No description available.

This thesis investigates the relationships between mercury (Hg) and stable isotope of carbon (δ13C) in marine pelagic zooplankton (Calanus spp., Themisto spp. and Euchaeta spp.) with water mass characteristics in the North Water Polynya (NOW) and in the Mackenzie shelf – Amundsen Gulf area. Two ship based sampling field expeditions were carried out in late summer of 2005 and 2006 in both regions on board the CCGS Amundsen. In the North Water (NOW) polynya, higher levels of water Hg, depleted δ18O, lower salinity and lower nitrate levels were measured at sampling locations near the Prince of Wales glacier (POW) on the eastern coast of Ellesmere Island in the Smith Sound area. These results suggest that the glacier may be a source of Hg to this region which, in turn, is responsible for the correspondingly high concentrations of THg and MMHg measured in Calanus spp. and Euchaeta spp. at the same locations. The Mackenzie shelf – Amundsen Gulf region was characterized by fresher surface water properties (low salinity and depleted δ18O) in the western part and was strongly linked to the influence of the Mackenzie River. Higher THg concentrations in zooplankton were associated with larger fractions of both meteoric water and sea-ice melt. These findings suggest that in the western Arctic, inorganic Hg uptake in zooplankton via-absorption near surface water was highly driven by freshwater inputs into the system. Based on the analysis of three main genus Calanus spp. (mostly adult females Calanus hyperboreus), Euchaeta spp. and Themisto spp. (mostly adult Themisto libellula), THg and MMHg concentrations were the highest in the carnivorous copepod Euchaeta spp. in the North Water polynya followed by the omnivorous hyperiid amphipod Themisto spp. The herbivorous copepod Calanus spp. had both the lowest THg and MMHg concentrations in the Eastern and the Western Arctic. In addition, the Western Arctic is the area in which each zooplankton genus had the most depleted carbon and the most enriched nitrogen. The highest concentrations of THg in Calanus spp., Euchaeta spp. and Themisto spp. were measured in the Western Arctic as well as the highest MMHg in Calanus spp. and Themisto spp. The highest %MMHg was calculated in the Archipelago for Themisto spp., in the Eastern Arctic for Euchaeta spp. and in the Western Arctic for Calanus spp. The relationships observed between THg, MMHg, %MMHg and δ13C in all three major zooplankton taxa and water mass properties were in agreement with what have been previously described in the literature. Our findings suggested that both Hg and δ13C can be used as tracers to help understand zooplankton vertical distribution, feeding ecology and ultimately to predict climate changes impact at lower trophic level in the pelagic food web. The implications for marine mammals foraging in these regions are also discussed.

This thesis presents research that improves our understanding of the relationship between climate and tree-ring stable isotopes in New Zealand kauri (Agathis australis (D. Don) Lindl.) and cedar (Libocedrus bidwillii Hook. F). As a whole, this research creates a framework from which future investigations of stable isotope dendroclimatology can pursued at high temporal resolution across longer term temporal intervals. Such a framework is required to realize the full potential of New Zealand tree-ring records as archives of palaeoclimatic information. In the Southern Hemisphere, mid-to-high latitude terrestrial climate proxy records are sparse; the long-lived endemic conifers of New Zealand present a rare opportunity to gain valuable insight into Late-Quaternary and Holocene climatic change. A major barrier to long stable isotope dendroclimatic proxy records has been the time-and-resource intensive nature of associated sample preparation and analytical processes. Through experimental assessment of the SBrendel α-cellulose extraction method, this research demonstrates that this simple processing method can, with some caveats, be successfully applied to resinous conifers, facilitating rapid chemical preparation of samples. Further efficiency gains are documented in through use of dual element low temperature pyrolysis of cellulose, providing carbon and oxygen stable isotope determinations on a single sample, rather than the traditionally separate analyses. These preliminary investigations into methodological efficiency enabled the ~3000 stable isotope determinations on kauri and cedar, on which the following investigations into isotopic variability, chronology quality and climate-isotope relationships are based. Both kauri and cedar exhibit substantial intra and inter-tree isotopic variability, resulting in greater than normal sample numbers being required to isolate the common variance in composite time-series. Despite sampling 7 trees (18 cores) at one site and 8 trees (21 cores) at another, only oxygen isotope time-series reach an Expressed Population Signal score of 0.85, a common benchmark of chronology quality. Further investigations using high-resolution sequential sampling of single rings show that this variability extends to a sub-annual scale. Within single rings there are large ranges in δ13C and δ18O, generally corresponding with regular annual cycles of up to 4.6‰ for δ13C and 8.1‰ for δ18O. These data show high frequency (sub weekly) changes in δ18O, demonstrating sufficiently fine resolution for event-to-seasonal scale climate/weather reconstruction. However, that potential is complicated by the lack of strong climatic correlations with isotopic cycles. Due to their stronger common signal, δ18O time series are investigated for inter-annual stable isotope dendroclimatic reconstruction from kauri and cedar. Bootstrapped correlation and multiple regression models show strong relationships between kauri and cedar δ18O and relative humidity, accumulated rainfall and soil moisture deficit. The correlations are strongest for all variables during the period from Autumn prior to growth to the current growth summer. Tree-ring δ18O in kauri and cedar is identified as an effective recorder of regional hydroclimate leading up to and during the Austral growth season. While it is demonstrated that tree-ring δ18O holds significant promise for inter-annual palaeoclimate reconstruction, it is equally apparent from this research that stable isotope dendroclimatology in New Zealand faces significant challenges. Foremost is gaining an improved understanding of seasonal dendrochemical cycles and their relationship with tree-physiology. Increasing the spatial and temporal coverage of tree-ring isotope records is vital to realising New Zealand’s vast potential for stable isotope dendroclimatic reconstruction.

