天津市大气降水化学组分变化趋势及来源研究

2001—2013年对天津市降水样品进行了采集,分析了p H、电导率(EC)、主要离子浓度(SO2-4、NO-3、Cl-、F-、NH+4、Ca2+、Mg2+、Na+、K+).结果表明:2001—2013年,降水的雨量加权平均p H、EC分别为5.48、87μS·cm-1.降雨的p H、EC及总离子当量浓度呈现上升趋势,酸雨频率呈现下降趋势.降水中各离子雨量加权平均当量浓度排列顺序为:SO2-4Ca2+NH+4NO-3Cl-Mg2+Na+F-K+,SO2-4、Ca2+、NH+4和NO-3是降水中的主要离子,占离子总量的84.8%.SO2-4雨量加权平均当量浓度表现为先轻微上升,后显著下降趋势.NO-3、Ca2+雨量加权平均当量浓度表现为明显上升趋势.NH+4雨量加权平均当量浓度显示为下降趋势.F-、Cl-、K+、Mg2+、Na+等雨量加权平均当量浓度变化趋势基本保持平稳.SO2-4对总阴离子的分担率、NH+4总阳离子的分担率均呈现下降趋势.NO-3对总阴离子的分担率、Ca2+对总阳离子的分担率均呈现明显上升趋势.[NO-3]/[SO2-4]、[Ca2+]/[NH+4]呈现出明显上升趋势.富集因子计算结果表明:Ca2+主要来自地壳.Mg2+和K+部分来自海源输入,但绝大部分来自地壳.大部分Cl-来自海源的输入,其余小部分来自地壳和人为排放.降水中SO2-4、NO-3主要来自人为活动.     

西藏羊卓雍湖流域土壤环境中物质含量与流失的初步探讨

本文利用随机布点法,布点采集西藏羊卓雍湖（羊湖）流域的土坯样品,测定了SiO2、Si、Al2O3、Al、TFe2O3、Fe、Ca、Mg、K、Na、MnO、SO3等12种物质含量。结果表明,七种主要类型土壤相互间元素含量有一定的差异;同一土壤中元素含量波动较大。本文还对羊湖流域的土壤进行了淋洗实验,计算了八种离子的淋失量。      

北京城区大气金属元素干湿沉降特征

为研究北京市大气中金属元素的干湿沉降特征,评估不同观测方法的差异性,于2014年5月至2015年4月在北京城区同步采集了混合沉降和湿沉降样品.利用电感耦合等离子体质谱仪(ICP-MS)测定了样品中19种金属(Na、Mg、Al、K、Ca、V、Cr、Mn、Fe、Cu、Zn、As、Se、Mo、Cd、Sb、Tl、Th和U)的浓度.结果表明,混合沉降样品中各金属浓度[7 160.68μg·L~(-1)(Ca)～0.02μg·L~(-1)(Th)]普遍高于湿沉降样品[4 237.74μg·L~(-1)(Ca)～0.01μg·L~(-1)(Th)].两种样品中相同金属的富集因子差异较小,其中Cu、As、Tl、Zn、Cd、Se和Sb的富集因子均大于100,表明这些重金属主要来自人为污染源.气团轨迹分析表明,北京城区降水过程主要受偏南气团的影响,其中来自西南气团的降水样品中Ca、Mg、Fe、Al、Cu、Mo、U和Th等金属浓度较高,而来自南部的气团K、Zn、Mn、Sb、Cd和Tl等金属浓度较高.观测期间大气中金属元素的混合沉降通量变化于3 591.35 mg·(m~2·a)~(-1)(Ca)～0.01 mg·(m~2·a)~(-1)(Th),湿沉降通量变化于1 847.78 mg·(m~2·a)~(-1)(Ca)～0.01mg·(m~2·a)~(-1)(Th).混合沉降与湿沉降差减得到19种金属的干沉降通量变化于1 743.57 mg·(m~2·a)~(-1)(Ca)～0.01mg·(m~2·a)~(-1)(Th).大气颗粒物的粒径大小对金属的干湿沉降过程具有重要影响.     

