Distribution of natural and anthropogenic thallium in the soils in an industrial pyrite slag disposing area

The total concentrations combined with the chemical speciation of thallium (Tl) were examined in order to track the distribution of natural and anthropogenic Tl in the soils in an industrial pyrite slag disposing area. Their geochemical behaviors in the soils were further discussed. Soil samples were collected from three soil profiles adjacent to a large open-disposed pile of industrial Tl-rich pyrite slag, and from one soil profile in the background area. The results show that the soil contamination with Tl derived from slag (slag-Tl) is generally limited; slag-Tl was mainly accumulated in the upper part (< 16.5 cm) of the vicinal soils of the slag pile and shows large variation in concentration among different sampling sites. Basically, the soils surrounding the slag pile within 5 m are more Tl-contaminated than those under the slag pile and those far away from the slag pile. In respect of the concentrations of total Tl, the deeper soils of the studied profiles seem to be uncontaminated. However, the percentages of Tl in the easily reducible fraction indicate that these soils have been actually contaminated by slag-Tl. Natural Tl and anthropogenic Tl are distributed differently among the soil components in the studied soils. Natural Tl in the background soils is predominantly hosted in the residual fraction ( approximately 98%), while anthropogenic Tl was significantly incorporated into the more labile fractions of the soil (up to approximately 80%), especially in the acid-extractable fractions and easily reducible fraction (up to approximately 30% and approximately 45%, respectively). Detailed analysis of speciation data of Tl suggests that despite being predominantly controlled by the degree of Tl pollution, the distribution of slag-Tl in the soils can be further affected by the general differences in soil properties. In this study, the order for preferential immobilization of anthropogenic Tl among major soil components can be roughly summarized as: Tl(III) carbonates and hydroxides > Mn oxide-hydroxides > Fe oxide-hydroxides > adsorption sites on the surface of soil, while the order can be significantly mediated by the pH conditions in the soils. The correlations between the fractions of Tl in the slag and in the soils indicate that the anthropogenic Tl in the soils in the studied slag disposing area should be mainly derived from the dissolved slag-Tl that was leached by rainwater rather than from the washed-out particles of slag.     

Impacts of mercury contaminated mining waste on soil quality, crops, bivalves, and fish in the Naboc River area, Mindanao, Philippines

Rice paddy fields in the Naboc area, near Monkayo on the island of Mindanao, Philippines, have been irrigated four times a year over the last decade using Naboc River water contaminated with mercury (Hg) by artisanal gold mining in the Diwalwal area. Silt containing up to at least 90 mg Hg/kg (d.w.) has been deposited in rice paddy fields during the 1990s and this has been repeatedly mixed into the rice root zone through ploughing. Hg in the rice paddy field soils averages 24 mg Hg/kg and generally exceeds the UK and Canadian soil quality thresholds for agricultural soils as well as the proposed Dutch Intervention value and the USEPA soil ingestion Soil Screening Level (SSL) for inorganic Hg. Much lower Hg concentrations (0.05-0.99 mg/kg) within the range expected for uncontaminated soils, characterise soils on which corn and bananas are cultivated, largely because these are not irrigated with Hg-contaminated water from the Naboc River. The estimated total weekly MeHg intake for a person living in the Naboc area related to the weekly consumption of 2.1 kg of rice grown on Hg-contaminated soils (15 microg MeHg) in conjunction with 1 kg of fish (220 microg MeHg) and 100 g of mussels (50 microg MeHg) from the Naboc River, would total 285 microg MeHg (equivalent to 4.75 microg/kg bw for a 60 kg adult), which is nearly three times the JECFA PTWI of 1.6 microg/kg bw. This will significantly contribute to the population mercury exposure and might explain why 38% of the local inhabitants were classified as Hg intoxicated during a mercury toxicity assessment [Drasch GS, B?se, O'Reilly S, Beinhoff C, Roider G, Maydl S. The Mt. Diwata study on the Philippines 1999-assessing mercury intoxication of the population by small scale gold mining. Sci Total Environ 2001; 267(1-3): 151-168.].     

