Geochemical distribution,bioavailability and potential toxicity of some trace metals in a complex micro-tidal estuary,Southwest India

The spatial and temporal variations of some trace metals in the surface sediments of Cochin Estuary were analyzed along with their geochemical associations to identify the possible sources, bioavailability and the health risks posed by them. The dominance of kaolinite and suggested that clay minerals distribution is influenced by sediment sorting. Total metal analysis revealed enrichment for Cd, Pb and Zn due to anthropogenic activities. The speciation analysis established that notwithstanding the large availability, carbonate as well as organic and sulfides bound fractions showed negligible associations with most of the metals. Hydrous Fe–Mn oxides appeared to play a major role in controlling the fate and transport of these metals in the sediments of Cochin Estuary. Lower contribution of the residual fractions for Cd (21%–26%), Pb (<60%) and Zn (24%–42%) indicated an obvious increase of other geochemical fractions. Risk assessment analysis revealed that regardless of total concentration, none of the analyzed metals were at safe levels in the estuary as appreciable percentages were found to be associated with mobile geochemical forms. The speciation study conspicuously established that the metals originating from non-geogenic sources are largely associated with the labile fractions and hence are more detrimental to the aquatic biota.     

AVS-SEM relationships and potential bioavailability of trace metals in sediments from the Southeastern Mediterranean sea,Egypt

In risk assessment of aquatic sediments, much attention is paid to the difference between acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) as indicators of metal bioavailability. Distribution of AVS and SEM (Cd, Cu, Ni, Pb and Zn) were determined in 20 representative sampling sites collected along the Egyptian Mediterranean coast. Total SEM concentration [ΣSEM] ranged from 0.012 to 0.241 μmoleg^?1. AVS concentrations were much more variable, showing significant spatial variations. The values ranged from 0.015 to 31.326 μmoleg^?1. The different relationships between AVS and SEM to establish mechanical models such as the ratio of ΣSEM and AVS [ΣSEM/AVS], the difference between the ΣSEM and AVS [ΣSEM–AVS], or the organic carbon normalised difference between SEM and AVS [ΣSEM-AVS]/f_oc models were used as parameters to evaluate potential bioavailability. Considering SEM/AVS model, sediments at the Western Harbour, Eastern Harbour, Ras El-Burr, El-Gamil East, and Port Said stations are occasionally toxic, while according to SEM-AVS model, no indication of associated adverse toxic effect would occur at any of the sampling sites. Calculated [ΣSEM-AVS]/f_oc was<130 μmoleg^?1 in the sediments indicating that sediments should pose a low risk of adverse biological effects owing to cadmium, copper, lead, nickel and zinc. Association of adverse effects to aquatic organisms was determined, using the classification of the sediments according to the Sediment Quality Guidelines (SQGs). The marine Threshold Effect Levels (TEL) and Probable Effect Levels (PEL) were used in this work and in order to obtain a more realistic measure of predicted toxicity, mean PEL quotients (PELq) were calculated. The mean PELq calculated for the sampling sites was (0.11–1.5) and categorised as slightly toxic at all stations except Baghoush, Nobarreya and western harbour, which had PELq<0.1 and categorised as non-toxic. The obtained data concluded that the remobility and bioavailability of trace metals contained in surfacial sediments of the Egyptian Mediterranean coastal area are low.     

干旱区绿洲土壤中重金属的形态分布及生物有效性研究

测定了Cd、Pb、Zn和Ni等重金属在不同处理土壤中的全量和各赋存形态,以及它们在盆栽试验油菜（Brassica cole）中的质量分数,并利用Pearson相关系数分析了该区土壤-油菜体系的生物有效性。结果表明,供试绿洲土壤原状土中,Cd、Pb、Zn和Ni均以稳定的残渣态形式存在;而在处理土壤中,重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Pb、Zn和Ni则主要以铁锰氧化态为主。根据相关性分析,油菜根部和叶部的Ni质量分数均与土壤中Ni的各非残渣态分布系数有相关性,表明当土壤中Ni以非残渣态存在时,活动性Ni的质量分数较高,其被生物吸收利用的可能性也较大;油菜根部的Zn质量分数与土壤中Zn的碳酸盐结合态分布系数显著的正相关性;油菜各部位Cd和Pb的质量分数与土壤中Cd和Pb的各形态分布系数之间无显著相关关系。     

Seasonal variations in trace metal levels,speciation and physicochemical determinants of metal availability in dumpsite soils within Akwa Ibom State,Nigeria

