Absorption of Heavy Metals in Wild Berries and Edible Mushrooms in an Area Affected by Smelter Emissions

The total concentrations of nickel, copper, chromium, strontium, arsenic, lead, cadmium and cobalt were measured in berries and mushrooms, as well as manganese and iron in mushrooms. The study area (about 3500 km²) is situated on the border of the northern taiga and tundra forests (68–69°N) and is affected by emissions from the extensive Ni-Cu smelter complex at Monchegorsk, Kola Peninsula, NW Russia. Part of the study area, extending along the railway line used for transporting apatite concentrate, contains elevated quantity of strontium. Berries of Vaccinium vitis-idaea (82 samples), Vaccinium myrtillus (28), Rubus chamaemorus (42) and Empetrum hermaphroditum (40) and mushrooms of Leccinum auantiacum (47 samples), Leccinum scabrum (32), Russula vesca (25), Lactarius torminosus (8), Lactarius trivialis (9), Suillus luteus (10) and Xerocomus subtomentosus (20 specimens) were collected from 98 locations during 1987–1992. The nickel and copper concentrations in the berries, and nickel in mushrooms, correlated satisfactorily with the corresponding metal concentrations in the soil. The berries and mushroons growing over an area of at least 3000 km² around the smelter complex are unsuitable for human consumption due to the elevated nickel concentrations caused by the smelter dust emissions. The berries and mushrooms gathered in the studied polluted forests were found to be contaminated by nickel by a factor of 15–30 times (berries) and 15–40 times (mushrooms) more than the background level. Increased levels of strontium were found close to the railway line. The concentrations of all the other metals in the studied area did not exceed sanitary standards.     

Characteristics of soil profiles affected by smelting of nickel and copper at Coniston,Ontario, Canada

Soil profiles were examined, described and sampled by horizons in various geomorphic positions along a transect originating at the Coniston smelter and extending in a southeasterly direction for approximately 12 km. The samples were then analyzed to determine particle-size distribution, pH, organic carbon and five heavy metals.Within the study area, elevated levels of nickel, copper and iron were found with maximum total concentrations of 1.2, 0.97 and 20.0%, respectively. Manganese and zinc did not occur in above-normal concentrations. The pH values of the soils were depressed with levels as low as 2.4.Near the smelter, erosion from soils on slopes has transferred materials into lower lying areas, thereby rearranging the areal distribution of nickel, copper and iron. Although the surface soil horizons along the entire transect have above-normal concentrations of these elements, only within the eroded area is there marked variability in their vertical distribution.     

Relationship between Metals Leached and Soil Type from Potential Acid Sulphate Soils under Acidic and Neutral Conditions in Western Australia

Metal contaminants are likely to be mobilised from soil when in contact with acidic drainage. Soils containing sulphide are often associated with significant quantities of trace metals. Understanding the source of metal pollution is of significant concern for management because sulphide-containing soils are found in close proximity to estuaries, lowland rivers and lakes. This study focuses on Western Australian soils, which are typically sandy and well weathered. Two leachate trials, a batch and a column method, investigated the possibility of characteristic leachate signatures with respect to future traceability of metal contamination from soil drainage. Leaching signatures were assessed for four soil types (grey sand (GS), iron-rich sand (FeRS), silty sand (SS) and peat) found coastally between Perth and Albany, in Western Australia. Trace metals leached from the four soil types showed significant differences for both the metals leached and the concentrations for the column leaching trial. No nickel (<1.0 µgL^?1) but relatively high concentrations of arsenic were leached from the peat site. The FeRS leachates contained chromium, copper, high aluminium and relatively high iron. The GS leached extremely high iron and relatively high manganese concentrations. In comparison, only small concentrations of nickel, iron, aluminium, arsenic and manganese leached from the SS columns. Selenium did not leach above reporting limits (<1.0 µg L^?1) from any of the soil types. This work suggests that leachate signatures from different soil types exist and that soil type should be considered when determining the risk of aquatic impact associated with acidic drainage.     

comparison of sulphur and heavy metal contents and their regional distribution in humus and moss samples from the vicinity of Nikel and Zapoljarnij,Kola Peninsula,Russia