No description available.

Records of stable oxygen isotope variations from a variety of proxies have been used in palaeoclimatic research since the 1950’s. Several studies have applied stable isotope analysis of lake sediments to reconstruct past climate changes in central and northern Sweden, including a study of Lake Blektjärnen in Jämtland, central Sweden, by Andersson (2010). In this study, sediments from that same lake were sampled for stable isotope analysis of bulk carbonates with the aim to improve the resolution of the isotopic record for the last two millennia. The results indicate a shift from relatively drier to wetter conditions between ~2,300–1,300 cal. years BP, generally wet conditions close to the Medieval Warm Period (~1,000–750 cal. years BP) and generally dry conditions during the Little Ice Age (~550–150 cal. years BP). These results are in agreement with previous palaeoclimatic reconstructions in the region. The isotopic record of Lake Blektjärnen was completed for the last ~2,350 years at a resolution of ~15 years per sample, three times higher than that of the previous study, displaying the advantages of bulk carbonate sampling for stable isotope analysis and providing a high-resolution dataset on humidity changes in central Sweden during the late Holocene.

Nitrous oxide (N???O) is a potent greenhouse gas, an important driver of climate change, and its concentration in the atmosphere is rising at an unprecedented rate. Agriculture is the leading contributor of all the anthropogenic N???O sources, and the vast majority of agricultural N???O emissions originate from soil. Of all the natural N???O emissions, two-thirds originate from soil and temperate forests contribute approximately one-sixth of the natural soil emissions. Consequently, there is great interest in understanding the soil nitrogen processes responsible for N???O production so that effective policies and management practises can be implemented to successfully mitigate climate change. The stable isotopes of nitrogen (N) and oxygen (O) in soil N???O emissions are hypothesized to be useful indicators of the biogeochemical processes that produce and consume N???O, and they may be used to apportion different environmental sources. The primary objective of this thesis was to assess the utility of ???????N and ???????O values to differentiate N???O produced by nitrification and denitrification. Most of the previous research on N???O isotopes has utilized microbial cultures of single organisms; yet natural systems contain a consortium of N-metabolizing microorganisms so the relevance of this early work to natural environments is uncertain. This thesis presents the results of experimental incubations of soil from an agricultural site and a temperate forest located within Ontario, Canada. Two well-drained soils (upland), two poorly-drained soils (wetland), and one stream sediment were incubated under varying conditions (temperature, moisture, and N-availability) to achieve a wide range in the rate of N???O production. The ???????N and ???????O values of N???O produced from the different experiments were characterized and the isotope effects (??) of N???O production were calculated. Experiments were conducted in aerobic or anoxic atmospheres to stimulate N???O formation by nitrification and denitrification, respectively. The ???????N-N???O produced by denitrification in all soils was 7???35??? lower than the ???????N-nitrate (NO??????). The ???????N-N???O produced by nitrification in the upland forest soil and the agricultural soils was 28???54??? lower than the ???????N-ammonium. Nitrification in the forested wetland soil yielded higher ???????N-N???O values (?? = ???16???), which was likely caused by an increase in the ???????N-substrate. With the exception of the latter soil, there was clear ?????N-separation between the nitrification- and denitrification-derived N???O in all soils. Consequently, ???????N values can be used to apportion different environmental sources of N???O on a site-by-site basis, provided that the rates of N metabolism are known and the isotopic endmembers are well-characterized. A novel approach was employed in this thesis to help unravel the key controls of ???????O-N???O and ???????O-NO?????? formation. Different ?????O-labelled soil waters were used to demonstrate that the abiotic exchange of oxygen atoms between water and nitrite (in equilibrium) is an important control of the ???????O-N???O formed by nitrifier-denitrification and the ???????O-NO?????? formed by nitrification. O-exchange in these incubations was highly variable between soils (37???88%) and it appeared to be rate-related. Furthermore, the ???????O value of microbial NO?????? is partially controlled by ?????O/?????O fractionation that occurs during O-exchange (equilibrium fractionation) and the uptake of molecular oxygen (O???) and water (H???O) (kinetic fractionation). This research showed that the ???????O value of microbially-produced NO?????? cannot be successfully predicted in soils based upon the commonly used ???one third, two-thirds rule???, which only takes into account the ???????O values of O??? and H???O. Successful predictions of ???????O-NO?????? using this rule appear to be fortuitous and are because of the range of ???????O-H???O at natural abundance and the magnitude of the isotope effects involved. Enzyme-catalyzed (biotic) O-exchange between water and nitrite/nitric oxide in denitrification was also quantified for the first time in soils. O-exchange during denitrification was significant and variable (39???95%), but uniquely confined to narrow ranges for each soil type. Almost complete O-exchange occurred in the well-drained agricultural and forested soils (86???95%); less O-exchange occurred in the agricultural and forested wetland soils (63???70%); and even less O-exchange occurred in the agricultural stream sediment (39???51%). The magnitude of O-exchange during denitrification was independent of soil temperature and moisture for a given soil, and it was not related to the rate of N???O production. This implies that the amount of O-exchange that occurs during soil denitrification is controlled by the dominant microbial community. For the first time, estimates of the net O isotope effect were determined for N???O production by soil denitrifiers that accounted for the complicating effects of O-exchange. The net ?????O-discrimination (N???O???NO??????) ranged between +32??? and +60???, with the exception of one treatment that was cooled (?? = +17???). The O isotope separation (??) that is actually observed in natural systems is often much lower, and in some cases negative. This is because the atomic O-exchange between water and nitrite/nitric oxide effectively diminishes the net ?????O separation between NO?????? and N???O because ???????O values of environmental water are usually lower than the ???????O values of N???O-precursors. The determinants of ???????O-N???O produced by nitrification pathways are complex and there is no holistic explanation of the O isotope dynamics in the literature. This thesis provides the first systematic model to describe ???????O-N???O formation by aerobic pathways. In addition to O-exchange between water and nitrite (at equilibrium), ???????O-N???O is controlled by ?????O/?????O fractionation that results from this O-exchange mechanism, and from fractionation that occurs during ammonia-oxidation and nitrite-reduction. Although explaining ???????O-N???O values produced by nitrification is complex, reports of nitrifier-derived ???????O-N???O in the literature and this thesis are narrowly confined between +13??? and +31??? (rel. VSMOW). This is distinct from much of the denitrifier-produced ???????O-N???O, which is often ?????O-enriched and higher than +33???. In three out of the five different soils investigated in this thesis, ???????O-N???O could be used to separate N???O formed by nitrification and denitrification. There was poor ???????O separation between nitrifier- and denitrifier-derived N???O in the well-drained soils because high amounts of biotic O-exchange and reduced O isotope separations yielded lower (predicted) estimates of denitrifier-produced ???????O-N???O. On the other hand, ???????N values could be used to apportion nitrifier- and denitrifier-derived N???O sources in these soils. Thus, stable isotope ratios of N???O are a valuable and promising tool that may help differentiate nitrifier-N???O from denitrifier-N???O in natural soil environments.

