重庆酸雨地区森林生态系统土壤、植被与地表水现状分析

酸沉降现象在重庆已成为一个严重的长期环境污染问题，本文根据东亚酸雨监测网土壤、植被监测技术规范的方法-研究了酸沉降对森林生态系统土壤、地表水以及植被的影响和危害。通过对土壤的分析：3个采样点的土壤pH值较低，这可能与大气S和N的输入有关，导致了土壤酸化。而南山采样点的盐基饱和度(BS)均值少于10％，盐基离子交换量(CEC)也较低．土壤中Al^3 浓度相对较高，土壤中C／N较低，南山可能存在土壤酸度增加的危险，以及土壤中Al浓度增高并伴有S或N沉降增加的危险。对地表水分析结果表明，南山采样点地表水的酸中和能力(ANC)较大，但是该采样点土壤剖面的盐基饱和度并不高，由此可推测该地表水可能是经由盐基离子丰富的土壤或岩石径流而来。通过对植被的分析，酸雨可能对杉木和柳杉这两种酸敏感性植物有一定的危害作用。     

我国酸雨地区水体会酸化吗——重庆水体酸化的调查

调查结果表明:重庆地区已出现酸化水体,水体 pH 值可低至4.57,ANC 低至77.92μg/L。酸化原因主要与酸沉降、集水区土壤及植被等有关。重庆的水体酸碱度的分布规律大致与土壤酸碱度分布一致。海拔在500m 以下的水体 pH 值多在7～8之间,甚至大于8,且 ANC 和HCO_3~-都高,有较强的缓冲性。而海拔500m 以上的水体,pH 值小于7.0,缓冲能力弱,在长期的酸沉降影响下,由于其集水区土壤缺乏缓冲能力,最终水体将面临进一步酸化。     

中国地表水酸化敏感性的区划

地表水体的酸化与集水区的许多环境因子密切相关,如土壤对酸的缓冲能力、基岩中和酸沉降的能力以及土地利用方式等.其中,土壤的抗酸化能力是关键因素.因此可以根据集水区土壤、基岩和土地利用方式等信息来评估地表水在不同流量下发生酸化的可能性.本研究成功地应用已有资料和数据得到了我国地表水对酸沉降的敏感性等级,并绘制了地表水酸化敏感性区划图.结果表明,我国大部分地表水对酸化并不敏感.极易酸化和较易酸化的地表水主要分布在东北的北部地区,占所有国土面积的2.67%,是该地区强酸性漂灰土、酸性母岩和针叶林植被共同作用的结果.对酸化敏感性为中级和低级,即不易酸化的地表水主要分布在东北暗棕壤地区和南方富铝土区域,占所有国土面积的15.2%.其余82.11%国土面积上的地表水对酸化不敏感,完全不可能发生酸化.北方地区主要是由于土壤的强缓冲能力,而在南方,石灰质土壤以及耕作农田的广泛分布是最重要因素.南方重酸雨区由于土壤对酸化并不很敏感,因此在短期内不会出现大面积水体酸化现象.由于东北近年来频频出现酸雨,因此东北的酸沉降必须及早防治,以免出现大面积酸化水体.     

应用稳态模型计算中国南方地表水的硫沉降临界负荷

为了解我国地表水体对酸沉降的响应情况,应用基于酸度平衡的稳态模型计算我国南方地表水的硫沉降临界负荷.文中根据我国实际情况获得了计算地表水背景硫酸盐浓度的经验公式.结果表明,我国南方绝大部分地表水的硫沉降临界负荷大于2.0 keq·(hm²·a)^-1,对酸沉降不敏感.临界负荷小于2.0 keq·(hm²·a)^-1的水体主要为部分山地水体.除了这部分山地水体外,其余水体的现状S沉降都没有超过临界负荷,表明它们在短期内不会发生酸化.超临界负荷的地区分布和临界负荷类似,均表现为东南沿海的福建、广东和江西3省低于西南和华中地区.对模型结果的不确定性分析表明,只要模型参数的取值在合适的范围内,参数的不确定性对结果造成的误差较小,可以接受.     

北京城市生态系统地表水硝酸盐污染空间变化及其来源研究

利用2009～2010年北京城市生态系统地表水10处监测点水环境监测数据,评价了北京城市生态系统地表水硝酸盐污染状况及其空间分布,结合水化学因子相关关系分析了硝酸盐的主要来源.结果表明,北京城市生态系统地表水硝态氮(NO3--N)质量浓度为0.7～7.6 mg.L-1,其中,位于北京市东南部的地表水监测点(东便门和通惠河)水体NO3--N质量浓度为7.0～7.6 mg.L-1,显著高于上游8个监测点NO3--N质量浓度(P<0.01);Cl-质量浓度为14.8～86.0 mg.L-1,东便门、通惠河地表水监测点水体Cl-质量浓度为81.5～85.0 mg.L-1,约为上游其他8个监测点的2.3～5.8倍.东便门、通惠河地表水监测点水体电导率(EC)、SO24-质量浓度也表现出同NO3--N、Cl-相似的变化规律,表明东便门、通惠河两处地表水监测点附近存在明显的污染源.相关分析表明,地表水Cl-/Na+和SO24-/Ca2+呈明显的线性相关,说明地表水NO3--N污染来源比较单一;水体中NO3--N/Cl-及NO3--N的质量浓度状况说明北京城市生态系统地表水NO3--N污染来源主要是城市污水,包括污水处理厂的废水、垃圾沥出液及生活污水.未来北京市地表水治理应重点关注东便门、通惠河等东南部下游水体污染治理.     

