Fluorescence Quenching and Energy Transfer Phenomena Associated with the Interactions of Terbium Ion and Humic Acid

Fluorescence of the hydrophobic acid fraction (HPOA) of Suwannee River natural organic matter and Tb³⁺ excitation spectra were measured in tandem using the instantaneous and time-resolved emission modes. The intensity of HPOA fluorescence decreased in the presence of Tb³⁺, while the intensity of the emission from Tb³⁺ cations bound by HPOA increased by up to several orders of magnitude due to energy transfer (ET) from HPOA to Tb³⁺ ions. To determine intrinsic ET and fluorescence quenching (FQ) coefficients, NICA–Donnan modeling was carried. It showed that phenolic groups in HPOA dominated both the ET and FQ processes and that the binding of Tb³⁺ by HPOA could be described using the non-ideality parameter n_Tb, median binding constant log \(\tilde{K}_{\text{Tb}}\) for the phenolic sites and intrinsic ET and FQ coefficients (denoted as η_TbΦ and α_TbΦ), and were 0.48, 8.5, 1385 and 0.12, respectively. The high value of the energy transfer coefficient of Tb³⁺ ions bound by the phenolic groups in HPOA is indicative of both the match between the electronic levels of the donor and acceptor, and the short distance between them. The deviation of the data of Nica–Donnan modeling of the ET and FQ dependence of versus [Tb]_total for a 1.0 M ionic strength highlights the need to quantify the distribution of donor–acceptor distances in HPOA molecules in more detail.     

双室电化学体系中产电微生物与黄铁矿单晶协同电子转移反应

通过构建产电微生物—黄铁矿双室体系, 应用电化学方法对以黄铁矿单晶电极作为产电微生物电子受体时, 两者间的电子转移过程进行表征和分析.结果显示, 与惰性石墨电极相比, 以黄铁矿单晶作为产电微生物电子受体时, 体系最大功率密度提升132.9%;电化学阻抗谱显示, 黄铁矿单晶电极极化电阻降低98.8%, 表现出优良的电化学反应特性, 表明产电微生物与黄铁矿单晶间具有良好的电子转移活性.籍由产电微生物对底物的氧化作用, 与黄铁矿单晶接受产电微生物电子在0.34 V(相对于饱和甘汞电极)处发生的还原反应, 构成了两者间完整的协同电子转移过程.      

Carbon Cycling and the Coupling Between Proton and Electron Transfer Reactions in Aquatic Sediments in Lake Champlain

We used fine-scale porewater profiles and rate measurements together with a multiple component transport–reaction model to investigate carbon degradation pathways and the coupling between electron and proton transfer reactions in Lake Champlain sediments. We measured porewater profiles of O₂, Mn²⁺, Fe²⁺, HS⁻, pH and pCO₂ at mm resolution by microelectrodes, and profiles of NO₃ ⁻, SO₄ ²⁻, NH₄ ⁺, total inorganic carbon (DIC) and total alkalinity (TA) at cm resolution using standard wet chemical techniques. In addition, sediment–water fluxes of oxygen, DIC, nitrate, ammonium and N₂ were measured. Rates of gross and net sulfate reduction were also measured in the sediments. It is shown that organic matter (OM) decomposes via six pathways: oxic respiration (35.2%), denitrification (10.4%), MnO₂ reduction (3.6%), FeOOH reduction (9.6%), sulfate reduction (14.9%), and methanogenesis (26.4%). In the lake sediments, about half of the benthic O₂ flux is used for aerobic respiration, and the rest is used for the regeneration of other electron acceptors produced during the above diagenetic reactions. There is a strong coupling between O₂ usage and Mn²⁺ oxidation. MnO₂ is also an important player in Fe and S cycles and in pH and TA balance. Although nitrate concentrations in the overlying water were low, denitrification becomes a quantitatively important pathway for OM decomposition due to the oxidation of NH₄ ⁺ to NO₃ ⁻. Finally, despite its low concentration in freshwater, sulfate is an important electron acceptor due to its high efficiency of internal cycling. This paper also discusses quantitatively the relationship between redox reactions and the porewater pH values. It is demonstrated here that pH and pCO₂ are sensitive variables that reflect various oxidation and precipitation reactions in porewater, while DIC and TA profiles provide effective constraints on the rates of various diagenetic reactions.     

