湛江湾红树林湿地土壤重金属含量分析及污染评价

采用电感耦合等离子体发射光谱仪(ICP-AES)和电感耦合等离子体质谱仪(ICP-MS)对湛江湾红树林湿地土壤中8种重金属(As、Cu、Cd、Cr、Hg、Ni、Pb、Zn)含量进行测定,采用单因子污染指数法、内梅罗综合污染指数法和地累积指数法进行污染评价,并结合相关性分析和因子分析方法探讨重金属来源。结果表明:除Ni外,其余7种重金属元素含量平均值均未超过国家土壤环境质量标准(GB15618-2018);但Ni、Zn、Cu、Hg、As和Cd元素均超过广东砖红壤环境背景值,其中As、Ni、Hg和Zn元素超标情况严重。8种重金属元素内梅罗综合污染指数评价结果为0.373~22.576,平均值为3.378,整体处于重度污染;单因子污染指数依次为Ni>Hg>Zn>Cd>As>Cu>Pb>Cr。单个重金属元素地累积指数评价结果与内梅罗综合污染评价相一致,均显示红树林土壤中Hg、Zn和Ni元素污染严重,是影响研究区土壤环境质量的重要因素。从站位看,位于湾内北部的北涯村、观海长廊以及西部的世乔村站位污染较严重,高污染站位约占总站位数的33%,主要为Cd、Hg和Zn。统计分析结果显示,除Ni外,湛江湾红树林土壤中7种重金属元素之间显著相关;结合实地调查结果推测重金属污染主要来自工业污染、船舶排污、养殖排污、生活排污及农业面源污染等人为活动的输入,其次为自然因子的输入。     

湛江湾红树林湿地土壤重金属含量分析及污染评价

采用电感耦合等离子体发射光谱仪(ICP-AES)和电感耦合等离子体质谱仪(ICP-MS)对湛江湾红树林湿地土壤中8种重金属(As、Cu、Cd、Cr、Hg、Ni、Pb、Zn)含量进行测定,采用单因子污染指数法、内梅罗综合污染指数法和地累积指数法进行污染评价,并结合相关性分析和因子分析方法探讨重金属来源。结果表明:除Ni外,其余7种重金属元素含量平均值均未超过国家土壤环境质量标准(GB15618-2018);但Ni、Zn、Cu、Hg、As和Cd元素均超过广东砖红壤环境背景值,其中As、Ni、Hg和Zn元素超标情况严重。8种重金属元素内梅罗综合污染指数评价结果为0.373～22.576,平均值为3.378,整体处于重度污染;单因子污染指数依次为NiHgZnCdAsCuPbCr。单个重金属元素地累积指数评价结果与内梅罗综合污染评价相一致,均显示红树林土壤中Hg、Zn和Ni元素污染严重,是影响研究区土壤环境质量的重要因素。从站位看,位于湾内北部的北涯村、观海长廊以及西部的世乔村站位污染较严重,高污染站位约占总站位数的33%,主要为Cd、Hg和Zn。统计分析结果显示,除Ni外,湛江湾红树林土壤中7种重金属元素之间显著相关;结合实地调查结果推测重金属污染主要来自工业污染、船舶排污、养殖排污、生活排污及农业面源污染等人为活动的输入,其次为自然因子的输入。     

