published_or_final_version / Environmental Management / Master / Master of Science in Environmental Management

Detta examensarbete syftade till att ta fram ett underlag för en regional åtgärdsplan avseende dibenso-p-dioxiner och dibensofuraner, gemensamt benämnda som PCDD/F eller dioxiner, i Gävleborgs län. Länet har historiskt varit ett av de mest utsatta områdena i Sverige beträffande dessa föroreningar och höga koncentrationer i bland annat strömming har medfört att denna inte får saluföras i övriga EU.   I arbetet har resultaten från den rådande forskningen på området studerats för att få kunskap om nuvarande källor och möjliga förklaringar till de fortsatt förhöjda koncentrationerna av dioxiner. Därefter har data från tidigare undersökningar av dioxinkoncentrationer i Gävleborgs län samlats in, sammanställts och använts för att studera hur koncentrationerna varierar geografiskt inom länet. Principalkomponentanalys (PCA) av specifika dioxinkongeners koncentrationer har sedan använts för att försöka identifiera verksamhetstyper som potentiellt kan ha bidragit till föroreningarna på olika platser - en analys som dock är behäftad med stora osäkerheter. De insamlade provresultaten har även använts för att genom massbalansmodellering undersöka återhämtningen i två känt förorenade fjärdar i länet; Norrsundet och Gårdsfjärden. Utifrån resultaten av ovanstående analyser diskuterades även nyttan av att genomföra eventuella åtgärder för att reducera halterna i kraftigt förorenade områden.   Proverna som sammanställts visade klara geografiska skillnader i sedimentkoncentration, och till viss del även i koncentration i muskel från abborre, vilket visar på en stark betydelse av lokala källor i vissa områden. Bland strömmingsproverna kunde inget liknande samband ses. Detta kan förklaras av att det migrerande beteendet hos strömming gör att fisken under sin livstid exponeras för varierande föroreningsnivåer i olika områden, medan abborren är mer stationär även som vuxen. Principalkomponentanalysen gav, för vissa prover, indikationer kring vilken typ av verksamhet som bidragit till de uppmätta koncentrationerna. Dessa resultat är dock mycket osäkra och bör inte på egen hand användas som underlag för att fastställa föroreningskällor. Massbalansmodelleringen visade att PCDD/F-koncentrationen i sediment inte har någon betydelse för koncentrationen i vattenmassan utan att inflödet från omgivande hav dominerar även i avgränsade fjärdar. De modellerade jämviktskoncentrationerna mellan sediment och vattenmassa indikerade även att koncentrationerna i sediment kommer fortsätta överskrida somliga gränsvärden tills koncentrationen i vattenmassan reducerats, vilket även stöds av att dessa gränsvärden överskreds i majoriteten av de sammanställda proverna.   Baserat på samtliga ovannämnda resultat drogs slutsatsen att lokala saneringsåtgärder sannolikt inte ger någon effekt på PCDD/F-koncentrationerna i strömming, samt att de inte är tillräckliga för att erhålla sedimentkoncentrationer under samtliga gränsvärden. De kan däremot effektivt minska den exponering som mer stationära organismer som abborre utsätts för i områden med kraftigt förorenade sediment, och kan även ha positiva effekter på förekomsten av andra miljöfarliga ämnen i området. För- och nackdelar måste således övervägas i varje enskilt fall. / The aim of this Master’s Thesis was to provide a basis for a regional plan of action regarding dibenzo-p-dioxins and dibenzofurans, commonly referred to as PCDD/F or dioxins, in Gävle-borg County. This region has historically been one of the Swedish areas most affected by these pollutants, and high concentrations in for example Atlantic herring (Clupea harengus) have resulted in restrictions where some fish species cannot be sold in other EU countries.   In this work, results of current research on the subject were studied in order to gain knowledge about current sources and possible explanations to the continued high concentrations of dioxins. Thereafter, data from earlier investigations of dioxin levels in Gävleborg County have been gathered, compiled and used to study the regional geographic variation of the concentrations. Principal component analysis (PCA) was then used on the concentrations of specific congeners in an attempt to identify source types that might have contributed to the contamination in various sites; this analysis is however marred by uncertainties. The gathered data have also been used to investigate the recovery in two bays with known contaminations, Norrsundet and Gårdsfjärden, using mass balance modelling. The benefits of implementing measures to reduce the PCDD/F-concentrations in highly polluted areas were then discussed based on the results of the above-mentioned analyses.   