Relationship between total concentration and dilute HCl extraction of heavy metals in sediments of harbors and coastal areas in Korea

Total concentrations of Cr, Ni, Cu, Zn, Cd and Pb in surface sediments were determined to investigate the regional trends of heavy metal contamination in 11 coastal areas in Korea. Enrichment factor (EF) of heavy metals was calculated by comparing the level of their regional background. The averages of EF values in study areas were 0.99 for Cr, 1.05 for Ni, 4.23 for Cu, 1.80 for Zn, 3.92 for Cd and 1.54 for Pb, respectively. Dilute HCl extractions were useful to deduce the anthropogenic sources of heavy metals and the 1 M HCl extractable fractions of each metal varied from 0.3 to 37.3% for Cr, 1.9 to 66.3% for Ni, 4.2 to 92.9% for Cu, 7.1 to 99.7% for Zn, 10.9 to 98.9% for Cd and 15.0 to 99.1% for Pb. Comparing 1 M HCl extractable fraction to total concentration, large portions of Cu, Zn, Cd and Pb were present as potentially bioavailable fractions from anthropogenic input and were significantly correlated with their EF values showing r > 0.68.     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

Assessment of toxicity of heavy metal contaminated soils by the toxicity characteristic leaching procedure

The concentrations of Cu, Zn, Pb and Cd in soils near a lead–zinc mine located in Shangyu, Zhejiang Province, China, were determined and their toxicity was assessed using the toxicity characteristic leaching procedure (TCLP) developed by the United States Environmental Protection Agency. The TCLP method is a currently recognized international method for evaluation of heavy metal pollution in soils. The available levels of Cu, Zn, Pb and Cd were 8.2–36, 23–143, 6.4–1367 and 0.41–2.2 mg kg⁻¹, respectively, while the international standards were 15, 25, 5 and 0.5 mg kg⁻¹, respectively. Soils around the mine were more polluted with Zn and Pb, followed by Cd and Cu. Moreover, the levels of heavy metals in the soils extracted by TCLP indicated that extraction fluid 2 was more effective than extraction fluid 1 in extracting the heavy metals from the polluted soils and there was a positive correlation between fluids 1 and 2. Available heavy metal contents determined by TCLP were correlated with soil total heavy metal contents.     

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.     

Heavy metal speciation,leaching and toxicity status of a tropical rain-fed river Damodar,India

Speciations of metals were assessed in a tropical rain-fed river, flowing through the highly economically important part of the India. The pattern of distribution of heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn) were evaluated in water and sediment along with mineralogical characterization, changes with different water quality parameters and their respective health hazard to the local population along the Damodar River basin during pre-monsoon and post-monsoon seasons. The outcome of the speciation analysis using MINTEQ indicated that free metal ions, carbonate, chloride and sulfate ions were predominantly in anionic inorganic fractions, while in cationic inorganic fractions metal loads were negligible. Metals loads were higher in sediment phase than in the aqueous phase. The estimated values of I_geo in river sediment during both the seasons showed that most of the metals were found in the I_geo class 0–1 which represents unpolluted to moderately polluted sediment status. The result of partition coefficient indicated the strong retention capability of Cr, Pb, Co and Mn, while Cd, Zn, Cu and Ni have resilient mobility capacity. The mineralogical analysis of sediment samples indicated that in Damodar River, quartz, kaolinite and calcite minerals were dominantly present. The hazard index values of Cd, Co and Cr were >?1 in river water, which suggested potential health risk for the children. A combination of pragmatic, computational and statistical relationship between ionic species and fractions of metals represented a strong persuasion for identifying the alikeness among the different sites of the river.     

外源铅铜镉在长三角和珠三角农业土壤中的转化

选择了我国经济发达地区的长江三角洲和珠江三角洲10个代表性农业土壤，采用室内培养和化学分级方法研究了加入外源铅、铜、镉在土壤中的动态变化及转化趋势，探讨了碳酸钙、粉煤灰、猪粪和钢渣等土壤改良剂对土壤重金属形态的影响。结果表明，随着土壤重金属负荷的提高，土壤中交换态重金属的比例增大，残余态比例下降，有效性提高，对环境威胁增大。当重金属加入最较低时，重金属优先向氧化物结合态、有机质结合态转化；而当加入最较高时，向交换态和碳酸盐结合态转化的比例明皿增加。pH和土壤组分对重金属在土壤中的转化有显著的影响，土壤pH下降可使交换态Cd、Cu、Pb的比例递增。加入碳酸钙、粉煤灰、猪粪和钢渣等改良剂可显著地降低土壤中交换态重金属比例，增加其它形态的重金属比例。     

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.     

Determination of total and bioaccessible metals in airborne particulate matter from an urban and a rural area at Sarajevo

Airborne particulate matter of up to 10 µm collected at an urban and a rural area at Sarajevo in 2013 and 2014 was acid digested for determination of total concentrations or extracted with synthetic gastric juice for the bioaccessible fractions of Cd, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn and determined by graphite furnace and flame atomic absorption spectrometry. The total concentrations of Cr, Cu, Fe, Mn, Pb, and V were higher at the urban site, while those of Cd, Ni, and Zn were virtually equal at both sites. The average bioaccessible fractions exhibited the following trend at both sites: Fe > Zn > Cu > Mn > Pb > Cr > V > Ni > Cd. Enrichment factors and daily intake of metals by inhalation were calculated.     

Risk assessment for safety of soils and vegetables around a lead/zinc mine

Concentrations of heavy metals (Pb, Zn, Cd, Cu) were determined in soils and vegetables (chrysanthemum, spinach and four cultivars of Chinese cabbage from the area adjacent to a Pb/Zn mine in Shaoxing, Zhejiang province, China, and compared with the Chinese National Standards for Soil Environmental Quality. The accumulation of heavy metals in cabbage cv. Siyuegreen was investigated at different distances from the center of the mine. The vegetable plantation soils were polluted with Pb, Cd, Cu and Zn, especially by Pb and Cd. The levels of Pb and Cd were 20 and 30 times higher than the permitted standards, indicating that this Pb/Zn mining area is unsuitable for agricultural use. Chinese cabbage, chrysanthemum and spinach had different enrichment coefficients. The enrichment coefficient of Cd from soil to roots of chrysanthemum was >80% and from roots to leaves of cabbage cv. Shanghaigreen was >120%. These vegetables were polluted by heavy metals and could not be regarded as safe for human consumption. Environmental accumulation of heavy metals in the vegetable plantation soils was proportional to heavy metal accumulation in vegetables and both were inversely proportional to the distance from the lead/zinc mine.     

Biosolids application affects the competitive sorption and lability of cadmium,copper, nickel,lead, and zinc in fluvial and calcareous soils

The objective of this research was to investigate the effects of biosolids on the competitive sorption and lability of the sorbed Cd, Cu, Ni, Pb, and Zn in fluvial and calcareous soils. Competitive sorption isotherms were developed, and the lability of these metals was estimated by DTPA extraction following their sorption. Sorption of all metals was higher in the fluvial than in the calcareous soil. Sorption of Cu and Pb was stronger than that of Cd, Ni, and Zn in all soils. Biosolids application (2.5%) reduced the sorption of all metals especially Cu and Pb (28–43%) in both soils (especially the calcareous soil) at the lower added metal concentrations (50 and 100 mg L^?1). However, it increased the sorption of all metals especially Pb and Cu in both soils (especially the calcareous soil; 15.5-fold for Cu) at the higher added concentrations (250 and 300 mg L^?1). Nickel showed the highest lability followed by Cd, Zn, and Pb in both soils. Biosolids increased the lability of the sorbed Ni in the fluvial soils at all added concentrations and the lability of Cd, Pb, and Zn at 50 mg L^?1, but decreased the lability of Cd, Pb, and Zn at 250 and 300 mg L^?1 in both soils. We conclude that at low loading rate (e.g., 50 mg L^?1) biosolids treatment might increase the lability and environmental risk of Cd, Cu, Pb, and Zn. However, at high loading rate (e.g., 300 mg L^?1) biosolids may be used as an immobilizing agent for Cd, Cu, Pb, Zn and mobilizing agent for Ni.     

污染土壤中有机质结合态重金属的研究

用物理与化学相结合的方法研究了2个污染土壤剖面中有机质结合重金属（Cd、Cu、Pb和Zn）的分布，把有机质相结合态重金属分为颗粒状有机质（POM）结合的重金属和与细土腐殖质结合的重金属。结果表明，土壤POM对重金属有明品的富集作用，其中〉2mmPOM重金属Cd、Cu、Pb和Zn的富集系数分别在1．4～3．2、2．5～2．6、2．8—3．9和3．0～3．9之间；而0．05～2mmPOM重金属Cd、Cu、Pb和Zn的富集系数分别在2．7～7．8、3．2～6．4、3．2～9．3和3．2～5．6之间，0．05～2mmPOM组分中重金属的平均富集高于〉2mmPOM组分。POM中重金属的富集程度与土壤重金属的积累呈正相关。有机质结合态重金属占土壤重金属总最的比例随土壤有机质积累而增高，表土层约40％以上的重金属以有机质结合态存在。     

Effects of sulphur deposition on trace metal solubility in soils

Concentrations of Fe, Mn, Zn, Pb, Cu and Cd in soil solutions taken in the vicinity of a sulphur mine range from 354 to 9080 μM L⁻¹, and exceeded the concentrations measured in solutions from light acid arable soils. The content of each metal was a negative function of either the solution pH or of Ca concentration. Reclamation of S-contaminated soil by an application of 2000 tonnes of limestone per hectare did not significantly affect the solubility of trace metals, whereas equilibration of soil samples with CaCO₃ in the laboratory decreased solubility of metals, especially in the soil under moist conditions. Sulphur deposition may modify the natural cycling of metals in soils.     

Effect of long-term irrigation with sewage effluent on the metal content of soils, Berlin, Germany

This study aimed to determine whether >110 years of sewage application has led to recognizable changes in the metal chemistry of soils from former sewage farms, Berlin, Germany. Background concentrations of soils and element enrichment factors were used for the evaluation of possible perturbations of natural element abundances in sewage farm soils. Calculations verify that precious metals (Ag, Au) as well as P, C_org, and heavy metals (Cd, Cu, Ni, Pb, Sn, and Zn) are invariably enriched in sewage farm topsoils (0–0.1 m depth) compared to local and regional background soils. Long-term irrigation of soils with municipal wastewater has caused significant heavy metal contamination as well as a pronounced enrichment in precious metals. Leaching of metals including Ag into underlying aquifers may impact on the quality of drinking water supplies.     

Assessing Cd,Pb, Zn human bioaccessibility in smelter-contaminated agricultural topsoils (northern France)

The extractability of Cd, Pb, and Zn was investigated in contaminated agricultural topsoils located in an area highly affected by the past atmospheric emissions of two smelters in northern France in order to assess their mobility and human bioaccessibility. The determination of Cd, Pb, and Zn bioaccessibility (Unified Barge Method, in vitro test) was made to evaluate the absolute trace element (TE) bioavailability. The results highlighted differences in bioaccessibility between Cd, Pb, and Zn (Cd > Pb > Zn). The mean values of the bioaccessible fractions of Cd, Pb, and Zn during the gastric phase were 82, 55, and 33%, respectively, of the pseudototal concentrations, whereas during the gastrointestinal phase, the bioaccessible fractions of metals decreased to 45, 20, and 10%, respectively. Stepwise multiple regression analysis showed that human bioaccessibility was affected by various physicochemical parameters (i.e., sand, carbonates, organic matter, assimilated P, free Al oxides, and pseudototal Fe contents). Sequential extractions were performed as an indication of the TE availability in these soils. Cadmium occurred in the more available fractions, Pb was mostly present as bound by oxides, and a significant contribution to the pseudototal Zn concentration was defined as the unavailable residual form related to the crystalline structures of minerals. The concepts of bioavailability and bioaccessibility are important for quantifying the risks associated with exposure to environmental pollutants and providing more realistic information for human health.     

宝鸡城市街尘、土壤及河流沉积物重金属形态迁移特征

在宝鸡城市街尘、土壤及河流沉积物基本理化性质和重金属元素含量分析的基础上,重点研究了重金属元素在街尘、土壤及河流沉积物中的赋存形态和迁移特征.结果表明:在街尘中Cu主要以可氧化态和残余态形式存在,Pb主要以可还原态和可氧化态形式存在,Zn和Cd主要以乙酸可提取态形式存在,Mn、Fe、Co、Ni和Cr主要以残余态形式存在...     

Metal distribution in urban soil around steel industry beside Queen Alia Airport,Jordan

The objective of this study was to assess the extent and severity of metal contamination in urban soil around Queen Alia Airport, Jordan. Thirty-two soil samples were collected around steel manufacturing plants located in the Al-Jiza area, south Jordan, around the Queen Alia Airport. The samples were obtained at two depths, 0–10 and 10–20 cm, and were analyzed by atomic absorption spectrophotometry for lead (Pb), zinc (Zn), cadmium (Cd), iron (Fe), copper (Cu) and chromium (Cr) levels. The physicochemical factors believed to affect the mobility of metals in the soil of the study area were also examined, including pH, electrical conductivity, total organic matter, calcium carbonate (CaCO₃) content and cation exchange capacity. The high concentrations of Pb, Zn and Cd in the soil samples were found to be related to anthropogenic sources, such as the steel manufacturing plants, agriculture and traffic emissions, with the highest concentrations of these metals close to the site of the steel plants; in contrast the concentration of Cr was low in the soil sampled close to the steel plants. The metals were concentrated in the surface soil, and concentrations decreased with increasing depth, reflecting the physical properties of the soil and its alkaline pH. The mineralogical composition of the topsoil, identified by X-ray diffraction, was predominantly quartz, calcite, dolomite and minor minerals, such as gypsum and clay minerals. Metal concentrations were compared using one-way analysis of variance (ANOVA) to compute the statistical significance of the mean. The results of the ANOVA showed significant differences between sites for Pb, Cd and Cu, but no significant differences for the remaining metals tested. Factor analysis revealed that polluted soil occurs predominantly at sites around the steel plants and that there is no significant variation in the characteristics of the unpolluted soil, which are uniform in the study area.     

Seasonal Variations of Trace Metal Chemical Forms in Bed Sediments of a Karstic River in Lebanon: Implications for Self-purification

Although Lebanon has abundant water, its rivers are polluted and aquifer water mismanaged. Effective river water usage requires an understanding of the geochemistry of polluting metals in catchments. Climate is “Mediterranean”: wet winters and dry summers. Active sediment flushing is restricted to winter high discharge episodes. Except in winter, water column pollutants are removed by precipitation or sorption to the surface of static bed sediments. Hence (1) does winter flushing of contaminated sediment and replacement by clean sediment favour self purification? (2) does the distribution of metals between extractable fractions change seasonally and thereby affect metal bioavailability ? Results on the distribution of metals are reported for Fe, Pb, Zn, Cu and Cd in bed sediments from Nahr Ibrahim (a karstic river) for summer and winter. A Tessier-like sequential extraction scheme was applied to samples (< 75 μm) for five locations along a 13 km stretch to the sea. Water pH was above 8.2 at all locations implying a very low solubility for Fe. Sediment was derived from catchment soils and limestone. Total sediment Fe increased in winter at all sites following deposition of eroded soil from upstream. Cadmium, Cu and Pb derived from polluting sources; the sources of Zn were more complex. Dilution by clean sediment explained winter reductions in total Cd, Cu and Pb; Zn changes were less consistent. Iron occurred mostly (> 77 sum of fractions) in the residual fraction compared with 6– 31 for pollutants; residual Cu and Zn showed a small increase in winter whereas Cd and Pb did not change. All readily exchangeable metals decreased in winter and the carbonate bound forms predominated in both seasons. Nahr Ibrahim has a high capacity for self purification and metal resolubilisation from sediment will be limited by the solubility of carbonate forms.     

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.     

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.     

Effects of salinity on the transformation of heavy metals in tropical estuary wetland soil

Tropical estuary wetlands are important for aquaculture and wildlife. However, many of them receive large amounts of anthropogenic heavy metals annually. Here, the transformation of spiked heavy metals, namely, Cd, Cr, Cu, Ni, Pb, and Zn, and the effects of salinity on their transformation in wetland soils after an eight-month-long incubation under moisture-saturation conditions were studied in the Pearl River estuary in China. Cd exhibited high mobility and bioavailability, with 12.2% to 25% Cd existing in the exchangeable fraction. Other heavy metals primarily existed in the reducible and oxidisable forms, and less than 2% were bound to the exchangeable fraction. Compared with the controls, contents of none of the metals associated with residual forms were significantly altered. These results imply that most exchangeable metals, except for Cd, transformed into other stable fractions through an eight-month-long ageing process, but not into the residual fraction. Thus, transformation from non-residual to residual forms was very slow in the tropical estuary wetland environment. Addition of NaCl increased the exchangeable fractions of Cd, Pb, and Zn, suggesting that increased soil salinity induced by flood tides during the dry season may enhance their mobility.