Determination of traces of fluorine,chlorine, bromine,cadmium and lead in plastic materials

This paper describes the quantitative determination of F, Cl, Br, Cd and Pb in plastic materials. The concentration of the elements Cl, Br, Cd and Pb is first semiquantitatively measured by X‐ray fluorescence spectrometry (XRF) directly in the solid sample with a detection limit of approximately 10 μg/g. Afterwards, F and any of the other elements which exceed the limit values for materials which are disposable without special precautions are measured after the digestion of the material. The samples are digested either under pressure in an oxygen atmosphere for F, Cl and Br or under pressure with nitric acid for Cd and Pb. The digestion converts the halides to the anions which are measured potentiometrically (F^‐, Br^‐) or with ion chromatography (Cl^‐). Cd and Pb are measured by graphite furnace atomic absorption spectrometry (GF‐AAS). The determination limits achieved are 20 μg/g for F and Br, 250 μg/g for Cl, 0.01 μg/g for Cd and 0.2 μg/g for Pb, all below the limit values set by current regulations in Switzerland.     

Interaction between cadmium,lead and potassium fertilizer (K<Subscript>2</Subscript>SO<Subscript>4</Subscript>) in a soil-plant system

A pot experiment was conducted to examine the influence of potassium (K) fertilizer (K₂SO₄) application on the phytoavailability and speciation distribution of cadmium (Cd) and lead (Pb) in soil. Spring wheat (Triticum aestivum L.) was selected as the test plant. There were seven treatments including single and combined contamination of Cd and Pb. CdCl₂·2.5 H₂O and Pb(NO₃)₂ were added to the soil at the following dosages: Cd + Pb = 0.00 + 0.00, 5.00 + 0.00, 25.0 + 0.00, 0.00 + 500, 0.00 + 1000, 5.00 + 500 and 25.0 + 1000 mg kg⁻¹, denoted by CK, T1, T2, T3, T4, T5 and T6, respectively. The K fertilizer had five levels: 0.00, 50.0, 100, 200 and 400 mg K₂O kg⁻¹ soil, denoted by K0, K1, K2, K3 and K4, respectively. The results showed that the K fertilizer promoted the dry weight (DW) of wheat in all treatments and alleviated the contamination by Cd and Pb. The application of K₂SO₄ reduced the uptake of Cd in different parts including roots, haulms and grains of wheat; the optimum dosage was the K2 level. K supply resulted in a significant (P < 0.05) decrease in the soluble plus exchangeable (SE) fraction of Cd and there was a negative correlation (not significant, P > 0.05) between the levels of K and the SE fraction of Cd in soil. The application of the K fertilizer could obviously restrain the uptake of Pb by wheat and there were significant (P < 0.05) negative correlations between the concentrations of Pb in grains and the levels of K in soil. K supply resulted in a decrease in the SE fraction of Pb (except the K1 level) from the K0 to K4 levels. At the same time, the application of the K fertilizer induced a significant (P < 0.05) decrease in the weakly specifically adsorbed (WSA) fraction of Pb and a significant (P < 0.05) increase in the bound to Fe–Mn oxides (OX) fraction of Pb. At different K levels, the concentration of Pb in the roots, haulms and grains had a positive correlation with the SE (not significant, P > 0.05) and WSA (significant, P < 0.05) fractions of Pb in the soil. All the K application levels in this experiment reduced the phytoavailability of Cd and Pb. Thus, it is feasible to apply K fertilizer (K₂SO₄) to alleviate contamination by Cd and/or Pb in soil. Moreover, the level of K application should be considered to obtain an optimal effect with the minimum dosage.     

