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1.
Flow-through experiments have been performed to study the thermodynamics of biogenic silica (opal) dissolution in deep-sea sediments. They were applied for the first time on sediment from the Southern Ocean [Van Cappellen and Qiu 1997a] and [Van Cappellen and Qiu 1997b] We have extended the use of these experiments to other deep-sea settings, thereby covering a wide range of in situ silicic acid asymptotic concentrations (Casympt; 200 to 900 μmol/L) and biogenic opal content (BSi; 0.5 to 80%). Performing these experiments under in situ bottom temperatures allows for the comparison between experimental apparent solubilities and Casympt concentrations. Low values of BSi apparent solubilities have been measured in the deepest sections of the multicores collected in the northeast Atlantic (229 μmol/L) and in the equatorial Pacific (505 μmol/L). They are only 10 to 20% higher than the in situ Casympt concentrations. This demonstrates a clear control of pore water silicic acid concentrations by the in situ apparent solubility of the BSi, i.e., the solubility of BSi within a complex sedimentary matrix that includes important quantities of silicate minerals.In regions where the percentage detrital/percentage biogenic ratio is low, the apparent solubility of the biogenic silica is close to that of in situ biogenic silica. In the opposite case, when the percentage detrital/percentage biogenic ratio is high, reprecipitation reactions induce strong interference on the dissolution properties of the opal, both in situ and in flow-through experiments. In such a sedimentary matrix, it is important to determine the appropriate opal solubility to be used in early diagenetic models, i.e., the solubility of the biogenic silica just before deposition on the seabed. This has been achieved by performing flow-through experiments on sediment trap material from the north Atlantic site. Comparison of apparent biogenic silica solubility measured by flow-through experiments and the silicic acid concentrations measured in the cups of the sediment traps suggested that the solubility of biogenic silica that reaches the sediment-water interface is not unique and varies spatially and temporally. In fact, it is the degree of coupling between surface waters and the sediment-water interface that will control the aging of biogenic silica in the water column and hence the dissolution properties of the biogenic silica deposited at the sediment-water interface. All these results call for a strong improvement of biogenic silica early diagenetic models that should include not only a reprecipitation term that takes into account interaction with silicate minerals but also the existence of several phases of biogenic silica and thus that should operate in a non-steady-state mode to account for seasonal variations in the quality of deposited biogenic silica.  相似文献   

2.
To carry out comparative geochemical investigation of refractory and reactive metals in different oceanic settings covering different θ-S characteristics, productivity, dissolved oxygen profiles, water and sediment discharge, etc., we have determined the vertical profiles of dissolved (<0.04 μm) Al, In and Ce, as well as 210Pb and 210Po in the eastern Indian Ocean (from 40°S in the Southern Ocean to 8°N in the Bay of Bengal) and the Southeast Asian Seas. In the Antarctic Circumpolar Region, the concentrations of these refractory metals are very low, presumably due to very low the atmospheric input and intensified scavenging. Resemblance in the vertical profiles of these metals is often seen in some other stations. However, there are also significant differences among their distributions, for example, in the magnitude of surface enrichment caused by the external input from eolian and fluvial-coastal sources. Comparison of Al distributions in surface waters with those of atmospherically derived 210Pb suggests the relative importance of eolian input over fluvial-coastal sources. Fluvial and coastal input appears to be insignificant for dissolved In, but may be important for Ce. The mean residence time of Al in the surface mixed layer was estimated to be ∼2 years which is similar to that of 210Pb.In the intermediate and deep waters, the concentrations of each element vary with depth and location. The range of variation is in the order of Al>Ce>In, depending upon particle reactivity. Although dissolved Al decreases along the water trajectory by particle scavenging, variations of dissolved In and Ce are relatively small which may be due to less scavenging for both elements. Compared with significantly high (>4 pM) dissolved Ce throughout the water column in the Bay of Bengal, dissolved Al concentration remains low, suggesting that it has higher affinity to particles and hence is scavenged by sinking particulate matter. This is consistent with the observation that the dissolved Al in the Antarctic Intermediate Water (AAIW) decreases from 4 to 6 nM in the 30°S Perth Basin to <0.7 nM in the 10°S West Australia Basin along its trajectory. Using the chlorofluorocarbons (CFCs) ventilation age of AAIW (Fine, 1993), the mean residence time of Al in the intermediate and deep waters in the eastern Indian Ocean is estimated to be <17 yr, approximately the same as that of 210Pb (10-15 yr). In the semiclosed basins of Southeast Asia, the distributions of Al, In and Ce are also very unique. In the South China Sea, there is a strong sediment source for dissolved In and Ce during the deepwater passage through the Luzon Strait.  相似文献   

