Pore Waters Of Marine Sediments Research Articles

Occurrence and prevalence of per- and polyfluoroalkyl substances in the sediment pore water of mariculture sites: Novel findings of PFASs from the Bohai and Yellow Seas using a newly established analytical method

A new method for the determination of 26 legacy and emerging per- and polyfluoroalkyl substances (PFASs) in marine sediment pore water was developed using online solid phase extraction coupled with liquid chromatography-tandem mass spectrometry. The proposed method requires only about 1 mL of pore water samples. Satisfactory recoveries of most target PFASs (83.55–125.30 %) were achieved, with good precision (RSD of 1.09–16.53 %), linearity (R2 ≥ 0.990), and sensitivity (MDLs: 0.05 ng/L–5.00 ng/L for most PFASs). Subsequently, the method was applied to determine PFASs in the sediment pore water of five mariculture bays in the Bohai and Yellow Seas of China for the first time. Fifteen PFASs were detected with total concentrations ranging from 150.23 ng/L to 1838.48 ng/L (mean = 636.80 ng/L). The ∑PFASs and PFOA concentrations in sediment pore water were remarkably higher than those in surface seawater (tens of ng/L), indicating that the potential toxic effect of PFASs on benthic organisms may be underestimated. PFPeA was mainly distributed in pore water, and the partition of PFHpA (50.99 %) and PFOA (49.01 %) was almost equal in the solid and liquid phases. The proportions of all other PFASs partitioned in marine sediments were significantly higher than those in pore water.

Direct Analysis of Marine Dissolved Organic Matter Using LC-FT-ICR MS.

Marine dissolved organic matter (DOM) is an important component of the global carbon cycle, yet its intricate composition and the sea salt matrix pose major challenges for chemical analysis. We introduce a direct injection, reversed-phase liquid chromatography ultrahigh resolution mass spectrometry approach to analyze marine DOM without the need for solid-phase extraction. Effective separation of salt and DOM is achieved with a large chromatographic column and an extended isocratic aqueous step. Postcolumn dilution of the sample flow with buffer-free solvents and implementing a counter gradient reduced salt buildup in the ion source and resulted in excellent repeatability. With this method, over 5,500 unique molecular formulas were detected from just 5.5 nmol carbon in 100 μL of filtered Arctic Ocean seawater. We observed a highly linear detector response for variable sample carbon concentrations and a high robustness against the salt matrix. Compared to solid-phase extracted DOM, our direct injection method demonstrated superior sensitivity for heteroatom-containing DOM. The direct analysis of seawater offers fast and simple sample preparation and avoids fractionation introduced by extraction. The method facilitates studies in environments, where only minimal sample volume is available e.g. in marine sediment pore water, ice cores, or permafrost soil solution. The small volume requirement also supports higher spatial (e.g., in soils) or temporal sample resolution (e.g., in culture experiments). Chromatographic separation adds further chemical information to molecular formulas, enhancing our understanding of marine biogeochemistry, chemodiversity, and ecological processes.

Mercury distribution, mobilization and bioavailability in polluted sediments of Scheldt Estuary and Belgian Coastal Zone

In this study, the vertical distribution of mercury (Hg) in estuarine and marine sediment porewaters and solid phases was assessed by conventional and passive sampling techniques in the historically polluted Scheldt Estuary and Belgian Coastal Zone (BCZ). The Diffusive Gradients in Thin-films (DGT) measured labile Hg concentrations (HgLA) were mostly lower than the porewater Hg concentrations (HgPW), and they also presented different vertical distribution patterns. Still high Hg concentrations in the sediment solid phases, comparable to the historical ones, were observed. Even though pH, redox potential and dissolved sulfide concentration could influence the Hg biogeochemical behaviour, organic matter (OM) played a key role in governing Hg mobilization from sediment solid phase to porewater and in its partitioning between porewater and solid phase over depth. In the marine sediments, where OM had a marine signature, higher labile Hg concentrations in the porewater and faster resupply from the solid phase were observed. The DGT technique showed significant potential not only for the measurement of bioavailable Hg fractions in porewater, but also for the assessment of kinetic parameters governing the release of labile Hg species from the solid phase with the assistance of the DGT Induced Fluxes in Sediments (DIFS) model.

