Creek and its major tributary, Burra Burra Creek, are two of the most heavily AMD-impacted streams in the district. The removal of dissolved metals from the water in these creeks is largely attributable to the sorption of Cu, Zn, Co, Al, and Mn on suspended hydroxide precipitates of Fe. The fraction of trace metals remaining in solution decreases with increasing pH in the sequence Pb?<?Cu?<?Zn?<?Co. The concentration of Fe in solution also decreases with increasing pH due to the formation of ferric hydroxide precipitates which accounted for up to 81.4% by weight of the total suspended sediment. The concentration of suspended sediment substantially decreases as the water of North Potato Creek flows through a large settling basin, where 1.3 (±0.3)?×?10⁶ kg/year of trace-metal-laden suspended sediment would be annually deposited. In spite of this attempt to purify it, the water discharged into the river is acidic (pH 3.6) and still contains high concentrations of dissolved trace metals, which would resorb on to suspended sediment and be ultimately transported to a downstream reservoir, Ocoee No. 3 Lake.     

Quantification of zearalenone in various solid agroenvironmental samples using D6-zearalenone as the internal standard

Because of its pronounced estrogenicity, zearalenone may be of concern not only in the aqueous but also in the terrestrial environment. Therefore, we developed several analytical methods to quantify zearalenone in different solid matrices of agroenvironmental relevance (i.e., plant organs, soil, manure, and sewage sludge). The use of D(6)-zearalenone as the internal standard (IS) was essential to render the analytical method largely matrix-independent because it compensated for target analyte losses during extract treatment and ion suppression during ionization. Soil and sewage sludge samples were extracted with Soxhlet, whereas plant material and manure samples were extracted by liquid solvent extraction at room temperature. Absolute recoveries for zearalenone were 70-104% for plant materials, 105% for soil, 76% for manure, and 30% for sewage sludge. Relative recoveries ranged from 86 to 113% for all matrices, indicating that the IS was capable to largely compensate for losses during analysis. Ion suppression, between 8 and 74%, was in all cases compensated by the IS but influenced the method quantification levels. These were 3.2-26.2 ng/g(dryweightdw) for plant materials, 0.7 ng/g(dw) for soil, 12.3 ng/g(dw) for manure, and 6.8 ng/g(dw) for sewage sludge. Plant material concentrations varied from 86 ng/g(dw) to more than 16.7 microg/g(dw), depending on the organ and crop. Soil concentrations were between not detectable and 7.5 ng/g(dw), depending on the sampling depth. Zearalenone could be quantified in all manure samples in concentrations between 8 and 333 ng/g(dw). Except for two of the 85 investigated sewage sludge samples, zearalenone concentrations were below quantification limit.     

Kinetics and Adsorption Isotherms of Bisphenol A, Estrone, 17β-Estradiol, and 17α-Ethinylestradiol in Tropical Sediment Samples

The sorption of four endocrine disruptors, bisphenol A (BPA), estrone (E1), 17β-estradiol (E2), and 17α-ethinylestradiol (EE2) in tropical sediment samples was studied in batch mode under different conditions of pH, time, and sediment amount. Data obtained from sorption experiments using the endocrine disruptors (EDs) and sediments containing different amounts of organic matter showed that there was a greater interaction between the EDs and organic matter (OM) present in the sediment, particularly at lower pH values. The pseudosecond order kinetics model successfully explained the interaction between the EDs and the sediment samples. The theoretical and experimentally obtained q _e values were similar, and k values were smaller for higher SOM contents. The k _F values, obtained from the Freundlich isotherms, varied in the ranges 4.2–7.4 × 10⁻² (higher OM sediment sample, S₂) and 1.7 × 10⁻³–3.1 × 10⁻² (lower OM sediment sample, S₁), the latter case indicating an interaction with the sediment that increased in the order: EE2 > > E2 > E1 > BPA. These results demonstrate that the availability of endocrine disruptors may be directly related to the presence of organic material in sediment samples. Studies of this kind provide an important means of understanding the mobility, transport, and/or reactivity of this type of emergent contaminant in aquatic systems.     

