Dissolved organic matter (DOM) was extracted by solid-phase extraction (SPE) from 137 water samples from different climate zones and different depths along an eastern Atlantic Ocean transect. The ...extracts were analyzed with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI). Δ14C analyses were performed on subsamples of the SPE-DOM. In addition, the amount of dissolved organic carbon was determined for all water and SPE-DOM samples as well as the yield of amino sugars for selected samples. Linear correlations were observed between the magnitudes of 43 % of the FT-ICR mass peaks and the extract Δ14C values. Decreasing SPE-DOM Δ14C values went along with a shift in the molecular composition to higher average masses (m/z) and lower hydrogen/carbon (H/C) ratios. The correlation was used to model the SPE-DOM Δ14C distribution for all 137 samples. Based on single mass peaks, a degradation index (IDEG) was developed to compare the degradation state of marine SPE-DOM samples analyzed with FT-ICR MS. A correlation between Δ14C, IDEG, DOC values and amino sugar yield supports that SPE-DOM analyzed with FT-ICR MS reflects trends of bulk DOM. DOM weighted normalized mass peak magnitudes were used to compare aged and recent SPE-DOM on a semi-quantitative molecular basis. The magnitude comparison showed a continuum of different degradation rates for the detected compounds. A high proportion of the compounds should persist, possibly modified by partial degradation, in the course of thermohaline circulation. Prokaryotic (bacterial) production, transformation and accumulation of this very stable DOM occur primarily in the upper ocean. This DOM is an important contribution to very old DOM, showing that production and degradation are dynamic processes.
Carbon cycling in the coastal zone affects global carbon budgets and is critical for understanding the urgent issues of hypoxia, acidification, and tidal wetland loss. However, there are no regional ...carbon budgets spanning the three main ecosystems in coastal waters: tidal wetlands, estuaries, and shelf waters. Here we construct such a budget for eastern North America using historical data, empirical models, remote sensing algorithms, and process‐based models. Considering the net fluxes of total carbon at the domain boundaries, 59 ± 12% (± 2 standard errors) of the carbon entering is from rivers and 41 ± 12% is from the atmosphere, while 80 ± 9% of the carbon leaving is exported to the open ocean and 20 ± 9% is buried. Net lateral carbon transfers between the three main ecosystem types are comparable to fluxes at the domain boundaries. Each ecosystem type contributes substantially to exchange with the atmosphere, with CO2 uptake split evenly between tidal wetlands and shelf waters, and estuarine CO2 outgassing offsetting half of the uptake. Similarly, burial is about equal in tidal wetlands and shelf waters, while estuaries play a smaller but still substantial role. The importance of tidal wetlands and estuaries in the overall budget is remarkable given that they, respectively, make up only 2.4 and 8.9% of the study domain area. This study shows that coastal carbon budgets should explicitly include tidal wetlands, estuaries, shelf waters, and the linkages between them; ignoring any of them may produce a biased picture of coastal carbon cycling.
Plain Language Summary
A carbon budget for a particular site or region describes the inputs and outputs of carbon to that site or region as well as the processes that change carbon from one form to another. A carbon budget is needed to fully understand many important issues facing coastal waters. We constructed the carbon budget for coastal waters of eastern North America. We found that about 60% of the carbon entering the domain is from rivers and about 40% is from the atmosphere, while about 80% of the carbon leaving the domain goes to the open ocean and about 20% is buried. Transfers of carbon from wetlands to estuaries and from estuaries to the ocean were as important as transfers of carbon at the domain boundaries. Tidal wetlands and estuaries were found to be important to the carbon budget despite making up only 2.4 and 8.9% of the study domain area, respectively. This study shows that coastal carbon budgets should explicitly consider tidal wetlands, estuaries, shelf waters, and the linkages between them; ignoring any of them may produce a biased picture of coastal carbon cycling.
