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Humic substances, a component of terrestrial dissolved organic matter (tDOM), contribute to dissolved organic matter (DOM) and chromophoric DOM (CDOM) in coastal waters, and have significant impacts on biogeochemistry. There are concerns in recent years over browning effects in surface waters due to increasing tDOM inputs, and their negative impacts on aquatic ecosystems, but relatively little work has been published on estuaries and coastal waters. Photodegradation could be a significant sink for tDOM in coastal environments, but the rates and efficiencies are poorly constrained. We conducted large-scale DOM photodegradation experiments in mesocosms amended with humic substances and nutrients in the Gulf of Finland to investigate the potential of photochemistry to remove added tDOM and the interactions of DOM photochemistry with eutrophication. The added tDOM was photodegraded rapidly, as CDOM absorption decreased and spectral slopes increased with increasing photons absorbed in laboratory experiments. The in situ DOM optical properties became similar among the control, humic- and humic+nutrients-amended mesocosm samples toward the end of the amendment experiment, indicating degradation of the excess CDOM/DOM through processes including photodegradation. Nutrient additions did not significantly influence the effects of added humic substances on CDOM optical property changes, but induced changes in DOM removal.

Eutrophication has been linked to increased greenhouse gas emissions from inland waters. Phytoplankton blooms in Lake Erie have increased since the 1990s, although its greenhouse gas emissions are not well characterized. We measured CH4 and N2O concentrations and diffusive fluxes in four seasons around the entire lake, and CO2 fluxes in one summer season. Lake Erie is a source of CH4 all year across the lake, concentrated in spring and summer in the Western Basin. Methane emissions ranged from 0.03 to 14.87 mg C m−2 d-1. Methane is predominantly biogenic, and natural gas leaks are an insignificant source. While Lake Erie is an overall N2O source, it is an N2O sink in winter and occasionally during summer. Emissions of N2O ranged from −0.08 to 1.22 mg N m−2 d-1. We also measured CO2 fluxes in summer only, when Lake Erie is a small atmospheric CO2 sink. While areal fluxes of CH4 and N2O are similar to those observed elsewhere, total fluxes from Lake Erie are higher due to its surface area. Lake Erie emits ~ 6300 (±19%) metric tons of CH4-C yr−1 and ~600 (±37%) metric tons N2O-N yr−1: almost 500,000 metric tons CO2-eq yr−1 total. This is the first comprehensive dataset of CH4 and N2O concentrations and diffusive emissions in a very large lake. More measurements and monitoring are needed to determine whether increased eutrophication in the Great Lakes is tied to increased emissions of these powerful climate forcers in a possible positive feedback to climate warming.

Marine microplastic (plastic particles smaller than 5 mm in length) pollution is a recognized and growing threat to the environment. Microplastic particle estimates number in the trillions and are under sampled in ecosystems worldwide (Eriksen et al. 2014, Zhao et al. 2019). Sources of microplastics include manufactured particles (fibers, beads, industrial abrasives) or microplastics generated from breakdown of larger plastics through mechanical, photochemical, or biologically mediated degradation (Schwarz et al. 2019). Little is known about the fate or effect of microplastics on marine environments thus emphasizing the importance of scientific research. The University of Georgia Skidaway Institute of Oceanography (UGA SkIO) and Marine Extension and Georgia Sea Grant (UGA MAREX) are mapping the distribution and abundance of microplastics in Georgia’s coastal waters. There are many challenges to studying microplastic abundances, including intensive sampling and measurement efforts on a temporal and spatial scale that require trained personnel. Volunteer-based research is well suited for studying microplastic pollution. We have developed a successful volunteer-based monitoring program to assist with research efforts. We have established partnerships with environmental programs and groups including the UGA MAREX volunteer program, and the Satilla, Altamaha and Ogeechee Riverkeepers to assist with monitoring efforts. Everyone involved understands the critical importance of proper research technique, strict protocols and training in order to obtain “believable” data. Our research to date suggests that a dedicated, trained group of scientists and volunteers can provide the mechanism for conducting detailed studies of microplastics on a local to regional scale.

Photochemical reactions in natural waters are a sink for dissolved organic carbon (DOC) and a source of dissolved inorganic carbon (DIC). Although considered significant to the carbon budget of the oceans, DIC photoproduction rates remain poorly constrained due to the analytical challenge involved in accurately measuring very low production rates (likely sub-μM h− 1 for blue ocean waters) relative to high background DIC concentrations (~ 2 mM). In an attempt to overcome this analytical limitation, almost all previous DIC photoproduction studies in marine systems have relied on the stripping of background DIC prior to irradiation, with unknown consequences for the integrity of the DOC pool and its photoreactivity, and none have resulted in a satisfactory determination of photoproduced DIC in open ocean waters. Here, we use small additions of NaH13CO3 (

Southeastern salt marshes are important repositories of sediment and carbon, and their formation is heavily dependent on deposition and accumulation of inorganic sediment. This study examined Groves Creek marsh near Savannah, GA, a typical Spartina alterniflora salt marsh of the southeastern US. Analyses were focused on the character, deposition and accumulation of material within the marsh on daily, monthly, decadal and centennial timescales, to determine the dominant factors in material supply and redistribution, and on its stratigraphy to determine the 1,000-year history of Groves Creek salt marsh development. Modern processes create gradients in grain size, which shows little variation from the tidal channel flanks up to mean sea level, and which coarsens with distance into the marsh from mean sea level to mean high water. This unexpected result suggests that, although floc transport is an important mechanism of sediment supply near the channel margins, energetic events must supply coarser materials to the marsh platform, where they are not readily removed by typical energy regimes. Daily deposition can approach ~3 g/cm2 year; however, centennial accumulation rates are orders of magnitude lower (0.11±0.05 g/cm2 year) and are similar to those present over the past 300 years (0.05–0.2 g/cm2 year), indicating that much of the daily deposition is remobilized. Stable isotopic δ13C (average –18.7‰) and δ15N (average 5.7‰) values most likely indicate a large contribution from S. alterniflora as a carbon source throughout the marsh, although heavier δ15N on the channel flanks suggest that benthic algae may be locally important. Geologic, geochemical and microfossil evidence suggests that depositional conditions in the Groves Creek marsh have changed significantly over the past ~1,000 years, creating a distinct fining-upward sequence. This sequence preserves the signature (from bottom to top) of subtidal flats grading to intertidal sandflats, an erosional lag created by a migrating tidal channel, point bar deposits, channel fill deposits, and a capping salt marsh. A significant change in environmental conditions occurred between 360–500 cal years BP, which changed the character of geological, geochemical and microfossil components in the marsh, and, because this observation is robust throughout the southeastern US, hints at a major change in estuarine and coastal systems at this time.

