Microbial activity occurs year-round in Arctic soils, including during the winter when soils are frozen. From 2004 to 2008 I monitored soil microbial and nutrient dynamics in low Arctic wet and dry sedge meadows near Churchill, Manitoba. I documented a consistent annual pattern in which soil microbial biomass (MB) and soil nutrients peak in late winter, and decrease during the early stages of spring thaw, remaining in low abundance during the summer. Based on a series of experiments, resource shortages do not appear to be the cause of the microbial decline, as has been hypothesized. Observations and theoretical considerations regarding soil physical properties indicate that this decrease is driven by the influx of liquid water at thaw that brings about a rapid change in the chemical potential of water, leading to cell lysis. I have used 15N isotope tracing to show that inorganic nitrogen is taken up very quickly at thaw by the roots of the dominant plant, Carex aquatilis. This represents a critical window of opportunity for these plants, as nitrogen remains abundant only for a short time. The described annual pattern was pronounced in wet sedge sites, but some inter-annual variation is evident, for example a post-thaw soil nitrogen pulse in 2006, and low winter MB in 2008. In the dry sedge meadow, fluctuations in MB and nutrients were dampened relative to wet sites, and the annual pattern was variable, particularly after 2006. Over four years, peak winter values of soil MB and nutrient variables declined in both wet and dry sites, and this could be related to a drying trend. This work improves our understanding of the controls on decomposition and primary productivity in a system that is experiencing climate warming and increased precipitation. Changes to hydrology, carbon and nitrogen cycling, and primary productivity will have further effects on vegetation communities and higher trophic levels, including several species of migratory birds.

Most undisturbed peatlands sequester carbon, and rising levels of atmospheric nitrogen deposition may have the potential to destabilize this function, possibly resulting in an increased release of carbon dioxide into the atmosphere.  It is therefore of vital importance to investigate further the link between atmospheric nitrogen deposition and carbon dynamics in exposed ecosystems such as peatlands. The work described in this thesis aimed to elucidate the impact of increasing nitrogen on aspects of carbon turnover in peatlands.  Using a long-term field-based experiment, I tested the effects of 4 years of ammonium and nitrate addition (8, 24 and 56 kg N ha^-1 y^-1) on the fate of newly photosynthesised carbon by plants and the turnover of labile and recalcitrant carbon.  A second set of experiments undertaken in the laboratory assessed the use of plant wax analysis as potential biomarkers of past changes in vegetation and carbon status in peat. Overall, this work has shown that the form of nitrogen (ammonium versus nitrate) is a crucial component of atmospheric pollution and must be taken into consideration when investigating or predicting effects of reactive nitrogen on peatlands.  In addition, nitrogen addition affected the fate of newly synthesised carbon differently in <i>Eriophorum vaginatum </i>and <i>Calluna vulgaris, </i>revealing the importance of considering plant traits when investigating environmental changes in terrestrial ecosystems.  Furthermore, it has led to the development of an investigative tool for further exploration of the historical effects of atmospheric nitrogen deposition on vegetation an carbon content in peatlands.