Preferential sorption of polysaccharides on mackinawite: A chemometrics approach

Marine sediments represent the most important sink for natural organic matter (NOM) across geological time spans. Strong associations between minerals, including iron oxides, and organic matter reaching the seafloor play a fundamental role in this preservation and have been known for some decades. Despite the importance of this protective mechanism in the balances of the global carbon budget, very little is known about the affinity of NOM for reduced iron species such as mackinawite (FeS) in the anoxic layers of sediment. In this study, equilibrium partition coefficients (Kd) for three types of NOM (soil extract, corn leaf extract and plankton extract) on FeS were determined through batch sorption experiments. Models were then built via multiple linear regression (MLR) and partial least squares regression (PLSR) in order to predict sorption Kd’s based on the chemical characteristics of the NOM. Investigation of the PLSR regression coefficients indicates that functional groups characteristic of polysaccharides are the greatest positive predictors of NOM sorption onto FeS at marine sediment porewater pH. This conclusion was independently verified by analyses of NOM FTIR spectra pre- and post-sorption. PLSR outperformed MLR with a lower root mean square error of prediction (RMSEP) of 53.4 L/kg compared to 64.0 L/kg. To our knowledge, this research presents a novel machine-learning approach to the quantitative modelling of NOM sorption to minerals found in anoxic marine environments.

Pore-Water Geochemical Gradients of Sulfate, Calcium, Magnesium, and Iodide Correlated With Underlying Gas Hydrate Potential: A Case Study of the Shenhu Area, South China Sea

Geochemical profiles in pore water of marine sediments have been considered as, important indicators of gas hydrate occurrence. In the gas hydrate area around the world, the decrease of sulfate, calcium, and magnesium concentrations with depth mainly results directly or indirectly from the anaerobic oxidation of methane (AOM). The ubiquitous abnormally high concentration gradients of iodide in the research area reflect the large methane-generating potential of the area. Thus, we explore the feasibility of using gradients of sulfate, iodide, and authigenic carbonate precipitation as indicators for gas hydrate in the regional exploration of gas hydrate formation. We test the criterion in the gas hydrate zone in the South China Sea (SCS) for the recognition of gas hydrate by using the gradients of sulfate, calcium plus magnesium, and iodide. Contour maps of pore-water gradients from expeditions in the study area are used to correlate the key gradients to underlying gas hydrate occurrence. The results show that the largest potential gas hydrate indicated by the contour maps of the indicators are well consistent with the discovery of GMGS1 and GMGS3 expedition. It implies the possible applicability of this geochemical method in gas hydrate exploration. Also, we identify a promising area in the South China Sea for future gas hydrate investigations. It is the first collective application of the gradients of sulfate, calcium plus magnesium, and iodide to a gas hydrate terrane, especially to a large area of the SCS. We believe that the result of this research will benefit the future exploration of gas hydrate and will arouse a lot of interest from other researchers.

Nature of Ore Fluid at the Sopokomil Zn-Pb Deposit, North Sumatra, Indonesia: Implications for Metal Transport and Sulfide Deposition

Little is known about the nature of ore fluid at the Sopokomil shale-hosted massive sulfide Zn-Pb deposit (North Sumatra, Indonesia). We therefore investigated its ore-fluid salinities, temperatures, densities, redox state, and pH using fluid inclusion microthermometry, sphalerite composition, and thermodynamic modelling. The fluid salinities and temperatures were ≈6 wt.% NaCl equiv and ≈165 °C, respectively, corresponding to an ore fluid less dense than seawater (≈0.96 g/mL). Sphalerite contains ≈9.9 mole% FeS in the stratiform ore and ≈3.4 mole% FeS in the feeder ore, suggesting a reduced fluid, which must have been acidic to be fertile. Such redox state and acidity invoke fluid dilution as the sulfide depositional mechanism. The bulk of the sulfides were precipitated in the early stage of mixing, within T = 165–155 °C. Key ingredients of sphalerite and galena at Sopokomil include (1) Zn that was primarily transported as ZnCl+, (2) Pb that predominantly occurred as PbCl2(aq), and (3) S that was largely supplied by marine sediment porewater. This study highlights the significance of a dramatic shift in thermal and chemical equilibrium induced by fluid dilution in the making of the first significant shale-hosted massive sulfide Zn-Pb deposit in Indonesia.

