Mercury in European agricultural and grazing land soils

Agricultural (Ap, A_p-horizon, 0–20 cm) and grazing land soil samples (Gr, 0–10 cm) were collected from a large part of Europe (33 countries, 5.6 million km²) at an average density of 1 sample site/2500 km². The resulting more than 2 × 2000 soil samples were air dried, sieved to <2 mm and analysed for their Hg concentrations following an aqua regia extraction. Median concentrations for Hg are 0.030 mg/kg (range: <0.003–1.56 mg/kg) for the Ap samples and 0.035 mg/kg (range: <0.003–3.12 mg/kg) for the Gr samples. Only 5 Ap and 10 Gr samples returned Hg concentrations above 1 mg/kg. In the geochemical maps the continental-scale distribution of the element is clearly dominated by geology. Climate exerts an important influence. Mercury accumulates in those areas of northern Europe where a wet and cold climate favours the build-up of soil organic material. Typical anthropogenic sources like coal-fired power plants, waste incinerators, chlor-alkali plants, metal smelters and urban agglomerations are hardly visible at continental scales but can have a major impact at the local-scale.     

Use of GEMAS data for risk assessment of cadmium in European agricultural and grazing land soil under the REACH Regulation

Over 4000 soil samples were collected for the “Geochemical Mapping of Agricultural and Grazing Land Soil of Europe” (GEMAS) project carried out by the EuroGeoSurveys Geochemistry Expert Group. Cadmium concentrations are reported for the <2 mm fraction of soil samples from regularly ploughed fields (agricultural soil, Ap, 0–20 cm, N = 2218) and grazing land soil (Gr, 0–10 cm, N = 2127). The samples were collected in 33 European countries, covering 5.6 million km² at a sample density of 1 sample each per 2500 km² and were analysed in an aqua regia extraction followed by an ICP-MS finish. The median Cd value is 0.181 mg/kg for the Ap and 0.202 mg/kg for the Gr soil samples. The data allow a directly comparable country-specific regional exposure and risk characterisation for all EU countries covered. Direct risks of Cd for terrestrial organisms are only predicted for a few isolated sample sites: 2.3% of the Ap and 4.5% of the Gr sites, respectively.     

Geochemical associations for evaluating the availability of potentially harmful elements in urban soils: Lessons learnt from Athens,Greece

The estimation of potentially harmful element (PHE) availability in urban soil is essential for evaluating impending risks for human and ecosystem health. In the present study five single extraction procedures were evaluated based on the analysis of 45 urban top-soil samples from Athens, Greece. The pseudototal (aqua regia), potentially phytoavailable (0.05 M EDTA), mobilizable (0.43 M HAc), bioaccessible (0.4 M glycine) and reactive pools (0.43 M HNO₃) of PHEs were determined. In general, geogenic elements in Athens soil (Ni, Cr, Co, As) are relatively less available than typical tracers of anthropogenic contamination (Pb, Zn, Cu, Cd). Results of principal component analysis (PCA) indicate an association between available fractions of Pb, Cu, Zn, Cd and amorphous Fe oxides, whereas amorphous Mn oxides account for the available concentrations of Mn, Ni and Co. Empirical multiple linear regression models demonstrate that pseudototal concentration is the predominant explanatory factor of variability for the available pools of the anthropogenic elements. Major elemental composition and total organic carbon (TOC) improve the predictions for the geogenic group of elements, although the explained variability remains low. Dilute HNO₃ is a better predictor of Zn, Ni, As and Mn availability, whereas Pb and Cu available fractions are predicted more accurately by the classical aqua regia protocol. This study contributes to the international database on the environmental behavior of PHEs and provides additional knowledge that can be used toward the harmonization of chemical extraction methodology in urban soil.     

