Distribution characteristics of matrix-bound phosphine along the coast of China and possible environmental controls

Matrix-bound phosphine (MBP) concentrations in surface sediments collected from 37 stations along the coast of China in 2006 are reported. MBP was found in all samples and the average concentration was 6.30 ng kg(-1) dry weight (dw). The distribution of MBP showed certain spatial variation characteristics with high MBP concentrations at stations near to the coast. The average concentrations of MBP in the northern Yellow Sea (NYS), the southern Yellow Sea (SYS), the northern area of East China Sea (NECS), the southern area of East China Sea (SECS), and South China Sea (SCS) were 5.57 +/- 3.78, 3.78 +/- 2.81, 5.27 +/- 3.07, 5.48 +/- 4.05 and 13.52 +/- 7.86 ng kg(-1) dw. respectively. The correlations between MBP and influencing factors, such as the sedimentary environmental characteristics (sediment type, the grain size, contents of phosphorous, organic matters and redox potential) and the aquatic environmental characteristics (temperature, salinity, depth and hydrodynamics) were studied. The results indicated that MBP was strongly influenced by various factors, such as total phosphorus (TP), organic phosphorus (OP), organic carbon (OC), the grain size and hydrodynamics, all of which not only offered reasonable interpretations for the distribution characteristics of MBP but also provided evidence to support the viewpoint that phosphine originated from OP decomposition. This work is the first comprehensive study of the distribution of MBP along the coast of China and its relationships with environmental factors which will lead to a better understanding of the phosphorus (P) biogeochemical cycle in the sea. (C) 2008 Elsevier Ltd. All rights reserved.

Studies on nitric oxide synthase activity in haemocytes of shrimps Fenneropenaeus chinensis and Marsupenaeus japonicus after white spot syndrome virus infection

The nitric oxide synthase (NOS) activity in the haemocytes of shrimps Fenneropenaeus chinensis (Osbeck) and Marsupenaeus japonicus (Bate) was Studied after white spot syndrome virus (WSSV) infection to determine its characteristics in response to virus infection. First, the NOS activity in haemocytes of shrimps was determined by the means of NBT reduction and changes in cell conformation. And the variations of NOS activity in shrimps after challenge with WSSV intramuscularly were evaluated through the analysis Of L-citrulline and total nitrite/nitrate (both as NO derivates) concentrations. The result showed that NOS activity in the haemocytes of F chinensis increased slightly from 0 to 12 h postchallenge, indicated by the variations Of L-Citrulline (from 11.15 +/- 0.10 to 12.08 +/- 0.64 mu M) and total nitrite/nitrate concentrations (from 10.45 +/- 0.65 to 12.67 +/- 0.52 mu M). Then it decreased sharply till the end of the experiment (84 h postchallenge), the concentrations Of L-Citrulline and total nitrite/nitrate at 84 It were 1.58 +/- 0.24 and 2.69 +/- 0.70 mu M, respectively. The LPS-stimulated NOS activity kept constant during the experiment. However, in M. japonicus, the NOS activity kept increasing during the first 72 It postchallenge, the concentrations Of L-Citrulline and total nitrite/nitrate increased from 7.82 +/- 0.77 at 0 h to 10.79 +/- 0.50 mu M at 72 h, and from 8.98 +/- 0.43 at 0 h to 11.20 +/- 0.37 mu M at 72 h, respectively. Then it decreased till the end of the experiment (216 h postchallenge), and the concentrations of L-Citrulline and total nitrite/nitrate at 216 h were 5.66 +/- 0.27 and 4.68 +/- 0.16 mu M, respectively. More importantly, an apparent increase of I-PS-stimulated NOS activity was observed in M japonicus at 48 h postchallenge, which was about 4 times higher than that in the control group of health shrimps. In correspondence with the difference of NOS activity between the two species of shrimps, the Cumulative mortalities of the shrimps were also different. All shrimps of F. chinensis in the mortality experiment died in 66 h, much more quickly than M. japonicus, Whose accumulative mortality reached 100% after 240 h. Data here reported let us hypothesize that NOS activity in the haemocytes of shrimps F chinensis and M. japonicus responses to WSSV infection differently, and this might be one of the reasons for the different susceptibility of F chinensis and M. japonicus to WSSV infection. (c) 2005 Elsevier Inc. All rights reserved.

