Interactions of hydrophobic fractions of dissolved organic matter with Fe(3+) - and Cu(2+)-montmorillonite

Interactions of dissolved organic matter (DOM) with clays can significantly affect a variety of soil processes. We studied adsorption and fractionation of hydrophobic acid (HoA) and hydrophobic neutral (HoN) fractions of DOM on Cu(2+)- and Fe(3+)-montmorillonite. Adsorption of both samples was higher on Fe(3+)-montmorillonite than on Cu(2+)-montmorillonite. A pH increase of about one unit was recorded followed by HoA adsorption by Fe(3+)-montmorillonite. This suggested exchange of negatively charged DOM groups on surface hydroxyl groups of Fe(3+)-montmorillonite surfaces. Adsorption of HoA on Cu(2+)-montmorillonite and HoN on Fe(3+)- and Cu(2+)-montmorillonites was governed mainly by van der Waals interactions. Spectroscopic analyses showed a distinct HoA fractionation by molecular size and aromaticity only by Fe(3+)-montmorillonite. On the basis of the pH measurements (increase in pH following adsorption of acid components) and enhanced DOM fractionation by molecular size and aromaticity we suggest that DOM reacted with Fe(3+)-montmorillonite similar to goethite.     

Molecular fractionation of dissolved organic matter with metal salts

Coagulation of dissolved organic matter (DOM) by hydrolyzing metals is an important environmental process with particular relevance, e.g., for the cycling of organic matter in metal-rich aquatic systems or the flocculation of organic matter in wastewater treatment plants. Often, a nonremovable fraction of DOM remains in solution even at low DOM/metal ratios. Because coagulation by metals results from interactions with functional groups, we hypothesize that noncoagulating fractions have a distinct molecular composition. To test the hypothesis, we analyzed peat-derived dissolved organic matter remaining in solution after mixing with salts of Ca, Al, and Fe using 15 T Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS). Addition of metals resulted in a net removal of DOM. Also a reduction of molecular diversity was observed, as the number of peaks from the ESI-FT-ICR-MS spectra decreased. At DOM/metal ratios of ～9 Ca did not show any preference for distinct molecular fractions, while Fe and Al removed preferentially the most oxidized compounds (O/C ratio >0.4) of the peat leachate. Lowering DOM/metal ratios to ～1 resulted in further removal of less oxidized as well as more aromatic compounds ("black carbon"). Molecular composition in the residual solution after coagulation was more saturated, less polar, and less oxidized compared to the original peat leachate and exhibited a surprising similarity with DOM of marine origin. By identifying more than 9200 molecular formulas we can show that structural properties (saturation and aromaticity) and oxygen content of individual DOM molecules play an important role in coagulation with metals. We conclude that polyvalent cations not only alter the net mobility but also the very molecular composition of DOM in aquatic environments.     

Facilitating effects of metal cations on phenanthrone sorption in soils

Effects of metal cations (Na+, Ca2+, and Al3+) on phenanthrene sorption were investigated using two soils with contrasting organic carbon (OC) contents. The presence of the polyvalent cations (i.e., Ca2+ or Al3+) at a concentration of 0.01 mol/L significantly increased the capacity and nonlinearity of phenanthrene sorption to soils compared with the monovalent Na+. The effects were governed by the content of soil OC. Rubbery OC (i.e., soft, amorphous OC including dissolved organic carbon (DOC)) tended to become condensed on soil surfaces as evidenced by a decrease in the signals of the 1H NMR spectra of DOC and an increase in the glass transition temperature (Tg) of the soils when the polyvalent cations were present. Increasing Ca2+ concentration led initially to an effect similar to that of the polyvalent cations in the low cation concentration range, and the effect was gradually attenuated as Ca2+ concentration further increased. These findings lead us to propose that the modifications in the physical configuration and chemical characteristics of OC resulting from the presence of metal cations account for the increase in the capacity and nonlinearity of phenanthrene sorption to the soils. This study points to an important role of metal cations in the sorption and fate of phenanthrene in the soil environment.     

