Lignin decomposition is sustained under fluctuating redox conditions in humid tropical forest soils

Lignin mineralization represents a critical flux in the terrestrial carbon (C) cycle, yet little is known about mechanisms and environmental factors controlling lignin breakdown in mineral soils. Hypoxia is thought to suppress lignin decomposition, yet potential effects of oxygen (O₂) variability in surface soils have not been explored. Here, we tested the impact of redox fluctuations on lignin breakdown in humid tropical forest soils during ten‐week laboratory incubations. We used synthetic lignins labeled with ¹³C in either of two positions (aromatic methoxyl or propyl side chain C_β) to provide highly sensitive and specific measures of lignin mineralization seldom employed in soils. Four‐day redox fluctuations increased the percent contribution of methoxyl C to soil respiration relative to static aerobic conditions, and cumulative methoxyl‐C mineralization was statistically equivalent under static aerobic and fluctuating redox conditions despite lower soil respiration in the latter treatment. Contributions of the less labile lignin C_β to soil respiration were equivalent in the static aerobic and fluctuating redox treatments during periods of O₂ exposure, and tended to decline during periods of O₂ limitation, resulting in lower cumulative C_β mineralization in the fluctuating treatment relative to the static aerobic treatment. However, cumulative mineralization of both the C_β‐ and methoxyl‐labeled lignins nearly doubled in the fluctuating treatment relative to the static aerobic treatment when total lignin mineralization was normalized to total O₂ exposure. Oxygen fluctuations are thought to be suboptimal for canonical lignin‐degrading microorganisms. However, O₂ fluctuations drove substantial Fe reduction and oxidation, and reactive oxygen species generated during abiotic Fe oxidation might explain the elevated contribution of lignin to C mineralization. Iron redox cycling provides a potential mechanism for lignin depletion in soil organic matter. Couplings between soil moisture, redox fluctuations, and lignin breakdown provide a potential link between climate variability and the biochemical composition of soil organic matter.     

湿地林土壤的Fe2+,Eh及pH值的变化

通过在不同含水量 (田间持水量的 6 0 % :对照处理 ;田间持水量的 2 5 0 % :淹水处理 )和不同温度 (2 0℃ ,2 5℃ ,30℃ )条件下的室内培养 ,对江苏省里下河地区池杉湿地林土壤的二价铁离子 (Fe2 )浓度 ,氧化还原电位 (Eh)及 p H值进行了研究。结果表明 ,与对照处理相比 ,淹水土壤的 p H值和 Fe2 浓度明显提高 (P<0 .0 1) ,而 Eh值则明显降低 (P<0 .0 1)。在淹水条件下 ,高温处理的土壤 p H值和 Fe2 浓度明显高于低温处理土壤 (P<0 .0 1) ,Eh值则相反。研究表明 ,土壤 Eh值与 p H值之间存在着密切的 3次方程式关系 (P<0 .0 0 1)。就里下河地区湿地林土壤而言 ,Eh值下降至 2 0 0 m V以下时 ,才会有大量的铁元素被还原为Fe2 。     

水稻土中铁氧化物对产甲烷古菌群落结构的影响

产甲烷菌广泛分布在淹水水稻土等各种厌氧环境中,在全球气候变化、碳循环和能源等领域都发挥着重要的作用。研究发现,厌氧条件下,水稻土中铁氧化物的生物还原会抑制产甲烷菌的甲烷合成作用。然而,目前关于铁氧化物对产甲烷菌群落结构的影响报道较少。通过泥浆厌氧培养实验,向采集的水稻土中添加甲酸盐作为甲烷合成的底物(Control,CK处理),并设置添加水铁矿作为体系中唯一电子受体的处理组(Ferrihydrite,Fh处理)。培养结束后,与CK相比,添加水铁矿显著降低了古菌在总微生物群落中的占比,但对古菌群落的物种多样性和均一度没有显著影响;且两组处理中优势种均为操作分类单元(Operational taxonomic unit,OTU)2056和OTU 911(76%—80%)。这说明碳源相同时,产甲烷菌的群落结构不受铁氧化物的影响。本研究为探索土壤中微生物铁还原与碳循环耦合的分子机制奠定基础。     

