Deep Pore Water Research Articles

Dating of Dissolved Iodine in Pore Waters from the Gas Hydrate Occurrence Offshore Shimokita Peninsula, Japan: 129I Results from the D/V Chikyu Shakedown Cruise

AbstractIodine concentration and radioisotopic composition (129I/I) were measured in the pore waters from the gas hydrate occurrence in the forearc basin offshore Shimokita Peninsula, north‐eastern Japan, to determine the source formation of I and accompanying hydrocarbons. Iodine concentrations correlate well with the alkalinity and SO4 patterns, reflecting degradation stages of I‐rich buried organic matter, rapidly increasing in the sulfate reduction interval, and becoming constant below 250 meters below the seafloor with an upwelling flux of 1.5 × 10−11 µmol cm−2 year−1. The 129I/I ratios of 300 × 10−15–400 × 10−15 in deep pore waters suggest ages for iodine and hydrocarbon sources as old as 40 Ma. These ages correlate well with the coaly source formations of the Eocene age thought to be responsible for the conventional natural gas deposits underlying the gas hydrate stability zone. Similar profiles are observed in 129I/I ratios of pore waters in the gas hydrate stability zone from the forearc basin in the eastern Nankai Trough, offshore central Japan, where pore waters are enriched in I and reach ages as old as ∼50 Ma through the sediment column. At the outer ridge site along the trough, on the other hand, relatively younger I are more frequently delivered probably through thrusts/faults associated with subduction. The nature of source formations of I and hydrocarbons in the offshore Shimokita Peninsula has a more terrestrial contribution compared with those in the Nankai Trough, but these formations are also considerably older than the host sediments, suggesting long‐term transport of I and hydrocarbons for the accumulation of gas hydrates in both locations.

In Situ Monitoring of Water Percolation and Solute Transport Using a Vadose Zone Monitoring System

Water percolation and tracer migration through the vadose zone underneath an ephemeral channel were studied using a vadose zone monitoring system (VMS) and application of a multitracer test. The VMS included flexible time‐domain reflectometry (FTDR) probes for continuous tracking of water content profiles, and vadose zone sampling ports (VSPs) for frequent sampling of the deep vadose pore water at multiple depths. The VMS was installed directly under an infiltration pond with several infiltration rings containing a traceable solution. Water content measurements by the FTDR probes allowed detailed visualization of the vadose wetting process; VSP samples allowed the establishment of tracer breakthrough curves at various depths. Flow velocities and fluxes were calculated from both the wetting process and the tracer breakthrough curves. The multitracer experiment revealed an unsteady flow pattern strongly affected by the layered structure of the sediments. The tracer breakthrough curves indicated domination of a mobile–immobile flow mechanism controlling contaminant migration across the vadose zone. The experimental setup demonstrated the ability of the VMS to provide real‐time monitoring of water flow and contaminant transport in the vadose zone.

A model for uranium, rhenium, and molybdenum diagenesis in marine sediments based on results from coastal locations