Tidal Spartina-dominated saltmarshes and estuaries on the Southeast US coast are global hotspots of productivity. In coastal Georgia, tidal amplitudes and saltmarsh productivity are the highest along the Southeast US coast. Coastal Georgia is characterized by a humid subtropical seasonal climate, and inter-annual variability in precipitation, and freshwater discharge. The 2012–2013 timeframe encompassed contrasting levels of discharge for the Savannah River, a major Georgia river, with a 4.3-fold greater discharge in summer 2013 relative to summer 2012. In situ measurements of temperature, salinity, precipitation and Secchi depth, and water samples were collected weekly at high tide throughout 2012 and 2013 from the Skidaway River Estuary, a tidal saltmarsh-dominated estuary in coastal Georgia influenced by Savannah River hydrology. The effects of elevated discharge on the seasonal trends of water column components were evaluated. The shift from low discharge (2012) to high discharge (2013) led to decreased salinity in summer 2013, but no significant increases in inorganic nutrient (NH4, NOx, SiO2 and PO4) concentrations. Dissolved inorganic carbon (DIC) concentrations decreased, and DIC stable isotopic signatures (δ13C-DIC values) were depleted in summer 2013 relative to summer 2012. In 2013 dissolved organic carbon (DOC) concentrations, chromophoric and fluorescent dissolved organic matter (DOM: CDOM, FDOM) intensities, specific UV-absorbance (SUVA254) and relative humic-like fluorescence were all higher than in 2012, indicating that, as discharge increased in 2013, estuarine water became enriched in terrigenous DOM. Secchi depth and particulate organic carbon (POC) and nitrogen (PON) concentrations displayed clear seasonal patterns that were not significantly altered by discharge. However, δ13C-POC and δ15N-PON isotopic signatures indicated higher terrigenous contributions at elevated discharge. Discharge influenced cyanobacterial composition, but did not affect total abundance of phytoplankton (

A portion of the charcoal and soot produced during combustion processes on land (e.g., wildfire, burning of fossil fuels) enters aquatic systems as dissolved black carbon (DBC). In terms of mass flux, rivers are the main identified source of DBC to the oceans. Since DBC is believed to be representative of the refractory carbon pool, constraining sources of marine DBC is key to understanding the long-term persistence of carbon in our global oceans. Here, we use compound-specific stable carbon isotopes (δ13C) to reveal that DBC in the oceans is ~6‰ enriched in 13C compared to DBC exported by major rivers. This isotopic discrepancy indicates most riverine DBC is sequestered and/or rapidly degraded before it reaches the open ocean. Thus, we suggest that oceanic DBC does not predominantly originate from rivers and instead may be derived from another source with an isotopic signature similar to that of marine phytoplankton., Rivers are thought to be the largest source of the recalcitrant and abundant black carbon in the ocean. Here, Wagner and colleagues find distinct pools of black carbon between rivers and the open ocean, challenging the long-held assumption that marine black carbon is of terrestrial origin.

Eutrophication is linked to greenhouse gas emissions from inland waters. Phytoplankton blooms in Lake Erie, one of Earth’s largest lakes, have increased with nutrient runoff linked to climate warming, although greenhouse gas emissions from this or other large eutrophic lakes are not well characterized. We measured greenhouse gases around Lake Erie in all four seasons and found that CH4and N2O emissions have increased 10 times or more with re-eutrophication, especially during and after phytoplankton blooms. Lake Erie is a positive source of CH4throughout the entire year and around the entire lake, with the highest emissions in spring and summer near the mouth of the Maumee River. While Lake Erie is an overall N2O source, it is an N2O sink in winter throughout the lake and in some locations during large phytoplankton blooms. We estimate that Lake Erie emits ~6300 metric tons of CH4-C yr−1(± 19%) and ~600 metric tons N2O-N yr−1(± 37%): almost 500,000 metric tons CO2-eq yr−1total. These results highlight the gravity of eutrophication-related increases in large lake GHG emissions: an overlooked, but potentially major feedback to global climate change.

Dissolved inorganic carbon (DIC) has long been recognized as the main identifiable product of dissolved organic carbon (DOC) photochemical remineralization. However, quantification of DIC photoproduction in natural waters has been hampered by low photoproduction rates (nM to μM h−1) relative to high DIC background concentrations (μM to mM). Here, we describe a novel method to determine the δ13C of photoproduced DIC in three southeastern US river water samples (Savannah, Altamaha, St. Marys) using liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Initial ( 14 h). Keeling plots indicated that the average δ13C value for photoproduced DIC (−33.3 ± 1.4‰) was depleted in 13C relative to bulk riverine DOC, consistent with the preferential photomineralization of lignin. This average was used with a simple isotope mass balance approach to calculate the concentration of photoproduced DIC. The LC-IRMS measures δ13C-DIC shifts (typically ± 0.01 to 0.1‰) more precisely than DIC concentration changes in the early stages of irradiation. Therefore, the combination of LC-IRMS analysis and our simple mass balance approach provides a new, higher precision method to quantify initial rates of DIC photoproduction and associated photochemical efficiency (i.e., apparent quantum yield) spectra in aquatic systems without any sample manipulation. A full description, sensitivity analysis and recommendations for the method are presented.

Complexities associated with dissolved organic matter (DOM) isolation from seawater have hampered compositional characterization of this key component of global carbon and nutrient cycles. DOM isolation efficiency by electrodialysis (ED) from salt-containing waters was optimized and evaluated on samples including coastal ocean seawater, open ocean seawater, artificial seawater from axenic cultures of marine phytoplankton, and artificial seawater samples containing standard compounds of different molecular sizes and charge. ED was performed with a system optimized for processing 2–10 L sample volumes. Additionally, the combination of ED and solid-phase extraction, using Bond Elut PPL exchange resin, was evaluated. Using only ED, the following DOC recoveries were achieved: coastal seawater, 71.3 ± 6.5 %; open ocean, 50.5 ± 3.1 %; phytoplankton cultures, 70.3 ± 12.5 %; glucose, 90.2 ± 2.1 %; EDTA, 67.5 ± 9.9 %; and vitamin B12, 98.3 ± 1.6 %. With the combination of PPL and ED techniques, an average DOC recovery of 76.7 ± 2.6 % was obtained for coastal seawater, but this recovery was not statistically different from seawater recoveries using only ED. Comparison of C/N ratios and fluorescence excitation emission matrices taken at the beginning and end of the recovery process for coastal samples processed using only ED indicated that the final recovered material was representative of the DOM present in the original samples. Typical recoveries using combined PPL and ED exceed those of previous isolation methods.

