基于DPeRS模型的海河流域面源污染潜在风险评估

运用DPeRS（diffuse pollution estimation with remote sensing）模型对海河流域面源污染物的空间分布特征和污染来源进行遥感像元尺度解析,结合地表水质评价标准,构建了面源污染潜在风险分级方法,评估了海河流域面源污染潜在风险.结果表明：污染量上,海河流域总氮（TN）、总磷（TP）、氨氮（NH₄⁺-N）和化学需氧量（COD）面源污染排放负荷分别为429.2、25.7、288.3和1017.0 kg ·km^-2,入河量分别为2.5万t、1597.2 t、1.7万t和6.6万t;污染类型上,农田径流是海河流域最主要的氮磷型（TN、TP和NH₄⁺-N）面源污染源,对于COD指标,城镇生活是首要污染类型,其次为畜禽养殖;空间分布上,海河流域中部和南部地区面源污染负荷较高,此区域也是该流域面源污染高风险集中分布区,氮磷型面源污染高风险区域分布相对较为集中,化学需氧量型则较为零散;海河流域有36%以上的区域存在氮磷型面源污染风险,有2.94%的区域存在化学需氧量型面源污染风险.     

沱江流域总氮面源污染负荷时空演变

根据四川省沱江流域水环境受总氮（TN）面源严重污染的现状,采用排污系数法估算2007~2017年该流域来自各面源污染源的TN污染负荷,并利用空间重心统计法和空间分析技术揭示沱江流域TN污染负荷时空分布特征及转移趋势,以期为相关部门精准防控和预警沱江流域面源污染提供理论依据.结果表明,2007~2017年畜禽养殖污染源对整个流域的TN污染负荷贡献率每年均在45%以上,是TN面源污染的主要污染源.农村生活和农村生活垃圾污染源的贡献率呈逐年减少趋势,农田固废和农田径流污染源的贡献率则呈增加趋势.TN总污染负荷总体呈下降趋势,2010年污染负荷最大,达到5.7×10⁴ t,2017年最小,为4.69×10⁴ t.污染负荷在空间上的异质性变化及降雨径流的不均匀分布驱使畜禽养殖、农田固废类和农田径流污染源的TN污染负荷重心由西北向东南方向移动,流域东南部是畜禽养殖、农田固废类和农田径流TN污染的重点防控区域.东南部各区县的农业人口大量向城市人口转化,进而驱动农村生活和农村生活垃圾污染源的TN污染负荷重心由东南向西北方向转移,其转移范围高达66.35 km²,由此确定的最小边界圆是污染源污染负荷变化的重点识别区域,沱江流域西北部则是农村生活和农村生活垃圾TN污染的重点防控区域.本研究拓展了环境科学领域对流域污染负荷时空演变的探究方法,对于改善水环境质量,促进流域经济可持续发展具有重要意义.     

基于机器学习的长江流域农田氮径流流失负荷估算

定量解析长江流域农田氮径流流失特征是实现长江及其河口氮污染有效控制的关键科学基础.基于收集的长江流域570个旱地和434个水田田间氮径流流失数据组,采用相关性分析、结构方程模型、方差分解和机器学习方法,探究了影响旱地和水田总氮径流流失强度的主要因素,建立了基于机器学习的长江流域旱地和水田总氮径流流失强度预测模型,量化了长江流域农田总氮径流流失负荷.结果表明,径流深、施氮量和土壤氮含量是影响旱地总氮径流流失强度的主要因素;径流深和施氮量是水田总氮径流流失强度的主要影响因素.与分类与回归树、多元线性回归和增强回归树方法相比,采用随机森林算法构建的长江流域旱地和水田总氮径流流失强度预测模型具有更高的精度（R²为0.65~0.94）.基于随机森林算法的预测模型估算的2013年长江流域农田总氮径流流失负荷（以N计）为0.47 Tg ·a^-1（旱地：0.25 Tg ·a^-1;水田：0.22 Tg ·a^-1）,中下游地区贡献了58%的流失负荷.模型预测5种防治情景下的长江流域农田氮流失负荷可削减2.4%~9.3%,其中减少径流量的削减效果最为显著.长江流域农田氮面源污染防治必须协同加强氮肥精准管理、减少农田径流量和提高土壤氮利用,且应将重点放在中下游地区.所发展的基于机器学习建模方法克服了氮径流流失强度与影响因素之间函数关系难以确定的问题,为估算区域或流域农田氮流失负荷提供了简便且可靠的方法.     