Determination of Rare Earth Elements in Pore Water Samples of Marine Sediments Using an Offline Preconcentration Method.

The concentrations of dissolved yttrium and rare earth elements (REY) in sediment pore water provide important geochemical information. However, due to the low REY concentration, complex matrix, and limited sample volume (often only a few milliliters), analysis of the REY in pore water often is highly challenging. In this study, a method was established to determine the dissolved REY in pore water of marine sediments using an offline preconcentration step with the ethylenediaminetriacetate chelating resin, followed by inductively coupled plasma-mass spectrometry. In addition, using a commercially available automated trace-element preconcentration system, the preconcentration step can be fully automated, saving labor and providing a better control of the final elution volume. The experimental conditions (pH, elution volume, elution acid concentration, and organic complexation effect) were assessed, and the optimal conditions were chosen. In particular, the organic complexation effect was found to be negligible. The procedure blank and limit of detection were satisfactory for studying REY in pore water of marine sediments, and the method also yielded satisfactory recoveries for the REY elements (83-110%). The method was then applied to analyze the dissolved REY concentrations of pore water samples collected in a sediment core (~ 30cm) in the central Indian Ocean. The vertical distribution, dissolved REY concentration, and the average Post Archean Australian Shale-normalized pattern of the REY showed similarities to the previously published pore water REY data. This method provides an accurate yet facile approach for the analysis of all 15 REY in marine pore water samples using the sample volume of only ~ 5mL.

An In Situ Analyzer for Two-Dimensional Fe(II) Distribution in Sediment Pore Water Based on Ferrozine Coloration and Computer Imaging Densitometry.

A novel integrated analyzer was developed for the in situ determination of two-dimensional (2D) dissolved Fe(II) distributions in sediment pore water. The analyzer utilized gel enrichment and optical imaging techniques. An image probe mainly consisting of a gel holder and portable document scanner was designed to be inserted into sediment. The gel holder exposed to the sediment was made to hold a polyacrylamide gel strip (diffusive gel) and polyacrylamide gel strip impregnated with C18 and coated with ferrozine (concentrating gel). The concentrating gel strip could accumulate the dissolved Fe(II) in pore water and produce a magenta-colored Fe(II)-ferrozine compound on the gel strip in two dimensions. The portable document scanner sealed in a transparent box and stuck onto the back of the gel holder could record gel images from the back of the concentrating gel strip. Gel images with grayscale intensities were acquired and analyzed using ImageJ software, and Fe(II) concentration was determined based on a deployment time related calibration curve established in the laboratory. The measurement accuracy and precision were investigated. The quantitative range reached up to 200 μmol L–1. The method and analyzer exhibit distinct characteristics of in situ enrichment and measurement; they were successfully applied to determine the 2D Fe(II) distribution in lake and marine sediment pore waters.

Factors controlling the carbon isotope composition of dissolved inorganic carbon and methane in marine porewater: An evaluation by reaction-transport modelling