Upwelling-favorable winds and an offshore-distributed Mississippi and Atchafalaya River plume trajectory were observed in summer 2009 in contrast to the mean conditions from 2002 to 2010 (upwelling-unfavorable winds and an alongshore river plume trajectory), a set of conditions which was also observed in summer 2007. The responses of dissolved inorganic carbon (DIC) distributions and dynamics to upwelling-favorable winds are studied by comparing the contrasting conditions between summer 2009 and summer 2007 on the northern Gulf of Mexico. Patterns of surface water partial pressure of CO2 (pCO2), DIC, δ13C in DIC, and total alkalinity (TA) determined in July 2009 and August 2007 were strongly related to river plume trajectories, and differed between the two summers. The slope of the relationship between dissolved oxygen (DO) and DIC in summer 2007 was comparable to the Redfield O/C ratio of 1.3, which was attributed to respiration of organic matter in the bottom water. The slope of the DO and DIC relationship and δ13CDIC values in bottom waters during July 2009 were clearly affected by mixing since their salinities were

Anthropogenic atmospheric loading of CO2 raises concerns about combined effects of increasing ocean temperature and acidification, on biological processes. In particular, the response of appendicularian zooplankton to climate change may have significant ecosystem implications as they can alter biogeochemical cycling compared to classical copepod dominated food webs. However, the response of appendicularians to multiple climate drivers and effect on carbon cycling are still not well understood. Here, we investigated how gelatinous zooplankton (appendicularians) affect carbon cycling of marine food webs under conditions predicted by future climate scenarios. Appendicularians performed well in warmer conditions and benefited from low pH levels, which in turn altered the direction of carbon flow. Increased appendicularians removed particles from the water column that might otherwise nourish copepods by increasing carbon transport to depth from continuous discarding of filtration houses and fecal pellets. This helps to remove CO2 from the atmosphere, and may also have fisheries implications.

Interactions between organic matter and mineral matrices are critical to the preservation of soil and sediment organic matter. In addition to clay minerals, Fe(III) oxides particles have recently been shown to be responsible for the protection and burial of a large fraction of sedimentary organic carbon (OC). Through a combination of synchrotron X-ray techniques and high-resolution images of intact sediment particles, we assessed the mechanism of interaction between OC and iron, as well as the composition of organic matter co-localized with ferric iron. We present scanning transmission x-ray microscopy images at the Fe L3 and C K1 edges showing that the organic matter co-localized with Fe(III) consists primarily of C=C, C=O and C-OH functional groups. Coupling the co-localization results to iron K-edge X-ray absorption spectroscopy fitting results allowed to quantify the relative contribution of OC-complexed Fe to the total sediment iron and reactive iron pools, showing that 25–62% of total reactive iron is directly associated to OC through inner-sphere complexation in coastal sediments, as much as four times more than in low OC deep sea sediments. Direct inner-sphere complexation between OC and iron oxides (Fe-O-C) is responsible for transferring a large quantity of reduced OC to the sedimentary sink, which could otherwise be oxidized back to CO2.

Biological productivity in many ocean regions is controlled by the availability of the nutrient phosphorus. In the Mediterranean Sea, aerosol deposition is a key source of phosphorus and understanding its composition is critical for determining its potential bioavailability. Aerosol phosphorus was investigated in European and North African air masses using phosphorus near-edge X-ray fluorescence spectroscopy (P-NEXFS). These air masses are the main source of aerosol deposition to the Mediterranean Sea. We show that European aerosols are a significant source of soluble phosphorus to the Mediterranean Sea. European aerosols deliver on average 3.5 times more soluble phosphorus than North African aerosols and furthermore are dominated by organic phosphorus compounds. The ultimate source of organic phosphorus does not stem from common primary emission sources. Rather, phosphorus associated with bacteria best explains the presence of organic phosphorus in Mediterranean aerosols.

Stable isotope ratios of carbon and nitrogen (δ13C and δ15N) from muscle samples were used to examine the feeding ecology of a heavily exploited shark species, the Sandbar Shark Carcharhinus plumbeus. Two hundred and sixty two Sandbar Sharks were sampled in five South Carolina estuaries. There were no significant differences in average δ13C or δ15N signatures between estuaries, between sampling years, or between male and female Sandbar Sharks, suggesting that these variables do not affect diet. A potential ontogenetic diet shift between young-of-year and juvenile Sandbar Sharks in South Carolina, similar to a shift previously described in Virginia and Hawaii populations, is suggested by significant differences in average δ13C and average δ15N signatures between these age-classes. Results confirm that Sandbar Sharks in South Carolina are generalist predators and that juvenile Sandbar Sharks have a wider diet breadth than young-of-year sharks, a pattern common in elasmobranchs. Sandbar Shark diet in...

Marine sediments of the Ross Sea, Antarctica, harbor microbial communities that play a significant role in the decomposition, mineralization, and recycling of organic carbon (OC). In this study, the cell densities within a 153-cm sediment core from the Ross Sea were estimated based on microbial phospholipid fatty acid (PLFA) concentrations and acridine orange direct cell counts. The resulting densities were as high as 1.7 × 10⁷ cells mL⁻¹ in the top ten centimeters of sediments. These densities are lower than those calculated for most near-shore sites but consistent with deep-sea locations with comparable sedimentation rates. The δ¹³C measurements of PLFAs and sedimentary and dissolved carbon sources, in combination with ribosomal RNA (SSU rRNA) gene pyrosequencing, were used to infer microbial metabolic pathways. The δ¹³C values of dissolved inorganic carbon (DIC) in porewaters ranged downcore from -2.5‰ to -3.7‰, while δ¹³C values for the corresponding sedimentary particulate OC (POC) varied from -26.2‰ to -23.1‰. The δ¹³C values of PLFAs ranged between -29‰ and -35‰ throughout the sediment core, consistent with a microbial community dominated by heterotrophs. The SSU rRNA gene pyrosequencing revealed that members of this microbial community were dominated by β-, δ-, and γ-Proteobacteria, Actinobacteria, Chloroflexi and Bacteroidetes. Among the sequenced organisms, many appear to be related to known heterotrophs that utilize OC sources such as amino acids, oligosaccharides, and lactose, consistent with our interpretation from δ¹³CPLFA analysis. Integrating phospholipids analyses with porewater chemistry, δ¹³CDIC and δ¹³CPOC values and SSU rRNA gene sequences provides a more comprehensive understanding of microbial communities and carbon cycling in marine sediments, including those of this unique ice shelf environment.

