Environmental pollution by wind blown lead mine waste: A case study in wales,U.K.

This paper reports an investigation of environmental Pb pollution by wind blown material from a spoil heap at a derelict Pb mine in West Wales. Most of the <2 mm fraction of the spoil is of sufficiently small particle diameter to move by saltation and the material <2 μm probably approximates to the composition of PbS. Meteorological data for 1977/1978 were analysed. During dry weather northerly winds predominate and these are probably funnelled in an east-west direction by the valley in which the mine is situated. It is calculated that the spoil can be set moving by winds of Force 4 or greater and such winds were experienced for 193 days in the reference year. Atmospheric transport of Pb-rich dust was monitored by moss bags and Pb isoline maps were constructed from the data. There is a marked movement of dust westwards from the spoil heap to nearly 1800 m down the valley. A survey of Pb in soil revealed a characteristic east-west alignment of the Pb isolines which suggests that air-borne dust is the major source of pollution. Pb in unwashed lettuce leaves was some 5 times greater than in washed leaves while the latter contained Pb in excess of the British legal limit. Pb in domestic water was not a problem. It is concluded that blowing spoil is an immediate environmental hazard through deposition on plant leaves and through inhalation by people or animals. Pb which has accumulated in the soil may present a dietary problem.     

Atmospheric deposition and migration of artificial radionuclides in Alpine soils (Val Piora, Switzerland) compared to the distribution of selected major and trace elements

Artificial radionuclides (¹³⁷Cs, ⁹⁰Sr, Pu, and ²⁴¹Am) are present in soils because of Nuclear Weapon Tests and accidents in nuclear facilities. Their distribution in soil depth varies according to soil characteristics, their own chemical properties, and their deposition history. For this project, we studied the atmospheric deposition of ¹³⁷Cs, ⁹⁰Sr, Pu, ²⁴¹Am, ²¹⁰Pb, and stable Pb. We compared the distribution of these elements in soil profiles from different soil types from an alpine Valley (Val Piora, Switzerland) with the distribution of selected major and trace elements in the same soils. Our goals were to explain the distribution of the radioisotopes as a function of soil parameters and to identify stable elements with analogous behaviors. We found that Pu and ²⁴¹Am are relatively immobile and accumulate in the topsoil. In all soils, ⁹⁰Sr is more mobile and shows some accumulations at depth into Fe-Al rich horizons. This behavior is also observed for Cu and Zn, indicating that these elements may be used as chemical analogues for the migration of ⁹⁰Sr into the soil.     

Health risk from heavy metals via consumption of food crops in the vicinity of Dabaoshan mine, South China

Heavy metal contamination of soils resulting from mining and smelting is causing major concern due to the potential risk involved. This study was designed to investigate the heavy metal (Cu, Zn, Pb and Cd) concentrations in soils and food crops and estimate the potential health risks of metals to humans via consumption of polluted food crops grown at four villages around the Dabaoshan mine, South China. The heavy metal concentrations in paddy and garden soils exceeded the maximum allowable concentrations for Chinese agricultural soil. The paddy soil at Fandong village was heavily contaminated with Cu (703 mg kg^− 1), Zn (1100 mg kg^− 1), Pb (386 mg kg^− 1) and Cd (5.5 mg kg^− 1). Rice tended to accumulated higher Cd and Pb concentration in grain parts. The concentrations of Cd, Pb and Zn in vegetables exceeded the maximum permissible concentration in China. Taro grown at the four sampled villages accumulated high concentrations of Zn, Pb and Cd. Bio-accumulation factors for heavy metals in different vegetables showed a trend in the order: Cd > Zn > Cu > Pb. Bio-accumulation factors of heavy metals were significantly higher for leafy than for non-leafy vegetable. The target hazard quotient (THQ) of rice at four sites varied from 0.66-0.89 for Cu, 0.48-0.60 for Zn, 1.43-1.99 for Pb, and 2.61-6.25 for Cd. Estimated daily intake (EDI) and THQs for Cd and Pb of rice and vegetables exceeded the FAO/WHO permissible limit. Heavy metal contamination of food crops grown around the mine posed a great health risk to the local population through consumption of rice and vegetables.     

