Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River,Romania

Background, aim and scope

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.

Results and discussion

Sediment texture was uniform in the cores from both reservoirs. Laminated sediment structure, without any obvious discontinuities, was observed. Hg concentrations in the sediment core from the Valcea Reservoir were low and constant (0.01–0.08 mg/kg). In Babeni Reservoir sediments, Hg concentrations were very high in the deeper core section (up to 45 mg/kg in the longest core) and decreased to lower concentrations toward the top of the cores (1.3–2.4 mg/kg). This decrease probably reflects technological progress in control of emissions from the Hg-cell-based chlor-alkali industry. Two strong peaks could be distinguished in older sediments. The mean rate of sedimentation (5.9 cm/year) was calculated from the depth of the ¹³⁷Cs Chernobyl peak. This was in good agreement with the sedimentation rate estimated at this site from a bathymetric study. Assuming a constant sedimentation rate, the two Hg peaks would reflect two contamination events in 1987 and 1991, respectively. However, it is also possible that the two peaks belong to the same contamination event in 1987 but were separated by a sediment layer richer in sand and silt. This layer had a low Hg concentration, which can be interpreted as a mass deposition event related to a major flood bringing Hg-free sediments.

Conclusions

Whilst the chlor-alkali plant partly switched to a cleaner technology in 1999, no obvious decrease of Hg concentrations was observed in recent decade. Results from the sediment core reflected the historical trend of Hg release from the chlor-alkali plant, revealed important contamination episodes and confirmed a legacy of contamination of Hg in recent sediments even if the concentrations of Hg decreased toward the surface due to a more efficient emission control.

Recommendations and perspectives

Although the Hg concentrations in Babeni Reservoir sediments were extremely high in the late eighties and they remain one order of magnitude higher in the surface sediments than in sediments from the upstream reservoir, little is known about the transfer of Hg to the biota and human population. Our initial measurements indicate the presence of monomethyl-Hg (MMHg) in pore water, but further studies are necessary to evaluate fluxes of MMHg at the sediment–water interface. Samples of fish and hair from various groups of the local population were recently collected to evaluate the potential hazard of Hg contamination to human health in the Rm Valcea region.

     

Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River, Romania

Background, aim and scope  

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.     

Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River,Romania

Background, aim and scope

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.

Results and discussion

Sediment texture was uniform in the cores from both reservoirs. Laminated sediment structure, without any obvious discontinuities, was observed. Hg concentrations in the sediment core from the Valcea Reservoir were low and constant (0.01–0.08 mg/kg). In Babeni Reservoir sediments, Hg concentrations were very high in the deeper core section (up to 45 mg/kg in the longest core) and decreased to lower concentrations toward the top of the cores (1.3–2.4 mg/kg). This decrease probably reflects technological progress in control of emissions from the Hg-cell-based chlor-alkali industry. Two strong peaks could be distinguished in older sediments. The mean rate of sedimentation (5.9 cm/year) was calculated from the depth of the ¹³⁷Cs Chernobyl peak. This was in good agreement with the sedimentation rate estimated at this site from a bathymetric study. Assuming a constant sedimentation rate, the two Hg peaks would reflect two contamination events in 1987 and 1991, respectively. However, it is also possible that the two peaks belong to the same contamination event in 1987 but were separated by a sediment layer richer in sand and silt. This layer had a low Hg concentration, which can be interpreted as a mass deposition event related to a major flood bringing Hg-free sediments.

Conclusions

Whilst the chlor-alkali plant partly switched to a cleaner technology in 1999, no obvious decrease of Hg concentrations was observed in recent decade. Results from the sediment core reflected the historical trend of Hg release from the chlor-alkali plant, revealed important contamination episodes and confirmed a legacy of contamination of Hg in recent sediments even if the concentrations of Hg decreased toward the surface due to a more efficient emission control.

Recommendations and perspectives

Although the Hg concentrations in Babeni Reservoir sediments were extremely high in the late eighties and they remain one order of magnitude higher in the surface sediments than in sediments from the upstream reservoir, little is known about the transfer of Hg to the biota and human population. Our initial measurements indicate the presence of monomethyl-Hg (MMHg) in pore water, but further studies are necessary to evaluate fluxes of MMHg at the sediment–water interface. Samples of fish and hair from various groups of the local population were recently collected to evaluate the potential hazard of Hg contamination to human health in the Rm Valcea region.

