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硫酸盐还原菌对海水状态和碳钢腐蚀行为的影响 总被引：4，自引：0，他引：4
采用溶液环境参数和电极电化学参数测量技术研究了海水中硫酸盐还原菌生长和衰亡过程对溶液状态和D36碳钢腐蚀过程的影响。结果表明，硫酸盐还原菌通过新陈代谢作用把溶液中的硫酸盐转化为硫离子而增大了氧化还原电位和酸度，并导致D36钢的腐蚀电位负移和腐蚀速度增加。极化曲线和电化学阻抗谱证实，虽然金属腐蚀过程在上述过程中并未发生机理性变化，但阳极过程和部分阴极过程的加速是腐蚀速度增加的主要原因。上述结果同时表明．硫酸盐还原菌本身和新陈代谢中间体并未直接参与腐蚀过程，主要是通过产生的硫离子改变溶液状态来加速腐蚀过程的。 相似文献
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海洋环境中氧化还原敏感性微量元素的地球化学行为及环境指示意义 总被引：1，自引：0，他引：1
依据国内外最新研究成果,初步讨论了氧化还原敏感性微量元素(RSE)Re、Cd、Mo、U、V等的地球化学行为,其中包括海洋沉积物中RSE的来源、RSE在缺氧和无氧海区的沉淀富集机理及其环境指示意义。在此基础上讨论了利用RSE研究氧化还原环境时应注意的一些问题。RSE的沉淀富集机制不尽相同,但具有以下共同特点:①对底层海水的溶解氧浓度敏感。在正常溶解氧条件下,氧化还原敏感性微量元素在海水中呈溶解态稳定存在,而当底层海水处于缺氧或无氧条件时容易发生还原。②当底层海水处于缺氧或无氧条件时,经过沉积物—海水界面过程,受缺氧程度不同的制约,海水中呈溶解态的RSE依次在沉积物中沉淀,出现不同程度的富集。③持续还原条件下,RSE在沉积物中稳定存在;受氧化作用后,容易在沉积物中发生二次迁移和重新富集。不同的RSE其氧化还原电位不同,在氧化还原序列中的位置不同,Re在U之后Mo之前发生还原。因此,RSE在海洋沉积物中的不同富集特征和富集程度可作为还原程度指标研究底层海水的缺氧程度和底质的氧化还原环境。研究RSE的氧化还原环境指示意义,必须对RSE陆源碎屑来源组分进行剔除,同时,还应充分注意到还原沉积区发生氧化后,RSE在沉积物中会发生重新迁移和二次富集。 相似文献
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采用去极化法测量氧化还原标准溶液——醌氢醌标准溶液,初步探讨了去极化法测定氧化还原电位的准确度,结果发现运用去极化方法测定氧化还原电位是一种快速、准确的方法,相对传统方法而言,具有测量时间短、测量精度高、数据重现性好的优点。进一步开展去极化方法测定海水氧化还原电位,为海洋氧化还原电位的快速测量提供依据。 相似文献
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钛/碳钢在海水中电偶腐蚀的研究 总被引：4，自引：0，他引：4
研究了国产纯钛和碳钢Q235在青岛近海海水中的电偶腐蚀情况。测定这两种金属材料的自然腐蚀电位和失重速率；用IM6e电化学工作站测定两种金属材料在海水中的稳态极化曲线，研究其极化性能；测定了碳钢与钛组成不同面积比、不同温度、不同海水流速时电偶电流的大小、方向，电偶电位，以及不同面积比时阳极的失重速率。结果表明，阳极的腐蚀速率随阴／阳极面积比、环境温度、海水流速的增大而增加，且阳极腐蚀速率随阴／阳极面积比的增大趋于极限值。 相似文献
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锰细菌对锰、铁金属离子的转移作用 总被引：15，自引：2，他引：15
本文报道了锰细菌对锰的氧化和铁的氧化还原作用的实验结果.在好氧的条件下锰细菌能使可溶性的Mn2+氧化为Mn4+.在锰细菌的生长繁殖过程中其环境的pH不断升高,更有利于锰的氧化;环境的温度升高可加快细菌对锰的氧化速度.锰细菌在含低价铁的培养液中可以较快地把Fe2+氧化为Fe3+,它的氧化速度要比锰的氧化速度快;在厌氧的培养条件下,锰细菌可将溶液中的高价铁还原为低价铁,而且使其环境的pH明显下降. 相似文献
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M. Gonzlez-Dvila J.M. Santana-Casiano A.G. Gonzlez N. Prez F.J. Millero 《Marine Chemistry》2009,115(1-2):118-124
The oxidation and reduction of nanomolar levels of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17–8.49), temperature (5–35 °C) and ionic strength (0.1–0.7 M). The oxidation rates were fitted to an equation valid at different pH and ionic strength conditions in sodium chloride and seawater solutions:The reduction of Cu(II) was studied in both media for different initial concentrations of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) productions were 20% and 9% for NaCl and seawater, respectively. The effect of speciation of copper(I) reduced from Cu(II) on the rates was studied. The Cu(I) speciation is dominated by the CuCl2− species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range of 0.1 M to 0.7 M chloride concentrations. 相似文献
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The objective of this study was to examine the redox reactions and other transformations of mercury (Hg) species in surface waters, and the factors determining the rates of these reactions. For the redox studies completed at the Chesapeake Biological Laboratory (CBL), two isotopes (199HgII and 202Hg0) were added into different types of filtered water (fresh to seawater) to examine the oxidation and reduction reactions. Further studies of both the redox reactions and methylation/demethylation reactions of Hg were conducted with unfiltered water on board research vessels during cruises in May and July 2005 on the Chesapeake Bay and shelf. While CH3199HgII was added to allow the examination of demethylation, 201HgII was used to examine both reduction and methylation, and 202Hg0 was used to examine oxidation. Overall, the results showed that both Hg oxidation and reduction were simultaneously occurring and were photochemically mediated in the waters investigated. In contrast to the