Stabilities of heavy metals in soils treated with red mud

This paper discussed the stabilities of heavy metals in soils treated with red mud. Soil has been polluted by heavy metals more and more seriously during recent several decades, and they are harmful to mankind and animals. The current tendency is to develop in-situ technique by using industrial processing waste as additives to stabilized heavy metals to minimize the disturbance of contaminated soils. Soil samples were collected from the Niujiaotang mining area, Guizhou Province, southwestern China. They were farmed soils polluted weakly by fly ash （QBT） and polluted badly by waste water （BXT） from smelter, respectively. One of the red mud samples （BRM） was collected from Bayer process and the other （CRM） from confederate process in the Alumina Plant of Guizhou. Free metal ion concentrations were analyzed with Donnan Membrane Technique and predicted with ECOSAT. The concentrations of free heavy metal ions in QBT increased after appending CRM, but decreased when adding BRM. The more the red mud was added, the higher the concentration would be, and the free concentrations of nickel and cadmium ions would vary more greatly than those of copper and zinc ions. When appending red muds into BXT, the free concentrations of copper and zinc ions varied little. While those of free nickel and cadmium decreased obviously at the ratio of 2.00%. The variation of the concentration was still biggish after appending BRM at the ratio of 0.50%, but smaller than that of 2.00%. The concentrations of free cadmium ions increased after adding CRM at the ratio of 0.50%. All experimental processes were modeled through ECOSAT. The predicted and measured results were consistent, except for zinc. Contributions of soil sorbents to the heavy metal adsorptions were also modeled through ECOSAT. The sorbents in soil included soil organic matter, iron hydroxides, clay and the Donnan gel of soil organic matter. Compared to the soils without red muds, no matter what kind of red mud and how much was added in soil, the contributions changed slightly.     

Fractionation of heavy metals in bottom sediments using Tessier procedure

The study presents the results of Cu, Pb, Zn, Mn and Fe determination in the samples of bottom sediments collected from the Oder and Warta rivers. The sequential extraction of metals in the samples of bottom sediments was performed after introducing the modification of the extraction scheme suggested by Tessier et al. (Anal Chem 51(7):844–851, 1979). The extraction times of particular stages were optimised. The fifth stage was altered by introducing the new methods of performing extraction. The samples of bottom sediments submitted the following granulometric analyses: dry, wet and wet with (HMP) dispersing reagent. Seven granulometric fractions with the following grain sizes were isolated: >2.0, 2.0–1.0, 1.0–0.5, 0.5–0.25, 0.25–0.1, 0.1–0.063 and <0.063 mm. The sequential extraction of particular granulometric fractions was performed. The concentration of metals variability was analysed depending on the method of sample preparation for the chemical analysis, granulometric fraction of sediments subjected to the analysis, extraction conditions and the site of samples collection. The lack of linearity between the metal concentration and the size of granulometric fraction was observed. The highest concentrations of metals were observed in fractions >2.0, 2.0–1.0 and 0.1–0.063 and <0.063 mm while the lowest concentrations occurred in fractions 1.0–0.5, 0.5–0.25, and 0.25–0.1 mm. The atomic absorption spectrometry with flame atomisation (F-AAS) was used for the determination of the investigated elements.     

Effect of red mud on the mobility of heavy metals in mining-contaminated soils

The mobility of Cu2+, Zn2+, Ni2+, and Cd2+ in soils treated with red mud was experimentally studied to explore the feasibility of remediation of smelter-contaminated soils. Red mud samples were collected with the Bayer process (BRM) and confederate process (CRM) in the Aluminous Plant of Guizhou Province. Two farmed soil samples were collected from the Niujiaotang mining area, Guizhou Province, Southwest China. One sample was weakly polluted by fly ash; and the other was polluted severely by waste water from the smelter. For evaluating the potential of remediation, the concentrations of free metal ions and the distributions of metals in the soil were determined. The concentrations of free metal ions were measured by using the Donnan Membrane Technique, and the contributions of soil sorbents to the heavy metals adsorptions were calculated with Equilibrium Calculation of Speciation and Transport (ECOSAT). BRM reduced the concentrations of free metal ions in two kinds of soils, while CRM only favored the decrease of the concentrations of free metal ions in seriously contaminated soils. The experimental data also showed a tendency that the concentrations of free metal ions decreased proportionally with the amount of added red mud, which resulted from the increasing adsorption of heavy metal ions in the form of metal ion hydroxides.     