     

Sedimentary record of PAHs in the Liangtan River and its relation to socioeconomic development of Chongqing, Southwest China

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were detected in sediment cores and surface sediment samples from the Liangtan River of Chongqing, Southwest China. The total concentration of 16 PAHs ranged from 69 to 6251 ng g⁻¹. The spatial distribution of the PAHs reflects the intensity and scope of human activity in the catchment. A historical record of PAH contamination was reconstructed using a sediment core from a background segment of the river. The characteristic changes of concentrations, fluxes and patterns of 16 PAHs over the past ∼90 years were captured in detail. An obvious peak of PAH concentration and flux was found in the 1940s, i.e., during war time, and then a sharp increase was observed from the early 1980s to the present. The maximum concentration and flux reached 1260 ng g⁻¹ and 470 ng cm⁻² year⁻¹, respectively. The sharp increase was attributed to the contribution of pyrogenic sources of PAHs. The population, length of highways and energy consumption of Chongqing, as indexes of socioeconomic development, were positively correlated with PAH input in the sediment core from the 1950s to the present. The results clearly show that the local socioeconomic development in the last decades remarkably aggravated the environmental load of sedimentary PAHs.     

A comprehensive investigation and assessment of mercury in intertidal sediment in continental coast of Shanghai

The aims of this paper were to survey the total Hg levels and distribution character in intertidal sediment in continental coast of Shanghai, and identify the environment factors that might influence the sediment Hg concentrations, and to assess the pollution degree and potential ecological risk of Hg in sediment. Eighty-eight surface sediment samples and 18 sediment cores were collected for Hg contamination analysis. Physicochemical properties including Eh, particle size, content of total organic carbon (TOC), and acid volatile sulfide (AVS) were also measured. Index of geo-accumulation (I _geo) and potential ecological risk index were used respectively to assess the pollution levels and the ecological risk of sediment Hg. The average of total Hg concentrations in surface sediments was 107.4?±?90.9 ng/g with the range from 0 to 465.9 ng/g. Higher Hg concentrations were generally found in surface sediments near sewage outfalls and the mouth of rivers. Total Hg concentrations were significantly correlated with TOC (p?<?0.05) both in surface (r?=?0.24) and core (r?=?0.29) sediments, but not with the other environment factors (Eh, AVS, and particle size). Geo-accumulation index indicated that Hg contamination in intertidal sediments was generally at none to moderate degree, while potential ecological risk index demonstrated that the risk caused by Hg were at moderate to considerable level. Intertidal sediment in continental coast of Shanghai has generally been contaminated by Hg, and it might pose moderate to considerable risk to the local ecosystem. The Hg contamination is related more to the coastal pollution sources and complicated hydrodynamic and sedimentary conditions than the other environment factors studied.     

Spatial distribution and ecological risk assessment of sediment metals in a highly industrialized coastal zone southwestern Taiwan

Spatial variations of Cr, Cu, Hg, Ni, Pb, and Zn in the surface sediments from 34 stations of the Kaohsiung coastal zone southwestern Taiwan were studied to address the current pollution status, sediment quality, and potential ecological risk. The study revealed that the concentrations of sediment metals in Kaohsiung Harbor were alarmingly high compared to the other region of Kaohsiung coast. The concentrations of Cr, Cu, Hg, Ni, Pb, and Zn in the harbor sediments were as high as 351, 247, 1.93, 61.8, 60.9, and 940 mg kg⁻¹, respectively. The current situation of metal pollution was assessed by different pollution indices and results showed moderate to severe enrichment of Cu, Hg, and Zn in the harbor sediments. According to the degree of contamination, pollution load index, and contamination severity index, the sediments from the inner Kaohsiung Harbor show high degree and high severity of metal contamination, while the rest of Kaohsiung coastal areas show uncontaminated or low-level pollution. Results of mean ERM quotient and potential ecological risk index also indicated that the harbor sediments posed a 49% probability of biological toxicity and very high ecological risk. The toxic units indicated that the negative biological effects of the six metals in the harbor sediments were Zn > Cu > Cr > Ni > Hg > Pb. In contrast to Kaohsiung Harbor as a trap where considerable amount of anthropogenic metal loadings accumulated in sediments, low metal concentrations were observed in most Kaohsiung coastal sediments. It probably resulted from the limited fine-grained sediment deposition. In the wave-dominated Kaohsiung coastal zone, fine-grained sediments associated with polluted metals tend to be easily resuspended and transported offshore via waves and wave-induced currents. The results of this study can provide valuable information for river and coastal zone management.