Invasive species are a known stressor on aquatic ecosystems, particularly in the waters of the Great Lakes basin. A recent invader, Hemimysis anomala, has had significant impacts on the food webs of Europe, where it invaded previous to its spread to North America. However, despite the fact that Hemimysis is now widespread in the Great Lakes basin, no analysis has been done on the trophic position of Hemimysis in North America invaded sites. This thesis used carbon (??13C) and nitrogen (??15N) stable isotopes to examine spatial and temporal patterns in Hemimysis trophic niche use in invaded North American sites in an attempt to broaden the knowledge base on this invader and to examine potential impacts this invader may have on the food webs of the Great Lakes. A spatial comparison of trophic niche use by Hemimysis among 13 sites in Lake Erie, Lake Ontario, and the St. Lawrence River was conducted between late July and mid-September of 2011. Main sources of carbon (benthic versus pelagic production) and trophic offset, or trophic distance from basal food web items, of Hemimysis were quantified using Hemimysis ??13C and ??15N values. Results indicated that: 1) Hemimysis relied predominantly on pelagic carbon sources at the majority of sites, and isotopic differences between life-stages existed at two of the 13 sites examined, 2) the trophic offset and reliance on pelagic food sources did not differ significantly between lotic and lentic sites, and 3) the isotopic niche width of Hemimysis was spatially heterogeneous, varying by an order of magnitude among sites, but was unrelated to the degree of isotopic variation in the basal food web at each site. Observed ranges in trophic offset and the pelagic fraction of dietary carbon indicate that Hemimysis derives carbon from both benthic and water column sources, as well as at multiple trophic levels. Results support the notion that Hemimysis is an opportunistic omnivore that displays significant dietary flexibility. To test the relative importance of key biotic and abiotic factors, taken from the literature, in driving Hemimysis isotopic variation, a temporal analysis was conducted at two North American sites, one in Lake Ontario and one in the St. Lawrence River, which were repeatedly sampled for Hemimysis and related food web items between September 2008 and January 2012. Seasonal patterns of winter enrichment ??? summer depletion were found in Hemimysis ??15N in Lake Ontario, but a similar pattern was not seen in the St. Lawrence River. Multiple regression models were used to determine the importance of water temperature, Hemimysis C:N ratios, Hemimysis length, and the isotopic values of basal food web components in explaining observed variation in Hemimysis ??13C and ??15N values. Significant relationships were found between Hemimysis isotopic values and water temperature, but relationships with the isotopic signatures of the pelagic basal food web were weak or nonexistent. Hemimysis ??13C values were significantly correlated with C:N ratios. Strong evidence of an ontogenetic dietary shift was found in Lake Ontario, with length showing a significant positive correlation with Hemimysis ??15N. All together the factors included in the models explained little of the observed variation in Hemimysis isotopic values, with approximately 20 % of the observed variation in Hemimysis ??13C, and just under half of Hemimysis ??15N variation, being explained by the included factors. As such, Hemimysis isotopic variation must be explained by factors not included in this study and may include factors such as species composition of the invaded site and availability of prey. Overall, the results of this thesis highlight the opportunistic and flexible nature of Hemimysis diet, and demonstrate the need for future work to determine the main drivers of isotopic variability and trophic niche selection of Hemimysis. The degree of trophic flexibility seen in Hemimysis implies that potential food web impacts will be site specific and heavily reliant on food web dynamics and environmental characteristics of the invaded site.

