Carbon Oxidation Pathways Research Articles

Evidence that mitochondrial alternative oxidase respiration supports carbon balance in source leaves of Nicotiana tabacum

Alternative oxidase (AOX) represents a non-energy conserving pathway within the mitochondrial electron transport chain. One potential physiological role of AOX could be to manage leaf carbohydrate amounts by supporting respiratory carbon oxidation reactions. In this study, several approaches tested the hypothesis that AOX1a gene expression in Nicotiana tabacum leaf is enhanced in conditions expected to promote an increased leaf carbohydrate status. These approaches included supplying leaves with exogenous carbohydrates, comparing plants grown at different atmospheric CO2 concentrations, comparing sink leaves with source leaves, comparing plants with different ratios of source to sink activity, and examining gene expression over the diel cycle. In each case, the pattern of AOX1a gene expression was compared with that of other genes known to respond to carbohydrates and/or other factors related to source:sink activity. These included GPT1 and GPT3 (that encode chloroplast glucose 6-phosphate/phosphate translocators), SPS (that encodes sucrose phosphate synthase), SUT1 (that encodes a sucrose/H+ symporter involved in phloem loading) and UCP1 (that encodes a mitochondrial uncoupling protein). The AOX1a transcript amount was higher following the leaf sink-to-source transition, and in plants with higher source relative to sink activity due to increasing plant age. Further, these effects were amplified in plants grown at elevated CO2 to stimulate source activity, particularly at end-of-day time periods. The AOX1a transcript amount was also higher following treatment of leaves with carbohydrate, in particular sucrose. Overall, the results provide evidence that, while source leaf sucrose accumulation may signal for a down-regulation of sucrose synthesis and transport, it also signals for means to manage the excess cytosolic carbohydrate pools. This includes increased AOX respiration to support carbon oxidation pathways even if energy charge is high, in combination perhaps with some return flux of carbohydrate from cytosol to stroma through the GPT3 translocator. As discussed, these activities could contribute to maintaining plant source:sink balance, as well as photosynthetic and phloem loading capacity.

Polysaccharide utilization by a marine heterotrophic bacterium from the SAR92 clade.

SAR92 is one of the few examples of a widely distributed, abundant oligotroph that can be cultivated to study pathways of carbon oxidation in ocean systems. Genomic evidence for SAR92 suggests that this gammaproteobacterium might be a primary consumer of polysaccharides in the epipelagic zone, its main habitat. Here, we investigated cell growth, polysaccharide utilization gene expression, and carbohydrate-active enzyme abundance of a culturable SAR92 strain, HTCC2207, grown with different polysaccharides. Xylan and laminarin, two polysaccharides mainly produced by phytoplankton, supported the growth of HTCC2207 better than other polysaccharides. HTCC2207 possessed polysaccharide utilization loci (PULs) consisting of TonB-dependent receptor (TBDR) and glycoside hydrolase (GH) family genes. GH genes such as GH17 and GH3 presented no substrate-specificity and were induced by different sugar substrates, while expressions of GH16, GH10 and GH30 were enhanced in the glucose-treatment but suppressed in the polysaccharide-treatment, indicating complex polysaccharide utilization by HTCC2207. Metabolic pathways for laminarin and xylan were re-constructed in HTCC2207 based on the PULs genes and other predicted carbohydrate-active enzymes. This study reveals features of the epipelagic niche of SAR92 and provide insight into the biogeochemical cycling of labile, high-molecular carbohydrate compounds in the surface ocean.

Carbonyl Identification and Quantification Uncertainties for Oxidative Polymer Degradation

The most revealing indicator for oxidative processes or state of degraded plastics is usually carbonyl formation, a key step in materials degradation as part of the carbon cycle for man-made materials. Hence, the identification and quantification of carbonyl species with infrared spectroscopy have been the method of choice for generations, thanks to their strong absorbance and being an essential intermediate in carbon oxidation pathways. Despite their importance, precise identification and quantification can be challenging and rigorous fully traceable data are surprisingly rare in the existing literature. An overview of the complexity of carbonyl quantification is presented by the screening of reference compounds in solution with transmission and polymer films with ATR IR spectroscopy, and systematic data analyses. Significant variances in existing data and their past use have been recognized. Guidance is offered how better measurements and data reporting could be accomplished. Experimental variances depend on the combination of uncertainty in exact carbonyl species, extinction coefficient, contributions from neighboring convoluting peaks, matrix interaction phenomena and instrumental variations in primary IR spectral acquisition (refractive index and penetration depth for ATR measurements). In addition, diverging sources for relevant extinction coefficients may exist, based on original spectral acquisition. For common polymer degradation challenges, a relative comparison of carbonyl yields for a material is easily accessible, but quantification for other purposes, such as degradation rates and spatially dependent interpretation, requires thorough experimental validation. All variables highlighted in this overview demonstrate the significant error margins in carbonyl quantification, with exact carbonyl species and extinction coefficients already being major contributors on their own.

