WO2024243772A1 - 用于现场连续检测羟基自由基的便携式化学发光装置 - Google Patents

用于现场连续检测羟基自由基的便携式化学发光装置 Download PDF

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WO2024243772A1
WO2024243772A1 PCT/CN2023/096850 CN2023096850W WO2024243772A1 WO 2024243772 A1 WO2024243772 A1 WO 2024243772A1 CN 2023096850 W CN2023096850 W CN 2023096850W WO 2024243772 A1 WO2024243772 A1 WO 2024243772A1
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detection
sample
terminal
tested
instrument housing
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于万超
褚驰恒
唐珊珊
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Zhejiang University
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Zhejiang University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/76—Chemiluminescence; Bioluminescence

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  • the invention belongs to the technical field of hydroxyl free radical detection, and in particular relates to a portable chemiluminescent device for on-site continuous detection of hydroxyl free radicals.
  • Hydroxyl radical is a highly active species that is ubiquitous in various types of environments and plays an important role.
  • ⁇ OH controls the oxidative capacity of the natural atmosphere and is one of the main driving forces for atmospheric cleanliness. It can degrade harmful organic pollutants and greenhouse gases.
  • ⁇ OH can react with other substances in the atmosphere to produce a series of harmful compounds, leading to environmental problems such as photochemical smog, ozone pollution and haze, and excessive ⁇ OH can cause oxidative stress in biological cells, thereby affecting human health.
  • ⁇ OH can decompose most pollutants such as organic compounds, inorganic compounds and bacteria.
  • ⁇ OH can participate in the degradation and transformation of organic matter, but when there is too much ⁇ OH in the soil, they may also damage the soil environment, leading to a decline in soil quality and ecosystem collapse.
  • ⁇ OH can play an important role in scavenging and decomposing in the environment, but it may also produce oxidative stress that endangers human health. Therefore, adopting reliable analytical methods to monitor OH in the natural environment is of great research significance for understanding the environmental quality, chemical reaction mechanism and environmental governance of the atmosphere, water and soil.
  • Chemiluminescence technology is a very sensitive, fast and simple analytical technology that can be used in various analytical detection fields. Chemiluminescence is produced by a chemical reaction, usually an oxidation reaction. The excited product returns to the ground state by emitting photons and is accompanied by the generation of chemiluminescence. As long as the two reagents are mixed to undergo a redox chemical reaction, the chemiluminescence will be released immediately. Therefore, chemiluminescence detection has the advantage of rapid response and is very suitable for the detection of short-lived chemically active species such as reactive oxygen. In the prior art, some devices based on chemiluminescence technology for detecting ⁇ OH have been developed.
  • the purpose of the embodiments of the present application is to provide a portable chemiluminescent device for on-site continuous detection of hydroxyl radicals in order to achieve on-site continuous detection of OH in a variety of environmental media in order to address the problems of the prior art.
  • This device is portable and highly sensitive and can effectively detect the concentration of OH, providing a convenient, fast, accurate and reliable method for environmental monitoring and research.
  • the device since the device has adaptability to a variety of environments, it can be widely used in a variety of environmental scenarios such as air, water and soil, helping people to better understand environmental quality and provide technical support for environmental protection and governance, and has strong practicality and promotion value.
  • the embodiment of the present application provides a portable chemiluminescent device for on-site continuous detection of hydroxyl radicals, including a peristaltic pump, a mixing cell, a detection cell, a photomultiplier tube, a photon counter, a terminal and an instrument housing for packaging; the terminal is arranged outside the instrument housing, and the remaining components are arranged inside the instrument housing.
  • the instrument housing is provided with two oxidant inlets for respectively inputting two oxidants and a sample inlet for inputting a sample to be tested.
  • the peristaltic pump drives the sample to be tested and the oxidant to be transported to the mixing cell, and the mixing cell mixes the sample to be tested and the two oxidants and inputs them into the detection cell. Chemiluminescence occurs in the detection cell, and the photomultiplier tube converts the light signal generated in the detection cell into an electrical signal, and transmits the signal to the terminal through the photon counter, so that the terminal displays the detection result of the hydroxyl radical.
