环境有机地球化学:有机污染物—土壤/沉积物吸附作用研究回顾

农药、有机溶剂的大量使用以及大量废水、废物的排放,导致全球范围内土壤、沉积物、地表及地下水源和生态系统的严重污染。有机污染物在生物圈内的分布、迁移、富集、降解以及最终归宿是环境有机地球化学重要的研究方向之一。有机污染物与土壤、沉积物以及水中悬浮物（如...     

沉积物中PCBs分析测定与迁移转化研究进展

多氯联苯(PCBs)是一种具有亲脂性、低水溶性、高稳定性和高生物富集性等特性的持久性有机污染物(POPs),而沉积物作为疏水性有机污染物(HOCs)的重要地质宿体,PCBs在POPs中发生的环境过程是研究的热点。本文综述国内外近几年来沉积物中PCBs分析测定以及迁移转化的研究动态,并对今后PCBs污染的生物修复研究提出了自己的见解。     

湖泊湿地生态地球化学评价的标准体系

湖泊湿地生态地球化学评价的研究重点为湖泊湿地生态系统中的重金属、植物营养元素及一些有机污染物,评价标准体系相应地包括水质基准、营养物基准、水体沉积物质量基准、饮用水卫生标准、土壤环境质量标准、食品卫生标准、湖泊水库富营养化标准等.     

沿海表层沉积物中重金属的有效结合态

以浙江沿海表层沉积物为研究对象,系统地研究了重金属有效结合态与沉积环境、矿物组成和人为排放等环境因素之间的相互关系.结果表明:沿海表层沉积物中重金属的积累数量,呈现出潮汐河口沉积物>沿海沉积物>强潮汐河口沉积物的趋势,这反映了不同沉积类型对重金属富集作用的差异;重金属的有效结合态,总体上以铁锰氧化物结合态>碳酸盐结合态>硫化物及有机结合态>可交换态的顺序存在,但是不同的重金属或同种重金属在不同的采点,主要有效结合态的比例存在明显的差异,这不仅与重金属的地球化学性质、沉积环境和沉积物中的粘土矿物组成有关,更受到重金属污染物的人为排放量的影响.     

持久、迁移性有机污染物的水污染现状、分析检测方法和去除技术

持久、迁移性有机污染物(PMOC)具有高极性、化学性质稳定的特点,故难被土壤以及沉积物吸附.该类化学物质的环境释放可导致其在地下水以及饮用水中富集.目前,由于缺乏有效的分析技术手段,水体中大量未知的PMOC仍待进一步分析和识别.本次研究将从定义、特性和判别标准等方面系统介绍该类污染物,同时,对欧洲国家的PMOC管控现状...     

湖泊湿地生态地球化学评价的标准体系

湖泊湿地生态地球化学评价的研究重点为湖泊湿地生态系统中的重金属、植物营养元素及一些有机污染物,评价标准体系相应地包括水质基准、营养物基准、水体沉积物质量基准、饮用水卫生标准、土壤环境质量标准、食品卫生标准、湖泊水库富营养化标准等。     

沉积物样品中干扰物的去除及多种持久性有机污染物气相色谱分析

建立了沉积物样品中17种有机氯农药和8种多氯联苯持久性有机污染物的气相色谱分析方法。针对沉积物样品基质复杂、含有大量硫干扰的特点,重点研究了前处理技术。采用加速溶剂提取(ASE)技术提取样品中的有机污染物,比较了加入铜粉后ASE在线除硫和超声波提取除硫的效果。结果表明,加入铜粉ASE提取不能完全去除硫的干扰,需进一步采用超声波提取10 min除硫才能大大减少杂质对目标化合物的干扰。沉积物样品中的色素类及小分子干扰物质采用凝胶渗透色谱结合固相萃取技术进行净化,满足了气相色谱-电子捕获检测器分析的要求。25种化合物的平均添加回收率为68%～131%,方法精密度(RSD,n=6)小于22.3%,检出限为0.10～0.51μg/kg。建立的样品前处理技术净化彻底,适合用于不同地区、不同类型的沉积物样品气相色谱分析。     

