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In the process of investigating ecological and environmental pollution cases, problems such as difficulty in identifying the attributes of unknown solid waste, complex identification processes, and slow identification time have always affected the efficiency of case investigation. Through personnel interviews, on-site investigations, and initial screening of on-site rapid detection equipment, comprehensive analysis is conducted to determine the detection indicators for the hazardous characteristics of unknown solid volatile organic compounds. The leaching toxicity and toxic substance content of volatile organic compounds are analyzed to identify unknown solid waste as hazardous waste. Accurate identification of hazardous characteristics greatly saves emergency inspection time and provides scientific basis for emergency disposal of unknown solid waste, improves case handling efficiency, and has guiding significance for similar ecological environment damage cases. At the same time, this article also studies the toxicity detection method of volatile organic compounds in solid waste.

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*QING Cheng-Zhi, Assistant Engineer, Zhongshan Pubilc Water Investment Co., Ltd., Zhongshan 528403, China. E-mail:
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在生态环境污染案件调查过程中,不明固体废物属性认定难、鉴别流程复杂、鉴别时效慢等问题一直影响着案件侦办效率。本文通过人员访谈、现场调查、现场快速检测设备初筛等手段,综合分析确定涉挥发性有机物不明固体危险特性检测指标,分析挥发性有机物的浸出毒性与毒性物质含量,鉴别不明固体废物属于危险废物。准确的危险特性识别大大节约了应急检测时间,为不明固体废物应急处置提供了科学依据,提升了办案效率,对同类型生态环境损害案件具有指导意义,本文同时对于固体废物挥发性有机物毒性检测方法进行了研究。

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*卿承志,助理工程师,研究方向为环境监测。E-mail:
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周伦,硕士,高级工程师,研究方向为环境监测、环境损害鉴定评估。

