Pollution, fractionation, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils from a Pb/Zn mining area

This study was conducted to investigate the pollution load index, fraction distributions, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils collected from a Pb/Zn mine in Chenzhou City, China. The samples were analyzed using Leleyter and Probst’s sequential extraction procedures. Total metal concentrations including Pb, Cd, Cu, and Zn exceeded the maximum permissible limits for soils set by the Ministry of Environmental Protection of China, and the order of the pollution index was Cd > Zn > Pb > Cu, indicating that the soils from both sites seriously suffered from heavy metal pollution, especially Cd. The sums of metal fractions were in agreement with the total contents of heavy metals. However, there were significant differences in fraction distributions of heavy metals in garden and paddy soils. The residual fractions of heavy metals were the predominant form with 43.0% for Pb, 32.3% for Cd, 33.5% for Cu, and 44.2% for Zn in garden soil, while 51.6% for Pb, 40.4% for Cd, 40.3% for Cu, and 40.9% for Zn in paddy soil. Furthermore, the proportions of water-soluble and exchangeable fractions extracted by the selected analytical methods were the lowest among all fractions. On the basis of the speciation of heavy metals, the mobility factor values of heavy metals have the following order: Cd (25.2–19.8%) > Cu (22.6–6.3%) > Zn (9.6–6.0%) > Pb (6.7–2.5%) in both contaminated soils.     

湘江干流沉积物中铅和镉的污染特征与评价

2007—2011年连续5 a采集了湘江干流水体沉积物,测定了沉积物样品中铅、镉的含量,同时对霞湾港沉积物中铅、镉的形态进行了分析,并利用地积累指数法、次生相与原生相比值法分别对沉积物中铅、镉的污染状况及生态风险进行了评价。结果表明:湘江水体沉积物中铅、镉的含量较高,其中松柏断面水体沉积物中的铅和镉最高;湘江霞湾港水体沉积物中镉以有机质和硫化物结合态为主;湘江松柏断面的地积累指数在时间上呈上升趋势,霞湾断面、马家河断面和昭山断面的地积累指数在时间上呈弱下降趋势,但松柏断面和霞湾断面沉积物中铅和镉的地积累指数较高,达到6级以上极强污染水平;生态风险评价结果显示,在湘江霞湾港沉积物中镉具有相对较高的生态风险指数,其潜在的生态风险应该引起重视。     

Chemical speciation and partitioning of trace metals (Cd, Co, Cu, Ni, Pb) in the lower Athabasca river and its tributaries (Alberta, Canada)

Concentrations of Cd, Co, Cu, Ni and Pb were measured in particulate and dissolved phases at 11 sites located upstream and near Athabasca oil sands development. The in situ discrimination between non-labile and labile dissolved metals was done using diffusive gradients in thin-films (DGT) devices. The DGT-labile fraction of Co and Ni was 30% lower near development sites whereas Cu, Cd and Pb showed minor changes spatially. It was found that an 8-fold increase in dissolved organic matter (DOM) near development induced a rapid decrease in DGT-labile metals. Dissolved metal concentrations were used along with DOM, major ions, nutrients, pH and conductivity to calculate the distribution of dissolved metal species using the speciation model WHAM. Labile-DGT metal concentrations agreed well with WHAM-predicted concentrations. It was also found that a significant amount of metals were associated with the non-DGT labile fraction (i.e. colloidal DOM) and colloid abundance was more important than suspended particulate matter abundance in influencing metal mobility near Athabasca oil soils development. Since changes in colloidal DOM levels are likely to be the result of surface mining activities, this confirms the serious effects of oil sands activities on metal biogeochemical cycles in the lower Athabasca River.     

M3法测定土壤有效态Cd、Cr、Pb和Ni

通过M3法对耕地土壤重金属的联合测定,为土壤重金属污染监测应用提供快速联合测定的方法。用M3法测定北方耕地土壤的有效Cd、Cr、Pb和Ni,通过对M3法与其他方法进行有效重金属测定值差异性及其相关性比较,与全量的浸出率分析等探讨M3法对耕地土壤有效重金属测定的特征。结果表明,M3法在《土壤环境质量标准》(GB 15618—1995)的土壤重金属含量范围内可以测定土壤有效态重金属Cd、Cr、Pb和Ni,且呈线性极显著相关。M3法与其他方法有效Cd、Cr、Pb和Ni有较好的相关性,与DTPA法呈极显著相关;与NaNO₃法除有效Pb外,呈极显著和显著相关;与HCl法除褐土和潮土的有效Pb外,也呈极显著和显著相关。M3法的有效态Cd、Cr、Pb和Ni的测定值均为最大。M3法对4种耕地土壤有效Cd、Cr、Pb和Ni的浸出率,因土壤类型不同,有效重金属含量所占比率不同,但利用M3法测定的有效态Cd、Cr、Pb和Ni的浸出率最大。     