吉林某弹药销毁场土壤炸药污染调查及其赋存状态研究

研究吉林某军事弹药销毁场土壤炸药污染程度以及炸药在土壤中的赋存状态,为炸药和重金属污染土壤修复提供针对性策略。采集了某弹药销毁厂焚烧销毁区表层土壤样品,分析了其理化性质和常见重金属元素含量,测试了土壤全样和不同颗粒度土壤样品中炸药污染物的含量,并结合热重-傅里叶变换红外光谱(TGA-FTIR) 对炸药污染土壤样品热力学行为的表征,探讨了炸药污染物的赋存状态,炸药和重金属组合污染特征等。土壤中含有高浓度的TNT、DNT、ADNT、RDX等炸药污染物及其降解产物,并表现出土壤细颗粒富集趋势,其中土壤全样中TNT总浓度达到了1.66×104 mg·kg-1,远远高于EPA推荐的土壤TNT指导限值,RDX超过了以土壤环境为目标的指导限值;销毁活动还造成了土壤中Pb、Cu、Zn重金属浓度的升高,分别为400 mg·kg-1,318 mg·kg-1,1030 mg·kg-1。土壤中受到重金属和有机质等因素的影响,土壤中经过长期老化的炸药污染物的热解行为明显不同于自由态的炸药分子,热解温度升高、过程延长。在销毁区炸药污染土壤的修复中,应加强炸药污染物与重金属相互作用的研究,并在修复治理实践中采取协同修复的策略。     

褐煤SHELL气化飞灰黏附影响因素的研究

通过激光粒度仪、X射线荧光光谱仪、扫描电子显微镜等现代化分析测试技术对褐煤样、飞灰样以及换热废锅中的积灰样进行了粒度分布、化学组成、晶体矿物组成、微观形貌、微区化学组成等特征的分析,研究影响飞灰黏附特性的因素。并通过引入富集系数,描述各个元素在煤灰、正常飞灰、废锅积灰中的迁移富集情况。结果表明,在废锅积灰中有含铁矿物的生成,同时Na、K、Fe、S、P元素在废锅积灰中发生富集,在飞灰与积灰颗粒边缘处有大量的Fe、Na元素的富集。     

耐高盐碱蓬对湿地土壤中金属元素的富集特征研究

基于秦皇岛滨海湿地人工种植耐高盐碱蓬修复工程试验,通过分析湿地土壤沉积物及耐高盐碱蓬中不同金属元素的含量与变化,研究了耐高盐碱蓬对金属元素的富集特征。结果显示:湿地沉积物中Fe、Mn、Cr、Pb和Zn的浓度较高,分别为8 210. 94、110. 04、8. 78、8. 25、10. 95 mg/kg,Cd的浓度最低,平均值为0. 022 mg/kg,湿地试验区土壤中同一金属元素变异程度较小,分布较均匀。碱蓬体内重金属含量根据采集地点的不同有差异,但与各站位中土壤的重金属分布特征存在正相关性;其中碱蓬内Fe、Mn、Zn、Cu的平均含量相对较高,且Fe、Mn、Ni、Cu、As、Cd、Pb元素在碱蓬根中的平均含量高于茎叶,而Cr在茎中的平均含量最高,Zn和Mo在叶中的含量最高。碱蓬的根、茎、叶对Cd的富集效果最好,其次为Mo、Cu,对Fe、Mn、Zn、As和Pb的富集效果相对较差,说明碱蓬对沉积物中不同金属元素的富集移出率存在差异。金属元素在碱蓬中的转移系数研究表明,Mo、Zn、Cd和Mn等元素可由根部转移到叶中,而Fe、Ni、Pb、As和Cu等金属元素固定在根部,该研究可为利用碱蓬修复湿地重金属污染提供理论基础。     

铁(Ⅲ)—邻菲罗啉溶液体系的光化学还原——Ⅰ.溶液体系发生光化还原反应的条件、影响因素及完成程度

在有过量邻菲罗啉(phen)存在的铁(Ⅲ)—phen溶液体系中,当溶液pH>1.0～1.5时(与Fe(Ⅲ)浓度有关),能够发生光化还原反应,形成配离子[Fe(phen)3]~+。导致光化还原反应的光的有效波长与溶液体系组成有关:当溶液中不含其他有机配体时,有效波长为<300nm;含有柠檬酸等有机配体时,为420～450nm;而含有乙酸时,在上述两波长范围内均可缓慢地发生光化还原反应。反应速率随照射光强度的增大而增大。太阳光、荧光高压汞灯、高压铟灯等是光化反应的有效光源。OH~-、X~-、PO_4~(3-)等能与Fe(Ⅲ)配位的无机离子初始阶段严重抑制光化反应。除大量Co~(2+)、Cr~(3+)外,一般金属离子对光化反应无干扰。Fe(Ⅲ)浓度(<10μg-Fe/ml)较低时,量子产率近似与Fe(Ⅲ)浓度成正比;Fe(Ⅲ)浓度(>50μg-Fe/ml)较高时,还原反应难以完全。     

