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1.
《Applied Geochemistry》1999,14(1):41-52
Concentrations of S, organic C and Fe were investigated in profiles of sediments from two estuarine systems in the SW of Western Australia. In marine-affected sediments, inorganic S dominates total S and concentrations of total S correlate with Fe and not with organic C. In freshwater sediments, organic S dominates total S and concentrations of total S correlate with organic C and not with Fe. Molar Fe/S ratios in the estuarine sediments decrease with increasing salinity and approach unity for marine conditions. Net accumulation rates of S in sediments were estimated with a numerical computer model, calibrated with published data on profiles of marine sediments for diffusion of SO2−4, sedimentation rates and distributions of S. Measured depth-integrated reduction rates of SO2−4 in the marine-affected estuarine sediments approach those obtained for Fe-limited marine conditions at similar rates of sedimentation. Measured concentrations of inorganic S in anoxic freshwater sediments fit a numerically calculated relationship between inorganic S and sedimentation rate.  相似文献   

2.
Bacterial sulfate reduction in marine sediments generally occurs in the presence of high millimolar concentrations of sulfate. Published data indicate that low sulfate concentrations may limit sulfate reduction rates below 0.2-2 mM. Yet, high sulfate reduction rates occur in the 1-100 μM range in freshwater sediments and at the sulfate-methane transition in marine sediments. Through a combination of 35S-tracer experiments, including initial velocity experiments and time course experiments, we searched for different sulfate affinities in the mixed community of sulfate reducers in a marine sediment. We supported the radiotracer experiments with a highly sensitive ion chromatographic technique for sulfate with a detection limit of 0.15 μM SO42− in marine pore water. Our results showed that high and low affinities for sulfate co-occur and that the applied experimental approach may determine the observed apparent half saturation constant, Km. Our experimental and model data both show that sulfate reduction in the studied marine sediment could be explained by two dominating affinities for sulfate: a low affinity with a mean half saturation constant, Km, of 430 μM SO42− and a high affinity with a mean Km of 2.6 μM SO42−. The high-affinity sulfate reduction was thermodynamically un-constrained down to <1 μM SO42−, both in our experiments and under in situ conditions. The reduction of radio-labeled sulfate was partly reversible due to concurrent re-oxidation of sulfide by Fe(III) and possibly due to a reversibility of the enzymatic pathway of sulfate reduction. A literature survey of apparent Km values for sediments and pure cultures is presented and discussed.  相似文献   

3.
We examined the effects of seasonal salinity changes on sediment ammonium (NH4 +) adsorption and exchange across the sediment–water interface in the Parker River Estuary, by means of seasonal field sampling, laboratory adsorption experiments, and modeling. The fraction of dissolved NH4 + relative to adsorbed NH4 + in oligohaline sediments rose significantly with increased pore water salinity over the season. Laboratory experiments demonstrated that small (∼3) increases in salinity from freshwater conditions had the greatest effect on NH4 + adsorption by reducing the exchangeable pool from 69% to 14% of the total NH4 + in the upper estuary sediments that experience large (0–20) seasonal salinity shifts. NH4 + dynamics did not appear to be significantly affected by salinity in sediments of the lower estuary where salinities under 10 were not measured. We further assessed the importance of salinity-mediated desorption by constructing a simple mechanistic numerical model for pore water chloride and NH4 + diffusion for sediments of the upper estuary. The model predicted pore water salinity and NH4 + profiles that fit measured profiles very well and described a seasonal pattern of NH4 + flux from the sediment that was significantly affected by salinity. The model demonstrated that changes in salinity on several timescales (tidally, seasonally, and annually) can significantly alter the magnitude and timing of NH4 + release from the sediments. Salinity-mediated desorption and fluxes of NH4 + from sediments in the upper estuary can be of similar magnitude to rates of organic nitrogen mineralization and may therefore be important in supporting estuarine productivity when watershed inputs of N are low.  相似文献   

