The industrial port of Richards Bay on the eastern seaboard of KwaZulu-Natal, South Africa has undergone rapid growth over the last 25 years. This industrial growth has inevitably led to an increase in the anthropogenic pollutant inputs in the area. However, the degree of this contamination has not previously been assessed not been accompanied by an awareness of its environmental impacts. This project serves to assess the current environmental situation of the area and provide background levels against which the environmental impacts of further growth in the area can be assessed. The main pollution point sources in the area were identified as a pulp and paper plant, a sulfuric acid/fertiliser plant and aluminium smelters. The chemical and physical processes involved within these industries were identified and discussed in detail. The common inorganic pollutants emitted by these industries were identifies as trace metals, sulfur dioxide, NOx gases and fluoride. It was these pollutants that therefore became the focus of this study. Reservoirs within Richards Bay that may become sinks for contamination were identified and water, sediment and soil samples were taken from these reservoirs. The samples were analysed for trace metal contamination, pH, alkalinity and fluoride levels. Analysis of the acidity and alkalinity of water, sediment and soils samples demonstrated that there is presently no long-term acidification of the environment in Richards Bay. The only samples that showed increased acidity were the soils taken from the roadside sites immediately outside the industries. This lack of overall acidification indicates that, at present, there are no detrimental effects of acidic emissions on the hydrosphere and geosphere. Only cursory investigations were conducted into the fluoride levels found in water samples. None of the samples analysed demonstrated detectable amounts of fluoride present. Comprehensive trace metal analyses were performed on the water, sediment and soil samples through the use of ICP-AES. Levels obtained were compared with levels from samples taken from relatively uncontaminated background sites. Trace metal analysis indicated contamination of the freshwater reservoirs when compared with the background, while the soils and saltwater reservoirs remain largely uncontaminated. However, the contaminated areas did not show levels greater than quality guideline concentrations. Further studies should be conducted with regards to the trace metal contamination of the biosphere and the bioavailability of the contaminants already present in the waters, sediments and soils. More detailed investigations should also be conducted into the levels of atmospheric pollutants and fluoride levels in all reservoirs. / Thesis (M.Sc.) - University of KwaZulu-Natal, Pietermaritzburg, 2004.

The origin of compositional gaps in volcanic deposits remains controversial. In Akaroa Volcano (9.6 to 8.6 Ma), New Zealand, a dramatic compositional gap exists between basaltic and trachytic magmas. Previously, the formation of more evolved magmas has been ascribed to crustal melting. However, the interpretation of new major and trace element analysis from minerals and bulk-rocks coupled with the mechanics of crystal-liquid separation offers an alternative explanation that alleviates the thermal restrictions required for crustal melting models. In a two-stage model, major and trace element trends can be reproduced by polybaric crystal fractionation from dry melts (less than 0.5 wt.% H2O) at the QFM buffer. In the first stage, picritic basalts are separated from an olivine-pyroxene dominant mush near the crust-mantle boundary (9 to 10 kbar). Ascending magmas stagnated at mid-crustal levels (5 to 6 kbar) and fractionated an olivine-plagioclase assemblage to produce the alkali basalt-hawaiite trend. In the second stage, trachyte melt is extracted from a crystal mush of hawaiite to mugearite composition at mid-to-upper crustal levels (3 to 5 kbar) after the melt has crystallised 50 vol.%. The fractionated assemblage of plagioclase, olivine, clinopyroxene, magnetite, and apatite is left in a cumulate residue which corresponds to the mineral assemblage of sampled ultramafic enclaves. The results of trace element modelling of Rayleigh fractionation using this extraction window is in close agreement with the concentrations measured in trachyte (= liquid) and enclaves (= cumulate residue). The compositional gap observed in the bulk-rock data of eruptive products is not recorded in the feldspar data, which show a complete solid solution from basalt and co-magmatic enclaves to trachyte. Complexly zoned plagioclases further suggest episodical magma recharge events of hotter, more mafic magmas, which lead to vigorous convection and magma mixing. In summary, these models indicate that the Daly Gap of Akaroa Volcano formed by punctuated melt extraction from a crystal mush at the brittle-ductile transition.