垃圾焚烧飞灰颗粒的微观形态特征及能谱研究

利用SEM/EDX，观察了垃圾焚烧飞灰颗粒的微观形态特征，探讨了其主要组成元素及其质量分数。实验结果表明，飞灰颗粒形态多样化，其中以不规则形状聚合体居多，球形体、絮状集合体相对较少，少数颗粒为棒状集合体。球形飞灰颗粒很少有重金属分布，不规则形状聚合体或絮状集合体的表面易分布重金属。从飞灰颗粒表面、内部组成元素的质量分数来看，Si、Ca、Al为主要元素。飞灰颗粒表面、内部有重金属Pb、Cu等分布，局部测定点其质量分数可高达16.2%和14.5%。     

土壤环境生态对重金属元素迁移影响分析

作物中重金属元素主要来自土壤，其含量与作物种类和土壤环境有关。土壤中重金属元素含量、土壤pH值、Eh值、土壤化学组成、土壤质地等环境因素都影响作物中重金属元素含量。土壤pH值和Eh值影响重金属元素的活动性。重金属元素的水溶态容易被作物吸收，而难溶态和被土壤胶体固定的重金属元素，不能被作物吸收。同种作物重金属元素含量的差异主要取决于土壤环境。     

N-(2-氨乙基)-月桂酰胺浮选铝硅酸盐矿物的研究

研究了N (2 氨乙基) 月桂酰胺对高岭石、伊利石和叶腊石等铝硅酸盐矿物的浮选行为.发现该表面活性剂对叶腊石的浮选回收率最高可达97.7％，对伊利石和高岭石的回收率相对较低，一般不超过82％.矿浆pH对高岭石、伊利石和叶腊石的回收率影响较小.酸性矿浆中表面活性剂通过静电引力吸附在矿粒表面；碱性矿浆中，表面活性剂通过氢键吸附在矿粒表面.红外吸收光谱证明，三种矿物表面中均存在－OH；在一个较宽的pH范围内，三种矿物矿浆的Zeta电位均为负值，表明矿粒表面荷负电.矿粒的扫描电镜（SEM）照片（×15000）表明，叶腊石主要呈薄片状颗粒，高岭石和伊利石颗粒呈不规则形状.     

从工艺矿物学角度分析稀土尾矿作为NH3-SCR催化剂的可行性

选择性催化还原法(SCR)是工业上广泛应用的控制NO_x排放比较成熟的技术,矿物催化剂逐渐成为脱硝领域的研究热点,稀土金属元素和过渡金属元素具有联合协同作用,白云鄂博稀土尾矿堆积量巨大且共伴生元素丰富,二次资源的利用“迫在眉睫”。本文从稀土尾矿的工艺矿物学角度深入分析其作为脱硝催化剂的可行性,稀土尾矿含有赤铁矿/磁铁矿、黄铁矿、氟碳铈矿、钛矿物和锰矿物等矿物,其中Fe,Ce,Mn均可作为催化剂的活性元素。矿物间的连生有利于活元素的联合作用,磁铁矿和氟碳铈矿与碳酸盐矿物、硅酸盐矿物、萤石及其他矿物连生有利于活性元素分散。含有Fe和Ce元素的矿物小颗粒(18.75～89.19μm)占比较高。酸活化后稀土尾矿脱硝活性最高为83%,N₂选择性在88%以上。稀土尾矿经过机械力或酸等活方式活化后,有希望成为脱硝催化剂。     

