豫西旱作褐土剖面土壤的氧化铁还原与亚铁氧化特征

土壤铁氧化物的氧化还原过程不仅与重金属的生物有效性和有机污染物降解转化关系密切,也与旱地土壤肥力关系密切,因而备受关注。然剖面土壤耕层以下是否存在铁氧化物的还原、氧化过程,其特征如何尚未可知。本文采用恒温厌氧泥浆培养的方法研究旱地褐土剖面中铁的氧化还原特征。结果表明,旱地土壤剖面0~100cm中均存在铁的厌氧还原过程,还原潜势、最大速率均随剖面深度增加而显著降低;剖面0~80cm土层中均存在光合型Fe(II)氧化现象,0~40cm土层Fe(II)氧化量和氧化速率显著高于40~80cm。剖面的铁氧化还原过程不仅受有机碳含量影响,也受N、K等养分元素的影响。结果可为拓展对铁氧化还原微生物生境的认识、深入理解土壤剖面中铁氧化还原过程提供依据。     

淹水对石灰性土壤无机磷形态转化的影响

  【目的】  磷肥施入土壤后大部分转化为与铁氧化物关系密切的Fe-P和O-P,而淹水后土壤中铁的氧化还原过程可能影响与铁氧化物结合的磷的形态及有效性的变化。研究不同施磷处理下淹水土壤Fe (II) 、无机磷组分等的变化,以期明确淹水后土壤无机磷形态及磷有效性变化及其与铁氧化还原过程的关系。  【方法】  用不施磷土壤 (P0) 和连续6年施用P 180 kg/hm2的土壤 (P180) 进行室内模拟培养试验。将土壤装于西林瓶内,加水模拟淹水条件,西林瓶密封后,分别在避光或者光照条件下,于 (30 ± 1)℃恒温培养40天。测定供试土壤以及淹水培养土壤中的速效磷、无机磷以及不同形态无机磷组分含量,测定培养过程Fe (II) 的动态变化,以探讨磷形态转化与铁氧化还原过程的关系。  【结果】  施用磷肥显著增加土壤中的速效磷含量和无机磷总量,P0处理土壤速效磷含量为 (7.65 ± 1.65) mg/kg,P180处理土壤速效磷含量高达 (33.5 ± 2.01) mg/kg。施入土壤中的磷只有很小部分以Ca₂-P存在,主要以Ca₁₀-P、Ca₈-P、Al-P和Fe-P形态存在。避光淹水培养后,土壤速效磷含量增加,P0和P180处理土壤速效磷含量的增量分别为8.44、2.95 mg/kg。淹水培养降低了土壤Ca₈-P含量,提升了Fe-P、O-P、Al-P含量。光照和避光条件下P180处理土壤中Ca₈-P含量分别降低106.8、156.2 mg/kg,Fe-P含量分别增加23.4、47.0 mg/kg,O-P含量分别增加64.1、92.9 mg/kg,Al-P含量分别增加38.8、34.7 mg/kg,避光时Ca₈-P降幅以及Fe-P和O-P的增量均大于光照条件下。避光条件下,铁还原量和还原最大速率与Ca₈-P变化量之间存在显著负相关关系,与Fe-P、O-P增量之间存在显著正相关关系。  【结论】  淹水条件下,石灰性土壤中的Fe (Ⅲ) 还原形成Fe (Ⅱ) 和Fe (Ⅲ) 混合物,增加了铁氧化物的比表面积和磷吸附点,可促进Ca₈-P向O-P、Fe-P和Al-P转化。光照降低了Fe (Ⅲ) 的还原量,可能是Ca₈-P向O-P、Fe-P和Al-P转化率低的原因之一。     