4.
《Applied Geochemistry》1997,12(5):643-660
In the Busko and Solec Spas, saline sulphide and sulphate waters are exploited at different depths. The shallow water system in Busko is related to an interglacial or interstadial period shown by the lack of tritium and14C and its δ18O and δD values equal to that of modern water. The noble gas temperatures (NGT) are somewhat lower than the present air temperatures, but the4He and40Ar ages of about 90–480 ka confirm a Pleistocene recharge. The δ18O and δD values of the deep system are much heavier than those of local modern waters, which may mean the recharge of a warm pre-Quaternary climate. The4He,40Ar and21Ne contents and the NGT values confirm the deep system to be recharged at the pre-Quaternary stages of the present hydrologic cycle, i.e. after the sea transgression in the Badenian. High SO42− contents indicate that the Cl− and SO42− in both systems originated from simultaneous leaching of NaCl and gypsum. Other components can be explained by cation exchange between water and Badenian clay minerals in marls (e.g. Ca2+ for Mg2+ and Na+ for K+) and by the decay of marine organic matter supplying Br−, I− and B.  相似文献   

5.
《Chemical Geology》1999,153(1-4):53-79
Marine sediment sequences with CH4 hydrate are characterized by an atypical depth profile in dissolved Cl− squeezed from pore space: a shallow subsurface Cl− maximum overlies a lengthy and pronounced Cl− minimum. This pore water Cl− profile represents a combination of multiple processes including glacial–interglacial variations in ocean salinity, advection and diffusion of ions that are excluded during gas hydrate formation at depth, and release of fresh water from dissociation of hydrate during core recovery. In situ quantities of gas hydrate can be determined from a measured pore water Cl− profile provided the in situ pore water signature prior to core recovery can be separated. Ocean Drilling Program (ODP) Site 997 was drilled into a large CH4 hydrate reservoir on the Blake Ridge in the western Atlantic Ocean. Previously we have constructed a high-resolution pore water Cl− profile at this location; here we present a `coupled chloride-hydrate' numerical model to explain basic trends in the Cl− profile and to isolate in situ Cl− concentrations. The model is based on thermodynamic and ecological considerations, and uses established equations for describing chemical behavior in marine sediment–pore water systems. The model incorporates four key concepts: (1) most gas hydrate is formed immediately below the SO42− reduction zone; (2) fluid, dissolved ions and gas advect upward through the sediment column; (3) CH4 hydrate dissociates at the base of hydrate stability conditions; and (4) seawater salinity fluctuates during glacial–interglacial cycles of the late Pliocene and Quaternary. Rates of upward advection in the model are sufficient to account for measured Br− and I− concentrations as well as CH4 oxidation at the base of the SO42− reduction zone. In situ pore water Cl− inferred from the model is similar to that determined by limited direct sampling; in situ CH4 hydrate amounts inferred from the model (an average of about 4% of porosity) are broadly consistent with those determined by direct gas sampling and indirect geophysical techniques. The model also predicts production of substantial quantities of free CH4 gas bubbles (>2.5% of porosity) at a depth immediately below the lowest accumulation of CH4 hydrate in the sediment column. Our explanation for the pore water Cl− profile at Site 997 is important because it provides a theoretical mechanism for understanding the distribution of interstitial water Cl−, gas hydrate, and free gas in a marine sediment column.  相似文献   