Sequestered carbon on clay mineral probed by electron paramagnetic resonance and X-ray photoelectron spectroscopy

This paper describes the interaction among soil organic matter components with kaolinite, an important clay mineral present in tropical soils, especially in Brazil. XPS data show that the soil organic matter adsorbed on kaolinite has aromatic and aliphatic structures, with phenolic and/or alcoholic functions and carbonyl carbons (CO) of amide and/or carboxylic groups. The N1s spectrum of the kaolinite shows an asymmetric peak that is assigned to amide and protonated ammines probably from humin. The interaction between them is strong enough to resist chemical oxidative or reductive attack besides loose amide functionalities. EPR data show that reductive treatment reduces some Fe3+ of the kaolinite structure, loosing organic components. A schematic representation of the reduction of structural Fe3+ in the concentrated domains and consequently increased concentration of Fe3+ ions in diluted domains of the spectrum is presented. This reinforces the hypothesis that humin is a stable carbon sink in soils when adsorbed to clays.     

Monitoring of heavy metals in topsoils, atmospheric particles and plant leaves to identify possible contamination sources

The research reveals results of metal pollution on urban topsoil in relation to the metal content in leaves of two plant species and atmospheric particles. The content of pollutants (Ba, Cd, Cu, Fe, Mn, Ni, Pb, V and Ti) was determined by ICP-OES. Twenty-two samples of soil were collected over a six-month period from two different urban sites and one from a rural zone. Regarding the pollution level, the studied soils were found to be low. Results for enrichment (EF) and concentration (CF) factors showed that soils were enriched in Pb, Ba, Cu and Ni. However, both species of plants showed a common behavior for all elements acting as excluders. ANOVA and different multivariate statistical analyses confirmed that the main pollution source of soil was traffic and fertilizers. Cd, Fe, Mn, Ti and V elements were attributed to natural sources. Also, it was suggested that N. oleander leaf is useful as a bio-monitors of soil pollution by Cu. Similarly, a direct relationship was found between the content of Cu in soils with the Cu level in PM₁₀ atmospheric particles. The origin was attributed to dry and wet atmospheric deposition processes.     

Elemental analysis of size-fractionated particulate matter sampled in Göteborg,Sweden

The aim of the study was to investigate the mass distribution of trace elements in aerosol samples collected in the urban area of Göteborg, Sweden, with special focus on the impact of different air masses and anthropogenic activities. Three measurement campaigns were conducted during December 2006 and January 2007. A PIXE cascade impactor was used to collect particulate matter in 9 size fractions ranging from 16 to 0.06 µm aerodynamic diameter. Polished quartz carriers were chosen as collection substrates for the subsequent direct analysis by TXRF. To investigate the sources of the analyzed air masses, backward trajectories were calculated. Our results showed that diurnal sampling was sufficient to investigate the mass distribution for Br, Ca, Cl, Cu, Fe, K, Sr and Zn, whereas a 5-day sampling period resulted in additional information on mass distribution for Cr and S. Unimodal mass distributions were found in the study area for the elements Ca, Cl, Fe and Zn, whereas the distributions for Br, Cu, Cr, K, Ni and S were bimodal, indicating high temperature processes as source of the submicron particle components. The measurement period including the New Year firework activities showed both an extensive increase in concentrations as well as a shift to the submicron range for K and Sr, elements that are typically found in fireworks. Further research is required to validate the quantification of trace elements directly collected on sample carriers.     

