富硫化物隐伏矿地球化学勘查技术:含硫气体地球化学测量

doi:10.13745/j.esf.sf.2024.10.31

摘要/Abstract

摘要：

含硫气体地球化学测量在找矿勘查中具有悠久的历史。但是由于含硫气体的高活动性和反应性、测试结果低重现性、分析测试高成本等缺点,含硫气体未能大规模应用于隐伏矿勘查。矿产勘查由近地表易发现矿转向隐伏矿以及便携式经济、高效和实时气体测量设备的成功研发,为气体地球化学勘查方法体系的完善升级和推广应用提供了一个新的契机。本文重点梳理了富硫化物隐伏矿气体地球化学测量研究进展、面临的挑战和未来发展方向。动力学平衡模拟、矿物(矿石)风化实验和矿区实例研究表明,富硫化物隐伏矿上方土壤中气体地球化学异常受多种因素影响,如矿体矿物组成、盖层特征、微生物作用、地球化学景观类型和含硫气体物理化学特征等。在土壤覆盖区可采用便携式多组分气体测量仪实现现场实时测量,若隐伏矿直接被运积层覆盖,则含硫气体异常与隐伏矿倾向于具有垂向对应关系。在基岩出露区则可采用岩石热解吸的方式测量含硫气体。隐伏矿与含硫气体异常的空间关系取决于断层和裂隙等渗透性通道的发育情况。案例研究统计表明,含硫气体地球化学测量不仅适用于半干旱-干旱地区,在半湿润-湿润地区也具有一定潜力。未来研究主要聚焦含硫气体在表生环境中的形成演化过程(查明主控因素)、不同地球化学景观区(尤其是半湿润-湿润气候区)含硫气体地球化学测量有效性以及便携式土壤气体测量设备小型化和智能化升级改造3个方面。

关键词: 地球化学勘查, 覆盖区, 隐伏矿, 土壤气, 含硫气体

Abstract:

Sulfur gas geochemical detection has long been applied in mineral exploration. However, this method has not been widely used due to the high activity and reactivity of sulfur gases, low reproducibility of test results, and high cost. Today, as mineral exploration shifts from near-surface, easy-to-discover ore deposits to deep concealed ones, and with the successful development of portable, economical, efficient, real-time gas detection systems, a new opportunity arises to improve and promote this method. This paper reviews research progress, challenges, and future development directions regarding to concealed sulfide-rich deposits. Equilibrium thermodynamic models, simulation experiments on weathering and oxidation of sulfide minerals, and field studies suggest that gas geochemical anomalies of concealed sulfide-rich ore deposits are influenced by their mineral compositions, cover characteristics, geochemical landscapes, and physicochemical characteristics of sulfur gases. In regolith-covered terrains, portable multi-component gas analyzers can be used to obtain on-site, real-time measurements of soil gases including sulfur gases; more importantly, sulfur gas anomalies in soils tend to appear directly above the blind deposits if the blind deposits are covered by regolith directly. In bedrock outcrops, sulfur gases can be measured by rock thermal desorption; and the spatial relationship between the blind deposits and sulfur gas anomalies is primarily influenced by the development of permeable channels such as faults and fractures. Case studies indicate the sulfur gas geochemical detection is effective for mineral exploration in semi-arid and arid terrains and has great potential for mineral exploration in semi-humid and humid terrains. Future research directions should focus on three aspects: the formation and evolutionary process of sulfur gases in surface environment to ascertain the dominant controlling factors; the effectiveness of geochemical detection of sulphur-containing gases under different geochemical landscapes, especially in semi-humid and humid terrains; and the miniaturization and intelligent upgrading of portable soil gas detection equipment.

Key words: geochemical exploration, covered terrain, blind deposits, soil gas, sulfur gases

中图分类号:

P632
P632.5

王强, 程志中, 颜廷杰, 林成贵, 杜泽忠, 袁慧香, 李晓蕾. 富硫化物隐伏矿地球化学勘查技术:含硫气体地球化学测量[J]. 地学前缘, 2025, 32(1): 302-321.

WANG Qiang, CHENG Zhizhong, YAN Tingjie, LIN Chenggui, DU Zezhong, YUAN Huixiang, LI Xiaolei. Geochemical exploration of blind sulfide-rich ore deposits: Sulphur gas geochemical detection[J]. Earth Science Frontiers, 2025, 32(1): 302-321.