6.
The regulatory effect of salinity on nitrogen dynamics in estuarine sediments was investigated in the Randers Fjord estuary, Denmark, using sediment slurries and intact sediment cores and applying 15N-isotope techniques. Sediment was sampled at three representative stations varying in salinity, and all experiments were run at 0‰, 10‰, 20‰, and 30‰. The sediment NH4 + adsorption capacity decreased markedly at all stations when salinity was increased from 0‰ to 10‰; further increase showed little effect. In situ nitrification and denitrification also decreased with increasing salinities, with the most pronounced reduction of approximately 50% being observed when the salinity was raised from 0‰ to 10‰. The salinity-induced reduction in NH4 + adsorption capacity and stimulation of NH4 + efflux has previously been argued to cause a reduction in nitrification activity since the nitrifying bacteria become limited by NH4 + availability at higher salinities. However, using a potential nitrification assay where NH4 + was added in excess, it was demonstrated that potential nitrification activity also decreased with increasing salinity, indicating that the inhibitory salinity effect may also be a physiological effect on the microorganisms. This hypothesis was supported by the finding that denitrification based on NO3 − from the overlying water (Dw), which is independent of the nitrification process, and hence NH4 + availability, also decreased with increasing salinity. We conclude that changes in salinity have a significant effect on nitrogen dynamics in estuarine sediments, which must be considered when nitrogen transformations are measured and evaluated.  相似文献   

7.
Kinetics of microbial sulfate reduction in estuarine sediments   总被引：2，自引：0，他引：2  
Kinetic parameters of microbial sulfate reduction in intertidal sediments from a freshwater, brackish and marine site of the Scheldt estuary (Belgium, the Netherlands) were determined. Sulfate reduction rates (SRR) were measured at 10, 21, and 30 °C, using both flow-through reactors containing intact sediment slices and conventional sediment slurries. At the three sites, and for all depth intervals studied (0-2, 2-4, 4-6 and 6-8 cm), the dependence of potential SRR on the sulfate concentration followed the Michaelis-Menten rate equation. Apparent sulfate half-saturation concentrations, Km, measured in the flow-through reactor experiments were comparable at the freshwater and marine sites (0.1-0.3 mM), but somewhat higher at the brackish site (0.4-0.9 mM). Maximum potential SRR, Rmax, in the 0-4 cm depth interval of the freshwater sediments were similar to those in the 0-6 cm interval of the marine sediments (10-46 nmol cm−3 h−1 at 21 °C), despite much lower in situ sulfate availability and order-of-magnitude lower densities of sulfate-reducing bacteria (SRB), at the freshwater site. Values of Rmax in the brackish sediments were lower (3.7-7.6 nmol cm−3 h−1 at 21 °C), probably due to less labile organic matter, as inferred from higher Corg/N ratios. Inflow solutions supplemented with lactate enhanced potential SRR at all three sites. Slurry incubations systematically yielded higher Rmax values than flow-through reactor experiments for the freshwater and brackish sediments, but similar values for the marine sediments. Transport limitation of potential SRR at the freshwater and brackish sites may be related to the lower sediment porosities and SRB densities compared to the marine site. Multiple rate controls, including sulfate availability, organic matter quality, temperature, and SRB abundance, modulate in situ sulfate-reducing activity along the estuarine salinity gradient.  相似文献   

8.
《Applied Geochemistry》2000,15(6):791-805
This paper describes the geochemical evolution of groundwater in the Bathonian and Bajocian aquifer along its flowpath. Since this aquifer represents one of the main sources of fresh water supply in the Caen area and has been subjected to a Holocene marine intrusion, its management requires a sound knowledge of (1) the primary conditions and (2) the potential influence of either natural or anthropogenic pressures. Groundwater vertical sampling validity is discussed with the contribution of high resolution temperature logging. The main processes of geochemical evolution along a groundwater flow line and the sea-water intrusion characteristics are discussed using ionic concentrations (Br−, F− and major elements) and isotopes (water δ2H and δ18O, TDIC δ13C and A14C, sulphate δ18O and δ34S). As the 13C content of TDIC is used as a tracer of water-rock interaction, it shows evidence of specific chemical and isotopic evolutions of groundwater within the aquifer, both related to water-rock interaction and mineral equilibria in groundwater. All the above-mentioned tracers evolve downflow: cation concentrations are modified by exchange with clay minerals allowing a high F− concentration in groundwater, whereas Br− and SO2−4 concentrations appear to be redox condition dependant. Superimposed on these geochemical patterns, δ18O and δ2H compositions indicate that aquifer recharge has varied significantly through time. The chemical evolution of groundwater is locally affected by a salty water intrusion that is characterised by mixing between Flandrian fresh water and sea-water which has interacted with peat as evidenced by a high Br−/Cl− ratio and SO2−4 reduction.  相似文献   

