Sulphur Enrichment in Organic Matter of Eastern Mediterranean Sapropels: A Study of Sulphur Isotope Partitioning

Sulphur isotope compositions and S/C ratios of organic matter were analysed in detail by combustion-isotope ratio monitoring mass spectrometry (C-irmMS) in eastern Mediterranean sediments containing three sapropels of different ages and with different organic carbon contents (sapropel S1 in core UM26, formed from 5–9 ka ago with a maximum organic carbon content of 2.3 wt%; sapropel 967 from ODP Site 160-967C, with an age of 1.8 Ma and a maximum organic carbon content of 7.4 wt%; and sapropel 969 from ODP Site 160-969E, with an age of 2.9 Ma and a maximum organic carbon content of 23.5 wt%). Sulphur isotopic compositions (34S) of the organic matter ranged from -29.5 to +15.8 and the atomic S/C ratio was 0.005 to 0.038. The organic sulphur in the sediments is a mixture of sulphur derived from (1) incorporation of 34S-depleted inorganic reduced sulphur produced by dissimilatory microbial sulphate reduction; and (2) biosynthetic sulphur with an isotopic signature close to seawater sulphate. The calculated biosynthetic fraction of organic sulphur in non-sapropelic sediments ranges from 68–87%. The biosynthetic fraction of the organic sulphur of the sapropels (60–22%) decreases with increasing organic carbon content of the sapropels. We propose that uptake of reduced sulphur into organic matter predominantly took place within sapropels where pyrite formation was iron-limited and thus an excess of dissolved sulphide was present for certain periods of time. Simultaneously, sulphide escaped into the bottom water and into sediments below the sapropels where pyrite formation occurred.     

A detailed pyrolysis-GC/MS analysis of a black carbon-rich acidic colluvial soil (Atlantic ranker) from NW Spain

Despite the potentially large contribution of black carbon (BC) to the recalcitrant soil organic matter pool, the molecular-level composition of aged BC has hardly been investigated. Pyrolysis-GC/MS, which provides structural information on complex mixtures of organic matter, was applied to the NaOH-extractable organic matter of an acidic colluvial soil (Atlantic ranker) sampled with high resolution (5 cm) that harbours a fire record of at least 8.5 ka. Additionally, 5 charcoal samples from selected soil layers were characterised using pyrolysis-GC/MS for comparison. Pyrolysis-GC/MS allowed distinguishing between BC and non-charred organic matter. It is argued that a large proportion of the polycyclic aromatic hydrocarbons (PAHs), benzenes and benzonitrile in the pyrolysates of the extractable organic matter, together accounting for 21–54% of total identified peak area, derived from BC. In charcoal samples, these compounds accounted for 60–98% of the pyrolysis products. The large quantity of BC in almost all samples suggested a key role of fire in Holocene soil evolution. The high C content of the soil (up to 136 g C kg⁻¹ soil) may be attributed to the presence of recalcitrant organic C as BC, in addition to the sorptive preservation processes traditionally held responsible for long-term C storage in acid soils. Interactions between reactive Al hydroxides and BC could explain the longevity of BC in the soil. This work is the first thorough pyrolysis-GC/MS based study on ancient fire-affected organic matter.     

Chemical and spectroscopic characterization of marine dissolved organic matter isolated using coupled reverse osmosis-electrodialysis

The coupled reverse osmosis-electrodialysis (RO/ED) method was used to isolate dissolved organic matter (DOM) from 16 seawater samples. The average yield of organic carbon was 75 ± 12%, which is consistently greater than the yields of organic carbon that have been commonly achieved using XAD resins, C₁₈ adsorbents, and cross-flow ultrafiltration. UV-visible absorbance spectra and molar C/N ratios of isolated samples were consistent with the corresponding properties of DOM in the original seawater samples, indicating that DOM samples can be isolated using the coupled RO/ED method without any bias for/against these two properties. Five of the samples were desalted sufficiently that reliable measurements of their ¹³C and ¹HNMR spectra and their Fourier transform ion cyclotron resonance (FTICR) mass spectra could be obtained. The ¹³C and ¹HNMR spectra of RO/ED samples differed distinctly from those of samples that have been isolated in much lower yields by other methods. In particular, RO/ED samples contained a relatively lower proportion of carbohydrate carbon and a relatively greater proportion of alkyl carbon than samples that have been isolated using cross-flow ultrafiltration. From the FTICR mass spectra of RO/ED samples, samples from the open ocean contained a much lower proportion of unsaturated compounds and a much higher proportion of fatty acids than coastal samples.     

