The extensive acidification of fresh waters across Europe and North America during the 20th century led to extensive and widespread loss of species, which fundamentally changed the structure of resident communities. While attempts to limit or halt acidifying emissions have been successful in reversing the chemical consequences of acidification, any corresponding biological recovery has been patchy at best. The main aim of this thesis was to investigate potential ecological constraints on this biological recovery, ranging from interactions between individuals to ecosystem-level processes, using a model stream system that has been extensively studied for over 40 years. I used a combination of long-term survey data and experiments, both in the field and the laboratory, to provide evidence that the lag in recovery of acidified aquatic communities is due to intrinsic resistance to re-colonisation by acid-sensitive species, as a result of both direct and indirect interactions between predators and prey. However, there is also evidence of recovery at an ecosystem level, with rates of microbial decomposition increasing – a key link in the transfer of energy to higher trophic levels, which could be facilitating population increases in large-bodied predators. These findings increase our understanding of the drivers which govern the structure and function of ecological networks in response to an important climatic stressor. This is especially relevant given the rapid industrialisation of countries such as India and China, which could well soon experience anthropogenic acidification on a significant scale.

Planktonic organisms form the base of the marine food web and may be impacted by environmental change in many ways. The interactive effects of multiple, simultaneous climate-driven changes on these organisms are not well understood. This dissertation examined the impacts of ocean acidification in combination with other environmental stressors on marine plankton and determined spatial patterns of one of these potential interactive drivers. Chapter 2 investigated the synergistic effects of ocean acidification and hypoxia on the harmful dinoflagellate Amphidinium carterae. Findings indicated that empirical studies may be crucial to accurately predict organismal responses to multi-stressors. Results also suggested that photorespiration may serve a previously unrecognized role in dinoflagellate metabolism. Chapter 3 examined the combined effects of ocean acidification and lithogenic trace metals on the growth of another harmful dinoflagellate, Cochlodinium polykrikoides. Results indicated that high suspended sediment loads may deliver toxic concentrations of trace elements to marine phytoplankton in acidified coastal ecosystems. Chapter 4 examined the interactive effects of ocean acidification and bacteria on the severity and extent of dissolution in the shells of larval gastropods and the adult pteropod Limacina helicina. Research findings indicated that microbial communities on the shell surfaces of some planktonic molluscs may mediate certain types of shell dissolution in acidified, upwelled waters. Chapter 5 explored the use of thorium isotope fluxes as a proxy for dust and lithogenic iron in the Indian Ocean. Results suggested that the gradient of dust fluxes in the region could impose thresholds for biological productivity. Together, these interdisciplinary studies demonstrate coupled biological and chemical changes in marine ecosystems as a result of increased anthropogenic environmental change.

Pasteurized skim milk was acidified using glucono-δ-lactone (GDL) at 10, 20, 30, and 40°C or with 1.2% freeze-dried yogurt starter culture at 40°C. Milk coagulation was followed by measuring turbidity, curd firmness, particle size, and casein micelle microstructural changes using transmission electron microscopy . The pH of milk was gradually lowered during acidification with GDL or starter culture. Acidification rate showed greater influence on turbidity change at 10°C than at 20, 30, or 40°C. Average casein micelle size increased with decreasing temperature. The patterns of average micelle size versus pH were not affected by temperature. No great variation of average micelle size was observed above pH 5.2. Below pH 5.0 the size increased exponentially as the milk gelled. Acidification rate did not influence average micelle size at 10°C. Acidification rate, types of acidifying agents, and temperature had no effect on the Formagraph gelation pH and the rate at which curd firmness developed. Casein micelles became less compact and less distinct with decreasing temperature before acidification. As pH was lowered, protein was dissociated from and then reassociated with casein micelles. Acidification rate had no effect on microstructure change of casein micelles at 10°C.

