胶体TiO2颗粒对不同来源溶解性有机质光降解的影响:基于分子量差异分析

溶解性有机质(DOM)广泛存在于多种水环境介质,其光降解过程显著影响水体污染物的化学形态及生态风险.本文以典型陆源天然有机质(NOM)和藻源有机质(AlgOM)为研究对象,采用切向超过滤技术将初始DOM样品(Bulk,0.45μm)分为高分子量(HMW, 1 kDa～0.45μm)和低分子量(LMW,1 kDa)组分,研究胶体TiO2颗粒存在下不同分子量有机组分的光降解行为差异.表征结果表明,DOM样品的有机质均相对较多地分布在LMW组分中(55.3%～57.8%),但HMW的芳香性比LMW组分高;三维光谱结果表明AlgOM富含类蛋白和类腐殖物质,而NOM只含类腐殖物质;进一步分析发现类蛋白物质主要分布于HMW组分,类腐殖物质则主要分布于LMW组分.胶体颗粒的存在通过吸附作用抑制AlgOM中有机质及芳香性物质的光降解,而通过催化作用促进NOM中有机质及芳香性物质的光降解.胶体颗粒不改变不同分子量DOM中有机质的光降解效率顺序,均为HMWBulkLMW,说明HMW有机质更易光降解.但无胶体颗粒时AlgOM和NOM芳香物质的光降解效率为LMWBulkHMW,且胶体颗粒的存在改变不同分子量NOM芳香性物质的光降解顺序.另外,无胶体颗粒存在时陆源类腐殖物质比藻源类腐殖物质更易光降解,而胶体颗粒的存在均可促进藻源和陆源类腐殖质物质光降解;相比于HMW类腐殖质,LMW类腐殖物质具有较高的光敏性和优先降解特性.     

典型湖泊天然有机质与四环素的相互作用

采用荧光滴定法研究四环素(tetracycline,TC)与太湖溶解性有机质(dissolved organic matter,DOM)和玄武湖DOM的相互作用.三维荧光光谱结合平行因子分析显示,2个湖泊的DOM含有3个荧光组分:类富里酸组分C1、类色氨酸组分C2和类络氨酸组分C3.其中C2的荧光强度远高于C1和C3,是DOM的主要荧光组成.3个荧光组分与TC发生了不同程度的静态猝灭,特别当TC浓度为45.5μmol/L时,类蛋白组分的荧光强度完全被猝灭(100%),并且猝灭作用改变了DOM分子的微环境极性.同步荧光光谱联合二维相关图谱进一步表明类色氨酸组分优先和TC发生猝灭作用,其次为类络氨酸组分和类富里酸组分.Ryan-Weber方程适于拟合DOM与TC的猝灭过程,2个湖泊的DOM中3个荧光组分的络合常数lg K值范围为5.05~5.85,大小顺序为C2C3C1.因此,类蛋白组分为主的DOM对TC的络合作用大于类腐殖组分为主的DOM,影响抗生素在湖泊水体中的生物有效性和生态毒性.     

珠江口沉积物溶解性有机质来源及光谱特征的空间变化

作为海陆交互作用的重要区域,河口在海洋碳循环中扮演着重要角色.近年来,溶解性有机质(dissolved organic matter,DOM)在河口区的来源、降解和保存一直是关注的热点.本研究结合三维荧光光谱和紫外可见吸收光谱,对珠江口3个沉积柱(S1、S2、S3站位,盐度依次增加)孔隙水溶解性有机质的空间分布和来源进行了表征分析.利用平行因子分析(parallel factor analysis,PARAFAC)方法对三维荧光光谱数据进行解析共得到5种荧光组分:类腐殖质组分C1、C3、C4,以及类蛋白荧光组分C2和C5.三个站位的C2组分同沉积物微生物DNA浓度表现出显著的正相关关系(R²=0.69,P<0.01),说明类蛋白组分C2可能主要来源于原位微生物的分解代谢.C5同DNA浓度相关性较弱(R²=0.40,P<0.05),推测是混入了荧光峰同类蛋白组分十分接近的酚类化合物所致.类腐殖质荧光组分来源复杂,S1站位类腐殖质荧光组分含量最高(1.45~8.83R.U.),推测是受到了显著的陆源输入影响.S2和S3站位3种类腐殖质荧光组分含量很低(<1R.U.),且分布规律十分相似,可能主要来源于水体和沉积物藻类微生物的代谢释放.三个站位的腐质化指标HIX随深度增加,类蛋白组分荧光相对含量随深度降低,并且同指示DOM分子量的光谱斜率比值S_R分别呈显著的负相关和正相关关系.这说明从沉积物表层到深层,DOM由低分子量的类蛋白组分向高分子量的类腐殖质组分过渡.本研究结果对理解河口区沉积物中的孔隙水DOM分子量/活性模型(pore water size/reactivity,PWSR)以及DOM的生物有机地球化学过程提供了补充参考.     