<p>The Arctic Ocean and Western Antarctic Peninsula (WAP) are the fastest warming regions on the planet and are undergoing rapid climate and ecosystem changes. Until we can fully resolve the coupling between biological and physical processes we cannot predict how warming will influence carbon cycling and ecosystem function and structure in these sensitive and climactically important regions. My dissertation centers on the use of high-resolution measurements of surface dissolved gases, primarily O2 and Ar, as tracers or physical and biological functioning that we measure underway using an optode and Equilibrator Inlet Mass Spectrometry (EIMS). Total O2 measurements are common throughout the historical and autonomous record but are influenced by biological (net metabolic balance) and physical (temperature, salinity, pressure changes, ice melt/freeze, mixing, bubbles and diffusive gas exchange) processes. We use Ar, an inert gas with similar solubility properties to O2, to devolve distinct records of biological (O2/Ar) and physical (Ar) oxygen. These high-resolution measurements that expose intersystem coupling and submesoscale variability were central to studies in the Arctic Ocean, WAP and open Southern Ocean that make up this dissertation. </p><p>Key findings of this work include the documentation of under ice and ice-edge blooms and basin scale net sea ice freeze/melt processes in the Arctic Ocean. In the WAP O2 and pCO2 are both biologically driven and net community production (NCP) variability is controlled by Fe and light availability tied to glacial and sea ice meltwater input. Further, we present a feasibility study that shows the ability to use modeled Ar to derive NCP from total O2 records. This approach has the potential to unlock critical carbon flux estimates from historical and autonomous O2 measurements in the global oceans.</p> / Dissertation

Significant discrepancies exist in global estimates of the atmospheric methane (CH4) budget. This is particularly true for tropical South America where bottom-up approaches, rooted in field observation, tend to under estimate atmospheric observations. As such, a better understanding of soil environments, which are capable of acting as both source and sink for atmospheric CH4, is required. Soil-atmosphere CH4 exchange is fundamentally determined by the balance between strictly anaerobic methanogenic and aerobic methanotrophic microbial processes. For this reason, CH4 emissions are typically associated with anoxic wetland soils, whilst, oxic upland soils are thought to uptake CH4 from the atmosphere. However, there is increasing evidence that upland soils may act as sources of CH4 through methanogenic activity within cryptic wetlands or anoxic microsites. This thesis aims to: document soil-atmosphere CH4 fluxes in poorly represented tropical upland and montane ecosystems, investigate controls on CH4 flux with a focus on soil oxygen (O2) concentration and investigate relationships between methanogenic and methanotrophic processes under oxic conditions. These aims are addressed in three chapters focusing on lowland terra firme, premontane and montane forests and montane humid puna grasslands and wetlands along an Amazonian to Andean transect spanning ~ 3300 m of elevation in southeastern Peru. In the lowland rainforest intensive seasonal field campaigns and laboratory incubations were conducted on higher porosity ultisol and lower porosity inceptisol soils. Mean (s.e.) net CH4 fluxes for dry and wet seasons were, respectively, -1.59 (0.06) and - 1.39 (0.07) mg CH4-C m−2 d−1 for the ultisol and -0.95 (0.06) and -0.41 (0.10) mg CH4-C m−2 d−1 for the inceptisol. Greater uptake rates in the ultisol than the inceptisol were best explained by lower water-filled pore space (WFPS). Similarly, WFPS best explained between season variation in net CH4 flux from the inceptisol, whilst, we were unable to explain the smaller variations observed for the ultisol. Methanogenic processes were active in both the ultisol and inceptisol soils despite oxic conditions. In the premontane and montane forests, long-term monthly field measurements were conducted over two and a half years in premontane, lower montane and upper montane settings. Mean (s.e.) net CH4 fluxes for aggregated dry and wet season months were, respectively, -0.20 (0.15) and -0.08 (0.13) mg CH4-C m−2 d−1 for the premontane forest, -1.12 (0.13) and -0.97 (0.11) mg CH4-C m−2 d−1 for the lower montane forest and -1.55 (0.13) and -1.04 (0.11) mg CH4-C m−2 d−1 for the upper montane forest. Increased uptake with elevation was best explained by decreases in WFPS. Significant variation in net CH4 flux between seasons, driven by variation in WFPS, was only identified for the upper montane forest.