Unveiling the role of carbon oxidation in irreversible degradation of atomically-dispersed FeN4 moieties for proton exchange membrane fuel cells

Irreversible degradation of FeN4 catalysts for proton exchange membrane fuel cells at the atomic level, caused by Fe de-metalation and chemical oxidation of carbon via a proposed new carbon oxidation pathway.

Influence of Manila clam aquaculture on rates and partitioning of organic carbon oxidation in sediment of Keunso Bay, Yellow Sea

We investigated the effects of Manila clam aquaculture on the rates and pathways of anaerobic organic carbon (OC) oxidation in highly bioturbated (HB) and poorly bioturbated (PB) sediment in Keunso Bay, Yellow Sea. Due to the labile organic matter supply via sediment reworking by Manila clams, the anaerobic OC oxidation rate in HB sediment (38.8 mmol m-2 d-1) was ~1.5 times higher than that in PB sediment (26.8 mmol m-2 d-1). Microbial Fe(III) reduction (FeR) dominated OC oxidation pathways in HB sediment, comprising 55 to 76% of anaerobic OC oxidation, whereas sulfate reduction (SR) was the dominant oxidation pathway in PB sediment, accounting for up to 92% of anaerobic OC oxidation. Despite higher anaerobic respiration rates at the HB site, concentrations of NH4+, PO43-, oxalate-extractable iron (Fe(II)(oxal)), and total reduced inorganic sulfur were 2 to 3 times lower in HB than in PB sediment. Conversely, the concentration of reactive Fe(III)(oxal) at the HB site (2243 mmol m-2) exceeded that at the PB site (1127 mmol m-2) by a factor of 2. These results indicate that bioturbation by Manila clams enhances the re-oxidation processes of reduced metabolites in the sediment, thereby prohibiting SR and promoting FeR. Overall, the results suggest that aquaculture activities of Manila clams shift the dominant OC oxidation pathways in sediment from SR to FeR, which generates relatively oxidized and less sulfidic environments.

Invasive Spartina anglica Greatly Alters the Rates and Pathways of Organic Carbon Oxidation and Associated Microbial Communities in an Intertidal Wetland of the Han River Estuary, Yellow Sea

This research was supported by the Korean Long-term Marine Ecological Researches (K-LTMER) funded by the Korean Ministry of Oceans and Fisheries, and by the Mid-career Scientist Research Program funded by the Korean Ministry of Science and ICT (No. 2018R1A2B2006340).

Manganese and iron reduction dominate organic carbon oxidation in surface sediments of the deep Ulleung Basin, East Sea

Abstract. Rates and pathways of benthic organic carbon (Corg) oxidation were investigated in surface sediments of the Ulleung Basin (UB) characterized by high Corg contents ( > 2.5 %, dry wt.) and very high contents of Mn oxides ( > 200 µmol cm−3) and Fe oxides (up to 100 µmol cm−3). The combination of geochemical analyses and independently executed metabolic rate measurements revealed that Mn and Fe reduction were the dominant Corg oxidation pathways in the center of the UB, comprising 45 and 20 % of total Corg oxidation, respectively. By contrast, sulfate reduction was the dominant Corg oxidation pathway, accounting for 50 % of total Corg mineralization in sediments of the continental slope. The relative significance of each Corg oxidation pathway matched the depth distribution of the respective electron acceptors. The relative importance of Mn reduction for Corg oxidation displays saturation kinetics with respect to Mn oxide content with a low half-saturation value of 8.6 µmol cm−3, which further implies that Mn reduction can be a dominant Corg oxidation process even in sediments with lower MnO2 content as known from several other locations. This is the first report of a high contribution of manganese reduction to Corg oxidation in offshore sediments on the Asian margin. The high manganese oxide content in the surface sediment in the central UB was maintained by an extreme degree of recycling, with each Mn atom on average being reoxidized ∼ 3800 times before permanent burial. This is the highest degree of recycling so far reported for Mn-rich sediments, and it appears linked to the high benthic mineralization rates resulting from the high Corg content that indicate the UB as a biogeochemical hotspot for turnover of organic matter and nutrient regeneration.

