Chemical fractionation of metals in core sediments of Orogodo River,southern Nigeria

Sequential chemical extraction of metals (Cu, Ni, Mn, Fe, Pb, Cr, and Zn) from core sediments of the Orogodo River was carried out with a view of providing information on the phase distribution of these metals with respect to depths and seasons. The results indicate that copper was speciated into organic matter/sulfide, Fe–Mn oxides, and residual forms at 0–5?cm depth while at deeper sections copper was predominantly in the residual form. Nickel was speciated mainly into Fe–Mn oxides and residual forms. The average of lead in various particulate phases of the sediment are 0–100% for residual; 0–8% for carbonate; 0–16.2% for exchangeable; 0–10% for organic matter/sulfide form and 22–56% for Fe–Mn oxides bound metals. Manganese was speciated into exchangeable (10–36%) and Fe–Mn oxides bound (10–48%) at the surface layers of 0–20?cm depths and predominantly in the residual form in deeper sections implying partitioning into trioctahydral clay and/or well-defined crystalline oxides. Iron was predominantly in the Fe–Mn oxides and residual fractions, less than 8% in the organic fraction, and 24.4–37.3% in the exchangeable and carbonates fractions at the surface. The percentage contributions of iron in the exchangeable and carbonate fractions decreased to 3.2% at 55–60?cm depth. The amount of chromium in the exchangeable fraction ranged from 0% to 7% for exchangeable; 0–26.5% for organic matter/sulfide bound; 3.8–17.9% for Fe–Mn oxides; and 46.8–100% for residual fraction. The mobility factors of the metals indicated that these metals were relatively mobile at top sections as compared with deeper sections. The overall picture of metal mobility and availability indicates potential contamination risk by Fe, Zn, Mn, and Pb in the Orogodo River sediment system.     

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.     

Fractionation of trace metals (Mn,Zn, Cu,Pb) in Red Sea sediments,Gulf of Aden,Yemen

A sequential extraction technique was applied to estimate the chemical association of Mn, Zn, Cu and Pb in five chemical phases (exchangeable, carbonate, Fe–Mn oxides, organic matter and residual) in sediments of the Gulf of Aden, Yemen. The results indicated that a higher level of Mn was associated with the residual fraction (natural sources) than the non-residual fraction (anthropogenic sources). Zn fractionations revealed that it was associated more with Fe–Mn oxides and organic fractions than exchangeable and carbonate fractions. Most of the Cu was present in the residual form (60–72%) except for in the main port area (zone III), where it was associated with the organic phase (77% of the total Cu content, the organic matter content was 5%). Similarly, most Pb was bound in the residual fraction (56–71%) except the main port area where ～ 62% of the total Pb was bound in non-residual fractions. It was also found that the Pb concentration in the exchangeable fraction was very high compared with other metals. The risk assessment code for the metals showed a low risk for Zn and Cu, but low to medium risk for Mn. Fractionation of Pb showed medium risk at most of the regions except at the eastern area, which revealed a high risk for the aquatic environment.     

Aluminum fractionation in acidic soils and river sediments in the Upper Mero basin (Galicia,NW Spain)

This study aims to determine aluminum fractions in the fine earth of acidic soils under different land uses (forest, pasture and cultivation) and in the river bed sediments of the headwater of the Mero River in order to identify and quantify Al-bearing phases to assess Al mobility and potential bioavailability (environmental availability) in the monitoring area. Sequential extraction is used to evaluate the Al partitioning into six fractions operationally defined: soluble/exchangeable/specifically adsorbed, bound to manganese oxides, associated with amorphous compounds, aluminum bound to oxidizable organic matter, associated with crystalline iron oxides, and residual fraction (aluminum within the crystal lattices of minerals). The mean concentration of total aluminum (24.01 g kg^?1) was similar for the three considered uses. The mean percentage of the aluminum fractions, both in soils and sediments, showed the following order: residual fraction ? amorphous compounds ≈ crystalline iron oxides > water-soluble/exchangeable/specifically adsorbed > bound to oxidizable organic matter ≈ Mn oxides. However, in the soils, the amorphous compounds and water-soluble/exchangeable/specifically adsorbed fraction showed considerable differences between some types of uses, the percentage of aluminum linked to amorphous compounds being higher in forest soils (16% of total Al) compared to other uses (mean about 8% of total Al). The highest values of water-soluble/exchangeable/specifically adsorbed Al were also found in forest soils (mean 8.6% of the total Al versus about 4% of pasture and cultivation), which is consistent with the lower pH and higher organic matter content in forest soils. Nevertheless, the potentially bioavailable fraction (sum of the first three fractions) is low, suggesting very low geoavailability of this element in both soils and sediments; hence, the possibility to affect the crops and water quality is minimal.     

