Early Diagenetic Reactions Research Articles

Early Diagenetic Processes in the Sediments of the Krka River Estuary

To study the processes that govern the post-depositional mobility of metals in the estuarine sediment, five sediment cores were sampled in the Krka River estuary (Croatia). The obtained concentration ranges in the pore water were 0.057–49.7 μM for Fe, 0.310–100 μM for Mn, 0.068–26.8 nM for Co, 0.126–153 nM for Cu, 11.5–2793 nM for Zn, 0.222–31.3 nM for Pb, 4.09–59.4 nM for U, 38.8–2228 nM for Mo, and 0.065–2.29 nM for As. The vertical distribution of metals in the dissolved and solid fraction of the sediment, coupled with other diagenetic tracers (e.g., dissolved sulphide), demonstrate the importance of early diagenetic reactions, in particular Fe and Mn oxyhydroxide and sulphate reduction, for the cycling of metals in the sediment. The redox zonation in the sediment was compressed, and the suboxic zone occurs immediately below the sediment–water interface. The estimated benthic fluxes in the estuary were 5220 kg y−1 for Fe, 27,100 kg y−1 for Mn, 6.00 kg y−1 for Co, 20.5 kg y−1 for Cu, 5.16 kg y−1 for Pb, 111 kg y−1 for Mo, and 87.3 kg y−1 for As. The riverine input was more important than the benthic flux, except in the case of Mn and Fe.

Rare earth element distributions in salt marsh sediment cores reveal evidence of environmental lability during bioturbation and diagenetic processes

The distribution and accumulation of rare earth elements (REE) in the labile fraction of sediment cores collected from salt marshes in the Patos Lagoon estuary from southern Brazil were investigated. Sediment cores (ca. 40 cm) were obtained from three locations within the estuary to capture possible changes in REE content across the salinity gradient (i.e., where saline, brackish, and freshwater dominate). Salt marsh sediments from all three coring locations were enriched in the light REE (LREE) over the heavy REE (HREE) when normalized to the North American shale composite (NASC). Shale normalized values for the LREE of marsh sediments from sites M2 and M3 in the mid- and upper estuary commonly approximates unity indicating these sediments chiefly exhibit a terrigenous signature. In contrast, all 14 naturally occurring REE are depleted in the sediments from the M1 coring location in the lower estuary compared to shale. Sediments from the mid-estuary (M2 core location) where typical salinity values are ca. 10 practical salinity units, exhibit the greatest shale normalized LREE enrichments. The higher LREE contents of the M2 sediments likely reflect preferential removal of LREE from the water column owing to salt-induced coagulation of river-borne colloids that occurs during estuarine mixing processes. Sediments samples collected from the salt marsh in the lower estuary nearer the Atlantic Ocean (i.e., M1), have substantially lower REE contents than salt marsh sediments from sites M2 and M3 in the mid- and upper estuary, respectively. The more sand-rich lower estuary sediments are exposed to higher salinity water from the South Atlantic compared to the generally finer grained sediments from the mid- and upper estuary, which are dominated by brackish and freshwater conditions, respectively. Negative Ce-anomalies (i.e., Ce/Ce* < 1) in marsh sediments from depths generally greater than 27 cm support the occurrence of early diagenetic reactions consistent with suboxic to anoxic conditions whereby reductive dissolution of ferromanganese oxide/oxyhydroxide carrier phases, and/or Ce(IV) phases, release Ce(III) to the marsh pore waters. The negative Ce anomalies suggests that a suboxic or anoxic environment predominates to a depth of 9 cm, and then again below 27 cm depth in sediments from the M2 salt marsh core, and below a depth of 13 cm in the upper estuary marsh sediments (i.e., M3). In contrast, positive Ce anomalies (Ce/Ce* > 1) for much of the sediment from the M1 core, the mid depths of core M2 (i.e., 9 cm to 27 cm), and shallower than 13 cm in sediments from core M3 support oxic conditions where Ce is enriched in sediments from these depths by preferential scavenging from pore waters onto Fe/Mn oxides/oxyhydroxides. These trends in Ce/Ce* with depth in each sediment core are also consistent with known bioturbation that occurs within these marsh sediments. The relatively high REE contents of the sediments from location M3 are also related to the fact that these sediments are dominantly composed of clay-silt deposits that are enriched in organic matter. Finally, we find no conclusive evidence that the studied salt marsh sediments have been impacted by addition of REE from the local fertilizer manufacturing industry.

