Lignin biomarkers as tracers of mercury sources in lakes water column

This study presents the role of specific terrigenous organic compounds as important vectors of mercury (Hg) transported from watersheds to lakes of the Canadian boreal forest. In order to differentiate the autochthonous from the allochthonous organic matter (OM), lignin derived biomarker signatures [Lambda, S/V, C/V, P/(V ? S), 3,5-Bd/V and (Ad/Al)v] were used. Since lignin is exclusively produced by terrigenous plants, this approach can give a non equivocal picture of the watershed inputs to the lakes. Moreover, it allows a characterization of the source of OM and its state of degradation. The water column of six lakes from the Canadian Shield was sampled monthly between June and September 2005. Lake total dissolved Hg concentrations and Lambda were positively correlated, meaning that Hg and ligneous inputs are linked (dissolved OM r2 = 0.62, p\0.0001; particulate OM r2 = 0.76, p\0.0001). Ratios of P/(V ? S) and 3,5-Bd/V from both dissolved OM and particulate OM of the water column suggest an inverse relationship between the progressive state of pedogenesis and maturation of the OM in soil before entering the lake, and the Hg concentrations in the water column. No relation was found between Hg levels in the lakes and the watershed flora composition—angiosperm versus gymnosperm or woody versus non-woody compounds. This study has significant implications for watershed management of ecosystems since limiting fresh terrestrial OM inputs should reduce Hg inputs to the aquatic systems. This is particularly the case for largescale land-use impacts, such as deforestation, agriculture and urbanization, associated to large quantities of soil OM being transferred to aquatic systems

Fate of Allochthonous Dissolved Organic Carbon in Lakes: A Quantitative Approach

Inputs of dissolved organic carbon (DOC) to lakes derived from the surrounding landscape can be stored, mineralized or passed to downstream ecosystems. The balance among these OC fates depends on a suite of physical, chemical, and biological processes within the lake, as well as the degree of recalcintrance of the allochthonous DOC load. The relative importance of these processes has not been well quantified due to the complex nature of lakes, as well as challenges in scaling DOC degradation experiments under controlled conditions to the whole lake scale. We used a coupled hydrodynamic-water quality model to simulate broad ranges in lake area and DOC, two characteristics important to processing allochthonous carbon through their influences on lake temperature, mixing depth and hydrology. We calibrated the model to four lakes from the North Temperate Lakes Long Term Ecological Research site, and simulated an additional 12 ‘hypothetical’ lakes to fill the gradients in lake size and DOC concentration. For each lake, we tested several mineralization rates (range: 0.001 d−1 to 0.010 d−1) representative of the range found in the literature. We found that mineralization rates at the ecosystem scale were roughly half the values from laboratory experiments, due to relatively cool water temperatures and other lake-specific factors that influence water temperature and hydrologic residence time. Results from simulations indicated that the fate of allochthonous DOC was controlled primarily by the mineralization rate and the hydrologic residence time. Lakes with residence times <1 year exported approximately 60% of the DOC, whereas lakes with residence times >6 years mineralized approximately 60% of the DOC. DOC fate in lakes can be determined with a few relatively easily measured factors, such as lake morphometry, residence time, and temperature, assuming we know the recalcitrance of the DOC

Isotopic and molecular distributions of biochemicals from fresh and buried Rhizophora mangle leaves†

Rhizophora mangle L. (red mangrove) is the dominant species of mangrove in the Americas. At Twin Cays, Belize (BZ) red mangroves are present in a variety of stand structures (tall >5 m in height, transition ~2–4 m and dwarf ~1–1.5 m). These height differences are coupled with very different stable carbon and nitrogen isotopic values[1] (mean tall δ(13)C = -28.3‰, δ(15)N = 0‰; mean tall δ(13)C = -25.3‰, δ(15)N = -10‰). To determine the utility of using these distinct isotopic compositions as 'biomarkers' for paleoenvironmental reconstruction of mangrove ecosystems and nutrient availability, we investigated the distribution and isotopic (δ(13)C and δ(15)N) composition of different biochemical fractions (water soluble compounds, free lipids, acid hydrolysable compounds, individual amino acids, and the residual un-extractable compounds) in fresh and preserved red mangrove leaves from dwarf and tall trees. The distribution of biochemicals are similar in dwarf and tall red mangrove leaves, suggesting that, regardless of stand structure, red mangroves use nutrients for biosynthesis and metabolism in a similar manner. However, the δ(13)C and δ(15)N of the bulk leaf, the biochemical fractions, and seven amino acids can be used to distinguish dwarf and tall trees at Twin Cays, BZ. The data support the theory that the fractionation of carbon and nitrogen occurs prior to or during uptake in dwarf and tall red mangrove trees. Stable carbon and nitrogen isotopes could, therefore, be powerful tools for predicting levels of nutrient limitation at Twin Cays. The δ(13)C and δ(15)N of biochemical fractions within preserved leaves, reflect sedimentary cycling and nitrogen immobilization. The δ(15)N of the immobilized fraction reveals the overlying stand structure at the time of leaf deposition. The isotopic composition of preserved mangrove leaves could yield significant information about changes in ecosystem dynamics, nutrient limitation and past stand structure in mangrove paleoecosystems