图/表 9

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序号仪器系统	成分和参数	原理	精度	参考文献
ST-SO₂-1型仪器	SO₂	未知	10^-6级	[69]
多组分羽流传感器系统	CO₂	便携式LI-COR红外CO₂分析仪(LI-800)	10^-6级	[37]
	SO₂	便携式SO₂分析仪KP-1(Komyo Rikagaku KK),恒电位电解式传感器	10^-6级
	湿度和温度	Vaisala HMP45D
基于膜的气体收集/ 分析系统	H₂S	通过它们与荧光素-乙酸汞(FMA)反应的能力来测量	<10^-9~10^-9级	[71]
	SO₂		<10^-9~10^-9级
	CH₃-SH		<10^-9~10^-9级
PMGRA	CO₂	红外吸收光谱法	(1~99 999)×10^-6	[38,49,72]
	CH₄	红外吸收光谱法	(0.1~10 000)×10^-6
	SO₂	电化学气体测量传感器	(0.001~5)×10^-6
	H₂S	电化学气体测量传感器	(0.01~1)×10^-6
实时气体测量装置	汞气	Lumex© RA-915M便携式塞曼原子吸收光谱仪	10^-9级	[39]
实时气体测量装置	H₂S	Thermo© 450i脉冲荧光气体分析仪	10^-6级	[39]
UV-DOAS痕量气体检测平台	SO₂、CS₂和 H₂S	紫外吸收光谱与最小二乘拟合	SO₂和H₂S:(0.5~10)×10^-6; CS₂:(10~300)×10^-9	[40]
便携式气体分析仪	CO₂	Gascard II红外光谱仪	(0~4 000)×10^-6	[73]
	SO₂	SO₂-S-100型Membrapor气体电化学传感器	(0~100)×10^-6
	H₂S	H₂S-S-50型Membrapor气体电化学传感器	(0~50)×10^-6

序号仪器系统	成分和参数	原理	精度	参考文献
ST-SO₂-1型仪器	SO₂	未知	10^-6级	[69]
多组分羽流传感器系统	CO₂	便携式LI-COR红外CO₂分析仪(LI-800)	10^-6级	[37]
	SO₂	便携式SO₂分析仪KP-1(Komyo Rikagaku KK),恒电位电解式传感器	10^-6级
	湿度和温度	Vaisala HMP45D
基于膜的气体收集/ 分析系统	H₂S	通过它们与荧光素-乙酸汞(FMA)反应的能力来测量	<10^-9~10^-9级	[71]
	SO₂		<10^-9~10^-9级
	CH₃-SH		<10^-9~10^-9级
PMGRA	CO₂	红外吸收光谱法	(1~99 999)×10^-6	[38,49,72]
	CH₄	红外吸收光谱法	(0.1~10 000)×10^-6
	SO₂	电化学气体测量传感器	(0.001~5)×10^-6
	H₂S	电化学气体测量传感器	(0.01~1)×10^-6
实时气体测量装置	汞气	Lumex© RA-915M便携式塞曼原子吸收光谱仪	10^-9级	[39]
实时气体测量装置	H₂S	Thermo© 450i脉冲荧光气体分析仪	10^-6级	[39]
UV-DOAS痕量气体检测平台	SO₂、CS₂和 H₂S	紫外吸收光谱与最小二乘拟合	SO₂和H₂S:(0.5~10)×10^-6; CS₂:(10~300)×10^-9	[40]
便携式气体分析仪	CO₂	Gascard II红外光谱仪	(0~4 000)×10^-6	[73]
	SO₂	SO₂-S-100型Membrapor气体电化学传感器	(0~100)×10^-6
	H₂S	H₂S-S-50型Membrapor气体电化学传感器	(0~50)×10^-6

