Runoff and effluent discharge from mining activities has resulted in elevated concentrations of selenium in aquatic ecosystems. Bioavailability is dependent on chemical speciation. Although dissolved inorganic Se species are not directly toxic to organisms, uptake by primary producers and subsequent biotransformation to organo-selenium species substantially increase risk and bioaccumulation potential, potentially impairing reproduction in high-order organisms. The effects of dietary selenium exposure were assessed in two aquatic invertebrates: Ceriodaphnia dubia and Chironomus dilutus. Two generations of these organisms were exposed to seleniferous algae grown in 0-40 μg L-1 selenate. Dissolved selenate was readily absorbed and concentrated by algal species Pseudokirchneriella subcapitata and Chlorella kesslerii. Se had no effect on survival at treated concentrations. Dietary selenium exposures had little effect on reproductive endpoints in either invertebrate species, suggesting that invertebrates have the ability to regulate chronic Se exposures from dietary sources. These results provide valuable information concerning the effects of dietary selenium in aquatic invertebrates.

Despite the importance of tropical rivers to the global carbon cycle, the nature of carbon cycling within these watersheds has been dealt with by only a handful of studies. The current work attempts to address this lack of information, using stable isotope and concentration measurements to constrain sources and sinks of carbon in two Peninsular Malaysian watersheds. The basins are located on the central-western and northeastern coasts of the Malaysian Peninsula, and are drained by the Langat and Kelantan Rivers, respectively. Water samples were collected from three points along the two rivers twice a month, in addition to the sampling of groundwater in adjacent aquifers. Principal component analyses (PCA) on water chemistry parameters in the Langat and Kelantan Rivers show the dominance of geogenic and anthropogenic influences, grouped in 4 to 6 components that comprise over 50 % of the total dataset variances. The geogenic input is reflected by components showing strong loadings by Ca, Mg, Mn, Si, and Sr, while anthropogenic influences via pollution are indicated via strong loadings by NO3, SO4, K, Zn and Cl. The carbon isotope and concentration data appear unrelated to these groups, suggesting that the riverine carbon cycle in both locations is dominated by other factors. These may include alternative sources of organic pollution, or inputs from the local vegetation and soils. The mean riverine 13CDOC of -27.8 ± 2.9 ‰ and -26.6 ± 2.2 ‰ in the Langat and Kelantan Basins, respectively, are consistent with the dominance of C3-type vegetation in both watersheds. Riverine 13CDIC signatures approach C3-like values at high DIC concentrations, with measurements as low as -19 ‰ in the Kelantan Basin and -20 ‰ observed in the Langat Basin, consistent with a biological origin for riverine DIC. However, the average 13CDIC in river water is 13C-enriched by about 10 ‰ relative to the expected C3 source in both rivers, and this 13C- enrichment appears to be largest with smaller DIC concentrations. Because of the overpressures of CO2 in the rivers, entrainment of isotopically-heavy atmospheric CO2 is not a likely explanation for the observed 13C-enrichment. Theoretically, dissolution of carbonates could be an alternative source of 13C-enriched carbon, but this lithology is scarce, particularly in the Langat watershed. The increase in DIC downstream and generally high pCO2 values in most river sections argues against aquatic photosynthesis as a primary causative factor for the observed isotopic enrichment. This elimination process leaves the speciation of riverine DIC and the evasion of CO2 as the most likely mechanisms for 13C-enrichment in DIC, via isotope fractionation during HCO3- hydration and CO2 diffusion. Potentially, methanogenic activity could also be, at least partially, responsible for the 13C-enrichment in DIC, particularly immediately downstream of the Langat Reservoir, but due to the absence of empirical data, this must remain only a theoretical proposition. The aquatic chemistry and dissolved carbon data suggests that pollution discharge into the Langat and Kelantan Rivers is the major factor that is responsible for the considerable CO2 overpressures and high DIC and DOC concentrations in the river waters, particularly in the downstream sections. This pollution is likely of biological origin, via sewage and palm oil mill effluent (POME) discharge, and therefore isotopically indistinguishable from natural C3 plant sources. Carbon budgets of the Langat and Kelantan River show CO2 degassing to be a significant mechanism of fluvial carbon loss, comprising roughly 50 %, or more, of the total riverine carbon export in both watersheds. The remainder of the river carbon is transported to the ocean in the form of DIC, DOC and POC in broadly comparable proportions. However, the combined riverine carbon export from the Kelantan and Langat Basins amount to 2 % or less of the total carbon sequestration of the watersheds. Thus, most of the sequestered carbon is returned to the atmosphere via respiration, with smaller amounts incorporated into ecosystem biomass . These results highlight the complexity of carbon cycling in tropical rivers, and agree with previous studies in showing riverine systems to be more than simple conduits of carbon from the land to the ocean.