Fe(Ⅱ)/铁氧化物表面结合铁系统还原有机污染物的研究进展

在土壤和沉积物的自然厌氧环境中,铁氧化物可被铁还原茵等微生物异化还原产生Fe(Ⅱ),形成的Fe(Ⅱ)/铁氧化物表面结合铁系统具有还原活性,可使有机污染物还原转化.综述了含卤和含硝基有机污染物的非生物还原转化过程和表面结合铁系统与有机污染物之间的界面反应机理,进而揭示了污染物在环境中的赋存状态和迁移转化规律;重点分析了影响该还原过程的因素,如铁氧化物类型、pH值、Fe(Ⅱ)与铁氧化物接触时间,以及过渡金属、腐殖酸等竞争因子对反应过程的影响.强化自然界中天然的Fe(Ⅱ)/铁氧化物表面结合铁系统在有机污染治理中的作用,在受污染环境修复领域具有广阔的应用前景.     

湖泊湿地生态地球化学评价的标准体系

湖泊湿地生态地球化学评价的研究重点为湖泊湿地生态系统中的重金属、植物营养元素及一些有机污染物，评价标准体系相应地包括水质基准、营养物基准、水体沉积物质量基准、饮用水卫生标准、土壤环境质量标准、食品卫生标准、湖泊水库富营养化标准等。     

近20年来我国沉积物环境与污染控制研究进展与展望

内陆水体(湖泊、水库、沼泽、河流)和河口海洋等底部,广泛且连续分布着沉积物质,在其形成过程中受自然和人类活动影响,具有与污染物有关的环境意义和特征.中国区域差异大,环境问题较为突出,经过近几十年来围绕沉积物环境和污染控制开展的研究,我国相关成果不断涌现.首先介绍了国际上有关沉积物环境的若干里程碑性研究,回顾了前70年我国沉积物研究的发展历程.然后侧重于与人为活动有关的环境污染,分别从沉积物环境和污染控制修复两个方面,总结和归纳了近20年来中国在沉积物水环境中的作用及效应、污染物在沉积物-水界面环境行为与影响因素、沉积物生态风险与质量基准、污染沉积物的原位修复、污染沉积物疏浚及异位处置利用等方面的主要研究进展,评述了其中一些研究成果的联系和差异.最后对我国沉积物环境研究中存在的问题进行了分析,提出关于多学科交叉、复合污染、新兴/非传统污染物、质量基准、治理技术创新等几个亟需和深入开展研究的科学和技术问题,给出了解决的思路和途径,并进行了展望.     

Nitrogen and phosphorus in the sediments of a tidal,freshwater marsh in Massachusetts

Total organic nitrogen (TON) and phosphorus (TOP) were measured as a function of depth in 14 cores taken from a New England, tidal, freshwater marsh. TON and TOP ranged from 1.56 to 1.97% and 0.11 to 0.30% of dry weight sediments, respectively. The variation in both pool sizes over time was small and TON varied inconsistently with depth; however, TOP decreased regularly down to 20 cm. Consequently, the TON: TOP ratio increased linearly from 14∶1 at the surface to 32∶1 at 20 cm, then was nearly constant to 70 cm. This pattern may be a general feature of marsh sediments and may indicate 1) that phosphorus is recycled less efficiently than nitrogen, 2) that over time proportionately more introgen than phosphorus is incorporated into recalcitrant compounds, or 3) that phosphorus is more mobile than nitrogen in these marsh sediments. The total inorganic nitrogen pool was measured in this marsh also and was dominated by ammonium (97% of total). The annual average free ammonium concentration was 3.70±0.64 mg N per 1 at the surface and decreased to 0.92±0.18 mg N per 1 at 20 to 22 cm in the sediments. Sorptiondesorption studies showed that, on a fresh sediment volume basis, sediment sorbed ammonium was roughly equivalent to free porewater ammonium (K=0.8). The relationship between free and sorbed ammonium was linear between 0.4 and 24.0 mg NH₄·N per 1 of pore water. The depth distribution of ammonium in these sediments is probably maintained by a dynamic balance between net microbial mineralization of litter, plant uptake, transpiration, diffusion, and porewater advection.     

