我国硫资源供需状况及需求预测

全球硫资源特征及国内硫资源供需现状表明,国内硫资源贫乏,硫资源生产与消费逐年增加,尤其磷肥生产对硫资源的需求越来越迫切,预计到2020~2025年磷肥用硫量将达到峰值1620万t左右,不包括出口磷肥耗硫量。因此,加强硫资源的综合利用、加大硫铁矿找矿及矿山设计是非常有必要的。     

高峰100号矿体硫、铅同位素特征

10 0号矿体的成矿物理化学环境为 :成矿温度 30 0± 30℃ ;成矿压力为 84.2× 10 5Pa ;LogfO2 =- 30 .4～- 35 .6 ,LogfCO2 =- 2 .5 5～ +0 .36 ,LogfS2 =- 8.3～ - 11.0 ,pH =4.2～ 4.9。同位素的分析结果 :硫化物的硫同位素为 6 4‰～ 12 .3‰ ,δ3 4 SΣS 值为 6 6～ 13 8;2 0 6Pb 2 0 4Pb值为 17 4 91～ 18 96 0 ,2 0 7Pb 2 0 4Pb值为 15 5 39～15 940 ,2 0 8Pb 2 0 4Pb值为 37 95 7～ 39 4 90。表明 10 0号矿体的硫源是混合硫 ,铅源是两种异常铅混合的结果。     

微量硫化物、硫酸盐硫同位素EA-IRMS在线测试分析

常规EA-IRMS硫同位素测试中,硫化银(Ag2S)的需样量为0.2~1.0 mg,硫酸钡(BaSO4)的需样量为0.35~1.5 mg,较大的需样量已难以满足珍贵样品及微区样品的分析要求,因此如何减少测试样品量已成为EA-IRMS测试分析工作中急需解决的问题.通过对EA-IRMS测试系统的研究发现,在采用常规方法测试样品时,由于初始He载气流速(100 mL/min)、进入分流接口时的流速(10 mL/min)与进入离子源时流速(0.3 mL/min)的差异导致样品燃烧产生的目标气体中99.7%的气体被浪费,样品的总体利用率仅有0.3%.因此如何减少样品在测试过程中的损耗,提高样品的利用率,从而减少需样量的关键在于缩小载气流速的差距.本实验在常规EA-IRMS测试技术基础上进行了关键改进,在元素分析仪和分流接口之间设计增加一个由六通阀和自动加热冷阱构成的装置,自动加热冷阱可在Load模式时收集SO2气体,六通阀在Load-Inject模式之间切换时可改变He载气流速,通过与分流接口匹配的反吹He载气(10 mL/min)将冷阱中富集的SO2气体送入分流接口,从而保证进入分流接口前样品燃烧产生的SO2气体全部收集.这一改进,理论上可以将样品的利用率提高10倍,该系统需硫量降至3~13μg,并且可以提高反应管的寿命,降低清灰的频率,提高工作效率.同时有效避免了拖尾的产生,提高分析结果的精密度.本次微量样品实验获得的硫同位素数据与常规方法一致,分析精度优于0.15‰(1SD),测量值与真值的差异在0.4‰以内,达到国际同类实验室先进水平.此外,该方法可为微量有机碳、氮同位素EA-IRMS测试分析工作的开展提供参考经验.     

高频燃烧—红外碳硫仪测定地质样品中的碳和硫

应用HIR-944B型高频-红外碳硫分析仪,对不同地质样品中碳、硫的测定进行了研究,称样30～60mg,加入0.4g纯铁屑及1.7g钨粒助熔剂,高温燃烧分解试样,红外检测,可定量地质样品中质量为0～O.9mg的硫及质量为0～15mg的碳.用该仪器测定地质标样中碳、硫的结果与标准值符合,碳和硫11次测定的RSD分别是＜2.6%和＜3.0%.     

The effect of gas-phase chemistry on aqueous-phase sulfur dioxide oxidation rates

The rates and mechanisms of both gas and liquid phase reactions for the oxidation of sulfur dioxide play an important role in the production of atmospheric acids and aerosol particles. Rhodeet al. (1981) concluded that sulfate production rates were highly non-linear functions of sulfur dioxide emission rates. Their modelling study used an HO _x termination mechanism for the HO—SO₂ reaction in the gas-phase. Stockwell and Calvert (1983) determined that one of the products of the overall reaction of HO with sulfur dioxide was an HO₂ radical. The National Research Council (1983) using a version of the Rhodeet al. (1981) model modified to include HO₂ production from the HO—SO₂ reaction concluded that sulfate production becomes much more linear with respect to reductions in sulfur dioxide emissions. However, the cause of this increased linearity was not explained by the National Research Council report. It is demonstrated that the increased linearity is due to the coupling of gas-phases and aqueous phase chemistry. The gas-phase sulfur dioxide oxidation mechanism has a very significant effect on hydrogen perodide production rates.     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