Terrigenous dissolved organic matter along an estuarine gradient and its flux to the coastal ocean

The contribution of terrigenous organic matter (TOM) to high molecular weight dissolved and particulate organic matter (POM) was examined along the salinity gradient of the Delaware Estuary. Dissolved organic matter (DOM) was fractionated by ultrafiltration into 1–30 kDa (HDOM) and 30 kDa–0.2 μm (VHDOM) nominal molecular weight fractions. Thermochemolysis with tetramethylammonium hydroxide (TMAH) was used to release and quantify lipids and lignin phenols. Stable carbon isotopes, fatty acids and lignin content indicated shifts in sources with terrigenous material in the river and turbid region and a predominantly algal/planktonic signal in the lower estuary and coastal ocean. Thermochemolysis with TMAH released significant amounts of short chain fatty acids (C₉–C₁₃), not seen by traditional alkaline hydrolysis, which appear to be associated with the macromolecular matrix. Lignin phenol distributions in HDOM, VHDOM and particles followed predicted sources with higher concentrations in the river and turbid region of the estuary and lower concentrations in the coastal ocean. TOM comprised 12% of HDOM within the coastal ocean and up to 73% of HDOM within the turbid region of the estuary. In the coastal ocean, TOM from high molecular weight DOM comprised 4% of total DOC. The annual flux of TOM from the Delaware Estuary to the coastal ocean was estimated at 2.0×10¹⁰ g OC year⁻¹ and suggests that temperate estuaries such as Delaware Bay can be significant sources of TOM on a regional scale.     

Sources and transport of carbon and nitrogen in the River Sava watershed, a major tributary of the River Danube

Carbon and nitrogen dynamics were examined throughout the River Sava watershed, a major tributary of the River Danube, in 2005 and 2006. The River Sava exported 2.1 × 10¹¹ mol C/yr as dissolved inorganic carbon (DIC), and emitted 2.5 × 10¹⁰ mol C/yr as CO₂ to the atmosphere. Stable carbon isotope ratios indicate that up to 42% of DIC originated from carbonate weathering and 23% from degradation of organic matter. Loads of dissolved and particulate organic carbon increased with discharge and export rates were calculated to be 2.1 × 10¹⁰ mol C/yr and up to 4.1 × 10⁹ mol C/yr, respectively. Isotopic compositions (δ¹³C and δ¹⁵N) and C/N ratios indicated that soil organic matter was the dominant source of particulate organic matter for 59% of the samples. Eighteen percent of the samples were dominated by plankton, 12% by periodic inputs of fresh terrestrial plant detritus with C/N > 15, and about 11% of the samples were dominated by the contribution of aquatic vascular plants. Nitrate inputs were controlled by land use in the River Sava watershed. δ¹⁵N_NO3 values <6‰ were found in predominantly forested watersheds, while values >6‰ typically represented watersheds with a higher percentage of agricultural and/or urban land use. Elevated δ¹⁵N_NO3 values (up to +25.5‰) at some sites were probably due to the combined effects of low-flow and inputs from sewage and/or animal waste.     

