关于成矿流体地球化学研究的几个问题

成矿流体地球化学是当前正蓬勃发展的流体地质学研究的一个重要分支。本文对八十年代以来国际上关于成矿流体地球化学研究的几个问题做了阐述，涉及到元素在熔体－溶液平衡体系中的分配、热水溶液系统中成矿元素的配合物形式及其主要影响因素，金属从成矿流体中沉淀机理研究等。提出了在成矿流体地球化学研究方面应重视的问题。     

赣南─粤西中生代岩浆杂岩与W、Sn、Nb、Ta的成矿

赣南-粤西地区的地壳自早元古代晚期开始形成，地壳成熟度较低。该区是我国华南重要的W、Sn、Nb、Ta等矿的重要产地，与中生代岩浆活动有关。成矿的岩浆杂岩具有高硅、富铝、富钾、高F／C1和Rb／Sr值，稀土配分具“海鸥型”模式，以及高Isr、b18O值和低εNd值的同位素特征，岩石成因属S型系列。矿石铅和长石铅同位素组成相似，反映成矿物质与成岩物质的原区相同，都由地壳物质衍生为主。矿床的形成与地壳演化历史，岩浆成因和岩浆源区物质组成等深部地质作用有关。     

宁镇山脉岩基的水平分带和垂直分带

宁镇山脉岩基中四个花岗岩类杂岩体具分带性。水平分带表现在单个杂岩体从边缘向核部的结晶顺序总是为:石英闪长岩→石英二长岩(花岗闪长岩)→二长花岗岩,斑晶含量随岩石酸度增加而降低,以致由斑状结构演化为等粒状结构,岩浆定位后的对流作用是这种水平分带的主要机理。与岩浆房内部对流结合起来的边界层环流作用使富钾流体在高位富集,导致晚期分异熔体从早期结晶外壳冲破出来移向高处而具垂直分带。认为每个杂岩体代表一批同源岩浆的演化系列或一个超单元。     

Critical Loads of Acidity for Forest Soils: Tentative Modifications

We reviewed the current methods for calculatingcritical loads of acidity for forest soils. The consequencesof four sets of assumptions concerning the soil modelstructure, parameter values and the critical loads criterionwere explored by comparing the values of the averageaccumulated exceedance (AAE) calculated for Finland withdeposition values for the year 1995. The AAE index is given inthe unit of deposition and is a measure of how far a region isfrom being protected in terms of fulfilling a certaincriterion, taking into account the size of the ecosystem areas.Using a critical limit for the molar ratio of theconcentrations of base cations to aluminium in soil solutiongave the lowest average accumulated exceedance. Assumingorgano-aluminium complexes and leaching of organic anions gaveAAE = 4 eq ha^-1 a^-1, which was close to the valueobtained with the standard approach used in Finland, assuminggibbsite equilibrium and no leaching of organic anions,yielding AAE = 5 eq ha^-1 a^-1. With a critical basesaturation limit, instead of the concentrations criterion, theAAE index was 17 eq ha^-1 a^-1. The highest averageaccumulated exceedance (AAE = 25 eq ha^-1 a^-1),corresponding to the lowest critical load, was obtained whenthe effects-based criterion (critical concentration or criticalbase saturation) was substituted with one restricting thedeterioration of the neutralizing capacity of the soil, ANC _le(crit) = 0. These tests illustrate the variabilityof the critical load values for acidity that can be introducedby changing the criterion or by varying the calculation method,without, however, representing the extreme values of criticalloads that could be derived.     

Removal of pentachlorophenol from contaminated soil by catalytic oxidation with iron(III)-porphyrin complexes and potassium monopersulfate

Pentachlorophenol (PCP) in contaminated soil was removed by treatment with aqueous solutions of iron(III)-porphyrin complexes as catalysts and potassium monopersulfate (KHSO₅) as the oxygen donor. The contaminated soils were artificially prepared by spiking PCP to the kaolin and ando soils. Three types of iron(III)-porphyrin complexes, tetra(?p-sulfophenyl) porphineiron(III) (Fe(III)-TPPS), tetra(N-methyl-4-pyridil)porphineiron(III) (Fe(III)-TMPyP) and heme, were examined, and Fe(III)-TPPS was found to be the most effective for removing PCP. Although the sequential addition of KHSO₅ was examined, in an attempt to improve the efficiency of PCP removal, it was not effective. In a preliminary test of various aqueous solutions, the addition of humic acid (HA), with a lower degree of humification, led to a significant enhancement in PCP removal. When HA was added to the soil system, the percentages of PCP removal were increased by up to 10% compared to the absence of HA. Therefore, the addition of HA to the catalytic system was useful in enhancing PCP removal from contaminated soil.     

Toxic effect of transition metal complexes on Salmonella typhi,Escherichia coli and Serratia marcescens

The present article describes the synthesis, structural features and toxicological studies of the complexes of the type [M(L)(dipy-amine)(H₂O)] or [M(L)(bendan)(H₂O)] where M?=?Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), H₂L?=?salicylidene-o-aminothiophenol, dipy-amine?=di(2-pyridyal)amine, or bendan?=?bis(benzylidene)1,8-diaminonaphthalene. The complexes have been characterized on the basis of elemental analyses, electronic spectra, magnetic measurement and thermogravimetric analyses. The nature of the bonding has been discussed on the basis of infrared spectral data. A thermal study of the complexes has been carried out to ascertain their thermal stability. Magnetic susceptibility measurements and electronic spectral data suggest a six-coordinated octahedral structure for these complexes. The complexes of Mn(II), Co(II), Ni(II), Cu(II) are paramagnetic, while Zn(II) and Cd(II) are diamagnetic in nature. The toxic effects of the investigated complexes were tested against three Gram-negative bacteria, Salmonella typhi, Escherichia coli and Serratia marcescens by the “Disc Diffusion Method”. It is observed that the complexes show higher toxic effects as compared to the ligands, metal salts and control (DMSO), but moderate toxic effects as compared to the standard drug (tetracycline) and the results are discussed.     

