Selenium cycling in volcanic environments: the role of soils as reactive interfaces

Selenium (Se) is an element with important health implications that is emitted in significant amounts from volcanoes. Attracted by the fertility of volcanic soils, around 10% of the world population lives within 100 km of an active volcano. Nevertheless, the behaviour of Se in volcanic environments is poorly understood. Therefore, the main aim of this thesis is to investigate the role of soils in the Se cycling in volcanic environments. Prior to the geochemical studies, precise and accurate methods for the determination of Se contents, speciation and isotopic signatures were developed. Afterwards, a combination of field studies and lab controlled experiments were performed with soils from two contrasting European volcanic settings: Mount Etna in Sicily (Italy) and Mount Teide in Tenerife (Spain). The results showed a strong link between Se behaviour and soil development, indicating that Se mobility in volcanic soils is controlled by sorption processes and soil mineralogy.

Trace elements biogeochemistry in high mountain lake catchments: identifying anthropogenic versus natural components from the atmospheric contamination legacy in remote natural areas

Human activities have been interfering with the natural biogeochemical cycles of trace elements since the ancient civilizations. Although they are inaccessible and remote, high mountain lake catchments are irrefutably trace-element contaminated by anthropogenic emissions, which can travel by long-range atmospheric transport before they are deposited. This has been revealed by several natural archives. High mountain lake catchments are thus excellent sentinels of long-range contamination. Continuous accumulation can lead to a build up of potentially toxic trace elements in these remote, or relatively remote, ecosystems. The thesis focuses on the biogeochemistry of a suite of trace elements of environmental concern (Ni, Cu, Zn, As, Se, Cd and Pb) in Pyrenean lake catchments, with special emphasis on discerning the “natural” components from the “anthropogenic” contributions. Five other metallic elements (Al, Fe, Ti, Mn and Zr) have also been studied to trace natural fluxes and biogeochemical processes within the lake catchment systems.

Lagrangian analysis of low level anthropogenic plume processing across the North Atlantic

The photochemical evolution of an anthropogenic plume from the New-York/Boston region during its transport at low altitudes over the North Atlantic to the European west coast has been studied using a Lagrangian framework. This plume, originally strongly polluted, was sampled by research aircraft just off the North American east coast on 3 successive days, and 3 days downwind off the west coast of Ireland where another aircraft re-sampled a weakly polluted plume. Changes in trace gas concentrations during transport were reproduced using a photochemical trajectory model including deposition and mixing effects. Chemical and wet deposition processing dominated the evolution of all pollutants in the plume. The mean net O3 production was evaluated to be -5 ppbv/day leading to low values of O3 by the time the plume reached Europe. Wet deposition of nitric acid was responsible for an 80% reduction in this O3 production. If the plume had not encountered precipitation, it would have reached the Europe with O3 levels up to 80-90 ppbv, and CO levels between 120 and 140 ppbv. Photochemical destruction also played a more important role than mixing in the evolution of plume CO due to high levels of both O3 and water vapour showing that CO cannot always be used as a tracer for polluted air masses, especially for plumes transported at low altitudes. The results also show that, in this case, an important increase in the O3/CO slope can be attributed to chemical destruction of CO and not to photochemical O3 production as is often assumed.

Vertical structure of anthropogenic zonal-mean atmospheric circulation change

The atmospheric circulation changes predicted by climate models are often described using sea level pressure, which generally shows a strengthening of the mid-latitude westerlies. Recent observed variability is dominated by the Northern Annular Mode (NAM) which is equivalent barotropic, so that wind variations of the same sign are seen at all levels. However, in model predictions of the response to anthropogenic forcing, there is a well-known enhanced warming at low levels over the northern polar cap in winter. This means that there is a strong baroclinic component to the response. The projection of the response onto a NAM-like zonal index varies with height. While at the surface most models project positively onto the zonal index, throughout most of the depth of the troposphere many of the models give negative projections. The response to anthropogenic forcing therefore has a distinctive baroclinic signature which is very different to the NAM

Anthropogenic snowfall events in the UK: examples of urban weather modification?

Snow in the UK is generally associated with synoptic or mesoscale weather systems, thus snowfall during quiescent anticyclonic conditions is surprising and might not even be forecast. Consequently it could present a hazard. Snowfall during anticyclonic freezing fog conditions at Didcot and Hereford in December 2006 is investigated here. These two snowfalls seem to present circumstances in which anthropogenically-produced aerosols could have provided ice nuclei within the freezing fog, and therefore might provide characteristic examples of Anthropogenic Snowfall Events (ASEs).