Control of variability of primary grain assemblages on the stratigraphic differences in diagenetic processes and products in organic-rich sediments

Diagenesis exerts a key control on the evolution of mineralogical systems in shales, and by extension, on the development of rock properties amenable to unconventional reservoir prospectivity. To develop an understanding of the control of primary grain assemblage on the diagenetic pathways and products in shales, integrated high-resolution petrographic and multiple geochemical studies were conducted on samples from a vertical transect of oil-gas mature (vitrinite reflectance ranging from 0.98 to 2.72%) Whitehill Formation, a shale unit identified as the main potential gas reservoir in South Africa. Results show that the formation comprises three intervals with contrasting primary grain assemblages, including organic matter content, maceral type, and detrital mineral grains, as well as the submillimeter-scale arrangement of these constituents. The lower interval occurs as parallel-laminated black shale dominated by components derived from primary production, such as Tasmanites cysts, colonial algae, radiolarian tests, and amorphous organic matter with up to 5.78% TOC, and depleted in siliciclastic detritus. The mid and upper intervals contain biologically produced components (up to 16.57% TOC) and high quantities of siliciclastic mud dominated by clay minerals and micas, and are organized into thick discontinuous gray laminae. Petrographic data suggest that the high organic content supported a variety of bacterial metabolic pathways, which caused the precipitation of mineral cements in the sediment pore spaces prior to compaction. However, the early diagenetic reactions and products in these intervals display systematic variations that reflect heterogeneity in their primary grain assemblages. The presence of framboidal pyrite throughout the lower interval suggests sulfate reduction as the predominant metabolic pathway. In absence of significant volumes of siliciclastics, the acidity associated with this process was poorly buffered, and the pore waters were reducing. These conditions led to the dissolution of opaline radiolarian tests, which recrystallized within Tasmanites cysts and interstitial pores to quartz. On the contrary, carbon isotopes indicate that organic oxidation in the mid and upper sections was mainly promoted by methanogenic archaea and that the associated acidity was effectively buffered by the detrital aluminosilicates. The resulting bicarbonate alkalinities allowed for the formation of interstitial carbonate cements (dolomite, calcite). Aluminum released during the acid-consumption reactions recrystallized within sheltered and interstitial pores to chlorite. Considering that many other shale successions exhibit similar stratigraphic variability of primary grain assemblages as the Whitehill Formation, this type of study will improve the characterization of shale mineralogical systems and bulk properties amenable to sustainable unconventional exploration.

The Carbon-Sulfur Link in the Remineralization of Organic Carbon in Surface Sediments

Here we present the carbon isotopic composition of dissolved inorganic carbon (DIC) and the sulfur isotopic composition of sulfate, along with changes in sulfate concentrations, of the pore fluid collected from a series of sediment cores located along a depth transect on the Iberian Margin. We use these data to explore the coupling of microbial sulfate reduction (MSR) to organic carbon oxidation in the uppermost (up to nine meters) sediment. We argue that the combined use of the carbon and sulfur isotopic composition, of DIC and sulfate respectively, in sedimentary pore fluids, viewed through a δ13CDIC vs. δ34SSO4 cross plot, reveals significant insight into the nature of carbon-sulfur coupling in marine sedimentary pore fluids on continental margins. Our data show systemic changes in the carbon and sulfur isotopic composition of DIC and sulfate (respectively) where, at all sites, the carbon isotopic composition of the DIC decreases before the sulfur isotopic composition of sulfate increases. We compare our results to global data and show that this behavior persists over a range of sediment types, locations and water depths. We use a reactive-transport model to show how changes in the amount of DIC in seawater, the carbon isotopic composition of organic matter, the amount of organic carbon oxidation by early diagenetic reactions, and the presence and source of methane influence the carbon and sulfur isotopic composition of sedimentary pore fluids and the shape of the δ13CDIC vs. δ34SSO4 cross plot. The δ13C of the DIC released during sulfate reduction and sulfate-driven anaerobic oxidation of methane is a major control on the minimum δ13CDIC value in the δ13CDIC vs. δ34SSO4 cross plot, with the δ13C of the organic carbon being important during both MSR and combined sulfate reduction, sulfate-driven AOM and methanogenesis.