Aluminium,boron and molybdenum availability and uptake by rice in acid sulfate soils

Although Al toxicity is believed to be a problem in acid sulfate soils cropped to rice (Oryza, sativa L.), little is known about the behavior of other trace metals such as B and Mo in these soils. The objectives of this study were to measure the availability of Al, B, and Mo in these soils, to determine what governs the availability of these metals and to investigate the relationships between metal availability and uptake by rice. Metal availability and uptake by rice were evaluated in 134 flooded acid sulfate soils in the Central Plains region of Thailand and in a growth chamber study using 50 of the same soils. Soil and plant metal analyses were conducted at the panicle differentiation stage of growth in both studies and in the soil prior to transplanting in the growth chamber study. Metal activities were determined with GEOCHEM. The mineral phases believed to be governing Al³⁺ activities were jurbanite under low pH conditions and amorphous Al(OH)₃ at high pH. The Al chemistry is believed to be intimately linked to the redox-pH cycle, which is driven by the monsoonal climate. Mortality of rice associated with Al toxicity was observed under field and growth chamber conditions. Interference in P uptake and/or assimilation was believed to be the mechanism of Al toxicity. Activities of B(OH) ₄ ^– and B(OH) ₃ ⁰ were found to be highly correlated to pH and ionic strength, respectively, with the latter being the dominant B ion found in these soils. Activities of MoO ₄ ^2– were positively correlated to pH and appeared to be controlled by wulfenite. Leaf Mo contents were found to be positively correlated with MoO ₄ ^2– activity.     

酸性硫酸盐土中的硫及其形态演变探讨

研究了酸性硫酸盐土中S及其形态演变。结果表明,酸性硫酸盐土S含量高,以无机态为主;S积累和S形态演变与酸性硫酸盐土形成、发育与利用密切相关。与红树林盐渍沼泽土(潜在酸性硫酸盐土)比较,酸性硫酸盐水稻土黄钾铁矾S含量较高,但FeS2含量较低。酸性硫酸盐水稻土S形态剖面分布明显,其氧化层的黄钾铁矾S含量较高,pH值较低;其还原层的FeS2含量较高。防治酸害是酸性硫酸盐土持续利用要解决的关键问题。     

Effect of submergence on availability of certain plant nutrients in three Ultisol catenas

Soil samples from surface and sub-surface horizons in the well-drained and poorly-drained members of three soil catenas were incubated under submergence or at field capacity to study the effects of these incubation conditions and prior natural drainage on the solubility of four plant micro-nutrients. Iron, Mn, Zn and Cu were extracted by water using a 11 water:soil ratio. The four micronutrient metals were also extracted by DTPA solutions buffered at either pH 5.3 or pH 7.3 to compare the effectiveness of these two extractants under these incubation conditions with acid soils. Generally the extractability of the nutrients was much affected by the horizon (A, E or B) with A horizons having the greatest amounts of all nutrients and undergoing greater changes in water- and DTPA-extractability during incubation. Soil drainage class (wellvs. poorly drained) had few effects. Incubation moisture regime had major effects on water extractable Fe and Mn with lesser effects on Zn and Cu. Submerged soils generally had the greatest levels of water extractable nutrients, though rice uptake did not reflect this. DTPA at pH 5.3 extracted 2 to 3 times as much Fe, Mn, Zn and Cu as did DTPA at pH 7.3 and about 50 to 100 times as much as did water. Correlations between DTPA extractable nutrients and rice uptake were significant only for Fe and Cu and declined during incubation. The changes in all variables during incubation were complex, being related to soil properties such as organic matter content, pH and mineralogy as well as to incubation conditions.     

