冰相中六氯苯的紫外光降解和结冰过程中Fenton试剂对六氯苯的氧化作用
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摘要
近些年，随着人类生产生活对各种化工原料和各种有机化肥的利用日益增多，使这些有机物对环境的污染程度也明显加大。有机氯农药六氯苯是常见的一种有机氯污染物。虽然近十几年来，有机氯农药已经在农业生产方面全面被禁用，但工业生产和其他工业活动依然产生数量不少的六氯苯。同时有报道称在两极地区已检测到六氯苯，冬季降雪及常年结冰地区也会受到六氯苯的污染；另外，由于有机物在这些地区的雪冰中微生物作用及迁移作用都相对微弱，使得光化学作用在这些环境中表现的尤为重要。因此，本文研究的六氯苯在冰相中的光化学作用及在结冰过程中六氯苯在Fenton试剂作用下的转化就有着重要的意义，对于掌握六氯苯在环境中的转化方式具有重要的参考价值。虽然国内外对冰雪介质中光化学作用的研究已经有了一定的基础，但目前研究方向主要集中在有机污染物的直接光解，以及在H_2O_2, N_O~(2-)和NO_3~-等作用下的间接光解。而在实际的冰雪环境中还存在着其他许多可能会参与光化学作用的组分，如Fe~(2+)、Fe~(3+)、SO42-、PO43-及Fenton试剂。这些组分对有机污染物在冰雪介质中的光化学转化的影响尚未引起人们的关注。
本实验以六氯苯为研究对象，研究紫外光照射作用下六氯苯在冰相中的光降解规律，考察了两种紫外光源条件下六氯苯的光降解；不同pH值以及不同浓度无机离子（包括SO42-、PO43-、N_O~(2-)、NO_3~-、HCO_3~-、Fe~(2+)和Fe~(3+)）、H_2O_2和有机试剂对其降解规律的影响；并对六氯苯的降解产物进行了分析测定，推断了冰相中六氯苯的降解途径；在结冰过程中Fenton试剂对六氯苯的氧化作用研究中，实验初步探究了在六氯苯溶液中加入Fenton试剂后，结冰过程中诸如时间、温度及结冰融冰循环次数对六氯苯转化程度的影响；并在结冰融冰条件下Fenton试剂对六氯苯作用的中间产物进行了测定，分析推断了此过程中水-冰相微界面在六氯苯降解过程中的作用机理。
在六氯苯的紫外光降解实验中，冰相中的六氯苯在没有光照的情况下，不发生任何降解；在254nm低压汞灯下照射，光照8h降解率达到60%；在UVA340nm紫外灯的照射下六氯苯也没有任何光降解。在254nm紫外低压汞灯的照射下，改变冰相的pH值，发现在强酸和强碱的作用时，冰相中的六氯苯光降解程度最大。加入SO_4~(2-)、PO_4~(3-)、H_2O_2、N_O~(2-)、NO_3~-、HCO_3~-和Fe~(3+)，发现不同的无机离子及H_2O_2对冰相中六氯苯的光降解有不同的作用。SO_4~(2-)、PO_4~(3-)对HCB冰相中光降解的表现为促进作用；而H_2O_2、N_O~(2-)、NO_3~-、HCO_3~-和Fe~(3+)对HCB冰相中光降解则为抑制作用。丙酮、甲醇、乙腈、二甲亚砜四种有机试剂对冰相中六氯苯的紫外光降解作用大小依次为：乙腈＞丙酮≈甲醇＞二甲亚砜。冰相中的HCB直接光解的机理实际上是一系列的脱氯过程。光照1h得到的产物为有苯、氯苯、二氯苯（1,2-二氯苯、1,3-二氯苯、1,4-二氯苯）、三氯苯（1,2,4-三氯苯），而光照48h得到的中间产物中还检测到了五氯苯。
在研究结冰过程中Fenton试剂对HCB的氧化作用实验中，加入Fenton试剂的HCB溶液在不同温度、和不同的结冰时间，会有不同程度的降解。HCB的溶液中加入Fenton试剂以后进行结冰融冰循环实验，随着循环的次数的增加，HCB浓度在减小。可能由于循环过程的进行使得Fenton试剂不断产生·OH自由基，在冰-水界面上不断的分配，并与HCB发生降解反应。结冰融冰循环实验中HCB的降解产物有五氯酚，可能是由于Fenton试剂除了·OH自由基团外还会产生多种活性基团，如·OOH、H_2O·等，这些基团综合作用下生成了五氯酚。
通过以上实验研究结果，揭示了冰相中六氯苯的光降解机制，阐明了结冰过程中Fenton试剂对HCB的转化作用，从而对于六氯苯在冰雪环境中预测和评估提供了理论依据。
In recent years, along with the need of human life and production in a variety ofchemical material and organic fertilizer utilization increase day by day, these organicpollution to the environment are also significantly increasing. Hexachlorobenzene(HCB) is an organic chlorine pesticide and organic pollutant. Although in recent years,organic chlorine pesticides in agricultural production are banned overall, the industrialproduction and other industrial activities still have many HCB. At the same time，there are some reports that HCB has been detected in polar regions, in the wintersnowfall area and perennial frozen area; in addition, the microbial action andmigration for the organic pollutants in snow and ice are relatively weak, so that thephotochemical effect are particularly important. Therefore, this paper carried out theresearch on the transformation of photochemical effect of HCB in ice phase andFenton effect during the freezing of HCB is