Terrestrial moss and humus (the O-horizon) are often used separately for determining and monitoring airborne heavy metal pollution. Here, we directly compare the results of analyses of moss and humus samples taken at a density of one site per 300 km² in a 12 000 km² area (45 samples) around the nickel smelter in Nikel, the nickel ore roasting plant in Zapoljarnij, both in Russia, and the iron ore mine and mill near Kirkenes in Norway. The samples were air dried, digested in conc. HNO₃ and analysed for more than 30 elements by ICP-MS and ICP-AES at the laboratory of the Geological Survey of Finland (GTK). For most elements, observed levels and variations are considerably greater in soil than in moss. The main contaminants, Ni and Cu, reach equally high median levels in the moss and soil, but maximum values are far higher in soil. Both media show comparable regional distribution patterns for the heavy metals, but not for sulphur. Cu and Ni can be used to delineate the limits of contamination in the survey area. Both media show the same picture, with a generally very steep gradient from east to west and background levels being reached 30–50 km from the nickel smelter. When moss is used, Cu/Ni, Cu/S and Ni/S ratios can be used to separate input from the smelting and roasting proccesses in Russia. Both media are well suited to use separately to detect airborne pollution in this heavily contaminated area. The moss data are generally easier to interpret, but moss is not available at the most polluted sites. Levels for many elements other than Cu and Ni are close to the detection levels in moss samples, but not in humus samples. Information gathered from both media thus complement each other in a regional multi-element survey.     

Metal Enrichment in Zlatna, a Romanian Copper Smelting Town

A preliminary survey of metal concentrations in soil and vegetable samples was undertaken in the town of Zlatna, in western Romania that is dominated by a large copper smelter. One data set (town survey) consisted of soil samples taken from sites both in the centre of the town (near smelter and school grounds) and the outskirts and included those from roadside verges and wooded areas. The second data set consisted of soil samples taken from vegetable garden plots together with an associated sample of spring onion (Allium fistulosum). The aim of this study was to measure levels of the elements Cu, Zn, Pb, Cd and As in soil samples from Zlatna in general, and to assess their uptake into home grown vegetables and thus into the food chain. Concentrations of the elements of interest in soils and vegetables peaked southwest of the smelter and also in soils near the school in the town centre. Concentrations of elements in soils from the town, including those near the school, had the following ranges: Cu, 41–12,000, geometric mean 863 μg/g; Zn, 89–15,600, geometric mean 920 μg/g; Pb, 32–7860, geometric mean 740 μg/g; Cd, BDL–329.5, geometric mean 3.35 μg/g; As, 15–1440 geometric mean 223 μg/g; Thus, the residents of Zlatna are potentially exposed to levels of these elements that are higher than the recommended guideline values. Mean concentrations of the toxic elements in spring onions were: Cu, 10.2; Zn, 95; Pb, 11; Cd, 0.8; As 2.6 μg/g dry weight.     

The effects of acid rainfall and heavy metal particulates on a boreal Forest ecosystem near the sudbury smelting region of Canada

Sulphur dioxide and particulate pollution have been occurring over a wide area in the Sudbury region, Ontario, as a result of massive smelting operations. In excess of 3Z million short tons of SO₂ were released into the atmosphere in the area in 1972, and this pollutant is now discharged through a 1250-foot smokestack. The particulate contribution is an additional complicating and phytotoxic factor. For example, in 1971, 192 tons of nickel, 145 tons of copper, 1130 tons of iron and 4.5 tons of cobalt per 28 days from two of the smelters were released as airborne pollutants (Hutchinson and Whitby, 1974). The natural vegetation of the area is a mixed deciduous boreal forest, with white pine (Pinus strobus), jack pine (Pinus banksiana), red maple (Acer rubrum), red oak (Quercus rubra), etc. as dominant trees. This forest, which previously surrounded the mining town of Sudbury, has been devastated over the past 50 yr, especially by the SO₂ emissions and the increased acidity of rainfall and soils. An area in excess of 100 mi² is now almost devoid of vegetation and damage to the forest vegetation is visible over an area of approximately 1800 mil. The increased stack heights to dilute local pollution problems have spread the problem more widely. The pH of rainfall sampled up to 12 mi east of the smallest smelter in 1970 was less than 4.3 and that within 2 mi of the stacks was frequently of less than pH 3.0. Soil erosion has occurred on a large scale as a consequence of loss of vegetation. Metal accumulation in the soils has also been a complicating and probably highly persistent phenomenon. Concentrations of nickel in excess of 3000 ppm and copper of 2000 ppm in surface soils occur widely. The increased acidity of these soils has increased metal mobility and solubility, presenting phytotoxic problems. The effects on the soil chemistry, especially of organic composition have been profound. They involve an increased metal binding capacity of these soils, and very high levels of sulphur in the purified Tulvic acid′ fraction itself. Indeed, the evidence is suggestive of the incorporation of sulphonic groups into the changed extracts. Such profound and damaging changes may be merely a consequence of the extreme conditions experienced at Sudbury or they may be a harbinger of things to come in many potentially podsolic soils in areas of increasing acidity of rainfall.     

