Volatile transport of metals in the andesitic magmatic-hydrothermal system of White Island

<p>Volcanic gases observed at active volcanoes originate from the magma at depth. These volatiles exsolve as a result of decompression, crystallization and cooling of the silicate melt. The transport of metals in a magmatic volatile phase arises from complexation with the main volatile species, sulfur and halides. Composition of the magma, temperature, pressure and redox state have thus strong implications on metal mobility in these environments. Moreover, a variety of interactions and phase separations can affect these fluids after exsolution from the parental magma. This thesis aims at constraining the volatile transport of trace metals at White Island, a subduction-related magmatic-hydrothermal system, through a characterization and metal budget of the magmatic reservoir and the different atmospheric discharges. The metal content of the reservoir, as well as the effects of degassing and magma mixing on the magma are explored through the study of ejecta from the 1976-2000 eruptive cycle. CO₂, SO₂ and H₂O are degassing from a mafic melt at ~ 5 km depth, regularly feeding a shallower and evolved reservoir at ~ 800 m. Average contents of 164 ppm of Cu, 73 ppm of Zn, 12 ppm of Pb and 0.4 ppm of Au and Ag were detected in melt inclusions. A fraction of these metals partition into the exsolving aqueous fluid. Onset of magnetite crystallization may trigger exsolution of sulphide melt, found to contain around 30 wt% of Cu, and as much as 36 wt% Ni, 21 wt% Ag, 0.10 wt% Au in small inclusions, representing a considerable source of metals available for an aqueous fluid phase upon resorption. The volatile transport of metals is indicated by their enrichment in a variety of discharges at the surface. The hyperacidic waters of the crater lake absorb metals from the magmatic gases injected at subaqueous vents. Concentrations of ~ 12 ppm of As and Zn, 6 ppm of Cu and Pb were observed. Hydrolysis of the host rock by the reactive waters is responsible for the high cation contents of the fluids. Precipitation of secondary minerals such as silica, anhydrite, gypsum, sulfur and alunite occurs within and underneath the crater lake. The predicted speciation of metals greatly varies, dominated by CuI and FeII chloride complexes in the more reduced environment at the lake bottom, whereas CuII and FeIII are stable in the oxidized surficial waters. Arsenic is mainly present as As(OH)₃ at depth, with H₃AsO₄ dominating at the surface. Ag, Pb and Zn are complexed with chloride, and are not redox dependent. The presence of a body of molten sulfur at the bottom of the lake is indicated by sulfur spherules, both floating at the lake surface and in sediments. Pyrite crystals coat the surface of some globules, and chemical analyses reveal an enrichment in a variety of chalcophile metals (Tl, Sb, Bi, Au, As, Ag. Re, Cu). The volcanic gases emitted at fumaroles are enriched in metals compared to the magma. The effective transport of Se, Te, Sb, B, Au, As, and Bi is indicated by enrichment factors larger than 1000. In contrast, Cu is relatively depleted, suggesting deposition in the subsurface environment. Variations in composition are observed with time, mainly depending on temperature and major composition of the emissions. Values > 100 ppb of Sb, Bi, Ni, Zn, As and Se, > 10 ppb of Te, Pb, and Cu, and up to 8 ppb of Tl were recorded. Chloride is predicted to be the main ligand responsible for metal transport, even at higher temperature. The lack of thermodynamic data for complex solvated metal clusters may nevertheless bias our results. The low temperature of the studied fumaroles (maximum 192.5 °C) is in accordance with the small abundance of sulfides in the sublimates, whereas the high proportion of sulfates indicates oxidized conditions. The volcanic plume is enriched in metals such as Bi, Cd, Tl, Se, Te and Sb. The most common particles emitted are sulfates, halides, silicates, sulphuric acid and Zn ± Cu oxides. Metal emission rates are in the range of 1-10 kg/day for As, Se, Cu and Zn, 0.1-1 kg/day for Pb, Tl and Bi. Emissions of high-temperature magmatic gases are indicated by elevated SO₂/HCl ratio and the presence of Au in the particulate phase. Mass balance calculations in White Island magmatic-hydrothermal system indicate a segregation of around 4900 tons of copper per year, either accumulated from a dense brine at ~ 500 m depth, or deposited by low-density vapors on their way to the surface. Metal-rich sulfide blebs trapped in phenocrysts may also retain Cu at depth. These results thus reinforce the belief that White Island is an actively forming porphyry copper deposit.</p>