Kinetic Controls on the Partitioning of Trace Elements Between Silicate and Sulfide Liquids

Mass transfer between sulfide and silicate liquids is oftendiscussed by reference to a mass ratio between hypotheticalliquid reservoirs at equilibrium, defined as R. In an open systemnot at equilibrium the mass of silicate melt from which a growingsulfide droplet appears to have scavenged chalcophile elementswill depend on diffusivities D_i and D_FeS of the element andof the FeS component in the silicate melt, respectively, onthe degree of supersaturation of the melt with FeS C^FeS_o, onthe radius a of the droplet and on the velocity v with whichthe droplet is advected through the melt, so that     

Effect of Atmosphere and Temperature Treatment on Leoanardite for Increasing Humic Acid Yield

In this review, the shifts in organic matter (OM) accumulation and C:N ratios in lake sediments to reconstruct paleoclimate and paleo-environmental changes since the early Holocene period are presented. The C:N proxy data of total OM reflect wet climatic conditions during early Holocene (10 to 8.2 kyrs BP) due to enhanced southwest monsoon. This was followed by intermittent arid conditions during the mid and late Holocene period (8.2 to 2.8 kyr BP). Enhanced values of C:N ratio during middle to late Holocene (7.8–2.3 kyrs B.P) indicate periods with lower lake levels and minimum precipitation, while decreased C:N ratio point to stronger SW monsoon and expansion of the lakes. Further, C:N and δ¹³C results from the lake sediments reveal a detailed and continuous paleo-environmental changes in the relative sources of OM (allochthonous vs autochthonous). Proxy records using such natural archives have also been utilized to reconstruct past extreme events and environmental changes around the lake systems, such as causes for lake desiccation, hydrographic changes, alternations between C₃ and C₄ vegetation and historical disturbances in the catchment area since the early-late Holocene period coupled with the Indian summer monsoon.     

过硫酸钠氧化-流动注射化学发光法在地下水腐植酸含量测定中的应用

在碱性条件下过硫酸钠能氧化腐植酸发生化学发光反应。本研究以过硫酸钠-腐植酸化学发光体系为基础,建立了腐植酸的过硫酸钠氧化-流动注射化学发光测定方法,同时对测定方法的负高压及增益、泵速、过硫酸钠浓度、氢氧化钠浓度等影响因素进行了优化实验。方法的线性范围为0.1～500 mg/L(相关系数为0.9985),检出限为0.076 mg/L,对浓度为0.5 mg/L的腐植酸进行11次平行测定,相对标准偏差(RSD)为3.47%。利用该方法对5种不同地区地下水中的腐植酸进行测定,样品的加标回收率在98.33%～107.50%之间。该方法无需分离,简单易行,对实际样品测定结果满意。     

Acidithiobacillus ferrooxidans-硫酸酸溶联合浸出金川铜镍硫化矿尾矿砂实验研究

金川铜镍硫化矿尾矿砂富含Cu、Ni和Co等金属,为对其进行回收,对新尾矿库不同深度的尾矿砂分别进行了直接硫酸酸溶浸出与A.f.-硫酸酸溶联合浸出实验,利用ICP-AES分析了不同阶段浸出液中Cu2+、Ni2+、Co2+含量。实验结果表明,A.f.-硫酸酸溶联合浸出工艺对尾矿砂中有价金属Cu、Ni和Co的浸出效果优于单独酸溶浸出工艺。其中,A.f.-硫酸酸溶联合浸出法对1m深度的尾矿砂中Cu、Ni、Co的浸出率最高,分别达到95.78%、98.01%和75.13%,而单独硫酸酸溶作用的离子浸出率分别为75.69%、74.33%和42.33%。     

Humic Ion-Binding Model VI: An Improved Description of the Interactions of Protons and Metal Ions with Humic Substances

Humic Ion-Binding Model VI, a discrete site/electrostatic model of the interactions of protons and metals with fulvic and humic acids, is applied to 19 sets of published data for proton binding, and 110 sets for metal binding. Proton binding is described with a site density, two median intrinsic equilibrium constants, two parameters defining the spread of equilibrium constants around the medians, and an electrostatic constant. Intrinsic equilibrium constants for metal binding are defined by two median constants, log K_MA and log K_MB, which refer to carboxyl and weaker-acid sites respectively, together with a parameter, LK₁, defining the spreads of values around the medians. A further parameter, LK₂, takes account of small numbers of strong binding sites. By considering results from many data sets, a universal average value of LK₁ is obtained, and a correlation established between log K_MB and log K_MA. In addition, a relation between LK₂ and the equilibrium constant for metal-NH₃ complexation is tentatively suggested. As a result, metal-binding data can be fitted by the adjustment of a single parameter, log K_MA. Values of log K_MA are derived for 22 metal species. Model VI accounts for competition and ionic strength effects, and for proton-metal exchange.     