Preparation and characterization of calcium alginate-based composite adsorbents for the removal of Cd,Hg, and Pb ions from aqueous solution

Composite adsorbent materials containing calcium alginate, clinoptilolite, and coal-derived humic acid were prepared. Humic acid (HA), clinoptilolite (CL), alginate (AL), alginate-entrapped humic acid (AL/HA), clinoptilolite (AL/CL), and humic acid/clinoptilolite (AL/HA/CL) samples were characterized. The effectiveness of the samples as adsorbents for the removal of cadmium (Cd), mercury (Hg), and lead (Pb) were studied in a series of batch-adsorption experiments. For the AL, AL/HA, AL/CL, and AL/HA/CL adsorbents, uptake versus time data were evaluated using two kinetic models, a linear and a non-linear pseudo-first-order and a pseudo-second-order model. The data for each metal ion on all adsorbents showed good correspondence with the pseudo-second-order kinetic model. The equilibrium data were fitted to Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin isotherm models. The results show that a non-linear method seems more appropriate for obtaining isotherm parameters. The non-linear Freundlich and Langmuir models for Pb and Hg produced a best fit with high R ² value (0.99). For HA adsorbent, the equilibrium data for Cd removal better fit to the non-linear Dubinin–Radushkevich isotherm.     

Regression models for some solute distribution equilibria in the terrestrial environment

Sorption coefficients (K_p) of several organochlorine insecticides (OCs) in volcanic ash silt from Central Java are presented.

Selected experimental and estimated octanol‐water partition coefficient (P) values are used to study log‐log regressions with K_p data collected from the literature (PAHs, chlorophenols, phenylureas, chloro‐s‐triazines, carbamates and organophosphorus insecticides) and those of the OCs determined in the present study. Leaching distances and bioactivities in soil are correlated with the K_p values of the pesticides, and with the organic matter and the water content of the soil.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Heavy metal concentration in soil and woody plants in a quarry

This study determined the concentration of three heavy metals zinc (Zn), lead (Pb), and cadmium (Cd) in soil and in a woody plant species, Milicia excelsa, at Ishiagu quarry, Nigeria. The highest soil concentrations of Zn, Pb, and Cd in soil were obtained at 1?m from the quarry site. In M. excelsa, the highest concentrations of Zn, Pb, and Cd were 3.12–9.1, 3.9–6.01, and 0.51–1.12?mg?kg^?1, respectively. There were significant positive correlations between Cd and Zn (r?=?0.963) and Cd and Pb (r?=?0.974) in plants as well as between Cd and Pb (r?=?9.84) in soil. The level of Cd in soil reflected significant pollution compared to average global concentrations in soils.     

Levels of heavy metals in blue whiting caught from the eastern Black Sea area of Turkey

This paper presents data on the concentrations of 5 metals, copper (Cu), cadmium (Cd), iron (Fe), zinc (Zn) and lead (Pb) in Blue Whiting sampled from the Eastern Black Sea coast of Turkey. The highest metal concentrations of Cu, Cd, Fe, Zn and Pb were recorded in Blue Whiting with the values of 2.71, 0.601, 14.137, 15.322 and 1.078 μg g^‐1 dry weight, respectively. On average the metal concentrations in Blue Whiting followed the order of Zn > Fe > Cu > Pb > Cd. Temporal differences of concentrations of these metals were significant (p < 0.05). Spatial fluctuations of Cu, Cd, Fe, Zn and Pb concentrations in Blue Whiting were also significant (p < 0.01). It was found that the concentrations of Cu, Cd, Fe, Zn and Pb in the muscle in Blue Whiting were below the limit of Public Health Regulation in Turkey.     

Heavy metals in contemporary Chinese sewage sludges

The heavy metal content in sewage sludges from a big Chinese city was investigated. Concentrations of zinc (Zn), lead (Pb), copper (Cu), chromium (Cr), nickel (Ni), cadmium (Cd) and mercury (Hg) in the sludges were 258–4050 mg kg^‐1, bd: 994 mgkg^‐1, 8.3–566 mg kg^‐1, 26.3–370mgkg^‐1 4.2–113 mg kg^‐1 0.9–6.4 mg kg^‐1 and 1.8–12.4 mg kg^‐1 respectively. The concentrations of Zn and Pb in the sewage sludges from the residential areas were higher than those in the mixed ones (from both residential and industrial areas). The concentrations of heavy metals in the flocculently dewatered sewage sludges were higher than those in the sediment of the centrifuged undewatered sewage sludges. After centrifuging, more than 60% of heavy metals remained in the sludge sediment with an exception of Cd. The content of organic matter, total phosphorus (T‐P) and total potassium (T‐K) in these sewage sludges was also measured.     