典型酸雨城市降水、降尘中阴阳离子分布特征及其相关性

对贵州省都匀市2013年3月—2014年2月降水和降尘样品的p H值及主要阴阳离子(NH+4、K+、Ca2+、Na+、Mg2+、F-、Cl-、NO-3、SO2-4)进行测定,分析其分布规律及相应离子之间的相关性.结果表明,降水和降尘水溶液p H的加权平均值分别是5.47、5.06.Ca2+、SO2-4是降水和降尘的主要离子,均值分别是141.29μeq·L-1、191.67μeq·L-1,52022.33 mg·kg-1、87590.52 mg·kg-1.降水和降尘中的总离子浓度、[SO2-4]/[NO-3]、[SO2-4+NO-3]/[Ca2++NH+4]以及NH+4、K+、Na+、F-、NO-3、SO2-4浓度在冬季达到最大,且其[SO2-4]/[NO-3]均都大于3,表明都匀市酸雨类型仍为燃煤型.从季节的变化上看,降水和降尘中的NH+4、K+、Na+、F-、SO2-4、Ca2+、Mg2+存在明显的相关性,相关系数|r|﹥0.70.降水和降尘中[SO2-4+NO-3]/[Ca2++NH+4]表现出相似的季节变化规律,[SO2-4+NO-3]/[Ca2++NH+4]与p H相关系数|r|﹥0.80,与降雨量、污染物来源、能源使用等有关.     

青岛近海不同天气状况下大气气溶胶中金属元素浓度分布特征研究

为探究青岛近海不同天气下气溶胶中金属元素的浓度分布特征,于2012年4~5月,2012年8月~2013年3月在青岛近海采集了总悬浮颗粒物(TSP)样品,利用电感耦合等离子体质谱法(ICP-MS)和电感耦合等离子体原子发射光谱法(ICPAES)分析了主要微量金属元素.结果表明,Al、Ca、Fe、Na、K和Mg是TSP中主要的金属元素,质量浓度占所测元素总浓度的94.2%.TSP及金属元素浓度月变化明显,Fe、Al、K、Ca、Mg、Zn、Ba、Mn、Ti、Sr和Li均在11月和1月浓度最高,Be、Sc、Co、Ni和Cr在1月最高,Na在8、11和2月较高,12月最低,Pb在1月和2月最高,8月和12月最低.富集因子表明Be、Co、Al、Ca、Fe、K、Mg、Mn、Sr和Ti主要受自然源影响,Li、Cr、Ni、Zn、Ba和Na除受自然源外,还受部分人为源影响,Pb主要来自人为源.不同天气状况对TSP及其金属元素浓度影响较大,除Ti外,所测元素浓度均在烟雾天最高.与晴天相比,烟雾天除Ti外,其余元素均升高,增幅为1~4倍,雾天Li、Be、Cr、Ni、Al、Fe、Mg和Mn变化不大,Pb和Na升高较多,Co、Ca和Ti降低较多,霾天Cr、Co和Ti降低,其余元素浓度升高,增幅为1~3倍.大部分元素在晴天富集因子最小,雾天富集因子最大.Ni、Zn、Ba、K、Na、Pb和Sr富集因子为晴<霾<烟雾<雾,Fe和Mn为晴<烟雾<霾<雾,Al和Mg为晴<雾<霾<烟雾,其余金属不同天气下富集因子的变化规律各不相同.     

南昌市秋季大气PM2.5中金属元素富集特征及来源分析

采集2013年秋季南昌市6个不同区域的大气PM_(2.5)样品,分析PM_(2.5)质量浓度及其中18种金属元素(Mg、Al、K、Ca、Ti、V、Ba、Co、Cr、Mn、Fe、Ni、Cu、Zn、Cd、Pb、As、Hg)的富集特征,并用多元统计分析法探讨了PM_(2.5)中上述元素主要来源.结果表明,南昌市秋季大气PM_(2.5)日均质量浓度满足《环境空气质量标准》(GB 3095-2012)二级标准限值(≤75μg·m~(-3)).Mn、Ti、Al和V的富集因子小于1.0,表明这些元素基本没有富集;Fe、Cr、Co、K、Mg、Ba、Ca、Cu和As的富集因子范围为1.7~7.8,表明这些元素受到自然源和人为源的共同影响;Hg、Zn、Pb、Ni和Cd的富集因子范围为21.9~481.2,表明这些元素受到明显的人为污染.综合相关分析、主成分分析和聚类分析结果表明:PM_(2.5)中Mg、K、Al、Ca、Ti主要来源于土壤及建筑尘;As、Hg主要来自燃煤;Ba、Ni、Mn主要来自金属冶炼排放;V、Cu、Fe、Cd、Pb、Cr、Co主要来自交通源;Zn主要受金属冶炼和燃煤的影响.     