The role of hydrothermal fluids in sedimentation in saline alkaline lakes: Evidence from Nasikie Engida, Kenya Rift Valley

AbstractSaline alkaline lakes that precipitate sodium carbonate evaporites are most common in volcanic terrains in semi‐arid environments. Processes that lead to trona precipitation are poorly understood compared to those in sulphate‐dominated and chloride‐dominated lake brines. Nasikie Engida (Little Magadi) in the southern Kenya Rift shows the initial stages of soda evaporite formation. This small shallow (&lt;2 m deep; 7 km long) lake is recharged by alkaline hot springs and seasonal runoff but unlike neighbouring Lake Magadi is perennial. This study aims to understand modern sedimentary and geochemical processes in Nasikie Engida and to assess the importance of geothermal fluids in evaporite formation. Perennial hot‐spring inflow waters along the northern shoreline evaporate and become saturated with respect to nahcolite and trona, which precipitate in the southern part of the lake, up to 6 km from the hot springs. Nahcolite (NaHCO3) forms bladed crystals that nucleate on the lake floor. Trona (Na2CO3·NaHCO3·2H2O) precipitates from more concentrated brines as rafts and as bottom‐nucleated shrubs of acicular crystals that coalesce laterally to form bedded trona. Many processes modify the fluid composition as it evolves. Silica is removed as gels and by early diagenetic reactions and diatoms. Sulphate is depleted by bacterial reduction. Potassium and chloride, of moderate concentration, remain conservative in the brine. Clastic sedimentation is relatively minor because of the predominant hydrothermal inflow. Nahcolite precipitates when and where pCO2 is high, notably near sublacustrine spring discharge. Results from Nasikie Engida show that hot spring discharge has maintained the lake for at least 2 kyr, and that the evaporite formation is strongly influenced by local discharge of carbon dioxide. Brine evolution and evaporite deposition at Nasikie Engida help to explain conditions under which ancient sodium carbonate evaporites formed, including those in other East African rift basins, the Eocene Green River Formation (western USA), and elsewhere.

Controls on abnormally high porosity in a deep burial reservoir of the Lingshui Formation in the Qiongdongnan Basin, South China Sea

Based on information including porosity and permeability, petrography, the stable isotopic composition of carbonate cements, and homogenization temperatures of aqueous fluid inclusions, we have studied the main factors for the development of abnormally high porosity in the Lingshui Formation reservoir of the Yacheng area. We found the sandstones were mainly subarkose, arkose, and lithic arkose and were texturally and compositionally immature. The research suggested that the sandstones existing close beneath the regional unconformity were formed during the Late Oligocene. Early diagenetic calcite cements leached to form intergranular secondary pores without the precipitation of late-diagenetic calcite cements in most sandstones. The isotopic composition of carbonate cements suggested a significant incursion of meteoric freshwater in the sandstones. Early diagenetic meteoric freshwater leaching reactions provided favorable conduits for the penetration of organic acids during the later period. Thermal fluid activities allowed source rocks to mature rapidly; therefore, the organic acid generation period was extended and feldspars were corroded to form abundant intragranular secondary pores. The abundant corroded minerals and the small amounts of associated authigenic minerals suggested that the dissolution of minerals most likely occurred in an open geochemical system. The dissolution of feldspars and calcite minerals generated an enhanced secondary porosity of approximately 9%–13% in thin sections of these sandstones.

Quantification of diagenetic transformation of continental margin sediments at the Holocene time scale

Early diagenesis processes in the Bay of Biscay have been studied previously on short interface cores. In order to complete the data base and to characterize anoxic biogeochemical processes that affect Quaternary deposits, 1–3 m long gravity cores were collected at 150, 550, 1000 and 2000 m water depth on the continental slope of the south-eastern part of the Bay of Biscay. The aim of this work was to determine how a recorded signal could be changed in the several thousand-year situation of the Holocene period. For that, we determined radiocarbon and 210Pb dating, sedimentological characteristics, and the vertical distribution of particulate and pore water biogeochemical compounds. The sediment consists of a muddy facies deposited continuously during the Holocene. Results show that the distribution of redox sensitive compounds follows the well-established depth sequence of diagenetic reactions governed by the preferential use of the electron acceptor for the bacterially mediated oxidation of organic matter. Mineralization of organic matter occurs down to the bottom of the cores studied, indicating that Holocene sediment of the Bay of Biscay are in a transient state and they keep on being diagenetically transformed today. Effects of anoxic processes on buried sediments were estimated from fluxes induced by chemical gradients in pore waters. Anoxic processes consume up to 3.6 mg particulate organic carbon (POC) per g of dry sediment. They yield also precipitation of secondary calcium carbonate, which represent up to 5% of total buried carbonates. Early diagenetic reactions, which affect proxies commonly used in paleo-oceanography, such as POC, carbonates, phosphorus, or manganese, should be quantified in order to distinguish the part of a sedimentary record being the result of past environmental conditions from that due to post-depositional diagenetic processes. Diagenesis of Holocene deposits also contributes to a low, but significant fraction of N and P flux to the Bay of Biscay sea water.

