South Africa remains the 5th largest producer and 4th largest exporter of coal in the world. It is also the largest supplier of coal to the European Union. This fact is significant as the European Union has recently supported the environmental lobby that threatens the combined full scale use of coal in Europe and other first world countries. This promotes the development of clean coal technologies in order to counter the ever increasing number of environmental constraints threatening the export market. One critical development in clean coal technologies is coal beneficiation, which allows the reduction of ash and inert content. Permian coals from South Africa have characteristically high ash and inertinite contents and therefore require further beneficiation. The Witbank coalfield No. 4 seam is no exception. It can be described as being more inert and having a higher mineral content compared to the No. 2 seam in the same coalfield also mined for export purposes. With the increase in environmental legislation and the push towards “clean coal” this raises a concern in terms of the performance and marketability of export coal produced from the No. 4 seam. This seam will in the future be economically significant and is still a great source for export steam coal. Due to the nature and composition of the No. 4 seam, coal beneficiation is essential to reduce the mineral and inert content to be in line with export quality specification levels. Washability characteristics of the No. 4 seam coal indicate that the No. 4 seam is difficult to beneficiate. Until recently the main clean-ability parameters evaluated in South African export coals as per customer specification included mainly heating value, moisture and ash reduction with little to no work being done on trace element concentration reduction. This paper focuses on the partitioning of the trace elements within the seam in relation to the organic and inorganic affinity of the trace elements and possible methods of trace element reduction by removal using coal beneficiation techniques. The techniques investigated include reduction by washing using dense medium beneficiation and flotation. In each evaluation the focus was on trace-element-tomineral and trace-element-to-organic matter relationship and hence setting the basis for liberation analysis to evaluate reducibility. By the evaluation of the coal mineralogy, petrography and trace element relationships, methods of optimum trace element reduction can be established. With the focus on marketing it was shown that carbon loss need not be sacrificed in the reduction of specific trace elements in the No. 4 seam and that the trace element distribution itself allows for beneficiation whilst maintaining acceptable yields. Processes and possible beneficiation techniques for optimum trace element reduction and marketability in the case of the No.4 seam are proposed.

Thesis (MTech (Physical Sciences))--Peninsula Technikon, Cape Town, 1999. / Wet deposition of toxic trace metals is the dominant mode of deposition in terrestrial ecosystems and contributes very significantly to their pollution burden. Wet deposited metals are dissolved in rainwater. They reach the vegatation in a form most favourable for uptake. Reliable analysis of toxic trace metals in rainwater is important in order to determine the impact they make on the environment. In this study, trace metals in rainwater and in dry deposition (as a control measure), have been analysed over a period of a year. These metals include cadmium, copper, cobalt, lead, nickel and zinc. The rainwater was filtered, acidified to pH2 and irradiated with UV-light. Dry deposition samples, were digested by heating in nitric acid before analysis. Differential-pulse anodic stripping voltammetry was used to determine cadmium, lead and zinc. Copper was determined by adsorptive cathodic stripping at pH7 after complexation with catechol. Cobalt and nickel were measured at pH9 by adsorptive cathodic stripping after formation of their dimethylglyoximes. Sampling was done on a daily basis from April 1996 to March 1997, on the campus of the Peninsula Technikon. The samples were collected over a 24-hour period. The total average concentration for the metals was 16.11 flg/dm3 for rainwater and 427flg/dm3 for dry deposition. Meteorological factors such as wind speed, humidity and temperature affect the distribution of pollutants and thus the trace metal levels. The levels of the metallic pollutants were thus evaluated against meteorological data. Differential-pulse stripping voltammetry is shown to be applicable for heavy metal analysis of rainwater.

