泥炭沼泽源酚酸对铁有机复合体的溶解作用及其环境意义

泥炭沼泽是具有全球意义的湿地类型,研究泥炭沼泽源酚酸对铁有机复合体的溶解作用有助于深入了解铁碳耦合地球化学循环过程.以中国东北金川泥炭沼泽为研究对象,提取了泥炭腐殖质,并实验合成了铁有机复合体及一系列的铁氧化物.选择原儿茶酸、咖啡酸和没食子酸等代表性泥炭沼泽源酚酸对铁有机复合体以及铁氧化物等系统开展了不同条件下的溶解试验.结果表明酚酸对无定型的水铁矿和新合成的铁有机复合溶解能力相对较弱,而对结晶态的赤铁矿、针铁矿和老化后的铁有机复合体的溶解能力较强.pH值、酚酸浓度和铁氧化物自身的结构和组成都对铁矿物的溶解作用产生影响.反映了铁有机复合体在酚酸溶液体系中比无机铁氧化物更稳定,这与泥炭沼泽中有机结合态铁比例较高、而普通矿质土壤中结晶态铁氧化物占比更大的事实相吻合.证明了铁有机复合体是泥炭沼泽中影响铁碳循环耦合的关键载体.泥炭沼泽中铁碳作用十分复杂,既能以铁有机络合物形式向海洋等水生生态系统输出大量的溶解性铁,也能通过铁有机复合体的形成促进泥炭沼泽有机碳的保存,进而影响全球铁碳循环耦合,具有重要的生态环境意义.      

大九湖泥炭沼泽源铁有机配合物的络合稳定性及其生态环境意义

为了研究泥炭沼泽源铁有机配合物的络合稳定性,利用pH电位滴定法和荧光淬灭滴定法测定了大九湖泥炭沼泽中不同分子量段的DOM和Fe2+、Fe3+的络合稳定常数.pH电位滴定法结果（4.0~6.1）和荧光淬灭滴定法（1.5~4.1）差异较大,这与高pH条件下OH被脱质子化及Fe2+的氧化有关.相对而言,pH滴定法更适用于探究不同分子量段DOM与铁的络合稳定性,荧光淬灭法不改变样品酸碱条件,更适于研究不同价态铁与DOM的络合稳定性.研究结果表明:DOM与Fe3+的络合稳定常数大于Fe2+,低分子量段（< 3 kDa）的DOM与Fe2+、Fe3+的络合稳定常数更大.泥炭沼泽源铁有机配合物具有较好的络合稳定性,分子量相对较小的DOM与铁的络合能力更强.即便Fe2+氧化为Fe3+,仍能与DOM络合并保持较强的稳定性,这有利于陆源溶解性铁向水生态系统的输出.沼泽源铁有机配合物的络合稳定性还会影响铁的生物可利用性.      

三江平原土地利用变化对水体中铁环境行为的影响

三江平原湿地农田化对铁的赋存形态、迁移转化特征及输出量产生影响。以湿地沼泽水体和稻田水体为研究对象,利用切向超滤技术分离铁的形态,研究土地利用变化前后铁的形态、迁移转化特征的差异。结果表明：湿地农田化后水体中可溶态总铁质量浓度下降16.9%;由于水体pH值的升高,Fe²⁺质量浓度下降56.3%,非溶解态酸性不稳定铁含量显著升高。沼泽水和稻田水在迁移过程中,铁均以络合态铁和酸性不稳定态铁2种形态迁移。沼泽水在迁移过程中Fe2+和络合态铁含量下降,酸性不稳定态铁含量升高,胶体态铁含量变化不大;稻田水在迁移过程中,络合态铁和酸性不稳定态铁含量下降,Fe²⁺和胶体态铁含量较稳定。2种水体铁形态的转化有较大差异：日间沼泽水中非溶解态的酸性不稳定态铁向可溶态铁转化;稻田水体可溶态铁向酸性不稳定态铁转化。     