Interaction between electrical double layers of soil colloids and Fe/Al oxides in suspensions

Phyllosilicates with net negative surface charge and Fe/Al oxides with net positive surface charge coexist in variable-charge soils, and the interaction between these oppositely charged particles affects the stability of mixed colloids, aggregation, and even the surface chemical properties of variable-charge soils. The interaction of the diffuse layers of electrical double layers between the negatively charged soil colloidal particles and the positively charged particles of goethite or gamma-Al(2)O(3) was investigated in this article through the comparison of zeta potentials between single-soil colloidal systems and binary systems containing soil colloids and Fe/Al oxides. The results showed that the presence of goethite and gamma-Al(2)O(3) increased the zeta potential of the binary system containing soil colloids and Fe/Al oxides, which clearly suggests the overlapping of the diffuse layers in soil colloids and Fe/Al oxides. The overlapping of the diffuse layers leads to a decrease in the effective negative charge density on soil colloid and thus causes a shift of pH-zeta potential curves toward the more positive-value side. The interaction of the electrical double layers is also related to the charge characteristics on the Fe/Al oxides: the higher the positive charge density on Fe/Al oxides, the stronger the interaction of the electrical double layers between the soil colloid particles and the Fe/Al oxides.     

Determination of δ18O in soils: measuring conditions and a potential application

The stable oxygen isotope signature (δ¹⁸O) of soil is expected to be the result of a mixture of components within the soil with varying δ¹⁸O signatures. Thus, the δ¹⁸O of soils should provide information about the soil's substrate, especially about the relative contribution of organic matter versus minerals. As there is no standard method available for measuring soil δ¹⁸O, the method for the measurement of single components using a high‐temperature conversion elemental analyser (TC/EA) was adapted. We measured δ¹⁸O in standard materials (IAEA 601, IAEA 602, Merck cellulose) and soils (organic and mineral soils) in order to determine a suitable pyrolysis temperature for soil analysis. We consider a pyrolysis temperature suitable when the yield of signal intensity (intensity of mass 28 per 100 µg) is at a maximum and the acquired raw δ¹⁸O signature is constant for the standard materials used and when the quartz signal from the soil is still negligible. After testing several substances within the temperature range of 1075 to 1375°C we decided to use a pyrolysis temperature of 1325°C for further measurements. For the Urseren Valley we have found a sequence of increasing δ¹⁸O signatures from phyllosilicates to upland soils, wetland soils and vegetation. Our measurements show that the δ¹⁸O values of upland soil samples differ significantly from wetland soil samples. The latter can be related to the changing mixing ratio of the mineral and organic constituents of the soil. For wetlands affected by soil erosion, we have found intermediate δ¹⁸O signatures which lie between typical signatures for upland and wetland sites and give evidence for the input of upland soil material through erosion. Copyright © 2008 John Wiley & Sons, Ltd.     

Retention of tannic acid and condensed tannin by Fe-oxide-coated quartz sand

This paper intends to shed light on the interactions between tannin and mineral soil particles. For that purpose, aqueous solution of condensed tannin (CT) (derived from Black pine (Pinus nigra var. maritima)) and commercially available tannic acid (TA) were added to purified quartz (Qtz) sand and quartz sand coated with either goethite (Gt) or ferrihydrite (Fh). After solvent removal by evaporation the samples were extracted by water. The extracts were analysed for organic carbon, total phenolics and CT. The extractability of the two tannins was small and increased in the order Qtz-Fh < Qtz-Gt < Qtz. For all mineral samples, TA was more extractable than CT. Bonding of tannins to the mineral samples and the partial peptisation of the Fe oxide coatings upon the binding resulted in complex tannin release curves. Our results suggest that the inextractability of tannins from natural soils and the absence of tannins in soil leachates might be caused by strong adsorption on soil minerals such as Qtz and Fe (oxy)(hydr)oxides. The results of competition experiments with mixtures of both tannins demonstrate that the CTs, and TA in particular, can release large amounts of Fe (oxides), suggesting that the tannins are excellent metal-mobilising agents. We therefore suggest that the fate of tannins in the mineral soil environment is highly dependent on the abundance of weakly bonded secondary oxides.     

