Geochemical index of trace metals in the surficial sediments from the western continental shelf of India, Arabian Sea

The present study focuses on the determination and abundance of trace metals (viz. Cu, Ni, Zn, Cr, Co, Cd, Mn and Fe) in the surficial sediments of west coast of Arabian Sea along the Indian subcontinent. Sediment samples were collected from three transects along the western continental shelf of Arabian Sea. The enrichment of Fe and Mn in coastal oxic-sediments indicates the precipitation of these redox sensitive elements as Fe- and Mn-hydroxides and oxides, whereas the low Fe and Mn concentrations in the oxygen deficient sediments of deeper stations reflects the dissolution of their hydroxides and oxides. Concentrations of fairly redox insensitive trace metals like Cu, Ni, Zn, Cr and Cd (with the exceptions of Cr) showed higher values at nearshore sediments, then it decreased towards seaward and again showed a slight increase at oxygen minimum stations in all the three transects. This geochemical variability in their distributional characteristics is mainly associated with the extent to which the precipitation or dissolution of Fe- and Mn-oxides/hydroxides occur since the scavenging or releasing effects of Fe- and Mn-oxides/hydroxides act as significant ‘sinks’ or ‘sources’ of heavy metals. The change in wind pattern, coastal upwelling and increased productivity are also the reported factors which influence the biogeochemical cycling of trace metals in the surface sediments of west coast of India. Enrichment factor generally showed a high gradient accumulation from nearshore to shelf.     

城市生活垃圾向土壤释放重金属研究

以南京为例，研究了城市生活垃圾对堆放环境土壤中重金属元素含量（总含量、各形态含量）的影响及其量比关系。结果表明，重金属元素在土壤中的含量和形态分布特征受其从垃圾中释放率的影响。自垃圾堆放环境土壤中释放的重金属含量与其有效态部分含量正相关。     

Major and trace elements in paddy soil contaminated by Pb–Zn mining: a case study of Kočani Field,Macedonia

The objective of this study was to assess the bulk chemical composition as well as the extent and severity of heavy metal contamination in the paddy soil of Kočani Field (eastern Macedonia). The results revealed that the paddy soil of the western part of Kočani Field is severely contaminated with Pb, Zn, As and Cd in the vicinity of the Zletovska River due to irrigation with riverine water that is severely affected by acid mine and tailing effluents from the Pb–Zn mine in Zletovo. The detected total concentrations of these metals are far above the threshold values considered to be phytotoxically excessive for surface soil. The paddy soil in the vicinity of the Zletovska River was also found to exhibit elevated levels of Ba, Th, U, V, W, Mo, Cu, Sb, Bi, Ag, Au, Hg and Tl, with concentrations above their generally accepted median concentration values obtained during this study. A correlation matrix revealed that the Mn and Fe oxides/hydroxides are the most important carrier phase for several trace elements, with the exception of rare earth elements (REEs). These also represent a major sink for the observed heavy metal pollution of the soil. REEs are mostly associated with two phases: light (L)REEs are bound to K-Al, while heavy (H)REEs are bound to Mg-bearing minerals. Although there is no direct evidence of a health risk, the paddy soil in the vicinity of Zletovska River needs further investigation and an assessment should be made of its suitability for agricultural use, particularly in view of the highly elevated concentrations of Pb, Zn, As and Cd.     

Uranium and other trace elements’ distribution in Korean granite: implications for the influence of iron oxides on uranium migration