针铁矿对湖泊草、藻来源可溶有机质的非均质吸附

为探究富营养化湖泊中自生源可溶有机质(DOM)在泥水界面的吸附行为,以马来眼子菜(Potamogeton malaianus)和铜绿微囊藻(Microcystis aeruginosa)释放的DOM为代表,考察针铁矿对草、藻源DOM中不同组分的吸附特征.三维荧光平行因子分析表明类富里酸组分C1和类胡敏酸组分C4的含量很低,而类蛋白物质(类酪氨酸组分C2和类色氨酸组分C3)分别占草、藻源DOM荧光组成的70%和93%. 2种DOM均可被针铁矿吸附,吸附过程符合伪一级动力学.通过等温线拟合发现针铁矿吸附藻源DOM的非线性更强,饱和吸附量(23.77 mg/g)高于草源DOM(19.10 mg/g).特别地,类蛋白组分呈现非线性吸附,而类腐殖物质的吸附近似线性,且针铁矿对于DOM各荧光组分的吸附量顺序为:C3C2 C4 C1,此非均质吸附特征与DOM组分的初始含量、分子大小、芳香性及有效吸附位点有关.红外光谱证实氨基、羧基和羟基是吸附过程中的重要官能团.因此,草、藻源DOM显著改变了针铁矿表面的有机物质组成,影响湖泊沉积物的生物地球化学行为.     

富营养化条件下浙江象山港可溶性有机质的光谱和分子特征初探

利用碳稳定同位素、紫外-可见吸收和三维荧光光谱和傅里叶变换离子回旋共振质谱等手段,分区域研究了2019年5月浙江象山港这一代表性的半封闭富营养化港湾水体可溶性有机质(DOM)的组成、来源,并初步推断了其迁移转化过程.通过三维荧光建模识别出一个类蛋白荧光组分(C1)和两个类腐殖质荧光组分(C2和C3),利用高分辨率质谱获得了各类分子的数量和相对强度.可溶性有机碳(DOC)浓度, C2、C3和黑碳类分子组分的相对强度均和盐度呈显著负相关,指示象山港存在海水对陆源信号的稀释作用.象山港在空间上光透射能力存在差异从而导致光降解程度不同,光降解作用可能在象山港惰性有机质转化中发挥了重要作用. C1组分和盐度的弱相关性表明自生源不能主导象山港地区的类蛋白荧光组分,富营养化条件下外源(如人类输入、孔隙水释放)均影响了类蛋白荧光组分的分布.将象山港和我国其他代表性沿海港湾对比,可发现象山港的类蛋白荧光组分在荧光溶解有机质(FDOM)中的相对占比处于中等水平.在富营养化背景下,人类活动输入可能是我国港湾DOM的重要来源.     