Identification and mapping of amplified fragment length polymorphism markers linked to shell color in bay scallop, Argopecten irradians irradians (Lamarck, 1819)

Amplified fragment length polymorphisms (AFLP) were used to study the inheritance of shell color in Argopecten irradians. Two scallops, one with orange and the other with white shells, were used as parents to produce four F-1 families by selfing and outcrossing. Eighty-eight progeny, 37 orange and 51 white, were randomly selected from one of the families for segregation and mapping analysis with AFLP and microsatellite markers. Twenty-five AFLP primer pairs were screened, yielding 1138 fragments, among which 148 (13.0%) were polymorphic in two parents and segregated in progeny. Six AFLP markers showed significant (P < 0.05) association with shell color. All six loci were mapped to one linkage group. One of the markers, F1f335, is completely linked to the gene for orange shell, which we designated as Orange1, without any recombination in the progeny we sampled. The marker was amplified in the orange parent and all orange progeny, but absent in the white parent and all the white progeny. The close linkage between F1f335 and Orange1 was validated using bulk segregation analysis in two natural populations, and all our data indicate that F1f335 is specific for the shell color gene, Orange1. The genomic mapping of a shell color gene in bay scallop improves our understanding of shell color inheritance and may contribute to the breeding of molluscs with desired shell colors.

Speciation Analysis of Organotin Compounds in Shellfish by Hyphenated Technique of High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry(HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds in the shellfish samples. Agilent TC-C-18 column was selected, mobile phase of the HPLC was CH3CN:H2O: CH3COOH = 65:23:12 (V/V), 0. 05% TEA, pH = 3.0 at flow rate 0.4 mL/min. Five mixed organotin standards from 100 mu g/L to 0. 5 mu g/L was used for the method evaluation. The experimental results indicate that the linearity (R-2) for each compound was over 0.998. The shellfish samples were treated by supersonic extraction with mobile phase for 30min. Four organotin compounds including dibutyltin (DBT), tributyltin (TBT), diphenyltin (DphT) and triphenyltin (TPhT) in shellfish samples were detected with method mentioned above. It was found that the domain compounds in the samples were tributyltin (TBT) and triphenyltin (TPhT). The recoveries test from the standard addition for trimethyltin (TMT tributyltin (TBT), and triphenyltin (TPhT) were, over 80%. However, the recoveries for diphenyltin (DPhT) and dibutyltin (DBT) were relatively low, 37.3% and 75.2% respectively. The reason might be attributed to the decomposition of those compounds during the extraction procedure. The further study on this subject is under the progress.

青藏高原高寒草甸植物群落物种组成和生物量沿环境梯度的变化

生物多样性与生态系统功能的关系及其机制是生态学领域的重大科学问题．人们越来越关注环境因子对多样性-生产力关系的影响．植物群落组成、物种丰富度、物种特征、生物量的分布结构和植物枯枝落叶对高寒草甸物种多样性和生产力有着重要的影响．因此，我们利用2001～2004年中国科学院海北生态系统定位站高寒草甸群落的实测资料，研究了不同环境梯度（土壤含水量和营养）下，植物群落生物量，物种丰富度及组成的变化．结果表明，植物群落物种组成的不同反应在生物量的分布上，以藏嵩草为优势种的藏嵩草沼泽化草甸群落总生物量（地上、地下）最高（13196．96±719．69g／m~2），次之是以杂类草和莎草科为主的小嵩草草甸（2869．58±147．52g／m~2），以禾本科和杂类草为主的矮嵩草草甸最低（2153．08±141．95g／m~2）．藏嵩草沼泽化草甸中，草本植物枯枝落叶显著高于小嵩草、矮嵩草草甸，土壤含水量对草本植物枯枝落叶有较大的影响．不同类型草甸群落中，地上生物量与土壤有机质、全氮和群落盖度之间均呈显著正相关（P〈0．05）；藏嵩草沼泽化草甸中，总生物量与物种丰富度呈负相关（rs=-0．907，P〈0．05）、地下生物量与土壤含水量呈正相关（rs=-0．900，P〈0．05）；而在小嵩草和矮嵩草草甸中它们之间均没有达到显著水平，说明不同类型高寒草甸群落生产力除受物种多样性、功能群内物种密度和均匀度的影响，同时也受物种本身特征和外部环境资源的影响．不同类型草甸群落生物量的分布与土壤含水量和土壤养分的变化相一致．