meaningful. Although some research onthe photochemical reaction has been carried out domestic and overseas, the presentresearch mainly concentrated on the organic pollutants by direct photolysis andindirect photolysis of H_2O_2, N_O~(2-)and NO_3~-. But in the actual ice environment stillexist many other components may take part in the photochemical actions, such as Fe~(2+),Fe~(3+), SO_4~(2-), PO_4~(3-)and Fenton reagent. The effects of these fractions on organicpollutants in ice have not been attracted.
This experiment, took HCB as the research object, and carried out the researchon the photodegradation of HCB in ice phase under the UV irradiation, inspected the effect of two kinds of UV light sources condition for HCB photodegradation; italso research on the influence of different pH values and different concentrations ofinorganic ions (including SO42-, PO43-, N_O~(2-), NO_3~-HCO_3~-, Fe~(2+)and Fe~(3+)), H_2O_2andorganic reagents; and the HCB degradation products were analyzed and determined,inferred the ice phase HCB degradation pathway; in the oxidation of HCB by Fentonreagent in the freezing process experiment, it also carried out preliminary research oneffect of different time, temperature and icing-thawing cycles during freezing ofHCB; it also determined the intermediate products of HCB in icing conditions byFenton reagent, and inferred the effect of water-ice phase interface in actionmechanism of degradation process.
In HCB photodegradation experiment, there has no degradation for HCB in icephase without any light; and degradation rate reached60%after8h in254nm light;while there has no degradation in340nm lamp. In254nm lamp irradiation,photodegradation rate would be different when changing the ice phase pH; it hasfound that photodegradation rate were maximum in strong acid and strong alkalicondition. When adding SO_4~(2-), PO_4~(3-), H_2O_2, N_O~(2-), NO_3~-, HCO_3~-and Fe~(3+), it found thatdifferent inorganic ions and H_2O_2in ice phase HCB photodegradation have differenteffects. SO_4~(2-), PO_4~(3-)showed stimulative effect for photodegradation of HCB in icephase; while H_2O_2, N_O~(2-), NO_3~-HCO_3~-and Fe~(3+)exhibit inhibition effect forphotodegradation of HCB in ice phase. Four different kinds of organic reagents effecton photodegradation of HCB in ice phase are: methanol> acetone≈acetonitrile>dimethyl sulfoxide. Actually, direct photolysis mechanism of HCB in ice phase is aseries of dechlorination process. There four different products after1h light irradiation:benzene, benzene, dichlorobenzene (1,2-dichlorobenzene,1,3-dichlorobenzene,1,4-dichlorobenzene), trichlorobenzene (1,2,4-trichlorobenzene), and after48h reachedanother intermediate products-pentachlorobenzene.