To understand trace radionuclide (uranium) migration occurring in rocks, a granitic batholith located at the Korea Atomic Energy Research Institute (KAERI) site was selected and investigated. The rock samples obtained from this site were examined using mineralogical methods, including scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). The changes in the distribution pattern of uranium (U) and small amounts of trace elements, and the mineralogical textures affected by weathering, were examined. Based on the element distribution analyses, it was found that Fe²⁺ released from fresh biotite is oxidized in short geological time, forming amorphous iron oxides, such as ferrihydrite, around silicate minerals. In that case, the amorphous ferrihydrite does not show distinct adsorption for U. However, as it gradually crystallizes to goethite or hematite, the most U-rich phases were found to be associated with the secondary iron oxides having granular forms. This evidence suggests that the geological subsurface environment is favorable for the crystallized iron oxides to keep their structures more stable for a long time as compared with the amorphous phases. There is a possibility that the long residence of U which is in contact with the stable crystalline phases of iron may finally lead to the partial sequestration of U in their structure. Consequently, it seems that Fe-oxide crystallization can be a dominating mechanism for U uptake and controls long-term U transport in granites with low U contents.     

Chemical fractionation of metals in core sediments of Orogodo River,southern Nigeria

Sequential chemical extraction of metals (Cu, Ni, Mn, Fe, Pb, Cr, and Zn) from core sediments of the Orogodo River was carried out with a view of providing information on the phase distribution of these metals with respect to depths and seasons. The results indicate that copper was speciated into organic matter/sulfide, Fe–Mn oxides, and residual forms at 0–5?cm depth while at deeper sections copper was predominantly in the residual form. Nickel was speciated mainly into Fe–Mn oxides and residual forms. The average of lead in various particulate phases of the sediment are 0–100% for residual; 0–8% for carbonate; 0–16.2% for exchangeable; 0–10% for organic matter/sulfide form and 22–56% for Fe–Mn oxides bound metals. Manganese was speciated into exchangeable (10–36%) and Fe–Mn oxides bound (10–48%) at the surface layers of 0–20?cm depths and predominantly in the residual form in deeper sections implying partitioning into trioctahydral clay and/or well-defined crystalline oxides. Iron was predominantly in the Fe–Mn oxides and residual fractions, less than 8% in the organic fraction, and 24.4–37.3% in the exchangeable and carbonates fractions at the surface. The percentage contributions of iron in the exchangeable and carbonate fractions decreased to 3.2% at 55–60?cm depth. The amount of chromium in the exchangeable fraction ranged from 0% to 7% for exchangeable; 0–26.5% for organic matter/sulfide bound; 3.8–17.9% for Fe–Mn oxides; and 46.8–100% for residual fraction. The mobility factors of the metals indicated that these metals were relatively mobile at top sections as compared with deeper sections. The overall picture of metal mobility and availability indicates potential contamination risk by Fe, Zn, Mn, and Pb in the Orogodo River sediment system.     

Chemical speciation and bioaccessibility of lead in surface soil and house dust,Lavrion urban area,Attiki, Hellas

In the Lavrion urban area study, Hellas, a five-step sequential extraction method was applied on samples of ‘soil’ (n = 224), affected by long-term mining and metallurgical activities, and house dust (n = 127), for the purpose of studying the potential bioaccessibility of lead and other metals to humans. In this paper, the Pb concentrations in soil and house dust samples are discussed, together with those in rocks and children’s blood. Lead is mainly associated with the carbonate, Fe–Mn oxides and residual fractions in soil and house dust. Considering the very low pH of gastric fluids (1–3), a high amount of metals, present in soil (810–152,000 mg/kg Pb) and house dust (418–18,600 mg/kg Pb), could be potentially bioaccessible. Consequently, children in the neighbourhoods with a large amount of metallurgical processing wastes have high blood-Pb concentrations (5.98–60.49 μg/100 ml; median 17.83 μg/100 ml; n = 235). It is concluded that the Lavrion urban and sub-urban environment is extremely hazardous to human health, and the Hellenic State authorities should urgently tackle this health-related hazard in order to improve the living conditions of local residents.     

