牛栏江流域(昆明段)水质现状、存在问题及对策研究

牛栏江是金沙江的一级支流,为常流河,在昆明境内由多条河流汇集而成,通过对牛栏江流域(昆明段)水质现状分析,阐述了流域内存在的环境保护问题,提出相应的对策措施和建议.     

Adsorption and chlorination of dibenzo-p-dioxin and 1-chlorodibenzo-p-dioxin on fly ash from municipal incinerators

Adsorption and chlorination reactions for dibenzo-p-dioxin (DD) and 1-chlorodibenzo-p-dioxin (1-MCDD) on fly ash were characterized quantitatively using laboratory-based simulation of stack emissions with air and HCl-air atmospheres. Influences of contact time and temperature were studied and results showed behavior of DD and 1-MCDD consistent with that for 1,2,3,4-tetrachlorodibenzo-p-dioxin. Di-, tri-, and tetra-chlorinated dioxins were major compounds produced from heterogenous phase reactions of DD and 1-MCDD with HCl in air. Total conversion through reactions alone were as high as 81% and 58% respectively.     

Presence of nitro-chlorinated dioxins on fly ash from municipal incinerators and from laboratory production through reactions between NO2 and T4CDD on fly ash

Treatment of tetrachlorodibenzo-p-dioxin (T₄CDD) on municipal incinerator fly ash at 30 to 150°C for 10 minutes using 5% (Vol/Vol) NO₂ in air resulted in production of nitro-T₄CDD. Percent conversion was between 40% at 50°C to 100% at 150°C. Nitro-T₄CDD produced in the laboratory was unstable in hexane/methanol or hexane/acetone solutions and decomposed at ?5°C with half-lives of 8–10 days^?1 to the original T₄CDD.Fly ash from a municipal incinerator in Toronto, Ontario was extracted using toluene/methanol for 12 hrs in a Soxhlet extractor. Condensate of this extract was analyzed using capillary gas chromatography with flame ionization, nitrogen-selective, and mass spectrometric detectors. Retention times for nitro-T₄CDD, multi-ion selected ion monitoring, and nitrogen detector response were used as supporting evidence for the presence of nitro-chlorinated dioxins as naturally occurring in this sample.     

Chlorination reactions of 1,2,3,4-tetrachlorodibenzo-p-dioxin on fly ash with HC1 in air

Chlorine substitution reactions of 1,2,3,4-TCDD to higher chlorinated PCDD occurred on fly ash between 50°C to 250°C with an HC1 in air atmosphere in a laboratory reaction apparatus used to simulate emission conditions in municipal incinerators. Percent conversion of 1,2,3,4-TCDD through such reactions was as high as 66% by mass corrected for losses to irreversable absorption. Production of penta-, hexa-, hepta- and octa-CDD was evident and a maximum in production of P₅CDD and H₆CDD was reached in 10 to 30 min. Results showed that these reactions may involve complex mechanisms which include several states of adsorption with different reactivities of 1,2,3,4-TCDD on fly ash.     

添加玉米秸秆对绿花菜尾菜堆肥植物毒性的影响

为揭示不同比例作物秸秆和蔬菜尾菜堆肥过程中种子毒性变化及其影响机理,开展了为期55 d的以玉米（Zea mays L.）秸秆为辅料,绿花菜（Brassica oleracea L.var.botrytis L.）尾菜为主料的工厂化条垛堆肥,分别设置加入高（湿重比4∶12）和低（湿重比1∶12）比例秸秆与尾菜的堆肥处理.测定了不同时期堆肥p H、电导率（EC）、可溶性有机碳（DOC）、硝氮（NO₃^--N）、氨氮（NH₄⁺-N）、碳氮比（C/N）、大白菜种子（Brassica rapa L.）的发芽指数（Germination Index,GI）、相对生长指数（Relative Growth Index,RGI）和α-淀粉酶、蛋白酶、脂肪酶的变化.结果表明,高比例秸秆堆肥处理的高温（>55℃）持续期显著高于低比例处理.堆肥结束时两个处理的堆肥均呈碱性,且EC、DOC、NH₄⁺-N和NO₃^--N含量均降低,C/N...     