卿承志,助理工程师,研究方向为环境监测。

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articleId=1156967454795718733, language=CN, orderNo=5, keyword=危险特性)], refs=[Reference(id=1156967491374244561, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, doi=null, pmid=null, pmcid=null, year=2019, volume=47, issue=09, pageStart=26, pageEnd=29, url=null, language=null, rfNumber=[1], rfOrder=0, authorNames=郑洋, 蒋文博, 李克, journalName=环境保护, refType=null, unstructuredReference=郑洋, 蒋文博, 李克, 等. 规范危险废物管理推进“无废城市”建设[J]. 环境保护, 2019, 47(09): 26-29., articleTitle=规范危险废物管理推进“无废城市”建设, refAbstract=null), Reference(id=1156967491466519250, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, doi=null, pmid=null, pmcid=null, year=2019, volume=39, issue=01, pageStart=84, pageEnd=87, url=null, language=null, rfNumber=[2], rfOrder=1, authorNames=路忻, 张清敏, 李祥华, journalName=环境保护与循环经济, refType=null, unstructuredReference=路忻, 张清敏, 李祥华, 等. 某非法倾倒危险废物事件环境损害鉴定评估研究[J]. 环境保护与循环经济, 2019, 39(01): 84-87., 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检测项目 检测方法 使用仪器
苯 甲苯 乙苯 邻 - 二甲苯 间,对 - 二甲苯 氯苯 1,2- 二氯苯 1,4- 二氯苯 固体废物 挥发性有机物的 测定 顶空 / 气相色谱 - 质 谱法 (HJ 643-2013),前 处理方法(HJ/T 299) 气相色谱质谱联用仪 GC7890B -5977B
苯并(a)芘 固体废物 多环芳烃的测 定高效液相色谱法(HJ 892-2017),前处理方法 ( HJ/T 299 ) 高效液相色谱仪 Agilent 1100
), ArticleFig(id=1156967490619269834, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, language=CN, label=表 1, caption=固体废物 - 浸出毒性检测方法和使用仪器, figureFileSmall=null, figureFileBig=null, tableContent=
检测项目 检测方法 使用仪器
苯 甲苯 乙苯 邻 - 二甲苯 间,对 - 二甲苯 氯苯 1,2- 二氯苯 1,4- 二氯苯 固体废物 挥发性有机物的 测定 顶空 / 气相色谱 - 质 谱法 (HJ 643-2013),前 处理方法(HJ/T 299) 气相色谱质谱联用仪 GC7890B -5977B
苯并(a)芘 固体废物 多环芳烃的测 定高效液相色谱法(HJ 892-2017),前处理方法 ( HJ/T 299 ) 高效液相色谱仪 Agilent 1100
), ArticleFig(id=1156967490778653387, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, language=EN, label=Table 2, caption=Solid waste-total amount detection methods and instruments used, figureFileSmall=null, figureFileBig=null, tableContent=
检测项目 检测方法 使用仪器及编号
石油溶剂 《危险废物鉴别标准 毒性物 质含量鉴别》(GB 5085.6-2007)附录 O 固体废物可回 收石油烃总量的测定 红外光 谱法 红外测油仪 /OIL 480
苯 苯乙烯 1,2- 二氯苯 1,3- 二氯苯 1,4- 二氯苯 固体废物 挥发性有机物的测 定 顶空 / 气相色谱 - 质谱法 ( HJ 643-2013 ) 气相色谱质谱联用仪 GC7890B-5977B
苯并 (a) 蒽 苯并 (b) 荧蒽 苯并 (k) 荧蒽 苯并 (a) 芘 二苯并 (a, h) 蒽 固体废物 半挥发性有机物 的测定 气相色谱 - 质谱法 ( HJ 892-2017 ) 气相色谱质谱联用仪 GC8890-5977B
), ArticleFig(id=1156967490896093900, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, language=CN, label=表 2, caption=固体废物 - 总量检测方法、使用仪器, figureFileSmall=null, figureFileBig=null, tableContent=
检测项目 检测方法 使用仪器及编号
石油溶剂 《危险废物鉴别标准 毒性物 质含量鉴别》(GB 5085.6-2007)附录 O 固体废物可回 收石油烃总量的测定 红外光 谱法 红外测油仪 /OIL 480
苯 苯乙烯 1,2- 二氯苯 1,3- 二氯苯 1,4- 二氯苯 固体废物 挥发性有机物的测 定 顶空 / 气相色谱 - 质谱法 ( HJ 643-2013 ) 气相色谱质谱联用仪 GC7890B-5977B
苯并 (a) 蒽 苯并 (b) 荧蒽 苯并 (k) 荧蒽 苯并 (a) 芘 二苯并 (a, h) 蒽 固体废物 半挥发性有机物 的测定 气相色谱 - 质谱法 ( HJ 892-2017 ) 气相色谱质谱联用仪 GC8890-5977B
), ArticleFig(id=1156967490992562893, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, language=EN, label=Table 3, caption=Results of leaching toxicity test, figureFileSmall=null, figureFileBig=null, tableContent=
检测项目 份样数 (个) 检出率 (% ) 最小值 (mg/L) 最大值 (mg/L) 浓度限值 (mg/L) 超标份 样数 (个)
苯并 (a) 芘 8 100 0.0018 0.031 0.0003 8
8 100 0.0766 4.48 1 2
甲苯 8 100 0.677 2.61 1 3
乙苯 8 100 0.113 0.407 4 0
二甲苯 8 100 0.137 0.747 4 0
氯苯 8 100 0.341 1.77 2 0
1,2- 二氯苯 8 100 0.478 2.52 4 0
