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The input and fate of dissolved organic matter (DOM) can have important consequences for coastal zone productivity in large lakes and oceans. Chromophoric DOM (CDOM) is often delivered to coastal zones from rivers and streams and affects light penetration in a water column. CDOM can protect biota from damaging ultraviolet (UV) light by acting as sunscreen, resulting in increased ecosystem productivity. Alternatively, CDOM can decrease ecosystem productivity by absorbing light needed for photosynthesis and forming photoreaction products that are harmful to coastal zone biota. Increased urbanization of watersheds and seasonal differences in weather patterns change the delivery pathways, reactivity, input, and energy flow of DOM (and its CDOM component) into aquatic systems. This study investigated the effects of watershed and season on the concentrations and potential photodegradation of stream-derived DOM in Lake Superior tributaries, chosen to be geographically and geologically similar but differing in land use. Organic carbon analysis, UV–Visible spectrophotometry, and terrestrial (land use) analysis were used to investigate differences among samples and sample treatments. The major differences in DOM concentration and photochemical response appeared seasonal rather than site specific, with snow-melt samples showing stronger and more consistent changes in UV–Visible parameters while base-flow samples showed stronger and more consistent losses in DOC.  相似文献   
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Reversed-phase liquid chromatography/mass spectrometry (LC/MS) is introduced as a new molecular fingerprinting technique for tracing terrigenous dissolved organic matter (DOM) and its photochemical decay in the ocean. DOM along a transect from the mangrove-fringed coast in Northern Brazil to the shelf edge was compared with mangrove-derived porewater DOM exposed to natural sunlight for 2–10 days in a photodegradation experiment. DOM was isolated from all samples via solid-phase extraction (C18) for LC/MS analysis. DOM in the estuary and ocean showed a bimodal mass distribution with two distinct maxima in the lower m/z range from 400 to 1000 Da (intensity-weighted average of 895 Da). Terrigenous porewater DOM from the mangroves was characterized by a broad molecular mass distribution over the detected range from 150 to 2000 Da (intensity-weighted average of 1130 Da). Polar compounds, i.e., those that eluted early in the reversed-phase chromatography, absorbed more UV light and had on average smaller molecular masses than the more apolar compounds.  相似文献   
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In this study, samples were taken from three contrasting freshwater sources and amended with salt in order to determine the influence of salinity and dissolved organic matter (DOM) composition on DOM recovery via ultrafiltration and solid phase extraction (SPE) with C18 disks. Salt addition caused variable recovery of DOM when using C18 SPE, and ultraviolet–visible spectroscopic characterization of the extracted material showed spectral responses that varied among sample sources. In contrast, increasing sample salinity from 0 to 30 ppt consistently caused a 15–25% reduction in the amount of high molecular weight DOM isolated by ultrafiltration for both dissolved organic carbon (DOC) and chromophoric DOM (CDOM), regardless of DOM composition. We hypothesize that a change in conformation (such as coiling or disaggregation) of DOM molecules occurs in the presence of salt, allowing them to pass through the ultrafiltration membrane and thereby decreasing the DOM retained by ultrafiltration. These results are important because they demonstrate that changes in salinity can influence DOM recovery in estuaries. Interpretation of DOM characteristics along estuarine gradients needs to account for potential artifacts introduced by sample isolation techniques.  相似文献   
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Major components of lacustrine sediments, such as carbonates, organic matter, and biogenic silica, provide significant paleoenvironmental information about lake systems. Fourier transform infrared spectroscopy (FTIR) and scanning X-ray fluorescence (XRF) techniques are fast, cost effective, efficient methods to determine the relative abundances of these components. We investigate the potential of these techniques using sediments from two large lakes, Lake Malawi in Africa and Lake Qinghai in China. Our results show statistically significant correlations of conventionally measured concentrations of carbonate (%CaCO3), total organic carbon (%TOC), and biogenic silica (%BSi), with absorbance in the corresponding FTIR spectral regions and with XRF elemental ratios including calcium:titanium (Ca/Ti), incoherent:coherent X-ray scatter intensities (Inc/Coh), and silicon:titanium (Si/Ti), respectively. The correlation coefficients (R) range from 0.66 to 0.96 for comparisons of FTIR results and conventional measurements, and from 0.70 to 0.90 for XRF results and conventional measurements. Both FTIR and XRF techniques exhibit great potential for rapid assessment of inorganic and organic contents of lacustrine sediments. However, the relationship between XRF-ratios or FTIR-absorbances and abundances of corresponding sedimentary components can vary with sediment source and lithology.  相似文献   