Volatile transport of metals in the andesitic magmatic-hydrothermal system of White Island

<p>Volcanic gases observed at active volcanoes originate from the magma at depth. These volatiles exsolve as a result of decompression, crystallization and cooling of the silicate melt. The transport of metals in a magmatic volatile phase arises from complexation with the main volatile species, sulfur and halides. Composition of the magma, temperature, pressure and redox state have thus strong implications on metal mobility in these environments. Moreover, a variety of interactions and phase separations can affect these fluids after exsolution from the parental magma. This thesis aims at constraining the volatile transport of trace metals at White Island, a subduction-related magmatic-hydrothermal system, through a characterization and metal budget of the magmatic reservoir and the different atmospheric discharges. The metal content of the reservoir, as well as the effects of degassing and magma mixing on the magma are explored through the study of ejecta from the 1976-2000 eruptive cycle. CO₂, SO₂ and H₂O are degassing from a mafic melt at ~ 5 km depth, regularly feeding a shallower and evolved reservoir at ~ 800 m. Average contents of 164 ppm of Cu, 73 ppm of Zn, 12 ppm of Pb and 0.4 ppm of Au and Ag were detected in melt inclusions. A fraction of these metals partition into the exsolving aqueous fluid. Onset of magnetite crystallization may trigger exsolution of sulphide melt, found to contain around 30 wt% of Cu, and as much as 36 wt% Ni, 21 wt% Ag, 0.10 wt% Au in small inclusions, representing a considerable source of metals available for an aqueous fluid phase upon resorption. The volatile transport of metals is indicated by their enrichment in a variety of discharges at the surface. The hyperacidic waters of the crater lake absorb metals from the magmatic gases injected at subaqueous vents. Concentrations of ~ 12 ppm of As and Zn, 6 ppm of Cu and Pb were observed. Hydrolysis of the host rock by the reactive waters is responsible for the high cation contents of the fluids. Precipitation of secondary minerals such as silica, anhydrite, gypsum, sulfur and alunite occurs within and underneath the crater lake. The predicted speciation of metals greatly varies, dominated by CuI and FeII chloride complexes in the more reduced environment at the lake bottom, whereas CuII and FeIII are stable in the oxidized surficial waters. Arsenic is mainly present as As(OH)₃ at depth, with H₃AsO₄ dominating at the surface. Ag, Pb and Zn are complexed with chloride, and are not redox dependent. The presence of a body of molten sulfur at the bottom of the lake is indicated by sulfur spherules, both floating at the lake surface and in sediments. Pyrite crystals coat the surface of some globules, and chemical analyses reveal an enrichment in a variety of chalcophile metals (Tl, Sb, Bi, Au, As, Ag. Re, Cu). The volcanic gases emitted at fumaroles are enriched in metals compared to the magma. The effective transport of Se, Te, Sb, B, Au, As, and Bi is indicated by enrichment factors larger than 1000. In contrast, Cu is relatively depleted, suggesting deposition in the subsurface environment. Variations in composition are observed with time, mainly depending on temperature and major composition of the emissions. Values > 100 ppb of Sb, Bi, Ni, Zn, As and Se, > 10 ppb of Te, Pb, and Cu, and up to 8 ppb of Tl were recorded. Chloride is predicted to be the main ligand responsible for metal transport, even at higher temperature. The lack of thermodynamic data for complex solvated metal clusters may nevertheless bias our results. The low temperature of the studied fumaroles (maximum 192.5 °C) is in accordance with the small abundance of sulfides in the sublimates, whereas the high proportion of sulfates indicates oxidized conditions. The volcanic plume is enriched in metals such as Bi, Cd, Tl, Se, Te and Sb. The most common particles emitted are sulfates, halides, silicates, sulphuric acid and Zn ± Cu oxides. Metal emission rates are in the range of 1-10 kg/day for As, Se, Cu and Zn, 0.1-1 kg/day for Pb, Tl and Bi. Emissions of high-temperature magmatic gases are indicated by elevated SO₂/HCl ratio and the presence of Au in the particulate phase. Mass balance calculations in White Island magmatic-hydrothermal system indicate a segregation of around 4900 tons of copper per year, either accumulated from a dense brine at ~ 500 m depth, or deposited by low-density vapors on their way to the surface. Metal-rich sulfide blebs trapped in phenocrysts may also retain Cu at depth. These results thus reinforce the belief that White Island is an actively forming porphyry copper deposit.</p>

