Chromium transformation driven by iron redox cycling in basalt-derived paddy soil with high geological background values

The flooding and drainage of paddy fields has great effects on the transformation of heavy metals, however, the transformation of Cr in basalt-derived paddy soil with high geological background values was less recognized. The typical basalt-derived paddy soil was incubated under alternating redox conditions. The Cr fractions and the dynamics of Fe/N/S/C were examined. The HCl-extractable Cr increased under anaerobic condition and then decreased during aerobic stage. The UV-vis spectra of the supernatant showed that amounts of colloids were released under anaerobic condition, and then re-aggregated during aerobic phase. The scanning transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) revealed that Fe oxides were reduced and became dispersed during anaerobic stage, whereas Fe(II) was oxidized and recrystallized under aerobic condition. Based on these results, a kinetic model was established to further distinguish the relationship between the transformation of Cr and Fe. During anaerobic phase, the reduction of Fe(III) oxides not only directly released the structurally bound Cr, but also enhanced the breakdown of soil aggregation and dissolution of organic matter causing indirect mobilization of Cr. During aerobic phase, the oxidation of Fe(II) and further recrystallization of newly formed Fe(III) oxides might induce the re-aggregation of soil colloids and further incorporation of Cr. In addition, the kinetic model of Cr and Fe transformation was further verified in the pot experiment. The model-based findings demonstrated that the Cr transformation in the basalt-derived paddy soil with high geological background values was highly driven by redox sensitive iron cycling.     

微生物铁氧化作用对砷迁移转化的影响

采用厌氧培养的方法,从砷污染的水稻上中富集依赖硝酸盐的铁氧化菌群,通过监测培养体系中Fe和A$的形态变化模拟水稻厌氧条件下微生物铁氧化过程对As迁移转化的影响.结果表明,约96%外源添加的Fe(Ⅱ)可在10d内氧化成Fe(Ⅲ),As(Ⅲ)对Fe(Ⅱ)的初期氧化速率具有一定的抑制作用;在微生物铁氧化过程中,As(Ⅲ)被氧...     

水分管理对稻田土壤铁氧化物形态转化的影响及其与镉活性变化的耦合关系

稻田土壤水分管理过程中铁氧化物的形态转化对土壤镉（Cd）活性和水稻Cd累积具有重要影响.以西南地区紫色水稻土为研究对象,通过室内培养试验,探讨了淹水管理方式（持续淹水,CW;干湿交替,DW）联合铁氧化物（针铁矿,G-Fe;铁粉,Fe）施用对Cd污染土壤的pH、氧化还原性质（Eh、pe+pH）、铁氧化物形态转化和Cd有效性变化的影响,分析了水分管理驱动下铁氧化物形态转化与土壤Cd活性演变的耦合关系.结果表明CW管理可显著降低土壤Cd有效性,淹水93 d后DTPA-Cd降低了17.7%~39.2%,CW联合Fe或G-Fe施用显著提升了对土壤Cd的钝化效果,其中G-Fe短期钝化效果好,淹水14 d后DTPA-Cd的含量较对照降低24.3%,而Fe则可持续钝化土壤Cd,淹水93 d后DTPA-Cd的降幅为39.2%,干湿交替下施用铁氧化物则对土壤Cd无钝化效应.相关性分析表明,无定形铁（Fe_o）的形成（P<0.01）是驱动土壤Cd有效性变化的主要原因：CW使土壤pH逐渐降低并稳定在7.4左右,且土壤保持还原状态,促进了土壤铁氧化物由结晶态（Fe_c）向Fe_o转化,进而促使Cd由可交换态向铁锰结合态转化,并最终导致Cd有效性降低;CW联合Fe、G-Fe施用显著提升了Fe_o的含量和比例,从而强化了对土壤Cd的钝化效果.研究结果揭示了水分管理联合铁氧化物施用对稻田土壤Cd活性的调控效应和机制,为Cd污染稻田土壤安全利用中水分优化管理和含铁钝化剂施用提供了科学依据.     