土壤重金属化学形态的生物可利用性评价

重金属化学形态是近年来土壤化学、植物营养和环境科学研究领域的一个热点和难点,利用重金属的化学形态分布和含量变化来评价重金属的生物可利用性,有利于全面研究重金属的危害性和治理重金属污染土壤。结果表明,水溶态和交换态的重金属易被生物吸收利用,而残留态重金属一般不被生物利用,其它形态如碳酸盐结合态、铁锰氧化物结合态和有机物结合态的生物可利用性主要取决于外界环境的变化。     

Heavy Metals in the Bed and Suspended Sediments of Anyang River, Korea: Implications for Water Quality

The objective of this study is to compare Anyang River bed sediments with water chemical composition and to assess the anthropogenic chemical inputs into the river system. Eight sampling locations were chosen along the river channel. Bed and suspended river sediments and water samples were collected, and analyzed for their chemical and physical composition. Data revealed that trace element concentrations in the river water were generally below world average, except for As, Mn, Ni and Cr. Among the three phases: water, bed and suspended sediment, more than 99% of the trace elements was associated with the bed sediment. Concentrations of trace elements in the sediment were a function a particle size distribution and organic content. The calculated degrees of enrichment based on the least influenced sample (ASD 1) indicated the river sediments were enriched with respect to background. The enrichment factors for Pb, Zn and As were relatively lower than for Cr, Co, Ni and Zn. The difference in the enrichment seems to reflect the human activities influence in the basin, and specially for Cd. Speciation of the elements in the five different chemical forms in the sediment by sequential extraction indicated that the reducible fraction was predominant for Fe, Zinc and Cu showed an irregular variation among the different fractions; whereas, Cd and Pb were more regular. Zinc and Cu highly existed mostly in exchangeable forms. Acid soluble and reducible forms were also important for most metals. The speciation implies that the metals associated with the sediment are subject to release into water bodies as goechemical variables (pH and Eh) change. Currently, the introduced metals are deposited near the source area and are mostly associated with the sediment, implying that the river bed sediment acts mainly as a sink, rather than a pool. The accumulated and enriched toxic trace elements can pose a potential pollution of river water.     

Speciation of heavy metals in suspended particulates in urban air†

An anayltical procedure based on a sequential extraction scheme is applied to samples of suspended particulates from an urban area of Barcelona. This area presents high levels of air pollution owing to automotive emissions and industrial activity.

The procedure allows the partitioning of particulate trace metals into four fractions: soluble and exchangeable, bound to carbonates and iron‐manganese oxides, bound to organic matter and residual. In this work, the chemical associations of Fe, Pb, Cu, Mn, Cr and Cd have been investigated.

In the analysed samples, only the cadmium is predominantly in the first fraction whereas the other metals are largely associated to carbonates and Fe‐Mn oxides.     

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.     

模拟酸雨条件下降尘中Cu,Pb,Zn,Cr各形态的溶出和转化研究

本文用Ｔｅｓｓｌｅｒ方法，研究了模拟酸雨条件下，降尘中Ｃｕ，Ｐｂ，Ｚｎ，Ｃｒ各形态的溶出和相互转化。试验表明：（１）降尘中Ｃｕ，Ｃｒ的溶出量随酸雨酸度的增大而增加；Ｐｂ，Ｚｎ没分别在ＰＨ＝３．５和ＰＨ＝４．５时溶出量最大，溶出的金属多源于可交换态和碳酸盐结合态，说明这两种形态的稳定性较差。（２）在模拟酸雨条件下，Ｃｕ，Ｐｂ，Ｚｎ，Ｃｒ各形态的含量发生了较大变化；Ｃｕ从其优势形态有机结合态向可交换态     