Seasonal variations of arsenic at the sediment–water interface of Poyang Lake,China

Arsenic species including arsenite, arsenate, and organic arsenic were measured in the porewaters collected from Poyang Lake, the largest freshwater lake of China. The vertical distributions of dissolved arsenic species and some diagenetic constituents [Fe(II), Mn(II), S(−II)] were also obtained in the same porewater samples in summer and winter. In sediments the concentration profiles of total As and As species bound to Fe–Mn oxyhydroxides and to organic matter were also determined along with the concentrations of Fe, Mn and S in different extractable fractions. Results indicate that, in the summer season, the concentrations of total dissolved As varying from 3.9 to 55.8 μg/L in sediments were higher than those (5.3–15.7 μg/L) measured in the winter season, while the concentrations of total As species in the solid phase varied between 10.97 and 25.32 mg/kg and between 7.84 and 30.52 mg/kg on a dry weight basis in summer and winter, respectively. Seasonal profiles of dissolved As suggest downward and upward diffusion, and the flux of dissolved As across the sediment–water interface (SWI) in summer and winter were estimated at 3.88 mg/m² a and 0.79 mg/m² a, respectively. Based on porewater profiles and sediment phase data, the main geochemical behavior of As was controlled by adsorption/desorption, precipitation and molecular diffusion. The solubility and migration of inorganic As are controlled by Fe–Mn oxyhydroxides in summer whereas they appear to be more likely controlled by both amorphous Fe–Mn oxyhydroxides and sulfides in winter. A better knowledge of the cycle of As in Poyang Lake is essential to a better management of its hydrology and for the environmental protection of biota in the lake.     

Levels of selected potential harmful elements (PHEs) in soils and vegetables used in diet of the population living in the surroundings of the Estarreja Chemical Complex (Portugal)

This study was carried out to analyze the distribution and soil–plant transfer of selected potential harmful elements (PHEs: As, Hg and Zn) in soils and in two edible horticultural crops (cabbage, Brassica oleracea L., and tomato, Lycopersicon esculentum Mill). randomly sampled in kitchen gardens/small farms around one of the most important and old Portuguese industrial areas (Estarreja Chemical Complex-ECC). The results show that 46% and 11.5% of the soils present high total As (12–532 mg/kg) and Hg (6.6–13.65 mg/kg) concentrations that exceed protective health Canadian soil quality guidelines. Soil As and Zn available fractions are also of concern for groundwater and crops contamination as more than 84% of the samples were above the trigger value proposed by the German legislation for both elements (0.4 and 2 mg/kg, respectively). In the horticultural crops the cabbage leaves concentrate more the PHEs (max.: 3.5, 0.08 and 746 mg/kg dw for As, Hg and Zn, respectively) than the tomato fruit (max.: 0.4, 0.02 and 82 mg/kg dw, respectively). The highest concentration of the study PHEs in soils and horticultural crops were found near sewage outlets that are chiefly related to historical industrial activities mostly from arsenopyrite roasting and a chloralkali plant. The values of estimated bioaccumulation and bioconcentration coefficients suggested exclusion mechanisms for transfer of As to edible cabbage and tomato tissues and cabbage Zn tolerance capacity. The concentration of the PHEs in the edible horticultural crops tissues were not directly related with respective soil total concentration or available fractions, specially for As and Hg. Sampling locations with the highest concentrations of As, Hg, Zn in soil and vegetable foodstuffs should be sites to foregoing research and human daily intakes should be investigated in order to evaluate potential health risks.     

Bioavailability and mobility of trace metals in phosphogypsum from Aqaba and Eshidiya,Jordan

As, Cd, Cr, Cu, U, and Zn in Aqaba and Eshidiya phosphogypsum showed relative uniformity in particle size presented by coarse (>0.212 mm); medium (0.212–0.053 mm); and fine (<0.053 mm) in the stacks by age of deposition. Jordan phosphogypsum contains low concentrations of As, Cd, Cr, Cu, U, and Zn compared to those reported worldwide. The bioavailability and mobility of trace metals were estimated using aqua regia leaching experiments. Leaching results have shown that around 3% of the As, 1% of the Cd, 5% of the Cr, 9% of the Cu, 4% of the U, and 3% of the Zn are transferred to the surrounding aquatic environment and/or soils. Mobility of trace metals in phosphogypsum was classified into three degrees: elements with high mobility were Cu and U; those with moderate mobility were As and Zn; and those with low mobility were Cd and Cr. It can be concluded that As, Cd, Cr, Cu, U, and Zn were not only uniformly distributed in the stack, but they are not leached from the phosphogypsum stacks in any significant amount, and then they are not easily transferred to the surrounding aquatic environment and/or soils.     

