高效液相色谱-电感耦合等离子体质谱测定大米粉中的硒形态

建立了高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定大米粉中硒代胱氨酸(SeCys_2)、甲基-硒代半胱氨酸(MeSeCys)、亚硒酸根(Se(Ⅳ))、硒代蛋氨酸(SeMet)、硒酸根(Se(Ⅵ))等5种硒形态的分析方法.采用Hamilton PRP-X100分析柱,以pH 4和pH 6的20 mmol·L~(-1)的柠檬酸溶液辅以少量甲醇为流动相,在梯度洗脱条件下,9 min内可实现5种硒形态完全分离.SeCys_2、MeSeCys、Se(Ⅳ)、SeMet、Se(Ⅵ)的检出限分别为0.88、0.69、1.00、0.90、0.82μg·L~(-1).利用富硒小麦粉标准物质RM8436探讨了不同提取方式的提取效果.最终确定75 mmol·L~(-1) Tris-HCl(pH 7.5)添加XIV蛋白酶和Driselase酶作为提取剂,在37℃振荡提取3 h为大米样品前处理方法.利用该方法分析了富硒地区大米粉中的硒形态,结果表明,大米粉中的硒主要以有机硒形态为主,其中SeMet是最主要的硒形态,占总硒的90%左右.     

Cd和Cu在草甸棕壤-植物系统中行为特性的研究

在沈阳生态站开展了重金属迁移积累行为特性的试验研究，探讨了不同重金属元素在土壤及作物体内迁移积累变化规律。外源重金属元素Cd、Cu施入土壤后，无论是低剂量还足高剂量处理，水田土壤Cd元素已迁移到45cm的深度，而Cu元素迁移到30cm的深度。早田土壤低剂量和高剂量处理Cd迁移到30cm，而Cu元素只有高剂量处理迁移到30cm的深度。土壤Cd、Cu元素向下层迁移的量微乎其微，重金属元素大多滞留在土壤表层。水稻、玉米吸收的Cd大部分积累在作物体的根和茎叶中，而Cu大部分积累在作物体的根系中，Cd、Cu籽实吸收量占植物体总吸收量的1．16％～3％。水稻、玉米地上部吸收Cd的量〉地卜部吸收Cu的量，在作物体中Cd的迁移能力强于Cu的迁移能力。     

四川省屏山县土壤硒地球化学特征及影响因素

通过对屏山县土壤、岩石和水稻样品的系统采集,测定了它们的硒含量,研究该地区硒的地球化学特征,探讨土壤富硒来源和影响因素,查明当地富硒水稻的开发利用前景.结果表明,表层土壤总硒量范围为0.046—1.270 mg·kg~(-1),平均含量为0.240 mg·kg~(-1).研究区为富硒和足硒土壤分别占总面积的15.95%和52.96%,主要分布在三叠系和侏罗系地层.垂向剖面上,土壤硒表层富集.成土母质、土壤p H值、有机质和Fe、Mn的含量对Se的地球化学行为有重要影响.超过51%的水稻硒含量已达到现有的富硒农产品含量标准要求,具有广阔的开发富硒农产品前景.     

砷-硒交互作用对水稻吸收转运砷和硒的影响

采用溶液培养法,研究了两种形态无机As与四价Se交互作用对水稻吸收转运As和Se的影响.结果表明,不同形态As与Se交互作用对水稻吸收转运As和Se影响较大,Se(Ⅳ)显著地提高水稻根系而降低水稻茎叶对As的吸收积累.与对照处理相比,在1.0μmol·L-1As(Ⅲ)和As(Ⅴ)处理下添加1.0μmol·L-1Se(Ⅳ)分别导致水稻根系As含量提高59.5%和21.3%,而水稻茎叶As浓度减少10.4%和21.9%.As(Ⅲ)或As(Ⅴ)处理显著降低水稻茎叶对Se的吸收积累,但As(Ⅴ)处理对水稻根系积累Se没有影响.在1.0μmol·L-1Se(Ⅳ)处理下,添加1.0μmol·L-1As(Ⅲ)和1.0μmol·L-1As(Ⅴ)导致水稻茎叶Se浓度分别比对照处理降低41.9%和30.3%.Se(Ⅳ)与As(Ⅲ)或As(Ⅴ)对水稻转运As、Se的能力具有交互拮抗作用.研究结果表明,在As污染农田中,可通过施用Se肥来提高植物的Se营养,降低植物对As的吸收积累,从而降低As对人体健康的危害.     

