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1.
Subsurface regions of alluvial sediments characterized by an abundance of refractory or lignitic organic carbon compounds and reduced Fe and S bearing minerals, which are referred to as naturally reduced zones (NRZ), are present at the Integrated Field Research Challenge site in Rifle, CO (a former U mill site), and other contaminated subsurface sites. A study was conducted to demonstrate that the NRZ contains a variety of contaminants and unique minerals and potential contaminant hosts, investigate micron-scale spatial association of U with other co-contaminants, and determine solid phase-bounded U valence state and phase identity. The NRZ sediment had significant solid phase concentrations of U and other co-contaminants suggesting competing sorption reactions and complex temporal variations in dissolved contaminant concentrations in response to transient redox conditions, compared to single contaminant systems. The NRZ sediment had a remarkable assortment of potential contaminant hosts, such as Fe oxides, siderite, Fe(II) bearing clays, rare solids such as ZnS framboids and CuSe, and, potentially, chemically complex sulfides. Micron-scale inspections of the solid phase showed that U was spatially associated with other co-contaminants. High concentration, multi-contaminant, micron size (ca. 5–30 μm) areas of mainly U(IV) (53–100%) which occurred as biogenic UO2 (82%), or biomass – bound monomeric U(IV) (18%), were discovered within the sediment matrix confirming that biotically induced reduction and subsequent sequestration of contaminant U(VI) via natural attenuation occurred in this NRZ. A combination of assorted solid phase species and an abundance of redox-sensitive constituents may slow U(IV) oxidation rates, effectively enhancing the stability of U(IV) sequestered via natural attenuation, impeding rapid U flushing, and turning NRZs into sinks and long-term, slow-release sources of U contamination to groundwater.  相似文献   

2.
Subterranean estuaries are characterized by the mixing of terrestrially derived groundwater and seawater in a coastal aquifer. Subterranean estuaries, like their river water-seawater counterparts on the surface of the earth, represent a major, but less visible, hydrological and geochemical interface between the continents and the ocean. This article is the first in a two-part series on the biogeochemistry of the subterranean estuary at the head of Waquoit Bay (Cape Cod, MA, USA). The pore-water distributions of salinity, Fe and Mn establish the salt and redox framework of this subterranean estuary. The biogeochemistry of Fe, Mn, P, Ba, U and Th will be addressed from the perspective of the sediment composition. A second article will focus on the groundwater and pore-water chemistries of Fe, Mn, U and Ba.Three sediment cores were collected from the head of Waquoit Bay where the coastal aquifer consists of permeable sandy sediment. A selective dissolution method was used to measure the concentrations of P, Ba, U and Th that are associated with “amorphous (hydr)oxides of iron and manganese” and “crystalline Fe and Mn (hydr)oxides.” The deeper sections of the cores are characterized by large amounts of iron (hydr)oxides that are precipitated onto organic C-poor quartz sand from high-salinity pore waters rich in dissolved ferrous iron. Unlike Fe (hydr)oxides, which increase with depth, the Mn (hydr)oxides display midcore maxima. This type of vertical stratification is consistent with redox-controlled diagenesis in which Mn (hydr)oxides are formed at shallower depths than iron (hydr)oxides. P and Th are enriched in the deep sections of the cores, consistent with their well-documented affinity for Fe (hydr)oxides. In contrast, the downcore distribution of Ba, especially in core 3, more closely tracks the concentration of Mn (hydr)oxides. Even though Mn (hydr)oxides are 200-300 times less abundant than Fe (hydr)oxides in the cores, Mn (hydr)oxides are known to have an affinity for Ba which is many orders of magnitude greater than iron (hydr)oxides. Hence, the downcore distribution of Ba in Fe (hydr)oxide rich sediments is most probably controlled by the presence of Mn (hydr)oxides. U is enriched in the upper zones of the cores, consistent with the formation of highly reducing near-surface sediments in the intertidal zone at the head of the Bay. Hence, the recirculation of seawater through this type of subterranean estuary, coupled with the abiotic and/or biotic reduction of soluble U(VI) to insoluble U(IV), leads to the sediments acting as a oceanic net sink of U. These results highlight the importance of permeable sediments as hosts to a wide range of biogeochemical reactions, which may be impacting geochemical budgets on scales ranging from coastal aquifers to the continental shelf.  相似文献   