Reactive Fe(III) minerals can influence methane (CH4) emissions by inhibiting microbial methanogenesis or by stimulating anaerobic CH4oxidation. The balance between Fe(III) reduction, methanogenesis, and methane oxidation in ferruginous Archean and Paleoproterozoic oceans would have controlled CH4fluxes to the atmosphere, thereby regulating the capacity for CH4to warm the early Earth under the Faint Young Sun. We studied CH4and Fe cycling in anoxic incubations of ferruginous sediment from the ancient ocean analogue Lake Matano, Indonesia over three successive transfers (500 days total). Iron reduction, methanogenesis, methane oxidation, and microbial taxonomy were monitored in treatments amended with ferrihydrite or goethite. After three dilutions, Fe(III) reduction persisted only in bottles with ferrihydrite. Enhanced CH4production was observed in the presence of goethite, highlighting the potential for reactive Fe(III)-oxides to inhibit methanogenesis. Supplementing the media with hydrogen, nickel and selenium did not stimulate methanogenesis. There was limited evidence for Fe(III)-dependent CH4oxidation, although some incubations displayed CH4-stimulated Fe(III)-reduction. 16S rRNA profiles continuously changed over the course of enrichment, with ultimate dominance of unclassified members of the order Desulfuromonadales in all treatments. Microbial diversity decreased markedly over the course of incubation, with subtle differences between ferrihydrite and goethite amendments. These results suggest that Fe(III)-oxide mineralogy and availability of electron donors could have led to spatial separation of Fe(III)-reducing and methanogenic microbial communities in ferruginous marine sediments, potentially explaining the persistence of CH4as a greenhouse gas throughout the first half of Earth history.

Phosphorus K-edge XANES spectra are presented for a diverse set of 44 phosphate minerals., Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was performed on phosphate mineral specimens including (a) twelve specimens from the apatite group covering a range of compositional variation and crystallinity; (b) six non-apatite calcium-rich phosphate minerals; (c) 15 aluminium-rich phosphate minerals; (d) ten phosphate minerals rich in either reduced iron or manganese; (e) four phosphate minerals rich in either oxidized iron or manganese; (f) eight phosphate minerals rich in either magnesium, copper, lead, zinc or rare-earth elements; and (g) four uranium phosphate minerals. The identity of all minerals examined in this study was independently confirmed using X-ray powder diffraction. Minerals were distinguished using XANES spectra with a combination of pre-edge features, edge position, peak shapes and post-edge features. Shared spectral features were observed in minerals with compositions dominated by the same specific cation. Analyses of apatite-group minerals indicate that XANES spectral patterns are not strongly affected by variations in composition and crystallinity typical of natural mineral specimens.

The measurement of the carbon isotopic composition (δ13C) of dissolved inorganic carbon (DIC) in natural systems has provided a tool for examining a variety of processes, from net primary production to anthropogenic signatures of CO2 uptake in the oceans. Over the past decade, new δ13C-DIC methods have steadily decreased the sample analysis time and volumes for this measurement. The development of a new interface capable of inline acidification and extraction of CO2 from a liquid stream (LC-Isolink™; Thermo Electron) provides break-throughs in sample size, ease of sample handling, and speed of analyses. Typical sample size injections of 25 µL provide precision and accuracy of 0.04‰, comparable to that obtained by off-line extractions/dual inlet analyses on much larger samples. Single-sample injection runs can be accomplished within 4 min, whereas sample preparation is limited to filtration to remove particulates. Thus combined runs of 200 samples over a 20-h period are possible. Highest-precision triplicate injection analyses of single samples require 11 min. Manually injected marine sample sizes of 2.5 µL provide nearly the same precision and accuracy as the larger loop sizes. For maximum precision, care must be taken to match sample and standard sizes to correct for linearity effects. Over wider concentration ranges typically found within estuarine systems, the overall precision of the method decreases to 0.06‰ with such correction.

Scanning transmission X-ray microscopy and micro carbon X-ray Absorption Near Edge Spectroscopy (C-XANES) can provide quantitative information regarding the distribution of the biopolymers cellulose, hemicellulose, and lignin in vascular plant cell walls. In the case of angiosperms, flowering plants, C-XANES may also be able to distinguish variations in lignin monomer distributions throughout the cell wall. Polysaccharides are susceptible to soft X-ray irradiation induced chemical transformations that may complicate spectral analysis. The stability of a model polysaccharide, cellulose acetate, to variable doses of soft X-rays under conditions optimized for high quality C-XANES spectroscopy was investigated. The primary chemical effect of soft X-ray irradiation on cellulose acetate involves mass loss coincident with de-acetylation. A lesser amount of vinyl ketone formation also occurs. Reduction in irradiation dose via defocusing does enable high quality pristine spectra to be obtained. Radiation induced chemical modification studies of oak cell wall reveals that cellulose and hemicellulose are less labile to chemical modification than cellulose acetate. Strategies for obtaining pristine C-XANES spectra of polysaccharides are presented.

X-ray spectromicroscopy (combined X-ray spectroscopy and microscopy) is uniquely capable of determining sub-micron scale elemental content and chemical speciation in minimally-prepared particulate samples. The high spatial resolutions achievable with this technique have enabled the close examination of important microscale processes relevant to the cycling of biogeochemically important elements. Here, we demonstrate the value of X-ray microscopy to environmental and biological research by examining the phosphorus and metal chemistry of complete individual cells from the algal genera Chlamydomonas sp. and Chlorella sp. X-ray analysis revealed that both genera store substantial intracellular phosphorus as distinct, heterogeneously distributed granules whose X-ray fluorescence spectra are consistent with that of polyphosphate. Polyphosphate inclusions ranged in size from 0.3-1.4 μm in diameter and exhibited a nonspecies-specific average phosphorus concentration of 6.87 ± 1.86 μg cm ‐2 , which was significantly higher than the average concentration of phosphorus measured in the total cell, at 3.14 ± 0.98 μg cm ‐2 (95% confidence). Polyphosphate was consistently associated with calcium and iron, exhibiting average P:cation molar ratios of 8.31 ± 2.00 and 108 ± 34, respectively (95% confidence). In some cells, polyphosphate was also associated with potassium, zinc, manganese, and titanium. Based on our results, X-ray spectromicroscopy can provide high-resolution elemental data on minimally prepared, unsectioned cells that are unattainable through alternative microscopic methods and conventional bulk chemical techniques currently available in many fields of marine chemistry.

