Accumulation of As, Cd and selected trace elements in tubers of Scirpus maritimus L. from Doñana marshes (South Spain)

The collapse of a pyrite-mining, tailing dam on 1998 contaminated an area of 4286 ha along the Agrio and Guadiamar river valleys in southern Spain. Over 2700 ha of the Do?ana marshes, an important wintering area for wetland European birds, were contaminated. This study reports analyses of the tubers of Scirpus maritimus (an important food for greylag geese, Anser anser) collected in 2000 in the "Entremuros" (spill-affected area) and in nearby unaffected Do?ana marshes (control areas). In the spill-affected area mean tuber tissue concentrations of Cd (0.25 mg kg-1) and Zn (61 mg kg-1) were greater than in those tubers from the control area (0.02 mg kg-1 for Cd, and 22 mg kg-1 for Zn); values of Cd and Zn in "Entremuros" (samples collected two years after the mine spill) were much smaller than those reported only a few months after the accident. Trace elements (As, Fe, Mn and Tl, and to a lesser extent Cd and Pb) showed a preferential accumulation in the outer skin of tubers. Surprisingly, concentrations of As and Fe were greater in tubers from some marsh sites not affected by the mine-spill than in tubers from the "Entremuros". We suggest that relic river channels within the Do?ana marshes may be contaminated by trace elements from historic mining activities. An exhaustive study of macrophytes and other plant species in this area is recommended to identify potential risks to wildlife.     

Arsenic levels in the soils and macrophytes of the 'Entremuros' after the Aznalcóllar mine spill

In April 1998, a holding lagoon containing pyrite ore processing waste rich in arsenic, failed and released 5-6 million m(3) of highly polluting sludge and acidic water. Over 2700 ha of the internationally important Do?ana National and Natural Parks were contaminated. The area of Natural Park to sustain the greatest impact was known as the Entremuros. This paper presents 0-5 cm soil monitoring data from the Entremuros, from sampling campaigns 6 and 18 months after the disaster; as well as macrophyte root, rhizome and stem data from samples taken 18 months after the spill. Results show a clear, decreasing, north-south arsenic soil pollution trend, both 6 and 18 months after the spill, and suggest a small reduction in total soil arsenic levels occurred over time; although a significant increase in extractable arsenic is also noted. The two macrophytes (Typha dominguensis and Scirpus maritimus) studied herein are not accumulating arsenic in stem parts, however, accumulation of arsenic on iron plaque on the roots of these plants may be occurring. Further work is recommended in order to determine the ecotoxicological significance of this process in relation to the avian food-chains of Do?ana, and elsewhere.     

PCDDs, PCDFs, dioxin-like PCBs and indicator PCBs in soil from five selected areas in Slovakia

There is a lack of information regarding persistent organic pollutants (POPs) in soil from Slovakia. This paper reports the concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and 6 indicator PCBs associated with 32 soil samples collected in 2007 from areas in the vicinity up to several kilometres from four selected industrial PCDD/F sources in Slovakia and one background area.The results show that the total WHO₁₉₉₈-PCDD/F/dl-PCB-TEQ concentrations varied from 0.34 to 18.05 pg g⁻¹ dry weight (dw) and the average total TEQ concentrations in samples collected at the Šala, Košice, Krompachy and Dubová areas were 3.18, 2.64, 7.80, and 3.19 pg g⁻¹ dw respectively. The average of the total WHO₁₉₉₈-TEQ values in three soil samples representing the background Starina area was 0.66 pg g⁻¹ dw. The predominant contaminants among 2,3,7,8-substituted PCDD/Fs, dl-PCB, and indicator PCBs was OCDD, PCB 118, and PCB 153 respectively. The major contributors to the TEQ were 2,3,4,7,8-PeCDF, PCB 126, 1,2,3,7,8-PeCDD, PCB 156 and 1,2,3,4,7,8-HxCDF + 1,2,3,4,7,9-HxCDF in descending order.     