EXAFS speciation and phytoavailability of Pb in a contaminated soil amended with compost and gypsum

Due to unregulated uses of lead pellets for hunting purposes in Japan, soils and sediments in some river basins and wetlands have become highly contaminated with Pb. Deterioration of natural vegetation has occurred sporadically in these areas, and therefore revegetation is needed for ecological restoration. The objectives of the present study were to assess the effects of surface applications of compost and gypsum amendments on Pb availability to a watercress plant (Nasturtium officinale W.T. Aiton) and molecular-scale speciation of Pb in soil solid phases. The compost and gypsum amendments significantly decreased dissolved Pb and Sb in pore water. The concentration of Pb in aboveground plant tissues was 190 mg kg^− 1 in the control soil and was reduced to < 20 mg kg^− 1 in the compost and gypsum-amended soils. The concentration of Sb in plants grown in the control soil was 13 mg kg^− 1, whereas that in the soils receiving compost and gypsum decreased below detectable levels. Redox potential was higher in vegetated soils (ave. 349 mV) than in the unvegetated soils (ave. 99 mV) due to oxygen introduced by plant roots. Extended X-ray absorption fine structure (EXAFS) spectroscopy illustrated that Pb occurred as Pb sorbed on birnessite and/or ferrihydrite (Pb-Mn/Fe, ~ 60%) and Pb sorbed on organic matter (Pb-org, ~ 15%), and galena (PbS, ~ 10%) in the vegetated and unvegetated control soils. The compost amendment increased the proportion of Pb-org by 2-fold than in the control soils. The amended soils with plant growth decreased the proportion of Pb-Mn/Fe phases by half of that without plant growth. Galena and anglesite (PbSO₄) were not detected in compost-amended soils and even in gypsum-amended soils since a significant soil reduction to anoxic levels did not occur in the entire soil. The present study indicated that, under flooded conditions, surface applications of compost and gypsum amendments reduced plant Pb uptake from the Pb contaminated soil.     

Heavy metal distribution in some French forest soils: evidence for atmospheric contamination

This study is one of very few dealing with the distribution and the origin of heavy metals in French soils from a priori non-polluted forest areas. The abundance of heavy metals measured in these soils decreases as follows: Cr>Zn>Pb>Ni>Cu>Co>Cd. Total concentrations of Pb, Cr and Ni in some soils exceed the European thresholds for non-polluted soils and even the French association of normalization critical values for sludge spreading. The lowest heavy metal contents are observed in acid soils while the highest concentrations are in the calcaric cambisol and in the mollic andosol, which is rather scarce as compared with the other French forest soils. With the exception of the podzol, Cr and Ni concentrations increase with depth in all soil profiles. The distribution pattern of Co, Cu, Zn depends on the soil characteristics. In some acid soils, however, Cu and Zn decrease with depth. Pb and Cd are accumulated in the upper soil horizons. Heavy metals accumulate in deep soil horizons in relation to important clay content in the dystric planosol and stagnic luvisol. The concentration of each heavy metal is always controlled by different parameters (soil pH, iron and aluminum oxide content, clay content, organic matter and cation exchange capacity), which are heavy metal specific. This study highlights the metal-trapping character of andosol and calcaric soil, the weak heavy metal retention in acid soils, the leaching and trapping character in leached clayed soils, and the migration of heavy metals in the podzol. Pb and Cr concentrations indicate a significant enrichment in surface horizons from various soils in areas which receive significant acid atmospheric pollution. Particularly, the highest Pb content is observed in a soil located in the N-NE part of France. Lead isotope ratios measured in the cambic podzol and the calcaric cambisol, exhibit the importance of the anthropogenic sources and particularly the influence of global atmospheric inputs from leaded gasoline compared to regional and local industrial emissions. The anthropogenic Pb contribution is estimated to 83, 30 and 11%, respectively, for surface, intermediate and deep horizons of the cambic podzol located in the northern part of France, and to 68% in surface horizon of the calcaric cambisol located in the Alps.     