3.
Continuous core sediments (to a depth of 90.1 m) taken at a transitional area of Holocene and Pleistocene deposits in Sonargaon, Bangladesh were characterized for their mineralogy and chemistry. Among the sediments of the lower part of the Holocene aquifer (depth: 18–29 m), where most domestic wells are installed, As is mostly fixed in biotite and organic phases. A positive correlation of As concentration with those of Al and Fe but not that of total organic C clearly suggests that biotite is a primary source of As. Although microbial reduction–dissolution of As-containing Fe oxyhydroxides is thought to cause As-enriched groundwater in the Ganges–Brahmaputra–Meghna delta plain, the authors conclude that chemical weathering of biotite is the primary formation mechanism and prevailing reducing conditions contribute to the expansion of As-enriched groundwater in the study area.  相似文献   

4.
Enriched As in drinking water wells in south and Southeast Asia has increased the risk of cancer for nearly 100 million people. This enrichment is generally attributed to the reductive dissolution of Fe oxides; however, the complex expression of As enrichment in these areas is not yet well understood. Here, the coupled sedimentological and geochemical factors that contribute to the extent and spatial distribution of groundwater As concentrations in the Mekong River delta, Cambodia in an avulsed scroll bar sequence are examined. X-Ray absorption spectroscopy (XAS) was used to determine Fe and As speciation in redox preserved sediment collected from drilled cores. Dissolved As, Fe and S solution concentrations in existing and newly drilled wells (cores) differed considerably depending on their source sedimentology. The rapid burial of organic matter in the scroll bar sequence facilitated the development of extensive Fe-reducing conditions, and As release into the aquifer. In older features organic C levels are high enough to sustain extensive Fe reduction and provide ample SO4 which is reduced to sulfide. This S reduction impacts As levels; As is sequestered in sulfide minerals outside of the scrollbar sequence, decreasing pore water concentrations. In contrast, As is depleted in sediments from the scroll sequence, and associated with elevated pore water aqueous concentrations. The concentration and form of organic C in the scrollbar sequence is related to depositional environment, and can facilitate Fe and S mineral transformations, distinct sedimentary environments explain a portion of the inherent heterogeneity of aquifer As concentrations.  相似文献   

5.
Sediments from the Red River and from an adjacent floodplain aquifer were investigated with respect to the speciation of Fe and As in the solid phase, to trace the diagenetic changes in the river sediment upon burial into young aquifers, and the related mechanisms of arsenic release to the groundwater. Goethite with subordinate amounts of hematite were, using Mössbauer spectroscopy, identified as the iron oxide minerals present in both types of sediment. The release kinetics of Fe, As, Mn and PO4 from the sediment were investigated in leaching experiments with HCl and 10 mM ascorbic acid, both at pH 3. From the river sediments, most of the Fe and As was mobilized by reductive dissolution with ascorbic acid while HCl released very little Fe and As. This suggests As to be associated with an Fe-oxide phase. For oxidized aquifer sediment most Fe was mobilized by ascorbic acid but here not much As was released. However, the reduced aquifer sediments contained a large pool of Fe(II) and As that is readily leached by HCl, probably derived from an unidentified authigenic Fe(II)-containing mineral which incorporates As as well. Extraction with ascorbic acid indicates that the river sediments contain both As(V) and As(III), while the reduced aquifer sediment almost exclusively releases As(III). The difference in the amount of Fe(II) leached from river and oxidized aquifer sediments by ascorbic acid and HCl, was attributed to reductive dissolution of Fe(III). The reactivity of this pool of Fe(III) was quantified by a rate law and compared to that of synthetic iron oxides. In the river mud, Fe(III) had a reactivity close to that of ferrihydrite, while the river sand and oxidized aquifer sediment exhibited a reactivity ranging from lepidocrocite or poorly crystalline goethite to hematite. Mineralogy by itself appears to be a poor predictor of the iron oxide reactivity in natural samples using the reactivity of synthetic Fe-oxides as a reference. Sediments were incubated, both unamended and with acetate added, and monitored for up to 2 months. The river mud showed the fastest release of both Fe and As, while the effect of acetate addition was minor. This suggests that the presence of reactive organic carbon is not rate limiting. In the case of the river and aquifer sediments, the release of Fe and As was always stimulated by acetate addition and here reactive organic carbon was clearly the rate limiting factor. The reduced aquifer sediment apparently can sustain slower but prolonged microbially-driven release of As. The highly reactive pools of Fe(III) and As in the river mud could be due to reoxidation of As and Fe contained in the reducing groundwater from the floodplain aquifers that are discharging into the river. Deposition of the suspended mud on the floodplain during high river stages is proposed to be a major flux of As onto the floodplain and into the underlying aquifers.  相似文献   

