Immobilization of Cu and As in two contaminated soils with zero-valent iron – Long-term performance and mechanisms

Immobilization of trace elements in contaminated soils by zero-valent iron (ZVI) is a promising remediation method, but questions about its long-term performance remain unanswered. To quantify immobilization and predict possible contaminant remobilization on long timescales detailed knowledge about immobilization mechanisms is needed. This study aimed at assessing the long-term effect of ZVI amendments on dissolved copper and arsenic in contaminated soils, at exploring the immobilization mechanism(s), and at setting up a geochemical model able to estimate dissolved copper and arsenic under different scenarios. Samples from untreated and ZVI-treated plots in two field experiments where ZVI had been added 6 and 15 years ago were investigated by a combination of batch experiments, geochemical modeling and extended X-ray absorption fine structure (EXAFS) spectroscopy. Dissolved copper and arsenic concentrations were described by a multisurface geochemical model with surface complexation reactions, verified by EXAFS. The ZVI remained “reactive” after 6–15 years, i.e. the dissolved concentrations of copper and arsenic were lower in the ZVI-treated than in the untreated soils. There was a shift in copper speciation from organic matter complexes in the untreated soil to surface complexes with iron (hydr)oxides in the ZVI-treated soil. The pH value was important for copper immobilization and ZVI did not have a stabilizing effect if pH was lower than about 6. Immobilization of arsenic was slightly pH-dependent and sensitive to the competition with phosphate. If phosphate was ignored in the modeling, the dissolution of arsenate was greatly underestimated.     

The Effect of Organic Carbon-Iron Oxide Association on the Preservation of Sedimentary Organic Carbon in Marine Environments

Understanding the mechanisms responsible for long-term storage of organic carbon (OC) in marine environment is important for studying the marine carbon cycling and predicting how the global carbon cycle will respond to climate change. It is estimated that more than 20% of the OC in marine sediments is associated with iron oxides and thus these complexes are one of the most important factors in the long-term storage of OC. The OC-iron oxide (OC-Fe) association can be formed through either adsorption or co-precipitation, but the dominant mechanism of OC-Fe association in marine environments is co-precipitation. The combination of OC from different sources with iron oxides is selective. Iron oxides preferentially combine with marine OC in most marine environments, but in estuarine delta regions they prefer terrestrial OC. Due to large inputs of terrestrial materials, high primary production and frequent re-suspension, estuarine and marginal seas are suitable sites for OC-Fe association studies, which should be emphasized in the future.     

Fluxes of iron and manganese across the sediment–water interface under various redox conditions

Fluxes of dissolved forms of iron and manganese across the sediment–water interface were studied in situ in the Gulf of Finland and the Vistula Lagoon (Baltic Sea), and in the Golubaya Bay (Black Sea) from 2001 to 2005. Fluxes were measured using chamber incubations, and sediment cores were collected and sliced to assess the porewater and solid phase metal distribution at different depths. Measured and calculated benthic fluxes of manganese and iron were directed out of sediment for all sites and were found to vary between 70–4450 and 5–1000 µmole m^− 2 day^− 1 for manganese and iron, respectively. The behavior of the studied metals at various redox conditions in the near-bottom water and in the sediment was the main focus in this study. Our results show the importance of bottom water redox conditions for iron fluxes. We measured no fluxes at oxic conditions, intermediate fluxes at anoxic conditions (up to 200 μmole m^− 2 day^− 1) and high fluxes at suboxic conditions (up to 1000 μmole m^− 2 day^− 1). Total dissolved iron fluxes were generally dominated by iron(II). Contribution of iron(III) to the total iron flux did not exceed 20%. Obtained fluxes of manganese at all studied regions showed a linear correlation (r² = 0.97) to its concentration in the porewater of the top sediment layer (0–5 mm) and did not depend on dissolved oxygen concentrations of bottom water. Organically complexed iron and manganese were in most cases not involved in the benthic exchange processes.     