<p>Wetland ecosystems provide many valuable ecosystem services, including carbon (C) storage and improvement of water quality. Yet, restored and managed wetlands are not frequently evaluated for their capacity to function in order to deliver on these values. Specific restoration or management practices designed to meet one set of criteria may yield unrecognized biogeochemical costs or co-benefits. The goal of this dissertation is to improve scientific understanding of how wetland restoration practices and waterfowl habitat management affect critical wetland biogeochemical processes related to greenhouse gas emissions and nutrient cycling. I met this goal through field and laboratory research experiments in which I tested for relationships between management factors and the biogeochemical responses of wetland soil, water, plants and trace gas emissions. Specifically, I quantified: (1) the effect of organic matter amendments on the carbon balance of a restored wetland; (2) the effectiveness of two static chamber designs in measuring methane (CH4) emissions from wetlands; (3) the impact of waterfowl herbivory on the oxygen-sensitive processes of methane emission and coupled nitrification-denitrification; and (4) nitrogen (N) exports caused by prescribed draw down of a waterfowl impoundment.</p><p>The potency of CH4 emissions from wetlands raises the concern that widespread restoration and/or creation of freshwater wetlands may present a radiative forcing hazard. Yet data on greenhouse gas emissions from restored wetlands are sparse and there has been little investigation into the greenhouse gas effects of amending wetland soils with organic matter, a recent practice used to improve function of mitigation wetlands in the Eastern United States. I measured trace gas emissions across an organic matter gradient at a restored wetland in the coastal plain of Virginia to test the hypothesis that added C substrate would increase the emission of CH4. I found soils heavily loaded with organic matter emitted significantly more carbon dioxide than those that have received little or no organic matter. CH4 emissions from the wetland were low compared to reference wetlands and contrary to my hypothesis, showed no relationship with the loading rate of added organic matter or total soil C. The addition of moderate amounts of organic matter (< 11.2 kg m-2) to the wetland did not greatly increase greenhouse gas emissions, while the addition of high amounts produced additional carbon dioxide, but not CH4. </p><p>I found that the static chambers I used for sampling CH4 in wetlands were highly sensitive to soil disturbance. Temporary compression around chambers during sampling inflated the initial chamber CH4 headspace concentration and/or lead to generation of nonlinear, unreliable flux estimates that had to be discarded. I tested an often-used rubber-gasket sealed static chamber against a water-filled-gutter seal chamber I designed that could be set up and sampled from a distance of 2 m with a remote rod sampling system to reduce soil disturbance. Compared to the conventional design, the remotely-sampled static chambers reduced the chance of detecting inflated initial CH4 concentrations from 66 to 6%, and nearly doubled the proportion of robust linear regressions from 45 to 86%. The new system I developed allows for more accurate and reliable CH4 sampling without costly boardwalk construction. </p><p>I explored the relationship between CH4 emissions and aquatic herbivores, which are recognized for imposing top-down control on the structure of wetland ecosystems. The biogeochemical consequences of herbivore-driven disruption of plant growth, and in turn, mediated oxygen transport into wetland sediments, were not previously known. Two growing seasons of herbivore exclusion experiments in a major waterfowl overwintering wetland in the Southeastern U.S. demonstrate that waterfowl herbivory had a strong impact on the oxygen-sensitive processes of CH4 emission and nitrification. Denudation by herbivorous birds increased cumulative CH4 flux by 233% (a mean of 63 g CH4 m-2 y-1) and inhibited coupled nitrification-denitrification, as indicated by nitrate availability and emissions of nitrous oxide. The recognition that large populations of aquatic herbivores may influence the capacity for wetlands to emit greenhouse gases and cycle nitrogen is particularly salient in the context of climate change and nutrient pollution mitigation goals. For example, our results