辽东湾河口底质重金属环境地球化学

对辽东湾诸河口底质样进行了 Pb、Zn、Cu、Cd等含量分析.辽东湾底质重金属污染物主要是 Cd、Zn、Pb,尤其是 Cd平均含量为 1.16 mg/kg,超过土壤环境质量三级标准; Zn平均含量为 105.28 mg/kg,超过土壤环境质量一级标准.运用地累积指数法对其污染程度评价,认为辽东湾西北及北部河口底质污染严重,葫芦岛市五里河桥下> 大凌河口北> 辽河口> 双台子河口等处.与历史资料的对比表明,4种重金属的平均含量均有所提高.     

Speciation and mobility of heavy metals in mud in coastal reclamation areas in Shenzhen,China

Coastal reclamation has been carried out along the coastal areas near Shenzhen, China in a large scale since 1980s by dumping fill materials over the marine mud at the sea bottom. Usually the area to be reclaimed is drained first and some of the mud is air-dried for a few weeks before it is buried by fill. After reclamation, the terrestrial groundwater, which is relatively acidic and with high dissolved oxygen, gradually displaces the seawater, which is alkaline with high salinity. The changes in the burial conditions of mud and the properties of the pore water in the mud may induce the release of some heavy metals into the mud. Field survey confirms that the pH and salinity of the groundwater in the reclamation site are much lower than the seawater. Chemical analyses of mud and groundwater samples collected from the reclamation sites reclaimed in different years indicate that most of the heavy metals in the mud decrease gradually with time, but the heavy metals in the groundwater are increased. The release of heavy metals into pore water due to reactivation of heavy metals in the mud is of environmental concern. To understand why some of the heavy metals can be released from the mud more easily than others, a sequential extraction method was used to study the operationally determined chemical forms of five heavy metals (Cu, Ni, Pb, Zn, and Cd) in the mud samples. Heavy metals can be presented in five chemical forms: exchangeable, carbonate, Fe–Mn oxide, organic, and residual. Ni and Pb were mainly associated with the Fe–Mn oxide fraction and carbonate fraction; Zn was mainly associated with organic fraction and Fe–Mn oxide fraction, while Cu and Cd were associated with organic fraction and carbonate fraction, respectively. If the residual fraction can be considered as an inert phase of the metal that cannot be mobilized, it is the other four forms of heavy metal that cause the noticeable changes in the concentration of heavy metals in the mud. On the basis of the speciation of heavy metals, the mobility of metals have the following order: Pb (36.63%) > Cu (31.11%) > Zn (20.49%) > Ni (18.37%) > Cd (13.46%). The measured metal mobility fits reasonably well with the degree of concentration reduction of the metals with time of burial observed in the reclamation site.     

河流分类体系研究综述

简要阐述河流分类的目的和方法,重点对基于地貌、水文、生态、价值的分类体系进行了回顾,按照时间顺序说明了各种分类体系的发展过程。河流分类体系不断走向系统与综合,体现在从单要素到多要素、从定性到定量、从结构到过程、从单尺度线状河流到多尺度等级系统,以及从自然系统到包含社会价值。随着河流生态学实验及理论的发展、多学科的合作以及多尺度数据源条件的改善,具有预测功能的分类体系将逐步取代描述性的分类体系。国际河流分类体系的研究成果对于我国多类型河流的生态恢复与管理具有重要的借鉴意义。     

Speciation of some heavy metals in bottom sediments of the Ob and Yenisei estuarine zones