Modeling the transport of metals with rate-limited EDTA-promoted extraction and dissolution during EDTA-flushing of copper-contaminated soils

EDTA-flushing of artificially contaminated soils enhanced Cu extraction but also induced mineral dissolution simultaneously. The mobilization and transport of these metal-EDTA complexes was investigated with column experiments. A quantitative transport model was proposed for simulating the experimental breakthrough curves of Cu, Fe, Al, and Ca. The rate-limited EDTA-promoted extraction and dissolution could be described by respective second-order kinetic terms, which were necessary for explaining the time-dependent depletion of extractable metals (sorbed and indigenous) in soils with continuous EDTA-flushing. Simultaneous simulation of extraction of sorbed Cu and dissolution of soil Fe, Al, and Ca is more conceptually accurate than individual modeling of each metal because the latter approach tends to overestimate the concentration of free EDTA during transport and thus underestimate the rate coefficients of EDTA-promoted dissolution. The fitted rate coefficients of Cu were about an order of magnitude larger than those of Fe and Al; these values probably reflect Cu extraction from weakly sorbed fractions and Fe and Al dissolution from amorphous oxides. The apparent retardation of Fe, Al, and Ca transport had to be taken into account by empirical determination, which was attributed to the metal lability in soils and thermodynamics of surface complexation.     

不同金属离子对多酚氧化酶的影响

采用匀浆法从茄子中提取多酚氧化酶(PPO),以绿茶粉为底物,研究Cu2+、Mn2+、Mg2+、Ca2+、Na+、Al3+和Fe3+7种金属离子对PPO活性的影响。结果表明:Cu2+、Mn2+和Mg2+3种金属离子对PPO的活性有不同程度的促进作用,而Ca2+、Na+、Al3+和Fe3+对PPO的活性有抑制作用。其中,Cu2+浓度为3mmol/L时对PPO有激活作用,此时茶黄素总量达到7.45mg;Fe3+浓度为5mmol/L对PPO有显著抑制作用,此时茶黄素总量降低至0.26mg。     

Metal complexation properties of freshwater dissolved organic matter are explained by its aromaticity and by anthropogenic ligands

Dissolved organic matter (DOM) in surface waters affects the fate and environmental effects of trace metals. We measured variability in the Cd, Cu, Ni, and Zn affinity of 23 DOM samples isolated by reverse osmosis from freshwaters in natural, agricultural, and urban areas. Affinities at uniform pH and ionic composition were assayed at low, environmentally relevant free Cd, Cu, Ni, and Zn activities. The C-normalized metal binding of DOM varied 4-fold (Cu) or about 10-fold (Cd, Ni, Zn) among samples. The dissolved organic carbon concentration ranged only 9-fold in the waters, illustrating that DOM quality is an equally important parameter for metal complexation as DOM quantity. The UV-absorbance of DOM explained metal affinity only for waters receiving few urban inputs, indicating that in those waters, aromatic humic substances are the dominant metal chelators. Larger metal affinities were found for DOM from waters with urban inputs. Aminopolycarboxylate ligands (mainly EDTA) were detected at concentrations up to 0.14 μM and partly explained the larger metal affinity. Nickel concentrations in these surface waters are strongly related to EDTA concentrations (R2=0.96) and this is underpinned by speciation calculations. It is concluded that metal complexation in waters with anthropogenic discharges is larger than that estimated with models that only take into account binding on humic substances.     