Early diagenetic behaviour of selenium in freshwater sediments

The vertical distributions of dissolved Se species [Se(IV), Se(VI) and organic Se] and diagenetic constituents [Fe(II) and Mn(II)] were obtained in porewater samples of two Sudbury area lakes (Clearwater and McFarlane). The sedimentary concentration profiles of total Se, Se species bound to Fe–Mn oxyhydroxides and to organic matter, and of elemental Se were also determined along with the concentrations of Fe, Mn and S in different extractable fractions. Results indicated that the concentrations of total dissolved Se in porewater samples were very low, varying from around 2.0 nM to a maximum level of 6.5 nM, while the concentrations of total Se species in the solid phase varied between 2 and 150 nmol/g on a dry weight basis. The two lakes showed striking differences in the presence of Se(IV) and Se(VI) at the sediment–water interface (SWI). In Clearwater Lake, Se(VI) was present at this interface and Se(IV) was not detectable, whereas the opposite was found in McFarlane Lake. This suggests that reducing conditions might have existed near the SWI of McFarlane Lake at the sampling time; this hypothesis was confirmed by several other measured chemical parameters. The profiles of total dissolved Se of both lakes suggest upward and downward diffusion of dissolved Se species along the concentration gradients. Assuming that no precipitation occurred at the SWI, the fluxes of dissolved Se species across the SWI in Clearwater and McFarlane lakes were estimated to be 0.108 and 0.034 nmol cm⁻² a⁻¹, respectively. These values do not include the possible losses of volatile Se species due to microbial methylation. In the reducing sediments of both lakes, the formation of elemental Se and pyritic Se were found to be important mechanisms for controlling the solubility of Se in this environment. The main geochemical processes involving Se identified in this study are: the adsorption of Se onto Fe–Mn oxyhydroxides at or near the SWI, the release of adsorbed Se by the reduction of the same oxyhydroxides and the mineralization of organic matter, and the removal of Se from porewaters to form elemental Se and a S mineral phase such as Se–pyrite or pure ferroselite.     

Carbon biogeochemistry of the Betsiboka estuary (north-western Madagascar)

Madagascar’s largest estuary (Betsiboka) was sampled along the salinity gradient during the dry season to document the distribution and sources of particulate and dissolved organic carbon (POC, DOC) as well as dissolved inorganic carbon (DIC). The Betsiboka was characterized by a relatively high suspended matter load, and in line with this, low DOC/POC ratios (0.4–2.5). The partial pressure of CO₂ (pCO₂) was generally above atmospheric equilibrium (270–1530 ppm), but relatively low in comparison to other tropical and subtropical estuaries, resulting in low average CO₂ emission to the atmosphere (9.1 ± 14.2 mmol m⁻² d⁻¹). Despite the fact that C4 vegetation is reported to cover >80% of the catchment area, stable isotope data on DOC and POC suggest that C4 derived material comprises only 30% of both pools in the freshwater zone, increasing to 60–70% and 50–60%, respectively, in the oligohaline zone due to additional lateral inputs. Sediments from intertidal mangroves in the estuary showed low organic carbon concentrations (<1%) and δ¹³C values (average −19.8‰) consistent with important inputs of riverine imported C4 material. This contribution was reflected in δ¹³C signatures of bacterial phospholipid derived fatty acids (i + a15:0), suggesting the potential importance of terrestrial organic matter sources for mineralization and secondary production in coastal ecosystems.     

Geochemical features of re-deposited organic matter occurring in fluvioglacial sediments in the Racibórz region (Poland): A case study

The erosion of rocks rich in organic matter typically leads to the complete mineralization of the organic material. However, in some cases, it is re-deposited to become a part of sediments once more. This process should be considered to be a part of global carbon cycle, possibly much more significant than assumed to-date. The research presented here aims to characterize re-worked organic matter occurring in post-glacial sediments of southern part of Poland, in the Oder river valley (the Racibórz town region, Miocene, Pleistocene and Holocene age). Organic substances extracted from the sediments originated from organic matter that had resided in rocks eroded by glaciers. Sediments were sampled in two boreholes which sediments were correlated. Sediments were extracted and extracts analyzed with gas chromatography-mass spectrometry (GC-MS) to assess distributions of biomarker groups. Organic matter of selected samples was pre-concentrated and analyzed with Py/GC-MS. In the extracts several biomarker parameters of source/environment and thermal maturity were calculated. Organic substances in the investigated sediments come from variable re-deposited organic matter occurring in rocks eroded by glaciers. Three main parent types of re-deposited organic material are identified showing variable geochemical features: 1) organic matter of recent or almost recent age being the source of polar labile compounds; probably formed in situ, 2) re-deposited organic matter of the middle diagenesis showing features similar to lignites (huminite reflectance Rf ~ 0.25–0.35%) deriving from angiosperm remains, mainly monocotyledons and to the lower extend also deciduous trees, 3) re-deposited organic matter at the middle catagenesis (Rf ~ 0.65–0.75%) being the source of most of aromatic hydrocarbons and biomarkers such as steranes, hopanes of the more thermally advanced distribution type. Its geochemical properties and assumed directions of sediment transport indicate bituminous coals of Upper Silesian Coal Basin together with coaly shales as a possible source of this organic matter. Such mixed origin of organic matter caused large discrepancies in values of thermal maturity parameters depending on input from the particular sources and occurrence both geochemical biomarkers and their biochemical precursors in the same samples.     