鄱阳湖湿地溶解性有机质的光化学属性对水体光活性中间体(PPRIs)季节性变化的影响

湿地的水文和水化学在时空尺度上会呈现显著差异,进而会引发光化学反应的变化,光活性中间体(PPRIs)是水体间接光反应的产物,具有极强的氧化性,对水环境中有机物和污染物的归驱具有重要的影响,因此迫切需要探究湿地中PPRIs的产生过程。本研究通过捕获剂法监测了鄱阳湖湿地4个季节水体中3种PPRIs(¹O₂、·OH及³CDOM^*)的产生速率和稳态浓度的变化,并通过紫外吸收光谱、三维荧光光谱、以及傅立叶变换离子回旋共振质谱等技术对水体中可溶性有机质(DOM)组分的化学特征进行分析,揭示了鄱阳湖湿地不同季节水体中的DOM的光化学反应特性及与PPRIs产生的相关性。结果发现:鄱阳湖夏季和秋季水体的pH值、溶解有机碳(DOC)浓度较高,相反,硝酸盐、亚硝酸盐浓度在夏季和秋季较低。夏季和秋季的DOM中芳香族化合物丰度较高,并且木质素丰度明显高于冬季和春季。不同季节鄱阳湖水体有色可溶性有机物产生能力依次为秋季>夏季>冬季>春季。夏季和秋季水体中¹O₂和·OH产生速率和稳态浓度显著高于春季和冬季水体。pH、DOC、E2/E3、脂类、蛋白类及木质素类与PPRIs产生速率展现出了良好的正相关关系,尤其是其中的DOC与木质素类组分;另外在三维荧光指标结果中,荧光指数(FI)和新鲜度指数(β/α)与PPRIs呈现负相关关系,证明FI值越低即DOM陆源性越高、非新生DOM比例越高,则PPRIs产生速率越高。综上,PPRIs的光化学产生与植物源DOM密切相关。与春季和冬季相比,夏季和秋季鄱阳湖水体的有机质高,而其中DOM组分中芳香族化合物丰度较高,主要来自陆生植物和土壤有机质,其有机质的腐殖化水平较高,而在春季和冬季水体有机质主要来自湖泊本身和微生物产生的有机质,属于内源。淹水植物残体降解过程释放的有机组分,对夏、秋季DOM的来源和组成有着极易被忽视的影响和作用,而其中光化学活性较强的有机组分如木质素是造成其PPRIs产率更高的主要原因。     

新建人工深水湖泊沉积物上覆水和孔隙水中溶解性有机质的光谱特征

为了揭示湖库内源性污染物的分布、来源、组成及垂向分布特征,以新建人工深水湖泊龙景湖为研究对象,采用紫外-可见光谱和三维荧光光谱技术,研究了该湖泊以成湖前用途划分的3个特征区域(原河道底部、新淹没区底部和新淹没区边坡)的沉积物上覆水和孔隙水中的溶解性有机质(DOM)的光谱特征.结果表明,孔隙水中的DOM芳香性和腐殖化程度高于上覆水;孔隙水中疏水组分含量大于上覆水,且水体中可能存在内源孔隙水释放的低分子量DOM.龙景湖上覆水和孔隙水中的DOM主要源于水体自身的微生物,自生源特征明显,且可能存在新近释放到水体的有机质.龙景湖沉积物上覆水和孔隙水中的DOM以类腐殖酸和类蛋白质为主,且随着深度增加,类腐殖酸峰强度增强,与龙景湖的建湖背景有明显联系.     

山东省周村水库季节演替中沉积物上覆水溶解性有机物的紫外-可见与三维荧光光学特征

运用三维荧光光谱（EEMs）技术结合平行因子分析法（PARAFAC）以及紫外-可见光谱技术（UV-vis）,对周村水库季节演替过程中沉积物上覆水溶解性有机物（DOM）的紫外-可见以及三维荧光光谱特征进行分析.结果表明：周村水库上覆水的总氮、溶解性总氮、总有机碳和溶解性有机碳的季节性差异显著,并且冬季总氮浓度最高、夏秋季总有机碳浓度较高;夏秋季上覆水DOM的吸收系数a₂₅₄和a₃₅₅均高于冬春季,与有机物的分布相一致;4个季节上覆水DOM的E3/E4均大于3.5,说明DOM以富里酸为主,E2/E3（富里酸占DOM的比例）在夏秋季低于冬春季,而且各季节S_R均大于1,表明DOM主要为生物源;三维荧光通过PARAFAC解析出3种组分：类腐殖质（C1）、可见区富里酸（C2）和类蛋白（C3）;对3个组分进行相关性分析,结果显示C1、C2、C3之间具有显著的相关性;DOM的总荧光强度以及各组分的荧光强度均呈现出夏秋季高、冬春季低的特征,且各季节间差异显著;周村水库4个季节的DOM生物源指数（BIX）在0.8~1.0之间,表明水库DOM具有较强的自生源特征,与腐殖程度指标（HIX）的结果相吻合;主成分分析显示周村水库上覆水DOM的光谱特征差异明显,夏秋季的DOM光谱特征相近、冬春季的水体DOM特征相似;并且组分C1、C2、C3与DOM特征参数（a₂₅₄、SUVA₂₈₀、HIX、FI、BIX）以及溶解性有机碳呈显著相关.各荧光组分与水质参数（溶解性总氮和溶解性有机碳）的多元线性回归呈现很好的拟合,通过建立回归方程可以为以后研究周村水库水体四季的DOM光谱特征,分析水库水体的有机物污染特征,并为水库水质管理提供技术支持.     

