Early diagenetic processes in Labrador Sea sediments: uranium-isotope geochemistry

1994 ◽  
Vol 31 (1) ◽  
pp. 28-37 ◽  
Author(s):  
C. Gariépy ◽  
B. Ghaleb ◽  
C. Hillaire-Marcel ◽  
A. Mucci ◽  
S. Vallières
Keyword(s):  
Isotopic Composition ◽  
Pore Water ◽  
Iron Reduction ◽  
Molecular Diffusion ◽  
Solid Phase ◽  
Redox Conditions ◽  
Labrador Sea ◽  
Benthic Boundary Layer ◽  
Ionization Mass ◽  
Pore Waters

The concentration and isotopic composition of U dissolved in pore waters from hemipelagic sediments of the Labrador Sea were determined by thermal ionization mass spectrometry in two 30 cm long box cores. The present fluxes of seawater U that diffuses across the sediment–seawater interface are on the order of 2–4 μg/(cm2∙ka). This diffusion imposes decreasing gradients of dissolved U downwards, but the U concentration in pore waters immediately below the surface is much lower than that of open-ocean seawater. This is a primary feature that cannot be explained by carbonate precipitation due to decompression during core retrieval. More likely, it reflects the presence of a stagnant benthic boundary layer above the sediment–water interface, in which molecular diffusion of U is slower than in the overlying turbulently mixed seawater, and (or) of microzones near the interface where U is bioaccumulated. Uranium is adsorbed at depths onto the solid phase in response to changes in the redox conditions within the sediments. In the Labrador Sea, this occurs at the onset of iron reduction and corresponds to a colour transition from brown to grey. Adsorption of U is sufficiently large to alter the initial content and the isotopic composition of U in the detrital component. Accumulation of authigenic U on the solid phase does not proceed at a steady state. This is due to the uneven burial rates of organic matter, which is essential to the establishment of redox conditions appropriate for U reduction, and concomitant stepwise displacement of the redox fronts. This indicates that discrete periods of enhanced primary productivity recurred over the last millenium in the Labrador Sea, inducing U fluxes to the sediments greater than they are now. Measured pore-water U concentrations are greater than the overlying seawater at depth in the cores, despite the fact that none of the conditions necessary to release U under reducing conditions are present in the sediments. More likely, U-bearing particles < 0.45 μm were transferred with the solution phase through the filtering device, artificially increasing the pore-water U content.

In Situ Measurements of Pore Water Diffusion Coefficients Using Tritiated Water

1980 ◽  
Vol 37 (3) ◽  
pp. 545-551 ◽  
Author(s):  
R. H. Hesslein
Keyword(s):  
Pore Water ◽  
Diffusion Coefficients ◽  
Molecular Diffusion ◽  
Solid Phase ◽  
Tritiated Water ◽  
Water Diffusion ◽  
Pore Waters ◽  
Sediment Depth ◽  
Constant Diffusivity

In situ diffusion coefficients in the pore waters of Lake 227 were measured by monitoring the movement of tritiated water into the pore waters. The diffusion coefficients were determined by analytical and numerical modeling of the tritium profiles. During the summer, tritiated water diffuses into the sediment by molecular diffusion and this process is well approximated by a constant diffusivity model. The summer coefficients for diffusion were 1–2 × 10−5 cm2∙s−1 at a water depth of 1.5 m (20 °C) and 0.3–0.8 × 10−6 cm2∙s−1 at 8.75 m (4 °C). During fall overturn, clear evidence was found for enhanced mixing of pore waters to a sediment depth of 10 cm at water depths of 0.75 and 3.85 m. This enhanced mixing was not accompanied by mixing of the solid phase of the sediments.Key words: sediments, pore water, diffusion coefficients, tritium, lake sediments

Dissolution and recrystallization in modern shelf carbonates: evidence from pore water and solid phase chemistry