电镀企业周边大气颗粒物PM_(2.5)、PM_(10)和TSP中重金属分布特征及健康风险评价

以东莞市5个镇区为研究对象,采集电镀企业周边大气样品,分析了样品中重金属(包括As、Co、Cd、Cr、Cu、Mn、Ni、Pb、Sb、V、Zn和Hg)的含量分布,使用富集因子(enrich factor)、地累积指数(index of geoaccumulation)、Hakanson法和美国国家环境保护局(US EPA)的人体暴露健康风险评价模型,对PM_(2.5)、PM_(10)、总悬浮颗粒物(TSP)中重金属进行人体健康风险评价。结果表明,PM_(2.5)、PM_(10)和TSP中As、Cd和Cr平均浓度皆超标。Cr、Ni和V元素在3种颗粒物中非富集,主要为自然源;As、Co、Cu、Pb和Zn,可能来源于自然源和叠加的工业污染。Cd、Hg和Sb浓度受人为污染影响严重。Cd、Sb、Cu、Zn、Pb为生物可利用元素(K>0.6),在环境中的可迁移性高且易于被生物体和人体吸收。Mn元素的非致癌风险值较其他重金属要高1~4个数量级,且儿童的非致癌暴露风险值HQ均高于成人的。3种颗粒物中重金属元素通过呼吸吸入途径产生的非致癌风险HI值均高于人体可接受的上限1.0,其主要贡献来源于Mn的影响,研究区非致癌风险较为严重。除PM_(10)中Co元素和TSP中Co、Cr的成人致癌风险CR值大于10-4之外,其余大部分重金属元素通过呼吸途径产生的致癌风险CR值均在可接受范围之内,此外,3种颗粒物中的成人的致癌暴露风险值CRT均高于儿童的CRT值,并且除了PM_(2.5)中儿童的重金属致癌暴露风险CRT值(4.70E-05)低于人体可接受范围的上限(10-4),其余CRT值均高于10-4,致癌风险较为严重。     

Lead(II) and cadmium(II) removal from aqueous solution using processed walnut shell: kinetic and equilibrium study

The biosorption potential of processed walnut shell for Pb(II) and Cd(II) ions from aqueous solutions was explored. The effects of pH, contact time, initial ion concentration, and amount of dried adsorbent were studied in batch experiments. The maximum adsorption was achieved within the pH range 4.0–6.0. The equilibrium data were well fitted by the Langmuir isotherm model. The maximum monolayer adsorption capacities were found to be 32?g?kg^?1 and 11.6?g?kg^?1 for Pb(II) and Cd(II) ions, respectively. Kinetic data were best described by the pseudo-second-order model. The structural features of the adsorbent were characterized by Fourier transform infrared spectroscopy, which confirmed the involvement of hydroxyl (–OH), carboxyl (–COO^–), and carbonyl (C=O) groups in metal sorption. This readily available adsorbent is efficient in the uptake of Pb(II) and Cd(II) ions from an aqueous solution and could be used for the treatment of wastewater streams bearing these metal ions.     