太湖五里湖水体悬浮物中水溶性有机质(WSOM)的荧光光谱组分鉴别及其与氮形态的关系

采用三维荧光光谱-平行因子法(EEMs-PARAFAC)分析太湖五里湖水体悬浮物中水溶性有机质(WSOM)的荧光光谱特征,研究其组分类型、分布规律以及来源,进一步探讨悬浮物中水溶性有机氮和无机氮含量与WSOM荧光组分之间的关系.结果表明,悬浮物中WSOM荧光组分主要由2个类腐殖质(C1、C2)和1个类色氨酸类蛋白质(C3)组成.总荧光强度在57.56~200.01 R.U./g之间,平均为115.42 R.U./g,其中C1、C2、C3的相对比例分别为35.55%、34.05%和30.40%;空间上由西向东逐渐增强,东五里湖高于西五里湖,沿岸区高于湖心区.荧光指数和生物源指数变化范围分别在1.48~2.34和0.65~0.87之间,反映了悬浮物中WSOM主要来源于微生物、藻类的自生生物源.多元回归统计分析结果表明,悬浮物WSOM与氮元素的迁移转化密切相关,且有机氮与WSOM荧光组分的相关系数大于无机氮.     

东北地区典型湖沼沉积物溶解态有机质组成特征及来源解析：以库里泡为例

溶解态有机质(DOM)是湖泊沉积物的重要组分,解析DOM的组成和来源对于深入理解湖泊有机质生物地球化学循环及控制水体富营养化具有重要意义。 本研究于2021年5月和8月采集了大庆市库里泡表层及柱状沉积物、泡内水生物(浮游藻类、挺水植物和沉水植物)、岸边土壤、陆生C3和C4植物、禽畜粪便以及城镇污水等样品,分析了样品DOM的稳定同位素(δ¹³C 和 δ¹⁵N)组成及三维荧光光谱特征,并利用IsoSource软件计算了不同来源样品对沉积物DOM的贡献率。结果显示:(1)库里泡内表层沉积物DOM的δ¹³C和δ¹⁵N组成存在季节性差异,5月δ¹³C和δ¹⁵N均值分别为-25.54‰和9.02‰,8月分别为-26.81‰和8.40‰。(2)库里泡内柱状沉积物DOM的δ¹³C和δ¹⁵N组成在垂直方向存在差异,表层(0~3 cm)δ¹³C和δ¹⁵N均值分别为-26.58‰和9.04‰,深层(3~30 cm)均值分别为-25.40‰和10.61‰。(3)表层沉积物DOM的三维荧光组分存在季节性差异。5月以类腐殖质荧光组分为主,占比为87.89%,HIX和BIX分别为6.27和0.67;8月蛋白类荧光组分占比为49.58%,HIX和BIX指数均值分别为1.72和0.87。(4)5月表层沉积物DOM外源输入占比为61%,以土壤(21.40%)和城镇污水(18.08%)为主;而8月内源贡献占比稍高(55.10%),且以挺水植物为主(48.68%)。(5)柱状沉积物(0~30 cm)不同深度DOM来源组成相近,主要为城镇污水、沉水植物/藻和挺水植物,贡献率均值分别为42.13%、25.07%和18.53%。整体上,库里泡沉积物DOM来源主要受到流域内人类活动及气候特征的影响,本文研究结果有利于加深对我国东北地区湖泊沉积物有机质迁移转化及累积规律的认识。     

