连续萃取法研究海湾养殖区沉积物中重金属形态

以连续萃取法研究海湾养殖区沉积物中重金属(Cd, Cu, Pb, Zn)的形态,将重金属分离为酸溶态、还原态、有机质结合态、硫化物结合态和残渣态.分别采用基体匹配法和内标法消除高盐基体对电感耦合等离子体光谱法(ICP-OES)和质谱法(ICP-MS)分析结果的影响.对海洋沉积物标准物质分析结果表明,样品稀释后测定值与标准值一致.比较了本连续萃取法和BCR法对沉积物样品中重金属形态的提取结果,并考察了萃取剂的选择性.实验表明,本方法可用于有机质污染和富营养化环境沉积物中重金属形态分析,特别是有机质结合态和硫化物结合态的分析.     

缺氧沉积物中重金属形态连续萃取方法的稳定性研究

考察了海水养殖区域缺氧沉积物中重金属形态连续萃取法萃取过程中溶液pH值、温度变化和胶体形成对形态分离结果的影响。结果表明,连续萃取法Step1萃取酸溶态时,萃取液pH值的轻微升高使Pb和Zn的萃取结果明显降低;Step2萃取还原态时,萃取液pH值明显升高对重金属的萃取结果影响很小;Step3萃取有机质结合态时,萃取液pH值的降低对重金属萃取结果影响较小(除Pb外)。由于连续萃取法中各步萃取反应的热力学过程不同,Step1和Step2萃取后溶液温度轻微升高而在Step3中溶液温度稍微降低,溶液温度变化(<2.5℃)对重金属形态的影响很小。在Step1、Step2和Step4萃取过程中胶体的形成和存在,对萃取液Cd、Zn和Cu有明显的吸附影响;而在Step3萃取中萃取剂的分散作用有效控制了溶液中胶体的形成。因此采用连续萃取方法评价沉积物中的重金属形态时,控制萃取液pH值和胶体形成有利于提高萃取结果的稳定性和准确性。     

可溶性有机质对污染土壤中铊迁移行为的影响

目的 为了查明可溶性有机质（DOM）对土壤中污染元素铊赋存形态的影响,方法 采用形态分级提取方法,将土壤中的铊重金属分成酸可交换态、铁锰氧化物结合态、有机质结合态和残留态4组分,并采用Elan 6100型ICP-MS质谱仪测定各组分中铊的质量浓度.结果 DOM可降低酸可交换态的Tl,增加铁锰氧化物结合态和有机质结合态Tl的百分含量,但对残留态Tl的百分含量没有明显影响.因此,DOM可降低铊在土壤中的活动性,从而改变了铊在土壤中的迁移行为.结论 可溶性有机质（DOM）自身的络合（螯合）能力及其吸附特性是改变重金属铊形态分布的主要因素.     

氧化与还原条件下伊通河长春区段沉积物重金属形态特征的对比研究

利用改进的Tessier连续萃取法研究了伊通河长春市自由大桥处不同深度沉积物样品在氧化及还原条件下Cu,Pb,Zn和Ni的形态变化规律,同时分析了沉积物样品中酸可挥发性硫(Acid volatile sulfide,AVS)和同时提取重金属(Simultaneous extract metals,SEM)的含量. 实验结果表明，样品经干燥、研磨处理后,Cu有机/硫化物结合态比例减少40%,锰氧化物结合态的比例显著增加; Pb,Zn和Ni 3种元素有机/硫化物结合态比例均略有下降,变化幅度小于Cu,并重新分配到不同的化学相中. 通过SEM中各金属含量与有机/硫化物结合态中金属含量的对比可知,还原性沉积物中Cu除了与硫化物结合外,很大一部分是以有机物形态存在的,Pb,Zn,Ni,Fe和Mn则主要以硫化物形态存在,各元素形态分析均不同程度地受到萃取剂的影响.     