3.
Chesapeake Bay sediments were examined for biogeochemical evidence of eutrophication trends using two mesohaline sediment cores. Measurements of 210Pb geochronology and sediment profiles of organic carbon, nitrogen, organic phosphorus, inorganic phosphorus, and biogenis silica (BSi) were used used to develop temporal concentration trends. Recent sediments have 2–3 times as much organic carbon and nitrogen as sediments from 80 to 100 yr ago, but the increases result from both changes in organic matter deposition and time-dependent changes in organic matter decomposition rates. Despite increases in phosphorus loading, no major changes in phosphorus concentration were noted throughout most of the century; anthropogenic phosphorus deposition, though not evident in sulfidic mid-bay sediments, must occur in more oxidizing sediment environments in both the northern and southern bays. Temporal trends in BSi concentrations are much less evident and the lack of substantial increases in this century suggest that BSi inputs may be capped by late spring-summer Si limitation.  相似文献   

4.
生物硅的测定及其生物地球化学意义   总被引：19，自引：1，他引：19  
生物硅（BSi）指用化学方法测定的沉积物中的无定形硅含量。生物硅的含量与水体中初级生产息息相关。硅藻、放射虫、海绵骨针和硅鞭毛虫产生的生物硅是地球化学和古海洋学研究的重要参数。重点讨论了目前生物硅测定方法中的化学提取法，评述了提取过程中存在的一些问题，并对BSi测定的生物地球化学意义进行了讨论。  相似文献   

5.
《Applied Geochemistry》2000,15(4):425-438
The dissolution of silica and diffusion of reactive dissolved Si in the porewaters of river sediments are investigated using sediments of different physical and chemical properties. Three sediments are considered: (a) from sectioned cores taken from a river-bed, (b) fine organic-rich surface sediment (<5 cm depth) installed in a fluvarium channel and, (c) coarse river sediment of low organic matter content also installed in a fluvarium channel. Dissolution rates of silica are measured at 10°C using batches of suspended material. The derived dissolution rate constants show large differences between the sediments. The river bed-sediment cores had vertical concentration profiles of dissolved Si that are consistent with the diffusion and dissolution of biogenic silica. Experiments in a fluvarium channel enabled Si fluxes to be calculated from a mass-balance of the overlying solution. The results are consistent with the attainment of a steady-state concentration profile of dissolved Si in the sediment. There are no discernible effects of water velocity over the sediment between 5 and 11 cm s−1. However, at 20 cm s−1, the flux increases as a result of either entrainment of fine particles at the surface or advective effects in the surface sediment. A fluvarium experiment with the fine sediment (<125 μm) over 61 days, produced a concentration profile with the highest concentration of 1025 μmol dm−3 at a depth of 4–5 cm in the sediment. A FORTRAN program is used to model the results of the increase in dissolved Si in the overlying water and development of a concentration profile in the porewater. This leads to a sediment diffusion coefficient of 1.21×10−9 m2 s−1 at 8.8°C at the beginning of the experiment and rate constant k=13.1×10−7 s−1 at pH=7.82 and average temperature of 7.6°C for the entire experiment. Fluxes measured at the sediment–surface interface and calculated assuming steady-state profiles had developed are typically 0.01–0.04 μmol m−2 (of river bed) s−1. The approach enables the efflux of dissolved Si from bottom-sediments to be estimated from dissolution rates measured using suspensions of bed-sediment.  相似文献   

