Bacterial reworking of terrigenous and marine organic matter in estuarine water columns and sediments

Amino acids and the bacterial biomarkers muramic acid and d-amino acids were quantified in the ultrafiltered dissolved, particulate and sedimentary organic matter (UDOM, POM and SOM) of the St. Lawrence system (Canada). The main objectives were to better describe the fate of terrigenous and marine organic matter (OM) in coastal zones and to quantify the bacterial contributions to OM composition and diagenesis. Regardless of their origin, the carbon (C) content of the particles substantially decreased with depth, especially near the water-sediment interface. Major diagenetic transformations of organic nitrogen (N) were revealed and important differences were observed between terrigenous and marine OM. Amino acid contents of particles decreased by 66-93% with depth and accounted for 12-30% of the particulate C losses in marine locations. These percentages were respectively 18-56% and 7-11% in the Saguenay Fjord where terrigenous input is important. A preferential removal of particulate N and amino acids with depth or during transport was measured, but only in marine locations and for N-rich particles. This leads to very low amino acid yields in deep marine POM. However, these yields then increased to a level up to three times higher after deposition on sediments, where SOM showed lower C:N ratios than deep POM. The associated increase of bacterial biomarker yields suggests an active in situ resynthesis of amino acids by benthic bacteria. The N content of the substrate most likely determines whether a preferential degradation or an enrichment of N and amino acid are observed. For N-poor OM, such as terrigenous or deep marine POM, the incorporation of exogenous N by attached bacteria can be measured, while the organic N is preferentially used or degraded in N-rich OM. Compared to the POM from the same water samples, the extracted UDOM was poor in N and amino acids and appeared to be mostly made of altered plant and bacterial fragments. Signs of in situ marine production of UDOM were observed in the most marine location. The POM entering the St. Lawrence Upper Estuary and the Saguenay Fjord appeared made of relatively fresh vascular plant OM mixed with highly altered bacterial debris from soils. In contrast, the POM samples from the more marine sites appeared mostly made of fresh planktonic and bacterial OM, although they were rapidly degraded during sinking. Based on biomarker yields, bacterial OM represented on average ∼20% of bulk C and approximately 40-70% of bulk N in POM and SOM, with the exception of deep marine POM exhibiting approximately two times lower bacterial contributions.     

澳大利亚北卡那封盆地中上三叠统Mungaroo三角洲陆源有机质分布特征

北卡那封盆地中上三叠统Mungaroo组发育巨型浅水辫状河三角洲——Mungaroo三角洲。利用钻井、岩心资料,并结合区域地质背景,将Mungaroo三角洲划分为近端三角洲平原、远端三角洲平原、三角洲前缘、前三角洲4个沉积亚相,其中近端三角洲平原与远端三角洲平原亚相分布广泛,三角洲前缘与前三角洲亚相欠发育。陆源有机质分析表明:(1)研究区目的层段沉积时期,在环特提斯洋巨型季风洪水的影响下,泥炭沼泽普遍遭受冲刷改造,有机质类型主要为分散有机质,仅远端三角洲平原发育薄煤层;(2)不同相带受季风洪水的影响差异较大,近端三角洲平原受洪水改造强烈,砂砾岩发育,夹薄层泥岩,泥岩中有机质显微组分主要为惰质组,镜质组大部分遭受氧化;(3)远端三角洲平原的沼泽沉积尽管受到洪水频繁冲刷,但仍发育多套薄煤层,泥岩中陆源有机质最为丰富,显微组分以镜质组为主;(4)三角洲前缘和前三角洲相带窄,沉积物中陆源有机质含量较低。远端三角洲平原烃源岩有机质生烃潜力最大,除发育广泛的薄煤层外,暗色泥岩中平均TOC含量可达4.11％。上述沉积相带与陆源有机质分布规律体现了强季风洪水影响下大型辫状河三角洲的沉积特点。     

Sources and distribution of terrigenous organic matter delivered by the Atchafalaya River to sediments in the northern Gulf of Mexico

