A multi-method approach for the study of lanthanum speciation in coastal and estuarine sediments

Two independent analytical methods (sequential extraction and kinetic extraction methods) were applied in order to understand the distribution and speciation of La in the coastal and estuarine sediments from the central east coast of India. Sequential extraction study revealed that La was primarily present as inert complexes (~ 50–60% of the total La) in all the sediments. Amounts of ~ 20–30% of the total La in all the sediments were found to associate with the total organic carbon (TOC) in the sediments. The dissociation rate constants of La–sediment complexes obtained from kinetic extraction studies revealed that the concentration of thermodynamically weak complexes of La gradually increased with the increasing La/TOC ratio in the sediments.     

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.     

Valency Study of Vanadium in Stone Coal Ash of Jiangxi Province

Vanadium-bearing stone coal is a new vanadium resource;recovery ofV_2O_5 from the coal has been investigated.It has been found that a satisfactoryextraction of V_2O_5 depends on both the oxidation of V and its reaction with so-dium salt.V in the coal ash of Yushan mainly exists in two oxidation states:98％V(Ⅲ)and2％V(Ⅳ).The distribution of valency of V shows that organicmatter determines V valency at low temperatures,at about470℃,V(Ⅲ)iscompletely oxidized to V(Ⅳ);above500℃,the temperature is the most impor-tant factor for the oxidation of V .At higher temperatures no more V is oxidizedto V(Ⅴ);an equilibrium is established after92％of V is oxidized to V(Ⅴ).The roles of NaCl in the recovery of V_2O_5 from the coal ash were discussed.The best conditions for roasting are temperature750-800℃for1 h.underthe oxidation-chlorination atmosphere.When the ore:NaCl=100:10 by weight,η_roast reaches85.5％.According to the results,a flowsheet for V_2O_5 extrac-tion from coal ash has been proposed.     

云南安宁磷矿区水系沉积物磷赋存形态及分布特征

磷污染是水污染的重要组成部分,因其可造成水体富营养化、水质下降,从而引起人们的广泛关注。研究沉积物中不同磷赋存形态及其分布特征有助于了解沉积物中磷的行为特征及迁移能力,从而为水体富营养化防治提供支撑。磷矿的开采、冶炼对矿区内水资源环境可能产生严重影响,本文以安宁磷矿区内河流、水库为研究区域,分析了不同水系沉积物磷元素赋存形态及分布特征,并对其生态风险进行评估。采用X射线荧光光谱法测定研究区水系沉积物总磷（TP）含量,并基于顺序提取及Hupfer改进的磷形态分析方法,将研究区各水系沉积物中磷分为弱吸附态磷（NH4Cl-P）、可还原态磷（BD-P）、金属氧化物结合态磷（NaOH-P）、钙结合态磷（Ca-P）、残渣态磷（Res-P）等5种形态,采用单因子污染指数法对其进行生态风险评估。结果表明：研究区水系沉积物样品中TP含量范围为567.6~48115.5mg/kg,NH4Cl-P含量范围为0.07~115.2mg/kg,BD-P含量范围为8.84~802.5mg/kg,NaOH-P含量范围为21.3~3129.5mg/kg, Ca-P含量范围为12~45098mg/kg,Res-P含量范围为28.5~515.4mg/kg。研究区各水系沉积物样品磷形态具有相似的分布特征,即磷主要以Ca-P和NaOH-P形态存在,其他磷形态的相对含量大小顺序为NH4Cl-P     