6.
This study introduces an alkaline leaching technique for the simultaneous analysis of biogenic silica and aluminium in sediments. Measuring aluminium facilitates the discrimination between silica from the biogenic (BSiO2) and the non-biogenic fraction, because it originates almost solely from the lithogenic phase. The method was tested using fine-grained silicagel, standard clay minerals, artificial sediments, and natural samples ranging from fresh diatoms to aged sediment from different depositional settings. To determine the BSiO2 content, four different models each describing the dissolution curves, but of increasing complexity, were applied and for each different type of sample the optimum model was selected on the basis of F-test statistics. For mixtures of silicagel and clay minerals, the contribution of Si from the dissolution of clay was negligible compared to Si originating from silicagel. For natural samples with high clay content, complex dissolution curves were observed and single-phase first order dissolution was the exception. This deviation from `ideal' behavior could only be recognized because of high-resolution sampling, especially in the first 20 minutes of the experiment. For most of the samples, the distinction between the biogenic silica fraction and the silica originating from dissolution of clays could be made on the basis of the Si/Al ratios and reactivity constants of the dissolving phases calculated with the models. Clay minerals typically dissolve slowly at a Si/Al ratio close to 1–2, depending on the type of clay mineral. In contrast, biogenic silica displays a wide range of reactivities and Si/Al ratios. Fresh biogenic silica from the water column usually has a high reactivity and a low Al content. Aged biogenic silica from the sediments has a lower reactivity, but Si/Al ratios as low as 5 were found. The method as described here therefore presents an accurate method to analyze biogenic silica in marine sediments with a relatively high clay mineral content.  相似文献   

7.
As an essential nutrient for diatoms, silica plays a key role in the estuarine and coastal food web. High concentrations of dissolved silica (DSi) were found in the seepage water of tidal freshwater marshes, which were therefore assumed to contribute to the silica supply to estuarine waters in times of silica limitation. A comprehensive budget calculation for European salt marshes is presented in this study. Earlier, salt marshes were considered to have even higher silica recycling rates than tidal freshwater marshes. Between 2009 and 2011, concentrations, pools and fluxes of silica in two salt marshes at the German Wadden Sea coast were determined (in soil, pore water, aboveground vegetation, freshly deposited sediments and seepage water). Subsequently, a budget was calculated. Special emphasis was placed on the influence of grazing management on silica cycling. Our results show that the two salt marshes were sinks for silica. The average import of biogenic silica (BSi) with freshly deposited sediments (1,334 kmol km?2 year?1) largely exceeded the DSi and BSi exports with seepage water (80 kmol km?2 year?1). Grazing management can affect silica cycling of salt marshes by influencing hydrology and vegetation structure. Abandoned sites had larger DSi export rates than grazed sites. One third of all BSi imports occurred in only one major flooding, underlining the relevance of rare events in the silica budget of tidal marshes. This aspect has been widely neglected in earlier studies, what might have led to an underestimation of silica import rates to tidal marshes hitherto.  相似文献   

8.
Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50-150 mg dm−3) may promote the dissolution of silicate phases through complexation of Al3+ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4-99.2 mmol CO2 m−2 year−1) are lower than the marine weathering rates calculated from the solid phase data (198-245 mmol CO2 m−2 year−1) suggesting a decrease in marine weathering over time. The production of CO2 through reverse weathering in surface sediments (4.22-15.0 mmol CO2 m−2 year−1) is about one order of magnitude smaller than the weathering-induced CO2 consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO2 consumption through marine silicate weathering estimated here as 5-20 Tmol CO2 year−1 is as high as the global rate of continental silicate weathering.  相似文献   

9.
《Applied Geochemistry》2002,17(4):387-398
Chemical characteristics of grain coatings in a Coastal Plain sandy aquifer on the Eastern Shore of Virginia were investigated where sediments have been exposed to distinct groundwater redox conditions. Dissolved O2 was 5.0 to 10.6 mg L−1 in the regionally extensive aerobic groundwater, whereas in a narrow leachate plume it was only <0.001 to 0.9 mg L−1. The amount of dissolved Fe in the aerobic groundwater was only 0.005 to 0.01 mg L−1, but it was 12 to 47 mg L−1 in the anaerobic zone. The amount of extractable Fe was an order of magnitude higher for the aerobic sediments than for the anaerobic sediments indicating that reductive dissolution removed the oxide coatings. The capacity for anion sorption on the sediment surfaces, as indicated by the sorption of 35SO42-, was an order of magnitude higher in the aerobic vs. anaerobic sediments. The presence of anaerobic groundwater did not significantly alter the amount of extractable Al oxides on the surface of the sediments, and those coatings helped to maintain a high surface area. The removal of the Fe oxides from the grain surfaces under anaerobic conditions was solely responsible for the significant reduction of SO4 sorption observed. This loss of capacity for anion sorption could lead to more extensive transport of negatively charged constituents such as some contaminant chemicals or bacteria that may be of concern in groundwater.  相似文献   