Physicochemical properties, total metals and metal species were investigated in surface soil samples from six urban dumpsites within Akwa Ibom State, Nigeria. Results obtained indicated that Pb, Cd and Cr levels were higher in the dry season than in wet season, whereas Ni levels were higher during the wet season. Soil pH, organic matter and cation-exchange capacity (CEC) showed higher values in wet season than in dry season, whereas sand and clay levels were higher in the dry season. Speciation analysis showed the principal fraction of the metals to be Pb (reducible), Cd (acid extractable) and Ni (residual), whereas Cr existed in the residual fraction during the dry season and in the acid-extractable fraction during the wet season. Soil pH was positively correlated at p<0.1 with all metals in both seasons, sand was negatively correlated with the metals in both seasons, and CEC was negatively correlated with all metals in both seasons, except Pb in the wet season. Organic matter showed variable relationships with metals in both seasons. Seasonal variations affected metal availability and physicochemical properties of the soil. Total metal concentrations followed the order Pb>Ni>Cd>Cr, whereas their bioavailability followed the trend Cd>Pb>Cr>Ni.     

Application of the electrochemical speciation of heavy metals in tracking groundwater pollution

The application of the electrochemical speciation of heavy metals in tracking groundwater is presented. Three fractions interchangeable, associated to the organic materials and associated to the matter in suspension of the metals Zn, Cd, Pb and Cu by means of the anodic stripping voltammetry were determined. The parameters of the determination were: electrodeposition potential ‐1.2 V, time of deaerating with nitrogen 300 s, time of the electrolysis 90 s (with stirring) and the rest time 40 s. The core of this work was to determine the validity of this scheme of electrochemical speciation in the pursuit of the follow‐up of groundwater pollution caused by heavy metals after the breakdown of the mining raft at the River Guadiamar Basin (Andalusia, Spain).     

Speciation study of trace elements in surface sediment of Winam Gulf,Lake Victoria,by sequential extraction,aqua-regia acid digestion,and ICP-OES

The speciation of trace metals in surface sediment in Kisumu Carwash area of Winam Gulf, was studied and results compared with those found at Usoma beach which was found to be several orders of magnitude less polluted. High proportions of the metals were bioavailable (fractions 1–6) with BA% ranging from 21.7% (Al) to 94.5% (Pb) at Carwash and 19.6% (Al) to ～100% (for Cd and Pb) at Usoma beach. The readily mobilizable fraction (fractions 1–4) decreased in the order: Pb > Mn > Sn > Cu > Co > Zn > Mg > Cd > Mo > Ni > Cr > Fe > Al at Carwash and Mn > Mo > Sn > Pb > Cd > Mg > Cu > Zn > Co > Ni > Fe > Cr > Al at Usoma beach. The total Zn, Cd, Cr, and Cu sediment concentrations at Carwash were higher than the threshold effect concentrations (TECs), although their bioavailable concentrations were lower than these limits. Both the total and bioavailable concentrations of Pb in surface sediment at Kisumu Carwash area were higher than the TEC threshold limit indicating significant contamination from this heavy metal. Although there was a general good agreement on data obtained by sequential extraction as compared with those obtained by direct aqua-regia digestion, there were large discrepancies for some specific metal analytes which could be accounted for in terms of analytical variations and lack of uniformity in physical and chemical composition of the sediment samples analyzed.     

Distribution and speciation of heavy metals in Apulian coastal sediments

In the framework of the Interreg II Project Italy–Greece, distribution and speciation of trace metals in surface coastal sediments of Apulian regions were studied. A sequential extraction technique was used to determine the chemical association of heavy metals (Zn, Pb, Ni, Fe, Cr, Mn, Cu and Cd) with major sedimentary phases (acid soluble phases, easily reducible fraction and oxidizable matter). The relationship between the metals' content and the grain-size composition of the sediments was also considered: generally the elements resulted associated with the fine fraction, even if in some cases (Cu in the oxidizable phase) the opposite behaviour was observed. The studied area is not particularly polluted, except for some defined zones, as for example Brindisi's harbour. Speciation analysis revealed that the major part of the heavy metals are not easily mobilizable and bioavailable. Even in this case, there are some exceptions to the general behaviour: Cu and Pb in several samples are largely present in the oxidizable phase, which even if not immediately available can become a source of associated elements when redox conditions change.     

