Evaluation of heavy metals and arsenic speciation discharged by the industrial activity on the Tinto-Odiel estuary, SW Spain

This study reports the annual amount of heavy metals discharged by industrial activity into the estuary of the Ría of Huelva (SW Spain). The findings showed that the discharged metals found in highest amounts were Fe (11 t y⁻¹), Zn (3.4 t y⁻¹) and Mo (0.88 t y⁻¹). There were other metals with high pollutant charge, such as Ti (232 kg y⁻¹), As (228 kg y⁻¹), Ni (195 kg y⁻¹), Pb (100 kg y⁻¹), Cr (39 kg y⁻¹) and Cd (33 kg y⁻¹). These results were compared with pollutants transported via the Tinto and Odiel rivers from abandoned mining activities in the Iberian Pyrite Belt (IPB), and it was deduced that the amounts spilled exclusively by industries were less than 1% in relation to the total discharge. Hence, the treatment of residues from the IPB should be the priority goal to improve water quality in the estuary.     

Patterns of rare earth and other trace elements in different size fractions of clays of Campanian–Maastrichtian deposits from the Portuguese western margin (Aveiro and Taveiro Formations)

The Upper Cretaceous (Campanian–Maastrichtian) Taveiro and Aveiro Formations belong to the northern sector of the Lusitanian basin (Portuguese western margin). The Taveiro Formation was deposited in alluvial fans, including mud flow beds, lakes and sinuous rivers. The Aveiro Formation was deposited in a flat region with low hydrodynamics channels, with the formation of a barrier island-tidal system. The reconstruction of this sedimentary basin may be difficult due to its complex architecture. This work aims a methodology to be used in the reconstruction of Cretaceous sedimentary environments of the Lusitanian basin, through the establishment of geochemical patterns of different size fractions of those deposits. Chemical analysis was performed by instrumental neutron activation analysis (INAA), and the mineralogical composition obtained by X-ray diffractometry (XRD). The whole rock and different size fractions (? ≥ 125 μm, 63–125 μm, 20–63 μm, 2–20 μm and ? < 2 μm) of selected samples were studied aiming the rare earth elements (REE) and other trace elements distribution and its correlation with the grain size and mineralogy.The results obtained for the studied Cretaceous sediments showed that REE patterns and other trace elements distribution in the different size fractions may be used as a tool to differentiate deposits within and between sedimentary formations. Within the Taveiro Formation, REE are concentrated in the silt fractions (20–63 μm and 2–20 μm) of the Reveles deposit, and in the clay size fraction of S. Pedro deposit, which is richer in kaolinite. The 1st transition elements, particularly Zn, are correlated with the presence of smectite in the clay fraction of Reveles deposit. In the sand and silt size fractions (>2 μm) of samples from Taveiro Formation correlations were found between: Ga and 1st transition elements, and phyllosilicates; Cs and mica; and Rb and Ba, and K–feldspars.The Bustos deposit (Aveiro Formation) samples are very fine-grained and with a high proportion of the fine silt fraction where REE are concentrated, especially the heavy ones. Incorporation of MREE, Co and U in carbonates of the coarser fraction appears to occur. The abundances of the 1st transition elements, Ga and As, are correlated with phyllosilicates.Significant differences were found in the trace elements patterns of the various analysed size fractions of the Lusitanian basin of Cretaceous sediments, between and even within formations, which can be used as a methodological approach for a fine paleogeographic reconstruction.     

沉积物中磷的赋存形态及磷形态顺序提取分析方法

阐述了当前我国水体富营养化的现状,水体的富营养化与水体中磷、氮的浓度以及二者的浓度比值有着密切的关系。水体富营养化时氮和磷的浓度均很高,但没有一个固定的值,是在一个较宽泛的富营养范围内,氮和磷的浓度比值大多在10∶1～20∶1。湖泊沉积物作为湖泊水体中磷的重要蓄积库,是湖泊流域磷循环的重要归属,也是湖泊水体内源性磷的主要来源,沉积物中极少量的稳定磷转化为活性磷就会造成湖泊水体富营养化。文中介绍了沉积物中无机磷形态的分类,评述了欧盟标准局在研制湖泊沉积物磷形态标准物质时比对采用的4种提取方法(Willimas法、Hieltjes-Lijklema法、Ruttenberg法、Golterman法),总结了国内外学者所应用的沉积物中磷的各种形态提取方法和磷各形态的分析测定方法,国内学者应用的方法是在国外学者方法的基础上提出的,阐述了顺序提取方法及其地球化学意义。简要评述了湖泊沉积物中磷的生物释放、物理释放和化学释放三种释放机制,这三种释放机制相辅相成,在一特定的环境条件下某一过程可能占主导地位来控制沉积物磷的释放。最后提出应该加强对沉积物中磷的各种形态的专属提取剂及其提取有效性的分子表征和检测,更加细化对于沉积物中磷形态的分类和创新各种磷形态的分析方法,建立沉积物-水体磷的迁移、循环和转化模型,这对于从根本上解决富营养化问题具有重要意义。     

贵州纳雍水东铅锌矿矿床地球化学特征

对贵州纳雍水东乡洗米沟、坟山脚一带灯影组地层中铅锌矿石采样,进行镜下观察和全岩主量、微量元素、稀土元素以及硫同位素地球化学研究。微量元素研究表明,矿床中N i、Mo、As、Sb等成矿元素富集明显,Sr、Ba、V等元素强烈亏损,认为早寒武世热水对铅锌矿源层进行了淋滤和改造;稀土元素研究表明,铅锌矿石稀土配分曲线向右倾斜,...     