10.
Surface chemistry and reactivity of biogenic silica   总被引：2，自引：0，他引：2  
The surface chemistry of cultured diatoms was compared to that of biosiliceous material in Southern Ocean sediments, using potentiometric titrations and aluminum adsorption experiments. Aerosil 200, a well-studied synthetic amorphous silica, served as reference solid. Surface charge development and aluminum adsorption on cultured diatom shells were comparable to Aerosil. The surface chemical properties of biosiliceous material buried to depths of 15-25 cm in Southern Ocean sediments, however, deviated markedly from those of the cultured diatoms. In pH range 4-8.5, the surface charge density was systematically lower for biogenic silica from the sediments. In addition, the aluminum adsorption edge on the biosiliceous sediments was shifted to higher pHs by about 0.4 units. The results indicate that ionizable surface silanol groups on diagenetically altered diatom shells are less abundant and, possibly, less acidic than on freshly cultured diatoms. The observed differences in surface chemical structure are consistent with the progressive loss of reactivity, or aging, of biogenic silica which promotes its preservation in sediments.  相似文献   

11.
The supply and accumulation of silica in the marine environment   总被引：4，自引：0，他引：4  
Rivers and submarine hydrothermal emanations supply 6.1 × 1014g SiO2/yr to the marine environment. Approximately two-thirds of the silica supplied to the marine environment can be accounted for in continental margin and deep-sea deposits. Siliceous deep-sea sediments located beneath the Antarctic Polar Front (Convergence) account for over a fourth (1.6 × 1014g SiO2/yr) of the silica supplied to the oceans. Deep-sea sediment accumulation rates beneath the Polar Front are highest in the South Atlantic with values as large as 53cm/kyr during the last 18.000 yr. Siliceous sediments in the Bering Sea, Sea of Okhotsk, and Subarctic North Pacific accumulate 0.6 × 1014g SiO2/yr or 10% of the dissolved silica input to the oceans. The accumulation of biogenic silica in estuarine deposits removes a maximum of 0.8 × 1014g SiO2/yr. Although estuarine silica versus salinity plots indicate extensive removal of riverine silica from surface waters, the removal rates must be considered as maximum values because of dissolution of siliceous material in estuarine sediments and bottom waters. Siliceous sediments from continental margin upwelling areas (e.g. Gulf of California, Walvis Bay, or Peru-Chile coast) have the highest biogenic silica accumulation rates in the marine environment (69 g SiO2 cm2/kyr). Despite the rapid accumulation of biogenic silica, upwelling areas account for less than 5% of the silica supplied to the marine environment because they are confined laterally to such small areas.  相似文献   

12.
The present investigation tests a model to explain the behavior of dissolved Si during early diagenesis in sediments. The model assumes that low-Fe clays and other minerals can be treated simply as Al hydroxides, having attached silica. When the minerals are placed in seawater solutions, Si is released, causing exposure of fresh Al-octahedra. which are reactive toward Si and other elements in solution. Standard clays (kaolinite, montmorillonite) and solid silicic acid were suspended in seawater solutions in various combinations and dissolved Al, Si, Ca, pH and alkalinity were determined as a function of time. The theoretical model correctly predicts the behavior of Si in mixtures of the different minerals, based upon the dissolution behavior of the minerals in suspension alone. Further, the decrease in the alkalinity of kaolinitecontaining seawater solutions, where carbonate dissolution, organic matter decomposition and reduced sulfur oxidation are apparently unimportant, can be predicted from a simple extrapolation of the silica model results. The alkalinity changes observed in this study, as well as the pH changes observed in standard clay suspensions by other researchers, can be explained simply by equilibration of the charge on exposed Al-octahedra with the pH of the surrounding waters. The results of this study indicate that theoretical models of Si diagenesis in sediments should have general usefulness for predicting the effects of clay dissolution on sediment properties.  相似文献   

