A preliminary investigation into mining and smelting impacts on trace element concentrations in the soils and vegetation around Tharsis, SW Spain

Toxic trace elements present an environmental hazard in the vicinity of mining and smelting activities. However. the processes of transfer of these elements to groundwater and to plants are not always clear. Tharsis mine. in the Iberian pyrite belt (SW Spain), has been exploited since 2500 BC, with extensive smelting, taking place front the 1850S until the 1920s. Sixty four soil (mainly topsoils) and vegetation samples were collected in February 2001 and analysed by ICP-AES for 23 elements. Concentrations are 6-6300 mg kg(-1) As and 14-24800 mg kg(-1) Pb in soils, and 0.20-9 mg kg(-1) As and 2-195 mg Pb in vegetation. Trace element concentrations decrease rapidly away from the mine. with As and Pb concentrations in the range 6-1850 mg kg(-1) (median 22 mg kg(-1)) and 14-31 mg, kg(-1) (median 43 mg, kg(-1)), respectively, 1 km away from the mine. These concentrations are low when compared to other well-studied mining and smelting areas (e.g. 600 mg kg(-1) As at 8 km from Yellowknife smelter, Canada; >100 mg kg(-1) Pb over 270 km(2) around the Pb-Zn Port Pirie smelter. South Australia: mean of 1419 mg kg(-1) Pb around Aberystwyth smelter, Wales, UK). The high metal content of the vegetation and the low soil pH (mean pH 4.93) indicate the potential for trace element mobility which Could explain the relatively low concentration of metals in Tharsis topsoils and cause threats to plans to redevelop the Tharsis area as an orange plantation.

Remediation of soils contaminated with petrol and diesel with lime

Lime treatment of hydrocarbon-contaminated soils offers the potential to stabilize and solidify these materials, with a consequent reduction in the risks associated with the leachate emanating from them. This can aid the disposal of contaminated soils or enable their on-site treatment. In this study, the addition of hydrated lime and quicklime significantly reduced the leaching of total petroleum hydrocarbons (TPH) from soils polluted with a 50:50 petrol/diesel mixture. Treatment with quicklime was slightly more effective, but hydrated lime may be better in the field because of its ease of handling. It is proposed that this occurs as a consequence of pozzolanic reactions retaining the hydrocarbons within the soil matrix. There was some evidence that this may be a temporary effect, as leaching increased between seven and 21 days after treatment, but the TPH concentrations in the leachate of treated soils were still one order of magnitude below those of the control soil, offering significant protection to groundwater. The reduction in leaching following treatment was observed in both aliphatic and aromatic fractions, but the latter were more affected because of their higher solubilty. The results are discussed in the context of risk assessment, and recommendations for future research are made.

Fate of prions in soil: Detergent extraction of PrP from soils

The transmissible spongiform encephalopathies (TSEs) are caused by infectious agents whose structures have not been fully characterized but include abnormal forms of the host protein PrP, designated PrPSc, which are deposited in infected tissues. The transmission routes of scrapie and chronic wasting disease (CWD) seem to include environmental spread in their epidemiology, yet the fate of TSE agents in the environment is poorly understood. There are concerns that, for example, buried carcasses may remain a potential reservoir of infectivity for many years. Experimental determination of the environmental fate requires methods for assessing binding/elution of TSE infectivity, or its surrogate marker PrPSc, to and from materials with which it might interact. We report a method using Sarkosyl for the extraction of murine PrPSc, and its application to soils containing recombinant ovine PrP (recPrP). Elution properties suggest that PrP binds strongly to one or more soil components. Elution from a clay soil also required proteinase K digestion, suggesting that in the clay soil binding occurs via the N-terminal of PrP to a component that is absent from the sandy soils tested.

