不同作物根系多环芳烃吸收特征差异的比较研究

为选育不/少或超量吸收多环芳烃(PAHs)的植物品种进而进行农产品的安全生产和PAHs污染环境的植物修复,以菲为PAHs的代表物,比较了水培条件下3种常见农作物(大豆、小麦、胡萝卜)根系吸收菲的动力学特征差异.结果表明,3种作物根系对水培液中的菲有明显的吸收和累积作用,且菲的吸收量随时间延长而增加,整个吸收过程可分为快速吸收和慢速吸收2个阶段;3种作物根系菲吸收能力的大小为大豆>胡萝卜>小麦;作物根系吸收菲量与吸收时间的关系可以用Elovich方程拟合,大豆、胡萝卜和小麦根系菲吸收速率常数分别为4.31、4.10和2.84 mg.(kg.h)-1;作物根系菲吸收的动力学曲线可用米氏方程表征,大豆、胡萝卜和小麦根系菲的Km值分别为0.117、0.124和0.540 mg.L-1;根系菲吸收会导致营养液pH升高,pH升高的趋势和吸收速率常数k与Km值相对应,且与3种作物根系吸收能力的大小一致.因此可用根系吸收速率常数k、米氏常数Km值和水培液pH的变化表征作物根系吸收PAHs的能力差异,且从受影响因素的多寡角度考虑,吸收速率常数k和米氏常数Km较pH变化更适合.     

几种多环芳烃的植物吸收作用及其对根系分泌物的影响

采用水培试验方法,以多年生黑麦草(Lolium multiflorum Lam.)为供试植物,研究了芘、菲、苊和萘的植物吸收作用及其对根系分泌物的影响.结果表明,黑麦草能明显吸收富集多环芳烃(PAHs);随培养液中PAHs浓度的升高,其在黑麦草根和茎叶中的含量增大,且根的PAHs含量、富集系数要远大于茎叶.芘、菲、苊、萘污染胁迫下,黑麦草根系分泌物中可溶性有机碳、草酸和可溶性总糖的含量均高于无污染对照.供试污染浓度范围内,随着培养液中菲、苊、萘浓度提高,可溶性有机碳、草酸及可溶性总糖的分泌量增大;但在芘胁迫下,与污染对照相比,分泌量的增加幅度随着芘浓度的升高则呈先增大后减小的趋势.在较低污染强度下,供试PAHs对根系分泌物的促分泌效应由强到弱依次为芘、菲、苊和萘.4种PAHs对可溶性糖类的促分泌作用最强,其分泌量的增加幅度明显大于可溶性有机碳和草酸.     

水溶性有机物对植物吸收菲的影响及其机制研究

水培小麦试验研究了水溶性有机物(DOM)对植物吸收多环芳烃(菲)的影响,并对其机制进行了初步探讨.结果表明:菲抑制了植物的生长,抑制率达到18.01%,DOM可加剧菲对植物生长的抑制作用,使生长抑制率升至24.38%;植物可吸收和富集水培液中的菲,而DOM能明显地促进植物对菲的吸收和富集作用,使得其根部浓缩系数高达37.63 L·kg^-1,同时DOM还能促进根部吸收的菲向地上部转运;植物在吸收菲的同时,使得营养介质的pH显著升高,DOM与菲存在显著的协同交互作用,可使介质pH值的升高     

土壤中芘、菲、萘、苯对小麦的生态毒性影响

采用生物培养和物理化学试验,研究了芘、菲、萘、苯对土壤中小麦的生态毒性.结果表明,芘对小麦根毒害的敏感区间浓度为0～300mg/kg;土壤中芘的50%小麦根伸长抑制率浓度为500mg/kg.PAHs的生态毒性与其溶解度和结构有关,且随着溶解度的增大和苯环数目的减少而增加.PAHs会降低土壤的土水势,土水势降低的程度随着PAHs溶解度的增大而增大.     

限制分配模型预测黑麦草吸收PAHs

采用水培体系检验了限制分配模型预测黑麦草同时吸收苊、芴、菲和芘4种多环芳烃(PAHs)的准确性.结果表明,限制分配模型能够较好地预测黑麦草吸收积累PAHs的程度.但由于该模型仅考虑根部传输,忽略了叶面吸收,导致模型对茎叶中PAHs含量预测的准确性较差.根系和茎叶的预测误差(预测值与实测值之差除以实测值的百分数)分别小于57.4%和98.5%.若考虑叶面吸收对模型预测的影响,则能显著降低茎叶中4种PAHs的预测误差.由于叶面吸收的影响随PAHs脂溶性升高而增大,预测误差降低程度为芘>菲>芴>苊,其中芘的最大预测误差由98.5%下降至69.4%.     