Developing critical loads for nitrogen (N) in the Athabasca Oil Sands Region (AOSR) requires an understanding of the hydrological connectivity and potential for N transport among uplands, fens and bogs typical in the wetland-rich Boreal region of northern Alberta. The Cumulative Environmental Management Association’s (CEMA) overarching mandate is to determine a nitrogen critical load specific to the Boreal region of northern Alberta. To this end, nitrogen amendment experiments were initiated at two Boreal wetland sites: an upland – rich fen gradient at Jack Pine High (JPH) and an upland – fen – bog mosaic at Mariana Lakes (ML), 45 km north and 100 km south of Fort McMurray respectively. The objectives of this study are to use geochemical and isotopic tracers to describe baseline hydrogeochemical variability and connectivity between bog, fens and upland areas in the AOSR. Sites were instrumented with piezometer nests and water table wells along transects that cover the targeted landscape units (n = 108 sampling locations). Fieldwork related to this thesis was conducted during the open-water season: in June and August 2011, and in May, July, and September 2012. Field campaigns also included a snow survey (March 2012), and spring melt/freshet sampling (April 2012). The analysis of spatiotemporal variability of water isotopes and geochemistry in the years 2011-2012 yielded: i) a characterization of baseline conditions from which perturbations can be assessed, and ii) evidence of connectivity among landscape units. No evidence for elevated concentrations of nitrogen related to the amendment experiments was found in 2011 or 2012. The baseline characterization and annual monitoring did show increasing concentrations of inorganic ammonium with increasing depth associated with increasing solute concentrations: average concentrations of inorganic ammonium were 23 mg/L at deepest sampling locations (7 m) at ML bog and ML fen landscape units. These ammonium concentrations in porewaters, given a porosity of 0.90 for peatlands, constitute a store of ammonium that may be a significant source of nitrogen if the hydrology is altered due to co-occurring changes in vegetation (due to, for example, elevated nitrogen inputs), climate and/or landuse. Hydrologic connectivity at JPH is likely driven by topography. Hydraulic head in 2011 and 2012 field seasons showed that flow persisted from the upland to the fen. The consistent and distinct geochemical signatures and isotopic labelling of mid-depth and deep groundwater samples of fen and upland landscape units is consistent with such a stable groundwater continuum. Near-surface water samples at JPH fen however varied hydrogeochemically in response to seasonal changes in precipitation inputs, water levels, and biogeochemical productivity. At ML, hydrological connectivity is a function of antecedent moisture conditions (which determines run-off) and low and variable (10-6 to 10-9 m/s) hydrological conductivity of the peatland substrate (which may result in lateral flow where hydraulic head shows potential for vertical re- or discharge). Near-surface samples showed greater temporal than spatial variability as snowmelt inputs, variations in antecedent moisture conditions and seasonal changes in biogeochemical process rates affected nutrient and solute concentrations. In contrast, shallow, mid-depth and deep samples showed greater spatial than temporal variability. The spatial distributions of parameters could be associated to some degree with vegetation, distance along a surficial flowpath, or depth to mineral substrate or distance from the upland/edge transition. / Graduate / 0996 / 0388 / 0425 / cbkusel@yahoo.ca

This thesis investigates the relationships between mercury (Hg) and stable isotope of carbon (δ13C) in marine pelagic zooplankton (Calanus spp., Themisto spp. and Euchaeta spp.) with water mass characteristics in the North Water Polynya (NOW) and in the Mackenzie shelf – Amundsen Gulf area. Two ship based sampling field expeditions were carried out in late summer of 2005 and 2006 in both regions on board the CCGS Amundsen. In the North Water (NOW) polynya, higher levels of water Hg, depleted δ18O, lower salinity and lower nitrate levels were measured at sampling locations near the Prince of Wales glacier (POW) on the eastern coast of Ellesmere Island in the Smith Sound area. These results suggest that the glacier may be a source of Hg to this region which, in turn, is responsible for the correspondingly high concentrations of THg and MMHg measured in Calanus spp. and Euchaeta spp. at the same locations. The Mackenzie shelf – Amundsen Gulf region was characterized by fresher surface water properties (low salinity and depleted δ18O) in the western part and was strongly linked to the influence of the Mackenzie River. Higher THg concentrations in zooplankton were associated with larger fractions of both meteoric water and sea-ice melt. These findings suggest that in the western Arctic, inorganic Hg uptake in zooplankton via-absorption near surface water was highly driven by freshwater inputs into the system. Based on the analysis of three main genus Calanus spp. (mostly adult females Calanus hyperboreus), Euchaeta spp. and Themisto spp. (mostly adult Themisto libellula), THg and MMHg concentrations were the highest in the carnivorous copepod Euchaeta spp. in the North Water polynya followed by the omnivorous hyperiid amphipod Themisto spp. The herbivorous copepod Calanus spp. had both the lowest THg and MMHg concentrations in the Eastern and the Western Arctic. In addition, the Western Arctic is the area in which each zooplankton genus had the most depleted carbon and the most enriched nitrogen. The highest concentrations of THg in Calanus spp., Euchaeta spp. and Themisto spp. were measured in the Western Arctic as well as the highest MMHg in Calanus spp. and Themisto spp. The highest %MMHg was calculated in the Archipelago for Themisto spp., in the Eastern Arctic for Euchaeta spp. and in the Western Arctic for Calanus spp. The relationships observed between THg, MMHg, %MMHg and δ13C in all three major zooplankton taxa and water mass properties were in agreement with what have been previously described in the literature. Our findings suggested that both Hg and δ13C can be used as tracers to help understand zooplankton vertical distribution, feeding ecology and ultimately to predict climate changes impact at lower trophic level in the pelagic food web. The implications for marine mammals foraging in these regions are also discussed.

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.