suggest that annual emissions of 23 Gg of CH4 y-1 from ~55,000 ha of publicly owned waterfowl impoundments in the Southeastern U.S. could be tripled by overgrazing. </p><p>Hydrologically controlled moist-soil impoundment wetlands provide critical habitat for high densities of migratory bird populations, thus their potential to export nitrogen (N) to downstream waters may contribute to the eutrophication of aquatic ecosystems. To investigate the relative importance of N export from these built and managed habitats, I conducted a field study at an impoundment wetland that drains into hypereutrophic Lake Mattamuskeet. I found that prescribed hydrologic drawdowns of the impoundment exported roughly the same amount of N (14 to 22 kg ha-1) as adjacent fertilized agricultural fields (16 to 31 kg ha-1), and contributed approximately one-fifth of total N load (~45 Mg N y-1) to Lake Mattamuskeet. Ironically, the prescribed drawdown regime, designed to maximize waterfowl production in impoundments, may be exacerbating the degradation of habitat quality in the downstream lake. Few studies of wetland N dynamics have targeted impoundments managed to provide wildlife habitat, but a similar phenomenon may occur in some of the 36,000 ha of similarly-managed moist-soil impoundments on National Wildlife Refuges in the southeastern U.S. I suggest early drawdown as a potential method to mitigate impoundment N pollution and estimate it could reduce N export from our study impoundment by more than 70%.</p><p>In this dissertation research I found direct relationships between wetland restoration and impoundment management practices, and biogeochemical responses of greenhouse gas emission and nutrient cycling. Elevated soil C at a restored wetland increased CO2 losses even ten years after the organic matter was originally added and intensive herbivory impact on emergent aquatic vegetation resulted in a ~230% increase in CH4 emissions and impaired N cycling and removal. These findings have important implications for the basic understanding of the biogeochemical functioning of wetlands and practical importance for wetland restoration and impoundment management in the face of pressure to mitigate the environmental challenges of global warming and aquatic eutrophication.</p> / Dissertation

Thesis advisor: Tara Pisani Gareau / Salt marshes provide important ecosystem services, including carbon sequestration. Permanently inundated ponds are prominent features in the marsh landscape, encompassing up to 60% of the total marsh area, but they are rarely considered in biogeochemical assessments. I investigated two ponds in Plum Island Estuary, MA to measure and analyze their metabolism. The ponds varied in size and vegetation cover. Oxygen concentrations and pH values were recorded in 15-minute intervals during the entire study period. The ponds regularly become hypoxic or anoxic during night. This is a problem for the estimation of respiration rates which are based on nighttime measurements. To investigate this potential underestimation, several approaches to estimate respiration were used. First, additional measurements of surface water concentrations of dissolved inorganic carbon were made. A comparison of respiration estimates based on oxygen and DIC changes during tidal isolation revealed a reasonable agreement for the most time but not during periods of high productivity during the day or late at night. At this point, oxygen concentrations are so depleted that a change in concentration – the indicator of respiration – is barely detectable. However, DIC based respiration rates indicate that respiration is occurring under these hypoxic/anoxic conditions. This saturation changes during periods of tidal inundation, when a nighttime peak in oxygen concentrations indicates that the flood water is relatively enriched in oxygen compared to the pond water. On three days, it was tested whether under these conditions the oxygen-based respiration rate was higher than under hypoxic conditions (i.e., during tidal isolation). The rates were indeed higher than those under tidal isolation but still not in the range of DIC-based rates. Overall, metabolic rates differed between the two ponds in magnitude, which is likely caused by different vegetation cover, but may be influenced by size, sampling period, and duration as well. / Thesis (BS) — Boston College, 2018. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: Departmental Honors. / Discipline: Earth and Environmental Sciences.