Geochemistry of shallow sediments in Guaymas Basin, gulf of California: hydrothermal gas and oil migration and effects of mineralogy

Offset of prograde hydrothermal alterations by retrograde reactions is evident in sediments from a piston core (PC6, 8 m long) from the Guaymas Basin, Gulf of California. Geochemical and mineralogical analyses of sediments and pore fluids show superimposed geochemical signals that indicate currently active reactions are modifying previously formed secondary solids. Hydrothermal barite was formed in a previously active flow channel between 150 and 250 cm depth. Hydrothermal gypsum is presently dissolving at depths > 780 cm, below which hydrothermal fluid flow is channeled by a secondary dolomite layer. Thermal stress of organic matter generates hydrothermal gas and petroleum having wide ranges of compositions and maturities. A significant amount of hydrothermally generated oil has been transported laterally through a porous debris flow (approx. 240 cm subbottom), overwhelming the indigenous bituminous matter. Water soluble petroleum constituents have disseminated throughout the cored sediments. From 400 to 700 cm depth the immature organic matter continues to experience thermally-enhanced diagenesis, and an even higher thermal stress has occurred at the bottom of the core. Enhanced bacterial degradation of organic matter has led to depletion of pore water sulfate and enrichment of ammonium (NH₄⁺) in both pore fluid and sediment, resulting in formation of NH₄⁺ bearing secondary clay minerals at depths below 780 cm.     

The influence of tidal action on porewater nitrate concentration and dynamics in intertidal sediments of the Sado estuary

The change in porewater nitrate (NO₂ ^? + NO₃ ^?) concentrations during exposure of intertidal sediment was studied at a fixed location in the Sado estuary, southwest Portugal, in November 1994. In order to follow nitrate concentration and dynamics from pre-ebb to post flood, during the day, high vertical resolution profiles (0.2 cm) were studied. As a complement, in February 1995, potential nitrification rates in the sediment were measured by laboratory incubations, with high vertical resolution (0.2 cm) up to 3 cm depth. Oxygen penetration was measured with polarographic mini-electrodes. The sediment’s texture as well as the organic matter composition in carbon and nitrogen were studied in deeper (30 cm) cores. In February 1993,²¹⁰Pb activity depth profiles were measured in a core sampled at the beginning of exposure, in order to evaluate the possibility of nonlocal particle exchange. C:N ratios and²¹⁰Pb activity profiles show evidence of nonlocal exchange of solid phase particles between the surface and deeper sediment, most likely due to macrofaunal activity. As a consequence, fresh organic matter is brought from the surface to 7–9 cm depth, causing enhancement of nutrient concentrations. Results of this study suggest nitrate dynamics in intertidal sediments of the Sado estuary are strongly influenced by tidal action. Periodic submersion and exposure allow for the diversification of pathways of oxygen supply to the sediment. Tidal stress at the sediment-water interface during the arrival (flooding) and departure (exposure) of the tidal front at the site has an important bearing on the effective depth of the nitrification zone. A denitrification rate of 2.16 μmol N dm^?5 h^?1 was measured directly from the nitrate inventory in the 1.5–6 cm depth layer. The schematic model of N cycling in these sediments suggests that 20% of the N pool is denitrified during exposure, and that this process is limited by O₂ availability for nitrification.     

海南红树林湿地可培养硫酸盐还原菌的垂直分布特征研究

利用厌氧微生物分离技术,对深度为1.2 m 的海南红树林湿地沉积物钻孔样品进行了分离培养,共获得11 株 厌氧sulfate-reducing bacteria（SRB） 菌株。经显微观察和16S rDNA序列分析,可归纳为6个属,其中已经报道有芽孢杆菌 属（Bacillus）、弧菌属（Vibrio） 和梭状芽胞杆菌属（Clostridium）,另外3个属分别为伯克霍尔德菌属（Burkholderia）、希瓦氏菌属（Shewanella） 和海杆菌属（Marinobacterium）。不同属的细菌对硫酸盐还原的速率最低为14.71%,最高可达 56.78%,并且以上6属11株菌都能将+6价的硫还原生成-2价硫,并与培养基中的Fe2+结合生成黑色FeS沉淀,而这些无定 形FeS沉淀是生成黄铁矿的前体。红树林湿地SRB种群数量随沉积物深度的增加而降低,结合沉积物的地球化学分析测试 结果表明,表层（0 cm） 水界面的沉积物由于处于氧化-还原界面,氧气的周期性输入在一定程度上抑制了SRB的生长;随着 深度增加（10~40 cm）,充足的有机质、偏中性的pH值以及厌氧环境的增强,使得SRB种类和数量明显增加;而60 cm以下 沉积物中因TOC含量降低,减少了微生物可利用的碳源,pH值明显降低,Na+和Ca2+离子浓度明显增加,这些因素都抑制了 SRB的生长,使得深部沉积物中SRB的种类和数量显著减少。     