  • a portable mobile power supply which is used to power the peristaltic pump, the photomultiplier tube, the photon counter and the terminal.
  • the output end of the portable mobile power source is provided with a power controller to control the output power.
  • sample to be tested and the two oxidants enter the mixing tank through a peristaltic pump.
  • the two oxidants are H 2 O 2 and K 5 Cu(HIO 6 ) 2 (Cu(III)), respectively.
  • the detection pool is spiral-shaped and is provided with a waste liquid outlet.
  • the present application also provides an application of the above device in an on-site continuous detection environment.
  • the air is passed through an atmospheric sampler into a ⁇ OH capture agent solution of a predetermined concentration to obtain a sample to be tested.
  • a ⁇ OH capture agent of a predetermined concentration is added to the water or soil sample, and the sample to be tested is obtained after filtration.
  • the ⁇ OH scavenger is phthalic acid hydrazide (Phth).
  • the portable chemiluminescence detection device of the present invention can measure the ⁇ OH produced in various environmental media such as air, water and soil, and can realize the measurement of ⁇ OH generation behavior. Through the kinetic information of the change of luminescence signal, the generation law of ⁇ OH in the environment is studied, and the influence of environmental conditions on ⁇ OH generation can be quickly evaluated.
  • the device is packaged with components such as photomultiplier tubes, photon counters and small peristaltic pumps in the device through the instrument housing to achieve integration of the device, greatly reducing the volume and weight of the instrument, and realizing the portability of the OH detection instrument in the natural environment.
  • the external sample to be tested and the oxidant are input into the device through the two oxidant inlets and sample inlets on the instrument housing.
  • the specific reaction of phthalic acid hydrazide with OH forms 5-hydroxyphthalic acid hydrazide (5-OH-Phth) with strong chemiluminescent properties, realizing high-sensitivity and high-specificity on-site continuous detection of OH in the wild environment.
  • the coupling of the atmospheric sampler and the sample filter device can make the device adaptable to multiple environments, and it can be applied to the on-site continuous detection of OH in multiple environmental scenes such as the atmosphere, water and soil, realizing the determination of the generation behavior of OH, studying the generation law of OH in the environment through the kinetic information of the change of the luminescent signal, and realizing the rapid evaluation of the impact of environmental conditions on the generation of OH.
  • FIG1 is a schematic diagram of the structure of a portable chemiluminescent device for on-site continuous detection of hydroxyl radicals according to an exemplary embodiment, wherein (a) is an external view of the device; and (b) is an internal view of the device.
  • FIG. 2 is a schematic diagram showing the principle of a portable chemiluminescent device for on-site continuous detection of hydroxyl radicals according to an exemplary embodiment.
  • Figure 3 is a schematic diagram of the detection results of detection using the portable chemiluminescent device of the present application for on-site continuous detection of hydroxyl radicals according to an exemplary embodiment, wherein (a) is the concentration change of ⁇ OH in the air within 24 hours; (b) is the concentration change of ⁇ OH in lake water within 24 hours; and (c) is the concentration change of ⁇ OH in soil within 24 hours.
  • Terminal 1. Terminal; 2. Instrument housing; 3. Photomultiplier tube; 4. Photon counter; 5. Peristaltic pump; 6. Power controller; 7. Portable power supply; 8. Waste liquid outlet; 9. Oxidant inlet; 10. Sample inlet.
  • first, second, third, etc. may be used in the present application to describe various information, these information should not be limited to these terms. These terms are only used to distinguish the same type of information from each other.
  • first information may also be referred to as the second information, and similarly, the second information may also be referred to as the first information.
  • word "if” as used herein may be interpreted as "at the time of” or "when” or "in response to determining”.
  • Figure 1 is a physical picture of a portable chemiluminescent device for on-site continuous detection of hydroxyl radicals according to an exemplary embodiment.
  • the device may include a mixing cell, a detection cell, a photomultiplier tube 3, a photon counter 4, a terminal 1 and an instrument housing 2 for packaging; the terminal 1 is arranged outside the instrument housing 2, and the remaining components are arranged in the instrument housing 2.
