Dissolved organic carbon in sediments from the eastern North Atlantic

Profiles of dissolved organic carbon (DOC) were measured in the pore water of sediments from 1000, 2000 and 3500 m water depth in the eastern North Atlantic. A net DOC accumulation in the pore waters was observed, which followed closely the zonation of microbial respiration in these sediments. The concentration of pore water DOC in the zone of oxic respiration was elevated relative to that in the bottom ocean water. The resulting upward gradient across the sediment–water interface indicated a steady state diffusive benthic flux, F_DOC, of 0.25–0.44 mmol m⁻² day⁻¹ from these sediments. Subsequent increase in the concentration of DOC in the pore water occurred only in the sediments from 1000 and 2000 m water depth that supported anoxic respiration, leading to a deep concentration maximum. By contrast, in the sediments from 3500 m water depth, a deep concentration minimum was measured, coincident with minimal postoxic respiration in this near-abyssal setting. The gradient-based F_DOC represented approximately 14% of the total remineralized organic carbon (TCR=sum of F_DOC and depth-integrated organic carbon oxidation rate) in the sediments from 1000 and 2000 m water depth, while it was 36% of the TCR in the sediments from 3500 m water depth. A covariance of particulate organic carbon (POC) and pore water DOC with depth in the sediments was evident, more consistently at the deepest site. While the covariance can be related to biotic processes in these sediments, an alternative interpretation suggests a possible contribution of sorption to the biotic control on sedimentary organic carbon cycling. The steady state diagenetic conditions in which this may occur can be conceivable for some organic-poor deep-sea locations, but direct evidence is clearly required to validate them.     

Impact of hydrotalcite deposition on biogeochemical processes in a shallow tropical bay

The biogeochemistry of a tropical shoal bay (Melville Bay, Australia) impacted by the effluent release, precipitation, and deposition of hydrotalcite from an alumina refinery was studied in both wet and dry seasons. Within the deposition zone, sulfate reduction dominated benthic carbon cycling accounting for ≈100% of total microbial activity, with rates greater than those measured in most other marine sediments. These rapid rates of anoxic metabolism resulted in high rates of sulfide and ammonium production and low C:S ratios, implying significant preservation of S in stable sulfide minerals. Rates of total microbial activity were significantly less in control sediments of equivalent grain size, where sulfate reduction accounted for ≈50% of total benthic metabolism. Rates of planktonic carbon cycling overlying the deposition zone were also greater than those measured in the control areas of southern Melville Bay. At the sediment surface, productive algal and cyanobacterial mats helped stabilize the sediment surface and oxidize sulfide to sulfate to maintain a fully oxygenated water-column overlying the impacted zone. The mats utilized a significant fraction of dissolved inorganic N and P released from the sea bed; some nutrients escaped to the water-column such that benthic regeneration of NH?+ and PO?3? accounted for 100% and 42% of phytoplankton requirements for N and P, respectively. These percentages are high compared to other tropical coastal environments and indicate that benthic nutrient recycling may be a significant factor driving water-column production overlying the deposition zone. With regard to remediation, it is recommended that the sea bed not be disturbed as attempts at removal may result in further environmental problems and would require specific assessment of the proposed removal process.     

Multivariate analysis of .uorescence and source identi. cation of dissolved organic matter in Jiaozhou Bay, China

Hierarchical clustering analysis and principal component analysis (PCA) methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy (EEMs) data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter (DOM). The distribution of di.erent water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.     

Multivariate analysis of fluorescence and source identification of dissolved organic matter in Jiaozhou Bay, China

Hierarchical clustering analysis and principal component analysis (PCA) methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy (EEMs) data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter (DOM). The distribution of different water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.     