The nature and distribution of Cu,Zn, Hg,and Pb in urban soils of a regional city: Lithgow,Australia

This study investigates the concentration and spatial distribution of Cu, Zn, Hg and Pb in the surface (0–2 cm) soils of a regional city in Australia. Surface soils were collected from road sides and analysed for their total Cu, Zn, Hg and Pb concentrations in the <180 μm and <2 mm grain size fractions. The average metal concentration of surface soils, relative to local background soils at 40–50 cm depth, are twice as enriched in Hg, more than three times enriched in Cu and Zn, and nearly six times as enriched in Pb. Median surface soil metal concentration values were Cu – 39 mg/kg (682 mg/kg max), Zn – 120 mg/kg (4950 mg/kg max), Hg – 44 μg/kg (14,900 μg/kg max) and Pb – 46 mg/kg (3490 mg/kg max). Five sites exceeded the Australian NEPC (1999) 300 mg/kg guideline for Pb in residential soils. Strong positive correlations between Cu, Zn and Pb, coupled with the spatial distribution of elevated soil concentrations towards the city centre and main roads suggest traffic and older housing as major sources of contamination. No spatial relationships were identified between elevated metal loadings and locations of past or present industries.     

GEMAS: Source,distribution patterns and geochemical behaviour of Ge in agricultural and grazing land soils at European continental scale

Agricultural soil (Ap-horizon, 0–20 cm) and grazing land soil (Gr-horizon, 0–10 cm) samples were collected from a large part of Europe (33 countries, 5.6 million km²) as part of the GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil mapping project. GEMAS soil data have been used to provide a general view of element mobility and source rocks at the continental scale, either by reference to average crustal abundances or to normalized patterns of element mobility during weathering processes. The survey area includes a diverse group of soil parent materials with varying geological history, a wide range of climate zones, and landscapes.The concentrations of Ge in European soil were determined by ICP-MS after an aqua extraction, and their spatial distribution patterns generated by means of a GIS software.The median values of Ge and its spatial distribution in Ap and Gr soils are almost the same (0.037 vs. 0.034 mg/kg, respectively). The majority of Ge anomalies is related to the type of soil parent material, namely lithology of the bedrock and minor influence of soil parameters such as pH, TOC and clay content. Metallogenic belts with sulphide mineralisation provide the primary source of Ge in soil in several regions in Europe, e.g. in Scandinavia, Germany, France, Spain and Balkan countries.Comparison with total Ge concentrations obtained from the Baltic Soil Survey shows that aqua regia is a very selective method with rather low-efficiency and cannot provide a complete explanation for Ge geochemical behaviour in soil. Additionally, large differences in Ge distribution are to be expected when different soil depth horizons are analysed.     

Arsenic mobility in mildly alkaline drainage from an orogenic lode gold deposit,Bralorne mine,British Columbia

The historical (1932–1971) Bralorne mine produced over 87 million grams of Au from an archetypal orogenic lode gold deposit in southwest British Columbia. High concentrations of As in mine drainage, however, represent an on-going environmental concern prompting a detailed study of effluent chemistry. The discharge rate at the mine portal was monitored continuously over a fourteen-month period during which effluent samples were collected on a quasi-weekly basis. Water samples were also collected on synoptic surveys of the adit between the portal and the main source of flow in the flooded workings. Total concentrations of As in the mildly alkaline (pH = 8.7) portal drainage average 3034 μg/L whereas at the source they average 5898 μg/L. As emergent waters from the flooded workings flow toward the portal, their dissolved oxygen content and pH increase from 0 to 10 mg/L and from 7.7 to 9, respectively. Near the emergence point, dissolved Fe precipitates rapidly, sorbing both As(III) and As(V). With increasing distance from the emergence point, dissolved As(III) concentrations drop to detection limits through sorption on hydrous ferric oxide and through oxidation to As(V). Concentrations of dissolved As(V), on the other hand, increase and stabilize, reflecting lower sorption at higher pH and the lack of available sorbent. Nonetheless, based on synoptic surveys, approximately 35% of the source As load is sequestered in the adit resulting in As sediment concentrations averaging 8.5 wt%. The remaining average As load of 1.34 kg/d is discharged from the portal. Partitioning of As(V) between dissolved and particulate phases in portal effluent is characterized by a sorption density of 0.37 mol As (mol Fe)⁻¹ and by a distribution coefficient (K_d) of 130 L/g HFO. The relatively high sorption density may reflect co-precipitation of As with Fe oxyhydroxides rather than a purely adsorption-controlled process. Results of this study show that the As self-mitigating capacity of drainage from orogenic lode gold deposits may be poor in high-pH and Fe-limited settings.     

