旱作褐土中铁氧化物的厌氧还原动力学特征

异化铁还原是厌氧环境中有机物降解的重要微生物过程,不仅影响Cr、U等无机污染物在环境中的迁移,还与CH4、N2O、H2S等温室气体的释放关系密切.本文选择7个旱作褐土样品,采用泥浆厌氧恒温培养的方法,研究了旱作褐土中氧化铁的厌氧还原特征,结果表明旱作褐土在淹水条件下可以发生铁氧化物的异化还原,其还原潜势介于4.47～5.95 mg g-1之间,还原速率常数介于0.15 ～0.27 d-1之间.褐土中部分晶态铁氧化物可在这一过程中被还原,游离铁的平均还原率为41.95％.经过40 d厌氧培养后,99.26％的NO3-和88.82％的SO42-被还原.还原过程的速率常数κ、Vmax、Tmax随着土壤有机碳含量增加而增加,还原潜势与土壤SO42-含量呈显著负相关关系.     

褐土中铁的氧化还原与碳素转化

采用泥浆厌氧恒温培养的方法,研究了光照对旱作褐土中氧化铁的厌氧还原过程的影响,探讨了土壤中铁氧化物的还原-氧化过程与碳素转化的关系。结果表明,旱作褐土中游离铁氧化物的55.31%可在厌氧避光条件下发生还原,厌氧光照条件下游离铁氧化物的还原率最大仅为38.90%,还原产生的Fe(Ⅱ)可能被蓝细菌中的鱼腥蓝细菌属光合过程产生的氧氧化,40 d培养后其游离铁氧化物还原率低至7.95%。厌氧避光条件下培养40 d后土壤中水溶性总碳、无机碳含量分别增加了69%和246%,厌氧光照条件下水溶性总碳和无机碳则呈现先增加后降低的趋势,40 d培养后仅为反应前的47%和70%。水溶性总碳和无机碳含量分别与Fe(T)和Fe(Ⅱ)含量呈极显著线性正相关关系。     

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。     

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.     

水稻土中铁氧化还原循环的光照水分效应

水稻土中铁的氧化还原循环与CO2和CH4排放关系密切。采用恒温厌氧培养试验分别在黑暗、光照条件下研究了不同水分状况对水稻土中铁氧化还原过程、水溶性碳含量及CO2和CH4排放的影响。结果表明,水分和光照是调控土壤铁氧化还原过程及其耦合的碳转化过程的关键环境因子。避光时增加含水量缩短铁还原最大速率出现的时间,促进CH4排放。光照条件下含水量小于50%时增加含水量可促进亚铁的再氧化,大于50%时则抑制了亚铁的再氧化。避光时增加含水量可增加体系的水溶性无机碳含量(WSIC),WSIC与CH4的排放存在显著正相关关系。光照可显著降低体系的WSIC,降低幅度随含水量的增加而增大。在含水量25%～200%范围内,光照可使CO2和CH4排放量分别降低95.80%和96.08%。     

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。     

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。     

不同种植年限大棚菜田土壤水溶性盐分的变化特征

采集新乡市不同种植年限大棚菜田、露天菜田及大田土壤共计160个样品,调查分析水溶性盐总量、各盐分离子的变化及土壤pH值。结果表明,大棚土壤在连续种植不同年限后,水溶性盐总量上升幅度与种植年限呈极显著相关(r=0.92**);K+、Na+、Cl-、NO2-、NO3-、SO24-含量与种植年限呈正相关,而Ca2+、Mg2+、HCO3-含量变化与种植年限呈负相关;土壤pH值降低幅度与种植年限呈极显著相关;K+、Na+、Cl-、NO3-、SO42-的含量均与土壤水溶性盐总量呈极显著相关。新乡市大棚菜田土壤中Cl-、NO2-、NO3-含量与pH值变化存在极显著负相关;SO42-含量与pH值变化存在显著负相关;HCO3-与土壤pH值变化存在极显著正相关。新乡市大棚菜田阳离子以K+、Na+为主,阴离子主要以Cl-、NO2-、NO3-、SO42-为主;不同种植年限对大棚土壤盐渍化和酸化有极显著影响,K+、Na+、Cl-、NO2-、NO3-、SO42-则是造成土壤盐渍化的重要原因,Cl-、NO2-、NO3-、SO42-是造成土壤酸化的重要原因。     