The measured sediment concentrations, and partly also the concentrations in European perch (Perca fluviatilis), of the compiled samples showed distinct geographic differences, which indicates a strong influence from local sources in some areas. Among the herring samples, no such connection could be seen. This could be explained by the migrating behaviour of adult herring, resulting in an exposure to various levels of contamination in different areas as they migrate, while adult perch has a more stationary behaviour. For some samples, the principal component analysis gave indications on source types that might have contributed to the local contamination levels. These results are however very uncertain and they should not be used as the sole basis when determining emission sources. The mass balance modelling showed that the PCDD/F-concentrations in sediments have no influence on the concentrations in the water body; the inflow from the surrounding sea is predominant also in enclosed bays. The modelled equilibrium concentrations between sediments and water body also indicated that the sediment concentrations will continue to exceed the guideline values until the water concentrations have decreased. This is also supported by the fact that the majority of the samples showed concentrations exceeding these guideline values.   Based on all of the abovementioned results it was concluded that local remediation measures would most likely not affect the PCDD/F-concentrations in herring. It was also concluded that such measures would not suffice to obtain sediment concentrations that fall below all guideline values. They can however be used to lessen the exposure that stationary organisms are subjected to in areas with highly contaminated sediments, and can also have positive effects on the levels of other hazardous substances in the area. Thus, the benefits and disadvantages need to be considered in each specific case.

Three approaches were employed to examine the effects of elevated sediment trace metal concentrations on estuarine/marine macrobenthic invertebrate assemblages. The initial study examined macroinvertebrate communities along a known polymetallic gradient, Lake Macquarie, NSW (gradient study). The second study experimentally tested if sediments sourced from different locations within Lake Macquarie differentially influenced the recolonisation of benthic invertebrates. The third study investigated the different recolonisation patterns of benthic invertebrates into sediments spiked with increasing concentrations of sediment-bound cadmium. In the Lake Macquarie gradient study, four locations (Cockle Bay, Warner's Bay, Kooroora Bay and Nord's Wharf) were sampled in winter 2000 and summer 2003 using a hierarchical design (location > site > plot). On both sampling occasions, the sediments showed strong gradients in lead, cadmium and zinc concentrations emanating from the Cockle Bay industrialised region in the lake's north, with concentrations being significantly lower in the most southern and less urbanised location (Nord's Wharf). In general, concentrations of lead, cadmium and zinc in the sediments increased among locations in the following order: Nord's Wharf > Kooroora Bay > Warner's Bay > Cockle Bay. AVSJSEM analyses indicated that in some sites in Cockle Bay, and to a lesser extent Warner's Bay, SEM concentrations exceeded their molar equivalence of AVS, indicating the potential for trace metals to be labile within the porewaters. Granulometry also changed along the gradient, with a higher proportion of silt/clay occurring in the locations with high metal concentrations. Conversely, the percentage of total organic carbon was higher in the less contaminated locations. In winter 2000, changes in benthic communities along the gradient supported the a priori hypotheses, with diversity and richness being greater in locations with lower concentrations of metals. Polychaetes were most numerous in Cockle Bay and Warner's Bay, whilst bivalves and gastropods were more abundant in Nord's Wharf and Kooroora Bay. Crustaceans were more numerous in Nord's Wharf; with all other locations having similar, lower, abundances. Ordination maps of the assemblages provided relatively clear separation of the assemblages among locations, with nonparametric multivariate analysis of variance (NPMANOVA) and subsequent pair-wise comparisons finding significant differences among the assemblages from all locations. SIMPER analyses found the highest level of dissimilarity was between the Nord's Wharf and Cockle Bay assemblages - primarily attributable to differences in the relative contributions of isopods; tellenid bivalves; and the polychaete families Spionidae, Opheliidae and Nephytidae. Weighted Spearman rank correlations (BIOENV) identified cadmium (Pw =0.74) as the strongest environmental (single or combination) variable to correlate with biotic assemblages. Benthic patterns along the gradient were less defined in summer 2003 due to a dramatic reduction in the abundance and diversity of fauna in Nord's Wharf. This decline was possibly attributable to a sustained reduction in salinity caused by a prolonged rainfall event. With the exception of Nord's Wharf, trends in the community indices and abundances of key taxa among the other locations were similar to those reported in winter 2000. Multivariate analyses discriminated the benthic assemblages from the four locations, with the findings from the NPMANOVA pair-wise comparisons indicating that the assemblages from all four locations were significantly different. SIMPER analyses showed the highest level of dissimilarity was between Nord's Wharf and Warner's Bay, with these differences being primarily attributable to their relative