Extraction of Co,Ni, Cu,Zn and Cd ions using 2-aminophenylaminopropylpolysiloxane

Insoluble porous solid functionalized ligand system bearing 2-aminophenylaminopropyl chelating ligand of the general formula P–(CH₂)₃NH–(C₆H₄)–NH₂ was prepared via the sol–gel process, where P represents [Si–O] _n polysiloxane network. First, the 2-aminophenylaminopropylsilane agent was prepared by substitution reaction between 3-chloropropyltrimethoxysilane and 1,2-phenylenediamine, followed by hydrolytic polycondensation between 2-aminophenylaminopropylsilane agent and tetraethylorthosilicate(TEOS). The immobilized 2-aminophenylaminopropylpolysiloxane P–(CH₂)₃NH–(C₆H₄)–NH₂(P–AphA) was characterized by ¹³C NMR, XPS, and FTIR. The results showed that 1,2-phenylenediamine groups were introduced onto polysiloxane network. The functionalized ligand system exhibits 90–100% metal uptake capacity for all metal ions except Cd²⁺. The elemental analysis data and the metal uptake capacities of the immobilized ligand system suggest that over than 90% ligand sites were involved in coordination with metal ions except that of cadmium forming 1:1 metal to ligand ratio complexes.     

Cu Ni As Cr对萝卜出苗的影响

利用盆栽试验研究Ｃｕ、Ｎｉ、Ａｓ、Ｃｒ４个元素不同浓度对萝卜出苗的影响．结果表明，土壤含Ｃｕ５０ｍｇ／ｋｇ以上时，随着含Ｃｕ量的增加，出苗数随之减少．在酸性土壤上发生Ｃｕ和Ｎｉ危害时，可用提高土壤ｐＨ至中性的办法来消除．在中性土壤上，含Ｎｉ５０ｍｇ／ｋｇ以上对萝卜出苗有害．Ｃｕ、Ｎｉ复合污染比单一元素污染的危害大，且毒性Ｎｉ＞Ｃｕ．土壤Ｃｒ、Ａｓ含量越大，对萝卜出苗的危害也越大，并且毒性Ｃｒ（６＋）＞Ｃｒ（３＋）．     

Human risk assessment of As,Cd, Cu and Zn in the abandoned metal mine site

The cancer risk and the non-cancer hazard index for inhabitants exposed to As, Cd, Cu and Zn in the soils and stream waters of the abandoned Songcheon Au–Ag mine area were evaluated. Mean concentrations of As, Cd, Cu, Pb and Zn in agricultural soils were 230, 2.5, 120, 160, and 164 mg kg⁻¹, respectively. Mean concentrations of As, Cd and Zn of the water in the stream where drinking water was drawn was 246 μg L⁻¹, 161 μg L⁻¹ and 3899 μg L⁻¹, respectively. These levels are significantly higher than the permissible levels for drinking water quality recommended by Korea and WHO. The resulting human health risks to farmers who inhabited the surrounding areas due to drinking water were summarized as follows: (1) the non-cancer health hazard indices showed that the toxic risk due to As and Cd in drinking water were 10 and 4 times, respectively, greater than those induced by the safe average daily dosages of the respective chemicals. (2) the cancer risk of As for exposed individuals through the drinking water pathway was 5 in 1000, exceeded the acceptable risk of 1 in 10,000 set for regulatory purposes.     

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.     

Heavy metals availability (Fe, Mn, Zn, Cu and Cr) in Aden Gulf sediments under aerobic and anaerobic conditions

The present study aims to analyse the chemical speciation of heavy metals in relation to aerobic and anaerobic conditions. Two sediment samples (from the Gulf of Aden, Yemen) were incubated under flooded conditions. In particular, the chemical forms of Fe, Mn, Zn, Cu and Cr under the experimental conditions were studied using a sequential chemical extraction method. The pH and Eh of the suspension were measured as critical parameters controlling the fate of the metals in the environment. The results showed that the metals concentration in the different forms varied with time incubation and affected by the variation of redox potential and pH value. Also, the changes in both redox potential (Eh) and pH values had evident effects on heavy metals transformation. It is obvious that the highest redox potential affected the amount of iron and manganese in the oxides form. When the redox potential decreased to-133 and-170 mV, it caused a significant transformation of the Fe-Mn oxide form to the water-soluble and exchangeable fractions. Under anaerobic conditions, the relative percentage of all five metals including the summation of four fractions (the water-soluble and exchangeable, carbonate, oxides and organic fractions) constituted 45-60% of the total amount of iron, 33-50% for manganese, 33-63% for Zn, 63-74% for Cu and 19-43% for Cr. Both zinc and copper among water-soluble and exchangeable fraction were high at the end of incubation period, this accompanied by a significant decrease in the content of the organically bound fraction. In general, the reducing conditions were more favorable for metal bound to water soluble and exchangeable fraction.     

Contamination and vertical distribution of As,Cd, Cr,Cu, Pb,Tl, and Zn in paddy soil irrigated with untreated leachate from tailings retention ponds

The contamination and vertical distribution of As, Cd, Cr, Cu, Pb, Tl, and Zn in paddy soil irrigated with untreated leachate from the tailings retention pond were investigated. As, Cr, Cu, and Zn were slightly contaminated in the surface soil and hence their vertical distribution was not obvious. However, Cd and Pb were highly contaminated in the surface soil, while their concentrations decreased with depth, being negatively correlated with pH and positively with total organic matter. Tl was considerably contaminated in the surface soil and a V-shaped vertical distribution was observed where the concentration increased to a maximum at about 30 cm depth and decreased thereafter. The findings revealed that the regular irrigation with untreated leachate from the tailings retention ponds could cause considerable contamination of Cd, Pb, and Tl, and thus tailings should be stringently treated before disposal to minimize their potential environmental impacts on the surroundings.     

电镀废水中铜锌铬镍对农业环境的影响

电镀废水排入河涌会污染农业环境。以广东省南 海市平洲地区为例,农田灌溉水中Ｃｕ、Ｚｎ、Ｎｉ的含量超过允许限值１ ～１４ 倍,河涌底泥Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ超标１２ ～３７倍,土壤超标０．５ ～２．９倍,作物超标０．３ ～８ 倍。进入河涌的Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ能较快沉积于底泥中。进入土壤的Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ主要累积在耕作层中。作物对Ｃｕ、Ｚｎ 的吸收能力远远高于对Ｃｒ、Ｎｉ的吸收能力,作物吸收系数是Ｚｎ ＞ Ｃｕ ＞ Ｎｉ＞ Ｃｒ     

Human bioaccessibility of Cr, Cu, Ni, Pb and Zn in urban soils from the city of Torino, Italy

Several physiologically based extraction procedures have been proposed to estimate the fraction of the potentially toxic element content that would be bioaccessible in the human gastro-intestinal tract following accidental ingestion of soil. Many of these procedures are complex, they have been applied to a very limited range of soils, and most work has focussed on arsenic and lead. In the present study, a simplified, two-stage extraction, simulating the human stomach and intestine, was developed and applied to urban soil samples from ten public-access areas in the City of Torino, Italy. The human oral bioaccessibility of chromium, copper, nickel, lead and zinc was estimated. Lead and zinc bioaccessibilities were found to be higher in the stomach, but chromium was more bioaccessible in the intestine. Analyte concentrations were higher in roadside soils than in soils from parks. A higher proportion of the soil metal content was found in bioaccessible forms at roadsides than in parks. Comparison of the current findings with results of earlier work involving sequential extraction of the same soils indicated that the sequential procedure gave a relative, but not an absolute, indication of bioaccessibility. Calculations based on the bioaccessible analyte concentrations suggest that ingestion of only 2–3 g of some of the roadside soil samples from Torino could deliver the tolerable daily oral intake of chromium, nickel and lead to a 20-kg child. The developed procedure is useful for preliminary screening of soils and prediction of whether their bioaccessible metal contents are likely to pose a risk to human health.     

复合污染下Cu、Cr、Ni和Cd在水稻植株中的富集特征

掌握水稻对污染土壤中重金属的吸收和富集特征,为科学认识水稻中重金属的残留问题、健康风险提供理论依据。采用田间试验,研究了4个不同处理量Cu、Cr、Ni、Cd复合污染下水稻的富集特征及其随生育期的变化规律。结果表明,重金属在水稻植株各部位中吸收富集系数的大小依次为：Cd〉Cu〉Ni〉Cr,根部重金属吸收富集系数是地上各部位的吸收富集系数的2~100倍。各重金属在水稻植株不同部位的积累分布明显不同,成熟期水稻植株中Cu在水稻不同部位的质量分数为根〉茎≥叶〉米粒〉谷壳,Ni的分布规律为根〉叶〉茎〉米粒〉谷壳,Cr的分布规律为根〉叶〉谷壳≥茎〉米粒,Cd的分布规律为根〉茎〉叶〉米粒〉谷壳;且随着重金属处理量的增加,水稻植株不同部位的重金属质量分数也呈上升趋势。成熟期米粒中Cu、Ni、Cr和Cd的质量分数范围分别为：4.50~6.19、1.86~4.63、0.72~0.76和0.08~0.39 mg·kg-1,与无公害食品标准（GB15199-94、GBT2762-2005）相比,米粒中Cu和Cr的质量分数均未超标,而Ni和Cd（Cd高剂量处理时）的质量分数均超标,存在食用安全风险。重金属在水稻植株不同部位的质量分数随生育期均呈现先升后降的趋势,灌浆中期达到最大,而到成熟期又明显降低。不同重金属在水稻植株中的富集能力和分布规律均呈现明显差异,不同生育期水稻植株中重金属的质量分数明显不同但其质量分数变化呈明显规律性。     

Seasonal variation and partition of trace metals (Fe, Zn, Cu, Mn, Cr, Cd and Pb) in surface sediments: relationship with physico-chemical variables of water from the Calabar River, South Eastern Nigeria

The seasonal variation and partition of trace metals (Fe, Cu, Zn, Mn, Cd, Cr and Pb) in the surface sediments of the Calabar River are reported. Chemical partition of the metals in the sediments reveals that 2–30% of the total metal load was contributed by the non-detrital (acid-soluble) fraction, while fine-grained host minerals/compounds are the main carriers of the detrital (acid-insoluble) fraction (70–98%). Using multivariate statistical analysis, the seasonal fluctuations in the distribution of some of the metals show significant influence by physio-chemical changes (dissolved oxygen, pH, salinity and conductivity) in the water column. Fe–Mn oxide grain coatings and sulphide materials have been identified as scavengers of some of the non-detrital and detrital trace metals in the sediments. On the basis of index of geoaccumulation (I-geo) and comparison with previous studies, the Calabar River surface sediments have been classified as unpolluted.     

Fractionation of Mn, Fe, Zn and Cu in Sediments of Khor Kalabsha, Lake Nasser, Egypt

Khor Kalabsha is the second largest Khor in Lake Nasser, which is a freshwater side-branch of the main lake. Chemical analysis of the samples indicates that calcium carbonate and organic matter content in the surface sediments average 17.8 and 3.07%, respectively. Moreover, manganese, iron, zinc and copper concentrations are lower in Khor Kalabsha than in other lakes of Egypt. It has been found that both oxides and residual forms constitute the major part of the measured elements in the study area, while manganese and iron play an important role in building up clay minerals. It is noted that both zinc and copper fractions are controlled by biological and biochemical processes.     

Modelling the concentrations of dissolved contaminants (Cd,Cu, Ni,Pb, Zn) in floodplain soils

Central European floodplain soils are often contaminated with potentially toxic metals. The prediction of their aqueous concentrations is a prerequisite for an assessment of environmental concerns. We tested the aqueous concentrations of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) derived from multi-surface adsorption modelling (on hydrous iron, aluminum and manganese oxides, clay and soil organic matter) against those analyzed in situ in the soil solution of four horizons of floodplain soils at the Elbe River, Germany. The input data for the reactive metals were derived from a seven-step sequential extraction scheme or from extraction with 0.43 M nitric acid (HNO₃) and evaluated in four modelling scenarios. In all scenarios, measured and modelled concentrations were positively related, except partially for Pb. Close reproduction of the measured data was obtained using measured data of accompanying cations and anions together with amounts of reactive metals from both the sequential extraction or from 0.43 M HNO₃ extraction, except for Cu, which was often strongly overestimated, and partially Cd. We recommend extraction with 0.43 M HNO₃ to quantify reactive metals in soil because the modelling results were metal-specific with better or equal results using the single extractant, the application of which is also less laborious. Approximations of ion concentrations and water contents yielded similar results. Modelled solid-phase speciation of metals varied with pH and differed from that from sequential extraction. Multi-surface modelling may be an effective tool to predict both aqueous concentrations and solid-phase speciation of metals in soil.     

Study of the ambient air metallic elements Cr,Cu, Zn,Cd and Pb at HAF sampling sites

This study characterized diurnal variations in the compositions of total suspended particulates (TSP) and dry deposits of particulates from ambient air, and the metallic elements that are contained in them at harbor, airport and farmland (HAF) sampling sites from August, 2013 to July, 2014. Two-way ANOVA of the amounts of metallic elements in the TSP and dry deposits was carried out in all four seasons at the HAF sampling sites. The metallic elements Cr and Cu originated in local emission sources at the airport. Metallic elements Zn and Pb originated in local emission sources at the harbor. Finally, metallic element Cd originated in local emissions form farmland. The following results were also obtained. (1) The metallic composition of the TSP differed significantly from that of the dry deposits in all four seasons at the harbor and farmland sampling sites, but not at the airport sampling site. (2) High correlations coefficients were found between the amounts of metallic elements Cr and Cu in the TSP and those in the dry deposits at the airport sampling site. (3) Pb was present in the TSP and the dry deposits at the harbor sampling site.     

Selective recovery of Cu, Zn, and Ni from acid mine drainage

In Korea, the heavy metal pollution from about 1,000 abandoned mines has been a serious environmental issue. Especially, the surface waters, groundwaters, and soils around mines have been contaminated by heavy metals originating from acid mine drainage (AMD) and mine tailings. So far, AMD was considered as a waste stream to be treated to prevent environmental pollutions; however, the stream contains mainly Fe and Al and valuable metals such as Ni, Zn, and Cu. In this study, Visual MINTEQ simulation was carried out to investigate the speciation of heavy metals as functions of pH and neutralizing agents. Based on the simulation, selective pH values were determined to form hydroxide or carbonate precipitates of Cu, Zn, and Ni. Experiments based on the simulation results show that the recovery yield of Zn and Cu were 91 and 94 %, respectively, in a binary mixture of Cu and Zn, while 95 % of Cu and 94 % of Ni were recovered in a binary mixture of Cu and Ni. However, the recovery yield and purity of Zn and Ni were very low because of similar characteristics of Zn and Ni. Therefore, the mixture of Cu and Zn or Cu and Ni could be recovered by selective precipitation via pH adjustment; however, it is impossible to recover selectively Zn and Ni in the mixture of them.     

Concentrations of iron-55 in commercial fish species from the North Atlantic

Concentrations of the weapon-test, fallout radionuclide iron-55 have been reported for migratory species, such as the Pacific salmon, which suggest a marked decrease in concentration with decrease in latitude of the point of capture. This situation has been examined for North Atlantic cod stocks in order to provide data for a species representative of a large geographical area, but divided into more or less distinct stocks each with a restricted territory, in order to provide further data on the importance of latitude in determining iron-55 concentrations. The data obtained show that there is a marked dependence upon latitude, Arctic cod averaging 90 pCi ⁵⁵Fe/mg Fe compared with 15 pCi ⁵⁵Fe/mg Fe for cod from middle latitudes. The mechanisms that could lead to such distribution are examined, and it is concluded that deposition of this radionuclide was exceptionally high over the sea in northern latitudes compared with its deposition on land, and that this pattern of deposition, taken together with the very high biological availability of the material at the time of deposition, has led to the very high specific activities found in northern latitudes and recorded for Arctic cod stocks in particular.     

耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全,但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法,欧共体标准物质局提出的三步提取法（BCR法1,中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品,采用中国地质调查局地质连续提取法（DD2005．03）进行耕地中重金属元素（Cu、Cd、Zn）的形态分布,结果表明：Cu、Zn主要以残渣态存在,其残渣态分别占全量的55．80％和67．35％。Cd以离子交换态为主,占全量的27．30％。Cu、Cd、Zn各态含量占全量比例的顺序是,Cu：残渣态〉弱有机结合交换态〉铁锰氧化态〉碳酸盐结合态〉强有机结合态〉水溶态〉离子交换态。Cd：离子交换态〉弱有机结合交换态〉强有机结合态〉残渣态〉碳酸盐结合态〉铁锰氧化态〉水溶态。Zn：残渣态〉铁锰氧化态〉弱有机盐结合态〉离子交换态〉强有机结合态〉碳酸盐态〉水溶态。从生物可利用性系数k来看,Cd主要以活动性较大的状态存在,很容易被作物吸收。     

耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全,但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法,欧共体标准物质局提出的三步提取法(BCR法),中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品,采用中国地质调查局地质连续提取法(DD2005-03)进行耕地中重金属元素(Cu、Cd、Zn)的形态分布,结果表明:Cu、Zn主要以残渣态存在,其残渣态分别占全量的55.80%和67.35%。Cd以离子交换态为主,占全量的27.30%。Cu、Cd、Zn各态含量占全量比例的顺序是,Cu:残渣态弱有机结合交换态铁锰氧化态碳酸盐结合态强有机结合态水溶态离子交换态。Cd:离子交换态弱有机结合交换态强有机结合态残渣态碳酸盐结合态铁锰氧化态水溶态。Zn:残渣态铁锰氧化态弱有机盐结合态离子交换态强有机结合态碳酸盐态水溶态。从生物可利用性系数k来看,Cd主要以活动性较大的状态存在,很容易被作物吸收。     

Coal fly ash and straw immobilize Cu,Cd and Zn from mining wasteland

Soil heavy metal contamination is a major health issue. Chemical immobilization of toxic metals is a promising technique to solve this issue. In this study, soil was sampled from a copper mining-polluted area in eastern China. Coal fly ash and straw were applied to soil samples at 5 % w/w ratio and 2 % w/w ratio, and incubated for 6 weeks. The CaCl₂-extractable Cu, Cd and Zn, phytoavailability and soil microbial activity were measured. The results showed that coal fly ash, straw and the mixture of coal fly ash and straw decreased CaCl₂-extractable metals. Coal fly ash or the mixture of the two amendments are therefore efficient metal stabilizers.     

蔬菜对土壤镉铜锌富集能力的研究

调查了福建部分污染严重地区不同蔬菜对镉、锌、铜的富集能力。结果表明蔬菜对镉的平均富集系数为0.017,锌的平均富集系数为0.116.铜的平均富集系数为0.014。蔬菜对镉的富集系数的品种间差异最大,达315倍,远高于锌和铜的富集系数的品种间差异。茭白、豇豆和莲藕对镉的富集能力较低,可作为镉污染土壤优先选种的蔬菜品种,而青包菜、白包菜、芥菜、空心菜、芋头等对镉的富集系数较高,不宜在镉污染土壤上栽培。     

Four-decade responses of soil trace elements to an aggrading old-field forest: B, Mn, Zn, Cu, and Fe

In the ancient and acidic Ultisol soils of the Southern Piedmont, USA, we studied changes in trace element biogeochemistry over four decades, a period during which formerly cultivated cotton fields were planted with pine seedlings that grew into mature forest stands. In 16 permanent plots, we estimated 40-year accumulations of trace elements in forest biomass and O horizons (between 1957 and 1997), and changes in bioavailable soil fractions indexed by extractions of 0.05 mol/L HCl and 0.2 mol/L acid ammonium oxalate (AAO). Element accumulations in 40-year tree biomass plus O horizons totaled 0.9, 2.9, 4.8, 49.6, and 501.3 kg/ha for Cu, B, Zn, Mn, and Fe, respectively. In response to this forest development, samples of the upper 0.6-m of mineral soil archived in 1962 and 1997 followed one of three patterns. (1) Extractable B and Mn were significantly depleted, by -4.1 and -57.7 kg/ha with AAO, depletions comparable to accumulations in biomass plus O horizons, 2.9 and 49.6 kg/ha, respectively. Tree uptake of B and Mn from mineral soil greatly outpaced resupplies from atmospheric deposition, mineral weathering, and deep-root uptake. (2) Extractable Zn and Cu changed little during forest growth, indicating that nutrient resupplies kept pace with accumulations by the aggrading forest. (3) Oxalate-extractable Fe increased substantially during forest growth, by 275.8 kg/ha, about 10-fold more than accumulations in tree biomass (28.7 kg/ha). The large increases in AAO-extractable Fe in surficial 0.35-m mineral soils were accompanied by substantial accretions of Fe in the forest's O horizon, by 473 kg/ha, amounts that dwarfed inputs via litterfall and canopy throughfall, indicating that forest Fe cycling is qualitatively different from that of other macro- and micronutrients. Bioturbation of surficial forest soil layers cannot account for these fractions and transformations of Fe, and we hypothesize that the secondary forest's large inputs of organic additions over four decades has fundamentally altered soil Fe oxides, potentially altering the bioavailability and retention of macro- and micronutrients, contaminants, and organic matter itself. The wide range of responses among the ecosystem's trace elements illustrates the great dynamics of the soil system over time scales of decades.