聚环氧琥珀酸对污泥中锌的萃取

研究了环境友好高分子聚环氧琥珀酸(PESA)对污水厂污泥中重金属锌的萃取作用.结果表明,PESA对污泥中的重金属锌具有良好的萃取效果,利用改进的BCR法对萃取前后污泥中的锌进行了形态分析.结果表明.被PESA萃取的锌主要来自水溶态、酸溶态和可还原态等3种结合态.随着萃取体系pH值的升高.锌的萃取效率逐渐下降;在实验范围内,PESA与污泥中重金属总量的摩尔比为1:1～10:1时,随着PESA浓度的增加.锌的萃取效率逐渐提高,且对萃取体系pH值的依赖性减小.在pH=4时,在PESA与污泥中重金属总量的摩尔比为3:1～10:1范围内,锌的萃取效率均大于70%.     

采集的生物膜中痕量重金属的形态分布特征

采用改进的Tessier连续萃取方法对从松花江中采集的生物膜中锰、 铁、 铜、 铅、 锌及镉的化学形态进行分析, 考察了生物膜上铁、 锰氧化物和有机质吸附重金属的相对作用, 同时讨论了在研究培养的生物膜吸附痕量重金属时所建立的选择性萃取方法对于采集的生物膜组分分离的适用性. 研究结果表明, 在采集的生物膜上痕量重金属以铁、 锰的氧化物为主要结合形态存在, 以此种形态存在的铜、 锌、 铅和镉分别占其总含量的62.9%, 58.3%, 53.8%和32.6%, 而以有机结合态存在的铜、 锌、 铅和镉, 分别占其总含量的1.1%, 0.6%, 9.9%和1.8%, 表明采集的生物膜上铁、 锰氧化物在吸附重金属的过程中起主要的控制作用, 而有机质的作用相对较小, 与以往利用选择性萃取技术研究培养的生物膜吸附重金属的规律一致. 进一步分析表明, 如扣除生物膜上铁的残渣态部分, 则选择性萃取分离技术可以有效地将采集的生物膜上的铁、 锰氧化物及有机质分离开.     

改进BCR法在活性污泥样品重金属形态分析中的应用

利用改进的BCR三步顺序提取法研究了活性污泥中重金属的形态分布。所研究的可提取态包括可交换态,还原态-铁锰氧化物结合态和氧化态-有机物和硫化物结合态。这三态的含量之和加上残渣态的含量与各重金属的总量进行了比较。利用ICP-MS测定了活性污泥提取液以及残渣态中Cr,Mn,Co,Ni,Cu,Zn,As,Cd,Pb的含量。实验表明,采用改进的BCR法可以用来分析活性污泥样品中的金属形态。     

重金属形态连续萃取法对沉积物矿物相态的影响

采用X-射线衍射法(XRD)对海水养殖区沉积物中重金属形态的连续萃取法进行了考察,并与BCR法萃取能力进行了比较.根据XRD分析结果,连续萃取法和BCR法的非残留态萃取对其结合矿物有较强的提取能力,对残留态的结合矿物影响很小.相比BCR法,连续萃取法的可还原态萃取对其所结合的铁氧化物矿物溶解释放能力较强,对弱酸提取态的...     

CuO的添加方式对合成二甲醚反应中脱水性能的影响

CuO以不同的添加方式对-γA l2O3进行改性.用H2-TPR、还原态NH3-TPD、XRD表征技术以及浆态床CO H2合成二甲醚反应对催化剂的还原性能、还原态的酸中心分布、物相分布和反应活性进行了考察.H2-TPR结果表明,在沉积法制备的催化剂上可还原的氧化铜的量最大,且容易还原;还原态NH3-TPD结果说明了沉积法制备的催化剂上适合脱水反应进行的弱酸中心的比例最大;XRD结果发现在浸渍法制备的催化剂上,有少量的铜和铜铝化合物存在,其它方法制备的催化剂上CuO均匀分散在催化剂表面;目标反应的结果指出了沉积法制备的催化剂上,二甲醚的选择性最佳.     