腐植酸改性强化磁铁矿吸附水体中铅镉的实验研究

磁铁矿是一种绿色廉价的矿物材料,对水体中重金属离子具有良好的吸附性,但吸附容量低,选择性差,易团聚,通过改性可以克服该缺点并提高其吸附性能。本文以腐植酸为改性剂,采用常温水相反应制备了腐植酸改性磁铁矿吸附材料。通过傅里叶红外光谱(FTIR)、扫描电镜(SEM)和X射线光电子能谱(XPS)表征研究其表面形貌和微观结构。采用静态平衡实验考察了pH、吸附时间等因素对铅、镉吸附性能的影响,探讨了吸附动力学规律,拟合了吸附等温线。结果表明:腐植酸上的羧基、羟基被成功地接枝到了磁铁矿表面。在室温下,溶液初始pH对Pb~(2+)的吸附率几乎无影响,对Cd~(2+)的影响较大,当pH=7时,Pb~(2+)和Cd~(2+)吸附率均达到了95%。对初始质量浓度为10mg/L的Pb~(2+)、Cd~(2+)最佳吸附平衡时间为360min,吸附过程符合准二级动力学方程。吸附等温线实验得到的竞争吸附顺序为Pb~(2+)Cd~(2+),由Langmuir等温吸附模型得到Pb~(2+)、Cd~(2+)饱和吸附容量分别为39.27mg/g、28.95mg/g,显著大于磁铁矿的饱和吸附容量,表明磁铁矿经腐植酸改性后增强了对水中铅镉的吸附能力。     

西南印度洋中脊多金属硫化物矿产资源评价方法与指标体系

Based on the research of minerogenetic condition, ore-control factors, metallogenic geological environment and geological anomaly of polymetallic sulfide in Indian Ocean, the nine evaluation factors include water depth, structure, earthquake, gravity anomalies, magnetic anomalies, etc. were extracted and standardized. According to hierarchy analysis method, a structural model of four levels was designed. The comparison matrix was established to determinate thefactor weight. A set of perfectEvaluation methodology and indicator system was established. The results showed that the most favorable prospecting areas cover 58.33% of the research area and the more favorable prospecting areas cover 32.41% of the research area. This two areas are mainprospecting targets. This research findings provided a basis for lessening the target area in the future.     

针铁矿与盐酸反应的化学动力学研究

本文研究了针铁矿αFeOOH与盐酸反应的化学动力学特性,测定了它们的反应级数、速率常数、实验活化能和指(数)前因子。     

电子探针分析过程钠计数不稳定与物质结构关系的探讨

在以往工作的基础上,根据大量矿物的试验结果,探讨了Ｎａ不稳定程度与物质结构的关系。将不稳定矿物划分成３种结构类型,讨论了产生不稳定的机理与影响离子迁移的因素,较满意地解释了各种实验种象,且能预测可能出现Ｎａ不稳定的矿物种类,对寻找与研究快离子导体材料也有重要参考意义。     

内蒙古炭窑口硫化物矿床Fe、S同位素组成及对硫化物成矿的制约

古—中元古代时期是地质历史上最重要的铅-锌硫化物爆发性成矿阶段,位于我国华北板块北缘西段的狼山多金属成矿带是这个时期的典型案例.作为成矿带内最大的硫化物矿床,炭窑口和东升庙矿床赋矿层位和矿化特征一致,被认为是同一个次级盆地内一次大型热液成矿事件的产物.这两个矿床所赋存的数亿吨硫化物矿石均不同程度富集重S同位素(平均值>+30‰),而对于矿石硫的具体来源及34S富集机制尚存争议.本文对炭窑口围岩和矿石中黄铁矿进行了Fe-S同位素研究,对其沉积-成岩环境和矿化过程给出综合制约.炭窑口碳质板岩中粗粒黄铁矿δ56FeIRMM值在?0.51‰ ~ ?0.15‰之间,δ34SV-CDT值在+35.0‰ ~+39.6‰之间,相比东升庙矿床围岩中不规则黄铁矿明显富集轻Fe同位素且更加富集重S同位素,可能是盆地边缘、相对氧化的浅水环境下Fe以氧化态几乎完全沉淀后成岩期转化的产物.该认识与炭窑口矿区常见层状重晶石所指示的比东升庙更加氧化的盆地边缘浅水环境一致.本文认为炭窑口矿石与围岩中硫化物均强烈富集重S同位素(δ34SV-CDT值均在+26.6‰ ~+41.0‰之间)表明成岩环境同样是矿石硫化物结晶沉淀的主战场,其中半局限环境中浓缩海水硫酸盐在较封闭成岩条件下被甲烷为主的还原剂几乎完全还原."局限盆地+成岩环境"模式可以解释炭窑口—东升庙盆地围岩和矿石均异常富集重S同位素的特征.前人报道的与成矿关系密切的碳酸盐相对富集轻C同位素所指示的有机碳参与成矿为成岩环境成矿提供了可靠证据.尽管不能完全排除细菌还原硫酸盐的作用,炭窑口—东升庙盆地各个层位围岩与矿石轻S同位素完全缺失表明开放体系细菌还原作用导致的硫化水体环境主导成矿的可能性较小.     