Adsorption and thermal reactions of 1,2,3,4-tetrachlorodibenzo-p-dioxin on fly ash from a municipal incinerator

Adsorption and thermal reactions of 1,2,3,4-tetrachlorodibenzo-p-dioxin (TCDD) on fly ash from a municipal incinerator were determined for temperatures between 100 to 300°C in air and in helium atmospheres. Results show 1,2,3,4-TCDD undergoes partial irreversable adsorption or decomposition in air at these temperatures. However, no decomposition products in air atmosphere were detected using gas chromatographic/mass spectrometric analysis of fly ash extracts and effluent.     

Effect of matrix on heterogeneous phase chlorine substitution reactions for dibenzo-p-dioxin and HCl in air

Five materials were used in gas-solid phase reactions between dibenzo-p- dioxin(DD) and HCl in order to determine the role of organic and inorganic components in fly ash on chlorine substitution reactions of chlorinated dioxins. The five solids were: granular activated carbon, silica gel, diatomaceous earth, Tenax-GC, and fly ash. Conditions for reactions were 10 min at 150°C with 5% HCl in air. Extent of chlorination was measured using GC/MS analyses of extracts of fly ash after treatment processes and was expressed as the ratio monochloroDD/original unreacted DD. These ratios were: fly ash, 1.082; silica gel, 0.059; activated carbon, 0.024; and Tenax-GC, 0.001. Measurement of similar behavior on diatomaceous earth was impossible since starting material and possible products were irreversibly adsorbed completely. The major chlorinated dioxin produced under these conditions was 2-chlorodibenzo-p- dioxin which is the isomer favored through an electrophilic substitution mechanism.     

对比研究槽式堆肥处理不同畜禽粪便对植物毒性的影响

为揭示槽式堆肥过程中不同畜禽粪便堆肥理化性质的变化及其对植物毒性的影响,分别开展了以羊、牛、鸡、猪粪便与木屑为堆料、为期44 d的好氧槽式堆肥对比试验,采集了不同堆肥期的堆肥样品,测定了堆肥的pH、电导率（EC）、可溶性有机碳（DOC）、硝氮（NO₃^--N）、氨氮（NH₄⁺-N）、全氮（TN）、碳氮比（C/N）、全磷（TP）、全钾（TK）、铜（Cu）、锌（Zn）含量及水堇的相对生长指数（RGI）和种子发芽指数（GI）,并通过相关分析和线性回归拟合,分析了堆肥过程粪便对水堇种子植物毒性的影响机制.结果表明,槽式堆肥过程中,羊粪的高温期持续时间最长,牛粪其次,猪粪和鸡粪最短;堆肥结束时4种粪便均呈弱碱性.堆肥过程中猪粪和鸡粪的EC降低,其他粪便的EC变化幅度较小,各粪便的DOC、NH₄⁺-N含量降低,NO₃^--N、TP、TK、Cu和Zn含量增加,牛粪和鸡粪的C/N逐渐降低,而猪粪和羊粪的C/N呈先升后降的趋势,羊粪和猪粪的TN含量下降,鸡粪和牛粪的TN含量缓慢上升.堆肥过程中4种粪便对水堇种子的植物毒性均降低,且RGI和GI升幅由高到低为：牛粪 > 羊粪 > 鸡粪 > 猪粪.相关分析表明,堆肥过程中羊粪的TP、Cu、Zn,牛粪的Zn、TK、TP、NO₃^--N,鸡粪的NO₃^--N、TN、Cu,猪粪的NO₃^--N、TP、Zn、TK与RGI呈显著正相关（p<0.01）;而羊粪的Cu、TP、TK,牛粪的Zn、TK、TP,鸡粪的Cu、TN、NO₃^--N、TK,猪粪的TP、Zn、NO₃^--N与GI呈显著正相关（p<0.01）.由此表明,不同粪便堆肥的以上指标促进了植物的根伸长和种子发芽.但堆肥过程中羊粪的NH₄⁺-N、TN、DOC,牛粪的NH₄⁺-N、DOC、C/N、EC,鸡粪的C/N、EC、DOC,猪粪的NH₄⁺-N、DOC、EC与RGI呈显著负相关（p<0.01）;羊粪的NH₄⁺-N、TN、DOC,牛粪的NH₄⁺-N、DOC、C/N,鸡粪EC、DOC、C/N,猪粪的NH₄⁺-N、DOC、EC与GI呈显著负相关（p<0.01）.由此表明,不同粪便的以上指标显著抑制了植物的根伸长和种子发芽.多元回归分析说明,堆肥过程羊粪和牛粪的NH₄⁺-N,鸡粪的NO₃^--N、Cu、C/N和EC,猪粪的NO₃^--N和TK对水堇种子根伸长具有显著的影响,而羊粪的NH₄⁺-N和TK,牛粪的DOC、pH和EC,鸡粪Cu、TN和NO₃^--N,猪粪的TK对水堇种子发芽具有显著的影响.以上对比研究结果可为不同畜禽粪便槽式堆肥处理和土地利用提供重要的理论依据和决策支持.     