previously assumed “unreactive” nature of Hg0, the studies found that the magnitude of the rate constant for Hg0 oxidation was greater than that for reduction, indicating its importance in estuarine and coastal waters. In addition, both experiments at CBL and on board ship showed that HgII reduction was similar in magnitude, suggesting that biotic processes were relatively unimportant. While no measurable methylation occurred during the incubation period during the on board studies, concentration of CH3199HgII decreased over the time during the experiments. It appeared that the demethylation processes were not dominantly photochemically driven, but could be microbially mediated. Further studies are needed in order to help better understand Hg redox and transformations in natural water systems. 相似文献
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Calibration of a chalcogenide glass membrane, Fe(III)ISE [Fe2.5(Ge28Sb12Se60)97.5], in buffered saline media has been undertaken in order to assess the suitability of this ISE for seawater analyses. The electrode slopes in saline citrate and salicylate buffers were 26.3 and 28.2 mV/decade, respectively, for Fe3+ concentrations ranging from 10−10 M to less than 10−25 M Fe3+. The calibration lines in the citrate and salicylate buffers were essentially collinear with the response in unbuffered chloride-free standards containing >10−5 M Fe3+, demonstrating that the response of the FeISE is unaffected by chloride ions. A mechanism involving a combination of charge transfer and ion-exchange of Fe(III), at the electrode diffusion layer, can be used to explain the ≈30 mV/decade slope of the FeISE. The response of the FeISE in UV photooxidised seawater containing 8 nM total Fe was measured as the pH was changed from 8.27 to 3.51. The slope of the response was 24.2 mV/decade [Fe3+] calculated as a function of pH using Fe(III) hydrolysis constants for seawater. Moreover, the response was essentially collinear with that in citrate buffers and in unbuffered solutions containing >10−5 M Fe3+ and the slope for the combined data was 26.2 mV/decade. This study was restricted to organic-free seawater because the certainty in Fe(III)–ligand stability constants is insufficient to warrant the selection of an ideal calibration buffer system, and there is evidence that powerful chelating ligands (e.g., EDTA along with humic and fulvic acids) may alter the response of the Fe(III)ISE. The Fe dissolution rate of the FeISE in UV photooxidised seawater was found to be 1.6×10−2 nmol Fe/min, as measured by cathodic stripping voltammetry (CSV). This would contaminate a 100-ml sample by 0.8–1.6 nM Fe over a typical measurement period of 5–10 min obtained using a stability criterion of 0.5 mV/min. Various methods are proposed for reducing the level of contamination in open ocean samples that contain sub-nanomolar concentrations of iron. The FeISE has the potential to detect free Fe3+ at concentrations typically found in natural seawater. 相似文献
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本研究提出了一种用于检测海水中锌离子（Zn2+）含量的电化学检测方法。该方法首先应用水热法合成SiO2@PDA-Sb复合材料，然后将该复合材料修饰到玻碳电极上制备SiO2@PDA-Sb-Nafion/GCE，利用差分脉冲阳极溶出伏安法（DPASV）对珠江口海水水样中Zn2+进行测定。研究结果表明，Zn2+在SiO2@PDA-Sb-Nafion/GCE上具有较强的溶出峰。在最优条件下，SiO2@PDA-Sb-Nafion/GCE对Zn2+浓度在1~1 000 nmol/L范围内可实现灵敏、准确的检测，Zn2+的检测出限为0.71 nmol/L。加标回收率实验显示Zn2+加标回收率为93.19%~100.12%，表明该方法可应用于现场海水样品Zn2+测定。本方法具有电极制作简单、稳定性和抗干扰性良好，能够提高现有测定方法的检测限和精确度，在现场海水检测痕量Zn2+具有较好的应用前景。 相似文献
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采用Devanathan-Stachurski 双面电解池检测氢渗透电流技术和扫描电镜分析, 研究了热镀锌钢材在灭菌海水、灭菌培养基和接种了硫酸盐还原菌(SRB)的培养基等3 种介质中的氢渗透行为。氢渗透电流检测结果表明, 培养基的部分组分对热镀锌钢材的氢渗透行为有促进作用, 试样在灭菌培养基中的氢渗透电流密度的平均值比在灭菌海水中提高了约6 倍。尽管活性SRB 代谢产生的S2?和HS?能够促进热镀锌钢材的氢渗透行为, 但是, 由SRB 及其代谢产物和它们所黏附的腐蚀产物所形成的致密微生物膜减少了氢的析出和试样对氢的吸收量, 导致热镀锌钢材氢渗透行为最终被抑制, 因此, 试样在接菌培养基中的氢渗透电流密度的平均值比其在灭菌培养基中降低77%。扫描电镜分析表明, 热镀锌钢材在灭菌海水中能够形成腐蚀产物膜, 而暴露于灭菌培养基中的试样表面未形成明显的腐蚀产物膜, 但在接菌培养基中试样表面能形成黏附了腐蚀产物的致密微生物膜的附着, 表明热镀锌钢材表面的微生物膜与其氢渗透行为之间存在明显的相关性。 相似文献
