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离子色谱-脉冲安培法测定空气中痕量硫化氢

[Ion chromatography-pulsed amperometry method for determination of trace hydrogen sulfide in air].

作者信息

Gao Xiao-Jing, Ni Tong, Shen Rui, Shi Chao-Ou

机构信息

Analysis and Testing Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.

出版信息

Se Pu. 2024 Aug;42(8):766-772. doi: 10.3724/SP.J.1123.2023.10028.

Abstract

Hydrogen sulfide (HS) is a pervasive gaseous pollutant that emits the characteristic odor of rotten gas, even at low concentrations. It is generated during various industrial processes, including petroleum and natural gas refining, mining operations, wastewater treatment activities, and refuse disposal practices. According to statistics from the World Health Organization (WHO), over 70 occupations are exposed to HS, rendering it a key monitoring factor in occupational disease detection. Although HS has legitimate uses in the chemical, medical, and other fields, prolonged exposure to this gas can cause severe damage to the respiratory and central nervous systems, as well as other organs in the human body. Moreover, the substantial release of HS into the environment can lead to significant pollution. This noxious substance has the potential to impair soil, water, and air quality, while disrupting the equilibrium of the surrounding ecosystems. Therefore, sulfide has become one of the most commonly measured substances for environmental monitoring worldwide. Achieving the stable enrichment and accurate detection of low-level HS is of great significance. Common methods for detecting this gas include spectrophotometry, chemical analysis, gas chromatography, rapid field detection, and ion chromatography. Although these methods provide relatively reliable results, they suffer from limitations such as high detection cost, low recovery, lack of environmental friendliness, and imprecise quantification of low-concentration HS. Furthermore, the sampling processes involved in these methods are complex and require specialized equipment and electrical devices. Additionally, approximately 20% of the sulfides in a sample are lost after 2 h in a conventional alkaline sodium hydroxide solution, causing difficulties in preservation and detection. In this study, an accurate, efficient, and cost-saving method based on ion chromatography-pulse amperometry was developed for HS determination. A conventional IonPac AS7 (250 mm×4 mm) anion-exchange column was employed, and a new eluent based on sodium hydroxide and sodium oxalate was used to replace the original sodium hydroxide-sodium acetate eluent. The main factors influencing the separation and detection performance of the proposed method, including the pulse amperage detection potential parameters and integration time, as well as the type and content of additives in the stabilizing solution, were optimized. The results showed that the proposed method had a good linear relationship between 10 and 3000 μg/L, with correlation coefficients () of up to 0.999. The limits of detection (=3) and quantification (=10) were 1.53 and 5.10 μg/L, respectively. The relative standard deviations (RSDs) of the peak area and retention time of sulfides were less than 0.2% (=6). The new method exhibited excellent stability, with up to 90% reduction in reagent costs. Compared with conventional ion chromatography-pulse amperometry, this method is more suitable for detecting low concentrations of sulfides in actual samples. Sulfides in a 250 mmol/L sodium hydroxide-0.8% (mass fraction) ethylenediaminetetraacetic acid disodium salt solution were effectively maintained for over 10 h. The new stabilizer significantly improved the reliability of both large-scale and long-term detection. The recovery of the proposed method was investigated by combining the system with a badge-type passive sampler. This sampling method requires no power devices; it is inexpensive, simple to operate, and can realize long-term sampling without the need for skilled personnel. Moreover, it can overcome the influence of short-term changes in pollutant concentration. The sampling results have high reference value for large-scale intervention-less pollutant monitoring in ultraclean rooms, museum counters, and other places. The results demonstrated that the recovery of the proposed method was greater than 95% for the blank sample and 80% for the sample plus standard solution. Finally, the newly established method was applied to determine HS levels in air samples collected via passive sampling at school garbage stations. The measured results did not exceed the national limit.

摘要

硫化氢(HS)是一种普遍存在的气态污染物,即使在低浓度时也会散发出腐臭气体的特征气味。它在各种工业过程中产生,包括石油和天然气精炼、采矿作业、废水处理活动以及垃圾处理操作。根据世界卫生组织(WHO)的统计,超过70种职业会接触到HS,使其成为职业病检测中的一个关键监测因素。尽管HS在化学、医学和其他领域有合理用途,但长期接触这种气体会对呼吸系统、中枢神经系统以及人体的其他器官造成严重损害。此外,HS大量释放到环境中会导致严重污染。这种有害物质有可能损害土壤、水和空气质量,同时破坏周围生态系统的平衡。因此,硫化物已成为全球环境监测中最常测量的物质之一。实现低水平HS的稳定富集和准确检测具有重要意义。检测这种气体的常用方法包括分光光度法、化学分析法、气相色谱法、快速现场检测法和离子色谱法。尽管这些方法能提供相对可靠的结果,但它们存在检测成本高、回收率低、缺乏环境友好性以及对低浓度HS定量不准确等局限性。此外,这些方法涉及的采样过程复杂,需要专门的设备和电气装置。另外,在传统的氢氧化钠碱性溶液中,样品中的硫化物约20%在2小时后会损失,给保存和检测带来困难。在本研究中,开发了一种基于离子色谱 - 脉冲安培法的准确、高效且节省成本的HS测定方法。采用常规的IonPac AS7(250 mm×4 mm)阴离子交换柱,并使用一种基于氢氧化钠和草酸钠的新型洗脱液替代原来的氢氧化钠 - 乙酸钠洗脱液。对影响该方法分离和检测性能的主要因素进行了优化,包括脉冲安培检测电位参数和积分时间,以及稳定溶液中添加剂的类型和含量。结果表明,该方法在10至3000 μg/L之间具有良好的线性关系,相关系数()高达0.999。检测限(=3)和定量限(=10)分别为1.53和5.10 μg/L。硫化物峰面积和保留时间的相对标准偏差(RSDs)小于0.2%(=6)。新方法具有出色的稳定性,试剂成本降低了多达90%。与传统的离子色谱 - 脉冲安培法相比,该方法更适合检测实际样品中的低浓度硫化物。在250 mmol/L氢氧化钠 - 0.8%(质量分数)乙二胺四乙酸二钠盐溶液中的硫化物能有效保持超过10小时。这种新型稳定剂显著提高了大规模和长期检测的可靠性。通过将该系统与徽章式被动采样器结合来研究该方法的回收率。这种采样方法不需要动力装置;成本低、操作简单,无需技术人员即可实现长期采样。此外,它可以克服污染物浓度短期变化的影响。采样结果对于超净室、博物馆柜台等场所的大规模无干预污染物监测具有很高的参考价值。结果表明,该方法对空白样品的回收率大于95%,对加标样品的回收率为80%。最后,将新建立方法应用于测定学校垃圾站通过被动采样收集的空气样品中的HS水平。测量结果未超过国家限值。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f7c/11292478/38c586ed067f/cjc-42-08-766-img_1.jpg

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