Many brackish water aquaculture ventures in Australia and overseas have established ponds in coastal regions with acid sulfate soils (ASS). Acid sulphate soils are known to leach relatively high concentrations of metals, acid (metal and H+ ion) and sulfur, however very little is known about how these leached elements affect the water quality of aquaculture ponds. The main objective of this thesis was to describe the hydrochemical processes controlling the water chemistry in the water column and sediment pore water in the studied aquaculture ponds over time and space. Water samples providing the spatio-temporal data were collected from the ponds with the use of adapted sampling methods commonly used in the groundwater environment. A transect of five nested piesometers was installed in two prawn ponds at Pimpama, south east Queensland, Australia. Each piesometer nest contained a multilevel with eight outtakes, a mini ?? horizontal, and a slotted piesometer. Water samples were collected from each nested piesometer on a bi-monthly basis over the prawn-growing season. The unstable elements and water quality variables (pH, Eh, DO, EC, water temperature) were measured in the field. Stable elements were analysed in the laboratory using ICP-OES and ICP-MS. Soil samples were collected at the end of the season for elemental analysis. A number of key sediment/water interactions and processes such as precipitation/dissolution reactions, oxidation-reduction reactions, photosynthesis, adsorption and seawater buffering were identified as important controls on pond water conditions. This is the first study to provide detailed hydrochemcial analysis of the pond water over time and space and aided in identifying that even shallow water bodies can be chemically heterogeneous. Analysis of the water and sediment highlighted the selection of metals that can be associated with ASS and that are mobilised from pond sediments under certain chemical conditions. In Pond 7 Al, As, Ni and Zn concentrations were generally higher at the beginning of the grow-out season. Variability of the metal concentration was observed between the water column (0 ?? 1500 mm) and the pore-water (0 - -1000 mm). The highest concentration of Al (1044 ??g/L) and Zn (104 ??g/L) were sampled in the water column (approximately 400 mm from the surface of the pond). The highest concentration of As (130 ??g/L) and Ni (73 ??g/L) were sampled in the pore water sediment (associated with ASS). Elevated Mn and Fe2+ concentrations were also associated with the sediment pore water. The highest concentrations of Mn and Fe2+ were 4717 ??g/L and 5100 ??g/L respectively. In Pond 10, Ni concentrations (167 ??g/L) were the highest at the beginning of the grow-out season. However, As (97 ??g/L), Al (234 ??g/L) and Zn (308 ??g/L) were most concentrated during the middle of the cycle. The highest mean concentrations of these elements are As (63 ??g/L), Al (91 ??g/L) and Zn (69 ??g/L) which are each associated with the sediment-water interface. These metals are integral in degrading the pond water quality and lead to a loss of beneficial algal blooms, a reduction in pond water pH, poor growth rates and high mortality in shrimp. It is also possible that the dissolved ions and precipitated compounds that are leached from the ASS are discharged into the adjacent coastal estuary of Moreton Bay. With knowledge obtained from this PhD study, effective management and treatment systems can be developed and implemented to minimise the impact of these soils on the pond system and the water discharging into natural coastal ecosystem.

Acid sulfate (AS) soils are characterized by a large pool of sulfates which may provide significant amounts of acidity and heavy metals – commonly nickel (Ni), Cobolt (Co), Zinc (Zn) and Arsenic (As) - to surrounding surface waters. The occurrence of AS soils is widespread, covering 17 million ha globally, and they are known for threatening freshwaters in Australia, North America as well as in many tropical regions. Mobilization of mercury (Hg) from AS soils is however poorly studied and could potentially be an environmental problem of concern due to its toxicity and capacity of bioaccumulating in food webs. In this study I investigated whether Hg is mobilized from AS soils by conducting chemical analyses on sediment samples from a 1,6 m deep lake core and a transect of surficial sediment samples in an adjacent sea bay. Here, I used zircon (Zr) and zinc (Zn) as proxies for silicate sources and sulfide soil sources, respectively. I found that Zn and Hg concentrations normalized to the organic matter content (LOI) showed a significant correlation in the lake core; hence, Hg in the sediment co-varied with my sulfide proxy and showed no correlation to my silicate proxy, and I then conclude that a considerable fraction of mercury in the studied sediment has a likely origin from AS soils.