Carbon K-edge soft X-ray spectromicroscopy was used to obtain information on the orientation, purity and chemical composition of graphite within natural samples. Highly crystalline natural graphite had spectra indistinguishable from highly ordered pyrolytic graphite, but contained a wide variety of internal structures in the 100–500 nm size range. These structures were both physical (domains with differing sheet orientations) and chemical in nature. Graphite sheet orientations could vary from normal to the X-ray beam to nearly perpendicular within a few hundred nanometers. Chemical compositions ranged from pure crystalline material to nearly amorphous carbon. Little evidence for significant addition of O- or N-bearing groups was observed in these samples, although this may have been a result of the extraction techniques used. The range of carbon types found in the environment may provide clues to the types of thermal alteration and source mechanisms behind graphitic kerogen fractions.

The in situ or authigenic formation of calcium phosphate minerals in marine sediments is a major sink for the vital nutrient phosphorus. However, because typical sediment chemistry is not kinetically conducive to the precipitation of these minerals, the mechanism behind their formation has remained a fundamental mystery. Here, we present evidence from high-sensitivity x-ray and electrodialysis techniques to describe a mechanism by which abundant diatom-derived polyphosphates play a critical role in the formation of calcium phosphate minerals in marine sediments. This mechanism can explain the puzzlingly dispersed distribution of calcium phosphate minerals observed in marine sediments worldwide.

Few studies have examined the dynamics of sediments and suspended organic matter and their export from headwater basins in the Andes Mountains to the Amazon River, despite the fact that the Andes are the primary source of sediments to the lower Amazon basin. We measured river discharge as well as the concentration, δ15N, δ13C, %N, and %OC of coarse and fine suspended sediments (CSS and FSS) in the Chorobamba River, located in the central Andean Amazon of Peru. Samples were taken at least weekly over an entire year (July 2004–July 2005), with additional sampling during storms. Concentrations of particulate organic matter (POM) were generally low in the study river, with concentrations increasing by up to several orders of magnitude during episodic rain events. Because both overall flow volumes and POM concentrations increased under stormflow conditions, the export of POM was enhanced multiplicatively during these events. We estimated that a minimum of 80% of annual suspended sediment transfer occurred during only about 10 days of the year, also accounting for 74% of particulate organic carbon and 64% of particulate organic nitrogen transport. Significant differences occurred between seasons (wet and dry) for δ13C of coarse and fine POM in the Chorobamba River, reflecting seasonal changes in organic matter sources. The time series data indicate that this Andean river exports approximately equal amounts of fine and coarse POM to the lower Amazon. The observation that the vast majority of sediments and associated OM exported from Andean rivers is mobilized during short, infrequent storm events and landslides has important implications for our understanding of Amazon geochemistry, especially in the face of incipient global change.

Identification of sources of nutrient pollution is a first step towards remediation of eutrophication in aquatic ecosystems. The stable isotope nitrogen-15 (15N) is a natural indicator of nitrogen (N) source and biogeochemistry. We sampled Lake Taihu, a hyper-eutrophic lake in eastern China, and major inflow rivers during winter and spring of 2004 to determine concentration and δ15N of nitrate (NO 3 − ). Nitrate concentrations in rivers and the lake were higher, in most cases, in spring than in winter. δ15N of NO 3 − was not correlated with NO 3 − concentration, indicating that concentrations alone are insufficient to describe N sources. Results show that riverine N inputs in winter are influenced by discharge of human sewage into rivers and the lake. In spring, however, wastewater inputs to the lake appear to be balanced by fertilizers, atmospheric, and/or N2 fixation sources. Rain NO 3 − concentrations were seasonally high and isotopically enriched compared to potential sources, indicating that rain may be a significant or even dominant source of N to the lake during the rainy season. δ15N values show that urbanized areas of the lake have more sewage-derived N than those areas dominated by agriculture, aquaculture, or industry. This observation has important implications for human health, since Lake Taihu is a source of drinking and irrigation water as well as fish for human consumption.

Phosphorus Near Edge X-ray Fluorescence Spectroscopy (P-NEXFS) data were collected on phosphorus containing phases including organic and inorganic compounds and minerals. Although phases containing P in the plus five oxidation state P(V) in a tetrahedral PO4 structure have similar primary fluorescence peak positions, the size, shape, and positions of secondary spectral features are diagnostic for different compounds and minerals. In particular, calcium phosphates exhibited a notable post-peak shoulder at 2154.5 eV, while oxidized iron phosphates had a distinctive pre-peak feature at 2148 eV. Polyphosphates have a broad secondary peak located approximately 2 eV higher in energy than a similar feature in phosphate esters and diesters. Compounds containing P(V) in structures other than PO4 tetrahedra such as phosphonates have a primary peak shifted about 1 eV lower than corresponding organo-phosphates. Organo-phosphates with P in the plus three oxidation state P(III) such as phosphines had primary fluorescence peaks shifted still further down in energy (2–3 eV). The substitution of aromatic carbon groups in close proximity to P structures in organic compounds generated both pre- and post-peak features as well as a number of secondary peaks. In addition, X-ray fluorescence mapping of P, Si, Al, Mg, and Na was conducted on a marine sediment sample with sub-micron spatial resolution. Phosphorus was heterogeneously distributed in the sample and not correlated on a broad scale with any other element examined. Much of the P present in the sample was located in small, 0.6–8 μm size, P-rich domains. Several P-rich regions were examined with P-NEXFS using a focused beam with 60 nm resolution and were found to consist of either calcium phosphate or polyphosphate phases. The presence of significant polyphosphate-dominated regions in a marine sediment sample supports the recent observations that such phases can play an important role in marine P cycling. The combination of fluorescence mapping and P-NEXFS data collection on fine particles provides a powerful new tool for environmental phosphorus studies.

Rates of canonical, i.e. heterotrophic, water-column denitrification were measured by 15 N incubation techniques at a number of coastal and open ocean stations in the Arabian Sea. Measurements of N 2 :Ar gas ratios were also made to obtain independent estimates of N 2 excess resulting from denitrification. Measured denitrification rates ( 15 NO 3 − → 15 − 14 N 2 ) at open ocean stations averaged 9.1±1.0 nmol N l −1 d −1 ( n = 15 ), and coastal rates averaged 33.2±12.4 nmol N l −1 d −1 ( n = 18 ). When extrapolated to the entire Arabian Sea, deep measurements within the offshore perennial suboxic zone indicate an overall denitrification rate of 41 Tg N a −1 ±18 Tg N a −1 , which is within the range (10–44 Tg N a −1 ) of previous estimates for canonical denitrification in the region based on stoichiometric calculations and electron transport system activity. Nitrogen excess gas measurements predict a larger nitrogen anomaly than estimated by classical stoichiometric methods (maximum anomaly=23 μg at N l −1 vs. 13 μg at N l −1 , respectively). This mismatch may result from incorrect assumptions of Redfield stoichiometry inherent in the nitrate deficit calculation, inputs of new nitrogen through N-fixation, N 2 contributions from sedimentary denitrification along continental margins, the anammox reaction, and metal catalyzed denitrification reactions. Nevertheless, if denitrification is defined as the conversion of combined nitrogen to a gaseous end product, then the data suggest that denitrification in the Arabian Sea may have been underestimated so far.

