Research progress of cyanide detection technology

doi:10.11894/iwt.2019-0329

Abstract

Abstract:

Cyanide is a toxic and hazardous chemical widely used in industrial and mining production. Therefore, it is of great practical significance to monitor the presence of cyanide in different forms in the environment. Methods of cyanide detection were reviewed, including chromatography, spectroscopy, electrochemical detection, nuclear magnetic resonance, fluorescent molecular probe and flow injection analysis. The special attention was given to the cyanide detection methods from the technical principle, operational characteristics, analysis results and application scope. Finally, the development trend of cyanide detection technology was discussed and forecasted.

Key words: cyanide, detection technology, pretreatment

摘要：

氰化物是广泛应用于工矿生产的一类有毒危险化学品，对环境中不同形式的氰化物进行监测具有重要的实际意义。对近年来氰化物检测方法进行了综述，主要包括色谱法、光谱法、电化学传感器法、核磁共振法、荧光分子探针法以及流动注射分析等。对氰化物的检测方法重点从技术原理、操作特点、分析效果以及应用范围做了简单述评。最后对氰化物检测技术手段的发展趋势进行了讨论和展望。

关键词: 氰化物, 检测技术, 预处理

CLC Number:

X830

Xin Zu,Lingjuan Yang,Yufei Li,Jia Zhou,Feiyi Zhao,Chengjin Jiao. Research progress of cyanide detection technology[J]. Industrial Water Treatment, 2020, 40(3): 11-16.

祖新,杨玲娟,李羽翡,周佳,赵菲佚,焦成瑾. 氰化物检测技术研究进展[J]. 工业水处理, 2020, 40(3): 11-16.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.11894/iwt.2019-0329