国家	矿区/矿床	景观和盖层	采样和测试方法	气体异常	参考文献
美国	Yankee金矿区	0.3~1 m土壤,植被稀疏	土壤气(孔深为1.0 m)、基岩界面处土壤解吸气、收集器(浅部0.3~0.7 m、深入基岩3 m)	CH₄、COS和CS₂;土壤解吸气效果较好	[45]
	科罗拉多矿带金银脉			矿体上方SO₂含量高达50×10^-9	[74]
	Gas Hills、Shirley盆地和Powder River铀矿			SO₂	[74]
	Tyrone硫化物矿床			矿体上方SO₂含量高达25×10^-9	[74]
	Johnson Camp铜锌矿	半干旱区,盖层厚度:Zone Ⅰ为10 m,Zone Ⅱ为90~150 m,Zone Ⅲ为225 m	分子筛,深度为30~45 cm,8周	COS含量为(0~300)×10^-9,50×10^-9为异常下限;H₂S含量为(0~1 000)×10^-9,300×10^-9为异常下限	[14]
			抽气法,孔深为1.0 m	Zone 1和Ⅱ上方CO₂和ΔO₂异常	[32]
			土壤表层0~2 cm,深层45~50 cm,150 ℃热解吸	表面微层含硫气体(COS、CS₂和CH₃)₂S₂和有机挥发物异常;深层样品效果差	[32,44]
			抽气法,孔深为0.5 m	Ⅱ号带上方COS、CS₂、CO₂和O₂	[16-17]
			土壤微表层(粒径<150 μm)解吸	Ⅱ号带,COS含量>0.3×10^-9,背景区含量为0.1×10^-9	[19]
	North Silver Bell斑岩铜矿	丘陵区,局部冲洪积物覆盖	土壤(0~5 cm,-30目)解吸气(均衡3天,47 ℃)	矿体上方He、CS₂和SO₂;蚀变带:CO₂和O₂异常;H₂S和COS异常少	[33]
	Crandon块状硫化物矿床	盖层冰碛物,厚度约65 m	抽气法,孔深为0.5 m	CO₂和CH₄正异常,O₂负异常,未检测到含硫气体	[18]
	Crandon块状硫化物矿床	盖层冰碛物,厚度约65 m	抽气法,孔深为0.75 m	O₂负异常,CO₂正异常	[75]
	Torpedo铜矿	半干旱,冲洪积物,厚度为5~10 m	微表层,粒径<150 μm土壤,解吸气	矿化带COS异常模式不规则,COS含量峰值为(0.4~0.8)×10^-9	[19]
	Quartzburg金矿脉	第四系覆盖,厚度为几米	孔深为0.75 m	矿体上方:C₃H₈、CO₂/O₂值、含硫气体(COS)	[47]
	Cripple Creek金矿区			H₂S	[76]
爱尔兰	Keel块状硫化物Pb-Zn矿床	湿润,牧场,富黏土耕地,2~7 m冰碛物覆盖	土壤解吸	矿化断层上方COS含量高达1.5×10^-9,背景区含量<0.75×10^-9	[15]
爱尔兰	Keel块状硫化物Pb-Zn矿床	湿润,牧场,富黏土耕地,2~7 m冰碛物覆盖	表面微层,粒径<150 μm土壤,解吸气	COS,矿化断层和氧化带上方含量>0.75×10^-9	[19]
纳米比亚	Witvlei地区黄铜矿	半干旱,氧化深度达30 m,表层2 m沙覆盖	土壤深度为0.3~0.5 m;孔深约1.0 m	土壤Cu异常;CO₂正异常和O₂负异常	[16]
沙特	AshSha‘ib锌铜矿	极端干旱气候区,松散砂质沉积物覆盖,厚度为4~8 m	土壤深度为0.3~0.5 m;孔深约1.0 m	O₂负异常,含硫气体和CO₂正异常	[16]
沙特	AshSha‘ib锌铜矿	极端干旱气候区,松散砂质沉积物覆盖,厚度为4~8 m	粒径<150 μm土壤,解吸气	异常区COS含量>0.4×10^-9,局部含量高达1.5×10^-9,背景区含量为0.2×10^-9	[19]