The bacterial response regulator ArcA uses a diverse binding site architecture to regulate carbon oxidation globally.

Despite the importance of maintaining redox homeostasis for cellular viability, how cells control redox balance globally is poorly understood. Here we provide new mechanistic insight into how the balance between reduced and oxidized electron carriers is regulated at the level of gene expression by mapping the regulon of the response regulator ArcA from Escherichia coli, which responds to the quinone/quinol redox couple via its membrane-bound sensor kinase, ArcB. Our genome-wide analysis reveals that ArcA reprograms metabolism under anaerobic conditions such that carbon oxidation pathways that recycle redox carriers via respiration are transcriptionally repressed by ArcA. We propose that this strategy favors use of catabolic pathways that recycle redox carriers via fermentation akin to lactate production in mammalian cells. Unexpectedly, bioinformatic analysis of the sequences bound by ArcA in ChIP-seq revealed that most ArcA binding sites contain additional direct repeat elements beyond the two required for binding an ArcA dimer. DNase I footprinting assays suggest that non-canonical arrangements of cis-regulatory modules dictate both the length and concentration-sensitive occupancy of DNA sites. We propose that this plasticity in ArcA binding site architecture provides both an efficient means of encoding binding sites for ArcA, σ70-RNAP and perhaps other transcription factors within the same narrow sequence space and an effective mechanism for global control of carbon metabolism to maintain redox homeostasis.

Alternative oxidase: a mitochondrial respiratory pathway to maintain metabolic and signaling homeostasis during abiotic and biotic stress in plants.

Alternative oxidase (AOX) is a non-energy conserving terminal oxidase in the plant mitochondrial electron transport chain. While respiratory carbon oxidation pathways, electron transport, and ATP turnover are tightly coupled processes, AOX provides a means to relax this coupling, thus providing a degree of metabolic homeostasis to carbon and energy metabolism. Beside their role in primary metabolism, plant mitochondria also act as “signaling organelles”, able to influence processes such as nuclear gene expression. AOX activity can control the level of potential mitochondrial signaling molecules such as superoxide, nitric oxide and important redox couples. In this way, AOX also provides a degree of signaling homeostasis to the organelle. Evidence suggests that AOX function in metabolic and signaling homeostasis is particularly important during stress. These include abiotic stresses such as low temperature, drought, and nutrient deficiency, as well as biotic stresses such as bacterial infection. This review provides an introduction to the genetic and biochemical control of AOX respiration, as well as providing generalized examples of how AOX activity can provide metabolic and signaling homeostasis. This review also examines abiotic and biotic stresses in which AOX respiration has been critically evaluated, and considers the overall role of AOX in growth and stress tolerance.

Dissolved inorganic carbon and alkalinity fluxes from coastal marine sediments: model estimates for different shelf environments and sensitivity to global change

Abstract. We present a one-dimensional reactive transport model to estimate benthic fluxes of dissolved inorganic carbon (DIC) and alkalinity (AT) from coastal marine sediments. The model incorporates the transport processes of sediment accumulation, molecular diffusion, bioturbation and bioirrigation, while the reactions included are the redox pathways of organic carbon oxidation, re-oxidation of reduced nitrogen, iron and sulfur compounds, pore water acid-base equilibria, and dissolution of particulate inorganic carbon (calcite, aragonite, and Mg-calcite). The coastal zone is divided into four environmental units with different particulate inorganic carbon (PIC) and particulate organic carbon (POC) fluxes: reefs, banks and bays, carbonate shelves and non-carbonate shelves. Model results are analyzed separately for each environment and then scaled up to the whole coastal ocean. The model-derived estimate for the present-day global coastal benthic DIC efflux is 126 Tmol yr−1, based on a global coastal reactive POC depositional flux of 117 Tmol yr−1. The POC decomposition leads to a carbonate dissolution from shallow marine sediments of 7 Tmol yr−1 (on the order of 0.1 Pg C yr−1. Assuming complete re-oxidation of aqueous sulfide released from sediments, the effective net flux of alkalinity to the water column is 29 Teq. yr−1, primarily from PIC dissolution (46%) and ammonification (33%). Because our POC depositional flux falls in the high range of global values given in the literature, the reported DIC and alkalinity fluxes should be viewed as upper-bound estimates. Increasing coastal seawater DIC to what might be expected in year 2100 due to the uptake of anthropogenic CO2 increases PIC dissolution by 2.3 Tmol yr−1and alkalinity efflux by 4.8 Teq. yr−1. Our reactive transport modeling approach not only yields global estimates of benthic DIC, alkalinity and nutrient fluxes under variable scenarios of ocean productivity and chemistry, but also provides insights into the underlying processes.