The purpose of this research is to characterize the mobilization and immobilization processes that control the authigenic accumulation of uranium (U), rhenium (Re), and molybdenum (Mo) in marine sediments. We analyzed these redox-sensitive metals (RSM) in benthic chamber, pore water, and solid phase samples at a site in Buzzards Bay, Massachusetts (USA) that has high bottom water oxygen concentrations (230–300 μmol/L) and high organic matter oxidation rates (390 μmol C/cm 2/y). The oxygen penetration depth varies from 2 to 9 mm below the sediment-water interface, but pore water sulfide is below detection (<2 μM). The RSM pore water profiles are modeled with a steady-state diagenetic model that includes irrigation, which extends 10–20 cm below the sediment-water interface. To present a consistent description of trace metal diagenesis in marine sediments, RSM results from sediments in Buzzards Bay are compared with previous research from sulfidic sediments (Morford et al., GCA 71). Release of RSM to pore waters during the remineralization of solid phases occurs near the sediment-water interface at depths above the zone of authigenic RSM formation. This release occurs consistently for Mo at both sites, but only in the winter for Re in Buzzards Bay and intermittently for U. At the Buzzards Bay site, Re removal to the solid phase extends to the bottom of the profile, while the zone of removal is restricted to ∼2–9 cm for U and Mo. Authigenic Re formation is independent of the anoxic remineralization rate, which is consistent with an abiotic removal mechanism. The rate of authigenic U formation and its modeled removal rate constant increase with increasing anoxic remineralization rates and is consistent with U reduction being microbially mediated. Authigenic Mo formation is related to the formation of sulfidic microenvironments. The depth and extent of Mo removal from pore water is closely associated with the balance between iron and sulfate reduction and the consumption of pore water sulfide via iron sulfide formation. Pore water RSM reach constant asymptotic concentrations in sulfidic sediments, but only pore water Re is constant at depth in Buzzards Bay. The increases in pore water U at the Buzzards Bay site are consistent with addition via irrigation and subsequent upward diffusion to the removal zone. Deep pore water Mo concentrations exceed its bottom water concentration due to irrigation-induced oxidation and remobilization from the solid phase. In sulfidic sediments, there is no evidence for higher pore water U or Mo concentrations at depth due to the absence of irrigation and/or the presence of more stable authigenic RSM phases. There are good correlations between benthic fluxes and authigenic accumulation rates for U and Mo in sulfidic sediments. However, results from Buzzards Bay suggest irrigation ultimately results in the partial loss of U and Mo from the solid phase, with accumulation rates that are 20–30% of the modeled flux. Irrigation can augment (Re, possibly U) or compromise (U, Mo) authigenic accumulation in sediments and is important when determining burial rates in continental margin sediments.

Deep pore water profiles reflect enhanced microbial activity towards tidal flat margins

Microbial activity in permeable tidal flat margin sediments is enhanced by two main processes. First, organic matter is supplied by rapid sedimentation at prograding tidal flat margins. Second, surface and deep pore water advection lead to a replenishment of the dissolved organic matter and sulfate pools. Increasing microbial activity towards the low water line is reflected in sulfate and methane profiles as well as in total cell numbers, sulfate reduction rates, and remineralization products. The impact of high sedimentation rates on pore water biogeochemistry is confirmed by inverse modeling reproducing the depth profiles obtained by measurements. In central parts of the tidal flats, low sedimentation rates and pore water flow velocities limit microbial activity despite the high availability of electron acceptors for microbial respiration such as sulfate. Therefore, tidal flat margins with high microbial activity are of special importance for budgeting biogeochemical cycling in tidal flat areas.

Sulphate, dissolved organic carbon, nutrients and terminal metabolic products in deep pore waters of an intertidal flat

This study addresses deep pore water chemistry in a permeable intertidal sand flat at the NW German coast. Sulphate, dissolved organic carbon (DOC), nutrients, and several terminal metabolic products were studied down to 5 m sediment depth. By extending the depth domain to several meters, insights into the functioning of deep sandy tidal flats were gained. Despite the dynamic sedimentological conditions in the study area, the general depth profiles obtained in the relatively young intertidal flat sediments of some metres depth are comparable to those determined in deep marine surface sediments. Besides diffusion and lithology which control pore water profiles in most marine surface sediments, biogeochemical processes are influenced by advection in the studied permeable intertidal flat sediments. This is supported by the model setup in which advection has to be implemented to reproduce pore water profiles. Water exchange at the sediment surface and in deeper sediment layers converts these permeable intertidal sediments into a “bio-reactor” where organic matter is recycled, and nutrients and DOC are released. At tidal flat margins, a hydraulic gradient is generated, which leads to water flow towards the creekbank. Deep nutrient-rich pore waters escaping at tidal flat margins during low tide presumably form a source of nutrients for the overlying water column in the study area. Significant correlations between the inorganic products of terminal metabolism (NH4 + and PO4 3−) and sulphate depletion suggest sulphate reduction to be the dominant pathway of anaerobic carbon remineralisation. Pore water concentrations of sulphate, ammonium, and phosphate were used to elucidate the composition of organic matter degraded in the sediment. Calculated C:N and C:P ratios were supported by model results.