Selenium in soil and endemic diseases in China

Selenium is an essential element for humans, animals and some species of microorganisms. The biological function of selenium shows dual characteristics. The selenium content range between toxic and deficient concentration is very narrow. The present paper discusses the geographical distribution of two forms (total and water-soluble) of selenium in topsoil (plough layer for cultivated soils, eluvial horizon for natural soils) and evaluates its relationship with some human health problems in China. Topsoil samples, 354 in total, including 156 natural and 198 cultivated soils of 21 main soil types were collected. The total Se concentration in soil samples was determined with DAN (di-aminonaphthalene)-fluorescence spectrophotometer method. Soil water-soluble Se concentration was determined with the same method after extraction with water (water/soil = 5:1). The results showed that the geometric and arithmetic means of total Se concentration in soil, for all samples, were 0.173 mg/kg and 0.239 mg/kg, respectively, with the lowest value being 0.022 mg/kg and the highest being 3.806 mg/kg. For the cultivated soil, the geometric mean of total Se was 0.188 mg/kg, its arithmetic mean was 0.269 mg/kg and higher than those in the natural soil, 0.154 mg/kg and 0.206 mg/kg, respectively. The geometric and arithmetic means of water-soluble Se in soil for all the samples were 4.0 and 6.4 microg/kg, the lowest 0.6 microg/kg and the highest value being 109.4 microg/kg. For the cultivated soils, the average concentration of water-soluble Se was 4.3 microg/kg, similar to that of natural soil, they are and 4.4 microg/kg by geometric mean. Two sequences of the soil types, arranged separately in the concentration of total Se and water-soluble Se, are different and this demonstrates that the proportions of the two forms of selenium existing in various soils are different. The percentages of water-soluble Se to total Se in different types of soils varied from 1.07 to 6.69%. However, generally the laterite and other subtropic soil still have relatively high absolute water-soluble Se contents because of their higher total Se contents. A very significant correlation between total Se and water-soluble Se has been found in cultivated soil with a correlation coefficient of 0.58 (P < 0.01). The relationships between soil Se and human endemic diseases Keshan disease, Kashin-Back diseases and selenosis have been discussed. The reference criteria for evaluating Se deficiency and Se excess in soil were suggested.     

Spatial distribution of total Hg in urban soils from an Atlantic coastal city (Aveiro, Portugal)

The aim of this study was to investigate the levels and the spatial distribution of total Hg concentrations in soils from the urban area of Aveiro (Portugal) in order to assess the impact of industrial activities and identified Hg emission sources in these urban soils. For this purpose, soils were collected in 25 sampling points (at two depths) within the urban perimeter and in places considered representative of the main green areas of the city. A median concentration of 0.091 mg kg(-1) (dry weight) was obtained, regardless the depth. Aveiro was considered a low polluted city in terms of total Hg and no direct effects of emissions of Hg from industrial activities nearby could be detected in these urban soils. Despite of the low values obtained, high variability (range of approximately 0.5 mg kg(-1)) was observed in the results. Such was considered to be related to characteristic features of soils in urban settings and to the behaviour of Hg in the urban environment.     

Metal contamination of soils and crops affected by the Chenzhou lead/zinc mine spill (Hunan, China)

In 1985, the collapse of the tailing dam in Chenzhou lead/zinc mine (Hunan, southern China) led to the spread of mining waste spills on the farmland along the Dong River. After the accident, an urgent soil cleaning up was carried out in some places. Seventeen years later, cereal (rice, maize, and sorghum), pulses (soybean, Adzuki bean, mung bean and peanut), vegetables (ipomoea, capsicum, taro and string bean) and the rooted soils were sampled at four sites: (1) the mining area (SZY), (2) the area still covered with the mining tailing spills (GYB), (3) the cleaned area from mining tailing spills (JTC), and (4) a background site (REF). Metal concentrations in the crops and soils were analyzed to evaluate the long-term effects of the spilled waste on the soil and the potential human exposure through food chains. The results showed that the physical-chemical properties of the soils obviously changed due to the different farming styles used by each individual farmer. Leaching effects and plant extraction of metals from some soils were quite weak. Certain soils were still heavily polluted with As, Cd, Zn, Pb and Cu. The contamination levels were in the order of GYB>SZY>JTC showing that the clean-up treatment was effective. The maximum allowable concentration (MAC) levels for Chinese agricultural soils were still highly exceeded, particularly for As and Cd (followed by Zn, Pb and Cu), with mean concentrations of 709 and 7.6 mg kg(-1), respectively. These concentrations exceed the MAC levels by 24 times for As and 13 times for Cd at GYB. Generally, the edible leaves or stems of crops were more heavily contaminated than seeds or fruits. Ipomoea was the most severely contaminated crop. The concentrations of Cd and Pb were 3.30 and 76.9 mg kg(-1) in ipomoea leaves at GYB, which exceeded the maximum permit levels (0.5 mg kg(-1) for Cd and 9 mg kg(-1) for Pb) by 6.6 and 8.5 times, respectively. Taro (+skin) could accumulate high concentrations of Zn and Cd in the edible stem, and rice and capsicum had high Cd concentration in the edible parts. However, the toxic element concentrations in maize, sorghum, Adzuki bean, soybean and mung bean remained lower than the threshold levels. The bio-accumulation factors (BAFs) of crops were in the order: Cd>Zn>Cu>Pb>As. BAF was typically lower in the edible seeds or fruits than in stems and leaves. The accumulation effect strongly depends on the crop's physiological properties, the mobility, of the metals, and the availability of metals in soils but not entirely on the total element concentrations in the soils. Even so, the estimated daily intake amount of Cu, Zn, Cd, and Pb from the crops grown in the affected three sites and arsenic at SZY and GYB exceeded the RDA (Recommended dietary allowance) levels. Subsequently, the crops grown in Chenzhou Pb/Zn mine waste affected area might have a hazardous effect on the consumer's health. This area still needs effective measures to cure the As, Cd, Pb, Zn and Cu contamination.     