高硫石油焦燃烧过程中不同赋存形态钒的变迁行为研究

采用逐级化学提取结合ICP-OES方法,研究了高硫石油焦燃烧过程中重金属元素钒的赋存形态和迁移转化行为,并结合热力学分析方法,探讨了其化学反应机理。石油焦中钒的赋存形态主要为有机质结合态和稳定态。随着燃烧温度的升高,有机质结合态的钒发生快速分解直至消失,且与Ca、Na、Fe和K等矿物质反应,转化为水溶态和部分离子可交换态、碳酸盐结合态、氧化物结合态钒。稳定态钒主要是与其他矿物质形成非晶态结构物质存在于石油焦中,在高温燃烧过程中,会部分熔融转化并释放出少量的钒。石油焦中钒的挥发性随着燃烧温度和燃尽率的升高逐渐增大,且呈现阶段性挥发的特点。温度高于1100℃,有机质结合态的钒快速分解,且部分转化为具有挥发性的VO2等化合物,致使钒的挥发率急剧增大。     

Assessment of heavy metals leachability from metallo-organic sorbent-iron humate-with the aid of sequential extraction test

The sequential extraction test, known as a BCR procedure, was used to assess a leachability of heavy metals (Zn, Cd, Pb, Cu) from the metallo-organic sorbent—iron humate—loaded with these metals. The sequential test allowed to discriminate between various fractions of heavy metals, namely the acid-extractable fraction, the fraction bound to Fe oxides, and the fraction bound to organic matter. It was proven that the heavy metals are bound mainly to Fe oxides and organic matter, and thus they may be relatively hardly liberated into the environment. The BCR sequential extraction test exhibited a very good repeatability, when it was applied to the loaded sorbent—relative standard deviations were typically lower than 10%.     

A new luminol chemiluminescence reaction using a tetravalent nickel-periodate complex as the oxidant

A modified sequential extraction procedure was developed and applied to characterize the species of metals in fly ash. Two fly ash samples were collected from a coal-fired thermal power plant located in the north of China. A sample was collected from the conventional pulverized coal (PC) combustor and another from the circulating fluidized bed (CFB) combustor. After extraction by the proposed sequential extraction procedure, the elements in the fly ash samples were divided into a water-extractable fraction (F1), an acid-soluble fraction (F2), a reducible fraction (F3), an oxidizable fraction (F4) and a residual fraction (F5). Except for Cu, V, Cd in the PC sample and V, Zn in the CFB sample, most of the other metals were present in the residual fraction (F5), which was very difficult to release into the environment. The fraction distribution patterns in the two samples were also compared. The results indicated that the distribution of metals in different fractions in fly ash samples were probably impacted by different combustion processes.     

Metal fractionation in olive oil and urban sewage sludges using the three-stage BCR sequential extraction method and microwave single extractions

The conventional three-stage BCR sequential extraction method was employed for the fractionation of heavy metals in sewage sludge samples from an urban wastewater treatment plant and from an olive oil factory. The results obtained for Cu, Cr, Ni, Pb and Zn in these samples were compared with those attained by a simplified extraction procedure based on microwave single extractions and using the same reagents as employed in each individual BCR fraction. The microwave operating conditions in the single extractions (heating time and power) were optimized for all the metals studied in order to achieve an extraction efficiency similar to that of the conventional BCR procedure. The measurement of metals in the extracts was carried out by flame atomic absorption spectrometry. The results obtained in the first and third fractions by the proposed procedure were, for all metals, in good agreement with those obtained using the BCR sequential method. Although in the reducible fraction the extraction efficiency of the accelerated procedure was inferior to that of the conventional method, the overall metals leached by both microwave single and sequential extractions were basically the same (recoveries between 90.09 and 103.7%), except for Zn in urban sewage sludges where an extraction efficiency of 87% was achieved. Chemometric analysis showed a good correlation between the results given by the two extraction methodologies compared. The application of the proposed approach to a certified reference material (CRM-601) also provided satisfactory results in the first and third fractions, as it was observed for the sludge samples analysed.     