STUDIES ON SOIL COPPER

Adsorption isotherms were determined for the specific adsorption of copper by soils and soil constituents. Adsorption was found to conform to the Langmuir equation. The Langmuir constants, a (adsorption maximum) and b (bonding term), were calculated. Soils were found to have specific adsorption maxima at pH 5.5 of between 340 and 5780 μg g^?1, and a multiple regression analysis revealed that organic matter and free manganese oxides were the dominant constituents contributing towards specific adsorption. Adsorption maxima for soil constituents followed the order manganese oxides > organic matter > iron oxides > clay minerals, which supported the findings for whole soils. The cation exchange capacities (non-specific adsorption) of the test soils were found to be far greater than the specific adsorption maxima. However, evidence suggests that, for the relatively small amounts of copper normally present in soils, specific adsorption is the more important process in controlling the concentration of copper in the soil solution.     

Copper in Scots pine forests around a heavy-metal smelter in south-western Finland

Distribution and fluxes of copper within Pinus sylvestris stands were studied during 1992–1994 along a heavy-metal pollution gradient in south-western Finland. The stands are situated at distances of 0.5, 4 and 8 km from a copper-nickel smelter that started operating in 1945 at Harjavalta. According to the results, copper concentrations in the soil, in the understorey vegetation and in the trees increased steeply towards the smelter. Almost 50 years' accumulation of heavy metals in the soil has caused direct toxic effects to soil microbes, thus decreasing decomposition and nutrient mineralisation. During the past few years, sulphur and heavy metal emissions from the copper and nickel smelter have been radically decreased. However, the heavy metals which have been accumulating in the soil for decades continue to affect the vegetation for a long time through soil processes. Consequently, long-term accumulation in the soil has to be taken into account when determining the critical loads of forest ecosystems for heavy metals.     

Heavy Metal Concentrations,Partitioning, and Storage in Slovak Forest and Arable Soils Along a Deposition Gradient

Along a heavy metal deposition gradient, caused by a Cu smelter, heavy metal concentrations, partitioning, and storage in forest and arable soils were examined. We sampled organic and mineral soil horizons (0—50 cm) at ten pairs of forest and arable sites derived from the same parent material. A-horizons were extracted with a seven-step sequence; O- and subsoil horizons were digested with strong acids (HNO₃/HClO₄). We found high concentrations of Cd (up to 17.38 mg kg^—1 in the O horizons/up to 2.44 mg kg^—1 in the A horizons), Cu (8437/415), Pb (3343/126), and Zn (1482/637) which decreased exponentially with distance from the smelter and with soil depth. The metal concentrations in the organic layers indicate that the average transport distance decreases in the order Cd > Zn > Pb > Cu. With regard to metal partitioning, NH₄NO₃- + NH₄OAc-extractable forms in the A horizons were most affected by the deposition being more pronounced under forest. In the uppermost 50 cm of the four soils nearest to the smelter two to four times higher Cd, Cu, Pb, and Zn storages were found in forest than in arable soils. At greater distance, the higher deposition onto forest soils due to the scavenging effect of the canopy obviously was compensated by stronger leaching.     

