果蔬中硒形态的研究进展

硒是人体必需微量元素之一,人体缺乏硒元素或补充过量皆可导致多种疾病。我国绝大部分地区的居民缺硒,使用不同的方法将硒添加到果蔬中,可以提高果蔬的附加价值与经济效益,也使得硒在日常饮食中得到适当的补充。因此,果蔬富硒研究是一项利于全民健康的、具有重大意义的课题研究。本篇文章为一个简短的综述,主要内容是富硒果蔬近十年来的研究现状,同时讨论了果蔬中硒的富集方法及检测过程中的分析方法。      

Selenium speciation in enriched vegetables

The ability of several plants to accumulate and transform inorganic forms of selenium into bioactive organic compounds has important implications for human nutrition and health. Se-enriched Allium group vegetables such as garlic, onion and ramps have been mainly the subject of several studies in the recent years. Apart from the total Se uptake, enrichment treatments normally undergo certain metabolic changes that determine the final product as well as its translocation and accumulation in different plant tissues. For this reason, it is important to find which form of selenium should be used for supplementation to obtain a high content of this element in the final plant. Moreover, its distribution in different parts of plants as well as characterisation and quantification of individual species becomes an issue. This review gives a brief, critical overview of the studies carried out to characterise selenium species produced by different enriched vegetables. The use of different extraction and clean-up methodologies will be discussed in conjunction with different selenium enrichment procedures.     

News: EPA, environmentalists clash over proposal to test contaminated dredged sediments

Government.     

Macro- and microscale investigation of selenium speciation in Blackfoot river, Idaho sediments

The transport and bioavailability of selenium in the environment is controlled by its chemical speciation. However, knowledge of the biogeochemistry and speciation of Se in streambed sediment is limited. We investigated the speciation of Se in sediment cores from the Blackfoot River (BFR), Idaho using sequential extractions and synchrotron-based micro-X-ray fluorescence (micro-SXRF). We collected micro-SXRF oxidation state maps of Se in sediments, which had not been done on natural sediment samples. Selective extractions showed that most Se in the sediments is present as either (1) nonextractable Se or (2) base extractable Se. Results from micro-SXRF showed three defined species of Se were present in all four samples: Se(-II,O), Se(IV), and Se(VI). Se(-II,O) was the predominant species in samples from one location, and Se(IV) was the predominant species in samples from a second location. Results from both techniques were consistent, and suggested that the predominant species were Se(-II) species associated with recalcitrant organic matter, and Se(IV) species tightly bound to organic materials. This information can be used to predict the biogeochemical cycling and bioavailability of Se in streambed sediment environments.     

Heavy metal immobilization through phosphate and thermal treatment of dredged sediments

Disposal of dredged sediments is expensive and poses a major challenge for harbor dredging projects. Therefore beneficial reuse of these sediments as construction material is highly desirable assuming contaminants such as heavy metals are immobilized and organics are mineralized. In this research, the effect of the addition of 2.5% phosphate, followed by thermal treatment at 700 degrees C, was investigated for metal contaminants in dredged sediments. Specifically, Zn speciation was evaluated, using X-ray absorption spectroscopy (XAS), by applying principal component analysis (PCA), target transformation (TT), and linear combination fit (LCF) to identify the main phases and their combination from an array of reference compounds. In dredged sediments, Zn was present as smithsonite (67%) and adsorbed to hydrous manganese oxides (18%) and hydrous iron oxides (15%). Phosphate addition resulted in precipitation of hopeite (22%), while calcination induced formation of spinels, gahnite (44%), and franklinite (34%). Although calcination was previously used to agglomerate phosphate phases by sintering, we found that it formed sparingly soluble Zn phases. Results from the U.S. EPA toxicity characteristic leaching procedure (TCLP) confirmed both phosphate addition and calcination reduced leachability of heavy metals with the combined treatment achieving up to an 89% reduction.     

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.     

Selenium speciation in the soil solution and its relevance to plant uptake

The relationship between soil and plant selenium has been investigated using two ⁷⁵SeO₃ spiked silt loam soils from the Hoosfield series with long-term equilibration pH values of 4.5 and 7. Lolium perenne plants were grown in the soils over a 15-week period, and seven harvests were made. Plant samples and soil solutions were assayed for radioactivity, and selenium compounds found in the soil solutions separated by high voltage paper electrophoresis. Throughout the 15-week experimental period selenium speciation was observed to change in soil solution. Samples collected at day 2 from pH 4.5 soil revealed that selenate accounted for 71% and selenite 8% of the soluble selenium compounds present, whereas for the pH 7 soil the relative percentages were 51 and 23% respectively. After 105 days selenate accounted for 22% and selenite 20% at pH 4.5, and 12 and 22% respectively at pH 7. The occurrence of selenoglutathione was noted in the soil solution and its concentration increased significantly with time. Statistically significant correlations (r=0.82) were found between the concentration of selenium in Lolium perenne at harvest and selenate selenium removed from the soil solution.     