Os contaminantes lançados no ambiente decorrente das atividades humanas podem se movimentar de um compartimento ambiental para o outro e assim chegar nos corpos hídricos, onde se associam rapidamente ao material particulado e incorporam-se aos sedimentos. Desta forma, a relação água com o sedimento faz deste compartimento um dos principais alvos de preocupação e análise, dada sua importância na ciclagem de matéria e na biodisponibilidade de diversos compostos químicos para o ambiente aquático. O objetivo deste trabalho foi avaliar o comportamento geoquímico dos elementos Al, Fe, Cr, Cu, Zn, Mn, e P em sedimento superficial do reservatório Guarapiranga por meio da técnica de extração sequencial constituída de quatro etapas, seguido pela detecção em espectrometria de emissão ótica com plasma acoplado indutivamente (ICP-OES). Foram coletadas amostras de sedimento superficial em 14 (quatorze) estações estrategicamente escolhidas, de modo a conhecer a heterogeneidade do sistema e determinar a mobilidade de elementos-traço persistentes e sua distribuição espacial no compartimento sedimentar da represa. As amostras passaram por processo de secagem e foi separada a fração silte/argila. A extração sequencial foi realizada em quatro etapas, a fração 1 ácido solúvel ligada a carbonatos, a fração 2 redutível a óxidos de ferro e manganês, a fração 3 oxidável ligada a matéria orgânica e a fração 4 residual. Todo o processo foi feito em triplicata e as concentrações dos elementos foram determinadas no ICP-OES. Com base nos resultados obtidos da extração sequencial, foi possível avaliar a distribuição dos elementos nas quatro frações geoquímicas distintas bem como o fator de mobilidade individual e total desses elementos no reservatório. A soma das três primeiras frações compõe a fração considerada biodisponível enquanto que a diferença do total extraído representou a fração residual. A partir dos resultados obtidos infere-se que o reservatório do Guarapiranga apresenta dois compartimentos distintos, um mais degradado que vai do ponto GU-05 ao GU-14 que sofre os impactos da ocupação do seu entorno e um mais preservado que vai do ponto GU-01 a GU-04, com pouca influência de ocupação urbana no seu entorno. O grau de mobilidade global segue uma tendência de montante à jusante do reservatório, próxima a barragem. / The contaminants produced by human activities released in the environment may move from one environmental compartment to another and reach the water bodies, where they rapidly associate to particulate matter and are incorporated to the sediments. Thus, the relationship between water and sediment makes this compartment on of the main targets for concern and analysis, given its importance in cycling matter and in bioavailability of various chemical compounds to the water environment. The objective of this work was to study the geochemical behaviour of the elements Al, Fe, Cr, Cu, Zn, Mn and P in the surface sediments of the Guarapiranga reservoir (23°47\'S and 46°32\"W) by means of the sequential extraction technic consisting of four stages, followed by the detection in inductively coupled plasma optical emission spectroscopy (ICP-OES). Samples were collected from the superficial sediment in 14 (fourteen) stations strategically chosen, this way being able to know the heterogeneity of the system and to determinate the mobility of persistent trace elements and their spatial distribution in the sedimentary compartment of the reservoir. The samples were subjected to a drying process and then separating the silt fraction. The sequential extraction was made in four steps, fraction 1 acid soluble linked to carbonates, fraction 2 reducible to iron and manganese oxides, fraction 3 oxidable linked to organic matter and fraction 4 residual. All the process was done in triplicate and the concentration of the elements was determined by ICP-OES. Based on the results obtained by the sequential extraction, it was possible to evaluate the distribution of the elements in the four distinct geochemical fractions, as well as the individual mobility factor of those elements in the reservoir. The sum of the first three fractions composes the fraction considered bioavailable, while the difference from the total extracted represented the residual fraction. Parting from the results obtained it is inferred that the Guarapiranga reservoir has two distinct compartments, one more degraded that goes from point GU-05 to GU-14 that suffers from the impacts of the occupations in the surroundings and one more preserved that goes from point GU-01 to GU-04, with little influence from urban occupation in the surroundings. The degree of global mobility follows the tendency of up and down stream in the reservoir, next to the barrage.