Observations on the association between mercury and organic matter dissolved in natural waters

Dissolved mercury in estuarine waters from the Mississippi Delta and Florida Everglades is associated with dissolved organic matter which has the properties of fulvic matter found in soils. Ultrafiltration of water samples demonstrated that mercury and dissolved organic carbon are selectively enriched in the < 500 molecular size cut-off fraction. A decrease in high molecular weight dissolved organic matter with increasing salinity in the Everglades exerts a partial control on the mercury content of these estuarine waters.     

Origin and formation pathways of kerogen-like organic matter in recent sediments off the Danube delta (northwestern Black Sea)

The chemical structure, source(s), and formation pathway(s) of kerogen-like organic matter (KL) were investigated in recent sediments from the northwestern Black Sea, off the Danube delta. Three sections from a sediment core collected at the mouth of the Sulina branch of the delta, under an oxic water column, were examined: S₀ (0–0.5 cm bsf), S₁₀ (10–13 cm bsf), and S₂₀ (20–25 cm bsf). The bulk geochemical features of these sediments (total organic carbon, organic C/N atomic ratio, δ¹³C_org) were determined. Thereafter, KL was isolated from the samples, as the insoluble residue obtained after HF/HCl treatment. KL chemical composition was investigated via spectroscopic (FTIR, solid state ¹³C and ¹⁵N NMR) and pyrolytic (Curie point pyrolysis–gas chromatography–mass spectrometry) methods, and the morphological features were examined by scanning and transmission electron microscopy. Similar morphological features and chemical composition were observed for the three KLs and they suggested that the selective preservation of land-plant derived material as well as of resistant aliphatic biomacromolecules (probably derived from cell walls of freshwater microalgae) was the main process involved in KL formation. Besides, some melanoidin-type macromolecules (formed via the degradation-recondensation of products mainly derived from proteinaceous material) and/or some encapsulated proteins also contributed to the KL chemical structure.     

Elucidation of different forms of organic carbon in marine sediments from the Atlantic coast of Spain using thermal analysis coupled to isotope ratio and quadrupole mass spectrometry

Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO₂) and m/z 18 (H₂O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ¹³C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.     

Laboratory sulfurisation of the marine microalga Nannochloropsis salina

To understand more fully the mode of preservation of organic matter in marine sediments, laboratory sulfurisation of intact cells of the cultured microalga Nannochloropsis salina was performed using inorganic polysulfides in seawater at 50°C. Solvent extractable and non-extractable materials were analysed by GC–MS and Py–GC–MS, respectively, to study the incorporation of sulfur into the microalgal organic matter. No GC-amenable sulfur-containing compounds were found in the extracts apart from some minor thiophenes with a phytanyl carbon skeleton. The residue after extraction and hydrolysis contained abundant macromolecular sulfur-containing moieties as revealed by the presence of dominant C₂₈–C₃₂ thiols, thiophenes, thianes and thiolanes in the flash pyrolysates. These products are thought to be formed from moieties derived from sulfurisation of C₂₈–C₃₂ diols and alkenols, characteristic lipids of N. salina. C₁–C₂ alkylated thiophenes were also found in the pyrolysates and probably result from moieties formed upon sulfurisation of carbohydrates. The highly resistant biomacromolecule (algaenan) synthesised by N. salina remains unaffected by sulfurisation. The non-hydrolysable residue isolated from the sulfurised N. salina thus comprises algaenan and (poly)sulfide-bound long alkyl chains. The sulfurisation experiments show that both selective preservation of algaenans and lipid and carbohydrate “vulcanisation” can be involved in the preservation of algal organic matter in marine environments.     