外加芘在2种水稻土及其团聚体培养中的老化及其可浸提性和生物有效性的变化

老化是指有机污染物进入土壤后,随着时间的增加,其生物有效性、毒性和可浸提性会逐渐下降的现象.采用室内培养法研究了外加多环芳烃芘在2种水稻土乌栅土(潜育型水稻土)和黄泥土(潴育型水稻土)及其不同粒组团聚体中的老化现象,并采用二氯甲烷提取和蚯蚓吸收试验比较了培养老化后外加多环芳烃芘的可浸提性和生物有效性的变化.结果表明,培养90d后芘的浸提率下降了15%~23%,蚯蚓的摄食量也下降了37%~67%,说明外加有机污染物进入水稻土后发生了显著的老化现象,从而降低了其环境移动性和生物有效性.但不同粒径团聚体中老化程度没有差异,不过对蚯蚓的生物有效性存在差异.因此,并不能根据土壤中有机污染物的含量来预测其环境风险和生物有效性.     

湖南省典型地区水田土壤锑和砷元素纵向迁移行为分析

为探讨锑(Sb)和砷(As)在土壤中的纵向迁移行为及其差异,采集湖南省典型地区水田土壤20个剖面共100个样品,对水田土壤中Sb和As的含量、垂直分布特征及其纵向迁移行为差异进行研究,为湖南省水田土壤环境影响评价和污染防控以及进一步探寻Sb和As环境行为和来源提供科学依据。结果表明：水田土壤Sb和As含量分别为1.61±1.79 mg/kg和13.48±6.57 mg/kg; Sb在表层土壤富集,Sb随深度的增加含量逐渐下降,As在土壤剖面中累积明显,随深度的增加含量逐渐上升。两者相比,As元素在水田土壤周期性氧化还原过程中淋溶释放更强烈,其纵向迁移能力也更强。Sb和As在土壤中表现不同氧化还原性质是影响其纵向迁移行为的主要因素,土壤理化性质及成土母质也在一定程度上影响了Sb、As的纵向迁移。     

土壤中铜的形态及其转化

本文报告了使用连续提取方法研究加铜培育的黄棕壤、水稻土、红壤、砖红壤中铜的形态,并初步考察了土壤酸度、氧化还原状况等因素对铜形态的影响,对铜在不同矿物之间结合形态的转化进行了模拟。     

Arsenic release from microbial reduction of scorodite in the presence of electron shuttle in flooded soil

Scorodite (FeAsO₄·H₂O) is a common arsenic-bearing (As-bearing) iron mineral in nearsurface environments that could immobilize or store As in a bound state.In flooded soils,microbe induced Fe(Ⅲ) or As(Ⅴ) reduction can increase the mobility and bioavailability of As.Additionally,humic substances can act as electron shuttles to promote this process.The dynamics of As release and diversity of putative As(Ⅴ)-reducing bacteria during scorodite reduction have yet to be investigat...     

An evaluation of the bioavailability and bioaccumulation of selected metals occurring in a wetland area on the volcanic island of Guam, Western Pacific Ocean

This initial research examined the presence, distribution and bioavailability of Cu, Cr, Ni, Mn and Fe in a wetland area of southern Guam. The research sites are within an area covered with saporite, a soil type derived from volcanic deposits on the island. Leaf tissue of Pandanus tectorius was extracted and analysed to determine the bioaccumulation of the target metals. Metal accumulation at sites considered aerobic and anaerobic was investigated together with an attempt to correlate actual accumulation of the target metals in the plant tissue with a recognised bioavailability indicator, in this case, three step sequential extraction scheme. Manganese was found to be accumulated in relatively high concentrations and to a lesser extent Cu was also accumulated. Chromium, Ni and Fe however exhibited very low accumulation factors. Accumulation of Mn in particular was significantly a ected by aerobic conditions whereas the converse e ect was experienced by Cu. Significant correlation between various steps of a Sequential Extraction Scheme and actual accumulation was not achieved although the degree of aerobic conditions at each site and soil pH did a ect concentrations of metals extracted by di ering steps of SES. Results obtained suggest that further research in the area should be undertaken using di erent plant species and tissues.     