     

Accumulation of mercury and methylmercury by mushrooms and earthworms from forest soils

Accumulation of total and methyl-Hg by mushrooms and earthworms was studied in thirty-four natural forest soils strongly varying in soil physico-chemical characteristics. Tissue Hg concentrations of both receptors did hardly correlate with Hg concentrations in soil. Both total and methyl-Hg concentrations in tissues were species-specific and dependent on the ecological groups of receptor. Methyl-Hg was low accounting for less than 5 and 8% of total Hg in tissues of mushrooms and earthworms, respectively, but with four times higher concentrations in earthworms than mushrooms. Total Hg concentrations in mushrooms averaged 0.96 mg Hg kg⁻¹ dw whereas litter decomposing mushrooms showed highest total Hg and methyl-Hg concentrations. Earthworms contained similar Hg concentrations (1.04 mg Hg kg⁻¹ dw) whereas endogeic earthworms accumulated highest amounts of Hg and methyl-Hg.     

Long-term mercury dynamics in UK soils

A model assuming first-order losses by evasion and leaching was used to evaluate Hg dynamics in UK soils since 1850. Temporal deposition patterns of Hg were constructed from literature information. Inverse modelling indicated that 30% of 898 rural sites receive Hg only from the global circulation, while in 51% of cases local deposition exceeds global. Average estimated deposition is 16 μg Hg m⁻² a⁻¹ to rural soils, 19 μg Hg m⁻² a⁻¹ to rural and non-rural soils combined. UK soils currently hold 2490 tonnes of reactive Hg, of which 2140 tonnes are due to anthropogenic deposition, mostly local in origin. Topsoil currently releases 5.1 tonnes of Hg⁰ per annum to the atmosphere, about 50% more than the anthropogenic flux. Sorptive retention of Hg in the lower soil exerts a strong control on surface water Hg concentrations. Following decreases in inputs, soil Hg concentrations are predicted to decline over hundreds of years.     

Mercury transport between sediments and the overlying water of the St. Lawrence River area of concern near Cornwall, Ontario

Contaminated sediments in the St. Lawrence River remain a difficult problem despite decreases in emissions. Here, sediment and pore water phases were analyzed for total mercury (THg) and methyl mercury (MeHg) and diffusion from the sediment to the overlying water was 17.5 ± 10.6 SE ng cm⁻² yr⁻¹ for THg and 3.8 ± 1.7 SE ng cm⁻² yr⁻¹ for MeHg. These fluxes were very small when compared to the particle-bound mercury flux accumulating in the sediment (183 ± 30 SE ng cm⁻² yr⁻¹). Studies have reported that fish from the westernmost site have higher Hg concentrations than fish collected from the other two sites of the Cornwall Area of Concern, which could not be explained by differences in the Hg flux or THg concentrations in sediments, but the highest concentrations of sediment MeHg, and the greatest proportions of MeHg to THg in both sediment and pore water were observed where fish had highest MeHg concentrations.     

One century sedimentary records of polycyclic aromatic hydrocarbons, mercury and trace elements in the Qinghai Lake, Tibetan Plateau

Sediments from a remote lake of northeastern Tibetan Plateau were analyzed for polycyclic aromatic hydrocarbons (PAHs) and trace metals. USEPA priority PAHs, ranged from 11 in 1860 to 279 ng g⁻¹ in 2002, while, the deposition fluxes were in the range of 0.2-11.4 ng cm⁻² yr⁻¹. Similarly, from 1860 to 2002, an increased trend of Hg flux was observed (0.5-3.2 ng cm⁻² yr⁻¹). Remarkable increase of PAHs and Hg concentration began from 1970, nearly the same period of the “Reform and Open” Policy had been embarked (1978) in China. Good correlations were found between concentrations of Pb, Zn, Cd, As, Hg, and PAHs, which suggested the sources of these chemicals in the sediment is analogous, likely from anthroprogenic sources. Based on isomer ratios, PAHs in core were dominantly from the incomplete combustion of coal. Owing to the proximity to dust source area (Qaidam Basin) and the close association between PAHs, Hg, Pb, and particle matters, atmospheric dust-transport and deposition might be the main pathways that pollutants enter into Qinghai Lake.     