Key Points
Tidal wetlands, estuaries, and shelf waters each contribute substantially to the carbon budget of eastern North American coastal waters
Study region net ecosystem production, atmospheric uptake, and burial are 20.2 ± 4.4, 5.1 ± 2.4, and 2.5 ± 0.7 Tg C yr−1, respectively
Net lateral carbon fluxes between tidal wetlands, estuaries, and shelf waters are large terms in the carbon budget of eastern North American coastal waters
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Integration of inland waters into regional and global carbon (C) budgets requires a comprehensive understanding of factors regulating organic carbon (OC) delivery and in situ processing. This study ...reviews advances in optical, molecular, and isotopic approaches to resolve the sources, ages, and transformations of OC in aquatic systems. OC characterization using excitation emission matrix spectra, Fourier transform ion cyclotron mass spectrometry, and nuclear magnetic resonance provides detailed molecular level insight. Radiocarbon isotopic approaches and compound‐specific techniques resolve the input, metabolic fate, and turnover time of OC in ecosystems ranging in size from streams to the open ocean. Accumulating evidence suggests that aquatic OC is composed of diverse biogeochemical components. We conclude with enduring and emerging questions that underscore the role of inland systems in the global C cycle and propose unique combinations of approaches to better discern their role in the delivery and transformation of OC from soils to seas.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Microbial communities are recognized as major drivers of the biogeochemical processes in the oceans. However, the genetic diversity and composition of those communities is poorly understood. The aim ...of this study is to investigate the composition of bacterial assemblages in three different water layer habitats: surface (2-20 m), deep chlorophyll maximum (DCM; 28-90 m), and deep (100-4600 m) at nine stations along the eastern Atlantic Ocean from 42.8° N to 23.7° S. The sampling of three discrete, predefined habitat types from different depths, Longhurstian provinces, and geographical locations allowed us to investigate whether marine bacterial assemblages show spatial variation and to determine if the observed spatial variation is influenced by current environmental conditions, historical/geographical contingencies, or both. The PCR amplicons of the V6 region of the 16S rRNA from 16 microbial assemblages were pyrosequenced, generating a total of 352 029 sequences; after quality filtering and processing, 257 260 sequences were clustered into 2871 normalized operational taxonomic units (OTU) using a definition of 97% sequence identity. Community ecology statistical analyses demonstrate that the eastern Atlantic Ocean bacterial assemblages are vertically stratified and associated with water layers characterized by unique environmental signals (e.g., temperature, salinity, and nutrients). Genetic compositions of bacterial assemblages from the same water layer are more similar to each other than to assemblages from different water layers. The observed clustering of samples by water layer allows us to conclude that contemporary environments are influencing the observed biogeographic patterns. Moreover, the implementation of a novel Bayesian inference approach that allows a more efficient and explicit use of all the OTU abundance data shows a distance effect suggesting the influence of historical contingencies on the composition of bacterial assemblages. Surface bacterial communities displayed a general congruency with the ecological provinces as defined by Longhurst with modest exceptions usually associated with unique hydrographic and biogeochemical features. Collectively, our findings suggest that vertical (habitat) and latitudinal (distance) biogeographic signatures are present and that both environmental parameters and ecological provinces drive the composition of bacterial assemblages in the eastern Atlantic Ocean.
The global ocean contains a massive reservoir of dissolved organic carbon (DOC), rivaling the atmosphere's pool of CO2. The most recalcitrant fractions have mean radiocarbon ages of ~4,000 years in ...the Atlantic to ~6,000 years in the Pacific. Knowing the radiocarbon signatures of DOC and the molecular composition of dissolved organic matter (DOM) is crucial to develop understanding of the persistence and lifetime of the DOC pool. In this research, we collected samples from the deep North Pacific in August 2013 (aboard the RV Melville) to couple the Δ14C content of solid‐phase‐extracted DOM (Δ14C‐SPE‐DOM) with its molecular composition in the ocean's oldest deep waters. We find that deep waters in this region held a mean Δ14C‐SPE‐DOM value of −554 ± 9‰ (~6,400 14C years), substantially more depleted than that in the deep Atlantic, which held a mean Δ14C‐SPE‐DOM value of −445 ± 5‰. While we find a more degraded molecular composition of DOM in the deep Pacific than the deep Atlantic, the molecular formulae within the Island of Stability (Lechtenfeld et al., 2014, https://doi.org/10.1016/j.gca.2013.11.009), are largely retained. These results imply that a fraction of deep DOM is resistant to removal and present in both the deep Atlantic and Pacific Oceans.
Key Points
Solid‐phase extracted DOM (SPE‐DOM) from deep waters in the far North Pacific has a 14C age of ~6,400 years
Deep Pacific SPE‐DOM has an intrinsically stable component
Specific molecular formulae are largely preserved in SPE‐DOM as it undergoes meridional overturning circulation
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Objectives. The purpose of this study was to assess the effects of estrogen replacement therapy on long-term outcome, including restenosis, myocardial infarction, stroke and death after a first ...percutaneous transluminal coronary angioplasty (PTCA) procedure, in postmenopausal women.
Background. Observational and epidemiologic studies, basic laboratory research and clinical trials consistently suggest that estrogen replacement therapy is associated with beneficial cardiovascular effects in women. These cardioprotective actions may be particularly relevant to women with coronary artery disease, such as those who have undergone PTCA.
Methods. This was a retrospective study that included 337 women who underwent elective PTCA between 1982 and 1994. The treatment group consisted of 137 consecutive women receiving long-term estrogen therapy at the time of elective PTCA and during follow-up. The control group comprised 200 women who were computer-matched with the estrogen group. The mean follow-up period was 65 ± 35 months.
Results. Actuarial survival was superior in the estrogen group; the 7-year survival rate was 93% for the estrogen group versus 75% for the control group (p = 0.001). The cardiovascular event rate (death, nonfatal myocardial infarction or nonfatal stroke) was significantly lower in the estrogen group at 7 years (12% vs. 35% in the control group, p = 0.001). The need for subsequent revascularization during follow-up was similar in the two groups. Multivariable analysis identified diabetes, estrogen therapy (adjusted risk ratio 0.38, 95% confidence interval 0.19 to 0.79) and left ventricular ejection fraction <40% as independent correlates of cardiovascular death or myocardial infarction during follow-up.