高效液相色谱-电感耦合等离子体质谱联用快速同时分析水中5种砷和7种硒

建立了高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)同时测定水样中硒酸盐(Se(Ⅵ))、亚硒酸盐(Se(Ⅳ))、硒代蛋氨酸(Se Met)、硒代胱氨酸(SeCyS_2)、甲基硒代半胱氨酸(MeSeCyS)、硒代乙硫氨酸(SeEt)、硒脲(SeUr)和砷甜菜碱(AsB)、一甲基砷酸(MMA)、二甲基砷酸(DMA)、亚砷酸盐(As(Ⅲ))、砷酸盐(As(Ⅴ))共12种不同形态元素的分析方法.采用安捷伦ZORBAX SB-Aq反相色谱柱,使用20 mmol·L~(-1)柠檬酸+5 mmol·L~(-1)己烷磺酸钠体系(pH=4.4)为流动相,流速为1.0 mL·min~(-1),电感耦合等离子体质谱(ICP-MS)检测,在7.5 min内完全分离12种不同砷、硒形态.12种元素形态的线性相关系数均大于0.9995,检出限分别为0.15、0.13、0.15、0.18、0.12、0.29、0.25、0.26、0.10、0.15、0.14、0.10μg·L~(-1),精密度均在10%以内,加标回收率为76.9%—106.2%.该方法完全满足水样中7种硒和5种砷形态的准确定量分析.     

环境水样中Se(Ⅳ)/Se(Ⅵ)的分析方法研究进展

硒是生物体中不可缺少的微量元素,具有双重生物效应.摄入量不足,会引发缺硒性疾病,而摄入量过多,又会引起硒中毒,其在人体中的日均摄入量安全范围为40—400μg·d~(-1).近些年来,由于硒的污染日趋严重,硒在环境水体(包括淡水、海水、工业废水和生活污水)中的形态分布及其含量测定备受关注.本文在对硒的来源、物理化学性质、生物效应及环境行为总结的基础上,重点综述了环境水体中Se(Ⅳ)/Se(Ⅵ)的分离富集和分析测定方法,并就硒的形态分析进行了展望.     

沉积物中无机硒对霍甫水丝蚓的生物效应研究

硒是动物体必需微量元素之一,水体沉积物中无机硒主要以Se(Ⅳ)和Se(Ⅵ)形态存在,而目前有关无机硒对底栖动物的生物效应研究较为匮乏.本实验以典型底栖动物霍甫水丝蚓(Limnodrilus hoffmeisteri)为研究对象,通过测定抗氧化、神经和消化系统中生化指标的变化,分析了暴露浓度(2～40μg·g-1)、暴露时间(2周和2个月)和硒价态(Se(Ⅳ)和Se(Ⅵ))对其生物效应的影响.结果显示,脂质过氧化水平(以TBARS含量表示)在暴露2周和2个月后,均未受到硒价态的影响,但是暴露2周后,在5μg·g-1组有一升高峰值,而暴露2个月后,在5μg·g-1组有一降低峰值.抗氧化酶活性在暴露2周后,受到硒价态显著影响,Se(Ⅳ)导致3种抗氧化酶活性逐渐升高并在20μg·g-1达到平衡,而Se(Ⅵ)在5μg·g-1即造成抗氧化酶活性升高,并随浓度的升高恢复到对照组水平;暴露2个月后,抗氧化酶未受到硒价态影响,过氧化氢酶(CAT)活性在5μg·g-1浓度附近有一降低峰值,超氧化物歧化酶(SOD)活性在5μg·g-1浓度附近有一升高峰值,而谷胱甘肽硫转移酶(GST)活性没有变化.乙酰胆碱酯酶(AChE)活性受到硒价态影响较小,暴露2周后只有5μg·g-1 Se(Ⅳ)导致AChE酶活性升高,而暴露2个月后,随着浓度升高Se(Ⅳ)和Se(Ⅵ)均导致AChE酶活性降低.α-葡糖苷酶(α-Glu)活性仅在5μg·g-1暴露组升高,且受到暴露时间和价态差异的影响.研究表明,硒的暴露浓度、时间和硒价态显著影响硒的生物效应,这为阐明沉积物中无机硒对底栖无脊椎动物生物效应及机制提供了基础数据.     