6.
《Applied Geochemistry》2003,18(6):823-843
The unmined Coles Hill U deposit of south central Virginia represents a natural setting where U is stabilized by phosphate mineral precipitation in an oxidizing bedrock aquifer. Drill cores from the shallow portion of the deposit preserve a sharp Fe redox front defined by Fe(III) oxide staining. This front is located near a discontinuity in U mineralogy with U(IV) assemblages (e.g. coffinite, uraninite) on the reducing side, and U(VI) assemblages on the oxidizing side. The discontinuity in U mineralogy does not, however, represent a major discontinuity in whole rock U concentrations, with sample groups from both oxidized and reduced sides of the front generally ranging from 500 to 1000 ppm. This observation suggests that the volume of shallow bedrock associated with the deposit has not lost significant amounts of U during the oxidation and incipient chemical weathering. The precipitation of Ba uranyl phosphate (Ba meta-autunite) is responsible for U retention within this zone. Ground waters sampled from the weathered bedrock aquifer associated with the deposit contain less than 15 μg l−1 dissolved U. This suggests that the low solubility of the Ba meta-autunite limits U concentrations to values lower than the US-EPA maximum contaminant level of 30 μg l−1. Ground water speciation and mineral saturation calculations show that, in addition to Eh and pH, the most important factor controlling this U fixation process is the activity ratio of dissolved phosphate to dissolved carbonate. Experimental results suggest that, at the Coles Hill site, the oxidation of U(IV) to U(VI) and subsequent precipitation of uranyl phosphate occurs rapidly (time scale of weeks) relative to ground water transport (e.g. 20 m/a). Furthermore, based on the rate of downward migration of the redox front, it is estimated that the oldest U(VI) phosphate assemblages associated with the Coles Hill U deposit have been stable for up to 150 ka. These observations have important implications for the design and long term performance assessment of phosphate-based stabilization and reactive barrier techniques.  相似文献   

7.
Incubation experiments were adopted to characterize the rates and pathways of iron reduction and the contributions to anaerobic organic matter mineralization in the upper 0–5 cm of sediments along a landscape-scale inundation gradient in tidal marsh sediments in the Min River Estuary, Southeast China. Similar sediment characteristics, single-species vegetation, varied biomass and bioturbation, distinct porewater pH, redox potential, and electrical conductivity values have resulted in a unique ecogeochemical zonation along the inundation gradient. Decreases in solid-phase Fe(III) and increases in nonsulfidic Fe(II) and iron sulfide were observed in a seaward direction. Porewater Fe2+ was only detected in the upland area. High rates of iron reduction were observed in incubation jars, with significant accumulations of nonsulfidic Fe(II), moderate accumulations of iron sulfides, and negligible accumulations of porewater Fe2+. Most of the iron reduction was microbially mediated rather than coupled to reduced sulfides. Microbial iron reduction accounted for 20–89 % of the anaerobic organic matter mineralization along the inundation gradient. The rate and dominance of microbial iron reduction generally decreased in a seaward direction. The contributions of microbial iron reduction to anaerobic organic matter mineralization depended on the concentrations of bioavailable Fe(III), the spatial distribution of which was significantly related to tidal inundation. Our results clearly showed that microbial iron reduction in the upper sediments along the gradient is highly dependent on spatial scales controlled primarily by tidal inundation.  相似文献   