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.     

长江口东南泥质区百年来稀土元素的组成及控制因素

在210pb定年的基础上,分析了长江口外东南泥质区柱样沉积物稀土元素含量、特征参数分布特征及其与粒径、常量元素等的相关性,探讨了150 a以来稀土元素的来源、制约因素及对沉积环境的响应.结果表明,柱样稀土元素总量(ΣREE)变化范围不大,分布范围为158.38～197.87 μg/g,平均值为183.49μg/g,总体...     

Molecular weight and chemical reactivity of dissolved trace metals (Cd,Cu, Ni) in surface waters from the Mississippi River to Gulf of Mexico

It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (<0.4 μm) were linearly related to salinity (10.8–36.6), suggesting that the distribution of these elements was mainly controlled by continuous mixing processes. Dissolved concentrations across the salinity gradient ranged for Cd: 87–187 pM; Cu: 1.4–18.3 nM; and Ni: 2.6–18.8 nM, with highest values near the Mississippi river mouth, and lowest concentrations in a warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (<10 kDa, 97 ± 1%) and cationic fraction (Chelex-100 extractable, 94 ± 4%). A novel observation across the estuarine mixing zone was that colloidal metal concentrations were identical to either inert (for Cu, Ni) or AMPG-labile anionic (Cu, Cd) fractions. The difference in behavior between Cu and the other two metals might indicate differences in the biopolymeric nature of the metal–organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 ± 1%, on average. However, for Cu, it was 24 ± 4%, and for Ni, it was 9 ± 6%. The fractions of the total dissolved metal fractions that were “inert” averaged 31 ± 10% for Cu and 29 ± 12% for Ni. Small but noticeable amounts (6 ± 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of ‘inert’ and ‘anionic’ metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico.     

Major and trace element geochemistry of Lake Bogoria and Lake Nakuru,Kenya, during extreme draught

The physico-chemical properties of water samples from the two athalassic endorheic lakes Bogoria and Nakuru in Kenya were analysed. Surface water samples were taken between July 2008 and October 2009 in weekly intervals from each lake. The following parameters were determined: pH, salinity, electric conductivity, dissolved organic carbon (DOC), the major cations (FAAS and ICP-OES) and the major anions (IC), as well as certain trace elements (ICP-OES). Samples of superficial sediments were taken in October 2009 and examined using Instrumental Neutron Activation Analysis (INAA) for their major and trace element content including rare earth elements (REE). Both lakes are highly alkaline with a dominance of Na > K > Si > Ca in cations and HCO₃ > CO₃ > Cl > F > SO₄ in anions. Both lakes also exhibited high concentrations of Mo, As and fluoride. Due to an extreme draught from March to October 2009, the water level of Lake Nakuru dropped significantly. This created drastic evapoconcentration, with the total salinity rising from about 20‰ up to 63‰. Most parameters (DOC, Na, K, Ca, F, Mo and As) increased with falling water levels. A clear change in the quality of DOC was observed, followed by an almost complete depletion of dissolved Fe from the water phase. In Lake Bogoria the evapoconcentration effects were less pronounced (total salinity changed from about 40‰ to 48‰). The distributions of REE in the superficial sediments of Lake Nakuru and Lake Bogoria are presented here for the first time. The results show a high abundance of the REE and a very distinct Eu depletion of Eu/Eu* = 0.33–0.45.     

扬子板块北缘马元铅锌矿床稀土元素地球化学研究

马元铅锌矿床是近年来在扬子板块北缘铅锌找矿的新突破。文章通过对马元铅锌矿床原生矿体中不同脉石矿物及矿区出露地层中稀土元素地球化学特征的研究,探讨了其成矿物质来源。马元矿区热液脉石矿物及出露的沉积地层稀土元素北美页岩标准化配分曲线总体呈比较平坦的特点,而且在Y-∑REE图解中呈线性分布,表明成矿物质主要来源于沉积地层。晚期方解石较早期热液白云石具有轻稀土元素总量高且相对富集的特点,表明二者是不同来源流体演化的结果。早期热液白云石在稀土元素总量(ΣREE)、轻、重稀土元素比值LREE/HREE以及在Y-∑REE图解上的分布等方面与灯影组白云岩比较接近,说明早期热液白云石主要来源于灯影组白云岩的溶解;而晚期方解石稀土元素总量明显高于灯影组白云岩而低于基底及古生代沉积碎屑岩系,晚期流体可能流经了具有高稀土元素总量的基底及沉积盆地中的碎屑岩系。矿区热液脉石矿物北美页岩标准化稀土元素配分曲线均显示出有较明显的Eu异常,表明成矿流体具有相对较高温(>200℃)和还原的环境。     

云南祥云马厂箐斑岩微量元素与稀土元素特征

马厂箐斑岩体与铜、钼、金等多金属矿成矿关系密切.斑岩体微量元素与稀土元素显示斑岩体物质来源具有壳幔混合特征.