Monitoring Potentially Toxic Element Pollution in Three Wheat-Grown Areas with a Long History of Industrial Activity and Assessment of Their Effect on Human Health in Central Greece

Agricultural lands, especially those where wheat is cultivated, in the vicinity of intense anthropogenic activities may be laden with potentially toxic elements (PTEs), resulting in increased risk for human health. In this study we monitored three regions located in central Greece, currently cultivated with wheat: Domokos and Eretria, two areas with abandoned chromium mines, but never studied before, and the industrial area of Volos, near a major steel factory. All soils were alkaline with medium CaCO3 content. As expected, Cr was extremely high in the first two areas (705.2 in Eretria and 777.5 mg kg−1 in Domokos); Ni was also found elevated (1227 in Eretria, 1315 in Domokos and 257.6 mg kg−1 in the steel factory), while other harmful metals (Cd, Cu, Pb and Zn) were rather low. As a result, pollution load index, a cumulative index showing the contamination level of an area, was higher than 1.0 in all three areas (Eretria = 2.20, Domokos = 2.28, and steel factory = 1.61), indicating high contamination and anthropogenic inputs. As for the wheat parts (shoots and grains), they were found to have no elevated concentrations of any of the measured metals in all three study areas, probably due to the alkaline soil pH that decelerates metal mobility. This was also confirmed by the very low soil-to-plant transfer coefficient values for all metals. In assessing the possible risk concerning human health, we found that the soil-to-human pathway would induce no significant risk (exhibited by hazard index of less than 1.0), while the risk from grain-to-human resulted in considerable risk for human health in the steel factory of Volos (where HI > 1.0). Our findings suggest that rural areas never studied before with a history in some offensive anthropogenic activity can prove to be a contamination hotspot; we regard this study as a pivotal for similarly never-visited-before areas casually cultivated with wheat (or other important crops for human nutrition). We further recognize the need for a more in-depth study that would acknowledge the geochemical speciation of the studied metals and also monitor other important crops and their possible uptake of PTEs.

Brassica Species in Phytoextractions: Real Potentials and Challenges

The genus Brassica is recognized for including species with phytoaccumulation potential and a large amount of research has been carried out in this area under a variety of conditions, from laboratory experiments to field trials, with spiked or naturally contaminated soils, using one- or multi-element contaminated soil, generating various and sometimes contradictory results with limited practical applications. To date, the actual field potential of Brassica species and the feasibility of a complete phytoextraction process have not been fully evaluated. Therefore, the aim of this study was to summarize the results of the experiments that have been performed with a view to analyzing real potentials and limitations. The reduced biomass and low metal mobility in the soil have been addressed by the development of chemically or biologically assisted phytoremediation technologies, the use of soil amendments, and the application of crop management strategies. Certain issues, such as the fate of harvested biomass or the performance of species in multi-metal-contaminated soils, remain to be solved by future research. Potential improvements to current experimental settings include testing species grown to full maturity, using a greater amount of soil in experiments, conducting more trials under real field conditions, developing improved crop management systems, and optimizing solutions for harvested biomass disposal.