Distribution and mobility of arsenic in soils of a mining area (Western Spain)

High levels of total and bioavailable As in soils in mining areas may lead to the potential contamination of surface water and groundwater, being toxic to human, plants, and animals. The soils in the studied area (Province of Salamanca, Spain) recorded a total As concentration that varied from 5.5 mg/kg to 150 mg/kg, and water-soluble As ranged from 0.004 mg/kg to 0.107 mg/kg, often exceeding the guideline limits for agricultural soil (50 mg/kg total As, 0.04 mg/kg water-soluble As). The range of As concentration in pond water was < 0.001 μg/l-60 μg/l, with 40% of samples exceeding the maximum permissible level (10 μg/l) for drinking water. Estimated bioavailable As in soil varied from 0.045 mg/kg to 0.760 mg/kg, around six times higher than water-soluble As fraction, which may pose a high potential risk in regard to its entry into food chain. Soil column leaching tests show an As potential mobility constant threatening water contamination by continuous leaching. The vertical distribution of As through soil profiles suggests a deposition mechanism of this element on the top-soils that involves the wind or water transport of mine tailings. A similar vertical distribution of As and organic matter (OM) contents in soil profiles, as well as, significant correlations between As concentrations and OM and N contents, suggests that type and content of soil OM are major factors for determining the content, distribution, and mobilization of As in the soil. Due to the low supergenic mobility of this element in mining environments, the soil pollution degree in the studied area is moderate, in spite of the elevated As contents in mine tailings.     

Environmental assessment of mercury contamination from the Rwamagasa artisanal gold mining centre, Geita District, Tanzania

This study presents the results of an environmental assessment of mercury (Hg) contamination in the Rwamagasa artisanal gold mining area, northwest Tanzania, and the potential downstream dispersion along the River Malagarasi to Lake Tanganyika. At the time of sampling, generally low concentrations of Hg (<0.05 mg/kg) occurred in most cultivated soils although higher Hg (0.05-9.2 mg/kg) was recorded in urban soils and vegetable plot soils where these are impacted by Hg-contaminated water and sediment derived from mineral processing activities. Hg in vegetable and grain samples is mostly below the detection limit of 0.004 mg/kg Hg, apart from 0.007 and 0.092 mg/kg Hg in two yam samples and 0.011 to 0.013 mg/kg Hg in three rice samples. The standardized (i.e., standardized to 10 cm length) Hg concentrations in Clarias spp. increase from about 0.01 mg Hg/kg for the River Malagarasi delta to 0.07, 0.2, and 1.6 mg/kg, respectively, for the Rwamagasa 'background', moderately and most contaminated sites. For piscivorous (Lates, Brycinus, and Hydrocynus spp.), insectivorous (Barbus spp.), and planktivorous (Haplochromis spp.) fish species, the 10-cm standardized Hg concentrations increase from about 0.006 mg/kg for the River Malagarasi-Lake Tanganyika area to 0.5 and 3.5 mg/kg, respectively, for the Rwamagasa moderately and most contaminated sites. The low concentrations of Hg in fish from the Malagarasi River delta and Lake Tanganyika indicate that Hg contamination from the Rwamagasa area does not have a readily discernible impact on the biota of Lake Tanganyika. Many of the fish samples from Rwamagasa exceed guidelines for human consumption (0.5 mg/kg) as well as the WHO recommended limit for vulnerable groups (0.2 mg/kg). Tissue total Hg (THg) of all fish collected from the River Malagarasi-Lake Tanganyika subarea is well below these guidelines. Potential human exposure through consumption of 300 g/day of rice grown on Hg-contaminated soils is 5.5 microg/week. Consumption of 250 g Nile perch (Lates spp.), 500 g tilapia (Oreochromis spp.), and 250 g of catfish (Clarias spp.) each week would result in an intake of 65 microg Hg/week for people consuming only fish from the Mara and Mwanza regions of Lake Victoria and 116 microg Hg/week for people in the Rwamagasa area consuming tilapia and Nile perch from Lake Victoria and catfish from mining-impacted streams. This is lower than the Provisional Tolerable Weekly Intake (PTWI) of 300 microg for Hg in the diet set by the WHO and the FAO. Inadvertent ingestion of soil containing 9 mg Hg/kg at a rate of 80 mg/day would give an additional estimated weekly intake of 5 microg THg, whereas the persistent and purposeful consumption of soil (geophagia) at a rate of 26 g soil/day would produce an additional chemical exposure of 230 microg Hg/day.     