The changing carbon cycle of the coastal ocean

The carbon cycle of the coastal ocean is a dynamic component of the global carbon budget. But the diverse sources and sinks of carbon and their complex interactions in these waters remain poorly understood. Here we discuss the sources, exchanges and fates of carbon in the coastal ocean and how anthropogenic activities have altered the carbon cycle. Recent evidence suggests that the coastal ocean may have become a net sink for atmospheric carbon dioxide during post-industrial times. Continued human pressures in coastal zones will probably have an important impact on the future evolution of the coastal ocean's carbon budget

The genesis and exodus of vascular plant DOM from an oak woodland landscape

Evaluating the collective impact of small source inputs to larger rivers is a constant challenge in riverine biogeochemistry. In this study, we investigated the generation of dissolved organic matter (DOM) in a small oak woodland catchment in the foothills of northern California, the subsequent transformation in lignin biomarkers and chromophoric DOM (CDOM) parameters during transport through the landscape to an exporting stream, and finally the overall compositional impact on the larger receiving stream and river. Our study included a natural leaching experiment in which precipitation passing through oak, pine, and grass litter and duff samples was collected after each of a series of storms. Also included were soil trench samples to capture subsurface lateral flow, stream samples along with point-source reservoir inputs, and samples of canopy throughfall, stemflow, and gopher hole (bypass) flow. The litter/duff leaching study demonstrated changing DOM fractionation patterns throughout the season, as evidenced by changing lignin compositions in the leachates with each successive storm. This adds a necessary seasonal component to interpreting lignin compositions in streams, as the source signatures are constantly changing. Released DOM from leaching was modified extensively during transit through the subsurface to the stream, with preferential increases in aromaticity as evidenced by increases in carbon-normalized absorbance at 254 nm, yet preferential decreases in lignin phenols, as evidence by carbon-normalized lignin yields in the headwater stream that was less than half that of the litter/duff leachates. Our extensive number of lignin measurements for source materials reveals a much more complex perspective on using lignin as a source indicator, as many riverine values for syringyl:vanillyl and cinnamyl:vanillyl ratios that have previously been interpreted as degraded lignin signatures are also possible as unmodified source signatures. Finally, this study demonstrated that the impact of numerous small headwater streams can significantly overprint the DOM signatures of much larger rivers over relatively short distances spanning several to tens of kilometers. This finding in particular challenges the assumption that river studies can be adequately conducted by focusing only on the main tributaries

The genesis and exodus of vascular plant DOM from an oak woodland landscape

Evaluating the collective impact of small source inputs to larger rivers is a constant challenge in riverine biogeochemistry. In this study, we investigated the generation of dissolved organic matter (DOM) in a small oak woodland catchment in the foothills of northern California, the subsequent transformation in lignin biomarkers and chromophoric DOM (CDOM) parameters during transport through the landscape to an exporting stream, and finally the overall compositional impact on the larger receiving stream and river. Our study included a natural leaching experiment in which precipitation passing through oak, pine, and grass litter and duff samples was collected after each of a series of storms. Also included were soil trench samples to capture subsurface lateral flow, stream samples along with point-source reservoir inputs, and samples of canopy throughfall, stemflow, and gopher hole (bypass) flow. The litter/duff leaching study demonstrated changing DOM fractionation patterns throughout the season, as evidenced by changing lignin compositions in the leachates with each successive storm. This adds a necessary seasonal component to interpreting lignin compositions in streams, as the source signatures are constantly changing. Released DOM from leaching was modified extensively during transit through the subsurface to the stream, with preferential increases in aromaticity as evidenced by increases in carbon-normalized absorbance at 254 nm, yet preferential decreases in lignin phenols, as evidence by carbon-normalized lignin yields in the headwater stream that was less than half that of the litter/duff leachates. Our extensive number of lignin measurements for source materials reveals a much more complex perspective on using lignin as a source indicator, as many riverine values for syringyl:vanillyl and cinnamyl:vanillyl ratios that have previously been interpreted as degraded lignin signatures are also possible as unmodified source signatures. Finally, this study demonstrated that the impact of numerous small headwater streams can significantly overprint the DOM signatures of much larger rivers over relatively short distances spanning several to tens of kilometers. This finding in particular challenges the assumption that river studies can be adequately conducted by focusing only on the main tributaries