Impact of sewage sludge applications on the biogeochemistry of soils

This report describes an investigation into the bioavailability and fate of trace metals and their subsequent impact on important soil microbiological functions such as nitrification, denitrification and methane oxidation in low and high Cu containing soils in the presence and absence of residual organic matter from sewage sludge additions made 10 years earlier. The soils being studied are part of long term sewage sludge trials and include a low Cu soil ( 13.3mg Cu/ kg soil, 4.18 LOI %), left un- amended to serve as a control soil, soil amended with a high Cu sewage sludge ( 278.3mg Cu/ kg soil, 6.52 LOI %) and soil amended with a low Cu sewage sludge ( 46.3mg Cu/ kg soil, 6.18 LOI %). Soil was also amended with inorganic metal salts ( 273.4mg Cu/ kg soil, 4.52 LOI %) to further investigate the impact of Cu in the absence of additional organic matter contained in applied sewage sludge. Data from the first two years of a project are presented which has included field- based studies at long term sewage sludge trials based in Watlington, Oxford, UK and laboratory based studies at the Institute of Grassland & Environmental Research, North Wyke, Devon, UK.

A preliminary investigation into the use of ochre as a remedial amendment in arsenic-contaminated soils

Ochre is an unwanted waste product that accumulates in wetlands and streams draining abandoned coal and metal mines. A potential commercial use for ochre is to remediate As contaminated soil. Arsenic contaminated soil (605 mg kg(-1)) was mixed with different ochres (A, B and C) in a mass ratio of 1:1 and shaken in 20 mL of deionised water. After 72 h As concentration in solution was ca. 500 mu g kg(-1) in the control and 1-2.5 mu g kg(-1) in the ochre treated experiments. In a second experiment soil:ochre mixtures of 0.05-1:1 were shaken in 20 mL of deionised water for 24 h. For Ochres A and C, as Solution concentration was reduced to ca. 1 mu gkg(-1) by 0.2-1:1 ochre:soil mixtures. For Ochre B, as concentration only reached ca. 1 mu g kg(-1) in the 1:1 ochre:soil inix. Sorption of As was best modelled by a Freundlich isotherm using As sorption per mass of goethite in the ochre (log K= 1.64, n = 0.79, R-2 = 0.76, p <= 0.001). Efficiency of ochre in removing As from solution increased with increasing total Fe, goethite, citrate dithionite extractable Fe and surface area. (c) 2005 Elsevier Ltd. All rights reserved.

Contributions of matric and osmotic potentials to the unfrozen water content of frozen soils

Recent reports show that biogeochemical processes continue when the soil is frozen, but are limited by water availability. However, there is little knowledge about the interactive effects of soil and environmental variables on amounts of unfrozen water in frozen soils. The aims of this study were to determine the contributions of matric and osmotic potentials to the unfrozen water content of frozen soil. We determined the effects of matric and osmotic potential on unfrozen water contents of frozen mineral soil fractions (ranging from coarse sand to fine silt) at -7 degrees C, and estimated the contributions of these potentials to liquid water contents in samples from organic surface layers of boreal soils frozen at -4 degrees C. In the mineral soil fractions the unfrozen water contents appeared to be governed solely by the osmotic potential, but in the humus layers of the sampled boreal soils both the osmotic and matric potentials control unfrozen water content, with osmotic potential contributing 20 to 69% of the total water potential. We also determined pore size equivalents, where unfrozen water resides at -4 degrees C, and found a strong correlation between these equivalents and microbial CO2 production. The larger the pores in which the unfrozen water is found the larger the microbial activity that can be sustained. The osmotic potential may therefore be a key determinant of unfrozen water and carbon dynamics in frozen soil. (C) 2008 Elsevier B.V. All rights reserved.

Zinc sorption in selected soils

The adsorption of nutrient elements is one of the most important solid- and liquid-phase interactions determining the retention and release of applied plant nutrients and the efficiency of fertilization. The study showed that the soils with high cation exchange capacity (CEC), CaCO3 , organic matter contents, and heavy texture adsorbed more zinc (Zn). The alkaline soils from Pakistan adsorbed more Zn than English acidic soils. Langmuir and Freundlich isotherm fit was excellent, and r(2) values for the Langmuir isotherm were highly significant (r(2) =0.84 to 0.99). The Langmuir b values, representing the adsorptive capacity of a soil, increased as the texture fineness increased in the soil, with increases in the concentration of adsorptive material (such as organic matter and CaCO3) and with increases in CEC and pH. The alkaline soils from Pakistan had higher bonding energy constant and higher log Kf values than the acidic English soils. Sequential extraction of Zn in these soils showed that most of the Zn was held in CaCO3 pool in the alkaline soils, whereas in acidic soils adsorbed Zn was in exchangeable form.