abundances of amphipods and polychaetes from the families Spionidae, Cirratulidae, Opheliidae and Capitellidae. BIOENV found that the combination of the sedimentary concentrations of cadmium and iron provided the best correlation (Pw =0.73) with biotic patterns, with similar correlations occumng with the addition of lead and its covariate, zinc (Pw =0.72). The combined findings from the gradient study established a strong correlation between trace metal concentrations within the sediments and suite of univariate and multivariate measurements. The low abundance and diversity of fauna in Nord's Wharf in the summer of 2003 highlighted the dynamic changes which can occur in the distributions of macrobenthic invertebrates. Although the study indicated that there was a strong relationship between trace metal concentrations and benthic community structure, the study was correlative, and requires subsequent experimental testing to confirm the causality of the observed relationships. The second component of the research was a translocation experiment using benthic recolonisation as an end-point. The experiment was performed to identify if the sediments, and not location, were influencing the composition of benthic assemblages in Lake Macquarie. Sediments were collected from three locations (Cockle Bay, Warner's Bay and Nord's Wharf), defaunated, and transplanted in three new locations along the south-east edge of the lake. At each location, 10 containers of each treatment were randomly placed in the sediment and allowed to recolonise for 22 weeks. Upon retrieval, the benthic communities were sampled and enumerated in conjunction with a variety of chemical and sedimentary measurements. Ten replicate invertebrate samples were also collected in the sediments adjacent to the experiment (ambient samples) at the completion of the experiment. Due to human interference, the containers from only two locations were analysed. Upon retrieval, pH and redox profiles of the sediments were similar to those expected in natural sediments. In general, concentrations of metals were low in the porewaters; however, iron precipitation on the porewater collection devices may have artificially increased the diffusion of metals, increasing concentrations near the sediment-water interface. Concentrations of SEM exceeded their AVS equivalence in some samples taken from the Cockle Bay and Warner's Bay treatments. Two-way ANOVAs found significant interactions between location and sediment treatments in diversity, evenness and the number of polychaetes, as well as significant differences in the number of capitellids and crustaceans among locations. Post-hoc comparisons of means found the Nord's Wharf sediment contained a higher mean number of individuals than the other treatments, including the ambient samples. nMDS ordination plots for both locations provided poor graphical discrimination of the assemblages among treatments; however, NPMANOVA detected significant location and treatment interactions. In both locations, pair-wise comparisons indicated that the assemblages within the Nord's Wharf treatments were significantly different to the Cockle Bay, Warner's Bay and ambient assemblages. No significant differences were detected between the Cockle Bay and Warner's Bay assemblages at either location. SIMPER analyses found the highest level of dissimilarity occurred between the ambient assemblages in Location 2 and the Nord's Wharf treatment, primarily due to the relative difference in the abundances of Capitellidae, Spionidae, Oweniidae, Nereididae and isopods among the assemblages. The findings from the translocation experiment suggest that the sediments are influencing the recolonisation of benthos. However, because differences were not detected between the Cockle Bay and Warner's Bay treatments, the approach used in the study shows potential as an in situ technique which could be used to assess the potential ecological risks of sediments fiom specific locations. Excluding cost and time considerations, the technique's primary disadvantage is the lack of a true control. As a result, the technique can only identify if the sediments are modifying benthic recolonisation, and not causality. The final component of the research experimentally tested if elevated concentrations of sediment-bound cadmium affected benthic invertebrate recolonisation. Sediments from the south coast of New South Wales (Durras Lake) were defaunated, and spiked with cadmium under anaerobic conditions to obtain three targeted cadmium concentrations: control (<O.1 ug/g), Low-Cd (15 Cd ug/g) and High-Cd (150 Cd ug/g). The physio-chemical properties of the waters and porewater concentrations of cadmium were monitored over a 28-day equilibration period, with declines in pH mediated with the addition of NaOH(aq). At the end of the equilibration period, porewater concentrations of cadmium were low in the Low-Cd and High-Cd treatments (maximum <l.5 ug/L in High-Cd), and below the detection limit in the control. Cadmium was not detected in the control sediments, with concentrations in the Cd-Low and Cd-High sediments exceeding their targeted concentrations, with final mean concentrations of 17 ug/g and 183 ug/g, respectively. The experimental