Shortened periods of inundation due to water management have led to the encroachment and expansion of Carolina willow (Salix caroliniana) in sawgrass (Cladium jamaicense) marsh communities. Morphologic and physiologic differences between sawgrass and willow have potential consequences for microhabitat conditions and ecosystem function such as a reduction in temperatures and light availability and changes in primary productivity. Since it is a woody shrub, willow is often assumed to exhibit higher rates of transpiration than non woody plants, which in turn can affect photosynthesis and carbon exchange and ultimately wetland water management. In this study willow was found to have higher rates of stomatal conductance (gs) and photosynthesis (Anet) than sawgrass. However, sawgrass had greater intrinsic water use efficiency (WUE) than willow. This suggests that willow is capable of greater gas exchange and carbon assimilation than sawgrass but requires more water. Understanding the implications of willow expansion will improve landscape models of wetland water and carbon exchange and inform water management decisions. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2015. / FAU Electronic Theses and Dissertations Collection

The plants and sediments of two shallow, sub-tropical lakes in north Florida (Lake Jackson and Lake Hall located in Leon County) were sampled, identified, and analyzed for PAH content at 16 different stations quarterly. Stations were chosen so that areas affected by stormwater and relatively pristine areas were surveyed. Sediments from areas that received stormwater runoff were found to have elevated PAH concentrations, while stations distant were characterized by lower PAH concentrations. / The PAH content of rooted vegetation was found to have a significant relationship with the concentrations of PAHs in the sediments upon which they grew. There was no relationship between the PAH concentrations in non-rooted plants and the sediments where they were found. Plant growth and PAH assimilation experiments were performed on sixty-six plants that included indigenous rosette monocots and vittate dicots which were planted in sediments spiked with varying concentrations of PAHs. These sediments were completely segregated from the water column which was verified by analysis. / It was conclusively shown that the sediment PAHs exerted a deleterious effect on the growth of the subject aquatic macrophytes, and that the PAHs from the sediment entered the plants through their root systems. These experiments showed that the roots of aquatic plants will reach a PAH concentration almost nine times higher than the PAH concentrations of their shoots. There was a difference in the types of PAHs which were accumulated by the plants: the most readily accumulated PAHs were the most water soluble. The evidence indicates that partitioning occurs from the aqueous phase. / There were species-specific differences in the degree of accumulation of sediment PAHs. Saturation phenomena for PAH bioconcentration were observed. A model was developed that incorporated equilibrium constants, constants for adsorption and desorption, and saturation levels of PAHs for aquatic plants. The field data, the microcosm experiments and the model all lead to the conclusion that aquatic macrophytes accumulate sediment PAHs acropetally and transport them to their shoots. / Source: Dissertation Abstracts International, Volume: 56-12, Section: B, page: 6491. / Major Professor: Robert J. Livingston. / Thesis (Ph.D.)--The Florida State University, 1995.

Les systèmes ultramafiques sont souvent synonymes de fortes teneurs en chrome (Cr) dans des roches, qui est naturellement lixivié vers les eaux de surface et souterraines. En raison de cet enrichissement naturel, les zones ultramafiques font souvent l’objet d’extractions massives. Le processus minier inclut l'exploitation et les activités d'enrichissement, dans lesquelles la grande quantité de résidus produits riches en métaux, tels que les gangues et les terrils, sont stockés à l’air libre. Ces processus peuvent considérablement augmenter les teneurs en Cr trivalent (Cr (III)) et hexavalent (Cr (VI)) disséminé dans l'environnement. Ce dernier (Cr (VI)), est connu pour être fortement soluble dans l'eau, biodisponible et toxique. Ce travail de thèse a porté sur i) la zone d’exploitation minière du nickel de Barro Alto (BA, Etat du Goiás, Brésil); ii) la zone d'exploitation minière historique de chromite de Cromínia (CA, Etat du Goiás, Brésil) et iii) une exploitation minière actuelle dans la vallée de Sukinda (Odisha, l'Inde). Le principal objectif