湘南某矿区菜园土中典型重金属的形态分析

分别运用Tessier连续提取法和Leleyter连续提取法研究湘南某矿区菜园土中Pb,Zn,Cu和Cd的形态分布特征.结果表明：菜园土中Pb,Zn,Cu和Cd的总浓度严重超过国家土壤环境质量标准.Pb,Zn,Cu和Cd的主要形态是残渣态,水溶态和交换态所占比例较小.重金属生物可利用性的研究表明,Pb,Zn,Cu和Cd生物可利用的含量较少;在Tessier方法中,除Cu之外,生物不可利用态是主要形态,其次是潜在生物可利用态,而在Leleyter方法中,潜在生物可利用态是主要形态,其次是生物不可利用态.     

Speciation of Heavy Metals in Floodplain and Flood Sediments: a Reconnaissance Survey of the Aire Valley, West Yorkshire, Great Britain

A five-step sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Zn, Cu and Cd), with major sedimentary phases (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions), in samples from floodplain and recent flood sediments of the River Aire, West Yorkshire. Analysis indicates that metals Pb and Zn are primarily associated with the Fe and Mn oxides, Cu with the organic fraction and Cd with exchangeable and surface oxide and carbonate metal ions. Knowledge of the chemical speciation of heavy metals in river sediment, despite the procedure's inherent limitations, facilitates an understanding of their bioavailability, storage and remobilisation in floodplain and river channel environments.     

Heavy-metal fractionation and distribution in soil profiles short-term-irrigated with sewage wastewater

Six soil profiles irrigated and non-irrigated with sewage wastewater were investigated for soil pH, electrical conductivity (EC), organic matter (OM), and CaCO₃. The distributions and chemical fractions of Cu, Zn, Cd, and Pb, and their lability were also studied. The results indicated that pH, EC, OM, and CaCO₃, as well as metal fractionation in soil profiles were affected by wastewater irrigation, especially in the surface layer. The surface layer (0-15 cm) irrigated with wastewater exhibited a 0.6 unit decrease in soil pH, a 40.6% decrease in CaCO₃, and a 200% increase in EC as compared with that of the non-irrigated soil. The soil OM increased from 0.04% to 0.35% in the surface layer. The irrigation of soil with wastewater resulted in transformation of metals from the carbonate fraction (CARB) towards the exchangeable (EXCH), Fe-Mn oxide (ERO), and organic (OM) fraction for Zn, towards the EXCH, the OM, and residual fraction for Cu, and towards the exchangeable (EXCH) fraction for Cd. It was concluded that the use of sewage wastewater led to salt accumulation and an increase in the readily labile fraction of Zn, Cu, and Cd in the surface layer. Therefore, this reason may limit the use of wastewater under arid and semi-arid conditions.     

填埋场内重金属总量及其形态分布对迁移性的影响

以杭州市天子岭填埋场为例,对不同深度填埋层中的重金属总量、重金属迁移率和重金属形态分布进行了研究．结果表明,尽管填埋层中的重金属总量是土壤背景值的数十倍,超出土壤环境质量标准,但是重金属的迁移率却很低．另外,重金属迁移率与可交换态含量相关;Cd,Cu,Pb,Cr,Ni和Zn在填埋层中均以残渣态为主,填埋场中重金属都得到了有效固定,迁移性很差;各元素的易还原态与难还原态是重金属除残渣态之外主要的结合态(除Cr),铁锰氧化物循环是控制填埋场中重金属转化行为的主要机制之一;Cu的酸可溶态与易还原态具有较好的相关性,说明cu这两种形态的转化行为相似．     

Geochemical fractions and phytoavailability of Zinc in a contaminated calcareous soil affected by biotic and abiotic amendments