Since the industrial revolution, CO sub 2 has increased in the atmosphere and about 40% of the increase has been taken up by the ocean. An artifact of increasing CO sub 2 in the ocean is ocean acidification; it changes the calcium carbonate saturation state, which in turn alters the calcification rate of shelled organisms. The purpose of this dissertation is to estimate the changes in the carbonate system in the oceans, and whether these changes are due to natural (biological activity, chemical transformation or mixing of water masses) or anthropogenic (human activities) perturbations. The first hypothesis states that the presence of boric acid (B(OH) sub 3) in seawater changes the thermodynamic constants of CO sub 2, pK sup * sup 1 and pKsup * sup 2. Due to experimental limitations, the solubility of B(OH) sub 3 was determined in electrolyte solutions (LiCl, NaCl, KCl, RbCl and CsCl) instead of real or artificial seawater. The results can be used to estimate the B(OH) sub 3 activity coefficients gamma sub B and solubility [B] in natural mixed electrolyte solutions. The second hypothesis states that filtering seawater sampled in the open ocean is necessary for the determination of total alkalinity (TA). Measurement of 180 samples of surface, oxygen minimum, and deep waters in the Pacific and Indian oceans revealed that the at- sea measured TA of filtered and unfiltered samples were not statistically different. Finally, a synthesis and analysis of the carbonate parameters in the Atlantic and Indian oceans is undertaken. Results from repeat hydrographic cruises in these oceans were used for this task. Parameters TA and total CO sub 2 (TCO sub 2) are predicted using hydrographic properties and a multi-linear regression method to obtain a more homogenous dataset. The results of the predicted TA prove to be successful, which is not the case for TCO sub 2 at the surface of the ocean. Finally, it is found that the increase in anthropogenic CO sub 2 signal remineralization and mixing of water masses increase the acidity of the ocean at the surface and in deep waters, respectively. This causes the aragonite saturation horizon to shoal. Recommendations for further studies are provided in the "Summary and conclusion" chapter.

Human activities have contributed to the increase in atmospheric greenhouse gases such as carbon dioxide (CO2). This anthropogenic gas emission has led to a rise in the average Earth temperature. Moreover, the ocean constitutes the major sink for anthropogenic CO2 and its dissolution in surface waters has already resulted in an increase of seawater acidity since the beginning of the industrial revolution. This is commonly called ocean acidification. The increase in water temperature could induce modifications of the physical and chemical characteristics of the ocean. Also, the structure and the functioning of marine ecosystems may be altered as a result of ocean acidification. Phytoplankton productivity is one of the primary controls in regulating our climate, for instance via impact on atmospheric CO2 levels. Coccolithophores, of which Emiliania huxleyi is the most abundant species, are considered to be the most important pelagic calcifying organisms on Earth. Coccolithophores are characterized by calcium carbonate platelets (coccoliths) covering the exterior of the cells. They form massive blooms in temperate and sub-polar oceans and in particular along continental margin and in shelf seas. The intrinsic coupling of organic matter production and calcification in coccolithophores underlines their biogeochemical importance in the marine carbon cycle. Both processes are susceptible to change with ocean acidification and warming. Coccolithophores are further known to produce transparent exopolymer particles (TEP) that promote particle aggregation and related processes such as marine snow formation and sinking. Thus, the impact of ocean warming and acidification on coccolithophores needs to be studied and this can be carried out through a transdisciplinary approach. The first part of this thesis consisted of laboratory experiments on E. huxleyi under controlled conditions. The aim was to estimate the effect of increasing water temperature and acidity on E. huxleyi and especially on the calcification. Cultures were conducted at different partial pressures of CO2 (pCO2); the values considered were 180, 380 and 750 ppm corresponding to past, present and future (year 2100) atmospheric pCO2. These experiments were conducted at 13°C and 18°C. The cellular calcite concentration decreases with increasing pCO2. In addition, it decreases by 34 % at 380 ppm and by 7 % at 750 ppm with an increase in temperature of 5°C. Changes in calcite production at future pCO2 values are reflected in deteriorated coccolith morphology, while temperature does not affect coccolith morphology. Our findings suggest that the sole future increase of pCO2 may have a larger negative impact on calcification than its interacting effect with temperature or the increase in temperature alone. The evolution of culture experiments allows a better comprehension of the development of a bloom in natural environments. Indeed, in order to predict the future evolution of calcifying organisms, it is required to better understand the present-day biogeochemistry and ecology of pelagic calcifying communities under field conditions. The second part of this dissertation was dedicated to results obtained during field investigations in the northern Bay of Biscay, where frequent and recurrent coccolithophorid blooms were observed. Cruises, assisted by remote sensing, were carried out along the continental margin in 2006 (29 May – 10 June), 2007 (7 May – 24 May) and 2008 (5 May – 23 May). Relevant biogeochemical parameters were measured in the water column (temperature, salinity, dissolved oxygen, Chlorophyll-a and nutrient concentrations) in order to determine the status of the bloom at the time of the different campaigns. Calcification has been shown to be extremely important in the study area. In addition, TEP production was significant at some stations, suggesting that the northern Bay of Biscay could constitute an area of important carbon export. Mortality factors for coccolithophores were studied and the first results of lysis rates measured in this region were presented. Results obtained during culture experiments and comparison with data reported in the literature help to better understand and to predict the future of coccolithophores in a context of climate change. Data obtained during either culture experiments or field investigations allowed a better understanding of the TEP dynamics. Finally, the high lysis rates obtained demonstrate the importance of this process in bloom decline. Nevertheless, it is clear that we only begin to understand the effects of global change on marine biogeochemistry, carbon cycling and potential feedbacks on increasing atmospheric CO2. Thus, further research with a combination of laboratory experiments, field measurements and modelling are encouraged.