富硒农业生产基地土壤硒资源空间分布特征及评价

以山东省淄博市博山区作为富硒产业基地的代表,在该区域网格化均匀布点采集表土样品,测定总硒含量,利用GIS技术分析土壤硒的空间分布特征并对其含量水平进行评价,提出富硒产业发展建议,以期为富硒农业发展提供支持.结果表明,博山区土壤全硒含量的范围为0.105—1.460 mg·kg~(-1),几何均值为0.305 mg·kg~(-1),与全国土壤硒元素平均水平(0.29 mg·kg~(-1))相当.土壤硒元素与地质构造密切相关,与土壤总有机碳、总氮呈极显著相关关系,且表土全硒浓度基本呈现出随海拔升高而降低的趋势.缺硒土壤(含缺硒7%和少硒13%)所占比例为20%,足硒土壤约占55%,富硒土壤所占比例为25%,博山南部农业规划区土壤主要是缺硒和足硒土壤,需添加外源硒肥才能实现发展富硒产业的目标.     

喀斯特深水湖泊富硒沉积物中Se的赋存特征

采用硒的循环提取技术,改进后对湖区沉积物中重金属元素硒进行地球化学形态分析.分析结果表明,红枫湖沉积物中Se的硫化物结合态平均含量最高,占总量的45.7%,其含量顺序为硫化物结合态>残渣态>有机结合态>可交换态>酸溶态>水溶态.并采用次生相富集系数法(SPEF)评价红枫湖沉积物中的Se,结果得KSPEF=2.58,即重金属元素Se可能存在某种人为污染.利用配备X射线能谱的电子显微镜进行微形貌的观察,结果表明,沉积物中除去土壤中常见的元素含量外,S的含量较高,约为0.61%(重量比),但并未发现自然Se的存在.应用X射线多晶衍射仪对沉积物中Se的晶型进行分析,红枫湖沉积物中MSe、MSeO4、MSeO3、MSe2O5和含Se的有机化合物是Se元素存在的主要晶型(其中M为金属离子).加之沉积物中有机质及Se的可利用态含量较高,故红枫湖沉积物经植物修复后,可用于富硒农作物的种植.     

施硒肥方式对强筋小麦产量、硒累积分配及籽粒营养品质的影响

采用二因素裂区设计,设置8个处理,研究有机富硒肥施硒量与施硒方式对强筋小麦生长、产量、硒在小麦不同器官中富集状况以及籽粒营养品质的影响.结果显示:与不施有机富硒肥比较,播种前土施有机富硒肥使强筋小麦总生物量、籽粒产量、各器官(根、茎+叶、颖壳+穗轴、籽粒)干物质量分别提高1.0%-14.7%、2.4%-42.4%、1.9%-21.9%、1.5%%-10.6%、1.8%-19.5%和1.3%-18.2%,且在同一土施处理下,叶面喷施硒肥对小麦总生物量、籽粒产量和各器官干物质量无显著影响.不论采用土施、叶面喷施或土施+叶面喷施,小麦地上部硒含量占植株总硒含量的比例最大,而对于根部硒含量占植株总硒含量的比例则表现为土施>土施+叶面喷硒>喷施.此外,施有机富硒肥明显改善了强筋小麦籽粒蛋白质、总淀粉、直链淀粉、支链淀粉、可溶性糖和蔗糖等营养品质含量(P <0.05),提高幅度分别为0.2%-0.4%、2.9%-10.1%、1.6%-5.1%、1.3%-5.0%、2.1%-7.0%和1.2%-3.5%,且硒肥用量相同的条件下,营养品质含量均表现为土施+叶面喷硒处理高于单一土施硒肥处理,以S30+F(土壤基施30 g/hm²+叶面喷施15 g/hm²)处理达到最高值.因此,综合考虑产量、籽粒硒积累量以及品质等因素,实际生产中建议选用施肥量45 g/hm²(土壤基施30 g/hm²+叶面喷施15g/hm²)较为合适;土施+叶面喷施有机富硒肥可促进强筋小麦生长,提高籽粒产量、硒积累量以及营养品质;结果可为有机富硒肥调控下小麦富硒栽培提供理论参考.(图2表6参46)     