Abstract Carbon isotope compositions of dissolved inorganic carbon (DIC) and methane (CH4) in porewater of marine sediments at seafloor temperatures show very large variation covering a δ13C range from −100‰ to +35‰. These extreme values are the result of isotope fractionation during microbial carbon metabolism, but the combined effect of all factors controlling the isotope distributions is still not completely understood. We used a model approach to evaluate the effects of reaction and transport on carbon isotope distributions in modern sediment porewater under steady state. Simulated δ13CDIC profiles typically show negative values in the sulphate reduction zone and more positive values in the methanogenic zone. With increasing depth in the methanogenic zone, δ13C values approach a distribution where the offset of δ13CDIC from δ13C of total organic carbon (TOC) to more positive values is similar to the offset of δ13CCH4 to more negative values (δ13CDIC and δ13CCH4 approach a symmetric distribution relative to δ13CTOC). The model never exceeds this symmetry of the DIC-CH4 couple towards more positive values under steady-state conditions in a purely diffusive system. Our model shows that to reach an offset in δ13C between DIC and CH4 in the order of 70‰, as frequently observed in methanogenic zones, a larger fractionation than reported from culture experiments with acetoclastic or autotrophic methanogens would be required. In fact, the observed isotope offset in natural systems would be consistent with the known inorganic equilibrium fractionation factor at in-situ temperature, which may suggest isotope exchange via a microbial pathway, during methanogenesis. Furthermore, the model reproduces strongly negative δ13CCH4 values at the sulphate methane-transition (SMT) as result of a reverse flux of carbon from DIC to CH4 during AOM. Such a reverse AOM has no influence on the δ13CDIC at the SMT as methane is almost completely consumed. Only at high sedimentation rate combined with low porosity, δ13CDIC values significantly more negative than δ13CTOC occur at the SMT.

Impact of sampling techniques on the concentration of ammonia and sulfide in pore water of marine sediments

AbstractThree ex situ pore water sampling procedures (I – rhizon samplers, II – centrifugation of sediment subsamples collected from different sediment depths without core sectioning, III – core sectioning and centrifugation of sediment sections) were compared to indicate factors that may affect concentrations of pore water constituents (ammonia and sulfides). The methods were selected and modified in such a way as to determine how the concentrations are affected by different factors related to sampling procedures, e.g. contact with atmospheric air, filtration and sediment core disturbance. They were tested on nine sediment cores collected at one site in the southern Baltic Sea. The concentration of ammonia in pore water from centrifuged sediment sections was significantly higher compared to pore water extracted by rhizons – probably due to the impact of changing pH. The factor with the greatest impact on the H2S/HS–concentration in the analyzed pore water was the contact with atmospheric air and/or the extrusion of sediments from a core liner. Rhizons proved to be the best option for sampling pore waters analyzed for H2S/HS–and NH4+/NH3. In the case of H2S/HS–we noticed the smallest loss of the analyzed constituents. For ammonia, the centrifugation of the whole sediment sections was likely to cause interferences in the indophenol blue method.

Constituents of organic alkalinity in pore water of marine sediments

Abstract In this study we investigated the components of organic alkalinity (AO) in pore water from marine sediments. We used absorbance and fluorescence of pore water to characterize dissolved organic matter (DOM), the source of AO. Research material was collected during growing season (September 2016) from two sites located in the eutrophic Gulf of Gdansk (southern Baltic). Concentration of AO ranged from 104 to 1505 μmol l−1 and increased with sediment depth. Our results demonstrate a clear link between AO and composition of DOM in pore water. Measurements of pore water fluorescence showed that the main source of AO is humic substances. The protein-like fluorescence, pointing to presence of freshly produced organic substances, was clearly visible in the upper layers and diminished with depth. There are changes in absorbance spectra with depth indicating decrease of molecular weight of DOM. In anoxic sediments the concentration of AO was close to the alkalinity from non‑carbonate inorganic bases (N-CIBs) and did not exceed 8% of total alkalinity (AT). In the sediments where organic matter was mineralized with the use of substances preceding sulfate in the sequence of oxidants (i.e. oxygen, nitrate, Mn, Fe), DOM was the source of up to 17% of AT. The results from this study indicate that DOM has a large effect on acid neutralizing capacity of pore water of marine sediments. We suggest the production of AO in sediment and its benthic efflux should be taken into account in modeling acid-base system in shelf seas.