甘肃胡麻地方种质资源品质特性研究

对甘肃省116份胡麻地方品种的重要品质指标--粗脂肪、硬脂酸、棕榈酸、油酸、亚油酸、亚麻酸含量和碘值进行测定,并根据这些品质指标对供试品种进行聚类分析.结果显示:(1)供试品种粗脂肪含量平均值为37.48%,变异系数3.8%;硬脂酸、油酸含量平均值分别为5.32%和29.05%,变异系数分别为19.5%和11.6%;棕榈酸、亚麻酸、亚油酸含量平均值分别为5.9%、48.76%、10.95%,变异系数分别为8.4%、8%、8%;平均碘价175.60,变异系数2.76%;(2)聚类分析结果显示,116个品种聚为7大类,其中:b亚组群硬脂酸和油酸含量最高,而亚麻酸含量最低;d亚组群品种亚麻酸含量最高;e亚组群粗脂肪含量和碘价最高,油酸含量最低;f亚组群硬脂酸含量最低;g亚组群棕榈酸含量最高,碘价最低.

海北高寒草甸辐射能量的收支及植物生物量季节变化

高寒草甸植物生长,可用Logistic方程描述.生物量的瞬时增长率过程是一个先缓慢增大,后快速增大,逐渐达到最大值,然后快速降低,最后缓慢下降,逐渐逼近零;生物量达到最大时需累积78d左右:讯据生物量的变化,将生长过程划分为返青期、茂盛期和枯黄期.枯黄期的反射率明显高于返青期和茂盛期,而返青期与茂盛期的反射率之间没有差异;返青期与茂盛期的日均辐射能量差异不显著(日均总辐射:Z=0.61,P0.81=0.05;日均辐射净:Z=0.87,P=0.44=0.05;日均有效辐射:Z=0.92,P=0.37=0.05):返青期和胶盛期的日均辐射能量均显著地高于枯黄期(日均总辐射:H=45.36,df=2,P＜0.01;日均辐射净:H:=32.41,df=2,P＜0.01:日均有效辐射:H=12.69,df=2,P＜0.01).有效辐射和反射辐射是影响地上生物量最重要的两个变量,但两个变量对地上生物量的作用效应各异,有效辐射是正效应,而反射辐射则是负效应.

放牧强度对高寒地区多年生混播禾草叶片特征及草地初级生产力的影响

在青藏高原东北缘-天祝县金强河地区进行了无芒雀麦(Bromus inermis)50%+垂穗披碱草(Clinelymusnutans)50%、无芒雀麦50%+多叶老芒麦(Elymu.s nutans)25%+扁穗冰草(Agropyron cristatum)25%、无芒雀麦25%+多叶老芒麦25%+垂穗披碱草25%+扁穗冰草25%,3类禾草混播草地的放牧试验,研究了不同放牧强度对混播禾草草地牧草叶片特征和草地生产力的影响.结果表明,重牧(70%左右的采食率)条件下,牧草和草群叶面积指数(LAI)下降(P＜0.05),叶片光合速率(Pn)减弱(P＜0.05),草地牧草现存量减少(P＜0.05);轻牧(30%左右的采食率)有利于无芒雀麦+垂穗披碱草草地和无芒雀麦+多叶老芒麦+扁穗冰草草地补偿性再生和生物量积累,中牧(50%左右的采食率)有利于无芒雀麦+多叶老芒麦+垂穗披碱草+扁穗冰草草地补偿性再生和生物量积累.青藏高原高寒地区,前2类混播草地适宜的放牧利用率为30%左右,后1类混播草地适宜的放牧利用率为50%左右.

