海洋沉积物中磷化氢的分布、释放与转化研究

磷化氢（PH3）是磷循环的气相载体，以气体自由态和基质结合态（MBP）两种形式存在于环境中。自然环境中磷化氢的发现是对磷生物地球化学循环的重要补充，它在磷循环中的地位和作用及产生机制开始成为人们关注的热点。目前国内外在湖泊、陆地土壤及大气中已开展了较为广泛的研究，但是关于海洋中的研究还较少。开展磷化氢在海洋沉积物中的分布特征，及其释放通量、与其它磷形态的转化、对微藻生长的影响等行为研究对弄清海洋环境中磷化氢的迁移转化机制及其在磷循环中的作用和地位具有重要的科学意义。 本论文以不同环境条件下的海洋沉积物为研究对象，采用野外实验与室内模拟相结合的方法，运用改进的柱前二次低温冷阱富集和气相色谱-氮磷检测器联用技术等分析手段，系统研究了海洋沉积物中磷化氢的分布特征、环境因子对其分布的影响、沉积物磷化氢向水体、大气中的释放、迁移、转化规律；初步了解了海洋沉积物中结合态磷化氢的分布特征及其释放通量；揭示了磷化氢对海洋环境的可能影响。主要研究结果如下： MBP广泛存在于海洋沉积物中。中国沿海表层沉积物中MBP的浓度范围为：0.89-25.86 ng/kg, dry，其分布也表现出一定的空间分布特征，在同一离岸断面上，有近岸浓度高，远岸浓度低的分布规律；在北黄海、南黄海、东海北部海域、东海南部海域和南海海域的平均浓度分别为：5.57±3.78、3.78±2.81、5.27±3.07、5.48±4.05 和 13.52±7.86 ng/kg dry，与其它海域相比，南海海域的MBP浓度要相对较高一些。长江口海域表层沉积物中MBP的浓度范围为：1.93-94.86 ng/kg, dry。其分布也表现出一定的空间和季节分布特征。上游河口沉积物中MBP的浓度要普遍高于下游河口，平均浓度分别为31.34和4.79 ng/kg, dry。靠近石洞口、竹园排污口以及黄浦江口��S3和S4站位处MBP的浓度要显著高于其它站位，季节平均浓度分别为43.01和61.54 ng/kg, dry。MBP浓度的季节差异并不显著，上游河口和下游河口MBP浓度表现出相似的季节变化特征，一般来说8月和11月要稍高于2月和5月。澳大利亚伊拉瓦拉海湾柱状沉积物中的MBP表现出一定的垂直分布特征。两个柱状沉积物样品均在中下层存在MBP的高值区，且该海湾MBP的含量要远高于中国近海及长江口海域MBP的含量，两个柱状沉积物中MBP的平均浓度分别为637.3和542.6 ng/kg, dry。 环境因子与MBP含量关系的研究结果表明：较高的TP、OP、IP、OC、TN含量均有利于高浓度MBP的产生；TP、OP、OC与MBP含量之间存在着较强的线性相关关系，是控制MBP分布的主要因素；氧化还原电位与MBP含量存在着显著的线性负相关，说明还原环境更有利于沉积物中高浓度MBP的存在；平均粒径与MBP含量存在着一定的线性负相关，说明小粒径有利于高浓度MBP的存在；水深、上升流引起的扰动等也是影响MBP分布的可能原因。并且，在本论文对中国沿海沉积物、长江口沉积物和澳大利亚海湾沉积物的研究中，均得到了MBP含量与OP存在着强烈的线性相关关系，而与IP的线性相关关系较弱或不相关的结论，说明海洋沉积物中的MBP更可能来源于微生物对有机磷成分的降解。另外，长江口海域沉积物中MBP含量与上层海水中活性磷酸盐、总磷、叶绿素a的含量也存在着一定的线性相关关系，说明沉积物中磷化氢的释放可能会对上层水环境产生影响。 静态箱法释放通量的研究结果显示，胶州湾海域沉积物存在着磷化氢的释放现象。沉积物-大气界面和水-大气界面磷化氢的释放通量分别为：27.77和17.37 ng/(m2•h)，该结果要高于Louisiana湿地、水稻田和太湖水体磷化氢的排放通量。并据此估算出胶州湾的磷化氢年排放量为75.75kg/y，高于太湖及比利时垃圾填埋场的磷化氢年排放量。不同底质沉积物释放磷化氢的顺序为：虾池沉积物>滩涂沉积物>海滩黑泥沉积物>海滩排污口旁的砂质泥；践踏能显著促进磷化氢的释放。磷化氢的释放通量与沉积物中MBP的含量有显著的线性相关关系；胶州湾养殖池、滩涂沉积物及海域水体是大气中磷化氢的重要来源，沉积物中的磷化氢可连续向上层水体或大气中释放。晴天，胶州湾近海海域空气中磷化氢的浓度范围为1.06-16.90 ng/m3，且表现出早上和傍晚高，中午时分相对较低的变化规律；空气中磷化氢的浓度与光照强度及释放源释放量的大小有关。 利用室内模拟方法，研究了磷化氢在海水中的转化过程及其对海洋微藻生长的影响，并得出了一些初步结论。日光灯照射条件下，通入海水中的磷化氢可部分转化为磷酸盐和总磷，并且转化后主要以磷酸盐的形式存在。环境条件会对该转化过程产生影响，避光条件下，磷化氢的转化率较低，日光灯照射和紫外灯照射均能促进该转化过程，特别是紫外灯照射，促进效果显著；添加氧气或三价铁离子氧化剂也能促进该转化过程。微藻生长实验结果表明，适量磷化氢气体的通入，能显著刺激并促进磷限制条件下东海原甲藻和赤潮异弯藻的生长，但这种刺激作用并不是无限制的，后期刺激生长作用会变弱或停止生长；低量磷化氢气体的通入，刺激作用不明显；高量磷化氢气体的通入，则会抑制两种海洋微藻的生长。东海原甲藻和赤潮异弯藻对通入磷化氢的响应略有差异，后者对磷化氢的反应更为灵敏； 次磷酸盐和亚磷酸盐也都能刺激两种海洋微藻的生长，但与磷化氢相比，其影响作用相对较小。 本论文的初步研究结果表明，在磷的海洋生物地球化学循环中，需要考虑磷化氢的作用，其长期、连续的释放对磷循环的贡献不可忽视，并可能是磷限制海域赤潮形成的补充机制。