Cycling of trace metals (Mn, Fe, Mo, U, V, Cr) in deep pore waters of intertidal flat sediments

Trace metals (Mn, Fe, Mo, U, Cr, V) were studied in pore waters of an intertidal flat located in the German Wadden Sea. The study system is an example of a permeable tidal flat system where pore water exchange is affected by tidal driven pressure gradients besides diffusion. Permanently installed in situ samplers were used to extract pore waters down to 5m depth throughout one year. The samplers were either located close to the tidal flat margin or in central parts of the tidal flat. Despite dynamic sedimentological and hydrological conditions, the general trends with depth in deep tidal flat pore waters are remarkably similar to those observed in deep sea environments. Rates of trace metal cycling must be comparably large in order to maintain the observed pore water profiles. Trace metals further show similar general trends with depth close to the margin and in central parts of the tidal flat. Seasonal sampling revealed that V and Cr vary concurrent with seasonal changes in dissolved organic carbon (DOC) concentration. This effect is most notable close to the tidal flat margin where sulphate, DOC, and nutrients vary with season down to some metres depth. Seasonal variations of Mn, Fe, Mo, and U are by contrast limited to the upper decimetres of the sediment. Their seasonal patterns depend on organic matter supply, redox stratification, and particulate matter deposited on sediment surfaces. Pore water sampling within one tidal cycle provides evidence for pore water advection in margin sediments. During low tide pore water flow towards the creekbank is generated by a hydraulic gradient suggesting that deep pore waters may be seeping out of creekbank sediments. Owing to the enrichment of specific elements like Mn in pore water compared to sea water, seeping pore waters may have an impact on the chemistry of the open water column. Mass balance calculations reveal that the impact of deep pore waters on the Mn budget in the open water column is below 4%. Mn deep pore water discharge of the whole Wadden Sea is estimated to be about 9% of the total dissolved riverine Mn input into the Southern North Sea.

Spatial and seasonal variations of sulphate, dissolved organic carbon, and nutrients in deep pore waters of intertidal flat sediments

Spatial and seasonal variations of sulphate, dissolved organic carbon (DOC), nutrients and metabolic products were determined down to 5 m sediment depth in pore waters of intertidal flats located in NW Germany. The impact of sediment permeability, pore water flow, and organic matter supply on deep pore water biogeochemistry was evaluated. Low sediment permeability leads to an enrichment of remineralisation products in pore waters of clay-rich sediments. In permeable sandy sediments pore water biogeochemistry differs depending on whether tidal flat margins or central parts of the tidal flat are studied. Pore water flow in tidal flat margins increases organic matter input. Substrate availability and enhanced temperatures in summer stimulate sulphate reducers down to 3.5 m sediment depth. Sulphate, DOC, and nutrient concentrations exhibit seasonal variations in deep permeable sediments of the tidal flat margin. In contrast, seasonal variations are small in deep pore waters of central parts of the sand flat. This study shows for the first time that seasonal variations in pore water chemistry are not limited to surface sediments, but may be observed down to some metres depth in permeable tidal flat margin sediments. In such systems more organic matter seems to be remineralised than deduced from surface sediment studies.

