采煤沉陷积水区土壤覆水初期氧化还原反应过程与磷迁移转化的耦合研究

以淮南潘谢某采煤沉陷积水区为研究对象,通过设计室内模拟实验,对其农业耕作层土壤初期覆水条件下的氧化还原过程进行了考察.在此基础上研究了磷(P)自农业土壤内部向"水-土"界面迁移转化潜能,模拟实验持续近4个月.同时,实验采取土壤理化性质分析和孔隙水表征相结合的方法进行,土壤主要分析了淹水前后有机质含量(OM)、铁氧化物、P含量及其赋存形态等相关变化,而孔隙水则分析了pH、氧化还原电位(E_h)、溶解无机碳(DIC)和有机碳(DOC)、Fe²⁺、NO₃^--N、SO₄^2--S,较为保守元素Cl^-作为其他可变指标的参考.结果发现,研究过程中观察到了微生物活动所对应的不同氧化还原过程,1~2周后土柱内部的NO₃^--N和SO₄^2--S由于呼吸作用趋于耗竭,孔隙水Fe²⁺持续升高,并伴随着活性磷(DRP)的释放.此后整个体系氧化还原反应趋于平衡,在"水-土"界面观察到了明显的Fe"泵升"现象,弱吸附态磷(NH₄Cl-P)和有机磷(OP)有向金属氧化物结合态磷(NaOH-P)迁移转化的趋势,但孔隙水内部DRP能否向表层迁移短时间内不能确定.     

水锰矿氧化水溶性硫化物过程及其影响因素

作为表生环境中易生成且分布广泛的氧化锰矿物,水锰矿参与水溶性硫化物的氧化反应,影响其迁移、转化和归趋.本研究考察了水锰矿氧化水溶性硫化物(S~(2-))的过程与产物,探讨了初始pH、氧气对反应速率与中间产物的影响,X-射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)和透射电镜(TEM)表征水锰矿与水溶性硫化物反应固相产物晶体结构、组分和微观形貌;分光光度计、高效液相色谱仪和离子色谱仪分析S~(2-)及其氧化物的浓度与变化趋势.结果表明水锰矿氧化S~(2-)产物主要为单质S,起始pH降低可加速S~(2-)的初始氧化反应,对产物组成并无显著影响;有氧环境中单质S会进一步氧化生成S_2O_3~(2-),且水锰矿表现出良好的催化作用与化学稳定性,反应约10 h,晶体结构保持稳定.     

Fenton试剂法降解餐厨垃圾异味

自行设计Fenton试剂法降解还原性气体异味的反应器,研究了Fenton试剂法处理餐厨垃圾异味主要成分(苯、乙酸乙酯、苯乙烯)的降解效果。以苯为典型代表物,优化得出该实验的最佳反应条件为:pH=3,FeSO4.7H2O投加量为1 g/L液相,30%H2O2投加量为10 mL/L液相,紫外光源辅助。结果证明,Fenton试剂法处理单一异味气体的效果较理想,在前180 min内能达到90%以上,该法在处理气态异味污染物方面具有广阔的应用前景。     

水稻土中铁的厌氧生物氧化还原循环对砷的影响（The Effect of Anaerobic Redox Cycling of Iron on Arsenic Mobility in Paddy）

应用砷污染水稻土的厌氧富集培养,探讨水稻土中潜在存在铁厌氧生物循环及其对氮和砷的耦合作用.富集培养直接证明了水稻土中铁的厌氧生物循环:三价铁(人工合成针铁矿)在厌氧条件下被逐渐还原成二价铁;铁还原过程结束并外源添加硝酸根时,培养基中新生的二价铁在依赖于硝酸根的铁氧化菌的作用下被氧化;当提供新的电子供体乙酸时,生物合成的铁矿重新被还原.在铁氧化还原循环过程中,随着铁的还原,培养基中砷的浓度不断增加,反之,当铁逐渐氧化的同时不断地吸附固定培养基中的砷.在铁的厌氧氧化阶段,铁氧化的同时硝酸根被还原,培养基中积累了NH4+和NO2-.因此,厌氧水稻土中可以进行完整的铁氧化还原循环,同时这个循环过程耦合了氮和砷的迁移转化.     