复配表面活性剂APG/SDBS对菲、芘的增溶特性

研究了烷基糖苷(Alkyl Polyglycoside,APG)和十二烷基苯磺酸钠(Sodium Dodecyl Benzene Sulfonate,SDBS)混合体系的不同复配比α(α=C_(SDBS)/C_总)、pH和温度(T)对菲和芘的溶解行为的影响.结果表明,当α=0.4时,复配体系具有最小的表面张力(γ)和临界胶束浓度(Critical Micelle Concentration,CMC),且菲、芘的表观溶解度(Sw)、增溶倍数(Sw/S*,S*为菲或芘在纯水中的溶解度)和摩尔增溶比(Molar Solubilization Ratio,MSR)均达到最大值.菲、芘的Sw随pH增加先增加后缓慢降低,pH=9时达到最大.随温度的升高,菲、芘的Sw逐渐增加,当T≥40℃时,增加变缓;因此,该复配体系的最佳反应条件为α=0.4、T=40℃、pH=9.本研究可为多环芳烃(PAHs)污染土壤的淋洗修复提供科学依据.     

Tween80对植物吸收菲和芘的影响

以水培体系模拟研究了非离子表面活性剂Tween80对黑麦草吸收菲和芘的影响.结果表明,当培养液中菲和芘的起始浓度分别为1 00mg·L-1和0 12mg·L-1时,0～105 6mg·L-1范围内,低浓度Tween80可促进根和茎叶吸收菲和芘,Tween80浓度为6 6mg·L-1时促进作用最为明显,根和茎叶中菲和芘含量、富集系数为无表面活性剂对照处理的116%～216%;而高浓度则有抑制作用.当培养液中菲和芘的起始浓度为相应Tween80浓度下的表观溶解度时,根和茎叶中菲和芘含量随Tween80浓度上升明显增大,Tween80的增溶作用有利于根和茎叶对菲和芘的吸收.     

非一阴离子表面活性剂对PAHs的增溶作用及无机盐的强化效果研究

文章研究了几种非离子和阴离子表面活性剂在单一或混合条件下对多环芳烃（PAHs）萘和菲的增溶作用,并分析了无机盐对表面活性剂增溶PAHs的强化效果.结果表明,在相同浓度条件下,非离子表面活性剂对菲和萘的增溶效果均高于阴离子表面活性剂,其增溶能力大小顺序为：Tween 80 ＞TX-100＞ Tween 20＞ SDS＞SDBS.将非离子与阴离子表面活性剂混合后,对萘和菲的增溶作用大于单一阴离子表面活性剂而小于单一非离子表面活性剂,且增溶效果随着非离子表面活性剂比例的增加而增大.低浓度（0.03 mol/L）的NaCl和Na2SO4可大幅度促进表面活性剂对萘和菲的增溶效果,但随着无机盐浓度的提高,对增溶效果的促进作用不明显.     

大豆和小麦根系对菲的吸持作用及其生物有效性

不同作物根系对多环芳烃(PAHs)的吸持作用及其生物有效性研究有助于深入揭示PAHs在生态系统中的环境行为和科学评估PAHs的生态风险.然而,不同作物根系吸持PAHs的差异性及其生物有效性鲜有报道.为此,本研究以菲作为PAHs的代表,探究了不同条件下大豆和小麦根系对菲的吸持/解吸及其吸持菲的有效性.结果表明,根系菲吸持随时间的变化表现为:活体根处理先增加再降低而后趋于平衡,这与活体根系存在菲转运延迟有关;灭活根和烘干根处理则先增加而后趋于平衡.根系的比表面积越大,脂肪含量越高,菲的吸持速率越快.不同菲浓度条件下,各处理根系菲的吸持量均随平衡浓度的增加而增大,Henry吸附等温式拟合R2均大于0.973,灭活根和烘干根用Freundlich吸附等温式拟合效果更好,小麦根系的Langmuir吸附等温式拟合效果优于大豆根系,说明分配作用和表面吸附共同控制作物根系菲的吸持,而活体根系与菲存在特殊的键合作用,其拟合效果较差.脂肪含量越高、含水率越高、膜的通透性越大,根系的吸持容量也越大.吸持在根系上的菲的解吸率的大小顺序为活体根烘干根灭活根;大豆各处理根系小于相应的小麦根系.不同根系吸持菲的生物有效性与解吸结果一致,因此可以用解吸率评价其生物有效性.研究结果可为作物根系吸持PAHs的当季和后茬作物有效性评估提供依据.     

麻疯树籽壳生物质炭的制备及其吸附水中PAHs性能研究

麻疯树籽壳经磷酸处理,在300~700℃下炭化处理50min,制备了麻疯树籽壳生物质炭.以萘、蒽、菲、芘4种多环芳烃(PAHs)为目标物,考察了吸附剂投加量、反应时间、反应温度等因素对麻疯树籽壳生物质炭吸附性能的影响,探讨了麻疯树籽壳生物质炭对4种PAHs的吸附效果及机理.结果表明,随炭化温度升高,生物质炭的比表面积逐渐增大;在25℃、生物质炭投加量为0.15g、吸附时间为60min的条件下,萘、蒽、芘和菲的去除率分别为97.4%、94.6%、93.1%和92.1%.麻疯树籽壳生物质炭对4种PAHs的吸附机理服从准二级动力学方程,吸附等温线服从Langmuir方程,萘、蒽、芘和菲的饱和吸附量分别为8.849、8.547、8.097和7.633mg/g.     

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.     

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.     

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.     

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.     

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.     

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.     

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.