Geochemical characterisation of organic matter in Keg River Formation (Elk point group, Middle Devonian), La Crete Basin, Western Canada

Carbonates from the Keg River Formation, La Crete Basin, Alberta, western Canada were examined in order to define: (a) oil source rock potential; (b) bulk maceral composition; (c) extract yield; and finally (d) facies variations using PY-GC-MS. Thirty samples from 6 different wells were examined from the lower Keg River member and 4 from the upper Keg River member using conventional geochemical methods. As maturity differences are absent within the sample set, variations in TOC, T_max, hydrogen index, organic petrography and extract yields are caused by variability in organic matter input, which is revealed by molecular characterisation using PY-GC-MS. Lower Keg River member bituminous wackestones are excellent potential source rocks containing Types I–II and Type II organic matter. Types I–II organic matter contains large well preserved (up to 200μm in diameter) thick-walled Tasmanites (10–15% of sample) and akinete algal cells indicative of algal blooms within an amorphous bituminite. Type II organic matter contains a higher proportion of degraded alginites/bituminite relative to well-preserved alginites. Extract yields (mg/g TOC) were seen to increase from Types I–II to Type II organic matter. PY-GC-MS revealed that 1,2,3,4-tetramethylbenzene was a major peak in most samples. This is a pyrolysis product arising from β-cleavage of C₄₀ diaromatic carotenoids incorporated within the kerogen during diagenesis. The source of this compound is thought to be from an unknown diaromatic compound with a 2,3,6-/3,4,5-trimethyl substitution pattern and isorenieratene, which is specific to photosynthetic green sulphur bacteria (Chlorobiaceae) suggesting that the photic zone was at least partially anoxic during deposition of these samples. The relative abundance of this compound/n-C11-alkene and organic sulphur (calculated from the thiophene ratio) both increase from Types I–II to Type II organic matter. This trend was grossly similar to the trend seen in the variability of extract yield with hydrogen index. A similar trend for HI and T_max indicates samples containing a higher proportion of degraded alginites/bituminite relative to well-preserved alginite are more labile than Type I–II organic matter. Upper Keg River member marls contain Type II organic matter, which is characterised by heavily degraded algal material within a bituminous groundmass. Pyrolysates of two of the marl samples contain only low amounts of 1,2,3,4-tetramethylbenzene, in contrast to the bituminous wackestones, indicating that the depositional environment/source input was different during deposition of the marl samples. Although both marls contain similar organic matter, their pyrolysates were significantly different. One marl (1141.9 m) was highly paraffinic containing dominantly short-chain alkene/alkane doublets, while the other marl (1137.6 m) contained a bimodal n-alkane/alkene distribution and high amounts of alkylphenols, which may be derived from preservation of resistant algal polyphenolic molecules or suggest a terrestrial input.     

Origins and accumulation of organic matter in expanded Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian–Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, δ¹³C_org values lie mostly between −30‰ and −27‰, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C₃ land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low δ¹³C_org values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian–Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.     

The effects of surface area, grain size and mineralogy on organic matter sedimentation and preservation across the modern Squamish Delta, British Columbia: the potential role of sediment surface area in the formation of petroleum source rocks

Surface sediment samples were collected from the Squamish River Delta, British Columbia, in order to determine the role of sediment surface area in the preservation of organic matter (OM) in a paralic sedimentary environment. The Squamish Delta is an actively prograding delta, located at the head of Howe Sound.Bulk total organic carbon (TOC) values across the Squamish Delta are low, ranging from 0.1 to 1.0 wt.%. The carbon/total nitrogen ratio (C_org/N) ranges from 6 to 17, which is attributed to changes in OM type and facies variations. The <25-μm fraction has TOC concentrations up to 2.0 wt.%, and a C_org/N ratio that ranges from 14 to 16. The 53–106-μm fraction has higher TOC concentrations and C_org/N ratios relative to the 25–53-μm fraction. The C_org/N ratio ranges from 9 to 18 in the 53–106-μm fraction and 5.5–10.5 in the 25–53-μm fraction. Surface area values for bulk sediments are low (0.5–3.0 m²/g) due to the large proportion of silt size material. Good correlation between surface area and TOC in bulk samples suggests that OM is adsorbed to mineral surfaces. Similar relationships between surface area and TOC were observed in size-fractionated samples. Mineralogy and elemental composition did not correlate with TOC concentration.The relationships between surface area, TOC and total nitrogen (TN) can be linked to the hydrodynamic and sedimentological conditions of the Squamish Delta. As a result, the Squamish Delta is a useful modern analogue for the formation of petroleum source rocks in ancient deltaic environments, where TOC concentrations are often significantly lower than those in source rocks formed in other geological settings.     