1,4- 二氯苯 8 0 未检出 未检出 4 0
), ArticleFig(id=1156967491063866062, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, language=CN, label=表 3, caption=浸出毒性检测结果, figureFileSmall=null, figureFileBig=null, tableContent=
检测项目 份样数 (个) 检出率 (% ) 最小值 (mg/L) 最大值 (mg/L) 浓度限值 (mg/L) 超标份 样数 (个)
苯并 (a) 芘 8 100 0.0018 0.031 0.0003 8
8 100 0.0766 4.48 1 2
甲苯 8 100 0.677 2.61 1 3
乙苯 8 100 0.113 0.407 4 0
二甲苯 8 100 0.137 0.747 4 0
氯苯 8 100 0.341 1.77 2 0
1,2- 二氯苯 8 100 0.478 2.52 4 0
1,4- 二氯苯 8 0 未检出 未检出 4 0
), ArticleFig(id=1156967491151946447, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, language=EN, label=Table 4, caption=Accumulated toxicity statistics table for toxic substance content, figureFileSmall=null, figureFileBig=null, tableContent=
样品 编号 致突变性 物质 致癌性物质 有毒物质 累积 毒性
苯并 (a) 芘 苯并 (a) 蒽 苯并 (b) 荧蒽 苯并 (k) 荧蒽 二苯并 (a, h) 蒽 苯乙烯 1,2- 二氯苯 1,3- 二氯苯 1,4- 二氯苯 石油溶剂
标准 限值 0.1% 0.1% 3% 1
01 0.0115 0.00216 0.0119 0.00965 0.00864 0.00140 0.00349 0.000223 0.000169 0.0000504 1.06 1.11
02 0.0193 0.00108 0.0190 0.0155 0.0146 0.00240 0.000999 0.000166 0.0000827 0.000107 1.11 1.18
03 0.0217 0.000900 0.0216 0.0187 0.0154 0.00290 0.00112 0.000161 0.0000974 0.0000873 0.735 0.82
04 0.0237 0.00214 0.0232 0.0210 0.0161 0.00320 0.00196 0.000198 0.000135 0.000136 1.07 1.16
05 0.00890 0.00789 0.00986 0.00744 0.00689 0.00120 0.00567 0.000354 0.000191 0.000229 1.57 1.62
06 0.0368 0.00281 0.0445 0.0332 0.0277 0.00690 0.00208 0.000185 0.000101 0.000100 1.33 1.48
07 0.0966 0.0216 0.104 0.0865 0.0681 0.0108 0.0111 0.000426 0.000242 0.0000843 2.33 2.73
08 0.00100 0.000122 0.00103 0.000820 0.000750 0.000100 0.00399 0.000127 0.0000633 0.0000487 0.274 0.28
), ArticleFig(id=1156967491231638224, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967454795718733, language=CN, label=表 4, caption=毒性物质含量累计毒性统计表, figureFileSmall=null, figureFileBig=null, tableContent=
样品 编号 致突变性 物质 致癌性物质 有毒物质 累积 毒性
苯并 (a) 芘 苯并 (a) 蒽 苯并 (b) 荧蒽 苯并 (k) 荧蒽 二苯并 (a, h) 蒽 苯乙烯 1,2- 二氯苯 1,3- 二氯苯 1,4- 二氯苯 石油溶剂
标准 限值 0.1% 0.1% 3% 1
01 0.0115 0.00216 0.0119 0.00965 0.00864 0.00140 0.00349 0.000223 0.000169 0.0000504 1.06 1.11
02 0.0193 0.00108 0.0190 0.0155 0.0146 0.00240 0.000999 0.000166 0.0000827 0.000107 1.11 1.18
03 0.0217 0.000900 0.0216 0.0187 0.0154 0.00290 0.00112 0.000161 0.0000974 0.0000873 0.735 0.82
04 0.0237 0.00214 0.0232 0.0210 0.0161 0.00320 0.00196 0.000198 0.000135 0.000136 1.07 1.16
05 0.00890 0.00789 0.00986 0.00744 0.00689 0.00120 0.00567 0.000354 0.000191 0.000229 1.57 1.62
06 0.0368 0.00281 0.0445 0.0332 0.0277 0.00690 0.00208 0.000185 0.000101 0.000100 1.33 1.48
07 0.0966 0.0216 0.104 0.0865 0.0681 0.0108 0.0111 0.000426 0.000242 0.0000843 2.33 2.73
08 0.00100 0.000122 0.00103 0.000820 0.000750 0.000100 0.00399 0.000127 0.0000633 0.0000487 0.274 0.28
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涉挥发性有机物不明固体废物危险特性鉴别研究
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周伦 1 , 卿承志 1, * , 谢娟 2 , 邹欣君 2 , 李朝圣 2
实验室检测 | 评价与分析 2024,2(6): 98-101
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实验室检测 | 评价与分析 2024, 2(6): 98-101
涉挥发性有机物不明固体废物危险特性鉴别研究
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周伦1, 卿承志1, * , 谢娟2, 邹欣君2, 李朝圣2
作者信息
  • 1 中山公用水务投资有限公司 中山 528403
  • 2 四川中环联蜀环境咨询服务有限公司 成都 610100
  • 周伦,硕士,高级工程师,研究方向为环境监测、环境损害鉴定评估。