外源氮对滨海围垦稻田土壤N2O还原速率的影响机制研究

滨海湿地位于海陆交错带,具有很高的生态价值;近百年来的人类活动深刻改变了湿地土壤的N2O排放通量。为探明外源氮对滨海围垦稻田土壤N2O还原潜力的影响,选取长江口崇明岛东滩芦苇湿地和围垦区不同围垦年限(19、27、51、86年)的稻田土壤为研究对象,添加不同形态外源氮后研究湿地土壤N2O还原速率的变化情况。结果表明,无氮添加条件下芦苇湿地土壤N2O还原速率最高,为36.6 μg·g-1·d-1,相比围垦19年稻田土壤提高了103%;添加硝态氮条件下围垦86年稻田土壤N2O还原速率最高,是围垦19年稻田土壤的3.9倍,添加铵态氮和硝态氮条件下稻田土壤N2O还原速率年增长率分别为0.37和0.69 μg·g-1·d-1·年-1,比无氮处理分别高出140%和343%。对于同一样地土壤而言,外源氮输入对其N2O还原速率的影响效应各异。其中,与无氮对照相比,添加铵态氮条件下芦苇湿地土壤的N2O还原速率降低了32%,而添加硝态氮条件下围垦86年稻田土壤的N2O还原速率增加了91%。相关性分析发现,稻田N2O还原速率与土壤有机碳、总氮呈显著正相关,而与电导率、SO42-呈显著负相关。因此,在围垦区水稻生产中,不同形态氮肥施用对稻田土壤的N2O还原过程产生重要的影响效应。     

亚热带土壤亚铁与厌氧反硝化

本文就亚热带土壤亚铁参与反硝化的可能性进行了探讨。研究结果表明:厌氧还原条件下加入KNO3的处理中,Fe2+浓度随培养时间延长而下降,且Fe2+浓度的降低和NO3–-N浓度的降低呈显著正相关。预培养结束后的亚铁浓度(In-Fe2+)和厌氧培养期间Fe2+浓度降低速率与反硝化势表征指标k、b、v7,以及与无定形铁氧化物(活性铁)含量的显著正相关性初步证明,活性铁通过不同价态铁离子(Fe2+和Fe3+)之间的转化,参与了反硝化的电子传递过程。当有机碳等电子供体受限时,Fe2+可作为电子供体参与反硝化还原NO3–-N。这一结果表明,NO3–-N作为电子受体参与厌氧条件下Fe2+氧化成Fe3+的反应可能在铁氧化物含量丰富的亚热带土壤中普遍存在。     

Light inhibition of carbon mineralization associated with iron redox processes in calcareous paddy soil

Purpose

The iron redox cycle is closely tied to the fate of carbon in terrestrial ecosystems, especially paddy soils. Varies diurnally and seasonally, light—the crucial environmental factor—may be a fundamental factor elucidating temporal and spatial variabilities of carbon-containing gases emission. The role of sunlight in the iron-mediated carbon cycle, however, has not been fully elucidated. We conduct this study to test the role of light in the iron-mediated carbon cycling.

Materials and methods

In this study, we conducted anaerobic incubation experiments of a calcareous paddy soil in serum vials under alternating dark and light conditions. The dynamic evolution of the carbon and iron contents was evaluated by measuring the CO₂, CH₄, and O₂ concentrations in the headspace of the vials, as well as the water-soluble inorganic carbon, microbial biomass carbon, and HCl-extractable ferrous iron contents in soil slurries. We also analyzed the soil microbial community structure by high-throughput 16S rRNA gene sequencing.

Results and discussion

The results highlighted the positive correlation between carbon mineralization and ferric iron reduction under dark conditions. Under light conditions, however, ferrous iron was oxidized by the O₂ generated via oxygenic photosynthesis of phototrophic bacteria such as Cyanobacteria, along with a decreased production of CO₂, CH₄, and water-soluble inorganic carbon. The abundance of Cyanobacteria positively correlated to O₂ levels and MBC content significantly. Light-induced periodic variations in the redox conditions facilitated carbon fixation in microbial biomass and up to 31.79 μmol g^?1 carbon was sequestrated during 30 days light incubation.

Conclusions

These results indicate that light inhibits the emission of carbon-containing greenhouse gases associated with the iron redox cycle in calcareous paddy soil. Assimilation of inorganic carbon by phototrophs may responsible for the inhibition of carbon mineralization. Our study suggests that procedures allowing more light to reach the soil surface, for instance, reducing the planting density, may mitigate greenhouse gas emissions and promote carbon sequestration in paddy soils.

     

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。     

Denitrification characteristics of subtropical soils in China affected by soil parent material and land use