The speciation of Fe, Mn, Zn, Cu, Co, Ni, Cr, Pb, and Cd was studied in 52 samples of bottom sediments collected during Cruise 49 of the R/V Dmitrii Mendeleev in estuaries of the Ob and Yenisei rivers in the southwestern Kara Sea. Immediately after sampling, the samples were subjected to on-board consecutive extraction to separate metal species according to their modes of occurrence in the sediments: (1) adsorbed, (2) amorphous Fe-Mn hydroxides and related metals, (3) organic + sulfide, and (4) residual, or lithogenic. The atomic absorption spectroscopy of the extracts was carried out at a stationary laboratory. The distribution of Fe, Zn, Cu, Co, Ni, Cr, Pb, and Cd species is characterized by the predominance of lithogenic or geochemically inert modes (70–95% of the bulk content), in which the metals are bound in terrigenous and clastic mineral particles and organic detritus. About half of the total Mn amount and 15–30% Zn and Cu is contained in geochemically mobile modes. The spatiotemporal variations in the proportions of metal species in the surface layer of sediments along the nearly meridional sections and through the vertical sections of bottom sediments cores testify that Mn and, to a lesser extent, Cu are the most sensitive to changes in the sedimentation environment. The role of their geochemically mobile species notably increases under reducing conditions.     

The inhibition of microorganisms by heavy metals

This paper examines the effects of heavy metals on microorganisms in the aqueous environment; the mechanisms by which metals may exert toxic effects on microbes and the factors affecting microbial response to metals; the ways in which microbial activity may alter the metal balance of an environment and the modifications produced in microbes by heavy metal ions; the effects of the toxic copper ion on the growth, respiration, magnesium content, cytochrome synthesis and osmotic sensitivity of some organisms studied in the laboratory; and the feasibility of the participation of microbes in geochemical processes considering the demonstrable resistance to toxic metals by some bacteria and the fact that natural environments may contain high levels of metals rendered less toxic by binding to natural chelating compounds.

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Zusammenfassung In dieser Arbeit werden verschiedene Wirkungen von Schwermetallen auf Mikroorganismen in wäßrigem Milieu untersucht. Es wird gezeigt, daß Schwermetalle toxische Wirkungen auf Mikroorganismen ausüben können und welche Faktoren die Reaktionen von Mikroben gegenüber Metallen bestimmen. Weiter wird beschrieben, wie die Mikrobenaktivität das Metallgleichgewicht in einem gegebenen Milieu verändern und beeinflussen kann und wie andererseits Änderungen in den Mikroben selbst durch Schwermetall-Ionen hervorgerufen werden. Dabei wird besonders die Wirkung des toxischen Kupfer-Ions auf das Wachstum, die Atmung, den Magnesiumgehalt, die Cytochromsynthese und die osmotische Empfindlichkeit einiger Mikroorganismen dargestellt. Die Anwesenheit von Mikroben bei geochemischen Prozessen wird unter Berücksichtigung der Resistenz einiger Bakterien gegenüber toxischen Metall-Ionen diskutiert. Dabei spielt die Tatsache eine große Rolle, daß durch Chelatbildung die Schwermetall-Ionen in der natürlichen Umwelt der Mikroorganismen ihre toxische Wirkung verlieren.

     

青藏高原典型金属矿山河流重金属污染对比

为研究青藏高原金属矿山勘探、开采、闭坑阶段不同开发阶段河流重金属污染的严重程度,通过野外调查,室内测试分析,对比5个金属矿山河流重金属元素含量、污染指数沿程变化,得出以下结果:(1)勘探阶段和闭坑后河流水质污染较小,开采阶段矿业活动对河水水质污染较大。(2)As、Pb、Cd、Cu和Zn五种元素是金属矿山的特征污染物。开采矿区中德尔尼铜矿区、下柳沟铅锌矿、甲玛矿区河流均有重金属元素污染,微碱性环境中德尔尼铜矿区,主要污染物为As,单项污染指数为0～10.6;下柳沟铅锌矿Pb、Cd、Cu和Zn元素单项污染指数分别为0.2～2.1、0～55、0.4～24、0.3～1550;偏酸性环境中甲玛矿区的特征污染物主要为Cu、Cd。其中Cu、Cd单项污染指数为0～4174、0～4;勘探矿区大场金矿、闭坑矿区罗布莎铬铁矿区河流未出现污染元素。(3)青藏高原5处典型的高海拔山地矿山河流由于稀释作用重金属流经2km后达到安全水平,研究结果可为青藏高原矿山开采中河流水环境保护提供参考依据。     

Importance of different types of marine particles for the scavenging of heavy metals in the deep-sea bottom water