Total concentration,speciation and mobility of potentially toxic elements in soils around a mining area in central Iran

The current study was designed to investigate the extent and severity of contamination as well as the fractionation of potentially toxic elements (As, Cd, Cr, Cu, Pb, Zn, Ni) in minesoils and agricultural soils around a Pb–Zn mine in central Iran. For this purpose, 20 agricultural soils and eight minesoils were geochemically characterized. Results showed that minesoils contained elevated concentrations of As (12.9–254 mg kg⁻¹), Cd (1.2–55.1 mg kg⁻¹), Pb (137–6239 mg kg⁻¹) and Zn (516–48,889 mg kg⁻¹). The agricultural soils were also polluted by As (5.5–57.1 mg kg⁻¹), Cd (0.2–8.5 mg kg⁻¹), Pb (22–3451 mg kg⁻¹) and Zn (94–9907 mg kg⁻¹). The highest recorded concentrations for these elements were in soils influenced directly by tailing ponds. Chromium, Cu and Ni content in agricultural soils (with average value of 74.1, 34.6 and 50.7 mg kg⁻¹, respectively) were slightly higher than the minesoils (with average value of 54.5, 33.1 and 43.4 mg kg⁻¹, respectively). Sequential extraction data indicated that there were some differences between the speciation of PTEs in soil samples. In the agricultural soils, Zn and Cd were mainly associated with carbonate bound fraction, As and Pb with reducible fraction, Cu with oxidisable fraction and Cr and Ni with residual phase. With respect to mobility factor values, Zn and Cd in the agricultural soils have been found to be the most mobile while As mobility is negligible. Also, the mobility factor of As, Cd and Pb in agricultural soils adjoining tailing ponds was high. In minesoil sample Cd was most abundant in the carbonate form, whereas other studied elements were mainly present in the reducible and residual fractions; therefore, despite the high total concentrations of As, Pb and Zn in the minesoils, the environmental risk of these elements was low. Based on the obtained data, a portion of Cu, Cr and Ni input was from agricultural activities.     

Contemporary lead concentration and stable lead isotope ratio distribution in forest moss across the Czech Republic

Lead concentrations and stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about ²⁰⁴Pb/²⁰⁶Pb = 0.0550, ²⁰⁶Pb/²⁰⁷Pb = 1.167, ²⁰⁶Pb/²⁰⁸Pb = 0.478 and ²⁰⁷Pb/²⁰⁸Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km²) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.     

Arsenic in the water–soil–plant system and the potential health risks in the coastal part of Chianan Plain,Southwestern Taiwan

The present study investigates the bioavailability, soil to plant transfer and health risks of arsenic (As) in the coastal part of Chianan Plain in southwestern Taiwan. Groundwater used for irrigation, surface soils from agricultural lands and locally grown foodstuffs were collected from eight locations and analyzed for As to assess the risks associated with consuming these items. The concentration of As in groundwater ranged from 13.8 to 881 μg/L, whereas surface soil showed total As content in the range of 7.92–12.7 mg/kg. The available As content in surface soil accounted for 0.06–6.71% of the total As content, and was significantly correlated with it (R² = 0.65, p < 0.05). Among the leachable fraction, the organic matter (3.23–54.8%) and exchangeable portions of oxides (6.03–38.4%) appear to be the major binding phases of As. The average As content in fourteen studied crops and vegetables varied from 10.3 to 151 μg/kg with maximum in mustard and minimum in radish. All the plants showed considerably higher As content (21.5 ± 3.64–262 ± 36.2 μg/kg) in their roots compared to the edible parts (9.15 ± 1.44–75.8 ± 22.9 μg/kg). The bioaccumulation factor (BAF) based on total As (ranging from 0.0009 to 0.144) and available As in soil (ranging from 0.039 to 0.571) indicate that mustard, rice, amaranth and spinach are the highest accumulators of As. Although the health risk index (HRI) of the studied crops and vegetables ranged from only 0.0068–0.454, with the maximum in rice, the combined HRI indicates an alarming value of 0.88. Therefore, the possible health risks due to long-term consumption of rice and other As-rich foodstuffs could be overcome by controlling the contamination pathways in the water–soil–plant system.     