Forty‐five soil samples were collected from rice paddy land (R), tea garden land (T), forestland (F), brush land (B), and upland (U) in Jiangxi province, a subtropical region of China. These soils were derived from Quaternary red earth (Q), Tertiary red sandstone (S), and granite (G). Their denitrification capacities were determined after treatment with 200 mg NO₃⁻‐N kg⁻¹ soil by measuring changes in NO₃⁻‐N content during a 28‐day anaerobic incubation under N₂ gas in the headspace, at 30°C. The subtropical soils studied here were characterized by generally small denitrification capacities, ranging from no denitrification capacity to complete disappearance of added NO₃⁻‐N within 11 days of incubation. With few exceptions, NO₃⁻‐N reduction with incubation time followed a first‐order relationship with reaction constants of 0 – 0.271 day⁻¹, but the data could be simulated better by a logarithmic relationship. Thus, denitrification capacity was determined by the reaction constant of the first‐order reaction, the slope of the logarithmic relationship, and the averaged NO₃⁻‐N reduction rate in the first 7 days of anaerobic incubation (ranging from 0 to 28.5 mg kg⁻¹day⁻¹), and was significantly larger in the soils derived from G than from Q and S for all land uses except for rice paddy land. Soil organic carbon and nitrogen availability are the key factors that determine differences in denitrification capacity among the three soil parent materials. Rice cultivation significantly promoted denitrification capacity compared with the other four land uses and masked the effect of soil parent materials on denitrification capacity. This is most likely due to increases in organic carbon and total N content in the soil, which promoted the population and biological activities of microorganisms which are able to respire anaerobically when the rice soil is flooded. Neither the increased pH of upland soil caused by the addition of lime for upland crop production, nor the decreased pH of the tea garden soil by the acidification effect of tea plants altered soil denitrification capacity. Our results suggest that land use and management practices favour soil carbon and/or nitrogen accumulation and anaerobic microorganism activities enhance soil denitrification capacity.     

不同开垦年限水稻土还原性物质含量及其分布

以辽宁省各地棕壤型、草甸土型水稻土为研究对象,探讨了不同开垦年限的棕壤型、草甸土型水稻土中还原性物质总量、活性还原性物质、络合态铁、水溶性亚铁、水溶性亚锰含量及其分布状况。结果表明,不同开垦年限供试水稻土随着开垦年限增加表层还原性物质总量、活性还原性物质、络合态铁、水溶性亚铁和水溶性亚锰含量明显增加,且均随土壤深度增加而减少,其积累主要集中在土壤上层。土壤络合态铁与还原性物质总量和活性还原性物质均呈极显著正相关,表层土壤有机质对铁、锰的络合减少了铁、锰元素向剖面下层的迁移数量。开垦10年以上,水稻土耕层中还原性物质就明显积累,直至60年,其积累量仍不断增加,因此生产上必须采取措施抑制水稻土中还原性物质的累积。     

Microbial Reduction of Iodate

The different oxidation species of iodine have markedly different sorption properties. Hence, changes in iodine redox states can greatly affect the mobility of iodine in the environment. Although a major microbial role has been suggested in the past to account for these redox changes, little has been done to elucidate the responsible microorganisms or the mechanisms involved. In the work presented here, direct microbial reduction of iodate was demonstrated with anaerobic cell suspensions of the sulfate reducing bacterium Desulfovibrio desulfuricans which reduced 96% of an initial 100 µM iodate to iodide at pH 7 in 30 mM NaHCO₃ buffer, whereas anaerobic cell suspensions of the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens were unable to reduce iodate in 30 mM NaHCO₃ buffer (pH 7). Both D. desulfuricans and S. putrefaciens were able to reduce iodate at pH 7 in 10 mM HEPES buffer. Both soluble ferrous iron and sulfide, as well as iron monosulfide (FeS) were shown to abiologically reduce iodate to iodide. These results indicate that ferric iron and/or sulfate reducing bacteria are capable of mediating both direct, enzymatic, as well as abiotic reduction of iodate in natural anaerobic environments. These microbially mediated reactions may be important factors in the fate and transport of¹²⁹ I in natural systems.     

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe – DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe²⁺) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide‐rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well‐drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.     

控制光照条件下添加SO_4~（2-）对水稻土中Fe（Ⅲ）还原的影响

为探讨光照和硫酸盐对微生物Fe（Ⅲ）还原的影响,在光照和光暗转换条件下,采用厌氧泥浆恒温培育方法分别在四川和天津2种石灰性水稻土中添加不同浓度硫酸盐溶液（20、50、800mmol·kg-1）,培养过程中定期测定土壤泥浆的Fe（Ⅱ）、叶绿素a含量和pH值。结果表明：光照条件下,添加20mmol·kg-1和50mmol·kg-1硫酸盐能减缓光照培养中因为蓝细菌光合作用放氧引起的Fe（Ⅱ）氧化反应,Fe（Ⅱ）氧化反应启动时间与对照处理相比延迟3～7d;蓝细菌在光照培养5d后开始迅速繁殖生长,叶绿素a增长速率表现为随硫酸盐浓度增大而增加,其最终含量在四川和天津水稻土中分别为20mg·kg-1和16mg·kg-1;800mmol·kg-1硫酸盐则完全抑制了Fe（Ⅱ）的重新氧化,且在整个培养周期中没有发现光合细菌存在。pH值变化呈现先微弱下降后升高的趋势,但始终维持在弱碱性范围内。当由光照转入避光培养后,Fe（Ⅱ）累积量又重新回升,增长速率表现为对照〉20mmol·kg-1S处理〉50mmol·kg-1S处理。表明光照并非直接影响铁还原微生物,而是通过光合微生物繁殖间接影响铁还原过程。