9.
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10.
《Applied Geochemistry》2004,19(3):343-358
Ion-exchange batch experiments were run on Cretaceous (Magothy aquifer) clay cores from a nearshore borehole and an inland borehole on Long Island, NY, to determine the origin of high SO42− concentrations in ground water. Desorption batch tests indicate that the amounts of SO42− released from the core samples are much greater (980–4700 μg/g of sediment) than the concentrations in ground-water samples. The locally high SO42− concentrations in pore water extracted from cores are consistent with the overall increase in SO42− concentrations in ground water along Magothy flow paths. Results of the sorption batch tests indicate that SO42− sorption onto clay is small but significant (40–120 μg/g of sediment) in the low-pH (<5) pore water of clays, and a significant part of the SO42− in Magothy pore water may result from the oxidation of FeS2 by dissolved Fe(III). The acidic conditions that result from FeS2 oxidation in acidic pore water should result in greater sorption of SO42− and other anions onto protonated surfaces than in neutral-pH pore water. Comparison of the amounts of Cl− released from a clay core sample in desorption batch tests (4 μg/g of sediment) with the amounts of Cl− sorbed to the same clay in sorption tests (3.7–5 μg/g) indicates that the high concentrations of Cl− in pore water did not originate from connate seawater but were desorbed from sediment that was previously in contact with seawater. Furthermore, a hypothetical seawater transgression in the past is consistent with the observed pattern of sorbed cation complexes in the Magothy cores and could be a significant source of high SO42− concentrations in Magothy ground water.  相似文献   

11.
《Applied Geochemistry》2004,19(11):1837-1853
Iron monosulfide formation and oxidation processes were studied in the extensively drained acid sulfate soil environment of the Tweed River floodplain in eastern Australia. Porewater profiles of pH, Eh, SO42−, Fe2+, Fe3+, Cl−, HCO3−, and metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) were obtained using in situ dialysis membrane samplers (`peepers'). Concentrations of acid volatile S (AVS), pyrite, total S, reactive Fe, total and organic C, simultaneously extracted metals (SEMs) and total elemental composition by X-ray fluorescence, were determined on sediment samples. The oxidation of pyrite in the surrounding landscape provides a source of acidity, Fe, Al, SO4 and metals, which are exported into the drainage system where they accumulate in the sediments and porewaters. Negative porewater concentration gradients of SO42− and Fe2+, and large AVS concentrations in the sediments, indicate Fe monosulfides form rapidly under reducing conditions and consume acidity and metals. Oxidation of the sediments during previous drought episodes has resulted in the conversion of monosulfides and pyrite to oxidised Fe minerals and the release of acidity, SO42−, Fe3+, and metals to the surface waters. These formation and oxidation cycles show that Fe monosulfides play an important role in controlling water quality in the drainage system.  相似文献   

12.
《Applied Geochemistry》1998,13(6):767-778
A small-scale artificial tracer test performed on a schist aquifer in Brittany has helped clarify mechanisms and kinetics of in situ autotrophic denitrification. NO3 was injected as a pulse simultaneously with a conservative tracer -Br−. During the test, which lasted 210 h, 73% of the injected Br− was recovered, as against only 47% of the NO3. The 26% difference in the recovery of the two injected species is interpreted as being the result of denitrification, in part due to the direct oxidation of pyrite present in the solid aquifer according to the reaction: 5FeS2+14NO3−+4H+→7N2+10SO42−+5Fe2++2H2O, and in part due to subsequent iron oxidation according to the reaction: NO3−+5Fe2++6H+→1/2N2+5Fe3++3H2O. Despite the potential increase in SO4 and Fe resulting from denitrification through pyrite oxidation, the concentrations of these elements in the groundwater remain moderate due to the precipitation of minerals such as jarosite and/or natroalunite. Tracer transfer takes place in a heterogeneous medium which, according to the breakthrough curves, can be simplified to a dual-porosity aquifer comprising a high-permeability (fractures or large fissures) medium of low porosity from which only minor denitrification of circulating NO3-bearing water was observed and a low-permeability (small fissures) medium of high porosity which induces a higher denitrification rate in the circulating NO3-bearing water. The kinetics of the denitrification reaction are high compared with results obtained for other environments and can be described by a first-order model with a half life of 7.9 days for the low-porosity medium and only 2.1 days for the high-porosity medium.  相似文献   