  • the instrument housing 2 is provided with two oxidant inlets 9 for respectively inputting two oxidants and a sample inlet 10 for inputting a sample to be tested.
  • the mixing cell mixes the sample to be tested and the two oxidants and inputs them into the detection cell, chemiluminescence occurs in the detection cell, the photomultiplier tube 3 converts the light signal generated in the detection cell into an electrical signal, and transmits the signal to the terminal 1 through the photon counter 4, so that the terminal 1 displays the detection result of the hydroxyl radical.
  • the material of the instrument housing 2 is aluminum alloy, which increases the strength of the instrument for field operations.
  • the sample to be tested and the two oxidants enter the mixing tank through the peristaltic pump 5, where the three are uniformly mixed.
  • the two oxidants are H2O2 and K5Cu ( HIO6 ) 2 (Cu(III)), which have been proven to be relatively insensitive to a series of interferences that may be encountered in complex environmental systems.
  • the detection cell is spiral-shaped and has a waste liquid outlet 8. After the sample to be tested and the two oxidants enter the mixing cell through the peristaltic pump 5, they immediately flow into the spiral detection cell. Chemiluminescence is immediately generated and captured by the photomultiplier tube 3. The waste liquid flows out of the detection cell from the waste liquid outlet 8, realizing continuous flow analysis.
  • the device may also include a portable mobile power supply 7, which is used to power the photomultiplier tube 3, the photon counter 4, the peristaltic pump 5 and the terminal 1.
  • the output end of the portable mobile power supply 7 may be provided with a power controller 6 to control the output power to achieve stable operation of the photomultiplier tube 3 and the photon counter 4.
  • a tablet computer is selected as the terminal 1 .
  • FIG2 is a schematic diagram of the principle of a portable chemiluminescent device for on-site continuous detection of hydroxyl radicals according to an exemplary embodiment.
  • the operation method and principle of the device are as follows: First, a certain concentration of phthalic acid hydrazide is added to the sample to be tested, and the ⁇ OH generated by the sample is captured in situ to generate stable 5-hydroxyphthalic acid hydrazide with strong chemiluminescent properties, which is then transported to the mixing pool by the peristaltic pump 5. At the same time, two oxidants H 2 O 2 and Cu (III) are sent to the mixing pool to mix with the sample to be tested, and then flow into the spiral detection pool.
  • the present application also provides the application of the above device in the on-site continuous detection of OH in various environments such as air, water and soil.
  • ⁇ OH capture agent described in the present application is phthalohydrazide (Phth), which can capture ⁇ OH in situ and convert it into a stable chemiluminescent product.
  • the capture agent needs to be in excess. For this reason, the applicant has tried different concentrations of capture agents, and the best chemiluminescent signal can be achieved at 50 ⁇ M, so the subsequent examples are all carried out with 50 ⁇ M Phth.
  • ⁇ OH in surface water is detected.
  • 5.0 mL of lake water is taken every 1.0 h at a fixed position in the lake, and 50 ⁇ M Phth is added and fixed at the sampling location to ensure the same reaction conditions.
  • chemiluminescence detection is performed.
  • ⁇ OH is almost not produced in the lake water between 0 and 6 o'clock. It begins to increase after 6 o'clock and reaches a peak at 12 o'clock, and then begins to decline. It is almost no longer produced after 19 o'clock in the afternoon.
  • the change of ⁇ OH in the lake water within 24 hours is consistent with the change law of sunlight intensity corresponding to the location. This is in line with the law of photochemical production of ⁇ OH in surface water.
  • ⁇ OH in the soil was detected. 2.0 mL of soil was taken every 1.0 h at a fixed location on the seashore and 50 ⁇ M Phth was added. The soil was fixed at the sampling location to ensure the same reaction conditions. After 2.0 min of reaction, the filtrate was filtered and diluted 2.0 times, followed by chemiluminescence detection. As shown in (c) in Figure 3, the concentration of ⁇ OH in the soil was higher after low tide, and tended to decrease with time. After high tide, there was almost no ⁇ OH produced due to the lack of oxygen contact. When the tide receded again, the ⁇ OH concentration immediately rose to the highest, and then slowly decreased. The above results are consistent with the law of coastal tide-mediated reactive oxygen generation.

