Qualitative interpretation of physico-chemical and isotopic parameters in the Krka River (Croatia) assessed by multivariate statistical analysis

Multivariate statistical analyses were applied on the measured physico-chemical (Cd, Pb, Cu, Zn, Mg, Ca, O₂, alkalinity, temperature, pH, SAS, DOC and DIC) and isotopic parameters (δ¹³C and δ¹⁸O) to estimate and distinguish anthropogenic from natural influences to the water system of the Krka River. Analyses were conducted on the data collected during six years from twelve sampling sites. On the basis of orientation, positioning and grouping of parameters arranged by biplots, four main hypotheses were defined and finally statistically confirmed. Thereof, two main and distinct processes occurring in the Krka River could be highlighted: (i) upstream pollution, caused by the inflow of untreated waste-waters of city of Knin and (ii) downstream self-purification, caused by the sedimentation and/or co-precipitation of pollutants coupled by the inflow of clean subterranean water (groundwater recharge). Grouping of (i) hydrological and carbon cycle connected parameters, and (ii) anthropogenically influenced correlated parameters were proposed as a result of statistical analysis. Regarding the pH, it is shown that a stream section influenced by the subterranean inflow of Zrmanja River is statistically significantly different for all sampling campaigns during six years, being lower for about 0.5 pH unit.     

Separation and determination of homogenous fatty alcohol ethoxylates by liquid chromatography with mulitstage mass spectrometry

Alcohol ethoxylates (AEs) are a significant component of a stream of surfactants directed to the aquatic environment. The aim of this work was the investigation of the dependence of the analytical signals of homogeneous AE homologues on liquid chromatography with tandem mass spectrometry conditions, as well as the separation of AEs from the water matrix and, on this basis, the development of an analytical procedure suitable for the determination of AEs in environmental samples. Homogeneous homologues containing dodecyl moiety and 2–9 oxyethylene subunits were investigated. The analytical signals of the investigated homologues were optimized in terms of concentration of ammonium acetate in the mobile phase (optimum 5 mM) and a column temperature (optimum 35°C) of the liquid chromatography with tandem mass spectrometry system. A separation of AEs from the water matrix by liquid–liquid extraction (ethyl acetate, chloroform) or solid‐phase extraction (C₁₈, styrene divinylbenzene, H‐RX) was investigated. In a model investigation, the best recoveries (>90%) were obtained with a styrene divinylbenzene cartridge eluted with a 1:1 mixture of chloroform and methanol. However, much worse recoveries were obtained from the river water sample. Better results were obtained for liquid–liquid extraction with ethyl acetate. Recoveries of 62–80% were obtained for homologues having 4–9 oxyethylene subunits, at the lowest spike.     

鄂尔多斯盆地马家沟组白云岩储层特征及成因机理

以鄂尔多斯盆地下奥陶统马家沟组白云岩为研究对象,对不同类型白云岩的岩石矿物学属性、地球化学特征、孔隙结构特征、发育层位及分布规律进行对比研究,并结合成因,将白云岩分为3类:(1)泥粉晶白云岩,以岩盐矿物溶蚀型孔隙为主,在含膏云坪相带呈带状分布,横向分布稳定,形成于准同生白云岩化作用;(2)粉-细晶白云岩,以白云石晶间孔为主,主要发育于蒸发岩层系的短期海侵沉积期,受控于浅埋藏期渗透回流白云岩化作用;(3)中-粗晶白云岩,以残余原始粒间孔及格架孔为主,主要发育于台地边缘礁滩及古隆起周边高能颗粒滩相带,并经历了埋藏白云岩化作用.奥陶系白云岩分布具有“层控性”和“相控性”,形成了现今白云岩储层多层叠合发育的特点,为奥陶系多套含气组合的发育创造了有利条件.     