黄河中下游湿地土壤铁还原氧化过程的温度敏感性

土壤中铁的还原氧化过程因与重金属的生物有效性、有机污染的降解及含碳温室气体排放等环境问题关系密切而备受关注。温度可能通过影响铁还原菌或者Fe(II)氧化菌的活性、底物的生物可用性等而影响铁的还原过程。以黄河中下游地区新乡市原阳大米产区的湿地土壤为样品,利用厌氧泥浆控温培养试验方法研究了黄河中下游湿地中土壤铁还原氧化过程的温度敏感性。结果表明:黄河中下游湿地土壤铁的还原容量在16~31℃范围内不受温度影响,但在16~40℃之间升高温度可显著增加铁还原过程的最大速率、速率常数,亦可缩短最大速率出现的时间。铁还原的温度敏感系数介于1.18~3.05之间,且随温度上升而升高。光照可降低铁还原的温度敏感性,平均降幅39.0%。光照时土壤中Fe(II)氧化对温度不敏感。光照条件和铁氧化物的种类和数量可能是影响土壤有机碳矿化的因素之一。研究结果对于深入理解土壤铁的生物地球化学循环及其与土壤呼吸的关系具有重要意义。     

厌氧条件下水稻土中铁硫循环与光照的关系

采用恒温厌氧培养试验研究了黑暗、光照、黑暗转光照和光照转黑暗条件下水稻土中硫酸盐还原和铁的氧化还原.结果表明光照是调控土壤铁、硫生物化学转化的一个关键环境因素,光照对铁、硫还原的抑制作用体现在5d后.黑暗培养30 d土壤游离铁的70.07％可被还原;光照培养时35.60 μmol g-1Fe(Ⅲ)先被还原后被氧化,30 d后仍有32.70％的游离铁被还原,转黑暗后被氧化的铁可再次被还原.黑暗时土壤中99.50％的水溶性硫酸盐(WSS)在可5d内被还原,光照培养30 d有42.73％的WSS被还原.水溶性无机碳(WSIC)与体系中Fe(Ⅱ)和WSS之间存在显著相关关系.无光照转换时水溶性有机碳(WSOC)与Fe(Ⅱ)和WSS的转化速率存在显著正相关关系;黑暗条件下WSOC＞ 7.89 μmol g-1时,体系中Fe(Ⅲ)和WSS还原;光照条件下WSOC＞ 8.27 μmol g-1时体系中Fe(Ⅲ)还原,WSOC＞8.40μmol g-1时WSS还原.     

pH与石灰性水稻土铁氧化还原过程的关系

光照和pH是调控土壤铁氧化物厌氧生物氧化还原的关键环境因素。本文采用恒温厌氧培养试验研究了黑暗、光照条件下土壤pH的变化及pH对铁氧化还原的影响,探索了pH与Fe(II)和水溶性无机碳的关系。结果表明,光照可改变土壤厌氧培养过程中pH的变化趋势,避光培养时土壤pH呈降低趋势,光照时呈先降低后增加趋势。pH介于4~9之间均可发生铁的还原反应,pH=7时还原量最大,128.5μmol g-1,pH调至4和9均可抑制避光条件下的铁还原。光照条件下pH 6~8时可发生Fe(II)的再氧化,控制初始pH为7时可使其再氧化量增加77.13%,达49.17μmol g-1。厌氧培养过程中Fe(II)与水溶性无机碳在避光时存在显著线性正相关关系,pH与Fe(II)和水溶性无机碳之间均存在显著线性负相关关系。     

淹水还原条件下红壤中葡萄糖及腐殖酸对铁锰形态的影响

通过设置不同的葡萄糖/腐殖酸配比模拟还原性土壤体系,考察长期(约74 d)淹水培养过程中铁锰元素在土壤溶液/矿物相中的分布形态演变。结果表明:在淹水培养初期,葡萄糖的添加可以促进铁锰离子的还原溶出,同时土壤中可交换态和酸可提取态铁、以及可交换态锰的含量也会随之增加;而腐殖酸的添加则会促进土壤中可氧化态铁/锰含量的升高。随着培养时间的增加,铁锰离子浓度及各个土壤提取形态的铁锰含量大多呈现降低趋势,铁锰元素逐渐转化成提取性更低的矿物形态。因此,淹水环境中铁锰还原溶出-分布形态演变受到土壤中有机物质种类和含量的显著影响,呈现出不同的金属移动性和生物有效性。     

