Organic and total mercury determination in sediments by cold vapor atomic absorption spectrometry: methodology validation and uncertainty measurements

The purpose of the present study was to validate a method for organic Hg determination in sediment. The procedure for organic Hg was adapted from literature, where the organomercurial compounds were extracted with dichloromethane in acid medium and subsequent destruction of organic compounds by bromine chloride. Total Hg was performed according to 3051A USEPA methodology. Mercury quantification for both methodologies was then performed by CVAAS. Methodology validation was verified by analyzing certified reference materials for total Hg and methylmercury. The uncertainties for both methodologies were calculated. The quantification limit of 3.3 µg kg-1 was found for organic Hg by CVAAS.

DISTRIBUIÇÃO E FRACIONAMENTO DO Hg EM SEDIMENTOS DO RIO PARAÍBA DO SUL – RJ, BRASIL

Mercury distribution and fractionation were determined in sediments from the Paraíba do Sul River – RJ, Brazil. Total mercury concentration ranged from 1 to 158 ng g-1. Hg associated with the weakly bound fraction was dominant in the estuarine areas (main - 60% and secondary - 55%); followed by fluvial end member (48%) and mangrove (18%). These results reinforce the mercury availability to fluvial and estuarine areas and emphasize the key role played by mangroves as an efficient biogeochemical barrier. In conclusion, the continuous reduction of the mangrove ecosystem around the world can exacerbate the damage resulting from the mercury accumulation.

Holocene Varved Lake Sediments as Records of Palaeoenvironmental Change and Geomagnetic Palaeosecular Variation in Eastern Finland

This dissertation discusses Holocene palaeoenvironmental and palaeomagnetic secular variation (PSV) records reconstructed from sediments preserved in Lake Lehmilampi (63º37´N, 29º06´E) and Lake Kortejärvi (63º37´N, 28º56´E) in eastern Finland. Several piston and freeze cores were obtained from both lakes for varve and magnetic analyses. Sediment samples were impregnated in low-viscosity epoxy and physical parameters of varves, including varve thickness and relative grey-scale values, were recorded using x-ray densitometry combined with semiautomatic digital image analysis. On average, varve records of Lehmilampi and Kortejärvi cover 5122 and 3902 years, respectively. Past solar activity, as estimated by residual ₁₄C data, compares favourably with varve thicknesses from Lehmilampi during the last 2000 years. This indicates the potential of clastic-organic varves to record sensitively climatic variations. Bulk magnetic parameters, including magnetic susceptibility together with natural, anhysteretic and isothermal remanent magnetizations, were measured to describe mineral magnetic properties and geomagnetic palaeosecular variation recorded in the sediments. Main stages in the development of the investigated lakes are reflected in the variations in the mineral magnetic records, sediment lithology and composition. Similar variations in magnetic parameters and sediment organic matter suggest contribution of bacterial magnetite in the magnetic assemblages of Lehmilampi. Inclination and relative declination records yielded largely consistent results, attesting to the great potential of these sediments to preserve directional palaeosecular variation in high resolution. The PSV data from Lehmilampi and Kortejärvi were stacked into North Karelian PSV stack, which may be used for dating homogenous lake sediments in the same regional context. Reconstructed millennial variations in relative palaeointensity results are approximately in agreement with those seen in the absolute palaeointensity data from Europe. Centennial variations in the relative palaeointensity, however, are influenced by environmental changes. Caution is recommended when using varved lake sediments in reconstructing relative palaeointensity.

Humic substances from sediments of Lobos Pond (Argentina). Isolation, characterization and limnological implications

Humic substances (HS) were isolated from the sediments of Lobos Pond (Argentina) using mild conditions to preserve their native structure. The HS (humic and fulvic acids) were characterized by means of elemental analysis and FTIR spectroscopy. Also a by-product obtained during fulvic acids (FA) fractionation (an amorphous white solid residue) was analyzed. Results revealed possible interactions between FA and inorganic-organic substances that may have implications referring to bioavailability. Other limnological implications, such as autochtonous origin of HS linked with the hydrology, and change of pH during stormy weather that affects HS interactions, are discussed.

Turbidimetry as an alternative method to determine the rating curve of suspended sediments

Understanding hydrosedimental behavior of a watershed is essential for properly managing and using its hydric resources. The objective of this study was to verify the feasibility of the alternative procedure for the indirect determination of the sediment key curve using a turbidimeter. The research was carried out on the São Francisco Falso River, which is situated in the west of the state of Paraná on the left bank of ITAIPU reservoir. The direct method was applied using a DH-48 sediment suspended sampler. The indirect method consisted of the use of a linigraph and a turbidimeter. Based on the results obtained, it was concluded that the indirect method using a turbidimeter showed to be fully feasible, since it gave a power function-type mathematical model equal of the direct method. Furthermore, the average suspended sediment discharge into the São Francisco Falso River during the 2006/2007 harvest was calculated at 7.26 metric t day-1.

Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

Lithostratigraphy and age of pre-Late Weichselian sediments in the Suupohja area, western Finland

Different types of laterally extensive sand- and gravel-dominated deposits, up to several tens of metres thick, were investigated in the Suupohja area of western Finland. The studied sediments were deposited in glacial, ice-marginal, glaciofluvial, sea or lake, littoral and terrestrial environments during several glacial-non-glacial cycles. Seventeen pre-Late Weichselian and three Late Weichselian/Holocene sedimentary units were identified. These were divided into ten formally and two informally defined formations that were together termed the Suupohja Group. Every unit are nevertheless not detectable throughout the study area. The informally defined “Karhukangas lower deposits” represent the lowest units in the Suupohja Group. The Karhukangas lower deposits with 5 till units, 3 glaciolacustrine/-marine units and 2 sand units, were interpreted as having been deposited during possibly four glacial-non-glacial cycles before the Late Pleistocene Subepoch (MIS 6 or earlier). The Kankalo Sand above the Karhukangas lower deposits comprises glaciofluvial and aeolian sands of Late Saalian, Eemian or Early Weichselian origin (MIS 6–MIS 5c). The Kariluoma Till above the Kankalo Sand was possibly deposited during the Late Saalian glacial advance, although an Early Weichselian origin is also possible. The Harrinkangas Formation, with glaciofluvial and quiet-water sediments, is interpreted as having been deposited during the Late Saalian and Eemian Stages (MIS 6–MIS 5e). The uppermost units in the deposits studied, the Kodesjärvi Formation (shore deposit), Isojoki Sand (aeolian), Rävåsen Formation (glaciofluvial), Vanhakylä Formation (shore line deposit), Dagsmark Till and Kauhajoki Till, were deposited during the Weichselian Stage (MIS 5d–MIS 2). In addition, Early Holocene (MIS 1) eskers without till cover were informally termed the “Holocene esker deposits”. The Lumikangas Formation represents gravelly shore deposits formed in the Holocene Epoch, when these areas last emerged from the sea. The first Weichselian ice expansion possibly reached the western part of Suupohja in the Early Weichselian Substage (MIS 5d?), but it did not expand further to the east. The second Weichselian glaciation of relatively short duration occupied the southern part of Finland in the later part of Middle Weichselian (MIS 3). Thus, the southern half of the country remained ice-free for the majority (~65–75%) of the Weichselian Stage. Instead, both humid temperate and periglacial conditions alternated. In the initial part of Middle Weichselian, this area was partly submerged, which indicates eastward expansion of the Scandinavian ice sheet(s), depressing the lithosphere. The exceptionally thick sediment cover, multiple lithofacies, relict landscape and preserved preglacially weathered bedrock are evidence of weak glacial erosion in the Suupohja area during the latest as well as earlier glaciations, making this area one of the key areas in Quaternary research.

Acute and chronic effects of cadmium on blood homeostasis of an estuarine crab, Chasmagnathus granulata, and the modifying effect of salinity

Whole body oxygen consumption and some hemolymph parameters such as pH, partial pressure of gases, level of ions and lactate were measured in the estuarine crab Chasmagnathus granulata after both acute (96 h) and chronic (2 weeks) exposure to cadmium at concentrations ranging from 0.4 to 6.3 mg/l. In all instances, the crabs developed hemolymph acidosis, but no respiratory (increased PCO2) or lactate increases were evident. Hemolymph levels of sodium and calcium were always increased by cadmium exposure. The chronic toxicity of cadmium was enhanced at 12‰ salinity, even causing a significantly higher mortality in comparison with the higher salinity (30‰) used. A general metabolic arrest took place at 12‰ salinity in the crabs chronically exposed to cadmium, as indicated by decreases of oxygen consumption and PCO2, an increase of PO2, along with no changes in lactate levels. These imbalances were associated with severe necrosis and telangiectasia in the respiratory gills, probably leading to respiratory impairment and finally histotoxic hypoxia and death of the animals.

