锡的地球化学性质与华南晚白垩世锡矿成因

锡在地质过程中表现出亲氧、亲硫和亲铁三重特性。在地幔岩浆过程中,锡是一种中等不相容的金属元素。锡成矿主要与酸性岩浆活动有关,其地球化学性质决定了其成矿主要受源区性质、氧逸度以及挥发分含量、岩浆结晶分异等因素控制。高度结晶分异可使锡在岩浆中进一步富集,是锡成矿相关花岗岩的普遍特征;锡为变价元素,岩浆体系氧逸度影响源区中锡的迁移能力和分离结晶过程中锡的元素行为,还原性岩浆体系有利于锡富集成矿。富含F、Cl和B等挥发组分对锡元素的迁移和富集起积极的作用。全球锡矿床分布与俯冲带关系密切,特提斯和环太平洋构造域是主要蕴藏区。重要的锡成矿事件表现出区域性和阶段性的特征。结合锡的地球化学特性以及锡矿分布特征,我们认为最有利锡成矿的动力学机制是俯冲板片后撤机制。俯冲板片后撤引发深部软流圈地幔上涌,导致强烈的壳幔相互作用,形成低氧逸度、富F、Cl和B等花岗岩,有利于锡成矿。对于华南晚白垩世锡成矿事件,新特提斯洋俯冲板片发生后撤是其成矿地球动力学背景。     

黑云母地球化学特征对武山铜矿和竹溪岭钨矿成矿岩浆体系差异的指示

黑云母化学成分差异可反映出岩浆岩的性质(全岩铝饱和指数、I/S型花岗岩)、氧逸度、挥发分特征并指示岩浆源区。为了探究不同岩浆体系的性质对成矿差异性的影响,本文选择与长江中下游成矿带的武山铜矿和江南造山带的竹溪岭钨(钼)矿相关的花岗闪长斑岩中的黑云母作为研究对象,对其开展了岩相学、主量元素和原位微量元素分析。结果表明,两地黑云母均富镁贫铁,竹溪岭岩体中的黑云母相对富集Li、Nb等不相容元素,而武山岩体的黑云母富集Ni、V等相容元素。基于黑云母地球化学特征建立了成岩体系与成矿体系的联系:武山铜矿与黑云母相平衡的岩浆体系具有高Cl、高氧逸度特征,有利于Cu富集成矿;而竹溪岭钨(钼)矿的岩浆体系具高F、低氧逸度特征,有利于W富集成矿。     

氟化物固体缓冲剂-交流电弧直读发射光谱法测定化探样品中易挥发与难挥发微量元素

应用电弧直读发射光谱法测定化探样品,样品无需消解,采用固体进样的方式可以同时测定多个元素。但目前化探分析中常采用的固体缓冲剂(如焦硫酸钾、氟化钠)的电弧温度较低,只能分析银、硼、锡、铅、钼、铜等易挥发元素,而不能分析铬、锰、钛等沸点较高的难挥发性元素。本文通过碱金属控制较低的电弧温度,并利用难挥发元素能在高温条件下与氟离子发生化学反应降低其激发温度,配制了一种以氟化铝、聚三氟氯乙烯等氟化效率较高的化合物为主要成分的固体缓冲剂,通过优化分析线对的选择、曝光时间、电极形状等分析条件,实现了一次制样可同时分析地球化学样品中14种易挥发和难挥发元素。方法检出限为0.016~46.93μg/g,相对标准偏差为4.1%~12.3%,通过国家标准物质验证了准确度,测定值与标准值相符,各项参数都能满足地球化学普查规范要求。本方法分析效率高,在化探分析中具有一定的实用性。     

吹扫-捕集气相色谱法测定海水中挥发性卤代烃

挥发性卤代烃(VHC)是大气中的痕量气体,对臭氧层损耗和温室效应有重要作用。海洋是大气中VHC的主要自然排放源,开展海洋VHC的研究有助于了解海洋对大气VHC和全球变暖的贡献。本文建立了吹扫-捕集与气相色谱-微池电子捕获检测器联用技术(P-T-GC-(ECD)分析海水中6种VHC的方法,确定了吹扫-捕集条件和气相色谱分离条件。该方法的检测限在0.003~0.369 ng.L-1之间;相对标准偏差是1.83~3.97;加标回收率为98.1%~110.2%;相关系数在0.997 3~0.999 8之间。可准确地测定海水中6种VHC。     

无磷条件诱导铜绿微囊藻(Microcystis aeruginosa)释放挥发性有机化合物对莱茵衣藻(Chlamydomonas reinhardtii)的影响

为了揭示磷(P)营养缺乏对蓝藻释放挥发性有机化合物(VOCs)的影响及其对其他藻类的化感作用,以形成蓝藻水华的主要种类铜绿微囊藻(Microcystis aeruginosa)为材料,在无P培养条件下对其释放的VOCs进行分析,同时测定VOCs对莱茵衣藻(Chlamydomonas reinhardtii)生长、光合色素含量和光合性能的影响.结果表明,采用无P培养基培养铜绿微囊藻24 h后,其释放的VOCs种类和含量均明显增加,与标准培养基培养相比,VOCs总释放量增加了73.4%,并出现7种新化合物.将铜绿微囊藻释放的VOCs通入莱茵衣藻溶液中,在标准培养基中铜绿微囊藻释放的VOCs对莱茵衣藻生长无显著影响,而无P条件下释放的VOCs则明显抑制莱茵衣藻生长,其响应指数(RI)为-0.25.此外,莱茵衣藻光合色素含量、光系统II(PSII)最大光化学量子产量(Fv/Fm)、有效光化学量子产量[Y(II)]、光化学淬灭系数(q P)和光合电子传递速率(ETR)也明显降低,而非光化学淬灭系数(NPQ)则明显升高,其RI为0.26.由此可见,蓝藻在富营养化水体中大量繁殖以及P自身沉降特性导致的P缺乏会促进蓝藻释放VOCs,同时这些VOCs在保持蓝藻营养竞争优势和水体藻类多样性减少中具有化感抑制作用.     