三峡库区消落带典型土壤厌氧呼吸对铁还原及磷释放的影响

分别采集三峡库区开县和涪陵消落带土壤,进行室内模拟淹水实验,研究淹水土壤有机质分解对Fe(Ⅲ)还原行为及磷释放的影响。结果表明,淹水过程中土壤磷向上覆水体迁移,引起上覆水体总磷含量先增加后降低最后趋于平衡。上覆水体总磷的变化与底泥中有效磷呈极显著负相关(p0.01),且有效磷与无机磷各形态的相关性分析表明磷释放的主要来源是Ca8-P、Al-P和Fe-P。淹水形成的厌氧还原环境导致铁氧化物的还原,无定形铁生成,且二价铁与有效磷呈显著正相关(p0.05),说明三价铁的还原促进P的释放。淹水过程中,土壤CO2和CH4产生揭示有机质的分解过程,CO2/CH4的比值变化反映淹水土壤无机电子受体的消耗情况,解释Fe3+的还原过程,其与二价铁和有效磷的相关性分析证实有机质分解与铁的还原及磷的释放显著相关,说明有机质分解促进了铁的还原,并进一步促进磷的释放。     

消落带土壤铁的形态变化及其对有效磷的影响

Fe3+还原为Fe2+的过程中会增加磷酸铁的溶解,影响磷的化学行为及有效性。本文采用室内模拟试验研究了三峡库区消落带土壤铁的形态变化及其对有效磷的影响。消落带旱地和水田土壤经淹水和落水处理后,活性铁、水溶性铁增加,其他各形态铁变化较小。旱地土壤在不同的有机质和淹水落水处理下,其活化铁、游离铁、络合铁、水溶性亚铁、和交换性亚铁均为淹水处理高于落水处理,其中活性铁在各处理间呈现出显著性差异,其他则各处理间差异均未达到显著性水平;水田下层活性铁高于上层,且落水处理间呈显著差异。氧化铁及亚铁之间总处于不断的相互转化中,活性铁、络合铁和有机质正相关。旱地土壤中的有效磷各处理间差异显著,水田有效磷淹水处理高于落水处理。     

宁夏引黄灌区干湿交替过程中土壤pH的动态变化及影响因素

地处干旱半干旱区的黄灌区干湿交替过程中引起土壤环境因素的周期性变化,从而影响农田生态系统关键过程。通过连续测定黄河上游宁夏引黄灌区稻田在灌溉淹水和落干过程中的土壤pH,研究在水稻生育期内表层土壤pH在高频次灌溉排水干湿交替过程中的变化规律。结果表明:在灌水之后淹水过程中,表层土壤pH升高;相反在淹水之后落干过程中表层土壤pH降低;但在最后一次灌水之后,经过长时间的落干烤田过程,土壤pH随表层土壤表层盐分积累过程逐渐升高。土壤电导率(EC)与土壤pH在灌溉淹水和落干过程中具有相同的变化趋势,具有显著正相关性(p0.05),土壤氧化还原电位(Eh)与pH呈极显著负线性相关(p0.01),而灌溉量、施肥量、降水、地表5 cm土壤温度对表层土壤pH的影响均不显著。     

亚硫酸盐对三价砷在土壤中氧化固定作用机制研究

土壤中硫的氧化还原过程对砷的释放与固定具有重要的影响,但有关硫形态对三价砷(As(Ⅲ))的氧化过程的机制与贡献并不清楚.基于此,本研究以土壤中普遍存在的硫转化中间产物亚硫酸盐为研究对象,研究其对土壤中As(Ⅲ)的氧化固定机制.结果表明,亚硫酸盐显著促进了土壤中As(Ⅲ)的氧化,与对照组相比,10 h内土壤悬液中As(Ⅲ...     