Migration and transformation of Sb are affected by Mn(III/IV) associated with lepidocrocite originating from Fe(II) oxidation

Antimony (Sb) is a recognized priority pollutant with toxicity that is influenced by its migration and transformation processes. Oxidation of Fe(II) to Fe(III) oxides, which is a common phenomenon in the environment, is often accompanied by the formation of Mn(III/IV) and might affect the fate of Sb. In this study, incorporated Mn(III) and sorbed/precipitated Mn(III/IV) associated with lepidocrocite were prepared by adding Mn(II) during and after Fe(II) oxidation, respectively, and the effects of these Mn species on Sb fate were investigated. Our results indicated that the association of these Mn species with lepidocrocite obviously enhanced Sb(III) oxidation to Sb(V), while concomitantly inhibiting Sb sorption due to the lower sorption capacity of lepidocrocite for Sb(V) than Sb(III). Additionally, Mn oxide equivalents increased in the presence of Sb, indicating that Sb oxidation by Mn(III/IV) associated with lepidocrocite was a continuous recycling process in which Mn(II) released from Mn(III/IV) reduction by Sb(III) could be oxidized to Mn(III/IV) again. This recycling process was favorable for effective Sb(III) oxidation. Moreover, Sb(V) generated from Sb(III) oxidation by Mn(III/IV) enhanced Mn(II) sorption at the beginning of the process, and thus favored Mn(III/IV) formation, which could further promote Sb(III) oxidation to Sb(V). Overall, this study elucidated the effects of Mn(III/IV) associated with lepidocrocite arisen from Fe(II) oxidation on Sb migration and transformation and revealed the underlying reaction mechanisms, contributing to a better understanding of the geochemical dynamics of Sb.     

稻田微氧层和还原层土壤有机碳矿化对氮素添加的响应

田间条件下,淹水稻田由于上覆水中溶解氧的扩散作用,使其表层土壤存在约1 cm厚的微氧层,这个特殊层次中碳氮转化的特征尚未明晰.以亚热带典型稻田土壤为对象,采用100 d室内模拟培养试验,结合¹³C稳定同位素示踪和磷脂脂肪酸(PLFA)分析技术,研究稻田土壤微氧层(0～1 cm)和还原层(1～5 cm)外源新鲜有机碳(¹³C-水稻秸秆)和原有土壤有机碳矿化对氮肥施用[(NH₄)₂SO₄]的响应规律及其微生物过程.结果表明,氮素添加使土壤总CO₂和¹³C-CO₂累积排放量分别提高11.4%和12.3%;培养结束时,氮素添加下还原层比微氧层土壤总有机碳含量和¹³C回收率分别降低2.4%和9.2%.培养前期(5 d),氮素添加提高还原层微生物总PLFAs,且细菌和真菌PLFAs响应一致,但对微氧层微生物丰度无显著影响;氮素添加对微氧层和还原层总¹³C-PLFAs丰度均无显著影响...     

水稻土中硫酸二乙酯分解产生含硫气体的研究

为了探讨水稻土中含硫气体产生和释放的途径，在室内培养条件下，测定了南京水稻土中含硫气体的释放。结果从该淹水土壤中测出3种含硫气体；硫化氢（H2S），羰基硫（COS）和二甲基硫（DMS）气体。当土壤中加入硫酸二乙酯后，不仅上述3种气体的释放量增加了，而且还明显测出甲硫醇（CH3SH）和二硫化碳（CS2）。据此推测，水稻土中硫酸二乙酯的分解可能是CH3SH、CS2、COS、H2S、DMS5种气体产生释放的来源之一。在好氧条件（普通大气）下：（1）H2S和COS的释放量低于厌氧条件（充氮）。（2）CS2和CH3SH的释放量高于厌氧条件。（3）DMS的释放量不受空气中氧气含量的影响。分析了培养前后土壤pH和Eh的变化和影响。     

