Isotopic Compositions Of Pore Fluids Research Articles

Hydrologic windows into the crystalline basement and their controls on groundwater flow patterns across the Paradox Basin, western USA

Conceptual models of sedimentary basin groundwater flow systems typically assume that the crystalline basement acts as an impermeable boundary and can be neglected. In this study, we use hydrologic models constrained by isotopic and geochemical datasets to argue that the La Sal Mountains, Utah, USA, act as a hydrologic window into the Paradox Basin’s lower aquifer system and underlying crystalline basement. We conducted a sensitivity study in which we varied crystalline basement/laccolith permeability as well as fault zone connectivity along a cross-sectional transect from the La Sal Mountains to Lisbon Valley. When the crystalline basement/laccolith units are set at relatively permeable levels (10−14 m2), simulated tracers that include total dissolved solids, oxygen isotopic composition of pore fluids (δ18O), and groundwater residence times are in closest agreement with field measurements. Model results indicate that pore fluids in the basal aquifer system underlying the Paradox Formation confining unit are a mixture of relatively young meteoric fluids and older Paradox Formation brines. The presence of faults did not significantly modify fluid exchange between the upper and lower aquifer systems. This was due, in part, to underpressuring within the Paradox Formation. Our study concludes that the Paradox Basin represents a regional recharge area for the Colorado Plateau, with groundwater discharge occurring along the Colorado River within the Grand Canyon some 375 km away to the southwest. This is only possible with a permeable crystalline basement. Our findings help explain the genesis of Mississippi Valley-type ore deposits of the US Midcontinent, where the presence of a permeable basement may be useful in addressing issues related to solute mass and energy balance.

Clay authigenesis in carbonate-rich sediments and its impact on carbonate diagenesis

The Mg (δ26Mg), Ca (δ44Ca), and Sr (87Sr/86Sr) isotopic compositions of pore fluids, bulk carbonates, planktonic foraminiferal tests, and bulk clays from ODP Site 762 Hole B are presented, as are pore fluid and bulk carbonate δ26Mg and 87Sr/86Sr from ODP Site 806 Hole B and pore fluid δ26Mg from ODP Site 807 Hole A. The primary objective of the study is to elucidate the major processes controlling marine pore fluid δ26Mg, specifically the effects of calcite recrystallization and authigenic clay precipitation in sedimentary sections with relatively high carbonate contents. Such studies are critical for evaluating the potential of pore fluids in carbonate section to drive diagenetic alteration, which can compromise applications of geochemical proxies to the past. Pore fluid δ26Mg values at all three sites range from −0.83 to −0.13‰ and exhibit a systematic increase with depth. Bulk carbonate δ26Mg generally decrease with depth, ranging from −3.60 to −5.27‰, at Sites 762 and 806, while mixed species foraminiferal tests (∼250–500 μm) from Site 762 range between −5.08 and −4.36‰. Residual siliciclastics at depths of ∼105 to 145 mbsf at Site 762 have δ26Mg values (−0.09 to 0.27‰) that are markedly higher than carbonate and pore fluid δ26Mg values. Simple 1-D reactive transport modeling suggests that the general increase in pore fluid δ26Mg with depth, accompanied by a decrease in carbonate δ26Mg, is a result of calcite recrystallization (assuming an isotopic fractionation factor of ∼0.9955). However, subtle but significant deviations from the carbonate recrystallization-only scenario suggest that another process impacts δ26Mg at all three sites. Scanning electron microscope images document clay particles embedded in nannofossils and foraminiferal tests at Site 762, which suggest that clay authigenesis is active in carbonate sediments and could affect pore fluid δ26Mg. The formation of secondary clays preferentially sequesters isotopically heavy Mg (αclay-Mg2+≈1.0005), driving pore fluid δ26Mg to lower values. An increase in carbonate δ26Mg within the clay-rich layer at Site 762 and an increase in bulk carbonate Na/Ca supports the hypothesis that clay authigenesis also impacts the preservation of proxy archives. Multi-component reactive transport modeling suggests that authigenic rates of ∼1·10−13 mol/m3/s (∼3.15 µmol/m3/a; assuming that the authigenic clay is sepiolite) can generate deviations from the carbonate recrystallization-only case by several tenths of a permil, indicating that carbonate sediment-associated clay authigenesis (CSCA) may be more relevant in deep-sea carbonate sections than has been previously considered.