外源铜和镍在土壤中的化学形态及其老化研究

采用连续提取法测定了外源铜和镍进入田间土壤后的化学形态分布,比较研究了这2种重金属在3种不同类型土壤(红壤,水稻土和潮土)中随老化时间的形态转化和分布.结果表明,外源铜以残留态(40%～60%)和EDTA可提取态(40%)为主;随老化时间,EDTA可提取态、易还原锰结合态及铁铝氧化态向残留态转化;外源镍在酸性红壤中以可交换态(40%)和残留态(30%～50%)为主,在中性水稻土中以EDTA可提取态(30%)和残留态(30%～50%)为主,在碱性潮土中以铁铝氧化态(20%)和残留态(40%)为主.随老化时间,水溶态、可交换态、EDTA可提取态等向残留态转化.土壤pH较低时水溶态和可交换态含量较高,但是同时随老化时间的降低量也明显;pH较高时有利于易还原锰结合态和有机质结合态的转化.     

三江平原白浆土中Fe、Mn、Cu和Zn生物有效性的研究

在三江平原上,测定 42 个小区中玉米、大豆、小麦籽实 Fe、Mn、Cu 和 Zn 含量和土壤中各形态 Fe、Mn、Cu 和Zn含量.通过相关分析和通径分析,探讨了土壤中各形态Fe、Mn、Cu 和 Zn 的生物有效性,旨在为该地区合理施用微量元素提供科学依据.试验结果表明,玉米、大豆和小麦籽实含 Fe、Mn、Cu 和 Zn 量与土壤中有效态和交换态 Fe、Mn、Cu和Zn含量呈显著或极显著正相关.有机态 Fe、Mn、Cu 和 Zn含量与玉米、大豆和小麦籽实Fe、Mn、Cu 和 Zn含量也有很好的相关关系.交换态对有效态 Fe、Mn、Cu 和 Zn 影响最大,其次是有机质结合态.铁锰氧化物结合态 Fe、Cu 对有效态 Fe、Cu 及碳酸盐结合态 Mn、Zn 对有效态 Mn、Zn 具有一定正效应.而残留态 Fe、Cu 对有效态 Fe、Cu 和铁锰氧化物结合态 Mn 对有效态 Mn 产生负效应.     

亚热带地区土壤硝酸盐异化还原成铵速率的空间差异和驱动因素

土壤硝酸盐异化还原成铵(DNRA)是生态系统土壤氮转化的重要途径，理清环境因素对土壤DNRA速率的影响意义重大。本研究通过收集246项试验观测值采用整合分析方法(Meta-analysis)研究了亚热带地区不同生态系统中DNRA速率的变化范围及其影响因素。结果表明：纬度对亚热带土壤DNRA速率无显著影响；土壤p H、全氮(TN)、SOC/NO₃^–-N、Fe(Ⅱ)、阳离子交换量(CEC)、易氧化有机碳(EOC)、有效磷(AP)、黏粒含量和年平均气温(MAT)的增加均会促进DNRA速率；年平均降水量(MAP)和土壤NH₄⁺-N含量的增加会抑制土壤DNRA速率。此外，环境因子对DNRA速率的影响随生态系统的不同表现出较大差异。结构方程模型分析结果显示，SOC/NO₃^–-N是DNRA主要驱动因素，p H、NH₄⁺-N、MAP和MAT对土壤DNRA也有较大影响。     

Combined impact of pH and organic acids on iron uptake by Caco-2 cells

Previous studies have shown that organic acids have an impact on both Fe(II) and Fe(III) uptake in Caco-2 cell. However, to what extent this effect is correlated with the anion of organic acids per se, or with the resulting decrease in pH, has not yet been clarified. Therefore, we studied the effect of five organic acids (tartaric, succinic, citric, oxalic, and propionic acid) on the absorption of Fe(II) and Fe(III) in Caco-2 cells and compared this with sample solutions without organic acids but set to equivalent pH by HCl. The results showed that the mechanisms behind the enhancing effect of organic acids differed for the two forms of iron. For ferric iron the organic acids promoted uptake both by chelation and by lowering the pH, whereas for ferrous iron the promoting effect was caused only by the lowered pH.     