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High‐elevation mountain catchments are often subject to large climatic and topographic gradients. Therefore, high‐density hydrogeochemical observations are needed to understand water sources to streamflow and the temporal and spatial behaviour of flow paths. These sources and flow paths vary seasonally, which dictates short‐term storage and the flux of water in the critical zone (CZ) and affect long‐term CZ evolution. This study utilizes multiyear observations of chemical compositions and water residence times from the Santa Catalina Mountains Critical Zone Observatory, Tucson, Arizona to develop and evaluate competing conceptual models of seasonal streamflow generation. These models were tested using endmember mixing analysis, baseflow recession analysis, and tritium model “ages” of various catchment water sources. A conceptual model involving four endmembers (precipitation, soil water, shallow, and deep groundwater) provided the best match to observations. On average, precipitation contributes 39–69% (55 ± 16%), soil water contributes 25–56% (41 ± 16%), shallow groundwater contributes 1–5% (3 ± 2%), and deep groundwater contributes ~0–3% (1 ± 1%) towards annual streamflow. The mixing space comprised two principal planes formed by (a) precipitation‐soil water‐deep groundwater (dry and summer monsoon season samples) and (b) precipitation‐soil water‐shallow groundwater (winter season samples). Groundwater contribution was most important during the wet winter season. During periods of high dynamic groundwater storage and increased hydrologic connectivity (i.e., spring snowmelt), stream water was more geochemically heterogeneous, that is, geochemical heterogeneity of stream water is storage‐dependent. Endmember mixing analysis and 3H model age results indicate that only 1.4 ± 0.3% of the long‐term annual precipitation becomes deep CZ groundwater flux that influences long‐term deep CZ development through both intercatchment and intracatchment deep groundwater flows.  相似文献   
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A multi-method approach was applied to study changes in dissolved organic matter (DOM) at three estuarine sites with varying salinity, as well as changes resulting from experimental photodegradation. Following measurement of ultraviolet and visible absorption spectra of bulk samples, DOM was isolated using C18 solid phase extraction. The extract was characterized using high performance size exclusion chromatography (HP-SEC) and molecular level characterization was conducted via direct temperature-resolved mass spectrometry (DT-MS) and electrospray ionization mass spectrometry (ESI-MS). The molecular weight distribution of DOM as determined from HP-SEC and ESI-MS varied between techniques, but generally decreased down estuary and with photodegradation for both approaches. Relative differences in molecular weight were significantly correlated with the ratio of absorption coefficients at 254/365 nm. Additionally, photobleaching was significantly correlated with mass spectral characteristics from both DT-MS and ESI-MS. Principal component analysis of DT-MS spectra showed that photoexposure removed different mass spectral characteristics depending on sampling site; however, upon photodegradation, the mass spectral characteristics of both marine DOM and terrestrially dominated DOM approached a common spectrum. We interpret this spectrum, characterized by fragments from aromatic and carbohydrate-like precursors, as photochemically refractory DOM. Our results show that multiple approaches that characterize different aspects of DOM can provide complementary information about its sources and transformation. More specifically, photobleaching results in decreased light absorbance, decreased molecular weight and shifts in the relative abundance of classes of compounds (and broad shifts in m/z values); moreover, these transformations result in photodegraded samples from a low-salinity site which are compositionally similar to samples collected from a mid-salinity site further downstream.  相似文献   
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Over the past decade, sinking particulate organic matter (POM) samples from depth profiles in the equatorial Pacific have been analyzed by multiple techniques to evaluate the organic matter preservation mechanisms most dominant in the oceanic water column. How the samples were analyzed strongly influenced which organic matter preservation scheme appeared to dominate. Bulk functional group analysis by solid-state 13C-NMR showed that organic matter composition varied very little in light of the extreme degree of remineralization (>98%) that occurred with water column depth. This indicates preservation by a physical mechanism, such as sorption to mineral grains or protection within a mineral aggregate. However, detailed lipid studies of the characterizable fraction showed that selective preservation was important, with lipid structure being correlated with preservation over depth. However, the characterizable fraction decreases greatly with depth. Therefore, in this paper, direct temperature-resolved mass spectrometry (DT-MS), was used to further characterize POM, with the assumption that this approach could “see” a substantial proportion of the “uncharacterized” organic matter. DT-MS, which provides compositional information at an intermediate level between the detailed wet chemical studies and one-dimensional solid-state C13-NMR, also indicates an intermediate view between the mechanistic extremes of selective preservation and physical protection.  相似文献   
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