by Wong Chi Kin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 131-133). / Acknowledgement / Abstract --- p.1 / General introduction --- p.4 / Part I Determination of Some Minor Elements in Cement by Energy Dispersive X-Ray Fluorescence Spectrometry / Introduction --- p.7 / Experimental --- p.14 / Results and discussions --- p.18 / Part II Determination of Mercury in Water by Static Cold Vapour Atomic Absorption Spectrometry / Introduction --- p.78 / Experimental --- p.84 / Results and discussions --- p.89 / Conclusion --- p.130 / References --- p.131

by Leung Ho-yin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references. / Abstract also in Chinese. / Acknowledgement --- p.i / Abstract --- p.ii / Table of Contents --- p.iv / List of Tables and Figures --- p.v / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2 --- Methodology --- p.12 / Chapter Chapter 3 --- Experimental --- p.17 / Chapter 3.1 --- Sample Collection --- p.17 / Chapter 3.2 --- Preliminary Sample Treatment --- p.18 / Chapter 3.3 --- Dissolution Test Apparatus --- p.18 / Chapter 3.4 --- Reagents --- p.20 / Chapter 3.5 --- ICP Experimental Conditions --- p.21 / Chapter Chapter 4 --- Determination of Total Contents in Chinese Mineral Drugs --- p.28 / Chapter 4.1 --- Procedure --- p.28 / Chapter 4.2 --- Results --- p.39 / Chapter Chapter 5 --- Determination of the Effective Contents --- p.51 / Chapter 5.1 --- General Procedure --- p.51 / Chapter 5.2 --- Results --- p.52 / Chapter Chapter 6 --- Recovery Test for Dissolution --- p.77 / Chapter 6.1 --- General Procedure --- p.77 / Chapter 6.2 --- Results --- p.78 / Chapter Chapter 7 --- Discussion --- p.80 / Chapter 7.1 --- The Presence of Toxic Elements in many CMD --- p.80 / Chapter 7.2 --- Mass of Samples Added in the Dissolution --- p.80 / Chapter 7.3 --- Height of the Dissolution Paddle of the Dissolution --- p.81 / Chapter 7.4 --- Particle Sizes of the Sample in the Dissolution --- p.83 / Chapter 7.5 --- The Total and the Effective Contents --- p.83 / Chapter 7.6 --- Discussion for each CMD --- p.84 / Chapter 7.7 --- Conclusion --- p.103 / Appendix English 一 Chinese table of CMD --- p.108

Digitized by Kansas Correctional Industries

Thesis. 1978. Ph.D. cn--Massachusetts Institute of Technology. Dept. of Chemistry. / Includes bibliographical references. / Ph.D.cn