烤后烟叶类胡萝卜素的稳定性及其影响因素

为了探明烤后烟叶褪色的成因,进行了光照、温度、相对湿度、酸、碱、金属离子和还原剂等影响烤后烟叶中类胡萝卜素稳定性的因素试验。结果表明:烤后烟叶在贮藏过程中光照强度越强,类胡萝卜素越易降解,而室内避光条件下烤后烟叶类胡萝卜素的稳定性较强;低温贮藏有利于减缓类胡萝卜素的降解,而高温贮藏条件下易加快其分解;干燥的环境有利于维持类胡萝卜素的稳定性,而潮湿环境促进了类胡萝卜素的降解;在Cu2+,Fe2+,Fe3+,Zn2+和Al3+存在条件下类胡萝卜素稳定性较差,但在其他金属离子存在条件下则较稳定;还原剂对类胡萝卜素有一定的保护作用。因此,推荐烟叶在低温、避光、干燥、偏碱性或适宜的还原剂处理下贮藏,通过农业生产措施降低烟叶中Cu2+,Fe2+,Fe3+,Zn2+和Al3+等金属离子含量,有助于抑制烤后烟叶类胡萝卜素降解及烟叶褪色。      

Complexation with dissolved organic matter and solubility control of heavy metals in a sandy soil

The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The results show that the DOM-complexed species is generally more significant for Cu and Pb than for Cd, Zn, and Ni. The ability of two advanced models for ion binding to humic substances, e.g., model VI and NICA-Donnan, in the simulation of metal binding to natural DOM was assessed by comparing the model predictions with the measurements. Using the default parameters of fulvic and humic acid, the predicted concentrations of free metal ions from the solution speciation calculation using the two models are mostly within 1 order of magnitude difference from the measured concentrations, except for Ni and Pb in a few samples. Furthermore, the solid-solution partitioning of the metals was simulated using a multisurface model, in which metal binding to soil organic matter, dissolved organic matter, clay, and iron hydroxides was accounted for using adsorption and cation exchange models (NICA-Donnan, Donnan, DDL, CD-MUSIC). The model estimation of the dissolved concentration of the metals is mostly within 1 order of magnitude difference from those measured except for Ni in some samples and Pb. The solubility of the metals depends mainly on the metal loading over soil sorbents, pH, and the concentration of inorganic ligands and DOM in the soil solution.     

Complexation of arsenite with humic acid in the presence of ferric iron

In the presence of iron (Fe), dissolved organic matter (DOM) may bind considerable amounts of arsenic (As), through formation of Fe-bridged As-Fe-DOM complexes and surface complexation of As on DOM-stabilized Fe-colloids (collectively referred to as As-Fe-DOM complexation). However, direct (e.g., chromatographic and spectroscopic) evidence and fundamental kinetic and stability constants have been rarely reported for this As-Fe-DOM complexation. Using a size exclusion chromatography (SEC)-UV-inductively coupled plasma mass spectrometry (ICP-MS) technique, arsenite (As(III))-Fe-DOM complexation was investigated after adding As(III) into the priorly prepared Fe-DOM. A series of evidence, including coelution of As, Fe, and DOM from the SEC column and coretention of As, Fe, and DOM by 3 kDa MWCO centrifugal filtration membrane, demonstrated the occurrence of As(III)-Fe-DOM complexation. The kinetic data of As(III)-Fe-DOM complexation were well described by a pseudofirst order rate equation (R(2) = 0.95), with the rate constant (k') being 0.17 ± 0.04 1/h. Stability of As(III)-Fe-DOM complexation was characterized by apparent stability constant (K(s)) derived from two-site ligand binding model, with log K(s) ranging from 4.4 ± 0.2 to 5.6 ± 0.4. Considering the kinetics (within hours) and stability (similar to typical metal-humates) of As(III)-Fe-DOM complexation, this complexation needs to be included when evaluating As mobility in Fe and DOM rich environments.     