A series of studies was undertaken at Plastic Lake-1 (PC1) to determine the sources and controls on S cycling in small headwater catchments on the Precambrian Shield in south-central Ontario. Two observations were made about the S cycle in this region: (1) all streams exhibit highly coherent temporal patterns in SO4 concentrations and export, and (2) most catchments exported more SO4 in stream water than is received in bulk deposition during the past 2 decades. Synchronous temporal patterns in annual SO4 concentrations in both upland and wetland-draining streams were related to changes in climate, specifically those factors that determine catchment dryness. The number of days with no stream flow or stream flow below a critical threshold was a good predictor of the average stream SO4 concentration in a particular year. Sulphate chemistry in the PC1 outflow is highly dependent on processes occurring in a conifer <i>Sphagnum</i> swamp located immediately upstream of the chemical sampling station. Hydrologic inputs to the swamp during the summer determine whether S is retained or released from peat on an annual basis. Drying and re-wetting of <i>Sphagnum</i>-derived peat caused a substantial increase in soluble SO4 in laboratory experiments, which was slightly enhanced at higher temperature, but alternating moisture conditions had no immediate effect on <i>Sphagnum</i>. Despite large inter-annual changes in SO4 release, over the long-term (<i>i. e. </i> 20-years) SO4 inputs and exports from the swamp are in approximate balance. In contrast, the upland portion of PC1 (<i>i. e. </i> PC1-08) consistently exports more SO4 than is input in bulk deposition in every year of record. Even when inputs are increased to account for potential underestimates in dry deposition or weathering, the majority of catchments in this region exhibit net export in many years. Two internal sources are suggested to account for negative budgets: desorption and mineralization. Adsorption/desorption reactions respond directly to changes in SO4 input concentration, and lysimeter data indicate the importance of these processes for buffering short-term changes in SO4 concentration in LFH percolate. Desorption may be the primary direct response of upland soil to decreasing SO4 inputs in deposition and may substantially extend the period of net SO4 export in catchments that have large adsorbed SO4 pools such as PC1. However, the adsorbed pool may be sustained by continuous net release from mineralization, and should also be considered in budget calculations. Mineralization was shown to be responsive to drying and re-wetting events and temperature, although results varied among different materials. Sulphate release from mineral soil did not appear to be influenced by changing moisture, temperature or deposition chemistry in laboratory experiments, although adsorption/desorption reactions may have largely masked small changes in SO4 release <i>via</i> mineralization. The magnitude of organic S storage in mineral soil indicates that this pool could be an important source of export over the long-term. While it is unknown why (or if) mineralization is a net source of SO4 to drainage streams, changes in climate and/or deposition could potentially influence SO4 release from organic compounds. Soil moisture and temperature are important controls on microbial processes in soil, and changes in climate that bring about changes in soil moisture or temperature conditions could affect decomposition and mineralization processes. Similarly, historically high inputs of S and N in deposition may have brought about slow shifts in litter quality (<i>i. e. </i> decreased C:N, C:S) which could also potentially influence decomposition and mineralization rates. In order to predict the future response of surface water chemistry to changes in SO4 (and N) deposition, it is important to consider not only the magnitude of S pools in soil, but also the potential for SO4 cycling between pools. Likewise, models that predict changes in stream SO4 by adsorption isotherm data alone will underestimate the importance of desorption unless the potential for continual replenishment of the adsorbed pool through the relatively slower process of mineralization is also considered. In general, predictions of recovery from S deposition can only be made from a complete understanding of S pools, transformations, and the effects of climate, which are superimposed upon the long-term trend in deposition.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1947. / Includes bibliographical references (p. 88-91).