湖南省主要茶园土壤锌的形态及其有效性

采用野外调查采样分析和田间试验方法研究了湖南省主要茶园生态系统中土壤Zn的形态及其有效性.结果显示:①成土母质明显影响土壤中各种形态Zn的含量,与母质本身的特性有关;②生物 秸秆和秸秆覆盖处理能明显提高茶园土中有效态Zn与有机态Zn的含量,而对其他形态Zn的含量影响不太明显;③土壤中对有效态Zn(AZn)含量影响最大的是交换态Zn(ExZn)与无定形氧化铁结合态Zn(AFeZn),其次为氧化锰结合态Zn(MnOZn)、有机态Zn(OMZn)及晶形氧化铁结合态Zn(CFeZn).     

污灌土壤中氟及硫的形态分布特征

以乌鲁木齐雅马里克山的石灰性土壤为研究对象,采用连续提取法和分步提取法对土壤氟和硫的化学形态进行了测定,研究了不同水质及外源对土壤氟和硫各形态的含量及其分布的影响.结果表明土壤氟主要以残渣态为主,占全氟含量99.5%以上.各形态氟呈残余态氟>有机束缚态氟>水溶态氟>可交换态氟>铁锰结合态氟的趋势.不同水质浇灌后,土壤硫主要以有机硫为主,占71.5%～81.2%.并且呈现有机硫>盐酸可溶性硫>水溶性硫>吸附性硫的趋势.外源物质对土壤理化性质及对土壤中氟和硫各形态有不同程度的影响.土壤氟和硫各形态之间以及各形态与土壤理化性质之间的相关性分析表明,全氟与残余态氟极显著相关.土壤全硫与有机硫之间具有十分密切的相关性.土壤pH值、有机质和CaCO₃含量是影响土壤中氟及硫赋存形态的主要土壤因子.     

Effects of artificial aeration and iron inputs on the transformation of carbon and phosphorus in a typical wetland soil

Purpose

Artificial aeration changes the redox conditions at the soil surface. The introduction of iron (Fe) into wetlands can influence carbon (C) and phosphorus (P) cycling under the fluctuating redox conditions. However, artificial Fe introduced into wetlands is uncommon, and there are no Fe dose guidelines. We compared aerobic and anaerobic conditions to test the hypothesis that Fe addition can, although redox-dependent, affect P forms and the coupling of organic C.

Materials and methods

Twenty-four intact soil cores were collected randomly from a lacustrine wetland of Lake Xiaoxingkai. And representative and homogeneous seedlings of Glyceria spiculosa were collected. The incubation was designed with two treatment factors: Fe/P ratio (5 or 10) and high and low dissolved oxygen (DO) concentrations (>?6 and <?2 mg L^?1, respectively). Four groups with three replicates were separated randomly and labeled as aerobic + plant treatment, anaerobic + plant treatment, and aerobic or anaerobic treatment (control).

Results and discussion

The DO concentrations were stratified, decreasing with soil depth and increasing with time, especially under aerobic conditions. The Eh values generally increased with fluctuations under aerobic conditions. The artificial aeration substantially changed the redox environment at the water–soil interface. Of the total P, 45% was in the reactive Fe-bound P, indicating that Lake Xiaoxingkai had high internal P loading. No significant differences were observed in total Fe, amorphous Fe, and organic C at the soil surface between the two Fe/P ratios; however, a significant difference in free Fe was observed. And soil amorphous Fe was found to be a significant correlation with soil organic C, indicating that iron oxides were related with the soil chemical properties.

