春季中国南黄海与东海海水中溶解氨基酸的分布和组成

以2011年3月南黄海与东海部分海域为研究对象,对其中48个站位海水样品的总溶解氨基酸(THAA)、溶解结合氨基酸(DCAA)、溶解游离氨基酸(DFAA)的浓度分布和组成进行了研究。结果表明:表层海水中THAA的平均浓度为2.981.72 mol/L(1.27~8.54 mol/L),DCAA的平均浓度为2.761.63 mol/L(0.91~7.70 mol/L),DFAA的平均浓度为0.310.21 mol/L(0.11~1.14 mol/L)。溶解态氨基酸水平分布的趋势大致呈现出近岸高、远岸低的特点,其中,DCAA与THAA分布规律基本一致。溶解态氨基酸的垂直分布特点为次表层与海水底层出现了高值区。春季南黄海与东海表层海水中溶解氨基酸主要由天门冬氨酸、谷氨酸、丝氨酸、甘氨酸及丙氨酸构成。表层海水中个体氨基酸间的相关性矩阵显示DFAA中有5对氨基酸之间存在显著正相关。研究发现海水中溶解氨基酸与Chl a、DOC、DIN等环境因子均无显著相关性。     

南海北部表层海水中溶解氨基酸的分布与组成研究

测定了2009年冬季南海北部表层海水中总水解氨基酸(THAA)、溶解游离氨基酸(DFAA)、溶解结合态氨基酸(DCAA)及叶绿素a、溶解有机碳(DOC)的浓度。调查海区THAA浓度的分布总体呈现近岸高、远岸低的特点,并且在陆坡处出现高值;DFAA浓度分布规律性则较差,但是在陆坡处也出现高值;DCAA周转速度较慢,是THAA浓度变化的主要控制因素(R=0.9935,n=48,P<0.0001)。冬季南海北部表层海水THAA主要由甘氨酸、丝氨酸、谷氨酸、丙氨酸和天门冬氨酸构成,它们占THAA的67.03%,DFAA、DCAA中的主要成分与THAA基本相同。个体氨基酸间的相关性矩阵分析显示THAA中有5对个体氨基酸间存在显著性正相关,DFAA、DCAA中分别有9对及6对个体氨基酸之间存在显著性正相关。溶解氨基酸与环境因子如叶绿素a和DOC之间均没有相关性。     

长江大通站溶解有机氮生物可利用性潜力及输入通量

根据2012~2013年度隔月对长江大通站的6次调查,分析了长江水体中溶解态总氮(TDN)的构成,包括溶解无机氮(DIN)及溶解有机氮(DON)中的尿素、自由态氨基酸(DFAA)、结合态氨基酸(DCAA)的构成和丰度,并评价了DON的生物利用性潜力,估算了不同形态氮的输入通量.结果表明,受稀释作用和悬浮颗粒物吸附影响,长江水体中DON浓度呈现出春冬季高、夏秋季低的变化特征,平均浓度为(33.28±21.35)μmol/L,占TDN比例平均为20.05%±13.53%;DON中组分尿素、DFAA和DCAA占DON的氮摩尔占比分别为21.94%±19.89%、0.84%±0.52%、3.68%±2.61%.其中,尿素浓度受季节性施肥灌溉影响,与径流量呈现出明显的正相关.总溶解态氨基酸(TDAA)占溶解有机碳(DOC)的碳摩尔分数和氨基酸降解指数均表明长江水体中DON具有较高的生物可利用性,且呈现出春夏季高、秋冬季低的变化趋势.DON的年输入通量为42.04万t,约占TDN年输入通量的17%.其中,具有高生物可利用性的尿素、DFAA、DCAA分别占DON年通量的15.50%、0.64%、2.80%.上述结果表明,长江输入的DON具有相当高的生物可利用性,对长江口及其邻近海域富营养化的贡献不可忽视.     

沼液中溶解游离氨基酸的测定——柱前衍生-反相高效液相色谱法

针对沼液特点开发pH值调节（pH 10.2）旋蒸浓缩（去除氨氮和挥发性生物胺）联合3K Millipore超滤离心分离的预处理方法.并以邻苯二甲醛（OPA）和氯甲酸芴甲酯（FMOC-Cl）为柱前衍生化试剂,结合反向高效液相色谱和荧光检测分析,对沼液中溶解游离氨基酸（DFAA）进行了定性和定量考察.该方法保证了各氨基酸在一定浓度范围内呈现良好的线性关系（R²均大于0.99）,标准样品中所选用的24种氨基酸,除谷氨酸回收率为70.5%外,其它氨基酸回收率为89%～115%,相对标准偏差为1.1%～5.0%.用所建立的方法对样品中溶解游离氨基酸的测定结果为：原料即剩余污泥中的溶解游离氨基酸量为2.0mol/L,5%和20%含固率反应器的沼液中的溶解游离氨基酸量分别为0.04mol/L和1.94mol/L,且种类不同,初步表明了不同厌氧消化反应系统中氨基酸的利用和产生机制的差异.     