In experiments of 7 days duration using voltammetric and radiotracer measurement techniques, the role of different particle types in the sorption of dissolved metal species in a disturbed deep-sea bottom seawater system were investigated. Resuspension of oxic to suboxic surface sediment into the bottom water in the deep sea (either by natural events or industrial activities like Mn nodule mining) has been shown to be followed quickly by scavenging of dissolved heavy metals, e.g. released from interstitial water, on the resuspended particles. Compared to other deep-sea particles (like clay minerals, calcite and apatite), Mn and Fe oxides and oxyhydroxides were found to be by far the most important phases in scavenging many dissolved heavy metals. Only Pb was sorbed strongly on all particles used, with highest affinity to carbonate fluorapatite. Caesium⁺ was significantly scavenged only by clay minerals like illite. The sorption experiments support a simple electrostatic model: Hydrated cations and labile cationic chloro-complexes in seawater like Mn²⁺, MnCl⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ba²⁺, and PbCl⁺, are preferentially adsorbed or ion-exchanged on the negatively charged surfaces of Mn oxides. In contrast, oxyanions and neutrally or negatively charged complexes like HVO₄²⁻, MoO₄²⁻, HAsO₄²⁻, UO₂(CO₃)₂²⁻, and PbCO₃⁰ associate with neutral to slightly positive amphoteric Fe oxyhydroxide particles. Metals forming strong chloro-complexes in seawater like Cd (CdCl₂⁰), are less readily sorbed by oxides than others. A comparison of the results of voltammetric and radiotracer techniques revealed that after fast sorption within the first hour, isotopic exchange dominated reactions on MnO₂-rich particles in the following days. This was especially pronounced for Mn and Co which are bound to the Mn oxide surface via a redox transformation.     

Analysis of labile form of aluminum and heavy metals in bottom sediments from Kongsfjord, Isfjord, Hornsund fjords

The paper presents study results obtained for the bottom sediment samples of fjords Kongsfjord, Isfjord, Hornsund in the form of surface samples and their core profiles. The concentrations of labile form of aluminum and heavy metals were determined using the single-stage extraction with 3 mol L^?1 HCl. The obtained results allowed defining the occurrence of variability of labile aluminum form in the samples of bottom sediments of the studied fjords depending on the point and depth of sample collection. The conducted chemometric analysis allowed for the study of spatial variability of aluminum occurrence in the area of the investigated fjords. Based on the analysis, the correlations between aluminum and heavy metals were determined.     

Behavior of heavy metals in sulfide mine tailings and bottom sediment (Salair,Kemerovo region,Russia)

The given work focused on solving the problem of environmental geochemistry related to investigation of element speciation, their mobility, and migration in polluted areas. The purpose was to describe quantitatively migration, distribution, and redistribution of heavy metals by the example of the old tailings (Talmovaya sands) of the Lead Zinc Concentration Plant (Salair, Kemerovo region, Russia) and technogenic bottom sediments of the Malaya Talmovaya river. Contents of elements in the sulfide tailings range in the following limits: Zn: 1,100–27,000 ppm, Cd: 1.3–240 ppm, Pb: 0.01–0.81 ppm, Cu: 220–960 ppm, As: 15–970 ppm, Fe: 19,000–76,000 ppm, and Ba: 80,000–1,00,000 ppm. Element concentrations in the river sediment are proportional to the element contents in the sulfide tailings. Element speciations in the sulfide tailings and technogenic bottom sediments were investigated by the modified sequential extraction procedure. Chemical forms of heavy metals in pore water and surface water were calculated by WATEQ4F software. Principles of heavy metal migration in the sulfide tailings and technogenic bottom deposits were established. The obtained results about element species in the sulfide tailings and sediment explain the main principles of element migration and redeposition. In the mine waste and technogenic bottom deposits, there is vertical substance transformation with formation of geochemical barriers.     

