skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Characterization of Dissolved Organic Matter in Anoxic rock Extracts and in situ Pore Water of the Opalinus Clay

; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
Report Number(s):
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Applied Geochemistry; Journal Volume: 22
Country of Publication:
United States
national synchrotron light source

Citation Formats

Courdouan,A., Christl, I., Meylan, S., Wersin, P., and Kretzschmar, R. Characterization of Dissolved Organic Matter in Anoxic rock Extracts and in situ Pore Water of the Opalinus Clay. United States: N. p., 2007. Web. doi:10.1016/j.apgeochem.2007.09.001.
Courdouan,A., Christl, I., Meylan, S., Wersin, P., & Kretzschmar, R. Characterization of Dissolved Organic Matter in Anoxic rock Extracts and in situ Pore Water of the Opalinus Clay. United States. doi:10.1016/j.apgeochem.2007.09.001.
Courdouan,A., Christl, I., Meylan, S., Wersin, P., and Kretzschmar, R. Mon . "Characterization of Dissolved Organic Matter in Anoxic rock Extracts and in situ Pore Water of the Opalinus Clay". United States. doi:10.1016/j.apgeochem.2007.09.001.
title = {Characterization of Dissolved Organic Matter in Anoxic rock Extracts and in situ Pore Water of the Opalinus Clay},
author = {Courdouan,A. and Christl, I. and Meylan, S. and Wersin, P. and Kretzschmar, R.},
abstractNote = {},
doi = {10.1016/j.apgeochem.2007.09.001},
journal = {Applied Geochemistry},
number = ,
volume = 22,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
  • Pore water dissolved organic matter (DOM) plays an important role in the distribution, mobility, and bioavailability of hydrophobic organic chemicals (HOCs) in sediment environments. The effect of aeration on the partitioning of 2,2{prime},4,4{prime}-tetrachlorobiphenyl (TeCB) to anoxic pore water DOM from three estuarine sites was investigated. Pore water DOM was fractionated into molecular size and polarity fractions by ultrafiltration and XAD-8 resin chromatography. Total organic carbon analysis was utilized to determine shifts in molecular size and polarity distributions. Changes in functional groups and aromaticity were evaluated for whole and fractionated pore waters by specific UV absorbance at 254 nm (SUVA{sub 254}).more » The solubility enhancement method was used to determine the partitioning of TeCB to whole and fractionated pore water DOM. At two sites, the overall TeCB-DOM distribution coefficient decreased by an order of magnitude after aeration. The higher molecular size and all polarity fractions exhibited a decrease in partitioning behavior upon aeration. The aromaticity and TeCB-DOM distribution coefficient of the lowest molecular size fraction decreased upon aeration. The highest and lowest molecular size fractions contributed the most to overall partitioning. The observed aeration effects in anoxic estuarine sediment pore waters differed significantly from those previously reported in freshwater systems.« less
  • Pore water dissolved organic matter is an overlooked pool of organic matter important to the environmental fate of hydrophobic organic pollutants. The association of polychlorinated biphenyls, polyaromatic hydrocarbons and chlorinated pesticides with pore water dissolved organic matter influences their distribution and mobility within the bottom sediment environment. Steep physical, biological and chemical gradients at the sediment/water interface isolate the pore water and create unique conditions within the sediment. This study indicates that any disturbance of this environment will alter the distribution and mobility of organic pollutants by changing their association to the pore water dissolved organic matter. A small volumemore » closed equilibration method was developed to measure the solubility enhancement of 2,2' 4,4'-tetrachlorobiphenyl (TeCB) by natural dissolved organic matter. Chemical coated micro-glass beads were equilibrated with anoxic and laboratory aerated (oxic) pore water samples in flame sealed ampules. The TeCB enhanced solubilities were used to determine the pore water dissolved organic matter partition coefficient, K[sub pwdom]. The measured TeCB solubility and K[sub pwdom] were much smaller for anoxic than oxic pore waters. The dissolved organic matter sorptive capacity for the TeCB increased as the water was aerated. This change is attributed to coagulative fractionation and structural changes of the pore water dissolved organic matter during aeration and was characterized by differences in the dissolved organic matter concentration, UV absorption at 254 nm, interfacial surface tension, and sorption capacity of molecular weight fractions of anoxic and oxic pore water dissolved organic matter. The increase in partitioning indicates that there will be an increase in the mobility of the TeCB as an anoxic bottom sediment environment is disturbed and aerated.« less
  • Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less
  • Elemental composition data were obtained for bulk precipitation and throughfall samples and for aqueous extracts of leaves of three woody plant species common in the subalpine Sierras Nevada range, California: chinquapin (Chrysolepis sempervirens Hjelmqvist), western white pine (Pinus monticola Dougl.), and willow (Salix orestera Schneider). The acid-base equilibria of the extracts were characterized by potentiometric titration and proton formation functions were computed. The latter then were modeled assuming four classes of quasiparticle acidic functional groups, yielding negative logarithms of conditional protonation constants in the range 4.8 to 5.0, 6.1 to 6.6, 7.4 to 7.7, and 9.1 to 9.4. The relativemore » concentration of a given acidic functional group class varied markedly among the three woody species, but the conditional protonation constants were very similar. The model parameters, along with dissolved organic C concentration and pH values, were used to estimate net anion deficits in throughfall samples collected from the same sites as the leaf samples. On average, the calculated charge concentration of free organic anions in the western white pine extract matched the throughfall anion deficit, whereas the deficits in the chinquapin and willow throughfall samples were not accounted for by free anion concentrations. Metal complexation and in situ, species-dependent leaf surfaces processes may account for these latter differences.« less
  • A significant fraction (~ 20%) of microbial life is found in the terrestrial deep subsurface, yet the metabolic processes extant in those environments are poorly understood. Here we show that H 2, injected into the Opalinus Clay formation in a borehole located 300 meters below the surface, fuels a community of microorganisms with interconnected metabolisms. Metagenomic binning and metaproteomic analysis reveal a complete carbon cycle, driven by autotrophic hydrogen oxidizers. Dead biomass from these organisms is a substrate for a fermenting bacterium that produces acetate as a product. In turn, complete oxidizer heterotrophic sulfate- reducing bacteria utilize acetate and oxidizemore » it to CO 2, closing the cycle. This metabolic reconstruction sheds light onto a hydrogen-driven carbon cycle, and a sunlight-independent ecosystem in the deep subsurface.« less