8.
The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens-like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy.All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of FeTOT. The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments.  相似文献   

9.
Reductive biostimulation is currently being explored as a possible remediation strategy for U-contaminated groundwater, and is being investigated at a field site in Rifle, CO, USA. The long-term stability of the resulting U(IV) phases is a key component of the overall performance of the remediation approach and depends upon a variety of factors, including rate and mechanism of reduction, mineral associations in the subsurface, and propensity for oxidation. To address these factors, several approaches were used to evaluate the redox sensitivity of U: (1) measurement of the rate of oxidative dissolution of biogenic uraninite (UO2(s)) deployed in groundwater at Rifle, (2) characterization of a zone of natural bioreduction exhibiting relevant reduced mineral phases, and (3) laboratory studies of the oxidative capacity of Fe(III) and reductive capacity of Fe(II) with regard to U(IV) and U(VI), respectively.  相似文献   

10.
Aquifer sediments from areas of low- and high-As groundwater were characterized mineralogically and geochemically at a field site in the Nadia district of West Bengal, India. Leaching experiments and selective extraction of the sediments were also carried out to understand the release mechanism of As in the sub-surface. The correlation between measured elements (major, minor and trace) from low- and high-As groundwater areas are only significant for As, Fe and Mn. The borehole lithology and percentage of silt and clay fraction demonstrates the dominance of finer sediments in the high-As aquifer. Multivariate analysis of the geochemical parameters showed the presence of four different mineral phases (heavy-mineral fraction, phyllosilicates/biotite/Fe-oxyhydroxides, carbonates and sulphides) in the sediments. Selective extraction of sediment reveals that amorphous Fe-oxyhydroxide acts as a potential sink for As in the sub-surface. The result is consistent with microbially mediated redox reactions, which are controlled in part by the presence of natural organic matter within the aquifer sediments. The occurrences of As-bearing redox traps, primarily formed of Fe- and Mn-oxides/hydroxides, are also important factors that control the release of As into groundwater at the study site.  相似文献   

11.
《Applied Geochemistry》1999,14(5):655-667
Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.  相似文献   

12.
The sediments of the Port Camargue marina (South of France) are highly polluted by Cu and As (Briant et al., 2013). The dynamics of these pollutants in pore waters was investigated using redox tracers (sulfides, Fe, Mn, U, Mo) to better constrain the redox conditions.In summer, pore water profiles showed a steep redox gradient in the top 24 cm with the reduction of Fe and Mn oxy-hydroxides at the sediment water interface (SWI) and of sulfate immediately below. Below a depth of 24 cm, the Fe, Mn, Mo and U profiles in pore waters reflected Fe and Mn reducing conditions and, unlike in the overlying levels, sulfidic conditions were not observed. This unusual redox zonation was attributed to the occurrence of two distinct sediment layers: an upper layer comprising muddy organic-rich sediments underlain by a layer of relatively sandy and organic-poor sediments. The sandy sediments were in place before the building of the marina, whereas the muddy layer was deposited later. In the muddy layer, large quantities of Fe and Mo were removed in summer linked to the formation of insoluble sulfide phases. Mn, which can adsorb on Fe-sulfides or precipitate with carbonates, was also removed from pore waters. Uranium was removed probably through reduction and adsorption onto particles. In winter, in the absence of detectable pore water sulfides, removal of Mo was moderate compared to summer.Cu was released into solution at the sediment water interface but was efficiently trapped by the muddy layer, probably by precipitation with sulfides. Due to efficient trapping, today the Cu sediment profile reflects the increase in its use as a biocide in antifouling paints over the last 40 years.In the sandy layer, Fe, Mn, Mo and As were released into solution and diffused toward the top of the profile. They precipitated at the boundary between the muddy and sandy layers. This precipitation accounts for the high (75 μg g−1) As concentrations measured in the sediments at a depth of 24 cm.  相似文献   