de ces travaux est l'identification de l'impact d'activités minières (extraction du nickel et du chrome) sur la mobilité de Cr et sa disponibilité dans des zones ultramafiques, à l'aide des techniques isotopiques. Les compartiments chimiquement et isotopiquement échangeables de Cr(VI) (ECr (VI)) les plus hauts ont été mesurés dans des échantillons de minerai à BA, où l'enrichissement en isotopes légers de Cr (-0.76 à -0.16 ‰) a été attribué à la perte de Cr isotopiquement lourd et échangeable Cr(VI) pendant l’altération. Des valeurs étonnamment lourdes de δ53Cr ont été aussi trouvées dans des minerais saprolitiques à BA et dans des sols affectés par l’extraction à CA, jusqu’à +3.9 ‰ alors qu’ils étaient fortement enrichis en Cr(III). Les causes principales ont été attribuées à l'existence de chromite hydrothermale à CA et/ou à l’altération naturelle suivie par la réduction de Cr(VI), induisant la reprécipitation de Cr mobile et isotopiquement lourd. Le chrome était présent dans les lixiviats des échantillons de minerais saprolitiques et lateritiques de BA, sous la forme de Cr(VI) isotopiquement lourd (jusqu’à +4.84 ‰), en cohérence avec le Cr échangeable (ECr(VI)) (jusqu’à +4.37 ‰). Ces valeurs étaient dans la même gamme de compositions isotopiques que celles mesurées dans les eaux douces de surface (ruisseaux et réservoirs) situés dans la zone ultramafique. Ces résultats impliquent que Cr est principalement disséminé sous sa forme toxique Cr(VI), dont la disponibilité augmente depuis i) le profil de sol ii) les minerais et iii) les résidus miniers. Lors de tests de bioaltération réalisés sur les terrils avec Acidithiobacillus thiooxidans (pH~2) ou Pseudomonas putida (pH~9), Cr a été initialement extrait sous sa forme Cr(VI) puis réduit en Cr (III). Dans les expériences avec A. thiooxidans, la réduction du chrome est dû à l’important pouvoir réducteur d'une série de composés soufrés, tandis que P. putida utilise probablement pour la réduction des chromates une variété d'accepteurs d’électrons. Ces mécanismes, de même que l’augmentation de la concentration en matière organique et la carbonatation minérale, pourraient expliquer la plus faible concentration en Cr(VI) échangeable dans les terrils âgés par rapport aux terrils récents. Par la technique d’échange isotopique, la contribution des SPM au transport du chrome échangeable, ainsi que l’impact des colloïdes contenant des phases porteuses de Cr sur la mesure de ce compartiment échangeable associé aux SPM (EWCr) a été mise en évidence. Les plus grosses particules (> 0.2 µm) jouent un rôle prépondérant dans la zone impactée par l’activité minière, tandis que le chrome est principalement associé aux colloïdes (1 kDa-500 kDa) dans la zone vierge. La présence de colloïdes organiques et inorganiques contenant du chrome non-échangeable induit une surestimation de la valeur de EWCr, qui peut être corrigée par le biais d’un scénario du pire / Ultramafic systems are often synonym of high chromium (Cr) content in rocks, which is naturally leached to surface and groundwater. Due to this natural enrichment, ultramafic areas are massively mined. The mining process includes exploitation and beneficiation activities, in which large amount of metal-rich residues, such as overburden, waste rock and tailings, stored in open air, are produced. These processes may considerably increase the amount of both trivalent (Cr(III)) and hexavalent chromium (Cr(VI)) released to the environment. The later (Cr(VI)), known to be highly soluble in water, bioavailable and toxic. Within these mining residues, many chemical and biological processes may take place, which will control Cr speciation, mobility and availability. The present work was conducted on i) the nickel exploitation and metallurgic area of Barro Alto (BA, Goiás state, Brazil); ii) the antique chromite exploitation area of Cromínia (CA, Goiás State, Brazil) and iii) the current chromite mine in the Sukinda valley (Odisha, India). The main focus of this research is the identification of the impact of mining activities (nickel and chromium mining) on Cr mobility and availability in ultramafic environments, through the use of isotopic techniques. The chemically and isotopically exchangeable pools of Cr(VI) (ECr(VI)) were higher in BA ore samples, where the enrichment in light chromium isotopes (-0.76 to -0.16‰) was attributed to the loose of isotopically heavy and exchangeable Cr(VI) during weathering. Astonishingly, heavy δ53Cr values were also found in saprolitic ores in BA and in mining-affected soils in CA up to +3.9‰, strongly enriched in Cr(III). The main causes have been attributed