High-resolution Reconstruction of a Holocene Coastal Sequence (NW Germany) Using Inorganic Geochemical Data and Diatom Inventories

Holocene deposits of the NW German coastal plain consist of many different lithological facies, for example tidal flats, brackish water sediments and peat beds. The effects of the Holocene sea-level rise on palaeoenvironmental conditions of this coastal sequence were studied by inorganic geochemical methods in conjunction with diatom analyses. Three hundred samples from two parallel sediment cores which cover the entire NW German Holocene were taken at high resolution and were examined for major and minor elements and bulk parameters. Selected samples were analysed for redox-sensitive trace elements and REE distribution, reactive iron and bulk sediment³⁴S/³²S-ratios. Chemical parameters, for example Si/Al and Ca/Sr-ratios and total organic carbon (TOC) contents correlate with depositional factors such as wave-energy and lithofacies changes, which allow a detailed reconstruction of the palaeoenvironment. Diatom analyses reveal information about changes between marine, brackish and limnic conditions and serve to reconstruct palaeosalinity. Early diagenetic effects are evident in the TOC-rich intervals. Most peat layers are affected by sulphate reduction and resulting pyrite formation as well as by enrichments in redox-sensitive trace elements. The highest enrichments are seen for As, Mo, Re and U, indicating a distinct seawater influence. S-isotope ratios of peat samples are compatible with pyrite formation under both open- and closed-system conditions, depending on exposition to seawater. The inorganic geochemical and diatom data suggest limnic conditions at the base of the sequence and repeated changes towards marine conditions within the overlying clastic units. On the other hand, data obtained from the clastic units yield evidence of a recurrent succession from open to restricted marine, brackish-lagoonal, and finally fen environments. Clastic sediments overlying peat layers, correlate with the increase of marine-derived geochemical signatures and pelagic diatoms attest transgressive overlaps. The analyses suggest that major controls on the palaeoenvironments were (i) climate-related oscillations of the coast line and (ii) the morphology of the coastal region allowing marine incursions even into distal semi-terrestrial lowlands.     

固相萃取法提取典型海水溶解有机质及其红外光谱和固态13C核磁共振表征

由于海水盐度大、有机质含量低,从海水中提取和纯化克级溶解性有机质(dissolved organic matter,DOM)一直十分困难。基于Bond Elut PPL固相萃取小柱法进行海水DOM固体样品提取的放大试验,建立DOM自动化调酸、PPL树脂吸附技术,最后形成提纯、冷冻干燥PPL-DOM(通过PPL树脂提取的DOM)完整工艺。采用元素分析、三维荧光光谱、红外光谱和固态¹³C核磁共振(NMR)波谱法进行样品表征。结果表明:(1)该方法对近海表层海水DOM回收率稳定在50%以上,搭建的提取装置DOM日吸附量可达230mg;(2)鳌山湾四个季节批次PPL-DOM整体分析结果表明,样品的元素组成和光谱特征相似,表明方法适用性和稳定性较好;(3)三种水生态环境的PPL-DOM¹³C NMR谱图显示样品的基本特征相似,以烷基碳、碳水化合物碳、芳香碳和羧基碳/酰胺碳为主,其中偶极去相(dipolar dephasing)谱显示了DOM前体化合物来源的差异。多种结果表明放大后的PPL固相萃取法可稳定提取克级DOM样品。     

Phosphorus regeneration and burial in near-shore marine sediments (the Gulf of Trieste, northern Adriatic Sea)