水稻田土壤甲烷厌氧氧化在整个甲烷氧化中的贡献率

对黄松土水田土壤中>0.02mm的颗粒和<0.02mm的颗粒按不同比例组合成的土壤、不同绝对含水量的黄松土水田土壤、不同温育时段的水田土壤和长期定位不同施肥的水稻田土壤中的甲烷好氧氧化和厌氧氧化的速率的检测结果进行比较,结果相当一致,不仅证实了水稻田土壤甲烷厌氧氧化过程的存在,而且表明水田土壤中的甲烷厌氧氧化活性远较甲烷好氧氧化活性要低,如以两者的氧化活性作为对甲烷氧化的贡献来计,则甲烷厌氧氧化的贡献率一般都在整个甲烷氧化的10%以下.但在水田土壤被水淹没的情形下,由于土壤厌氧条件的形成和甲烷扩散受阻,甲烷厌氧氧化的速率明显超过好氧氧化的速率,甲烷厌氧氧化在整个甲烷氧化中的贡献率可到达30%以上.长期施肥对于水稻田土壤的甲烷好氧氧化活性和甲烷排放通量影响显著,而对甲烷的厌氧氧化活性有影响但未达到显著水平.长期施肥处理的土壤中甲烷好氧氧化活性在(9.072～41.088)×10^-6mol·(d·g)^-1之间,而甲烷厌氧氧化活性仅在(0.325～0.671)×10^-6mol·(d·g)^-1之间,仅及甲烷好氧氧化活性的1.31%～4.43%,占整个甲烷氧化的1.3%～4.14%.     

Effect of moisture regime on the redistribution of heavy metals in paddy soil

Sequential extraction procedure was applied to assess the dynamics of solid-phase transformation of added Cu, Pb, Cd, and Hg in a typical Chinese paddy soil incubated under three moisture regimes (75% field capacity, wetting-drying cycle, and flooding). The heavy metals spiked in the soil were time-dependently transferred from the easily extractable fraction (the exchangeable fraction) into less labile fractions (Fe-Mn oxide- and organic matter-bound fractions), and thus reduced lability of the metals. No significant changes were found for the carbonate-bound and residual fractions of the heavy metals in the soil during the whole incubation. Change rate of the mobility factor (MF), a proportion of weakly bound fractions (exchangeable and carbonate-bound) in the total metal of soil, reflected the transformation rate of metal speciation from the labile fractions toward stable fractions. It was found that soil moisture regime did not change the direction and pathways of transformation of metal speciation, but it significantly a ected the transformation rate. In general, the paddy soil under flooding regime had higher metal reactivity compared with 75% field capacity and wetting-drying cycle regimes, resulting in the more complete movement of metals toward stable fractions. This might be related to the increased pH, precipitation of the metals with sulfides and higher concentration of amorphous Fe oxides under submerged condition.     

Antimony transformation and mobilization from stibnite by an antimonite oxidizing bacterium Bosea sp. AS-1

Soils and waters are heavily contaminated by antimony in Xikuangshan（XKS） mine area.It is widely accepted that oxidative dissolution of sulfide minerals and aqueous dissolution are the most prevalent geochemical mechanisms for the release of Sb to the environment.Bosea sp. AS-1 is an antimonite-oxidizer isolated from the mine slag in Xikuangshan Sb mine. Whole genome sequencing revealed the presence of multiple sulfur-oxidizing genes,antimony（Sb） metabolism genes and carbon fixation genes in AS-...     