Formation of magnesium‐smectite during lacustrine carbonates early diagenesis: Study case of the volcanic crater lake Dziani Dzaha (Mayotte – Indian Ocean)

AbstractThe volcanic crater lake of Dziani Dzaha in Mayotte is studied to constrain the geochemical settings and the diagenetic processes at the origin of Mg‐phyllosilicates associated with carbonate rocks. The Dziani Dzaha is characterized by intense primary productivity, volcanic gases bubbling in three locations and a volcanic catchment of phonolitic/alkaline composition. The lake water has an alkalinity of ca 0·2 mol l−1 and pH values of ca 9·3. Cores of the lake sediments reaching up to one metre in length were collected and studied by means of carbon–hydrogen–nitrogen elemental analyzer, X‐ray fluorescence spectrometry and X‐ray powder diffraction. In surface sediments, the content of total organic carbon reaches up to 20 weight %. The mineral content consists of aragonite and hydromagnesite with minor amounts of alkaline feldspar and clinopyroxene from the volcanic catchment. Below 30 cm depth, X‐ray diffraction analyses of the &lt;2 μm clay fraction indicate the presence of a saponite‐like mineral, a Mg‐rich smectite. The saponite‐like mineral accumulates at depth to reach up to ca 30 weight %, concurrent with a decrease of the contents of hydromagnesite and organic matter. Thermodynamic considerations and mineral assemblages suggest that the evolution of the sediment composition resulted from early diagenetic reactions. The formation of the saponite‐like mineral instead of Al‐free Mg‐silicates resulted from high aluminum availability, which is favoured in restricted lacustrine environments hosted in alkaline volcanic terrains commonly emplaced during early stages of continental rifting. Supersaturation of the lake water relative to saponite is especially due to high pH values, themselves derived from high primary productivity. This suggests that a genetic link may exist between saponite and the development of organic‐rich carbonate rocks, which may be fuelled by the input of CO2‐rich volcanic gases. This provides novel insights into the composition and formation of saponite‐rich deposits under a specific geodynamic context such as the Cretaceous South Atlantic carbonate reservoirs.

Influence of early diagenesis on geotechnical properties of clay sediments (Romania, Black Sea)

The geotechnical properties of clay sediments were investigated using laboratory and in-situ measurements as part of the geohazard assessment in the Romanian sector of the Black Sea affected by landslides and seafloor deformation features. The sediments were characterized as predominantly high plastic silty clay of high compressibility, low undrained shear strength, low cohesion and moderate sensitivity. A shallow increase in shear strength exceeding the general trend could have been reconciled with evidence for the precipitation of iron sulfides and calcium carbonates related to early diagenetic reactions of sulfate reduction (e.g. cryptic sulfur cycle) and anaerobic oxidation of methane. Comparison of the compression behaviour of natural and reconstituted samples indicated that precipitation of these materials at particle contacts produced cementation. The analysis of deeper sediments sharing similar geochemical properties illustrated that the early precipitation of even low quantity of sulfur and carbonate cements allowed clays to develop sufficient strength to preserve an abnormal high water content even under tens of meters burial depth. Because this cementation process was observed to be associated with an enhanced sensitivity and a strain softening response to undrained shearing it was concluded that such early diagenesis should be considered as a key environmental factor, leading to weak layer formation that may influence the susceptibility of seafloor to failure.

Trace metal behavior in sediments of Jiulong River Estuary and implication for benthic exchange fluxes

Severe metal pollution due to industrial effluents releases has been documented in Jiulong River estuary, Southern China. However, integrated understanding of trace metal behavior in the sediment is lacking. In the present study, DGT (diffusive gradients in thin films) technique was employed together with sediment cores to study the porewater dynamics of trace metals as well as the benthic exchange fluxes from four sampling sites over three different months. The sedimentary environment showed distinct spatial and temporal variations due to effluent discharge and biological activities. Metal behavior was controlled by early diagenetic reactions below the interface, in suboxic layer and in deeper sediment. Precipitation as sulfides and adsorption onto Mn/Fe (hydr)oxides were important in scavenging trace metals. Estimated exchange fluxes at sediment-water interface in this estuary indicated that the overlying water was a major source for trace metals, whereas sediments could also be the source if surface remobilization (Mn/Fe reduction) dominated. Our results highlighted the impacts of both natural and anthropogenic processes on the source, fate and transformation of trace metals in this dynamic system.