Improved analytical techniques of sulfur isotopic composition in nanomole quantities by MC-ICP-MS

We propose an improved method for precise sulfur isotopic measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in conjunction with a membrane desolvation nebulization system. The problems of sulfur loss through the membrane desolvation apparatus are carefully quantified and resolved. The method overcomes low intrinsic sulfur transmission through the instrument, which was initially 1% when operating at a desolvation temperature of 160 °C. Sulfur loss through the membrane desolvation apparatus was resolved by doping with sodium. A Na/S ratio of 2 mol mol−1 produced sulfur transmissions with 98% recovery. Samples of 3 nmol (100 ng) sulfur achieved an external precision of ±0.18‰ (2 SD) for δ34S and ±0.10‰ (2 SD) for Δ33S (uppercase delta expresses the extent of mass-independent isotopic fractionation). Measurements made on certified reference materials and in-house standards demonstrate analytical accuracy and reproducibility. We applied the method to examine microbial-induced sulfur transformation in marine sediment pore waters from the sulfate-methane transition zone. The technique is quite versatile, and can be applied to a range of materials, including natural waters and minerals.

Unraveling signatures of biogeochemical processes and the depositional setting in the molecular composition of pore water DOM across different marine environments

Dissolved organic matter (DOM) in marine sediment pore waters derives largely from decomposition of particulate organic matter and its composition is influenced by various biogeochemical and oceanographic processes in yet undetermined ways. Here, we determine the molecular inventory of pore water DOM in marine sediments of contrasting depositional regimes with ultrahigh-resolution mass spectrometry and complementary bulk chemical analyses in order to elucidate the factors that shape DOM composition. Our sample sets from the Mediterranean, Marmara and Black Seas covered different sediment depths, ages and a range of marine environments with different (i) organic matter sources, (ii) balances of organic matter production and preservation, and (iii) geochemical conditions in sediment and water column including anoxic, sulfidic and hypersaline conditions. Pore water DOM had a higher molecular formula richness than overlying water with up to 11,295 vs. 2114 different molecular formulas in the mass range of 299–600Da and covered a broader range of element ratios (H/C=0.35–2.19, O/C=0.03–1.19 vs. H/C=0.56–2.13, O/C=0.15–1.14). Formula richness was independent of concentrations of DOC and TOC. Near-surface pore water DOM was more similar to water column DOM than to deep pore water DOM from the same core with respect to formula richness and the molecular composition, suggesting exchange at the sediment–water interface. The DOM composition in the deeper sediments was controlled by organic matter source, selective decomposition of specific DOM fractions and early diagenetic molecule transformations. Compounds in pelagic sediment pore waters were predominantly highly unsaturated and N-bearing formulas, whereas oxygen-rich CHO-formulas and aromatic compounds were more abundant in pore water DOM from terrigenous sediments. The increase of S-bearing molecular formulas in the water column and pore waters of the Black Sea and the Mediterranean Discovery Basin was consistent with elevated HS- concentrations reflecting the incorporation of sulfur into biomolecules during early diagenesis. Sulfurization resulted in an increased average molecular mass of DOM and higher formula richness (up to 5899 formulas per sample). In sediments from the methanogenic zone in the Black Sea, the DOM pool was distinctly more reduced than overlying sediments from the sulfate-reducing zone. Bottom and pore water DOM from the Discovery Basin contained the highest abundances of aliphatic compounds in the entire dataset; a large fraction of abundant N-bearing formulas possibly represented peptide and nucleotide formulas suggesting preservation of these molecules in the life inhibiting environment of the Discovery Basin. Our unique data set provides the basis for a comprehensive understanding of the molecular signatures in pore water DOM and the turnover of sedimentary organic matter in marine sediments.

Numerical evaluation of the use of granulated coal ash to reduce an oxygen-deficient water mass

Granulated coal ash (GCA), which is a by-product of coal thermal electric power stations, effectively decreases phosphate and hydrogen sulfide (H2S) concentrations in the pore water of coastal marine sediments. In this study, we developed a pelagic–benthic coupled ecosystem model to evaluate the effectiveness of GCA for diminishing the oxygen-deficient water mass formed in coastal bottom water of Hiroshima Bay in Japan. Numerical experiments revealed the application of GCA was effective for reducing the oxygen-deficient water masses, showing alleviation of the DO depletion in summer increased by 0.4–3mgl−1. The effect of H2S adsorption onto the GCA lasted for 5.25years in the case in which GCA was mixed with the sediment in a volume ratio of 1:1. The application of this new GCA-based environmental restoration technique could also make a substantial contribution to form a recycling-oriented society.