Fractionation of sulfur isotopes by Desulfovibrio vulgaris mutants lacking hydrogenases or type I tetraheme cytochrome c3

The sulfur isotope effect produced by sulfate reducing microbes is commonly used to trace biogeochemical cycles of sulfur and carbon in aquatic and sedimentary environments. To test the contribution of intracellular coupling between carbon and sulfur metabolisms to the overall magnitude of the sulfur isotope effect, this study compared sulfur isotope fractionations by mutants of Desulfovibrio vulgaris Hildenborough. We tested mutant strains lacking one or two periplasmic (Hyd, Hyn-1, Hyn-2, and Hys) or cytoplasmic hydrogenases (Ech and CooL), and a mutant lacking type I tetraheme cytochrome (TpI-c3). In batch culture, wild-type D. vulgaris and its hydrogenase mutants had comparable growth kinetics and produced the same sulfur isotope effects. This is consistent with the reported redundancy of hydrogenases in D. vulgaris. However, the TpI-c3 mutant (ΔcycA) exhibited slower growth and sulfate reduction rates in batch culture, and produced more H2 and an approximately 50% larger sulfur isotope effect, compared to the wild type. The magnitude of sulfur isotope fractionation in the CycA deletion strain, thus, increased due to the disrupted coupling of the carbon oxidation and sulfate reduction pathways. In continuous culture, wild-type D. vulgaris and the CycA mutant produced similar sulfur isotope effects, underscoring the influence of environmental conditions on the relative contribution of hydrogen cycling to the electron transport. The large sulfur isotope effects associated with the non-ideal stoichiometry of sulfate reduction in this study imply that simultaneous fermentation and sulfate reduction may be responsible for some of the large naturally-occurring sulfur isotope effects. Overall, mutant strains provide a powerful tool to test the effect of specific redox proteins and pathways on sulfur isotope fractionation.

Microbial carbon oxidation rates and pathways in sediments of two Tanzanian mangrove forests

Temporal and spatial variations in benthic metabolism and anaerobic carbon oxidation pathways were assessed in an anthropogenically impacted (Mtoni) and a pristine (Ras Dege) mangrove forest in Tanzania. The objectives were (1) to evaluate how benthic metabolism is affected by organic carbon availability; (2) to determine the validity of diffusive release of CO2 as a measure benthic carbon oxidation; and (3) to assess the partitioning of anaerobic carbon pathways and factors controlling the availability of electron acceptors (e.g. oxidized iron). Microbial carbon oxidation measured as diffusive exchange of O2 and CO2 (32–67 and 28–115 mmol m−2 day−1, respectively) showed no specific temporal patterns. Low intertidal sediments at Mtoni fed by labile algal carbon of anthropogenic origin had higher diffusive CO2 release than high intertidal sediments that primarily received less reactive mangrove detritus. Diffusive release of CO2 apparently underestimated total sediment carbon oxidation due to CO2 loss from deep sediments via emission through biogenic structures (i.e. crab burrows and pneumatophores) and porewater seepage into creeks. We propose that diffusive fluxes in the present mangrove sediments are roughly equivalent to depth-integrated reactions occurring in the upper 12 cm. Anaerobic carbon oxidation was dominated by FeR irrespective of anthropogenic influence in sediments where the oxidizing effects of biogenic structures increased the Fe(III) level. More than 80% of the anaerobic carbon oxidation in Mtoni and Ras Dege sediments was due to FeR when reactive Fe(III) exceeded 30 μmol cm−3. The anthropogenic influence at Mtoni was primarily noted as up to one order of magnitude higher denitrification than at Ras Dege, but this process always accounted for less than 1% of total carbon oxidation. It is noteworthy that organic and nutrient enrichment of anthropogenic origin in Mtoni has no measurable effect on microbial processes, other than carbon oxidation in the low intertidal area and denitrification throughout the forest, and indicates a strong resilience of mangrove environments towards disturbances.