Manipulation of snow in small headwater catchments at Storgama, Norway: effects on leaching of total organic carbon and total organic nitrogen

Projected increases in winter temperature due to future climate change may cause decreased snow accumulation at lower and intermediate altitudes in northern temperate regions. The resulting changes in soil temperature and water regime may affect the leaching of total organic carbon (TOC) and total organic nitrogen (TON). We manipulated the snow cover of small headwater catchments in a montane heathland area of southern Norway to quantify its effect on concentrations and fluxes of TOC and TON in runoff. Manipulations included snow removal, to promote soil frost, and insulation, to prevent soil frost. Snow removal resulted in increased TOC and TON concentrations, but decreased fluxes. Insulation caused a slight decrease in concentrations and fluxes of TOC. Our experiments show that a change in snow depth, and thus soil temperature, is not likely to have serious effects on TOC and TON leaching in the montane heathland area studied.     

Manipulation of snow in small headwater catchments at Storgama, Norway: effects on leaching of inorganic nitrogen

We have manipulated the winter-time soil temperature regime of small headwater catchments in a montane heathland area of southern Norway to study the possible effects on concentrations and fluxes of inorganic nitrogen in runoff. The experiments included extra insulation of soils in two catchments to prevent subzero temperatures during winter, and removal of snow in two other catchments to promote soil frost. Increased soil temperatures during winter increased the springtime concentrations and fluxes of ammonium (NH4) and nitrate (NO3) in runoff. By contrast, snow removal with development of significant soil frost showed no systematic effects on mean concentrations or fluxes of inorganic N. The results from our experiments suggest that warmer soils during winter caused by exceptionally mild winters, or alternatively a heavy snowpack, imply a greater risk for inorganic N leaching in this region than a possible increase of soil frost events because of reduced snow cover.     

Characteristics,sources, and transport of tetrabromobisphenol A and bisphenol A in soils from a typical e-waste recycling area in South China

We studied the tetrabromobisphenol A (TBBPA) and bisphenol A (BPA) patterns and their sources and transport in different land-use soils from Longtang, South China, a typical electronic waste recycling center. We also studied the reductive debromination of TBBPA in paddy soils. TBBPA and BPA concentrations (on a dry weight basis) were undetected–220 and 0.50–325 ng/g, respectively, and both increased, by similar factors, in the following order: pond sediments?<?paddy soils?=?vegetable soils?<?wasteland?<?dismantling sites?<?former open burning sites. BPA concentrations were higher than TBBPA concentrations in all six land-use soils, and they correlated significantly. TBBPA and BPA were transported through the soil profiles, being found at relatively high concentrations in soil 0–40 cm deep, but only at low concentrations in soil 40–80 cm deep. The surface soil concentrations appear to have been strongly affected by crude recycling activities, and former open burning and dismantling sites were the main point sources. The areas surrounding the open burning sites and dismantling sites have been contaminated not only by the dumping of waste residues but also by fly ash deposition, even though the agricultural soils are far from the point pollution sources. Some BPA in the soils is likely to be the reductive debromination product of TBBPA because the long rainy season promotes TBBPA transformation and because BPA can persist for a long time. Incubation experiments confirmed that TBBPA could be transformed into BPA and that BPA could accumulate in waterlogged paddy soils, and this may be why BPA concentrations were higher than TBBPA concentrations in the Longtang area.     

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.     

Heavy metals in soils from a typical industrial area in Sichuan,China: spatial distribution,source identification,and ecological risk assessment

Anthropogenic activities could result in increasing concentrations of heavy metals in soil and deteriorating in soil environmental quality. Topsoil samples from a typical industrial area, Shiting River Valley, Sichuan, Southwest China, were collected and determined for the concentrations of Cu, Zn, Cr, Cd, As, and Hg. The mean concentrations of these metals were lower than the national threshold values, but were slightly higher than their corresponding background values, indicating enrichment of these metals in soils in the valley, especially for Cu, Zn, and Hg. The topsoils in this area demonstrated moderate pollution and low potential ecological risk. Principal component analysis coupled with cluster analysis was applied to analyze the data and identified possible sources of these heavy metals; the results showed that soil Cd, Hg, As, Cu, and Zn were predominantly controlled by human activities, whereas Cr was mainly from the parent material. The spatial distribution of the heavy metals varied distinctly and was closely correlated to local anthropogenic activities. Furthermore, the concentrations of heavy metals in the industrial land demonstrated relatively higher levels than those of other land use patterns. Soil metal concentrations decreased with the distance increase from the traffic highway (0–1.0 km) and water system (0–2.0 km). Additionally, soil properties, especially pH and soil organic matter, were found to be important factors in the distribution and composition of metals.     