13.
《Comptes Rendus Geoscience》2014,346(11-12):279-286
The Southern Ocean is a major opal sink and plays a key role in the silica cycle of the world ocean. So far however, a complete cycle of silicon in the Southern Ocean has not been published. On one hand, Southern Ocean surface waters receive considerable amounts of silicic acid (dissolved silica, DSi) from the rest of the world ocean through the upwelling of the Circumpolar Deep Water, fed by contributions of deep waters of the Atlantic, Indian, and Pacific Oceans. On the other hand, the Southern Ocean exports a considerable flux of the silicic acid that is not used by diatoms in surface waters through the northward pathways of the Sub-Antarctic Mode Water, of the Antarctic Intermediate Water, and of the Antarctic Bottom Water. Thus the Southern Ocean is a source of DSi for the rest of the world ocean. Here we show that the Southern Ocean is a net importer of DSi: because there is no significant external input of DSi, the flux of DSi imported through the Circumpolar Deep Water pathway compensates the sink flux of biogenic silica in sediments.  相似文献   

14.
Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO2-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO2 nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.  相似文献   

15.
沉积物岩心记录着沉积环境的演变过程,其中生物硅(BSi)记录能反映硅质生物的生产力时间和空间变化,2012年5月在下辽河平原西南缘得到了ZK2钻孔柱状样,通过对其沉积物原位密度、生物硅、碳埋藏、粒度、AMS~(14)C和OSL测年、有孔虫鉴定、孢粉鉴定,将ZK2孔的沉积环境主要划分为上三角洲平原相沉积、海洋主导的沉积、湖相沉积、河道沉积4个沉积单元,其相应的生物硅(BSiO_2)浓度分布依次为(2.85±0.23)%、(1.55±0.10)%、(1.96±0.10)%、(0.92±0.05)%,并且生物硅的波动与颗粒有机碳浓度的波动同步。特别是在17~25 cal ka BP冰期形成的湖沼沉积出现较大的颗粒无机碳(PIC)浓度的波动,推测与当时干冷气候条件下CaCO_3过饱和从湖水中沉淀析出有关。钻孔沉积物生物硅浓度记录对格陵兰冰芯~(18)O同位素值的响应存在大约300 a的滞后现象。  相似文献   

16.
Vertical distributions of particulate silica, and of production and dissolution rates of biogenic silica, were determined on two N-S transects across the Pacific sector of the Antarctic Circumpolar Current during the austral spring of 1978. Particulate silica profiles showed elevated levels in surface water and near the bottom, with low (35–110 nmol Si · 1?1) and vertically uniform values through the intervening water column. Both the particulate silica content of the upper 200 m and the production rate of biogenic silica in the photic zone increased from north to south, reaching their highest values near the edge of the receding pack ice. A significant, but variable, fraction (18–58%) of the biogenic silica produced in the surface layer was redissolving in the upper 90–98 m. Net production of biogenic silica in the surface layer (production minus dissolution) was proceeding at a mean rate of ca. 2 mmol Si · m?2 · day?1. This is ca. 4 times greater than the most recent estimate of the mean accumulation rate of siliceous sediments beneath the ACC. We estimate, based on mass balance, that the mean dissolution rate of biogenic silica in subsurface water column in the Southern Ocean is 1.2–2.9 mmol Si · m?2 · day?1.  相似文献   

17.
Numerous previous studies indicate that several different authigenic aluminosilicates form in the oceans. In this study we show, using dissolved Al distributions in sediments and waters from the nearshore regions of the East China Sea, that the process of aluminosilicate formation probably begins rapidly upon contact of detrital clays with seawater. Statistical analyses of dissolved Al-Si-H+ relations in surface sediments indicate that the minerals forming in East China Sea sediments low in dissolved Fe are dioctahedral chlorites with an average composition EX0.91Mg0.77Al5.0Si2.7O10(OH)8 (where EX = exchangeable + 1 cation). This composition is also consistent with dissolved Al and Si measurements as a function of salinity in turbid overlying waters. Results suggest a dissolution—reprecipitation mechanism for clay mineral reconstitution. This mechanism can help to explain why different authigenic clays are found in different areas of the oceans. In the East China Sea the total amount of authigenic clays present must constitute a very minor fraction of the bottom sediments. Thus, the formation of these minerals has a relatively small impact upon dissolved Si distributions. Clay mineral reconstitution in nearshore regions may provide a mechanism for buffering sediments and overlying waters with respect to pH, as the composition of minerals formed should be a direct function of the H+ activity in the surrounding environment.  相似文献   

