硒在土壤-农作物系统中的分布特征及富硒土壤阈值

为查明Se在土壤-农作物系统中的分布特征,开展富Se土壤阈值研究,在重庆市黔江区采集表层土壤8789件,深层土壤155件,并采集玉米籽实141件和水稻籽实159件（同时分别采集对应根系土样品141件和159件）,分析了土壤及农作物中的Se、有机质、S、Mn、TFe₂O₃、Al₂O₃和K₂O等含量及土壤pH,利用地统计法分析了表层及深层土壤Se的分布特征,基于多元回归分析,研究Se生物有效性的影响因素,基于根系土各组分含量及农作物Se含量进行土壤富Se阈值研究.结果表明,研究区高Se土壤占全区的32.72%;表层土壤及深层土壤Se含量的分布主要受到成土母质的控制,土壤Se源稳定且表层富集现象明显.玉米和水稻的富Se率分别为75.35%、46.81%,土壤有机质和S含量均会限值Se的生物有效性.若种植作物为玉米,建议以0.3 mg·kg^-1作为富Se土壤阈值;若种植作物为水稻,在土壤pH≤7.5时,建议以0.3 mg·kg^-1作为富Se土壤阈值;在土壤pH>7.5时,建议以0.4 mg·kg^-1作为富Se土壤阈值.同样地,若研究区种植有其他大宗农作物,亦可用该方法进行建议富Se土壤阈值研究.     

我国硒淡水水生生物水质基准值推导

水体中硒含量过高会导致水生生态系统退化,而中国现有的地表水环境质量标准对硒的标准值设定并不是基于我国水生生物相关毒理学研究得出的,难以因地制宜地保护我国水生生物.为保护我国水生生物,本研究利用物种敏感度分布法,推导出基于最大无效应浓度（NOEC）、最低有效应浓度（LOEC）的慢性硒（无机）淡水水质一级基准值和基于半数致死效应浓度（LC₅₀）、半数最大效应浓度（EC₅₀）、半数抑制浓度（IC₅₀）的急性硒（无机）淡水水质二级基准值分别为0.58 μg·L^-1、0.52 mg·L^-1,发现我国现有的水质标准可能会对我国水生生物造成欠保护.进一步推导出为保护我国鱼类的硒（无机）淡水水质一级、二级基准值分别为0.21 μg·L^-1、1.60 mg·L^-1,以及硒淡水鱼类饲料有机硒和无机硒含量一级基准值分别为97 μg·kg^-1和98 μg·kg^-1.本研究基于硒对水生生物的急性和慢性毒性效应,推导出硒的系列基准值,为保护我国淡水水生生物安全的标准制定提供数据支撑和科学依据.     

基于有效硒的富硒土壤阈值及有效硒的影响因素

土壤中有效硒(Se)含量是影响作物硒含量的主导因素.为合理有效在有效硒含量高、全硒含量低的土壤中圈定富Se土壤范围并提出天然富Se作物培育理论性指导,在宁夏北部石嘴山市采集表层土壤样品8 814件和根系土-作物配套样品195件,以有效硒为分析主线,通过对表层土壤和根系土中全Se、有效Se含量和Se形态以及根系土配套作物硒含量的综合研究,确定适合研究区的基于有效Se的富Se土壤阈值,建立有效Se的多元回归模型确定影响有效Se的主要理化指标以期通过提高有效硒的方式提高作物富硒率.结果表明,根系土-作物中Se的特征可代表表层土壤全Se和有效Se特征,根系土全Se、有效Se及作物Se含量的协调性分析确定0.24mg·kg^-1的全Se含量作为富Se土壤界定阈值;有效Se的多元回归模型显示,土壤中全Se和土壤肥力元素含量的增加可促进有效Se的富集.     