Diagenetic history and porosity evolution of Upper Carboniferous sandstones from the Spring Valley #1 well, Maritimes Basin, Canada–implications for reservoir development

Eighty-two core samples were collected from the Spring Valley #1 well which penetrates the Upper Carboniferous strata in the Late Devonian–Early Permian Maritimes Basin. The strata consist of alternating sandstones and mudstones deposited in a continental environment. The objective of this study is to characterize the relationship of sandstone porosity with depth, and to investigate the diagenetic processes related to the porosity evolution. Porosity values estimated from point counting range from 0% to 27.8%, but are mostly between 5% and 20%. Except samples that are significantly cemented by calcite, porosity values clearly decrease with depth. Two phases of calcite cement were distinguished based on Cathodoluminescence, with the early phase being largely dissolved and preserved as minor relicts in the later phase. Feldspar dissolution was extensive and contributed significantly to the development of secondary porosity. Quartz cementation was widespread and increased with depth. Fluid inclusions recorded in calcite and quartz cements indicate that interstitial fluids in the upper part of the stratigraphic column were dominated by waters with salinity lower than that of seawater, the middle part was first dominated by low-salinity waters, then invaded by brines, and the lower part was dominated by brines. Homogenization temperatures of fluid inclusions generally increase with depth and suggest a paleogeothermal gradient of 25 °C/km, which is broadly consistent with that indicated by vitrinite reflectance data. An erosion of 1.1–2.4 (mean 1.75) km of strata is inferred to have taken place above the stratigraphic column. δ¹⁸O values of calcite cements (mainly from the late phase) decrease with depth, implying increasing temperatures of formation, as also suggested by fluid-inclusion data. δ¹³C values of calcite cements range from −13.4‰ to −5.7‰, suggesting that organic matter was an important carbon source for calcite cements. A comparison of the porosity data with a theoretical compaction curve indicates that the upper and middle parts of the stratigraphic column show higher-than-normal porosity values, which are related to significant calcite and feldspar dissolution. Meteoric incursion and carboxylic acids generated from organic maturation were probably responsible for the abundant dissolution events.     

Stable isotope analysis of carbon cycling in the Perdido estuary, Florida

Stable carbon isotope (δ¹³C) analysis was used in the Peridido Estuary, Florida U.S. to determine the predominant carbon source that supports the bacterial assemblage. Stable carbon isotope values were measured in the suspended particulate matter (SPM), dissolved organic and inorganic matter, and bacteria. Stable nitrogen isotope (δ¹⁵N) ratios were measured in SPM and nitrate to assist in understanding carbon cycling through the estuary. Analyses were conducted on samples from riverine, coastal, and anthropogenic sources and compared with samples from the bay. Stable isotope ratio analysis was coupled with estimates of mixing of riverine and coastal waters into the bay. Preliminary observation of the °¹³C data indicates that terrestrial organic matter is the primary carbon source that is assimilated by bacteria in the ecosystem. Stable isotope data from carbon and nitrogen pools in combination with analysis of estuarine current velocities indicates that primary production is an important factor in the carbon cycle. This study demonstrates the importance of stable isotope analysis of multiple carbon and nitrogen pols to assess sources and cycling of organic matter.     

Organic geochemical characteristics and depositional environments of the Jurassic coals in the eastern Taurus of Southern Turkey

In this study, organic matter content, type and maturity as well as some petrographic and physical characteristics of the Jurassic coals exposed in the eastern Taurus were investigated and their depositional environments were interpreted.The total organic carbon (TOC) contents of coals in the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc areas are 24.54, 66.78 and 49.15%, respectively. The Feke–Akkaya and Kozan–Kizilinc coals have low Hydrogen Index (HI) values while the Kozan–Gedikli coals show moderate HI values. All coal samples display very low Oxygen Index (OI) values. The Kozan–Gedikli coals contain Type II organic matter (OM), the Feke–Akkaya coals contain a mixture of type II and type III OM; and the Kozan–Kizilinc coals are composed of Type III OM. Sterane distribution was calculated as C₂₇ > C₂₉ > C₂₈ from the m/z 217 mass chromatogram for all coal samples.T_max values for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 439, 412 and 427 °C. Vitrinite reflectance values (%R_o) for the Feke–Akkaya and Kozan–Kizilinc coal samples were measured as 0.65 and 0.51 and these values reveal that the Feke–Akkaya and Kozan–Kizilinc coals are at subbituminous A or high volatile C bituminous coal stage. On the basis of biomarker maturity parameters, these coals have a low maturity.The pristane/phytane (Pr/Ph) ratios for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 1.53, 1.13 and 1.25, respectively. In addition, all coals show a homohopane distribution which is dominated by low carbon numbers, and C₃₅ homohopane index is very low for all coal samples. All these features may indicate that these coals were deposited in a suboxic environment.The high sterane/hopane ratios with high concentrations of steranes, low Pr/Ph ratios and C₂₅/C₂₆ tricyclic ratios > 1 may indicate that these coals formed in a swamp environment were temporarily influenced by marine conditions.     