基于广义帕累托分布的地震震级分布尾部特征分析

极值理论在地震危险性分析中有着重要应用,发震震级超过某一阈值的超出量分布可以近似为广义帕累托分布.基于广义帕累托分布给出了若干地震活动性参数的估计公式,包括强震震级分布、地震复发周期和重现水平、期望重现震级、地震危险性概率和潜在震级上限等;以云南地区震级资料为基础数据,讨论了阈值选取、模型拟合诊断和参数估计;在此基础上计算了该地区的地震活动性参数.结果表明,广义帕累托分布较好地刻画了强震震级分布,通过超阈值(POT)模型计算的复发周期与实际复发间隔统计基本一致,高分位数估计在一定阈值范围内表现稳定,为工程抗震中潜在震级上限的确定提供了一种途径.     

基于广义帕累托分布的地震震级分布尾部特征分析

极值理论在地震危险性分析中有着重要应用, 发震震级超过某一阈值的超出量分布可以近似为广义帕累托分布. 基于广义帕累托分布给出了若干地震活动性参数的估计公式, 包括强震震级分布、 地震复发周期和重现水平、 期望重现震级、 地震危险性概率和潜在震级上限等; 以云南地区震级资料为基础数据, 讨论了阈值选取、 模型拟合诊断和参数估计; 在此基础上计算了该地区的地震活动性参数. 结果表明, 广义帕累托分布较好地刻画了强震震级分布, 通过超阈值(POT)模型计算的复发周期与实际复发间隔统计基本一致, 高分位数估计在一定阈值范围内表现稳定, 为工程抗震中潜在震级上限的确定提供了一种途径.      

Global distribution of coastal cliffs

Previous studies have estimated that coastal cliffs exist on about 80% of the global shoreline, but have not been validated on a global scale. This study uses two approaches to capture information on the worldwide existence and erosion of coastal cliffs: a detailed literature survey and imagery search, and a GIS-based global mapping analysis. The literature and imagery review show coastal cliffs exist in 93% of the combined recognized independent coastal states and non-independent coastal regions worldwide (total of 213 geographic units). Additionally, cliff retreat rates have been quantified in at least one location within 33% of independent coastal states and 15% of non-independent regions. The GIS-based mapping used the near-global Shuttle Radar Topography Mission 3 arc second digital elevation model and Arctic Coastal Dynamics Database to obtain near-global backshore coastal elevations at 1 km alongshore intervals comprising about 1,340,000 locations (81% of the world vector shoreline). Backshore coastal elevations were compared with the mapped distribution of European coastal cliffs to produce a model training set, and this relationship was extended globally to map the likelihood of coastal cliff locations. About 21% of the transects (17% of the world vector shoreline) were identified as mangroves and eliminated as potential cliff locations. The results were combined with estimates of cliff percentages for Greenland and Antarctica from the literature, extending the global coverage to estimate cliff occurrence across 89% of the world vector shoreline. The results suggest coastal cliffs likely exist on about 52% of the global shoreline. © 2018 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.     

Bayesian improver of a distribution

 An estimate of a distribution obtained from a sample by any method of classical statistics may be erroneous when the sample is not representative of the population. A subjective distribution elicited from an expert may be miscalibrated when information is scanty and experience limited. The Bayesian Improver of a Distribution (BID) exploits a coherence principle and improves, in the ex ante sense, an initial estimate of a continuous distribution by using (i) the known distribution of a related variate and (ii) information about the dependence structure between the two variates. The theory of BID is developed into an applied (ABID) procedure. The ABID estimator is applicable to any continuous, monotone likelihood ratio dependent variates with arbitrary, strictly increasing marginal distributions, parametric or nonparametric; it is analytic in form and easy to implement via statistical or judgmental methods; it converges to the true distribution, provided the initial estimator does, as the sample size n→∞; it outperforms the initial estimator in the expected Kolmogorov–Smirnov distance for all n; and it offers the greatest gains when n is small – precisely when improved estimates are needed most.     