Modelling the potential mobility of Cd,Cu, Ni,Pb and Zn in Mollic Fluvisols

European floodplain soils are frequently contaminated with potentially toxic inorganic substances. We used a multi-surface model to estimate the aqueous concentrations of Cd, Cu, Ni, Pb and Zn in three Mollic Fluvisols from the Central Elbe River (Germany). The model considered complexation in solution and interactions with soil organic matter (SOM), a clay mineral and hydrous Al, Fe and Mn oxides. The amounts of reactive metals were derived from extraction with 0.43 M HNO₃. Modelling was carried out as a function of pH (soil pH ± 1.4) because it varies in floodplain soils owing to redox processes that consume or release protons. The fraction of reactive metals, which were dissolved according to the modelling, was predominantly <1%. Depending on soil properties, especially pH and contents of SOM and minerals of the clay fraction, the modelled concentrations partially exceeded the trigger values for the soil–groundwater pathway of the German soil legislation. This differentiation by soil properties was given for Ni, Pb and Zn. On the other hand, Cd was more mobile, i.e., the trigger values were mostly exceeded. Copper represented the opposite, as the modelling did not predict exceeding the trigger values in any horizon. Except for Pb and partially Zn (where oxides were more important), SOM was the most important adsorbent for metals. However, given the special composition and dynamics of SOM in mollic horizons, we suggest further quantitative and qualitative investigations on SOM and on its interaction with metals to improve the prediction of contaminant dynamics.     

Effect of weathering on abundance and release of potentially toxic elements in soils developed on Lower Cambrian black shales, P. R. China

This paper examines the geochemical features of 8 soil profiles developed on metalliferous black shales distributed in the central parts of the South China black shale horizon. The concentrations of 21 trace elements and 8 major elements were determined using ICP-MS and XRF, respectively, and weathering intensity (W) was calculated according to a new technique recently proposed in the literature. The data showed that the black shale soils inherited a heterogeneous geochemical character from their parent materials. A partial least square regression model and EF_bedrock (enrichment factor normalized to underlying bedrock) indicated that W was not a major control in the redistribution of trace metals. Barium, Sn, Cu, V, and U tended to be leached in the upper soil horizons and trapped by Al and Fe oxides, whereas Sb, Cd, and Mo with negative EF values across the whole profiles may have been leached out during the first stage of pedogenesis (mainly weathering of black shale). Compared with the Chinese average soils, the soils were strongly enriched in the potentially toxic metals Mo, Cd, Sb, Sn, U, V, Cu, and Ba, among which the 5 first listed were enriched to the highest degrees. Elevated concentrations of these toxic metals can have a long-term negative effect on human health, in particular, the soils in mining areas dominated by strongly acidic conditions. As a whole, the black shale soils have much in common with acid sulfate soils. Therefore, black shale soils together with acid sulfate soils deserve more attention in the context of metal exposure and human health.     

Species of Trace Metals, Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^-1, dry weight in fulvic acid and 820μg g^-1 in humic acid) and lead (821μg g^-1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Sequestration of heavy metals from soil with Fe–Mn concretions and nodules

In recent years, heavy metal contamination has become a major environmental issue in many parts of the world. Fe and Mn oxides, oxyhydroxides and hydroxides have long been recognized as scavengers playing an important role in controlling the location, mobility and bioavailability of metal contaminants in soils. Fe–Mn concretions and nodules are discrete bodies made of soil or sediment materials cemented together under the influence of Fe and Mn oxides. Here metals sorption by Fe–Mn concretions and nodules are surveyed and critical reviewed. Valuable available literature data demonstrate that the formation of Fe–Mn concretions and nodules is the most efficient and durable process for metal contaminants sequestration in the soils. The papers discussed in this review show that the application of Fe–Mn concretions and nodules, as geochemical scavengers for remediating metal contaminated soils, is strongly recommended.     