Mineral formation during bacterial sulfate reduction in the presence of different electron donors and carbon sources

Sulfate-reducing bacteria have long been known to promote mineral precipitation. However, the influence of electron donors (energy sources) and carbon sources on the minerals formed during sulfate reduction is less well understood. An investigation was therefore undertaken to determine how these nutrients affect sulfate reduction by the bacterium Desulfovibrio alaskensis G20 in a marine sediment pore water medium. Monohydrocalcite and a small amount of calcite formed during sulfate reduction with formate as the electron donor; Mg-phosphates and calcite precipitated when hydrogen served as the electron donor and when acetate and dissolved inorganic carbon served as carbon sources; and greigite and elemental sulfur were deposited when lactate was used as the electron donor and carbon source. The experimental results were generally consistent with geochemical modeling, suggesting that it may be possible to predict the processes and conditions during formation of these minerals in natural environments.

Dissolved proteins characterization and speciation studies of metal-protein complexes in marine sediment pore water

Dissolved proteins characterization in marine sediment pore water has been performed by offgel electrophoresis (OGE) and microfluidic lab-on-chip (LOC) electrophoresis, assessing for the first time dissolved protein characteristics such as isoelectric point (pIs), and molecular weight (MW). In addition, speciation studies of metal-protein complexes in sediment pore water have also been performed by direct analysis of offgel fractions by electrothermal atomic absorption spectrometry (ETAAS), and inductively coupled plasma optical emission spectrometry (ICP-OES). Samples were subjected to a tangential flow ultrafiltration (UF) followed by a centrifugal UF (10kDa molecular weight cut-off, MWCO) procedure, which offered a pre-concentration factor of 450. Isolation of dissolved proteins from the extracts has been performed by treating the ultrafiltrated fractions with methanol-chloroform as a precipitating reagent. The protein pellets were dried, dissolved in the offgel buffer, and subjected to optimized OGE and LOC electrophoresis procedures. Results showed proteins of MWs ranging from 5.1 to 87.0kDa, and proteins exhibiting the highest MW were found in offgel fractions comprising pIs within the 6.34–7.76 range. Regarding metal-protein complexes, cadmium (Cd), and lead (Pb) were not found in any of the analyzed offgel fractions, which implies low affinity of these elements to the isolated proteins. However, iron (Fe) was found to be associated to proteins with pIs between 3.0 and 10 (the highest Fe concentrations were found in proteins from offgel fractions with pIs 6.3 to 7.7). Finally, copper (Cu), manganese (Mn), and zinc (Zn) were found to be bound to proteins exhibiting low MWs.

Estimation of hydrogen sulfide removal efficiency with granulated coal ash applied to eutrophic marine sediment using a simplified simulation model

Hydrogen sulfide generated in eutrophic marine sediment is harmful for living organisms. It is therefore necessary to remove hydrogen sulfide from the sediment to restore benthic ecosystems. Previous studies revealed that granulated coal ash, which is a by-product of coal thermal electric power stations, could remove and oxidize hydrogen sulfide. In this study, we propose a simplified simulation model to estimate the hydrogen sulfide removal efficiency of granulated coal ash. Hydrogen sulfide concentrations in eutrophic marine sediment pore water with and without the application of granulated coal ash were calculated by the proposed model, and the outputs were compared with semi-field or field observation data. The model outputs reproduced the observed data well. Using the proposed model outputs, we suggest an optimum application dosage of granulated coal ash for remediating eutrophic marine sediment.