1993 ◽  
Vol 344 (1670) ◽  
pp. 27-36 ◽  
Keyword(s):  
Organic Matter ◽  
Pore Water ◽  
Solid Phase ◽  
Chemical Exchange ◽  
Isotope Composition ◽  
Geochemical Data ◽  
Carbonate Sediments ◽  
Pore Waters ◽  
Carbonate Minerals ◽  
Carbonate Production

We present an overview of geochemical data from pore waters and solid phases that clarify earliest diagenetic processes affecting modern, shallow marine carbonate sediments. Acids produced by organic matter decomposition react rapidly with metastable carbonate minerals in pore waters to produce extensive syndepositional dissolution and recrystallization. Stoichiometric relations among pore water solutes suggest that dissolution is related to oxidation of H 2 S which can accumulate in these low-Fe sediments. Sulphide oxidation likely occurs by enhanced diffusion of O 2 mediated by sulphide-oxidizing bacteria which colonize oxic/anoxic interfaces invaginating these intensely bioturbated sediments. Buffering of pore water stable isotopic compositions towards values of bulk sediment and rapid 45 Ca exchange rates during sediment incubations demonstrate that carbonate recrystallization is a significant process. Comparison of average biogenic carbonate production rates with estimated rates of dissolution and recrystallization suggests that over half the gross production is dissolved and/or recrystallized. Thus isotopic and elemental composition of carbonate minerals can experience significant alteration during earliest burial driven by chemical exchange among carbonate minerals and decomposing organic matter. Temporal shifts in palaeo-ocean carbon isotope composition inferred from bulk-rocks may be seriously compromised by facies-dependent differences in dissolution and recrystallization rates.

scholarly journals DOC-dynamics in a small headwater catchment as driven by redox fluctuations and hydrological flow paths – are DOC exports mediated by iron reduction/oxidation cycles?

2013 ◽  
Vol 10 (2) ◽  
pp. 891-904 ◽  
Author(s):  
K.-H. Knorr
Keyword(s):  
Ionic Strength ◽  
Pore Water ◽  
Surface Waters ◽  
Iron Reduction ◽  
Stream Water ◽  
Riparian Wetlands ◽  
Pore Waters ◽  
Flow Paths ◽  
Discharge Patterns ◽  
Iron Concentrations

Abstract. Dissolved organic carbon (DOC) exports from many catchments in Europe and North-America are steadily increasing. Several studies have sought to explain this observation. As possible causes, a decrease in acid rain or sulfate deposition, concomitant reductions in ionic strength and increasing temperatures were identified. DOC often originates from riparian wetlands; but here, despite higher DOC concentrations, ionic strength in pore waters usually exceeds that in surface waters. In the catchment under study, DOC concentrations were synchronous with dissolved iron concentrations in pore and stream water. This study aims at testing the hypothesis that DOC exports are mediated by iron reduction/oxidation cycles. Following the observed hydrographs, δ18O of water and DOC fluorescence, the wetlands were identified as the main source of DOC. Antecedent biogeochemical conditions, i.e., water table levels in the wetlands, influenced the discharge patterns of nitrate, iron and DOC during an event. The correlation of DOC with pH was positive in pore waters, but negative in surface waters; it was negative for DOC with sulfate in pore waters, but only weak in surface waters. Though, the positive correlation of DOC with iron was universal for pore and surface water. The decline of DOC and iron concentrations in transition from anoxic wetland pore water to oxic stream water suggests a flocculation of DOC with oxidising iron, leading to a drop in pH in the stream during high DOC fluxes. The pore water did not per se differ in pH. There is, thus, a need to consider processes more thoroughly of DOC mobilisation in wetlands when interpreting DOC exports from catchments. The coupling of DOC with iron fluxes suggested that increased DOC exports could at least, in part, be caused by increasing activities in iron reduction, possibly due to increases in temperature, increasing wetness of riparian wetlands, or by a shift from sulfate dominated to iron reduction dominated biogeochemical regimes.

scholarly journals Diagenetic Processes in Aquaculture Ponds Showing Metal Accumulation on Shrimp Gills