According to bioassay studies and high dissolved nutrient N/P ratios in the seawater column, phosphorus (P) is thought to control marine productivity in the northern Adriatic Sea. P in near-shore marine sediments of the Gulf of Trieste, the northernmost part of the Adriatic Sea, was investigated using pore water P distributions, and benthic P flux studies under oxic and anoxic conditions. The data show that P regeneration is up to three-fold more extensive in sediments overlain by oxygen-depleted waters and proceeds in parallel with Fe and Mn enhanced benthic fluxes. It appears from the incubation experiments that degradation of sedimentary organic matter is the main contribution to the flux of P at the sediment–water interface, while the release of phosphate adsorbed on the iron oxide surface is of minor importance.It appears that about 50% of P in the Gulf of Trieste is retained within in the sediments, probably bonded to clay minerals and carbonate grains or precipitated as fluoroapatite. In these sediments total P (P_tot) is preserved preferentially over organic C (C_org). P regenerated from surficial sediments contributes about 1/3 of the P that is assimilated by benthic microalgae. The phytoplankton P requirement should be entirely supplied from fresh-water sources. These results suggest that oxygen depletion in coastal areas caused by eutrophication enhances P regeneration from sediments, providing the additional P necessary for increased biological productivity. The development of anoxic bottom waters in coastal areas enhances the recycling of P, exacerbating the nutrient requirement in the area. A geochemical record of P burial in a longer sedimentary sequence revealed an increasing trend of P_tot and organic P (P_org) contents occurring approximately 50 years BP (after 1950), probably due to increasing use of inorganic fertilizers and detergents in the area.     

Molybdenum in pore waters of anoxic marine sediments by electron paramagnetic resonance spectroscopy

Pore water samples of anoxic sediments from Great Bay, N.H. and Jeffrey's Basin, New England continental shelf, have been analyzed for dissolved molybdenum by the electron paramagnetic resonance (EPR) spectroscopy technique of Hanson et al. (1977). The method has been modified so that only 0.50 ml of pore water sample is utilized for the analysis. The concentrations of Mo in the Jeffrey's Basin pore fluids are as much as an order of magnitude higher than that of the overlying water, while the estuarine water concentrations are only twice that of the overlying water.The Mo in the pore water is negatively correlated to dissolved Fe²⁺ and positively correlated to the precent of organic carbon in the sediments. This suggests that Mo is remobilized by the anaerobic degradation of sedimentary organic matter and is not directly incorporated into iron pyrite during early diagenesis.     

高原湖泊溶解有机质的三维荧光光谱特性初步研究

提要近年来,荧光光谱技术被广泛应用于研究天然水体中溶解有机质(Dissolved Organic Matter,DOM)的物理化学特性。为了理解高原湖泊中DOM的组成、荧光光谱特性及其在湖泊水体中的垂直分布情况,作者利用荧光发射光谱、三维荧光光谱研究云贵高原湖泊红枫湖和百花湖中的DOM。结果显示,高原湖泊DOM主要表现为类富里酸荧光,包括可见区和紫外区两种类型的荧光峰,各种天然水体中都有报道的类蛋白荧光在红枫湖DOM中并不明显,而在百花湖DOM中则有较强的类蛋白荧光。溶解有机质所含三种类型荧光峰(PeakA:紫外区类富里酸荧光峰;PeakB:可见区类富里酸荧光峰;PeakC:类蛋白荧光峰)的荧光强度与溶解有机碳之间没有明显的线性相关关系,可能与高原湖泊水体pH值、DOM在湖泊不同深度由于受到光降解、微生物降解等作用存在差异等因素有关。与有机质结构和成熟度有关的荧光峰比值r(A,C)在1.40—2.09范围内,红枫湖南湖、百花湖DOM样品的r(A,C)值随着水体深度有下降的趋势,而红枫湖北湖DOM的r(A,C)值则随着水体深度有较大起伏,揭示了高原湖泊水体中DOM的结构以及分布情况存在差异。另外,r(A,C)值与pH之间具有良好的正相关关系,其相关系数红枫湖南湖DOM为0.95,百花湖两个采样点DOM分别为0.67、0.75,而红枫湖北湖DOM则显示出一定的负相关性(R2=0.45)。     

The partitioning of organic carbon fluxes and sedimentary organic matter decomposition rates in the ocean