Geochemistry of clayey aquitard pore water as archive of paleo-environment, western Bohai Bay

The record of paleo-environment in clayey aquitard pore water is much more effective relative to aquifer groundwater owing to the low permeability of clayey aquitard. Oxygen-18 ( 18 O), deuterium (D), and chemical patterns were determined in pore water samples extracted from two 500 m depth boreholes, G1 and G2, in western Bohai Bay, China. Shallow pore water samples (depth<102 m) are saline water, with the TDS (total dissolved solids) of 3.69-30.75 g/L, and deeper ones (depth=102-500 m) are fresh water, with the TDS<1 g/L. Content of major ions (i.e., Cl - , Na + , K + , Mg 2+ , SO4 2- , Ca 2+ ) is high in marine sediment pore water samples and gradually decrease towards to terres- trial sediment pore waters, together with the Cl/Br and Sr/Ba ratios changing significantly in different sedimentary facies along the study profile, indicating that pore water may be paleo-sedimentary water and not replaced by modern water. δ 18 O profile and positive correlation between δ 18 O and Cl - of shal- low saline pore water indicated diffusion as the main transport mechanism, and distinguished four transgressive layers since Late Quaternary (i.e., Holocene marine unit, two Late Pleistocene marine units and Middle Pleistocene marine unit), further supporting the finding that pore water retained the feature of paleo-sedimentary water. Climate was identified as the main influence on the isotopic signa- ture of aquitard pore waters and four climate periods were determined by δ 18 O profile.

Direct analysis of volatile fatty acids in marine sediment porewater by two‐dimensional ion chromatography‐mass spectrometry

Volatile fatty acids (VFAs) are key intermediates in the microbial food web. However, the analysis of low concentrations of VFAs in marine porewater is hampered by interference from high concentrations of inorganic ions. Published methods often use sample pretreatment, including distillation or derivatization, to overcome this problem. This is not only labor intensive but also increases the risk of contamination. We have developed an analytical procedure that enables the direct quantification of several VFAs (formate, acetate, propionate, butyrate, valerate, pyruvate, and lactate) in marine porewater by two‐dimensional ion chromatography‐mass spectrometry (2D IC‐MS). The first chromatographic dimension is used to separate the VFAs from the inorganic ions whereas the second dimension separates the individual VFAs. Quantification and identification are achieved by online mass spectrometry in selected ion monitoring mode. No sample pretreatment is required and statistically determined detection limits are below 25 ppb (µg L−1). The method can also be used without the online coupling to a mass spectrometer. In the latter case, quantification of the VFAs can be done by the conductivity detector signal of the second dimension with the limitation that lactate cannot be quantified due to signal interference with an unidentified peak and pyruvate and valerate have slightly higher detection limits (&lt;100 ppb).

Gas chromatographic analysis of methanol and ethanol in marine sediment pore waters: Validation and implementation of three pretreatment techniques

Low-molecular-weight (LMW) alcohols are produced during the microbial degradation of organic matter from precursors such as lignin, pectin, and carbohydrates. The biogeochemical behavior of these alcohols in marine sediment is poorly constrained but potentially central to carbon cycling. Little is known about LMW alcohols in sediment pore waters because of their low concentrations and high water miscibility, both of which pose substantial analytical challenges. In this study, three alternative methods were adapted for the analysis of trace amounts of methanol and ethanol in small volumes of saline pore waters: direct aqueous injection (DAI), solid-phase microextraction (SPME), and purge and trap (P&T) in combination with gas chromatography (GC) coupled to either a flame ionization detector (FID) or a mass spectrometer (MS). Key modifications included the desalination of samples prior to DAI, the use of a threaded midget bubbler to purge small-volume samples under heated conditions and the addition of salt during P&T. All three methods were validated for LMW alcohol analysis, and the lowest detection limit (60nM and 40nM for methanol and ethanol, respectively) was achieved with the P&T technique. With these methods, ambient concentrations of volatile alcohols were determined for the first time in marine sediment pore waters of the Black Sea and the Gulf of Mexico. A strong correlation between the two compounds was observed and tentatively interpreted as being controlled by similar sources and sinks at the examined stations.