Electrocoagulation process for the treatment of metal-plating wastewater: Kinetic modeling and energy consumption

The wastewater from industrial area was treated by EC via Fe and Al electrodes. Cu, Ni, Cr and Zn were highly removed at the first minutes, simultaneously. Pseudo-2nd-order was found to be more suitable for kinetics. Adsorption capacities based on kinetic modeling were observed as Cr>Cu>Ni>Zn. The chemical cost in the case of pH adjustment after EC was less as 3.83 $/m³. It is known that wastewater produced by the metal-plating industry contains several heavy metals, which are acidic in nature and therefore toxic for the environment and for living creatures. In particular, heavy metals enter the food chain and accumulate in vital organs and cause serious illness. The precipitation of these metals is mostly achieved by pH adjustment, but as an alternative to this method, the electrocoagulation process has investigated in this study using iron and aluminum electrodes. The effects of the pH adjustment on removal before and after the electrocoagulation process were investigated, and cost analyses were also compared. It was observed that a high proportion of removal was obtained during the first minutes of the electrocoagulation process; thus, the current density did not have a great effect. In addition, the pH adjustment after the electrocoagulation process using iron electrodes, which are 10% more effective than aluminum electrodes, was found to be much more efficient than before the electrocoagulation process. In the process where kinetic modeling was applied, it was observed that the heavy metal removal mechanism was not solely due to the collapse of heavy metals at high pH values, and with this modeling, it was seen that this mechanism involved adsorption by iron and aluminum hydroxides formed during the electrocoagulation process. When comparing the ability of heavy metals to be adsorbed, the sequence was observed to be Cr>Cu>Ni>Zn, respectively.     

Sediment and porewater geochemistry in a metal contaminated estuary,Dulas Bay,Anglesey

Remobilisation of contaminant metals from sediments can occur by chemical, biological or physical changes. This in turn can lead to contaminant fluxes to the porewaters and ultimately the water column. The aim of the research presented here is to document post-depositional controls on metal mobility and fluxes in a heavily metal-contaminated estuary. This will allow for an improved understanding of the impact of contaminated sediments on water quality from both a short-term and long-term perspective. Dulas Bay is situated on the east coast of Anglesey, North Wales, and receives polluted waters from Parys Mountain. Metals within Dulas Bay sediments show surface enrichment and variations in mineralogical form. Diagenesis clearly plays a role in post-depositional behaviour of the metals, forming sulphides and potentially carbonates. The presence of a dominant exchangeable/carbonate fraction, and elevated porewater metals, in this sulphidic system is significant and could indicate the presence of freshwater diagenesis, or, reflect the high levels of metals in the sediment.     

Speciation of Heavy Metals in Floodplain and Flood Sediments: a Reconnaissance Survey of the Aire Valley, West Yorkshire, Great Britain

A five-step sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Zn, Cu and Cd), with major sedimentary phases (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions), in samples from floodplain and recent flood sediments of the River Aire, West Yorkshire. Analysis indicates that metals Pb and Zn are primarily associated with the Fe and Mn oxides, Cu with the organic fraction and Cd with exchangeable and surface oxide and carbonate metal ions. Knowledge of the chemical speciation of heavy metals in river sediment, despite the procedure's inherent limitations, facilitates an understanding of their bioavailability, storage and remobilisation in floodplain and river channel environments.     

The role of sulphur in cadmium(II) ions detoxification demonstrated in in vitro model: Dionaea muscipula Ell.

Fertilization by phosphorus and also nitrogen fertilizers are the main source of cadmium soil contamination. Cadmium is relatively easily taken up by plants and then consequently enters their food chain. We investigated whether the cultivation medium with or without sulphates supplement affects the synthesis of protective low molecular mass thiols such as cysteine, reduced glutathione, oxidized glutathione and phytochelatins (PC2) in Dionaea muscipula treated with cadmium(II) ions at 0, 1, 5, 10, 25, 50, 100, 250, 500 and 1,000 μM for 6 weeks. The plants cultivated in the presence of sulphates showed higher cadmium tolerance due to faster growth and lesser number of necrosis hallmarks. Further, we utilized liquid chromatography with electrochemical detection for determination of the thiols in plant tissues. In the case of the plants cultivated on media supplemented with sulphates for 6 weeks the average PC2 level was 2,830 ng/g of fresh weight (FW). However, the plants cultivated on media without the presence of sulphates on average contained 1,160 ng PC2/g FW. Results obtained showed the positive effect of sulphur supplementation in cadmium detoxification processes in plants. In addition to thiol content, we also determined level of majority secondary metabolite of Venus flytrap, naphthoquinone plumbagin. Generally, the presence of sulphates in the media enhanced the protective mechanism and did not affect directly the synthesis of secondary metabolite plumbagin.     