紫胶色酸A的荧光性质及其在检测中的应用

考察紫胶色酸A的荧光性质和影响因素,探索其对金属离子的识别作用以及在实际检测中的应用。结果表明,溶剂的化学特性和极性、其自身浓度以及溶液的pH值都会影响紫胶色酸A的荧光强度和发射波长;Cu2＋、Fe3＋、Fe2＋和Pb2＋使紫胶色酸A的荧光猝灭,而Zn2＋和Al3＋使其荧光增强,其中Al3＋体现出显著增强紫胶色酸A荧光强度的特异性,其他金属离子对其荧光强度几乎没有影响。在Al3＋（0.04?mol/L）存在的条件下,紫胶色酸A的荧光强度与其浓度呈良好的线性关系。应用实验结果表明,以Al3＋为标准液,用荧光法检测两种不同饮料中添加的紫胶色酸A的含量,样品回收率在95.0%～109.3%之间,相对标准偏差在1.9%～5.4%之间。本实验开发了一种新的检测紫胶色酸A的方法,该方法具有实际应用价值。     

Chemical speciation of Zn,Cd, Cu,and Pb in pore waters of agricultural and contaminated soils using Donnan dialysis

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. Numerous analytical methods have been utilized for determining trace metal speciation in aqueous environmental matrixes; however, most of these methods suffer from significant interferences. The Donnan dialysis membrane technique minimizes these interferences and has been used in this study to determine free Zn2+, Cd2+, Cu2+, and Pb2+ activities in pore waters from 15 agricultural and 12 long-term contaminated soils. The soils vary widely in their origin, pH, organic carbon content, and total metal concentrations. Pore water pM2+ activities also covered a wide range and were controlled by soil pH and total metal concentrations. For the agricultural soils, most of the free metal activities were below detection limit, apart from Zn2+ for which the fraction of free Zn2+ in soluble Zn ranged from 2.3 to 87% (mean 43%). Five of the agricultural soils had detectable free Cd2+ with fractions of free metal ranging from 59 to 102% (mean 75%). For the contaminated soils with detectable free metal concentrations, the fraction of free metal as a percentage of soluble metal varied from 9.9 to 97% (mean 50%) for Zn2+, from 22 to 86% (mean 49%) for Cd2+, from 0.4 to 32.1% (mean 5%) for Cu2+, and from 2.9 to 48.8% (mean 20.1%) for Pb2+. For the contaminated soils, the equilibrium speciation programs GEOCHEM and WHAM Model VI provided reasonable estimates of free Zn2+ fractions in comparison to the measured fractions (R2 approximately 0.7), while estimates of free Cd2+ fractions were less agreeable (R2 approximately 0.5). The models generally predicted stronger binding of Cu2+ to DOC and hence lower fractions of free Cu2+ as compared with the observed fractions. The binding of Cu2+ and Pb2+ to DOC predicted by WHAM Model VI was much strongerthan that predicted by GEOCHEM.     

多酚类物质和金属离子对火龙果果皮色素稳定性的影响

本试验以火龙果果皮色素为原料,以不同金属离子损伤火龙果果皮色素为基础,进而研究不同多酚类物质对金属离子损伤火龙果果皮色素的护色作用.结果表明Fe3+、Al3+和Cu2+对该色素的损伤较大,多酚类物质中抗坏血酸的护色效果最优.     

Characterization and copper binding of humic and nonhumic organic matter isolated from the South Platte River: evidence for the presence of nitrogenous binding site

Humic substances typically constitute 40-60% of the dissolved organic matter (DOM) in surface waters. However, little information is available regarding the metal binding properties of the nonhumic hydrophilic portion of the DOM. In this study, humic and nonhumic DOM samples were isolated from the South Platte River (Colorado, DOC = 2.6 mg x L(-1), SUVA254 = 2.4 L/mg x m) using a two-column array of XAD-8 and XAD-4 resins. The three major isolated fractions of DOM, which accounted for 57% of the bulk DOM,were characterized using a variety of analytical tools. Proton and copper binding properties were studied for each fraction. The main objective of this work was to compare the structural and chemical characteristics of the isolated fractions and test models describing DOM reactivity toward metal ions. The characterization work showed significant structural differences between the three isolated fractions of DOM. The hydrophobic acid fraction (i.e., humic substances isolated from the XAD-8 resin) gave the largest C/H, C/O, and C/N ratios and aromatic carbon content among the three isolated fractions. The transphilic acid (TPHA) fraction ("transphilic" meaning fraction of intermediate polarity isolated from the XAD-4 resin) was found to incorporate the highest proportion of polysaccharides, whereas the transphilic neutral (TPHN) fraction was almost entirely proteinaceous. The gradual increase of the charge with pH for the three DOM fractions is most likely caused by a large distribution of proton affinity constants for the carboxylic groups, as well as a second type of group more generally considered to be phenolic. In the case of the DOM fraction enriched in proteinaceous material (i.e., TPHN fraction), the results showed that the amino groups are responsible for the charge reversal. For low copper concentrations, nitrogen-containing functional groups similar to those of amino acids are likely to be involved in complexation, in agreement with previously published data.     