Environmental contamination and seasonal variation of metals in soils,plants and waters in the paddy fields around a PbZn mine in Korea

The objective of this study is to investigate the extent and degree of heavy metal contamination of paddy fields influenced by metalliferous mining activity. Paddy soils, rice plants and irrigation waters were sampled along six traverse lines in the vicinity of the mine and nearby control site. Soil samples were taken 30, 80 and 150 days after rice transplanting, to study seasonal variation of their chemical properties and heavy metal concentrations. Sampling of rice plants and irrigation waters was also undertaken with seasons. The analysis of the samples were carried out using ICP-AES for 25 elements including Cd, Cu, Pb and Zn. Physical and chemical properties of soils (pH, loss-on-ignition, cation exchange capacity and texture) and waters (pH, Eh and temperature) were also measured. The properties of soils were similar to the average Korean soils, with the exception of some samples taken in the vicinity of the mine. Concentrations of Cd, Cu, Pb and Zn in paddy soils, rice plants and irrigation waters sampled in the immediate vicinity of the mine were relatively high due to the seepage of metals from mining dump sites. Although there was variation between sampling sites, soil pH values under reducing conditions were on average higher than those under oxidising conditions. Relatively low content of organic matter and low cation exchange capacity of soils were found at 80 days after rice transplanting (P < 0.05). No seasonal variations in metal concentrations were found in paddy soils throughout the period of the rice growing, in which soils ranged from flooded reducing conditions through most of the growing season to drained oxidising conditions before and at harvest. Relatively high metal concentrations were found in the rice stalks and leaves under oxidising conditions. The sequential extraction analysis of selected soil samples confirmed that high proportions of exchangeable fractions of the metals were found under oxidising conditions. It was shown that Cd and Zn concentrations in rice leaves and stalks and rice grain increased with increasing metal concentrations in paddy soils to a greater extent than for Cu and Pb. This difference in uptake is in agreement with the greater proportions of Cd and Zn, compared with Cu and Pb, in the exchangeable soil fraction extracted with MgCl₂. Average daily intake from locally grown rice by the residents was estimated to be 121 μg Cd and 126 μg Pb. Thus, long-term metal exposure by regular consumption of the rice poses potential health problems to residents in the vicinity of the mine, although no adverse health effects have as yet been observed.     

Heavy metals contamination in soils around tailing heaps with various degrees of weathering in Zimapán,Mexico

Dispersion of mine tailings is the main cause of heavy metal (HM) contamination in soils in Zimapán, Mexico; however, the extent of this problem has not been assessed. Therefore, the aims of this study were to determine the degree of contamination and to assess the influence of mine tailings with different degrees of weathering on the spatial distribution of HM in soils. Soil and mine tailing sampling was carried out. The HM concentration was determined by atomic absorption spectrophotometry; spatial analysis and the size of the contaminated areas were calculated using GIS software; the mine tailings were characterized physically, chemically and mineralogically. The results suggest that all the tailing heaps have contributed to the HM dispersion. High HM concentrations were founded in soils around mine tailings (9402 mg kg^?1 Pb and 52 mg kg^?1 Cd). Surface area contaminated with Pb and Cd was estimated at 6.2 and 2.7 km², in urban soils, respectively.     

Remediation measures and displacement of pollutants in soils affected by the spill of a pyrite mine