柄海鞘中矿物元素含量分析

采用微波消解—火焰原子吸收分光光度法对烟台海域柄海鞘中Mg,Fe,Ca,Mn,Zn,Co,Cu,Ni,Pb,Cr,Cd共11种矿物元素的含量进行了测定。方法的相对标准偏差为0.07%～2.85%,回收率95%～103%。柄海鞘的外背囊和内囊中含有人体必需的矿物元素Cu,Zn,Fe,Mn,Co,Ni,Cr,Ca,Mg和少量的有害元素Cd和Pb,它们的含量顺序依次为:Mg>Mn>Fe>Ni>Ca>Zn>Cu>Cr>Pb>Co>Cd。大规格的海鞘中的各种矿物元素含量均高于中、小规格的海鞘。各种元素在外被囊中的含量要高于内囊。     

岩浆岩岩石化学分析计算的新方法

为了划分岩浆岩的岩石化学组,提出了利用多维空间的问题。其空间坐标是:石英标准度[S=(Si-(2Ca″+3Na+3K—Na′))/M],碱度[NKS=(Na+K)/Si]、碱度类型(K/Na)、浅色度[AF=(Al+Al′)/M]、铁度(Fe/Mg)、钙-铝度[CAF=(Ca′+Al′)/(Fe+Mg)。式中Ca′、Al′、Na′对长石矿子来说是过剩的钙、铝和碱,Ca″为长石和似长石中的钙,M=Fe+Mn+Mg+Ca′+Al′+Ti。岩浆岩样品所占据的多维空间区的特征是岩石化学参数具有平均的和标准的偏差。确定所研究的样品属于哪一种标准属性,要通过关于多维平均偏差平衡的假设检验的方法或者利用A.提出的均一性标准来完成。     

四川省典型工业行业PM_(2.5)成分谱分析

利用荷电低压颗粒物撞击器(ELPI+)对四川省水泥行业、玻璃行业、陶瓷行业、砖瓦行业、燃煤锅炉、生物质锅炉、电厂、钢铁行业等典型行业开展排放特征测试,通过组分分析,获取各行业PM2.5成分特征谱。结果表明:(1)水泥、玻璃、陶瓷、砖瓦等建材行业均以Si、Ca、Mg等元素为主要排放组分,双碱法脱硫SO42-排放占比高于其他脱硫工艺;(2)电厂PM2.5中SO42-、Ca2+、NH4+、Mg和Si为特征组分;燃煤锅炉中OC、Al、Si和Ca等为特征组分;(3)OC和EC是生物质锅炉PM2.5主要排放组分,成型生物质燃料锅炉中K排放占比也较高,非成型生物质燃料锅炉中Cl-排放占比为所有行业中最高;(4)钢铁行业中Ca含量最高,为18.11%,其次为SO42-、Na+和Fe。     

钱塘江杭州段沿岸土壤中铁锰的分布特征

对钱塘江杭州段沿岸土壤11个采样点中的铁锰及相关指标进行了系统研究.结果表明,土壤中Fe,Mn的平均质量分数分别为1.97％(425 mg/kg),变异系数分别为13％,37％.土壤pH值范围在4.64～7.56,处于酸性-弱碱性.变化幅度较大.矿质元素Al的平均质量分数5.68％,变异系数11％.K,Na,Mg的平均质量分数分别为1.76％,1.21％,0.76％:3个指标的变异系数均不超过25％.Ca的质量分数范围为0.55％～1.85％,变异系数较大,为33％.土样矿质元素聚类分析结果表明,钱塘江沿岸土样分为3类:第1类Fe,Mn,Al最低,Ca,Na,Mg较高,主要位于萧山;第2类Fe,Mn,Al次之,Ca,Mg最低,主要位于桐庐以及富阳东郊;第3类Fe,Mn,Al相对较高,主要位于富阳.相关性分析结果表明.Fe与Mn,Al呈极显著相关,Mn与Al呈显著相关,Ca与Na,Mg呈极显著相关,矿质元素与粉砂粒(2～20μ m)的相关性较好,而与粘粒不具相关性.     

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.