三江平原河水中铁的形态研究

采集三江平原河流(主要河流和沼泽性河流)水体,利用切向超滤和玻璃纤维滤膜技术分离铁的形态,研究了三江平原河水中铁的含量、形态和潜在络合竞争能力,以揭示湿地开垦对铁形态和输出通量的影响.结果表明,含有丰富有机质的典型沼泽性河流中可溶铁和酸性不稳定铁平均含量高达1.16和0.81 mg.L-1,是主要河流铁的重要补给来源,主要输送络合态铁(占可溶铁70.9%)和离子态铁(占可溶铁9.3%).河流中可溶态铁均以低分子量铁为主要迁移形态,在主要河流中低分子量铁占可溶态铁的68.7%,含量为0.13 mg.L-1,在典型沼泽性河流中占可溶态铁的82.2%,含量为0.88 mg.L-1;典型性河流中Fe3+含量是主要河流的3.1倍,Fe2+含量相差不大.通过菲咯嗪的配位竞争实验发现,络合态和胶体态铁中也存在Fe(Ⅱ)的结合形态;在典型沼泽性河流中,络合态铁具有更高的潜在络合竞争能力,更容易形成稳定不易分解的络合态铁.因此,三江平原湿地开垦导致沼泽性河流铁输出的减少,稳定络合态铁输出的减少直接影响铁的迁移距离,对近海铁的输送产生巨大影响.     

不同价态外源硒在石灰性土壤中的形态转化及其生物有效性

通过盆栽试验和连续浸提的方法,研究了外源硒酸盐(六价硒)和亚硒酸盐(四价硒)施入石灰性土壤后的形态转化及其对小白菜生物有效性的影响.结果表明,不同价态外源硒施入土壤后,土壤各形态硒含量均随外源硒添加量的增加而显著增大(p0.01).但两种外源硒在土壤中的形态变化明显不同,施入土壤的硒酸盐主要以可溶态形式存在,在土壤中的移动性相对较大;而亚硒酸盐主要以可交换态及碳酸盐结合态形式存在,并可由可溶态转化为其他土壤形态,从而降低了其生物有效性.Monod方程拟合结果表明,小白菜根系对六价硒的亲和能力显著大于四价硒,从而使得硒酸盐处理小白菜地上和地下部最大硒含量分别为亚硒酸盐处理的5倍和2倍,说明在石灰性土壤上硒酸盐比亚硒酸盐的生物有效性更高.另外,亚硒酸盐处理小白菜地下部最大硒含量是地上部的2.3倍,而硒酸盐处理小白菜地下部和地上部最大硒含量相近,说明小白菜根系吸收在硒累积和转运过程中起着至关重要的作用.     

松嫩平原西部稻田回归水中污染物的输出规律

对松嫩平原西部稻田回归水中盐分及N、P的可溶态、颗粒吸附态进行了分析。结果表明，洗盐水中主要污染物浓度相比灌溉水均明显增加，特别是Na^ 、HCO3^-等；随洗盐次数增加，洗盐排水中盐分等污染物浓度呈降低趋势。第2次洗盐排水中盐分、NO3^--N、TP、PO4^3--P浓度相比第1次分别降低了4％－50％、72％－92％、805－98％、9％－84％；洗盐水中盐分以可溶态为主，P以悬浮态为主，N的规律不明显，且N、P的形态变化受洗盐水中悬浮颗粒物及胶体多少的影响很大；洗盐回归水中污染物含量主要取决于土壤中的含盐量，耕作历史对其影响不明显，河水灌区回归水中Na^ 、HCO3^-一般低于井水灌区；生长季稻田回归水中污染物浓度受降雨、施肥等影响变化较大，但生长季回归水中可溶盐离子含量均明显低于泡田期。     

电解废渣中硒含量及赋存形态的研究

由于电解废渣原始、粗放的堆放,导致了大量重金属离子和有毒有害元素在自然环境中极易迁移并造成污染。为了掌握废渣中硒在多重氧化态中含量及形态分布,对进一步研究其在自然环境中的矿化、迁移规律及毒理学特性等意义重大,该实验采用了改进的SES连续浸提法,提取了电解废渣样品的水溶态、交换态、酸溶态、有机态、单质态及残渣态,以ICP-MS测定提取液中总硒含量,HPLCICP-MS研究了硒赋存形态。研究表明:CCT动态反应碰撞模式优化了ICP-MS检测环境,有效降低了多原子离子造成的干扰;电解废渣的硒含量极高,在自然环境中容易迁移,尤其是酸性环境下;前三态的硒含量超过了总硒的50%,且主要以毒性较高的亚硒酸盐形式存在,小部分以硒酸盐形式存在,含硒电解废渣存在较大的潜在环境风险。     

青阳县富硒土壤中硒的形态与水稻富硒的相关性研究

通过对青阳县富硒土壤中各形态硒的含量及种植水稻中硒的含量测定,研究青阳县富硒土壤中各形态硒的赋存分布特征,探讨水稻中硒含量及分布特点,同时对土壤中各形态的硒与水稻中硒的相关性进行研究。研究结果显示:青阳县富硒土壤中各形态硒的含量差异较大,其中强有机结合态、腐殖酸态和残渣态的硒,含量较高,占到总量的10%以上;而水溶态、离子态、铁锰态、碳酸盐态的硒含量较低,占总量比例皆低于5%;研究区水稻籽粒中硒的含量均值为0. 063 8 mg/kg高于全国平均水平0. 032 mg/kg,达到了国家富硒水稻的标准;水稻对土壤中硒的富集利用与土壤中硒的形态关系密切,当地土壤中水溶态和腐殖酸态的硒与水稻中硒的含量呈显著相关,而其它形态的硒相关性不明显,说明水稻吸收利用的主要是土壤中水溶态与腐殖酸态的硒。据此可以通过施加有机生物质的生产措施,增大土壤腐殖酸态硒的含量,提高土壤中有效硒的供给含量,以有利于水稻对土壤中硒的吸收富集,提高水稻中硒的含量。     