Lowering of glacial atmospheric CO2 in response to changes in oceanic circulation and marine biogeochemistry

We use an Earth system model of intermediate complexity, CLIMBER‐2, to investigate what recent improvements in the representation of the physics and biology of the glacial ocean imply for the atmospheric concentration. The coupled atmosphere‐ocean model under the glacial boundary conditions is able to reproduce the deep, salty, stagnant water mass inferred from Antarctic deep pore water data and the changing temperature of the entire deep ocean. When carbonate compensation is included in the model, we find a CO2 drawdown of 43 ppmv associated mainly with the shoaling of the Atlantic thermohaline circulation and an increased fraction of water masses of southern origin in the deep Atlantic. Fertilizing the Atlantic and Indian sectors of the Southern Ocean north of the polar front leads to a further drawdown of 37 ppmv. Other changes to the glacial carbon cycle include a decrease in the amount of carbon stored in the terrestrial biosphere (540 Pg C), which increases atmospheric CO2 by 15 ppmv, and a change in ocean salinity resulting from a drop in sea level, which elevates CO2 by another 12 ppmv. A decrease in shallow water CaCO3 deposition draws down CO2 by 12 ppmv. In total, the model is able to explain more than two thirds (65 ppmv) of the glacial to interglacial CO2 change, based only on mechanisms that are clearly documented in the proxy data. A good match between simulated and reconstructed distribution of δ13C changes in the deep Atlantic suggests that the model captures the mechanisms of reorganization of biogeochemistry in the Atlantic Ocean reasonably well. Additional, poorly constrained mechanisms to explain the rest of the observed drawdown include changes in the organic carbon:CaCO3 ratio of sediment rain reaching the seafloor, iron fertilization in the subantarctic Pacific Ocean, and changes in terrestrial weathering.

Bubble-induced porewater mixing: A 3-D model for deep porewater irrigation

Porewater data from vent sites of the northeastern shelf off Sakhalin Island, Sea of Okhotsk, exhibit bottom-water concentrations down to a sediment depth of up to 300 cm. Below this depth, solute concentrations rapidly change due to methanogenesis and anaerobic methane oxidation (AMO). The profile shapes suggest an irrigation-like process that mixes on a meter scale. At these sites active gas emanation into the overlying water column and near-surface gas hydrates are commonly observed. We propose that methane gas bubbles rise through the soft surface sediments and cause mixing of the porewater. Mathematically, the bubble-induced irrigation can be described by eddy diffusion enhancing the diffusive transport of solutes by several orders of magnitude. A 3-D numerical transport-reaction model was developed to investigate the parameters defining the mixing process, such as bubble rise velocity, tube size, tube distribution in the sediment, and ebullition frequency. Model consistency with the field data requires eddy diffusivities ⩾1 × 10 5 cm 2/a, tube densities of >4 tubes/m 2 (equivalent to a tube spacing of <40 cm), active gas seepage for more than a few weeks or months, and moderate to low diagenetic reaction rates of solutes. The corresponding methane gas fluxes that are predicted from the results of the model realizations range from 1 × 10 3–5 × 10 5 L/(m 2 a). Due to bubble mixing, solute fluxes in these sediments are increased by a factor of 3 and the maximum AMO rate by a factor of 7.

In situ evaluation of nearshore marine and fresh pore water transport into Flamengo Bay, Brazil

Transport between pore waters and overlying surface waters of Flamengo Bay near Ubatuba, Brazil, was quantified using natural and artificial geochemical tracers, 222Rn, Cl −, and SF 6, collected from multi-level piezometers installed along a transect perpendicular to the shore. Eight sampling ports positioned along the length of the piezometers allowed sampling of pore waters at discrete depth intervals from 10 to 230 cmbsf (centimeters below seafloor). Small volume samples were collected from the piezometers using a peristaltic pump to obtain pore water depth profiles. Pore water 222Rn is deficient in shallow sediments, allowing application of a diffusion-corrected 222Rn exchange rate. This model estimates the magnitude of pore water exchange rates to be about 130–419 cm/day. An SF 6-saturated fluorescein dye tracer was gently pumped into deep pore waters and exchange rates estimated from this method range from 29 to 185 cm/day. While absolute rates are higher using 222Rn than SF 6, rates are of similar magnitudes and the trends with distance from shore are the same – flow is greatest 6 m from shore and decreases by more than 50% further offshore. A Cl − mass balance indicates the greatest fraction of fresh SGD occurs along an apparent preferential flow path in sediments within 5–7 m of the shoreline (87%). Recirculating bay waters through sediments dominate pore water advection at 10 m offshore where only 4% of the flow can be attributed to a freshwater source. Both fresh and marine sources combine to make up submarine groundwater discharge to coastal water bodies. The magnitude of fresh aquifer discharge is often a spatially variable and minor component of the total discharge.