Trout were introduced into a flow-through enclosure constructed in the headwaters of a small fishless stream to examine the effects of trout predation on the density, standing crop and production of lotic insect populations. Following the trout introduction, the density and standing crop of 3 of the 9 insect species examined decreased in the experimental stream study section (enclosure) while the density and standing crop of 2 insect species increased in the experimental stream section compared with the control stream section. Data on the food habits of the trout indicated that trout predation had reduced the density and standing crop of these insect populations in the experimental stream section. Competitive release was suggested as the reason for the increase in density and standing crop of the insect populations in the experimental stream section. The role of trout predation in structuring stream insect communities is briefly discussed. Production estimates of lotic species in the experimental stream section were not significantly different from those in the control section. Trout consumed only 0.4 times the mean standing crop or 9-10% of the production of prey species. However, trout were thought to be intensively grazing the available food supply. / Science, Faculty of / Zoology, Department of / Graduate

This thesis considers the methodologies and organisational impacts of Environmental Reviews and Environmental Management Systems in Local Authorities, Universities and Conservation organisations. It assesses the practical impacts of these tools, identifies elements of good practice and discusses the organisational and political factors which affect the success of environmental management activity in these organisations. Chapter 1 describes the growth of global, European and national policy initiatives aimed at minimising environmental degradation and delivering sustainable development and the subsequent development of environmental strategies and environmental management tools in organisations. Chapter 2 discusses environmental management activity in Local Government in the context of Local Agenda 21, using the results of a survey of environmental management techniques in local authorities and a case study of Lancashire County Council. These findings are discussed in the context of changes to local government organisation in the UK and in relation to local government management theory. Chapter 3 considers environmental management activity in Universities in the context of institutional performance using the results of a survey of approaches to environmental management in Universities and a case study of environmental management in the University of Central Lancashire. These findings are then considered in relation to changes in the orgamsation of the Higher Education Sector in the UK and in the context of university management theory. Chapter 4 considers the use of environmental management techniques in the Conservation sector in the context of Local Agenda 21, using a survey of conservation organisations and a case study of The National Trust's environmental management strategy. These findings are then discussed with regard to changes occurring in the management and funding of NGOs and quangos in the UK. Based upon the research findings, a number of recommendations are made for successful organisational environmental management strategies and the long term application of these techniques within each of these sectors. These findings are then drawn together in Chapter 5 to identify common methodological, organisational and political factors which affect the success of organisational environmental management strategies and to discuss their potential contribution to sustainable development. An alternative approach to TQM based environmental management is offered for organisations, based upon the elements of good practice identified in the non-profit sector, which include conscensus building, wide participation, and democratic decision making. Within the organisation, this approach closely resembles the Local Agenda 21 process used by local government to consult and empower local communities in sustainable development.

Reduced organic sulfur (ROS) compounds are environmentally ubiquitous and play an important role in sulfur cycling as well as in biogeochemical cycles of toxic metals, in particular mercury. Development of effective methods for analysis of ROS in environmental samples and investigations on the interactions of ROS with mercury are critical for understanding the role of ROS in mercury cycling, yet both of which are poorly studied. Covalent affinity chromatography-based methods were attempted for analysis of ROS in environmental water samples. A method was developed for analysis of environmental thiols, by preconcentration using affinity covalent chromatographic column or solid phase extraction, followed by releasing of thiols from the thiopropyl sepharose gel using TCEP and analysis using HPLC-UV or HPLC-FL. Under the optimized conditions, the detection limits of the method using HPLC-FL detection were 0.45 and 0.36 nM for Cys and GSH, respectively. Our results suggest that covalent affinity methods are efficient for thiol enrichment and interference elimination, demonstrating their promising applications in developing a sensitive, reliable, and useful technique for thiol analysis in environmental water samples. The dissolution of mercury sulfide (HgS) in the presence of ROS and dissolved organic matter (DOM) was investigated, by quantifying the effects of ROS on HgS dissolution and determining the speciation of the mercury released from ROS-induced HgS dissolution. It was observed that the presence of small ROS (e.g., Cys and GSH) and large molecule DOM, in particular at high concentrations, could significantly enhance the dissolution of HgS. The dissolved Hg during HgS dissolution determined using the conventional 0.22 µm cutoff method could include colloidal Hg (e.g., HgS colloids) and truly dissolved Hg (e.g., Hg-ROS complexes). A centrifugal filtration method (with 3 kDa MWCO) was employed to characterize the speciation and reactivity of the Hg released during ROS-enhanced HgS dissolution. The presence of small ROS could produce a considerable fraction (about 40% of total mercury in the solution) of truly dissolved mercury (< 3 kDa), probably due to the formation of Hg-Cys or Hg-GSH complexes. The truly dissolved Hg formed during GSH- or Cys-enhanced HgS dissolution was directly reducible (100% for GSH and 40% for Cys) by stannous chloride, demonstrating its potential role in Hg transformation and bioaccumulation.