托柄菝葜果色素提取及其性质研究

以民族药托柄菝葜的成熟果实为材料,对其红色素的提取条件及理化性质进行研究.结果表明,托柄菝葜果色素提取的最佳条件为:40％vol乙醇水溶液、浸提温度60℃、浸提时间lh.托柄菝葜果色素在自然光照下稳定,但添加金属离子的色素溶液对光不稳定;色素溶液在酸性环境中呈现鲜艳的橙红色,在中性及碱性环境中变为褐绿色.VC对托柄菝葜色素具有增色作用;柠檬酸、EDTA对色素无明显影响;亚硫酸钠、高锰酸钾及苯甲酸钠对色素具有减色作用.金属离子Ca2+、Mn2+、Zn2+、K+、Na+、Fe2+、Mg2+、Cu2+、Co2+、Al3+、Pb2+等离子能减弱托柄菝葜果色素对光的稳定性;Sn2+、Fe3+影响色素稳定性.     

栗子壳色素的分级与稳定性研究

根据溶解性不同,将栗子壳色素分级得到3种色素组分Fr.1、Fr.2和Fr.3。Fr.1只溶于碱性水溶液;Fr.2溶于碱性水溶液和亲水性有机溶剂;Fr.3在任何pH值的水溶液中都能溶解,在亲水性有机溶剂中也能溶解。对栗子壳色素各分级组分进行了化学定性分析和紫外-可见光光谱分析,并研究了它们的稳定性。各分级组分均具有酚类物质的性质,但不具有黄酮类化合物的典型性质,也不具有鞣性。3种栗子壳色素组分的紫外-可见光光谱都是随着波长增大而吸光度逐渐减小的曲线,在可见光区没有明显的吸收峰,仅在270 nm左右有一肩峰。3种色素组分的溶液颜色均随着pH值的增大而逐渐加深,Fr.1对加热和紫外线相对稳定,而Fr.3最为敏感。氧化剂可使栗子壳色素褪色,且Fr.1褪色幅度最大,Fr.2最小。各色素组分均对还原剂、蔗糖、Na+、Mg2+稳定而对Al3+、Ca2+、Fe2+、Fe3+、Cu2+和Zn2+的稳定性较差。     

南极磷虾虾壳中虾青素稳定性的研究

为了研究南极磷虾虾壳中虾青素的稳定性,以提取液中总类胡萝卜素含量为指标,测定了其在光照、温度、酸碱、金属离子等不同条件下的保留率。结果表明,虾青素在光照条件下很不稳定,尤其在阳光直射时降解迅速;随着温度的升高,虾青素损失加快,当温度在60～90℃范围时,褪色加剧;碱浓度较低时虾青素比较稳定,过高的酸浓度或碱浓度都会引起虾青素的损失;钠、钾、镁、钙、锌和铝离子对虾青素基本没有影响,而铜、亚铁离子和铁离子有明显的破坏作用,其中铁离子对虾青素的影响最大。     