全二维气相色谱-电子捕获检测器测定复杂基质土壤中24种有机氯和拟除虫菊酯类农药

目前针对环境样品中有机氯和拟除虫菊酯类农药的检测方法主要有气相色谱法和气相色谱-质谱法（GC-MS）,由于气相色谱法采用电子捕获检测器从而具有较高的灵敏度,在污染物的环境行为研究中得到广泛应用,GC-MS法的定性效果好,但检测灵敏度相对偏低。本文研究了2018年土壤详查江苏地区样品中有机氯农药和拟除虫菊酯的残留状况,结果显示,即使经过多次净化仍有20%的样品存在假阳性或基质干扰现象。为了提高定性准确度,同时保证检测灵敏度,实验建立了复杂基质土壤中20种有机氯农药和4种拟除虫菊酯的全二维气相色谱-电子捕获检测器检测方法,最终选择中等极性的TG-35MS为第一色谱柱,非极性的（DB-1）为第二色谱柱,将鲜样与无水硫酸钠混合均匀后,以正己烷-丙酮（1：1,V/V）为提取剂进行索氏提取,采用全二维气相色谱-电子捕获检测器进行检测,外标法定量。各物质的质量浓度均在1.0~500μg/L内与其峰面积呈线性关系,相关系数均大于0.995,检出限为0.02~0.17μg/kg。用标准加入法进行回收实验,测得回收率为80.7%~103.5%,测定值的相对标准偏差（n=6）为1.84%~10.12%。本方法将高灵敏度检测器与全二维色谱相结合,在保证检测灵敏度的同时增加了峰容量,有效去除了基质干扰。相比2018年土壤详查参考方法HJ 835—2017的检出限0.02~0.09mg/kg（全扫模式）,本方法检出限显著降低,且操作简单,可为复杂基质样品中的痕量超痕量检测提供参考。     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

不同方法对提取原煤中PAHs分布的影响

选取超声提取法和索氏提取法,对淮北煤田主采煤层新鲜煤样中多环芳烃进行提取,并利用气相色谱-质谱联用仪对提取液中的多环芳烃进行定量分析,研究了不同方法对提取原煤中(US-EPA)优先控制的多环芳烃种类、质量分数和分布的影响。结果表明,在本实验条件下索氏提取法在提取原煤中多环芳烃能力上优于超声提取法。     

固态存储水位精简摘录的研究

讨论了固态存储水位数据精简摘录存在问题及所需满足的要求。介绍了曲线矢量压缩的Douglas-Peucker算法,对它做了改进并应用于水位过程线的精简摘录。应用实例表明该法能够以精简的数据反应出水位变化完整过程,是使用计算机完成固态存储水位摘录的有效方法。     

无锡、常州郊区发生地裂缝

无锡、常州郊区发生地裂缝近年来，无锡石塘湾西蔡一秦村～带、常州横林分别出现了地裂缝，其中以钱桥毛村园最为严重，该处地裂缝于１９９１年夏初步形成，随后不断扩大，目前已具一定规模，长约７００ｍ，总体宽约６０ｍ，呈近东西向分布，并造成附近数十间楼房产生大量...     

鄂尔多斯盆地大营铀矿铀的赋存状态研究

鄂尔多斯盆地大营铀矿是近几年新发现的砂岩型铀矿,详细研究该矿床铀矿物的赋存状态,对其矿床成因认识及之后的选冶开采均具有重要的意义。笔者利用电子探针和逐级化学提取分析以及α径迹分析等方法,研究了大营铀矿铀的赋存状态。结果发现,铀一部分以铀矿物为主,主要是铀石,另外存在少量的水硅铀石和钛铀矿。在电子探针镜下观察,表明铀矿物呈微粒集合体形式存在于黄铁矿、方解石及有机质裂缝中。逐级化学提取分析发现,各形态铀的含量不均一,其中有机质黄铁矿态占40.88%;其次为碳酸盐态,占28.33%;另外残渣态占24.89%,少部分为离子吸附态和铁锰氧化态,分别占3.2%和2.64%。反映其中铀矿物形式的铀占53.22%,分散吸附态的铀占46.72%。分散吸附态的铀以有机质及黄铁矿吸附占主导。综上所述,大营铀矿铀的赋存状态主要为铀矿物和吸附两种形式,二者所占比例大体相当,以铀矿物存在的铀主要为铀石,以吸附形式存在的铀主要赋存在黄铁矿和有机质中。