川西拗陷雷四3亚段高频层序特征及控制因素

在川西拗陷中三叠统雷口坡组沉积背景研究基础上,通过岩心、薄片观察和测井、地震资料分析,运用层序地层学原理,研究雷四3亚段高频层序发育特征,对雷四3亚段进行精细层序地层对比,落实层序地层在研究区展布情况,探讨其发育控制因素及与储层发育的关系.雷口坡组可划分出2个Ⅲ级层序,雷四3亚段发育于第2个Ⅲ级旋回sQ2高水位体系域,进一步可识别出2个Ⅳ级层序和7个Ⅴ级层序.在高频层序划分的基础上,建立了雷四3亚段高频层序地层格架,以Ⅴ级层序为单元,对研究区雷四3亚段地层进行精细对比发现,层序地层横向具有较好的对比性,XS1井、DS1井、TS1井缺失顶部地层,分析认为与印支期地层剥蚀有关.川西拗陷雷四3亚段层序发育主要受海平面升降、构造运动及气候影响,Ⅴ级层序以向上变浅的旋回为主,溶蚀作用主要发育在Ⅴ级层序中上部,易形成优质溶蚀型储层.     

Sensitive Determination of 17β-Estradiol using a Magneto Sensor Based on Magnetic Molecularly Imprinted Polymer

The analysis of 17β-estradiol with high sensitivity and selectivity is extremely relevant to control the impacts that this compound can cause on health and the environment. Thus, we describe the development and application of a magneto carbon paste electrode based on magnetic molecularly imprinted polymer (MCPE-MMIP) for determination of 17β-estradiol. The analyte adsorbed on the MMIP was immobilized on the electrode surface by magnetic capture. The morphological and structural characterization of the obtained MMIP suggests that the material was effectively synthesized. MCPE-MMIP showed an improvement in the sensitivity for 17β-estradiol detection when compared to electrode configurations in the absence of this material. The optimum conditions (0.10 mol L⁻¹ phosphate buffer pH 7.0) were reached by differential pulse adsorptive stripping voltammetry (DPAdSV), in which the method presented linearity ranged from 0.06 to 175 μmol L⁻¹ with limits of detection and quantification of 0.02 and 0.06 μmol L⁻¹, respectively. The proposed sensor was applied effectively in the analysis of 17β-estradiol in river water and raw milk samples, exhibiting excellent recovery values (between 96.20 and 104 %), which were confirmed by HPLC analysis.     

黄河山陕峡谷保德-克虎段高阶地砾石层的初步研究

野外考察发现山西黑峪口地区存在七级阶地序列,其中上覆红粘土的T6、T7阶地为晚第三纪阶地.对该区阶地上砾石的岩性和粒径进行了研究,岩性对比表明,T6、T7阶地上砾石的岩性与黄河低阶地上砾石的岩性相似,而与东西向的蔚汾河阶地岩性差别较大;上下游之间对比发现,灰岩砾石岩性由保德地区占主导地位到克虎地区退居次要地位,灰岩砾石的粒径也从上游向下游变小,说明该区晚第三纪阶地并非东西向河流形成的,而是古黄河或古南北向水系的产物.T7阶地上覆盖厚度70m以上的粉、细砂层和晚第三纪红土层,磁性地层研究表明,该层的底部时代在6.8Ma左右,T6阶地上覆红粘土的底部年龄在3.3Ma左右,山陕峡谷由北向南流的古河流在6.8Ma之前已经形成,T6阶地的形成时代与青藏运动A幕相对应.青藏运动A幕以来河流在该区下切了160m,平均下切速率约为青藏运动A幕以前平均下切速率的5倍以上.     