Competitive sorption of Cd, Cu, Mn, Ni, Pb and Zn in polluted and unpolluted calcareous soils

The objectives of this study were to investigate competitive sorption behaviour of heavy metals (Cd, Cu, Mn, Ni, Pb and Zn) under different management practices and identify soil characteristics that can be correlated with the retention and mobility of heavy metals using 65 calcareous soil samples. The lowest sorption was found for Mn and Ni in competition with the other metals, indicating the high mobility of these two cations. The Freundlich equation adequately described heavy metals adsorption. On the basis of Freundlich distribution coefficient, the selectivity sequence of the metal adsorption was Cu?>?Pb?>?Cd?>?Zn?>?Ni?>?Mn. The mean value of the joint distribution coefficient (K _dΣsp) was 182.1, 364.1, 414.7, 250.1, 277.7, 459.9 and 344.8 l kg^?1 for garden, garlic, pasture, potato, vegetables, wheat and polluted soils, respectively. The lowest observed K _dΣsp in garden soil samples was due to the lower cation exchange capacity and lower carbonate content. The results of the geochemical modelling under low and high metal addition indicated that Cd, Ni, Mn and Zn were mainly retained via adsorption, while Pb and Cu were retained via adsorption and precipitation. Stepwise forward regression analysis showed that clay, organic matter and CaCO₃ were the most important soil properties influencing competitive adsorption of Cd, Mn, Ni and Zn. The results in this study point to a relatively easy way to estimate distribution coefficient values.     

Determination of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) by ICP-OES and their speciation in Algerian Mediterranean Sea sediments after a five-stage sequential extraction procedure

Surface sediment samples (n = 18) were collected from the Algerian Mediterranean coasts and analyzed for seven metals using inductively coupled plasma-optical emission spectrometry in order to asses the distribution and bioavailability of metals and to study the anthropogenic factors affecting their concentrations. Sediment samples were size-fractionated into three sizes: 1,080–500 (coarse), 500–250 (medium), and <250 mm (fine). Bulk sediments were subjected to both sequential extraction and total digestion to evaluate the reliability of the sequential extraction procedure (SEP), while the fractions have been only sequentially extracted for metals speciation. The metals were sequentially extracted into five phases namely exchangeable (P1), carbonates (P2), Fe–Mn oxides (P3), organic (P4) and residual (P5). Metal recoveries in sequential extractions were ±20% of the independently measured total metal concentrations; the high recovery rates indicate the good reliability of the SEP used in this study. Correlation coefficients indicated that the grain size has an effect on the distribution of metals in the investigated samples. The order of metal levels in the fractions was medium > fine > coarse for all the metals. The average total extractable metal concentrations for Cd, Cr, Cu, Fe, Ni, Pb, and Zn were 1.1, 8.8, 4.7, 1,291.3, 13.9, 5.7 and 20.4 μg/g, respectively. The northeastern shelf had the lowest metal levels while the highest were in northwestern part mainly due to the significant tourism activities in the northwestern part. Comparison of our results to Earth’s crust values and to previous studies points out that our samples were relatively unpolluted with respect to the heavy metals investigated; most of the metals are not from anthropogenic sources. Enrichment factors as the criteria for examining the impact of the anthropogenic sources of heavy metals were calculated, and it was observed that the investigated samples were not contaminated with Cr, Cu, and Fe, moderately contaminated with Ni, Pb, and Cd, and contaminated with Cd in some sites. The P5 phase had the highest percents of Cr, Cu, Fe, Ni, and Zn. Cadmium and lead were predominant in the P4 phase, while Cu, Fe and Zn were distributed in the order P5 > P3 > P4 > P2 > P1. The following order of bioavailability was found with the heavy metals Pb > Cr > Cd > Ni > Zn > Cu > Fe.     

Determination of Cu, Pb, Zn, Ni, Co, Cd, and Mn in road dusts of Samsun City

The dust samples from 52 different locations in central roads of Samsun City were collected in a study area of 40 km long for the purpose of determining total metal concentrations of dust samples by flame atomic absorption spectrometry. The concentrations of Cu, Pb, Co, Zn, Ni, Mn, and Cd were found in the ranges of 11.92–352.43, 5.47–223.57, 4.52–41.69, 40.85–173.10, 18.71–131.29, 133.19–179.13, and 0.02–6.16 mg/kg, respectively. The results showed that metal levels were higher around the industrial area than other locations. Principal component analysis was also carried out to ascertain the possible contributing factors towards the metal concentrations. Validation of the analytical results was tested by analysis of the BCR 032 Moroccan phosphate rock certified reference material.     