Os contaminantes lançados no ambiente decorrente das atividades humanas podem se movimentar de um compartimento ambiental para o outro e assim chegar nos corpos hídricos, onde se associam rapidamente ao material particulado e incorporam-se aos sedimentos. Desta forma, a relação água com o sedimento faz deste compartimento um dos principais alvos de preocupação e análise, dada sua importância na ciclagem de matéria e na biodisponibilidade de diversos compostos químicos para o ambiente aquático. O objetivo deste trabalho foi avaliar o comportamento geoquímico dos elementos Al, Fe, Cr, Cu, Zn, Mn, e P em sedimento superficial do reservatório Guarapiranga por meio da técnica de extração sequencial constituída de quatro etapas, seguido pela detecção em espectrometria de emissão ótica com plasma acoplado indutivamente (ICP-OES). Foram coletadas amostras de sedimento superficial em 14 (quatorze) estações estrategicamente escolhidas, de modo a conhecer a heterogeneidade do sistema e determinar a mobilidade de elementos-traço persistentes e sua distribuição espacial no compartimento sedimentar da represa. As amostras passaram por processo de secagem e foi separada a fração silte/argila. A extração sequencial foi realizada em quatro etapas, a fração 1 ácido solúvel ligada a carbonatos, a fração 2 redutível a óxidos de ferro e manganês, a fração 3 oxidável ligada a matéria orgânica e a fração 4 residual. Todo o processo foi feito em triplicata e as concentrações dos elementos foram determinadas no ICP-OES. Com base nos resultados obtidos da extração sequencial, foi possível avaliar a distribuição dos elementos nas quatro frações geoquímicas distintas bem como o fator de mobilidade individual e total desses elementos no reservatório. A soma das três primeiras frações compõe a fração considerada biodisponível enquanto que a diferença do total extraído representou a fração residual. A partir dos resultados obtidos infere-se que o reservatório do Guarapiranga apresenta dois compartimentos distintos, um mais degradado que vai do ponto GU-05 ao GU-14 que sofre os impactos da ocupação do seu entorno e um mais preservado que vai do ponto GU-01 a GU-04, com pouca influência de ocupação urbana no seu entorno. O grau de mobilidade global segue uma tendência de montante à jusante do reservatório, próxima a barragem. / The contaminants produced by human activities released in the environment may move from one environmental compartment to another and reach the water bodies, where they rapidly associate to particulate matter and are incorporated to the sediments. Thus, the relationship between water and sediment makes this compartment on of the main targets for concern and analysis, given its importance in cycling matter and in bioavailability of various chemical compounds to the water environment. The objective of this work was to study the geochemical behaviour of the elements Al, Fe, Cr, Cu, Zn, Mn and P in the surface sediments of the Guarapiranga reservoir (23°47\'S and 46°32\"W) by means of the sequential extraction technic consisting of four stages, followed by the detection in inductively coupled plasma optical emission spectroscopy (ICP-OES). Samples were collected from the superficial sediment in 14 (fourteen) stations strategically chosen, this way being able to know the heterogeneity of the system and to determinate the mobility of persistent trace elements and their spatial distribution in the sedimentary compartment of the reservoir. The samples were subjected to a drying process and then separating the silt fraction. The sequential extraction was made in four steps, fraction 1 acid soluble linked to carbonates, fraction 2 reducible to iron and manganese oxides, fraction 3 oxidable linked to organic matter and fraction 4 residual. All the process was done in triplicate and the concentration of the elements was determined by ICP-OES. Based on the results obtained by the sequential extraction, it was possible to evaluate the distribution of the elements in the four distinct geochemical fractions, as well as the individual mobility factor of those elements in the reservoir. The sum of the first three fractions composes the fraction considered bioavailable, while the difference from the total extracted represented the residual fraction. Parting from the results obtained it is inferred that the Guarapiranga reservoir has two distinct compartments, one more degraded that goes from point GU-05 to GU-14 that suffers from the impacts of the occupations in the surroundings and one more preserved that goes from point GU-01 to GU-04, with little influence from urban occupation in the surroundings. The degree of global mobility follows the tendency of up and down stream in the reservoir, next to the barrage.

