Sulfate Attack on Concrete in an Inland Salt Lake Environment

INTRODUCTIONSulfate attack is one of the reasons for concretestructures deteriorating earlier than usual,thusshowing poor durability.The SO42-from the sur-rounding environment such as ocean,saline,groundwater,and even the concrete itself,reacts with thehydration products of cement,whichleads to the de-terioration of the concrete(Li et al.,2000;Kang,1995;Neville,1983;Samarai,1976).The deteriora-tionincludes three processes:the external swelling,cracking,peeling,and disjointing caused by …     

An Atomic Force Microscopy study of the growth of calcite in the presence of sodium sulfate

In situ atomic force microscopy (AFM) has been used to compare the growth of pure calcite and the growth of calcite in the presence of sulfate ions from aqueous solutions at a constant value of supersaturation (S.I. = 0.89) with respect to calcite. The effect of sulfate ions on calcite growth rates is determined and a potential incorporation of sulfate ions is identified in the calcite during growth. Solutions supersaturated with respect to calcite with solution concentration ratio of one and a constant pH of 10.2, were prepared and sulfate was added as Na₂SO₄ aqueous solution. The solution composition was readjusted in order to keep the supersaturation and pH constant. PHREEQC was used to determine relevant solution concentrations. In situ AFM experiments of calcite growth were performed using a fluid cell and flowing solutions passed over a freshly cleaved calcite surface. Growth rates were determined from the closure of the rhombohedral etch pits induced by initial dissolution with pure water. The spreading rate of 2-dimensional nuclei was also measured. At low concentrations of sulfate (≤ 0.5 mM), no effect on the growth rate of the calcite was observed. At higher concentrations (2 to 3 mM) of sulfate, the growth rate increased, possibly because a higher concentration of calcium and carbonate was necessary to maintain the supersaturation constant. At much higher concentrations of additional sulfate (up to 60 mM) the growth rate of the calcite was substantially decreased, despite the fact that a further increase of calcium and carbonate was required. The morphology of 2-dimensional growth nuclei became increasingly elongated with increasing sulfate content. Measurements of step height showed that newly grown steps were approximately 1 Å higher when grown in high sulfate concentrations, compared to steps grown in sulfate-free solutions. At sulfate concentrations above 5 mM the growth mechanism changes from layer growth to surface roughening. These observations suggest that the new growth has incorporated sulfate into the calcite surface.     

硫酸盐还原菌及异化铁还原菌对 黄钾铁矾还原作用的对比

选取酸性矿坑水环境中常见的次生含铁硫酸盐矿物———黄钾铁矾[KFe3(SO4)2(OH)6]为研究对象,用硫酸盐还原菌 Desulfovibriovulgaris 和异化铁还原菌Shewanellaputrefaciens CN32对其进行还原实验,探讨作为重金属治理潜在材料的 黄钾铁矾的微生物稳定性.实验采用非增长型培养基,在中性、厌氧、30℃的条件下进行.采用湿化学方法测量水溶液及还原产 生的总Fe2+ ,利用X射线衍射(X-raydiffraction,简称XRD)来分析反应后残余固体物质的矿物组成,用扫描电镜(scanning electronicmicroscopy,简称SEM)观察固体残余物的形貌特征.结果表明,没有微生物的参与,黄钾铁矾的稳定性较好.异化铁 还原菌S.putrefaciens CN32和硫酸还原菌D .vulgaris 在营养极其匮乏的中性厌氧条件下均能还原黄钾铁矾晶格中的 Fe3+ ,显示出黄钾铁矾被微生物还原的可能性.S.putrefaciens CN32还原黄钾铁矾晶格中Fe3+ 的最大还原速率和最终Fe3+ 还原率分别为0.001mmol·L-1·h-1和0.37%.与S.putrefaciens CN32不同,D .vulgaris 对黄钾铁矾的还原能力较强,不 含有电子穿梭体(Anthraquinone-2,6-disulfonate,简称AQDS)的实验体系中Fe3+ 的最大还原速率和最终Fe3+ 还原率分别为 0.017mmol·L-1·h-1和16.80%,而添加了AQDS的实验体系的则分别达到了0.026mmol·L-1·h-1和24.30%,这可能与 黄钾铁矾中含有SO42- 有关.D .vulgaris 优先还原黄钾铁矾晶格中的SO42- 产生的H2S是强还原剂,也可促进Fe3+ 的还原, 微生物以及H2S的双重作用可能是导致D .vulgaris 体系中Fe3+ 还原率较高的原因.XRD分析表明,黄钾铁矾经过S.putrefaciens CN32的作用,物相没有发生变化;而经过D .vulgaris 作用后,黄钾铁矾的特征峰消失,固相残余物中出现了菱铁 矿(FeCO3)、蓝铁矿[Fe3(PO4)2·8H2O]等次生矿物.由于培养基中没有添加任何的磷酸盐,因此蓝铁矿的出现可能是由于培 养基中添加的少量酵母浸膏降解后产生的磷酸根与D .vulgaris 还原黄钾铁矾产生的Fe2+ 相互作用的结果.这些认识对深入 理解地球表层铁的生物地球化学循环具有重要意义,为矿山环境重金属的污染治理提供了实验依据.      