Cement–fly ash stabilisation/solidification of contaminated soil: Performance properties and initiation of operating envelopes

This study was aimed at evaluating the mechanical and pH-dependent leaching performance of a mixed contaminated soil treated with a mixture of Portland cement (CEMI) and pulverised fuel ash (PFA). It also sought to develop operating envelopes, which define the range(s) of operating variables that result in acceptable performance. A real site soil with low contaminant concentrations, spiked with 3000 mg/kg each of Cd, Cu, Pb, Ni and Zn, and 10,000 mg/kg of diesel, was treated with one part CEMI and four parts PFA (CEMI:PFA = 1:4) using different binder and water contents. The performance was assessed over time using unconfined compressive strength (UCS), hydraulic conductivity, acid neutralisation capacity (ANC) and pH-dependent leachability of contaminants. With binder dosages ranging from 5% to 20% and water contents ranging from 14% to 21% dry weight, the 28-day UCS was up to 500 kPa and hydraulic conductivity was around 10⁻⁸ m/s. With leachant pH extremes of 7.2 and 0.85, leachability of the contaminants was in the range: 0.02–3500 mg/kg for Cd, 0.35–1550 mg/kg for Cu, 0.03–92 mg/kg for Pb, 0.01–3300 mg/kg for Ni, 0.02–4010 mg/kg for Zn, and 7–4884 mg/kg for total petroleum hydrocarbons (TPHs), over time. Design charts were produced from the results of the study, which show the water and/or binder proportions that could be used to achieve relevant performance criteria. The charts would be useful for the scale-up and design of stabilisation/solidification (S/S) treatment of similar soil types impacted with the same types of contaminants.     

A preliminary study of mineralogy and geochemistry of four coal samples from northern Iran

This study is related to four Jurassic-age bituminous coal (0.69–1.02 Ro%) samples collected from coal mines from the west, central and east of central, Alborz in northern Iran. Geological settings played key roles in determining the geochemistry and mineralogy of coals from the central Alborz region of northern Iran. The mineralogy of coals from the eastern part of the region is dominated by kaolinite; halloysite; and carbonates such as calcite, dolomite/ankerite, and siderite. The coals were deposited in a lacustrine environment. In the western part of the region, where the depositional setting was also lacustrine with volcanic input and tonstein deposition (glass shards present), the coal primarily contains kaolinite (68%) and fluorapatite (26%). In contrast, coal from the central part of the region, which was deposited in a terrestrial environment and on eroded limestone and dolomite rocks, is dominated by dolomite (98%) with little input by kaolinite. These coals have low sulphur (0.35–0.70 wt.%), which is mostly in the organic form (0.34–0.69 wt.%). Pyritic sulphur is detected only in one coal and in small quantities. The boron contents of these coals range from 9 to 33 mg/kg, indicating that deposition occurred in a fresh water environment. Coal with higher concentrations of Ba, Sr, and P contain fluorapatite and goyazite–gorceixite series [BaAl₃ (PO₄)₂ (OH)₅, H₂O] minerals, which indicates volcanoclastic input. Compared to world coal averages, these coals exhibit low concentrations of elements of environmental concern, such as As (1.3–5.9 mg/kg), Cd (< 0.02–0.06 mg/kg), Hg (< 0.01–0.07 mg/kg) Mo (< 0.6–1.7 mg/kg), Pb (4.8–13 mg/kg), Th (0.5–21 mg/kg), Se (< 0.2–0.8 mg/kg) and U (0.2–4.6 mg/kg). Two of the northern Iranian coals have concentrations of Cl (2560 and 3010 mg/kg) that are higher than world coal average.     

New insights on mobility and bioavailability of heavy metals in soils of the Padanian alluvial plain (Ferrara Province,northern Italy)