Uptake and translocation of selenium by maize (Zea mays) from its environmentaly important forms

Pot culture studies were conducted to examine the effect of selenite (SeO3(2-)) and selenate (SeO4(2-)) on the uptake and translocation of root absorbed selenium in maize Zea mays plants grown in sand and soil culture. Increasing selenium supplementation (0.5-6.00 microg/ml), increased the selenium retention in roots, but there was little transfer of selenium from shoot to grains. The study indicates that selenite species (less mobile) also accumulates in maize plants when supplied in solution form. Selenium does not cause any adverse effect on the maize plants (dry matter yield vs concentration, no significant correlation, p>0.05).     

Effects of the Interactions Between Selenium and Phosphorus on the Growth and Selenium Accumulation in Rice (Oryza Sativa)

The solution culture, paddy soil culture and the simulation experiments in the laboratory were conducted to clarify the interactions between selenium and phosphorus, and its effects on the growth and selenium accumulation in rice. Results revealed that a suitable supply of selenium could promote rice growth and excessive selenium could injure rice plant, causing lower biomass, especially in the roots. The supply of selenite could enhance the selenium contents of rice shoots and roots in solution culture and in soil culture. The selenium concentrations in roots were much higher than those in shoots supplied with the same rates of selenium and phosphorus. The interaction between selenium and phosphorus was evident. When the phosphorus supply increased to meet the needs of plant growth, phosphorus could promote absorption and accumulation of selenium in the shoots. If the phosphorus supply was excessive, phosphorus could inhibit the accumulation of selenium in the shoots at the lower selenite level (2 mol l^–1), but could not at the higher selenite level (10 mol l^–1). With the supply of phosphate increased, the selenium concentrations in the roots decreased significantly at both selenite levels. The presence of phosphate could decrease Se sorption on the soil surface and increase the selenium concentration in the soil solution. The concentrations of selenium in shoots and roots supplied with 0.08 g kg^–1 phosphorus were lower than those with no phosphorus supplied. With the increase of phosphorus added to 0.4 g kg^–1, the selenium concentration in shoots and roots increased. The effect of phosphorus on the concentration was statistically significant at all three selenium levels.     

Effects of the interactions between selenium and phosphorus on the growth and selenium accumulation in rice (Oryza sativa)

The solution culture, paddy soil culture and the simulation experiments in the laboratory were conducted to clarify the interactions between selenium and phosphorus, and its effects on the growth and selenium accumulation in rice. Results revealed that a suitable supply of selenium could promote rice growth and excessive selenium could injure rice plant, causing lower biomass, especially in the roots. The supply of selenite could enhance the selenium contents of rice shoots and roots in solution culture and in soil culture. The selenium concentrations in roots were much higher than those in shoots supplied with the same rates of selenium and phosphorus. The interaction between selenium and phosphorus was evident. When the phosphorus supply increased to meet the needs of plant growth, phosphorus could promote absorption and accumulation of selenium in the shoots. If the phosphorus supply was excessive, phosphorus could inhibit the accumulation of selenium in the shoots at the lower selenite level (2 micromol l(-1)), but could not at the higher selenite level (10 micromol l(-1)). With the supply of phosphate increased, the selenium concentrations in the roots decreased significantly at both selenite levels. The presence of phosphate could decrease Se sorption on the soil surface and increase the selenium concentration in the soil solution. The concentrations of selenium in shoots and roots supplied with 0.08 g kg(-1) phosphorus were lower than those with no phosphorus supplied. With the increase of phosphorus added to 0.4 g kg(-1), the selenium concentration in shoots and roots increased. The effect of phosphorus on the concentration was statistically significant at all three selenium levels.     