Suspended sediments (SS) from the Atchafalaya River (AR) and the Mississippi River and surficial sediment samples from seven shallow cross-shelf transects west of the AR in the northern Gulf of Mexico were examined using elemental (%OC, C/N), isotopic (δ¹³C, Δ¹⁴C), and terrigenous biomarker analyses. The organic matter (OM) delivered by the AR is isotopically enriched (∼−24.5‰) and relatively degraded, suggesting that soil-derived OM with a C4 signature is the predominant OM source for these SS. The shelf sediments display OC values that generally decrease seaward within each transect and westward, parallel to the coastline. A strong terrigenous C/N (29) signal is observed in sediments deposited close to the mouth of the river, but values along the remainder of the shelf fall within a narrow range (8-13), with no apparent offshore trends. Depleted stable carbon isotope (δ¹³C) values typical of C3 plant debris (−27‰) are found near the river mouth and become more enriched (−22 to −21‰) offshore. The spatial distribution of lignin in shelf sediments mirrors that of OC, with high lignin yields found inshore relative to that found offshore (water depth > 10 m).The isotopic and biomarker data indicate that at least two types of terrigenous OM are deposited within the study area. Relatively undegraded, C3 plant debris is deposited close to the mouth of the AR, whereas more degraded, isotopically enriched, soil-derived OM appears to be deposited along the remainder of the shelf. An important input from marine carbon is found at the stations offshore from the 10-m isobath. Quantification of the terrigenous component of sedimentary OM is complicated by the heterogeneous composition of the terrigenous end-member. A three-end-member mixing model is therefore required to more accurately evaluate the sources of OM deposited in the study area. The results of the mixing calculation indicate that terrigenous OM (soil-derived OM and vascular plant debris) accounts for ∼79% of the OM deposited as inshore sediments and 66% of OM deposited as offshore sediments. Importantly, the abundance of terrigenous OM is 40% higher in inshore sediments and nearly 85% higher in offshore sediments than indicated by a two-end-member mixing model. Such a result highlights the need to reevaluate the inputs and cycling of soil-derived OM in the coastal ocean.     

Isotopic markers of organic matter transformation at the water-sediment geochemical boundary

Doklady Earth Sciences -     

Early evolution and transformation of organic matter in the active continental Jordan Rift Valley

A sequence of alternating lacustrine marls, peat and basalts was penetrated in the Notera-3 well in the northern part of the Jordan Rift, Israel. The 2781 m thick sequence, ranges from Upper Miocene to Recent, reflects high sedimentation rate in the active continental rift associated with the Dead Sea Transform. The deep burial and the relatively high geothermal gradient (40°C km⁻¹) compensate for the short time span so that coalification expressed by vitrinite reflectance consistently increases with depth, from about 0.32% Ro at 1040 m to 0.48% Ro at 2495 m.Analysis of the peat reveals that the O/C, S/C and δ¹³C of the humic acids (HA) and the heavy to light normal alkane ratios are the only parameters sensitive enough to express this slight maturation increase with depth. A sharp δ¹³C change from about − 18‰ prevailing in the uppermost meters to an average of − 27.5‰ at 15 m and deeper reflects a change in the higher plant source of the peat (from C4 to C3 plants) rather than an early diagenetic modification.The δ¹³C, O/C, S/C and N/C ratios are usually lower in the kerogens than in the corresponding HA. The decrease in the δ¹³C and the O/C ratios are explained by elimination of oxygen-containing functional groups during transformation and by polymerization effects. The gradual decrease in the ¹²C and the O/C of the HA with depth are attributed to decarboxylation coupled with kinetic effects. The N/C depletion during the transformation from HA to kerogens probably results from the breakdown of amino acids. The S/C ratio which decreases both during this transformation and also with maturation is most readily explained by the breakdown of ester sulfate-containing groups such as sulfated polysaccarids, which formed diagenetically during the humification process.     

Mineral matrix influence on the dynamics and products of organic matter catagenetic transformation

Geochemical data available on concrete geological objects are examined in terms of catagenetic changes of kerogen elemental composition and amounts and compositions of chloroform extract and hydrocarbons. The results obtained by the authors testify to a significant influence of mineral matrix type and content on the dynamics and compositions of products derived from the organic matter alteration. This influence is primarily observable up to the middle catagenesis grades.     

Revisiting amorphous organic matter in Kimmeridgian laminites: what is the role of the vulcanization process in the amorphization of organic matter?

Kimmeridgian bituminous laminites from Orbagnoux (France) contain abundant amorphous organic matter (AOM). Previous studies have shown that the vulcanization pathway was the dominant preservation mechanism of AOM in these laminites, and led to its structureless aspect (a process called amorphization) at the nanoscale. In contrast, new observations in scanning electron microscopy and transmission electron microscopy demonstrate that this AOM exhibits typical cyanobacterial structures (exopolymeric substances, filamentous and coccoid bacteria) and ultralaminae. This identification is supported by a comparison with a recent cyanobacterial biofilm considered as an analogue. Moreover, this comparison demonstrates that ultralaminae in the Orbagnoux environment cannot solely be attributed to microalgal cell walls, but also to constituents of cyanobacteria. The microscopic identification of a ubiquitous cyanobacterial imprint demonstrates that the selective preservation pathway has been largely underestimated in Orbagnoux AOM and/or that the vulcanization process does not lead to the amorphization of organic matter automatically.     