The role of biogenic structures on the biogeochemical functioning of mangrove constructed wetlands sediments – A mesocosm approach

Benthic metabolism (measured as CO2 production) and carbon oxidation pathways were evaluated in 4 mangrove mesocosms subjected daily to seawater or 60% sewage in the absence or presence of mangrove trees and biogenic structures (pneumatophores and crab burrows). Total CO2 emission from darkened sediments devoid of biogenic structures at pristine conditions was comparable during inundation (immersion) and air exposure (emersion), although increased 2–7 times in sewage contaminated mesocosms. Biogenic structures increased low tide carbon gas emissions at contaminated (30%) and particularly pristine conditions (60%). When sewage was loaded into the mesocosms under unvegetated and planted conditions, iron reduction was substituted by sulfate reduction and contribution of aerobic respiration to total metabolism remained above 50%. Our results clearly show impacts of sewage on the partitioning of electron acceptors in mangrove sediment and confirm the importance of biogenic structures for biogeochemical functioning but also on greenhouse gases emission.

Rapid organic matter mineralization coupled to iron cycling in intertidal mud flats of the Han River estuary, Yellow Sea

Organic matter oxidation represents a transfer of elements to inorganic nutrients that support biological productivity and food web processes. Therefore, quantification of the controls of organic matter mineralization is crucial to understanding the carbon cycle and biogeochemical dynamics in coastal marine environments. We investigated the rates and pathways of anaerobic carbon (C) oxidation in an unvegetated mud flat (UMF) and a vegetated mud flat (VMF) of the Ganghwa intertidal zone of the macro-tidal Han River estuary, Yellow Sea. Analyses of geochemical constituents revealed relatively oxidized conditions and high reactive Fe(III) concentrations (40–100 μmol cm−3) in the sediments. A pronounced depth stratification in Fe(III) was observed at the VMF site likely due to the lower number of infaunal burrows along with dense root formation by the macrophytes, Suaeda japonica. Depth-integrated rates of anaerobic C mineralization as well as sulfate- and Fe(III) reduction at the VMF were consistently higher than those at the UMF, likely driven by the dense vegetation that supplied organic C substrates and electron acceptors to the rhizosphere. Sediment inventories revealed that solid Fe(III) was up to 17 times more abundant than pore water sulfate, and direct rate measurements showed that microbial Fe(III) reduction comprised an equal or larger percentage of C oxidation (36–66 %) in comparison to sulfate reduction (36–40 %) at both sites studied. Time-course experiments indicated that sulfate reduction rates were likely underestimated, especially in the VMF rhizosphere, due to the reoxidation of reduced S in the presence of high Fe(III). The high rates of C mineralization suggest that the Ganghwa intertidal mud flats are a significant sink against the external loading of organic compounds, and organic matter mineralization is enhanced by chemical exchange regulated by extreme tidal flushing and macro-microorganisms interactions.

High Glycolate Oxidase Activity Is Required for Survival of Maize in Normal Air

A mutant in the maize (Zea mays) Glycolate Oxidase1 (GO1) gene was characterized to investigate the role of photorespiration in C4 photosynthesis. An Activator-induced allele of GO1 conditioned a seedling lethal phenotype when homozygous and had 5% to 10% of wild-type GO activity. Growth of seedlings in high CO2 (1%-5%) was sufficient to rescue the mutant phenotype. Upon transfer to normal air, the go1 mutant became necrotic within 7 d and plants died within 15 d. Providing [1-14C]glycolate to leaf tissue of go1 mutants in darkness confirmed that the substrate is inefficiently converted to 14CO2, but both wild-type and GO-deficient mutant seedlings metabolized [1-14C]glycine similarly to produce [14C]serine and 14CO2 in a 1:1 ratio, suggesting that the photorespiratory pathway is otherwise normal in the mutant. The net CO2 assimilation rate in wild-type leaves was only slightly inhibited in 50% O2 in high light but decreased rapidly and linearly with time in leaves with low GO. When go1 mutants were shifted from high CO2 to air in light, they accumulated glycolate linearly for 6 h to levels 7-fold higher than wild type and 11-fold higher after 25 h. These studies show that C4 photosynthesis in maize is dependent on photorespiration throughout seedling development and support the view that the carbon oxidation pathway evolved to prevent accumulation of toxic glycolate.