基于三维荧光光谱特征研究土壤腐殖质氧化还原特性

以国际腐殖质协会腐殖酸和实验室提纯腐殖酸为研究对象,发现被H2还原前后腐殖酸的三维荧光光谱明显不同,但有共同的变化趋势:还原态腐殖酸的三维荧光光谱图的波峰荧光强度均明显低于还原前,说明腐殖酸还原过程有类似π-π*化学键断开的结构变化.对苯醌是腐殖酸氧化还原醌基官能团的代表化合物,将其还原前后与腐殖酸还原前后的荧光光谱对比,发现两组变化趋势一致,这一发现是利用荧光特性量化腐殖质氧化还原官能团的基础.利用铁氰化钾测定腐殖酸的得失电子能力,发现不同土壤提纯的腐殖酸得失电子能力有一定差别:鹰潭土壤腐殖酸和桃源土壤腐殖酸在原态下对三价铁的还原能力都较弱,分别为0.998和0.465 meq.g-1C(原态转移电子数);但还原后得电子数(还原态转移电子数减原态转移电子数)分别为3.384 meq.g-1C(鹰潭土壤腐殖酸)和1.187 meq.g-1C(桃源土壤腐殖酸).鹰潭土壤腐殖酸具有较高的得电子数,与其具有较高荧光峰值这一结果互相支持.结合得失电子能力测定,利用光学分析方法,量化官能团,预测氧化还原反应进程,使三维荧光光谱法测定土壤有机质的氧化还原性在实际应用中具有广阔的前景.     

Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol

The effect of goethite (α-FeOOH), hematite (α-Fe₂0₃) and maghemite (γ-Fe₂0₃) on the aqueous photoreduction of divalent mercury with organic acids (oxalate, formate and acetate) is investigated. Laboratory photochemistry experiments with synthetic iron oxides and simulated sunlight were performed to assess the role of the oxides on the photoreduction. Ambient aerosol was also collected and introduced as the solid phase to compare its effect with that of synthetic oxides. It is observed that the presence of various iron oxides or aerosol particles enhances the photoreduction. It is also found that the hydroxyl radicals produced in the hematite-oxalate systems can re-oxidize the reduced mercury back to Hg(II). Based on the experimental observations, mechanisms responsible for the Hg(II) reduction are proposed. The kinetics of Hg⁰ oxidation by hydroxyl radicals was also studied by a steady-state kinetic technique using nitrate photolysis as the * OH radical source. The second-order rate constant is determined to be 2.0 × 10⁹ M⁻ s⁻¹. The implications of the studied reactions on the atmospheric chemistry of mercury are discussed.     

pH、钙和磷对砷在水稻土中溶解度的影响及表面络合机制解析

为深入理解稻田土壤砷(As)的环境行为,以及不同环境因素对土壤溶液中As有效性的影响机制,通过吸附实验结合天然有机质-电荷分配(NOM-CD)模型分析了pH、 Ca²⁺和PO₄^3-对As在湖南株洲稻田土壤中溶解度和化学形态分布的影响,并揭示其影响机制.结果表明,土壤总As溶解度在pH 6.0左右最低,主要受Ca²⁺、 PO₄^3-、 As(Ⅲ)和As(Ⅴ)的静电作用及位点竞争作用控制;土壤溶液中Ca²⁺浓度的增加会促进As的吸附,降低土壤溶液中As的浓度,尤其在碱性条件下由于Ca²⁺的吸附增加了土壤氧化物表面正电荷,因而土壤溶液中As(Ⅴ)浓度随Ca²⁺浓度的升高明显降低;pH低于5.5时,添加PO₄^3-抑制了土壤As(Ⅴ)的还原,但pH高于5.5后,添加PO₄^3-促进了土壤As(Ⅴ)的还原,并由于PO     