提高南四湖综合治理工程的投资效益

南四湖治理的中心任务是降低洪水位,在尽快续建两项主要工程—扩大韩庄运河和扩大湖腰—的前提下,湖内清障是保证洪水畅泄、降低水位、缩短滞洪时间,减少洪灾损失的重要措施。本文着重对以往湖内清苇实施困难、效果不佳的原因进行了分析,为了提高今后治湖工程的综合经济效益,对开展清障工作提出了建议。     

Parameterization of iron and manganese cycling in the Black Sea suboxic and anoxic environment

New and published data on the distribution and speciation of manganese and iron in seawater are analyzed to identify and parameterize major biogeochemical processes of their cycling within the suboxic (15.6σ_t16.2) and anoxic layers (σ_t16.2) of the Black Sea. A steady-state transport-reaction model is applied to reveal layering and parameterize kinetics of redox and dissolution/precipitation processes. Previously published data on speciation of these elements in seawater are used to specify the nature of the transformations. Two particulate species of iron (Fe(III) hydroxide and Fe(II) sulfide) are necessary to adequately parameterize the vertical profile of suspended iron, while three particulate species (hydrous Mn(IV) oxide, Mn(II) sulfide, and Mn(II) carbonate) are necessary to describe the profile of suspended manganese. In addition to such processes as mixing and advection, precipitation, sinking, and dissolution of manganese carbonate are found to be essential in maintaining the observed vertical distribution of dissolved Mn(II). These results are used to interpret the observed difference in the form of vertical distribution for dissolved Mn(II) and Fe(II). Redox transformations of iron and manganese are coupled via oxidation of dissolved iron by sinking suspended manganese at σ_t16.2±0.2 kg m⁻³. The particulate manganese, necessary for this reaction, is supplied through oxidation of dissolved Mn(II). The best agreement with observations is achieved when nitrate, rather than oxygen, is set to oxidize dissolved Mn(II) in the lower part of the suboxic layer (15.90σ_t16.2). The results support the idea that, after sulfides of these metals are formed, they sink with particulate organic matter. The sinking rates of the particles and specific rates of individual redox and dissolved-particulate transformations have been estimated by fitting the vertical profile of the net rate.     

Mesozooplankton responses to iron-fertilization in the western subarctic Pacific (SEEDS2001)

A mesoscale iron-fertilization experiment was carried out in the western subarctic Pacific during summer 2001. The iron-patch was traced for 14 days after the fertilization, and the abundance and behavior of mesozooplankton were compared with those outside of the patch. The phytoplankton biomass in the patch rapidly increased to over 15 times the initial level by the later half of the observation period, and was composed of large-sized (>10 mm), centric diatoms. Dominant zooplankton species in the upper 200-m depth were large copepods: Neocalanus plumchrus, Neocalanus cristatus, Eucalanus bungii and Metridia pacifica. Mesozoplankton biomass as well as species composition did not change significantly in the patch over the observation period. Furthermore, no changes of vertical distribution or diel vertical migration were observed for any species or stages of mesozooplankton throughout the observation period. However, the abundance of the first copepodite stages of N. plumchrus and E. bungii increased several fold in the patch after the diatom bloom formation compared to the densities outside the patch. The increases of both species are considered to be due to lowered mortality during the egg and nauplius stages. Spawning of N. plumchrus takes place at depth using lipid storage, while spawning of E. bungii takes place in the surface layer supported by grazing. These facts suggest that the relative importance of nauplii in the diets of the large copepods was decreased in the patch by the diatom bloom. Gut-pigment contents of dominant copepods in the patch increased 4–18 times, and the maximum values were observed during the bloom peak. However, the grazing impact on phytoplankton was low throughout the experiment, especially during the bloom period (<6% of the primary production).     

西南三江金厂河矽卡岩型多金属矿床铁同位素分馏机制及其对成矿物质来源的制约SCIEI北大核心CSCD

金厂河矿床是西南三江成矿省保山地块最具代表性的远端矽卡岩型多金属矿床之一,查明其成矿金属来源对理解该类矿床成因以及区域成矿规律具有重要意义。本文通过分析不同成矿阶段代表性含铁矿物的铁同位素组成,探讨其在成矿过程中的分馏机制,从而示踪成矿金属的源区特征。金厂河矽卡岩型矿床中成矿前阶段未蚀变的石榴子石和氧化物成矿阶段的磁铁矿均相对富集铁的重同位素,其δ;Fe值分别为0.05‰~0.16‰和0.07‰~0.18‰,而硫化物成矿阶段的黄铁矿和黄铜矿则相对富集铁的轻同位素,其δ;Fe值分别为-0.12‰~0.17‰和-0.54‰~-0.38‰,整体显示出从高氧逸度的成矿前阶段向低氧逸度的硫化物成矿阶段演化过程中矿物δ;Fe值逐渐降低的趋势,指示Fe;富集铁的重同位素,Fe;富集铁的轻同位素。同时,金厂河矿床各阶段矿物的δ;Fe值均显著低于碳酸盐围岩,而接近全球花岗岩的δ;Fe值,表明成矿的铁不是由围岩贡献,而是来自于隐伏的中酸性岩体。     