Microbial Mn(IV) and Fe(III) reduction in northern Barents Sea sediments under different conditions of ice cover and organic carbon deposition

Carbon oxidation rates and pathways were determined in two sediments at latitude 751 and 771N southeast of Svalbard in the northern Barents Sea. Seasonal ice cover restricts primary production to few months a year, which determines the sedimentation rate of organic material to the seafloor. At one station, with seasonally extended ice cover, low organic carbon content and sedimentation rate combined with relatively high concentrations of Mn and Fe(III) oxides favored dissimilatory Fe and Mn reduction (98% of anaerobic carbon oxidation) over sulfate reduction in the top 12 cm of the sediment. In contrast, in a sediment that had not been ice covered for at least 12 months and with more organic carbon and a higher sedimentation rate, sulfate reduction was the most important anaerobic electronaccepting process (480% of anaerobic carbon oxidation). In the upper 3 cm, microbial Fe and sulfate reduction occurred simultaneously, and sulfate reduction dominated at 3–12 cm. Oxygen consumption rates (1.9 and 3.7 mmol m � 2 d � 1 ) and anaerobic CO2 production rates (1.3 and 6.4 mmol m � 2 d � 1 ) of both

Pathways of carbon oxidation in an Arctic fjord sediment (Svalbard) and isolation of psychrophilic and psychrotolerant Fe(III)-reducing bacteria

The main mineralization pathways were determined in permanently cold fjord sediment on the west coast of Svalbard. In whole core incubations, the total oxygen uptake rate was 4.2 ± 0.4 mmol m -2 d -1 and the sulfate reduction rate 2.6 ± 0.6 mmol m -2 d -1 at 0 to 20 cm depth. Sulfate reduction was the most important anaerobic mineralization process, accounting for 57% of anaerobic organic carbon oxidation in anoxic bag incubations of the top 5 cm of the sediment. The remaining 43% oxidation was attributed to microbial Fe(III) reduction. Both processes occurred con- currently in the uppermost 2 cm, and the Fe-reducing community appeared to be limited mainly by the availability of Fe(III). Below 2 cm, sulfate reduction was the dominant electron-accepting process. Calculations for the uppermost 10 cm of the sediment yielded the following contribution of the differ- ent respiratory pathways to total carbon oxidation: aerobic respiration 53%, sulfate reduction 34%, Fe(III) reduction 13%. In situ, the importance of Fe(III) reduction may vary through competition for substrate with oxygen- and nitrate-reducing bacteria in the surface sediment. Fe(III)-reducing bacte- ria belonging to the genera Desulfuromonas, Desulfuromusa, Shewanella and Desulfovibrio were isolated from enrichment cultures of 2 fjord sediments from Svalbard. Strains related to Desulfovib- rio reduced Fe(III) without energy generation for growth. All isolates were psychrophilic or psychro- tolerant and grew at -2°C, the freezing point of sea water, indicating adaptation to permanently cold temperatures. Besides Fe(III), the strains reduced other electron acceptors such as oxygen, man- ganese, elemental sulfur and sulfate.

Carbon mineralization in Arctic sediments northeast of Svalbard: Mn(IV) and Fe(III) reduction as principal anaerobic respiratory pathways