津巴布韦	Dalny矿区金矿	1 m残积土和0.3 m季节性积水土壤	抽气法,孔深为0.75 m	O₂负异常,CO₂正异常	[75]
加纳	Ashanti矿区金矿	热带雨林气候带,残余土壤厚度为5 m	抽气法,孔深为0.75 m	CO₂异常	[75]
博茨瓦纳	Ngwako Pan铜矿	沙漠区	抽气法,孔深为0.75m	CO₂和Tn异常(不同深度对比,埋深较大的异常弱)	[75]
序号	矿区/矿床	景观/盖层	采样和测试方法	气体异常	参考文献
澳大利亚	North Miitel镍矿	半干旱盐碱地,矿体深度为200~400 m	被动式采样	COS	[21]
澳大利亚	Junction金矿	半干旱,风化壳上方1~3 m覆盖物	被动式采样,孔深为0.9 m	CO₂-O₂-轻烃异常	[77]
南非	Geelvloer铅锌矿	干旱气候区,风成沙和残积物厚度为10 m	表面微层,粒径<150 μm土壤,解吸气	COS含量为(0.3~0.4)×10^-9	[19,78]
中国	江苏小茅山多金属矿区	高温潮湿区,第四系,厚度为50 m	土壤深度为0.8~1.0 m,解吸气	H₂S、SO₂、甲烷和丁烷异常	[46]
	甘肃铅锌多金属矿区	半干旱半荒漠区,50~100 m黄土,基岩面下约20 m	土壤深度为0.5~1.0 m,解吸气	H₂S和SO₂;烃类异常,衬度低	[46]
	山西辛庄金矿区	风积黄土厚度几米至120 m,一般为30~40 m	土壤深度为0.5~1.0 m,解吸气	SO₂、H₂S和烃类	[46]
	江西朱砂红斑岩型铜钼矿区	岩石裸露区盲矿	岩石解吸气	SO₂、H₂S和烃类	[46]
	安徽胡村夕卡岩铜钼矿区	岩石裸露区盲矿,埋深为250~300 m	岩石解吸气	SO₂、H₂S和烃类	[46]
	湖北铜山口矿区某夕卡岩-斑岩复合型铜矿	岩石裸露区盲矿	岩石解吸气	SO₂、H₂S和烃类	[46]
	内蒙古拜仁达坝银铅锌矿	第四系,覆盖物厚度为0.2~34 m	孔深为0.6~0.7 m	CO₂、SO₂和H₂S,与矿体头部位置对应	[38]
	江西景德镇朱溪钨铜矿	多为隐伏矿体,仅可见零星矿体出露	孔深为0.6~0.7 m	CO₂、SO₂和H₂S	[38]
	江西乐平月形铜矿	第四系覆盖厚,矿体深度为180 m	孔深为0.6~0.7 m	CO₂、SO₂和H₂S	[38]
	湖南黄金洞金矿区	低山丘陵区	抽气法,孔深为0.6~0.7 m	CO₂	[79]
	辽宁五龙金矿区石英脉型金矿	湿润丘陵区,第四系盖层厚度分别为 0.7~5 m和1~10 m	抽气法,孔深为0.7~1.0 m	CO₂、CH₄、SO₂和H₂S	[49]
	辽宁青城子矿田	湿润丘陵区,第四系	抽气法,孔深为0.7~1.0 m	CO₂、CH₄、SO₂和H₂S	[49]
	河北秦家营银铅锌矿区	半干旱地区,第四系	抽气法,孔深为0.7~1.0 m	CO₂、CH₄、SO₂和H₂S	[80]
	内蒙古皂火壕铀矿区	半干旱-干旱地区,第四系	抽气法	Rn、CO₂、⁴He、SO₂和H₂S	[81]
葡萄牙	Neves-Corvo铜锡矿	低渗透变质岩盖层,矿体埋深为400~500 m	抽气法孔深约1.0 m	Rn、He、CO₂(24.3%)、O₂、烃气、SO₂和COS	[48]
意大利	Tolfa矿区块状硫化物矿	山区,废弃矿山,埋深为30~100 m	抽气法孔深约1.0 m	Rn、CO₂(9.5%)、O₂、烃气、SO₂(含量为0.3×10^-6)和COS(含量为3.7×10^-6)	[48]
哈萨克斯坦	中部铜钼矿	盖层厚度为0.6~3.0 m	孔深为1.0~1.8 m	总硫	[53]
加拿大	高地山谷硫化物矿床			SO₂	[74]