N2 fixation rates for several Virginia salt marshes were determined using in situ acetylene-reduction assays. A control and a chronically polluted oil marsh of the mesohaline Mobjack Bay area were sampled over a 1975-76 annual cycle. N2 fixation occurred in all transects which extended from upper mudflat to the Spartina patens zone. An isolated blue-green algal mat exhibited some of the highest N2 fixation rates. Intertidal sediment N2 fixation was patchy, both spatially and seasonally. However average rates (91.45 μg N/m2/h) compared to the estimated N requirement of the graminoid vegetation indicated a significant contribution to the N budget. Vegetation associated nitrogen fixation yielded higher average rates. N2 fixation rates for Wachapreague high salinity and Yorktown relic low salinity marshes were similar to the mesohaline marshes although blue-green algae fixation seemed to be more significant. The seasonal pattern of mesohaline marsh N2 fixation was positively related to temperature. Light-dark and anaerobic-aerobic experiments support the hypothesis that heterotrophic bacteria are the predominant N2 fixers and that availability of oxidizable substrates contribute to the seasonal pattern. Chronic oil treatment showed little effect on fixation rates with the possible exception of median tidal elevation sediments where summer rates were considerably higher than those of the control. This dissertation is from the Joint Program Degree from the College of William & Mary and University of Virginia and awarded by the University of Virginia.

This project investigated the feasibility of using the brackish water clam Rangia cuneata as a heavy metal pollution indicator, and further investigated the state of heavy metal pollution in the James River. Rangia cuneata were sampled in the fall of 1972 from the Rappahannock and James Rivers , and meats were analyzed by atomic absorption spectrophotometry for wet weight concentrations of copper, zinc, cadmium and lead. Levels of copper and zinc in Rangia cuneata were shown to be unaffected by clam size, spawning differences, salinity or distance upriver, and substrate grain size. Heavy metal concentrations in the oxidized channel sediments, determined from other studies conducted at the same time, were compared to levels in Rangia cuneata, but no relationships were found. Lead was below detection limits (0.2 ppm) in Rangia cuneata at all stations, and cadmium levels appeared to be consistent in both rivers. Copper was found to increase upriver in the James, indicating an upstream source, and zinc concentrations were found to peak at the mouth of the Chickahominy River. A number of possible causes were cited. This dissertation is from the Joint Program Degree from the College of William & Mary and University of Virginia and awarded by the University of Virginia.