design was similar to that employed in the translocation experiment, with 10 containers from each treatment transplanted into the sediments at three locations within Lake Macquarie. After 20 weeks, the containers were collected, along with benthic invertebrate samples from the ambient sediments. Data was not used from Location C due to extensive sediment deposition on the transplanted treatments. Significant declines occurred in the concentrations of cadmium in both the Low-Cd and High-Cd sediments, with the greatest loss occumng in the surficial sediments. The loss of cadmium was probably due to the differential loss of the fine fraction through physical means (hydrodynamic) rather than fluxing, as it assumed that the cadmium was primarily sediment-bound and relatively insoluble under anoxic conditions. Mean porewater concentrations of cadmium were below the detection limit in the control treatments; < 1 ug/L in the Low-Cd treatment, and generally < 2ug/L in the High-Cd, with the exception of some samples in Location B (maximum 5.6 ug/L) Concentrations of ammonia were low in the porewaters from the surficial sediments, with concentrations being significantly higher, and potentially toxic, in the anoxic porewaters (7 cm depth). In comparison to the previous recolonisation experiment, the number of individuals which recolonised the cadmium-spiked treatments was low, and significantly lower than the mean number of individuals sampled in the ambient sediments. No significant differences were detected among the treatments or locations (and their interactions) in diversity (H'), richness (d) or evenness (J). The number of polychaetes and molluscs significantly differed among the treatments, with post-hoc analyses indicating these differences were not among the cadmium-spike treatments, but were due to a greater mean abundance of these taxa in the ambient sediments. A significant interaction between treatment and location was detected in the mean abundance of crustaceans, with the ambient sediments having significantly lower mean abundances in both Location A and B. Ordination plots of the experiments in Location A and B provided poor graphical discrimination among the spiked treatments, although the ambient assemblages appear to be separated from the cadmium-spiked assemblages. NPMANOVA detected a significant interaction between treatments and locations, as well as among treatments. In both Location A and B, pair-wise analyses found the assemblages in the ambient sediments to be significantly different to the assemblages in all three cadmium treatments, with no differences being detected among the latter. SIMPER analyses found the highest levels of dissimilarity occurred between the spike-treatments and the ambient sediments, with these differences being primarily due to the relatively higher abundance of decapods in the spiked treatments, and capitellids in the ambient sediments. The cadmium-spiking component of the experiment clearly illustrated that artificially increasing the trace metal concentrations of metals in estuarine sediments is a complex process which needs to be performed in a methodological manner in order to obtain homogenous treatments with low porewater concentrations, and minimal artefacts. Furthermore, the results confirmed that the equilibration time for sediments can be extensive (several weeks), even in the case of organically rich sediments. The timing of the experiment (commenced late summer, February, 2003) appears to the major factor for the relatively low recolonisation rates, with the experiment missing the main larval recolonisation period between spring and early summer. Even in the highest treatment, elevated concentrations of cadmium did not appear to affect benthic recolonisation. This finding is supported by other experimental studies which suggest that concentrations of a single isolated metal must considerably exceed current guideline values (or contain high porewater concentrations) in order to elicit a biological effect. Nevertheless, as trace metals generally co-occur with other contaminants - with the response of multiple contaminants being possibly additive or synergistic - a conservative guideline value may be suitable in the interim as a precautionary measure. The findings of this thesis suggest that elevated concentrations of trace metal mixtures in estuarine sediments can affect the structure and composition of benthic communities; however, identifying causality is difficult. Although there has been an increase in the use of manipulative field experiments as a means of reducing the confounding influence of covariables found in field studies, this approach also has limitations, e.g. spatial and temporal scale issues, container effects, cost and biogeochemical changes to the sediments. Measuring stress at a community level is a fundamental component of estuarine risk assessment programs; and in isolation this approach can produce subjective and confounded findings. In order to accurately assess the risks associated with trace metal contaminated sediments, an integrated approach (e.g. weight of evidence) is required, one which uses multiple lines of evidence sourced from various chemical, environmental biological measurements.