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Abstract

一种用于现场连续检测羟基自由基(·OH)的便携式化学发光装置，包括蠕动泵(5)、混合池、检测池、光电倍增管(3)、光子计数器(4)、终端(1)以及仪器外壳(2)；终端(1)设置在仪器外壳(2)之外，其余元件均设置在仪器外壳(2)内，仪器外壳(2)上设置有用于分别输入两种氧化剂的两个氧化剂入口(9)和用于输入待测样品的样品入口(10)，混合池将三者混合并输入检测池发生化学发光，光电倍增管(3)将检测池中产生的光信号转换成电信号，经过光子计数器(4)将信号传输到终端(1)显示·OH的检测结果。能够测定空气，水体和土壤多种环境介质中产生的·OH，实现对·OH生成行为的测定。

Description

用于现场连续检测羟基自由基的便携式化学发光装置 技术领域
本发明属于羟基自由基检测技术领域，尤其涉及用于现场连续检测羟基自由基的便携式化学发光装置。
背景技术
羟基自由基(·OH)是一种高活性的物种，普遍存在于各种类型的环境中发挥着重要作用。在大气中，·OH控制着自然大气的氧化能力，是大气清洁的主要驱动力之一，能够降解有害的有机污染物和温室气体。同时，·OH可以与大气中的其他物质反应，产生一系列有害的化合物，导致光化学烟雾、臭氧污染和雾霾等环境问题的发生，并且过多的·OH可以导致生物体细胞产生氧化应激，从而影响人体健康。在天然水体中，·OH可以分解大部分污染物如有机化合物、无机化合物和细菌等。然而，当水中存在过多的·OH时，它们也可能破坏水体中的有机物和微生物，从而导致水体污染和生态失衡。在土壤中，·OH能够参与有机物的降解和转化，但当土壤中存在过多的·OH时，它们也可能破坏土壤环境，导致土壤质量下降和生态系统崩溃。综上所述，·OH可以在环境中发挥重要的清除和分解作用，但也可能产生氧化应激危害人体健康。因此，采取可靠的分析方法对自然环境中·OH进行监测对于了解大气、水体和土壤的环境质量、化学反应机理及环境治理具有重要的研究意义。
然而，由于·OH的活性高、寿命短以及浓度低等特性，给·OH的检测带来了巨大挑战。尽管已经开发了很多·OH检测方法，例如电子自旋共振法、荧光法、色谱法等，但是这些方法都有其局限性。例如，这些方法通常需要复杂的捕获和分离过程和特定的实验条件，往往需要繁琐的步骤和复杂的仪器，从采样到检测的时间较长并不能反映·OH在天然环境中的真实生成情况。
化学发光技术是一种非常灵敏、快速、简便的分析技术，可以用于各种分析检测领域。化学发光是由化学反应产生的，通常是氧化反应，产生激发态的产物通过发射光子回到基态并伴随着化学发光的产生，只要当两种试剂混合发生氧化还原化学反应时，化学发光就会立即释放出来。因此，化学发光检测具有迅速响应的优势，非常适合活性氧这类短寿命的化学活性物种的检测。在现有技术中，已经有一些基于化学发光技术检测·OH的装置被开发出来。但是，这些装置大多数都不具备便携性，需要在实验室内使用，并且样品处理和操作比较繁琐，不能满足实时检测的需求。基于此，目前亟需一种便携式、操作简单、实时性好、特异性强的·OH检测装置，以实现·OH的现场连续检测的需求。
发明内容
本申请实施例的目的在于针对现有技术存在的问题，提供一种用于现场连续检测羟基自由基的便携式化学发光装置，以实现对多种环境介质中·OH的现场连续检测。这种装置具有便携性和高灵敏度可以有效地检测·OH的浓度，为环境监测和研究提供了一种方便、快速、准确、可靠的方法。此外，由于装置具有多种环境适应性，可以广泛应用于空气、水体和土壤等多个环境场景，帮助人们更好地了解环境质量，为环境保护和治理提供技术支持，具有很强的实用性和推广价值。