The soils affected by the spill of a pyrite mine were analysed in 100 sampling points at three depths (0-10, 10-30, and 30-50 cm) in 1998 (after the tailings were removed), 1999 (after the cleaning of the highly contaminated areas), and 2004 (after the tilling of the upper 20-25 cm). The comparative study reveals that the removal of the tailings left a heterogeneous distribution pattern of the contaminants, with highly polluted spots alternating with less contaminated areas. The cleanup did not substantially lower the concentration in the highly polluted soils, and the spread of the pollutants increased the concentration in As and Pb in the uppermost 10 cm of 60% of the soils, while the Zn and Cd concentrations increased in only 30% of the soils. Given the high concentration of pollutants in the topsoil (especially As), the tilling of the upper 20-25 cm, despite reducing the average concentration of pollutants in the uppermost 10 cm, did not substantially lower the percentage of soils that exceeded the concentration of 40 mg As kg^− 1 dry soil and almost doubled the percentage of soils that surpassed this concentration between 10 and 30 cm. Meanwhile, the displacement of Zn and Cd within the soil supported the reduction in the percentage of soils that in the upper 10 cm exceeded the reference concentrations of these elements (900 mg Zn kg^− 1 dry soil and 2 mg Cd kg^− 1 dry soil), and the percentage of soils exceeding these concentrations between 10 and 50 cm in depth did not increase. Six years after the spill and at the end of all remediation measures, the intervention levels defined by the Environmental Agency of the Regional Government of Andalusia for natural parks were exceeded in the uppermost 10 cm in 35% of the soils.     

Naturally Pb-contaminated soils in uranium and thorium anomaly

The paper reports an examination of the primary sources of stable lead (Pb) occurring in rocks and soils on dairy farms in the municipalities of Pedra and Venturosa in Pernambuco, Brazil. Lead in rock and soil was quantified by flame atomic absorption spectrophotometry. The Pb concentration in calcium silicate rock varied from 21 to 1124.00 mg.kg^?1 and soil varied from 18 to 96 mg.kg^?1. The lead concentration in granite rock varied from 6 to 440 mg.kg^?1 and soil varied from 8 to 15 mg.kg^?1. The results point to the rocks as the primary sources of lead.     

Trace metals in Shatt al-Arab River,Iraq

The distribution of 10 trace metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn have been determined along the northern section of the Shatt al-Arab River, Iraq. Analyses were carried out, employing a flameless AAS instrument. The mean concentrations of the dissolved species were as follows (expressed in μg l^?1): 0.25 Cd, 0.9 Cu, 716 Fe, 1.3 Mn, 0.3 Pb, 0.2 V and 1.8 Zn. Mean concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn in the particulate matter were 55.2, 6.0, 188, 77, 31 472, 1731, 3807, 93, 207 and 77 μg g^?1 respectively. In the exchangeable fraction of the sediment were 0.15, 5.5, 11.1, 11.9, 1625, 482, 42, 30.5, 25.7 and 6 μg g^?1, whereas in the residual were 0.025, 11.5, 96.1, 22, 5176, 258, 613, 3.9, 162 and 56.8 μg g^?1 respectively. Thus, the exchangeable trace metals represent the following mean percentage of the total; 75% Cd, 33% Co, 10% Cr, 34% Cu, 24% Fe, 63% Mn, 7% Ni, 74% Pb, 14% V and 23% Zn. The concentration of Ni and V were relatively high, this was attributed to the petroleum-rich deposits of the region. The concentrations observed for other metals were lower or equal to those reported for control sites except for Pb which was slightly higher. The data obtained were subjected to simple linear regression analysis and expressed in the form of correlation coefficients. It was found that the inter-elemental relationships are rather complex.     

Comparative value of phosphate sources on the immobilization of lead, and leaching of lead and phosphorus in lead contaminated soils