Perspectives on geochemical proxies: The impact of model and parameter selection on the quantification of carbonate recrystallization rates

Diagenetic reactions in marine sediments, such as the recrystallization of carbonates, can impact the accuracy of paleo-environmental and paleo-climatic reconstructions by geochemical proxies. The extent to which the recrystallization of carbonates affects the chemistry of sedimentary archives depends on the reaction rate, extent of isotopic disequilibrium, and duration of reaction. The reaction rate, which is obviously critical, can be constrained by the elemental and isotopic compositions of pore fluids. Such constraints are affected by assumptions regarding the temperature in the sedimentary column relative to the temperature of formation, the burial rate, pore fluid advection, the composition of the sediments (carbonate-rich versus siliciclastic), and the porosity of the sediment column. In this study, we use a steady-state analytical solution to the diagenetic equations to constrain depth-dependent reaction rates (and extents of recrystallization) based on the Ca isotopic compositions of pore fluids in sedimentary columns at multiple ocean drilling sites (Sites 807, 984, 1170, and 1171), which encompass a diverse range of sedimentary compositions and conditions. We find that carbonates in siliciclastic sediments are generally less altered by diagenesis than their carbonate-rich counterparts. The discrepancy in recrystallization rates between siliciclastic and carbonate-rich sedimentary sections is, however, significantly smaller than previously estimated, suggesting that siliciclastic archives are not immune to diagenetic effects. While we find that diagenesis can decouple contemporaneous proxies of sea surface temperature (Mg/Ca and δ18O), our calculations also reveal that δ18O-based temperature estimates are more robust in siliciclastic sections relative to carbonate-rich sections. Sensitivity tests of the calculated extent of recrystallization suggest that uncertainties in porosity and burial rate are generally the greatest sources of error to proxy reconstruction from diagenetically altered sediments. The conclusions drawn using the analytical solution are benchmarked against a depth-dependent, forward numerical model using the CrunchFlow software (Steefel et al., 2015); ultimately, this comparison demonstrates that the assumptions necessary in deriving the analytical solutions have a relatively minor impact on the resulting conclusions.

Long-term freshening of the Dead Sea brine revealed by porewater Cl− and [formula omitted] in ICDP Dead Sea deep-drill

The geological evolution of the unique Dead Sea Ca-chloride brine has been the focus of many research efforts for several decades. These studies relied on the information obtained from sedimentary exposures of the marginal terraces of the modern Dead Sea, mostly documenting the history of the surface lake brine during its high stands periods. The present study is the first attempt to establish the history of the deepest part of the lake by direct measurements of the chemical and isotopic composition of pore-fluids that were extracted from cores drilled during 2011 by ICDP in the deep basin of the Dead Sea at water depth of 300 m. The vertical profiles of chloride (Cl−) and oxygen isotopes (δO18) in pore brines reveal a substantial decrease in the salinity of the hyper-saline lake during the last glacial and particularly during MIS2 (∼31–17 kaBP). The Cl− concentration of the deep brine in the lake decreased gradually, reaching a minimum of less than 2/3 of its present value while the δO18 increased to maximum of ∼7‰ (3‰ higher than today). The low Cl− indicates significant dilution of the bottom water mass (hypolimnion) of Lake Lisan (the last glacial predecessor of the modern Dead Sea) during its highest stand period. Beforehand, during the interglacial and later during the post-glacial and the Holocene the Cl− concentrations and δO18 values were similar to those of the modern Dead Sea. The slow dilution of the deep Ca-chloride brine was caused probably by continuous turbulent mixing of the hypolimnion with the less saline high δO18 epilimnetic brine, across the epilimnion/hypolimnion interface (EHI). While the increase in δO18 during the salinity decrease of Lake Lisan is a result of “normal” evaporation of the less saline epilimnetic brine, the post-glacial δO18 decrease (contemporaneous with salinity increase) is attributed to the “reversed” behavior of δO18 during evaporation of high salinity brine. During the long freshening period the hypolimnion was enriched with dissolved sulfate supplied by the freshwater and transported by the turbulent mixing across the EHI until reaching gypsum saturation that commenced massive gypsum deposition at the end of this period, when full overturn took place.