In the study of oxidation of HCB by Fenton reagent in freezing processexperiments, adding Fenton reagent HCB solution at different temperature anddifferent freezing time, would have different effect on degradation. Fenton reagentwas added to the HCB solution and carried out icing-thawing cycle experiment. With the cycle times increasing, HCB concentration was decreased. It may be due to thecyclic process made Fenton reagents continuously generated·OH radicals, andwould be distributed in ice-water interface continuously, and HCB degraded. Inicing-thawing circulation experiments, HCB degradation products contained PCP, itmight be the result of Fenton reagent addition·OH radical produced various activegroups, such as·OOH and H_2O· etc, these groups take part in the comprehensivereaction and generated PCP.
Above all, experimental results revealed the photodegradation mechanism ofHCB in ice phase, expounds HCB transformation by Fenton reagents in freezingprocess, which will provide a theoretical basis for the prediction and assessment forHCB in ice environment.
本实验以六氯苯为研究对象，研究紫外光照射作用下六氯苯在冰相中的光降解规律，考察了两种紫外光源条件下六氯苯的光降解；不同pH值以及不同浓度无机离子（包括SO42-、PO43-、N_O~(2-)、NO_3~-、HCO_3~-、Fe~(2+)和Fe~(3+)）、H_2O_2和有机试剂对其降解规律的影响；并对六氯苯的降解产物进行了分析测定，推断了冰相中六氯苯的降解途径；在结冰过程中Fenton试剂对六氯苯的氧化作用研究中，实验初步探究了在六氯苯溶液中加入Fenton试剂后，结冰过程中诸如时间、温度及结冰融冰循环次数对六氯苯转化程度的影响；并在结冰融冰条件下Fenton试剂对六氯苯作用的中间产物进行了测定，分析推断了此过程中水-冰相微界面在六氯苯降解过程中的作用机理。
在六氯苯的紫外光降解实验中，冰相中的六氯苯在没有光照的情况下，不发生任何降解；在254nm低压汞灯下照射，光照8h降解率达到60%；在UVA340nm紫外灯的照射下六氯苯也没有任何光降解。在254nm紫外低压汞灯的照射下，改变冰相的pH值，发现在强酸和强碱的作用时，冰相中的六氯苯光降解程度最大。加入SO_4~(2-)、PO_4~(3-)、H_2O_2、N_O~(2-)、NO_3~-、HCO_3~-和Fe~(3+)，发现不同的无机离子及H_2O_2对冰相中六氯苯的光降解有不同的作用。SO_4~(2-)、PO_4~(3-)对HCB冰相中光降解的表现为促进作用；而H_2O_2、N_O~(2-)、NO_3~-、HCO_3~-和Fe~(3+)对HCB冰相中光降解则为抑制作用。丙酮、甲醇、乙腈、二甲亚砜四种有机试剂对冰相中六氯苯的紫外光降解作用大小依次为：乙腈＞丙酮≈甲醇＞二甲亚砜。冰相中的HCB直接光解的机理实际上是一系列的脱氯过程。光照1h得到的产物为有苯、氯苯、二氯苯（1,2-二氯苯、1,3-二氯苯、1,4-二氯苯）、三氯苯（1,2,4-三氯苯），而光照48h得到的中间产物中还检测到了五氯苯。
在研究结冰过程中Fenton试剂对HCB的氧化作用实验中，加入Fenton试剂的HCB溶液在不同温度、和不同的结冰时间，会有不同程度的降解。HCB的溶液中加入Fenton试剂以后进行结冰融冰循环实验，随着循环的次数的增加，HCB浓度在减小。可能由于循环过程的进行使得Fenton试剂不断产生·OH自由基，在冰-水界面上不断的分配，并与HCB发生降解反应。结冰融冰循环实验中HCB的降解产物有五氯酚，可能是由于Fenton试剂除了·OH自由基团外还会产生多种活性基团，如·OOH、H_2O·等，这些基团综合作用下生成了五氯酚。
通过以上实验研究结果，揭示了冰相中六氯苯的光降解机制，阐明了结冰过程中Fenton试剂对HCB的转化作用，从而对于六氯苯在冰雪环境中预测和评估提供了理论依据。
In recent years, along with the need of human life and production in a variety ofchemical material and organic fertilizer utilization increase day by day, these organicpollution to the environment are also significantly increasing. Hexachlorobenzene(HCB) is an organic chlorine pesticide and organic pollutant. Although in recent years,organic chlorine pesticides in agricultural production are banned overall, the industrialproduction and other industrial activities still have many HCB. At the same time，there are some reports that HCB has been detected in polar regions, in the wintersnowfall area and perennial frozen area; in addition, the microbial action andmigration for the organic pollutants in snow and ice are relatively weak, so that thephotochemical effect are particularly important. Therefore, this paper carried out theresearch on the transformation of photochemical effect of HCB in ice phase andFenton effect during the freezing of HCB is meaningful. Although some research onthe photochemical reaction has been carried out domestic and overseas, the presentresearch mainly concentrated on the organic pollutants by direct photolysis andindirect photolysis of H_2O_2, N_O~(2-)and NO_3~-. But in the actual ice environment stillexist many other components may take part in the photochemical actions, such as Fe~(2+),Fe~(3+), SO_4~(2-), PO_4~(3-)and Fenton reagent. The effects of these fractions on organicpollutants in ice have not been attracted.