Mercury in United Kingdom topsoils; concentrations, pools, and Critical Limit exceedances

The median total mercury concentration in 898 UK rural topsoils, sampled between 1998 and 2008, was 0.095 μg g⁻¹. Approximate adjustment for unreactive metal produced an estimate of 0.052 μg g⁻¹ for reactive Hg. The highest concentrations were in the north and west, where organic-rich soils with low bulk densities dominate, but the spatial pattern was quite different if soil Hg pools (mg m⁻²) were considered, the highest values being near to the industrial north of England and London. Possible toxic effects of Hg were best evaluated by comparison with soil Critical Limits expressed as ratios of Hg to soil organic matter, or soil solution Hg²⁺ concentrations, estimated by chemical speciation modelling. Only a few percent of the rural UK soils showed exceedance, and this also applied to rural soils from the whole of Europe. UK urban and industrial soils had higher Hg concentrations and more cases of exceedance.     

Mercury concentrations and air/soil fluxes in Wuchuan mercury mining district,Guizhou province,China

Wuchuan Hg mine, located in the Circum-Pacific Global Mercuriferous Belt, is one of the important Hg production centers in Guizhou province, China. Soil Hg concentrations in this area are elevated by 2–4 orders of magnitude compared to the national background value in soil which is 0.038 μg g⁻¹. In situ air Hg concentrations and air/soil Hg fluxes were measured at five sampling sites in Wuchuan Hg mining area (WMMA) from 19 to 26 December 2003 and from 18 to 25 December 2004. The results showed that air Hg concentrations were 2–4 orders of magnitude higher than those observed in background areas in Europe and North America due to a large amount of Hg emission from artisanal Hg smelting activities. The average in situ Hg fluxes at site Laohugou, Jiaoyan, Luoxi, Sankeng and Huanglong were −5493, 124, −924, −13 and 140 ng m⁻² h⁻¹, respectively. Diurnal pattern of Hg flux was not found and a number of negative Hg fluxes were observed in our sampling campaigns. The correlations between Hg fluxes and meteorological parameters such as solar irradiation, air temperature, soil temperature and relative humidity and air Hg concentrations were investigated. The commonly observed significant correlations between Hg fluxes and meteorological parameters observed in many previous studies were not obtained in WMMA. However, significantly negative correlations between Hg flux and air Hg concentration were observed at all sites. Our study demonstrated that highly elevated air Hg concentrations could suppress Hg emission processes even from Hg-enriched soil. At specific conditions in WMMA, air Hg concentrations play a dominant role in controlling Hg emission from soil.     

Nationwide monitoring of mercury in wild and farmed fish from fresh and coastal waters of Korea

Mercury (Hg) concentrations were monitored in wild and cultured fish collected from fresh and coastal waters in the Korean peninsula from April 2006 to August 2008 nationwide. Total Hg concentrations were reported for 5043 fish samples, including 78 species from 133 locations. Significant interspecies variation was noted in the Hg levels. The average Hg concentration in each fish species ranged from 6.31 μg kg⁻¹ for mullet (Mugil cephalus) to 200 μg kg⁻¹ for mandarin fish (Siniperca scherzeri). Among the species collected, the maximum concentration of Hg, 1720 μg kg⁻¹, was measured in an Amur catfish (Silurus asotus). Only wild freshwater fish exceeded the WHO ingestion standard. Wild freshwater piscivorous fish samples from a large artificial upstream lake contained the highest Hg levels. Hg concentrations were compared between fish groups categorized as wild and farmed fish from freshwater and coastal waters. Although the wild freshwater fish had similar size ranges, their Hg concentrations were higher than those of the other groups. Compared to the feed of farmed marine and freshwater fishes, the prey of wild freshwater fish had a higher Hg concentration, and the total Hg concentrations in freshwater and associated sediment samples were higher than those in coastal water and associated sediment samples. In the freshwater environment, piscivorous fish bioaccumulated two times more Hg than carnivorous and omnivorous fish and four times more than planktivorous fish. The difference in Hg concentrations among trophic groups might have been due to differences in the size of fish, in addition to the variations among different trophic groups. These data will be useful for developing the fish consumption advisory as a management measure to reduce Hg exposure.     