The leakages of metals from acid sulfate soils and their potential toxicity to benthic invertebrates were studied in the sediment profiles of Lillkvasjön and Lövselefjärden - a lake and an estuary known to be affected by acid sulfate soils - in Västerbotten, northern Sweden. The concentrations of 25 different elements were analyzed throughout both sediment profiles through X-Ray Fluorescence (XRF) Spectrometer analysis. Organic matter was measured through loss-on-ignition (LOI). By performing correlation analysis and normalizations to LOI on all sediment variables, Cu, Fe, Ni, Pb, S and Zn were found to be leached from acid sulfate soils to both sites, while Mg and Mn were related to leakages from acid sulfate soils in Lövselefjärden. The concentrations of Cu (195 mg kg-1), Ni (55 mg kg-1), Pb (90 mg kg-1) and Zn (398 mg kg-1) in the surface sediment of Lövselefjärden were classified as potentially toxic to benthic invertebrates. In Lillkvasjön, Cu (210 mg kg-1) and Ni (87 mg kg-1) were classified to have an increased risk of negative impacts on benthic invertebrates, while the concentrations of Pb (121 mg kg-1) and Zn (329 mg kg-1) were likely to low to have any negative effects. These results strengthen previous finds of impacts from acid sulfate soils in the two catchment areas and elucidate the importance of further studies on the impact of acid sulfate soils on benthic invertebrates.

The study employed multi-variate methods to generate vulnerability maps for acid sulfate soils (AS) in the Norrbotten county of Sweden. In this study, the relationships between the reclassified datasets and each biogeochemical element was carefully evaluated with ANOVA Kruskal Wallis and PLS analysis. The sta-tistical results of ANOVA Kruskall-Wallis provided us a useful knowledge of the relationships of the preliminary vulnerability ranks in the classified datasets ver-sus the amount of each biogeochemical element. Then, the statistical knowledge and expert knowledge were used to generate the final vulnerability ranks of AS soils in the classified datasets which were the input independent variables in PLS analyses. The results of Kruskal-Wallis one way ANOVA and PLS analyses showed a strong correlation of the higher levels total Cu2+, Ni2+ and S to the higher vulnerability ranks in the classified datasets. Hence, total Cu2+, Ni2+ and S were chosen as the dependent variables for further PLS analyses. In particular, the Variable Importance in the Projection (VIP) value of each classified dataset was standardized to generate its weight. Vulnerability map of AS soil was a result of a lineal combination of the standardized values in the classified dataset and its weight. Seven weight sets were formed from either uni-variate or multi-variate PLS analyses. Accuracy tests were done by testing the classification of measured pH values of 74 soil profiles with different vulnerability maps and evaluating the areas that were not the AS soil within the groups of medium to high AS soil probability in the land-cover and soil-type datasets. In comparison to the other weight sets, the weight set of multi-variate PLS analysis of the matrix of total Ni2+& S or total Cu2+& S had the robust predictive performance. Sensitivity anal-ysis was done in the weight set of total Ni2+& S, and the results of sensitivity analyses showed that the availability of ditches, and the change in the terrain sur-faces, the altitude level, and the slope had a high influence to the vulnerability map of AS soils. The study showed that using multivariate analysis was a very good approach methodology for predicting the probability of acid sulfate soil.

Acid Sulfate soils (AS) are recognized for being a source of acidity in freshwaters in America, Europe, Australia, and Asia. Apart from the problematic acid leachate, AS soil serves as a possible source of toxic heavy metals in freshwaters, a problem which has received far less attention than problems related to acid leachate. This study assessed to what extent heavy metals enriched in sediments from the area around lake Persöfjärden (North-eastern Sweden) could be attributed to export from AS soils. I found that: i) Nickel (Ni), Zink (Zn), Copper (Cu) and Iron (Fe) in the sediments had a partial likely origin from AS soils; ii) vertical variations in Ni, Zn, Cu and Fe concentrations suggested events of increased metal transport in the past; and iii) there is a tendency that Zn and Ni assumed from AS soils have caused elevated metal concentration in marine sediment deposited in Persöfjärden. Inferred sediment rates suggest that elevated metal concentrations occurred in sediment deposited during the 18-19th and 20th century. I argue that these periods correspond to periods of increased drainage of the AS soils during past agricultural activities in the catchment.

