碳酸锰氧化实验和热力学分析

通过对碳酸锰氧化实验的结果分析和讨论，建立了一种适合于锰氧化过程的非平衡热力学模型，并利用此模型对硫酸锰氧化过程作了热力学可行性分析，研究结果表明，碳酸锰氧化过程是矿物组合的变化过程，也是锰自身价态的转为过程，整个过程既存在平衡状态，又存在非平衡状态，是一个不可逆的，多相的复杂反应。     

Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.     

Possible link between new coronavirus variants and atmospheric lightning and seawater intrusion

自新型冠状病毒肺炎暴发一年多以来,已经对全球产生深远影响.新型冠状病毒肺炎变异毒株的出现使当前疫情发展充满了不确定性.从这方面出发,我们讨论病毒变异与大气因素之间的联系.根据固氮过程和硝酸盐在人体中的转化过程,我们提出了新型冠状病毒肺炎变异毒株的出现或许和闪电以及海水入侵有联系.我们的研究对新型冠状病毒肺炎变异毒株可能的产生原因提供新的观点.     

极锋以南洋区N_2O源汇特性初析

N_2O是大气中最重要的温室气体之一,目前已经有大量的研究对海洋N_2O循环及海洋对N_2O收支的贡献进行追踪报道。然而,极区相关研究仍然十分有限。本研究利用中国第25、26次南极科学考察的机会,对南大洋进行的采样以及实验室分析,结果显示,南大洋表层海水存在亚热带锋附近N_2O过饱和,亚南极锋附近接近饱和,和极锋以南洋面的不饱和的特征。海冰融化后,其融冰水的注入是N2O不饱和特征形成的主要原因。运用正态分布选取站观测风速95%以上的风速范围进行平局估算出极锋以南洋区海气通量,结果显示,极锋区以南表层海水是大气N_2O的汇区,年吸收通量约为3.5×10~(-4)—7.7×10-4Tg·a-1(百万吨氮/年)。     

1999年和2000年夏季南极菲尔德斯半岛N_2O浓度对比

1999与 2 0 0 0年夏季对南极菲尔德斯半岛不同地点大气中 N2 O浓度进行了监测 ,分析了苔藓植被区 N2 O浓度季节变化特征 ;2 0 0 0年夏季该植被区 N2 O浓度均值为 ( 31 0 .7± 4.4)×1 0 - 9(体积百分比 ) ,比 1 999年的 ( 32 1 .9± 3.3)× 1 0 - 9约低 1 1× 1 0 - 9;阿德雷岛企鹅滩及其沙坝处N2 O浓度变化趋势与苔藓植被区相一致 ,浓度均值分别为 ( 31 2 .4± 5 .1 )× 1 0 - 9和 ( 31 2 .7± 5 .3)× 1 0 - 9,比 1 999年约低 9× 1 0 - 9;另外 ,不同地点大气中 N2 O浓度普遍比 1 999年低 ,但整体变化规律相似 :各考察站区 N2 O浓度普遍高于无人区 ;唯一例外的是企鹅聚集区 N2 O浓度却高于各考察站区 ,暗示了企鹅及其排泄物、人为源是南极大气中 N2 O主要的源。本文初步探讨了 N2 O浓度异常降低的原因     

低品位氧化钴矿石钴的赋存状态和浸取实验研究

基于我国钴资源分布分散、且多为伴生、品位低的现状，对某铜钴矿化区钴矿石中的钴碳酸盐矿物、含钴铁氧化物和具有吸附态的粘土矿物进行了钴的赋存状态和浸取试验研究，查明了钴的赋存状态，并以此为依据，运用逐一条件试验和正交试验相互验证的办法，确定了最优化的浸取试验方案，该方法对此低品位氧化钴矿石中钴的浸出率达到90%以上。     

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.     

Impact of trace metals on denitrification in estuarine sediments of the Douro River estuary,Portugal

Denitrification influences the nitrogen budget in estuaries by removing fixed nitrogen from the inorganic pool; rates are dependent on both geological and geographic conditions as well as increasing anthropogenic impacts. In this study the effects of copper (Cu), chromium (Cr), zinc (Zn), cadmium (Cd) and lead (Pb), on the denitrification pathway were evaluated in subtidal and intertidal sediments of the Douro River estuary. Dinitrogen, N₂O and NO₂⁻ production rates were measured in triplicate slurries of field samples under different treatments of metal concentrations. Results demonstrated that similar metal amendments led to different site responses for denitrification, suggesting that variations in sediment properties (metal concentrations, grain size, organic matter content, etc.) and/or differences in denitrifying community tolerance modulate the level of metal toxicity. Denitrifying communities in subtidal muddy sediments were not affected by increasing concentrations of metals. In contrast, intertidal sandy sites revealed high sensitivity to almost all trace metals tested; almost complete inhibition by Cr (95%) and Cu (85%) was observed for 98 and 79 μg per gram of wet sediment respectively, and by Zn (92%) at the highest concentration added (490 μg per gram of wet sediment). Moreover, the addition of trace metals stimulated N₂O and NO₂⁻ accumulation in intertidal sandy (Zn, Cu, Cr and Cd) and muddy sediments (Cu and Zn), demonstrating a pronounced inhibitory effect on specific steps within the denitrification enzymatic system. In summary, the results obtained suggest that, according to the type of estuarine sediment, trace metals cannot only reduce total N removal from an estuary via denitrification but also can enhance the release of N₂O, a powerful greenhouse gas.