Surficial and deep pore water circulation governs spatial and temporal scales of nutrient recycling in intertidal sand flat sediment

This study addresses organic matter decomposition in permeable sediment of a sloping intertidal sand flat (German Wadden Sea) affected by current-induced pore water exchange and pore fluid drainage. Seasonal and spatial scales of aerobic and anaerobic mineralization were investigated at 2 sites, one near the water line and one on the upper flat. Hydrodynamic forcing during inundation caused deeper oxygen penetration through flushing of the uppermost sediment layer. This flushing resulted in higher areal oxygen consumption rates and lower depth integrated sulfate reduction rates in the submerged flat compared to the rates measured during exposure. Mineralization rates in the top 15 cm of the sediment were similar between both study sites and ranged from 38 (winter) to 280 mmol C m–2 d–1 (summer), with sulfate reduction contributing 3 to 25% to total mineralization, depending on the season. At the upper flat, these seasonal differences were reflected in the pore water concentrations of nutrients, dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). Near the low water line, however, pore water nutrient and DIC concentrations were independent of the season and up to 15 times higher compared to the values recorded in the upper flat. The differences in concentrations of metabolic products between the 2 sites resulted from a low tide drainage extending deep below the uppermost flushed layer and causing seepage of pore water near the low water line. Mineralization and nutrient release in these permeable intertidal sediments is affected by 2 circulation processes that work on distinctly different temporal and spatial scales: (1) rapid ‘skin circulation’ through the uppermost sediment layer during inundation that is characterized by short flow paths, low pore water residence time and immediate feedback to the ecosystem, and (2) slow ‘body circulation’ through deeper sediment layers during low tide that is characterized by long flow paths and pore water residence times, and acts as a buffered nutrient source to the ecosystem.

Carbonate distribution in the East Baltic deep shelf in the late Ordovician—early Silurian

Calcite and dolomite diminished and disappeared offshore in the East Baltic shelf in the Ordovician—Silurian. The distribution was influenced by transgressions—regressions, transportation processes, and dissolution effects. Calcite dissolved due to the relatively low pH of deep seawater and pore waters. Only small amounts of dolomite were present in the deep shelf. Low pH was also evidenced by clay minerals of the Llandovery bentonite layers. The bentonite matrix varied in composition from illite—smectite to kaolinite-containing. Kaolinite formation was promoted by the decrease of seawater pH with depth. Three time intervals can be distinguished when different prevailing factors governed the carbonate distribution in the East Baltic shelf: the late Ordovician global regression, the Aeronian increased primary productivity, and the Telychian high atmospheric CO2.

Migration pathways in the Central North Slope foreland basin, Alaska USA: solute and thermal constraints on fluid flow simulations