Solid phase extraction of Cd,Pb, Ni,Cu, and Zn in environmental samples on multiwalled carbon nanotubes

A simple and sensitive solid phase extraction (SPE) method on multiwalled carbon nanotubes (MWCNTs) is presented for the determination of cadmium, lead, nickel, copper, and zinc at trace levels combined with flame atomic absorption spectrometry. The effects of parameters like pH, sample volume, sample and eluent flow rates, eluent concentration, and volume and type of eluent on the recovery of trace elements was examined. The metals retained on the nanotube at pH 6.5 as α-benzoin oxime complexes were eluted by 10 mL 2 M HNO₃ in acetone. The influence of matrix ions on the developed method was also evaluated. The preconcentration factor of the method was found to be 50. The detection limits for Cd(II), Pb(II), Ni(II), Cu(II), and Zn(II) were found as 1.7, 5.5, 6.0, 2.3, and 2.4 μg L^?1, respectively. To test the accuracy of the method, the method was applied to TMDA-70 fortified lake water and Spinach 1570A standard reference materials. Addition recovery studies were applied to tap water and cracked wheat samples, and determination of the analyte elements was carried out in some food samples with good results.     

湘江大源渡枢纽底泥中镉、铅的污染特征及其潜在生态风险评价

为研究湘江大源渡枢纽底泥中Cd、Pb的污染特征及其生态风险,采集6个断面的18个底泥样品,测定了沉积物中Cd、Pb的总量、化学形态及其生物有效性,并利用地积累指数法和单因子指数法评价其污染程度与等级.结果表明,湘江大源渡枢纽底泥中Cd、Pb存在很强的积累现象,尤其是Cd污染特别严重.各采样点底泥中Cd主要以碳酸盐结合态...     

Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure

Sequential extraction procedures have been used during the last decades to study and determine trace element mobility in aquatic sediments. However, the results obtained are operationally defined and, therefore, the significance of the analytical results is related to the extraction scheme used. So, there is a need for suitable reference materials for this type of study to enable the validation of the methodologies and to control the quality of the measurements. This paper describes the preparation of a sediment reference material, BCR-701, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a collaboratively tested and optimised sequential (three-step) extraction procedure. The paper contains all the results and gives the methods used to certify the extractable contents (mass fractions expressed as mg kg-1 on a dry matter basis) of Cd, Cr, Cu, Ni, Pb and Zn in all steps. Moreover, indicative values are given for the aqua regia extractable contents of the six elements in the sediment and the residue obtained after sequential extraction.     

广东某含铊硫酸冶炼堆渣场土壤中重金属的污染特征

选取广东某硫酸厂工业堆渣周围土壤样品,重点研究了土壤剖面T1、cd、Pb、Zn四种重金属元素总量及形态分布特征.研究结果表明,该废渣在自然淋滤条件下已经对周围土壤产生了T1、Cd、Pb、Zn污染,并且T1、Pb、Cd较Zn污染严重.形态分析表明,堆渣场周围土壤中这些重金属主要是以残渣态和铁锰氧化物(氢氧化物)结合态存在.外围土壤受到的这些重金属污染及对环境的潜在危害大于废渣下伏土壤,其中在堆渣下伏土壤中主要以富集为主,而外围土壤中主要以迁移为主,且已经向土壤深处约30cm处进行了迁移.这些重金属污染物在表层土壤中未达到饱和状态,将继续在下伏土壤表层发生累积作用并且使横向土壤受污染的范围进一步扩大.     

Quantification and source identification of polycyclic aromatic hydrocarbons in sediment, soil, and water spinach from Hanoi, Vietnam

Polycyclic aromatic hydrocarbons (PAHs) were quantified in sediment, soil, and plant material from Hanoi, Vietnam, and an aquatic production system in peri-urban Hanoi. The sum of the concentration of 16 US-EPA priority PAHs ( summation PAH16) ranged between 0.44 and 6.21 mg kg(-1) dw in sediment and between 0.26 and 1.35 mg kg(-1) dw in soil, with decreasing concentrations from the urban area to the peri-urban area, indicating contributions from urban and industrial sources. Double plots of diagnostic source ratios indicate that PAHs originate from mixed petrogenic and pyrogenic sources, the latter being predominant. The predominance of low molecular weight (LMW) PAHs in the sediment samples suggests that petrogenic sources are more prevalent in the water environment than in the soil. In contrast, high molecular weight (HMW) PAHs dominated in water spinach which probably reflects the plant's uptake of particle-bound PAHs that originate from pyrogenic sources.     