Solving mercury (Hg) speciation in soil samples by synchrotron X-ray microspectroscopic techniques

Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg⁻¹. Hg chemical forms were identified and quantified by sequential extractions and bulk- and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as μ-XRF, μ-XRD and μ-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 μm. The main Hg-species found in the soil samples were metacinnabar (β-HgS), cinnabar (α-HgS), corderoite (Hg₃S₂Cl₂), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 μm. No interaction among Hg-species and soil components was observed. All the observed Hg-species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Contents and sources of DDT impurities in dicofol formulations in Turkey

Background, aim, and scope  Dicofol is widely used as a pesticide in agriculture applications. Since dicofol is mainly synthesized from dichlorodiphenyltrichlorethane (DDT), it contains DDT as an impurity. The European Community has forced Prohibition Directive 79/117/EEC to reduce DDT in dicofol formulations. Specifically, DDT content in a dicofol formulation cannot exceed 0.1%. The goal of this project was to determine the DDT content in dicofol formulations used in Turkey. Materials and methods  Samples of all the dicofol formulations in Turkey were collected to quantify DDT and DDT-related compounds. Four replicates were used for each sample. GC/MS/MS was used to analyze p,p′ and o,p′ isomers of DDT, DDD, and DDE. A HPLC was used to determine p,p′-Cl-DDT concentrations. Results  The total DDT content of the formulated dicofol was found between 0.3% and 14.3%. The concentration of p,p′-DDE ranged from 167 to 1,042 mg kg⁻¹ in dicofol samples. p,p′-DDT concentrations were found to be 32 to 183 mg kg⁻¹. The o,p’-DDT level ranged from 2 to 34 mg kg⁻¹ in the dicofol formulations analyzed. Discussion  It was estimated that 617.8 kg of DDT was released from dicofol. The main impurity was identified as p,p-Cl-DDT. Based on these results, dicofol serves as a continuing source of DDT contamination. Conclusions  All DDT concentrations in dicofol samples analyzed were higher than the permitted 0.1% level of Prohibition Directive 79/117/EEC. The reduction of dicofol is critical since it serves as a continual source of DDT contamination. Recommendations and perspectives  DDT has been found in soil, water, and air samples. Dicofol has been identified as a contributor to continued DDT contamination in soil and water. More studies are needed to ascertain the source of DDT in the air.     

Characteristics of mercury exchange flux between soil and air in the heavily air-polluted area,eastern Guizhou,China

To investigate the characteristics of mercury exchange between soil and air in the heavily air-polluted area, total gaseous mercury (TGM) concentration in air and Hg exchange flux were measured in Wanshan Hg mining area (WMMA) in November, 2002 and July–August, 2004. The results showed that the average TGM concentrations in the ambient air (17.8–1101.8 ng m⁻³), average Hg emission flux (162–27827 ng m⁻² h⁻¹) and average Hg dry deposition flux (0–9434 ng m⁻² h⁻¹) in WMMA were 1–4 orders of magnitude higher than those in the background area. It is said that mercury-enriched soil is a significant Hg source of the atmosphere in WMMA. It was also found that widely distributed roasted cinnabar banks are net Hg sources of the atmosphere in WMMA. Relationships between mercury exchange flux and environmental parameters were investigated. The results indicated that the rate of mercury emission from soil could be accelerated by high total soil mercury concentration and solar irradiation. Whereas, highly elevated TGM concentrations in the ambient air can restrain Hg emission from soil and even lead to strongly atmospheric Hg deposition to soil surface. A great amount of gaseous mercury in the heavily polluted atmosphere may cycle between soil and air quickly and locally. Vegetation can inhibit mercury emission from soil and are important sinks of atmospheric mercury in heavily air-polluted area.     