13.
The concentrations and isotopic compositions of the various forms of nitrogen in silty clay sediments from the Bay of Quinte (Lake Ontario) have been determined. The total organic-N content is high throughout the sediment profiles and generally decreases with depth. On the contrary, exchangeable NH+4-N concentration is quite low and tends to increase with depth in two out of three sediment cores examined. The concentration of non-exchangeable NH+4-N and the 6 N HCl hydrolyzable NH+4-N are relatively constant with depth. Among the N fractions analyzed, the exchangeable NH+4-is most enriched in 15N. In most cases, the δ 15 N values of the N fractions remain relatively constant with sediment depth. There is no apparent correlation of δ 15 N values with the N concentration for any of the individual N fractions. The observed ranges in the δ 15 N values are: exchangeable NH+4, + 5–+10‰; 6 N HCl hydrolyzable total N and 6 N HCl hydrolyzable NH+4-N, + 3.5–+5.5‰.  相似文献   

14.
《Chemical Geology》1999,153(1-4):281-287
An empirical method is presented that allows the determination of the individual contributions of anions and cations to the effect of dissolved salts on hydrogen isotope fractionation in aqueous systems (isotope salt effect). The method is solely based on experimental data and does not involve the choice of arbitrary reference values or theoretical assumptions. Plotting experimental liquid–vapor D/H fractionation factors for aqueous solutions of sodium salts vs. O–D stretching frequencies of water molecules in the hydration shells of the anions shows an excellent linear correlation. The distance between this line and the pure water liquid–vapor fractionation data point in the same plot gives the cation contribution to the isotope salt effects. The anion contribution can then simply be derived as the difference between the total salt effect and the cation salt effect. The validity of the concept is demonstrated using precise literature data for the O–D stretching frequencies in the hydration shells of individual ions at 20°C [Bergström, P.A., 1991. Single ion hydration properties in aqueous solution: a quantitative infrared spectroscopic study. PhD Thesis. Uppsala University] and for the liquid–vapor hydrogen isotope fractionation between aqueous solutions and water vapor at the same temperature [Stewart, M.K., Friedman, I., 1975. Deuterium fractionation between aqueous salt solutions and water vapor. Journal of Geophysical Research 80, 3812–3818]. Within the limits of experimental uncertainties, the data set shows internal consistency. Cation salt effects, 1000 ln Γ at 20°C, are (in per mil per mole per liter, using the convention of Horita et al. [Horita, J., Cole, D.R., Wesolowski, D.J., 1993a. The activity–composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: II. Vapor–liquid water equilibration of mixed salt solutions from 50–100°C. Geochimica et Cosmochimica Acta 57, 4703–4711]): Na++0.7; K++0.7; Mg2++6.5; Ca2++1.8; Al3++12. The salt effect of H+ cannot be determined unequivocally. The combined effect of the fractionation of H+ itself plus its salt effect is +4.9. Anion effects are +1.4 for Cl−, +2.7 for Br−, +3.5 for I− and −1.4 for SO42−. Further single anion salt effects are being predicted as −1.8 for F−, +4.9 for NO3−, +6.9 for ClO4− and +5.4 for the triflate ion (CF3SO3−).  相似文献   