Volatile elements released from the subducting slab play a fundamental role during the formation of arc magmas in the mantle wedge. Advances of melt inclusion studies enlarged the data on volatile abundance in arc magmas, and it is now possible to characterize some volatile contents in arc primary magmas, in particular F and Cl. A recent study of Mt Shasta melt inclusions (LeVoyer et al., 2010) shows that fractionation of F and Cl potentially contains information about arc magma genesis. In order to trace the source of arc magmas, fluorine and chlorine partitioning was investigated. Here, I present new experimental determinations of Cl and F partition coefficients between dry and hydrous silicate melts and mantle minerals: olivine, orthopyroxene, clinopyroxene, plagioclase, garnet and also pargasite and phlogopite. The values were compiled from more than 300 measurements in 24 melting experiments, conducted between 8 and 25 kbars and between 1180 and 1430˚C. The low abundance F, Cl measurements in minerals were done by Cameca IMF 1280 at WHOI using the negative secondary ion mode. The results show that DOpx/meltF ranges from 0.123 to 0.021 and DCpx/meltF ranges from 0.153 to 0.083, while Cl partition coefficient varies from DOpx/meltCl from 0.002 to 0.069 and DCpx/meltCfrom 0.008 to 0.015, as well. Furthermore, DOl/meltF ranges from 0.116 to 0.005 and DOl/meltCl from 0.001 to 0.004; DGrt/meltF ranges from 0.012 to 0.166 and DGrt/meltCl from 0.003 to 0.087 with the increasing water amount and decreasing temperature. I also show that F is compatible in phlogopite DPhl/meltF > 1.2) while DAmp/meltF is incompatible in pargasite DAmp/meltF from 0.36 to 0.63). On the contrary, Cl is more incompatible in phlogopite (DPhl/meltCl > 1.2 on average 0.09 ± 0.02), than in pargasite (DPhl/meltCl from 0.12 to 0.38). This study demonstrates that F and Cl are substituted in specific oxygen site in minerals that lead then to be more sensitive than trace elements to crystal chemistry and water amount variations thus melting conditions. Using those new partition coefficients, I modelled melting of potential sub-arc lithologies with variable quantity aqueous-fluid. This model is able to decipher 1) amount of aqueous-fluid involved in melting, 2) melting induced by fluid or melting of an hydrous mineral-bearing source and 3) melting of either pargasite-bearing lithology or phlogopite-bearing lithology and shows that sources of some primitive melts, for instance from Italy, bear pargasite and phlogopite, while some primitve melts seem to be the results of fluid-induced melts.

[Truncated abstract] Fire creates charcoal from the partial burning of biomass which results in a biologically inert form of carbonaceous (non-living) organic matter that, once integrated into soil and sediments, can persist for long periods of time. Charcoal has a large surface area with a high sorptive capacity for organic and inorganic substances. As a repository for metal and non-metal elements charcoal has been given little, if any, attention in the fields of geochemistry, agriculture and environmental monitoring . . . Despite the differences in charcoal surface area, soil charcoal achieved nearly 100% sorption of 0.5 and 5 μg/g Au from 0.03 M NaCl and 0.01M Ca(NO3)2 solution, almost independent of solution pH. At low pH, charcoal sorbed between 10 and 60% of Cu with initial additions of 2 and 20 μg Cu/g. Similarly, between 15 and 40% of Zn was sorbed by charcoal with initial additions of 5 and 40 μg Zn/g. The role of surface area in sorption of elements by charcoal is clearly only one factor that is important. Charcoal aromatic and aliphatic chemical functional groups, which can be distinguished from other forms of organic matter through spectroscopic determination, are also important in charcoal’s capacity to sorb elements. Accumulation of Be, B, Na, Mg, Al, Si, K, Ca, Ti, Mn, Co, Ni, Cu, Se, Mo, Ba, Au and Pb (out of a range of 29 elements) in soil charcoal, above the concentrations in the matrix soil and plant reference charcoal, was confirmed by ICP-MS analysis. Concentrations of V, Mn, Co, Ni, Cu, Mo, Ba, Au, Pb and Bi were higher in soil charcoal than in values quoted for gossans and pisolites in the field area region (Smith and Perdrix, 1983). Higher values of Au in soil charcoal were associated with considerable amounts of included clay minerals and higher values of other elements including Mo, Mn and Fe.