AbstractThe North Slope foreland basin, Alaska, USA is an east–west asymmetrical trough‐shaped basin adjacent to the Brooks Range fold‐thrust mountain belt. Lower Cretaceous age rocks make up much of the sediment fill, including flysch‐like marine turbidites and shales of the Torok and Fortress Mountain formations and marine and sandstones, shales and conglomerates of the overlying Nanushuk group. Lower Cretaceous age rocks were deposited on top of a Palaeozoic and Mesozoic age passive margin sequence. We have conducted numerical simulations of fluid flow driven by topographic recharge in the Central North Slope foreland basin. These simulations are constrained by salinity estimates from well logs, location of oil and gas fields, vitrinite reflectance and heat flow measurements. Our model results indicate that there are two south to north pathways for fluid migration. The primary pathway for fluid movement is downward through the Fortress Mountain formation, then upwards along the interface between the Fortress Mountain and Torok Formation and finally northward through the permeable Nanushuk group. A smaller mass of groundwater moves along sands below the Torok formation and into offshore sediments north of Alaska. Very little meteoric water enters the underlying Palaeozoic rocks in our simulations, which could explain the presence of deep saline pore waters. Our results also show that permafrost is a primary control on the pathway and rate of fluid flow by controlling the distribution of surface recharge and discharge. For example, areas of high heat flow and low saline waters along the arctic coast may represent upward groundwater discharge because of the absence of permafrost. As surface temperatures were warmer in the Miocene, the absence of permafrost would produce a more local fluid circulation pattern and less transfer of heat energy from south to north.

Chemical weathering rates of a soil chronosequence on granitic alluvium: III. Hydrochemical evolution and contemporary solute fluxes and rates

Although long-term changes in solid-state compositions of soil chronosequences have been extensively investigated, this study presents the first detailed description of the concurrent hydrochemical evolution and contemporary weathering rates in such sequences. The most direct linkage between weathering and hydrology over 3 million years of soil development in the Merced chronosequence in Central California relates decreasing permeability and increasing hydrologic heterogeneity to the development of secondary argillic horizons and silica duripans. In a highly permeable, younger soil (40 kyr old), pore water solutes reflect seasonal to decadal-scale variations in rainfall and evapotranspiration (ET). This climate signal is strongly damped in less permeable older soils (250 to 600 kyr old) where solutes increasingly reflect weathering inputs modified by heterogeneous flow. Elemental balances in the soils are described in terms of solid state, exchange and pore water reservoirs and input/output fluxes from precipitation, ET, biomass, solute discharge and weathering. Solute mineral nutrients are strongly dependent on biomass variations as evidenced by an apparent negative K weathering flux reflecting aggradation by grassland plants. The ratios of solute Na to other base cations progressively increase with soil age. Discharge fluxes of Na and Si, when integrated over geologic time, are comparable to solid-state mass losses in the soils, implying similar past weathering conditions. Similarities in solute and sorbed Ca/Mg ratios reflect short-term equilibrium with the exchange reservoir. Long-term consistency in solute ratios, when contrasted against progressive decreases in solid-state Ca/Mg, requires an additional Ca source, probably from dry deposition. Amorphous silica precipitates from thermodynamically-saturated pore waters during periods of high evapotranspiration and result in the formation of duripans in the oldest soils. The degree of feldspar and secondary gibbsite and kaolinite saturation varies both spatially and temporally due to the seasonality of plant-respired CO 2 and a decrease in organically complexed Al. In deeper pore waters, K-feldspar is in equilibrium and plagioclase is about an order of magnitude undersaturated. Hydrologic heterogeneity produces a range of weathering gradients that are constrained by solute distributions and matrix and macropore flow regimes. Plagioclase weathering rates, based on precipitation-corrected Na gradients, vary between 3 and 7 × 10 −16 mol m −2 s −1. These rates are similar to previously determined solid-state rates but are several orders of magnitude slower than for experimental plagioclase dissolution indicating strong inhibitions to natural weathering, partly due to near-equilibrium weathering reactions.