A multi-proxy study of sedimentary humic substances in the salt marsh of the Changjiang Estuary, China

To better understand the origin, composition, and reactivity of sedimentary humic substances (HSs) in salt marshes in the Changjiang Estuary, HS samples were isolated from a sediment core that was collected from the Eastern Chongming salt marsh. Chemical and spectroscopic methods were used to analyze the features of these HSs. The results indicate that the studied HSs in the salt marsh sediments are mainly terrestrial-derived and that the sedimentary organic matter (SOM) in the top layer may contain more organic matter from marine sources and/or autochthonous materials due to the dramatic decreasing of the sediment supply as a result of damming. The degradation of labile carbohydrates and proteins and the preservation of refractory lignin components dominate the early diagenetic reactions of SOM in the salt marsh area. The average contents of the carboxylic groups in FAs and HAs are 11.64 ± 1.08 and 7.13 ± 0.16 meq/gC, and those of phenolic groups are 1.95 ± 0.13 and 2.40 ± 0.44 meq/gC, respectively. The content of carboxylic groups increased with increasing depth, while there were no obvious changes in the content of phenolic groups. The average concentration of total proton-binding sites is approximately 12.5 μmol/g sediment for the studied HSs. These values may provide insight into the migration and fate of HS-bound contaminants in sediments and the overlying sea water in the salt marsh areas of the Changjiang Estuary.

Hydrogeochemical models locating sulfate-methane transition zone in marine sediments overlying black shales: A new tool to locate biogenic methane?

Precise hydrogeochemical modeling of early diagenesis is a key in the reconstruction of sedimentary basin models. This determines the mineralogical evolution of the sediment and consequently the porosity of the rock. During early diagenesis also part of the initial organic matter is converted into biogenic gas: CH4 CO2, and H2S. These processes are part of complex reaction chains during sedimentation, and biogeochemical reactions leave different signals that can be observed today. In this work, we reproduce the early diagenetic processes as integrated signals over geological times in sediments of the Demerara Rise by applying chemical thermodynamics using the PHREEQC (version 2) computer code. The investigated sediments are characterized by the presence of black shales in 410–490 mbsf and by a diagenetic barite layer above in 300–350 mbsf at depth of sulfate-methane transition (SMT). We determine the parameters that influence the location of diagenetic barite peaks in sediments overlying black shales by means of a novel modeling approach. Crucial parameters are the amount of bacterial organic matter mineralization, sedimentation rates and bottom water sulfate concentrations. All parameters are intertwining and influence the sulfate-methane cycle. They affect the location of the SMT visualized by diagenetic barite peaks. However, our model approach opens a wide field in exploring early diagenetic reactions, processes and products (such as biogenic methane) over geological times mirrored by diagenetic minerals and pore water concentration profiles that can be detected in present-day sediments.

Benthic fluxes of dissolved organic nitrogen in the lower St. Lawrence estuary and implications for selective organic matter degradation

Abstract. The distribution of dissolved organic nitrogen (DON) and carbon (DOC) in sediment porewaters was determined at nine locations along the St. Lawrence estuary and in the gulf of St. Lawrence. In a previous manuscript (Alkhatib et al., 2012a), we have shown that this study area is characterized by gradients in the sedimentary particulate organic matter (POM) reactivity, bottom water oxygen concentrations, and benthic respiration rates. Based on the porewater profiles, we estimated the benthic diffusive fluxes of DON and DOC in the same area. Our results show that DON fluxed out of the sediments at significant rates (110 to 430 μmol m−2 d−1). DON fluxes were positively correlated with sedimentary POM reactivity and varied inversely with sediment oxygen exposure time (OET), suggesting direct links between POM quality, aerobic remineralization and the release of DON to the water column. DON fluxes were on the order of 30 to 64% of the total benthic inorganic fixed N loss due to denitrification, and often exceeded the diffusive nitrate fluxes into the sediments. Hence they represented a large fraction of the total benthic N exchange, a result that is particularly important in light of the fact that DON fluxes are usually not accounted for in estuarine and coastal zone nutrient budgets. In contrast to DON, DOC fluxes out of the sediments did not show any significant spatial variation along the Laurentian Channel (LC) between the estuary and the gulf (2100 ± 100 μmol m−2 d−1). The molar C / N ratio of dissolved organic matter (DOM) in porewater and the overlying bottom water varied significantly along the transect, with lowest C / N in the lower estuary (5–6) and highest C / N (&gt; 10) in the gulf. Large differences between the C / N ratios of porewater DOM and POM are mainly attributed to a combination of selective POM hydrolysis and elemental fractionation during subsequent DOM mineralization, but selective adsorption of DOM to mineral phases could not be excluded as a potential C / N fractionating process. The extent of this C- versus N- element partitioning seems to be linked to POM reactivity and redox conditions in the sediment porewaters. Our results thus highlight the variable effects selective organic matter (OM) preservation can have on bulk sedimentary C / N ratios, decoupling the primary source C / N signatures from those in sedimentary paleoenvironmental archives. Our study further underscores that the role of estuarine sediments as efficient sinks of bioavailable nitrogen is strongly influenced by the release of DON during early diagenetic reactions, and that DON fluxes from continental margin sediments represent an important internal source of N to the ocean.