[Tuncated abstract] Soil is a relatively low cost and robust geochemical sampling medium and is an essential part of most mineral exploration programs. In areas of covered terrain, however, soils are less reliable as a sampling medium because they do not always develop the geochemical signature of the buried mineralisation; possibly a result of limited upward transport of ore related elements into the surficial overburden. As economic demands on the resources industry grow, mineral exploration continues to expand further into areas of covered terrain where the rewards of finding a new deposit relative to the risks of finding it may be comparatively low. Thus, improving the costeffectiveness of a geochemical exploration program requires a sound understanding of the mechanisms by which soil geochemical anomalies form in transported overburden. This thesis examines the deep biotic uplift of ore related elements by deep rooting vegetation as a mechanism for the development of soil geochemical anomalies within transported overburdens, in semi-arid and arid regions. '...' Vegetation and soils were analysed at two Au prospects in Western Australia: Berkley, Coolgardie and Torquata, 210 km south-east of Kambalda, in semi-arid Western Australia to complement both the mass balance and the differential modelling. At Berkley, both the vegetation and soils located directly over the mineralisation showed high concentrations of Au. There may be indirect evidence for the operation of the deep plant uptake flux taking effect from the field evidence at Berkley. Firstly, anomalous concentrations of Au were found in the surface soils, with no detectable Au in the transported overburden. Secondly, the trace element concentrations in vegetation showed correlation to the buried lithology, which to our knowledge has not been reported elsewhere. The results from the samples at Torquata, in contrast, were less conclusive because the Au is almost exclusively associated with a surficial calcrete horizon (at <5 m soil depth). Strong correlations of Ca and Au in leaf samples however, suggest that the vegetation may be involved in the formation of calcrete and the subsequent association of Au with the calcrete. Among the vegetation components, the litter and leaf samples gave the greatest anomaly contrast at both prospects. Finally, three main drivers for the deep biotic uplift of elements were identified based on the results from the mechanistic numerical modelling exercise: i) the deep uptake flux; ii) the maximum plant concentration and; iii) the erosional flux. The relative sizes of these three factors control the rates of formation and decay, and trace element concentrations, of the soil anomaly. The main implication for the use of soils as exploration media in covered terranes is that soil geochemical anomalies may only be transient geological features, forming and dispersing as a result of the relative sizes of the accumulative and loss fluxes. The thesis culminates in the development of the first quantitative, mechanistic model of trace element accumulation in soils by deep biotic uplift.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2007. / Härtill 4 uppsatser.

Thesis (doctoral)--Uppsala University, 1982. / Includes bibliographical references (p. 35-39).

Thesis (M.S.)--Indiana University, 2007. / Department of Earth Sciences, Indiana University-Purdue University Indianapolis (IUPUI). Advisor(s): Gabriel M. Filippelli, Catherine Souch, Lenore P. Tedesco. Includes vitae. Includes bibliographical references (leaves 80-83).

O ambiente costeiro tem sido fortemente alterado em função de múltiplos impactos ambientais decorrentes das atividades antrópicas, como por exemplo, o escoamento de esgoto proveniente de áreas urbanas, a liberação de inúmeros produtos químicos das indústrias, a agricultura e o fluxo de embarcações, que podem acarretar vazamentos acidentais de petróleo e derivados, combustíveis e outros produtos transportados por via marítima. Neste contexto, um dos meios para avaliação da contaminação ambiental causada por essas substâncias potencialmente tóxicas em água do mar é a monitoração por meio de diferentes espécies de bivalves, que tem sido utilizada por diversos pesquisadores, do Brasil e do exterior. No que se refere aos moluscos bivalves, particularmente os mexilhões, o seu uso no biomonitoramento da contaminação marinha deve-se principalmente à sua ampla distribuição geográfica, hábito séssil e habilidade de concentrar metais tóxicos em até 102 - 105 vezes em relação às concentrações detectadas na água. No presente trabalho, foi empregado o biomonitoramento passivo com o uso do molusco bivalve Perna perna com relação aos elementos Br, Cl, K, Mg, Mn e V. Foram escolhidos estes elementos uma vez que eles podem ser determinados pelo método de INAA (Análise por Ativação com Nêutrons Instrumental), por meio da irradiação curta o que proporciona análises mais rápidas e também por serem importantes do ponto de vista nutricional ou ambiental. O objetivo do presente trabalho foi avaliar os teores de Br, Cl, K, Mg, Mn e V em amostras de mexilhões Perna perna (Linnaeus, 1758: Mollusca, Bivalvia) coletados em regiões costeiras de São Paulo sujeitas à contaminação antrópica (Ponta de Itaipu e Ilha das Palmas, em Santos), comparando os valores obtidos nos sítios possivelmente impactados com os valores do sítio