核磁共振T2分布评价岩石孔径分布的改进方法

岩芯核磁共振（NMR）T2分布和毛管压力分析数据均在一定程度上反映了岩石的孔隙结构,理论分析表明,这两组数据具有相关性.应用NMR T2分布研究岩石孔径分布，关键是在分析两者的相关性的基础上，从T2分布构造出可靠的毛管压力曲线.但以前用饱和水T2分布构造的毛管压力曲线的方法与实际毛管压力曲线匹配性差.事实上，薄膜束缚水部分的存在引起T2分布反映的孔隙空间与毛管压力曲线反映的孔隙空间有差异.本文提出一种改进方法，在消除薄膜束缚水对T2分布的贡献后，用自由水T2分布构造毛管压力曲线.应用本文方法,对24块岩芯数据自由水T2分布构造的毛管力曲线及其孔喉半径分布与隔板毛管压力分析结果进行了对比.结果表明，改进方法对于毛管压力曲线的构造精度有明显改进，从而为NMR T2分布研究孔隙结构提供了可靠的理论和方法上的支持.     

Ventifacts distribution in Qatar

This study attempts to investigate the distribution of ventifacts in Qatar. It is believed that ventifacts are confined to the areas within about 5 km of the Miocene or Mio-Pliocene Hofuf formations and the spreads of continental gravels derived from them. Three hypotheses were formulated: (1) Ventifacts in Qatar are confined to areas within about 5 km of the Hofuf formations and the spreads of continental gravels derived from them. The distribution of ventifacts within these areas varies according to the nature of the ground surface; (2) The most active ventifaction areas are where the continental gravels merge with the Eocene limestone because of the increase in saltation particle speed in these areas where bedrock or bare limestone is exposed; (3) The unit area ratio of ventifact to non-ventifact pebbles varies inversely with the total amount of pebbles. To test these hypotheses, nine land class categories were identified in the three major Hofuf formations. Line transects were carried out from randomly selected stations near the middle of the Hofuf formations. Along each transect systematic sampling was carried out at 200 m intervals. The data were processed using a WANG MVP 2200 computer with software developed for the project. It was found that ventifacts tend to concentrate on the outer edges of the continental gravels in areas of limestone outcrop and limestone pavement. Higher areas have big gravel counts and a low ratio of ventifacts while the low-lying plains have small gravel counts and a higher ratio of ventifacts. In certain areas ‘ventifact fields’ were found where the density of ventifacts was as high as 30 per m². Many of the ventifacts in these fields were buried beneath the surface suggesting that the ventifaction predates the present site conditions. Other high ventifact density areas were discovered where the ventifacts have collected in shallow depressions or hollows on the limestone plateaux. Water action has washed these ventifacts, a high proportion of which are dreikanters, into the hollows, where they have been partially buried in fine alluvial silts. These ‘ventifact graveyards’ are generally only a few metres wide but contain large numbers of fine specimens.     

Epicentral distribution in 2007

For showing the epicentral distribution in and near China as well as all over the world,two epicentral maps for the earthquakes occurred last year are published annually in the 6-th issue     

Alternative PWM-estimators of the Gumbel distribution

Probability weighted moments (PWM) are widely used in hydrology for estimating parameters of statistical distributions, including the Gumbel distribution. The classical PWM-approach considers the moments β_i=E[XFⁱ] with i=0,1 for estimation of the Gumbel scale and location parameters. However, there is no reason why these probability weights (F⁰ and F¹) should provide the most efficient PWM-estimators of Gumbel parameters and quantiles. We explore an extended class of PWMs that does not impose arbitrary restrictions on the values of i. Estimation based on the extended class of PWMs is called the generalized method of probability weighted moments (GPWM) to distinguish it from the classical procedure. In fact, our investigation demonstrates that it may be advantage to use weight functions that are not of the form Fⁱ. We propose an alternative PWM-estimator of the Gumbel distribution that maintains the computational simplicity of the classical PWM method, but provides slightly more accurate quantile estimates in terms of mean square error of estimation. A simple empirical formula for the standard error of the proposed quantile estimator is presented.     

Spatial distribution of near-fault ground motion

Introduction In order to explain severe damage of structures and ground surface near earthquake fault, many theoretical and numerical methods have been developed to study strong ground motion near the fault (Somerville, 1998) via the kinematic and dynamic source models. Moreover, a great number of valuable strong ground motion records, especially near the fault, have been acquired in recent years. These valuable records provide useful data for improving simulation approaches. Based on those r…