广州地区室内灰尘中典型非邻苯增塑剂的污染特征与暴露风险

非邻-苯二甲酸酯增塑剂作为邻-苯二甲酸酯的替代物被广泛用于生产和生活用品中,但目前对其环境存在和人体暴露风险知之甚少.为研究室内环境的污染状况及人体暴露,分析了广州市83户住宅灰尘中12种典型非邻苯增塑剂.结果表明,对-苯二甲酸二辛酯（DEHT）、偏苯三酸三辛酯（TOTM）、乙酰柠檬酸三丁酯（ATBC）、己二酸庚基壬基酯、己二酸二（2-乙基己基）酯和偏苯三酸三辛烷基酯100%检出.非邻-苯二甲酸酯增塑剂总含量中值为101 μg·g^-1,含量范围为22.4~615 μg·g^-1.DEHT的含量最高（含量范围9~487 μg·g^-1）,其次是TOTM （含量范围0.3~87 μg·g^-1）和ATBC （含量范围1.7~50 μg·g^-1）.通过暴露模型评估了成人与儿童经灰尘摄食的日暴露量,其中儿童摄入的非邻苯增塑剂总日暴露量为367 ng·（kg·d）^-1,是成人日暴露量43 ng·（kg·d）^-1的8~9倍.进一步通过危险商对暴露量进行风险评价,结果表明成人和儿童经灰尘摄食对非邻苯增塑剂的暴露风险均处于可接受范围.     

矿业废弃地复垦土壤-作物硒吸收特征及其对重金属拮抗效应

针对矿业废弃地复垦土壤硒与重金属"双高"现象,为充分开发其富硒土地资源,确保作物安全,本文基于"点对点"采集的土壤和玉米样品,利用反距离权重（inverse distance weighted,IDW）、多元线性回归（multiple linear regression,MLR）、偏最小二乘回归（partial least squares regression,PLSR）和随机森林回归（random forest regression,RFR）等方法,开展了西南某硫磺矿复垦区玉米硒元素吸收预测的同时,分析硒（Se）对重金属（Hg、As、Cd和Cr）的拮抗效应.结果表明研究区土壤中硒资源丰富,土壤Se平均含量达到0.83mg·kg^-1,是中国土壤Se平均含量的2.87倍,玉米籽粒硒含量处于0.02~0.16mg·kg^-1之间.由相关性分析和模型预测可知,研究区玉米籽粒硒含量主要影响因素为土壤硒、pH值、有机质和重金属As等,多元线性回归（MLR）对其预测最为有效,决定系数R²为0.52.通过比较研究区土壤硒不同含量梯度下玉米对重金属（Hg、As、Cd和Cr）富集特性,表明了土壤Se对重金属Hg、As、Cd和Cr存在一定的拮抗作用.本研究结果可为今后同类矿业废弃地复垦土地发展特色富硒农业提供依据.     

广西都安县典型水田硒地球化学特征及影响因素

为发展富硒水稻种植和巩固脱贫成果,在广西都安县百旺镇开展水稻种植区地球化学调查,采集21件岩石和193件水稻根系土-籽实协同调查样品,利用统计学和相关分析方法研究水田土壤硒的分布特征和影响因素.结果表明,百旺镇水田土壤和水稻籽实富硒率分别为67.4%和64.8%,但富硒土壤和富硒水稻籽实样品中镉含量普遍较高;对比显示百旺镇南部种植区水稻籽实富硒率达到61.1%,重金属风险低,发展无污染富硒水稻种植优势明显.相关分析表明次生富集作用是研究区土壤富硒的主要原因,根系土pH和质地不同程度影响土壤硒含量;水稻籽实硒含量主要受根系土硒含量、有效硒含量、pH和Al₂O₃等影响.镉膳食暴露风险评估显示研究区水稻整体安全,但中部区域水稻膳食暴露风险较高.     

开阳富硒农作物筛选研究

本文通过对贵州开阳禾丰乡和冯三镇富硒岩石出露区出产农作物的野外调查和室内分析研究,筛选了该区可供开发种植富硒农作物的土壤农田和农作物品种。研究结果表明:土壤硒含量为0.46~2.31 mg/kg,均值为1.42 mg/kg,冯三镇的安坪村、金龙村和禾丰乡的杨柳坝、甘塘村一带的土壤都达到了富硒水平;农作物的含硒量为0.007~0.61 mg/kg,筛选出的主要农作物有水稻、玉米、辣椒、油菜、洋芋等,大都达到了富硒等级。     