Records of Neogene seawater chemistry and diagenesis in deep-sea carbonate sediments and pore fluids

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10–20Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from −0.78‰ near the sediment–water interface to −0.15‰ at 778mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average δ26Mg value of −4.72‰. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Isotopic evidence ( 87Sr/ 86Sr, δ 7Li) for alteration of the oceanic crust at deep-rooted mud volcanoes in the Gulf of Cadiz, NE Atlantic Ocean

The chemical and isotopic composition of pore fluids is presented for five deep-rooted mud volcanoes aligned on a transect across the Gulf of Cadiz continental margin at water depths between 350 and 3860 m. Generally decreasing interstitial Li concentrations and 87Sr/ 86Sr ratios with increasing distance from shore are attributed to systematically changing fluid sources across the continental margin. Although highest Li concentrations at the near-shore mud volcanoes coincide with high salinities derived from dissolution of halite and late-stage evaporites, clayey, terrigenous sediments are identified as the ultimate Li source to all pore fluids investigated. Light δ 7Li values, partly close to those of hydrothermal vent fluids (δ 7Li: +11.9‰), indicate that Li has been mobilized during high-temperature fluid/sediment or fluid/rock interactions in the deep sub-surface. Intense leaching of terrigenous clay has led to radiogenic 87Sr/ 86Sr ratios (∼0.7106) in pore fluids of the near-shore mud volcanoes. In contrast, non-radiogenic 87Sr/ 86Sr ratios (∼0.7075) at the distal locations are attributed to admixing of a basement-derived fluid component, carrying an isotopic signature from interaction with the basaltic crust. This inference is substantiated by temperature constraints from Li isotope equilibrium calculations suggesting exchange processes at particularly high temperatures (>200 °C) for the least radiogenic pore fluids of the most distal location. Advective pore fluids in the off-shore reaches of the Gulf of Cadiz are influenced by successive exchange processes with both oceanic crust and terrigenous, fine-grained sediments, resulting in a chemical and isotopic signature similar to that of fluids in near-shore ridge flank hydrothermal systems. This suggests that deep-rooted mud volcanoes in the Gulf of Cadiz represent a fluid pathway intermediate between mid-ocean ridge hydrothermal vent and shallow, marginal cold seep. Due to the thicker sediment coverage and slower fluid advection rates, the overall geochemical signature is shifted towards the sediment-diagenetic signal compared to ridge flank hydrothermal environments.

Relationships between the stable isotopic signatures of living and fossil foraminifera in Monterey Bay, California

Fossil foraminifera are critical to paleoceanographic reconstructions including estimates of past episodes of methane venting. These reconstructions rely on benthic foraminifera incorporating and retaining unaltered the ambient isotopic compositions of pore fluids and bottom waters. Comparisons are made here of isotopic compositions of abundant live and fossil foraminifera (Uvigerina peregrina, Epistominella pacifica, Bulimina mexicana, and Globobulimina pacifica) collected in Monterey Bay, CA from two cold seeps (Clam Flats and Extrovert Cliffs) and from sediments ∼5 m outside of the Clam Flats seep. Clam Flats has steep δ13CDIC gradients (to <−45‰), but DIC at Extrovert Cliffs is less enriched in 12C (to approximately −22‰). Oxygen isotope values of fossil foraminifera at Clam Flats are ∼1.5‰ enriched in 18O over the living foraminifera, as well as those of both live and fossil foraminifera at Extrovert Cliffs, suggesting they may have lived during the last glacial maximum. Statistical comparisons (Student's t and Kolmogorov‐Smirnov tests) of δ13C and δ18O values indicate that live and fossil foraminifera come from different populations at both Clam Flats and Extrovert Cliffs. At Clam Flats, the difference appears to result from alteration enriching some fossil foraminifera in 12C over live foraminifera. At Extrovert Cliffs, the fossil foraminifera are enriched in 13C over the live foraminifera, suggesting they lived prior to the onset of venting and thus that venting began recently. The short time of venting at Extrovert Cliffs may be responsible for the less alteration there compared with Clam Flats. These results indicate that preservation of foraminifera is likely to be poor within long‐lived cold seeps, but that foraminifera living in the surrounding sediment may incorporate and preserve broad basin‐wide changes in isotopic compositions of the ambient water.