The partitioning of annual organic carbon fluxes from five stations located in the vicinity of the Pacific-Antarctic Ridge and the Peru continental margin suggests that 35–85% of the total near-bottom organic carbon flux is utilized at or near the sediment-water interface. These estimates have large uncertainties, but illustrate that assessments of organic carbon utilization can be made by several stepwise approaches which are generally applicable to a wide spectrum of marine environments.In one approach, the mineralization of organic carbon from the sediments was predicted from both sedimentary organic carbon and pore water nutrient profiles with comparable results. Neglecting sediment mixing, the rate constants of the anoxic sediments off Peru range from 0.1 × 10^?3 to 4 × 10^?3 y^?1, and rate constants derived for oxic SW Pacific sediments range from 3 × 10^?4 to 7 × 10^?4 y^?1. As with other values reported for sulfate reducing sediments by Toth and Lerman (1977) and for oxic central Pacific sediments by Müller and Mangini (1980), log-log plots of rate constants vs. sedimentation rate define two parallel linear relationships for oxic and anoxic sediments, respectively. The apparently enhanced rates for oxic environments may result from large benthic organisms which redistribute a portion of the available detritus and in doing so convert it into more easily accessible and metabolizable organic matter. In low-oxygen environments, bottom feeders and infauna are less abundant and more likely to irrigate rapidly accumulating sediments.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Trace element and molecular markers of organic carbon dynamics along a shelf–basin continuum in sediments of the western Arctic Ocean

Molecular organic biomarkers together with trace element composition were investigated in sediments east of Barrow Canyon in the western Arctic Ocean to determine sources and recycling of organic carbon in a continuum from the shelf to the basin. Algal biomarkers (polyunsaturated and short-chain saturated fatty acids, 24-methylcholesta-5,24(28)-dien-3β-ol, dinosterol) highlight the substantial contribution of organic matter from water column and sea-ice primary productivity in shelf environments, while redox markers such as acid volatile sulfide (AVS), Mn, and Re indicate intense metabolism of this material leading to sediment anoxia. Shelf sediments also receive considerable inputs from terrestrial organic carbon, with biomarker composition suggesting the presence of multiple pools of terrestrial organic matter segregated by age/lability or hydrodynamic sorting. Sedimentary metabolism was not as intense in slope sediments as on the shelf; however, sufficient labile organic matter is present to create suboxic and anoxic conditions, at least intermittently, as organic matter is focused towards the slope. Basin sediments also showed evidence for episodic delivery of labile organic carbon inputs despite the strong physical controls of water depth and sea-ice cover. Principal components analysis of the lipid biomarker data was used to estimate fractions of preserved recalcitrant (of terrestrial origin) and labile (of marine origin) organic matter in the sediments, with ranges of 12–79%, 14–45%, and 37–66% found for the shelf, slope, and basin cores, respectively. On average, the relative preserved terrestrial organic matter in basin sediments was 56%, suggesting exchange of organic carbon between nearshore and basin environments in the western Arctic.     

Characterization of dissolved organic matter fluorescence in the South Atlantic Bight with use of PARAFAC model: Interannual variability

Systematic water sampling for characterization of chromophoric dissolved organic matter (CDOM) in the coastal South Atlantic Bight, was conducted as part of the long term Coastal Ocean Research and Monitoring Program (CORMP). Water samples were collected during a 3.5 year period, from October 2001 until March 2005, in the vicinity of the Cape Fear River (CFR) outlet and in adjacent Onslow Bay (OB). During this study there were two divergent hydrological and meteorological conditions in the CFR drainage area: a severe drought in 2002, followed by the very wet year of 2003. CDOM was characterized optically by the absorption coefficient at 350 nm, the spectral slope coefficient (S), and by Excitation Emission Matrix (EEM) fluorescence. Parallel Factor Analysis (PARAFAC) was used to assess CDOM composition from EEM spectra and six components were identified: three terrestrial humic-like components, one marine humic-like component and two protein-like components. Terrestrial humic-like components contributed most to dissolved organic matter (DOM) fluorescence in the low salinity plume of the CFR. The contribution of terrestrial humic-like components to DOM fluorescence in OB was much smaller than in the CFR plume area. Protein-like components contributed significantly to DOM fluorescence in the coastal ocean of OB and they dominated DOM fluorescence in the Gulf Stream waters. Hydrological conditions during the observation period significantly impacted both concentration and composition of CDOM found in the estuary and coastal ocean. In the CFR plume, there was an order of magnitude difference in CDOM absorption and fluorescence intensity between samples collected during the drought compared to the wet period. During the drought, CDOM in the CFR plume was composed of equal proportions of terrestrial humic-like components (ca. 60% of the total fluorescence intensity) with a significant contribution of proteinaceous substances (ca. 20% of the total fluorescence). During high river flow, CDOM was composed mostly of humic substances (nearly 75% of total fluorescence) with minor contributions by proteinaceous substances. The impact of changes in fresh water discharge patterns on CDOM concentration and composition was also observed in OB, though to a lesser degree.     

Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

The sources and distribution of organic matter (OM) in surface waters and sediments from Winyah Bay (South Carolina, USA) were investigated using a variety of analytical techniques, including elemental, stable isotope and organic biomarker analyses. Several locations along the estuary salinity gradient were sampled during four different periods of contrasting river discharge and tidal range. The dissolved organic carbon (DOC) concentrations of surface waters ranged from 7 mg l⁻¹ in the lower bay stations closest to the ocean to 20 mg l⁻¹ in the river and upper bay samples. There was a general linear relationship between DOC concentrations and salinity in three of the four sampling periods. In contrast, particulate organic carbon (POC) concentrations were significantly lower (0.1–3 mg l⁻¹) and showed no relationship with salinity. The high molecular weight dissolved OM (HMW DOM) isolated from selected water samples collected along the bay displayed atomic carbon:nitrogen ratios ([C/N]a) and stable carbon isotopic compositions of organic carbon (δ¹³C_OC) that ranged from 10 to 30 and from −28 to −25‰, respectively. Combined, such compositions indicate that in most HMW DOM samples, the majority of the OM originates from terrigenous sources, with smaller contributions from riverine and estuarine phytoplankton. In contrast, the [C/N]a ratios of particulate OM (POM) samples varied significantly among the collection periods, ranging from low values of 5 to high values of >20. Overall, the trends in [C/N]a ratios indicated that algal sources of POM were most important during the early and late summer, whereas terrigenous sources dominated in the winter and early spring.In Winyah Bay bottom sediments, the concentrations of the mineral-associated OM were positively correlated with sediment surface area. The [C/N]a ratios and δ¹³C_OC compositions of the bulk sedimentary OM ranged from 5 to 45 and from −28 to −23‰, respectively. These compositions were consistent with predominant contributions of terrigenous sources and lesser (but significant) inputs of freshwater, estuarine and marine phytoplankton. The highest terrigenous contents were found in sediments from the river and upper bay sites, with smaller contributions to the lower parts of the estuary. The yields of lignin-derived CuO oxidation products from Winyah Bay sediments indicated that the terrigenous OM in these samples was composed of variable mixtures of relatively fresh vascular plant detritus and moderately altered soil OM. Based on the lignin phenol compositions, most of this material appeared to be derived from angiosperm and gymnosperm vascular plant sources similar to those found in the upland coastal forests in this region. A few samples displayed lignin compositions that suggested a more significant contribution from marsh C₃ grasses. However, there was no evidence of inputs of Spartina alterniflora (a C₄ grass) remains from the salt marshes that surround the lower sections of Winyah Bay.     