In vitro fungitoxic activity of some Schiff bases and their oxovanadium(IV) complexes

The oxovanadium(IV) (VO(IV)) complexes, Schiff bases, vanadyl sulphate, standard fungicides (bavistin and emcarb) and control (dimethyl sulphoxide) were tested for their in vitro fungitoxic activity on A. niger, F. oxysporum and A. flavus. The oxovanadium(IV) complexes show higher fungitoxic activity as compared with the free ligands, vanadyl sulphate and control (dimethyl sulphoxide), but moderate fungitoxic activity as compared with the standard fungicides (bavistin and emcarb). Oxovanadium(IV) complexes have been prepared with biologically active Schiff bases viz. the potassium salt of salicylidene-DL-alanine (sal-ala), 2,2′-bipyridylamine (bipym), bis(benzylidene)ethylenediamine (benen), thiophene-o-carboxaldeneaniline (tca), thiophene-o-carboxaldene-p-toluidine (tct), bis(benzylidene)-1,8-diaminonaphthalene (bendan) or bis(acetophenone)ethylenediamine (acphen). They have been characterized on the basis of elemental analysis, thermogravimetric analysis, magnetic measurements, electronic and infrared spectra. An octahedral geometry has been tentatively assigned to all the complexes.     

Sorption and mobility of polyethylene glycol (PEG 4000) in tropical soils

Millions of tons of polyethylene glycols (PEGs) are manufactured worldwide and most of them will reach conventional sewage disposal systems after industrial utilization. This raises environmental concerns, but not much is known about the environmental fate of these polymers. The main goals of this research were to evaluate sorption and mobility of PEG in sandier soils of Brazil. PEG 4000 was applied to the soils either freely in solution or as a simulated bioassay residue. The bioassay was prepared to simulate PEG as it is present in the animal feces. It allowed us to compare PEG mobility for both forms of environment disposal. PEG showed very low sorption (<22% of the applied PEG) and high mobility potential (>43% of the applied amount in the free-PEG and >24% of the applied amount in the bioassay-PEG experiment) in the studied soils. When PEG was applied, simulating its supply to animal diets, about 30% of its applied amount was retained into the bioassay residues and its leaching potential was reduced, whereas the remaining amount (about 70%) was readily available in solution and could be directly released into the environment.     

Fluorescence studies of dye displacement from DNA by chromium(III) complexes: Evidence for cation induced DNA condensations

The interactions of 10 different chromium(III) complexes with isolated calf thymus DNA have been analysed by studying the electronic and fluoresence spectra of intercalated ethidiumbromide. Triply charged cationic complexes including: [Cr(urea)₆]Cl₃.3H₂O, [Cr(1,10‐phenanthroline)₃](ClO₄)₃.2H₂O, [Cr(2,2'‐bipyridyl)₃] (ClO₄)₃.2H₂O, [Cr(ethylendiamine)₃]Cl₃.3.5H₂O and [Cr(NH₃)₆](NO₃)₃ displaced the dye from DNA. Similar effects were observed in experiments using the non‐intercalating dye bisbenzimidazole ("Hoechst 33258"). However, singly charged cationic, anionic and uncharged chromium(III) complexes such as: cis‐[Cr(1,10‐phenanthroline)₂Cl₂]Cl.2H₂O, cis‐[Cr(2,2'‐bipyridyl)₂Cl₂]Cl.2H₂O, [Cr(glutathione)₂]Na₂, [Cr(cysteine)₂]Na.2H₂O and [Cr(glycine)₃] were unable to displace both ethidiumbromide and bisbenzimidazole from DNA. There was no evidence for the formation of co‐ordinate bonds between chromium(III) and DNA for any of the above complexes. The charge and type of ligand are important in controlling the interaction of chromium(III) with isolated DNA in vitro. Our findings indicate that the outer sphere interaction of a chromium(III) complex with DNA is weak and unlikely to be the mechanism by which chromate causes DNA impairments in vivo and in vitro.     

Ti-Fe复合氢氧化物的制备及其对水中As(Ⅲ)的去除

采用共沉淀法制备了新型Ti-Fe复合氢氧化物吸附剂,并对其表面特性及除砷性能进行了初步研究。比表面和孔隙测试结果表明:2种Ti-Fe复合氢氧化物TF和TM的比表面积分别为148.6,147.6 m2/g,平均孔径分别为6.2,6.5 nm。Lagergren二级吸附动力学模型,可以很好地描述Ti-Fe复合氢氧化物吸附去除As(Ⅲ)的动力学过程。Freundlich和Langmuir方程均能较好地描述Ti-Fe复合氢氧化物吸附As(Ⅲ)的过程,而且Freundlich方程的拟合效果更好(R2>0.96);TF和TM对As(Ⅲ)的饱和吸附容量分别达到76.92,38.76 mg/g。当PO34-浓度小于2 mmol/L时,TF和TM对As(Ⅲ)的去除率分别可以达到空白样的90%和80%以上;浓度为10 mmol/L时,去除率也可分别达到60%和55%。Ti-Fe复合氢氧化物能够有效减轻PO34-对吸附性能的抑制。