This study investigates jarosite formation and stability patterns at the abandoned Davis Pyrite Mine in Rowe, Massachusetts. Jarosite, an iron-sulfate hydroxide, is found in acid mine drainage (AMD) environments, in acid sulfate soils, and on Mars. Jarosite and the iron oxides goethite and hematite are present at the site. Soil samples from the site were examined by XRD, SEM, and EDS. Five mineralogical areas were found, based on mineral abundance patterns. Jarosite exists in four of these areas. Two jarosite morphologies were identified. “Variable” jarosite, with partly-dissolved crystals of about 0.5 to 5 micrometers diameter, exists in spoil pile samples. “Donut” jarosite, with tightly-packed, sharp-edged crystals less than 0.5 micrometers that form a thin mantle on the surface of a second mineral, exists in native soil samples. Donut jarosite has not been previously characterized. These jarosite morphologies are controlled by the presence and relative mobility of pyrite oxidation products Fe and SO4, which in turn are controlled by water saturation levels. Three pathways are possible. On Path 1, both ions are mobile, go into solution, and variable jarosite forms at a distance from the pyrite source. On Path 2, only sulfur ions are mobile, an iron-oxide gossan develops. No jarosite forms. On Path 3, neither ion is mobile, and donut jarosite forms. On this path, Fe and SO4 ions are trapped in a thin film of stagnant water covering the pyrite. When sufficient ions are present, donut jarosite precipitates.

No description available.

Thesis (M.Eng.)--University of Wollongong, 2006. / Typescript. Includes bibliographical references: leaf 174-183.