A semi-empirical model of methane emission from flooded rice paddy soils

Reliable regional or global estimates of methane emissions from flooded rice paddy soils depend on an examination of methodologies by which the current high variability in the estimates might be reduced. One potential way to do this is the development of predictive models. With an understanding of the processes of methane production, oxidation and emission, a semi-empirical model, focused on the contributions of rice plants to the processes and also the influence of environmental factors, was developed to predict methane emission from flooded rice fields. A simplified version of the model was also derived to predict methane emission in a more practical manner. In this study, it was hypothesized that methanogenic substrates are primarily derived from rice plants and added organic matter. Rates of methane production in flooded rice soils are determined by the availability of methanogenic substrates and the influence of environmental factors. Rice growth and development control the fraction of methane emitted. The amount of methane transported from the soil to the atmosphere is determined by the rates of production and the emitted fraction. Model validation against observations from single rice growing seasons in Texas, USA demonstrated that the seasonal variation of methane emission is regulated by rice growth and development. A further validation of the model against measurements from irrigated rice paddy soils in various regions of the world, including Italy, China, Indonesia, Philippines and the United States, suggests that methane emission can be predicted from rice net productivity, cultivar character, soil texture and temperature, and organic matter amendments.     

Resuspension studies in cylindrical microcosms: Effects of stirring velocity on the dynamics of redox sensitive elements in a coastal sediment

Effects of resuspension on the release of dissolved, redox sensitive elements (Fe, Mn) was studied in cylindrical microcosms. Effects from changing water stirring velocity in sediment pools were evaluated through measurements of pore water profiles of dissolved Mn, Fe and redox potential. Mn was a good natural marker to follow such effects. At current velocities below the threshold velocity for resuspension (37 cm s-1), Mn release rates to overlying water were 100 times higher compared to steady-state values. Pulse increases in Mn concentration were the result of convective currents inside flow chambers. These results were strongly supported by measurements of Eh profiles in the sediment pore water. Furthermore, impacts from increasing stirring velocity were found down to 1.9 cm depth below the resuspended layer of sediment.     

Influence of redox potential on phosphate-uptake by sediments in two sub-tropical eutrophic lakes

Biogeochemical reactions in shallow eutrophic lakes areaffected bythe changes in redox potential (Eh) as bottom sedimentsundergotemporal resuspension and settling. The stability of varioussediment P fractions and kinetics of P-uptake were evaluatedfortwo sub-tropical lakes (Lake Apopka and Lake Okeechobee,Florida)using sediment suspensions in closed systems maintained atvariousEh levels ranging from –235 to 555 mV. Redox potential hadminimal effect on the stability of NaOH-P (Fe-/Al-bound P plusmoderately resistant organic P) and HCl-P (Ca-/Mg-P) fractionsinLake Apopka sediments. Increases in ortho-P and NH₄Cl-P(loosely-bound P plus labile organic P) concentrations wereobserved in highly reduced (Eh=–225 mV) Apopkasediments.Phosphate solubility diagrams and mineral equilibriacalculationssuggest that P-uptake by Apopka bottom sediments at elevated Pconcentrations (ortho-P110 M) was due toformationof Ca-P compounds and/or co-precipitation of P withCaCO₃. Incontrast, the ortho-P concentrations for Lake Okeechobeebottomsediments increased exponentially with decreasing Eh. Thequantityof NaOH-P fractions for these sediments decreased withdecreasingEh, suggesting the release of Fe- and Mn-bound P intosolution.Phosphate-uptake by Okeechobee bottom sediments (pH 7.5,ambient)followed first order kinetics, yielding a rate constant (k)of 0.51±0.05 h^-1. Unlike that of Apopka, the mudsediments in Lake Okeechobee have strong affinity for P ineitheraerobic or anaerobic conditions. Results suggest that even incalcareous systems, Fe and Al, when present in highconcentrations(as in the case of Lake Okeechobee), are actively involved inregulating P-uptake and geochemistry.     

Online control of cell culture redox potential prevents antibody interchain disulfide bond reduction

The phenomenon of monoclonal antibody (mAb) interchain disulfide bond reduction during manufacturing processes continues to be a focus of the biotechnology industry due to the potential for loss of product, increased complexity of purification processes, and reduced stability of the drug product. We hypothesized that antibody reduction can be mitigated by controlling the cell culture redox potential and subsequently established a threshold redox potential above which the mAb remained intact and below which there were significant and highly variable amounts of reduced mAb. Using this knowledge, we developed three control schemes to prevent mAb reduction in the bioreactor by controlling the cell culture redox potential via an online redox probe. These control methodologies functioned by increasing the concentration of dissolved oxygen (DO), copper (II) (Cu), or both DO and Cu to maintain the redox potential above the threshold value. Using these methods, we were able to demonstrate successful control of antibody reduction. Importantly, the redox control strategies did not significantly impact the cell growth, viability, mAb production, or product quality attributes including aggregates, C-terminal lysine, high mannose, deamidation, and glycation. Our results demonstrate that controlling the cell culture redox potential is a simple and effective method to prevent mAb reduction.     