羟基磷灰石对沉积物中重金属释放特性的影响

以羟基磷灰石掺杂前后模拟重金属污染沉积物为研究对象,利用混匀释放实验及化学连续萃取法分析沉积物中重金属的释放特征及形态分布特性,考察了羟基磷灰石对重会属污染沉积物中Cu、zn、Pb、Cd稳定性的影响.结果表明不同来源模拟污染沉积物中松花江沉积物中的重金属最易重新释放,而伊通河沉积物中的重金属释放量最小;同时伊通河沉积物中残渣态重金属的比例较其它沉积物高很多,而可交换态和碳酸盐结合态的重金属比例较其它沉积物低很多,说明同时进入沉积物中的重金属,伊通河沉积物中的重金属相对稳定一些.羟基磷灰石的掺杂不同程度降低了沉积物中重金属的释放能力,促使沉积物中的重金属由较不稳定结合态向较稳定结合态转化,减小了沉积物中重金属的生物可利用性,增强了重金属的稳定性.     

Health risk of aerosols and toxic metals from incense and joss paper burning

We report for the first time the distribution and hazard potential of aerosol and metals resulting from joss paper burning. Burning joss paper and incense is a traditional custom in many Oriental countries. Large amounts of air pollutants, including particles, polycyclic aromatic hydrocarbons, toxic metals and other gaseous pollutants, are released into the environment during the burning stage. Many investigations have reported on the emission of pollutants from the incense burning. However, no work has been reported until now on the analysis of the released pollutants apart from polycyclic aromatic hydrocarbons. In this study, a micro-orifice uniform-deposit impactor and inductively coupled plasma optical emission spectrometry were, respectively, used to collect aerosols and characterize the toxic metals from joss paper burning. We studied two types of particulate matter (PM): PM_2.5 that are particles with a diameter smaller than 2.5 μm and PM₁₀ that are particles with a diameter smaller than 10 μm. PM_2.5 are the most potentially toxic particles. Our results showed that PM_2.5 are the major component of the pollutants and that the PM_2.5 to PM₁₀ ratio ranged from 62 to 99%. The metals Na, Ca, Mg, Al and K were the main species in the aerosol and in the bottom ash.     

Comparative study of the fate and mobility of metals discharged in mining and urban effluents using sequential extractions on suspended solids

The fate, bioavailability and environmental impacts of metals discharged in municipal and mining wastewater discharge will depend to a large extent on chemical speciation and distribution. Previous studies on metal bioaccumulation have shown that total metal concentrations are not a good predictor of bioavailability in the dispersion plumes of municipal effluents. The objective of this study was to determine the solid phase speciation of metals in surface waters receiving urban and mining effluents in order to assess their fate and relative mobility in the receiving environment. Suspended particulate matter was sampled using sediment traps at several sites downstream of effluent outfall plumes as well as at reference upstream sites. Particulate metal in operationally defined fractions—exchangeable/carbonates, reducible, oxidisable and residual—were determined in suspended particulate matter with a series of selective chemical extractions. Metal enrichment in suspended particles was generally observed in both mining and urban effluent discharges. When compared to its receiving environment, the mining effluent appeared to release more particulate metals (Cu, Fe, Zn) in the most reactive fractions (i.e. exchangeable/carbonates + reducible forms, 23–43%), while other released metals, such as Cd and Mn, were predominantly in the least reactive forms (i.e., oxidisable + residual, 73–97%). In contrast, the reactivity of all particulate metals, with the exception of Mn, from the urban effluent was much higher, with up to 65, 42, 30 and 43% for Cd, Cu, Fe and Zn, respectively, in the two most reactive fractions. As expected in effluent dispersion plumes, parameters such as the organic carbon, Fe oxide and carbonate contents have specific effects on the partitioning of several trace metals, particularly Cd, Cu and Zn. Our results indicated that the relative distributions of metals among geochemical fractions varied in the effluent receiving waters where organic carbon and Fe oxides appeared as the most important parameters. This could therefore decrease the exposure for aquatic organisms that are exposed to those contaminated sediments as well as the risk to human health.     