Heterogeneous organic matter from the surface horizon of a temperate zone marsh

Abundance, bulk chemical composition and sources of the organic matter in the surface horizon of the permanently water-covered part of an intermittently water-covered marsh were investigated. Lipids, insoluble non-hydrolysable macromolecular organic matter and black carbon fractions were isolated and examined via Rock-Eval pyrolysis, elemental analysis, Fourier transform infrared spectroscopy, isotopic (δ¹³C, δ¹⁵N) methods and high resolution transmission electron microscopy. Integration of bulk Rock-Eval data, elemental and isotopic composition, together with spectroscopic features, suggested immature Type III organic matter derived mainly from C₃ vascular plants. The distribution of n-alkanes from the non-aromatic lipid fraction exhibited the importance of emergent macrophytes and terrestrial plants, as well as a moderate input of submerged/floating macrophytes to the source biomass. Mathematical deconvolution of a Rock-Eval pyrogram revealed highly heterogeneous organic matter composed of a mixture of thermally labile biopolymers (36%) at various stages of decomposition, as well as humic substances and highly refractory organic matter (64%) in the whole sample. Markedly lower heterogeneity and aliphaticity, together with a higher proportion of humic substances and highly refractory organic matter (ca. 84%) were observed in the macromolecular fraction. An abundant contribution of black carbon to the macromolecular fraction was indicated by mathematical deconvolution of the Rock-Eval pyrogram and was clearly shown by the isolation of this fraction and chemical oxidation. The black carbon fraction appeared to account for ca. half of the macromolecular fraction, the carbon in these two fractions representing 30% and 14% of the initial carbon, respectively. The electron microscopy observations directly evidenced the presence of black carbon, which was comprised of both amorphous poorly organized particles and highly ordered onion-shaped particles.     

Electron accepting capacity of dissolved organic matter as determined by reaction with metallic zinc

Information about the chemical electron accepting capacity (EAC) of dissolved organic matter (DOM) is scarce owing to a lack of applicable methods. We quantified the electron transfer from metallic Zn to natural DOM in batch experiments at DOC concentrations of 10–100 mg-C L^− 1 and related it to spectroscopic information obtained from UV-, synchronous fluorescence, and FTIR- spectroscopy. The electron donating capacity of DOM and pre-reduced DOM was investigated using Fe(CN)₆³⁻ as electron acceptor. Presence of DOM resulted in release of dissolved Zn, consumption of protons, and slower release of hydrogen compared to reaction of metallic Zn with water at pH 6.5. Comparison with reaction stoichiometry confirmed that DOM accepted electrons from metallic Zn. The release of dissolved Zn was dependent on pH, DOC concentration, ionic strength, and organic matter properties. The reaction appeared to be completed within about 24 h and was characterized by pseudo first order kinetics with rate constants of 0.5 to 0.8 h^− 1. EAC per mass unit of carbon ranged from 0.22 mmol g^− 1 C to 12.6 mmol g^− 1 C. Depending on the DOM, a calculated 28–127% of the electrons transferred from metallic Zn to DOM could be subsequently donated to Fe(CN)₆³⁻. EAC decreased with DOC concentration, and increased with aromaticity, carboxyl, and phenolic content of the DOM. The results indicate that an operationally defined EAC of natural DOM can be quantified by reaction with metallic Zn and that DOM properties control the electron transfer. Shortcomings of the method are the coagulation and precipitation of DOM during the experiment and the production of hydrogen and dissolved Zn by reaction of metallic Zn with water, which may influence the determined EAC.