Field controlled experiments of mercury accumulation in crops from air and soil

Field open top chambers (OTCs) and soil mercury (Hg) enriched experiments were employed to study the influence of Hg concentrations in air and soil on the Hg accumulation in the organs of maize (Zea mays L.) and wheat (Triticum aestivum L.). Results showed that Hg concentrations in foliages were correlated significantly (p < 0.05) with air Hg concentrations but insignificantly correlated with soil Hg concentrations, indicating that Hg in crop foliages was mainly from air. Hg concentrations in roots were generally correlated with soil Hg concentrations (p < 0.05) but insignificantly correlated with air Hg concentrations, indicating that Hg in crop roots was mainly from soil. No significant correlations were found between Hg concentrations in stems and those in air and soil. However, Hg concentrations in upper stems were usually higher than those in bottom stems, implying air Hg might have stronger influence than soil Hg on stem Hg accumulation.     

Local to regional emission sources affecting mercury fluxes to New York lakes

Lake-sediment records across the Northern Hemisphere show increases in atmospheric deposition of anthropogenic mercury (Hg) over the last 150 years. Most of the previous studies have examined remote lakes affected by the global atmospheric Hg reservoir. In this study, we present Hg flux records from lakes in an urban/suburban setting of central New York affected also by local and regional emissions. Sediment cores were collected from the Otisco and Skaneateles lakes from the Finger Lakes region, Cross Lake, a hypereutrophic lake on the Seneca River, and Glacial Lake, a small seepage lake with a watershed that corresponds with the lake area. Sediment accumulation rates and dates were established by ²¹⁰Pb. The pre-anthropogenic regional atmospheric Hg flux was estimated to be 3.0 μg m⁻² yr⁻¹ from Glacial Lake, which receives exclusively direct atmospheric deposition. Mercury fluxes peaked during 1971–2001, and were 3 to more than 30 times greater than pre-industrial deposition. Land use change and urbanization in the Otisco and Cross watersheds during the last century likely enhanced sediment loads and Hg fluxes to the lakes. Skaneateles and Glacial lakes have low sediment accumulation rates, and thus are excellent indicators for atmospheric Hg deposition. In these lakes, we found strong correlations with emission records for the Great Lakes region that markedly increased in the early 1900s, and peaked during WWII and in the early 1970s. Declines in modern Hg fluxes are generally evident in the core records. However, the decrease in sediment Hg flux at Glacial Lake was interrupted and has increased since the early 1990s probably due to the operation of new local emission sources. Assuming the global Hg reservoir tripled since the pre-industrial period, the contribution of local and regional emission sources to central New York lakes was estimated to about 80% of the total atmospheric Hg deposition.     

Influence of tidal regime on the distribution of trace metals in a contaminated tidal freshwater marsh soil colonized with common reed (Phragmites australis)

A historical input of trace metals into tidal marshes fringing the river Scheldt may be a cause for concern. Nevertheless, the specific physicochemical form, rather than the total concentration, determines the ecotoxicological risk of metals in the soil. In this study the effect of tidal regime on the distribution of trace metals in different compartments of the soil was investigated. As, Cd, Cu and Zn concentrations in sediment, pore water and in roots were determined along a depth profile. Total sediment metal concentrations were similar at different sites, reflecting pollution history. Pore water metal concentrations were generally higher under less flooded conditions (mean is (2.32 ± 0.08) × 10⁻³ mg Cd L⁻¹ and (1.53 ± 0.03) × 10⁻³ mg Cd L⁻¹). Metal concentrations associated with roots (mean is 202.47 ± 2.83 mg Cd kg⁻¹ and 69.39 ± 0.99 mg Cd kg⁻¹) were up to 10 times higher than sediment (mean is 20.48 ± 0.19 mg Cd kg⁻¹ and 20.42 ± 0.21 mg Cd kg⁻¹) metal concentrations and higher under dryer conditions. Despite high metal concentrations associated with roots, the major part of the metals in the marsh soil is still associated with the sediment as the overall biomass of roots is small compared to the sediment.