Trace element accumulation in woody plants of the Guadiamar Valley, SW Spain: a large-scale phytomanagement case study

Phytomanagement employs vegetation and soil amendments to reduce the environmental risk posed by contaminated sites. We investigated the distribution of trace elements in soils and woody plants from a large phytomanaged site, the Guadiamar Valley (SW Spain), 7 years after a mine spill, which contaminated the area in 1998. At spill-affected sites, topsoils (0-25 cm) had elevated concentrations of As (129 mg kg(-1)), Bi (1.64 mg kg(-1)), Cd (1.44 mg kg(-1)), Cu (115 mg kg(-1)), Pb (210 mg kg(-1)), Sb (13.8 mg kg(-1)), Tl (1.17 mg kg(-1)) and Zn (457 mg kg(-1)). Trace element concentrations in the studied species were, on average, within the normal ranges for higher plants. An exception was white poplar (Populus alba), which accumulated Cd and Zn in leaves up to 3 and 410 mg kg(-1) respectively. We discuss the results with regard to the phytomanagement of trace element contaminated sites.     

Assessing anthropogenic sources of mercury in soil in Wanshan Hg mining area, Guizhou, China

Long-term mining and smelting activities brought a series of environmental issues into soils in Wanshan mercury (Hg) mining area (WMMA), Guizhou, China. Several studies have been published on the concentrations of Hg in local soils, but a comprehensive assessment of the mass of Hg in soil induced by anthropogenic activities, as presented in this paper, has not been previously conducted. Three districts of WMMA were chosen as the study areas. We summarized previous published data and sampled 14 typical soil profiles to analyze the spatial and vertical distributions of Hg in soil in the study areas. The regional geologic background, direct and indirect Hg deposition, and Hg-polluted irrigation water were considered as the main sources of Hg contaminations in local soils. Furthermore, the enrichment factor (EF) method was applied to assess the extent of anthropogenic input of Hg to soil. Titanium (Ti) was chosen to be the reference element to calculate the EF. Generally, the elevated values of EF were observed in the upper soil layers and close to mine wastes. The total budget of Hg in soil contributed from anthropogenic sources was estimated to be 1,227 t in arable soil and 75 t in natural soil. Our data showed that arable soil was the major sink of anthropogenic Hg in the study area.     

Human intake of PCDDs, PCDFs, and dioxin like PCBs in Japan, 2001 and 2002

PCDDs, PCDFs, and dioxin like PCBs (dioxin) surveillance results derived from regular environmental monitoring as well as other dioxin surveys by national and local governmental bodies in Japan were collected and analyzed. Several thousand data for air and soil in fiscal year 2001 (from 01/04/2001 to 31/03/2002) and 2002, water (from the sea, rivers and lakes), sediment (from the sea, rivers and lakes), ground water, aquatic organisms, purified water from water purification plants, raw water from water purification plants, human breast milk, and human blood in fiscal 2001, and total diet study (TDS) and various kinds of foodstuff in fiscal 1998-2002 were collected. Average human uptake of dioxin in Japan in fiscal 2001 was estimated at 1.68 pg-TEQ/kg-bw/day, while uptake in fiscal 2002 was estimated at 1.52 pg-TEQ/kg-bw/day. Diet accounted for more than 90% of the total intake. Contributions of inhalation and soil ingestion were relatively small. Age-group-specific contribution of various foodstuff to total dietary intake was also estimated. The estimates of intake through fish and shellfish accounted for approximately 45-70% of total dietary intake in each age group. Monte Carlo simulation was conducted, using the data of the air and soil concentrations in fiscal 2001 and the total diet study data in fiscal 1998-2001, in order to obtain information on the variability of dioxin intake; The estimated average, median, 5th percentile and 95th percentile of the intake distribution were 1.78, 1.69, 0.95 and 2.91 pg-TEQ/kg-bw/day, respectively. This study found that the average total intake estimates in Japan in both fiscal 2001 and 2002 were estimated to be below tolerable daily intake level (TDI) defined by the Ministry of Health, Labour and Welfare, Japan (i.e. 4 pg-TEQ/kg-bw/day). The 95th percentile of the dioxin intake distributions estimated with Monte Carlo simulation using the data of the air and soil concentrations in fiscal 2001 and TDS data in fiscal 1998-2001 was also below the Japanese TDI.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment, soil, fish, shellfish and crab samples from Tokyo Bay area, Japan