川西獐牙菜中不同部位3种药用成分的反相高效液相色谱测定

目的：建立野生与栽培的川西獐牙菜中不同部位3种有效成分，即龙胆苦苷（S1）、芒果苷（S2）、7-O-β-D-吡喃木糖-1，8-二羟基-3-甲氧基山酮��S3）的反相高效液相色谱定量分析方法。方法：色谱柱为Kromasil C18（250mm×4．60mm，5μm），流动相为甲醇-0．02％磷酸水溶液，梯度洗脱，洗脱条件为0min→50min→55min，甲醇：20％→80％→100％；流速为1mL·min^-1，检测波长为260nm。结果：该方法具有很好的线性关系和回收率。结论：本方法简单、准确、快速、实用性强。川西獐牙菜中3种药效成分在花的部位含量最高。

东准噶尔和尔赛斑岩铜矿特征及其形成的构造背景

Hersai porphyry copper deposit(PCD) of eastern junggar, newly discovered copper deposit, is located at the eastern segment of the Xiemisitai-Kulankazigan-Zhifang-Qiongheba Paleozoic island arc, Eastern Junggar. The Hersai PCD is developed in a intrusive complex, characterized by intensive and multiform hydrothermal alteration, including potassic alteration, silification, chloritization，sericitization，kaolinitization and carbonatization. Granodiorite, grandiorite porphyry, granite and concealed explosion breccia are hosts of the ore bodies containing veinlet and disseminated ore. Ore-bearing granite (ZK107-1-9), granodiorite (ZK107-1-9) and Ore-barren granodiorite (HES2-1) are selected to date zircon U-Pb age by SHRIMP method, and have an age of 429.4±6.4Ma ,413.0±3.4Ma and 411.1±4.8Ma, respectively, showing that they were emplaced from Late Silurian to Early Devonian. In addition, sample ZK107-1-9 has some hydrothermal zircons with a weighted mean 206Pb/238U age of 404.9±3.7Ma which is interpreted to be related to the granodiorite porphyry. Re-Os dating of five molybdenite samples yielded a weighted average model age of 408.0±2.9Ma, indicating the metallogenic epoch of the Hersai PCD. The ore-forming age is close to the petrogenic time of garnodiorite (411-413Ma), this suggests the ore-forming porphyry is most possiblely granodiorite porphyry. Systematic major - trace elements and Rb-Sr-Sm-Nd-Pb-Hf isotopic characteristics were studied. Analysis results show that these intrusives have some interesting and special characteristics, as following:1) containing both calc-alkaline rocks and high potassium calc-alkaline rocks ; 2) have some characteristics of adakite, but not totally, such as much lower La/Yb ratios and no Eu anomaly or just faint Eu anomaly; 3) have an initial 87Sr/86Sr ratios(0.703852-0.704565) similar to that of BSE, positive εNd(t) values between 6.1 and 7.4, the initial 206Pb/204Pb values (17.576-17.912), 207Pb/204Pb values (15.400-15.453) , 208Pb/204Pb values (37.252-37.466) , and high εHf(t) values (10.2-15.4) close to the value of depleted mantle. These geochemical features suggest that these igneous rocks in the Hersai area not only have some characteristics of island arc, but also some characteristics that only appear in the continental margin arc. It is suggested that Hersai PCD is formed in the subduction setting by the partial melting of young crust. These works and advancements mentioned in the paper are helpful to understand the deposit geology, geochemistry and metallogenesis of Hersai PCD. It is also significant to understand mineralization and tectonic setting in the Qiongheba area.

濮城油田沙三中6-10高分辨率层序地层学研究

The foundation of reservoir model and residual oil prediction have been the core of reservoir detailed description for improved oil production and enhanced oil recovery. The traditional way of sandstone correlation based on the geometrical similarity of well-logs which emphasizes "based on the cycle and correlating from larger to smaller" has shown its theoretical limits when explaining the correlating and the scale, geometry, continuity, connectivity of sandstones and the law of the reservoir property. It has been an urgent and difficult subject to find new theory and methods to solve the reservoir correlation and property prediction. It's a new way to correlate strata and found framework of reservoir through the process-response analysis in the base-level cycles. And it is also possible to analyze the reservoir property in reservoir framework. Taking the reservoir of zonation 6-10 in S3~2 of Pucheng Oil Field in Henan Province as an example, we founded the detailed reservoir stratigraphic framework through base-level correlation. In the strata frame, sediment distribution and its development are discussed based on sediment volume partitioning and facies differentiation analysis. Reservoir heterogeneities and its relation to base-level are also discussed. The analysis of primary oil distribution shows the base-level controlled oil distribution in reservoir. In this paper, subjects as following are discussed in detail. Based on the analysis of sedimentary structure and sedimentary energy, the facies model was founded. Founding stratigraphy framework through base level analysis In the studying zone, one long term cycle, 6 middle term cycles and 27 short term cycles was identified and correlated. 3 Predicting the property of reservoir for improving oil development The base level controlled the property of sandbody. The short and very short term cycle controlled the pattern of heterogeneities in sandbody, and the middle and long term cycle controlled the area and inter-layer heterogeneities. On the lower location of the middle and long term base level, the sandbody is well developed, with a wide area and large thickness, while on the high location of base level, there is an opposite reservoir character. 4 The studying of reservoir development response and oil distribution making a solid base for development adjustment Primary oil distribution is controlled by base level location. It tells that the sandbody on the high base level location was poor developed for its difficulty to develop. While on the low location of the base level, the sandbody is well developed for its relative easy to develop and dominant role in the development, but high residual oil for its high original oil content.