15.
我国海洋地质分析测试技术   总被引：1，自引：0，他引：1  
陈道华  刁少波  张欣 《岩矿测试》2013,32(6):850-859
21世纪是海洋开发和利用的新世纪,随着国家对海洋地质调查工作的日益重视,海洋地质分析测试技术迎来了快速发展时期。本文对我国海洋地质分析测试技术的最新进展进行了简要评述:为满足海洋区域调查、海岸带地质调查的需要,建立了以大型分析仪器为主的多元素同时分析海洋地质样品的快速高效分析方法体系;针对新能源天然气水合物样品,开展了异常识别测试技术和应用测试技术研究,建立了用离子色谱法快速测定孔隙水中阴离子Cl-、Br-、SO42-和阳离子Na+、NH4+、K+、Ca2+、Mg2+ 的方法,开发出了以声学、电阻、时域反射(Time Domain Reflectometry, 简称为TDR)三种探测技术为主的适用于天然气水合物模拟实验的探测新技术;对于海洋沉积物中有机污染物样品,采用复合固相萃取净化柱,对海洋沉积物萃取液样品进行净化分离,依次选用正己烷和正己烷－二氯甲烷混合液淋洗固相萃取净化柱,可有效保留基体杂质,实现了海洋环境地质调查中基质复杂沉积物样品的同时净化、分离与测试,可显著提高实验效率;同时在大洋矿产样品分析技术、海洋地质标准物质研制、船载与原位化学探测技术等方面也取得了重要进展。本文还提出在海洋调查和监测的应用中,船载及原位测试技术将愈趋重要,加强海洋化学传感器的性能和检测集成化技术是今后的一个重要发展方向。  相似文献   

16.
《Applied Geochemistry》2000,15(8):1203-1218
Ca6[Al(OH)6]2(CrO4)3·26H2O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca6[Al(OH)6]2(CrO4)3·26H2O⇌6Ca2++2Al(OH)−4+3CrO2−4+4OH−+26H2O varies with pH unless a CaCrO4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca2++CrO2−4=CaCrO4(aq) was obtained by minimizing the variance in the IAP for Ca6[Al(OH)6]2(CrO4)3·26H2O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log KSP) of Ca6[Al(OH)6]2(CrO4)3·26H2O at 25°C is −41.46±0.30. The temperature dependence of the log KSP is log KSP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG0r,298 and ΔH0r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol−1. the values of ΔC0P,r,298 and ΔS0r,298 are −1506±140 and −534±83 J mol−1 K−1. Using these values and published standard state partial molal quantities for constituent ions, ΔG0f,298=−15,131±19 kJ mol−1, ΔH0f,298=−17,330±8.6 kJ mol−1, ΔS0298=2.19±0.10 kJ mol−1 K−1, and ΔC0Pf,298=2.12±0.53 kJ mol−1 K−1, were calculated.  相似文献   

17.
《Geochimica et cosmochimica acta》1999,63(13-14):1969-1980
The solubility of ettringite (Ca6[Al(OH)6]2(SO4)3 · 26H2O) was measured in a series of dissolution and precipitation experiments at 5–75°C and at pH between 10.5 and 13.0 using synthesized material. Equilibrium was established within 4 to 6 days, with samples collected between 10 and 36 days. The log KSP for the reaction Ca6[Al(OH)6]2(SO4)3 · 26H2O ⇌ 6Ca2+ + 2Al(OH)4− + 3SO42− + 4OH− + 26H2O at 25°C calculated for dissolution experiments (−45.0 ± 0.2) is not significantly different from the log KSP calculated for precipitation experiments (−44.8 ± 0.4) at the 95% confidence level. There is no apparent trend in log KSP with pH and the mean log KSP,298 is −44.9 ± 0.3. The solubility product decreased linearly with the inverse of temperature indicating a constant enthalpy of reaction from 5 to 75°C. The enthalpy and entropy of reaction ΔH°r and ΔS°r, were determined from the linear regression to be 204.6 ± 0.6 kJ mol−1 and 170 ± 38 J mol−1 K−1. Using our values for log KSP, ΔH°r, and ΔS°r and published partial molal quantities for the constituent ions, we calculated the free energy of formation ΔG°f,298, the enthalpy of formation ΔH°f,298, and the entropy of formation ΔS°f,298 to be −15211 ± 20, −17550 ± 16 kJ mol−1, and 1867 ± 59 J mol−1 K−1. Assuming ΔCP,r is zero, the heat capacity of ettringite is 590 ± 140 J mol−1 K−1.  相似文献   

