海底铁锰氧化还原过程的模拟研究

本文用室内海水-沉积物平衡箱研究了沉积物间隙水中铁、锰的垂直变化分布和随时间变化的分布,Fe~(2+)随深度、时间的变化幅度大,在六个月的实验期内均是如此,而Mn~(2+)在放置三个月后即趋于稳定;Fe~(2+),Mn~(2+)产生的宏观经验动力学表明:Fe~(2+)受pH影响远比Mn~(2+)大,且随着深度的增加更为明显,Fe~(2+)在较下层产生速率大,而Mn~(2+)反之;Fe~(2+)的扩散转移是上覆海水向沉积物中转移,扩散量为-60.7ug/m~2d,Nn~(2+)转移方向相反,扩散量为1746.2ug/m~2.d。     

Effect of natural organic matter on arsenic release from soils and sediments into groundwater

Arsenic (As) contamination in groundwater has received significant attention recently. Natural and anthropogenic sources contribute to the worldwide occurrence of As contamination. As speciation is an important factor related to its toxic and mobile behavior. The release of As from soils and sediments into groundwater is governed by several geophysicochemical processes, of which, As sorption behavior is of principle significance. This review paper summarizes existing information regarding the effects of natural organic matter (NOM) on the fate and mobility of As species in the environment. NOM may enhance the release of As from soils and sediments into the soil solution, thereby facilitating As leaching into the groundwater. The main influencing mechanisms include competition for available adsorption sites, formation of aqueous complexes, and/or changes in the redox potential of site surfaces and As redox speciation. NOM may also serve as binding agents, thereby reducing As mobility. However, comparably little research has been performed on this aspect. Since most investigations have been done on purified minerals under laboratory conditions, further research involving various geological materials under natural environmental conditions is required. Development of proper geochemical conceptual models may provide means of predicting the role of NOM in arsenic leaching and/or immobilization.     

处理含硫废水的新型催化剂

合成了适合处理含硫废水的固相催化剂,考察了催化剂的稳定性、活性及对实际废水的处理效果,开了含硫废水处理的一条新途径。     

沉降除藻协同沉积物覆盖对藻华水体甲烷释放的影响

本研究以藻华水体甲烷释放为对象,利用模拟柱培养实验,探究了沉降除藻和沉积物覆盖复合技术对富营养化甲烷释放的影响.结果表明,沉降除藻结合沉积物覆盖处理可有效改善水环境,实现对甲烷释放的控制,但不同覆盖材料的效果存在差异;活性炭效果要优于土壤和沸石.相比于对照体系水体溶解氧(DO)2. 5 mg·L-1和氧化还原电位(ORP)100 m V,沉积物界面ORP -125 m V,沉降除藻协同活性炭覆盖体系中水体DO和ORP分别升高至3. 1 mg·L-1和174 m V,沉积物界面ORP逆转为168 m V,实验期间甲烷释放量相对于对照组减少90. 2%.研究结果在富营养水体甲烷减排方面具有指导性意义.     

不同氧化还原条件下土壤中Cd/Zn/Cu共运移特征及数值模拟

以重金属离子镉（Cd）、锌（Zn）、铜（Cu）为研究对象,通过室内土柱混合置换实验和数值模拟方法,分析了5种不同氧化还原电位（E_h）对Cd、Zn、Cu在土壤中运移的影响.结果表明,不同E_h下,Cu的竞争吸附能力均大于Cd和Zn,移动性较小;并产生了“滚雪球效应”,导致出流液中Cd和Zn的浓度大于输入浓度.与原土相比,E_h的增加或降低均促进了Zn、Cd的迁移速率,但对实验周期内回收率的影响不同;E_h的增加促进了Cu的迁移.两点非平衡模型（TSM）和单点非平衡吸附模型（OSM）较好地模拟了重金属的迁移,且进一步表明了土壤对重金属的吸附受吸附反应速率的限制（f<0.7）.在复合污染土壤评价和防治中,不仅要考虑E_h的影响,还要关注由竞争吸附所产生的浓度叠加效应,避免低估重金属的污染风险.     

不同氧化还原条件下氯乙烯的微生物脱氯

氯乙烯是土壤和地下水中存在的污染物,其去除的有效途径之一为微生物降解.本研究在温度20℃、氯乙烯初始浓度100μmol/L条件下,对不同氧化还原条件下四氯乙烯、cis-二氯乙烯及一氯乙烯的微生物降解进行了实验.结果表明,在铁还原和碳酸氢盐存在条件下,四氯乙烯以0.26/d和0.31/d的速率分别脱氯为三氯乙烯和cis-二氯乙烯.在脂肪酸存在条件下,四氯乙烯、cis-二氯乙烯和一氯乙烯均完全脱氯为乙烯,但后两者脱氯速率(0.04/d)明显低于前者(0.57/d).在反硝化、锰还原及硫还原条件下,不同取代氯乙烯降解均不明显.当环境温度降至12℃,脱氯菌活性降低,但氯乙烯完全脱氯还原过程仍可发生.     