Free Eu(III) Determination by Donnan Membrane Technique with Electrochemical Detection: Implementation and Evaluation

Aquatic Geochemistry - The aim of this study was to develop an analytical method to determine free concentrations of Europium (Eu(III)) in natural waters. Europium(III) in solution was detected...     

Experimental Study Assessing the Role of Sedimentary Organic Materials to Control the Redox State of Ground Materials to Control the Redox State of Groundwater: Consumption of Dissolved Oxygen by Humic Acid

Abstract: A total of 189 runs were completed to determine the rate of dissolved oxygen consumption in water by the reaction humic acid at 25°, 45°, and 65°C. Glass vial bottles were used as reaction vessels, and humic aicd and pure water of different intitial O₂ concentration was loaded with humic acid/water weight of 0.008 and 0.009. Vials were opened periodically to measure O₂ concentrations. The pH of the solution fluctuated in the early stages of the experiments and gradually decreased to a constant value. Dissolved oxygen concentration decreased, for example, from initial value of 12 mg/l to 9 mg/l at 25°C, to 5 mg/l at 45°C, and to 2 mg/l at 65°C after the reaction of 500 hours. Analyses of rates suggest that the reaction is first order, and rate constants are 8.42 × 10^-9 at 25°C, 2.22 × 10^-8 at 45°C, and 1.28 × 10^-7 moles m^-2 s^-1 at 65°C.     

水力联系系数法定量评价含水层之间水力联系

为了定量研究与评价含水层之间地下水水力联系程度,首次提出了水力联系系数C（hydraulic connection coefficient）的概念。将水力联系系数C定义为观测孔目的含水层水位降深与该观测孔位置抽水含水层水位降深的比值。通过水力联系系数,可定量评价某含水层水平上同层之间和垂向上不同含水层之间的水力联系程度。依据鄂尔多斯盆地白垩系洛河组各含水层段的水力联系系数C值,将含水层之间水力联系分为5个等级。其中,0.000 0 ≤ C<0.062 5,0.062 5 ≤ C<0.125 0,0.125 0 ≤ C<0.250 0,0.250 0 ≤ C<0.500 0,C ≥ 0.500 0,分别代表水力联系等级为极弱、弱、中等、强、极强。以高家堡井田钻孔抽（放）水试验数据为例,采用水力联系系数和观测孔水位响应时间两个指标定量评价了区内巨厚层状非均质洛河组含水层内部水力联系。结果表明：洛河组中上段水平同层之间的水力联系系数分别为0.373 0、0.413 8,观测孔水位响应时间较短（约为5 min）,水力联系强;洛河组下段水平同层之间水力联系系数分别为0.440 1、0.491 1,观测孔水位响应时间较短（为9~20 min）,水力联系强;洛河组中上段与下段垂向水力联系系数分别为0.000 2、0.007 2、0.089 7,观测孔水位响应时间较长（大于60 min）,水力联系极弱至弱。     

Composition of particulate organic matter in the southern Chesapeake Bay: Sources and Reactivity

The distribution of two classes of lipid biomarker compounds (fatty acids and sterols) was used in conjunction with several bulk parameters (total suspended solids, chlorophyll a, and particulate carbon and nitrogen concentrations) to examine spatial and temporal variability in the sources of particulate organic matter (POM) important to southern Chesapeake Bay. Based on these geochemical parameters, we found that suspended and sedimentary organic matter in the southern Chesapeake Bay is derived from autochthonous sources including a mixture of fresh and detrital phytoplankton, zooplankton, and bacteria. The dominant factor contributing to temporal variability during our study was phytoplankton productivity. Enrichments in particulate organic carbon, chlorophyll a, total fatty acids, total sterols, and a number of biomarkers specific to phytoplankton sources were found in particles collected from surface (1 m) and deep (1 m above the bottom) portions of the water column at several sites during the spring bloom in March 1996 and during a localized bloom in July 1995. Comparison of sites at the mouths of two tributaries (York and Rappahannock rivers) to southern Chesapeake Bay with two sites located in the bay mainsterm indicates spatial variation in the composition of POM was not significant in this region of the bay. The energetic nature of this region of the Chesapeake Bay most likely contributes to the observed homogeneity. Comparison with biomarker studies conducted in other estuaries suggests the high levels of productivity characteristic of the Chesapeake Bay contribute to high background levels of POM.     