The mobility and bioavailability of lead (Pb) in soils can be mitigated by its immobilization using both soluble and insoluble phosphate (P) compounds. The effectiveness of insoluble P sources on Pb immobilization depends on their rate of dissolution which can be enhanced by phosphate solubilizing bacteria (PSB). In this study, the effect of soluble (potassium dihydrogen phosphate) and insoluble (rock phosphate in the presence and absence of PSB) P compounds on the immobilization of Pb, and leaching of Pb and P was examined using both naturally contaminated (SR soil: NH₄NO₃ extractable Pb: 28.7 mg/kg, pH: 5.88, organic matter: 0.7%) and Pb spiked (AH soil: NH₄NO₃ extractable Pb: 42.7 mg/kg, pH: 5.23, organic matter: 10.9%) soils. Phosphate compounds were added at the rate of 200 mg P/kg and 800 mg P/kg for SR and AH soils, respectively. Soluble P treatment immobilized 80% and 57% of Pb in SR and AH soils, respectively. Insoluble rock phosphate immobilized 40% and 9% of Pb without PSB, and 60% and 17% with PSB in SR and AH soils, respectively. Lead leaching was the lowest when soils were amended with rock phosphate in the presence of PSB, which reduced Pb leaching by 36% for SR soil and 18% for AH soil compared to the control. The leaching of Pb increased when the soils were amended with soluble P because soluble P treatment increased dissolved organic carbon (DOC) concentration of soil, thereby increasing Pb mobility. Soluble P treatment significantly increased P leaching and 9% of total added P was leached from low P retaining AH soil. The optimum level of P amendment is a critical issue when soluble P is used as a Pb immobilizing agent because of eutrophication resulting from excessive P leaching to surface and ground water. While the soluble P compound was effective in the immobilization of Pb, it resulted in P leaching which increased with increasing levels of P addition. However, rock phosphate amendment with PSB achieved the immobilization of Pb with a minimum effect on both Pb and P leaching.     

Long-term distribution, mobility and plant availability of compost-derived heavy metals in a landfill covering soil

The application of municipal waste compost (MWC) and other organic materials may serve to enhance soil fertility of earthen materials and mine spoils used in land reclamation activities, particularly in the recovery of degraded areas left by exhausted quarries, mines and landfill sites among others. The long-term distribution, mobility and phytoavailability of heavy metals in such anthropogenic soils were studied by collecting soil samples at different depths over a 10 y chronosequence subsequent to amendment of the top layer of a landfill covering soil with a single dose of mechanically-separated MWC. Amendment resulted in a significant enhancement of the metal loadings in the amended topsoils particularly for Cu, Zn and Pb, which were also the predominant metals in the compost utilised. Although metals were predominantly retained in the compost amended soil horizon, with time their vertical distribution resulted in a moderate enrichment of the underlying mineral horizons, not directly influenced by compost amendment. This enrichment generally resulted from the leaching of soluble organo-metal complexes and subsequent adsorption to mineral horizons. However, in the course of the 10-y experimental period, metal concentrations in the underlying horizons generally returned to background concentrations suggesting a potential loss of metals from the soil system. Analysis of the tissues of plants growing spontaneously on the landfill site suggests that metal phytoavailability was limited and generally species-dependent.     

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.     

Metal pollution and selenium distributions in soils and grass near a non-ferrous plant

Multi-element analysis results of direct energy-dispersive X-ray fluorescence of soil samples taken in the vicinity of a non-ferrous plant in Antwerp are reported. High concentrations of Pb, Cu, Zn, As and Se are found in nearby residential areas, especially in top-soil layers. Selenium pollution appears not to be leached significantly to lower soil horizons, but it is available for uptake by rye-grass, in which toxic levels are found. Results are compared to literature data. Hydride generation atomic absorption spectrometry proved to be unsuitable for direct analysis of the heavily contaminated soils.     

Biomonitoring of maritime pollution by heavy metals (Pb and Zn) in the coast of Jijel (Algeria)

This paper reports a study of pollution in the coastal waters of Jijel, Algeria, using algae Ulva lactuca and Corallina officinalis as bioindicators. Samples of seawater and algae were collected at four different stations from the coast of Jijel, during the period of April–June 2014. The heavy metal content (Pb and Zn) was determined in seawater and in the algae tissue by the technique of atomic absorption spectrophotometry. In seawater, the contents of heavy metals vary from 0.017 to 0.03 mg/l (Pb) and 0.235 to 0.873 mg/l. In the algae tissues, metals concentrations vary between 1.88 to 6.25 μg g^?1 dry weight (Pb), and from 92 to 178.9 μg g^?1 dry weight (Zn). These levels differ by site and species. The calculation of the bioconcentration factor (BCF) leads us to conclude that algae bioaccumulate significant levels of Pb and Zn metals in their tissues. Our results shows that the species of C. officinalis bioaccumulate the metals Pb and Zn more than U. lactuca, where, high biosorption of Zn was observed with BCF values between 203.21 and 238.40. Zn content in seawater and algae tissues appear higher than standards set by USEPA and guides values of Certified Reference Materials, but Pb levels appear lower than this standard.     