Selenium and arsenic speciation in fly ash from full-scale coal-burning utility plants

X-ray absorption fine structure spectroscopy has been used to determine directly the oxidation states and speciation of selenium and arsenic in 10 fly ash samples collected from full-scale utility plants. Such information is needed to assess the health risk posed by these elements in fly ash and to understand their behavior during combustion and in fly ash disposal options, such as sequestration in tailings ponds. Selenium is found predominantly as Se(IV) in selenite (SeO3(2-)) species, whereas arsenic is found predominantly as As(V) in arsenate (AsO4(3-)) species. Two distinct types of selenite and arsenate spectra were observed depending upon whether the fly ash was derived from eastern U.S. bituminous (Fe-rich) coals or from western subbituminous or lignite (Ca-rich) coals. Similar spectral details were observed for both arsenic and selenium in the two different types of fly ash, suggesting that the postcombustion behavior and capture of both of these elements are likely controlled by the same dominant element or phase in each type of fly ash.     

Concentration-dependent mobility, retardation, and speciation of iodine in surface sediment from the Savannah River Site

Iodine occurs in multiple oxidation states in aquatic systems in the form of organic and inorganic species. This feature leads to complex biogeochemical cycling of stable iodine and its long-lived isotope, (129)I. In this study, we investigated the sorption, transport, and interconversion of iodine species by comparing their mobility in groundwaters at ambient concentrations of iodine species (10(-8) to 10(-7) M) to those at artificially elevated concentrations (78.7 μM), which often are used in laboratory analyses. Results demonstrate that the mobility of iodine species greatly depends on, in addition to the type of species, the iodine concentration used, presumably limited by the number of surface organic carbon binding sites to form covalent bonds. At ambient concentrations, iodide and iodate were significantly retarded (K(d) values as high as 49 mL g(-1)), whereas at concentrations of 78.7 μM, iodide traveled along with the water without retardation. Appreciable amounts of iodide during transport were retained in soils due to iodination of organic carbon, specifically retained by aromatic carbon. At high input concentration of iodate (78.7 μM), iodate was found to be reduced to iodide and subsequently followed the transport behavior of iodide. These experiments underscore the importance of studying iodine geochemistry at ambient concentrations and demonstrate the dynamic nature of their speciation during transport conditions.     

Selenium speciation in kerogen from two Chinese selenium deposits: environmental implications

Selenium is an essential trace element for humans, animals, and vegetation. Its occurrence in the environment is characterized by specific chemical and biochemical properties that control its elemental solubility, toxicity, and environmental behavior. The Laerma Se-Au deposit and Yutangba Se deposit are two important Se-bearing deposits found recently in China. In one of these areas (Yutangba), a serious environmental impact happened involving Se poisoning. Previous studies have shown that Se in both deposits is closely related to organic matter, especially kerogen fractions, but detailed relationships between Se and kerogen and Se chemical forms were not reported. In this study, the different speciation of Se is identified by transmission electron microscopy (TEM) and other geochemical techniques (infrared spectra (IS) and X-ray diffraction (XRD)) from kerogen samples extracted from ore rocks of both deposits. The occurrence of organically bound Se in the Laerma deposit and elemental Se nanograins in the Yutangba deposit is observed, indicating the diversity of formation mechanisms and possible chemical forms of Se in Se-rich rocks. The formation of elemental Se associated with organic matter is likely related to redox conditions, whereas organic species are related to the higher sulfur content of kerogen and possibly result from S-Se substitutions. This discovery provides new evidence with which to assess potential Se mobility during weathering of ore-bearing rocks. In an altered rock, the elemental Se in kerogen is more steadily mobilized and is potentially accumulated by vegetation, which may explain the sudden prevalence of Se poisoning in the Yutangba area. In contrast, organically bound Se seems more resistant to chemical alteration compared to other Se species so that its bioavailability may be very restricted.     