Integrated transfers of terrigenous organic matter to lakes at their watershed level: A combined biomarker and GIS analysis

Terrigenous organic matter (TOM) transfer from a watershed to a lake plays a key role in contaminants fate and greenhouse gazes emission in these aquatic ecosystems. In this study, we linked physiographic and vegetation characteristics of a watershed with TOM nature deposited in lake sediments. TOM was characterized using lignin biomarkers as indicators of TOM sources and state of degradation. Geographical information system (GIS) also allowed us to integrate and describe the landscape morpho-edaphic characteristics of a defined drainage basin. Combining these tools we found a significant and positive relationship (R² = 0.65, p < 0.002) between mean slope of the watershed and the terrigenous fraction estimated by Λ8 in recent sediments. The mean slope also correlated with the composition of TOM in recent sediments as P/(V + S) and 3,5Bd/V ratios significantly decreased with the steepness of the watersheds (R² = 0.57, p < 0.021 and R² = 0.71, p < 0.004, respectively). More precisely, areas with slopes comprised between 4° and 10° have a major influence on TOM inputs to lakes. The vegetation composition of each watershed influenced the composition of recent sediments of the sampled lakes. The increasing presence of angiosperm trees in the watershed influenced the export of TOM to the lake as Λ8 increased significantly with the presence of this type of vegetation (R² = 0.44, p < 0.019). A similar relationship was also observed with S/V ratios, an indicator of angiosperm sources for TOM. The type of vegetation also greatly influenced the degradation state of OM. In this study, we were able to determine that low-sloped areas (0-2°) act as buffer zones for lignin inputs and by extension for TOM loading to sediments. The relative contribution of TOM from the soil organic horizons also increased in steeper watersheds. This study has significant implications in our understanding of the fate of TOM in lacustrine ecosystems.     

The role of hydrology in annual organic carbon loads and terrestrial organic matter export from a midwestern agricultural watershed

Defining the control that hydrology exerts on organic carbon (OC) export at the watershed scale is important for understanding how the source and quantity of OC in streams and rivers is influenced by climate change or by landscape drainage. To this end, molecular (lignin phenol), stable carbon isotope, and dissolved organic carbon (DOC) data were collected over a range of flow conditions to examine the influence of hydrology on annual OC export from an 850 km² Midwestern United States agricultural watershed located in west central Indiana. In years 2002 and 2003, modeled annual DOC loads were 19.5 and 14.1 kg ha⁻¹yr⁻¹, while 71% and 85%, respectively, of the total annual OC was exported in flow events occurring during less than 20% of that time. These results highlight the importance of short-duration, high-discharge events (common in smaller watersheds) in controlling annual OC export. Based on reported increases in annual stream discharge coupled with current estimates of DOC export, annual DOC loads in this watershed may have increased by up to 40% over the past 50 years. Molecular (lignin phenol) characterization of quantity and relative degradation state of terrestrial OC shows as much temporal variability of lignin parameters (in high molecular weight dissolved organic carbon) in this one watershed as that demonstrated in previously published studies of dissolved organic matter in the Mississippi and Amazon Rivers. These results suggest that hydrologic variability is at least as important in determining the nature and extent of OC export as geographic variability. Moreover, molecular and bulk stable carbon isotope data from high molecular weight dissolved organic carbon and colloidal organic carbon showed that increased stream flow from the study watershed was responsible for increased export of agriculturally derived OC. When considered in the context of results from other studies that show the importance of flood events and in-stream processing of terrestrial organic carbon, our results show how hydrologic variability in smaller watersheds can reflect landscape-scale carbon dynamics in ways that cannot necessarily be measured at the outlets of large rivers due to multiple source signals and attenuated hydrology.     

The Role of Organic Matter in the Formation of Siderite from Xuanlong Area,Hebei Province

Based on the analysis of siderite distribution,occurrence,chemical compositionk,structureal characteristics,carbon-oxygen isotopic characteristics and relationship between siderite and hematite,this paper presents a systematic study of siderite in the region studied.suggesting that the siderite in the Xuanlong area genetically resulted from organically reduced primary hematite during the diagenesis.The ferric and ferrous relations directly depend on organic contents.In the presence of organic matter ferrous iron can be converted to ferric iron through or ganic reduction.The above conclusion has also been proved by organic geochemistry.data.     

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.     