controle situado na Praia da Cocanha, em Caraguatatuba. Os pontos de coleta no litoral de São Paulo estão localizados nas regiões geográficas 23º 37 S 45º 24 W (Caraguatatuba) e 23º 57\' S - 46º 20\' W (Santos). A coleta dos organismos foi realizada em todas as estações do ano, com início na primavera de 2008 e término no inverno de 2009. As amostras coletadas foram limpas, trituradas, homogeneizadas e secas por meio da liofilização para posterior INAA. O procedimento de INAA consistiu em irradiar alíquotas das amostras obtidas na forma de pó em invólucros de polietileno no reator nuclear IEA R1 do IPEN/CNEN - SP juntamente com padrões sintéticos de elementos. O tempo de irradiação no reator foi de 8 a 10 s e sob o fluxo de nêutrons térmicos de 6,6 x 1012 n cm-2 s-1. As concentrações dos elementos foram calculadas pelo método comparativo. O procedimento de INAA foi validado com relação à exatidão e precisão, por meio das análises dos materiais de referência certificados NIST SRM 1566b Oyster Tissue e NIST SRM 2876 Mussel Tissue. Os resultados destes materiais de referência certificados indicaram uma boa qualidade dos resultados com relação à precisão e exatidão. As faixas das concentrações (em base seca) dos elementos obtidos nos mexilhões coletados em Santos e na Praia da Cocanha para as quatro estações do ano foram de: 173,80 a 358,99 mg kg-1 para Br; 45658 ± 1811 a 109166 ± 824 mg kg-1 para Cl; 7043 ± 856 a 12506 ± 675 mg kg-1 para K; 2774 ± 211 a 5691 ± 717 mg kg-1 para Mg; 7,01 ± 0,30 a 29,74 ± 3,32 mg kg-1 para Mn e 0,77 ± 0,02 a 3,43 ± 0,28 mg kg-1 para V. Foi estudada a variação sazonal e espacial das concentrações desses elementos e também foram comparados esses resultados com valores da literatura. A partir dos resultados obtidos pode - se concluir que os mexilhões da espécie Perna perna, podem ser utilizados como biomonitores da contaminação marinha. / The coastal environment has been heavily altered by multiple environmental impacts of human activities, such as disposal of sewage from urban areas, the release of numerous chemical industries, agriculture and the flow of vessels, which can lead to accidental spills of oil and oil products, fuels and other products transported by sea. In this context, a means of determining concentrations of these potentially toxic substances in the sea water is the biomonitoring by means of different types of bivalves, which have been used by various researchers, in Brazil and other countries. With regard to bivalve mollusks, particularly mussels, their use in monitoring the marine contamination is mainly due to their wide geographic distribution, sessile habit and ability to concentrate toxic metals to 102-105 times in relation to the concentrations detected in water. In the present study, we employed the passive biomonitoring using the Perna perna bivalve mollusk with respect to the elements Br, Cl, K, Mg, Mn and V. These elements were chosen since they can be determined by INAA method (Instrumental Neutron Activation Analysis), by means of short irradiation which provides faster analyzes and also due to their importance from the standpoint of environmental or nutritional studies. The aim of this study was to evaluate the content of Br, Cl, K, Mg, Mn and V in samples of Perna perna mussels (Linnaeus, 1758: Mollusca, Bivalvia) collected in coastal regions of São Paulo subject to anthropogenic contamination (Ponta de Itaipu and Palmas Island, in Santos), comparing the values obtained in sites potentially impacted with the values of the control site in Praia da Cocanha, in Caraguatatuba. The collection points located in São Paulo coast are located in the geographical areas 23º 37\'S - 45° 24\' W (Caraguatatuba) and 23º 57\'S - 46º 20\' W (Santos). The collection of organisms was performed in all seasons of the year, beginning in spring 2008 and ending in winter 2009. The samples were cleaned, crushed, homogenized and dried by lyophilization for further analysis by INAA. The INAA procedure consisted of irradiating aliquots of the samples obtained in powder form in polyethylene envelopes in the nuclear research reactor IEA - R1 of IPEN / CNEN - SP together with synthetic standards of elements. The irradiation time in the reactor was 8 to 10 s under the thermal neutron flux of 6.6 x 1012 n cm-2 s-1. The concentrations of the elements were calculated using the comparative method. The INAA procedure was validated with respect to accuracy and precision, through the analysis of certified reference materials NIST SRM 1566b Oyster Tissue and NIST SRM 2876 Mussel Tissue. The results of these certified reference materials indicated good quality of results with respect to precision and accuracy. The ranges of concentrations (dry basis weight) of the elements obtained in mussels collected in Santos and Praia da Cocanha for the four seasons of the year were: 173.80 to 358.99 mg kg-1 for Br; 45658 ± 1811 to 109166 ± 824 mg kg-1 for Cl; 7043 ± 856 to 12506 ± 675 mg kg-1 for K; 2774 ± 211 to 5691 ± 717 mg kg-1 for Mg; 7.01 ± 0.30 to 29.74 ± 3.32 mg kg-1 for Mn and 0.77 ± 0.02 to 3.43 ± 0.28 mg kg-1 for V. The seasonal and spatial variations of the concentrations of these elements were studied and the values compared to the literature. From the results obtained it can be concluded that the species of Perna perna mussels, can be used as biomonitors of marine contamination.