Concentrations of tetra- to octa-chlorinated dibenzo-p-dioxins and dibenzofurans in samples collected in or near Tokyo Bay, Japan, with a densely inhabited catchment area, were congener-specifically determined and discussed. Analyzed in this study were samples of surface sediment covering the whole bay area, reference soil representing atmospheric impact, and fish, shellfish and crab commonly consumed as food. The range of concentrations were comparable to or higher than those in other parts of Japan. The origins of these compounds in the catchment area of the bay were investigated in terms of homolog and isomeric compositions in the sediment samples. Biota-sediment accumulation factors for benthic species declined as the degree of chlorination increased.     

Polybrominated diphenyl ethers in soils of the modern Yellow River Delta, China: occurrence, distribution and inventory

The Yellow River is the second largest river in China. In this study, the levels of polybrominated diphenyl ethers (PBDEs) in the modern Yellow River Delta (mYRD) were firstly reported. Twenty PBDE congeners in soil/sediment samples from mYRD were measured. The total PBDE concentrations ranged from non-detectable to 18 257 ng kg⁻¹ with a mean value of 836 ng kg⁻¹. BDE-209 was the dominant congener, accounting for ∼86.1-99.5% of the total PBDEs. The congener profiles of PBDEs with higher abundances of BDE-153 and BDE-183 were similar to those in sediment of the Bohai Sea, indicating that they shared similar sources. The concentrations and congener patterns varied among different regions. Higher levels of PBDEs were found in the middle area (MA), and more complicated congener compositions were also observed in the MA, whereas lower levels of PBDEs were found in the modern course (MC) and the old course (OC). Much more PBDEs were detected in the top layer (TL) soil where more congeners were also held compared to lower soil layers, implying that more PBDEs were emitted into this area in recent years/decades. Organic matter controlled the PBDE distribution in the soil. Soil in this area might be a source of BDE209 for the Bohai Sea.     

Distribution, origin and fate of chromium in soils in Guanajuato, Mexico

Total, hexavalent and trivalent chromium were determined in surface and 30-cm depth soil samples from a highly chromium-polluted area in Guanajuato state, central México. Four samples were also analyzed by a sequential extraction procedure. Nearly 0.9 km(2) out of the 8 km(2) area sampled was polluted with chromium, at concentrations up to 12960 mg kg(-1), mostly as Cr(III). Concentrations of Cr(VI) were lower than 0.5 mg kg(-1) in most sampled points, with the exception of one, where the concentration was found to be 65.14 mg kg(-1). Chromiumcontaining dust from a chromate factory accounted for most of the contamination. The highest concentrations of hexavalent chromium in soil, were in the bottom sediments of an abandoned water reservoir used to store polluted water from a well, before use of the water in the factory process. Tannery wastes, dust from a sanitary landfill of chromate compounds and the transport of chromium products are the sources of chromium at other sites. Chromium is fixed preferentially in the hydrous Fe and Mn oxides in the more polluted soils. Less polluted soils have a high proportion of chromium associated with the sulfide and organic fraction. Cr(III) is retained preferentially in the superficial soil layer. Variations in the physical characteristics of the soil, relative abundance of the various soil components and characteristics of the contaminant source, give rise to differences in chromium soil concentrations with depth.     

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.     

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia,Spain

The construction in Constantí (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996–1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ng I-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ng I-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg (d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ng I-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg, respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.     