https://www.iwt.cn/EN/Y2020/V40/I3/11

Figures/Tables 1

References 50

1	Zhao H F , Nam P K S , Richards V L , et al. Thermal decomposition studies of EPS foam, polyurethane foam, and epoxy resin (SLA) as patterns for investment casting; analysis of hydrogen cyanide (HCN) from thermal degradation of polyurethane foam[J]. International Journal of Metalcasting, 2019, 13 (1): 18- 25. doi: 10.1007/s40962-018-0240-5
2	Rahimi S , Khosravi A , Aazami S , et al. Effect of smoking on cyanide, IL-2 and IFN-γ levels in saliva of smokers and nonsmokers[J]. Polish Annals of Medicine, 2018, 25 (2): 203- 206.
3	Vetter J . Plant cyanogenic glycosides[J]. Toxicon, 2000, 38 (1): 11- 36. doi: 10.1016/S0041-0101(99)00128-2
4	Wei Y M , Du L , Deng X , et al. Alkaline-assisted leaching of iron-cyanide complex from contaminated soils[J]. Chemical Engineering Journal, 2018, 354, 53- 61. doi: 10.1016/j.cej.2018.07.152
5	张苗苗, 陈皓, 郜洪文. 气热提取法快速测定液样中的痕量氰化物[J]. 理化检验:化学分册, 2018, 54 (4): 379- 382. URL
6	陈玉柱, 孙一鸣. 在线蒸馏-无人值守连续流动分析法测定地表水中的氰化物[J]. 仪器仪表与分析监测, 2017, (4): 36- 39. doi: 10.3969/j.issn.1002-3720.2017.04.010
7	张烨, 王珂, 刘石生. 外源β-葡萄糖苷酶处理结合异烟酸-吡唑啉酮分光光度法测定橡胶籽中氰化物含量[J]. 食品科学, 2017, 38 (14): 297- 303. doi: 10.7506/spkx1002-6630-201714046
8	吴小琼, 吕沈聪, 高薇薇, 等. 柱前衍生-顶空气相色谱法快速测定血中氰化物[J]. 中国卫生检验杂志, 2018, 28 (17): 37- 39. URL
9	于光. 顶空毛细管柱气相色谱法测定空气中氰化物[J]. 预防医学情报杂志, 2018, 34 (5): 161- 163. URL
10	Marton D , Tapparo A , di Marco V B , et al. Ultratrace determination of total and available cyanides in industrial wastewaters through a rapid headspace-based sample preparation and gas chromatography with nitrogen phosphorous detection analysis[J]. Journal of Chromatography A, 2013, 1300, 209- 216. doi: 10.1016/j.chroma.2013.03.004 URL
11	黄绳炳. 气相色谱法测定电镀废水中氰化物[J]. 海峡科学, 2008, (3): 27- 29. doi: 10.3969/j.issn.1673-8683.2008.03.010 URL
12	张学, 朱建民, 彭立核, 等. 吹扫捕集-气相色谱-质谱联用法测定白酒中氰化物[J]. 中国食品卫生杂志, 2016, 28 (3): 344- 347. URL
13	朱友, 蔚亦沛, 别振英, 等. 金属络合衍生-高效液相色谱法测定卷烟主流烟气中的氰化氢[J]. 中国烟草科学, 2015, 36 (5): 74- 78. URL
14	Lacroix C , Saussereau E , Boulanger F , et al. Online liquid chromatography-tandem mass spectrometry cyanide determination in blood[J]. Journal of Analytical Toxicology, 2011, 35 (3): 143- 147. doi: 10.1093/anatox/35.3.143 URL
15	Kang H I , Shin H S . Derivatization method of free cyanide including cyanogen chloride for the sensitive analysis of cyanide in chlorinated drinking water by liquid chromatography-tandem mass spectrometry[J]. Analytical Chemistry, 2015, 87 (2): 975- 981. doi: 10.1021/ac503401r
16	Jaszczak E , Ruman M , Narkowicz S , et al. Development of an analytical protocol for determination of cyanide in human biological samples based on application of ion chromatography with pulsed amperometric detection[J]. Journal of Analytical Methods in Chemistry, 2017, 2017, 1- 7. URL
17	栾绍嵘, 刘建云, 张芳芳, 等. 离子色谱安培法检测维生素B6与2-噻吩乙酸中的氰化物[J]. 药物分析杂志, 2018, 38 (3): 490- 494. URL
18	Huang Dongya , Peng Youkai , Yan Jinting . Detection of cyanide in pollution-free livestock product breeding water by ion chromatography[J]. Asian Agricultural Research, 2018, 10 (1): 34- 36. URL
19	Papezová K , Glatz Z . Determination of cyanide in microliter samples by capillary electrophoresis and in-capillary enzymatic reaction with rhodanese[J]. Journal of Chromatography A, 2006, 1120 (1/2): 268- 272. URL
20	关彩霞,郭一鹏,汪慬,等. "真空检测管-电子比色法"快检技术在天津大爆炸事件中的应用[C]//2015年现场检测仪器前沿技术研讨会论文集. 2015: 47-50.
21	向双全, 张志刚. 原子吸收石墨炉法测定白酒中的氰化物[J]. 酿酒科技, 2015, (3): 127- 129. URL
22	杨笑棣, 张玲艳. 水中痕量氰化物的高灵敏冷原子吸收间接测定方法[J]. 干旱环境监测, 1994, 8 (2): 81- 83. URL
23	朱颖洁, 郭磊, 刘易, 等. 基于壳层隔绝纳米粒子和在线裂解-吹扫捕集的血液氰化物表面增强拉曼光谱快速检测方法[J]. 分析化学, 2017, 45 (5): 10- 15. URL
24	刘易, 陈佳, 朱颖洁, 等. 基于表面增强拉曼光谱和顶空-气相色谱/氮磷检测技术的生氰糖苷类中成药中游离态氰化物含量测定[J]. 药物分析杂志, 2018, 38 (7): 1202- 1209. URL
25	Abbaspour A , Asadi M , Ghaffarinejad A , et al. A selective modified carbon paste electrode for determination of cyanide using tetra3, 4-pyridinoporphyrazinatocobalt(Ⅱ)[J]. Talanta, 2005, 66 (4): 931- 936. doi: 10.1016/j.talanta.2004.12.062
26	Cheng J , Jandik P , Avdalovic N . Pulsed amperometric detection of sulfide, cyanide, iodide, Thiosulfate, bromide and thiocyanate with microfabricated disposable silver working electrodes in ion chromatography[J]. Analytica Chimica Acta, 2005, 536 (1/2): 267- 274. URL
27	Kumar V , Kumar V , Singh A K , et al. A potentiometric biosensor for cyanide detection using immobilized whole cell cyanide dihydratase of flavobacterium indicum MTCC 6936[J]. Journal of Analytical Chemistry, 2018, 73 (10): 1014- 1019. doi: 10.1134/S1061934818100039
28	Hallaj R , Haghighi N . Photoelectrochemical amperometric sensing of cyanide using a glassy carbon electrode modified with graphene oxide and titanium dioxide nanoparticles[J]. Microchimica Acta, 2017, 184 (9): 3581- 3590. doi: 10.1007/s00604-017-2366-1
29	李腾, 黄桂兰, 袁铃, 等. 氟化物衍生-¹⁹F-核磁共振法检测水样中氰化物[J]. 理化检验:化学分册, 2018, 54 (4): 443- 448. URL
30	张连群, 张文珠, 何纯定. 流动注射法同时检测水中挥发酚和氰化物[J]. 中国食品卫生杂志, 2018, 30 (1): 49- 53. URL
31	卢杰映. 饮用天然矿泉水中氰化物的测定——异烟酸-巴比妥酸光谱法与流动注射在线蒸馏法的方法对比[J]. 现代食品, 2018, 40 (11): 123- 126. URL
32	Amayreh M Y , Abulkibash A M . Differential electrolytic potentiometry:a detector in the flow injection analysis of cyanide using silver electrodes modified with carbon nanotubes[J]. Arabian Journal for Science and Engineering, 2017, 42 (10): 4445- 4451. doi: 10.1007/s13369-017-2570-7
33	Beck H P , Zhang B , Bordeanu A . Fluorimetric determination of free cyanide by flow-injection analysis[J]. Analytical Letters, 2003, 36 (10): 2211- 2228. doi: 10.1081/AL-120023712
34	Dadfarnia S , Haji Shabani A M , Tamadon F , et al. Indirect determination of free cyanide in water and industrial waste water by flow injection-atomic absorption spectrometry[J]. Microchimica Acta, 2007, 158 (1/2): 159- 163. URL
35	US EPA Method OIA-1677 Available cyanide by flow injection, ligand exchange, and amperometry[S]. US EPA, Washington, DC, 2004.
36	Kang Jin , Huo Fangjun , Zhang Yongbin , et al. A novel near-infrared ratiometric fluorescent probe for cyanide and its bioimaging applications[J]. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy, 2019, 209, 95- 99. doi: 10.1016/j.saa.2018.10.037
37	Gimeno N , Li X E , Durrant J , et al. Cyanide sensing with organic dyes:studies in solution and on nanostructured Al₂O₃ surfaces[J]. Chemistry, 2008, 14 (10): 3006- 3012. doi: 10.1002/chem.200700412
38	周彬彬, 汪霞丽, 王芳斌, 等. 基于多肽识别基团的荧光探针及其对食品中氰化物的检测[J]. 食品与机械, 2016, 32 (10): 44- 47. URL
39	张春霞, 董昌刚, 张莹, 等. 新型荧光探针的合成与苦杏仁中氰化物含量的检测[J]. 食品科技, 2018, 43 (7): 337- 342. URL
40	Mohammadi A , Kianfar M . A simple colorimetric chemosensor with highly performance for detection of cyanide and copper ions and its practical application in real samples[J]. Journal of Photochemistry and Photobiology A:Chemistry, 2018, 367, 22- 31. doi: 10.1016/j.jphotochem.2018.08.015
41	Yu Xueying , Wang Kangnan , Cao Duxia , et al. Simple benzothiazole chemosensor for detection of cyanide anions via nucleophilic addition[J]. Chemistry of Heterocyclic Compounds, 2017, 53 (1): 42- 45. URL
42	Promchat A , Rashatasakhon P , Sukwattanasinitt M . A novel indolium salt as a highly sensitive and selective fluorescent sensor for cyanide detection in water[J]. Journal of Hazardous Materials, 2017, 329, 255- 261. doi: 10.1016/j.jhazmat.2017.01.024
43	Li Zheng , Liu Chong , Wang Shujun , et al. Visual detection of cyanide ion in aqueous medium by a new chromogenic azo-azomethine chemosensor[J]. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy, 2019, 210, 321- 328. doi: 10.1016/j.saa.2018.11.052
44	Maji S , Chowdhury B , Pal S , et al. An indolium ion functionalized naphtha imide chemodosimeter for detection of cyanide in aqueous medium[J]. Inorganica Chimica Acta, 2018, 483, 321- 328. doi: 10.1016/j.ica.2018.08.040
45	周彬彬, 张继红, 王芳斌, 等. 可视化分子探针的设计、合成及其对食品中氰化物的检测[J]. 食品科学, 2017, 38 (12): 304- 309. doi: 10.7506/spkx1002-6630-201712047
46	Al-Soliemy A M . Novel asymmetrical phenothiazine for fluorescent detection of cyanide anions[J]. Journal of Molecular Structure, 2019, 1179, 525- 531. doi: 10.1016/j.molstruc.2018.11.046
47	Li Qingyun , Wang Zhencao , Song Wenwen , et al. A novel D-π-A triphenylamine-based turn-on colorimetric and ratiometric fluorescence probe for cyanide detection[J]. Dyes and Pigments, 2019, 161, 389- 395. doi: 10.1016/j.dyepig.2018.09.074
48	夏晓东, 黄昊文. 蛋清生物模拟矿化合成荧光银纳簇和氰化物荧光探针[J]. 无机化学学报, 2011, 27 (12): 2367- 2371. URL
49	Achadu O J , Nyokong T . Fluorescence "turn-on" nanosensor for cy anide ion using supramolecular hybrid of graphene quantum dots and cobalt pyrene-derivatized phthalocyanine[J]. Dyes and Pigments, 2019, 160, 328- 335. doi: 10.1016/j.dyepig.2018.08.038
50	Feng Yang , Deng Dongyan , Zhang Lichun , et al. LRET-based functional persistent luminescence nanoprobe for imaging and detection of cyanide ion[J]. Sensors and Actuators B:Chemical, 2019, 279, 189- 196. doi: 10.1016/j.snb.2018.09.111