Synergistic Effect of Lithium Perchlorate and Sodium Hydroxide in the Preparation of Electrochemically Treated Pencil Graphite Electrodes for Selective and Sensitive Bisphenol A Detection in Water Samples

In this study, pencil graphite electrodes were activated electrochemically in the presence of different supporting electrolytes and used for the selective and sensitive determination of bisphenol A (BPA) in water samples. Synergistic effects of both LiClO₄ and NaOH supporting electrolytes on the performance of the electrochemically treated pencil graphite electrode (ETPGE) were demonstrated in the oxidation of BPA. The electrochemical behavior of BPA on the ETPGE showed two irreversible oxidation peaks at 0.744 V and 0.877 V (vs. SCE). The detection limit was determined to be 3.1 nM. This single‐use electrode is a very promising candidate to overcome the passivation problems arising from the oxidation of BPA. The analytical application of the ETPGE was performed in tap and river water samples.     

Preliminary regional estimation of carbon sink flux by carbonate rock corrosion: A case study of the Pearl River Basin

The formation of carbonate rocks has had a dramatic sink effect on atmospheric CO2 throughout geological time.The wide global distribution of carbonate rocks and their strong sensitivity to climate change mean that carbonate rock corrosion consuming air/soil CO2 can play an important role in the global carbon cycle.The carbon sink accounts for 12.00%-35.29% of the missing carbon in the global carbon cycle.Using the Pearl River Basin as a case study,we analyzed comprehensively the factors impacting karstific...     

The occurrence and significance of C25HBI in Cenozoic saline lacustrine source rocks from the Western Qaidam Basin,NW China

The saline lacustrine deposit of the Oligocene Lower Ganchaigou Formation is the main source rock for the Western Qaidam Basin,NW China.In this study,abundant highly branched isoprenoids with 25 carbon atoms (C25HBI) were detected in the upper section of the Lower Ganchaigou Formation.C25HBI is a biomarker for diatoms,and can provide information regarding biogeochemical processes during production and preservation of sedimentary organic matter.The carbon isotopic values of C25HBI in these source rocks were in the range of-18‰ to-20‰.The relative enrichment in 13C of C25HBI suggests that these isoprenoids were derived from diatom blooms.In this case,the diatoms used HCO3-as an additional carbon source to dissolved CO2 in water column due to their high biological productivity.Conversely,the diatom blooms indicated an abundant nutrient supply to the environment and high primary productivity.Thus,the occurrence of 13C-enriched C25HBI could be an ideal marker for good source rocks.The decreased concentration of CO2(aq) in the water column induced by diatom blooms can result in an enrichment in 13C of organic matter synthesized by primary producers.This may be a possible reason for the occurrence of 13C-enriched organic matter in the Cenozoic source rocks of the Western Qaidam Basin.Previous studies have shown that the high carbon number n-alkanes sourced from diatoms have no carbon preference.Hence,the sources of n-alkanes in regional source rocks are complex,and should be considered when discussing the sources of organic matter in future studies.     

Carbon and hydrogen isotopic compositions and their evolutions of gases generated by herbaceous swamp peat at different thermal maturity stages

Coalbed methane (CBM) accumulation models include continuous gas accumulation and staged gas accumulation.However,studied on the geochemical characteristics and indices to evaluate staged accumulation CBM are lacking.This study for the first time obtained the carbon and hydrogen isotopic compositions of methane and ethane generated at different evolution stages using thermal simulation of samples prepared by treating an herbaceous swamp peat at different temperatures.The results showed that the carbon isotopic compositions of methane and ethane were obviously affected by the thermal evolution level of the starting sample,while the hydrogen isotopic compositions were closely related to the maturity of gases.The carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter with Ro values from 1.2%,1.7%,2.4%,3.2% and 3.7% to 5.2% were determinated.The relationship between Ro values and the carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter at different evolution stages as well as the carbon or hydrogen isotopic relationships between methane and ethane were established.The results provide a scientific basis for studying the genesis of CBM generated at different maturity intervals and understanding the geochemical characteristics of staged accumulation CBM.These results were applied to a case study on CBM from the southern Qinshui basin,and it was found that the CBM accumulated after the Middle Jurassic and was characteristic of staged gas accumulation.This is consistent with the result of geological studies,and further showed that the results of thermal simulation experiments are very important for evaluating the genesis of natural CBM.