窝雏数处理对两种雀形目幼鸟生长的影响

基于1997～1999年野外实验，对高寒草甸小云雀和黄嘴朱顶雀两种雀形目鸟的窝雏数进行增减处理。结果表明，对照组的幼鸟生长率和离巢体重都大于增加组，说明窝雏数增加后，幼鸟质量下降。随着窝雏数增加，这两种幼鸟生长率显著下降（小云雀：r = -0.965, P = 0.035 < 0.05；朱顶雀：r = -0.828, P = 0.022 < 0.05）。窝雏数改变对小云雀幼鸟出飞重影响不显著（r = -0.418, P = 0.528 > 0.05），而对黄嘴朱顶雀有显著的影响（r = -0.901，P = 0.014 < 0.05）。

Emodin-induced apoptosis in human breast cancer BCap-37 cells through the mitochondrial signaling pathway

Emodin, a natural anthraquinone compound isolated from the rhizome of rhubarb, is reported to suppress the growth of tumor in many clinical situations. In this study, we focused on the effect of emodin in human breast cancer BCap-37 cells and further understand the underlying molecular mechanism in treating breast cancer. Using MTT assay and flow cytometry, we demonstrated the critical role of emodin in the suppression of the proliferation of BCap-37 cells based on a concentration- and time-dependent manner. The increase of apoptotic rate was also observed after incubation of BCap-37 cells on emodin at 20 mu M and 50 mu M for 48 h. The cells exhibited typical apoptotic features including cellular morphological change, chromatin condensation and membrane blebbing. The results of the study further showed that Bcl-2 level decreased, while Bax and cytosolic cytochrome c levels in sample cells increased after the emodin treatment by using Western blot. The decline in the Bcl-2/Bax ratio and the increase of cytosolic cytochrome c concentration were consistent with the increase of the apoptotic ratio. The results strongly suggest that the disruption of the mitochondrial signaling pathway was involved in emodin-induced apoptosis in BCap-37 cells.

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.

针式微萃取结合GC-IRMS测定水溶液中甲酸、乙酸的稳定碳同位素组成

甲酸和乙酸稳定碳同位素组成（δ^13C）的分析对环境、食品、制药和自然产品等的研究具有重要的应用价值。但目前尚缺乏有效的测定方法。本研究利用最近出现的针式固相微萃取技术（NeedlEX），以吹扫．捕集方式对水溶液中的有机酸进行了萃取，然后利用气相色谱．同位素比值质谱联用仪（GC—IRMS）对所萃取的有机酸分子进行了占δ^13C的测定。结果显示，质谱计的信号强度与水溶液中有机酸的浓度存在显著的线性相关关系（R^2〉0．99，P〈0．05），表明Needl EX对水溶液中有机酸具有稳定的萃取能力。在甲酸与乙酸含量分别不低于300μg／mL与200μg／mL的水溶液中，1000mL的吹扫体积可以使两者δ^13C多次分析结果的相对误差分别保持在3％和1％左右，且整个实验流程没有造成可检测的碳同位素分馏作用。低于这两个浓度界线，则分析误差随浓度的降低迅速增加。本研究虽然是针对水溶液中有机酸δ^13C的测定，其萃取方法对其他水溶性挥发和半挥发有机物δ^13C的分析也同样具有应用价值.