北方泥炭沼泽中酚类物质释放的热敏感性研究:以英国威尔士地区雨养和矿养泥炭沼泽为例

利用高精度多梯度热培养系统,对英国威尔士地区两类典型的北方泥炭沼泽中酚类物质和溶解有机碳释放的热敏感性进行了为期1年的调查研究.研究结果表明,雨养泥炭沼泽(Bog)酚类物质释放的热敏感性Q10(总酚)月变化为0.92～1.57,而矿养泥炭沼泽(Fen)的月变化范围为0.93～1.30.酚类释放的热敏感性与土壤温度大致呈正相关关系.此外,土壤温度与溶解有机碳释放的热敏感性Q10(DOC)也呈正相关关系.总体上,雨养泥炭沼泽的热敏感性比矿养泥炭沼泽略高.除温度外,水文条件和植被等多种环境因子对酚类物质和溶解有机碳释放的热敏感性也有较大影响.研究结果还表明酚碳热敏感性比值Q10o(总酚)/Q10(DOC)相对稳定,土壤温度的变化对其影响有限.     

中国典型泥炭区现代植物的碳、氧同位素组成及在古环境研究中的意义

本文测定了中国 3个典型泥炭沼泽四川红原、吉林金川和哈尼的现代沼泽植物中的碳、氧同位素组成。吉林金川和哈尼的沼泽在相似的气候和环境条件下发育演化 ,而四川红原的泥炭发育在截然不同的气候条件下。结果表明 ,每个泥炭沼泽现代植物中的碳、氧同位素均有较大的离散度 ,表现为不同营养状况下的成沼植物之间的同位素差异 ;从δ1 3C值来看 ,三个沼泽中的植物均属C3植物 ;红原与金川、哈尼有着明显不同的现代植物稳定氧同位素组成 ,前者更富集1 8O。同一泥炭植物碳、氧同位素的不均一性要求在利用泥炭沉积物恢复过去气候变化方面一定要谨慎。非常有意义的是贫营养泥炭 (高位泥炭 )的成沼植物有着非常接近的同位素组成 ,揭示贫营养型泥炭可能是更为理想的过去全球变化信息档案     

东北哈尼泥炭沉积物磁化率特征及古气候意义

东北哈尼泥炭沼泽位于长白山西麓和龙岗山脉中段,沉积连续,受人为干扰较小,记录了东北地区全新世以来的古气候、古环境演变信息。本研究采用AMS ¹⁴C测年技术建立了哈尼泥炭剖面年代学框架,并对泥炭柱心磁化率进行测定,分析其古气候意义,结合相关气候代用指标,重建了东北地区14 ka B.P.以来的古气候与环境演化历史。结果表明,哈尼泥炭磁化率总体偏低,说明在全新世的大部分时间内哈尼泥炭中的磁性矿物颗粒富集程度较低。哈尼泥炭磁化率记录了区域环境温度和湿度变化信息,较高的磁化率表明气候温暖湿润,较低的磁化率表明气候干燥寒冷。磁化率参数变化响应了全新世多次气候干冷事件,如0.4~0.6 ka B.P.(小冰期)、2.8 ka B.P.、4.3 ka B.P.和8.2 ka B.P.等气候突变事件。哈尼泥炭磁化率不仅反映了东北地区全新世以来的气候变化,而且呼应了全新世的多起气候突变事件。     

准东煤田煤质特征及分布规律

对准东煤田主要勘探区钻孔可采煤层煤质资料分析,从煤岩学和煤化学方面初步总结了煤田的煤质特征和分布规律.煤田煤的化学组成以低灰分、中高挥发份率、低硫、低磷和低氯为特征.煤田东部煤中灰分和镜质组含量相对高于西部.分析准东煤富惰质组和低灰分含量成因,认为可能在泥炭沼泽形成时期,泥炭的生长速率约大于基底沉降速率,泥炭沼泽表面长时期处于沼泽的潜水面之上,具有相对氧化、物源碎屑影响小的高位泥炭沼泽环境条件所致.煤田东部基底沉降速率相对较快,物源碎屑供应相对充分.     