有机质在铀成矿过程中作用的实验模拟研究

沉积型铀矿的形成与有机质存在密切联系。实验模拟研究表明:芳香有机酸在弱酸到弱碱性条件下很容易和铀酰根离子发生配位反应,它能通过羧基上的氧原子以多种配位形式和铀形成配位键。此结果验证了前人的一些结论,并直观地展现了有机质的主要官能团与铀离子在溶液中的一些迁移形式。模拟实验结果也显示了烃类在水热条件下对铀成矿的还原作用,它能将六价铀还原成四价铀而沉淀下来。     

Photodegradation of estuarine dissolved organic matter: a multi-method assessment of DOM transformation

A multi-method approach was applied to study changes in dissolved organic matter (DOM) at three estuarine sites with varying salinity, as well as changes resulting from experimental photodegradation. Following measurement of ultraviolet and visible absorption spectra of bulk samples, DOM was isolated using C₁₈ solid phase extraction. The extract was characterized using high performance size exclusion chromatography (HP-SEC) and molecular level characterization was conducted via direct temperature-resolved mass spectrometry (DT-MS) and electrospray ionization mass spectrometry (ESI-MS). The molecular weight distribution of DOM as determined from HP-SEC and ESI-MS varied between techniques, but generally decreased down estuary and with photodegradation for both approaches. Relative differences in molecular weight were significantly correlated with the ratio of absorption coefficients at 254/365 nm. Additionally, photobleaching was significantly correlated with mass spectral characteristics from both DT-MS and ESI-MS. Principal component analysis of DT-MS spectra showed that photoexposure removed different mass spectral characteristics depending on sampling site; however, upon photodegradation, the mass spectral characteristics of both marine DOM and terrestrially dominated DOM approached a common spectrum. We interpret this spectrum, characterized by fragments from aromatic and carbohydrate-like precursors, as photochemically refractory DOM. Our results show that multiple approaches that characterize different aspects of DOM can provide complementary information about its sources and transformation. More specifically, photobleaching results in decreased light absorbance, decreased molecular weight and shifts in the relative abundance of classes of compounds (and broad shifts in m/z values); moreover, these transformations result in photodegraded samples from a low-salinity site which are compositionally similar to samples collected from a mid-salinity site further downstream.     

The Role of Organic Matter During Metal Enrichment in Permian Kupferschiefer of the Rudna Mine,Southwest Poland

The bulk composition of organic matter and saturated and aromatic hydrocarbons extracted from 16 samples collected from two Kuperschiefer profiles in the Rudna mine,Southwest Poland has been analyzed to study the role of organic matter during base metal enrichment in the Kupferschiefer shale.The results indicated that the extract yields and saturated hydrocarbon yields decreased with increasing base metal contents.GC and GC/MS analyses indicated that n -alkanes and alkylated aromatic compounds were depleted and may have served as hydrogen donators for thermochemical sulfate reduction.The enrichment of base metal is closely connected with the destruction of hydrocarbons.     

Conditions of accumulation and transformation of organic matter in Recent and Quaternary deposits (Caspian shelf)

This paper reports the study of organic material in cores from several areas of the western Caspian Shelf, and the conditions of alterations of the organic material. Cores from a nearby onshore locality had a similar content and composition of organic material. Grain size, at least in the clay to silt range, appeared to have little effect on content or transformation of the organic material, although exceptions are noted. In general, the bitumen content of the older sediments is greater than that of Recent ones. Gaseous hydrocarbons heavier than methane (ethane, propane and butane) were found both in the gas phase of the cores and adsorbed in the sediments. Redox conditions appear to be critical in determining the direction and degree of transformation of the organic material. -- E. Ingerson.     

用三维荧光谱图分析原水输送过程中藻类和有机物的变化

采用新型分析技术三维荧光谱图方法对深圳东江水源工程水体中藻类进行了荧光分析。实验结果表明,水体中有较丰富的藻类,其中蓝藻、绿藻呈优势藻种,实验期间沿程水体叶绿素a浓度在1.71~16.43μg/L之间,藻密度在72.92万~1 375万个/L之间。三维荧光方法能较好表征水体中生长藻类种类和数量,三维荧光强度F(A.U)与叶绿素a浓度Chla(μg/L)、藻密度N(104个/L)呈较好的线性关系。三维荧光方法能较好的鉴别水体中可溶性有机物腐殖酸和蛋白质,并表征其含量多少。     

Alkane and PAH biomarkers as tracers of terrigenous organic carbon in Arctic Ocean sediments