Two Oregon reservoirs contaminated by different mercury sources were compared for mercury distribution in sediment and bioaccumulation by fish. The average mercury concentration in the sediment of Cottage Grove reservoir (0.67 �� 0.05 ��g/g dry wt) was higher than for Dorena Reservoir (0.12 �� 0.01 ��g/g dry wt). Sediment mercury in the main tributary of Cottage Grove Reservoir, which drains the tailing of past mercury mining activities, was ten fold higher than mercury in sediment from other reservoir tributaries with no evidence of mining. However, there were no significant differences between sediment mercury concentrations in the tributaries of the Dorena Reservoir, which has no mercury mining history within its watershed. Three fish species (largemouth bass, bluegill, crappie) from Cottage Grove Reservoir had significantly higher levels of mercury than the same species from Dorena Reservoir. These results indicated that a point source, Black Butte Mine, contributed amounts of mercury in excess of natural deposits based on differences in bioaccumulation among fish populations from these two systems. Cottage Grove Reservoir was examined for environmental evidence of point source mercury pollution. High mercury concentrations were found at various points around the suspected source, the Black Butte Mine area. The highest concentration occurred close to the kiln. The mercury concentration in the sediments of a creek below the mine dump was up to ten times higher than that of the sediments of a creek from a watershed adjacent to the watershed of the mine area. Two sediment cores from the deep area were collected to assess for pollution history profiles. These showed mercury loading in Cottage Grove Reservoir was consistent with the past mercury production in Black Butte Mine. Therefore most of mercury in Cottage Grove Reservoir was believed to be of Black Butte Mine origin. Mercury contents in pore water and food web indicated that continuing mercury transportation from the point source create a management problem in Cottage Grove Reservoir. / Graduation date: 1996

published_or_final_version / abstract / toc / Ecology and Biodiversity / Master / Master of Philosophy

Contaminated sediments represent a common environmental problem because they can sequester large quantities of contaminants which can remain long after the source of pollution has been removed. From the sediment these hazardous compounds are released into the sediment porewater where it can partition into organisms in the sediment and bioaccumulate up the food web; leading to an ecological and human health concern. The objective of this work is to investigate an emerging option in contaminated sediment remediation; specifically an option for in-situ treatment known as active capping. Conventional capping uses clean sediment or sands to separate contaminated sediment from overlying water and biota. Active capping is the use of a sorptive amendment to such a cap to improve its effectiveness. This work focuses on granular materials as direct amendments to conventional caps including; granular activated carbon (GAC), iron/palladium amended GAC, alumina pillared clay, rice husk char, and organically modified clays. All materials were investigated in batch sorption tests of benzene, chlorobenzene, and naphthalene in DI water. Additionally porewaters from three sites were extruded and the concentrations of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were measured. At Manistique Harbor and Ottawa River PCBs were identified as the primary contaminant of concern while PAHs were the contaminant of concern at the Grand Calumet River. At these sites a solvent extraction method was used to analyze the sediment concentrations of the contaminants of concern. From the former batch tests activated carbon and a commercially available organoclay were chosen for further investigation. This includes PAHs in batch sorption tests using extruded sediment porewater to investigate matrix effects, and PCB sorption in distilled water. / text