Response of spodic B horizons to acid precipitation in northernmost Fennoscandia

In northernmost Fennoscandia there is concern about the possible environmental effects of the sulphur emissions from Russian nickel smelters on the Kola Peninsula. The purpose of this study was to investigate to what extent the soils of this region may delay the response to pH changes through sulphate adsorption, and whether there are evidence for strong soil acidification effects. To this end 26 spodic B horizons were collected along a transect from northernmost Sweden to north-easternmost Norway, only 10 km from the Pechenganikel smelter. As the pH(H₂O) was > 4.8 in all soils, and as the exchangeable Ca/Al ratio was high, there were no evidence for strong soil acidification effects. Water-extractable SO₄ was clearly affected by the S deposition and thus SO₄ was at least partly mobile in the soils; it is therefore possible that soil solutions close to the smelter may have been acidified. In spite of this, sulphate adsorption was found to be more important than cation exchange reactions as a delaying process against soil acidification, at least in the top 10 cm of the B horizon. For the top 20 cm of the B horizon it was estimated that S04 adsorption can neutralize, on average, 700 mmol_c, m^?2 of acid before the pH is decreased to 4.4. Thus if the S deposition remains unchanged, decades are required to severely acidify most soils in the affected parts of Norway and Finland.     

土法炼锌区大气沉降Pb、Zn、Cd及其对土壤质量的影响

Dust emissions from smelters, as a major contributor to heavy metal contamination in soils, could severely influence soil quality. Downwind surface soils within 1.5 km of a zinc smelter, which was active for 10 years but ceased in 2000, in Magu Town, Guizhou Province, China were selected to examine Pb, Zn, and Cd concentrations and their fractionation along a distance gradient from a zinc smelter, and to study the possible effects of Pb, Zn, and Cd accumulation on soil microorganisms by comparing with a reference soil located at a downwind distance of 10 km from the zinc smelter. Soils within 1.5 km of the zinc smelter accumulated high levels of heavy metals Zn (508 mg kg-1), Pb (95.6 mg kg-1), and Cd (5.98 mg kg-1) with low ratios of Zn/Cd (59.1--115) and Pb/Cd (12.4--23.4). Composite pollution indices (CPIs) of surface soils (2.52--15.2) were 3 to 13 times higher than the reference soils. In metal accumulated soils, exchangeable plus carbonate-bound fractions accounted for more than 10% of the total Zn, Pb, and Cd. The saturation degree of metals (SDM) in soils within 1.5 km of the smelter (averaging 1.25) was six times higher than that of the reference soils (0.209). A smaller soil microbial biomass was found more frequently in metal accumulated soils (85.1--438 μg C g-1) than in reference soils (497 μg C g-1), and a negative correlation (P < 0.01) of soil microbial biomass carbon to organic carbon ratio (Cmic/Corg) with SDM was observed. Microbial consumption of carbon sources was more rapid in contaminated soils than in reference soils, and a shift in the substrate utilization pattern was apparent and was negatively correlated with SDM (R = -0.773, P < 0.01). Consequently, dust deposited Pb, Zn, and Cd in soils from zinc smelting were readily mobilized, and weredetrimental to soil quality mainly in respect of microbial biomass.     

Arsenic Contamination in Soils Affected by a Pyrite-mine Spill (Aznalcóllar, SW Spain)

On 1998, a settling pond of a pyrite mine in Aznalcóllar (SW Spain) broke open, spilling some 3.6?×?10⁶ m³ of water and 0.9?×?10⁶ m³ of toxic tailings into the Agrio and Guadiamar river basin 40 km downstream, nearly to Doñana National Park. The soils throughout the basin were studied for arsenic pollution. Almost all the arsenic penetrated the soils in the solid phase (tailings) in variable amounts, mainly as a result of the different soil structure. The chemical oxidation of the tailings was the main cause of the pollution in these soils. A study of the relationships between the main soil characteristics and arsenic extracted with different reagents (water, CaCl₂, acetic acid, oxalic–oxalate and EDTA) indicates a direct relationship with the total arsenic concentration. The highest amount of arsenic was extracted by oxalic–oxalate (24%–36% of the total arsenic), indicating the binding with the iron oxides.     