国家	矿区/矿床	景观和盖层	采样和测试方法	气体异常	参考文献
美国	Yankee金矿区	0.3~1 m土壤,植被稀疏	土壤气(孔深为1.0 m)、基岩界面处土壤解吸气、收集器(浅部0.3~0.7 m、深入基岩3 m)	CH₄、COS和CS₂;土壤解吸气效果较好	[45]
	科罗拉多矿带金银脉			矿体上方SO₂含量高达50×10^-9	[74]
	Gas Hills、Shirley盆地和Powder River铀矿			SO₂	[74]
	Tyrone硫化物矿床			矿体上方SO₂含量高达25×10^-9	[74]
	Johnson Camp铜锌矿	半干旱区,盖层厚度:Zone Ⅰ为10 m,Zone Ⅱ为90~150 m,Zone Ⅲ为225 m	分子筛,深度为30~45 cm,8周	COS含量为(0~300)×10^-9,50×10^-9为异常下限;H₂S含量为(0~1 000)×10^-9,300×10^-9为异常下限	[14]
			抽气法,孔深为1.0 m	Zone 1和Ⅱ上方CO₂和ΔO₂异常	[32]
			土壤表层0~2 cm,深层45~50 cm,150 ℃热解吸	表面微层含硫气体(COS、CS₂和CH₃)₂S₂和有机挥发物异常;深层样品效果差	[32,44]
			抽气法,孔深为0.5 m	Ⅱ号带上方COS、CS₂、CO₂和O₂	[16-17]
			土壤微表层(粒径<150 μm)解吸	Ⅱ号带,COS含量>0.3×10^-9,背景区含量为0.1×10^-9	[19]
	North Silver Bell斑岩铜矿	丘陵区,局部冲洪积物覆盖	土壤(0~5 cm,-30目)解吸气(均衡3天,47 ℃)	矿体上方He、CS₂和SO₂;蚀变带:CO₂和O₂异常;H₂S和COS异常少	[33]
	Crandon块状硫化物矿床	盖层冰碛物,厚度约65 m	抽气法,孔深为0.5 m	CO₂和CH₄正异常,O₂负异常,未检测到含硫气体	[18]
	Crandon块状硫化物矿床	盖层冰碛物,厚度约65 m	抽气法,孔深为0.75 m	O₂负异常,CO₂正异常	[75]
	Torpedo铜矿	半干旱,冲洪积物,厚度为5~10 m	微表层,粒径<150 μm土壤,解吸气	矿化带COS异常模式不规则,COS含量峰值为(0.4~0.8)×10^-9	[19]
	Quartzburg金矿脉	第四系覆盖,厚度为几米	孔深为0.75 m	矿体上方:C₃H₈、CO₂/O₂值、含硫气体(COS)	[47]
	Cripple Creek金矿区			H₂S	[76]
爱尔兰	Keel块状硫化物Pb-Zn矿床	湿润,牧场,富黏土耕地,2~7 m冰碛物覆盖	土壤解吸	矿化断层上方COS含量高达1.5×10^-9,背景区含量<0.75×10^-9	[15]
爱尔兰	Keel块状硫化物Pb-Zn矿床	湿润,牧场,富黏土耕地,2~7 m冰碛物覆盖	表面微层,粒径<150 μm土壤,解吸气	COS,矿化断层和氧化带上方含量>0.75×10^-9	[19]
纳米比亚	Witvlei地区黄铜矿	半干旱,氧化深度达30 m,表层2 m沙覆盖	土壤深度为0.3~0.5 m;孔深约1.0 m	土壤Cu异常;CO₂正异常和O₂负异常	[16]
沙特	AshSha‘ib锌铜矿	极端干旱气候区,松散砂质沉积物覆盖,厚度为4~8 m	土壤深度为0.3~0.5 m;孔深约1.0 m	O₂负异常,含硫气体和CO₂正异常	[16]
沙特	AshSha‘ib锌铜矿	极端干旱气候区,松散砂质沉积物覆盖,厚度为4~8 m	粒径<150 μm土壤,解吸气	异常区COS含量>0.4×10^-9,局部含量高达1.5×10^-9,背景区含量为0.2×10^-9	[19]