Groundwater inflow and associated transport of phosphorus to a hypereutrophic lake

Hydrogeochemical data from lake, sediment pore, and well waters were used to quantify groundwater seepage and the associated transport of phosphorus to Lake Persimmon, Florida, USA. The data show that lake chloride concentrations vary as a function of lake elevations that are controlled by groundwater inflow. A whole-lake average seepage rate, estimated using a simple one dimensional advection-diffusion model fitted to the lake chloride profile, currently averages 2.3 ± 0.3 cm yr-1 and is in reasonable agreement with the rate of advective flow obtained from the pore water chloride profile. The ratios of nutrient regeneration versus sulfate consumption indicate that the phosphorus enrichment in deeper portions of sediment pore water is most likely a result of groundwater phosphorus transport through sediment. Thus, the net inputs of groundwater phosphorus to the lake, calculated using the deep pore water phosphorus concentration, are about 7.4 ± 4.3 mg P m-2 yr-1 and comparable with recent in situ estimates from seepage meters. This study provides a simple hydrogeochemical method for estimating hydrologic and phosphorus inputs via groundwater to the lake, thereby supporting current efforts for lake management.

Multiphase Reactive Transport Modeling of Seasonal Infiltration Events and Stable Isotope Fractionation in Unsaturated Zone Pore Water and Vapor at the Hanford Site

Numerical simulations of transport and isotope fractionation provide a method to quantitatively interpret vadose zone pore water stable isotope depth profiles based on soil properties, climatic conditions, and infiltration. We incorporate the temperature‐dependent equilibration of stable isotopic species between water and water vapor, and their differing diffusive transport properties into the thermodynamic database of the reactive transport code TOUGHREACT. These simulations are used to illustrate the evolution of stable isotope profiles in semiarid regions where recharge during wet seasons disturbs the drying profile traditionally associated with vadose zone pore waters. Alternating wet and dry seasons lead to annual fluctuations in moisture content, capillary pressure, and stable isotope compositions in the vadose zone. Periodic infiltration models capture the effects of seasonal increases in precipitation and predict stable isotope profiles that are distinct from those observed under drying (zero infiltration) conditions. After infiltration, evaporation causes a shift to higher δ18O and δD values, which are preserved in the deeper pore waters. The magnitude of the isotopic composition shift preserved in deep vadose zone pore waters varies inversely with the rate of infiltration.

Multiphase Reactive Transport Modeling of Seasonal Infiltration Events and Stable Isotope Fractionation in Unsaturated Zone Pore Water and Vapor at the Hanford Site

Numerical simulations of transport and isotope fractionation provide a method to quantitatively interpret vadose zone pore water stable isotope depth profiles based on soil properties, climatic conditions, and infiltration. We incorporate the temperature-dependent equilibration of stable isotopic species between water and water vapor, and their differing diffusive transport properties into the thermodynamic database of the reactive transport code TOUGHREACT. These simulations are used to illustrate the evolution of stable isotope profiles in semiarid regions where recharge during wet seasons disturbs the drying profile traditionally associated with vadose zone pore waters. Alternating wet and dry seasons lead to annual fluctuations in moisture content, capillary pressure, and stable isotope compositions in the vadose zone. Periodic infiltration models capture the effects of seasonal increases in precipitation and predict stable isotope profiles that are distinct from those observed under drying (zero infiltration) conditions. After infiltration, evaporation causes a shift to higher δ18O and δD values, which are preserved in the deeper pore waters. The magnitude of the isotopic composition shift preserved in deep vadose zone pore waters varies inversely with the rate of infiltration.