富铁橄榄石的水溶性实验研究SCIEI北大核心CSCD

地幔的力学性质主要受橄榄石流变性的控制,含水对橄榄石流变性质的影响很大,而橄榄石的水溶性受到温度和铁含量的影响,因此,本文进行了不同铁含量橄榄石在不同温度下的水溶性实验研究。实验使用的样品为天然橄榄石单晶Fa_(17)和Fa_(24.7)(Fe_(No.)=100×molar Fe/(Mg+Fe))以及人工合成的橄榄石单晶Fa_(22);橄榄石单晶的水溶性实验在300MPa围压和1273~1473K的温度条件下进行,每隔50K进行一组实验,氧逸度被控制在Ni NiO水平上。实验结束后,对橄榄石单晶沿b面进行双面研磨抛光,用电子探针分析确定橄榄石单晶成分,采用EBSD精确测量橄榄石的单晶方向,使用红外光谱仪(FTIR)的非偏振光路测试橄榄石单晶在b轴上的吸收光谱。对FTIR吸收光谱进行积分得到富铁橄榄石的水溶性实验结果:当温度由1273K升至1473K时,橄榄石单晶Fa_(17)的水溶性变化为600~1200H/10^(6) Si,橄榄石单晶Fa_(24.7)的水溶性变化为1000~1300H/10^(6) Si,人工合成的橄榄石单晶Fa_(22)的水溶性变化为500~900 H/10^(6) Si。因此,相同铁含量橄榄石单晶的水溶性随温度的增加而增加,相同温度条件下,天然形成的橄榄石的水溶性随着铁含量的增加而增加,百分之一的铁含量的增加,可以导致约百分之十的水溶性的增加。本文所研究的不同铁含量的橄榄石可以为更好地估算上地幔水溶性提供依据。     

Reconstruction of paleo-redox conditions and early sulfur cycling during deposition of the Cryogenian Datangpo Formation in South China

In South China, the Datangpo black shales (663 Ma–654.5 Ma) were deposited during the Cryognian interglacial time between the Sturtian and Marinoan glaciations. Multi-geochemical proxies, including different iron speciation and relevant ratios (Fe_HR/Fe_T, Fe_P/Fe_HR and Fe_T/Al ratios) and molybdenum concentrations, were used to reconstruct the paleo-depositional environment of this black shale horizon. The ratios of different iron species (Fe_HR/Fe_T > 0.38 and Fe_P/Fe_HR < 0.80) suggest an overall anoxic conditions (ferruginous) over the deposition of the black shales, although intermittent euxinic (Fe_HR/Fe_T > 0.38 and Fe_P/Fe_HR ≈ 0.80) and oxic (Fe_HR/Fe_T < 0.38) intervals could have occurred. Furthermore, Fe_T/Al ratios (Fe_T/Al ≤ 0.51) confirm that water column may not be persistent euxinia during the deposition of the Datangpo black shales. Meanwhile, molybdenum concentrations show a decreasing trend towards the top of the black shales, reconciling the gradual oxygenating trend during this period as stated above. Compared to δ³⁴S_Py values in the Mesoproterozoic deep ocean, more positive δ³⁴S_Py values of this study may result from a small size of sulfate reservoir. The small-size sulfate reservoir and concurrent enrichment of molybdenum indicate that the ocean chemistry in the Cryogenian Period is similar to that in the Archean Eon.     

碳酸盐岩红色风化壳中的氧化铁矿物

氧化铁矿物是碳酸盐岩红色风化壳的主要矿物成分和重要结构单元。运用X射线衍射、透射电镜、扫描电镜、穆斯堡尔谱和电子探针等方法对碳酸盐岩红色风化壳中的氧化铁矿物进行了系统研究。碳酸盐岩红色风化壳中的氧化铁矿物主要有针铁矿、赤铁矿和磁赤铁矿。氧化铁矿物组合、含量和化学成分随成土环境和风化强度在剖面中呈明显的规律性变化,这为碳酸盐岩风化成土作用、红色风化壳成因与环境问题的深入研究提供了重要的矿物学依据。