Biological and chemical assessment of zinc ageing in field soils

As zinc (Zn) is both an essential trace element and potential toxicant, the effects of Zn fixation in soil are of practical significance. Soil samples from four field sites amended with ZnSO4 were used to investigate ageing of soluble Zn under field conditions over a 2-year period. Lability of Zn measured using 65Zn radioisotope dilution showed a significant decrease over time and hence evidence of Zn fixation in three of the four soils. However, 0.01 M CaCl2 extractions and toxicity measurements using a genetically modified lux-marked bacterial biosensor did not indicate a decrease in soluble/bioavailable Zn over time. This was attributed to the strong regulatory effect of abiotic properties such as pH on these latter measurements. These results also showed that Zn ageing occurred immediately after Zn spiking, emphasising the need to incubate freshly spiked soils before ecotoxicity assessments. Ageing effects were detected in Zn-amended field soils using 65Zn isotopic dilution as a measure of lability, but not with either CaCl2 extractions or a lux-marked bacterial biosensor.

Calcium carbonate solubilization through H-proton release from some legumes grown in calcareous saline-sodic soils

Increasing levels of CO2 and H+ proton in the rhizosphere from some legumes may play an important role in calcite dissolution of calcareous salt affected soils. Soils planted with white and brown varieties of cowpea (Vigna unguiculata L.) and hyacinth bean (Dolichos lablab L.) relying on either fertilizer N (KNO3) or N-fixation were compared against soils to which gypsum was applied and a control without plants and gypsum application to study the possibility of Ca2+ release from calcite and Na+ leaching. As compared to plants relying on inorganic N, leachates from all pore volumes (0·5, 1·0, 1·5, 2·0 pore volume) in lysimeters planted with N-fixing hyacinth bean contained significantly higher concentrations of HCO with lower concentrations from lysimeters planted with white cowpea relying on N-fixation. However, the lowest concentrations of HCO were recorded in the gypsum and control treatments. In initial leaching, lysimeters planted with N-fixing plants maintained similar leachate Ca2+ and Na+ concentrations compared to gypsum amended soils. However, gypsum amended soils were found to have a prolonged positive effect on Na+ removal. It might be concluded that some legumes that are known to fix N in calcareous salt affected soils may be an alternative ameliorant to the extremely expensive gypsum through calcite solubilization and a consequent release of Ca2+.

The effect of organic materials on the mobility and toxicity of metals in contaminated soils

Organic materials such as compost are often proposed as suitable materials for the remediation of contaminated brownfield sites intended for soft end-use. In addition to vitalising the soil, they are also believed to immobilise metals thereby breaking contaminant-receptor pathways and reducing the ecotoxicity of the contaminants. However, some research has demonstrated contradictory effects between composts on metal immobilisation. In the present study, four different composts and a liming product containing organic matter (LimeX70) were tested to examine both their metal retention and toxicity reduction capabilities on three different metal contaminated soils. Leaching tests, a plant growth test with Greek cress (Lepidium sativum), an earthworm (Eisenia fetida) survival and condition test and a bacterial toxicity test using Vibrio fischeri were carried out. The leaching test results showed that spent mushroom compost caused an increase in metal concentration in the leachates, while LimeX70 caused a decrease. The variation in behaviour between different amendments for each soil was high, so a generic conclusion could not be drawn. Toxicity tests showed significant reduction of metal bioavailability and toxicity for Greek cress, earthworms and bacteria. The results also suggest that more research should be undertaken to understand the mechanisms involved in metal complexation using different types of organic matter, in order to optimise the use of organic materials like compost for soil remediation. Crown Copyright (C) 2007 Published by Elsevier Ltd. All rights reserved.