Chloroform-labile trace elements in soil via fumigation-extraction: Steps towards the soil microbial ionome beyond C:N:P

Secondary and trace elements may be limiting soil microbial functioning, albeit microbial demand and content remain largely unknown and methods for their in situ detection are limited. Thus, the objective of the present study was to take the first step towards the method development for the assessment of the soil microbial ionome, that is, the elemental composition of soil microbial communities. Chloroform (CHCl₃) fumigation extraction was used for the detection of microbial CHCl₃-labile secondary and trace element concentrations in soils. The suitability of two extractants (NH₄NO₃, CaCl₂) for the quantification of CHCl₃-labile concentrations of phosphorus, sulphur, potassium, sodium, and magnesium, as well as selenium, iron, zinc, manganese, copper, cobalt, nickel, molybdenum, vanadium, boron, silicon, barium, arsenic, and cadmium, were tested in six agricultural soils. Additionally, three soil to extractant ratios (1:5, 1:10, and 1:20) and two extraction durations, 1 or 2 h, were tested in a subset of two soils. Out of the two extractants tested, 0.01 M CaCl₂ was found to be the best-suited extractant. For CaCl₂, a soil-to-extractant ratio of 1:20 with an extraction time of 1 h was best for the majority of elements in the two soils tested. In a limited number of agricultural soils, we were able to show that CHCl₃ fumigation extraction can successfully be applied to the elements phosphorus, sulphur, potassium, sodium, magnesium, zinc, manganese, copper, nickel, vanadium, boron, silicon, and barium to yield a CHCl₃-labile element fraction. Conversion values to microbial biomass, accounting for elements contained in the cell envelope components, which are mostly not extractable, and to account for adsorption to soil colloids during extraction are yet to be determined in a larger variety of soils. To overcome some of the limitations of the fumigation extraction approach for secondary and trace elements, a pre-extraction step may provide a suitable solution.     

Influence of microorganisms on arsenic mobilization and speciation in a submerged contaminated soil: Effects of citrate

Batch-type leaching experiments were performed on polluted soil contaminated by pyrite cinders to evaluate the effect of indigenous bacteria on arsenic mobilization. The bacteria, under submerged conditions using citrate as the carbon source, enhanced the solubilization of arsenic, iron and manganese. At the same time, 85 mg kg⁻¹ of copper were abiotically released. Iron reduction significantly (p < 0.05) enhanced the release of arsenic. During 7 days of incubation at high redox potential, the arsenite content increased suggesting aerobic arsenic-resistant bacteria bearing arsC genes as key players for arsenate reduction. Arsenate became prevalent in consequence of arsenic liberation from iron oxides and the lowering of redox potential, driven by citrate, inhibited the growth and activity of arsenate-resistant bacteria. Populations of Bacillus, Pseudomonas, and Geobacter were stimulated by the addition of citrate as evidenced by denaturing gradient gel electrophoresis analysis of 16S rRNA genes. Putative ars genes were retrieved in isolates of Bacillus and Pseudomonas. These isolates were able to reduce 2 mmol l⁻¹ of arsenate in liquid cultures. These results confirm that microorganisms play an important role in As cycling in soils and highlight the complex role of citrate on biotic and abiotic transformations of inorganic contaminants. The environmental dispersion of arsenic can be retarded by resorption or coprecipitation processes occurring during flooding. Nevertheless, periodic flooding can be a crucial factor for the groundwater quality and the soil–water–plant systems.     

Metal contamination from open-cast copper and sulphur mining in southeast Ireland

The metal content was determined in soil and vegetation around the eastern zone of the disused sulphur and copper mines at Avoca (southeast Ireland). A 250 m × 250 m grid survey was conducted covering a total area of 4 km². The mining belt was in the centre of the investigated site and was sampled separately. Iron, Zn, Cu and Cd concentrations in soil and plant material were determined, in addition to soil organic matter content and soil pH. Soil samples taken from the spoil showed elevated Cu and Cd concentrations, and low soil pH and organic matter content. At least 50 per cent of the agricultural sites examined around the East Avoca Mine showed elevated soil Cu and Cd concentrations, whereas Zn and Fe soil concentrations were within the range for unpolluted soils. None of the vegetation analysed had elevated Zn, Cd, Fe or Cu concentrations. Overall there was no indication of serious metal contamination in either soils or vegetation surrounding the mine in spite of extensive dust deposition during open-pit mining activity 15–30 years ago. However, a plume of elevated Cu in the soil was identified, which originated from a large spoil heap and had been spread for some 2·0 km by the prevailing wind.     