to the existence of hydrothermal chromite in CA and/or to natural weathering followed by Cr(VI) reduction that induces reprecipitation of mobile and isotopically heavy Cr. In such a mining context, the accelerated weathering would play an important role in this process. Chromium in the leachate, of BA lateritic and saprolitic ores samples, was present as Cr(VI) isotopically enriched in heavy isotopes (up to +4.84‰), consistently with the exchangeable Cr (ECr(VI)) (up to +4.37‰). These values were in the same range as isotopic compositions measured in the fresh waters (streams and ponds) in the ultramafic area. These results imply that Cr is mainly released as the toxic Cr(VI) specie, which availability increases from i) the soil profile to ii) the ores and iii) the mining residues. This also suggests that δ53Cr could be used as a tracer of Cr leaching in environmental studies in the dissolved phase.In bioleaching tests on tailings with Acidithiobacillus thiooxidans (pH ~ 2) or Pseudomonas putida (pH ~ 9), Cr was initially extracted as Cr(VI) and later reduced to Cr(III). In the experiments with A. thiooxidans the Cr reduction is due to the production of a series of sulfur compounds with high reducing power, while for P. putida probably uses a variety of electron acceptor for chromate reduction, enhanced by the presence of extracellular polymeric substances. Those mechanisms together with the increase of natural organic matter (NOM) and mineral carbonation, could explain the lower exchangeable pool of Cr(VI) in stockpiled chromite tailings compared to fresh tailings. Through the use of isotopic exchange, the contribution of SPM to the transport of exchangeable chromium and the impact of colloids containing Cr-bearing phases on the determination of the exchangeable pool of Cr associated to SPM (EWCr) was highlighted. Larger particles (>0.2 μm) were dominant in the impacted area, while chromium was mainly associated with colloids (1 kDa–500 kDa) in the pristine area. The presence of organic and inorganic colloids containing non-exchangeable chromium induces an overestimation of the EWCr values, which can be over-come thanks to a worst-case scenario correction

Globally, human activities are altering nutrient biogeochemical cycles. The impact of humans on silicon (Si) cycles remains largely unexplored. Understanding the cycle of Si is important because weathering of siliceous rocks is a substantial sink of atmospheric carbon. Additionally, Si is required by diatoms. Diatoms form the base of important socioeconomic food webs, responsible for ~50% of oceanic net primary production, and deliver atmospheric carbon to ocean sediments as part of the ocean’s biological pump. My dissertation aims to assess the role of anthropogenic activities in altering Si cycling across the land-ocean continuum. Chapter 2 focuses on how assimilation of biogenic silica (BSi) by trees may be impacted by projected changes in climate. Using samples collected during a multi-year, snow removal experiment, I show that increased frequency and duration of soil freezing in winter significantly decreased (-28%) BSi in sugar maple (Acer saccharum) fine roots compared to control plots. Importantly, I observed that fine roots are a previously undescribed pool of BSi within sugar maples, accounting for 29% of total sugar maple BSi while only 4% of sugar maple biomass. Chapter 3 examines the origin and fate of Si within wastewater for the City of Boston. I determined the total dissolved silica (DSi) load in wastewater influent (69,500 kmol DSi year-1), then parsed the total DSi flux between Si contributions of sewage (49%), groundwater infiltration (39%), and surface runoff inflow (12%). In Chapter 4, I study the DSi load carried by treated effluent. I determined that effluent load (67,800 kmol DSi year-1) is not statistically different from influent load, indicating that wastewater treatment does not remove DSi. In Chapter 5 I demonstrate how humans impact concentrations of DSi in urban groundwater. Groundwater DSi increases with human presence and urban areas have significantly higher concentrations of DSi compared to groundwater conditions along the Massachusetts coast. I demonstrate that historic variables defining fill techniques, fill material, and pre-fill land-use out preform geologic variables in predicting urban groundwater DSi concentrations. This dissertation highlights human alterations to biological assimilation, fate, and effects of Si in sewage, and centuries-long subsurface Si impacts that perturb the distribution and availability of a nutrient intimately tied to water quality and climate.