Effects of progressive anoxia on the solubility of technetium in sediments

Technetium is a significant radioactive contaminant from nuclear fuel cycle operations. It is highly mobile in its oxic form (as Tc(VII)O4-) but is scavenged to sediments in its reduced forms (predominantly Tc(IV)). Here we examine the behavior of Tc at low concentrations and as microbial anoxia develops in sediment microcosms. A cascade of stable-element terminal-electron-accepting processes developed in microcosms due to indigenous microbial activity. TcO4- removal from solution occurred during active microbial Fe(III) reduction, which generated Fe(II) in the sediments and was complete before sulfate reduction began. Microbial community analysis revealed a similar and complex microbial population at all three sample sites. At the intermediate salinity site, PauII, a broad range of NO3-, Mn(IV), Fe(III), and SO4(2-) reducers were present in sediments including microbes with the potential to reduce Fe(III) to Fe(II), although no differences in the microbial population were discerned as anoxia developed. When sterilized sediments were incubated with pure cultures of NO3(-)-, Fe(III)-, and sulfate-reducing bacteria, TcO4- removal occurred during active Fe(III) reduction. X-ray absorption spectroscopy confirmed that TcO4- removal was due to reduction to hydrous Tc(IV)O2 in Fe(III)- and sulfate-reducing estuarine sediments.     

外源硒处理的花生芽蛋白中五种硒形态分析

为了探究花生发芽后的富硒规律,本研究用不同浓度Na2SeO3浸泡花生子粒发芽5d后,分析外源硒对花生发芽情况的影响,并分别通过电感耦合等离子体质谱法（Inductively Coupled Plasma-Mass Spectrometry,ICP-MS）和高效液相色谱-电感耦合等离子体质谱联用（High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry,HPLC-ICP-MS）分析花生芽不同部位（子叶、胚轴、胚根）的总硒含量和花生芽蛋白中5种硒形态（硒代胱氨酸SeCys2、硒代半胱氨酸MeSeCys、亚硒酸根SeIV、硒代蛋氨酸SeMet、硒酸根SeVI）的组成特征及变化规律。结果表明,随着Na2SeO3浸泡浓度的升高,花生芽长、芽粗和发芽率均呈降低的趋势;高浓度的外源硒抑制了花生发芽过程中硒元素由子叶向胚轴和胚根的转移;未经硒浸泡的花生发芽后,三个部位均检测到三种硒形态,其中SeCys2占比最高,随着硒浓度升高,各部位硒形态种类增加,无机硒（SeIV和SeVI）占比逐渐升高,SeCys2和MeSeCys占比逐渐降低,SeMet占比没有规律性变化,各部位有机硒总量占比降低,无机硒向有机硒转化率收到抑制。     

富硒农产品中硒代氨基酸形态及其在不同蛋白组分中的分布

目的：探究富硒西兰花、富硒大豆、富硒玉米、富硒大麦苗不同溶解性蛋白组分中硒代氨基酸形态及分布情况。方法：利用高效液相色谱—氢化物发生—原子荧光光谱联用技术测定4种富硒禾谷类和十字花科农产品中硒代蛋氨酸(SeMet)、硒代胱氨酸(SeCys2)、甲基硒代半胱氨酸(MeSeCys)和硒代乙硫氨酸(SeEt)含量,并分析各硒代氨基酸在清蛋白、球蛋白、醇溶蛋白和谷蛋白等不同溶解性蛋白组分中的分布特点。结果：4种富硒植物的硒代氨基酸在不同蛋白组分中的含量及分布存在显著差异(P＜0.05)。富硒大豆、富硒玉米、富硒大麦苗的有机硒以SeMet形式存在,在4类蛋白组分中分布较一致且相对含量均高于66%,不存在SeEt;富硒西兰花的有机硒主要以SeCys2和SeMet为主、MeSeCys次之,前二者在清蛋白和谷蛋白组分中的分布较一致且约占有机硒含量的36%,但在球蛋白和醇溶蛋白组分中均以SeMet存在,相对含量最高达60%,其次为SeCys2约占有机硒含量的34%。富硒西兰花中存在极少量的SeEt约占有机硒含量的5%。结论：3种禾谷类农产品(富硒大豆、富硒玉米、富硒大麦苗)的不同溶解性蛋白中均以SeMet为主;而富硒西兰花的不同溶解性蛋白则以SeMet和SeCys2为主,并且其清蛋白和谷蛋白还富含较多的MeSeCys。     

Effect of organic co-contaminants on technetium and rhenium speciation and solubility under reducing conditions