探针类型	工作原理	荧光探针分子	检出限
识别报告型	利用氢键反应选择性识别氰离子，在强荧光基团或生色基团上引入对于氰化物有很高亲和力的酰胺、硫胺或脲，从而使受体发生光学变化	偶氮苯基硫脲	3 mg/L^〔37〕
置换取代型	利用过渡金属离子与氰离子的强亲和性作用置换出配合物中的金属离子，使体系荧光恢复，荧光强度与CN-浓度正相关	香豆素-甘氨酸-甘氨酸-组氨酸	0.015 μmol/L^〔38〕
		2-羟基苯基咪唑-联吡啶钌	0.18 μmol/L^〔39〕
		偶氮基-硝基苯	1×10-9 mol/L^〔40〕
化学计量型	CN-作为反应底物按1:1的化学计量方式直接相互作用，与探针发生不可逆的化学反应生成另一种与探针荧光不同的物质，也称为去质子化过程	咔唑-苯并噻唑	4.6×10-8 mol/L^〔41〕
		苯并烯二烯-吲哚盐	1×10-9 mol/L^〔42〕
		n'-（5-（2，4-二氯-苯基）重氮酰）-2-羟基苯基苯基肼	6.4 μmol/L^〔43〕
亲核加成型	CN-与探针分子的不饱和键发生亲核加成反应后，呈现显著的吸收峰蓝移，产生强烈的荧光发射	吲哚离子化萘	0.5 μmol/L^〔44〕
		萘酰亚胺偶氮苯	0.13 μmol/L^〔45〕
		非对称苯硫嗪	3.2×10-9 mol/L^〔46〕
		d-π-三苯胺	1.4×10-8 mol/L^〔47〕
贵金属纳簇型	具有独特光电性能的贵金属纳簇型荧光探针能快速响应氰离子（贵金属被CN-蚀掉），荧光强度明显猝灭	荧光银纳簇	1.2 μmol/L^〔48〕

