Challenges in mercury speciation and fractionation in soil and sediment

This investigation focused on the development, test and validation of methodologies for mercury fractionation and speciation in soil and sediment. After an exhaustive review of the literature, several methods were chosen and tested in well characterised soil and sediment samples. Sequential extraction procedures that divide mercury fractions according to their mobility and potential availability in the environment were investigated. The efficiency of different solvents for fractionation of mercury was evaluated, as well as the adequacy of different analytical instruments for quantification of mercury in the extracts. Kinetic experiments to establish the equilibrium time for mercury release from soil or sediment were also performed. It was found that in the studied areas, only a very small percentage of mercury is present as mobile species and that mobility is associated to higher aluminium and manganese contents, and that high contents of organic matter and sulfur result in mercury tightly bound to the matrix. Sandy soils tend to release mercury faster that clayey soils, and therefore, texture of soil or sediment has a strong influence on the mobility of mercury. It was also understood that analytical techniques for quantification of mercury need to be further developed, with lower quantification limits, particularly for mercury quantification of less concentrated fractions: water-soluble e exchangeable. Although the results provided a better understanding of the distribution of mercury in the sample, the complexity of the procedure limits its applicability and robustness. A proficiency-testing scheme targeting total mercury determination in soil, sediment, fish and human hair was organised in order to evaluate the consistency of results obtained by different laboratories, applying their routine methods to the same test samples. Additionally, single extractions by 1 mol L-1 ammonium acetate solution, 0.1 mol L-1 HCl and 0.1 mol L-1 CaCl2, as well as extraction of the organometallic fraction were proposed for soil; the last was also suggested for sediment and fish. This study was important to update the knowledge on analytical techniques that are being used for mercury quantification, the associated problems and sources of error, and to improve and standardize mercury extraction techniques, as well as to implement effective strategies for quality control in mercury determination. A different, “non chemical-like” method for mercury species identification was developed, optimised and validated, based on the thermo-desorption of the different mercury species. Compared to conventional extraction procedures, this method has advantages: it requires little to no sample treatment; a complete identification of species present is obtained in less than two hours; mercury losses are almost neglectable; can be considered “clean”, as no residues are produced; the worldwide comparison of results obtained is easier and reliable, an important step towards the validation of the method. Therefore, the main deliverables of this PhD thesis are an improved knowledge on analytical procedures for identification and quantification of mercury species in soils and sediments, as well as a better understanding of the factors controlling the behaviour of mercury in these matrices.

Spatial variability in surface sediment organic carbon structure in Barkley Sound, Vancouver Island, Canada

Senior thesis written for Oceanography 445

Caractérisation du cycle et des sources d'azote dans les lacs tempérés par l'utilisation d'isotopes stables

Nous avons étudié l’application de plusieurs mesures d’isotopes stables afin de caractériser les processus du cycle de l’azote et les sources d’azote dans les lacs tempérés à diverses échelles spatiales et temporelles. Les résultats d’une étude à travers 65 lacs sur un gradient trophique ont démontré que le ratio d’isotopes stables d’azote (δ15N) des sédiments de surface est un indicateur de l’importance relative des sources d’azote anthropique, mais que ce ratio peut être altéré par la diagenèse. La mesure du δ15N des sédiments demeure néanmoins un outil permettant de déterminer à long terme le changement des charges en azote anthropique aux écosystèmes lacustres et les causes de l’eutrophisation de ces systèmes. Nos résultats d’une étude sur la variation saisonnière de plusieurs isotopes stables dans trois lacs peu profonds situés sur un gradient trophique et ayant différents régimes de stratification ont démontré que cette approche est prometteuse dans les lacs mésotrophes et stratifiés. Dans ces systèmes, le δ15N de la matière organique particulaire (MOP) aurait le potentiel de déterminer les sources d’azote assimilées par le phytoplancton. Cependant les mesures d’isotopes stables du carbone (δ13C) et du ratio C:N indiquent que les apports de matières organiques du bassin versant peuvent altérer les relations observées. Nous avons également constaté une déviation de la relation 1:1 entre les isotopes stables d’azote et d’oxygène (δ18O) du nitrate (NO3-) indiquant son assimilation et sa nitrification simultanée. Cette application est particulièrement prometteuse puisque la nitrification est méconnue dans les lacs et peut exacerber les effets de l’eutrophisation.