18.
Pore water chemistry and 234U/238U activity ratios from fine-grained sediment cored by the Ocean Drilling Project at Site 984 in the North Atlantic were used as constraints in modeling in situ rates of plagioclase dissolution with the multicomponent reactive transport code Crunch. The reactive transport model includes a solid-solution formulation to enable the use of the 234U/238U activity ratios in the solid and fluid as a tracer of mineral dissolution. The isotopic profiles are combined with profiles of the major element chemistry (especially alkalinity and calcium) to determine whether the apparent discrepancy between laboratory and field dissolution rates still exists when a mechanistic reactive transport model is used to interpret rates in a natural system. A suite of reactions, including sulfate reduction and methane production, anaerobic methane oxidation, CaCO3 precipitation, dissolution of plagioclase, and precipitation of secondary clay minerals, along with diffusive transport and fluid and solid burial, control the pore fluid chemistry in Site 984 sediments. The surface area of plagioclase in intimate contact with the pore fluid is estimated to be 6.9 m2/g based on both grain geometry and on the depletion of 234U/238U in the sediment via α-recoil loss. Various rate laws for plagioclase dissolution are considered in the modeling, including those based on (1) a linear transition state theory (TST) model, (2) a nonlinear dependence on the undersaturation of the pore water with respect to plagioclase, and (3) the effect of inhibition by dissolved aluminum. The major element and isotopic methods predict similar dissolution rate constants if additional lowering of the pore water 234U/238U activity ratio is attributed to isotopic exchange via recrystallization of marine calcite, which makes up about 10-20% of the Site 984 sediment. The calculated dissolution rate for plagioclase corresponds to a rate constant that is about 102 to 105 times smaller than the laboratory-measured value, with the value depending primarily on the deviation from equilibrium. The reactive transport simulations demonstrate that the degree of undersaturation of the pore fluid with respect to plagioclase depends strongly on the rate of authigenic clay precipitation and the solubility of the clay minerals. The observed discrepancy is greatest for the linear TST model (105), less substantial with the Al-inhibition formulation (103), and decreases further if the clay minerals precipitate more slowly or as highly soluble precursor minerals (102). However, even several orders of magnitude variation in either the clay solubility or clay precipitation rates cannot completely account for the entire discrepancy while still matching pore water aluminum and silica data, indicating that the mineral dissolution rate conundrum must be attributed in large part to the gradual loss of reactive sites on silicate surfaces with time. The results imply that methods of mineral surface characterization that provide direct measurements of the bulk surface reactivity are necessary to accurately predict natural dissolution rates.  相似文献   

19.
This study focused on planktic foraminifera in plankton tows and surface sediments from the western Indian sector of Southern Ocean in order to evaluate the potential foraminiferal secondary calcification and/or dissolution in the sediment. It is found that the symbiotic foraminiferal species are abundant in the subtropical region, whereas non-symbiotic species dominate in the sub-Antarctic and polar frontal regions. The distribution of the symbiotic and non-symbiotic foraminiferal species is controlled by temperature, salinity, light, nutrients and phytoplankton biomass. There is also a lateral southern extent in abundance of planktic foraminifera from surface sediments to plankton tows. The shell weights of the planktic foraminifera N. pachyderma, G. bulloides and G. ruber within the surface sediments are on an average heavier by 27%, 34% and 40% respectively than shells of the same size within the plankton tows, indicative of secondary calcification. The planktic foraminiferal isotopes show the presence of heavier isotopes in the surface sediment foraminifera as compared to plankton tows, thus confirming secondary calcification. Secondary calcification in G. ruber occurs in the euphotic zone, whereas in case of N. pachyderma and G. bulloides it is at deeper depths. We also observed a decrease in the shell spines in surface sediment foraminifera as compared to plankton tows, indicative of the morphological changes that foraminifera underwent during gametogenesis.  相似文献   

20.
Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.  相似文献   

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