Oxygen dynamics in permeable sediments with wave‐driven pore water exchange

The effects of advective pore water exchange driven by shallow water waves on the oxygen distribution in a permeable (k = 3.3 x 10−12 to 4.9 x 10−11 m2) natural sediment were studied with a planar oxygen optode in a wave tank. Our experiments demonstrate that pore water flow driven by the interaction of sediment topography and oscillating boundary flow changes the spatial and temporal oxygen distribution in the upper sediment layer. Oxygenated water intruding in the ripple troughs and deep anoxic pore water drawn to the surface under the ripple crests create an undulating oxic‐anoxic boundary within the upper sediment layer, mirroring the topographical features of the sediment bed. Anoxic upwelling zones under ripple crests can separate the oxic sediment areas of neighboring ripple troughs with steep horizontal oxygen concentration gradients. The optode showed that migrating wave ripples are trailed by their pore water flow field, alternately exposing sediment volumes to oxic and anoxic pore water, which can be a mechanism for remobilizing particulate oxidized metal precipitates and for promoting coupled nitrification‐denitrification. More rapid ripple migration (experimental threshold ~20 cm h−1) produces a continuous oxic surface layer that inhibits the release of reduced substances from the bed, which under slowly moving ripples is possible through the anoxic vertical upwelling zones. Swift, dramatic changes in oxygen concentration in the upper layers of permeable seabeds because of surface gravity waves require that sediment‐dwelling organisms are tolerant to anoxia or highly mobile and enhance organic matter mineralization.

Dynamic processes in the Venice region outlined by environmental isotopes

Research carried out in the last 40 years has shown the scientific importance of groundwater circulation both in the Northern Adriatic sea bed and within the uppermost sedimentary layers of the Venice lagoon and of the Venice plain. Hydrodynamic processes are strictly controlled by a well-cemented sedimentary horizon lying under and around Venice (‘caranto’), which plays the role of regional aquitard. This layer was attributed to the subaerial cementation of the Flandrian (8–10 ka Before Present) sedimentary surface. The caranto is generalised as a continuum horizon, being an easy explanation for several environmental, hydrogeological and geotechnical problems, e.g., a base layer for landfills, a confining layer for deep aquifers and the best substratum for locating the oak wooden pile-dwelling needed to support the largest buildings. The preservation of the isotope signal within the deep aquifers and aquiclude system records the changes in surface and groundwater characteristics and suggests the present and past recharge regimes. In this region, the heavily perturbed hydrodynamic conditions do not allow for the use of isotopic signals to derive a correct reconstruction of the present recharge. The perturbations induced by the intensive anthropogenic activity force to follow climate evolution by considering deep groundwater and pore waters. In addition, the presence of carbonatic rocks inside terrigeneous sediments affects the reconstruction of the past. Results indicate that carbonatic rocks are created by seepage, through the sediments, of gaseous carbon compounds from decaying organic layers. The gas interactions with the intra-sedimentary saline and fresh waters produce CO2, inducing the cementation of the sediments.

Chemical stratigraphy of recent sediments from a depth gradient in a meromictic lake, Nordbytjernet, SE Norway, in relation to variable external loading and sedimentary fluxes

Cores of recent sediments were sampled along a depth gradient in a 23 m deep kettle lake with stagnant deep waters containing exceptionally high concentrations of dissolved iron and manganese. Sediment cores were taken on two occasions, in 1978 and 1997, before and after an incidence of full circulation. The aims of this study are to see how oxic and anoxic conditions in the water column influence stratigraphy and sediment focusing and, to compare cores from 1979 and 1998 to see how measured element fluxes and external events are reflected in the chemical stratigraphy. Element analyses show characteristic stratigraphic patterns that depend on the ability to undergo redox transformations, sorptive properties and chemical equilibria in the anoxic deep waters and porewaters. In sediments from the oxic part of the lake Al, Cr, Co, Ni, Zn Cu, Cd, and Pb were well correlated. Positive correlations are seen between elements associated with primary production and sulphur. In the anoxic part of the lake most metals were positively correlated with carbonate. Phosphorus correlated positively with iron in sediments from oxic waters and negatively with manganese and iron deep-water sediments. Porewater analyses indicate that recycling from the deep-water sediments was negligible. The stratigraphy of lead agrees with the historic variation in atmospheric input and is used as a chronological marker. Assessed deposition rates agree with measurements in sediment traps. Most elements more than double their rates of deposition towards the deepest point of the lake, while sulphur, manganese and carbonate had maxima around the depth of the redoxcline in the water. Variations in the external loading and variable redox conditions in the deep waters explain variations in the chemical composition of recent sediments.