Throughout midwestern North American ecosystems, semi-aquatic mammals including beaver (Castor canadensis), mink (Neovision vision), muskrat (Ondatra zibethicus), and river otter (Lontra canadensis) co-exist in wetlands. These species are ecologically important through their manipulation of habitats and interactions with other species present. The Lake County Forest Preserve District (Lake County, Illinois) is actively restoring forest preserves using several restoration practices and are interested in how these efforts may affect semi-aquatic mammal occupancy. We studied impacts of restoration practices and other environmental covariates on detection and occupancy of the 4 aforementioned focal species. Sign surveys were conducted during December-April in 2018-19 and 2019-20. Single species, multi-season models were run in RStudio using the package unmarked. Muskrat detection (p̂ = 0.60 ± 0.03) was positively affected by survey replicate, and negatively impacted by last precipitation amount and bank angle. Beaver detection (p̂ = 0.76 ± 0.03) was positively affected by survey replicate and previous 2-week precipitation amount, and negatively influenced by bank angle. Mink detection (p̂ = 0.26 ± 0.04) was positively impacted by survey replicate, and negatively affected by last precipitation amount and previous 2-week precipitation amount. River otter detection (p̂ = 0.10 ± 0.07) was not influenced by any covariates sampled. Muskrat had the highest occupancy (ψ ̂= 0.90 ± 0.05), followed by beaver (ψ ̂ = 0.57 ± 0.07), mink (ψ ̂ = 0.57 ± 0.10), and river otter (ψ ̂ = 0.28 ± 0.18). Both muskrat and river otter occupancy were not affected by any covariates sampled. Beaver occupancy was positively impacted by stream density and number of saplings. Mink occupancy was positively affected by stream density. No focal species’ occupancies were influenced by restoration practices. From these findings, I provide recommendations for future surveys and management for semi-aquatic furbearers in urban landscapes. Thank you to the Lake County Forest Preserve District for funding my research.

Neuroendocrine processes coordinate the behavioural, physiological, and seasonal aspects of reproduction. Some chemicals can disrupt the hypothalamus-pituitary-gonadal axis, impacting reproductive health. Naphthenic acids (NAs), the carboxylic acids in petroleum, are of emerging concern as they contaminate coastlines after oil spills and aquatic ecosystems of the Athabasca oil sands area. They are acutely toxic in fish and tadpoles and possibly endocrine disrupting at sublethal levels. I characterized courtship behaviours and disruption by NAs in the Western clawed frog, Silurana tropicalis. Courtship primarily consists of males producing low trills and achieving amplexus, a mating position where a male clasps a female. Adult frogs were exposed for five days to 20 mg/L NA, a dose low enough to not affect physical activity. In males, absolute calling activity was reduced. Other acoustic parameters such as dominant frequency, click rate, and trill length were not affected. Injecting human chorionic gonadotropin had a slight rescue effect. Vocalization and amplexus were both inhibited after exposure and restored after 2 weeks of recovery. However, calling behaviour did not predict competitive ability or mating success. In females, NA exposure reduced mating success, possibly through decreased attractiveness or receptivity. Receptivity can be indicated by attraction towards the sound of mating calls (phonotaxis), which is cryptic and subjective. I created an apparatus that measures phonotaxis by placing speakers inside traps with infrared lights to detect the time of entry. This novel method is widely applicable for low-visibility observations and studies of choice and preference. This work shows that an aquatic contaminant can reduce mating success in otherwise healthy frogs, and provides a detailed foundation for further investigation.

Due to recent advances in aquatic research, technology, and facilities, many modes of aquatic therapy now exist. These aquatic modes assist individuals (e.g., osteoarthritis patients) in the performance of activities that may be too difficult to complete on land. However, the biomechanical requirements of each aquatic therapy mode may elicit different physiological and functional responses. Therefore, the purpose of this thesis was to: (a) provide a review of the physiological and biomechanical differences between aquatic and land based exercises, and (b) examine the acute effects of underwater and land treadmill exercise on oxygen consumption (VO2), rating of perceived exertion (RPE), perceived pain, mobility, and gait kinematics for patients with osteoarthritis (OA). Methods consisted of the retrieval of experimental studies examining the physiological and biomechanical effects of deep water running (DWR), shallow water running (SWR), water calisthenics, and underwater treadmill therapy. The methods also examined the physiological and biomechanical effects on 19 participants during and after three consecutive exercise sessions on an underwater treadmill and on a land-based treadmill. Based on the studies reviewed, when compared to a similar land-based mode, VO2 values are lower during both DWR and SWR, but can be higher during water calisthenics and underwater treadmill exercise. RPE responses during DWR are similar during max effort, and stride frequency and stride length are both lower in all four aquatic modes than on land. Pain levels are no different between most water calisthenics, and most studies reported improvements in mobility after aquatic therapy, but no difference between the aquatic and land-based modes. The OA participants achieved VO2 values that were not different between conditions during moderate intensities, but were 37% greater during low intensity exercise on land than in water (p = 0.001). Perceived pain and Time Up & Go scores were 140% and 240% greater, respectively, for land than underwater treadmill exercise (p = 0.01). Patients diagnosed with OA may walk on an underwater treadmill at a moderate intensity with less pain and equivalent energy expenditures compared to walking on a land-based treadmill.