    卿承志,助理工程师,研究方向为环境监测。

通讯作者:

*卿承志,助理工程师,研究方向为环境监测。E-mail:
Dentification of hazardous characteristics of unknown solid waste involving volatile organic compounds
Lun ZHOU1, Cheng-Zhi QING1, * , Juan XIE2, Xin-Jun ZOU2, Chao-Sheng LI2
Affiliations
  • 1 Zhongshan Pubilc Water Investment Co., Ltd. Zhongshan 528403 China
  • 2 Sichuan Zhonghuanlianshu Environmental Consulting Service Co., Ltd. Chengdu 610100 China
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在生态环境污染案件调查过程中,不明固体废物属性认定难、鉴别流程复杂、鉴别时效慢等问题一直影响着案件侦办效率。本文通过人员访谈、现场调查、现场快速检测设备初筛等手段,综合分析确定涉挥发性有机物不明固体危险特性检测指标,分析挥发性有机物的浸出毒性与毒性物质含量,鉴别不明固体废物属于危险废物。准确的危险特性识别大大节约了应急检测时间,为不明固体废物应急处置提供了科学依据,提升了办案效率,对同类型生态环境损害案件具有指导意义,本文同时对于固体废物挥发性有机物毒性检测方法进行了研究。

现场调查  /  快速检测  /  不明固体废物  /  挥发性有机物  /  危险特性

In the process of investigating ecological and environmental pollution cases, problems such as difficulty in identifying the attributes of unknown solid waste, complex identification processes, and slow identification time have always affected the efficiency of case investigation. Through personnel interviews, on-site investigations, and initial screening of on-site rapid detection equipment, comprehensive analysis is conducted to determine the detection indicators for the hazardous characteristics of unknown solid volatile organic compounds. The leaching toxicity and toxic substance content of volatile organic compounds are analyzed to identify unknown solid waste as hazardous waste. Accurate identification of hazardous characteristics greatly saves emergency inspection time and provides scientific basis for emergency disposal of unknown solid waste, improves case handling efficiency, and has guiding significance for similar ecological environment damage cases. At the same time, this article also studies the toxicity detection method of volatile organic compounds in solid waste.