Carbon isotopic evidence of methane oxidation through sulfate reduction in sediment beneath cold seep vents on the seafloor at Nankai Trough

During the Kaiko-Tokai project, we took a total of 15 near-surface sediment push cores from inside and outside seafloor clam colonies and bacterial mats in the Nankai Trough. In this study, we present the chemical and isotopic composition of pore fluids extracted from the sampled cores, with special emphasis on those taken at the Ryuyo Canyon, and discuss (a) the chemical relation between the seeping fluid and biological communities, and (b) the origin of cold seep fluids. Compared with bottom seawater, up to 5% depletion of chloride concentration, extremely high CH 4 concentration of more than 300 μmol/kg, and slight δD H2O depletion are observed in pore fluids at the Ryuyo Canyon, which suggests that the Ryuyo Canyon is an active seep zone of low chloride, CH 4-rich, low δD H2O fluid from the sea bottom. Remarkable depletion of sulfate and significant enrichment of dissolved inorganic carbon and of hydrogen sulfide are also observed in the pore fluids, particularly those taken within bacterial mats, while the carbon isotopic composition of pore fluid dissolved methane (δ 13C CH4) shows large heterogeneity (up to 30‰) in and around the vents. These chemical and isotopic characteristics might be due to active anaerobic methane oxidation and hydrogen sulfide production (methane oxidation through sulfate reduction) in the sedimentary layer just below (within 30 cm) the vents on the seafloor. The carbon isotopic composition of methane can be considered direct evidence of the mediation process between methane-enriched cold seep fluid and the H 2S-dependent biological community on the cold seep vent. After correcting for the effect of methane oxidation at the sediment surface, we estimate the end-member carbon isotopic composition of methane as less than −90‰ PDB, and the end-member CH 4/C 2H 6 ratio as more than 10 3, which suggests a microbial, shallow layer is the origin of methane in the fluid.

Lithium isotopic compositions of pore fluids and sediments in the Costa Rica subduction zone: implications for fluid processes and sediment contribution to the arc volcanoes