Spatial and seasonal patterns in sediment nitrogen remineralization and ammonium concentrations in San Francisco Bay,California

Nitrogen remineralization and extractable ammonium concentrations were measured in sediments from several locations in North and South San Francisco bays. In South Bay, remineralization rates decreased with depth in sediment and were highest in the spring following the seasonal phytoplankton bloom. At the channel stations, peak remineralization lagged peak water-column phytoplankton biomass (as measured by chlorophylla) by a month. Remineralization rates were generally higher in South Bay than North Bay. The lower remineralization rates in North Bay may be a result of anomalously low phytoplankton production and thus reduced deposition to the sediments, as well as low reiverine organic inputs to the upper estuary in recent years. Remineralization rates were positively correlated to carbon and nitrogen content of the sediments. In general, ammonium profiles in South Bay sediments showed no increase in deeper (4–8 cm) sediments. In North Bay, ammonium concentrations were greatest at stations with highest remineralization rates, and, in contrast to South Bay, extractable ammonium increased in deeper sediment. Differences in ammonium pools between North Bay and South Bay may be a result of increased irrigation by deep-dwelling macrofauna, which are more abundant in South Bay.     

Sediment Phosphorus Chemistry and Microbial Biomass along a Lowland New Zealand Stream

An evaluation of the distribution of P concentrations in streamflow, P fractions andthe microbial biomass P pool was made of bed and bank sediments along a lowlandstream in New Zealand. Agricultural intensification increased downstream. However,most P fractions decreased downstream (total P decreased from c. 400 to 250 mg kg^-1) in bed sediments, while P in streamflow remained relatively constant (generally < 0.005 mg l^-1) and sediment microbial P increased from 2 to 8 mg kg^-1. An investigation of P release from dried and rewetted sediments showed that solution P (CaCl2-P) increased, on average > 300%, and proportional to the size of the microbial biomass P pool before drying, except in sediments with much organic carbon (OC). When supplied with a P source (1 mg l^-1) and then simultaneously with a C source (glucose, 100 mg l^-1), all sediment behaved similarly and biotic sorption accounted for, on average, 27 and 34% of the total sediment uptake, respectively (maximum of 58%). The quantity of P taken up was related to the initial size of the microbial biomass P pool, and the availability of P as influenced by organic P complexes and OC. The sediment microbial biomass represents a transient, but small store of P could be useful to indicate bioavailable P inputs.     

The geochemistry of redox sensitive trace metals in sediments

We analyzed the redox sensitive elements V, Mo, U, Re and Cd in surface sediments from the Northwest African margin, the U.S. Northwest margin and the Arabian Sea to determine their response under a range of redox conditions. Where oxygen penetrates 1 cm or less into the sediments, Mo and V diffuse to the overlying water as Mn is reduced and remobilized. Authigenic enrichments of U, Re and Cd are evident under these redox conditions. With the onset of sulfate reduction, all of the metals accumulate authigenically with Re being by far the most enriched. General trends in authigenic metal accumulation are described by calculating authigenic fluxes for the 3 main redox regimes: oxic, reducing where oxygen penetrates ≤1 cm, and anoxic conditions. Using a simple diagenesis model and global estimates of organic carbon rain rate and bottom water oxygen concentrations, we calculate the area of sediments below 1000 m water depth in which oxygen penetration is ≤1 cm to be 4% of the ocean floor. We conclude that sediments where oxygen penetrates ≤1 cm release Mn, V and Mo to seawater at rates of 140%–260%, 60%–150% and 5%–10% of their respective riverine fluxes, using the authigenic metal concentrations and accumulation rates from this work and other literature. These sediments are sinks for Re, Cd and U, with burial fluxes of 70%–140%, 30%–80% and 20%–40%, respectively, of their dissolved riverine inputs. We modeled the sensitivity of the response of seawater Re, Cd and V concentrations to changes in the area of reducing sediments where oxygen penetrates ≤1 cm. Our analysis suggests a negligible change in seawater Re concentration, whereas seawater concentrations of Cd and V could have decreased and increased, respectively, by 5%–10% over 20 kyr if the area of reducing sediments increased by a factor of 2 and by 10%–20% if the area increased by a factor of 3. The concentration variations for a factor of 2 increase in the area of reducing sediments are at about the level of uncertainty of Cd/Ca and V/Ca ratios observed in foraminifera shells over the last 40 kyr. This implies that the area of reducing sediments in the ocean deeper than 1000 m (4%) has not been greater than twice the present value in the recent past.     