Anaerobic oxidation of arsenite by bioreduced nontronite

The redox state of arsenic controls its toxicity and mobility in the subsurface environment. Understanding the redox reactions of arsenic is particularly important for addressing its environmental behavior. Clay minerals are commonly found in soils and sediments, which are an important host for arsenic. However, limited information is known about the redox reactions between arsenic and structural Fe in clay minerals. In this study, the redox reactions between As(III)/As(V) and structural Fe in nontronite NAu-2 were investigated in anaerobic batch experiments. No oxidation of As(III) was observed by the native Fe(III)-NAu-2. Interestingly, anaerobic oxidation of As(III) to As(V) occurred after Fe(III)-NAu-2 was bioreduced. Furthermore, anaerobic oxidization of As(III) by bioreduced NAu-2 was significantly promoted by increasing Fe(III)-NAu-2 reduction extent and initial As(III) concentrations. Bioreduction of Fe(III)-NAu-2 generated reactive Fe(III)-O-Fe(II) moieties at clay mineral edge sites. Anaerobic oxidation of As(III) was attributed to the strong oxidation activity of the structural Fe(III) within the Fe(III)-O-Fe(II) moieties. Our results provide a potential explanation for the presence of As(V) in the anaerobic subsurface environment. Our findings also highlight that clay minerals can play an important role in controlling the redox state of arsenic in the natural environment.     

鄱阳湖水体悬浮物反硝化潜力模拟研究

以鄱阳湖为对象,采用乙炔抑制法,分别模拟了厌氧和好氧状态下的悬浮物反硝化潜力和过程,结果表明,厌氧和好氧状态下水体悬浮物均能够产生明显的反硝化作用.受乙炔抑制,其反硝化产物N2O的浓度累积随时间呈“慢-快-慢”的节律,浓度累积曲线符合逻辑斯谛模型(P<0.01).拟合结果显示:悬浮物浓度为30g/L时,厌氧培养条件下快增期反硝化速率达到(81.76±10.37)μmolN/(L·d),好氧环境下为(14.12±2.31)μmolN/(L·d).CO2浓度累积曲线同样符合逻辑斯谛模型,但好氧条件下CO2浓度累积极值较高,约为厌氧条件下的5倍,表明好氧条件下好氧呼吸占更大的比例.水体悬浮物反硝化潜力与悬浮物浓度有关,相同悬浮物浓度下,好氧培养水体悬浮物反硝化潜力较厌氧培养弱,且达到累积极值的时间更长,水体溶解氧一定程度上抑制了悬浮物反硝化作用.依据好氧培养的试验结果,估算得到鄱阳湖悬浮物全年反硝化导致的氮素净损失为1010t,约占鄱阳湖氮素年输入量的0.74%和鄱阳湖沉积物反硝化氮去除量的14%,鄱阳湖水体悬浮物反硝化在氮素净去除中起到一定作用.     

Dissimilatory Fe(III) reduction characteristics of paddy soil extract cultures treated with glucose or fatty acids

Dissimilatory Fe(Ⅲ) reduction is a universal process with irreplaceable biological and environmental importance in anoxic environments. Our knowledge about Fe(Ⅲ) reduction predominantly comes from pure cultures of dissimilatory Fe(Ⅲ) reducing bacteria (DFRB). The objective of this study was to compare the effects of glucose and a selection of short organic acids (citrate, succinate, pyruvate, propionate, acetate, and formate) on Fe(Ⅲ) reduction via the anaerobic culture of three paddy soil solutions with Fe(OH)3 as the sole electron acceptor. The results showed significant differences in Fe(Ⅲ) reduction among the three paddy soil solutions and suhstrate types. Bacteria from the Sichuan paddy soil responded quickly to substrate supply and showed higher Fe(Ⅲ) reducing activity than the other two soil types. Bacteria in the Jiangxi paddy soil culture solution could not use propionate as a source of electrons for Fe(Ⅲ) reduction. Similarly, bacteria in the Jilin paddy soil culture could not use succinate effectively. Pyruvate was readily used by cultures from all three paddy soil solutions, thus indicating that there were some similarities in substrate utilization by bacteria for Fe(Ⅲ) reduction. The use of glucose and citrate as substrate for dissimilatory Fe(Ⅲ) reduction indicates important ecological implications for this type of anoxic respiration.     