Speciation evolutions of target metals （Cd,Pb） influenced by chlorine and sulfur during sewage sludge incineration

In sludge incineration, the thermal behavior of heavy metal is a growing concern. In this work, the combined analysis of metal partitioning behavior between vapor phase and condensed phase, speciation redistribu- tion in condensed phase and the difference of metal species in binding energy was carried out to investigate the possible volatilization-condensation mechanism of heavy metals in high-temperature sludge incineration. It was found that there were two steps in metal volatilization. The initial volatilization of heavy metal originated from their exchangeable （EXC）, carbonate bound （CAR） and iron- manganese bound （FM） fractions, which is primarily composed of simple substance, chlorides, oxides and sulfides. With the increase of chlorine and sulfur in sludge, the inner speciation redistribution of heavy metals occurred in condensed phase, which was an important factor affecting the potential volatility of heavy metals. A partial of metal species with complexed （COM） and residual （RES） fractions gradually decomposed into simple substance or ions, oxides and carbonates, which signifi- cantly strengthened the second volatility. In presence of chlorine, about 46% of Cd with the RES fraction disappeared when the volatility rate of Cd increased by 44.89%. Moreover, about 9% of Pb with COM fraction disappeared when there was an increase of nearly 10% in the volatilization rate. Thus, the second volatilization was mainly controlled by the decomposition of metal species with COM and RES fractions. By virtue of XRD analysis and the binding energy calculation, it was found that metal complex and silicates were inclined to decompose under high temperature due to poor thermo stability as compared with sulfates.     

Effect of lime on speciation of heavy metals during composting of water hyacinth

Composting is attractive and inexpensive method for treatment and biomass disposal of water hyacinth. However, the major disadvantage of water hyacinth composting is the high content of heavy metals in the final compost. Addition of lime sludge significantly reduced most bioavailable fractions (exchangeable and carbonate) of heavy metals. Studies were carried on composting of water hyacinth (Eichhornia crassipes) with cattle manure and sawdust (6:3:1 ratio) and effects of addition of lime (1%, 2% and 3%) on heavy metal speciation were evaluated during 30 days of composting period. The Tessier sequential extraction method was employed to investigate the changes in speciation of heavy metals such as Zinc (Zn), Copper (Cu), Manganese (Mn), Iron (Fe), Lead (Pb), Nickel (Ni), Cadmium (Cd) and Chromium (Cr) during water hyacinth composting. Effects of physicochemical parameters such as temperature, pH and organic matter on speciation of heavy metals were also studied during the process. Results showed that, the total metal content was increased during the composting process. The higher reduction in bioavailability factor (BF) of Cu, Fe, Ni, Cd and Cr was observed in lime 2 treatment about 62.1%, 64.4%, 71.9%, 62.1% and 58.9% respectively; however higher reduction in BF of Zn and Pb was observed in lime 1 treatment during the composting process. Reducible and oxidizable fractions of Ni, Pb and Cd were not observed during the process. Addition of lime was very effective for reduction of bioavailability of heavy metals during composting of water hyacinth with cattle manure and sawdust.     

Soil pollution by trace metals derived from animal feed and manure in the Bursa region of Turkey

The Bursa region of Turkey has important agricultural production areas. Animal producers use agricultural fields in this region for disposal of manure. Therefore, in this study the concentrations of the seven trace metals Zn, Mn, Cu, Ni, Cr, Pb, and Cd in 324 animal feed and manure samples from three dairy cattle, three laying hens farms, and three broiler farms have been determined. The average concentrations in dairy cattle manure were 130 (Zn), 150 (Mn), 4.2 (Cu), 6.8 (Ni), 44 (Cr), 0.8 (Pb), and 0.09 (Cd) mg kg^?1 dry weight; for laying hens manure 240 (Zn), 190 (Mn), 0.63 (Cu), 3.8 (Ni), 30 (Cr), 0.55 (Pb), and 0.12 (Cd) mg kg^?1 dry weight; and for broiler manure 240 (Zn), 280 (Mn), 1.4 (Cu), 3.8 (Ni), 35 (Cr), 3.4 (Pb), and 0.16 (Cd) mg kg^?1 dry weight. The calculated trace metal loading rate indicated that manure application might pose a potential risk to agricultural fields according to the current soil protection regulations of Turkey.     

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.     