Many studies have conducted to determine the best management practice to reduce the mobility and phytoavailability of the trace metals in contaminated soils. In this study, geochemical speciation and phytoavailability of Zn for sunflower were studied after application of nanoparticles (SiO₂ and zeolite, with an application rate of 200 mg kg^?1) and bacteria [Bacillus safensis FO-036b(T) and Pseudomonas fluorescens p.f.169] to a calcareous heavily contaminated soil. Results showed that the biotic and abiotic treatments significantly reduced the Zn concentration in the aboveground to non-toxicity levels compared to the control treatment, and the nanoparticle treatments were more effective than the bacteria and control treatments. The concentration of CaCl₂-extractable Zn in the treated soils was significantly lower than those of the control treatment. The results of sequential extraction showed that the maximum portion of total Zn belonged to the fraction associated with iron and manganese oxides. On the contrary, the minimum percent belonged to the exchangeable and water-soluble Zn (F₁). From the environmental point of view, the fraction associated with iron and manganese oxides is less bioavailable than the F₁ and carbonated fractions. On the basis of plant growth promotion, simultaneous application of the biotic and abiotic treatments significantly increased the aboveground dry biomass yield and also significantly reduced the CaCl₂-extractable form, uptake by aboveground and translocation factor of Zn compared to the control treatment. Therefore, it might be suggested as an efficient strategy to promote the plant growth and reduce the mobile and available forms of toxic metals in calcareous heavily contaminated soils.     

会泽某铅锌矿周边农田土壤重金属生态风险评价

为了了解云南会泽某铅锌矿废周边农田土壤中重金属含量及潜在的生态危害程度,利用野外采样与实验室分析相结合的方法,以会泽某铅锌矿周边农田土壤（0-20 cm）为研究对象,分析其中7种的重金属（Cd、As、Pb、Cr、Cu、Zn和Hg）含量,并采用风险评价代码法和Hankanson潜在生态风险指数法评价对重金属污染程度与潜在生态风险进行评价。结果表明：7种重金属都存在超标或污染,其中Pb、As、Cd等的污染较为严重。统计学分析结果表明,Pb、As、Hg、Zn、Cd来源相同,铅锌矿冶炼污染物的排放可能是导致研究区域农田土壤重金属含量升高的主要原因。7种重金属化学形态也不尽相同：在重金属有效态中,Cd的水溶态和可提取态较高（平均值达到31.2%）;Pb、Cu和Zn可还原态、可氧化态这两部分含量较高,两部分之和的平均值分别可达到27.9%、30%和27.2%;Hg、As和Cr的残渣态含量较高,平均值分别为90.4%、72.9%和76.8%。风险评价代码评价结果表明,54.4%的样点Cd为高生态风险,45.6%的样点Cd为中度生态风险;100%的样点Zn为中度生态风险;Cu有41.2%的点位属于低生态风险,58.8%的点位属于中度生态风险;As和Pb主要以低生态风险为主（所占比例分别为92.6%和91.8%）;Hg主要以无生态风险为主（所占97.1%）。Hakanson潜在生态风险指数法结果表明,7种重金属潜在生态危害大小顺序为：Cd（331）〉Hg（127.5）〉Pb（43.6）〉As（14.9）〉Cu（9.3）〉Zn（2.3）〉Cr（2.1）。7种重金属的综合潜在生态风险指数（RI）的范围为58.2-1839.3。11%的采样点处于轻微生态风险程度,27.1%的采样点处于中等生态风险程度,46.3%的的采样点处于强生态风险程度,15.6%的采样点处于很强的生态风险程度。综上所述,该矿区周边农田土壤受到了严重的重金属污染,由此引起的重金属生态风险不容忽视?     

Metal associations in anoxic sediments and changes following upland disposal†

The ecological effects of heavy metals in contaminated sediments are more determined by the chemical form and reactivity than by the level of accumulation. Dredging of anoxic sediments and disposal on land is attended by changes of redox conditions. Under oxidizing conditions some controlling solid compounds may change gradually thus changing the solubility of certain metals.

Chemical extraction experiments for estimating characteristic association forms of heavy metals in anoxic sediments were carried out, both under presence and absence of air during the analytical procedure. Drying of the sediment decreases the proportion of the sulfidic metal fractions to a stronger degree, and oxidized Cd and Zn are found in the most available, exchangeable fraction.