Carbon oxidation rates and pathways were determined in 3 sediments at latitude 79° to 81° N in the Barents Sea, where the ice cover restricts primary production to a few months of the year. Oxygen uptake (1.5 to 3.5 mmol m -2 d -1 ) and sulfate reduction (<0.1 to 0.22 mmol m -2 d -1 over 0 to 10 cm depth) rates were measured by whole core incubation. Pathways of anaerobic carbon oxida- tion were determined by combining results of anoxic sediment bag incubations with pore water and solid phase analyses of the sediments. In accordance with the high contents of solid Mn (≥60 µmol cm -3 ) and Fe(III) (≥108 µmol cm -3 ), dissimilatory Mn(IV) and Fe(III) reduction contributed between 69 and ≥90% to anaerobic carbon mineralization in the upper 10 cm of the sediments. At 2 of the 3 sta- tions, sulfate reduction rates were below our detection limit of 1 nmol cm -3 d -1 . Solid Mn and Fe(III) were abundant from the surface to 10 cm sediment depth and were apparently the only important anaerobic electron acceptors. At the third station, vertical zonation of anaerobic mineralization was observed, with Mn(IV) reduction at 0 to 3 cm followed by concurrent Fe(III) and sulfate reduction at 3 to 5 cm and sulfate reduction at 5 to 10 cm. Rates of microbial carbon oxidation were low compared to those in fjords on the west and south coasts of Svalbard. This is in accordance with the limited organic carbon supply by primary and secondary productivity caused by long periods of ice coverage.

Porewater Stoichiometry of Terminal Metabolic Products, Sulfate, and Dissolved Organic Carbon and Nitrogen in Estuarine Intertidal Creek-bank Sediments

Porewater equilibration samplers were used to obtain porewater inventories of inorganic nutrients (NH4+, NOx, PO43−), dissolved organic carbon (DOC) and nitrogen (DON), sulfate (SO42−), dissolved inorganic carbon (DIC), hydrogen sulfide (H2S), chloride (Cl−), methane (CH4) and reduced iron (Fe2+) in intertidal creek-bank sediments at eight sites in three estuarine systems over a range of salinities and seasons. Sulfate reduction (SR) rates and sediment particulate organic carbon (POC) and nitrogen (PON) were also determined at several of the sites. Four sites in the Okatee River estuary in South Carolina, two sites on Sapelo Island, Georgia and one site in White Oak Creek, Georgia appeared to be relatively pristine. The eighth site in Umbrella Creek, Georgia was directly adjacent to a small residential development employing septic systems to handle household waste. The large data set (>700 porewater profiles) offers an opportunity to assess system-scale patterns of porewater biogeochemical dynamics with an emphasis on DOC and DON distributions. SO42− depletion (SO42−)Dep was used as a proxy for SR, and (SO42−)Dep patterns agreed with measured (35S) patterns of SR. There were significant system-scale correlations between the inorganic products of terminal metabolism (DIC, NH4+ and PO43−) and (SO42−)Dep, and SR appeared to be the dominant terminal carbon oxidation pathway in these sediments. Porewater inventories of DIC and (SO42−)Dep indicate a 2:1 stoichiometry across sites, and the C:N ratio of the organic matter undergoing mineralization was between 7.5 and 10. The data suggest that septic-derived dissolved organic matter with a C:N ratio below 6 fueled microbial metabolism and SR at a site with development in the upland. Seasonality was observed in the porewater inventories, but temperature alone did not adequately describe the patterns of (SO42−)Dep, terminal metabolic products (DIC, NH4+, PO43−), DOC and DON, and SR observed in this study. It appears that production and consumption of labile DOC are tightly coupled in these sediments, and that bulk DOC is likely a recalcitrant pool. Preferential hydrolysis of PON relative to POC when overall organic matter mineralization rates were high appears to drive the observed patterns in POC:PON, DOC:DON and DIC:DIN ratios. These data, along with the weak seasonal patterns of SR and organic and inorganic porewater inventories, suggest that the rate of hydrolysis limits organic matter mineralization in these intertidal creek-bank sediments.

Enhanced deepwater circulation and shift of sedimentary organic matter oxidation pathway in the Okinawa Trough since the Holocene

High‐resolution biogeochemical and magnetic property analyses of a 20‐kyr sediment core in the Okinawa Trough revealed a significant upward decrease in total sulfur content (TS) at around 10 cal ka BP, which coincides with a transformation from foliation to anomalous sedimentary magnetic fabric, which indicates an enhancement of deepwater circulation. Synchronous change in biogeochemical and magnetic properties in sediments was likely triggered by the intensified Kuroshio Current, which strengthened surface water productivity and the relative input of marine organics to the sediments. However, this event did not promote sedimentary sulfur burial; instead, the synchronously enhanced deepwater circulation switched the organic carbon oxidation pathway from sulfate reduction to aerobic respiration which resulted in TS‐depleted sediments.