贵阳市大气总悬浮颗粒物(TSP)的化学特征及其影响因素研究

气溶胶对气候和人类的健康都有重要影响。因此，研究大气总悬浮颗粒物（TSP）的化学组成和物理特性对更深入地了解气溶胶对气候和人类健康的影响具有重要意义。贵阳是中国受燃煤污染比较严重的城市之一，大气中高含量的SO2是其最明显的特征。尽管最近几年空气质量有所改善，但是该区的大气污染问题还比较严重，空气质量仍然不容乐观。我们于2005年1月1日到2005年12月31日在中科院地球化学研究所内全年采集总悬浮颗粒物（TSP）样品，分析测试了其主要无机离子（F-、Cl-、SO42-、NO3-、NH4+、K+、Na+、Ca2+和Mg2+）的化学性质，并结合当地的气象参数（温度，风速，降雨量和相对湿度）系统地研究了TSP及其水溶性无机离子的季节变化特征。本论文的主要结论有： 1. TSP的浓度变化范围为36.91～313.44µg/m3，年均值106.60µg/m3；各离子摩尔浓度的大小顺序为：SO42-> NH4+> Ca2+ > NO3-> K+ > Na+ > Cl- > Mg2+ > F-；SO42- (23.04±12.16µg/m3)和NH4+(3.05±2.23µg/m3)是最主要的离子，分别占总离子摩尔数的37％和30％。TSP及其组分都有明显的季节变化，TSP、Cl-、SO42-、NO3-、NH4+、K+、Na+、Ca2+和Mg2+浓度的冬/夏比值分别为:1.29、5.23、1.35、2.37、1.73、1.22、1.84、1.23和1.02。 2. 温度对TSP及其水溶性无机组分的影响呈现一定的季节变化模式，冬天随温度的升高TSP及其水溶无机组分的浓度也升高，夏天随温度的升高TSP及其水溶性无机组分的浓度降低。但是从全年来看，温度与TSP及其水溶性无机组分之间有弱的负相关性，即随温度的升高，TSP及其水溶性无机组分的浓度有不同程度的下降。相对湿度与TSP及其水溶性无机组分之间存在明显的负相关关系，即随大气相对湿度的增加，TSP及其水溶性无机组分的浓度下降。在相对湿度与TSP及其水溶性无机组分浓度的日变化图中表现为相对湿度的波谷与TSP及其水溶无机组分的浓度的波峰相对应。风速与TSP及其水溶无机组分的浓度之间呈现弱的负相关性。在贵阳，风速对TSP及其水溶无机组分的影响主要表现为扩散作用和稀释作用，由风速导致的尘土再悬浮作用并不明显。雨量对TSP及其水溶性无机组分的影响主要是湿清除作用，具体表现为无雨天TSP及其水溶性无机组分的浓度较雨天高。影响TSP、Ca2+、Mg2+和F-的主要气象参数是相对湿度(RH)和风速，影响SO42-、NO3-、NH4+和Cl-的主要气象参数是温度。 3. 贵阳大气总悬浮颗粒物（TSP）总体偏酸性，TSP水溶液pH值的年均值为6.27±0.41，与总阴离子与总阳离子的当量比Q的年平均值为0.82一致；TSP中高含量的SO42-是贵阳的TSP显酸性的主要原因。 4. NH4+与SO42-和NO3-的相关系数（R）分别为0.85和0.65，NH4+与SO42-的摩尔比值为0.8，说明贵阳TSP中的NH4+主要以(NH4)2SO4的形式存在。Ca2+和Mg2+有较好的相关性（R=0.72）和相似的变化特征，说明二者可能有共同的来源。 5. 2005年贵阳TSP中SO42-/ Ca2+的平均值为13.64，几乎是干净大陆SO42-/ Ca2+的本底值的20倍，说明贵阳的大气污染主要是人为因素所致。NO3-/SO42-的平均值为0.15，说明固定源对贵阳气溶胶的贡献比移动源（通常指交通工具所排放的尾气）对气溶胶的贡献大；