Heavy metal pollution associated with mining activity in the Kouh-e Zar region,NE Iran

The Kouh-e Zar mining area is located in the central part of the “Khaf–Bardaskan” volcanic-plutonic zone, NE Iran. Mining activity has resulted in pollution of soil and water resources by potentially toxic elements including arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), antimony (Sb), nickel (Ni) and zinc (Zn). In this study, the major source of heavy metal pollution and elucidating the probable environmental risks associated with this area were determined by quantifying pollution in soils and water resources. Concentrations of Cd, Cr, Cu, Pb and Zn in the Kouh-e Zar mining area varied in the range of 5–470, 33–442, 25–5125, 81.15–12,096.27 and 55–4210 mg/kg, respectively. The geo-accumulation index for Cd in all samples was extremely high (I_geo > 5) and the enrichment factor also shows an extremely high amount (EF > 40), both representing evidence for highly polluted soil in the area. However, the coefficients of aqueous migration (K_x) of Cd, Cr, Cu, Pb and Zn were K_x < 0.1, so they are classified as “least mobile and inert” grade. Also, the heavy metals tend to remain in soil (solid environment). Cluster analysis (CA) determined the lithogenic origin for Zn, Cu, Cr and Cd, and the anthropogenic origin (mining activity) for Pb in the soils of the mining area. The concentrations of Cd, Cu, Pb and Zn in water are controlled by free Fe and Mn oxy-hydroxide content in the soils. Both water–rock interaction and mining activity have contributed to pollution in the area.

     

Soil arsenic availability and the transfer of soil arsenic to crops in suburban areas in Fujian Province, southeast China

The bioavailability, soil-to-plant transfer and associated health risks of arsenic in soils collected from paddy rice fields and vegetable fields in suburban areas of some major cities of Fujian Province were investigated. The total soil concentrations of arsenic ranged from 1.29 to 25.28 mg kg(-)(1) with a mean of 6.09 mg kg(-)(1). Available (NaH(2)PO(4)-extractable) arsenic content accounted for 0.7-38.2% of total soil arsenic and was significantly correlated with total soil arsenic content. For the vegetable soils, the available fraction (ratio of available As to total As) of arsenic decreased with decreasing silt (particle size 0.02-0.002 mm) and free iron (DCB extractable) contents and with increasing soil pH and organic matter content. The available fraction of arsenic in the paddy rice soils increased with increasing free iron and organic matter contents and decreasing soil pH and silt content. The correlation of NaH(2)PO(4)-extractable arsenic with the arsenic concentration of the vegetables was much better than that of total As. The transfer factor based on the soil available arsenic (TF(avail)) was chosen to compare the accumulation ability of the various crops. The TF(avail) values of rice grains (air-dried weight basis) ranged between 0.068 and 0.44 and were higher than those of the vegetables, ranging from 0.001 to 0.12. The accumulation ability of the crops decreased in the order of rice>radish>water spinach>celery>onion>taro>leaf mustard>fragrant-flowered garlic>pakchoi>Chinese cabbage>lettuce>garlic>cowpea>cauliflower>bottle gourd>towel gourd>eggplant. Daily consumption of rice and other As-rich vegetables could result in an excessive intake of arsenic, based on the provisional tolerable intake for adults for arsenic recommended by WHO.