Effect of soil salinity on the electro-chemical and chemical kinetics of some plant nutrients in submerged soils

Summary The electro-chemical and chemical kinetics of six California rice soils were significantly influenced by the presence of salts up to an EC of 9 mmhos/cm in saturation extract (EC_e). Subsamples of each soil salinity treatment were incubated for periods up to 10 weeks after flooding. Most of the changes in Eh and pH values took place in the first 3–4 weeks after submergence. Salinity decreased pH values, but slightly increased the redox-potential. Both ammonification and nitrate reduction were significantly decreased, by increasing soil salinity. Salinity up to 9 mmhos/cm did not affect levels of Bray and Kurtz extractable P, but increased the water extractable Ca, Mg, K and Mn. In DTPA extract, salinity in incubated soils had no effect on Zn in 4 soils, but it decreased Fe in acid and neutral soils. Possible explanations for the electro-chemical and chemical kinetic changes due to flooding and salinity are discussed.     

Redox conditions and iron chemistry in highland swamps of Burundi

Iron toxicity is a major soil constraint to rice (Oryza sative L.) cropping in highland swamps of Burundi. These swamps have a wide range of carbon content. This study aims at determining the influence of carbon content and redox conditions on the release of iron from Fe-bearing minerals. The pe-pH pairs distribution and oxalate dissolution data strongly suggest a control of Fe²⁺ activity by a pool of poorly crystallized ferric oxides. Flooding results in high values of KCl-extractable Fe (up to 22 cmolc kg^-1) being released from that pool. The iron release is positively correlated with organic matter. On the other hand, highly organic, peaty soils have large CEC and their adsorbed Fe fraction remains relatively low. As the exchangeable Fe fraction has previously been correlated with Fe toxicity to rice, we may conclude that very organic (> 25% C), peaty soils exhibit a lower Fe toxicity hazard than soils with intermediate carbon content (10–25%).     

Evidence for rapid microscale bacterial redox cycling of iron in circumneutral environments

The potential for microscale bacterial Fe redox cycling was investigated in microcosms containing ferrihydrite-coated sand and a coculture of a lithotrophic Fe(II)-oxidizing bacterium (strain TW2) and a dissimilatory Fe(III)-reducing bacterium (Shewanella alga strain BrY). The Fe(II)-oxidizing organism was isolated from freshwater wetland surface sediments which are characterized by steep gradients of dissolved O₂ and high concentrations of dissolved and solid-phase Fe(II) within mm of the sediment–water interface, and which support comparable numbers (10⁵–10⁶ mL⁻¹) of culturable Fe(II)-oxidizing and Fe(III)-reducing reducing. The coculture systems showed minimal Fe(III) oxide accumulation at the sand-water interface, despite intensive O₂ input from the atmosphere and measurable dissolved O₂ to a depth of 2 mm below the sand–water interface. In contrast, a distinct layer of oxide precipitates formed in systems containing Fe(III)-reducing bacteria alone. Examination of materials from the cocultures by fluorescence in situ hybridization indicated close physical juxtapositioning of Fe(II)-oxidizing and Fe(III)-reducing bacteria in the upper few mm of sand. Our results indicate that Fe(II)-oxidizing bacteria have the potential to enhance the coupling of Fe(II) oxidation and Fe(III) reduction at redox interfaces, thereby promoting rapid microscale cycling of Fe. This revised version was published online in August 2006 with corrections to the Cover Date.     

Utility of culture redox potential for identifying metabolic state changes in amino acid fermentation

We investigated the relationship of dissolved oxygen and culture redox potential (CRP) on amino acid production. Corynebacterium glutamicum ATCC 14296 was used for all experiments. The fermentation can be divided into a growth phase and a production phase. Our results indicate that in order to get higher amino acid production, a lower oxygen supply during the exponential phase is favored. A higher oxygen supply rate appears to be necessary during the production phase. Culture redox potential (CRP) was used to monitor the fermentation. CRP readings were observed to drop to a characteristic minimum value as the metabolic state changed from a growth to production phase. This was evidenced by the commencement of amino acid production and a simultaneous uptake of lactate. Upon lactate exhaustion, the CRP increased abruptly. At the same time, maximal amino acid yields were observed. By the use of minimum CRP as an indication of metabolic phase changes, the agitation rate was changed to increase oxygen supply during the production phase. This significantly increased amino acid production. These results show that culture redox potential measurements can be used to monitor and optimize amino acid production by process manipulation.     