两株高效好氧反硝化细菌的分离鉴定及其脱氮效率

从水稻土和活性污泥中分离到两株可以在好氧条件下进行反硝化作用的细菌ZW23和ZW27.通过对这两株细菌的形态观察和生理生化特征,以及16S rDNA序列测定认为菌株ZW23和ZW27分别是假单胞菌属类产碱杆菌(Pseudomonas pseudoalcaligenes)和假单胞菌属门多萨菌(Pseudomonas mendocina).好氧培养条件下,在初始氮源约为280.00mg·L-1的反应体系中,两株细菌在12h内均引起体系中总氮显著下降,削减率分别达66.43%和65.54%,其余总氮几乎全部转化为内源氮.脱氮速率分别达到约21.72mg·L-1·h-1和22.31 mg·L-1·h-1,比现已分离出的兼性好氧反硝化细菌的脱氮速率要快得多.反应过程中没有检测到亚硝态氮和氨态氮的积累.菌株ZW23和ZW27是两株典型的高效兼性好氧反硝化细菌,具有重要的应用价值.     

Dssimilatory Fe(Ⅲ) reduction characteristics of paddy soil extract cultures treated with glucose or fatty acids

Dissimilatory Fe(Ⅲ) reduction is a universal process with irreplaceable biological and environmental importance in anoxic environments. Our knowledge about Fe(Ⅲ) reduction predominantly comes from pure cultures of dissimilatory Fe(Ⅲ) reducing bacteria (DFRB). The objective of this study was to compare the effects of glucose and a selection of short organic acids (citrate, succinate, pyruvate, propionate, acetate, and formate) on Fe(Ⅲ) reduction via the anaerobic culture of three paddy soil solutions with Fe(OH)3 as the sole electron acceptor. The results showed significant differences in Fe(Ⅲ) reduction among the three paddy soil solutions and suhstrate types. Bacteria from the Sichuan paddy soil responded quickly to substrate supply and showed higher Fe(Ⅲ) reducing activity than the other two soil types. Bacteria in the Jiangxi paddy soil culture solution could not use propionate as a source of electrons for Fe(Ⅲ) reduction. Similarly, bacteria in the Jilin paddy soil culture could not use succinate effectively. Pyruvate was readily used by cultures from all three paddy soil solutions, thus indicating that there were some similarities in substrate utilization by bacteria for Fe(Ⅲ) reduction. The use of glucose and citrate as substrate for dissimilatory Fe(Ⅲ) reduction indicates important ecological implications for this type of anoxic respiration.     

水稻土中甲硫氨酸分解释放挥发性含硫气体的影响因素

为了探讨水稻土中含硫气体产生和释放的途径 ,在室内培养条件下 ,测定了南京水稻土中含硫气体的释放 .从该淹水土壤中测出 3种含硫气体 ;羰基硫 (COS)、二甲基硫 (DMS)和少量硫化氢 (H₂S)气体 .当土壤中加入甲硫氨酸后 ,DMS气体的释放量有了明显增加 ,此外还有大量甲硫醇 (CH₃SH)和二甲基二硫 (DMDS)气体测出 .而 COS在好氧条件 (普通大气淹水 )下的释放量明显增加 ,在厌氧条件 (充氮淹水 )下的释放量变化不明显 ;只有 H₂S的释放量几乎没变 .这些结果表明 ,甲硫氨酸的分解可能是 COS、DMS、CH₃SH和 DMDS的产生源之一 ,且释放含硫气体的种类明显不同于胱氨酸和半胱氨酸 .在好氧 (普通大气 )条件下 ,DMDS和 CH₃SH的释放量低于厌氧情况 (充氮气 )下的释放量 ,DMS则高于厌氧条件下的释放量 .这表明 ,水稻土中甲硫氨酸分解产生 DMDS和 CH3SH需较强的还原条件 ,产生这 2种气体的微生物需要严格的厌氧条件 .产生 DMS的微生物则比前者需要高一些的含氧量 .土壤 pH值和含水量及光照对甲硫氨酸分解释放含硫气体均有影响 .各含硫气体在持水率 50%、普通大气、光照条件下的释放量明显高于无光照条件下的释放量 .