Evaluation of metal concentrations in edible vegetables grown in compost amended soil

Agricultural uses of compost usually have a positive effect on the yield of vegetable crops for human consumption. However, compost that contains heavy metals can transfer these components to soils and plants. To evaluate the contamination levels of metals in soil, compost, and edible vegetables, the Mn, Zn, Pb, Cd, Cu, and Ni total contents were measured. Metal availability in soils, as well as other variables – the pH, CEC (cation exchange capacity), total nitrogen, organic carbon, particle size distribution and mineralogy of the clay fraction – were examined in the soil samples. The analysed compost samples were produced from urban solid waste, cattle manure, and edible vegetable and tree pruning residues. The values of pH, CEC, total nitrogen, organic matter, exchangeable hydrogen and carboxylic groups were measured in the compost samples. Of the six metals examined in the soils, in general, Mn and Zn attained the highest concentrations, followed by Cu. Relatively high Mn, Zn, Cu, Cd and Pb concentrations were found in the soils. Metal concentrations extracted with DTPA were below the critical levels in soils, i.e. the levels above which toxicity is likely. In general, Zn, Pb, Cd, Cu and Ni concentrations in compost were lower than those reported by other workers, while Mn levels were within the range for this metal in compost. The results showed that there was an effect of the vegetable type (p < 0.01) for all the parameters examined. High Pb concentrations were found in lettuce and chive as compared with the tolerance limit for this metal in fresh vegetables in Brazil. Cadmium concentrations were also enhanced in the fresh vegetables compared with the typical concentrations of metals in plants. Zinc, Cu, Cd, and Ni concentrations were lower than the tolerance limits established for foods by the Brazilian legislation.     

Heavy metal contamination of the soils used for stocking raw materials in the former ILVA iron-steel industrial plant of Bagnoli (southern Italy)

The total contents and the chemical and mineralogical forms of the metals Fe, Al, Cu, Co, Cr, Pb, Zn, Ni and Mn in the horizons of a soil profile, representative of an area devoted to stocking raw materials in the dismantled iron-steel industrial plant of ILVA of Bagnoli (Naples), were studied by physical and chemical methods. The geological setting of the study area is the result of volcanic activity in the Phlegrean Fields, a group of polygenic volcanoes to the west of Naples, which give rise to the parent soil material. Soil morphology appeared to be strongly disturbed by the occurrence and stratification of materials used in the industrial process. Fine sediments illuviation down the profile resulted in the occurrence of silt and clay coatings. The total contents of Cu, Co, Cr, Pb, Zn and Ni, in the whole soil samples, especially in the surface layers, were above the regulatory levels (Cu 120, Co 20, Cr 150, Pb 100, Zn 150, Ni 120 mg kg(-1)) stated by the Italian Ministry of Environment for soils in public, private and residential areas, and below the levels (Cu 600, Co 250, Cr 800, Pb 1000, Zn 1500, Ni 500 mg kg(-1)) outlined for soils and subsoils of industrial and commercial areas (Gazzetta Ufficiale della Repubblica Italiana, 1999). Speciation of heavy metals and the determination of the different chemical pools in the fraction < 2 mm identified the large presence of elements trapped in the mineralogical structure of oxides and silicates and occluded in easily reducible manganese or iron oxides. A constant amount of Cu was associated with organic compounds. A significant amount of Zn (> 20%) was extracted in diluted acetic acid solution, indicating that the element was present in a more readily and potentially available form. In the clay fraction (< 2 microm) heavy metals were associated with both amorphous and crystalline iron forms. The presence of iron-rich clay coatings was evident in the illuvial pores of deeper horizons. Enrichment in Cu, Co, Cr and Zn of the coatings was observed. Possible translocation of metals down through the soil profile mainly bound to fine particles of relatively inert forms of iron is hypothesised. The dispersion in water of the clay fraction resulted in an average percentage dispersion of approximately 20% with a peak of 41.7% at 68-72 cm depth. Magnetite, goethite, hematite, calcite and quartz mixed with K-feldspars, clynopyroxenes and mica occurred in the coarse sand fractions (2-0.2 mm) of the soil samples from all the surface horizons. Talcum and goethite together with clay minerals at 1.4 nm, kaolinite and illite were found in the clays (< 2 microm).     