Assessment of the effect of time and temperature on the availability of residual phosphate in a glasshouse study of four soils using the Olsen method

The Olsen method is an indicator of plant-available phosphorus (P). The effect of time and temperature on residual phosphate in soils was measured using the Olsen method in a pot experiment. Four soils were investigated: two from Pakistan and one each from England (calcareous) and Colombia (acidic). Two levels of residual phosphate were developed in each soil after addition of phosphate by incubation at either 10degreesC or 45degreesC. The amount of phosphate added was based on the P maximum of each soil, calculated using the Langmuir equation. Rvegrass was used as the test crop. The pooled data for the four soils incubated at 10degreesC showed good correlation between Olsen P and dry matter yield or P uptake (r(2) = 0.85 and 0.77, respectively), whereas at 45 degreesC, each soil had its own relationship and pooled data did not show correlation of Olsen P with dry matter yield or P uptake. When the data at both temperatures were pooled, Olsen P was a good indicator of yield and uptake for the English soil. For the Pakistani soils, Olsen P after 45 degreesC treatment was an underestimate relative to the 10 degreesC data and for the Colombian soil it was an overestimate. The reasons for these differences need to be explored further before high temperature incubation can be used to simulate long-term changes in the field.

The role of gypsum in the reactions of phosphate with soils

The aim of this study was to examine the mechanisms by which gypsum increases the sorption of fertilizer-P in soils of and and semi-arid regions. Either gypsum or soil (Usher from the UK; pH 7.8, 7% organic matter, 21% CaCO3: Yasouj from Iran; pH 8.2, 1.4% OM, 18% CaCO3: Ghanimeh from Saudi Arabia; pH 7.8, 1% OM, 26% CaCO3, 13% gypsum) was shaken for 24 It with KH2PO4 solutions in 10 mM CaCl2. With gypsum, grinding increased sorption by a factor of about 3, and increase in pH from 5.6 to 7.5 greatly increased sorption. Scanning electron micrographs (SEM) and EDX quantitative analysis showed that small crystals of gypsum disappeared and roughly spherical particles of dicalcium phosphate (DCPD) were formed. Analysis of equilibrium Solutions showed, using GEOCHEM, that octa-calcium phosphate (OCP) coated the DCPD. For the soils, sorption was in the order Ghanimeh > Yasouj > Usher. Removal of gypsum from Ghanimeh reduced sorption, with precipitated gypsum having a greater effect than gypsum mixed physically with the soil. Addition to Usher had no effect. SEM and EDX could not be used in the soil matrix, but solubility analysis again showed that solutions were close to equilibrium with OCP. Usher was unresponsive to added gypsum, presumably because of its small sorption capacity and high organic matter content. In Ghanimeh and Yasouj soils, gypsum increased sorption by being a source of readily available Ca2+ (c) 2005 Elsevier B.V. All rights reserved.

The importance of precision in sampling sludges, biowastes and treated soils in a regulatory framework

As part of the European Commission (EC)'s revision of the Sewage Sludge Directive and the development of a Biowaste Directive, there was recognition of the difficulty of comparing data from Member States (MSs) because of differences in sampling and analytical procedures. The 'HORIZONTAL' initiative, funded by the EC and MSs, seeks to address these differences in approach and to produce standardised procedures in the form of CEN standards. This article is a preliminary investigation into aspects of the sampling of biosolids, composts and soils to which there is a history of biosolid application. The article provides information on the measurement uncertainty associated with sampling from heaps, large bags and pipes and soils in the landscape under a limited set of conditions, using sampling approaches in space and time and sample numbers based on procedures widely used in the relevant industries and when sampling similar materials. These preliminary results suggest that considerably more information is required before the appropriate sample design, optimum number of samples, number of samples comprising a composite, and temporal and spatial frequency of sampling might be recommended to achieve consistent results of a high level of precision and confidence. (C) 2004 Elsevier Ltd. All rights reserved.