Organic matter mineralization and trace element post-depositional redistribution in Western Siberia thermokarst lake sediments

Abstract. This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m−2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions was suggested. This shift was likely promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development, the sediments were a source of dissolved Co, Ni and As to the water column. However, the concentrations of these trace elements remained low in the bottom waters, indicating that sorption processes on Fe-bounding particles and/or large-size organo-mineral colloids could mitigate the impact of post-depositional redistribution of toxic elements on the water column.

A rapid response, planar fluorosensor for measuring two‐dimensional pCO2 distributions and dynamics in marine sediments

CO2 distributions in marine sediments are closely coupled to early diagenetic reactions and transport processes. An existing planar optode designed to measure pCO2 in sediments and overlying water was modified to substantially lower response times and to allow for enhanced resolution of CO2 dynamics. Sensing foils are fabricated by entrapping fluorescent indicator 8‐hydroxy‐1,3,6‐pyrenetrisulfonic acid‐tetraoctylammonium ion‐pair (TOA+PTS4−, molar ratio 1:1) and tetraoctylammonium hydroxide (TOAOH) in a hydrophobic ethyl cellulose polymer matrix on an inert transparent polyester support, and coated with gas permeable silicone membrane. The response time of the optimized sensor is 18 s (0 → 5 matm), allowing measurement of transient pCO2 distributions associated with microenvironments such as burrows. As typically configured, the ratiometric sensor has a working range of 0 to ~40 matm pCO2 and a detection limit of 0.193 matm (3σ), and shows fluorescence emission at 515 nm with dual excitation at 470 and 407 nm, and a well‐defined isosbestic point. The sensor is sensitive, precise, stable, and reversible, and retains its properties after continuous exposure in marine sediments for approximately 2 weeks at 15°C, with a longer or shorter lifetime at lower or higher temperatures respectively. This sensor has been successfully used to measure two‐dimensional pCO2 distributions and dynamics in marine sediments and overlying water with a typical pixel resolution of ~ 50×50 µm over an area of ~150 cm2.

Exchange of Cu and Cd across the sediment-water interface in intertidal mud flats from Ria Formosa (Portugal)

Depth profiles of Fe, Mn, (HS)t, Cu and Cd concentrations in pore water were determined on a seasonal scale in intertidal sediments of Ria Formosa. Concentrations of Cu and Cd were also determined in near-bottom water during the short period that water inundates the sediment. A maximum near the sediment-water interface was observed in depth profiles of Mn and Fe concentrations followed by a decrease with depth. Otherwise, depth profiles of (HS−)t were irregular but peak concentrations was observed below Mn and Fe maximum. Although subsurface maximum was observed at deeper layers for Cu and Cd, the profiles shape varied among sites and sampling dates. This suggests site specificity and alterations associated with early diagenetic reactions. In order to assess exchanges of Cu and Cd across the sediment water interface, diffusive fluxes and advective transport were estimated. Both contribute substantially to the daily transfer of Cd from intertidal sediments to the water column of Ria Formosa. In the case of Cu, the flux associated with tidal flooding (advective flux) was the major contributor. Presumably, the exchange of trace elements between the sediment-water interface in intertidal areas of macro- and meso-tidal systems are underestimated since do not take into consideration the pulse contribution associated with tidal flooding.