Effects of hexachlorocyclohexane administration on distribution of trace metals in rat tissues

The effects of daily administration of hexachlorocyclohexane (HCH) for 90 days on the distribution of Cu, Zn, Fe and Mn in rat tissues were investigated. The results indicated that HCH caused a significant increase in weight of liver and spleen and decrease in the weight of kidney, heart and brain. The spleen and heart demonstrated the maximum mobilization of metals. Comparing the individual trace elements, zinc appeared to be the most active element. None of the metals assayed registered change in RBC's but there was increase in Zn, Fe and Mn concentration in plasma.     

Level,pattern, and risk assessment of the selected soil trace metals in the calcareous-cultivated Vertisols

Dynamics and distribution pattern of trace metals in agricultural lands are an increasing concern due to potential risks to the environment and human health. To ascertain more knowledge of this aspect, the fractions of total and available Fe, Mn, Zn, Cu, and Cd belonging to Vertisols under intensive cultivation and adjoining uncultivated soils were investigated. The order of abundance of metals in both cultivated and uncultivated soils was Fe?>?Mn?>?Cu?>?Zn?>?Cd and Fe?>?Mn?>?Zn?>?Cu?>?Cd for both available and total fraction, respectively. A relative enrichment was observed in the value of diethylene-triamine pentaacetic acid-extractable Fe (1.2–201%), Mn (2–31%), Cu (1–40%), and Cd (21–45%) as well as total fraction of Zn (3–17%), Cu (12–32%), and Cd (42–108%) after intensive cropping, which can be contributed to repeated application of agrochemical inputs and manure over long time. The values of RI (potential ecological risk) showed that cultivation caused a low potential ecological risk (33.3% of the soil samples) to moderate potential ecological risk (66.7% of the soil samples) in the study region and that cadmium made up 88%, on average, of the RI value.     

Temporal variation and distribution of trace metals in freshwater and fish from Calabar River, S.E. Nigeria

An investigation on the abundance and distribution of trace metals (Fe, Cu, Zn, Mn, Cr, Cd and Pb) in water, and nine species of fish samples from Calabar river was carried out in 1992. The concentrations of iron (6000–7240gl^–1), zinc (4910–7230gl^–1), and cadmium (3–7gl^–1) showed moderate pollution while those of copper (420–630gl^–1), manganese (23–48gl^–1), chromium (<10–20gl^–1) and lead (<1–10gl^–1) in water were well below WHO permissible levels. Significant seasonal changes (0.001p0.25) were obtained for iron, copper, zinc, manganese and cadmium in water. Furthermore, iron, zinc and cadmium showed statistically significant spatial changes (0.005p0.10). Of the nine fish species studied, no statistically significant relationship between body weight and the concentrations of the metals was observed. The concentrations of the metals per mean total body weight apparently decreases in the order Fe>Zn>Cu>Mn>Pb>Cd=Cr and were within the limits that were safe for consumption.     

黄河中下游干流沉积物中重金属的赋存形态及其生态风险

在黄河中下游干流采集6个表层沉积物样品,采用Han和Banin连续提取法提取并采用ICP-MS和ICP-OES测定不同化学形态的Pb、Cu、Cd、Cr、Ni、Zn、Mn含量,在计算重金属富集因子、迁移系数、次生相和原生相分布比值的基础上,对重金属赋存形态、迁移能力、生物活性、污染状况和潜在生态风险进行了研究.结果表明,黄河中下游干流表层沉积物中重金属元素含量沿河流向先增加后降低,高含量点位出现在汜水汇入黄河后,支流的输入对黄河重金属含量具有较为明显的贡献.形态分析研究表明,Pb、Cu、Cr、Zn、Ni等5种重金属残渣态在其不同形态中有绝对优势,Cd可浸取态占明显优势,Mn的残渣态与可浸取态所占比例相当.富集因子分析表明,黄河中下游表层沉积物中重金属可分为3类:Cu、Cr、Mn基本无富集,Pb、Ni、Zn轻度富集,Cd中度到极高度富集;迁移系数研究表明黄河中下游表层沉积物重金属迁移系数和生物活性顺序为MnCdZnNiPbCuCr.次生相原生相比值法表明Cu、Cr、Ni、Zn无污染,Pb在3点位轻度污染,其它点位无污染,Mn在1、3、6点位轻度污染,其它点位无污染.综合各种评价方法,Cd是黄河中下游沉积物中污染程度最高的重金属,具有潜在生态风险,应引起重视.     