三峡库区非点源污染氮磷负荷时空变化及其来源解析

三峡库区是我国重要水源保护区,也是长江流域经济迅速发展区域之一.非点源污染是库区水环境恶化的主要原因,因此研究库区非点源污染状况对于区域的生态安全以及可持续发展具有重要意义.研究采用改进输出系数模型,估算库区1990~2015年的非点源氮磷污染负荷总量,分析非点源氮磷污染的时空变化特征,并通过计算各污染源的贡献率确定主要污染来源.结果表明,氮磷污染负荷量在空间上均呈现库区腹地高,库尾次之,库首最低的分布特征;氮磷污染负荷总量在时间上均呈现先增加后降低的趋势,在2000年达到最高值,2015年降到最低值;各污染源对氮磷污染负荷量的贡献率按从大到小依此为：土地利用、农村生活以及畜禽养殖;其中,旱地这种土地利用类型是非点源氮磷污染的主要来源.     

1991～2016年黄河三角洲湿地变化的遥感监测

以1991、2000、2010和2016年的Landsat TM/OLI影像数据为基础,采用面向对象和目视解译的分类方法,提取了黄河三角洲湿地信息。同时,利用空间分析、动态度模型、非等间距序列灰色模型等分析方法,分析了湿地的时空变化特征,并结合相关文献资料讨论了湿地变化的驱动因素。结果表明,1991～2016年间,黄河三角洲湿地总面积逐渐减少,约91.39 km²。其中,以2000～2010年期间面积变化最为剧烈,自然湿地面积以30.21 km²/a的速度减少,而人工湿地以32.77 km²/a的速度增加。在各类型湿地中,草甸湿地面积减少最多,为312.83 km²;而人工湿地面积大幅增长,且以养殖池和盐田的增加最为迅速,增加了544.63 km²。从空间分布上来看,研究区人工湿地面积有逐渐向滨海区扩张的趋势。湿地养殖、农业开垦、工程修建等人类活动是导致黄河三角洲自然湿地减少的主要因素。     

京津冀地区高分辨率PM2.5浓度时空变化模拟与分析

为了全覆盖、高分辨率和高精度识别京津冀地区大气PM_2.5质量浓度时空变化,选取多角度大气校正算法遥感反演的1km AOD为主要预测因子,多种气象要素和土地利用要素为辅助预测因子,构建了混合效应模型+地理加权回归模型的两阶段统计模型,并针对京津冀地区PM_2.5污染较严重的特点,模型中引入了AOD²等独特预测因子.通过上述两阶段模型定量预测了研究区2017年1 km²空间分辨率的每日PM_2.5质量浓度.结果表明,模型交叉验证的决定系数R²为0.94,斜率为0.95,均方根预测误差为13.14 μg·m^-3,在前人基础上预测精度进一步提升,可用于PM_2.5浓度时空变化预测与分析.2017年,京津冀地区PM_2.5浓度年均值为44.96 μg·m^-3,年均值范围在0~89.89 μg·m^-3之间.PM_2.5浓度时空变化差异性明显,整体上呈现"平原西南部浓度高、平原东北部浓度中等和山区高原浓度低"的空间分布格局以及"冬季浓度高、夏季浓度低和春秋过渡"的季节变化特点.模型预测结果的高时空分辨率可以支持流行病学研究在较小区域的暴露评估和识别小尺度污染源的时空变化,分析发现在大气污染防治行动计划实施以来,污染较严重的冀中南山麓平原区可能出现了重要污染源的空间变化.模型预测与分析结果可以为京津冀大气污染防治提供科学支撑.     

基于土壤流失的农业面源TN和TP排海系数估算

以黄河三角洲为典型研究区,通过分析区域地表污染物流失风险与入海通量的关系,构建了海岸带农业总氮（TN）和总磷（TP）面源污染排海估算模型.在此基础上,计算了包含水田、水浇地和旱地等耕地类的TN和TP面源污染排海系数,验证表明输出系数估算结果较好.研究区耕地的TN和TP排海系数分别为18.33 kg·（hm²·a）^-1和1.02 kg·（hm²·a）^-1,在夏季面源污染负荷较高.子流域尺度较大的耕地类农业面源污染负荷主要位于支脉河、广利河和小岛河管控区域.TN和TP总负荷较大的行政区主要位于北部黄河口镇和永安镇;较大的单位面积负荷在西南部.因此,需要关注农业面源污染的时间效应,同时协调社会经济发展,从子流域和行政单元的角度制定综合性面源污染防控策略,陆海统筹治理海域污染.     