广西贺州市典型矿区周边耕层土壤Cd通量特征

广西是我国西南部典型的地质高背景区,碳酸盐岩、黑色岩系、基性-超基性岩体与金属矿床（矿化体）强烈的风化成壤作用,使土壤重金属镉（Cd）含量高于全国其他地区.为了查明在地质高背景区矿业活动对耕层土壤环境质量的影响程度,在广西贺州市选取矿业活动影响区和对照区为研究区,系统开展了耕层土壤Cd输送途径及输送通量密度的对比研究.结果表明,在矿区和对照区耕层土壤中,Cd大气干湿沉降通量密度平均值分别为1.87 g·（hm²·a）^-1和1.52 g·（hm²·a）^-1,分别占总输入通量密度的61.5%和60.3%,施肥和灌溉输入土壤Cd通量密度较低;Cd的输出途径均以地表水下渗为主,分别占总输出通量密度的75.4%和86.6%,农作物收割输出通量密度矿区高于对照区,且矿区内种植的水稻籽实Cd含量超标率更高,玉米籽实则未超标.整体上,矿区与对照区土壤Cd净输送通量密度分别为-3.05 g·（hm²·a）^-1和-4.05 g·（hm²·a）^-1,表现为土壤Cd淋失状态,但大气干湿沉降输入通量密度高值点和水稻籽实Cd含量超标点均主要分布在矿区周围,有可能对当地居民健康造成潜在威胁,因此建议通过监控和种植结构调整对该区域Cd污染土壤进行治理.     

安徽庐江潜在富硒土壤硒生物有效性及其影响因素

为研究潜在富硒土壤硒生物有效性,采集安徽庐江潜在富硒地区64组水稻及对应根系土壤样品,分析土壤理化性质、土壤养分、全硒、不同形态硒及大米硒含量,采用线性回归法探究土壤硒生物有效性的影响因素.结果表明,大米硒含量（记作Se_rice,下同）为0.037~0.120 mg/kg,土壤全硒含量（记作Se_tot,下同）为0.260~1.177 mg/kg,土壤硒以腐殖酸态硒（15.5%~44.7%）、强有机态硒（12.5%~53.3%）和残渣态硒（8.1%~68.5%）为主.土壤有效硫、有效磷通过提高强有机态、腐殖酸态和浸提性硒含量并促进水稻籽实（大米）对硒的吸收,而土壤阳离子交换量（cation exchange capacity,CEC）、速效钾、全铁和全锰通过降低水稻生物可利用态硒含量（包括水溶态、腐殖酸态、强有机态和浸提性硒）抑制水稻籽实（大米）对硒的吸收.Se_tot与Se_rice显著正相关（R=0.616,P < 0.01）,非残渣态硒含量与有机质含量之比（记作NRE-Se/OM）与Se_rice相关性最强（R=0.774,P < 0.01）.土壤NRE-Se/OM、有效硫、有效铁、全锰构建的多元逐步线性对数回归模型可解释水稻籽实（大米）吸收硒的76.0%的方差.因此引入变量NRE-Se/OM,并结合土壤有效硫、有效铁和全锰能有效评价和预测研究区土壤硒生物有效性.      

珠三角地区生活垃圾焚烧厂汞的排放特征

利用OH法对珠三角8家垃圾焚烧厂(6家采用炉排炉工艺,2家采用流化床工艺)进行烟气采样,同时采集飞灰、底渣、煤炭样品进行分析.研究结果表明,珠三角炉排炉焚烧烟气平均总汞(THg)排放浓度为(51.4±28.3) μg·Nm^-3,流化床为(19.5±13.6) μg·Nm^-3.炉排炉飞灰THg含量为6674 μg·kg^-1,流化床飞灰THg含量为2135 μg·kg^-1,底渣中炉排炉THg含量为70 μg·kg^-1,流化床为30 μg·kg^-1.飞灰中的汞含量要远远高于底渣.垃圾焚烧过程中炉排炉70.8%的汞由烟气排放,26.3%存在飞灰中,底渣中的汞仅占2.9%.流化床工艺烟气汞排放占总汞排放的33.2%.利用质量平衡法计算珠三角垃圾中汞含量平均值为0.293 mg·kg^-1,流化床工艺因添加燃煤所产生的汞排放占到垃圾焚烧总汞排放的31.6%.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.