贵阳市冬季PM_(2.5)中典型重金属元素的化学形态分析与健康风险评价

为了更准确地研究重金属的生物有效性和对环境与人体的潜在生态危害,采用改进BCR法分析了贵阳市冬季PM_(2.5)中Cu、Mn、Co、Cd、Pb这5种重金属元素的化学形态,并评价了它们的生物有效性和健康风险。结果表明:不同重金属元素形态分布存在差异,Cu主要是弱酸溶态,其次是可氧化态;Mn主要是弱酸溶态,其次是残渣态;Co没有检测出可还原态,而在其他3种形态分布比较平均;Pb和Cd绝大部分都是弱酸溶态。生物有效性系数(K)分析结果表明:重金属生物有效性强弱顺序为CdPbMnCuCo,其中Cd和Pb的K0.8,属于生物可利用性元素;Mn、Cu、Co的K值在0.4~0.7之间,属于潜在生物可利用性元素。健康风险评价表明:成人的致癌风险比儿童大,尤其Cd对成年人存在潜在的致癌风险,且成年男性高于成年女性;Mn存在潜在非致癌风险,且对儿童的风险最大。     

Assessment of As and Heavy Metal Contamination in the Vicinity of Duckum Au-Ag Mine, Korea

In order to assess the potential of As and heavy metal contamination derived from past mining activity and to estimate the human bioavailability quotients for As and heavy metals. Tailings, soils and crop samples were collected and analysed for As, Cd, Cu, Pb and Zn. The mean concentrations of As, Cd, Cu, Pb and Zn in the tailings were 68.5, 7.8, 99, 3,754 and 733 µg g^–1, respectively. Maximum Pb concentration in tailings was up to 90 times higher than its tolerable level. The concentrations of these metals were highest in the soils from the dressing plant area, and decreased in the order: farmland soil to paddy soil. In particular, some of the soils from the dressing plant area contained more than 1% of Pb and Zn. The pollution index ranged from 0.19 to 1.93 in paddy soils, and from 1.47 to 3.60 in farmland soils. The average concentrations of heavy metals in crops collected from farmland were higher than those in rice stalks or rice grains, and higher than the internationally accepted limits for vegetables. Element concentrations extracted from farmland soils within the simulated human stomach for 1 h are 9.4 mg kg^–1 As, 3.8 mg kg^–1 Cd, 37 mg kg^–1 Cu, 250 mg kg^–1 Pb and 301 mg kg^–1 Zn. In particular, the extracted concentrations of Cd, Pb and Zn are in excess of the tolerable levels. The results of the simple bioavailability extraction test (SBET) indicate that regular ingestion (by inhalation and from dirty hands) of soils by the local population could pose a potential health threat due to long-term toxic element exposure.     

Heavy metal pollution in soil and plants at bone char site

This study determined the heavy metal concentration in soil and plants at a bone char site in Umuahia, Nigeria. Soil and plant samples collected in a randomized complete block design (RCBD) were analyzed for zinc (Zn), lead (Pb), cadmium (Cd), nickel (Ni), and arsenic (As). The concentration of metals in soil and plants in the vicinity of the bone char site are as follows: Zn (172?mg?kg^?1) and Ni (0.62?mg?kg^?1) in soil were highest at site P₃, Pb (2.37?mg?kg^?1) and As (0.08?mg?kg^?1) at site P₁, and Cd (18.30?mg?kg^?1) at site P₂. In plants, the concentrations of Zn (41.17?mg?kg^?1) and Cd (3?mg?kg^?1) were highest in Albizia ferruginea, Ni in Dialium guineense (0.09?mg?kg^?1), while Pb was in D. guineense (0.08?mg?kg^?1) and Spathodea companulata (0.06?mg?kg^?1). The levels of Zn, Cd, Pb, Ni, and As in soil ranged from 11.2 to 172, 2.68 to 18.2, 0.026 to 2.37, 0.33 to 0.62, and 0.02 to 0.08?mg?kg^?1, respectively. In plants, the concentration of Zn, Cd, Pb, and Ni ranged from 2.01 to 41.17, 0.12 to 3, 0.02 to 0.08, and 0.03 to 0.09?mg?kg^?1, respectively. There were significant correlations between Zn and Cd, and Pb and As in soil. The high concentration of Cd in soil might affect soil productivity.     