The role of grain dissolution and diagenetic mineral precipitation in the cycling of metals and phosphorus: A study of a contaminated urban freshwater sediment

This paper describes the detrital mineralogy, early diagenetic reactions and authigenic mineral precipitates for freshwater contaminated sediments deposited in an urban water body (the Salford Quays of the Manchester Ship Canal, Greater Manchester, UK). These sediments contain a mix of natural and anthropogenic detrital grains. Detrital grains are dominated by quartz and clay grains, whilst anthropogenic grains are dominated by metal-rich glass grains, concentrated at a depth of 12–17 cm in the sediment as a result of historical inputs. Sediment porewaters contain significant concentrations of Fe, Mn, Zn and phosphate. Bacterial Fe(III) and Mn(IV) reduction are hypothesised to supply Fe 2+ and Mn 2+ to porewaters, with phosphate released from Fe oxide reduction or organic matter oxidation. Petrographic observations indicate that the metal-rich glass grains are undergoing chemical dissolution during early diagenesis, supplying Fe and Zn to porewaters. The most abundant authigenic mineral in the sediments is vivianite (Fe 3(PO 4) 2 · 8H 2O), containing a significant level of redlingite ( Mn 3 2 + ( PO 4 ) 2 · 8 H 2 O ) , with minor framboidal pyrite (FeS 2). Electron microprobe analysis shows the vivianite to contain Zn, Cu and Pb, suggesting that vivianite acts as a long-term sink for these metals in this sediment. This implies that authigenic vivianite in freshwater sediments may act as a long-term sink for metals, in a similar manner to sulphides in marine sediments. This study highlights that the nature of detrital and diagenetic mineralogy, in addition to porewater and sediment chemistry, needs to be considered in assessing contaminated sediments.

Benthic response to shellfish farming in Thau lagoon: Pore water signature

Vertical distributions of dissolved species across the sediment–water interface (SWI), including major cations (sodium, potassium, magnesium, calcium), minor cations (lithium, strontium, barium), redox sensitive species (dissolved manganese, iron, sulfate, sulfide, ammonium) and other chemical parameters (pH, alkalinity, soluble reactive phosphorous, dissolved silica) were studied in a Mediterranean lagoon used for intensive shellfish farming. In order to quantify the impact of this activity on diagenetic processes and the influence of seasonal changes, two stations contrasted with respect to organic carbon fluxes were sampled in Thau lagoon from March 2001 to August 2002 during four field campaigns in winter, spring, summer and fall. Well-defined layers enriched with redox sensitive species were observed following the conventional sequence of early diagenetic reactions. However, differences were observed between both stations in depths and thickness layers. Concentration gradients extended down to more than 92 cm depth at the central position of the lagoon (station C4 – 8 m depth) and down to 40 cm depth inside shellfish farming zones (station C5 – 9 m depth). Station C4 showed an unusual diagenetic signature: sharp dissolved oxygen, iron, nitrate and manganese gradients existed at the SWI but gradients of dissolved sulfide and alkalinity as well as other parameters (dissolved silica, Ba, etc.) were recorded only from 25 to 30 cm depth downward. Seasonal changes were observed in pore water composition as deep as 30–50 cm in station C4 (only 15 cm in station C5). The center of the lagoon is not directly subjected to biodeposits deriving from shellfish activity. Isotopic and bioturbation data allowed to rule out a reworking of the sediment deeper than a few centimeters. In addition to organic content of the sediment, physical parameters were likely to induce the 10–20 cm gap between dissolved iron and sulfide profile as well as the higher vertical extent of diagenetic sequence observed at station C4. Conversely to station C5, station C4 underwent stronger currents and wave effect probably generating advective transport of water through the sediment, but no permeability data were available to confirm this hypothesis. During summer, climatic conditions generated vertical stratification of the water column and transient suboxic conditions at the bottom. Such conditions drove the upward shift of redox fronts, compacting the diagenetic sequence. These effects were reinforced at station C5 by shellfish and its farm structures (mainly attenuation of current and increased heat absorption).