除草剂草甘膦在土壤中的吸附行为

研究了除草剂草甘膦在3种土壤中的吸附行为, 观察了pH和离子强度等因素对吸附的影响. 结果表明:草甘膦在3种土壤中的吸附过程均符合一级动力学规律, 吸附等温线均为直线,吸附常数K_d 2.2207～3.5280mL/g; 随着离子强度的降低, 草甘膦在3种土壤中的吸附量明显增大; 随着pH(9～3)逐渐减小, 草甘膦在呼和浩特特市土壤和东胜土壤中的吸附量增大, 在杭锦2号土中的吸附量先增大, 在pH=7时达到最大值, pH=5时开始下降, 下降到4时的吸附量与pH=9时的相等.     

不同配比农业废物堆肥过程中堆肥的阴阳离子和大分子对种子发芽的影响

为揭示不同配比农业废物堆肥过程中阴阳离子和大分子对植物毒性的影响机理，开展了以鸡粪和猪粪为主料，稻草秸秆为辅料的条垛堆肥试验，设置的试验处理包括：等质量的鸡粪+稻草秸秆+包菜（1∶1∶1）处理（T1）、鸡粪+稻草秸秆（1∶1）处理（T2）、大量猪粪+少量稻草秸秆（85∶15）处理（T3）.测定了各处理的堆温、堆肥的水溶性无机阴阳离子和有机大分子变化，以及对大白菜（Brassica rapa L.）和水堇（Lepidium sativum. L.）种子发芽指数（Germination Index， GI）等指标变化的影响.试验结果表明，T3处理堆肥的高温（>55 ℃）持续期最长，杀灭病原微生物和杂草种子的能力最好，且其堆肥的Cl^-、SO42-、K⁺、Na⁺、Ca²⁺和Mg²⁺浓度最低；T2处理堆肥的NH4+ 浓度最低.T1和T2处理堆肥过程中堆肥的脂肪烃可转化为稳定的芳香烃.T3处理堆肥对大白菜和水堇的种子发芽指数大于80%.堆肥中抑制种子发芽的阴阳离子及大分子浓度分别为：Ca²⁺浓度>0.98 mmol·L^-1，Mg²⁺浓度>0.92 mmol·L^-1，NH4+浓度均>5.75 mmol·L^-1，芳香C/多糖比值>0.33，羧基C/多糖比值>0.30.堆肥中脂肪族大分子增加、多糖类大分子减少可抑制种子发芽.综上所述，猪粪与稻草秸秆的质量配比为85∶15、初始C/N比为25、初始水分含量为60%、 堆肥期周为35 d是条垛式堆肥处理猪粪和稻草秸秆的最佳工艺参数.大白菜比水堇种子更能准确反映农业废物堆肥的植物毒性.本研究可为优化不同畜禽粪便与农作物秸秆的条垛堆肥工艺参数、减少土地利用的风险提供重要的决策支持.