Adsorption of pesticides by salorthids and camborthids of Punjab,Pakistan

This study was conducted to examine adsorption of pesticides bifenthrin, carbosulfan, λ-cyhalothrin, cypermethrin, endosulfan, parathion methyl, monocrotophos and 4-nitrophenol by sandy clay loam (S.C.L) and sandy loam (S.L) soils (with varying organic content). There was no significant difference between the observed soil water partitioning coefficient values (K _d) derived from linear and nonlinear Freundlich isotherms. Adsorption of pesticides on S.C.L soils was higher than those on S.L soils. K _d values showed significant correlations (r ²?=?0.8???0.99 and 0.65???0.97) with soil organic carbon content (OC) and weak correlations (r ²?=?0.2???0.29 and 0.1???0.18) with clay contents of S.C.L and S.L soil at p?≤?0.05, respectively for all pesticides (except monocrotophos). Observed K _oc values (soil-water partitioning constants based on the organic C fraction of the soil) were in accordance with the literature values of Wauchope and Tomlin with a maximum deviation of less than 0.5 log units. Ten Quantitative Property-Property Relationships (QPPR) among water solubility, n-octanol water coefficient (K _ow) and K _oc were proposed for studied pesticides except monocrotophos. The models were considered acceptable when predicted-observed difference for log?K _ow and log?K _oc were ≤?0.3 and ≤?0.5?log units, respectively, during the validation procedure. This work indicates that the log?K _oc derived from the log K_ow, from some of existing relationships, may be a fair predictor where observed values (i.e., K _d and K _oc) are not available. Furthermore, predicted leaching potential by groundwater ubiquity scores (GUS) equation was solved by using observed K _oc values and literature reported half lives of pesticides. GUS ranked the mobility of nonvolatile compounds i.e., bifenthrin, λ-cyhalothrin, cypermethrin and endosulfan extremely low; methyl parathion very low; 4-nitrophenol low; carbofuran and monocrotophos very high in S.C.L and S.L soils, respectively. Results discussed in this paper provide background to prioritize pesticides or chemical groups that should be evaluated under field conditions with regard to their leaching potential to groundwater in arid climates.     

水合欢对重金属Cd、Pb的耐受性及吸收富集特性

土壤重金属污染一直以来备受关注,作物能够吸收重金属从而对人体健康产生威胁,利用植物修复土壤重金属污染是当前环境科学和生态学领域的研究热点。本研究以一种水生豆科作物水合欢(Neptunia olerace)为研究对象,采用盆栽实验,研究水合欢对不同浓度Cd (0、50、100、180 mg·kg~(-1))、Pb (0、500、1 000、1 800 mg·kg~(-1))的耐受能力及吸收与富集情况。结果表明,(1)在Cd胁迫下,水合欢表现出一定的耐受性,生物量和植株长度与对照相比均显著降低(P0.05),可溶性蛋白、叶绿素以及根和茎中的MDA含量与对照均无显著差异,叶片中CAT活性显著提高(P0.05),但根中CAT、茎中SOD和叶片中POD活性及叶中MDA含量均先降低后升高;(2)在Pb胁迫下,水合欢表现出很强的耐受性,水合欢生物量、植株长度、可溶性蛋白、叶绿素和MDA含量与对照均无显著差异,但叶片中CAT活性显著提高(P0.05),根和茎中SOD、茎中CAT和叶片中POD活性均先降低后升高(P0.05);(3) Cd浓度为50、100、180 mg·kg~(-1)时,水合欢的富集系数分别为0.28、0.32和0.29,转运系数分别为0.05、0.06和0.08; Pb浓度为500、1 000、1 800 mg·kg~(-1)时,水合欢的富集系数分别为0.02、0.04和0.02,转运系数分别为0.04、0.08和0.05。水合欢对土壤中Cd、Pb的吸收均未达到超富集植物的标准,但本研究发现水合欢地下部重金属含量远高于地上部重金属含量,且水合欢为直根系植物,根系较浅,容易回收,基于此,可考虑将其与水稻等水生作物进行间套作,这种生产方式既可固氮,又可利用其根系来原位缓解土壤重金属污染对粮食等农产品生产所造成的安全风险。     