Conclusions

After short-term incubation, Fe addition can affect the cycling of major elements in wetlands, although this effect is redox dependent. Excessive Fe doses may result in regional environmental risks, such as eutrophication and C sinks of wetland ecosystems. Large-scale controlled experiments are needed to fully understand the behaviors of soil elements in wetlands.

     

Artificial permeable redox barriers for purification of soil and ground water: A review of publications

Artificial permeable barriers are used for purification of soil- and groundwater from organic (Cl-containing hydrocarbons and Cl-pesticides) and inorganic (heavy metals and nitrates) pollutants. Most of the created redox barriers are based on introducing electron donors—both inorganic (most often, Fe⁰ and Fe(II)) and organic. By their construction type, they are subdivided into one-time filled barriers arranged in trenches and multiple-time filled barriers that use boreholes for reagent injection. Fe⁰ barriers operate not only as reducers but also as sources of newly formed Fe(III) colloids adsorbing elements with permanent and variable valence. Iron sulfides are also used as a reagent, while Fe(II) and S(-I, -II) serve as reducers. Biochemical redox barriers are also applied, in which the activity of natural anaerobic metal-reducing bacteria is stimulated by adding an available organic substance.     

Mobility of sulphate in experimentally acidified soils from Galicia (NW Spain)

Retention of S0₄ ^2? was investigated in Galician soils throughout an intense regime of acidification. Experiments consisted of the addition of an H2SO4 solution (pH 2.7) to columns of 6 soils of contrasting properties over 1, 2, or 5 months. Leachates were obtained continuously throughout the experiment for analysis, and analysis made of the solid fractions after 1, 2 or 5 months. The greatest capacities for retention of S0₄ ^2? were found in soil developed from serpentine and micaschist; the lowest in soils from granite, slate and sandy sediments. The surface horizons, especially those rich in organic matter, displayed low retention of 5042-. The amount of S0₄ ^2? adsorbed throughout the experiment depended on the content of crystalline forms of Fe and with the Fe and Al extracted with dithionite-citrate.The low retention of S0₄ ^2? in the organic horizons and the slightly negative relation with the organic matter suggest an inhibitory effect of the organic matter on the S0₄ ^2? retention process. Results of the study show, that under conditions of moderate acidity, SO₄ ^2? retention occurs in the form of adsorption; in strongly acidic conditions, the precipitation of aluminium-sulphate minerals may provide an additional retention mechanism.     

Reduction processes in forest wetlands: Tracking down heterogeneity of source/sink functions with a combination of methods

Wetlands are considered to be the biggest unknowns regarding the influence of global climate change on element dynamics, so knowledge of processes and conditions controlling sink and source functions of redox processes is crucial. The aim of this study was to investigate the sink/source function of nitrate, Fe, sulfate reduction and methanogenesis of an upland and a lowland fen within a boreal spruce catchment, southern Germany. We used suction cups and anaerobic dialysis chambers for soil solution sampling, FeS probes for the determination of S oxidation potential and stability of anoxic conditions and analysis of the soil solid phase (contents of C, S and Fe species). Both fens had high rates of nitrate reduction and potentially high rates of CH₄ production. The upper few cm of all profiles were oxic with low CH₄ concentrations, suggesting low CH₄ emission rates from the soil, though emission by vascular plants cannot be excluded. Sulfate and Fe reduction processes differed significantly in the fens. The upland fen was characterized by relatively stable anoxic conditions, low Fe contents but high contents of organic S and low C/S ratios. We concluded that the upland fen is an effective sink for sulfate with long-term S storage. In contrast, the lowland fen was characterized by alternating oxidation-reduction cycles with high Fe contents, lower contents of organic S and higher C/S ratios. Thus, even though low sulfate and high Fe concentrations in soil solutions indicated high reduction rates in the lowland fen, long-term storage of S is not likely in this fen. Differences in biogeochemical processes between sites are most likely not associated with hydrology but rather with the role of vascular plants.