Sediment Budgeting Studies for the Kollam Coast

The Sediment budgeting studies are done to bring out the coastal processes at work, to understand the beach-innershelf sedimentary dynamics and to assess the stability of any coastal stretch. There is a dearth of such studies as far as the Indian coast is concerned. The Chavara coast of Kollam district, Kerala, is world famous for its rich heavy mineral resources. These mineral resources are being commercially mined by the Indian Rare Earths Ltd. (IREL) and Kerala Minerals and Metals Ltd. (KMML), two Public Sector Undertakings located in the area. The impact of mining on stability of the beach has been a point of debate among the local people as well as researchers. The coastal stretch of 22km length from Neendakara to Kayamkulam which is referred to as the Chavara coast. The tidal, wind driven and continental shelf currents, there could also be the contribution of coastal trapped waves and baroclinic flow associated with the plumes of fresh water coming from the estuaries. The main objectives of the study are the hydrodynamic processes and mechanism involved in the sediment movement along the Chavara coast, Identify the different sources and sinks of beach sand along the coast, Quantify the sediment input/output into/from the coast and assess the erosion/accretion scenario of the coast.

Diversity of Bacillus And Actinomycetes in the water and sediment samples from Kumarakom region of Vembanadu lake

Diversity of different groups of Bacillus and Actinomycetes in the water and sediment samples from kumarakom estuary was analysed to find out potential strains for further application. Bacillus genera was identified and grouped into five phenogroups .Phenogroups show differences in the shape of the spore,position of the spore,and swelling of the sporangium.Ability of the isolates to elaborate various hydrolytic enzymes and their ability to reduce nitrate and ferment various carbohydrate sources were also studied.

Toxic Metal Distribution in the Core Sediment of Cochin Estuarine System (CES)

This article present the result from a study of two sediment cores collected from the environmentally distinct zones of CES. Accumulation status of five toxic metals: Cadmium (Cd), Chromium (Cr), Cobalt (Co), Copper (Cu) and Lead (Pb) were analyzed. Besides texture and CHNS were determined to understand the composition of the sediment. Enrichment Factor (EF) and Anthropogenic Factor (AF) were used to differentiate the typical metal sources. Metal enrichment in the cores revealed heavy load at the northern (NS1 ) region compared with the southern zone (SS1). Elevation of metal content in core NS1 showed the industrial input. Statistical analyses were employed to understand the origin of metals in the sediment samples. Principal Component Analysis (PCA) distinguishes the two zones with different metal accumulation capacity: highest at NS1 and lowest at SS1. Correlation analysis revealed positive significant relation only in core NS1, adhering to the exposition of the intensified industrial pollution