Arsenate-induced phosphate release from soils and its effect on plant phosphorus

Adsorption of arsenic onto soil was investigated as a means of understanding arsenic-induced release of phosphate. In batch adsorption experiments As adsorption was accompanied by P desorption. At low As additions, the ratio As adsorbed: P desorbed remained constant. At higher As additions, P desorption reached a maximum while As adsorption continued to increase. The P desorption maximum coincided with an increase in pH. Barley plants were grown on soils spiked with arsenate (0-360 mg As kg(-1)) to investigate the effect on plant growth and P uptake. As arsenic concentration increased, above ground plant yield decreased and the plants showed symptoms typical of As toxicity and P deficiency. At low As additions to the soil, uptake of As and P by barley increased. At higher As additions P uptake decreased. It is argued that this was due to the change in As:P ratio in the soil solution. It is concluded that input of arsenic to the soil could mobilise phosphate. Crop yield is likely to be affected, either due to reduced phosphate availability at low arsenic additions or arsenic toxicity at higher additions.

Characterization and identification of mixed-metal phosphates in soils: the application, of Raman spectroscopy

The development of protocols for the identification of metal phosphates in phosphate-treated, metal-contaminated soils is a necessary yet problematical step in the validation of remediation schemes involving immobilization of metals as phosphate phases. The potential for Raman spectroscopy to be applied to the identification of these phosphates in soils has yet to be fully explored. With this in mind, a range of synthetic mixed-metal hydroxylapatites has been characterized and added to soils at known concentrations for analysis using both bulk X-ray powder diffraction (XRD) and Raman spectroscopy. Mixed-metal hydroxylapatites in the binary series Ca-Cd, Ca-Pb, Ca-Sr and Cd-Pb synthesized in the presence of acetate and carbonate ions, were characterized using a range of analytical techniques including XRD, analytical scanning electron microscopy (SEM), infrared spectroscopy (IR), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and Raman spectroscopy. Only the Ca-Cd series displays complete solid solution, although under the synthesis conditions of this study the Cd-5(PO4)(3)OH end member could not be synthesized as a pure phase. Within the Ca-Cd series the cell parameters, IR active modes and Raman active bands vary linearly as a function of Cd content. X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) suggest that the Cd is distributed across both the Ca(1) and Ca(2) sites, even at low Cd concentrations. In order to explore the likely detection limits for mixed-metal phosphates in soils for XRD and Raman spectroscopy, soils doped with mixed-metal hydroxylapatites at concentrations of 5, 1 and 0.5 wt.% were then studied. X-ray diffraction could not confirm unambiguously the presence or identity of mixed-metal phosphates in soils at concentrations below 5 wt.%. Raman spectroscopy proved a far more sensitive method for the identification of mixed-metal hydroxylapatites in soils, which could positively identify the presence of such phases in soils at all the dopant concentrations used in this study. Moreover, Raman spectroscopy could also provide an accurate assessment of the degree of chemical substitution in the hydroxylapatites even when present in soils at concentrations as low as 0.1%.

Survival, Pb-uptake and behaviour of three species of earthworm in Pb treated soils determined using an OECD-style toxicity test and a soil avoidance test

Mature (clitellate) Eisenia andrei Bouche (ultra epigeic), Lumbricus rubellus Hoffmeister (epigeic), and Aporrectodea caliginosa (Savigny) (endogeic) earthworms were placed in soils treated with Pb(NO3)(2) to have concentrations in the range 1000 to 10 000 mg Pb kg(-1). After 28 days LC50(-95%confidence limit) (+95%confidence limit) values were E. andrei 5824(-361)(+898) mg Pb kg(-1), L. rubellus 2867(-193)(+145) mg Pb kg(-1) and A. caliginosa 2747(-304)(+239) mg Pb kg(-1) and EC50s for weight change were E. andrei 2841(-68)(+150) Pb kg(-1), L. rubellus 1303(-201)(+204) mg Pb kg(-1) and A. caliginosa 1208(-206)(+212) Mg Pb kg(-1). At any given soil Pb concentration, Pb tissue concentrations after 28 days were the same for all three earthworm species. In a soil avoidance test there was no difference between the behaviour of the different species. The lower sensitivity to Pb exhibited by E. andrei is most likely due to physiological adaptations associated with the modes of life of the earthworms, and could have serious implications for the use of this earthworm as the species of choice in standard toxicological testing. (c) 2005 Elsevier Ltd. All rights reserved.