Distribution and Variation of Ribonucleic Acid （RNA） and Protein and Its Hydrolysis Products in Lake Sediments

Protein and RNA in lake sediments tend to be decomposed progressively with time and sedimentation depth. Their concentrations tend to decrease starting from the sedimentation depth of 17 cm and that of 19 cm, respectively. However, the products of their decomposition —amino acids and nucleotides show different rules of variation. At the depth from 27 cm to 30 cm the amino acids are most abundant in the pore waters of lake sediments. Such variation tendency seems to be related to the extent to which microbes utilize amino acids and nucleotides. Due to polymerization in the geological processes and the adsorption of protein on minerals and organic polymers, below the sedimentation depth of 17 cm there is still a certain amount of protein in the sediments. With the time passing by, protein has been well preserved in various sediment layers, indicating that its decomposition is relatively limited. The peak values of protein content in the sediments of the two lakes are produced in the surface layers at the depth of 10 cm, implicating that the surface sediments are favorable to the release of protein. The contents of amino acids in the pore waters of lake sediments are closely related to the activities of microbes. Below the depth of 27 cm, the amino acids are significantly accumulated in Lake Aha sediments, probably indicating the weakening of microbial activities. The research project was financially supported jointly by the Ntional Natural Science Foundation of China (No. 40173038) and the Guizhou Provincial Foundation (No. 3090) and the Chinese Academy of Sciences Knowledge-Innovation Foundation (KZCX2-105).     

Early diagenesis of fatty acids in lacustrine sediments—III. Changes in fatty acid composition in the sediments from a brackish water lake

A 3-m sediment core taken from Lake Suigetsu, in which a shift from fresh to brackish water occurred about three hundred years ago, has been examined for variation with depth of organic carbon and fatty acids. From the difference in total amounts of sulphur between sediments under fresh and brackish water environments, the surface sediments above approximately 35 cm depth were deduced to be accumulated under a brackish water environment. The total contents of organic carbon and fatty acids, and percentage composition of fatty acids gave discontinuous profiles above and below the 35–40 cm sediment layer. At a depth of 12.5 cm, the distribution in chain length of the fatty acids changed from a unimodal (the predominance of C₁₂-C₁₈ over C₂₀-C₃₄) to a bimodal pattern, which was mirrored by the composition diversity index (CDI).Although the fatty acids in the surface sediments (0–40 cm) from Lake Suigetsu seemed to suffer milder degradation through microbial activity than those in a core (0–150 cm) from Lake Suwa, a freshwater eutrophic lake, both lacustrine sediments showed similar trends in the alteration of fatty acid composition with depth.     

The effect of salinity on ammonium sorption in aquatic sediments: Implications for benthic nutrient recycling

Ambient exchangeable ammonium concentrations in freshwater sediments are generally considerably greater than those reported for marine sediments. Laboratory measurements indicate that competition for cation exchange sites by ions in seawater is a factor responsible for the lower exchangeable ammonium concentrations in marine sediments. Exchangeable ammonium concentrations were 3- to 6-fold higher when river and estuarine sediments were incubated with fresh water relative to the same sediments incubated with salt water (%.-23). A model was developed to explore the implications for benthic nitrogen cycling of this salinity effect on exchangeable ammonium concentrations. Ammonium diffusion, exchangeable and dissolved ammonium concentrations, and nitrification rates were components of the model formulation. The model output suggests that higher exchangeable ammonium concentrations predicted in fresh water relative to marine sediments can markedly increase the fraction of the ammonium produced in sediments that is nitrified (and subsequently denitrified). These results are consistent with field and experimental laboratory data which indicate that a larger percentage of net ammonium production in aerobic freshwater sediments is nitrified and denitrified (80–100%) relative to marine sediments (40–60%).