Community exposure to arsenic in the Mekong river delta, Southern Vietnam

We examined the daily inorganic arsenic (i-As) intake from drinking water and rice in 45 households (75 individuals) in the An Giang province, Southern Vietnam. The daily i-As intake ranged from 28-102 μg d(-1), equivalent to the daily dose of 0.6-1.9 μg d(-1) kg((body wt))(-1). Increased As concentrations were observed in human hair in the study location. Approximately 67% (n = 44), 42% (n = 28), and 15% (n = 10) of the hair samples had As levels exceeding 1, 3, and 10 μg g(-1), respectively. The total As concentrations in female and male hair correlated well with the total daily i-As intake. Measurement of As concentrations in the hair of people who were consuming or had previously consumed As from contaminated sources may help predict the onset of negative health effects. We suggested an application of the Bayes's theorem to calculate the probability that an individual in a population will acquire a negative health effect, given that the concentration of arsenic in the subject's hair has been determined.     

Pesticide residues in soils, sediments, and vegetables in the Red River Delta, northern Vietnam

This study assessed pesticide residues in soils, sediments, and vegetables in the Xuan Khe and Hop Ly communes located along the Chau Giang River in the Red River Delta, northern Vietnam. Samples were collected from agricultural areas within and outside of embankments built to prevent flooding. In Xuan Khe, the soils outside of the embankment were more clayey with higher organic matter contents compared with the inside, due to selective deposition during river flooding. Many of the soils contained significant amounts of pesticides including dichlorodiphenyltrichloroethane (DDT), dicofol, isoprothiolane, and metalaxyl although their levels were below the maximum allowable concentration set by the Vietnamese government. The spectrum of DDT derivatives found suggested that the source of DDTs was not contaminated dicofol. Soils in Hop Ly resembled soils in Xuan Khe but were relatively sandy; one field showed appreciable contents of DDT derivatives. The ratios of (p,p ^′-dichlorodiphenyldichloroethylene + p,p ^′-dichlorodiphenyldichloroethane)/∑DDT in the surface and subsurface soils in Hop Ly were 0.34 and 0.57, suggesting that the DDTs originated from recent application. Pesticide residues in soils were not likely to translocate into vegetable crops, except for metalaxyl. High concentrations of cypermethrins in kohlrabi leaves could be ascribed to foliar deposition.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Assessment of ozone effects on local rice cultivar by portable ozone fumigation system in Hanoi, Vietnam

This study examined the effects of troposphere ozone (O3) on rice by developing a portable ozone fumigation system and applied to the field in Hanoi, Vietnam. The system was nearly identical to the open top chamber but designed to easily and cheaply assess the O3 sensitivity of local agricultural crops in the actual field. The rice (Oryza sativa L.) was exposed to ozone during the flowering stage at peri-urban experimental site of Hanoi. The fumigation protocols covered five different levels, namely; non-filtered air (ambient) as the control treatment, 32, 62, 85 and 113 ppb in 7-h mean. It was found that observed impacts corresponded well to similar open-top chamber studies in other Asian countries. The methodology and the system left a large room for improvement and called for very careful interpretation and pre-conditions (e.g. low ambient O3 concentration). However, the portable O3 exposure in the field might open a door to the less developed countries to implement the phytotoxic risk assessment of the local agricultural species.     

Evaluation of Pb, Cu, Zn, Cd, Ni and Fe levels in Rosmarinus officinalis labaiatae (Rosemary) medicinal plant and soils in selected zones in Jordan

The concentration of heavy metals including Pb, Cu, Zn, Cd, Ni and Fe in different parts of Rosmarinus officinalis medicinal plant grown in Jordan were evaluated. Medicinal plant samples and soil samples were collected from three different zones in Jordan (Irbid, Al-Mafraq and Ma’an). Samples were analyzed by atomic absorption spectrometry (AAS) after chemical treatments using acid digestion procedures. Heavy metal levels in washed and unwashed in each part of R. officinalis were analyzed and compared statistically. Results show that concentrations of investigated heavy metals were varied from plant part to another part of R. officinalis. For example, Pb, Zn, Cu and Cd in most parts of R. officinalis in the three zones were concentrated in the following order: flowers, leaves, stems, whereas Pb, Ni and Fe were concentrated in order as follows: leaves, flowers and stems. Heavy metal concentrations in soil samples was evaluated and correlated with their levels in R. officinalis. Two standard reference materials of plant (SRM 1790a; spinach leaves and CRM 281; rye grass) and one standard reference materials of soil (GBW 07406) were examined to validate the method used. Results show that high recoveries were obtained.