上海市郊中小河流氮磷污染特征

：①上海市郊中小河流有很高的氮磷和有机负荷,其表层水凯氏氮、总磷和COD_Cr指标均数倍于V类水的最大允许值.②由于受纳污染物类型和总量上的差异,中小河流氮磷污染存在明显的空间分异:居民区附近的小河流氨氮和磷的污染很重;主要受农田径流影响的小河流,氨氮和磷的污染较轻,但受硝氮污染的风险加大;养殖场附近的小河流,氨氮和磷有突发性暴增的现象.③中小河流氮磷污染,还受河流季节性生态环境演变的影响.随着气温升高和河流表层生物量的增大,表层水NH₄⁺、NO₃^-因大量消耗而降低;有机N和颗粒态P含量因生物量的增加而上升;NO₂^-也会因硝化细菌活动的加剧而增加.水溶态磷和总磷也有随着气温和生物活动的增加而增高的趋势,但还要受到水体pH、DO等条件的影响.④在盛夏高温季节,水流滞缓的小河流表层水和底层水的氮磷指标存在明显分异:底层水NH₄⁺、水溶态磷和总反应态磷含量高于表层水;而表层水NO₃^-和NO₂含量高于底层水.这种富营养化水质分层现象的产生是夏季河流表层生物量暴增和底泥氮磷释放加剧的必然结果.至秋季,随着气温的回落,水质分层现象逐渐减弱.     

中国区域土壤表观氮磷平衡清单及政策建议

利用OECD表观氮平衡模型框架,建立了中国表观氮磷平衡核算的框架、方法和数据库.模型结果表明,2003年中国土壤表观氮磷盈余总量分别为640×10⁴　t和98×10⁴　t,氮磷盈余强度分别为16.56 kg/hm²和2.53 kg/hm².由于中国氮磷平衡区域分布严重不平衡,面临着氮磷盈余管理和氮磷缺损管理的双重压力.化肥和畜禽粪便是中国土壤氮磷投入最主要的来源,因此是中国氮磷盈余管理最佳切入点.由于各地氮磷投入结构各异,在氮磷盈余严重的中东部地区,不宜采用“一刀切”的政策,而应针对不同地区氮磷输入的特点进行氮磷盈余管理.     

非点源污染河流的水环境容量估算和分配

通过河流相应集水区内氮磷的各污染源分析(包括农地、畜禽养殖和生活排污等),利用输出系数模型估算各非点源的氮磷投(排)放量和入河量;采用河段氮磷输入-输出平衡关系分析方法,估算河流对氮磷的每月自净量.以此为基础,参照水功能区划所要求的水质目标,提出了水质未超标河段相应集水区的氮磷剩余水环境容量按月估算模型,和水质超标河段相应集水区内氮磷投放削减量的按月估算模型,及其在各污染源之间的分配方案.结果表明,长乐江的总氮和总磷自净量分别达到775.9 t·a^-1和30.9 t·a^-1,自净率分别为28.8%和51.2%.河流对氮磷的自净量不仅受水文生态条件的影响而表现出较大的季节性变化,而且随着污染负荷量本身的增加而提高.按照水功能区划中Ⅲ类水的水质要求,长乐江总氮含量全年超标;各非点源的总氮投(排)放量均须不同程度的削减,削减总量应达到1 581.0　t;氮源削减量分配结果表明,化肥是应削减的最大氮源,要求在河流相应集水区内的化肥氮投放削减量为1 047.4 t·a^-1;而与各种氮源的投排放现状相比,要求削减比例最高的是畜禽养殖的氮排放量,达32.4%.长乐江流域尚有一定的总磷剩余水环境容量(2 335.7 t·a^-1).根据目标水质要求,平水期是各污染源总氮投放需要削减的量最大的时期,丰水期则是总磷剩余水环境容量最小的时期.     

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.