Conclusions. Estrogen replacement therapy was associated with an improved long-term outcome after PTCA in postmenopausal women.
(J Am Coll Cardiol 1997;29:1–5)>
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Assessing the fate of organic matter (OM) in estuaries is challenging due to its numerous sources, diagenetic processing, and physical and biogeochemical sinks. In order to evaluate differences in ...the sources and potential transformations of OM, particulate organic matter (POM) and high molecular weight dissolved organic matter (HMW DOM (⩾3
kDa)) were characterized along the York River estuary (Virginia, USA) using lipid biomarker, elemental ratios, and stable isotope (
δ
13C and
δ
15N) analyses. Isotopic signatures of HMW DOM from the freshwater site were distinct from both its POM counterpart and HMW DOM from higher salinity regions of the estuary. Lipid compound classes were depleted in HMW DOM relative to POM. Saturated fatty acids (FA) dominated the dissolved organic pool while monounsaturated and polyunsaturated FA were the primary FA classes in POM. Concentrations of sterols diagnostic of allochthonous (i.e., plant/freshwater algae) sources were enriched in HMW DOM relative to the POM at higher salinities. Ternary plots based on FA biomarkers show that POM is characterized by contributions from polyunsaturated FA, labile compounds representing contributions from “fresh” phytoplankton/zooplankton sources. In contrast, FA in HMW DOM reflect bacterial and vascular plant signatures. Disparities in the composition of HMW DOM and POM likely reflect differences in the dominant biological sources, different susceptibilities to transformation and/or differential influences from abiotic processes (sorption–desorption, flocculation, etc.). Thus, the physical associations of OM (particulate vs. dissolved) may be a fundamental control on both the distribution and biogeochemical processing of OM whereby terrigenous DOM may be selectively exported while terrigenous POM is retained within the estuary. These observations have implications for the selective processing of different sources and forms of OM in rivers and estuaries prior to export to the coastal ocean.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
We used radiocarbon $(\Delta {}^{14}\text{C})$ and stable isotopic (δ 13C, δ 15N) signatures of bacterial nucleic acids to estimate the sources and ages of organic matter (OM) assimilated by bacteria ...in the Hudson River and York River estuary. Dualisotope plots of Δ 14C and δ 13C coupled with a three-source mixing model resolved the major OM sources supporting bacterial biomass production (BBP). However, overlap in the stable isotopic (δ 13C and δ 15N) values of potential source end members (i.e., terrestrial, freshwater phytoplankton, and marsh-derived) prohibited unequivocal source assignments for certain samples. In freshwater regions of the York, terrigenous material of relatively recent origin (i.e., decadal in age) accounted for the majority of OM assimilated by bacteria (49-83%). Marsh and freshwater planktonic material made up the other major source of OM, with 5-33% and 6-25% assimilated, respectively. In the mesohaline York, BBP was supported primarily by estuarine phytoplankton-derived OM during spring and summer (53-87%) and by marsh-derived OM during fall (as much as 83%). Isotopic signatures from higher salinity regions of the York suggested that BBP there was fueled predominantly by either estuarine phytoplankton-derived OM (July and November) or by material advected in from the Chesapeake Bay proper (October). In contrast to the York, BBP in the Hudson River estuary was subsidized by a greater portion (up to ∼25%) of old (∼24,000 yr BP) allochthonous OM, which was presumably derived from soils. These findings collectively suggest that bacterial metabolism and degradation in rivers and estuaries may profoundly alter the mean composition and age of OM during transport within these systems and before its export to the coastal ocean.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NMLJ, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK
An integrated multidisciplinary study utilizing geochemical and microbial ecological approaches was conducted to characterize the origins, chemical nature, and quantities of dissolved and particulate ...organic matter (OM) utilized by heterotrophic bacteria in a temperate estuary. C:N, stable isotope (δ13C), and lipid biomarker analyses revealed differences in the inferred reactivity of autochthonous versus allochthonous OM sources. Isotopic comparison of OM size fractions and bacterial nucleic acids suggests that high-molecular-weight dissolved OM (DOM) is consistently linked to bacterial biomass synthesis along the estuarine salinity gradient. Polyunsaturated fatty acids (as percent of total fatty acids, FA) were a reliable predictor of DOM decomposition in bioassays, thus providing an indicator directly linking DOM reactivity to its composition. Significant positive correlations between FA diagnostic of bacterial sources and lipid biomarker compounds diagnostic of planktonic origin indicate a systematic bacterial response to autochthonous DOM sources along the estuarine continuum. These findings further suggest that, although the geochemical signature of algal-derived OM in the dissolved phase may appear quantitatively insignificant, this fraction may nevertheless represent a principal source of bioreactive OM to heterotrophic bacteria in estuarine waters.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NMLJ, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK