Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

芦苇化感组分对羊角月牙藻和雷氏衣藻生长特性的影响

研究了从芦苇(Phragmitis communis Trin)中分离得到的化感组分对羊角月牙藻(Selenastrum caprtcornutum)和雷氏衣藻(Chlamydomonas reinhardtii)生长特性的影响.在藻类生长的对数期向培养液中投加不同浓度的化感组分,分别测定并观察了培养期间受试藻种藻密度和藻细胞形态的变化情况.结果表明,该化感组分对羊角月牙藻藻密度的增长具有明显的抑制作用,半效应浓度(EC50.7d)值为0.60mg/L,同时使羊角月牙藻细胞内部结构改变,形态变大.投加6mg/L化感组分后,藻细胞平均宽度是对照组的1.5倍.该化感组分对雷氏衣藻藻密度的增长没有明显的抑制作用,但使其运动性能降低.     

Terbuthylazine and Deethylterbuthylazine in Rain and Surface Water – Determination by Enzyme Immunoassay and Gas Chromatography/Mass Spectrometry

Rain and surface water samples from Southern Germany were investigated from 1991 to 1995 for terbuthylazine and one of its major metabolites, deethylterbuthylazine. The concentrations observed were compared to the concentrations found for atrazine and deethylatrazine in the same water samples. Concentrations ranged from < 0.02 μg/L to 0.7 μg/L for terbuthylazine and from < 0.02 μg/L to 0.6 μg/L for deethylterbuthylazine, compared to concentrations of < 0.02 μg/L to 3 μg/L and < 0.02 μg/L to 0.5 μg/L for atrazine and deethylatrazine, respectively. The ratios of metabolite concentrations to parent compound concentrations were calculated for deethylterbuthylazine to terbuthylazine (DTR) and deethylatrazine to atrazine (DAR). In rain water, DTR of 0.8…3.0 and DAR of 0.3… 1.9 were determined with mean values of 0.9… 1.7 for DTR and 0.6…0.9 for DAR in the different years. The ratios increased during summer periods. The highest ratios were observed in samples from forest stands, showing that degradation of the herbicide has occurred during transport between the source and the sampling site. The DTR in rain water were about 50… 100% higher than the DAR. This indicates a higher degradation rate of terbuthylazine during atmospheric transport. In surface water, DTR of 0.3… 1.2 with mean values of 0.5…0.8 and DAR of 0.2…2.2 with mean values of 0.2… 1.3 were observed. The ratios increased from June to September.     

Gewässergütebewertung und Bewertung von Abwasserfahnen in Rhein und Main auf der Basis mikrobieller Enzymaktivitäten

Quality Mapping of Surface Water and Assessment of Treated and Untreated Waste-water Inputs into the Rhine and Main River Based on Microbial Enzyme Activities Microbial enzyme activities are used for an extension of the traditional quality mapping of surface water. In the following study, the enzymatic parameters were proved and validated on samples from various creeks and rivers in Baden-Württemberg and on samples gathered from the Rhine and Main Rivers (Germany). The test parameters should also be used for the control and the preservation of the capacity of the biological self-purification, which is the only natural and essential process in drinking-water conditioning of surface water. Main subject of the surveys was the development of criteria for an assessment of the measured enzymatical inhibition effects. Therefore, classes of inhibition and indices of inhibition are defined.     

页岩气钻探冲洗液体系的研究与应用

中国页岩气资源开发潜力巨大,近年来页岩气勘探开发力度不断加大,对钻探工艺和技术的要求不断提高。页岩气地层岩性主要为泥岩、砂岩、页岩、碳质板岩、灰岩,该类地层胶结性差、破碎、井壁强度低,钻进中易出现孔壁失稳,发生坍塌、卡钻、埋钻等孔内事故,需要研制具有强抑制性、低成本、绿色环保的冲洗液体系来保证施工安全。本文通过对页岩气井壁稳定机理的探究,优选出一种适用于页岩地层双聚防塌和成膜防塌低固相冲洗液体系,该体系由抑制剂、防塌剂、降失水剂、润滑剂、封堵剂、流型调节剂等处理剂组成,具有良好的抑制性和胶结性。现场应用取得了良好的效果,保证了项目的顺利施工。     

栉孔扇贝(Chlamys farreri)外套膜一氧化氮合酶的研究

采用组织化学、免疫组化和生物化学方法对栉孔扇贝外套膜中的一氧化氮合酶(EC1.14.13.39,NOS)活性进行了研究。组织化学显示结果表明,帆状部上皮细胞呈NOS强阳性,血细胞和神经纤维呈阳性;外套触手内有较多近圆形细胞和大量波浪形神经纤维呈NOS强阳性;边缘膜内有大量神经细胞和神经纤维分别呈NOS强阳性和阳性,外套环走肌束附近和血管内皮周围均有大量近圆形的强阳性细胞分布;中央膜有大量近圆形阳性细胞聚集成团块或分散分布。免疫组化显示表明,血细胞、帆状部和边缘膜上皮细胞呈神经型NOS(nNOS)和内皮型NOS(eNOS)弱阳性,而呈诱导型NOS(iNOS)阳性。生化测定结果表明,总NOS(tNOS)活力和一氧化氮(NO)含量均为中央膜最高,边缘膜次之,外套触手较低,帆状部最低,其中结构型NOS(cNOS)活力也是帆状部的最低,而iNOS活力则是外套触手的最低。栉孔扇贝外套膜可能是其神经系统中NOS的发生中心,NO-NOS体系可在其免疫防御和调节等方面发挥重要的作用。     

盐穴能源储库氮气阻溶造腔气垫控制理论研究

盐穴具有良好的稳定性和密闭性,是储存天然气、石油、氢气等的理想场所。传统水溶造腔采用的油垫阻溶存在阻溶效果差、卤水油污重等问题,无法满足绿色矿山建设要求。气垫作为一种替代品备受关注,但因其起步较晚、控制难度大,加之我国复杂的盐层地质条件,阻碍着其推广应用。为此,首先分析了不同造腔阶段气垫控制特点,然后在对气-液界面处压力平衡分析的基础上提出了不同阶段气垫厚度预测及注气量计算方法,结合某井建槽期实例给出了建议气垫厚度及其波动范围,探明了气垫厚度和注气量随造腔推进的变化规律,最后探讨了气垫阻溶应用相关的关键问题。研究结果表明：建槽期及收顶期以气垫厚度控制为主,建腔期及腔体修复阶段则以气-液界面位置控制为主。建议建槽期平均气垫厚度不低于0.3 m,建槽期初期气垫厚度波动迅速,应设置较大的气垫厚度并及时补注氮气,随后气垫厚度波动趋于稳定,补气时间间隔可逐渐拉长。随造腔时间增加,单次补气量越来越大,累计补气量整体呈线性增长。造腔过程中井口气压及气-液界面处气垫压力先增加后线性减小,应实时监测井口气压变化。气垫阻溶与油垫阻溶成本相近但环境效益显著,可重复利用排出氮气及井口注气设施以节约成本。现场应...     

高密度抑制防塌冲洗液体系在四川营山SY-1地热井中的应用

四川营山地下热矿水探采井SY-1井是一口地热资源重点勘查井,实际完钻深度2758 m,揭露三叠系上统须家河组热储层岩性以长石砂岩、粉砂岩为主,埋藏深度2220~2758 m,厚度538 m。下沙溪庙组岩性为灰绿色页岩、暗紫红色粉砂质泥岩夹黄褐色中厚层状粉砂岩及块状细粒长石砂岩,含高压气、卤水混合物,施工过程中需解决坍塌掉块、井涌、井漏、卤水污染、缩径等复杂难题。室内通过开展高密度抑制防塌钻井液流变性、防塌性、稳定性等控制方面的技术攻关,在优选钠基膨润土的基础上,通过对包被剂、降滤失剂（抗盐）、防塌剂等材料的筛选及优化,形成了高密度抑制防塌冲洗液的最终配方：清水+4%膨润土+0.1%纯碱+0.1%烧碱+1%~2%增粘剂HN-1+0.2%~0.5%环保大分子包被剂+1%~3%环保降滤失剂HJ-1+1%~3%抗盐滤失剂HLY+1%~2%环保防塌剂HFJ+重晶石。该配方密度1.50~1.80 g/cm³可调,滤失量4.0 mL,流变性能好,抑制防塌效果显著,在现场取得了成功应用,保证了该项目的顺利实施。     

一种GNSS码跟踪环路中的多径抑制方法

主要介绍了一种在GNSS信号中抑制多径信号的鉴相方法,接收机接收到的GNSS信号中往往包含多径信号,GNSS信号进行下变频生成中频信号后,进行模数转换;将经过模数转换后的GNSS信号进行载波剥离,得到I路和Q路的信号,在码跟踪环路中,对I路和Q路信号进行码剥离,得到多径信号的互相关功率后,采用基于精密TK采样间隔的TK—EML5鉴相方法,能够起到有效地抑制多径信号的效果。     

钻进过程中天然气水合物的分解抑制和诱发分解

讨论了天然气水合物钻进过程中，抑制和诱发孔底出露水合物分解的途径、方法和原理，并介绍了一个诱发水合物分解的钻进过程。