本申请实施例提供一种用于现场连续检测羟基自由基的便携式化学发光装置，包括蠕动泵、混合池、检测池、光电倍增管、光子计数器、终端以及用于封装的仪器外壳；所述终端设置在所述仪器外壳之外，其余元件均设置在所述仪器外壳内，所述仪器外壳上设置有用于分别输入两种氧化剂的两个氧化剂入口和用于输入待测样品的样品入口，所述蠕动泵驱动待测样品和氧化剂输送到混合池，所述混合池将所述待测样品和两种氧化剂混合并输入检测池，所述检测池中发生化学发光，所述光电倍增管将所述检测池中产生的光信号转换成电信号，经过光子计数器将信号传输到终端，从而使得所述终端显示羟基自由基的检测结果。
进一步地，还包括便携式移动电源，所述便携式移动电源用于为所述蠕动泵、光电倍增管、光子计数器和终端供电。
进一步地，所述便携式移动电源的输出端设置有电源功率控制器，以进行输出功率的控制。
进一步地，所述待测样品和两种氧化剂通过蠕动泵进入所述混合池。
进一步地，所述两种氧化剂分别为H2O2和K5Cu(HIO6)2(Cu(III))。
进一步地，所述检测池为螺旋状并设有废液出口。
本申请还提供一种上述装置在现场连续检测环境中·OH中的应用。
进一步地，若检测空气中·OH，则通过大气采样器将空气通入预定浓度的·OH捕获剂溶液中，得到待测样品。
进一步地，若检测水或土壤中·OH，则通过将预定浓度·OH捕获剂加入到水或土壤样品中，经过滤后得到待测样品。
进一步地，所述·OH捕获剂为邻苯二甲酰肼(Phth)。
本发明便携式化学发光检测装置能够测定空气，水体和土壤多种环境介质中产生的·OH，可以实现对·OH生成行为的测定，通过发光信号变化的动力学信息，研究在环境中·OH的生成规律，实现环境条件对·OH产生影响的快速评价。
本申请的实施例提供的技术方案可以包括以下有益效果：
该装置通过仪器外壳对装置中的光电倍增管、光子计数器和小型蠕动泵等元件进行封装，实现装置的一体化，大大减少了仪器的体积和重量，实现了天然环境中·OH检测仪器的便携化，通过仪器外壳上的两个氧化剂入口和样品入口将外部的待测样品和氧化剂输入装置内，通过邻苯二甲酰肼与·OH的特异性反应形成具有强化学发光性质的5-羟基邻苯二甲酰肼(5-OH-Phth)，实现了对野外环境中·OH的高灵敏度、高特异性的现场连续检测，通过对·OH原位捕获和现场测定，解决了·OH现场检测难的问题。在该装置的应用中，可以通过大气采样器和样品过滤装置的耦合使装置具有多种环境适应性，可应用于大气、水体和土壤等多个环境场景中·OH的现场连续检测，实现对·OH生成行为的测定，通过发光信号变化的动力学信息，研究在环境中·OH的生成规律，实现环境条件对·OH产生影响的快速评价。
应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本申请。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本申请的实施例，并与说明书一起用于解释本申请的原理。
图1是根据一示例性实施例示出的用于现场连续检测羟基自由基的便携式化学发光装置的结构示意图，其中(a)为装置的外部图；(b)为装置的内部图。
图2是根据一示例性实施例示出的用于现场连续检测羟基自由基的便携式化学发光装置的原理示意图。
图3是根据一示例性实施例示出的利用本申请用于现场连续检测羟基自由基的便携式化学发光装置进行检测的检测结果示意图，其中(a)为空气中·OH在24小时内的浓度变化；(b)为湖水中·OH在24小时内的浓度变化；(c)为土壤中·OH在24小时内的浓度变化。
其中：1、终端；2、仪器外壳；3、光电倍增管；4、光子计数器；5、蠕动泵；6、电源功率控制器；7、便携式移动电源；8、废液出口；9、氧化剂入口；10、样品入口。
具体实施方式
这里将详细地对示例性实施例进行说明，其示例表示在附图中。下面的描述涉及附图时，除非另有表示，不同附图中的相同数字表示相同或相似的要素。以下示例性实施例中所描述的实施方式并不代表与本申请相一致的所有实施方式。