探针类型	工作原理	荧光探针分子	检出限
识别报告型	利用氢键反应选择性识别氰离子，在强荧光基团或生色基团上引入对于氰化物有很高亲和力的酰胺、硫胺或脲，从而使受体发生光学变化	偶氮苯基硫脲	3 mg/L^〔37〕
置换取代型	利用过渡金属离子与氰离子的强亲和性作用置换出配合物中的金属离子，使体系荧光恢复，荧光强度与CN-浓度正相关	香豆素-甘氨酸-甘氨酸-组氨酸	0.015 μmol/L^〔38〕
		2-羟基苯基咪唑-联吡啶钌	0.18 μmol/L^〔39〕
		偶氮基-硝基苯	1×10-9 mol/L^〔40〕
化学计量型	CN-作为反应底物按1:1的化学计量方式直接相互作用，与探针发生不可逆的化学反应生成另一种与探针荧光不同的物质，也称为去质子化过程	咔唑-苯并噻唑	4.6×10-8 mol/L^〔41〕
		苯并烯二烯-吲哚盐	1×10-9 mol/L^〔42〕
		n'-（5-（2，4-二氯-苯基）重氮酰）-2-羟基苯基苯基肼	6.4 μmol/L^〔43〕
亲核加成型	CN-与探针分子的不饱和键发生亲核加成反应后，呈现显著的吸收峰蓝移，产生强烈的荧光发射	吲哚离子化萘	0.5 μmol/L^〔44〕
		萘酰亚胺偶氮苯	0.13 μmol/L^〔45〕
		非对称苯硫嗪	3.2×10-9 mol/L^〔46〕
		d-π-三苯胺	1.4×10-8 mol/L^〔47〕
贵金属纳簇型	具有独特光电性能的贵金属纳簇型荧光探针能快速响应氰离子（贵金属被CN-蚀掉），荧光强度明显猝灭	荧光银纳簇	1.2 μmol/L^〔48〕