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The extent and kinetics of Np(V)O2+ adsorption from dilute aqueous solutions and seawater onto a variety of synthetic and natural solids were determined at 25°C and 1 atm total pressure. Extensive and complex adsorption reactions were found, contrary to speculations in the literature that NpO2+ should behave as a simple monovalent ion with a low affinity for surfaces. When normalized to adsorption per unit solid surface area, the ranking for the synthetic solids was aragonite ? calcite > goethite ? MnO2 ≈ clays. Natural materials generally followed the same behavior patterns as their synthetic counterparts. The dissolved/adsorbed ratio was found to be constant over a wide range (10?13–10?7M) of NpO2+ concentrations. At higher concentrations the extent of adsorption decreased until a solubility limit was reached at approximately 10?5 M.Solution composition had the most significant influence for NpO2+ adsorption on goethite, where much more extensive adsorption occurs in dilute solutions than in seawater. When seawater is added to a dilute solution, extensive desorption of NpO2+ from goethite occurs. Tests conducted on NpO2+ adsorbed on carbonates indicated that it remained in the V oxidation state.There is a growing consensus that Pu dissolved in natural waters also occurs dominantly in the V oxidation state as PuO2+ ion. Consequently, these results for NpO2+ may serve as a guide for Pu behavior when also in the V oxidation state. The fact that most adsorbed Pu is found in the III or IV oxidation states indicates that reduction of Pu may occur subsequent to adsorption in the V oxidation state. 相似文献
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Samantha B. Joye Mandy L. Mazzotta James T. Hollibaugh 《Estuarine, Coastal and Shelf Science》1996,43(6):747-766
Community metabolism and nutrient, iron (Fe) and manganese (Mn) cycling were examined in two intertidal, marine, microbial mat communities during short (4–5 days) incubations in closed, flow-through microcosms. Sediment microcosms were incubated under either light (light–dark cycles) or dark (continuous darkness) conditions to assess the effect(s) of photosynthetic oxygen production and microalgal activity on nutrient, Fe and Mn cycling. The effects of chemical redox reactions between reduced sulphur (S), Fe and Mn cycling were examined by blocking sulphate reduction, and reduced S production, with 25 mM molybdate while incubating under dark conditions.In light-incubated microcosms, negligible fluxes of nutrients (nitrogen and phosphorus) and trace metals were observed. A substantial sediment–water flux of reduced Fe (Fe2+) and Mn (Mn2+) was observed in microcosms incubated under continuous darkness; highest fluxes were observed in molybdate-amended microcosms. At both sites, biologically-mediated redox reactions accounted for a substantial (>50%) portion of the Fe2+and Mn2+flux. Both microbial mat communities exhibited similar rates of gross photosynthetic oxygen (O2) production, but dramatically different rates of net benthic O2flux. Distinct patterns of net O2production and trace metal cycling arose from differences in either trace metal oxide availability or reactivity (mineralogy), organic carbon mineralization rates, or sediment characteristics (porosity). Variations in the microbial community responsible for trace metal cycling could have also contributed to the pattern. The present data illustrate that chemically-mediated redox reactions between metal oxides and reduced S complicate interpretation of Fe and Mn fluxes, underscoring the need to separate chemical and biological reactions when attempting to determine the role of biological trace metal reduction in organic carbon oxidation. 相似文献