Heavy metals having both natural and anthropogenic origin are common contaminants in soils and sediments, and can be transferred and bioaccumulated at all levels of the food chain, posing serious environmental concern to the local population. In this paper, agricultural soils from the Province of Ferrara (easternmost part of the Padanian Plain, northern Italy) were investigated to assess the levels of potentially toxic metals in relation to their phytoavailability. Agricultural soils have been sampled in order to identify the origin, mobility and bioavailability of heavy metals, collecting superficial and deeper (depths of 20–30 and 100–120 cm, respectively) horizons. The “total” XRF analyses properly elaborated with a statistical approach reveal that soils evolved from two distinct types of alluvial sediments, in turn related to the Po and Reno rivers; the former type is distinctively enriched in heavy metals (particularly Cr and Ni), reflecting the presence of femic and ultrafemic rocks in the hydrological basin of River Po. The absence of Top Enrichment Factors for Ni, Co, Cr, V, and Pb suggests that the content of these elements is natural and unaffected by contamination, whereas superficial enrichments of Cu (and Zn) is ascribed to anthropogenic inputs related to agricultural activities. Multiple extraction tests using variously aggressive reactants (aqua regia, DTPA, EDTA, NH₄NO₃, and H₂O) analyzed by ICP gave insights on the specific mobility of the distinct elements, which decreases in the following order: Pb > Cu > Cd > Co > >Ni > Cr. Taking into consideration the elements that are inducing the main concerns, Cr appears scarcely mobile, whereas Ni could be more phytoavailable and has to be monitored in the local agricultural products. Cd although scarcely abundant has to be monitored for its mobility and toxicity, whereas Cu although abundant and extremely mobile doesn’t induce concerns as it is not hazardous for the living receptors.     

Mercury mobility in unsaturated gold mine tailings,Murray Brook mine,New Brunswick,Canada

Elevated concentrations of Hg are present (averaging 36 μg/g), mainly as cinnabar, in the Murray Brook Au deposit, located in northern New Brunswick, Canada. After the mined ore was subjected to CN leaching, the tailings were deposited in an unsaturated pile, and 10 a after mine closure an estimated 4.7 × 10³ kg of CN and 1.1 × 10⁴ kg of Hg remain in the pile. Elevated Hg concentrations have been measured in the groundwater (up to 11,500 μg/L) and surface water (up to 32 μg/L) down-gradient of the tailings. To investigate the controls on Hg mobility and leaching persistence, laboratory experiments were conducted using unsaturated columns filled with tailings. Within the first 0.2 pore volumes (PV) eluted, the concentrations of Hg and CN increased to peak concentrations of 12,900 μg Hg/L and 16 mg CN/L, respectively. In the subsequent 0.9 PV, concentrations decreased to approximately 1300 μg Hg/L and 2.8 mg CN/L. Thermodynamic calculations demonstrate that >99.8% of the mobilized Hg in the tailings pore water is in the form of Hg–CN complexes, indicating that Hg mobility to the surrounding aquatic environment is directly dependent on the rate of CN leaching. One-dimensional transport simulations suggest that leached CN can be partitioned into conservative (24%) and non-conservative (76%) fractions. Extrapolation of simulation results to the field scale suggests that CN, and by extension Hg, will continue to elute from the tailings for at least an additional 130 a.     

Metal and arsenic distribution in soil particle sizes relevant to soil ingestion by children

Ingestion of soil is a common behaviour in young children as a means of exploring their surroundings. Much attention has been given to remediation of point-source polluted sites with regard to potential health risks for children. However, because of diffuse pollution and long-range atmospheric deposition, soil contaminant levels are generally increased in urban areas compared to their rural counterparts, even in areas located away from any point sources of pollution. Intake of urban soil can thereby result in significant amounts of the child’s daily metal intake. In the present study, soil samples were collected from 25 playgrounds around urban Uppsala, Sweden and analysed for contents of Al, As, Fe, Cr, Cu, Cd, Hg, Mn, Ni, Pb, W and Zn. Prior to aqua regia digestion, the samples were wet-sieved in order to separate soil particle fractions representing deliberate (<4 mm) and involuntary (<50 μm) soil ingestion by children, as well as a third size fraction of 50–100 μm representing soil that is easily transported by suspension. While the metal and As contents in the 50–100 μm fraction were similar to those of the <4 mm fraction, the <50 μm fraction had metal and As contents on average one and a half times higher than those of the <4 mm fraction. The metal and As contents correlated negatively with the sand content in both particle size fractions <4 mm and 50–100 μm, suggesting a general decrease in metal and As content with increasing sand content. However, a positive correlation was found between sand content and the metal and As contents of the finest fraction (<50 μm), suggesting that when the sand content is high, the bulk of the sorbed elements are on the finest particles. The difference between metal and As contents in the different size fractions was greater in the soil sample with the highest sand content than in the sample with the lowest sand content. This implies that texture is a significant factor in metal and As distribution in soils with moderate metal and As contents, when the number of binding sites associated with small particles is low. Tolerable daily intake (TDI) values for Pb and As were exceeded at all sites, and at two sites for Cd, for children with pica behaviour. A high ingestion rate of mainly small particles could also result in the TDI value for Pb being exceeded at 10 sites and that for As at one site. This study also found that soil analysis by the procedure recommended by Swedish authorities accurately represents the metal intake from deliberate soil ingestion, whereas involuntary soil ingestion of mainly small particles could result in metal intakes which are up to twice as high.     

