环境中磷化氢的产生、分布及转化研究进展

doi:10.16085/j.issn.1000-6613.2018-2042

摘要/Abstract

摘要：

磷化氢广泛产生于稻田耕作、垃圾填埋、废水处理、工业生产等过程，但环境中磷化氢的形成机制、转化途径等问题尚不清晰。本文从磷化氢的环境效益出发，分析了气体自由态与基质结合态磷化氢的产生及时空分布特性，归纳了磷化氢催化转化、光化学氧化、微生物降解等转化途径及作用机理，探讨了磷化氢生物地球化学循环过程存在的相关问题。综合磷化氢源汇解析、迁移转化等方面的现有研究及发展态势，后续研究可聚焦如下3个方面：①废水中磷化氢厌氧生成机制及过程强化；②水体富营养化与磷化氢及其氧化产物的响应关系；③磷化氢生物氧化的具体途径及作用机制。

关键词: 磷化氢, 环境效应, 释放源, 分布特征, 转化途径

Abstract:

Phosphine is widely produced from paddy cultivation, refuse landfill, wastewater treatment, industrial production or other sources. However the formation mechanism and transformation pathway of phosphine in the environment are still unclear. Based on the environmental benefits of phosphine, this review investigated the release and spatiotemporal distribution of two kinds of phosphine, free gaseous PH₃ and matrix-bound PH₃, and analyzed the transformation pathways including catalytic conversion, photochemical oxidation, microbial degradation and so on, then explored the mechanism for PH₃ conversion and analyzed some significant problems related to the biogeochemical cycling of phosphine. According to the obtained research on source and sink analysis as well as phosphine’s transport and transformation in environment, follow-up research can focus on the following three aspects: ① the formation mechanism and process intensification of gaseous phosphine in the anaerobic wastewater treatment system; ② the response relationship between water eutrophication and phosphine and its oxidation products; ③ the mechanism and specific pathway of phosphine bio-oxidation system.

Key words: phosphine, environmental effects, the source of PH₃ release, distribution features, transformation pathways

中图分类号:

X701

刘树根, 李婷, 宁平, 吴孟, 余硕. 环境中磷化氢的产生、分布及转化研究进展[J]. 化工进展, 2019, 38(02): 1085-1096.

Shugen LIU, Ting LI, Ping NING, Meng WU, Shuo YU. Research progress of the release, distribution and transformation of phosphine in environment[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 1085-1096.

图/表 2

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环境介质	浓度	释放通量 /ng·m^-2·h^-1	研究者
大气中的磷化氢
污水处理厂	11.6～382ng·m^-3	0.09～9.17	Devai等^[1]
世界各地大气	0.041～0.885ng·m^-3	1300	Glindemann等^[24]
中国北方水稻田上空	137ng·m^-3	1.78	Han等 ^[8]
中国南方水稻田上空	14.25ng·m^-3	9.193～19.15	魏爱书^[64]
太湖湖面上空	20.2～46ng·m^-3	-8.1～36.9	韩超^[65]
南极米洛米岛大气	10.4～229ng·m^-3		朱仁斌等^[66]
北极海面/地面上空	16.3～600.2ng·m^-3	26.95～37.66	张蕤等^[67]
厌氧消化气中的磷化氢
填埋场大气	0～24646ng·m^-3		Glindemann等^[62]
动物腐败产生的沼气	24～20300ng·m^-3
含盐沼泽地		0.91～6.52
微咸沼泽地		0.42～3.03	Devai等 ^[9]
千层湖泊沉积物释放沼气
屠宰场废水释放沼气	179ng·m^-3		Roels等^[38]
人体排泄物释放沼气	42.3ng·m^-3
工农业生产活动产生的磷化氢
粮食仓储熏蒸仓内	1257.84～2632.60mg·m^-3		姜开友等^[68]
烟草熏蒸仓内	30.36～182.14mg·m^-3		张建中等^[69]
微电子产品生产	0.15～0.17mg·m^-3		贾晖等^[70]
黄磷尾气	500～1300mg·m^-3		Ning等^[54]