不同氧化还原环境对煤矸石污染物质释放的影响

为评价不同氧化还原环境对煤矸石污染物质释放的影响,设置处理1(充氧饱和的曝气去离子水,Eh=229mV)、处理2(煮沸30min的去离子水,Eh=250mV)两种氧化环境及处理3(添加富含有机质的过滤养殖废水,Eh=14mV)一种还原环境的水溶液做浸提剂,对煤矸石进行0～9d的连续振荡浸提试验.结果表明:在浸提初期(0～1d内),煤矸石表面已形成的氧化产物迅速溶出,使得两种氧化环境和还原环境下的煤矸石浸出液pH都迅速降低,EC、Eh及多种溶出离子浓度迅速升高,但还原环境下煤矸石浸出液中Cu、F-浓度变化不显著,且还原环境下浸出液中其他离子虽有上升但显著低于氧化环境下.随浸提时间延长(1～9d),两种氧化环境下煤矸石浸出液pH继续降低,浸出液中Fe、Mn、Cu、Zn和SO2-4、F-多种污染物质溶出数量明显增加并呈现典型的持续氧化产酸过程;而还原环境下煤矸石浸出液的pH随时间延长降低不明显,Fe、Mn、Zn等污染物质溶出数量显著低于两种氧化环境下,Cu和SO2-4的释放也受到明显抑制.说明还原环境能有效抑制煤矸石氧化产酸及多种污染物质的溶出,且显著低于氧化环境.因此,在煤矸石堆场投加有机质形成还原(厌氧)环境可进行矸石污染的原位控制及治理.     

固定化氧化还原介体加速亚硝酸盐生物反硝化作用

考察了利用循环伏安法所制备的固定化氧化还原介体(AQS/PPy/ACF)加速亚硝酸盐生物反硝化的特性,及其降解过程中pH和氧化还原电位(ORP)的变化特征。结果表明,AQS/PPy/ACF可显著地加速亚硝酸盐的生物降解;在不考虑各因子间交互作用的条件下,AQS/PPy/ACF加速亚硝酸盐降解的最佳条件为温度35℃,pH=8和碳氮比为6;AQS/PPy/ACF加速亚硝酸盐生物反硝化过程中pH的变化趋势与传统的亚硝酸盐生物反硝化过程中pH的变化趋势相似;AQS/PPy/ACF的加入可使亚硝酸盐生物反硝化过程中的ORP降低约45 mV;AQS/PPy/ACF具有较好的催化稳定性。本研究可为亚硝酸盐的生物降解提供新的技术途径,并为该技术的实际应用提供理论基础。     

GROUNDWATER GEOCHEMISTRY IN THE SEMINOLE WELL FIELD,CEDAR RAPIDS,IOWA1

The City of Cedar Rapids obtains its municipal water supply from four well fields in an alluvial aquifer along the Cedar River in east-central Iowa. Since 1992, the City and the U.S. Geological Survey have cooperatively studied the groundwater-flow system and water chemistry near the well fields. The geochemistry in the alluvial aquifer near the Seminole Well Field was assessed to identify potentially reactive minerals and possible chemical reactions that produce observed changes in water chemistry. Calcite, dolomite, ferrihydrite, quartz, rhodochrosite, and siderite were identified as potentially reactive minerals by calculating saturation indexes. Aluminosiicate minerals including albite, Ca-montmorillonite, gibbsite, illite, K-feldspar, and kaolinite were identified as potentially reactive minerals using hypothetical saturation indexes calculated with an assumed dissolved aluminum concentration of 1 microgram per liter. Balanced chemical equations derived from inverse-modeling techniques were used to assess chemical reactions as precipitation percolates to the water table. Calcite dissolution was predominate, but aluminosilicate weathering, cation exchange, and redox reactions also likely occurred. Microbial-catalyzed redox reactions altered the chemical composition of water infiltrating from the Cedar River into the alluvial aquifer by consuming dissolved oxygen, reducing nitrate, and increasing dissolved iron and manganese concentrations. Nitrate reduction only occurred in relatively shallow (3 to 7 meters below land surface) groundwater near the Cedar River and did not occur in water infiltrating to deeper zones of the alluvial aquifer.