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This study examines the mechanism of oxidation of dissolved organic matter (DOM) in a high-temperature combustion (HTC) carbon analyzer. The HTC analyzer, which is commonly used to measure the concentration of dissolved organic carbon (DOC) in seawater, is still largely empirical in its operation, and little information is yet available on the chemical and physical mechanisms responsible for oxidation of DOM. To examine the role of water, which has been hypothesized to be a source of reactive oxidants in HTC analyzers, several experiments were conducted using gaseous hexane samples and several wet/dry carrier gases. Because the quantity of O2(g) needed to oxidize an injected sample of DOM is quite small, a substantial effort has been made to exclude O2(g) from the combustion furnace of the HTC instrument. In this modified, “air-tight” instrument, the efficiency of conversion of hexane into CO2 was greatest in dry O2 and slightly lower in moist O2. Hexane was only slightly oxidized in dry N2, but it was largely converted into CO2 when moist N2 was used as the carrier gas. These experiments confirm that water provides reactive oxidizing species (perhaps hydroxyl radical) that rapidly convert hexane into CO2 in the combustion tube of a carbon analyzer. Additional experiments with aqueous solutions of potassium hydrogen phthalate and a variety of carrier gases support this basic hypothesis. 相似文献
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The interaction of Mn2+ with the surface of calcite in aqueous solutions is complex. In dilute solutions the Mn2+ is rapidly absorbed, MnCO33 nucleates on the calcite surface and then grows by a first order reaction with respect to the initial Mn2+ concentration. At higher ionic strengths in NaCl solutions, the rate of these processes is slower, but the same general pattern persists. In solutions containing Mg2+, at the concentration of seawater and in seawater, the nucleation phase of the uptake process does not appear to occur. The long-term uptake rate of Mn2+ on the surface of calcite in seawater is first order with respect to the dissolved Mn2+ concentration. The rate constant is over three orders of magnitude smaller than that found in dilute Mg2+-free solutions. A probable explanation for the slower growth rate in seawater is that MnCO3 is not nucleated on the calcite surface due to the presence of high Mg2+ concentrations. The Mg2+, through site competition, prevents enough Mn2+ from being adsorbed to reach a critical concentration for MnCO3 nucleation. This behavior is similar to that found for orthophosphate with calcite surfaces in dilute solutions and seawater. It indicates that rhodochrosite cannot nucleate in carbonate-rich recent sediments unless the Mg2+ concentration is lowered below that of seawater.Measurements of the solubility of rhodochrosite in seawater gave results from an undersaturation approach to equilibrium in excellent agreement with those found in previous studies in dilute solutions. When equilibrium was approached from supersaturation, approximately fifty times more calcium was precipitated than Mn2+. The measured solubility was over twice that determined from undersaturation. It is possible that a Mn—calcite containing 25 to 30 mol% MnCO3 formed on the rhodochrosite from the supersaturated solutions. Consequently, it is doubtful that pure rhodochrosite controls the concentration of Mn2+ even in calcium carbonate-poor marine environments. 相似文献