With respect to long‐term effects acidification of poorly buffered sludges after disposal on land is probably the most important factor affecting metal associations and mobility. For many metal examples a linear relationship has been found between decreasing pH values and increasing dissolved metal concentrations. To quantify these relationships and for better comparison of samples a simple test procedure is proposed which is based on pH differences before and after addition of acid.     

广州城市水体沉积物中重金属形态分布研究

选取广州城市水体中的４ 个污染沉积物样品,采用连续提取法研究沉积物中重金属元素（ Ｐｂ 、 Ｚｎ 、 Ｃｕ 、 Ｎｉ 、 Ｃｒ 、 Ｍｎ） 的形态分布,结果表明：重金属元素主要以残渣态、有机结合态和氧化铁结合态存在,其中 Ｐｂ 、 Ｎｉ、 Ｍｎ 以残渣态和氧化铁结合为主, Ｚｎ 以残渣态和有机结合态为主, Ｃｕ 以有机态和氧化铁结合态为主, Ｃｒ 以氧化铁结合态为主。沉积物中固相组分对重金属的富集能力为：无定型氧化锰＞ ＞ 碳酸盐＞ 氧化铁＞ 有机质,而富集量则是后两者大于前两者。     

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。     

Heavy metal and nutrient contamination of marine sediments in Hong Kong

A monitoring programme was performed to use marine sediments as an indicator of marine contamination in Hong Kong. A total of 51 samples were collected from eight marine sites and analysed for pH, redox potential, salinity, total‐N, total‐P, total organic carbon, and total Cu, Zn Pb, Cr and Cd. Sites with high industrial or aquacultural activities contained high total organic carbon contents, total‐N and total‐P contents. Sediments from sites with high industrial activities also enriched with heavy metals. Metal speciation results indicate that Cu and Cr existed mainly in the organic fraction, Pb and Zn were distributed approximately equally in both the organic and residual fractions while Cd mainly occurred in the residual fraction. The Cu, Cr and Zn contents were highly correlated with total organic carbon contents. All samples were classified as non‐acid forming according to the net acid generation test and only samples from the industrial site released a high concentration of heavy metals under a complete oxidising condition. The present study reveals that organic and heavy metal pollution is serious in the marine sediments of Hong Kong, and industrial and aquacultural activities are probably the major sources of contamination.     

中国三个不同富营养化湖泊沉积物中Cu、Zn赋存特征及其与营养盐的相关性分析

对太湖、南四湖、白洋淀三个不同富营养化湖泊沉积物进行采样,采用Tessier连续提取法,测定了3个湖泊表层沉积物中Cu、Zn两种重金属的赋存形态,并初步探讨了重金属各形态与沉积物及上覆水中营养盐的相关关系。结果表明,沉积物中重金属总量以白洋淀最高,太湖最低,但重金属污染程度为太湖＆gt;南四湖＆gt;白洋淀,太湖Cu污染指数为1.34~1.6,白洋淀Cu污染指数仅为0.79~1.17。沉积物中重金属赋存形态Cu主要以残渣态和有机质结合态为主（二者之和占73%以上）, Zn则以残渣态和Fe-Mn氧化态占优（二者之和比例达83%以上）,含量最少的均为可交换态。不同湖泊沉积物重金属赋存形态差异较大,太湖残渣态重金属占总量的比例最小（Cu为43%~56%,Zn为49%~63%）,南四湖残渣态占的比例最大（Cu为59%~82%、Zn为64%~77%）;可交换态比重在太湖中最高（Cu占3.2%~5.6%,Zn为1.3%~1.5%）,在南四湖中最低（Cu为1.1%~2.9%,Zn未检出）。从“非稳定态”重金属（除残渣态外的四种形态之和）所占比例看,相较其它两个湖泊,太湖沉积物中重金属污染人为输入的活性态占较大比重,具有较高的二次释放风险。相关性分析得出,重金属Cu的可交换态与上覆水中总氮及总磷之间存在着极显著的正相关关系,碳酸盐结合态Cu与沉积物中营养盐呈现出显著的负相关性,说明水体的富营养化程度加剧可能会增强沉积物中Cu向水体释放的风险。