EFFECT OF SULPHATE-REDUCING BACTERIA ON ELECTRO-CHEMICAL CORROSION BEHAVIOR OF 16Mn STEEL IN SEA MUD

ＩＮＴＲＯＤＵＣＴＩＯＮＩｔｗａｓｇｅｎｅｒａｌｌｙｃｏｎｓｉｄｅｒｅｄｐｒｅｖｉｏｕｓｌｙｔｈａｔｔｈｅｃｏｒｒｏｓｉｏｎｏｆｓｔｅｅｌｉｎｓｅａｍｕｄｗａｓｎｏｔｓｅｒｉｏｕｓ.Ｈｏｗｅｖｅｒ,ｉｔｗａｓｌａｔｅｒｆｏｕｎｄｔｈａｔｔｈｅｃｏｒｒｏｓｉｏｎｒａｔｅｏｆｓｔｅｅｌｉｎｓｏｍｅｓｅａｍｕｄｗａｓｈｉｇｈｅｒｔｈａｎｔｈａｔｉｎｓｅａｗａｔｅｒ(Ｋｉｎｇ,1980;Ｓｅｈｍｉｄｅ,1982;Ｇｕｏｅｔａｌ.,1997;Ｈｏｕ,1998).Ｔｈｅｒｅａｒｅｓｏｍｅｒｅｐｏｒｔｓｔｈａｔｔｈｅｃｏｒｒｏｓｉｏｎｒ…     

热化学硫酸盐还原作用对碳酸盐岩气藏的化学改造——以川东北地区长兴组-飞仙关组气藏为例

目前在川东北地区长兴组—飞仙关组已发现普光、渡口河、铁山坡、罗家寨等多个高含H2S的大、中型气田。通过天然气地球化学特征、流体包裹体盐度和岩心及薄片的镜下详细观察后认为,川东北地区长兴组—飞仙关组的大多数气藏遭受了热化学硫酸盐还原作用(TSR)的化学改造,TSR的改造主要表现在3个方面:1使C2 重烃相对于CH4、12C相对于13C优先被消耗,造成天然气干燥系数变大和碳同位素变重;2由于TSR产生的大量淡水的加入,使气藏的原生地层水被稀释,造成地层水盐度降低;3TSR相关流体(烃类和H2S等)与储层岩石之间的相互作用使储层被溶蚀和硬石膏发生蚀变,造成储层孔隙度增大,从而对改善其物性具有重要意义。     

低聚壳聚糖的美拉德反应及其衍生物的抗氧化性能研究

醇沉法制得低聚壳聚糖美拉德反应8、16 h以及24 h的衍生物,分别记为CC-8、CC-16以及CC-24。对3种衍生物进行红外表征和分子量测定,并研究其对超氧阳离子O 2&、DPPH的清除能力以及还原能力。结果显示:反应体系pH呈下降趋势;UV-Vis光谱在280 nm波长处吸收峰有明显增强,反应16 h后增长缓慢;在343 nm的激发波长和420 nm发射波长下的荧光强度明显增高,反应16 h后开始下降;3种衍生物均保留着低聚壳聚糖的特征吸收峰;其对O 2&、.DPPH的清除能力以及还原能力均得到显著提高,且CC-16抗氧化能力最好。     