Cycling of selenite and selenate in marine phytoplankton

The marine phytoplankton Dunaliella tertiolecta, Cachonina niei, Thalassiosira nordenskioldii, Phaeodactylum tricornutum, and Chaetoceros sp. were incubated with a range of molar concentrations of sodium-selenite (Na₂-SeIVO₃) and sodium-selenate (Na₂-SeVIO₄) to examine further their role in metabolic cycling of selenium in ocean waters. At low selenium concentrations, approaching those found naturally in seawater (10^-10 to 10^-9 M), all species distinguished between selenite and selenate, and actively concentrated selenite from the incubating medium while only marginally accumulating selenate. At much higher concentrations (10^-8 to 10^-6 M), selenate was also taken up. At the highest concentration tested, i.e., 10^-5 M with C. niei, after an immediate rapid uptake in the first 24 h, the intracellular selenite and selenate levels dropped to about 35 to 50% of the initial peak values. These observations suggest an uptake mechanism in these algae which, at normal ambient concentrations of selenium (10^-9 M), preferentially selects selenite and excludes selenate. At much higher concentrations (10^-8 M), the mechanism becomes overloaded and both selenium species enter the cells. Intracellularly, selenite became associated primarily with protein and amino acid fractions, in approximately equal proportions, while only ca. 4% of total intracellular selenium was found in the lipid fraction. Trace amounts of selenate that entered the cells, mainly during the first minutes of exposure, also entered the protein and amino acid components, but over time were increasingly associated with the protein fraction only. At the end of a 10-d incubation of algal cells in selenite-spiked medium, less than 25% of total Se in the medium could in fact be identified analytically as selenite. This suggests the presence of a non-selenite metabolite, possibly released back into the medium from the algae.     

外源硫输入对稻田土壤硒流失的影响

土壤中硒的甲基化可能会导致硒的挥发,加剧土壤硒的流失,而农田土壤硒的缺乏会造成农作物中硒含量偏低.施用硫肥是保障作物增产、增收的一种重要农艺措施,外源硫输入对土壤硒的含量可能产生重要的调控作用.本研究模拟稻田淹水环境,通过添加典型有机硫(甲硫氨酸)和无机硫(硫酸钠),测定硒的挥发量以及土壤中残留的硒含量,以揭示外源硫输...     

亚硒酸钠对蚯蚓的毒性及蚓体富硒作用的研究

以100mgkg^-1,200mgkg^-1,300mg kg^-1等不同质量分数（w)的亚硒酸钠（NaSeO2)添加到蚯吲饵料中,研究了亚硒酸钠处理对蚯蚓生长发育及死亡的影响和蚯蚓的富硒作用,结果表明,3个w(NaSeO2)处理对蚯蚓生长发育和富硒量的影响都达到极显著水平,w(NaSeO2)越高,用其处理饲养的蚯蚓死亡率也较高,富硒量也较大,二者存在一定的正相关性,在200mg kg^-1的w(NaSeO2)处理下,当蚯蚓饲养到84d时,蚯蚓的富硒量可达到332．5mg kg^-1,同时死亡率高达90％。     

Higher sorption of arsenate versus arsenite on amorphous Al-oxide, effect of ligands