主要金属离子对冷溶性速溶绿茶复水后品质的影响

采用Ca2+、Fe2+、Mg2+、K+、Al3+、Zn2+等6种不同金属离子含量的水冲泡冷溶性速溶绿茶,研究水中金属离子对速溶绿茶感官品质的影响。结果表明,不同离子水质对冷溶性速溶绿茶的溶解性及其感官品质差异显著,其中Ca2+、Fe2+、Al3+、Zn2+等金属离子影响较大。研究还初步提出了冷溶性速溶绿茶冲泡用水质指标。     

Metal solubility and speciation in the rhizosphere of Lupinus albus cluster roots

The objective of this study was to investigate the influence of root exudation of organic acid anions on the speciation of major and trace metal cations in the rhizosphere of Lupinus albus cluster roots. Plants were grown in rhizoboxes containing repacked weakly acidic loam. Bulk soil solutions and, during the lifetime of cluster roots, rhizosphere solutions were collected using micro suction cups. During organic acid anion exudation bursts, metals in the rhizosphere of cluster roots were strongly mobilized. The concentrations of dissolved organic carbon derived from soil organic matter increased parallel to organic acid anions. Speciation calculations revealed that, during exudation, Al, Ca, Mn, and Zn in the cluster root rhizosphere were mainly bound with citrate, while Cu and Pb were always strongly bound to soil-derived dissolved organic matter. Our results indicate that cluster root exudation led on one hand to direct mobilization and complexation of metals like Al, Fe, and Zn by citrate and on the other hand to the mobilization of soil organic matter which complexes and solubilizes Cu and Pb.     

Element fractionation analysis for infant formula and food additives by inductively coupled plasma optical emission spectrometry

Fractionation analyses are essential to investigate the effects of dietary constituents on bioavailability of elements. A sequential separation procedure has been applied for elemental fractionation patterns in infant formula, coffee cream, milk powder, whey powder and rice flour. The protein, lipid and serum fractions were separated successfully, and fractions were analysed for various essential (Fe, Cu, Zn, Mn, Mg, Ca, Cr and Co) and nonessential (Ni, V, Al, Mo, Pb, Sn, Ba and Cd) elements by ICP‐OES. Basically, three main fractions namely protein, lipid and serum were separated. Organically bounded fraction was calculated from the sum of the element contents in protein and lipid fractions. The organically bounded fraction can be retained longer in the body than the other fractions, and its percentages of whole elements are between 3.8% and 92.2% in the samples. Additionally, the distribution tendency of each studied metal was variable, which is based on the sample characteristics and complexation reactivity of the metal. The organically bounded fraction for Fe, Cu, Zn and Mn is higher than the other elements in whole samples except whey powder. Investigated elements are basically included in ionic forms in whey powder. Additionally, Mg and Ca are usually observed as uncomplexed structures in the samples.     

彩色电气石致色离子的化学状态研究

为探究不同颜色电气石中致色元素的化学状态及其化学环境,利用X射线光电子能谱方法对绿色调(墨绿色、蓝绿色、淡绿色)和粉红色调电气石样品进行分析。结果表明,绿色调和粉红色调电气石样品中均含有少量的过渡金属离子,如Fe,Mn,Ti,Cr,且不含Li和Be。不同颜色的电气石晶体中过渡金属阳离子的化学状态相同,且分别为Fe3+,Mn4+,Ti4+,Cr3+,但其与阴离子配位的环境有所差别。绿色调电气石样品中虽然Fe的质量分数有较大的差别,但均有部分Fe元素与F结合,即占据晶体结构中的Y位;粉红色电气石样品中,Fe离子没有与F形成配位,仅占据结构中的Z位。相反,在粉红色电气石样品中,Mn主要与F结合配位的方式存在,占据结构中的Y位,而绿色调电气石样品中大部分的Mn与O配位成键,只有少部分的Mn与F结合配位。由于Fe3+,Mn4+离子对之间电荷转移的可能性不大,故电气石的颜色可能主要由于d—d电子跃迁和氧与金属离子(O2--M)间电荷转移吸收引起,尤其是由于化学环境的差异(包括配位阴离子种类、杂质缺陷、结构畸变等)所引起。