山东地区典型金属罐喷涂企业VOCs排放特征研究

了解涂装行业挥发性有机物（VOCs）的排放特征是制定山东地区臭氧（O₃）和PM_2.5防控策略的重要环节.本研究在山东地区测定了两家典型食品金属包装企业喷涂过程中VOCs的排放组成,企业产品以饮料罐和罐头为主.结果表明：两家企业排放的总VOCs质量浓度水平相当,质量浓度变化范围在50~1 500 μg/m³;但两家企业喷涂过程中VOCs的排放组成具有一定的差异,以生产铝罐和马口铁罐为主的企业中的含氧挥发性有机物（OVOCs）含量最多,占比89.71%（质量分数,下同）;而生产铝罐的企业芳香烃（56.15%）是首要的排放种类,其次是OVOCs （32.32%）.通过分析两家企业内外喷涂工艺的VOCs源成分谱,发现同一企业不同工艺之间有一定差异,多种罐生产企业的内、外喷涂中乙醇占比最高,分别为94.28%、84.46%;单铝罐生产企业的内喷涂2-丁酮（24.33%）是重要组分,外喷涂中甲苯（36.40%）含量较高.     

西太平洋海域现场培养实验中挥发性卤代烃浓度的变化及其影响因素

CH₃I、CHCl₃、C₂HCl₃和CH₂Br₂是挥发性卤代烃4种重要成分,对大气化学产生重要影响。于2018年10月在西太平洋进行船基现场培养实验,研究微量元素Fe (50 nmol/L)、酸化(pH=7.9)、酸化(pH=7.9)和微量元素Fe (50 nmol/L)耦合作用、微量元素Fe (50 nmol/L)和N/P (16∶1)耦合作用及沙尘(4 mg/L)对浮游植物释放CH₃I、CHCl₃、C₂HCl₃和CH₂Br₂含量的影响。结果表明,与对照组相比,实验组CH₃I、C₂HCl₃和CH₂Br₂的释放均被不同程度抑制;CHCl₃的释放除添加沙尘时表现抑制作用外,其他条件下均为促进作用;实...     

Pre-eruptive Conditions of the Huerto Andesite (Fish Canyon System, San Juan Volcanic Field, Colorado): Influence of Volatiles (C-O-H-S) on Phase Equilibria and Mineral Composition

Crystallization experiments at 400 MPa, oxidized condition (logfO₂= NNO + 1, where NNO is nickel–nickel oxide buffer) andover a range of temperatures (850–950°C) and fluidcomposition (XH₂O_in = 0·3–1) have been carriedout to constrain the storage conditions of the sulphur-richmagma of the Huerto Andesite (an anhydrite, pyrrhotite, andS-rich apatite-bearing, post-Fish Canyon Tuff mafic lava). Theresults are used to evaluate the role of fluids released fromthe crystallization of magmas such as the Huerto Andesite onthe remobilization of the largely crystallized dacitic FishCanyon magma body. Experiments were performed using the naturalandesitic bulk composition with and without added sulphur. Thepresence of sulphur slightly affects the phase equilibria bychanging the phase proportions, stability fields of plagioclase,pyroxenes and ilmenite, and also affects the plagioclase composition.Phase equilibria and mineral composition data indicate thatthe magma may have contained 4·5 wt % water in the meltand that the pre-eruptive temperature was 875 ± 25°C.Assuming that the magma was in equilibrium with a fluid phase,the CO₂ concentration of the melt is estimated to be in therange 2000–4000 ppm (at 400 MPa). Before eruption, theandesite had an oxidation state very close to, or slightly within,the co-stability field of anhydrite–pyrrhotite at NNO+ 1·1. At these conditions, the sulphur content in themelt is 500 ppm. Assuming open-system degassing resulting fromcontinuing crystallization at depth, most of the CO₂ dissolvedin the andesitic melt should be released after the crystallizationof <10 vol. % of the magma, corresponding to a cooling from875 to 825–850°C. Thus, the fluids released owingto crystallization processes should be mainly composed of waterat temperatures below 825°C. KEY WORDS: experimental study; andesite; volatile; Fish Canyon Tuff; Huerto Andesite     

Exchange of Short-Chain Oxygenated Volatile Organic Compounds (VOCs) between Plants and the Atmosphere: A Compilation of Field and Laboratory Studies

Field and laboratory investigations of the exchange of the short-chain organic acids – formic acid and acetic acid – as well as their homologous aldehydes are discussed. Both acids are substantially released from several plant species. Emission measurements under field conditions are compiled to give an overview of three years of measurements. Emission rates from several tree species were found in the range between zero and 60 nmoles m^–2 min^–1 for acetic acid and between zero and 90 nmoles m^–2 min^–1 for formic acid though also a deposition has been observed to orange trees. Investigations under laboratory conditions showed an order of magnitude lower emission rates with significant differences under light and dark conditions, and a deposition was observed under certain conditions. Hence, low emission rates or even a bi-directional exchange, emission as well as deposition have to be taken into account. Further differences between field and laboratory studies are discussed considering age of trees, stress effects and a potential production of acids by photochemical conversion of precursors inside enclosures during sampling. Field data on the exchange of form- and acetaldehyde show a complex behavior. We found emission as well as uptake. The bi-directional exchange is significantly triggered by the ambient mixing ratios of both aldehyde species and exhibits a compensation point. Further studies are needed for generalization of the exchange of these and potentially also for other compounds.     

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.