Risk assessment of heavy metal pollution for detritivores in floodplain soils in the Biesbosch, The Netherlands, taking bioavailability into account

Floodplains of the European rivers Rhine and Meuse are heavily polluted. We investigated the risk of heavy metal pollution (Cd, Cu, Pb, Zn) for detritivores living in a floodplain area, the Biesbosch, the Netherlands, affected by these rivers. Total soil, pore water and 0.01 M CaCl(2) extractable concentrations and concentrations in plant leaves, earthworms, isopods and millipedes were measured in two sites and compared with literature data to assess possible risks. Based on total metal concentrations in soil, serious effects on detritivores were expected. However, 0.01 M CaCl(2) extractable, pore water and plant leaf concentrations were similar to metal concentrations found in unpolluted areas. Concentrations of Cu and Cd in earthworms and Cu in millipedes were higher in the Biesbosch than in animals from reference areas. All other measured concentrations of heavy metals in earthworms, isopods and millipedes were similar to the ones found in reference areas. Despite high total soil concentrations, effects of Zn, Cu, Pb and Cd pollution on isopods are therefore not expected, while millipedes may only be affected by Cu. Since Cu and Cd levels in earthworms were increased compared to animals in unpolluted soils, this faunal group seems to be most at risk. Given the engineering role of earthworms in ecosystems, effects on the ecological functioning of floodplain soils therefore cannot be excluded.     

Lichens as an integrating tool for monitoring PAH atmospheric deposition: A comparison with soil, air and pine needles

The aim of this study was to validate lichens as biomonitors of PAH atmospheric deposition; for that, an inter-comparison between the PAH profile and concentrations intercepted in lichens with those of air, soil and pine needles was performed. The study was conducted in a petro-industrial area and the results showed that PAH profiles in lichens were similar to those of the air and pine needles, but completely different from those of soils. Lichens accumulated higher PAH concentrations when compared to the other environmental compartments and its concentrations were significantly and linearly correlated with concentrations of PAHs in soil; we showed that a translation of the lichen PAHs concentrations into regulatory standards is possible, fulfilling one of the most important requirements of using lichens as biomonitors. With lichens we were then able to characterize the air PAHs profile of urban, petro-industrial and background areas.     

Soil solutions and surface water analysis in two contrasted watersheds impacted by acid deposition, Vosges mountains, N.E. France: interpretation in terms of Al impact and nutrient imbalance

Two acid watersheds in the Vosges mountains (N.E. France), one with a podzol, the other with an acid brown soil, were monitored by analysing soil solutions and two related springs for total chemistry and Al speciation. High concentrations of inorganic Al did not occur in the podzol upper horizons but were evident in the corresponding spring, together with low concentrations of Ca. In the acid brown soil area, high concentrations of inorganic Al occurred in the leaching water draining the upper soil horizons, but not in the undrained water nor in the spring, the latter exhibiting rather high Ca content. In both watersheds, needle yellowing in conifers could be observed and might be ascribed to Mg deficiency rather than to Al toxicity.     

Factors affecting the concentrations of lead in British wheat and barley grain

The entry of Pb into the food chain is of concern as it can cause chronic health problems. The concentration of Pb was determined in cereal grain samples collected representatively from British Cereal Quality Surveys in 1982 and 1998 (n = 176, 250 and 233 for wheat collected in 1982 and 1998, and barley in 1998, respectively). In addition, paired soil and grain samples were collected from 377 sites harvested across Britain in 1998-2000. Wheat grain Pb ranged from below the analytical detection limit (0.02 mg kg(-1) dry weight, DW) to 1.63 mg kg(-1) DW, and barley grain Pb from <0.02 to 0.48 mg kg(-1) DW. The vast majority of samples (>99% for both wheat and barley, excluding Scottish barley samples collected in 2000) were well below the newly introduced EU limit for the maximum permissible concentration of Pb in cereals (0.2 mg kg(-1) fresh weight, equivalent to 0.235 mg kg(-1) DW). There was a significant reduction in wheat grain Pb in the 1998 survey compared with the 1982 survey. However, 40 barley samples collected from Scotland in 2000 in the paired soil and crop survey showed anomalously high concentrations of Pb, with 10 samples exceeding the EU limit. Washing experiments demonstrated that surface contamination, introduced during grain harvest and/or storage, was the main reason for the high concentrations in these samples. In the paired soil and crop surveys, there were no significant correlations between grain Pb concentrations with total soil Pb and other soil properties, indicating low bioavailability of Pb in the soils and limited uptake and transport of Pb to grain. The Pb in cereal grain is likely to originate mainly from atmospheric deposition and other routes of surface contamination during harvest and storage.