The chemical composition of the graphitic black carbon (GBC) fraction of marine organic matter was explored in several marine and freshwater sedimentary environments along the west coast of North America and the Pacific Ocean. Analysis by carbon X-ray absorption near-edge structure spectroscopy and scanning transmission X-ray microscopy shows the GBC fraction of Stillaguamish River surface sediments to be dominated by more highly ordered and impure forms of graphite, together forming about 80% of the GBC, with a smaller percent of an aliphatic carbon component. Eel River Margin surface sediments had very little highly ordered graphite, and were instead dominated by amorphous carbon and to a lesser extent, impure graphite. However, the GBC of surface sediments from the Washington State Slope and the Mexico Margin was composed almost solely of amorphous carbon. Pre-anthropogenic, highly oxidized deep-sea sediments from the open Equatorial Pacific Ocean contained over half their GBC in different forms of graphite as well as highly aliphatic carbon, low aromatic/highly acidic aliphatic carbon, low aromatic/highly aliphatic carbon, and amorphous forms of carbon. Our results clearly show the impact of graphite and amorphous C phases in the BC fraction in modern riverine sediments and nearby marine shelf deposits. The pre-anthropogenic Equatorial Pacific GBC fraction is remarkable in the existence of highly ordered graphite.

We determined the carbon (C) and nitrogen (N) elemental and stable isotopic composition of riverine and terrestrial organic matter (OM), as well as the concentration of dissolved organic C (DOC), d 15 NO3 2 and d 18 O of river water along an altitudinal (4,043‐720 m above sea level [masl]) transect in the Andes of Peru. Plant d 13 C increased with increasing elevation, but unlike previous studies, foliar 13 C and %N were negatively correlated. Soil d 13 C values did not exhibit similar trends and were enriched by 1‐3‰ over plants. Isotopically, riverine fine particulate OM (FPOM, ,60 mm) resembled soils, and coarse particulate OM (CPOM, .60 mm) resembled leaves. Both FPOM and CPOM exhibited OM levels beyond those attributable to sorption. Percentage OC and N of soils and FPOM were positively correlated with altitude and highlight a trend of sequential downstream dilution of OM with inorganic material. FPOM began to resemble plant OM isotopically at lower altitudes, perhaps due to increased plant and surface soil inputs to lower rivers. The compositional similarity of particulate organic matter to terrestrial plants and soils indicates that the dominant processes affecting riverine OM are occurring on the landscape, not within the river. Dissolved OC (,0.2 mm) concentration, d 15 NO3 2 , and d 18 Oo f H 2O are variable in high-altitude tributaries but approach constant values downstream. Elemental and isotopic analyses of riverine OM suggest compositional differences between size fractions, similar to the lower Amazon; however, unlike previous studies, we have found significant within-stream changes with altitude in OM composition.

Marine sinking particulate organic matter (POM) represents the link between surface primary production and burial of organic matter in marine sediments. As such, the nature of this material has been the subject of numerous studies attempting to characterize its composition. The results of these studies have shown that a significant proportion of POM is not recognizable as known compounds, and that the proportion of uncharacterized material increases with age/depth/diagenesis. However, few studies have examined the spatial heterogeneity of this material. This study uses a new tool, scanning transmission X-ray microscopy (STXM), together with carbon X-ray absorption near edge structure (C-XANES), to examine POM collected from sediment traps deployed at one location in the Arabian Sea as part of the JGOFS program. The results indicate that POM is composed primarily of four distinct phases: protein, an aliphatic rich phase, a carboxylic-acid-rich phase, and a phase with complex unsaturated and quinone character. This last phase may be a condensation product between carbohydrates and proteins, or from degraded plant pigments. Many particles consisted of a single chemical phase; however, in particles with mixed compositions, individual domains retained distinctive chemical signatures at the instrument's resolution limit (50 nm). All major chemical phases were observed in sediment trap particles from 531 to 3369 m depth, supporting the hypothesis that non-selective degradation dominates particle remineralization, and that overall particle compositions are determined by near surface processes. Only one particle, out of more than 60 examined, exhibited soot-like composition. The lack of a significant black carbon/soot component may be attributable to sampling during the winter monsoon period.

A suite of nickel, cobalt, iron, copper, and zinc containing sulfides are assayed for the promotion of a model carbon fixation reaction with relevance to local reducing environments of the early Earth. The assay tests the promotion of hydrocarboxylation (the Koch reaction) wherein a carboxylic acid is synthesized via carbonyl insertion at a metal-sulfide-bound alkyl group. The experimental conditions are chosen for optimal assay, i.e., high reactant concentrations and pressures (200 MPa) to enhance chemisorption, and high temperature (250°C) to enhance reaction kinetics. All of the metal sulfides studied, with the exception CuS, promote hydrocarboxylation. Two other significant reactions involve the catalytic reduction of CO to form a surface-bound methyl group, detected after nucleophilic attack by nonane thiol to form methyl nonyl sulfide, and the formation of dinonyl sulfide via a similar reaction. Estimation of the catalytic turnover frequencies for each of the metal sulfides with respect to each of the primary reactions reveals that NiS, Ni3S2, and CoS perform comparably to commonly employed industrial catalysts. A positive correlation between the yield of primary product to NiS and Ni3S2 surface areas provides strong evidence that the reactions are surface catalytic in these cases. The sulfides FeS and Fe(1−x)S are unique in that they exhibit evidence of extensive dissolution, thus, complicating interpretation regarding heterogeneous vs. homogeneous catalysis. With the exception of CuS, each of the metal sulfides promotes reactions that mimic key intermediate steps manifest in the mechanistic details of an important autotrophic enzyme, acetyl-CoA synthase. The relatively high temperatures chosen for assaying purposes, however, are incompatible with the accumulation of thioesters. The results of this study support the hypothesis that transition metal sulfides may have provided useful catalytic functionality for geochemical carbon fixation in a prebiotic world (at least intially) devoid of peptide-based enzymes.