The effect of sewage‐sludge on the heavy metal content of soils and plant tissue

Abstract

Domestic sewage sludge applied to farm fields at a rate of 44.9 kg/ha in a mixture with lime and sawdust was found to increase the soil levels of cadmium, chromium, copper, lead, mercury, nickel and zinc. The average levels in sludge treated soil were: 0.11, 0.56, 3.59, 2.72, 0.068, 1.49 and 2.57 ppm, respectively. The increases were small and the overall loading factors were well below recommended maximums. The uptake of these heavy metals by grass and legume plants was variable with cadmium, copper and zinc levels being higher in those plants growing in the sludge treated soils but only copper was significantly higher. The heavy metal contents found were all within the levels normally found in grass and legume plants. The higher mean concentration in plants growing on the sludge treated soils were cadmium 0.495; chromium 1.22; copper 12.3; lead 1.54; mercury 0.022; nickel 4.08 and zinc 28.4 ppm.     

Trace elements in soils and food chains of the Balkan region

Abstract

The present review summarizes the available data on the concentration of trace elements (TEs) in soils and their availability to plants with a view to reflect the quality and safety of food and fodder crops. Most soils in western Balkan countries are not contaminated. However, soils around industrial centers and historical mining sites do create concern for food and feed safety. Also high concentrations of TEs are related to their geochemical original. For example, ultrabasic rocks and serpentinites in western Serbia and western Bosnia are very rich in chromium, nickel, magnesium, iron (Fe), and cobalt, and cover an area of 5200 km². High TE concentrations caused by anthropogenic activities are also reported. In vineyard soils in Croatia, concentrations of cadmium, copper (Cu), and zinc (Zn) were much higher than their background concentrations. On the other hand, TE deficiency in plants is also prevalent in the regions. For example, Zn and Fe deficiencies in eastern parts of Croatia and northern parts of Serbia, Cu deficiency in pasture and sheep's blood at Nisici Plateau of Bosnia and Herzegovina, and selenium (Se) deficiency almost in the whole region have been observed. Therefore, information on TEs' behavior and soil factors affecting their mobility and availability is highly needed in order to separate the areas of contamination and then propose agrotechnical measures to protect the entry of TEs into the food chain. Research is also required to assess the influence of agronomic management on TE supply to plants and for achieving a better utilization of essential TEs. Concentrations of Se in wheat in Serbia are so low that if people were fed exclusively with wheat, their daily requirements for Se would not be met. There is also a need for full implementation of new food safety regulations in the Balkan countries in accordance with the legislations of the European Union.     

Improving the Physical and Chemical Properties of a Disturbed Soil Using Drying-bed Biosolids

Disturbed soils might be improved by increasing organic matter content. The objective of this study was to determine if a large application of drying-bed biosolids would improve soil productivity and promote bermudagrass (Cynodon dactylon) and establishment on the Trinity clay soil. Anaerobically digested, air-dried biosolids were applied to Trinity clay (very-fine, montmorillonitic, thermic, typic, pelludert) at rates of 0, 112, 560, and 1120 Mg ha^?1. The biosolids were incorporated into the top 15 cm of the soil and bermudagrass sprigs were planted. Biosolids significantly reduced soil bulk density and soil resistance to penetration when measured during the second and third years after the application. Biosolids increased soil concentrations of organic carbon, nutrients (nitrogen, phosphorus, copper, zinc, iron) and heavy metals (cadmium, chromium, nickel, lead). Bermudagrass biomass production and nutrient uptake were increased due to biosolids, but heavy metals were not significantly transferred from soil to above-ground plant tissue.     

Emission of CO2 by soils in the impact zone of the Severonikel smelter in the Kola subarctic region

The intensity of the in situ soil respiration in the background northern taiga spruce forests of the Kola subarctic region reaches 120–290 mg C-CO₂/m² per h. In the impact zone of the Severonikel smelter, it decreases to 90–140, 30, and 15–30 mg C-CO₂/m² per h at the stages of spruce defoliation, spruce-birch woodland, and technogenic barrens of the technogenic succession, respectively. For the first time, the impact of the industrial pollution on root respiration has been assessed, and the dependences of the CO₂ emission, the contribution of mineral soil horizons to this process, the microbial biomass, and root respiration on the concentrations of available nickel and copper compounds have been determined. The efficiency of two remediation technologies applied to technogenic barrens near the smelter has been evaluated on the basis of four parameters of the soil biological activity. The results indicate that remediation with the creation of a new filled soil layer is more efficient than chemical and phytoremediation methods.