在本申请使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。还应当理解，本文中使用的术语“和/或”是指并包含一个或多个相关联的列出项目的任何或所有可能组合。
应当理解，尽管在本申请可能采用术语第一、第二、第三等来描述各种信息，但这些信息不应限于这些术语。这些术语仅用来将同一类型的信息彼此区分开。例如，在不脱离本申请范围的情况下，第一信息也可以被称为第二信息，类似地，第二信息也可以被称为第一信息。取决于语境，如在此所使用的词语“如果”可以被解释成为“在……时”或“当……时”或“响应于确定”。
图1是根据一示例性实施例示出的用于现场连续检测羟基自由基的便携式化学发光装置的实物图，如图1中的(a)及图1中的(b)所示，该装置可以包括混合池、检测池、光电倍增管3、光子计数器4、终端1以及用于封装的仪器外壳2；所述终端1设置在所述仪器外壳2之外，其余元件均设置在所述仪器外壳2内，所述仪器外壳2上设置有用于分别输入两种氧化剂的两个氧化剂入口9和用于输入待测样品的样品入口10，所述混合池将所述待测样品和两种氧化剂混合并输入检测池，所述检测池中发生化学发光，所述光电倍增管3将所述检测池中产生的光信号转换成电信号，经过光子计数器4将信号传输到终端1，从而使得所述终端1显示羟基自由基的检测结果。
在一实施例中所述仪器外壳2的材料选用铝合金，为在野外现场作业增加了仪器的强度。
具体地，所述待测样品和两种氧化剂通过蠕动泵5进入所述混合池，三者在其中均匀混合。在一实施例中，所述两种氧化剂分别为H2O2和K5Cu(HIO6)2(Cu(III))，已被证明对复杂环境体系中可能遇到的一系列干扰相对不敏感。
具体地，所述检测池为螺旋状并设有废液出口8，待测样品和两种氧化剂通过蠕动泵5进入所述混合池后随即流入螺旋检测池中，化学发光立即产生并被光电倍增管3捕获，废液从所述废液出口8流出检测池，实现连续流动分析。
具体地，该装置还可以包括便携式移动电源7，所述便携式移动电源7用于为所述光电倍增管3、光子计数器4、蠕动泵5和终端1供电，所述便携式移动电源7的输出端可以设置有电源功率控制器6，以进行输出功率的控制，以实现光电倍增管3和光子计数器4的稳定运行。
在一实施例中，考虑到装置的便携性，选择平板电脑作为终端1。
图2是根据一示例性实施例示出的用于现场连续检测羟基自由基的便携式化学发光装置的原理示意图，如图2所示，本装置的操作方法及原理具体如下：首先，将一定浓度的邻苯二甲酰肼加入待测样品中，原位捕获样品产生的·OH，产生稳定的具有强化学发光特性的5-羟基邻苯二甲酰肼，通过蠕动泵5输送至混合池中，同时两种氧化剂H2O2和Cu(Ⅲ)被送入到混合池中与待测样品混合，随即流入螺旋检测池中，在强碱性介质中，当5-羟基邻苯二甲酰肼与强氧化剂反应时化学发光立即产生，随即被检测池下的光电倍增管3捕获转换为电 信号，进一步经过光子计数器4将信号传输到点电脑终端1。该反应将羟基自由基的捕获过程与化学发光反应过程分开，实现了羟基自由基的原位捕获和连续检测。
本申请还提供上述装置在现场连续检测空气，水体和土壤多种环境中·OH中的应用。
具体地，若检测空气中·OH，则通过恒流大气采样器将空气通入一定浓度的·OH捕获剂溶液中，得到待测样品；若检测水或土壤中·OH，则通过将一定浓度·OH捕获剂加入到水或土壤样品中，经过滤后得到待测样品。本申请中所述·OH捕获剂为邻苯二甲酰肼(Phth)，可以原位捕获·OH转化为稳定的化学发光产物。在本检测体系中捕获剂需要过量，为此申请人已进行不同浓度的捕获剂尝试，在50μM时可以达到最佳的化学发光信号，因此后续实施例均以50μM的Phth进行。