环境因子对菲在黄河口沉积物上吸附的影响

为研究多环芳烃从河口到近海的环境归趋行为与生态风险,考察了沉积物质量浓度、溶解性有机质、温度、盐度4种典型环境因子对菲在黄河口沉积物上吸附的影响,比较了黄河口与近海两种沉积物对菲的吸附性能。研究结果表明,沉积物质量浓度越低,单位质量颗粒物的菲吸附量越高;共存的溶解性有机质对菲的吸附具有增促作用,且腐殖酸比黄腐酸的作用更显著;温度的升高不利于菲的吸附,而盐度的增加有利于菲的吸附。菲在沉积物上的吸附是分配作用与表面吸附两种行为的耦合,其中黄河口沉积物以表面吸附为主,而近海沉积物以分配作用为主。近海沉积物菲吸附量显著高于黄河口沉积物菲吸附量。基于此,菲从河口到近海的迁移过程中,更易于在沉积物表面发生吸附沉降,从而可能降低水相中的生态危害,但对近海底栖生物具有潜在的健康生态风险。     

Optical properties of low molecular weight and colloidal organic matter: Application of the ultrafiltration permeation model to DOM absorption and fluorescence

Cross-flow ultrafiltration (CFF) is often used to obtain separation and concentration of colloids from bulk natural water samples. Application of the ultrafiltration permeation model allows the quantitative determination of the low molecular weight material (LMW, < 1 kDa) and colloids in bulk dissolved organic matter (DOM) from measurements of time series permeate samples obtained from CFF. Detailed analysis of a Yukon River water sample shows that DOM absorption coefficient and fluorescence follow the permeation model and that the complex spectral optical properties of LMW DOM can be reconstructed from CFF data. A combination of measured and modeled data indicates that the LMW contribution to bulk DOM optical properties obtained from CFF can be grossly underestimated by the use of a low concentration factor (CF, the ratio of initial sample volume to retentate volume). Even at a relatively high CF of 19, optical properties of LMW DOM calculated from measurements of the retentate or integrated permeate would underestimate true values by 5–36%. In the Yukon River sample, LMW dissolved organic carbon represented 26% of the bulk concentration, but only 3–14% of the colored DOM was in the LMW fraction while 31–33% of bulk DOM florescence was due to LMW DOM. The contrasting optical properties of LMW and colloidal DOM support the concept that analysis of bulk DOM absorption and fluorescence properties reveals information about DOM molecular weight.     

Tracing of dissolved organic matter from the Sepetiba Bay (Brazil) by PARAFAC analysis of total luminescence matrices

Fluorescent excitation-emission matrices (FEEM) of the fluorescent dissolved organic matter (FDOM) are widely used for DOM characterization and tracing. In this work, a set of FEEM from sampling campaigns in the Sepetiba Bay (Brazil) was decomposed into independent components using the parallel factor analysis (PARAFAC) algorithm. Four independent components were extracted describing the total fluorescence of the FDOM. The well described peaks A, C, M, B and T were found, and a new peak, A', linked to the C peak, was detected. Relative contribution of each of four components to the total fluorescence confirms that the coastal water has DOM of terrestrial origin, except for the 275Ex/400-500Em range (nm), which primarily occurs in marine waters.     

Impacts of diverted freshwater on dissolved organic matter and microbial communities in Barataria Bay, Louisiana, U.S.A

Here we present results of an initial assessment of the impacts of a water diversion event on the concentrations and chemical composition of dissolved organic matter (DOM) and bacterioplankton community composition in Barataria Bay, Louisiana U.S.A, an important estuary within the Mississippi River Delta complex. Concentrations and spectral properties of DOM, as reflected by UV/visible absorbance and fluorescence, were strikingly similar at 26 sites sampled along transects near two western and two eastern areas of Barataria Bay in July and September 2010. In September 2010, dissolved organic carbon (DOC) was significantly higher (568.1-1043 μM C, x=755.6+/-117.7 μM C, n=14) than in July 2010 (249.1-577.1 μM C, x=383.7+/-98.31 μM C, n=14); conversely, Abs254 was consistently higher at every site in July (0.105-0.314) than in September (0.080-0.221), averaging 0.24±0.06 in July and 0.15±0.04 in September. Fluorescence data via the fluorescence index (FI450/500) revealed that only 30% (8 of 26) of the July samples had an FI450/500 above 1.36, compared to 96% (25 of 26) for the September samples. This indicates a more terrestrial origin for the July DOM. Bacterioplankton from eastern sites differed in composition from bacterioplankon in western sites in July. These differences appeared to result from reduced salinities caused by the freshwater diversion. Bacterioplankton communities in September differed from those in July, but no spatial structure was observed. Thus, the trends in bacterioplankton and DOM were likely due to changes in water masses (e.g., input of Mississippi River water in July and a return to estuarine waters in September). Discharge of water from the Davis Pond Freshwater Diversion (DPFD) through Barataria Bay may have partially mitigated some adverse effects of the oil spill, inasmuch as DOM is concerned.     