Concentrations of selenium (Se), manganese (Mn), zinc (Zn), cadmium (Cd), lead (Pb) and arsenic (As) were measured in the water column, sediment and biota, in conjunction with selected physicochemical data, from representative wetland types at a mining site within Salt Lake County, Utah, USA. The selected field sites included Oolitic Pond (lentic) and Lee Creek (lotic), which are moderately contaminated brackish, alkaline aquatic wetlands managed by a copper mining industry. These fishless wetlands are located in a geographic region that poses risk to migratory shorebird populations from dietary Se. A spatial sampling study demonstrated the extent of variation in total Se concentration within the wetlands. With the exception of the sediment compartment, Se concentration did not differ significantly along the 2-mile length of Lee Creek or within the Pond. The differences in sediment total Se concentrations between the Creek East and West segments characterize lower Lee Creek as having two segments distinguished by unique processes that influence the sediment Se accumulation profiles. Se accumulation trends were observed temporally over 3-years (2000 to 2002) and over two seasons (spring and autumn). Total Se body burden in benthic invertebrates was more clearly associated with sediment/detritus Se concentrations than with surface water concentrations. Three invertebrate groups dominated the aquatic invertebrates assemblage in the lotic and lentic benthos; primary consumers (Chironomidae, Diptera), generalist feeders (Hemiptera) and predators (Odonata). The chironomid larvae accumulated 1.3 to 39 times the trace metal concentrations of the Hemiptera or odonate taxa, independent of trace metal type (essential or non-essential) or wetland occupation. Organism-specific factors, such as habitat selection and preferential feeding habits, were proposed to influence benthic invertebrate accumulation profiles by modifying trace metal exposure. Mixed diets, trophic omnivory and the complexity of wetland biogeochemistry limit the power of stable nitrogen fractionation signatures to define benthic food web relationships. Wetland site-specific processes impacted Se accumulating efficiency, with trace metal concentrations from 4 to 7 times greater within the lentic benthic system than the lotic. The fractionation of the natural abundant stable carbon isotopes revealed the importance of sedimentary and detrital organic carbon as dietary sources for the benthic food web. Sediment organic content was not significantly associated with sediment, or invertebrate, Se accumulation profiles. Ecological risk assessments based on sound understanding of metal chemistry and the interactions between the sediment matrix and benthic organisms are necessary to provide tools for environmental management. / Graduation date: 2005

A regional survey of environmentally harmful substances in fish in autumn 2013 revealed elevated levels of polychlorinated biphenyls (PCBs) in perch from Lake Oxundasjön, north of Upplands Väsby in Stockholm County. Follow-up studies have shown that the quantity of PCBs contained in the lake is unique of its kind in Sweden, and that the area of influence also includes downstream Rosersbergsviken, a bay of Lake Mälaren. The elevated concentrations in fish exceed today's market limits and environmental quality standards for PCBs, as of this, responsible authorities discourage from consumption of fish from Lake Oxundasjön and Rosersbergsviken. The aim has been to use statistical analyses and mass-balance modelling to study the current state of the lake system and how it may evolve in the future under different circumstances. There is a statistically significant correlation between PCB levels in sediment and perch from 21 different sites in the Stockholm-Mälaren region, including Lake Oxundasjön and Rosersbergsviken, this was demonstrated with a linear regression model. With the multivariate analysis method principal component analysis (PCA), it was illustrated how the contaminant levels in fish from Lake Oxundasjön and Rosersbergsviken differed on contaminant levels in fish from other sites. The difference mainly concerned the size and composition of PCBs. Mass-balance modelling of quantities and flows of PCBs in Lake Oxundasjön and Rosersbergsviken was made in the simulation program STELLA®. The modelling indicated that the system currently serves as a secondary distribution source of PCBs to the environment. The recovery of PCB levels is slow in the system, it will take more than 25 years for concentrations in fish to reach today’s market limits and environmental quality standards for PCBs. The model was used to evaluate three different treatment methods for Lake Oxundasjön: dredging, capping and activated carbon treatment. Simulations of these treatments led to a substantial improvement of the PCB situation in Lake Oxundasjön. Moreover, they also had a positive impact on the recovery process in the downstream Rosersbergsviken. Future climate changes, with warmer temperatures and higher run off, led to a slightly faster recovery progress of PCBs in the system.