在一实施例中，不同浓度的捕获剂被尝试，在50μM时可以达到最佳的化学发光信号。因此，使用50μM的Phth作为气相·OH的捕获剂，使用恒流大气采样器在24h内不同时间点进行采集1.0h后进行化学发光检测。如图3中的(a)所示，空气中·OH在0-7点间浓度很低，8点后开始增加到14点达到峰值，随后开始下降，17点逐渐上升后下降，至午夜降至最低点浓度。
在一实施例中进行地表水中·OH的检测，在湖中固定位置每隔1.0h取5.0mL湖水加入50μM的Phth固定在取样地点保证反应条件相同反应2.0min后进行化学发光检测。如图3中的(b)所示，湖水中·OH在0-6点间几乎不产生·OH，6点后开始增加到12点达到峰值，随后开始下降，至下午19点后几乎不再产生。值得注意的是，湖水中24小时内·OH的变化情况与改地点对应的太阳光强度变化规律一致。这符合地表水光化学产·OH的规律。
在另一实施例中进行土壤中·OH的检测，在海滨固定位置每隔1.0h取2.0mL土壤加入50μM的Phth，固定在取样地点保证反应条件相同，反应2.0min后过滤，将滤液稀释2.0倍，随后进行化学发光检测。如图3中的(c)所示，土壤中的·OH在退潮后浓度较高，并随着时间的延长有下降的趋势，在涨潮后由于没有氧气接触几乎不产生·OH，当潮水再次退去，·OH浓度立刻上升至最高，接下来缓慢降低。以上结果符合滨海潮汐介导活性氧生成规律。
本领域技术人员在考虑说明书及实践这里公开的内容后，将容易想到本申请的其它实施方案。本申请旨在涵盖本申请的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本申请的一般性原理并包括本申请未公开的本技术领域中的公知常识或惯用技术手段。
应当理解的是，本申请并不局限于上面已经描述并在附图中示出的精确结构，并且可以在不脱离其范围进行各种修改和改变。

Claims (10)

  1. 一种用于现场连续检测羟基自由基的便携式化学发光装置，其特征在于，包括蠕动泵、混合池、检测池、光电倍增管、光子计数器、终端以及用于封装的仪器外壳；所述终端设置在所述仪器外壳之外，其余元件均设置在所述仪器外壳内，所述仪器外壳上设置有用于分别输入两种氧化剂的两个氧化剂入口和用于输入待测样品的样品入口，所述蠕动泵驱动待测样品和氧化剂输送到混合池，所述混合池将所述待测样品和两种氧化剂混合并输入检测池，所述检测池中发生化学发光，所述光电倍增管将所述检测池中产生的光信号转换成电信号，经过光子计数器将信号传输到终端，从而使得所述终端显示羟基自由基的检测结果。
  2. 根据权利要求1所述的装置，其特征在于，还包括便携式移动电源，所述便携式移动电源用于为所述蠕动泵、光电倍增管、光子计数器和终端供电。
  3. 根据权利要求2所述的装置，其特征在于，所述便携式移动电源的输出端设置有电源功率控制器，以进行输出功率的控制。
  4. 根据权利要求1所述的装置，其特征在于，所述待测样品和两种氧化剂通过蠕动泵进入所述混合池。
  5. 根据权利要求1所述的装置，其特征在于，所述两种氧化剂分别为H2O2和K5Cu(HIO6)2。
  6. 根据权利要求1所述的装置，其特征在于，所述检测池为螺旋状并设有废液出口。
  7. 一种权利要求1-6中任一项所述的装置在现场连续检测环境中·OH中的应用。
  8. 根据权利要求7所述的应用，其特征在于，若检测空气中·OH，则通过大气采样器将空气通入预定浓度的·OH捕获剂溶液中，得到待测样品。
  9. 根据权利要求7所述的应用，其特征在于，若检测水或土壤中·OH，则通过将预定浓度·OH捕获剂加入到水或土壤样品中，经过滤后得到待测样品。
  10. 根据权利要求8或9所述的应用，其特征在于，所述·OH捕获剂为邻苯二甲酰肼。
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