Bedload transport of mud as pedogenic aggregates in modern and ancient rivers

Abundant sand-sized mud aggregates in the Cooper and Diamantina Rivers, Lake Eyre Basin, Australia are attributed to bedload transport of aggregates formed in deeply-cracked floodplain soils. The conditions required for formation of pedogenic mud aggregates are: (i) abundant clay containing at least minor swelling clay, and (ii) a climate with at least seasonally hot dry periods. The worldwide distribution of these soils (Vertisols) suggests that a significant amount of mud is transported as pedogenic aggregates by modern rivers. Ancient analogues in which mud aggregates and Vertisol profiles have been recognized are the Jurassic East Berlin Formation (Connecticut, USA) and the Carboniferous Maringouin Formation (New Brunswick and Nova Scotia, Canada). The dominant red mudstones of these formations are interpreted as mainly bedload sediments deposited by sheet floods in semi-arid palaeoclimates. The Triassic Hawkesbury Sandstone (NSW, Australia) also contains sand-sized mudstone aggregates, thought to be pedogenic, but its paleosol and other facies point to formation in a wetter palaeoclimate. The indications are that bedload transport of mud as pedogenic aggregates was as significant a process in ancient rivers as it is at present.     

Concentration distribution and assessment of heavy metals in sediments of mud area from inner continental shelf of the East China Sea

Heavy metals (Cr, Cu, Zn, Cd, Pb, Hg, and As), grain-size, pH, Eh, and total organic material (TOM and TN) of 59 surficial sediments of mud area from the inner continental shelf of the East China Sea have been analyzed. The relations of the heavy metals to sediment composition, pH, reduction/oxidation conditions and total organic materials were evaluated with multivariate statistics analysis, and the hydrodynamic conditions such as coastal current and Taiwan warm current are the other important controlling factors to the distribution of heavy metals. Sediment enrichment factors and potential ecological hazard index ( E_\textRI E_{\text{RI}} ) were used to assess the heavy metals accumulation; the results indicate that moderate contamination of most heavy metals is prevalent, and the contamination level in the estuary is rather high, which is mainly from anthropogenic source. Compared with other areas in China, the contaminant level of the study area is moderate.     

Field analysis of heavy metals by portable digital voltammeter

Water samples and acid extractions of stream sediments, gossans, soils and crushed pisolite samples have been analyzed in the field, using a portable digital voltammeter. This instrument, which uses the polarographic technique of anodic stripping voltammetry, can analyze to a sensitivity of 1 ppb in waters and acid extractions — equivalent to approximately 1 ppm in solid samples. The technique is at present suitable for analysis of Cd, Ph, Cu, Bi (and Zn if Cu is at low concentrations); future developments could extend the instrument capabilities to include Hg, Ag, Au, As, Sb and other elements of interest to the exploration geochemist. Water samples can be analyzed directly in the analytical cell of the instrument; for rocks, soils and biological materials an acid extraction procedure must be employed, and an aliquot of the acid extract added to the 40ml of cell electrolyte. Where a partial extraction technique is employed, e.g. by using HCl and ascorbic acid, the technique clearly does not provide total elemental analyses for the solid material. However, comparison of field results with conventional analytical methods (e.g. AAS) suggests that the technique is sufficiently accurate for the use of in-field, inter-active sampling (i.e. where the results of analysis are used to influence future sampling locations and densities) to be considered in certain types of geochemical exploration programs.     

Study of heavy metals in urban runoff

A cross-sectional survey was conducted through Tehran city and a field study was conducted to prepare main and accessory drainage channels map. Three main drainage channels were identified for this research and some sampling stations were chosen. Three stations selected in south of Tehran. The reason for selecting these stations is that all urban surface runoff completelypass through these points and samples taken from these points are representative of all kinds of pollutants that transit from city surface. Another Three stations were selected in center and further three stations were selected at north of Tehran. Surface runoff flow in three main channels, from north to south of Tehran, converge at south of Rey city and finally end up to Ghom Salt lake. The stations were chosen at three trajectories, Sorkhe Hesar, Emad Avard, Kan. At each month two samples were prepared from nine different stations. After collection of samples with respect to standard methods, they were dissolved in nitric acid and then analyzed by atomic absorption device. The results show that the concentrations of pollutants increased from north to south. For instance, Zinc had most concentration with monthly average of 0.98 mg/l and Nickel had the lowest amount with 0.02 mg/l in southern stations. Average concentration of Zn, Pb, Cd, Cu and Ni were: 0.638, 0.097, 0.04 and 0.035 mg/l respectively. Total average concentrations of heavy metals at three main channels were of 0.177, 0.176 and 0.145 mg/l. Emad Avard was the most polluted channel.     