Carbon remineralization in the Amazon–Guianas tropical mobile mudbelt: A sedimentary incinerator

The Amazon River spawns a vast mobile mudbelt extending ∼1600 km from the equator to the Orinoco delta. Deposits along the Amazon–Guianas coastline are characterized by some of the highest C org remineralization rates reported for estuarine, deltaic, or shelf deposits, however, paradoxically, except where stabilized by mangroves or intertidal algal mats, they are usually suboxic and nonsulfidic. A combination of tides, wind-driven waves, and coastal currents forms massive fluid muds and mobile surface sediment layers ∼0.5–2 m thick which are dynamically refluxed and frequently reoxidized. Overall, the seabed functions as a periodically mixed batch reactor, efficiently remineralizing organic matter in a gigantic sedimentary incinerator of global importance. Amazon River material entering the head of this dynamic dispersal system carries an initial terrestrial sedimentary C org loading of ∼ 0.7 mg C m −2 particle surface area. Total C org loading is lowered to ∼ 0.2 mg C m −2 in the proximal delta topset, ∼60–70% of which remains of terrestrial origin. Loading decreases further to 0.12–0.14 mg C m −2 (∼60% terrestrial) in mudbanks ∼600 km downdrift along French Guiana, values comparable to those found in the oligotrophic deepsea. DOC/ΣCO 2 ratios in pore waters of French Guiana mudbanks indicate that >90% of metabolized organic substrates are completely oxidized. Within the Amazon delta topset at the head of the dispersal system, both terrestrial and marine organic matter contribute substantially to early diagenetic remineralization, although reactive marine substrate dominates (∼60–70%). The conditional rate constant for terrestrial C org in the delta topset is ∼0.2 a −1. As sedimentary C org is depleted during transit, marine sources become virtually the exclusive substrate for remineralization except very near the mangrove shoreline. The δ 13C and Δ 14C values of pore water ΣCO 2 in mudbanks demonstrate that the primary source of remineralized organic matter within ∼1 km of shore is a small quantity of bomb signature marine plankton (+80‰). Thus, fresh marine organic material is constantly entrained into mobile deposits and increasingly drives early diagenetic reactions along the transit path. Relatively refractory terrestrial C org is lost more slowly but steadily during sedimentary refluxing and suboxic diagenesis. Amazon Fan deposits formed during low sea level stand largely bypassed this suboxic sedimentary incinerator and stored material with up to ∼3X the modern high stand inner shelf C org load (Keil et al., 1997b. Proceedings of the Ocean Drilling Program, Scientific Results. Vol. 155. pp. 531–537). Sedimentary dynamics, including frequency and magnitude of remobilization, and the nature of dispersal systems are clearly key controls on diagenetic processes, biogeochemical cycling, and global C storage along the continental margins.

Pore-water and sediment geochemistry in the Marmara Sea (Turkey): early diagenesis and diffusive fluxes

Pore waters and sediments were analysed in two gravity cores from the Çinarcik Basin and the southern shelf of the Marmara Sea. The sediments are organic-rich (1.1 and 1.3 wt% C org ) and have been deposited at rates of 1.9 and 0.45 m/ka, respectively. The oxic+suboxic zone is 0.50–0.80 m thick and the sulphate–methane interface (SMI; defined here as the depth at which pore-water sulphates diminish below 1 mM) is 3.4 and 2.4 metres below sea floor (mbsf) in the southern shelf and Çinarcik Basin cores, respectively. Changes in the phosphate and ammonium gradients suggest that the sulphate reduction occurs by simple microbial organic matter degradation. Steep sulphate gradients at both sites may suggest that a part of the sulphate reduction may occur by anaerobic methane oxidation. The flux computations, assuming a steady-state situation, show that the fluxes of sulphate, alkalinity, ammonium, phosphate and manganese near the top of the sediment column in the Çinarcik Basin are c . 1.7, 1.8, 2.1, 1.5 and 7.7 times greater than the respective fluxes in the southern shelf. In both cores, Mn 2+ ions are released at 0.03–0.5 mbsf, and diffuse mainly upward. In the Çinarcik Basin core, a significant amount of dissolved Mn reprecipitates as Mn(IV) oxyhydroxides near the sediment top. Fe(II) produced from reduction of reactive Fe(III) minerals is precipitated as Fe sulphides in the sulphate reduction zone. Downward Mg flux into the sediments in the Çinarcik Basin is 2.5 times that in the southern shelf, whereas the Ca flux in both areas is similar, with a value of c. 26 mM m −2 a −1 . The downward Ca and Mg fluxes are used in dolomite precipitation in the sediments near the SMI in both regions. The flux amounts and pore water profiles all indicate that the rates of early diagenetic reactions (sulphate reduction and probably AMO) in the Çinarcik Basin are considerably higher than those in the southern shelf. The differences between the two areas can be explained mainly by the considerably higher sedimentation rate in the former area.