This experiment, took HCB as the research object, and carried out the researchon the photodegradation of HCB in ice phase under the UV irradiation, inspected the effect of two kinds of UV light sources condition for HCB photodegradation; italso research on the influence of different pH values and different concentrations ofinorganic ions (including SO42-, PO43-, N_O~(2-), NO_3~-HCO_3~-, Fe~(2+)and Fe~(3+)), H_2O_2andorganic reagents; and the HCB degradation products were analyzed and determined,inferred the ice phase HCB degradation pathway; in the oxidation of HCB by Fentonreagent in the freezing process experiment, it also carried out preliminary research oneffect of different time, temperature and icing-thawing cycles during freezing ofHCB; it also determined the intermediate products of HCB in icing conditions byFenton reagent, and inferred the effect of water-ice phase interface in actionmechanism of degradation process.
In HCB photodegradation experiment, there has no degradation for HCB in icephase without any light; and degradation rate reached60%after8h in254nm light;while there has no degradation in340nm lamp. In254nm lamp irradiation,photodegradation rate would be different when changing the ice phase pH; it hasfound that photodegradation rate were maximum in strong acid and strong alkalicondition. When adding SO_4~(2-), PO_4~(3-), H_2O_2, N_O~(2-), NO_3~-, HCO_3~-and Fe~(3+), it found thatdifferent inorganic ions and H_2O_2in ice phase HCB photodegradation have differenteffects. SO_4~(2-), PO_4~(3-)showed stimulative effect for photodegradation of HCB in icephase; while H_2O_2, N_O~(2-), NO_3~-HCO_3~-and Fe~(3+)exhibit inhibition effect forphotodegradation of HCB in ice phase. Four different kinds of organic reagents effecton photodegradation of HCB in ice phase are: methanol> acetone≈acetonitrile>dimethyl sulfoxide. Actually, direct photolysis mechanism of HCB in ice phase is aseries of dechlorination process. There four different products after1h light irradiation:benzene, benzene, dichlorobenzene (1,2-dichlorobenzene,1,3-dichlorobenzene,1,4-dichlorobenzene), trichlorobenzene (1,2,4-trichlorobenzene), and after48h reachedanother intermediate products-pentachlorobenzene.
In the study of oxidation of HCB by Fenton reagent in freezing processexperiments, adding Fenton reagent HCB solution at different temperature anddifferent freezing time, would have different effect on degradation. Fenton reagentwas added to the HCB solution and carried out icing-thawing cycle experiment. With the cycle times increasing, HCB concentration was decreased. It may be due to thecyclic process made Fenton reagents continuously generated·OH radicals, andwould be distributed in ice-water interface continuously, and HCB degraded. Inicing-thawing circulation experiments, HCB degradation products contained PCP, itmight be the result of Fenton reagent addition·OH radical produced various activegroups, such as·OOH and H_2O· etc, these groups take part in the comprehensivereaction and generated PCP.
Above all, experimental results revealed the photodegradation mechanism ofHCB in ice phase, expounds HCB transformation by Fenton reagents in freezingprocess, which will provide a theoretical basis for the prediction and assessment forHCB in ice environment.
引文
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