Factors influencing uranium reduction and solubility in evaporation pond sediments

Evaporation ponds in the San Joaquin Valley (SJV), CA, USA that are used for the disposal of irrigation drainage waters, contain elevated levels of U that may be a threat to pond wildlife. The ponds support euryhaline algae, which become incorporated in the sediments as depositional organic matter (OM) – facilitating reducing conditions. Our earlier studies have shown that U in one SJV sediment was primarily present as the highly soluble U(VI) species (as opposed to the less soluble U(IV) species), despite the presence of volatile sulfides. In this research, we investigated the effects of native pond algae (Chlorella) and potential reducing agents on U redox chemistry of SJV pond sediments. San Joaquin Valley pond sediments were equilibrated with natural and synthetic pond inlet waters containing approximately 10 mg U(VI) L-1 to which reducing agents (acetate, sucrose, and alfalfa shoot) were added. The equilibrations were done under oxic (Chlorella only) and O2-limiting conditions (remaining treatments). Sediments were examined for changes in average U oxidation state by X-ray near- edge absorption structure (XANES) spectroscopy and U concentration by ICP-MS.For the alfalfa treatments, a 95 percent loss of U(VI) from solution, the presence of sulfides, and results from the XANES studies suggest U(VI) was reduced to U(IV). Upon exposure to air, the precipitated U was readily oxidized, suggesting the reduced U is susceptible to oxidation. Much less reduction of U(VI) was observed in the other 3 treatments and the solid phase was dominated by U(VI) as in the natural pond sediments. A second study was conducted with pond sediment-water suspensions to determine the effects of controlled PCO2 and low redox potential (Eh) on U solubility. These suspensions were equilibrated at 0.22 and 5.26 kPa PCO2 and allowed to free-drift from an oxidized to a reduced state. At high Eh and high PCO2, dissolved U concentrations were higher than in the low PCO2 systems due to greater complexation with CO3. Dissolved U concentrations decreased only under intense sulfate reducing conditions, even at low Eh conditions. It appears that U reduction occurred by chemical reduction via sulfide ion. Comparing the XANES data of the pond sediments with the laboratory-produced solids we conclude that biosorption by algae and bacteria is the dominant mechanism depositing U in the sediments. Even though there are organisms that can use U(VI) as a terminal electron acceptor, we found that sulfate reduction was preferred in these high- SO4 waters. Mixed oxidation state U-solids were preferentially formed in the pond sediments and in the lab except under intense SO4 reducing conditions.     

Scale‐up of citric acid fermentation by redox potential control

To obtain high citric acid productivity in Aspergillus niger fermentation on beet molasses substrate, a certain redox potential profile with two maxima (260 and 280 mV) and two minima (180 and 80 mV) must be maintained. The most effective regulation of redox potential is by regulation of aeration and agitation. It has been shown that control of redox potential by aeration and agitation is a most successful method for scale‐up from 10‐L laboratory scale to the 100‐ and 1000‐L pilot‐plant scale, even in geometrically dissimilar stirred‐tank reactors. © 1999 John Wiley & Sons, Inc. Biotechnol Bioeng 64: 552–557, 1999.     

酸性硫酸盐土中硫的形态含量分布和酸化特征

对广东省台山市南部滨海平原酸性硫酸盐土(以下简称ASS)S的形态、含量、分布和酸化特征的研究表明,ASS全硫含量高达0.615%,比咸田高2～6倍,比砂泥田高3～9倍;其硫以无机硫为主,占全硫的82.3%～90.4%,其中,黄铁矿硫的含量最高,占全硫的30.3%～46.2%,黄铁矿硫在剖面中的分布与全硫含量同步。ASS硫含量的空间变异和剖面内部的分异十分显着。ASS发育过程中,适合黄铁矿累积的环境及其持续时间与地形地貌(山)的关系十分密切。ASS的主要致酸物质是黄铁矿的氧化,酸化的ASS的pH一般在5.5以下,最低达2.83.ASS可氧化总酸度一般比实际总酸度高2～3倍,潜在的环境风险极.     