field investigation  /  quick detection  /  unknown solid waste  /  volatile organic compounds  /  hazardous characteristics
周伦, 卿承志, 谢娟, 邹欣君, 李朝圣. 涉挥发性有机物不明固体废物危险特性鉴别研究. 实验室检测, 2024 , 2 (6) : 98 -101 .
Lun ZHOU, Cheng-Zhi QING, Juan XIE, Xin-Jun ZOU, Chao-Sheng LI. Dentification of hazardous characteristics of unknown solid waste involving volatile organic compounds[J]. Laboratory Testing, 2024 , 2 (6) : 98 -101 .
近些年“无废城市”“无废工厂”等先进环境管理概念的不断普及 [ 1 ] ,固体废物的无害化处置以及资源利用加快形成绿色生活方式。但是在各地生态环境损害案件办理过程中,地表水与污水涉及损害的案件较多 [ 2 ] ,然而非法处置固体废物尤其是危险废物导致土壤、地下水环境损害的案件仍占比例偏少。在生态环境污染案件调查过程中,不明固体废物属性认定难、鉴别流程复杂、现场情况变化快、鉴别周期长 [ 3 ] 、鉴别技术不足 [ 4 ] 、 鉴别费用高等问题一直影响着案件侦办的效率。尤其是涉及挥发性有机物固体废物污染案件, 毒性分析手段烦琐, 现场变化情况复杂, 各地发生案例并不多。本文以国内某地发生一起涉及挥发性有机物污染的非法填埋不明固体废物案件为例, 通过对不明固体废物数量、气味、形态、颜色、填埋状态等调查, 开展大量的人员访谈, 并利用快速检测设备进行危险特性识别, 制定合理精简的鉴别方案, 精准抓到不明固体废物中的特征污染挥发性有机物类别, 对此类不明固体废物精准鉴别提出建议, 节约突发环境案件办案时间。本文提出的精准鉴别技术路线对该类别案件侦办提供了可参考的快速鉴别技术流程, 同时对固体废物中挥发性有机物各类毒性检测方法进行了研究, 为生态环境损害案件中不明固体填埋案件提供了办案思路具有典型指导意义。
当地执法人员根据投诉人指定的刺鼻区域的位置, 现场使用吊车、叉车、小型挖掘机对该区域进行清理挖掘, 深度挖掘至 ${0.5}\mathrm{\;m}$ 后,露出黑色不明固体,并伴有疑似沥青的刺鼻气味。 开展大量周边居民人员访谈, 发现不明固体可能是由于开展道路修建工程中使用沥青后产生的中间物,其他溯源情况缺失。
清挖出的不明固体废物共计接近 20 吨,盛装于 30 个吨袋中, 外观形态基本一致, 均呈黑灰色固态, 有明显刺激性气味, 大部分较干,有少量部分沾染有黑色油状黏稠物质。通过便携式 VOC 检测仪 (PID), 进行总挥发性气体检测, 检测仪器数值显示在 ${30}\sim {130}\mathrm{{mg}}/{\mathrm{m}}^{3}$ 之间。
结合人员访谈、案件笔录以及现场实际调查情况, 初步判断不明固体可能来源为石油炼制 [ 5 ] 或石油化工行业 [ 6 ] 。确定特征污染物为:苯系物、卤代烃、多环芳烃、烯烃等。
结合石油相关行业特征污染物与现场调查实际情况, 筛选出毒性类别检测指标为:
(1)浸出毒性:苯并 (a) 芘、苯、甲苯、乙苯、二甲苯、氯苯、 1,2- 二氯苯、1,4- 二氯苯;
(2)毒性物质含量指标:石油溶剂、苯、苯乙烯、1,2-二氯苯、 1,3- 二氯苯、1,4- 二氯苯、苯并 (b) 荧蒽、苯并 (a) 蒽、苯并 (a) 芘、 苯并(k)荧蒽、二苯并(a, h)蒽。
根据危险废物鉴别技术规范中的固态废物样品采集的要求, 鉴定材料的原始可能最大粒径 $<{0.5}$ 厘米,因此本次样品采集的份样量为 ${500}\mathrm{\;g}$ 。产生来源不明的固体废物应采集能够代表固体废物组成特性的样品。
本次挥发性有机物总量与浸出检测主要使用安捷伦气象色谱质谱联用仪, 半挥发性有机物浸出检测主要使用安捷伦高效液相色谱仪, 石油溶剂主要使用红外测油仪, 前处理仪器主要有顶空进样器, ${20}\mathrm{\;{mL}}$ 顶空瓶,零顶空提取器,翻转振荡装置。 按照《浸出毒性浸出方法硫酸硝酸法》, 使用零顶空提取器进行样品浸出 [ 7 ] ,对挥发性有机物浸出毒性检测方法进行方法验证与研究 [ 8 ]