Essential and nonessential elements in the red-crowned crane Grus japonensis of Zhalong Wetland,northeastern China

The concentrations of four essential (Ca, Mg, Zn, and Cu) and two nonessential elements (Pb and Cd) in feathers and kidneys, livers, gut walls, and muscles of eight carcasses of migratory red-crowned cranes (Grus japonensis) from Zhalong Wetland, northeastern China, were examined. The concentrations of Cd in the feathers were between 0.4 mg kg^?1 dry weight (dw) and 3.1 mg kg^?1 dw, in the livers between 0.4 and 4.4 mg kg^?1 dw, the maximum of which exceeded a level considered to be environmental exposure risk (i.e., 3 mg kg^?1 dw in the liver or kidney). High Pb levels (0.4–3.2 mg kg^?1 dw, with an average of 1.8 mg kg^?1) were also detected in livers, which exceeded a level considered toxicosis in birds (1.7 mg kg^?1 dw). Pb and Cd had the highest scores in principal component analysis. Relatively high Pb and Cd concentrations in the migratory cranes were thought to be associated with their habitat and prey.     

Effects of salinity on the uptake of lead and cadmium by two mangrove species Rhizophora apiculata Bl. and Avicennia alba Bl.

The uptake of lead (Pb) and cadmium (Cd) by Rhizophora apiculata and Avicennia alba under various salinity levels was examined using hydroponic cultivations. After 3 months of exposure at four levels of Pb (0, 0.03, 0.3 and 3 mg·L^?1) and four levels of Cd (0, 0.005; 0.05 and 0.5 mg·L^?1) at different salinities (0, 15 and 30), uptake of the metals was shown to be differently affected by salinity. For uptake of Pb by R. apiculata, the salinity effect was not significant for the leaves and was most significant in the stem, whereas for A. alba, the effect of salinity was significant only in the stem. Uptake of Pb in the roots and stems of both species was similar, but a higher concentration was recorded in the leaves of A. alba. Salinity was shown to affect the uptake of Cd by all tissues of R. apiculata, but most significantly roots. For A. alba, salinity significantly affects the total uptake of Cd, but this is most significant in the roots. The two mangrove species demonstrated different mechanisms of metal distribution into their organs which may be related to different adaptation mechanisms to saline conditions.     

Biokinetic modeling of heavy metals in earthworms

Studies concerning bioaccumulation kinetics and bioconcentration factor (BCF) of heavy metals like zinc (Zn), lead (Pb), chromium (Cr), cadmium (Cd), and copper (Cu) in earthworm Eudrilus eugeniae tissues including integument, gizzard, clitellum, and head region were undertaken. Calculated BCF, predicted K _ow, and predicted K _oc showed a significant correlation between heavy metals in different earthworm tissues, in substrate spiked with heavy metals. The regression coefficient (r ²) between heavy metal uptake concentration and exposure time varied between 0.73 and 0.99, indicating significant correlation. The K _oc was a maximum of 13.9016 in case of Cu and integument at an exposure time of 100 days and a minimum of 0.1114 in case of Cr with respect to head at the same exposure time. Earthworms accumulated heavy metals following chronic exposure to municipal solid waste containing heavy metals. BCF and uptake rate kinetics of heavy metals were calculated and showed increased values in head tissue followed by integument.     

pH dependence of copper adsorption in vineyard soils of Geneva

Copper adsorption by vineyard soils of the Geneva canton was evaluated by batch equilibration experiments in a pH range from 4 to 6. The adsorption curves fit significantly to Freundlich function log q = n log C + log K_f, where q is adsorbed Cu concentration on the solid phase and C is solution Cu concentration at the end of the equilibration time. Moreover, we found that Freundlich parameters n and log K_f are moderately correlated to pH, yielding the following equations: log K_f = 0.23 pH + 0.51 (R ² 0.59) and n = –0.12 pH + 1.06 (R ² 0.59). Such equations may be useful to predict Cu mobility for risk assessment studies.