贵阳城市污水、河流及养鱼水域抗生素的地球化学行为

抗生素是广泛应用于人类和动物疾病治疗的药物，近年来在养殖业中抗生素更是常常作为动物催长剂。这些抗生素会通过人畜排泄物、药品的丢弃、污水排放、农业废物堆积等途径进入到环境中。环境中抗生素的残留会导致细菌耐药性的产生、微生态平衡的破坏，以及对生态环境和人类难以预知的影响。抗生素污染是近十年来才在国际上引起注意的新型环境问题，目前研究非常薄弱，要深入认识抗生素的环境影响特征就迫切需要对抗生素在环境中的迁移、归宿等地球化学行为进行针对性的研究。本文研究了贵阳城市污水、南明河及乌江渡水库中氯霉素（CAP）、土霉素（OTC）、四环素（TC）和金霉素（CTC）的环境地球化学特征，包括抗生素的分布、迁移特征及影响因素，并分析了贵阳市动物源性食品中抗生素的残留特征，探讨了环境因素对抗生素稳定性及吸附/解吸的影响，以期了解抗生素在环境中的降解、迁移等环境行为的特征，并据此评价抗生素的环境影响特点，为认识抗生素的污染特点、发展相应的控制、治理措施提供科学依据。主要内容包括： 1. 对环境样品中CAP和TCs的前处理过程和检测方法进行了优化。对水样的前处理采用固相萃取的方法，对土壤和沉积物的前处理采用EDTA-McIlvaine振荡萃取、SAX-HLB净化富集的方法；选择HPLC-UV作为分析的手段，对样品中的4种抗生素进行了检测，各化合物得到了很好的分离，该方法简便、快捷、重现性好。 2. 证实了抗生素在城市污水中的普遍存在。贵阳城市污水中以CAP的污染最为突出，其含量明显高于广州地区的城市污水；污水中四环素类药物（TCs）的含量和大多数欧美国家及地区城市污水中TCs的含量相当。这一结果证明，污水中抗生素的污染非常严重，对地表水环境形成严重的威胁。污水中抗生素的来源包括：人服用抗生素药物以及食用含有抗生素残留的食品之后的排泄物；食品中残留的抗生素随剩余食品的丢弃而进入污水。污水中抗生素的含量都具有明显的季节变化规律，冬春季含量明显高于夏秋季，我们认为这与各季节用水量和疾病特点有关。污水中抗生素的大量存在说明：1）抗生素存在滥用的现象，特别是CAP可能存在严重的违法使用，这一现象应当重视；2）污水中的抗生素会威胁水环境质量，应加强处理和控制技术。 3. 证明了城市河流受到多种来源的抗生素影响，其中城市污水是最重要的源，而且抗生素在河流中呈现一定的持久性。南明河上游河段中抗生素的来源包括郊区城镇污水、养鱼场、制药厂污水排放及地表垃圾。城市污水是抗生素的一大排放源，受其影响，排污口下游的河段受到的抗生素污染尤为严重，此外还有来自下游郊区城镇和农业污水的影响。对南明河中抗生素的来源及行为特点的剖析表明：1）抗生素在南明河的水和沉积物中具有不同的分布特征：河水中以CAP的污染最为严重，各水样中CAP的含量基本都高于TCs；而大部分沉积物中TCs的含量都高于CAP。CAP和TCs在水－沉积物之间的分布特征表明，它们在水环境中的地球化学行为明显受到吸附/解吸特点的影响，CAP的亲水性强，而TCs的亲粒性强。2）虽然在养殖业中已禁止使用CAP，但河水和污水中CAP的大量存在，这一结果揭露了CAP仍然存在大量违法使用的事实。3）河水中抗生素含量的季节差异明显，冬春季抗生素的含量高于夏秋季，其原因主要是夏秋季河水流量大，对河水中抗生素的稀释作用强。沉积物中抗生素的含量没有明显的季节变化规律，各季节抗生素的平均含量差异较小。4）受污水影响，各季节排污口下游的南明河水受到的抗生素污染尤为严重，污水口上下游之间的含量差异明显。沉积物在冬季受城市污水的影响大，在排污口下游的抗生素的含量明显高于上游，而春、夏、秋季受污水影响不明显。这可能是因为在春、夏和秋季其它污染源的影响较大，因此污水的影响强度减弱。