Spectroscopic studies of synthetic and natural ringwoodite, γ-(Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Synthetic ringwoodite γ-(Mg_1?x Fe _x )₂SiO₄ of 0.4 ≤ x ≤ 1.0 compositions and variously colored micro-grains of natural ringwoodite in shock metamorphism veins of thin sections of two S6-type chondrites were studied by means of microprobe analysis, TEM and optical absorption spectroscopy. Three synthetic samples were studied in addition with Mössbauer spectroscopy. The Mössbauer spectra consist of two doublets caused by ^VIFe²⁺ and ^VIFe³⁺, with IS and QS parameters close to those established elsewhere (e.g., O’Neill et al. in Am Mineral 78:456–460, 1993). The Fe³⁺/Fe_total ratio evaluated by curve resolution of the spectra, ranges from 0.04 to 0.1. Optical absorption spectra of all synthetic samples studied are qualitatively very similar as they are directly related to the iron content. They differ mostly in the intensity of the observed absorption features. The spectra consist of a very strong high-energy absorption edge and a series of absorption bands of different width and intensity. The three strongest and broadest absorptions of them are attributed to splitting of electronic spin-allowed ⁵ T _2g → ⁵ E _g transitions of ^VIFe²⁺ and intervalence charge-transfer (IVCT) transition between ferrous and ferric ions in adjacent octahedral sites of the ringwoodite structure. The spin-allowed bands at ca. 8,000 and 11,500 cm^?1 weakly depend on temperature, whilst the Fe²⁺/Fe³⁺ IVCT band at ~16,400 cm^?1 displays very strong temperature dependence: i.e., with increasing temperature it decreases and practically disappears at about 497 K, a behavior typical for bands of this type. With increasing pressure the absorption edge shifts to lower energies while the spin-allowed bands shift to higher energy and strongly decreases in intensity. The IVCT band also strongly weakens and vanishes at about 9 GPa. We assigned this effect to pressure-induced reduction of Fe³⁺ in ringwoodite. By analogy with synthetic samples three broad bands in spectra of natural (meteoritic) blue ringwoodite are assigned to electronic spin-allowed transitions of ^VIFe²⁺ (the bands at ~8,600 and ~12,700 cm^?1) and Fe²⁺/Fe³⁺ IVCT transition (~18,100 cm^?1), respectively. Spectra of colorless ringwoodite of the same composition consist of a single broad band at ca. 12,000 cm^?1. It is assumed that such ringwoodite grains are inverse (Fe, Mg)₂SiO₄-spinels and that the single band is caused by the split spin-allowed ⁵ E → ⁵ T ₂ transition of ^IVFe²⁺. Ringwoodite of intermediate color variations between dark-blue and colorless are assumed to be partly inversed ringwoodite. No glassy material between the grain boundaries in the natural colored ringwoodite aggregates was found in our samples and disprove the cause of the coloration to be due to light scattering effect (Lingemann and Stöffler in Lunar Planet Sci 29(1308), 1998).     

乌鲁木齐冬季大气细颗粒物水溶性离子特征及来源

为了探讨乌鲁木齐冬季大气细颗粒物的污染水平及其水溶性离子的特征,于2013年1-3月采集大气PM_2.5样品,并利用离子色谱仪分析其中的水溶性离子,采用硫转化率、离子相关性分析及后向轨迹模型对其可能来源进行了讨论。结果表明:观测期间采样点PM_2.5平均质量浓度为170.13±51.39 μg·m^-3,水溶性离子总浓度平均值为53.47±23.76 μg·m^-3,其中3种二次离子(SO₄^2-、NO₃^-和NH₄⁺)是水溶性离子的主要组分;不同天气类型下PM_2.5和离子浓度差异较大,雾、霾天气二次离子浓度占总浓度的81.99%和86.24%,硫转化率均大于0.1;春节期间由于燃放大量的烟花爆竹,使得PM_2.5可溶性离子K⁺和Cl^-浓度急剧上升;NH₄⁺与SO₄^2-、NO₃^-相关系数分别为0.975和0.748,(NH₄)₂SO₄、NH₄HSO₄和NH₄NO₃是细颗粒物水溶性组分的可能结合方式,Cl^-和K⁺的相关性显著,说明两者具有同源性;固定排放源仍然是乌鲁木齐大气污染物的主要来源,局地大气输送会使大气污染加重。     

Contribution of Secondary VOC to the Composition of Aqueous Atmospheric Particles: A Modeling Approach