检测方法、方法来源和使用仪器及检出限见 表 1表 2
本次固体废物挥发性有机物检测过程中对现行的检测方法做了验证, 并对检测过程中的关键因素进行了探究, 检测过程中的质控手段满足相关要求。8 个样品浸出毒性浸出分析结果见 表 3
由数据可知, 8 份样品苯并 (a) 芘的浸出浓度均超过《危险废物鉴别标准 浸出毒性鉴别》中规定的限值, 其中超标份样数量为 8 个; 部分样品中甲苯和苯的浸出浓度超过《危险废物鉴别标准 浸出毒性鉴别》中规定的限值, 苯的超标份样为 2 个, 甲苯的超标份样数量为 3 个;其余各浸出毒性检测指标数据均未超标。
毒性物质含量检测项目中, 检测指标为石油溶剂、苯、苯乙烯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、苯并 (a) 蒽、苯并 (b) 荧蒽、苯并 (k) 荧蒽、苯并 (a) 芘、二苯并 (a, h) 蒽的浓度, 需将检测结果换算为化合物含量, 最终换算成致突变性物质、 致癌性物质、有毒性物质当量含量。剧毒、有毒、致癌性物质、 突发性物质、生殖毒性物质总含量超过对应标准数值的是危险废物。
含有《危险废物鉴别标准 毒性物质含量鉴别》(GB 5085.6-2007)附录 A 至附录 E 中两种及以上不同毒性物质,如果符合下列等式, 按照危险废物管理 [ 9 ] :
$\sum \left\lbrack \left({\frac{{p}_{{T}^{+ }}}{{L}_{{T}^{+ }}}+ \frac{{p}_{T}}{{L}_{T}}+ \frac{{p}_{\text{Care }}}{{L}_{\text{Care }}}+ \frac{{p}_{\text{Muta }}}{{L}_{\text{Muta }}}+ \frac{{p}_{\text{Tera }}}{{L}_{\text{Tera }}}}\right)\right\rbrack \geq 1 $
文献报道中对于各类重金属等无机污染物累计毒性计算较多 [ 10 ] ,本文主要对持久性有机物进行毒性累计换算,8 个样品毒性物质按照特征污染物当量含量和累计毒性进行计算 [ 11 ] ,统计结果见 表 4 。由计算结果可知, 8 个鉴定材料样品中有 6 个样品的累积毒性超过标准限值 1 , 即超标份样数为 6 个。
根据《危险废物鉴别技术规范》(HJ 298-2019)规定本次样品各检测项目采样份样数为 8 个,如超标份样数量 等于 3, 即可判定该不明固体废物具有该种危险特性。本文中对鉴定材料具有的危险特性判定结果如下:(1) 浸出毒性判定:本次 8 个样品中苯并 (a) 芘的浸出浓度超标份样数为 8 个, 大于超标份样
数下限 ( 3 个 ); 甲苯的浸出浓度超标的份样数为 3 个, 等于超标份样数下限 ( 3 个 ); 苯的浸出浓度超标的份样数为 2 个, 小于超标份样数下限 ( 3 个 )。该鉴定材料具有苯并 (a) 芘和甲苯浸出毒性的危险特性。(2) 毒性物质含量判定: 本次 8 个鉴定材料样品中累积毒性超标份样数为 6 个, 大于超标份样数下限 ( 3 个)。该鉴定材料具有毒性物质含量的危险特性。该事件中的填埋不明固体废物浸出毒性与毒性物质含量超标, 属于危险废物, 危险特性为毒性 ( T )。
在突发不明固废倾倒填埋环境事件中, 对涉及挥发性有机物不明固体废物危险特性鉴别应通过人员访谈等多路径溯源出产废行业。结合对不明固体填埋现场开展详细调查,记录不明固体颜色、气味、物相等,利用快速检测设备开展相关定性分析, 全面准确地确定危险特性测试指标。为案件侦办提供了准确的科学依据, 同时节约了案件办理时间与减少了鉴别工作量, 对于生态环境损害案件的现场调查工作与突发环境事件的及时处理具有指导性意义。
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    1 中山公用水务投资有限公司 中山 528403
    2 四川中环联蜀环境咨询服务有限公司 成都 610100

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*卿承志,助理工程师,研究方向为环境监测。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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