泥炭沼泽的形成和演化

泥炭沼泽的形成可分为水域泥炭沼泽化和陆地泥炭沼泽化两大类。泥炭沼泽可分为低位泥炭沼泽、中位泥炭沼泽和高位泥炭沼泽。由泥炭沼泽发育的内在聚集规律所决定,泥炭沼泽形成后,可由低位泥炭沼泽经中位泥炭沼泽发展至高位泥炭沼泽。研究泥炭沼泽的形成和演化,对剖析泥炭层的生成以及成分和性质,具有实际意义;对分析成泥炭时的古气候和环境乃至构造活动的稳定性,也有一定的意义。      

内蒙古早白垩世五间房含煤盆地煤层煤相分析

内蒙古是我国非常重要的后备煤炭资源基地,煤层大多聚集在白垩纪断陷盆地中,其中,五间房含煤盆地煤炭资源丰富。通过对该盆地东南部3个钻孔57件煤样的煤岩学和煤化学分析,探讨了煤层的煤质特征、煤相类型及其演化规律。研究结果表明:本区煤层以低—中高灰、高挥发分产率和低—特低硫为特征;具有较高的镜/惰比和结构保存指数;煤相类型主要为潮湿森林沼泽相,自下而上,成煤泥炭沼泽覆水程度总体有所加深,上部泥炭沼泽具有水体逐渐加深的水进型特征,下部泥炭沼泽具有水体逐渐变浅的水退型特征。      

大气环境变化的泥炭地质档案

雨养泥炭沼泽是一种重要的泥炭沼泽类型,具有全球广泛分布的特点,其养分补给主要源于大气降水(包括雨、雪和空气尘埃).它是一个记录大气环境变化的积极的信息储备系统,记录有大气输入的海盐气溶胶、沙尘颗粒、酸沉降、重金属和有机污染物等信息.采用地质定年技术将泥炭深度剖面转化到年代坐标上,并结合泥炭生物地球化学指标检测分析,提取...     

Peatland ferruginization during late Quaternary in the Uberaba Plateau (South-Eastern Brazil)

Due to the poor preservation of old peat formations and the limited research developed on them, the contribution of peat oxidation to the global C cycle at geological scales is poorly understood. Iron duricrusts containing abundant well-preserved plant structures have been reported above Humic Gleysols in the Uberaba Plateau (Brazil). We show that the iron accumulation results from an in-situ impregnation of peat, fast enough to preserve the plant structures. The formation of iron oxides results from two processes: precipitation in the pores and C/Fe replacement. The iron duricrusts were probably triggered by oxidation of the peatland following dry climatic events during the last 50 kyr. The large amount of iron dissolved in peatland waters was immobilized contemporaneously with the destruction of organic matter. The oxidation of organic matter from the lower peat, dated at ca 24–27 kyr BP, may have released between 0.08 and 2.26 kg CO₂ m⁻² yr⁻¹ in the atmosphere. These rates are in a good agreement with present-day measurements of CO₂ release from drained peatlands. Although peatland formation has been identified as a significant contributor to the global CO₂ uptake, our findings suggest that natural peatland oxidation should also be considered as a source of atmospheric CO₂ during past climate change.     

Impacts of hydrological conditions on enzyme activities and phenolic concentrations in peatland soil: An experimental simulation

Impacts of hydrological conditions on peatland soil enzyme activities and phenolic concentrations were investigated using peat cores from two typical peatlands, the forest swamp and the marsh in North-east China, under water level manipulation in the laboratory. The results indicated varied impacts of dry and waterlogged conditions on soil enzyme activities, depending on the confounding factors including the peatland types and the variation frequency of hydrological conditions. Carbon-related enzyme activities, phenol oxidase and β-glucosidase, were much higher in the marsh than in the forest swamp. On the contrary, phenolic concentration was measured to be much higher in the latter. Soil enzyme activities and phenolic concentrations were found to vary between the two peatlands, much more remarkably than within the individual peatlands caused by the changes in the water level. The negative relationship or inconspicuous correlation between phenolics and phenol oxidase was found to vary with specific soil conditions. These results implied that the enzyme activities and phenolic concentrations might be related to the developmental stages or the types of wetlands more than to hydrological conditions.     