高效液相色谱-串联质谱法测定海水中孔雀石绿及其代谢物

建立了海水中孔雀石绿及其代谢物的高效液相色谱-串联质谱检测方法,取500 mL海水样品,以二氯甲烷萃取,旋转蒸发浓缩后,以甲醇定溶,经0.45μm滤膜过滤后,应用高效液相色谱-串联质谱测定海水中孔雀石绿及其代谢物残留量.本方法MG和LMG线性范围为0.5～100μg/L,相关系数为0.9978和0.9970,仪器检出限为0.2μg/L,定量限为0.5μg/L,MG回收率为74.0%～95.0%,LMG回收率72.0～91.5%.该方法灵敏度高、准确性好,适用于海水中痕量孔雀石绿及其代谢物的检测.     

浙江近岸海域海水和沉积物中铬形态分布特征研究

本研究在浙江近岸4个海域开展同步采样和观测,分析海水和沉积物中铬（Cr）形态分布特征。结果表明,表层海水总Cr浓度范围为0.405～0.653μg/L,Cr(Ⅵ)浓度范围为0.009～0.087μg/L;底层海水总Cr浓度范围为0.426～0.638μg/L,Cr(Ⅵ)范围为0.005～0.099μg/L,海水中Cr形态含量分布与深度无相关性。沉积物中Cr含量范围为50～82 mg/kg,以残渣态为主;有效态Cr的含量大小依次为有机结合态Cr>铁锰氧化物结合态Cr>离子交换态Cr>碳酸盐结合态Cr;沉积物中水溶态Cr(Ⅵ)含量范围为2.99～11.71μg/kg,小于0.02 mg/kg。上述结果表明,浙江近岸海域环境存在一定程度的Cr污染,但水溶态Cr(Ⅵ)含量低,潜在风险较小。     

全自动固相萃取-串联四级杆质谱测定水中16种多环芳烃

建立了采用全自动固相萃取(SPE)净化,浓缩,气相色谱-串联四级杆质谱二级质谱监测(GC-QQQ-MS/MS)同时测定水中16种多环芳烃的方法。通过优化样品前处理条件和仪器分析条件,取样体积为1.0L时多环芳烃的最低检出限为0.06~0.27μg/L,最低定量限为0.21~0.91μg/L。针对三组加标浓度为10μg/L、100μg/L、500μg/L的样品,平行测定6次,平均回收率在79.84%~108.43%,相对标准偏差在3.17%~9.27%。     

紫外分光光度法检测石油污染海域中有机组分的研究

石油泄漏流入海洋对环境和人类社会造成巨大威胁,实时监测存在原油泄漏风险海域的有机物非常必要。本文针对深圳市大鹏湾周边工业园区海域的石油污染监测建立紫外分光检测法。结果表明：用紫外分光光度法测定近海域油类芳香环组分含量,校准曲线相关系数r=0.9999;检出限为1.6μg/L,测定浓度为14.2±1.3 mg/L的有证标准样品,测定值为13.1～14.1 mg/L,测定结果均符合要求;测定近海的天然样品的精密度为2.7%,加标回收率在90.5%～109%之间。本实验室条件可精确测定近海、入海口中油类含量。     

快速溶剂萃取GC/MS-SIM法测定土壤中15种多环芳烃

文章采用全自动快速溶剂萃取仪,对土壤实际样品中多环芳烃进行萃取,将萃取液进一步浓缩、脱水、净化、定容,最后通过GC/MS-SIM法对其中15种多环芳烃浓度进行检测。该方法测定的15种多环芳烃在5.00～800.00μg/L曲线浓度范围内平均相对相应因子小于20%,方法检出限为0.02～0.17μg/kg,测定下限为0.07～0.69μg/kg,目标物相对标准偏差分别为2.7%～7.9%,土壤实际样品加标回收率为42%～128%。该方法相对国家标准检测方法检出限低,灵敏度和回收率高,准确、快速、便捷,适合于大批量土壤检测工作。     

上海大气冷凝水化学特性分析

2011年3月8日至4月11日期间利用新研制的大气冷凝水采样器收集了上海大气冷凝水样品.从冷凝水的化学组成及常见大气湿沉降的比较、冷凝水离子间的相关性、冷凝水离子浓度随时间变化等方面,分析了上海大气冷凝水的化学特性.结果表明,上海大气冷凝水pH值介于6.1~7.2,加权均值为6.5,多呈弱酸性;NH4+和SO42-是含量最高的2种离子,浓度分别为139.7μeq/L和125.7μeq/L,SO42-是主要致酸离子;NO2-含量为9.9μeq/L,比NO3-(9.5μeq/L)略高,且所有冷凝水样品中NO2-检出率为100%;4种低分子量有机酸MSA-(6.0μeq/L)、CH3COO-(5.9μeq/L)、C2O42-(3.9μeq/L)和HCOO-(3.7μeq/L)占阴离子总量的8.5%,含量远高于上海雨水;Ca2+(19.2μeq/L,4.0%)、Mg2+(4.9μeq/L,1.0%)含量比同期雾水低2~3个数量级;冷凝水离子浓度随时间变化较大,这与光化学反应、春季逆温等有关.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.