Pore fluid and sediment Li concentrations and isotopic ratios provide important insights on the hydrology, sediment contribution to the arc volcanoes and fluid–sediment reactions at the dominantly non-accretionary Costa Rica subduction zone. Ocean Drilling Program Site 1039 in the trench axis provides a reference section of 400 m of the incoming sediments, and Site 1040, situated arcward from the trench, consists of a deformed sedimentary wedge and apron sediments, the décollement, and the partially dewatered underthrust sediment section. At the reference site, pore fluids show important isotopic variations (δ 6Li=−21.7 to −37.8‰), reflecting the interplay of in situ alteration of volcanic material and ion exchange with clay minerals. In the basal section, a reversal of Li concentration and δ 6Li toward seawater values is observed, providing supporting evidence for a lateral seawater flow system in the upper oceanic basement underlying this sediment section. At Site 1040, pore fluid of the lower deformed wedge sediments and within the décollement is enriched in Li and the isotopic compositions are relatively light, suggesting infiltration of a deep-seated fluid. The δ 6Li value of −22‰ of this Li-enriched fluid (261 μM), when compared with the δ 6Li value of the subducted sediment section (−11‰), suggests that the deep source fluid originates from mineral fluid dehydration and transformation reactions at temperatures of 100 to 150°C, consistent with the temperature range of the up-dip seismogenic zone and of transformation of smectite to illite. The distribution of Li and its isotopes in the underthrust section are similar to those at the reference site, indicating near complete subduction of the incoming sediments and that early dewatering of the underthrust sediments occurs predominantly by lateral flow into the ocean. The hemipelagic clay-rich sediment section of the subducting plate carries most of the Li into this subduction zone, and the pelagic diatomaceous and nannofossil calcareous oozes contain little Li. The Li isotopes of both the clay-rich hemipelagic sediments and of the pelagic oozes are, however, similar, with δ 6Li values of −9 to −12‰. The observations that (1) the δ 6Li values of the underthrust sediments are distinctly lower than that of the mantle, and (2) the lavas of the Costa Rican volcanoes are enriched in Li and 7Li, provide an approximation of the contribution of the subducted sediments to the arc volcanoes. A first order mass balance calculation suggests that approximately half of the Li flux delivered by subducted sediments and altered oceanic crust into the Middle American Trench is recycled to the Costa Rican arc and at most a quarter of sedimentary Li is returned into the ocean through thrust faults, primarily the décollement thrust.

Chemical and isotopic evidence of gas‐influenced flow at a transform plate boundary: Monterey Bay, California

Chemical and isotopic compositions of pore fluids document upward flow through communities of vesicomyid clams in Monterey Bay, California. Within the clam communities, the sulfate reduction zone is only 10 cm thick, and Ca and Mg concentrations decrease to values as low as 2.2 mM and 34.5 mM, respectively, at depths less than 30 cm below the sediment‐water interface. Less than 5 m outside the communities, the base of the sulfate reduction zone is deeper than the greatest penetration of the cores (∼30 cm), and Ca and Mg exhibit only minor changes from seawater values. The sediment exhibits no significant variation in grain size, mineralogy, organic carbon, nitrogen, or carbonate content throughout the region. The composition of pore fluid within clam communities results from upward flow of altered fluid rather than different diagenetic reactions within and outside the communities. Isotopically light dissolved inorganic carbon (DIC), with δ13C values ranging from −3.2 to −54.1‰, could reflect carbon sources from either oxidized thermogenic methane and/or a mixture of oxidized microbial methane and solid organic carbon. The C1/(C2+C3) ratios (ranging from 34 to 1142) and the hydrogen and carbon isotopic compositions of methane (δD values of −109 to −156‰; δ13C values of −30.6 to −86.6‰) suggest that methane is primarily microbial but that a minor component could be thermally generated. Any thermogenic methane would have migrated from great depths, possibly >2 km. The presence of methane is likely to contribute to fluid flow by reducing the density of the fluids. Past fluid migration and venting are reflected by widespread carbonate mineralization at the sediment‐water interface. This mineralization and the geographic distribution and proportions of microbial and thermogenic methane suggest that vent sites migrate when permeability is reduced during carbonate cementation. These results demonstrate that along with convergent and divergent plate boundaries, transform plate boundaries are characterized by fluid flow and that the flow may be widespread, occurring at sites away from fault zones.

Constraints on water transport and alteration in the oceanic crust from the isotopic composition of pore water

The oxygen isotopic compositions of pore fluids from sediments of older oceanic crust commonly decrease with depth. Increases in calcium ion concentrations always accompany the 18O/16O decreases.These changes are attributed principally to the alteration of basalts or alteration of volcanic ash in the sediments. Oxygen isotope material balance calculations suggest that 5–20% of the upper kilometer of basalt is altered at the time of subduction of the oceanic crust. This corresponds to a flux of 18O into the oceanic crust of 2.3 × 1015 moles per million years. Evaluation of the oxygen and hydrogen isotope data from the pore fluids also suggests that the principal process of mass transfer in the sediments of older oceanic crust is diffusion. Convection of water in the basalts of the oceanic crust appears to continue until subduction.