We present the first sedimentary biomarker study encompassing the entire Arctic Ocean. A large data set of organic markers for terrigenous, petroleum and combustion inputs [alkanes, hopanes and steranes, parent and alkyl polycyclic aromatic hydrocarbons (PAHs)] is examined for patterns in space and time using principal components analysis (PCA) and partial least squares (PLS). Biomarker patterns reveal the central Arctic Ocean basin sediments to be compositionally distinct from those of the Mackenzie River/Beaufort Sea and Barents Sea, but similar to those of the Laptev Sea. PAH distributions reflected in PAH ratios and PCA projections demonstrate that Arctic Ocean sediment is dominated by natural inputs to the extent that anthropogenic combustion PAHs are not significant. We find only modest changes between the glacial and post-glacial sediments for atmospherically transported hydrocarbon biomarkers, while particle associated biomarkers were captured strongly at basin edges during the glacial period, and much more evenly transported across basins during the post-glacial period. The orders of magnitude decreases in particle associated petrogenic alkanes and PAHs in central basins during glacial times, coupled with the uniformity of most petrogenic biomarker parameters for most basin and shelf locations, reflect a massive reduction in ice transport that makes the margins the most likely source of petrogenic material for the Pleistocene/Holocene central Arctic basins. The proximity of large coal deposits of various maturity levels along the Lena River, the overlap in PAH and biomarker composition of the Laptev Sea and surficial sediments from the central Arctic Ocean and the location of the Laptev Sea at the origin of the main Transpolar Drift all point to eroded coals from the Lena River/Laptev Sea as the likely source of petrogenic hydrocarbons to the central Arctic Ocean. The ubiquitous presence of allochthonous coal in Arctic Ocean surface sediments provides a major constraint on the use of petrogenic biomarkers to infer the presence of subsurface petroleum reserves.     

The distribution and source of organic matter in reservoir sediments

The bottom sediments of two reservoirs, one with significant river sediment input and one without, were analyzed for organic matter content. Lake Texoma sediments average 1.0% organic carbon, of which 0.26% organic carbon is deposited by the river sediments of the Red and Washita River deltas. In Fort Gibson reservoir, where there is minimal river sediment input, the organic carbon averages 1.2% and is deposited with a strong correlation to water depth (+0.9). There is a significant difference between the C/N ratio of Lake Texoma sediments (11.5) and Fort Gibson sediments (9.6). The higher C/N ratio is suggested to be a result of the larger input of terrestrial plant debris (with a high original C/N ratio) by the rivers draining into Lake Texoma and the relatively high resistance of the lignin material in the plant debris to decomposition in the reservoir sediments.     

Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter

Mercury is a global contaminant of concern due to its transformation by microorganisms to form methylmercury, a toxic species that accumulates in biological tissues. The effect of dissolved organic matter (DOM) isolated from natural waters on reactions between mercury(II) (Hg) and sulfide (S(-II)) to form HgS_(s) nanoparticles across a range of Hg and S(-II) concentrations was investigated. Hg was equilibrated with DOM, after which S(-II) was added. Dissolved Hg (Hg_aq) was periodically quantified using ultracentrifugation and chemical analysis following the addition of S(-II). Particle size and identity were determined using dynamic light scattering and X-ray absorption spectroscopy. S(-II) reacts with Hg to form 20 to 200 nm aggregates consisting of 1-2 nm HgS_(s) subunits that are more structurally disordered than metacinnabar in the presence of 2 × 10⁻⁹ to 8 × 10⁻⁶ M Hg and 10 (mg C) L⁻¹ DOM. Some of the HgS_(s) nanoparticle aggregates are subsequently dissolved by DOM and (re)precipitated by S(-II) over periods of hours to days. At least three fractions of Hg-DOM species were observed with respect to reactivity toward S(-II): 0.3 μmol reactive Hg per mmol C (60 percent), 0.1 μmol per mmol C (20 percent) that are kinetically hindered, and another 0.1 μmol Hg per mmol C (20 percent) that are inert to reaction with S(-II). Following an initial S(-II)-driven precipitation of HgS_(s), HgS_(s) was dissolved by DOM or organic sulfur compounds. HgS_(s) formation during this second phase was counterintuitively favored by lower S(-II) concentrations, suggesting surface association of DOM moieties that are less capable of dissolving HgS_(s). DOM partially inhibits HgS_(s) formation and mediates reactions between Hg and S(-II) such that HgS_(s) is susceptible to dissolution. These findings indicate that Hg accessibility to microorganisms could be controlled by kinetic (intermediate) species in the presence of S(-II) and DOM, undermining the premise that equilibrium Hg species distributions should correlate to the extent or rate of Hg methylation in soils and sediments.