Field trials to assess the uptake of arsenic by vegetables from contaminated soils and soil remediation with iron oxides

The uptake of arsenic (As) by plants from contaminated soils presents a health hazard that may affect the use of agricultural and former industrial land. Methods for limiting the hazard are desirable. A proposed remediation treatment comprises the precipitation of iron (Fe) oxides in the contaminated soil by adding ferrous sulfate and lime. The effects on As bioavailability were assessed using a range of vegetable crops grown in the field. Four UK locations were used, where soil was contaminated by As from different sources. At the most contaminated site, a clay loam containing a mean of 748 mg As kg(-1) soil, beetroot, calabrese, cauliflower, lettuce, potato, radish and spinach were grown. For all crops except spinach, ferrous sulfate treatment caused a significant reduction in the bioavailability of As in some part of the crop. Application of ferrous sulfate in solution, providing 0.2% Fe oxides in the soil (0-10 cm), reduced As uptake by a mean of 22%. Solid ferrous sulfate was applied to give concentrations of 0.5% and 1% Fe oxides: the 0.5% concentration reduced As uptake by a mean of 32% and the 1% concentration gave no significant additional benefit. On a sandy loam containing 65 mg As kg(-1) soil, there was tentative evidence that ferrous sulfate treatment up to 2% Fe oxides caused a significant reduction in lettuce As, but calabrese did not respond. At the other two sites, the effects of ferrous sulfate treatment were not significant, but the uptake of soil As was low in treated and untreated soils. Differences between sites in the bioavailable fraction of soil As may be related to the soil texture or the source of As. The highest bioavailability was found on the soil which had been contaminated by aerial deposition and had a high sand content. (C) 2003 Elsevier Science B.V. All rights reserved.

The release of silicon from amorphous silica and rice straw in Sri Lankan soils

Silicon release from rice straw and amorphous silica when shaken in solution with five Sri Lankan soils was studied indirectly using sorption isotherms and changes in concentration and directly using straw in dialysis bags examined using electron microscopy. The aim was to further our understanding of the processes and factors affecting the release of straw-Si in soils and its availability to rice. The soils (alfisols and ultisols) shaken with 0.1 M NaCl (5 g per 125 mL for 250 days) produced concentrations of 1 - 4 mg L-1 of monosilicic acid-Si. Amorphous silica added to these suspensions (36.5 mg, containing 17 mg Si) raised the concentrations to 20 - 40 mg L-1, and added rice straw (0.5 g, containing 17 mg Si) gave 10 - 25 mg L-1. Sorption isotherms (7 days equilibrations) were used to calculate from the concentrations the amounts of Si released ( 24 - 38% and 8 - 21%, respectively). Both materials gave about 40 mg L-1 of monosilicic acid-Si plus 30 mg L-1 of disilicic acid-Si when shaken in solution alone (5 g per 125 mL). Straw in dialysis bags ( 0.5 g per 25 mL in 0.1 M NaCl) was shaken in soil suspension ( 5 g per 100 mL) for 60 days. Similar concentrations and releases were measured to those obtained above. About one fifth of the mass of straw was lost by decomposition in the first 15 days. A chloroform treatment prevented decomposition, but Si release was unaffected. Disintegration continued throughout the experiments, with phytoliths being exposed and dissolved. Compared to the rate of release from straw into solution without soil, the release of Si into soil suspensions was increased during the first 20 days by adsorption on the soil, but was then reduced probably through the effect of Fe and Al on the phytolith surfaces. The extent of this blocking effect varied between soils and was not simply related to soil pH.

The solubility of gypsum in calcareous soils

Three gypsiferous-calcareous soils from the Al-Hassa Oasis in Saudi Arabia were examined to determine the conditions under which dissolution of gypsum could be hindered by the formation of coatings of calcite during leaching. Batch extraction with water of a sandy clay loam, a sandy clay and a sandy loam containing 40, 26 and 5% gypsum and 14, 12 and 13% calcite respectively was followed by chemical analysis of the extracts, SEM examination and XRD and EDX microprobe analysis. Extraction in closed centrifuge tubes for I h or 5 h showed that initially gypsum dissolved to give solutions near to equilibrium but then in the sandy clay loam, between one quarter and one third of the gypsum could not dissolve. In the sandy clay about one fifth of the gypsum could not dissolve with none remaining in the sandy loam. All the extracts were close to equilibrium with calcite. SEM and EDX examination showed that coatings of calcite had formed on the gypsum particles. The sandy clay loam was also extracted using an open system in which either air or air +1% CO2 was bubbled through the suspensions for 1 h with stirring. The gypsum dissolved more rapidly and all of the gypsum dissolved. Thus, where the rate of dissolution of gypsum was rapid, calcite did not manage to cover the gypsum surfaces probably because the surface was being continuously removed. Slower leaching conditions in the field are likely to be conducive to the formation of coatings and less dissolution of gypsum. (c) 2006 Elsevier B.V. All rights reserved.