Polybrominated Diphenyl Ethers Mobility in Biosolids-Amended Soils Using Leaching Column Tests

Leaching column tests were conducted to determine the mobility of polybrominated diphenyl ethers (PBDEs) in biosolids-amended soils. Deionized water was introduced from the bottom of a glass leaching column containing a 14-mm layer of biosolids-amended soils (210 g) under 42 mm of agricultural soil (600 g). After 4 weeks of leaching, 3.75 L of deionized water had passed through the 210-g biosolids?Csoil layer and 600 g soil, corresponding to 34 volumes of the leachate per volume of solid. The agricultural soil was divided into three 14-mm layers to determine the PBDE distribution along the flow path of the infiltrating water. PBDEs were found to leach from the biosolids-amended soils layer and migrate through the soil. The predominant congeners BDE47, 85, 99, 100, 153, 154, 183, and 209 decreased to 3?C98% of their initial concentrations in the biosolids-amended soil, whereas the total concentration of these eight congeners decreased by 38%. PBDE concentrations in the first 14-mm soil layer increased from not detected (nd) to up to 234?×?10³ pg/g dry weight basis (dw). Concentrations in the second and third soil layers increased from nd to 20 and 25 pg/g dw. PBDE in the leachate increased from nd to 310?×?10³ pg/L. Mobilization of PBDEs is likely associated with dissolved organic matter and colloids in the infiltrating water.     

Occurrence of Organotin Compounds in the Aquatic Environment of Greece

The presence of organotin (OT) compounds was investigated in coastal areas (10 stations), wastewater treatment systems (six stations), rivers (19 stations) and lakes (12 stations) throughout Greece, in three sampling campaigns organized between October 1998 and September 1999. A screening method for the determination of toluene extractable organotins (TEOTs) by Electrothermal Atomic Absorption Spectrometry (ETAAS) was used during the first two sampling campaigns. TEOTs (sum of tributyltin, TBT, dibutyltin, DBT and triphenyltin, TPhT) were detected in most seawater and wastewater samples at concentrations up to 19.4 and 89.9 ng l^?1, respectively, while they were detected occasionally in surface water. During the third sampling campaign, OT compounds were extracted in selected stations using direct derivatization with NaBEt₄ in acidic medium and analysed by Gas Chromatography–Mass Spectrometry (GC–MS). In seawater, the levels of TBT, DBT and monobutyltin (MBT) were varied between < 2 and 70, 159 and 19 ng l^?1, respectively and tend to decrease with increasing distance from the coastline. TPhT was not detected in any of the samples. Significant concentrations of OT species were detected in influent wastewater, up to 384, 76.2 and 67.8 ng l^?1 for TBT, DBT and MBT, respectively. OTs were mainly associated with the suspended solids and were totally removed during wastewater treatment.     

Influence of Sediment Preservation on Total Mercury and Methylmercury Analyses

Estuarine and riverine sediments from fourlocations showing different sediment structures wereanalysed as fresh, thawed and lyophilised samples fortotal mercury (TotHg) and methylmercury (MeHg)concentrations, and results were compared to addresseffects of sample preservation on Hg speciation. TotHg was measured by cold vapour atomic absorptionspectrometry (CVAAS). MeHg was isolated bydistillation and ion-exchange and analysed by coldvapour atomic fluorescence spectrometry (CVAFS) afterpreconcentration on a gold trap. No loss of TotHg norMeHg due to lyophilisation was found. Concentrationsof TotHg and MeHg respectively ranged from 92 to 267ng g^-1 dw and 1.1 to 2.9 ng g^-1 dw in freshsamples, from 94 to 215 ng g^-1 dw and 1.1 to 2.8ng g^-1 dw in thawed samples, and from 100 to 256ng g^-1 dw and 1.2 to 3.1 ng g^-1 dw inlyophilised samples. Lyophilised samples showedbetter homogeneity and better MeHg analysisreproducibility compared with wet samples.     

Partitioning of Hg Between Solid and Dissolved Organic Matter in the Humus Layer of Boreal Forests