2021 ◽  
Vol 8 ◽  
Author(s):  
Hugues Lemonnier ◽  
Florence Royer ◽  
Florian Caradec ◽  
Etienne Lopez ◽  
Clarisse Hubert ◽  
...  
Keyword(s):  
Pore Water ◽  
Solid Phase ◽  
Acid Volatile Sulfide ◽  
Pore Waters ◽  
Dissolved Metals ◽  
Ecological Processes ◽  
Physico Chemical ◽  
Aquaculture Ponds ◽  
Tropical Aquaculture ◽  
Carbon Acid

The gill is the organ by which many toxic metals are taken up by crustaceans. Iron is known to precipitate at its surface, a phenomenon recently observed in some tropical aquaculture ponds. The present study uses a field approach to understand better the environmental conditions and ecological processes involved in this deposit. Because shrimp are exposed to reduced products originating from organic waste accumulated in the sediment, spatial variation in pH, redox potential and concentrations of dissolved metals in pore water were investigated in these ponds. Total organic carbon, acid volatile sulfide and pyrite were also analyzed in the solid phase. Fe2+ in pore waters showed high spatial variability between ponds and within the same pond with concentrations up to 1,193 μmol l–1. Behaviors of Fe2+, Mn2+ and Co2+ in pore water were similar. Four geochemical environments were identified, based on their physico-chemical characteristics. Highest concentrations for Fe2+, Mn2+ and Co2+ in sediment pore water occurred in slightly acidic and suboxic conditions. When the sediment became anoxic, the H2S produced reacted with Fe2+ and/or Co2+ to form acid volatile sulfide and pyrite. When pH increased, the concentration of free H2S rose up to 736 μmol l–1. With neutral and suboxic conditions, dissolved metal concentrations could be controlled by their precipitation as oxides and hydroxides. The production of pyrite suggested the existence of a possible process of sediment acidification between two crop periods through the production of sulfuric acid. This acidification could increase with pond age and be the cause of the accumulation of reduced metal after 30 years of aquaculture activity.

scholarly journals DOC-dynamics in a small headwater catchment as driven by redox fluctuations and hydrological flow paths – are DOC exports mediated by iron reduction/oxidation cycles?

2012 ◽  
Vol 9 (9) ◽  
pp. 12951-12984 ◽  
Author(s):  
K.-H. Knorr
Keyword(s):  
Ionic Strength ◽  
Pore Water ◽  
Surface Waters ◽  
Iron Reduction ◽  
Stream Water ◽  
Riparian Wetlands ◽  
Pore Waters ◽  
Flow Paths ◽  
Discharge Patterns ◽  
Iron Concentrations

Abstract. Dissolved organic carbon (DOC) exports from many catchments in Europe and North-America are steadily increasing. Several studies have sought to explain this observation. As possible causes, a decrease in acid rain or sulfate deposition, concomitant reductions in ionic strength and increasing temperatures were identified. DOC often originates from riparian wetlands; but here, despite higher DOC concentrations, ionic strength in pore waters usually exceeds that in surface waters. In the catchment under study, DOC concentrations were synchronous with dissolved iron concentrations in pore and stream water. This study aims at testing the hypothesis that DOC exports are mediated by iron reduction/oxidation cycles. Following the observed hydrographs, δ18O of water, and DOC fluorescence, the wetlands were identified as main source of DOC. Antecedent biogeochemical conditions, i.e. water table levels in the wetlands, influenced the discharge patterns of nitrate, iron, and DOC during an event. The correlation of DOC with pH was positive in pore waters but negative in surface waters; it was negative for DOC with sulfate in pore waters but only weak in surface waters. The positive correlation of DOC with iron was universal for pore and surface water, though. The decline of DOC and iron concentrations in transition from anoxic wetland pore water to oxic stream water suggests a flocculation of DOC with oxidizing iron, leading to a drop in pH in the stream during high DOC fluxes. The pore water did not per se differ in pH. There is thus a need to more thoroughly consider processes of DOC mobilization in wetlands when interpreting DOC exports from catchments. The coupling of DOC with iron fluxes suggested that increased DOC exports could at least in part be caused by increasing activities in iron reduction, possibly due to increases in temperature or wetness of riparian wetlands.