Water chemistry in rivers is impacted by a variety of natural and anthropogenic processes including agricultural runoff, urban runoff, storm runoff, groundwater inputs, and the built environment. In this study we used trace element concentrations (including As, B, Ce, Co, Cu, Li, Mn, Rb, Sb, Sr, Tl, V, and Zn) and continuous measurements of flow rates and specific conductance to investigate dynamic processes affecting water quality in a rapidly urbanizing agricultural area typical of the western U.S. The middle Provo River, located in northern Utah, USA, was selected as the study area because it is well instrumented with water quality stations and streamflow gauges. We sampled 6 sites on the middle Provo River and 15 sites on tributaries in the watershed a minimum of 5 times between April 2014 and March 2015 to evaluate potential contributions from surface water and groundwater inputs to the Provo River. Additional water samples were collected at 13 cold, thermal, and mixed cold/thermal springs in Heber Valley during summer 2014 to evaluate regional groundwater chemistry. Samples were also collected during two storm events including high frequency sampling in a tributary and road-puddle samples to characterize potential storm runoff chemistry. Specific conductance data loggers were deployed in tributaries to monitor effects of precipitation and other runoff on the middle Provo River at 15-min intervals. See Table 1 for a summary of sampling events. Middle Provo River water chemistry is impacted by natural groundwater inputs as well as surface water tributaries. Li, B, Sr, As concentrations increased dramatically (3-10 fold) downstream of the confluence with a major tributary, Snake Creek. Snake Creek had average As concentrations of ~15 µg/L above the confluence with Provo River and accounted for roughly 20% of the flow to the middle Provo River, but increased the As concentration in Provo River ~4 fold. Thermal springs had ~20 and ~80 times higher concentrations of As and Li, respectively, relative to cold springs and was found to be a major contributor of trace elements to Snake Creek and the middle Provo River. Cl mixing calculations indicated that groundwater contributions increased downstream with up to 15% of the flow to the middle Provo River being contributed within the most downstream reach. Tributaries were found to impact the Provo River based on specific conductance fluxes in tributaries corresponding to fluxes in the river. Notably, Spring Creek, a dominantly agricultural tributary, accounts for >40% of the annual V load and >18% of the annual U, Mn, Pb, Ba, La, and Ce loads to the middle Provo River. The trace elements B, Li, As, and Sr which are found in high concentrations in groundwater, were strongly correlated with Provo River specific conductance and may indicate a potential method of predicting select trace element concentrations in the middle Provo River based on specific conductance data. Filtered puddle samples collected during a storm event had higher concentrations of Co, Cu, V, and Zn, but lower concentrations of major and select trace elements including As, Li, and Sr, relative to the middle Provo River. This study has implications for understanding water quality in complex coupled human-natural systems.

Sediments from 21 Oregon lakes were analyzed for seven metals (Fe, Mn, Zn, Cu, Co, Ni, V) in three forms (exchangeable, organic+sulfides, and oxyhydroxides+ oxides+ carbonates) using a sequential fractionation procedure. The summer epilimnetic filterable concentration of an eighth (Mo) was also determined. Sedimentary diatom remains and summer phytoplankton populations of the lakes were correlated with the 22 metal parameters and with conservative water chemistry parameters, estimators of lake productivity, and watershed geology. Both the sedimentary metals and the two populations of primary producers correlated best with the ecoregions of Omernik and Gallant (1986). A number of species possessed correlations with specific trace metal extractions or ratios of those extractions. Bloom-forming Anabaenas strongly correlated with sedimentary organic and filterable epilimnetic nickel. Possible Ni limitation of this group was observed in one Cascade lake (Lava). The ratio of organic nickel to cobalt appeared to control the abundance of several sedimentary diatoms. Organic vanadium strongly correlated with a number of diatoms, particularly in the genera, Cyclotella and Fragilaria. Possible V pollution was observed in one lake (Woahink), and frustule remains of C. stelligera significantly increased with increasing total sedimentary V concentrations there. Zinc was the trace metal most frequently found to apparently limit diatom growth. Diatoms may have developed three different responses to Zn limitation; the three groups have been labelled affinity-, velocity-, and (possibly) storage- specialists following Sommer (1985). Possible Zn pollution was observed in two lakes (Oswego and Clear). Phytoplankton and sedimentary diatoms weakly correlated with sedimentary iron by comparison to Ni, V, or Zn. Few strong relationships were observed with manganese, copper, or cobalt. No statistically significant correlations were found with molybdenum, and few correlations between a conservative chemical parameter and a species of phytoplankton were found. There was poor correlation between trace metal concentrations and lake productivity, despite frequently observed correlations between individual species and particular trace metal fractions. These findings suggest that variations in absolute trace metal concentrations, and/or ratios, may be important factors for controlling species distribution, but have relatively little influence upon lake primary productivity or standing stocks.