[1]	Yang LI, Dongfang ZHANG, Jixian LIU, Haosheng DU, Xiaojie WANG. Case study on the comprehensive advanced treatment of PCB electroplating wastewater [J]. Industrial Water Treatment, 2025, 45(3): 212-218.
[2]	Xuan ZHANG, Lin CHEN, Xinqian ZHANG, Qinghong WANG, Chen HE, Yali ZHAN, Chunmao CHEN. Comprehensive analysis and characterization of overhaul wastewater from petrochemical refineries [J]. Industrial Water Treatment, 2024, 44(9): 151-159.
[3]	Chenfei ZHANG, Can HE, Zhongguo ZHANG, Jianbing WANG, Jian ZHANG, Mengyu WANG, Hongfang SUN, Zhifeng HU, Chenhao GONG, Junxing HAN, Yue SHAN. Pretreatment of phosphating wastewater with different advanced oxidation processes [J]. Industrial Water Treatment, 2024, 44(11): 61-66.
[4]	Chengxia XING, Yongli LI, Rongrong GU, Yuanxiang HU. Determination of trace aluminum in indirect air cooling unit circulating water by graphite furnace atomic absorption spectrophotometry [J]. Industrial Water Treatment, 2024, 44(11): 167-171.
[5]	Xin TONG, Wenjie LIU, Yifei LONG, Jiangjun HU. Treatment of desulfurization wastewater by electrocoagulation and its application in the pretreatment of reverse osmosis [J]. Industrial Water Treatment, 2024, 44(1): 169-176.
[6]	Suoxin ZHANG, Xiaodong ZHANG, Chongtao YU, Xin YANG, Li’na JIANG, Ke LI, Jun WANG, Jingguang CHEN, Chunxiao SUI, Li ZHOU. Research on high-efficiency pretreatment experiment for seawater desalination in low temperature and low turbidity sea area [J]. Industrial Water Treatment, 2023, 43(9): 174-179.
[7]	Wenhai WANG, Mei LI, Ning WANG, Hongbo WANG, Wei ZHANG, Guanhu XU. Research progress on enhanced anaerobic digestion of excess sludge by ferrate pretreatment [J]. Industrial Water Treatment, 2023, 43(9): 51-58.
[8]	Wenbin XU, Kai ZHOU, Yanhua ZHANG, Long HE, Lin YANG. Advanced treatment of high-concentration cyanide-containing wastewater by two-step precipitation coupled with H₂O₂ oxidation [J]. Industrial Water Treatment, 2023, 43(2): 124-129.
[9]	Changzi GUO, Jinyong ZHANG, Pei YU, Yi WU. Study on degradation effect of pretreatment to cephalosporin pharmaceutical wastewater and removal of organic matter [J]. Industrial Water Treatment, 2022, 42(4): 89-95.
[10]	Zhen JI, Liwei QIU, Yexin YIN. Project case of treatment window trim spraying wastewater by physicochemical pretreatment-biochemical process [J]. Industrial Water Treatment, 2022, 42(2): 173-176.
[11]	Xu LI, Caifeng LI, Yinhu WU, Yuqing XU, Hongyu ZHANG, Hongying HU. Project case study on high standard treatment and industrial utilization of reclaimed water [J]. Industrial Water Treatment, 2022, 42(2): 183-186.
[12]	Youjian ZONG, Qiang WANG, Xiuguo LU, Na YAO, Linkai HU, Meng ZHANG. Advances in pretreatment methods for degradation of algal biomass by microbial fuel cells [J]. Industrial Water Treatment, 2022, 42(12): 17-25.
[13]	Junren CHEN, Libin ZHANG, Qingqing LIU, Zian REN, Qingxiang HAN, Lijie ZHANG. Research progress in the cultivation of microalgae with landfill leachate： A step change towards carbon neutrality [J]. Industrial Water Treatment, 2022, 42(11): 32-39.
[14]	Zhigang WANG, Zhiguo ZHANG, Wenrui LI, Can WANG, Jing SU, Wenxin LU, Minghua ZHOU. Pretreatment of high concentration organic wastewater by peroxi⁃coagulation [J]. Industrial Water Treatment, 2022, 42(1): 108-114.
[15]	Sujie LIU, Xiang SUN, Liucheng ZHANG, Zhuanhuai LÜ, Yan ZHANG, Shoujian ZHANG. Case analysis of synthetic leather production integrated wastewater treatment project [J]. Industrial Water Treatment, 2022, 42(1): 167-170.

Please choose a citation manager

Content to export