粤西庙山铜多金属矿床硫化物微量元素LA-ICP-MS原位测定及S同位素对矿床成因的制约

庙山铜多金属矿床是在粤西阳春盆地内新近发现的一处铜多金属矿床。矿体主要呈似层状和透镜状产于泥盆系的陆源碎屑岩和含泥质的碳酸盐岩中。本文以矿石矿物黄铁矿和闪锌矿为研究对象,采用LA-ICP-MS原位微区分析新技术对其微量元素特征进行研究。结果表明,庙山铜多金属矿床中黄铁矿以富Se、Te和As,贫Ni元素为特征,其Co/Ni和S/Se比值特征指示其成因与岩浆热液型矿床密切相关;闪锌矿的微量元素组成指示其主要形成于中高温环境,以富Mn、In、Se,贫Ga、Ge、Tl等元素为特征,总体与国外一些典型的矽卡岩型矿床（如Baita Bihor、Majdanpek、Ocna de Fier和Valea Seaca）相似。同时,闪锌矿的部分微量元素比值（如Zn/Cd、Ga/In等）以及相关的微量元素图解（如Ge-In, Ge-Se等）均表明庙山矿床的成因类型与矽卡岩型矿床一致。硫同位素测试结果表明,矿石的δ34S值较为集中（-0.4‰ ~ +2‰）,平均0.69‰,具有较为明显的塔式分布特征,反映成矿物质具有岩浆来源的特征。以地质现象为基础,结合硫化物原位微区分析和硫同位素数据,我们认为庙山铜多金属矿床属于与岩浆热液有关的矽卡岩型矿床。     

与溢流性玄武岩有关的铜镍硫化物矿床地质地球学特征与成矿潜力分析——以广西罗城县清明山铜镍硫化物矿床为例

广西罗城县清明山铜镍硫化物矿床,镁铁质-超镁铁侵入岩与玄武岩广泛分布,时空关系密切,两者岩石化学成分丰度相同,均具有富MgO、贫SiO2、TiO2、K2O的特征,微量元素、稀土特征相同,具有成因上的联系和有先后演化的特征。含矿镁铁质岩体岩石化学成分SiO2含量为42.68～50.63%,K2O含量0.052～2.54%,TiO2含量0.326～0.63%;微量元素Rb,Ba富集,Ta、Nb亏损的特征,稀土元素含量中等ΣREE=27.56～52.36(10-6),ΣLREE/ΣHREE=7.17～12.31,(La/Yb)N=2.48～8.17,δEu=0.93～1.43,轻稀土富集,配分曲线右倾,无δEu负异常;硫同位素δ34S值4.52～17.04‰。镁铁质-超镁铁岩和铜镍硫化矿主要物质来源于幔源,有壳源混染;地质特征、地球化学特征等与美国Duluth铜镍硫化物矿床特征相同,为国内一种新的与溢流玄岩有关的岩浆铜镍硫化物矿床,资源潜力巨大。     

电子探针定量分析测定FeO和Fe2O3含量常用方法的评定

直接测氧法测定矿物中FeO和Fe2O3含量，在其众多影响因素中，经测量不确定度评定发现，超轻元素氧的影响显著。一方面受电子探针仪器因素和基体校正精度的限制，氧的电子探针定量分析值的准确度很低；另一方面氧对FeO和Fe2O3含量的不确定度灵敏系数分别为8．981、9．981，将氧的测量不确定度再扩大近10倍。可见直接测氧法测定FeO和Fe2O3含量，仅因超轻元素氧的测量不确定度传递就会使其误差范围过大，效果不是很理想。而利用Fe的Lα、Lβ谱线强度比的价态效应推测矿物中FeO和Fe2O3含量，由于Lβ/Lα强度比与Fe^2＋／Fe^3＋比值之间关系曲线的确定，需要对矿物进行大量的系统性研究，甚至是否必然存在这种对应都还缺乏理论依据，可见此法也并不可靠。相对而言，常用的电价差值法和剩余氧计算法仍为优选方案。