夏季上游沉积物中CAP的含量甚至高于下游，原因一方面是因为夏季城市污水中抗生素含量低，对南明河的影响减小，另一方面可能因为夏季雨水多、水量大，将上游的地表垃圾以及积累在小河沟中的垃圾冲刷到南明河中，而这些工业及生活垃圾通常是抗生素的一大来源。 抗生素在河流中呈现了一定的持久性，在20 km的范围内水和沉积物显示了明显的污染水平，可能会对水生生态以及流域的环境造成一定的影响。此外，贵阳市南明河两岸的农田通常是用河水进行灌溉的，从而可能使抗生素的污染危及到食物链，对人体的健康有潜在的威胁。 4. 由于食品（如鱼肉、猪肉等）中残留的抗生素是污水中抗生素的重要来源，因此我们研究了养殖业（水产养殖区）中抗生素的环境行为特点，还研究了常见动物源性食品中抗生素的残留特点。对养鱼区的研究表明，养鱼饲料中含有大量的抗生素，是养鱼区水环境中抗生素的来源。由于饲料的颗粒大，且河水流速快，因此饲料中的抗生素不会对水体造成很大的影响，但是在网箱区的沉积物中形成了高含量的残留，除此以外，在乌江渡主航道的河心沉积物中抗生素的含量也相当可观。这说明该区水产养殖的抗生素主要影响沉积物，且相应的污染不是局部的，而会影响到整个养鱼区。从沉积物中抗生素平均含量的季节差异来看，各季TCs的用药量可能不同，秋季的用量可能最大，而其它季节用量相当；CAP在每个季节的用量可能相当。尽管分析的饲料中CAP的含量高于TCs，但在各季节乌江渡水库主航道沉积物中TCs的含量几乎都远高于CAP，这是由于TCs比CAP更易存在于沉积物中。乌江渡水库上下游主航道沉积物中抗生素的含量差异日益减小，说明了乌江渡水库的污染已日益严重。这些抗生素虽然暂时被固定在了沉积物中，活性相对较小，但是在外界条件的影响下，它们的吸附/解吸作用是可以改变的。因此，乌江渡沉积物中高含量的抗生素残留对水生生态环境具有潜在的威胁。 对贵阳市动物源性食品（鱼肉、猪肉和牛奶）中抗生素的残留特征的分析表明，这些食品中普遍残留有高含量的抗生素，被人食用后，其中的抗生素也会被人体摄入，一部分抗生素会随着人的排泄物而进入到污水中，并最终进入环境中；另一部分抗生素会积蓄在人体中，到一定浓度后就会对人体造成伤害。鲩鱼、鲫鱼、鲤鱼、鳙鱼和鲢鱼中CAP、OTC、TC和CTC的平均含量范围分别在57.1～365.5 µg/kg、37.0～60.7µg/kg、34.3～72.4 µg/kg和22.3～68.0 µg/kg之间。秋季的长吻鲍、团头鲂、鲈鱼、长江洄鱼、对虾、黄鳝、泥鳅和猪肉中CAP、OTC、TC和CTC的平均含量分别为88.1 µg/kg、76.8 µg/kg、343.7 µg/kg和34.2 µg/kg；牛奶中的含量分别为4.2 µg/L、1.6 µg/L和2.5 µg/L和22.0 µg/L。 5. 确定了抗生素的稳定性、吸附/解吸作用与各因素的关系，据此可以探讨环境中抗生素的行为特点及机理，并为环境中抗生素的污染防治提供依据。在短时的加热中，TCs发生了部分降解，而CAP却几乎没有发生分解，说明烹饪过程中的加热不能去除食品中的抗生素，这些抗生素则会进入到人体和污水中。当pH在2～8之间时，TCs的性质较稳定；CAP在pH＝1～10的范围内性质都比较稳定。地表和地下水体的pH一般为7左右，说明了水环境中TCs受pH的影响小，而CAP几乎不受影响。在6个月的时间内，TCs在3种介质中都发生了不同程度的降解，但仍有大部分残留；CAP几乎没有发生明显的降解，这说明CAP和TCs的污染具有一定的持久性。TCs的吸附/解吸受颗粒物粒径的影响大，粒径越小，吸附越强；CAP不受影响。这证明了在环境中CAP更易以水溶态的形式存在，而TCs更易吸附在沉积物中。颗粒物中CaCO3含量越高，TC和CTC的吸附越强，证明CaCO3可以用来增强TC、CTC的吸附，这为环境中抗生素的治理提供了一条思路。