scholarly journals Benthic alkalinity and DIC fluxes in the Rhône River prodelta generated by decoupled aerobic and anaerobic processes

2019 ◽  
Author(s):  
Jens Rassmann ◽  
Eryn M. Eitel ◽  
Cécile Cathalot ◽  
Christophe Brandily ◽  
Bruno Lansard ◽  
...  
Keyword(s):  
Pore Water ◽  
Iron Reduction ◽  
Iron Sulfide ◽  
Dissolved Inorganic Carbon ◽  
River Mouth ◽  
Total Alkalinity ◽  
Pore Waters ◽  
Rhône River ◽  
Net Production ◽  
Rhone River

Abstract. Estuarine regions are generally considered a net source of atmospheric CO2 as a result of the high organic carbon (OC) mineralization rates in the water column and their sediments. Yet, the intensity of anaerobic respiration processes in the sediments tempered by the reoxidation of reduced metabolites controls the net production of alkalinity from sediments that may partially buffer the metabolic CO2 generated by OC respiration. In this study, a benthic chamber was deployed in the Rhône River prodelta and the adjacent continental shelf (Gulf of Lions, NW Mediterranean) to assess the fluxes of total alkalinity (TA) and dissolved inorganic carbon (DIC) from the sediment. Concurrently, in situ O2 and pH microprofiles, electrochemical profiles, pore water and solid composition were measured in surface sediments to identify the main biogeochemical processes controlling the net production of alkalinity in these sediments. The benthic fluxes of TA and DIC, ranging between 14 and 74 mmol m−2 d−1 and 18 and 78 mmol m−2 d−1, respectively, were up to 8 times higher than the DOU fluxes (10.4 ± 0.9 mmol m−2 d−1) close to the river mouth, but their intensity decreased offshore, as a result of the decline in OC inputs. Low nitrate concentrations and strong pore water sulfate gradients indicated that the majority of the TA and DIC was produced by sulfate and iron reduction. Despite the complete removal of sulfate from the pore waters, dissolved sulfide concentrations were low due to the precipitation and burial of iron sulfide minerals (12.5 mmol m−2 d−1 near the river mouth), while soluble organic-Fe(III) complexes were concurrently found throughout the sediment column. The presence of organic-Fe(III) complexes together with low sulfide concentrations and high sulfate consumption suggests a dynamic system driven by the variability of the organic and inorganic particulate input originating from the river. By preventing reduced substances from being reoxidized, the precipitation and burial of iron sulfide decouples the iron and sulfur cycles from oxygen, therefore allowing a flux of alkalinity out of the sediments. In these conditions, the sediment provides a source of alkalinity to the bottom waters which mitigates the effect of the benthic DIC flux on the carbonate chemistry of coastal waters.

scholarly journals First assessment of the pore water composition of Rupel Clay in the Netherlands and the characterisation of its reactive solids

2016 ◽  
Vol 95 (3) ◽  
pp. 315-335 ◽  
Author(s):  
Thilo Behrends ◽  
Iris van der Veen ◽  
Alwina Hoving ◽  
Jasper Griffioen
Keyword(s):  
The Netherlands ◽  
Pore Water ◽  
Solid Phase ◽  
Clay Material ◽  
Pore Waters ◽  
Calcium Carbonates ◽  
Boom Clay ◽  
Water Composition ◽  
Dilution Experiments ◽  
Chloride Concentrations