南华砷铊矿床雄黄标型特征

雄黄是云南省南华砷铊矿床中最主要工业矿物。它不仅与铊矿物共生，而且本身含有较高的铊，可高达（n×10～n×100）×10-6。砷铊矿床雄黄与砷矿床雄黄相比较在产出条件，微量元素、硫同位素和晶面间距等方面均有不同程度差别。前者富铊，低氯、高氟和硼，富轻硫同位素，相对贫稀土元素；后春富氯，低铊，高碘，富重硫同位素，相对贫碱土族元素。这些标型特征不仅有助于南华砷铊矿床进一步开发，而且有助于含雄黄的热液矿床，特别是As、Hg、Tl、Sb、Au等矿床的找矿勘探。     

滇东南都龙Sn-Zn多金属矿床交生硫化物微区主量元素、硫同位素特征及成因研究

都龙Sn-Zn多金属矿床位于滇东南老君山锡锌钨多金属成矿区南部,是中国3大锡石硫化物矿床之一。该矿床发育闪锌矿-黄铜矿-磁黄铁矿密切共生结构,即硫化物交生结构。文章利用电子探针和LA-MC-ICP-MS对具有交生结构的闪锌矿-黄铜矿-磁黄铁矿和毒砂进行了微区主量元素和硫同位素测试,以期明确其成因及硫的来源。主量元素测试结果显示,闪锌矿中的w(Zn)为52.23%~57.22%,w(S)为33.06%~36.10%,w(Fe)为9.92%~12.24%,w(Cu)为0.11%~0.30%;黄铜矿中的w(Cu)为33.95%~35.08%,w(S)为33.49%~35.27%,w(Fe)为30.74%~31.41%,w(Zn)为0.04%~1.50%;磁黄铁矿中的w(Fe)为49.30%~51.94%,w(S)为38.36%~39.69%,w(Zn)为9.35%~11.01%,w(Cu)为0.05%~0.15%。磁黄铁矿和黄铜矿包裹体边部和核部成分均一,且投影点全部落在固溶体出溶区域,说明都龙矿床交生闪锌矿-黄铜矿-磁黄铁矿是固溶体分离成因。原位S同位素分析结果显示,闪锌矿的δ³⁴S为0.9‰~3.2‰,磁黄铁矿的δ³⁴S为0.6‰~2.1‰,毒砂的δ³⁴S为2.9‰~4.2‰,黄铜矿的δ³⁴S为0.6‰~2.8‰,均显示为岩浆来源特征。主量元素温度计估算的闪锌矿-黄铜矿的形成温度介于285~394℃,指示该矿床主要硫化物形成于中高温阶段。     

珠江口沉积物酸挥发性硫化物与重金属生物毒性的研究

研究了2003年10月采于珠江口5个站位的沉积物剖面酸挥发性硫化物(AVS)和同时提取的重金属(SEM:Pb,Zn,Cu,Cd,Ni)。其中,站位1、2位于中滩,其沉积物的AVS含量变化范围较小,为0.25—4.06μmol.g-1;站位3、4位于西滩,其沉积物的AVS含量变化范围较大,为0—26.09μmol.g-1。中滩和西滩沉积物的AVS含量均随深度增加。西滩表层沉积物的AVS含量接近于零,这可能与该水域较强的底层流和沉积物的再悬浮作用有关。站位5位于珠江口外侧,其表层沉积物的AVS含量相对较高,且垂向变化较小,可能是还原性沉积物间歇性再悬浮后重新沉积的结果。站位1、2和5沉积物中同时提取的重金属含量大体在0.95±0.2μmol.g-1范围内,随深度增加略呈下降趋势;而西滩沉积物重金属含量相对较高,为1.43—2.42μmol.g-1,且在一定深度范围内随深度增加呈明显下降的趋势,表明珠江口西滩沉积物中的重金属污染有加重的趋势。对AVS/SEM摩尔比值和单个金属的毒性效应研究显示,珠江口内尤其是西滩的表层沉积物存在重金属污染,对其中生活的底栖生物具有潜在的毒性效应。     

农田生态系统大气硫沉降通量的观测研究

1998年 11月～ 1999年 10月间在中国科学院红壤站 (江西鹰潭 )农田小气候站进行了大气二氧化硫 (SO2 )、硫酸盐粒子 (SO2 -4)浓度采样和雨水样本收集 ,利用阻力模式和全年逐时气象资料计算 SO2 和 SO2 -4的干沉降速度 ,估算干沉降通量 ,利用降水资料和雨水中硫酸根离子浓度估计大气硫的湿沉降 ,从而定量研究大气硫沉降输入农田生态系统的通量 ,结果表明 :农田下垫面上 SO2 和 SO2 -4干沉降速度的年平均值分别是 0 .373± 0 .170 cm· s-1(月均值 0 .16 1～ 0 .5 45 cm·s-1)、0 .198± 0 .12 3cm· s-1(月均值 0 .15 2～ 0 .2 6 9cm· s-1)。农田下垫面硫年总沉降量为 10 .3g· m-2 ,其中干沉降占总沉降的 83.3%。硫的干沉降又以 SO2 的干沉降为主 ,占年干沉降总量的 92 .2 %。大气硫沉降输入占农田生态系统输入总量的 90 %以上 ,是农田生态系统获取硫素的一个重要途径