13.
Many cores from the deep basins of the Bering Sea have a thin oxidized zone within otherwise reduced sediment. This oxidized zone began to form about 6000 yr ago and represents an interval of about 3200 yr. Mineralogically, the oxidized and reduced sediments are similar, but chemically they differ. Concentrations of Fe and C are lower, and concentrations of Mn, Ba, Co, Mo, and Ni are higher in the oxidized than in the reduced sediment. Mn is enriched about 10-fold in the oxidized zone relative to its concentration in the reduced sediment, Mo about threefold, and Ba, Co, and Ni about twofold. These data suggest that the oxidized zone developed diagenetically as the result of the balance between the flux of organic matter and the available dissolved oxygen in bottom and interstitial waters.We propose that the Bering Sea was substantially ice covered when global glacial conditions prevailed. during the transition to global interglacial conditions, seasonal meltwater from thawing sea ice formed a lens of fresh water that decreased organic productivity. During the winter seasons, however, sea ice reformed and caused downwelling of dense, oxygen-rich waters to recharge bottom waters. The combination of lower organic productivity and more oxygen-rich bottom water allowed oxidized sediment to accumulate. Once full interglacial conditions were established, the volume of sea ice produced was insufficient to affect either productivity or the supply of dissolved oxygen and so bottom conditions again became reducing.Similar events probably occurred during the onset of global glacial conditions, and similar oxidized layers probably formed at these times. Such oxidized zones are highly unstable, however, in a reducing environment and, once buried beyond the influence of bacterial and infaunal activities, are depleted of their available oxygen and converted to reduced sediment.  相似文献   

14.
The geochemical processes, water–rock interactions and stable isotopes distribution (δ13C of DIC and δ18O and δ34S of \({\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}} \)) were investigated in the gasoline-contaminated aquifer at the Hnevice site, 50  km northwest of Prague, Czech Republic. Diesel, gasoline and oil leaks originate from a large fuel storage area causing heavy contamination of the saturated and unsaturated zones in an area of about 0.7  km2. Groundwater investigations were conducted using five multilevel sampler wells with emphasis on redox parameters and degradation by-products and a solid-phase study focused on iron speciation and determination of principal and secondary minerals. Based on the study of groundwater and solid-phase geochemistry, four different geochemical zones were described. Zone I is thought to be background consisting of an aerobic aquifer and the absence of reduced species in significant concentrations. Zone II is situated in the plume core with methanogenic, sulphate and iron-reducing conditions accompanied by ankerite and kutnahorite precipitates and significant depletion of the oxidation capacity of the aquifer. Zone III is a mixing (corona) zone, situated at the fringe of the plume with high biodegradation rates and Fe(III)-precipitants. In zone IV, reoxidation of Fe(II) minerals (with e.g. the occurrence of psilomelane and cornelite) is typical.  相似文献   

15.
Incubation studies were carried out using 5 freshly collected sediments from shallow aquifers of the Hetao Basin, Inner Mongolia. The aquifer sediments covering a range of redox conditions, as indicated by their deep grey to yellow color were mixed with degassed artificial As solution or degassed deionized water at a ratio of solid to water of about 1:10 (wt./wt.). Suspensions which were either amended with glucose or autoclaved, were incubated in parallel with unamended suspensions. Five microcosm cultures of unamended sediments gradually release the equivalent of 0.03–0.30 μg/g As to the dissolved phase. The addition of glucose as a potential electron donor results in a marked stimulation in the mobilization of As (0.71–3.81 μg/g) in the amended incubations for all sediments. The quantity of As released accounts for 60–70% of As bound to Fe/Mn oxides in the original sediments. The microbially mediated mobilization of As with the organic nutrient as an electron donor is strongly associated with the As bound to Fe/Mn oxides, as well as the exchangeable As. During the incubations amended with glucose, 2–4% of the sediment Fe is released. The results suggest that the introduction of labile dissolved organic C into the yellowish sediment aquifers with As-free groundwater would reduce a significant proportion of the Fe(III) oxyhydroxides mediated by anaerobic bacteria respiration and increase groundwater As concentrations.  相似文献   