The chemical and biogeochemical reduction of pertechnetate (TcO4-) and perrhenate (ReO4-) have been compared alongside complexation of the reduced species by three anthropogenic ligands relevant to nuclear waste (ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and isosaccharinic acid (ISA)). An HPLC size-exclusion column coupled to ICP-MS was used to separate the species and quantify Tc and Re. During method development, ReO4- showed recalcitrance to direct chemical reduction by Sn(ll) under conditions that readily reduced TcO4- and resulted in Tc(IV)-organic complexes. In microcosm experiments of a silty loam soil containing Tc04-, ReO4-, and ISA (3.0 mM), EDTA (0.17 mM), or NTA (2.4 mM), anoxia developed to iron-reducing conditions during the 42 day experimental period. The majority of the TcO4- was reduced to particle-reactive Tc(IV) and removed from solution during nitrate reduction, but there was no chromatographic evidence of Tc(IV)-organic complexes in the porewater. Overall, the excess organic complexants added did not cause a measurable difference in the solubility of Tc(IV) over the control experiments in this organic-rich (12% organic carbon) soil. ReO4- did not undergo reduction, as shown by the constant porewater concentration and the chromatographic data, and thus Re does notfunction as an analogue forTc under environmental nitrate- and iron-reducing conditions.     

Reduced inorganic sulfur speciation in drain sediments from acid sulfate soil landscapes

We examined processes regulating reduced inorganic sulfur (RIS) speciation in drain sediments from coastal acid sulfate soil (ASS) landscapes. Pore water sulfide was undetectable or present at low levels (0.6-18.8 microM), consistent with FeS(s) precipitation in the presence of high concentrations of Fe2+ (generally >2 mM). Acid-volatile sulfide (AVS), with concentrations up to 1019 micromol g(-1), comprised a major proportion of RIS. The AVS to pyrite-S ratios were up to 2.6 in sediment profiles containing abundant reactive Fe (up to approximately 4000 micromol g(-1)). Such high AVS:pyrite-S ratios are indicative of inefficient conversion of FeS(s) to pyrite. This may be due to low pore water sulfide levels causing slow rates of pyrite formation via the polysulfide and H2S oxidation pathways. Overall, RIS speciation in ASS-associated drain sediments is unique and is largely regulated by abundant reactive Fe.     

Changes in uranium speciation through a depth sequence of contaminated Hanford sediments

The disposal of basic sodium aluminate and acidic U(VI)-Cu(ll) wastes in the now-dry North and South 300 A Process Ponds atthe Hanford site resulted in a groundwater plume of U(VI). To gain insight into the geochemical processes that occurred during waste disposal and those affecting the current and future fate and transport of this uranium plume, the solid-phase speciation of uranium in a depth sequence of sediments from the base of the North Process Pond through the vadose zone to groundwater was investigated using standard chemical and mineralogical analyses, electron and X-ray microprobe measurements, and X-ray absorption fine structure spectroscopy. Near-surface sediments contained uranium coprecipitated with calcite, which formed due to overneutralization of the waste ponds with base (NaOH). At intermediate depths in the vadose zone, metatorbernite [Cu(UO2PO4)2 x 8H2O] precipitated, likely during pond operations. Uranium occurred predominantly sorbed onto phyllosilicates in the deeper vadose zone and groundwater; sorbed uranium was also an important component at intermediate depths. Since the calcite-bearing pond sediments have been removed in remediation efforts, uranium fate and transport will be controlled primarily by desorption of the sorbed uranium and dissolution of metatorbernite.     

Selenium speciation assessed by X-ray absorption spectroscopy of sequentially extracted anaerobic biofilms

Wet chemical methods such as sequential extraction procedures are commonly used to assess selenium fractionation in anoxic environments, allowing an estimation of the mobility and bioavailability of selenium. However, the interpretation can be biased by unselective extraction of targeted species and artifacts introduced during the extraction. Here, the selectivity of the single extraction steps to gain reliable selenium speciation information are scrutinized for the first time by direct, nondestructive X-ray absorption near edge structure (XANES) spectroscopy at the selenium K-edge. The sequential extraction procedures seriously overestimated the elemental selenium fraction, as major parts (58%) of the total selenium were present as metal selenides and organic selenium compounds, although extracted in the elemental fraction. Spectral fitting of the XANES spectra by the least-squares linear combinations utilizing a large set of model compounds, including previously neglected Se(-I) selenides, showed a novel degree of complexity in the speciation of selenium treating anaerobic biofilms, with up to 4 modeled selenium species contributing to the speciation, i.e., different elemental, organic, and metal-bound selenium species. Furthermore, a short exposure (10 min) to ambient air during the sequential extraction procedure induced the oxidation of organic selenium compounds, revealing the fragility of selenium speciation in anaerobic biofilms.