AbstractThe Rupel Clay member in the Netherlands largely corresponds to the Boom Formation in Belgium, and this marine, clay-rich deposit is a potential candidate to host radioactive waste disposal facilities. Prediction of the speciation of radionuclides in Rupel Clay pore water and their retardation by interactions with Rupel Clay components requires knowledge about the composition of Rupel Clay pore water, the inventory of reactive solids and understanding of interactions between Rupel Clay and pore water. Here, we studied Rupel Clay material which was obtained from cores collected in the province of Zeeland, the Netherlands, and from drilling cuttings retrieved from a drilling in the province of Limburg, the Netherlands. Pore water was obtained by mechanical squeezing of Rupel Clay material from Zeeland. Additionally, anaerobic dilution experiments were performed in which the clay material was suspended with demineralised water or a 0.1M NaHCO3solution. Solid-phase characterisation included determination of carbon, nitrogen and sulphur contents, measurement of cation exchange capacity (CEC) and sequential extraction of iron phases.In contrast to the pore water in Belgian Boom Clay, pore water collected from the location in Zeeland has a higher salinity, with chloride concentrations corresponding to 70–96% of those in seawater. The high chloride concentrations most likely result from the intrusion of ions from saline waters above the Rupel Clay in Zeeland. Cation exchange during salinisation might account for the observed deficit of marine cations (Na, K, Mg) and excess of Ca concentrations, in comparison with seawater. The measured CEC values at both locations in the Netherlands vary between 7 and 35 meq(100g)−1and are, for most samples, in the range reported for Boom Clay in Belgium (7–30meq(100g)−1).Pore water and solid-phase composition indicate that Rupel Clay from Zeeland has been affected by oxidation of pyrite or other Fe(II)-containing solids. When coupled to the dissolution of calcium carbonates, oxidation of pyrite can account for the elevated sulphate and calcium concentrations measured in some of the pore waters. The relatively low concentrations of pyrite, organic carbon and calcite in the Rupel Clay in Zeeland, in comparison to Limburg, might be an indicator for an oxidation event. Higher contents of dithionite-extractable Fe in Rupel Clay in Zeeland (0.7–2.6mg Fe / g clay) than in Limburg (0.4–0.5mg Fe / g clay) might also be a consequence of the oxidation of Fe(II) minerals. Oxidation in the past could have accompanied partial erosion of Rupel Clay in Zeeland before deposition of the Breda Formation. However, indications are given that oxidation occurred in some of the pore waters after sampling and that partial oxidation of the cores during storage cannot be excluded. Results from dilution experiments substantiate the influence of equilibration with calcium carbonates on pore water composition. Furthermore, removal of dissolved sulphate upon interaction with Rupel Clay has been observed in some dilution experiments, possibly involving microbial sulphate reduction.

scholarly journals Hydrochemistry of sediment pore water in the Bratsk reservoir (Baikal region, Russia)

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
V. I. Poletaeva ◽  
E. N. Tirskikh ◽  
M. V. Pastukhov
Keyword(s):  
Pore Water ◽  
Ionic Composition ◽  
Water System ◽  
Water Reservoir ◽  
Environmental Parameters ◽  
Water Area ◽  
Pore Waters ◽  
Overlying Water ◽  
Major Ion ◽  
Bratsk Reservoir

AbstractThis study aimed to identify the factors responsible for the major ion composition of pore water from the bottom sediments of the Bratsk water reservoir, which is part of the largest freshwater Baikal-Angara water system. In the Bratsk reservoir, the overlying water was characterized as HCO3–Ca–Mg type with the mineralization ranging between 101.2 and 127.7 mg L−1 and pore water was characterized as HCO3–SO4–Ca, SO4–Cl–Ca–Mg and mixed water types, which had mineralization varying from 165.9 to 4608.1 mg L−1. The ionic composition of pore waters varied both along the sediment depth profile and across the water area. In pore water, the difference between the highest and lowest values was remarkably large: 5.1 times for K+, 13 times for Mg2+, 16 times for HCO3−, 20 times for Ca2+, 23 times for Na+, 80 times for SO42−, 105 times for Cl−. Such variability at different sites of the reservoir was due to the interrelation between major ion concentrations in the pore water and environmental parameters. The major factor responsible for pore water chemistry was the dissolution of sediment-forming material coming from various geochemical provinces. In the south part of the reservoir, Cl−, Na+ and SO42− concentrations may significantly increase in pore water due to the effect of subaqueous flow of highly mineralized groundwater.

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