Sulfur speciation in marine sediments impacted by gas emissions in the northern part of the South China Sea

Three cores of marine sediments from the Shenhu area in the northern part of the South China Sea were analyzed by XANES analysis for sulfur speciation. The area has been investigated for the presence of hydrocarbons and potential gas hydrate formations. Cored samples of site 4B showed a specific profile of sulfur speciation with sharp and frequent variations in relative contents of sulfate and sulfide, which differed greatly from the profiles obtained for the sediments taken at sites 5B and 6A. The upper part of core 4B (of 0–95 cm) was soft and rich in pore water, containing mainly coarse silt sand. The lower part of the core (i.e., depth > 95 cm) was relatively dryer and darker in color, and dominated by silts and clay resembling sediments from mud volcanoes. The sulfur speciation results revealed that sulfate makes up almost 100 percent of all sulfur species in the upper part of the core 4B, which indicates strong oxidizing conditions, whereas the lower part of the same core has high relative contents of sulfide, sometimes close to 100% S²⁻. In the lower part of the core, the relative content of sulfide and sulfate changes rapidly and frequently, indicating rapid changes of oxidizing and reducing conditions. On the other hand, the vertical profiles of sulfur species for the cores from sites 5B and 6A are relatively consistent with lower sulfide contents indicative of stable and weaker reducing conditions. We hypothesize that the frequent and sharp variations in the ratios of sulfide to sulfate at site 4B may indicate some intermittent eruption of methane with clay from petroleum reservoirs underneath the sea floor over a relatively short period of time.     

A sulfur budget for the Black Sea anoxic zone

A budget for the sulfur cycle in the Black Sea is proposed which incorporates specific biogeochemical process rates. The average sulfide production in the water column is estimated to be 30–50 Tg yr⁻¹, occurring essentially in the layer between 500 and 2000 m. About 3.2–5.2 Tg sulfide yr⁻¹ form during sulfate reduction in surface sediments of the anoxic zone. Total sulfur burial in anoxic sediments of 1 Tg yr⁻¹ consists of 10–70% (ca. 40–50% is the average) water column formed (syngenetic) component, the rest being diagenetic pyrite. As a maximum, between 3 and 5 Tg yr⁻¹ contribute sulfide to the bottom water or diffuse downward in the sediment. About 20–50 Tg yr⁻¹ sulfide is oxidized mostly at the chemocline and about 10–20% of this amount (4.4–9.2 Tg yr⁻¹) below the chemocline by the oxygen of the Lower Bosphorus Current. A model simulating the vertical distribution of sulfide in the Black Sea water column shows net consumption in the upper layers down to ca. 500 m, essentially due to oxidation at the chemocline, and net production down to the bottom. On the basis of the calculated budget anoxic conditions in the Black Sea are sustained by the balance between sulfide production in the anoxic water column and oxidation at the chemocline. On average the residence time of sulfide in the anoxic zone is about 90–150 yr, comparable to the water exchange time between oxic and anoxic zones. Hydrophysical control on the sulfur cycle appears to be the main factor regulating the extent of anoxic conditions in the Black Sea water column, rather than rates of biogeochemical processes.