Arsenic pollution is currently a major health issue because As is toxic for human beings, animals, and plants. Knowledge of As mobility is therefore important to assess health risk. The sorption of arsenite and arsenate on metal oxides in the presence of various anionic ligands is closely linked to the mobility, bioavailability, and risk. It was reported that the sorption mechanisms and characteristics of arsenite and arsenate on Al-oxides were different from that on Fe-oxides. Previous work reports the sorption of arsenite and arsenate on Fe-oxides in the presence of ligands. Whereas there is few knowledge on the sorption of arsenite and arsenate by Al-oxides in the presence of ligands. Here, we studied the sorption of arsenite and arsenate on amorphous Al-oxide by batch experiments. We tested the effect of organic ligands: oxalate, malate, tartrate, citrate; and inorganic ligands: sulfate, phosphate, selenate, selenite. Results show that amorphous Al-oxide has more sorption affinity for arsenate than arsenite. The inhibition of As sorption by ligands at pH 6 is higher for arsenite than arsenate. For arsenite, the As sorption inhibition decreases in the order phosphate, citrate, malate, selenite, oxalate, tartrate, sulfate, and selenate. For arsenate, the As sorption inhibition decreases in the order phosphate, malate, citrate, selenite, tartrate, oxalate, sulfate, and selenate.     

Study on removing selenate from groundwater by autohydrogenotrophic microorganisms

Performance of autohydrogenotrophic bacteria for bio-reduction of selenate (Se(VI)) under anaerobic conditions was investigated with batch experiments. Results showed Se(VI) was bio-reduced to selenite (Se(IV)) as an intermediate product, and then to elemental selenium (Se⁰). Reduction kinetics could be described by the pseudo-first-order model. In particular, the influences of pH value and temperature on Se(VI) reduction by autohydrogentrophic organisms were examined. The high degradation rate was achieved at pH 7.0 to 8.0; and the best reduction temperature was between 25°C and 35°C. This study is of help for treating groundwater with selenium contamination by autohydrogenotrophic bacteria as well as its reactor development.     

The effect of humic substances on Cu migration in the soil profile

Humic substances (HS) are widely used for diverse purposes. The effect of HS on the metal’s status in contaminated soils is contradictory. The aim of this work was to investigate the Cu migration in soils treated with HS. A model field experiment with the addition of Cu (1.243?mg?Cu/kg) and HS Extra® (potassium humate) was performed. The Cu addition resulted in acidification (by 0.7 pH) after 3 months. The major part of the added Cu remained in the upper 7-cm-thick soil layer; 4% reached the lower soil layer, while only 0.1% were removed beyond the profile. The addition of HS mitigated soil acidification increased the content of Cu bound to solid-phase organic substances and abruptly reduced the Cu activity in the soil liquid phase. Simultaneously, the HS addition increased the water-soluble organic substances (WSOS) by four times, including those in the hydrophilic and hydrophobic fractions, resulting in a twofold increase in the content of soluble Cu. Copper complexes with hydrophilic WSOS mainly reached lysimeters, and hydrophobic organic substances were absorbed by the soil. The HS addition to a slightly acidic soil can accelerate the migration of Cu to adjacent environments.     

碳酸盐岩山地土壤施用有机肥的溶蚀作用探讨

选择碳酸盐岩山地常见耕植、未耕植土层,通过概化制作为系列模拟柱试验土层,按当地正常施肥方法,向土层定量施入有机肥并浇灌及控制其它相关条件变化,再定期观测预埋土层不同深度碳酸岩石片的溶蚀量和土层其它指标的变化,作了施用有机肥的土中碳酸岩石溶蚀变化研究。结果揭示,在未耕植红黏土表层施用有机肥,大大减弱了土中碳酸岩石的溶蚀作用,且减弱程度随土深加大而降低。但对其下伏碱性岩粉层而言,施肥又引起了溶蚀量的微小增加变化;另在耕植土表层施用有机肥,对其土中碳酸岩石的溶蚀作用改变不大,且无论施肥与否溶蚀作用随土深加大又略显增大变化。而其下部红黏土中碳酸岩石的溶蚀量要远大于耕植土中的溶蚀量,并受施肥的影响较小。表明,农业施肥对未耕植土土中包被、包裹的碳酸岩石溶蚀影响较大,对下伏碱性岩粉层的层中、层下碳酸岩石的溶蚀影响较小。同时,施肥对耕植土土中、土下碳酸岩石的溶蚀影响不大。人类可采取禁令开垦较薄土层措施,来有效规避耕作施肥对土中碳酸岩石溶蚀作用的抑制,减少反石漠化的不利因素。此将为丰富碳酸盐岩山地成土演化理论和石漠化灾害的防治提供依据。