中国地表水酸沉降临界负荷的区划

为了解中国地表水体对酸沉降的响应情况,应用基于酸度平衡的稳态法研究中国地表水酸沉降临界负荷区划.结果表明,中国地表水硫沉降临界负荷呈较明显的地带分布.其中,大兴安岭北端水体的硫沉降临界负荷最低,大部分小于2 keq·(hm²·a)^-1,东北北部部分水体和秦岭-淮河以南大部分地区水体的硫沉降临界负荷介于2～10 keq·(hm²·a)^-1之间,其余地区水体硫沉降临界负荷普遍大于10 keq·(hm²·a)^-1.地表水酸度临界负荷的地区分布和数值大小类似于硫沉降临界负荷由于中国地表水酸度临界负荷普遍大于2 keq·(hm²·a)^-1,因此大部分地表水对酸化并不敏感,近期内不易酸化.     

浙江宁波天童地区酸性降水化学特征研究

为了解浙江宁波天童地区降水的化学特征、离子来源及酸性降水的成因,于2010年3月—2011年2月在该地区采集了90个降水样品,并运用离子色谱法分析其化学组分.结果显示,天童地区降水的酸化频率和酸化程度非常高,酸雨频率为97%,雨量加权pH平均值为4.37,离子浓度的大小顺序为SO24->NH4+>NO3->Ca2+>Cl->Na+>Mg2+>K+>F-,降水较清洁;降水pH值和各离子含量存在明显的季节变化,总体表现为冬、春季污染程度高于夏、秋季;SO24-/NO3-的浓度比值为1.9,表明该地区酸雨类型为硫酸和硝酸复合型;SO24-、NO3-、NH4+和部分Ca2+主要来自人为污染源,Na+、Cl-和大部分Mg2+主要来自海洋源,K+和大部分Ca2+则主要来自地壳源,海洋对天童地区降水离子组分影响较大,但对降水酸度影响并不显著;NH4+与SO42-(r=0.90)、NO3-(r=0.88)的相关性分别大于Ca2+与SO24-(r=0.67)、NO3-(r=0.73)的相关性,且NH4+/Ca2+的浓度比值为1.47,说明NH4+对降水酸性的中和作用大于Ca2+,与我国其他城市降水相比,天童地区降水中的碱性离子,尤其是Ca2+浓度较低,从而导致降水酸度高于北方地区和西南其他地区.     

北京市近二十年(1987～2004)湿沉降特征变化趋势分析

通过分析降水酸度和沉降量2个酸沉降控制指标,得出北京市近二十年(1987～2004)湿沉降特征变化趋势.研究发现,1998年以后北京市的湿沉降污染有严重的趋势.pH值逐年下降至5.52,酸雨频率逐年上升.湿沉降中的硫组分来自北京本地污染源排放的SO2和远距离输送.含氮组分对湿沉降的贡献作用明显增加.钙沉降是湿沉降中变化最大的因素,钙沉降量明显下降.1998年以后所采取的使总悬浮颗粒物浓度大幅下降的污染控制措施,可能直接导致了湿沉降酸化的加剧.酸沉降污染控制是一个复杂的控制过程,不能单纯地依靠控制本地的SO2排放量,北京市SO2排放量虽然得到了削减,但是湿沉降污染并未减缓.     

中国酸沉降:来源、影响与控制

总结我国酸沉降观测与模拟、来源与影响以及控制与成效,不仅能为未来我国大气污染治理提供科学依据,也能为国际酸沉降控制提供参考.本文回顾了40年来我国酸沉降研究的发展历程,对有关酸雨时空分布特征、致酸气体排放、土壤和地表水酸化、酸化缓冲机制、临界负荷区划以及酸雨控制对策等研究进展进行综述.我国酸雨污染经历了快速发展、污染缓和、再次恶化和持续改善4个阶段,与酸性气体——二氧化硫和氮氧化物的排放趋势相一致.我国酸雨区主要分布在长江以南及青藏高原以东的广大地区以及四川盆地,而不是排放最为集中的华北地区,反映出氨气和盐基阳离子排放的较强中和作用.作为酸沉降的主要危害,我国土壤酸化严重,而地表水酸化与欧美相比并不突出,原因是盐基阳离子沉降和硫氮转化（如硫酸根吸附和反硝化等过程）提供了特别的缓冲作用.随着二氧化硫排放优先于氮氧化物得到初步控制,我国降水化学组成由硫酸型转变成硫酸-硝酸-铵混合型,从而氮沉降,特别是铵沉降对我国土壤酸化的贡献越发显现.国家“两控区”划分、大气污染物总量控制与“大气污染防治行动计划”等政策的实施,有效控制了我国酸沉降的发展,酸化的土壤和地表水开始出现恢复的趋势.     

酸化及化学修复剂对森林土壤有机物淋溶的影响

选择我国重庆典型的酸化森林土壤,针对自然酸沉降条件下以及投加2种碱性化学修复剂(石灰石和菱镁矿)后土壤溶液中的溶解性有机物(DOM)动态变化展开观测,研究土壤酸化和化学修复对森林土壤碳库的潜在影响.为期3a的研究表明,修复剂加入后,由于土壤溶液pH值迅速升高,凋落物层DOM的淋溶在较短时间内有明显升高,但是这种效果难以持久;同时,投加修复剂后矿质土壤DOM的浓度显著降低,上层土壤溶液的DOC浓度由对照样地的(20.32±3.19)mg·L-1分别降低到石灰石样地的(15.69±2.39)mg·L-1和菱镁矿样地的(11.44±1.87)mg·L-1.矿质土壤溶液的DOC浓度可能与土壤溶液pH值呈负相关关系,与离子强度呈正相关关系.因此从长期来看,修复剂加入不会引起凋落物层有机质向矿质土层加速迁移,并可缓解由于酸化而导致的土壤有机物加速淋溶和碳库降低.     

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.