Lead and zinc in the terrestrial environment around derelict metalliferous mines in Wales (U.K.)

Investigations centred on two derelict metalliferous (lead/zinc) mine complexes in central- and north-east Wales indicated heavy metal contamination of the local terrestrial environment. Dispersal of metallic pollutants was confirmed as an active phenomenon resulting from wind- and water-erosion of unstable mineral spoil tips containing residual quantities of sphalerite (ZnS) and galena (PbS). Lead and zinc concentrations in surface soil and vegetation decreased exponentially with distance along transects downwind of the pollutants origin. Analysis of dustfall, surface soil and vegetation suggested that wind re-entrainment has resulted in comparatively extensive but low level contamination over distances of up to 500–1000 metres from the spoil tips, and that water erosion has led to more severe contamination within relatively narrow zones of 50–100 metres around the perimeter of the sites. Differences in metal mobility within soil profiles were apparent between calcareous and acidic substrates indigenous to the study areas. Ground cover vegetation exhibited seasonal variations in lead concentration of up to 5–10 fold (April–September), but values exceeding the commonly adopted threshold concentration (100 μg Pb/g) associated with the onset of clinical symptoms of poisoning in horses, the most sensitive domestic livestock present, were restricted to within 20–80 metres of the spoil tips. Thus on present evidence, spoil redistribution is of only limited significance to contemporary management policies for agricultural land within the study areas.     

Assessing the fate of antibiotic contaminants in metal contaminated soils four years after cessation of long-term waste water irrigation

Spreading of urban wastewater on agricultural land may lead to concomitant input of organic and inorganic pollutants. Such multiple pollution sites offer unique opportunities to study the fate of both heavy metals and pharmaceuticals. We examined the occurrence and fate of selected antibiotics in sandy-textured soils, sampled four years after cessation of 100 years irrigation with urban wastewater from the Paris agglomeration. Previous studies on heavy metal contamination of these soils guided our sampling strategy. Six antibiotics were studied, including quinolones, with a strong affinity for organic and mineral soil components, and sulfonamides, a group of more mobile molecules. Bulk samples were collected from surface horizons in different irrigation fields, but also in subsurface horizons in two selected profiles. In surface horizons, three quinolones (oxolinic acid, nalidixic acid, and flumequine) were present in eight samples out of nine. Their contents varied spatially, but were well-correlated one to another. Their distributions showed great similarities regarding spatial distribution of total organic carbon and heavy metal contents, consistent with a common origin by wastewater irrigation. Highest concentrations were observed for sampling sites close to irrigation water outlets, reaching 22 μg kg⁻¹ for nalidixic acid. Within soil profiles, the two antibiotic groups demonstrated an opposite behavior: quinolones, found only in surface horizons; sulfamethoxazole, detected in clay-rich subsurface horizons, concomitant with Zn accumulation. Such distribution patterns are consistent with chemical adsorption properties of the two antibiotic groups: immobilization of quinolones in the surface horizons ascribed to strong affinity for organic matter (OM), migration of sulfamethoxazole due to a lower affinity for OM and its interception and retention in electronegative charged clay-rich horizons. Our work suggests that antibiotics may represent a durable contamination of soils, and risks for groundwater contamination, depending on the physicochemical characteristics both of the organic molecules and of soil constituents.