环境介质	浓度	释放通量 /ng·m^-2·h^-1	研究者
大气中的磷化氢
污水处理厂	11.6～382ng·m^-3	0.09～9.17	Devai等^[1]
世界各地大气	0.041～0.885ng·m^-3	1300	Glindemann等^[24]
中国北方水稻田上空	137ng·m^-3	1.78	Han等 ^[8]
中国南方水稻田上空	14.25ng·m^-3	9.193～19.15	魏爱书^[64]
太湖湖面上空	20.2～46ng·m^-3	-8.1～36.9	韩超^[65]
南极米洛米岛大气	10.4～229ng·m^-3		朱仁斌等^[66]
北极海面/地面上空	16.3～600.2ng·m^-3	26.95～37.66	张蕤等^[67]
厌氧消化气中的磷化氢
填埋场大气	0～24646ng·m^-3		Glindemann等^[62]
动物腐败产生的沼气	24～20300ng·m^-3
含盐沼泽地		0.91～6.52
微咸沼泽地		0.42～3.03	Devai等 ^[9]
千层湖泊沉积物释放沼气
屠宰场废水释放沼气	179ng·m^-3		Roels等^[38]
人体排泄物释放沼气	42.3ng·m^-3
工农业生产活动产生的磷化氢
粮食仓储熏蒸仓内	1257.84～2632.60mg·m^-3		姜开友等^[68]
烟草熏蒸仓内	30.36～182.14mg·m^-3		张建中等^[69]
微电子产品生产	0.15～0.17mg·m^-3		贾晖等^[70]
黄磷尾气	500～1300mg·m^-3		Ning等^[54]

磷化氢分布	基质中含磷化氢 /ng·kg^-1	消解方式	研究者
土壤、海洋沉积物
牛排泄物	13.9	碱消化	Gassmann等^[45]
猪排泄物	5.6～16.8	碱消化
土壤（工业地区）	7～103	酸消化
土壤（乡村）	0.8～2.5	酸消化
德国汉堡港表层沉积物	0.2～56.6	碱消化	Gassmann等^[23]
美国、匈牙利污水厂污泥	8.4～204	酸消化	Devai等^[28]
稻田土壤	2.3～269.7	酸消化	王谨丰^[73]
胶州湾海洋沉积物	60～271	酸消化	Yu等^[74]
太湖表层沉积物	5.39～919	酸消化	Niu等^[31]
大连湾海洋沉积物	116.8～554.3	酸消化	封颖等^[59]
南极生物圈
鸟粪沉积物	0.29～3.04	酸消化	Zhu等^[75]
北极生物圈
泰源土壤	2.15～50.42	酸消化	封颖等^[59]
湖泊表层沉积物	17.55～58.62	酸消化
海洋表层沉积物	26.2～140.9	酸消化

磷化氢分布	基质中含磷化氢 /ng·kg^-1	消解方式	研究者
土壤、海洋沉积物
牛排泄物	13.9	碱消化	Gassmann等^[45]
猪排泄物	5.6～16.8	碱消化
土壤（工业地区）	7～103	酸消化
土壤（乡村）	0.8～2.5	酸消化
德国汉堡港表层沉积物	0.2～56.6	碱消化	Gassmann等^[23]
美国、匈牙利污水厂污泥	8.4～204	酸消化	Devai等^[28]
稻田土壤	2.3～269.7	酸消化	王谨丰^[73]
胶州湾海洋沉积物	60～271	酸消化	Yu等^[74]
太湖表层沉积物	5.39～919	酸消化	Niu等^[31]
大连湾海洋沉积物	116.8～554.3	酸消化	封颖等^[59]
南极生物圈
鸟粪沉积物	0.29～3.04	酸消化	Zhu等^[75]
北极生物圈
泰源土壤	2.15～50.42	酸消化	封颖等^[59]
湖泊表层沉积物	17.55～58.62	酸消化
海洋表层沉积物	26.2～140.9	酸消化

[1]	赵瑞, 张翼, 余学海, 史晓宏, 刘毅, 王鹏, 韩涛. 中试平台SCR低温催化剂测试与氨逃逸分布特征[J]. 化工进展, 2021, 40(8): 4610-4615.
[2]	刘树根, 任林, 苏福家, 董占能. 磷化氢生物净化体系的微生物特性及过程强化[J]. 化工进展, 2021, 40(7): 4055-4063.
[3]	王彦,左宁,姜媛媛,陈芳媛. 污泥生物炭中氮硫行为及环境效应研究进展[J]. 化工进展, 2020, 39(4): 1539-1549.
[4]	李山, 郝吉明, 李凯, 汤立红, 刘烨. 粗乙炔中H₂S、PH₃同时脱除技术研究进展[J]. 化工进展, 2015, 34(02): 534-541.