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 2 - The sediment phase

This article investigates the temporal and spatial controls on sediment-phosphorus (P) dynamics in two contrasting sub-catchments of the River Kennet, England. Suspended sediment (collected under representative flow conditions) and size-fractionated bedload (collected weekly for one year) from the Rivers Lambourn and Enborne was analysed for a range of physico-chemical determinands. Total P concentrations were highest in the most mobile fractions of sediment: suspended sediment, fine silt and clay and organic matter (mean concentrations of 1758, 1548 and 1440 mug P g(-1) dry sediment, respectively). Correlation analysis showed significant relationships between total P and total iron (n = 110), total manganese (n = 110), organic matter (n = 110) and specific surface area (n = 28) in the Lambourn (r(2) 0.71, 0.68, 0.62 and 0.52, respectively) and between total P and total iron (n = 110), total manganese (n = 110) and organic matter (n = 110) in the Enborne (r(2) 0.74, 0.85 and 0.68, respectively). These data highlight the importance of metal oxyhydroxide adsorption of P on fine particulates and organic matter. However, high total P concentrations in the granule gravel and coarse sand size fraction during the summer period (mean concentration 228 mug P g(-1) dry sediment) also highlight the role of calcite co-precipitation on P dynamics in the Lambourn. P to cation ratios in Lambourn sediment indicated that fine silt and clay and granule gravel and coarse sand size fractions were potential sources of P release to the water column during specific periods of the summer and autumn. In the Enborne, however, only the granule gravel and coarse sand size fraction had high ratios and a slow, constant release of P was observed. In addition, scanning electron microscopy work confirmed the association of P with calcite in the Lambourn and P with iron on clay particles in the Enborne. The study highlighted the importance of the chemical and physical properties of the sediment in influencing the mechanisms controlling P storage and release within river channels. (C) 2004 Elsevier B.V. All rights reserved.

Sediment fingerprinting as an environmental forensics tool explaining cyanobacteria blooms in lakes

Cyanobacteria (blue-green algae) blooms in water bodies present serious public health issues with attendant economic and ecological impacts. Llyn Tegid (Lake Bala) is an important conservation and amenity asset within Snowdonia National Park, Wales which since the mid-1990s has experienced multiple toxic cyanobacteria blooms threatening the ecology and tourism-dependent local economy. Multiple working hypotheses explain the emergence of this problem, including climate change, land management linked to increased nutrient flux, hydromorphological alterations or changing trophic structure - any of which may operate individually or cumulatively to impair lake function. This paper reports the findings of a sedimentfingerprinting study using dated lake cores to explore the linkages between catchment and lake management practices and the emergence of the algal blooms problem. Since 1900 AD lake bed sedimentation rates have varied from 0.06 to 1.07 g cm−2 yr−1, with a pronounced acceleration since the early 1980s. Geochemical analysis revealed increases in the concentrations of total phosphorus (TP), calcium and heavy metals such as zinc and lead consistent with eutrophication and a rising pollution burden, particularly since the late 1970s. An uncertainty-inclusive sedimentfingerprinting approach was used to apportion the relative fluxes from the major catchment land cover types of improved pasture, rough grazing, forestry and channel banks. This showed improved pasture and channel banks are the dominant diffuse sources of sediment in the catchment, though forestry sources were important historically. Conversion of rough grazing to improved grassland, coupled with intensified land management and year-round livestock grazing, is concluded to provide the principal source of rising TP levels. Lake Habitat Survey and particle size analysis of lake cores demonstrate the hydromorphological impact of the River Dee Regulation Scheme, which controls water level and periodically diverts flow into Llyn Tegid from the adjacent Afon Tryweryn catchment. This hydromorphological impact has also been most pronounced since the late 1970s. It is concluded that an integrated approach combining land management to reduce agricultural runoff allied to improved water level regulation enabling recovery of littoral macrophytes offers the greatest chance halting the on-going cyanobacteria issue in Llyn Tegid.

Evaluation of field wetlands for mitigation of diffuse pollution from agriculture: sediment retention, cost and effectiveness