含水层中砷活化迁移的水化学与DOM三维荧光证据

为了认识高砷地下水中砷活化迁移的生物地球化学机制,对江汉平原地下水氧化还原敏感元素的水化学特征及溶解性有机物(DOM)三维荧光信息进行了研究.水化学研究显示,地下水中的砷与铁的还原和有机质的氧化分解过程有密切关系.水样DOM的三维荧光分析表明,地下水中存在微生物介导下氧化还原过程的反应性有机物组分,其中醌类腐殖质与铁、硫酸盐等的还原反应过程联系紧密.还原、氧化醌类及易降解DOM组分与还原产物、砷的关系进一步显示,砷的活化与微生物介导下的铁氧化物的还原过程联系在一起.在这一过程中,易降解有机物充当电子供体的角色并被消耗,而还原醌与氧化醌则很可能扮演了电子飞行过程中的电子飞行物,"催化"了砷活化的氧化还原过程.      

Revealing forms of iron in river-borne material from major tropical rivers of the Amazon Basin (Brazil)

The present study deals with the direct determination of colloidal forms of iron in river-borne solids from main rivers of the Amazon Basin. The contribution of different forms of colloidal iron have been assessed using ultrafiltration associated with various techniques including electron paramagnetic resonance spectroscopy (EPR), high resolution transmission electron microscopy (HRTEM), and micro proton-induced X ray emission analysis (μPIXE). EPR shows the presence of Fe³⁺ bound to organic matter (Fe³⁺-OM) and colloidal iron oxides. Quantitative estimate of Fe³⁺-OM content in colloidal matter ranges from 0.1 to 1.6 weight % of dried solids and decreases as the pH of the river increases in the range 4 to 6.8. The modeling of the field data with the Equilibrium Calculation of Speciation and Transport (ECOSAT) code demonstrates that this trend is indicative of a geochemical control resulting from the solubility equilibrium of Fe oxyhydroxide phase and Fe binding to organic matter. Combining EPR and μPIXE data quantitatively confirms the presence of colloidal iron phase (min. 35 to 65% of iron content), assuming no divalent Fe is present. In the Rio Negro, HRTEM specifies the nature of colloidal iron phase mainly as ferrihydrite particles of circa 20 to 50 Å associated with organic matter. The geochemical forms of colloidal iron differentiate the pedoclimatic regions drained by the different rivers, corresponding to different major weathering/erosion processes. Modeling allows the calculation of the speciation of iron as mineral, organic and dissolved phases in the studied rivers.     

Reductive Transformation of 2,4-Dinitrotoluene: Roles of Iron and Natural Organic Matter

This study investigated the effects of redox-active and iron-coordinating functional groups within natural organic matter (NOM) on the electron transfer interactions between Fe(II) and 2,4-dinitrotoluene (2,4-DNT), an energetic residue often encountered in aqueous environments as a propellant component and impurities in 2,4,6-trinitrotoluene (TNT). Experiments were first conducted in homogeneous phases as a function of pH in the presence of ligands that (1) complex iron (e.g., citric acid, oxalic acid), (2) complex and reduce iron (e.g., caffeic acid, ascorbic acid), and (3) humic substances with known carboxyl content and electron transfer capacity. Then, effects of these NOM components on Fe(II) reactivity in heterogeneous media were investigated by introducing goethite. Our results indicate complex catalytic and inhibitory effects of NOM components on the reaction between Fe(II) and 2,4-DNT, depending upon the ability of NOM component to (1) reduce dissolved and particulate Fe(III) (e.g., ascorbic acid), (2) form kinetically labile dissolved Fe(II) reductants (e.g., tiron and caffeic acid), and (3) produce surface-associated Fe(II) species that are accessible to 2,4-DNT.     

Dissolution and transport of manganese by organic acids and their role in sedimentary Mn ore formation

Dissolution experiments of Mn and Fe under natural conditions from fresh basalt, weathered basalt and Mn laterite by different organic acids show that Mn is highly enriched over Fe in solutions from the weathered rocks but that more Fe than Mn is dissolved from the fresh basalt. The enrichment of Mn is caused by sparingly soluble Fe-oxides and hydroxides and more soluble Mn-oxides. In addition from the weathered rocks the Mn concentration dissolved by the organic acids is up to 1000 times higher than in inorganic solutions. Mn enrichment is caused by acid attack, organic reduction of Mn⁴+ to Mn²+ and complexing by the organic acids. The complexed Mn is not attacked as easily by oxidation as free Mn ions. Higher concentrations of manganese in the organic dissolved stage can therefore be transported by rivers over greater distances. Organic complexed Mn, derived from lateritic weathered rocks may therefore contribute to the formation of low iron marine sedimentary Mn deposits.     