A reverse phase High Performance Liquid Chromatography (HPLC) method was developed to detect soluble reactive phosphate (SRP) in marine and freshwater samples. This technique is scalable over a range of sample volumes from 10 μl to 10 ml, requires minimal sample preparation, and responds linearly from 1 nM to 100 μM ( R 2 >0.964). Standard Murphy–Riley molybdenum blue reagents were used to react with phosphate in samples for analysis. Solid phase extraction tubes were used to clean the mixed complexing reagent prior to combining the reagent with samples. The method was applied to freshwater samples collected in July 2001 along an Andean mountain stream located in the Eastern Cordillera (∼2400 m) of Peru and marine samples collected in January 2002 within the low marsh of the estuarine Nueces Delta System, Texas Coastal Bend. For method comparison, field samples were analyzed using a standard manual spectrophotometric method. Field sample phosphate concentrations produced from each method were nearly identical. This method offers the advantages of low sample volume (1 ml or less) with high sensitivity, precision, and potential automation.

Headspace volatiles from dried sporocarps of the candy cap mushroom, Lactarius fragilis var. rubidus were analysed using solid phase microextraction (SPME) and gas chromatography–mass spectrometry (GC–MS). 3-Amino-4,5-dimethyl-2(5H)-furanone (quabalactone III) was identified as the source of the maple syrup odour of the dried mushrooms. The hydrolysis product of quabalactone III, 3-hydroxy-4,5-dimethylfuran-2(5H)-one (sotolon), a compound with an intense maple syrup-like odour, was not observed in mushroom's headspace volatiles.

Three lines of experimental research suggest that high pressure may have played a significant role in the origin of life. Discoveries of abundant life in high-pressure environments, including deep oceans, hydrothermal vents, and crustal rocks, point to the adaptation of life to a variety of aqueous habitats. Cultures of microbes at high pressure display both barotolerant and barophilic behaviour. And studies of high-pressure hydrothermal organic synthesis reveal unexpectedly facile reaction mechanisms for the production of a variety of requisite biomolecules.

Gorgonians are widespread sub-littoral benthic suspension feeders in the world oceans. However, data on their trophic ecology and role in benthic–pelagic coupling and biogeochemical cycles remain limited. This study assesses the trophic ecology of Leptogorgia virgulata in the Skidaway River estuary, USA (31.9896N, 81.0242W) by analysing carbon and nitrogen isotopic signatures of its soft tissue and different-sized fractions of particulate organic matter (POM) in its environment. Samples were taken in 5 April, 2 August, and 15 October 2012 and 11 January 2013. Results support a distinct temporal shift in the diet of L. virgulata from the POM fraction

Recent theories have proposed that life arose from primitive hydrothermal environments employ- ing chemical reactions analogous to the reductive citrate cycle (RCC) as the primary pathway for carbon fixation. This chemistry is presumed to have developed as a natural consequence of the intrinsic geochemistry of the young, prebiotic, Earth. There has been no experimental evidence, however, demonstrating that there exists a natural pathway into such a cycle. Toward this end, the results of hydrothermal experiments involving citric acid are used as a method of deducing such a pathway. Homocatalytic reactions observed in the citric acid-H2O experiments encompass many of the reactions found in modern metabolic systems, i.e., hydration- dehydration, retro-Aldol, decarboxylation, hydrogenation, and isomerization reactions. Three principal de- composition pathways operate to degrade citric acid under thermal and aquathermal conditions. It is concluded that the acid catalyzed decarboxylation pathway, leading ultimately to propene and CO2, may provide the most promise for reaction network reversal under natural hydrothermal conditions. Increased pressure is shown to accelerate the principal decarboxylation reactions under strictly hydrothermal conditions. The effect of forcing the pH via the addition of NaOH reveals that the decarboxylation pathway operates even up to intermediate pH levels. The potential for network reversal (the conversion of propene and CO2 up to a tricarboxylic acid) is demonstrated via the Koch (hydrocarboxylation) reaction promoted heterocatalytically with NiS in the presence of a source of CO. Specifically, an olefin (1-nonene) is converted to a monocar- boxylic acid; methacrylic acid is converted to the dicarboxylic acid, methylsuccinic acid; and the dicarboxylic acid, itaconic acid, is converted into the tricarboxylic acid, hydroaconitic acid. A number of interesting sulfur-containing products are also formed that may provide for additional reaction. The intrinsic catalytic qualities of FeS and NiS are also explored in the absence of CO. It was shown that the addition of NiS has a minimal effect in the product distribution, whereas the addition of FeS leads to the formation of hydrogenated and sulfur-containing products (thioethers). These results point to a simple hydrothermal redox pathway for citric acid synthesis that may have provided a geochemical ignition point for the reductive citrate cycle. Copyright © 2001 Elsevier Science Ltd 1. INTRODUCTION

An in-line X-ray beam energy and intensity monitor has been developed for use in focussed X-ray absorption near-edge spectroscopy (XANES) measurements. The monitor uses only the X-ray intensity that would otherwise bypass our zone-plate focussing optic and relies on a measurement of photoemission current. The monitor is inexpensive, easy to align, and provides valuable feedback about the X-ray energy. Operation of the monitor is demonstrated for measurements of phosphorus XANES. The precision of the energy determination is around 0.5 eV.

Measurements of15N/14N in dissolved molecular nitrogen (N2), nitrate (NO3−) and nitrous oxide (N2O) and18O/16O in N2O [expressed as δ15N and δ18O, relative to atmospheric N2 and oxygen (O2), respectively] have been made in water column at several locations in the Arabian Sea, a region with one of the thickest and most intense O2 minima observed in the open ocean. Microbially-mediated reduction of NO3− to N2 (denitrification) in the oxygen minimum zone (OMZ) appears to greatly affect the natural isotopic abundances. The δ15N of NO3− increases from 6‰ in deep waters (2500 m) to 15‰ within the core of the denitrifying layer (250–350 m); the δ15N of N2 concurrently decreases from 0.6‰ to 0.20‰ Values of the isotopic fractionation factor (e) during denitrification estimated using simple advection-reaction and diffusion-reaction models are 22‰ and 25‰, respectively. A strong decrease in δ15N of NO3− is observed from ∼ 200m (> 11‰) to 80m (∼ 6‰); this is attributed to the input of isotopically light nitrogen through nitrogen fixation. Isotopic analysis of N2O reveals extremely large enrichments of both15N and18O within the OMZ, presumably due to the preferential reduction of lighter N2O to N2. However, isotopically light N2O is observed to accumulate in high concentrations above the OMZ indicating that the N2O emitted to the atmosphere from this region cannot be very heavy. The isotope data from the intense upwelling zone off the southwest coast of India, where some of the highest concentrations of N2O ever found at the sea surface are observed, show moderate depletion of15N, but slight enrichment of18O relative to air. These results suggest that the ocean-atmosphere exchange cannot counter inputs of heavier isotopes (particularly18O) associated with the stratospheric back flux, as proposed by previous workers. This calls for additional sources and/or sinks of N2O in the atmosphere. Also, the N2O isotope data cannot be explained by production through either nitrification or denitrification, suggesting a possible coupling between the two processes as an important mechanism of N2O production.