Evaluation of a sequential extraction for the speciation of thorium in soils from Baotou area, Inner Mongolia

Sequential extraction procedures were widely applied for speciation of radioactive elements. In this study, the sequential extraction procedure developed by Martínez-Aguirre was employed for quantification of different chemical forms of thorium in the soil. The total amount of thorium in contaminated soil was much higher by four-fold than the local background value. The soil properties affect the amount of thorium and distribution of fractions in contaminated soil. Results showed that the proportion of thorium in soils from Baotou was found as the residual fraction (F5 + F6) > absorbed fraction (F3), coprecipitated fraction (F4) > carbonates fraction (F2) and exchangeable fraction (F1) that could be available to plants. The recovery, calculated by ratio of the sum of the six fractions to the pseudo-total content of thorium, was in the range from 96% to 110%. A comparison was carried out between the sequential extraction and the single extraction to evaluate the selectivity of the extractants. It was found that the amount of thorium of absorbed fraction (F3) was higher in the single extraction than that estimated in the sequential extraction, possibly duo to transform of the labile form. While for non-residual fraction analysis, the single extraction scheme was a desirable alternative to the sequential extraction procedure. According to correlativity analysis of various fractions, it might be predicted that how the non-residual fractions of thorium were directionally transformed into interrelated fractions under the changes of conditions.     

Kinetic speciation of BCR reference materials

The accurate study of heavy metal speciation is important in environmental monitoring. There has been much work developing various operationally defined speciation methods for soil and sediment, but there is a need to compare the different approaches by evaluating them for the same sample. In this article, a kinetic method was applied for the heavy metal speciation of the two BCR reference materials, CRM601 and BCR701, which have been specifically developed as materials to evaluate the validated BCR three-step sequential extraction method. When EDTA was used as an extractant, 81.0% of Cd, 68.0% of Cu, 21.5% of Ni, 80.3% of Pb and 71.9% of Zn was extracted from CRM601. For BCR701, the removal ratios were 92.0, 52.3, 18.7, 50.6 and 67.5% with EDTA and 95.7, 25.2, 20.0, 52.4 and 68.5% with hydroxylamine hydrochloride as an extractant, for Cd, Cu, Ni, Pb and Zn respectively. A two-component kinetic model was applied to the extraction curve and the extractable metals were readily classified into two categories, namely, labile fraction and non-labile fractions. The rate constants obtained from the regression model were found to be useful in quantifying the lability of an element. The rate constants obtained from the labile fractions in BCR701 were higher than that of obtained from CRM601, which indicated the high lability of metals in BCR701. When compared with the sequential extraction data, it seemed that the lability of an element was positively correlated to the first step extraction fraction.     

Chemical Speciation of Elements in Sediment Samples Collected at Lake Balaton

A modified sequential extraction procedure was applied to determination of the distribution of seven elements (Cd, Cu, As, Pb, Cr, Ni, Zn) in sediment samples collected at Lake Balaton. The fractions were (1) exchangeable and bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter and sulfide, and (4) acid soluble. These fractions have the advantage of providing better insight into the mechanism of association of metals with mineralogical phases of the sediments. Samples were taken in three seasons and the average concentration of the elements was calculated. Based on the results determined at 15 sampling points along the lake, it seems that Lake Balaton has not yet been polluted. Concentrations of species were below the Hungarian standard levels set for soils, and most of the elements were found in the acid-soluble fraction, indicating stable compounds in sediments. There were no significant changes in the individual seasonal concentrations of elements in this short monitoring period.     

桦甸油页岩中稀土元素赋存状态研究

以吉林省桦甸油页岩为研究对象,采用电感耦合等离子质谱( ICP-MS)和化学逐级提取方法相结合,对油页岩中稀土元素的分布特征以及油页岩中稀土元素的赋存状态进行研究.结果表明,相对于中国煤,桦甸油页岩表现为轻稀土元素富集程度高于重稀土元素.油页岩中稀土元素与陆源碎屑岩关系密切,且陆源物质的供应相对比较稳定.轻重稀土间分馏...     

Effect of air drying on speciation of heavy metals in flooded rice paddies

Flooded soil samples were collected in the typical area of the Yangtze Delta Region;fractions of heavy metals in flooded and air dried samples were measured with BCR sequential extraction method and atomic absorption spectrometry.In flooded soils, fractions of heavy metals increased in the order of acid soluble < oxidizable < reducible < residual.The acid soluble and reducible fractions significantly decreased but residual fraction significantly increased when the samples were air dried.The data obtained from air dried soil samples could not accurately represent the speciation of heavy metals in flooded field conditions.