Cadmium contamination of agricultural soils and crops resulting from sphalerite weathering.

The biogeochemistry and bioavailability of cadmium, released during sphalerite weathering in soils, were investigated under contrasting agricultural scenarios to assess health risks associated with sphalerite dust transport to productive soils from mining. Laboratory experiments (365 d) on temperate and sub-tropical soils amended with sphalerite (<63 µm, 0.92 wt.% Cd) showed continuous, slow dissolution (0.6-1.2% y(-1)). Wheat grown in spiked temperate soil accumulated ≈38% (29 µmol kg(-1)) of the liberated Cd, exceeding food safety limits. In contrast, rice grown in flooded sub-tropical soil accumulated far less Cd (0.60 µmol kg(-1)) due to neutral soil pH and Cd bioavailability was possibly also controlled by secondary sulfide formation. The results demonstrate long-term release of Cd to soil porewaters during sphalerite weathering. Under oxic conditions, Cd may be sufficiently bioavailable to contaminate crops destined for human consumption; however flooded rice production limits the impact of sphalerite contamination.

Geochemistry and mineralogy of arsenic in mine wastes and stream sediments in a historic metal mining area in the UK.

Mining generates large amounts of waste which may contain potentially toxic elements (PTE), which, if released into the wider environment, can cause air, water and soil pollution long after mining operations have ceased. The fate and toxicological impact of PTEs are determined by their partitioning and speciation and in this study, the concentrations and mineralogy of arsenic in mine wastes and stream sediments in a former metal mining area of the UK are investigated. Pseudo-total (aqua-regia extractable) arsenic concentrations in all samples from the mining area exceeded background and guideline values by 1-5 orders of magnitude, with a maximum concentration in mine wastes of 1.8×10(5)mgkg(-1) As and concentrations in stream sediments of up to 2.5×10(4)mgkg(-1) As, raising concerns over potential environmental impacts. Mineralogical analysis of the wastes and sediments was undertaken by scanning electron microscopy (SEM) and automated SEM-EDS based quantitative evaluation (QEMSCAN®). The main arsenic mineral in the mine waste was scorodite and this was significantly correlated with pseudo-total As concentrations and significantly inversely correlated with potentially mobile arsenic, as estimated from the sum of exchangeable, reducible and oxidisable arsenic fractions obtained from a sequential extraction procedure; these findings correspond with the low solubility of scorodite in acidic mine wastes. The work presented shows that the study area remains grossly polluted by historical mining and processing and illustrates the value of combining mineralogical data with acid and sequential extractions to increase our understanding of potential environmental threats.

Contamination from historic metal mines and the need for non-invasive remediation techniques: a case study from Southwest England.

The UK is legally required by the EU Water Framework Directive (WFD) to improve the environmental quality of inland and coastal waters in the coming years. Historic metal mine sites are recognised as an important source of some of the elements on the WFD priority chemicals list. Despite their contamination potential, such sites are valued for their heritage and for other cultural and scientific reasons. Remediating historic mining areas to control the contamination of stream waters, whilst also preserving the integrity of the mine site, is a challenge but might be achieved by novel forms of remediation. In this study, we have carried out environmental monitoring at a historic, and culturally-sensitive, lead-silver mine site in southwest England and have undertaken a pilot experiment to investigate the potential for a novel, non-invasive remediation method at the site. Concentrations of Pb and Zn in mine spoil were clearly elevated with geometric mean concentrations of 6,888 and 710 microg g(-1), respectively. Mean concentrations of Pb in stream waters were between 21 and 54 microg l(-1), in exceedance of the WFD environmental quality standard (EQS) of 7.2 microg l(-1) (annual average). Mean Zn concentrations in water were between 30 and 97 microg l(-1), compared to the UK EQS of 66.5 microg l(-1) (average). Stream sediments within, and downstream from, the mining site were similarly elevated, indicating transport of mine waste particles into and within the stream. We undertook a simple trial to investigate the potential of hydroxyapatite, in the form of bonemeal, to passively remove the Pb and Zn, from the stream waters. After percolating through bonemeal in a leaching column, 96-99% of the dissolved Pb and Zn in stream water samples was removed.

Bioaccessible arsenic in the home environment in southwest England.