亚洲主要河流的沉积地球化学示踪研究进展

发源于喜马拉雅—青藏高原的亚洲几条大河的河流地球化学研究揭示了高原隆升、流域风化剥蚀、大气CO2消耗和亚洲季风气候变化之间的耦合关系。研究认为南亚主要河流流域的化学风化对全球大气CO2消耗和海洋化学通量变化贡献较大,河流沉积地球化学研究反映的高原阶段性隆升过程、流域剥蚀速率以及亚洲季风演化信息也明显比东亚主要河流的记录清晰;尤其是最近几年运用河流碎屑单矿物化学和年代学方法来示踪流域构造演化、沉积物从源到汇过程以及河流演化历史等,取得了许多重要的研究成果。比较而言,我国的河流在元素地球化学和水化学组成方面虽然开展了大量基础研究工作,但目前急需进一步提炼科学目标,与国际性的研究计划结合,综合多学科的研究力量,在研究思路和关键方法上需要突破和深入,加强研究的广度和深度。长江更可以作为一个突破口和研究平台,来开展深入的沉积地球化学示踪研究。     

The geochemistry of iron in puget sound

The distribution of dissolved iron, ferrous iron and acid-reducing agent soluble iron has been investigated in the main basin of Puget Sound and its tributaries. Essentially all measurable iron in Puget Sound can be removed by filtration through 0.8 μm membrane filters, thus dissolved iron must be less than about 20 nM (our limit of detection). We could also detect no ferrous iron in Puget Sound. This is due to the rapid kinetics of oxidation of Fe(II). Our measured rate constant for the kinetics of oxidation suggests that strong ferrous-organic matter complexes do not exist in Puget Sound pore waters.The distribution of acid-soluble iron is low at mid-depth and increases toward the air-water and sediment-water interface and appears to be controlled by inputs from the rivers and the sediments. Only a small fraction of the river load appears to make it through the estuaries because the magnitude of the surface concentrations is smaller than predicted based on the calculated river flux. The “dissolved” iron in the rivers appears to be actually fine colloidal particles that coagulate before the salinity exceeds 5%. The increase towards the sediments is probably due to resuspension of botton sediments perhaps augmented by iron diffusing out of the sediments to form new iron oxide particles.     

Peatland initiation and carbon dynamics in northeast China: links to Holocene climate variability

Throughout northeast China, the widely distributed peatlands have formed a large carbon (C) pool. However, the relationship between peatland initiation and climate controls is still poorly documented and understood. Understanding the responses of these C‐rich ecosystems to past climate change will provide useful insights into projecting the fate of peatland C in the future. In this study, we present a detailed historical reconstruction of peatland development in northeast China based on 312 basal peat dates, and examine the relationship between Holocene peatland dynamics and climate sensitivity. Our results indicate that peatland initiation started in the early Holocene, and that the majority of peatlands were initiated by and developed during the late Holocene. After the most intensive initiation period of 4.2–0.8 ka, the rate of peatland development slowed, which was concomitant with decreasing insolation and monsoon intensity. The widespread peatland initiation in the late Holocene might have been caused by the cool and moist climate patterns. The optimum timing of the peatland development was not uniform across northeast China, and these spatio‐temporal differences indicate the influences of regional climate and terrain on peatland initiation. Peat‐core data show variations in the long‐term apparent rate of C accumulation (LORCA) during the Holocene, with an average rate of 37.2 g C m^?2 a^?1. The peak LORCA occurred during 10.5–9.0 ka, probably in response to higher temperatures and stronger East Asia summer monsoon intensities. Both temperature and humidity are important factors influencing the peatland initiation and C dynamics in this region.