贵州喀斯特高原湖泊物质循环过程中的铜锌同位素地球化学－以红枫湖、阿哈湖为例

近年来铜、锌同位素地球化学研究已经进入了快速发展时期。作为新兴的同位素技术手段，铜锌同位素工具已普遍应用于地球化学、矿床学、古海洋学和生物学等多种领域，然而铜、锌同位素在湖泊生态系统中的研究却相对较少。湖泊生态系统中，重金属的迁移、循环与转化一直是地球科学家们关注的焦点，但研究手段仅局限于含量与形态的测定。因此本论文旨在通过对湖泊生态系统中铜、锌同位素的研究，揭示影响铜、锌同位素组成的主要因素，为铜、锌同位素成为湖泊系统中新的重金属示踪工具奠定基础。 本论文通过一系列条件实验，确定了用于MC-ICP-MS测定环境样品中铜、锌同位素时最佳的化学分离条件。随后选取红枫湖和阿哈湖为主要研究对象，用此实验流程对湖泊水体及其主要支流悬浮物中的铜、锌同位素的季节及剖面变化进行了初步研究。除此之外，对水体中重金属如Cu、Zn、Mn、Ni、Co、Cr、Cd和Pb的形态分布特征及物质循环进行了研究。主要得出以下几点认识： 1、环境样品中铜锌的最佳分离条件是，采用AG MP-1(100-200目)阴离子交换树脂，分别以7 mol/L HCl + 0.001% H2O2，2 mol/L HCl+ 0.001% H2O2，0.5 mol/L HNO3作为淋洗液，并分别在适当的体积接收淋洗液，可以有效地分离沉积物、植物和悬浮物等样品中的铜和锌。化学分离过程中回收率接近100％，同位素比值的变化均在误差范围以内。 2、红枫湖、阿哈湖水体及主要支流悬浮物和红枫湖生物样品中的δ65Cu分布范围为-2.64‰~1.11‰，可达到3.75‰的变化。红枫湖夏季水体悬浮物的δ65Cu变化为-0.08‰~0.25‰，入湖河流水体悬浮物δ65Cu的变化范围为0.13‰~ 1.11‰；阿哈湖夏季水体悬浮物δ65Cu的变化范围为-0.62‰~0.37‰，入湖河流水体悬浮物δ65Cu的变化范围为-1.08‰~0.60‰。两湖冬季水体悬浮物的δ65Cu值均较负。红枫湖生物样品中δ65Cu较负（-1.54‰~ 0.03‰）。 红枫湖水体悬浮物中δ65Cu的随水深的变化趋势主要受到藻类吸收作用的控制，而阿哈湖δ65Cu的随水深的变化趋势主要受到其物源的控制。说明在贫营养化湖泊中，铜同位素组成可以示踪物源；而在富营养化湖泊中，铜同位素组成则可以示踪生物活动。同时水温的垂直变化也可能是其影响因素之一。 3、红枫湖水体及其主要支流水体悬浮物中的δ66Zn变化范围分别为-0.29‰~0.26‰和-0.04‰~0.48‰，阿哈湖水体及其主要支流水体悬浮物中的δ66Zn变化范围分别为-0.18‰~0.27‰和-0.17‰~0.46‰，均表现出支流中的锌同位素组成较重的趋势。而生物样品中的δ66Zn变化范围较大，为-0.35‰~0.57‰。说明湖泊生态系统中各端元的锌同位素组成存在明显差异。 红枫湖夏季δ66Zn随着湖水深度的变化，与Chla（叶绿素）呈极显著的正相关(R=0.97)。说明锌同位素组成与藻类生物量有一定的响应关系，主要是藻类对锌的有机吸附或是吸收过程改变了锌同位素组成。阿哈湖的锌同位素组成主要受到其源区的控制作用，从而可利用锌同位素示踪源区；此外，红枫湖和阿哈湖悬浮物中的锌同位素比值均表现出夏季小于冬季，说明大气的干湿沉降可能是一个较负的锌同位素源。生物样品中的δ66Zn变化范围较大，说明由于生物作用过程导致的锌同位素分馏大于非生物过程。 4、红枫湖重金属Mn、Ni、Co、Cr、Cd和Pb的含量在南湖高于北湖，主要是羊昌湖的输入所导致；重金属入湖通量的季节性变化，直接导致了重金属含量的季节性变化。沉积物－水界面在冬夏季节，由于“富氧”和“贫氧”状态的改变，导致了溶解态Mn、Ni和Cr的季节性变化；水粒相互作用过程中，溶解有机碳（DOC）、氧化铁胶体、氧化锰胶体和水生藻类的生长繁殖，影响了重金属不同结合形态的变化。