招远金矿区水体中硫同位素特征及其对污染来源的指示

稳定同位素因其指纹效应已成为分析矿区污染来源的重要技术手段。文章以招远金矿区为例,应用硫同位素联合水化学分析、聚类分析及氢氧同位素分析招远金矿区水污染特征和成因。通过分析可知,矿区内地表水和地下水主要接受大气降水补给,水力联系密切。水化学类型以SO4—Ca和SO4—Na型为主,阴离子以SO42-为主,地表水和地下水的NO3-和Cl-在空间上变异性较大。地表水硫酸盐含量普遍偏高,硫酸盐污染较为严重,高值区出现在玲珑金矿、金翅岭金矿和张星镇附近;而地下水高值区都出现在玲珑金矿附近,且SO42-浓度沿着径流方向逐渐降低。地表水中硫酸盐δ34S值介于1.8‰~9.8‰,地下水中硫酸盐δ34S值介于2.7‰~9.6‰,地表水和地下水硫酸盐含量受玲珑金矿硫化、玲珑花岗岩和胶东岩群影响明显。在地下水径流途中,有地表水入渗污染地下水的现象。另外,工业废水的排放也是硫酸盐含量升高的主要原因。研究表明：硫同位素在金矿区硫酸盐污染的来源和特征方面有很好的指示作用,是评价矿山开采对地下水污染的有效工具。     

全谱直读等离子发射光谱法直接测定天然矿泉水中的SO2-4

采用全谱直读等离子发射光谱(ICP-AES)直接测定天然矿泉水中SO2-4的方法在优化工作条件下SO42-的测定下限为0.09mgL-1,方法简便,快速,适用于批量生产.     

湿浸硫酸镍工艺中的二次浸取

湿法浸取硫酸镍工艺研究中,净化提纯工艺采取了蒸发浓缩浸液、分步沉淀杂质的技术方案。中试表明,采用此种工艺生产效率很低,还导致生产流水线上的设备匹配性差。为此,作者提出了二次浸取的技术方案。实验室及中试试验表明:采用二次浸取工艺替代蒸发浓缩工艺,行之有效。     

Origin of the hydrocarbon gases carbon dioxide and hydrogen sulfide in Dodan Field (SE-Turkey)

Gas occurrences consisting of carbon dioxide (CO₂), hydrogen sulfide (H₂S), and hydrocarbon (HC) gases and oil within the Dodan Field in southeastern Turkey are located in Cretaceous carbonate reservoir rocks in the Garzan and Mardin Formations. The aim of this study was to determine gas composition and to define the origin of gases in Dodan Field. For this purpose, gas samples were analyzed for their molecular and isotopic composition. The isotopic composition of CO₂, with values of −1.5‰ and −2.8‰, suggested abiogenic origin from limestone. δ³⁴S values of H₂S ranged from +11.9 to +13.4‰. H₂S is most likely formed from thermochemical sulfate reduction (TSR) and bacterial sulfate reduction (BSR) within the Bakuk Formation. The Bakuk Formation is composed of a dolomite dominated carbonate succession also containing anhydrite. TSR may occur within an evaporitic environment at temperatures of approximately 120–145 °C. Basin modeling revealed that these temperatures were reached within the Bakuk Formation at 10 Ma. Furthermore, sulfate reducing bacteria were found in oil–water phase samples from Dodan Field. As a result, the H₂S in Dodan Field can be considered to have formed by BSR and TSR.As indicated by their isotopic composition, HC gases are of thermogenic origin and were generated within the Upper Permian Kas and Gomaniibrik Formations. As indicated by the heavier isotopic composition of methane and ethane, HC gases were later altered by TSR. Based on our results, the Dodan gas field may have formed as a result of the interaction of the following processes during the last 7–8 Ma: 1) thermogenic gas generation in Permian source rocks, 2) the formation of thrust faults, 3) the lateral-up dip migration of HC-gases due to thrust faults from the Kas Formation into the Bakuk Formation, 4) the formation of H₂S and CO₂ by TSR within the Bakuk Formation, 5) the vertical migration of gases into reservoirs through the thrust fault, and 6) lateral-up dip migration within reservoir rocks toward the Dodan structure.