土壤中硒的形态

３种江苏省土壤,即潮盐土,灰潮土和黄棕壤原土硒和外加硒的形态分布研究结果表明,原土硒主要分布在残渣态Ｆ５上,３种土壤的Ｆ５的百分含量均达全量硒的８０％左右,而外加硒经４个培养后相对均匀地分布于可溶态Ｆ１（黄棕壤例外）,交换态Ｆ２、氨水提取态Ｆ３和残渣态Ｆ５上,２种处理下硒形态分布与土壤ＰＨ值,粘粒和游离氧化铁含量有一定关系,ＰＨ值是潮盐土≈灰潮土＞黄宗壤,粘粒及游离氧化铁含量是黄棕壤＞潮盐土＞灰质     

含磷污水淋滤条件下土壤中磷迁移转化模拟实验

以土柱实验为基础，结合磷在土壤中的化学转化机理，将磷在土壤中的形态分为可溶态磷、吸附态磷和沉淀态磷，根据磷在土壤中的迁移转化模拟实验，分析了这3种形态的磷在土壤中迁移转化的规律：可溶态磷进入土壤中，主要随水分作溶质迁移，在迁移的同时，不断转化为吸附态磷和各种沉淀态磷；吸附态磷由可溶态磷生成，并与可溶态磷一起发生沉淀反应生成沉淀态磷，但固着于土壤颗粒上，不发生迁移；沉淀态磷由可溶态磷和吸附态磷生成，在土壤中主要参与化学转化；沉淀态磷在土壤中有随水分迁移的现象。     

铁基硅盐对土壤环境镉砷赋存形态及转化影响

为探明铁基硅盐对土壤镉砷赋存形态影响及各形态间转化规律,采用室内长期淹水培养吸附实验,研究不同比例铁硅材料对土壤离子态镉砷活性影响;筛选适宜铁基硅盐(FS)配比同时添加腐殖酸(FSC)和金属氧化物(FSCa),明确复配处理土壤中镉砷分级形态转化程度.结果显示,铁:硅比值增加10%,土壤pH值平均降低0.35;F₂-S₈处理土壤离子态镉降幅71%;F₁₀-S₀处理土壤离子态砷降低59.9%,离子态镉砷含量与硅酸盐-铁盐施用量互呈反比;处理F₄-S₆和F₆-S₄之间镉、砷钝化率产生交点,约为25%~30%.土壤中镉主要以可溶态为主,占比58%;砷主要以铁铝氧化态和钙结合态为主,占比40%和23%.铁硅比例为5:5或5.5:4.5左右复配能有效将铝结合态砷和铁铝氧化态砷转变为钙结合态砷和残渣态砷,可溶态镉转化为碳酸盐结合态镉以及铁锰氧化态镉,同步降低土壤中镉砷的活性.     

三江平原水田灌溉-排水过程中铁形态变化及输出贡献

采集三江平原农田灌溉地下水、稻田积水、渠系排水、土壤侧渗水,并采用切向超滤技术分离水体中不同形态铁,分析在灌溉排水及地下侧渗水中铁的迁移特征,并估算水田排水中铁的输出贡献.结果表明,在灌溉排水过程中,铁主要以低分子量形态和酸性不稳定形态迁移,地下水中Fe2+含量占可溶态铁的80.45%;地下水抽取到稻田后Fe2+含量显著降低,络合态铁含量升高,稻田积水中络合态铁占可溶态铁的75.50%;稻田积水排入渠系后,络合态铁中不稳定弱配位铁含量降低13.58%,其他铁形态变化不大.稻田积水通过地下侧渗进入渠系,随侧渗水体深度加深,Fe2+含量升高,络合态和胶体态铁含量降低,地下侧渗水向渠系水主要提供络合态和胶体态铁.三江平原湿地水田化改变了水体中铁的输出形态,同时,排水过程中铁的输出也对河流形成补给,水田灌溉排水过程可溶态铁的输出通量约为390kg.a-.1km-2,输出系数为0.186,灌溉-排水过程中残留在稻田土壤中铁的量约为1460kg.a-.1km-2,残留在排水渠系土壤中铁的量约为250kg.a-.1km-2,这对三江平原水土环境产生了深远影响.     

大骨节病病区水-土体系中硒的赋存形态和吸附特征研究

以山西省运城市垣曲县历山镇大骨节病病区为研究区,在对研究区病区与非病区水土样品进行科学采集和硒含量水平准确测定的基础上,开展了土壤中硒赋存形态的连续化学浸提试验,研究了研究区病区与非病区土壤中7种硒赋存形态的分布特征,并利用等温吸附试验和吸附动力学试验,研究了研究区病区与非病区土壤/含水介质对硒的吸附特征。结果表明:研究区病区与非病区土壤/含水介质中总硒的含量水平基本相当;但与非病区相比较,研究区病区地下水饮用水源中总硒含量水平均偏低;研究区病区土壤中易溶态硒(水溶态硒和可交换态硒)平均含量低于非病区土壤;研究区病区土壤/含水介质对硒的吸附等温线符合Freundlich方程,吸附动力学为准二级动力学模型;研究区病区土壤/含水介质中较低的易溶态硒含量及其对硒具有较强的吸附能力是导致该地区地下水饮用水源中硒含量低的主要原因之一。     

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.