Chemical analysis of tobacco cigarette for organochlorine insecticides and heavy metal composition

The effects of cigarette smoking on smokers and the environment were investigated by analyzing some cigarette brands available to Nigerian smokers for the presence of some of the widely used organochlorine (OC) pesticides and heavy metals. OC pesticide residues were extracted from tobacco smoke, separated and identified using column chromatographic and thin layer chromatographic techniques respectively, while ashed and unashed commercial cigarettes were analyzed for heavy metals – Cr, Mn, Ni, Pb, Zn, Cd, Cu, and Co using atomic absorption spectrometry. TLC data indicated that dieldrin and p,p′-DDD were present in some of the cigarette brands. The results of heavy metal analysis showed that the levels of some toxic heavy metals and pollution index were higher in unashed cigarettes than corresponding ashes. Evidence suggests that significant amounts of these toxic metals are inhaled by the smoker and/or released into the environment in the process of cigarette smoking, thus confirming that cigarette smoking is harmful to the environment and human health.     

土壤重金属化学形态的生物可利用性评价

重金属化学形态是近年来土壤化学、植物营养和环境科学研究领域的一个热点和难点,利用重金属的化学形态分布和含量变化来评价重金属的生物可利用性,有利于全面研究重金属的危害性和治理重金属污染土壤。结果表明,水溶态和交换态的重金属易被生物吸收利用,而残留态重金属一般不被生物利用,其它形态如碳酸盐结合态、铁锰氧化物结合态和有机物结合态的生物可利用性主要取决于外界环境的变化。     

Geochemical speciation of trace metals in sediments of the northern Nile Delta Lake by sequential extraction technique

ABSTRACT

The present study was performed to investigate surface sediment samples from Lake Edku of the Nile Delta Lagoons, Egypt. The Lake is important for fishing in the region. The importance of research is to understand the mobility and bioavailability of each studied metal. The study was carried out on 10 sampling sites during 2017. The sediments were subjected to the technique of sequential extraction to examine the chemical forms of some trace metals (Fe, Mn, Zn, Cu, Pb and Ni). Five stage extractions were done as the following order: soluble and exchangeable, carbonate, iron and manganese oxides, organic matter fraction and residual fraction. Attained results from the five fractions showed variations in the concentrations of metal contents of different sites under study. The overall metal concentrations (%) in the initial four extractable fractions (exchangeable, carbonate, oxides and organic matter fractions) were assessed to configure the mobility of each studied metal. The risk assessment code (RAC) represents the summation of exchangeable and carbonate fractions, it was between low and medium risk for aquatic environment. The range percentage of RAC for the metals was in the following order: 1.8–13, 4–23.5, 15–26, 5.7–19.5, 9–25 and 4.8–18.2 for Fe, Mn, Zn, Cu, Pb and Ni, respectively. Approximately 30% of the total copper was associated to the organic fraction, which may represent a high mobility of copper in these sediments. The highest mobility of metals in the sediments could be confirmed by its bioavailability factor (BF), which was within the ranges of 0.32–0.61, 0.36–0.59, 0.64–0.83, 0.36–0.72, 0.37–0.62 and 0.52–0.78 for Fe, Mn, Zn, Cu, Pb and Ni, respectively. The BF exhibited the following order: Zn > Ni > Cu > Pb ≈ Mn?>?Fe. The high levels of BF for the studied metals may represent the potentiality for toxic metals to be easily released into the aquatic environment.