The potential ecological risk of soil trace metals following over five decades of agronomical practices in a semi-arid environment

The concentration and potential ecological risk of Mn, Zn, Cu, and Cd in the surface soils (0–30?cm) belonging to 12 soil profiles and 4 soil types (Vertisols, Chernozems, Calcisols, and Cambisols) from the cultivated soils and the corresponding uncultivated soils were investigated. Long-term cultivation caused a considerable build-up diethylene-triamine pentaacetic acid (DTPA)-extractable Mn (7–55%), and Cd (12–31%) as well as the total form of Zn (3–14%), Cu (8–25%), and Cd (33–78%) in all soil types. Following long-time cropping, total Zn (mean?=?73?mg?kg^?1), Cu (mean?=?33?mg?kg^?1), and Cd (mean?=?3.14?mg?kg^?1) and DTPA Zn (mean?=?1.2?mg?kg^?1) and Cu (mean?=?2.44?mg?kg^?1) were below their maximum allowable limits. However, the average amount of DTPA Cd in the tilled soils (min?=?0.4, max?=?0.75, mean?=?0.55?mg?kg^?1) was above its maximum permissible limit mainly due to the over application of phosphate fertilisers and the pesticides. Considering the potential ecological risk (RI) assessment of the cultivated soils (min?=?44, max?=?70, mean?=?54), the soil types were categorised as low (RI?≤?50) to moderate (50?相似文献   

Distribution and speciation of Zn and Pb in coastal sediments of Dumai Sumatera,Indonesia

Concentrations of Zn and Pb in surface sediments collected from 23 sampling stations of Dumai coastal waters have been geochemically [easily, freely or leachable and exchangeable (EFLE), acid reducible, oxidizable organic and resistant] analyzed in addition to their total concentrations [expressed in µg g^?1 dry weight (d.w.)]. Results showed that mean concentrations of total Zn and Pb were highest in Ferry Port (88.2 and 61.2 µg g^?1 d.w., respectively), while the lowest was in Batu Panjang (32.6 and 15.7 µg g^?1 d.w., respectively). Metal concentrations in 87% and 74% of the sampling stations for Zn and Pb were dominated by the resistant fraction. However, nonresistant fractions were found to be higher than resistant fractions at Cargo Port, Sungai Dumai, and Penyembal for Zn; and in Pelintung, Guntung, Mundam, Ferry Port, Fishing Port, and Purnama for Pb, indicating that anthropogenic inputs of Pb occurred in more stations when compared to Zn. Site I (eastern Dumai) was dominated by the nonresistant fraction for Pb (61%) suggesting dominant anthropogenic inputs of this metal. This might be attributed to the combination of large population, discharges of untreated domestic and industrial wastes, shipping activities and city run-off.     

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.     

污泥超声破解效应及厌氧消化性能研究

针对超声破解污泥的可行性进行了实验研究,重点考察了超声频率、比能耗、作用时间等因素对破解效应的影响,探讨了破解污泥的厌氧消化性能。结果表明,超声作用的施加可使污泥固体有效破解,污泥细胞内的活性有机物被释放至水相并形成溶解性有机物,表现为SCODCr的显著增加;采用低频、高比能耗及延长作用时间有利于获取高的SCODCr增加值;污泥在频率25kHz、比能耗2.0W/mL、作用时间30min条件下破解,其厌氧消化累计产气量可从破解前的268mL提高到473mL,相应TCODCr去除率、VS去除率分别从39.1%、33.5%提高至54.3%、61.7%。研究结果表明采用超声破解技术提高污泥的厌氧消化性是可行的。     

煤矸石风化物不同粒级中重金属镉含量及其形态变化

对抚顺西露天矿煤矸石山表层煤矸石风化母岩进行多点取样,风化物筛分成>2 mm、2～0.25 mm和<0.25 mm等3个粒级,分析测定了矸石山表层母岩及其风化物不同粒级中Cd含量及其形态变化特征.结果表明:煤矸石母岩及其风化物中cd含量超过土壤环境质量2级标准,页岩、泥岩及其风化物pH值7.2～8.6,但燃后泥岩pH值4.9.碳质页岩2～0.25 mm粒级风化物中Cd损失最多,为73.6%;<0.25 mm细粒级Cd损失较少,为17.0%,这与细颗粒的表面吸附作用有关;泥岩及其各粒级风化物Cd元素不易损失,其Cd含量变化也相对较小;但燃后泥岩风化物中的Cd较容易损失.煤矸石风化物各样品类型中的Cd均以残渣态为主,可还原态和弱酸可提取态所占比例次之,可氧化态所占比例最小.弱酸可提取态Cd在细颗粒风化物中所占比例较高.