The Possibility of Using Paulownia elongata S. Y. Hu × Paulownia fortunei Hybrid for Phytoextraction of Toxic Elements from Post-Industrial Wastes with Biochar

The potential of the Paulownia hybrid for the uptake and transport of 67 elements along with the physiological response of plants cultivated in highly contaminated post-industrial wastes (flotation tailings—FT, and mining sludge—MS) was investigated. Biochar (BR) was added to substrates to limit metal mobility and facilitate plant survival. Paulownia could effectively uptake and translocate B, Ca, K, P, Rb, Re and Ta. Despite severe growth retardation, chlorophyll biosynthesis was not depleted, while an increased carotenoid content was noted for plants cultivated in waste materials. In Paulownia leaves and roots hydroxybenzoic acids (C6-C1) were dominant phenolics, and hydroxycinnamic acids/phenylpropanoids (C6-C3) and flavonoids (C6-C3-C6) were also detected. Plant cultivation in wastes resulted in quantitative changes in the phenolic fraction, and a significant drop or total inhibition of particular phenolics. Cultivation in waste materials resulted in increased biosynthesis of malic and succinic acids in the roots of FT-cultivated plants, and malic and acetic acids in the case of MS/BR substrate. The obtained results indicate that the addition of biochar can support the adaptation of Paulownia seedlings growing on MS, however, in order to limit unfavorable changes in the plant, an optimal addition of waste is necessary.

Soil organic carbon mobility in equatorial podzols: soil column experiments

Transfer of organic carbon from topsoil horizons to deeper horizons and to the water table is still little documented, in particular in equatorial environments, despite the high primary productivity of the evergreen forest. Due to its complexing capacity, organic carbon also plays a key role in the transfer of metals in the soil profile and, therefore, in pedogenesis and for metal mobility. Here we focus on equatorial podzols, which are known to play an important role in carbon cycling. We carried out soil column experiments using soil material and percolating solution sampled in an Amazonian podzol area in order to better constrain the conditions of the transfer of organic carbon at depth. The dissolved organic matter (DOM) produced in the topsoil was not able to percolate through the clayey, kaolinitic material from the deep horizons and was retained in it. When it previously percolated through the Bh material, there was production of fulvic-like, protein-like compounds and small carboxylic acids able to percolate through the clayey material and increase the mobility of Al, Fe and Si. Podzolic processes in the Bh can, therefore, produce a DOM likely to be transferred to the deep water table, playing a role in the carbon balances at the profile scale and, owing to its complexing capacity, playing a role in deep horizon pedogenesis and weathering. The order of magnitude of carbon concentration in the solution percolating at depth was around 1.5–2.5 mg L−1. Our findings reveal a fundamental mechanism that favors the formation of very thick kaolinitic saprolites.

Sorption studies of Cd and Cu on Brazilian alluvial soils

The Local Production Arrangement, located in the Pernambuco’s Agreste state, has been significantly developing the region's economy. Despite its importance, industrial activity has caused relevant environmental concerns regarding the disposal of textile effluents, especially from industrial laundries. This waste is made up of many chemicals, and among them are various types of heavy metals. The evaluation of the sorption behavior of contaminant transport mechanisms such as heavy metals is essential to assess the risk of contamination of alluvial aquifers. This study evaluated the sorption of heavy metals (Cu and Cd) in an alluvial sediment deposit in the Capibaribe River. Kinetics and isotherm experiments allowed the analyses of Cu and Cd sorption. Kinetics sorption showed an equilibrium tendency after 16 h for Cu and 18 h for Cd and was better described by a pseudo-second order model. The isotherm data were adjusted to the Linear, Freundlich and Langmuir models. Both linear and Freundlich models satisfactorily described sorption isotherms for the two pollutants. The metals in the study represent a risk of contamination of the groundwater of alluvial aquifers, mainly due to physicochemical attributes of the soil, such as high sand content (85%), low MO (2.1 g kg-1) and alkaline pH (8.2). The environmental conditions decrease absorption and facilitate metal mobility, greatly increasing the environmental risks inherent in pollutant leaching. Cu showed a higher affinity with the soil studied in all assays performed compared with the results of the tests for Cd.