Kinetics of Au (III) extraction by DBC from hydrochloric solution using Lewis cell

The kinetics of forward extraction [AuCl₄]^? from aqua regia medium by diethylene glycol dibutyl ether (DBC) have been investigated by the Lewis cell (LC) technique. At first gold extraction has been carried out under different experimental conditions for achieving the stoichiometry coefficients and the value of the extraction equilibrium constant (K = 0.1). For kinetic data treatment, flux ‘F’ method has been applied. Reaction order with respect to DBC, pH and [AuCl₄]^? was determined and then the rate constant was calculated. The rate of gold extraction from 2 M chloride medium can be expressed as F = 10^0.88[AuCl₄^?]^1.25 [DBC]^0.4 [H⁺]^?0.22. Kinetics data were treated by EVIEWS software and coefficients were obtained. The comparison of manual and software results indicated that the results had good conformity. Influence of temperature was studied and then activation energy, E_a, (11.17 kJ/mol), activation enthalpy (11.66 kJ/mol) and entropy (?187 J/mol K) were calculated by using Arrhenius and activation complex theory respectively. E_a value (< 20.9 kJ/mol) indicates that, the extraction of gold (III) in the investigated system is controlled by diffusion process.     

Arsenic and other drinking water quality issues,Muzaffargarh District,Pakistan

In 49 samples of groundwater, sampled in Muzaffargarh District of south-western Punjab, central Pakistan, concentrations of As exceeded the World Health Organisation provisional guideline value, and United States Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL), of 10 μg L⁻¹ in 58% of samples and reached up to 906 μg L⁻¹. In this semi-arid region canal irrigation has lead to widespread water-logging, and evaporative concentration of salts has the potential to raise As concentrations in shallow groundwater well above 10 μg L⁻¹. In fact, in rural areas, concentrations stay below 25 μg L⁻¹ because As in the oxic shallow groundwater, and in recharging water, is sorbed to aquifer sediments. In some urban areas, however, shallow groundwater is found to contain elevated levels of As. The spatial distribution of As-rich shallow groundwater indicates either direct contamination with industrial or agricultural chemicals, or some other anthropogenic influence. Geochemical evidence suggests that pollutant organics from unconfined sewage and other sources drives reduction of hydrous ferric oxide (HFO) releasing sorbed As to shallow groundwater. The situation is slightly less clear for seven wells sampled which tap deeper groundwater, all of which were found with >50 μg L⁻¹ As. Here As concentrations seem to increase with depth and differing geochemical signatures are seen, suggesting that As concentrations in older groundwater may be governed by different processes. Other data on parameters of potential concern in drinking water are discussed briefly at the end of the paper.     

Chloride imbalance in a catchment undergoing hydrological change: Upper Barwon River,southeast Australia

Documenting whether surface water catchments are in net chemical mass balance is important to understanding hydrological systems. Catchments that export significantly greater volumes of solutes than are delivered via rainfall are not in hydrologic equilibrium and indicate a changing hydrological system. Here an assessment is made of whether a saline catchment in southeast Australia is in chemical mass balance based on Cl. The upper reaches of the Barwon River, southeast Australia, has total dissolved solids, TDS, concentrations of up to 5860 mg/L and Cl concentrations of up to 3370 mg/L. The high river TDS concentrations are due to the influxes of groundwater with TDS concentrations of up to 68,000 mg/L. Between 1989 and 2011, the median annual Cl flux from the upper Barwon catchment was 17.8 × 10⁶ kg (∼140 kg/a/ha). This represents 340–2230% of the annual Cl input by rainfall to the catchment. Major ion and stable isotope geochemistry indicate that the dominant source of solutes in the catchment is evapotranspiration of rainfall, precluding mineral dissolution as a source of excess Cl. The upper Barwon catchment is not in chemical mass balance and is a net exporter of solutes. The chemical imbalance may reflect the transition within the last 100 ka from an endorheic lake system where solutes were recycled producing shallow groundwater with high TDS concentrations to a better drained catchment. Alternatively, a rise in the regional water table following land clearing may have increased the input of groundwater with high TDS concentrations to the river system.