Submitted by (lucia.rodrigues@ufrpe.br) on 2016-08-16T14:23:12Z No. of bitstreams: 1 Suzana Kelley Gomes de Mendonca.pdf: 1457356 bytes, checksum: 55d06ce86944cd3f69644577e424587d (MD5) / Made available in DSpace on 2016-08-16T14:23:13Z (GMT). No. of bitstreams: 1 Suzana Kelley Gomes de Mendonca.pdf: 1457356 bytes, checksum: 55d06ce86944cd3f69644577e424587d (MD5) Previous issue date: 2011-02-25 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Low lands in Brazil have a great potential for agriculture, however, they have some limitations due to the presence of high water table and severe risk of flooding. When located near by the sea cost, these floodplains can have influence of the sea water, resulting in the presence of sulfide soils, which, if drained, can develop sulfuric horizons. The sulfuric horizons are mainly characterized by high levels of acidity and exchangeable aluminum, which can result in serious environmental impact to the ecosystem. The agriculture use of these soils requires a deep knowledge of soil physical, chemical and mineralogical properties, in order to support the development of sustainable management practices. The objective of this work was to study chemical and mineralogical properties of acid sulfate soils formed in the floodplain of Camocim river, Caaporã municipality, state of Paraíba. The main aim was to support decisions on the viability of sugarcane cropping in these areas. Soils were characterized morphologically and samples were collected along a transect from the high land towards the river channel. Besides the routine physical, chemical and mineralogical analysis, other determinations were carried out involving total sulfur, incubation pH, soluble anions, electrical conductivity of the saturation extract and sequential iron extraction. The soils were classified as: Argisolic,Dystric Tb Haplic Gleysol (P1) Typic Sapric Sulfide Organosol (P2), Organosolic Orthic Sulfide Gleysol (P3 and P4). Soil distribution in the landscape of the Camocim river floodplain is mainly related to the relief, which determines drainage, water table and, consequently, the soil forming processes related to water excess. The presence of sulfuric horizons occur at the surface, in the very poorly drained soil profiles, and at 43 cm depth in the poorly drained soils close to the river channel. The studied acid sulfate soils do not have salinity at present time, and the high electrical conductivity is determined by the formation sulfuric acid (H+ + SO4 2-) from pyrite oxidation. Sugarcane crop decay in the floodplain of Camocim River, after one year of cultivation was a consequente of the sulfuric horizon formation after the implementation of the drainage system in soils with sulfide materials. The main soil minerals, indentified by X-ray diffraction, in the clay fraction were jarosite quartz, feldspars, kaolinite, smectite (essentially montmorillonite), illite and gibbsite. Quartz and feldspars were the minerals identified in sand and silt fractions. The results of the iron sequential extraction showed predominance of non crystalline iron oxides and very low amounts or absence of iron associated with pyrite, reflecting the advanced oxidation stage determined by the drainage system. / As áreas de várzeas no Brasil apresentam um grande potencial para a agricultura, no entanto, estas áreas apresentam algumas limitações ao uso agrícola devido à presença de lençol freático elevado e risco freqüente de inundação. Quando localizadas em áreas litorâneas, estas áreas podem sofrer influência marinha podendo apresentar solos tiomórficos que, quando drenados, formam horizonte sulfúrico, caracterizados principalmente pela elevada acidez, elevados teores de alumínio trocável, podendo causar sérios impactos ambientais no ecossistema onde ocorrem. A incorporação destas áreas no processo produtivo depende de um profundo conhecimento das propriedades físicas, mineralógicas e principalmente químicas, de forma a subsidiar o desenvolvimento de técnicas sustentáveis de manejo. Neste contexto, foi realizada a caracterização física, química, mineralógica, além da extração sequencial de ferro de solos tiomórficos desenvolvidos na várzea do rio Camocim, no município de Caaporã, PB. O objetivo do estudo foi identificar a ocorrência de solos tiomórficos e caracterizá-los, com o fim de obter subsídios para a tomada de decisão de incorporar estas áreas ao cultivo de cana-de-açúcar ou mantê-las nas condições naturais. Para tanto foi feito um transecto perpendicular ao canal principal do rio, a partir das terras altas, onde foram descritos e coletados quatro perfis de solo. Em campo foi realizada a caracterização morfológica dos perfis e coletadas amostras para as análises físicas, químicas e mineralógicas de rotina, além de análises específicas para determinação do enxofre total, pH de incubação, ânions solúveis, CE do extrato da pasta saturada e extração sequencial de ferro. Os solos foram classificados como Gleissolo Háplico Tb Distrófico argissólico (P1), Organossolo Tiomórfico Sáprico típico (P2) e Gleissolo Tiomórfico Órtico organossólico (P3 e P4). A distribuição dos solos na várzea do rio Camocim guarda estreita relação com o relevo, que condiciona a drenagem e, consequentemente, os processos de formação relacionados com o excesso de água. A presença de horizonte sulfúrico foi constatada a partir do horizonte superficial nos perfis muito mal drenados da planície de inundação, e a partir de 43 cm, nos solos mal drenados da ombreira. Os solos tiomórficos estudados não apresentam salinidade, sendo a alta condutividade elétrica resultante da formação de ácido sulfúrico proveniente da oxidação da pirita (H+ e SO4 2-). A degradação do canavial em grandes áreas da várzea do rio Camocim, após um ano de cultivo, foi consequência da formação do horizonte sulfúrico com a drenagem da área, tendo em vista que os materiais sulfídricos ocorrem desde a superfície. Os minerais identificados por DRX foram: jarosita, quartzo, feldspatos, caulinita, esmectita (essencialmente montmorilonita), ilita e gibbsita, na fração argila. Quartzo e feldspatos foram os minerais identificados nas frações areia e silte. Os valores da extração sequencial de ferro mostraram predomínio de formas não cristalinas de óxidos de ferro e baixíssimos teores ou ausência de ferro associado à pirita, indicando que os solos tiomórficos estudados apresentam avançado estágio de oxidação, promovido pela drenagem realizada na área de estudo na tentativa de viabilizar o cultivo da cana-de-açúcar.