色谱

色谱

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一体化气相色谱-脉冲火焰光度检测系统的研制与性能验证

聂海云1, 王晓荣1,*, 程璨1, 王丽玮2, 孙邦耀1, 刘浩1   

  1. 1.南京工业大学电气工程与控制科学学院, 江苏 南京 211816;
    2.江苏省环境工程技术有限公司, 江苏 南京 210010
  • 收稿日期:2026-02-13
  • 通讯作者: * E-mail：wang@njtech.edu.cn.
  • 基金资助:
    江苏省基础研究计划自然科学基金-青年基金项目（BK20241715）; 国家自然科学基金面上项目（12575322）.

Development and performance validation of an integrated gas chromatography-pulsed flame photometric detection system

NIE Haiyun1, WANG Xiaorong1,*, CHENG Can1, WANG Liwei2, SUN Bangyao1, LIU Hao1   

  1. 1. College of Electrical Engineering and Control Science, Nanjing Tech University, Nanjing 211816, China;
    2. Jiangsu Environmental Engineering Technology Co., Ltd., Nanjing 210010, China
  • Received:2026-02-13
  • Supported by:
    Jiangsu Provincial Basic Research Program-Natural Science Foundation （Youth Fund Project） （No. BK20241715）; National Natural Science Foundation of China （General Program） （No. 12575322）.

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摘要： 针对含氧样品基质引发脉冲火焰光度检测器（PFPD）在痕量检测中存在非线性失真的问题,本文围绕痕量硫化氢（H₂S）检测需求,研制了一套包含气路控制、脉冲点火、光电检测与数据处理算法的一体化气相色谱-脉冲火焰光度检测器（GC-PFPD）系统,并完成了方法学验证：分别以氮气和空气为载气,对比全谱图信号积分与硫延时窗口积分两种处理策略的定量性能。实验结果表明,以氮气为载气的硫延时窗口积分平方根与H₂S浓度的线性决定系数（R2）达0.999 7,显著优于全谱图信号积分（R2=0.989 0）;以空气为载气的硫延时窗口积分平方根与H2S浓度的R2仍达0.998 9,同样显著优于全谱图信号积分平方根（R2=0.914 4）。浓度为1.277 nmol/L时硫的特征峰可与点火初期烃类发光干扰峰有效区分,信噪比（S/N）≥10;结合空白样本噪声与PFPD对硫的线性化响应得到系统的仪器检出限可达到0.613 nmol/L。在重复性测试中,5.109 nmol/L浓度下H₂S 10次测量的峰面积相对标准偏差为1.38%。研究结果表明,所构建的GC-PFPD系统及基于延时窗口的信号处理方法可实现含氧条件下痕量H₂S的高线性、高灵敏检测。该方法在抑制非线性失真方面具有明确优势,为PFPD检测技术在复杂气氛中的应用及国产化仪器优化提供了技术依据。

关键词: 气相色谱, 脉冲火焰光度检测器, 痕量检测, 硫化物

Abstract: Nonlinear response of a pulsed flame photometric detector （PFPD） in an oxygen-bearing sample matrix limits trace sulfur analysis, particularly at low concentration levels. In this study, a gas chromatography-pulsed flame photometric detector （GC-PFPD） system integrating gas control, pulsed flame ignition, detection, and signal processing was developed for trace H₂S detection. To address oxygen-induced nonlinearity, a signal processing method was proposed based on the sulfur-specific chemiluminescence delay characteristics. This method utilizes delay-window integration to isolate sulfur signals from hydrocarbon emission interference at the ignition onset, followed by a square-root transformation to linearize the response. The performance was evaluated using nitrogen and air as carrier gases by comparing full-spectrum signal integration and delay-window integration strategies. Under nitrogen, the square root of delay-window integration exhibited excellent linearity with a coefficient of determination （R2） of 0.999 7, significantly outperforming the full-spectrum integration （R2=0.989 0）. Under air, the square root of delay-window integration maintained high linearity （R2=0.998 9）, which was also markedly superior to that of the full-spectrum integration （R2=0.914 4）, demonstrating effective suppression of the oxygen-induced matrix effect. At a concentration of 1.277 nmol/L, the sulfur peaks were temporally separated and clearly distinguished from hydrocarbon interference peaks at the initial ignition stage, yielding a signal-to-noise ratio greater than or equal to 10. Based on blank noise and the linearized response, the instrument detection limit was determined to be 0.613 nmol/L. Repeatability tests with ten consecutive measurements at 5.109 nmol/L showed a relative standard deviation of 1.38%, indicating favorable short-term stability. The developed GC-PFPD system and delay-window method achieve high-linearity and high-sensitivity detection of trace H₂S under oxygen-containing conditions without hardware modifications. This approach enhances quantitative accuracy in complex gas matrices, providing a practical solution for environmental monitoring and the development of domestic analytical instruments.

Key words: gas chromatography （GC）, pulsed flame photometric detector （PFPD）, trace-level detection, sulfides

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