Persistent organic pollutants in sediments and fish from Lake Victoria, Uganda

This thesis describes the occurrence and sources of selected persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexachlorocyclohexanes (HCHs) in the northern watershed of Lake Victoria. Sediments and fish were collected from three highly polluted embayments (i.e. Murchison Bay, Napoleon Gulf and Thurston Bay) of the lake. The analysis for PCDD/Fs, PCBs and PBDEs was done using a high resolution mass spectrometer coupled to a gas chromatograph (GC), and a GC equipped with an electron capture detector was used for HCHs. Total (Σ) PCDD/Fs, PCBs and PBDEs in sediments ranged from 3.19 to 478, 313 to 4325 and 60.8 to 179 pg g-1 dry weight (dw), respectively. The highest concentrations of pollutants were found at sites close to industrial areas and wastewater discharge points. The maximum concentrations of PCDD/Fs, PCBs, PBDEs and HCHs in fish muscle homogenates were 49, 779, 495 and 45,900 pg g-1 wet weight (ww), respectively. The concentrations of the pollutants in Nile perch (Lates niloticus) were significantly greater than those in Nile tilapia (Oreochromis niloticus), possibly due to differences in trophic level and dietary feeding habits among fish species. World Health Organization-toxic equivalency quotient (WHO2005-TEQ) values in the sediments were up to 4.24 pg g-1 dw for PCDD/Fs and 0.55 pg TEQ g-1 dw for the 12 dioxin-like PCBs (dl-PCBs). 23.1% of the samples from the Napoleon Gulf were above the interim sediment quality guideline value of 0.85 pg WHO-TEQ g-1 dw set by the Canadian Council for Ministers of the Environment. The WHO2005-TEQs in fish were 0.001-0.16 pg g-1 for PCDD/Fs and 0.001-0.31 pg g-1 ww for dl- PCBs. The TEQ values were within a permissible level of 3.5 pg g−1 ww recommended by the European Commission. Based on the Commission set TEQs and minimum risk level criteria formulated by the Agency for Toxic Substances and Disease Registry, the consumption of fish from Lake Victoria gives no indication of health risks associated to PCDD/Fs and PCBs. Principal component analysis (PCA) indicated that anthropogenic activities such as agricultural straw open burning, medical waste incinerators and municipal solid waste combustors were the major sources of PCDD/Fs in the watershed of Lake Victoria. The ratios of α-/γ-HCH varied from 0.89 to 1.68 suggesting that the highest HCH residues mainly came from earlier usage and fresh γ-HCH (lindane). In the present study, the concentration of POPs in fish were not significantly related to those in sediments, and the biota sediment accumulation factor (BSAF) concept was found to be a poor predictor of the bioavailability and bioaccumulation of environmental pollutants.

The surficial geology, sedimentology and geochemistry of the late glacial sediments and Paleozoic bedrock in the Campbellford area, Ontario, with special reference to the Dummer Complex /

The Dummer Complex extends 180 km along the Precambrian - Paleozoic contact from Tamworth to Lake Simcoe. It is composed of coarse, angular Paleozoic clasts in discontinuous, pitted, hummocky deposits. Deposits are usually separated by bare or boulder strewn bedrock, but have been found in the southern drumlinized till sheet. Dummer Complex deposits show rough alignment with ice-flow. Eskers cross-cut many of the deposits. Dummer sediment subfacies are defined on the basis of dominant coarse grain size and lithology, which relate directly to the underlying Paleozoic formation. Three subglacial tills are identified based on the degree of comminution and distance of transport; the immature facies of the Dummer Complex; the mature facies of the drumlinized till sheet and; the submature facies which is transitional. Carbonate geochemistry was used for till-bedrock correlation in various grain sizes. Of the 3 Paleozoic formations underlying the Dummer Complex, the Gull River Fm. is geochemically distinctive from the Bobcaygeon and Verulam Formations using Ca, Mg, Sr, Cu, Mn, Fe and Na. The Bobcaygeon Fm. and Verulam Fm. can be differentiated using Ca and the Sr/Ca ratio. The immature facies from 1.0 phi and finer is dominated by the non-carbonate, long distance transported component which decreases slightly downice. The submature till facies contains more long distance material than the immature facies. Sr and Mn can be used to correlate the Gull River immature till facies to the underlying bedrock the other subfacies could not be distinguished from each other or their respective source formation. This method proved to be ineffective for sediments with greater than 35% non-carbonate component, due to leaching of elements by the dissolving acid.The Dummer Complex is produced subglacially , as the compressional ice encounters the permeable Paleozoic carbonates. The increased shear strength of the ice and pore pressures in the carbonates results in the basal ice zones becoming debris ladden. Cleaner ice overrides the basal debris . laden dead ice which then acts as the glacier bed. During retreat, the Simcoe lobe stagnates as flow is cut-off by the Algonquin Highlands.

Palynology of late-glacial and postglacial sediments in Georgian Bay, Ontario, Canada, as related to the Great Lakes history /

This investigation comprises three parts: (1) the source, mechanism of transport, and distribution of pollen, spores and other palynomorphs in Georgian Bay bottom sediments and a comparison of these data with the contemporary vegetation, (2) the relative significance of fluvial transportation of pollen and spores, and (3) the late- and postglacial history of vegetational and climatic changes in the Georgicin Bay region. Modem pollen and spore assemblages in Georgian Bay do reflect the surrovinding vegetation when preservation and pollen production by the different species are considered and accounted for. Relative pollen percentage and concentration isopoll patterns indicate that rivers contribute large quantities of pollen and spores to Georgian Bay. This is further substantiated by large amounts of pollen and spores which were caught in traps in the Moon, Muskoka, and Nottawasaga Rivers which flow into Georgian Bay. The majority of pollen and spores caught in these traps were washed into the rivers by surface water runoff and so reflect the vegetation of the watershed in a regional sense. In a 12.9 metre long sediment core from northeastern Georgian Bay the relative percentage and absolute pollen concentrations allow correlation of Georgian Bay Lake phases with climatic and forest history. Four distinct pollen zones are distinguished: zone GB IV which is the oldest, reflects the succession from open spruce woodland to boreal forest; zone GB III represents a period of pine-mixed hardwoods forests from about 10,000 to 7,500 years ago. A pine-maplehemlock association dominated in zone GB II, although during the culmination of postglacial warming about 4,000 to 5,000 years ago the Georgian Bay forests had a more deciduous character. Zone GB I clearly shows European man's disturbance of the forest by logging activities.