The δ15N composition of nitrate and N2 gas was measured in the eastern tropical North Pacific (ETNP) and central Arabian Sea (AS) suboxic regions. The δ15N of nitrate increased from 6‰ at 2,500 m to 15‰ at 250–350 m in both regions, while the δ15N of N2 concurrently decreased from 0.6‰ to 0.25‰. The denitrification isotopic fractionation factor (edenit) for each region was estimated using both advection-reaction and diffusion-reaction models. Values for edenit in the ETNP ranged from 25 ± 2 (advection-reaction) to 30 ± 3 (diffusion-reaction). Values for edenit in the central AS varied from 22 ± 3 (advection-diffusion) to 25 ± 4 (reaction-diffusion) using a starting nitrate isotopic composition of 6‰ but were indistinguishable from calculated values from the ETNP when an initial value of 5‰ was employed. Based upon the model results, an average global edenit of 27 ± 3 is proposed for marine suboxic water columns. Isotopic enrichment of nitrate in oxic waters beneath the active denitrification regions was observed and indicates the presence of significant cross-isopycnal ventilation at depth. The isotopic composition of nitrate decreased above 250 m to −80 m, and this pattern is hypothesized to be caused by the input of isotopically light nitrogen from nitrogen fixation in the euphotic zone. A simple isotopic mass balance indicates that a significant percentage of primary productivity in the central AS may be fueled by nitrogen fixation.

We evaluate the hypothesis that decomposition and adsorption reactions operating in upland soils of headwater catchments control the concentration and composition of dissolved and fine particulate organic matter in rivers of the Amazon basin. In two contrasting first-order catchments characteristic of the central Amazon basin, we analyzed plant, litter, soil, groundwater, and stream water chemistry. Our results indicate that clear and persistent differences exist in the concentration and elemental composition of dissolved organic matter (DOM) in stream waters and groundwaters from the two catchments, due mainly to corresponding differences in soil texture and chemistry. Within the more oxide and clay rich Oxisols underlying terra firme forest, groundwater DOM concentrations were uniformly low (120 μMC) and C/N ratios averaged 10. Conversely, within the oxide and clay deficient Spodosols underlying campinarana forest, groundwater DOM concentrations were greatly elevated (3000 μMC), and C/N ratios averaged near 60. We found that, in the terra firme/Oxisol terrain, the majority of DOM contributions to the stream derived from the riparian zone, while in the campinarana/Spodosol terrain, upland groundwater contributions could account for the concentration and composition of DOM in the stream. The implications of our findings are that in the terra firme terrains which dominate the region, upland soil profiles are not the site of definitive processes which impart compositional signatures to organic matter carried by the largest rivers of the Amazon basin, as was hypothesized. Instead, we suggest that definitive reactions are focused primarily in the river corridor.

The bulk and isotopic exchanges of O2, N2, NO3, and NH4+ between sediments and the overlying water (benthic flux) were measured at three shallow locations in Puget Sound using a benthic tripod. Oxygen consumption by the sediments averaged 4.4 mmol m−2 d−1, while N2 gas fluxes averaged 1.1 mmol M−2 d−1. The nitrogen gas flux out of the sediments was always greater than the corresponding NO3-flux into the sediments, indicating a large nitrification contribution to the N2 flux. Isotopic changes in overlying water δ18O of O2 were small, with an average apparent sediment respiration fractionation-factor, e, of 3. This fractionation-factor is much smaller than that measured in either the open ocean or in the laboratory. The low degree of fractionation is hypothesized to occur because of the interaction of diffusive layers around reactive microsites within these sediments. There was no apparent isotopic fractionation of downward-diffusing NO3− (e = 0), while the ammonium that diffused out of the sediments averaged 4.5%o heavier than both source organic matter within the sediments and overlying water NO3. The large discrepancy in isotopic composition between the source organic material and NH4+ can be attributed to significant isotopic fractionation of ammonium during nitrification in the oxic zone. Finally, the δ15N of N2 did not change significantly over the course of the incubations, in agreement with the nitrogen isotopic budget for these sediments.

The δ15N composition of the dominant form of dissolved inorganic nitrogen (DIN) was determined in upland groundwater, riparian groundwater, and stream water of the Barro Branco catchment, Amazonas, Brazil. The δ15N composition of organic nitrogen in riparian and upland leaf litter was also determined. The data for these waters could be divided into three groups: upland groundwater DIN predominately composed of NO3 − with δ15N values averaging 6.25 ± 0.9 riparian groundwater DIN primarily composed of NH4 + with δ15N values averaging 9.17 ± 1.0 and stream water DIN predominately composed of NO3 − with δ15N values averaging 4.52 ± 0.8‰ Nitrate samples taken from the stream source and from the stream adjacent to the groundwater transects showed a downstream increase in δ15N from 1.0to 4.5‰ Leaf litter samples averaged 3.5 ± 1.2‰ The observed patterns in isotopic composition, together with previously observed inorganic nitrogen species and concentration shifts between upland, riparian and stream waters, suggest that groundwater DIN is not the primary source of DIN to the stream. Instead, the isotopic data suggest that remineralization of organic nitrogen within the stream itself may be a major source of stream DIN, and that the majority of DIN entering the stream via groundwater flowpaths is removed at the riparian-stream interface.

Orca Basin, an intraslope basin on the Texas–Louisiana continental slope, hosts a hypersaline, anoxic brine in its lowermost 200 m. This brine contains a large reservoir of reduced and aged carbon, and appears to be stable at decadal time scales: concentrations and the isotopic composition of dissolved inorganic (DIC) and organic carbon (DOC) are similar to previous reports. Both DIC and DOC are more "aged" within the brine pool than in overlying water, and the isotopic contrast between brine carbon and seawater carbon is much greater for DIC than DOC. While the stable carbon isotopic composition of brine DIC points towards a combination of methane and organic carbon re-mineralization as its source, radiocarbon and box model results point to the brine interface as the major source region for DIC with oxidation of methane diffusing upwards from sediments supplying only limited DIC to the brine. This conclusion is consistent with previous studies reporting microbial activity focused at the seawater-brine interface. Isotopic similarities between DIC and DOC suggest a different relationship between these two carbon reservoirs than is typically observed in deep ocean basins. Radiocarbon values implicate the seawater-brine interface region as the likely source region for DOC as well as DIC. Further investigations of the seawater-brine interface are needed to advance our understanding of the specific microbial processes contributing to dissolved carbon storage in the Orca Basin brine.