16.
The arsenic accumulation process in intertidal sediments of Iriomote Island, Japan, is analyzed as a naturally balanced arsenic-fixation system. Major and minor element chemistry is analyzed by X-ray fluorescence photometry, mineralogy is investigated by X-ray diffractometry, and four arsenic compounds are characterized by hydrogen-generated atomic absorption photometry. It is found that arsenic is accumulated by iron hydroxides/oxides precipitated following the decomposition of humic acids in the shallower sediment, and is subsequently incorporated into iron sulfide minerals at depth. The arsenic is immobile during incorporation into arsenic-bearing phases, suggesting that arsenic is unlikely to be released into the porewater under natural conditions in early diagenesis. The formation and decomposition of arsenic-bearing organic compounds appear to be associated with the formation and decomposition of arsenic in oxyhydroxides/oxides, suggesting that microbial activity may play an important role in controlling the behavior of arsenic and arsenic-bearing phases in the sediment column.  相似文献   

17.
The mobility of subsurface arsenic is controlled by sorption, precipitation, and dissolution processes that are tied directly to coupled redox reactions with more abundant, but spatially and temporally variable, iron and sulfur species. Adjacent to the site of a former pesticide manufacturing facility near San Francisco Bay (California, USA), soil and groundwater arsenic concentrations are elevated in sediments near the prior source, but decrease to background levels downgradient where shallow groundwater mixes with infiltrating tidal waters at the plume periphery, which has not migrated appreciably in over two decades of monitoring. We used synchrotron X-ray absorption spectroscopy, together with supporting characterizations and sequential chemical extractions, to directly determine the oxidation state of arsenic and iron as a function of depth in sediments from cores recovered from the unsaturated and saturated zones of a shallow aquifer (to 3.5 m below the surface). Arsenic oxidation state and local bonding in sediments, as As-sulfide, As(III)-oxide, or As(V)-oxide, were related to lithologic redox horizons and depth to groundwater. Based on arsenic and iron speciation, three subsurface zones were identified: (i) a shallow reduced zone in which sulfide phases were found in either the arsenic spectra (realgar-like or orpiment-like local structure), the iron spectra (presence of pyrite), or both, with and without As(III) or As(V) coordinated by oxygen; (ii) a middle transitional zone with mixed arsenic oxidation states (As(III)–O and As(V)–O) but no evidence for sulfide phases in either the arsenic or iron spectra; and (iii) a lower oxidized zone in the saturated freshwater aquifer in which sediments contained only oxidized As(V) and Fe(III) in labile (non-detrital) phases. The zone of transition between the presence and absence of sulfide phases corresponded to the approximate seasonal fluctuation in water level associated with shallow groundwater in the sand-dominated, lower oxic zone. Total sediment arsenic concentrations showed a minimum in the transition zone and an increase in the oxic zone, particularly in core samples nearest the former source. Equilibrium and reaction progress modeling of aqueous-sediment reactions in response to decreasing oxidation potential were used to illustrate the dynamics of arsenic uptake and release in the shallow subsurface. Arsenic attenuation was controlled by two mechanisms, precipitation as sulfide phases under sulfate-reducing conditions in the unsaturated zone, and adsorption of oxidized arsenic to iron hydroxide phases under oxidizing conditions in saturated groundwaters. This study demonstrates that both realgar-type and orpiment-type phases can form in sulfate-reducing sediments at ambient temperatures, with realgar predicted as the thermodynamically stable phase in the presence of pyrite and As(III) under more reduced conditions than orpiment. Field and modeling results indicate that the potential for release of arsenite to solution is maximized in the transition between sulfate-reduced and iron-oxidized conditions when concentrations of labile iron are low relative to arsenic, pH-controlled arsenic sorption is the primary attenuation mechanism, and mixed Fe(II,III)-oxide phases do not form and generate new sorption sites.  相似文献   