Measurements show that 20–60% of the carbon mass present in fine atmospheric particulate matter consists of water soluble organic compounds (WSOC). However, only 5–20% of this WSOC has been identified, mainly as dicarboxylic acids. Because of their high solubility in water, multifunctional secondary compounds derived from the gas-phase oxidation of volatile organic compounds (VOC) are suspected to be key contributors to the WSOC. To test this assumption, an estimate of aqueous uptake of secondary VOC was included in a highly detailed gas-phase mechanism which treats explicitly the formation of the secondary VOC from a set of representative primary species. Simulations were conducted for 2 scenarios, representing typical rural and urban areas. It was observed that the uptake of secondary VOC can lead to WSOC mass concentrations in the range of a few C m^–3, in fairly good agreement with typical WSOC mass concentrations measured. Speciation of WSOC was found to be mainly as tri- or higher multifunctional hydroxy-carbonyl species and hydroxy-hydroperoxide-carbonyl species, in urban and rural environments, respectively. However, it was also found that taking into account only the absorption of secondary VOC does not bring the carboxylic acids mass concentration in agreement with measurements. An attempt was made to explain this discrepancy by introducing chemistry occurring within deliquescent aerosols.     

Removal of Cadmium Ions from Aqueous Solution by Silicate-incorporated Hydroxyapatite

This article reports a preliminary research on silicate-incorporated hydroxyapatite as a new environmental mineral used to remove cadmium ions from aqueous solutions. The silicate-incorporated hydroxyapatite was prepared by coprecipitation and calcining, and silicate was incorporated into the crystal lattice of hydroxyapatite by partial substitution of phosphate. The amount of cadmium ions removed by silicate-incorporated hydroxyapatite was significantly elevated, which was 76% higher than that of pure hydroxyapatite. But the sorption behavior of cadmium ions on silicate-incorporated hydroxyapatite was similar to that of pure hydroxyapatite. Morphological study revealed that silicate incorporation confined the crystal growth and increased the specific surface area of hydroxyapatite, which were in favor of enhancing the cadmium ion sorption capacity of the samples. Incorporation of silicate into hydroxyapatite seems to be an effective approach to improve the environmental property of hydroxyapatite on removal of aqueous cadmium ions.     

胶东大磨曲家金矿床成矿流体成分及稳定同位素研究

通过对大磨曲家金矿床不同类型矿石、蚀变岩中石英单矿物流体包裹体群体气液相成分,探讨金成矿流体由高温到低温流体成分演化与金成矿过程,结果证实:流体包裹体气相成分以H2O为主,其次为CO2,其余为CH4,C2H6,H2S,少量样品检测到少量N2和Ar2.流体包裹体液相成分中,阳离子主要为Na 和K ,Ca2 次之,少数样品检测到Mg抖;阴离子主要为Clˉ和SO42-,Fˉ含量也较高.高温阶段CO2含量缓慢降低,CH4 C2H6总量变化较大;低温阶段CO2含量快速降低,H2S含量缓慢降低,CH4 C2H6总量呈现增加趋势.由高温阶段到低温阶段K 含量降低,Na 含量增加,Ca2 变化不明显;阴离子组成SO42-含量急剧降低,Fˉ含量缓慢增加,Cl-含量快速增加.成矿流体稳定同位素组成δD水(SMOW)为-106.48‰～-95.52‰,δ18O石()(SM()w)为10.64‰～12.68‰,换算与之平衡δ18O水(SMOw)为1.88‰～5.78‰,δ13Cco2(PDB)为-6.264‰～-4.271‰.稳定同位素组成说明大磨曲家金矿床成矿流体可能为深部来源,可能与地幔排气和矿区内煌斑岩岩浆活动有关.     

Removal of Lead,Copper, Zinc and Cadmium from Water Using Phosphate Rock

Removal of Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from aqueous solutions by sorption on a natural phosphate rock （FAP） was investigated. The effects of the contact time and initial metal concentration were examined in the batch method. The percentage sorption of heavy metals from solution ranges generally between 50% and 99%. The amount of sorbed metal ions follows the order Cu〉Pb〉Cd〉Zn. Heavy metal immobilization was attributed to both surface complexation of metal ions on the surface of FAP grains and partial dissolution and precipitation of a heavy metal-containing phosphate. The very low desorption ratio of heavy metals further supports the effectiveness of FAP as an alternative and low-cost material to remove toxic Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from polluted waters.     

Major ions characteristics in a disturbed aquifer of an oceanic island——Sipadan, Malaysia