砷的水地球化学及其环境效应

砷在水环境中的迁移和富集可以产生严重的砷污染。砷在自然水系中主要以无机砷酸盐(A sO 43- ) 和亚砷酸盐(A sO 33- ) 两种形式存在, 而砷的有机化合物的含量一般都很低。砷酸盐在富氧化性的水体中占优势, 而亚砷酸盐则富集于还原性水体中。水体中A s3+ 和A s5+ 的相对含量主要受氧化还原条件和一些吸附—解吸平衡过程控制。A s3+ 类比A s5+ 类的毒性强得多, 而无机砷化合物比有机砷化合物的毒性大。在pH 值为5～ 6 时,A s5+ 不易被还原成气态A sH3, 而A s3+ 却能定量地被还原出来。根据这一性质, 可完成水体中A s3+ 和A s5+ 的测定。砷在饮用水中的安全阀值仅为10 LgöL 。水体中高砷的危害可以通过水质净化予以消除或降低。铁的化学沉淀和吸附法石灰软化法、活性氧化铝净化法和逆流渗透法等都可以有效地去除或降低饮用水中砷的含量。

新疆哈密香山基性—超基性杂岩体的岩石学和地球化学

香山基性—超基性杂岩体位于新疆哈密境内，地理坐标为东经94°30'-94°37'，北纬42°15'-42°20'。本文研究了该岩体的岩石学、地球化学、矿物学特征。最后提出了关于香山岩体成因的假设。香山岩体的主体是辉长苏长岩，它占整个杂岩体出露地表面积的绝大部分，其它岩石类型有斜长方辉橄榄岩、（斜长角闪）二辉橄榄岩，（斜长角闪）单辉橄榄岩、（角闪）橄榄辉长（苏长）岩，辉长岩。岩体中各种岩石均为中粗粒结构，块状构造。显微结构最特征的是包含结构，还有辉长结构，反应边结构，金属矿物较多时具海绵陨铁结构。主要蚀变类型有蛇纹石化，还有绿泥石化，透闪石化，滑石化、绢石化、钠黝帘石化、碳酸盐化等。杂岩体中的超基性岩的m/f = 1.9-4.6，属于铁质超基性岩，为与铜镍矿床有关的岩石类型。各种岩石在久野（1966）的Na_2O + K_2O → SiO_2变异图中，大部分属于碱性玄武岩系。但由于在CIPW标准矿物组成和薄片不均未发现富碱矿物（霞石或白榴石），因此，认为岩体的母岩浆是一种过渡型的碱性橄榄玄武岩浆。岩石的微量元素含量，从方辉橄榄岩至辉长苏长岩，随着基性度减小，Ti、V、Zn、Sr、Ba逐渐增加。Cr、Ni、Co、Cu逐渐减小。所有岩石均呈轻稀土富集型，从方辉橄榄岩、二辉橄榄岩、单辉橄榄岩直至辉长苏长岩，稀土总量和轻重稀土比L/HREE逐渐增加。方辉橄榄岩有Eu轻微正异常 、二辉橄榄岩Eu轻微负异常。单辉橄榄岩是具较大的Eu正异常，辉长苏长岩有正的或负的Eu异常，所有的岩石均具Ce轻微负异常。岩体中各种造岩矿物橄榄石为贵橄榄石，单斜辉石为顽透石或普通辉石，斜长石为拉长石，角闪石则为钙角闪石。岩石中各种矿物的结晶温度（用不同方法计算的结果比较一致）分别为：橄榄石1455～1654 ℃，单斜辉石976～1150 ℃（与母岩类型有关），斜长石1100 ℃左右，角闪石812-1002 ℃（与母岩有有关。岩体的母岩浆是在1200 ℃，25.9Kb（约80 KM深处）条件下上地幔岩经8-9%的部分熔融产生的（用平衡部分熔融状型计算得出）。岩浆结晶过程可用F_o-D_i-An三元相图定性说明，依次结晶生成：纯橄榄岩（未见）→ 辉石橄榄岩（方辉橄榄岩、二辉橄榄岩、单辉橄榄岩） → 橄榄辉长苏长岩，由于实际情况复杂，还有其它岩石类型生成。