Bioavailability of heavy metals in urban particles

Urban particles, as one of the toxic air pollutants, are important issues concerning air quality and public health, especially in large cities like Guangzhou （China）. Toxicological studies implicated heavy metals （particularly water-soluble metals） as a health hazard of particles. Once absorbed into human lung tissues, heavy metals are likely released from the particles and do harm to human body even in low concentrations. Thus, evaluating the bioavailability of heavy metals in urban particles is quite necessary. The particle samples used in this study were collected from a building roof in Guangzhou. Three different methods, sequential extraction procedure and two leaching tests, were employed to investigate the bioavailability of heavy metals in the particles. The sequential extraction scheme is specific for analyzing the chemical speciation of metals in particles, which consists of four fractions： F1： soluble and exchangeable metals; F2： carbonates, oxides and reducible metals; F3： bound to organic matter, oxidisable and sulphidic metals; and F4： residual metals. Leaching tests, GB 5086.2-1997 and TCLP, are standard methods developed by China-EPA and US-EPA and widely used in evaluating the toxicity of solid wastes. They were applied to gain additional information about more easily mobilized form of metal. Heavy metals in extraction solution, including Cu, Zn, Pb, Cd, Cr, and Ni, were analyzed by ICP-MS. According to the data from the total concentration analysis, the relative contents of 6 heavy metals in particles follow the order of Pb〉Zn〉Cu〉Cr〉Ni〉Cd. The results of sequential extraction showed that more than 50% of Cu, Zn and Cd were distributed in the F1, F2, and F3. This indicated that the bioavailability of Cu, Zn and Cd in the particles is much higher than that of Pb, Cr, and Ni. Leaching tests revealed that the concentrations of heavy metals in leachate are relatively lower than the regulatory level. The results of TCLP are much higher than those of GB 5086.2-1997, mainly due to the low pH value of the extraction fluid.     

A study on the physico-chemical speciation of heavy metals in waters of rivers, and lakes in the Changjiang River Valley, China

In the aquatic system, heavy metals always exist in a number of physico-chemical forms: particulate (Cp), soluble which consists of labile (MALI) and bound (inorganic MAb and organic MLb). The environmental behaviors of a metal are critically dependent on these forms. In this paper, the forms of heavy metals in waters from the Changjiang River source to mainstream and lakes were determined by ASV method. The main results are as follows: 1. The total contents (Ct) of Zn, Pb, Cu and Cd in the source were 4.0, 1.88, 1.28 and 0.07 (g/L) respectively, while Ct (g/L) in the mainstem were in the order of Zn (20.1) > Cu (14.9) > Pb (6.73) > Cd (0.15). Ct (g/L) in Dianchi Lake were Zn (7.2) > Pb (0.72) > Cu (0.53) > Cd (0.05), and in Poyang Lake were Zn (12.5) > Pb (4.2) > Cu (3.4) > Cd (0.05), and in Poyang Lake were Zn (12.5) > Pb (4.2) > Cu (3.4) > Cd (0.05). However, most of them were presented as Cp. Their dissolved contents (Cs, /L) were lower. 2. The distribution of soluble forms was related to the type of metal and to environmental variables. In general, Zn and Cd have a tendency to be present in MALi, Pb in MAb and Cu in MLb.     

Noble metals in the bottom sediments of the Chukchi Sea

Abundance of noble metals (NM) and bulk chemical composition have been studied in bottom sediments of the Chukchi Sea. Distribution of NM and their correlation with major and trace elements in the sediments have been analyzed using multicomponent statistics. It was established that the average contents of NM in the bottom sediments of the Chukchi Sea significantly exceed those both in shelf terrigenous sediments and stratisphere. Osmium and iridium enrich mixed and pelitic sediments relative to shallow-water areas and their influx is presumably determined by erosion of coastal and bottom loose deposits. High Ag, Ru, Au, and Pt contents were identified in the clayey sediments enriched in biogenic elements in the individual areas of the Southern Chukchi plain (Chukchi sea) confined to the intersection zones of submeridional and sublatitudinal structures of the graben-rift system, which was formed in the Mesozoic and activated in the late Cenozoic time.