The Sipadan island is the only oceanic island found in Malaysia, and is popularly known for its beautiful corals and diving activities. The aquifer of the island is affected by seawater intrusion associated with groundwater exploitation. Geologically, the aquifer is composed of several series of Quaternary bioherm facies, and its recharge merely depends on rainfall. This research attempts to understand the chemical changes of the groundwater attributed to the salinization processes based on major ion composition （Ca^2＋, Mg^2＋, Na^＋, K^＋, HCO, SO, Cl^-）. The initial assessments were done in years 1993 - 1994, followed by subsequent assessment in years 2004-2005. Methods of analyses were adopted from APHA （1995）. The hydrogeochemical saturation indices （SI） were computed using the PHREEQC program in order to assess the state of equilibrium between groundwater and the minerals present. The results of analyses indicated that the groundwater has been highly enriched in Na^＋, SO and CI, reflecting an encroachment of saline water into the aquifer. The groundwater facies can be classified as sodium chloride （Na-Cl） water type. There are positive correlations （moderate to strong）, except HCO3^-, between the studied parameters. The weak and inconsistent correlation of HCO3^- with the cations and anions related to dissolved salts suggests that saltwater intrusion has an insignificant impact on the chemistry of HCO3^- in the groundwater. Strong correlations （r 〉0.70） exist among the major elements （Na^＋, Mg^2＋, K^＋, Cl^- and SO4^-） and salinity （EC）. These relationships clearly identify the main elements contributing to the groundwater salinity and their tendency to depict a similar trend of salinization pattern. Chloride has a major influence on the salinity of groundwater based on the positive and strong correlation that exist between Cl^- and EC （r=0.97）.     

石灰土对硫酸型酸雨缓冲过程模拟及碳汇效应研究

硫酸型酸雨沉降至地表经石灰土缓冲后,参与碳酸盐岩溶蚀及对岩溶碳汇的影响尚不明确,严重制约了我国岩溶碳汇效应的准确评估。本研究通过设置不同土层厚度条件下pH 4.5的硫酸型酸雨淋滤实验,以明确石灰土对硫酸型酸雨的缓冲过程及关键控制因素。结果表明：石灰土对酸雨的缓冲作用主要发生在表层(10 cm),淋出液中Ca2+、Mg2+、${\rm{HCO}}_3^{-}$含量在淋溶初期均表现快速降低,当淋溶量(土壤水达饱和后)为1 020 mL时Ca2+、Mg2+、${\rm{HCO}}_{{3}}^{-}$淋失量趋于稳定,稳定淋失量分别为20 mg·L−1、6 mg·L−1、40 mg·L−1。淋出液中被酸雨H+交换出的Ca2+、Mg2+仅占很小一部分,土壤水溶性Ca2+、Mg2+是淋出液中Ca2+、Mg2+的主要部分,开放系统中,大气和土壤CO2溶于降雨形成H2CO3不仅增加碳汇,且H2CO3解离产生的H+交换土壤中交换态Ca2+、Mg2+,造成Ca2+、Mg2+的淋失量不容忽视。不同厚度石灰土中交换性钙镁可缓冲酸雨容量均大于土壤碳酸钙矿物可缓冲容量,前者是后者的1.17~1.59倍。相同酸度、同一降雨量(土壤水达饱和后)下土壤盐基离子参与酸雨缓冲产生的碳汇量约为碳酸盐矿物风化缓冲产生碳汇量的2.1倍,不同厚度(≥10 cm)石灰土产生的碳汇量大致相等。根据本次实验及桂林市降雨数据计算,桂林市质纯石灰岩风化残积土壤区(土层厚度≥10 cm),土壤盐基离子参与酸雨缓冲每年可产生0.59 ~0.93 mol·m−2的碳汇通量。     

应用SHRIMP铀-铅定年法研究腾冲地区中更新世英安岩的形成时代

腾冲火山岩群是我国著名的年轻火山岩群,前人主要采用K-Ar法、不平衡铀系等同位素定年方法研究该区火山岩的年龄并划分其喷发期次,采用K-Ar法获得腾冲火山岩0.013~17.84 Ma的年龄以及0.13~2.9 Ma的等时线年龄,不平衡铀系法主要用于该地区0.23 Ma以来的样品年龄研究。传统的同位素定年体系的精确度和定年范围对于研究该区火山岩的年龄存有很大局限性。近年来,微区原位离子探针U-Pb定年在年轻地质体年代学研究中表现出巨大潜力,在国际上已经应用于中更新世晚期地质体的年龄测定。本文报道了应用锆石SHRIMP U-Pb定年方法对腾冲曲石地区中更新世英安岩的3次测定结果,3次实验的年龄值在误差范围内一致。在对一次离子流选择及其强度、二次离子积分时间等实验条件探讨的基础上,综合分析3次实验中的二次离子计数表明第3次实验结果具有更高的精确度,年龄值为0.41±0.01 Ma,属中更新世,代表该英安岩的形成时代,该年龄结果是目前我国获得的最年轻的高精度锆石SHRIMP U-Pb年龄。本研究获得的中更新世锆石U-Pb年龄为年轻地质体的年代学研究提供了新的思路。     

海水中微量无机离子的气相色谱测定的研究

本文讨论了介绍了用气相色谱法测定海水中无机离子Ｓｅ（－Ⅱ，Ｏ，Ⅳ，Ⅵ）；Ｂｅ（Ⅱ）；Ｃｒ（Ⅲ，Ⅳ）；ＣＨ３Ｈｇ＾＋，ＮＯ３，ＮＯ２，Ｂｒ，Ｉ，ＣＮ的测定方法和色谱条件。