Neste trabalho, a decomposição por via úmida em sistema fechado assistida por radiação micro-ondas (MW-AD) e a decomposição por via úmida em sistema fechado assistida por radiação micro-ondas e ultravioleta (MW-UV) foram avaliadas para amostras comerciais de biodiesel para posterior determinação de Ba, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, V e Zn por espectrometria de massa com setor eletromagnético com plasma indutivamente acoplado (SF-ICP-MS). A MW-AD empregando ácido diluído foi primeiramente avaliada sendo possível a decomposição de até 700 mg de biodiesel com HNO3 7 mol L-1 e 2 mL de H2O2 30% (m/m). As soluções finais apresentaram teor de carbono residual (RCC) de 8,7% e acidez residual (RA) de 4%. Posteriormente, com o objetivo de obter maior eficiência de decomposição, o método MW-UV foi avaliado para a decomposição de biodiesel. Com o emprego deste método até 950 mg de amostra foram decompostas com HNO3 7 mol L-1 e soluções finais com RCC de 17,4% e RA de 19,3% foram obtidas. As soluções finais, para ambos os métodos, foram adequadas para a determinação de elementos traço por SF-ICP-MS. Possíveis interferências na etapa de determinação dos analitos, causadas pela presença de carbono residual, foram estudadas através do emprego de padrão interno 115In e de ensaios de recuperação de analito para monitorar a formação de espécies poliatômicas no plasma. Os resultados obtidos mostraram a necessidade da utilização de padrão interno, sendo o instrumento operado no modo de baixa resolução para a determinação da maioria dos analitos, com exceção de 52Cr, para o qual o instrumento foi operado no modo de média resolução. A exatidão dos métodos propostos foi avaliada mediante a análise de material de referência certificado, obtendo-se resultados concordantes, com nível de confiança de 95% (teste t-student), com os valores certificados para a maioria dos elementos. Ensaios de adição de analito também foram feitos para a avaliação da exatidão e recuperações de 92 à 109% foram obtidas. Os limites de detecção (LD) obtidos para o método MW-UV foram inferiores aos obtidos para MW-AD, na faixa de 0,08 a 6,9 ng g-1 e 1,0 a 14 ng g-1, respectivamente. / In this work, the microwave-assisted digestion (MW-AD) and microwave-assisted ultraviolet digestion (MW-UV) were evaluated for commercial biodiesel samples for subsequent determination of Ba, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, V and Zn by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). Using the MW-AD method with diluted acid up to 700 mg of biodiesel were digested with 7 mol L-1 HNO3 and 2 mL of 30% (w/w) H2O2. Final solutions presented residual carbon content (RCC) of 8.7% and residual acidity (RA) of 4%. In order to improve the digestion efficiency, the MW-UV method was evaluated for biodiesel digestion. Using MW-UV method up to 950 mg of sample were digested with 7 mol L-1 HNO3 and the final solutions with RCC of 17.4% and RA of 19.3% were obtained. The final solutions obtained for both methods were suitable for the determination of trace elements by SF-ICP-MS. Interferences in the determination step were studied using 115In as internal standard and analyte recovery to monitor the formation of polyatomic species in the plasma. The low resolution mode was used for the determination of almost of the analytes with the exception of 52Cr that was determine using medium resolution mode. Accuracy of the investigated methods were evaluated by analysis of certified reference material and the values obtained were in agreement with 95% confidence level (t-student test) with the certified values for all elements. Analyte recovery was also performed to evaluate the accuracy and recoveries of 92 to 109% were obtained. The limits of detection (LOD) obtained by the MW-UV method were lower than MW-AD method and are in the range of 0.08 to 6.9 ng g -1 and 1.0 to 14 ng g -1, respectively.