18.
Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments.Pelagic clays and slowly deposited (<1 cm/103yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters.In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/103 yr the changes chiefly involve gains of Ca2+ and Sr2+ and losses of Mg2+ which balance the Ca2+ enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr2+ may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg2+ for Ca2+ during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca2+ and Sr2+ enrichment is again characteristic, but Mg2+ losses exceed Ca2+ gains with the excess being balanced by SO4post staggered2? losses. The data indicate that the reactions are similar to those noted above, except that the Ca2+ released is not kept in solution but is precipitated by the HCO3post staggered? produced in SO4post staggered2? reduction. In both these types of pore waters Na+ is usually conservative, but K+ depletions are frequent.In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na+, Si and CO2, and slight enhancement in Cl?. The changes are attributed to exchange of Na+ for Ca2+ in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity.Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4post staggered2?, strong HCO3post staggered? enrichment, formation of NH4post staggered+, and methane synthesis from H2 and CO2 once SO4post staggered2? is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca2+ depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl? remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl? are observed in some sediments adjacent to continents.  相似文献   

19.
Studies of the composition of interstitial solutions of marine sediments have been carried out utilizing in situ sampling techniques. Samples were obtained from the Caribbean, North Atlantic and South Atlantic. In virtually all cases, diagenesis has led to the uptake of Mg2+ and K+ and the release of Ca2+, HCO?3 and Na+ by the solid phases. SO2?4 is slightly enriched at nearly all stations, reduction being observed only at continental margin stations. Cl? is conservative within experimental precision.The reactions controlling the fluxes of most components across the water-sediment interface occur almost entirely in the upper 100 cm of sediment. Contributions of Mg 2+, Ca 2+, K+ and HCO?3 from below 100 cm amount to less than 15% of the calculated fluxes across the interface. Reactions in the upper 30 cm account for 70–90% of the fluxes of these components across the interface. Only Na+ has a deep source, gradients often being linear in the upper 2m of sediment.Calculated fluxes across the sediment-water interface are of the same order of magnitude as river inputs for the components studied. In the case of Mg2+ and K +, 60–100% of the river input can be balanced by diagenetic uptake in the sediment. For Ca2+ and HCO?3 additions to seawater augment the river supply by 25–50%. When the uptake of Mg2+ and K+ by the sediment is calculated by integrating the fluxes across the interface, calculated concentrations of both of these elements are inconsistent with published average concentrations for the types of sediment studied.  相似文献   

20.
The study was carried out on the Sulejów dam reservoir (Central Poland). Water and sediment samples were collected between February and October 2006. Sulfur compounds in the sediment were chemically extracted and subjected to isotopic analysis.Large variability of SO42− concentration in the water column (from 10.3 to 36.2 mg/dm3) and the isotopic composition of sulfur (δ34S from 2.1 to 5.4‰) was observed. The main identified sources of SO42− were watercourses, surface runoff, and phosphorus fertilizers.Both oxidized sulfur species (SO42−) and its reduced forms were found in sediments. Particular sulfur forms were characterized by large variations in both, concentrations and the isotopic composition of sulfur. SO42− in the sediment and in the water column had different genesis. Bacterial oxidation of organic sulfur and its binding in SO42− were observed in the sediment. Under reducing conditions, oxidized and organic sulfur is converted to H2S which reacted with Fe or other metallic ions leading to metal sulfide precipitation. Monosulfides were shown to have a very low concentration, ranging up to 0.07 mg/g of sediment. The transformation of elemental sulfur from sulfides through their chemical oxidation occurred in the sediment.  相似文献   

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