Samples of household dust and garden soil were collected from twenty households in the vicinity of an ex-mining site in southwest England and from nine households in a control village. All samples were analysed by ICP-MS for pseudo-total arsenic (As) concentrations and the results show clearly elevated levels, with maximum As concentrations of 486 microg g(-1) in housedusts and 471 microg g(-1) in garden soils (and mean concentrations of 149 microg g(-1) and 262 microg g(-1), respectively). Arsenic concentrations in all samples from the mining area exceeded the UK Soil Guideline Value (SGV) of 20 microg g(-1). No significant correlation was observed between garden soil and housedust As concentrations. Bioaccessible As concentrations were determined in a small subset of samples using the Physiologically Based Extraction Test (PBET). For the stomach phase of the PBET, bioaccessibility percentages of 10-20% were generally recorded. Higher percentages (generally 30-45%) were recorded in the intestine phases with a maximum value (for one of the housedusts) of 59%. Data from the mining area were used, together with default values for soil ingestion rates and infant body weights from the Contaminated Land Exposure Assessment (CLEA) model, to derive estimates of As intake for infants and small children (0-6 years old). Dose estimates of up to 3.53 microg kg(-1) bw day(-1) for housedusts and 2.43 microg kg(-1) bw day(-1) for garden soils were calculated, compared to the index dose used for the derivation of the SGV of 0.3 microg kg(-1) bw day(-1) (based on health risk assessments). The index dose was exceeded by 75% (18 out of 24) of the estimated As doses that were calculated for children aged 0-6 years, a group which is particularly at risk from exposure via soil and dust ingestion. The results of the present study support the concerns expressed by previous authors about the significant As contamination in southwest England and the potential implications for human health.

The influence of soil characteristics on the extractability of Cd, Pb and Zn in upland and moorland soils.

A study was undertaken to investigate the feasibility of using existing data sets of total soil metal concentrations and soil parameters, such as pH, to predict available metal concentrations on a regional or national basis. The attraction of such an approach is that it would provide valuable data for initiatives requiring information on the availability and mobility of metals in soils without the need for costly soil sampling and analysis. Ninety-seven topsoil and subsoil samples were collected from 6 soil series in a catenary sequence in north Wales to provide data for the development of an empirical model. These were analysed for total, 0.01 M CaCl2-extractable and porewater metal concentrations and for a range of soil properties including pH, solid and dissolved organic matter and cation exchange capacity. Regression analysis showed that, of the soil parameters measured, pH was the most important predictor variable for the estimation of CaCl2-extractable Cd, Pb and Zn. pH accounted for up to 86% of the variance in the proportion of 'total' metals which were extracted by CaCl2, a reagent that is commonly used to estimate plant uptake of elements. However, the relationships recorded between soil parameters and Kd (total metal/porewater metal) were much weaker, indicating that porewater metal concentrations can less readily be predicted from total soil metal concentrations and soil properties.

The solid-solution partitioning of heavy metals (Cu, Zn, Cd, Pb) in upland soils of England and Wales.

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.

Seasonal and annual variations in air concentrations of Pb, Cd and PAHs in Cairo, Egypt.

A study is presented concerning the degree and extent of air pollution by cadmium, lead and polycyclic aromatic hydrocarbons (PAHs) in atmospheric particulates of an urban area (El-Abasya) in Cairo, Egypt. The average yearly and seasonal concentrations are presented. The correlation coefficients between metals, and between metals and suspended PAHs are also reported. Statistical analysis showed seasonal and annual variations. Concentrations of PAHs, Pb and Cd were higher in winter than those measured at other times in the study area. The concentration of lead decreased by 40% from 3.36 microg(-3) in 1994 to 2.4 microg m(-3) in 1997 in consequence of the reduction of the Pb concentration in leaded gasoline fuel. The average cadmium concentrations showed significant decrease in 1997. The sum of the concentrations of PAHs was higher during the winter season 1997 (14.79 ng m(-3)) than in summer (7.53 ng m(-3)) and a highly significant difference was observed between the two seasons. In addition, the ratio of benzo(a)pyrene [B(a)P] to Pb was higher in winter than in summer, suggesting the contribution of a non-vehicular source of lead. The levels of lead observed are higher than those recorded in various other parts of the world.