津巴布韦	Dalny矿区金矿	1 m残积土和0.3 m季节性积水土壤	抽气法,孔深为0.75 m	O₂负异常,CO₂正异常	[75]
加纳	Ashanti矿区金矿	热带雨林气候带,残余土壤厚度为5 m	抽气法,孔深为0.75 m	CO₂异常	[75]
博茨瓦纳	Ngwako Pan铜矿	沙漠区	抽气法,孔深为0.75m	CO₂和Tn异常(不同深度对比,埋深较大的异常弱)	[75]
序号	矿区/矿床	景观/盖层	采样和测试方法	气体异常	参考文献
澳大利亚	North Miitel镍矿	半干旱盐碱地,矿体深度为200~400 m	被动式采样	COS	[21]
澳大利亚	Junction金矿	半干旱,风化壳上方1~3 m覆盖物	被动式采样,孔深为0.9 m	CO₂-O₂-轻烃异常	[77]
南非	Geelvloer铅锌矿	干旱气候区,风成沙和残积物厚度为10 m	表面微层,粒径<150 μm土壤,解吸气	COS含量为(0.3~0.4)×10^-9	[19,78]
中国	江苏小茅山多金属矿区	高温潮湿区,第四系,厚度为50 m	土壤深度为0.8~1.0 m,解吸气	H₂S、SO₂、甲烷和丁烷异常	[46]
	甘肃铅锌多金属矿区	半干旱半荒漠区,50~100 m黄土,基岩面下约20 m	土壤深度为0.5~1.0 m,解吸气	H₂S和SO₂;烃类异常,衬度低	[46]
	山西辛庄金矿区	风积黄土厚度几米至120 m,一般为30~40 m	土壤深度为0.5~1.0 m,解吸气	SO₂、H₂S和烃类	[46]
	江西朱砂红斑岩型铜钼矿区	岩石裸露区盲矿	岩石解吸气	SO₂、H₂S和烃类	[46]
	安徽胡村夕卡岩铜钼矿区	岩石裸露区盲矿,埋深为250~300 m	岩石解吸气	SO₂、H₂S和烃类	[46]
	湖北铜山口矿区某夕卡岩-斑岩复合型铜矿	岩石裸露区盲矿	岩石解吸气	SO₂、H₂S和烃类	[46]
	内蒙古拜仁达坝银铅锌矿	第四系,覆盖物厚度为0.2~34 m	孔深为0.6~0.7 m	CO₂、SO₂和H₂S,与矿体头部位置对应	[38]
	江西景德镇朱溪钨铜矿	多为隐伏矿体,仅可见零星矿体出露	孔深为0.6~0.7 m	CO₂、SO₂和H₂S	[38]
	江西乐平月形铜矿	第四系覆盖厚,矿体深度为180 m	孔深为0.6~0.7 m	CO₂、SO₂和H₂S	[38]
	湖南黄金洞金矿区	低山丘陵区	抽气法,孔深为0.6~0.7 m	CO₂	[79]
	辽宁五龙金矿区石英脉型金矿	湿润丘陵区,第四系盖层厚度分别为 0.7~5 m和1~10 m	抽气法,孔深为0.7~1.0 m	CO₂、CH₄、SO₂和H₂S	[49]
	辽宁青城子矿田	湿润丘陵区,第四系	抽气法,孔深为0.7~1.0 m	CO₂、CH₄、SO₂和H₂S	[49]
	河北秦家营银铅锌矿区	半干旱地区,第四系	抽气法,孔深为0.7~1.0 m	CO₂、CH₄、SO₂和H₂S	[80]
	内蒙古皂火壕铀矿区	半干旱-干旱地区,第四系	抽气法	Rn、CO₂、⁴He、SO₂和H₂S	[81]
葡萄牙	Neves-Corvo铜锡矿	低渗透变质岩盖层,矿体埋深为400~500 m	抽气法孔深约1.0 m	Rn、He、CO₂(24.3%)、O₂、烃气、SO₂和COS	[48]
意大利	Tolfa矿区块状硫化物矿	山区,废弃矿山,埋深为30~100 m	抽气法孔深约1.0 m	Rn、CO₂(9.5%)、O₂、烃气、SO₂(含量为0.3×10^-6)和COS(含量为3.7×10^-6)	[48]
哈萨克斯坦	中部铜钼矿	盖层厚度为0.6~3.0 m	孔深为1.0~1.8 m	总硫	[53]
加拿大	高地山谷硫化物矿床			SO₂	[74]