Diffuse pollution, and the contribution from agriculture in particular, has become increasingly important as pollution from point sources has been addressed by wastewater treatment. Land management approaches, such as construction of field wetlands, provide one group of mitigation options available to farmers. Although field wetlands are widely used for diffuse pollution control in temperate environments worldwide, there is a shortage of evidence for the effectiveness and viability of these mitigation options in the UK. The Mitigation Options for Phosphorus and Sediment Project aims to make recommendations regarding the design and effectiveness of field wetlands for diffuse pollution control in UK landscapes. Ten wetlands have been built on four farms in Cumbria and Leicestershire. This paper focuses on sediment retention within the wetlands, estimated from annual sediment surveys in the first two years, and discusses establishment costs. It is clear that the wetlands are effective in trapping a substantial amount of sediment. Estimates of annual sediment retention suggest higher trapping rates at sandy sites (0.5–6 t ha�1 yr�1), compared to silty sites (0.02–0.4 t ha�1 yr�1) and clay sites (0.01–0.07 t ha�1 yr�1). Establishment costs for the wetlands ranged from £280 to £3100 and depended more on site specific factors, such as fencing and gateways on livestock farms, rather than on wetland size or design. Wetlands with lower trapping rates would also have lower maintenance costs, as dredging would be required less frequently. The results indicate that field wetlands show promise for inclusion in agri-environment schemes, particularly if capital payments can be provided for establishment, to encourage uptake of these multi-functional features.

Dust sources and deposition during the last glacial maximum and current climate: a comparison of model results with paleodata from ice cores and marine sediments

Mineral dust aerosols in the atmosphere have the potential to affect the global climate by influencing the radiative balance of the atmosphere and the supply of micronutrients to the ocean. Ice and marine sediment cores indicate that dust deposition from the atmosphere was at some locations 2–20 times greater during glacial periods, raising the possibility that mineral aerosols might have contributed to climate change on glacial-interglacial time scales. To address this question, we have used linked terrestrial biosphere, dust source, and atmospheric transport models to simulate the dust cycle in the atmosphere for current and last glacial maximum (LGM) climates. We obtain a 2.5-fold higher dust loading in the entire atmosphere and a twenty-fold higher loading in high latitudes, in LGM relative to present. Comparisons to a compilation of atmospheric dust deposition flux estimates for LGM and present in marine sediment and ice cores show that the simulated flux ratios are broadly in agreement with observations; differences suggest where further improvements in the simple dust model could be made. The simulated increase in high-latitude dustiness depends on the expansion of unvegetated areas, especially in the high latitudes and in central Asia, caused by a combination of increased aridity and low atmospheric [CO2]. The existence of these dust source areas at the LGM is supported by pollen data and loess distribution in the northern continents. These results point to a role for vegetation feedbacks, including climate effects and physiological effects of low [CO2], in modulating the atmospheric distribution of dust.

Sediment-contact fish embryo toxicity assay with Danio rerio to assess particle-bound pollutants in the Tiete River Basin (Sao Paulo, Brazil)

The Tiete River and its tributary Pinheiros River receive a highly complex organic and inorganic pollutants load from sanitary sewage and industrial sources, as well as agricultural and agroindustrial activities. The aim of the present study was to evaluate the embryotoxic and teratogenic effects of sediments from selected locations in the Tiete River Basin by means of the sediment contact embryo toxicity assay with Danio rerio, in order to provide a comprehensive and realistic insight into the bioavailable hazard potential of these sediment samples. Lethal and sub-lethal effects were recorded, and high embryo toxicity could be found in the samples not only in the vicinity of the megacity Sao Paulo (Billings reservoir and Pinheiros River samples), but also downstream (in the reservoirs Barra Bonita, Promissao and Tres Irmaos). Results confirm that most toxicity is due to the discharges of the metropolitan area of Sao Paulo. However, they also indicate additional sources of pollutants along the river course, probably from industrial, agricultural and agroindustrial residues, which contribute to the degradation of each area. The sediment contact fish embryo test showed to be powerful tool to detect embryo toxicity in sediments, not only by being a sensitive method, but also for taking into account bioavailability. This test provides an ecological highly realistic and relevant exposure scenario, and should therefore be added in ecotoxicological sediment quality assessments. (C) 2011 Elsevier Inc. All rights reserved.