Factors affecting potassium leaching in different soils

A set of lysimeter based experiments was carried out during 2000/01 to evaluate the impact of soil type and grassland management on potassium (K) leaching. The effects of (1) four soil textures (sand, loam, loam over chalk and clay), (2) grazing and cutting (with farmyard manure application), and (3) K applied as inorganic fertilizer, dairy slurry or a mixture of both sources were tested. Total K losses in the clay soil were more than twice those in the sand soil (13 and 6 kg K ha(-1), respectively) because of the development of preferential flow in the clay soil. They were also greater in the cut treatment than in the grazed treatment (82 and 51 kg K ha(-1), respectively; P less than or equal to0.01), associated with a 63% increase of K concentration in the leachates from the former (6.7 +/- 0.28 and 4.1 +/- 0.22 mg K L-1 for cut and grazed, respectively; P less than or equal to0.01) because of the K input from the farmyard manure. The source of fertilizer did not affect total K losses or the average K concentration in the leachates (P >0.05), but it changed the pattern of these over time.

Accumulated metal speciation in earthworm populations with multi-generational exposure to metalliferous soils: cell fractionation and high energy synchrotron analyses

Predicting metal bioaccumulation and toxicity in soil organisms is complicated by site-specific biotic and abiotic parameters. In this study we exploited tissue fractionation and digestion techniques, combined with X-ray absorption spectroscopy (XAS), to investigate the whole-body and subcellular distributions, ligand affinities, and coordination chemistry of accumulated Pb and Zn in field populations of the epigeic earthworm Lumbricus rubellus inhabiting three contrasting metalliferous and two unpolluted soils. Our main findings were (i) earthworms were resident in soils with concentrations of Pb and Zn ranging from 1200 to 27 000 mg kg(-1) and 200 to 34 000 mg kg(-1), respectively; (ii) Pb and Zn primarily accumulated in the posterior alimentary canal in nonsoluble subcellular fractions of earthworms; (iii) site-specific differences in the tissue and subcellular partitioning profiles of populations were observed, with earthworms from a calcareous site partitioning proportionally more Pb to their anterior body segments and Zn to the chloragosome-rich subcellular fraction than their acidic-soil inhabiting counterparts; (iv) XAS indicated that the interpopulation differences in metal partitioning between organs were not accompanied by qualitative differences in ligand-binding speciation, because crystalline phosphate-containing pyromorphite was a predominant chemical species in the whole-worm tissues of all mine soil residents. Differences in metal (Pb, Zn) partitioning at both organ and cellular levels displayed by field populations with protracted histories of metal exposures may reflect their innate ecophysiological responses to essential edaphic variables, such as Ca2+ status. These observations are highly significant in the challenging exercise of interpreting holistic biomarker data delivered by "omic" technologies.

Influence of time on the plant availability of Cd, Ni and Zn after sewage sludge has been applied to soils

A pot experiment was conducted to test the hypothesis that decomposition of organic matter in sewage sludge and the consequent formation of dissolved organic compounds (DOC) would lead to an increase in the bioavailability of the heavy metals. Two Brown Earth soils, one with clayey loam texture (CL) and the other a loamy sand (LS) were mixed with sewage sludge at rates equivalent to 0, 10 and 50 1 dry sludge ha(-1) and the pots were sown with ryegrass (Lolium perenne L.). The organic matter content and heavy metal availability assessed with soil extractions with 0.05 M CaCl2 were monitored over a residual time of two years, while plant uptake over one year, after addition of the sludge. It was found that the concentrations of Cd and Ni in both the ryegrass and the soil extracts increased slightly but significantly during the first year. In most cases, this increase was most evident especially at the higher sludge application rate (50 t ha(-1)). However, in the second year metal availability reached a plateau. Zinc concentrations in the ryegrass did not show an increase but the CaCl2 extracts increased during the first year. In contrast, organic matter content decreased rapidly in the first months of the first year and much more slowly in the second (total decrease of 16%). The concentrations of DOC increased significantly in the more organic rich CL soil in the course of two years. The pattern followed by the decomposition of organic matter with time and the production of DOC may provide at least a partial explanation for trend towards increased metal availability.