Fractionation of lead in soils affected by smelter activities using a continuous-flow sequential extraction system

A continuous-flow sequential extraction system was used to study the distribution of Pb, and its association with other elements (Fe, Al and Ca), in soils around a Pb smelter. Soil samples were analysed by a four-step continuous-flow sequential extraction procedure employing a modified Tessier/BCR scheme. Recoveries of Pb using the flow system (88–111%) were higher than those obtained using a conventional batch extraction system. There were also some differences in Pb distribution between fractions as determined using the two extraction systems. The most abundant fraction of Pb was extracted during the dissolution of soil oxides (Fe/Al). Extractograms (plots of concentration of elements vs. extractant volume/time) indicated that anthropogenic Pb was predominantly adsorbed onto Fe oxide surfaces in contaminated soils. In soil profiles, the highest amounts of Pb were found in the topsoil surface layers (0–5?cm) of the contaminated soils with only limited movement into subsurface layers.     

A spectroscopic study of mechanochemically activated kaolinite with the aid of chemometrics

The study of kaolinite surfaces is of industrial importance. In this work we report the application of chemometrics to the study of modified kaolinite surfaces. DRIFT spectra of mechanochemically activated kaolinites (Kiralyhegy, Zettlitz, Szeg, and Birdwood) were analyzed using principal component analysis (PCA) and multicriteria decision making (MCDM) methods, PROMETHEE and GAIA. The clear discrimination of the Kiralyhegy spectral objects on the two PC scores plots (400-800 and 800-2030 cm(-1)) indicated the dominance of quartz. Importantly, no ordering of any spectral objects appeared to be related to grinding time in the PC plots of these spectral regions. Thus, neither the kaolinite nor the quartz, are systematically responsive to grinding time according to the spectral criteria investigated. The third spectral region (2600-3800 cm(-1)OH vibrations), showed apparent systematic ordering of the Kiralyhegy and, to a lesser extent, Zettlitz spectral objects with grinding time. This was attributed to the effect of the natural quartz on the delamination of kaolinite and the accompanying phenomena (i.e., formation of kaolinite spheres and water). With the MCDM methods, it was shown that useful information on the basis of chemical composition, physical properties and grinding time can be obtained. For example, the effects of the minor chemical components (e.g., MgO, K(2)O, etc.) indicated that the Birdwood kaolinite is arguably the most pure one analyzed. In another MCDM experiment, some support was obtained for the apparent trend with grinding time noted in the PC plot of the OH spectral region.     

Retention of Metamitron by Model and Natural Particulate Matter

Abstract

Adsorption isotherms of metamitron on model soil colloidal components: kaolinite, illite, montmorillonite, iron oxide and humic acid, and their binary associations were obtained using a batch equilibration procedure. Sorption parameters, K_f and n_f, were calculated by fitting the sorption data to the Freundlich equation and results obtained for binary associations were compared with those obtained for the individual model components. The sorption efficiency of the humic acids and their binary associations was measured as Koc. The adsorption behaviour of the < 2 μm fraction of two soils from Southern Spain was also studied as natural particulate matter. Montmorillonite and humic acids were found to be the most important components responsible for metamitron retention by the model adsorbents studied. On the contrary, metamitron showed little interaction with kaolinite, illite or iron oxide. These individual adsorption behaviours were reproduced in the montmorillonite-iron oxide-humic acid binary systems, but with differences suggesting changes on the surface properties upon association. Differences in Koc values of isolated humic acids and their associations indicate that the interaction transforms the humic acid surfaces and suggest different types of bonding between colloids and metamitron. The results obtained with model adsorbents and their associations were in agreement with the highest adsorption of metamitron found for the natural clay fraction of two soils which displayed the largest adsorption in that with the highest content in montmorillonite and organic carbon. The importance of organic matter and montmorillonite in metamitron adsorption by colloidal components was also shown by the decrease in K_f and the increase in Koc observed after removal of organic matter from the soil clay fraction with the highest organic carbon content.