Ocean acidification is occurring in response to rapidly increasing concentrations of atmospheric CO2. Shallow-water hydrothermal vent systems have been proposed as natural laboratories for studying the effects of elevated pCO2 on benthic communities. Hydrothermal vents occur at depths of approximately 10m in Tutum Bay, Ambitle Island, Papua New Guinea; these vents are surrounded by a typical-appearing fringing coral-reef community. Groups of live specimens of seven species of reef-dwelling, larger benthic foraminifers, along with segments of calcareous green algae broken from live thalli, were collected from a reef location, placed in small mesh bags, and deployed for five days at six different sites along a gradient of temperature (29.6oC-59.3oC) and pH (5.9-8.1) with distance from a large hydrothermal vent in Tutum Bay. Foraminiferal taxa used in the experiment included Amphisorus hemprichii, a species with Mg-calcite porcelaneous shells, three species of Amphistegina that produce hyaline calcite shells, and three species with hyaline Mg-calcite shells (Heterostegina depressa and two Calcarina spp.). Several specimens of four of the seven foraminiferal species examined survived exposure to elevated temperatures of 59.3oC and low pH of 6.2 for five days, while at least one specimen of each of the seven species survived exposure to 39.9oC and pH 5.9. Examination of shells at 600-1000x magnification using scanning electron microscopy revealed fine-scale dissolution in specimens up to 30m from the vent. Results of this experiment, as well as previously reported observations from the study site, indicate that the calcifying reef-dwelling organisms examined can survive pH extremes that result in dissolution of their shells following death.

abstract / Biological Sciences / Doctoral / Doctor of Philosophy

The successful completion of the early developmental stages in organisms with complex life cycles is crucial to the persistence of a species both at the local and global scale. Thus changes in the abiotic environment experienced during larval and early benthic development can have profound effects on the development and ultimately dynamics of populations of marine invertebrates. The effects of elevated temperature and pCO2 in line with future predictions of anthropogenic climate change, ocean warming and ocean acidification (OA), on the survivorship and growth during early development of marine invertebrates is beginning to be understood, yet the underlying physiological ontogeny driving such changes, and the more subtle effects on physiological performance of climate change drivers, has yet to be distinguished. Therefore the aim of the present study is to investigate the effects of elevated temperature and pCO2 on the developmental eco-physiology of an economically and ecologically important species, the European lobster, Homarus gammarus, to characterise the underlying physiological responses of early development behind responses of survival and growth. The main findings relate to how changing optimal temperature conditions during larval development results in changes in metabolic performance and therefore aerobic scope, ultimately driving survival and growth. Larval stages which exhibit narrower aerobic scope were also sensitive to elevated pCO2 evident as reduced survival, changes to energetic demands and organic content, and reduced calcification. Furthermore, this is the first attempt to characterise the physiological response of early benthic juveniles to climate change drivers. Early benthic juveniles are quite different in underlying physiology to later juveniles and adults, cumulating in this stage being energy limited. Such limitations are expressed as a reduction in aerobic scope in relation to elevated temperature and pCO2, and associated sensitiveness to elevated pCO2 resulting in increased moult related mortalities and the breakdown of haemolymph buffering capacity under combinations of elevated temperature and pCO2. Throughout early development, elevated temperature and pCO2, through underlying physiological responses, may have dramatic effects on the geographic range and successful development of H. gammarus.