The mobility of mercury (Hg) deposited on soils controls the concentration and toxicity of Hg within soils and in nearby streams and lakes, but has rarely been quantified under field conditions. We studied the in situ partitioning of Hg in the organic top layer (mor) of podsols at two boreal forest sites differing in Hg deposition and climatic regime (S. and N. Sweden, with pollution declining to the north). Soil solution leaching from the mor layer was repeatedly sampled using zero-tension lysimeters over 2 years, partly in parallel with tension lysimeters. Concentrations of Hg and dissolved organic carbon (DOC) were higher while pH was lower at the southern site (means ± SD: Hg?=?44?±?15 ng L^?1, DOC?=?63.0?±?31.3 mg L^?1, pH?=?4.05?±?0.53) than at the northern site (Hg?=?22?±?6 ng L^?1, DOC?=?41.8?±?12.1 mg L^?1, pH?=?4.28?±?0.43). There was a positive correlation over time between dissolved Hg and DOC at both sites, even though the DOC concentration peaked during autumn at both sites, while the Hg concentration remained more constant. This correlation is consistent with the expected strong association of Hg with organic matter and supports the use of Hg/C ratios in assessments of Hg mobility. In the solid phase of the overlying O_f layer, both Hg concentrations and Hg/C ratios were higher at the southern site (means ± SD: 0.34?±?0.06 μg g^?1 dw and 0.76?±?0.14 μg g^?1 C, respectively) than at the northern site (0.31?±?0.05 μg g^?1 dw and 0.70?±?0.12 μg g^?1 C, respectively). However, concentrations in the solid phase differed less than might be expected from the difference in current atmospheric input, suggesting that the fraction of natural Hg is still substantial. At both sites, Hg/C ratios in the upper half of the mor layer were only about two thirds of those in the lower half, suggesting that the recent decrease in anthropogenic Hg deposition onto the soil is offset by a natural downward enrichment of Hg due to soil decomposition or other processes. Most interestingly, comparison with soil leachate showed that the average Hg/C ratios in the dissolved phase of the mor layers at both sites did not differ from the average Hg/C ratios in the overlying solid organic matter. These results indicate a simple mobilisation with negligible fractionation, despite differences in Hg deposition patterns, soil chemistry and climatic regimes. Such a straight-forward linkage between Hg and organic matter greatly facilitates the parameterisation of watershed models for assessing the biogeochemical fate, toxic effect and critical level of atmospheric Hg input to forest soils.     

Importance of bank erosion for sediment input, storage and export at the catchment scale

Purpose

The importance of bank erosion was quantified during three periods (October 2006–April 2007, May 2007–April 2008 and May 2008–April 2009) in the 486 km² catchment area of River Odense, Denmark. A catchment sediment budget was established including other sediment sources such as tile drains and surface runoff, in-channel and overbank sinks and storage and the resulting bed load and suspended sediment load exported from the catchment.

Material and methods

Bank erosion and sedimentation were measured using ca. 3,000 erosion pins established in 180 pin plots, each consisting of three vertical lines of pins. Thirty-six representative reaches, each with a length of 100 m, were selected by a stratified random procedure in GIS. Bed load and suspended sediment export from the catchment were measured using a bed load sampler and from continuous measurements of turbidity at the outlet gauging station.

Results and discussion

The gross sediment input from bank erosion during the three study periods amounted to 21,100–25,200 t in the River Odense catchment, which is considerably higher than the estimated input of sediment from tile drains and surface runoff, which amounted to 220–500 t and 0–100 t, respectively. The measured bed load (20–490 t) was five to 60 times lower than the suspended sediment export from the catchment (1,240–2,620 t) during the three study periods, with the largest difference occurring in the driest year. Sediment sinks and storage were of high importance for the catchment sediment budget as the measured in-channel storage of sediment on stream banks was as high as 16,200–20,100 t, and the overbank sediment sink was estimated at 360–3,100 t.

Conclusions

Bank erosion was the dominant sediment source (90–94 %) in the River Odense catchment during the three study years. In-channel and overbank sediment sinks and storage dominated the sediment budget as 79–94 % of the sediment input from all sources was not exported from the catchment during the three study years. Such a large attenuation of sediment in river channels and on floodplains is extremely important for fluvial habitats and ecology. Moreover, it has strong implications for attempts to document changes in sediment export following implementation of mitigation measures.     

Polycyclic Aromatic Hydrocarbons in Seawater, Sediment, and Rock Oyster Saccostrea cucullata from the Northern Part of the Persian Gulf (Bushehr Province)

The concentration of polycyclic aromatic hydrocarbons (PAHs) was determined in seawater, sediment, and Rock oyster Saccostrea cucullata collected from four sampling sites in the inter-tidal areas of Bushehr province. The total concentrations of 14 PAHs varied from 1.5 to 3.6 ng/L in seawater, 41.7 to 227.5 ng/g dry weight in surface sediment, and 126 to 226.1 ng/g dry weight in oyster tissue. In comparing PAH concentrations among the three matrices in Bushehr province, data showed that the pattern of individual PAHs in seawater, oyster, and sediment were different. The oysters tended to accumulate the lower molecular weight and the more water-soluble PAHs. Sediment samples were distinguished from the sea water and oyster samples by the presence of high molecular weight PAHs, especially six-ring PAHs. Three- and four-ring PAHs were the most abundant compounds among the 14 PAHs investigated in surface seawater, sediment, and oyster samples. As expected, differences in octanol/water partition coefficient among individual PAHs and the greater persistence of the higher molecular weight PAHs contributed to the accumulation patterns in oyster and sediment. The results of the study suggested that the main sources of PAHs in the seawater and sediment in the region were mixed pyrolitic and petrogenic inputs.