Redox potential and uranium sorption onto sediments: kinetic and thermodynamic characteristics

ABSTRACT

The effects of the flooding and initial Eh of sediments on the sorption of uranium onto the sediments were analysed by flooding and static experiments. The changes in uranium species with Eh and kinetic and thermodynamic characteristics of the uranium sorption onto the sediments were investigated. The flooding experiment indicates that the initial Eh of the sediment gradually decreased with the increase in flooding time. Based on the redox potential in the flooding experiment, simulation results obtained using the geochemical simulation software PHREEQC show that the concentration of U (VI) decreased. In contrast, the concentrations of U (III), U (IV), and U (V) gradually increased. The pseudo-second-order kinetic model well fitted the experimental data, which shows that the sorption was mainly chemical sorption. The thermodynamic parameters suggest that the entropy and enthalpy under the used conditions were positive and that ΔG^θ was negative. A thermodynamic analysis shows that the sorption was endothermic and spontaneous. These results are useful for the understanding of the sorption mechanism and migration of uranium onto the sediment under different initial sediment redox potentials and provide a good theoretical foundation for radioactive pollution remediation.     

氧化还原介体调控亚硝酸盐反硝化特性研究

采用实验室驯化的亚硝酸盐反硝化菌群作为菌种,优化亚硝酸盐降解条件,探究在氧化还原介体蒽醌-2-磺酸钠(AQS)存在条件下亚硝酸盐反硝化的特性.结果表明,反硝化菌群降解亚硝酸盐的最适条件为:温度35℃,pH为8,丁二酸钠为碳源,碳氮比4∶1,初始亚硝酸盐浓度100 mg.L-1;AQS的最佳投加量为0.16 mmol.L-1,介体调控的反硝化体系氧化还原电位略有降低,维持在-400～-500 mV之间,pH随亚硝酸盐降解速率增加而增大,最终稳定到9～10之间;通过分析反硝化中间代谢产物,推测AQS在亚硝酸盐反硝化过程中不仅起到辅酶CoQ的作用而且加速了细胞色素传递电子的全过程.本研究可为氧化还原介体调控亚硝酸盐反硝化实际应用提供理论基础和优化参数.     

北天堂垃圾污染场地氧化还原分带及污染物自然衰减研究

通过对北京市北天堂垃圾填埋场周围实际监测数据资料的分析,研究了垃圾填埋污染场地的氧化还原分带和污染物的自然衰减作用.结果表明,北天堂垃圾填埋污染场地存在氧化还原分带现象,依据各氧化还原带标志性物质浓度的分布规律和特点划分了5个氧化还原带,即产甲烷带、硫酸盐还原带、铁还原带、硝酸盐还原带和氧还原带.不同有机污染物在不同的氧化还原带中的衰减不同;挥发酚和氰化物在硫酸盐还原带中的含量相对较高,分别为0.005和0.019 μg/L;Cr、Pb、Ni、As、Cu、Cd、Zn和Mn等重金属在产甲烷带中的含量相对较高,分别为25.11、 33.82、 29.93、 3.18、 2.3、 0.1、 283.1、 1 220　μg/L.因此,氧化还原带对污染物的衰减起重要作用.     

水溶性有机物的电子穿梭功能研究

以源于污泥的DOM(dissolved organic matter)为供试材料,以中国希瓦氏菌(Shewanella cinica)D14T为电子转移驱动力,研究了DOM的氧化还原性能与电子穿梭功能.结果表明,污泥DOM可作为末端电子受体接受醌还原菌D14T呼吸链上的电子,从而转变为还原态DOM,而还原态DOM可将电子再次转移给Fe(Ⅲ).经D14T还原后,DOM电子供给量(e-/C)由初始2.2~14μmol.g-1增加到253~347μmol.g-1.循环伏安法与多次还原-氧化循环实验表明,DOM呈现2对明显的氧化还原峰,经3次还原-氧化循环后电子供给量可稳定维持在150~250μmol.g-1之间,说明DOM具有重复利用、反复转移电子的特性.在菌株D14T还原水铁矿的体系中,加入DOM可提高水铁矿的还原溶解速率,其原因是DOM在D14T与水铁矿之间充当了电子穿梭体的角色.这些结果反映了DOM在电子转移反应中的重要性,为DOM的环境属性提出了一个新见解.