Integrated sediment quality assessment in Paranagua Estuarine System, Southern Brazil

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Acute and chronic toxicity of sediment samples from Guanabara Bay (RJ) during the rainy period

A Baía de Guanabara é um ambiente marinho-estuarino de grande relevância ecológica e sócio-econômica, e sujeita a uma ampla gama de impactos ambientais. O sedimento é o principal destino para a maioria das substâncias introduzidas nos corpos d'água, podendo fornecer uma medida integrada da qualidade ambiental, a qual pode ser avaliada por várias abordagens. Neste projeto, a qualidade de sedimentos da Baía de Guanabara foi por uma abordagem ecotoxicológica, por meio de testes de toxicidade aguda de sedimento integral, utilizando Tiburonella viscana, e testes de toxicidade crônica de água intersticial, elutriato e interface sedimento-água, utilizando embriões de Lytechinus variegatus. Os sedimentos foram coletados em 14 estações de amostragem. Nos testes crônicos houve efeitos significativos na maioria das amostras, enquanto os sedimentos coletados nas estações 1, 2, 3, 6, 8, 10, 11, 12 e 15 apresentaram também toxicidade aguda. Houve grande concordância entre os resultados dos diferentes testes, e sua integração mostrou que os sedimentos analisados encontram-se inadequados à vida aquática, indicando degradação ambiental na baía da Guanabara. Nesse contexto, o controle das fontes poluidoras e o gerenciamento dos múltiplos usos da baía devem ser implementados, no sentido da melhora da qualidade ambiental.

Sediment quality assessment in a tropical estuary: The case of Ceará River, Northeastern Brazil

The present study aimed to assess the sediment quality in a tropical estuary located in the northeast of Brazil under semi-arid conditions and multiple sources of contamination, using both toxicity bioassays and metal distribution. The metal distribution followed a concentration gradient decreasing one order of magnitude from the inner station toward the outer estuary, with amounts in the following order: Fe > Al > Zn > Cr > Pb > Cu. The index of geoaccumulation indicated a metal enrichment in the Ceará river sediment, mainly at inner sites, considered from moderately to strongly contaminated by Al, Cu, Cr and Zn. Sediment samples were considered toxic by means of whole sediment tests with copepods (reproduction) and amphipods (survival), and also elutriate fraction and sediment-water interface with sea urchin embryos (development). Acute and chronic toxicity did not exhibit a significant correlation with metals, emphasizing the influence of other contaminants mainly related to the pollution sources installed in the mid-estuary. © 2013 Elsevier Ltd. All rights reserved.

Cumulative influences of a small city and former mining activities on the sediment quality of a subtropical estuarine protected area

This study aimed to evaluate the sediment quality in the estuarine protected area known as Canan,ia-Iguape-Peruibe (CIP-PA), located on the southeastern coast of Brazil. The study was designed considering possible negative effects induced by the city of Canan,ia on the sediment quality of surrounding areas. This evaluation was performed using chemical and ecotoxicological analyses. Sediments were predominantly sandy, with low CaCO3 contents. Amounts of organic matter varied, but higher contents occurred closer to the city, as well as did Fe and Total Recoverable Oils and Greases (TROGs) concentrations. Contamination by Cd and Cu was revealed in some samples, while concentrations of Zn were considered low. Chronic toxicity was detected in all tested sediments and acute toxicity occurred only in sediments collected near the city. The principal component analysis (PCA) revealed an association among Cd, Cu, Fe, TROG, fines, organic matter, CaCO3, and chronic toxicity, whereas acute toxicity was found to be associated with Zn and mud. However, because Zn levels were low, acute toxicity was likely due to a contaminant that was not measured. Results show that there is a broad area within the CIP-PA that is under the influence of mining activities (chronic toxicity, moderate contamination by metals), whereas poorer conditions occur closer to Canan,ia (acute toxicity); thus, the urban area seems to constitute a relevant source of contaminants for the estuarine complex. These results show that contamination is already capable of producing risks for the local aquatic biota, which suggests that the CIP-PA effectiveness in protecting estuarine biota may be threatened.