18.
Sediment cores from the middle to lower slope of the southern continental margin of Australia between the Great Australian Bight and western Tasmania are compared in terms of marine and terrigenous input signals during the Holocene. The mass accumulation rates of carbonate, organic carbon, biogenic Ba, and Al are corrected for lateral sediment input (focusing), using the inventory of excess 230Th in the sediment normalised to its known production rate in the water column above each site. The biogenic signal is generally higher in the eastern part of the southern margin probably due to enhanced productivity associated with seasonal upwelling off southeastern South Australia and the proximity of the Subtropical Front, which passes just south of Tasmania. The input of Al, representing the terrigenous signal, is also higher in this region reflecting the close proximity of river runoff from the mountainous catchment of southeastern Australia. The distribution pattern of Mn and authigenic U, together with pore‐water profiles of Mn++, indicate diagenetic reactions driven by the oxidation of buried organic carbon in an oxic to suboxic environment. Whereas Mn is reduced at depth and diffuses upwards to become immobilised in a Mn‐rich surface layer, U is derived from seawater and diffuses downward into the sediment, driven by reduction and precipitation at a depth below the reduction zone of Mn. The estimated removal rate of U from seawater by this process is within the range of U removal measured in hemipelagic sediments from other areas, and supports the proposition that hemipelagic sediments are a major sink of U in the global ocean. Unlike Mn, the depth profile of sedimentary Fe appears to be little affected by diagenesis, suggesting that little of the total Fe inventory in the sediment is remobilised and redistributed as soluble Fe.  相似文献   

19.
Four sediment cores representing adjacent mudflat and mangrove sub-environments of middle estuary (Shastri) were analyzed for sand, silt, clay, and organic carbon. Total metal concentration of iron (Fe), manganese (Mn), nickel (Ni), zinc (Zn), chromium (Cr), copper (Cu), cobalt (Co), and lead (Pb) and chemical speciation of Fe, Mn, and Co on selected samples was also carried out on mudflat cores. The sediments in the upper middle estuary were found to be deposited under highly varying hydrodynamic energy conditions; whereas lower middle estuary experienced relatively stable hydrodynamic energy conditions with time. The tributary joining the river near the upper middle estuary is found to be responsible for the addition of enhanced organic carbon and metal concentrations. Speciation study indicated Fe and Co are from natural lithogenic origin while Mn is derived from anthropogenic sources. Higher Mn and Co than apparent effects threshold can pose a high risk of toxicity to organisms associated with these sediments.  相似文献   

20.
Geochemistry of two sediment cores from the west coast of India   总被引：2，自引：0，他引：2  
Copper, Pb, Zn, Ni, Co, Mn, AI, Ca, magnetic susceptibility and loss on ignition of sediments from two cores near Mangalore along the western continental shelf of India have been studied. The sediments have high Al and organic matter contents due to the high sedimentation rate and their proximity to river mouths. Down-core variations of elements indicate a decrease of lithogenous component during probably the past few centuries. While abundance of calcareous shells in some zones has lead to the dilution of most of the metals, it appears that Pb and Mn are associated with this phase. Copper, Zn and Fe are associated with organic matter and detrital particles, whereas Ni and Co are predominantly associated with the insoluble fraction. Oxides/hydroxides of Fe and Mn are absent because of the reducing conditions and the high terrigenous influx. Geochemically, Mn and Fe are present in different phases of sediments (in the insoluble fraction and organic matter respectively). The Fe content of one of the cores is positively correlated with magnetic susceptibility.  相似文献   

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