Effect of potassium nutrition of rice on rhizosphere redox status

With four soils differing in K supplying power and with four rice cultivars (Oryza sativa L.) differing in K uptake kinetic parameters, the relationship between K fertilizer application and soil redox status in rhizosphere and; the distribution of ferrous iron and other toxic substances on the root surface and in the rhizosphere; and the effect of K supply on uptake of reduced iron by rice plants have been studied.The results show that K application on K-deficient soils reduced the content of active reducing substances and ferrous iron in the soil, raised the soil redox potential in the rhizosphere, increased the Eh value of rice roots and lowered the content of iron in the rice plants. These effects of K varied with different rice cultivars. When no K fertilizer was applied, active reducing substances and ferrous iron in rhizosphere soils were decreased more by the rice cultivars absorbing K strongly (e.g. Shanyou 64) than by cultivars absorbing K weakly (e.g. Zhongguo 91). Therefore, the diminution of the toxic substances by K application in the weakly K-absorbing cultivars was more significant.The observation of a rhizobox separated by a nylon screen showed that appreciably more iron oxides, compared with the control, were deposited at or adjacent to the root surfaces of the rice plant supplied with K fertilizer, fully demonstrating the relationship between K nutrition and the total oxidizing power of rice plants. According to the distribution of active reducing substances and ferrous iron, the oxidizing range of the rice root extended in K application treatment a few centimeters away from the root plane. K application to rice affected the soil redox status in rhizosphere in many ways. The main effect was an increase of the oxidizing power of the rice root. As a result, the value of soil Eh was increased, the contents of active reducing substances and ferrous iron were lowered, as well as the number of oxygen consuming microorganisms.     

Effect of temperature on rice growth in nutrient solution and in acid sulphate soils from Vietnam

Climatic and soil factors are limiting rice growth in many countries. In Vietnam, a steep gradient of temperature is observed from the North to the South, and acid sulphate soils are frequently devoted to rice production. We have therefore attempted to understand how temperature affects rice growth in these problem soils, by comparison with rice grown in nutrient solution. Two varieties of rice, IR64 and X2, were cultivated in phytotrons at 19/21°C and 28/32°C (day/night) for 56 days, after 3 weeks preculture in optimal conditions. Two soils from the Mekong Delta were tested. Parallel with the growing experiments, these two soils were incubated in order to monitor redox potential (E _h ), pH, soluble Al and Fe, soluble, and available P. Tillering retardation at 20°C compared to 30°C was similar in nutrient solutions and in soils. The effect of temperature on increasing plant biomass was more marked in solutions than in soils. The P concentrations in roots and shoots were higher at 20°C than at 30°C, to such an extent that detrimental effect was suspected in plants grown in solution at the lowest temperature. The translocation of Fe from roots to shoots was stimulated upon rising temperature, both in solutions and in soils. This led to plant death on the most acid soil at 30°C. Indeed, the accumulation of Fe in plants grown on soils was enhanced by the release of Fe²⁺ due to reduction of Fe(III)-oxihydroxides. Severe reducing conditions were created at 30°C: redox potential (E _h ) dropped rapidly down to about 0 V. At 20°C, E _h did not drop below about 0.2 V, which is a value well in the range of Fe(III)/Fe(II) buffering. Parallel to E _h drop, pH increased up to about 6–6.5 at 30°C, which prevented plants from Al toxicity, even in the most acid soil. Phosphate behavior was obviously related to Fe-dynamics: more reducing conditions at 30°C have resulted in enhancement of available P, especially in the most acid soil.     

Is nitrate reduced to ammonium in waterlogged acid sulfate soil?

Summary A study of transformations of added nitrate nitrogen in an acid sulfate soil under waterlogged conditions indicated that chemical reduction of NO₃–N to NH₄–N is effected by high concentrations of ferrous iron, released in the soil following flooding and reduction of ferric to ferrous iron.