Passive sampler and detection method for organophosphate and conversion products thereof

Abstract

The invention relates to a passive sampler and a detection method for organophosphorus esters and converted products thereof, which are characterized in that on the basis of an organic silica gel wrist strap, the novel passive sampler is designed by combining the organic silica gel wrist strap with a solid-phase extraction filler technology, and an SPE filler is used as a sampling medium of OPEs in air, so that the defects of a single silica gel wrist strap are overcome; the OPEs monitoring can be better served; the passive sampler comprises a nylon glass fiber shell, a polyethylene sieve plate and a full fluororubber gasket are arranged in the nylon glass fiber shell, HC-C18 / CN composite filler is contained in a formed space, and a silica gel ring can be arranged on the outer side of the nylon glass fiber shell in a sleeving mode. The composite passive sampler disclosed by the invention has the beneficial effects that compared with a single silica gel material, the composite passive sampler prepared by the invention has the advantages that the adsorption curves of OPEs and di-OPEs are improved; particularly, the effect of remarkably increasing the adsorption rate and the adsorption capacity on aromatic OPEs such as TPHP and TCRP is achieved.

Description

Technical Field

[0001] The invention belongs to the field of analysis and detection, and in particular relates to a passive sampler and a detection method for organic phosphates and their conversion products. Background Art

[0002] Organophosphate esters (OPEs) are triester compounds whose side chains are substituted by alkyl, aromatic or chloroalkyl groups. OPEs are widely used as flame retardants or plasticizers and in various household and industrial products due to their excellent performance in reducing the flammability of polymers and increasing plasticity. Chlorinated organophosphate esters (Cl-OPEs), such as tris(2-chloroisopropyl)phosphate (TCIPP) and tris(1,3-dichloro-2-propyl)phosphate (TDCIPP), can be used as flame retardants, TCIPP can be added to spray foam insulation materials, and TDCIPP is added to polyurethane foam; while alkyl OPEs (Alkyl organophosphate esters, Alkyl-OPEs) such as tris(2-butoxyethyl)phosphate (TBOEP) and aryl OPEs (Aryl organophosphate esters, Aryl-OPEs) such as triphenylphosphate (TPHP) are widely used in plasticizers. As traditional brominated flame retardants (i.e., polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD)) are gradually phased out and banned, the flame retardant market is in urgent need of new alternatives, and thus OPEs have attracted great environmental attention.

[0003] OPEs are high-yield compounds that are produced and used in large quantities worldwide. In addition to OPEs, other types of organophosphorus flame retardants (OPFRs) and plasticizers are also produced and used in large quantities. Although considered to be the main metabolites of OPEs, organophosphate diesters (di-OPEs) are also produced and used in large quantities as flame retardants. Due to structural differences, di-OPEs have higher water solubility and lower octanol-water partition coefficients compared to organophosphate triesters. At the same time, the octanol-air partition coefficient of di-OPEs is also higher than that of traditional triesters. The environmental behavior and ecotoxicity of OPEs and di-OPEs are directly related to their chemical structure and physicochemical properties.

[0004] Most OPEs are routinely added rather than chemically bonded to products, so they are easily released into the environment during product production, use, and disposal through volatilization, wear, or leaching. A large number of OPEs, especially some chlorinated OPEs, are relatively persistent in the environment and difficult to completely degrade. The commonly used TBOEP, TPHP, and TDCIPP even have similar environmental persistence to the PBDEs they replaced. Although the risk of low-dose long-term exposure to OPEs lacks sufficient research data worldwide, toxicological and epidemiological studies have shown that exposure to certain OPEs can lead to various adverse health problems, such as lipidome homeostasis disorders, endocrine disorders, serum hypertriglyceridemia, and reproductive disorders. Tris(2-chloroethyl)phosphate (TCEP), TDCIPP, and TCIPP are potentially carcinogenic at high doses of occupational exposure. Di-OPEs diesters have greater endocrine disrupting potential than their parent triesters and may produce endocrine disrupting effects comparable to or even higher than triesters. Most current environmental monitoring studies focus directly on organophosphate triesters, while the monitoring and analysis of di-OPEs in the environment are often neglected.

[0005] From the investigation and research on OPEs in recent years, passive sampling technology is currently more widely used in the monitoring of OPEs concentration levels in indoor ambient air, which can reflect the changes in the medium- and long-term average concentration levels of OPEs. Traditional passive samplers generally use PUF disks as enrichment media, and enrich OPEs in the gas phase and particle phase in the air at the same time, reflecting the total concentration level of OPEs in the air. However, due to the low enrichment efficiency, the sampling cycle is generally long, which cannot reflect the changes in air concentration, and the sampling volume needs to be calculated through a mathematical model. The model is affected by the air circulation rate and temperature and humidity, which brings uncertainty to the concentration estimation and comparison between different indoor environments.

[0006] Silicone wristbands provide a powerful quantitative tool that is very useful for exposure assessment. Commercial silicone wristbands have been modified to function as personal samplers that are worn on the wrist of an individual and then returned to the laboratory for analysis of a wide range of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs). The wristbands are inexpensive and non-invasive and have the potential to revolutionize the way researchers characterize personal chemical exposure. Chemical classes measured using silicone wristbands include PAHs, PCBs, phthalate and non-phthalate plasticizers, dioxins and furans, environmental phenols, pharmaceuticals (i.e., nicotine), pesticides, and flame retardants. The aforementioned silicone wristbands are defined as passive sampling devices (PSDs) composed solely of PDMS, in a wristband format, etc., that are worn on an individual or organism during the sampling period. Experiments with silicone wristbands have involved sampling times ranging from 4 hours to 30 days. The most commonly used sampling lengths are 5 and 7 days. The ideal sampling time length will depend on the physicochemical properties of the target analyte and the absorption profile of the wristband. Silicone wristbands can be easily integrated as exposure assessment tools for a variety of unique study populations.

[0007] Wristbands were first used to evaluate roofers using asphalt and have since been expanded to sample a variety of populations that may be exposed to environmental contaminants for occupational reasons, including firefighters, workers at electronic waste recycling facilities, fishermen, aircraft maintenance workers, and more. Using wristbands in occupational settings, the characteristics of potential acute exposures can be easily determined in a short period of time without overburdening workers with multiple sampling devices. Wristbands have been used to assess the exposure of populations that may be exposed to environmental contaminants. Wristbands eliminate the need for researchers to be present when collecting samples, such as when collecting indoor dust, hand towels, or biological samples (e.g., serum), reducing the time and resources required to conduct research. Therefore, silicone wristbands are an ideal tool for sampling ambient air that people breathe in different scenarios.

[0008] However, silicone wristbands, as the main form of new passive samplers, still have shortcomings. For example, in most wristband studies, participants were asked to wear the wristbands when showering and bathing. However, to date, there are still no studies showing how showering, bathing, or hand washing affects the concentration of SVOCs in the wristband. This may depend on the chemical and physical properties of the relevant compounds. In addition, volatile organic compounds from soaps and cleaning products that individuals may be exposed to when bathing may also be captured in the wristband. Since the wristband may be in direct contact with the surface of the object, the human exposure results obtained by the wristband are a combination of multiple exposure pathways, making it impossible to accurately determine the contribution of the respiratory exposure pathway, which confounds the exposure pathway results. And in existing studies, the enrichment effect of silicone wristbands on di-OPEs and some OPEs is relatively poor. Summary of the invention

[0009] In order to solve the above technical problems, the present invention provides a passive sampler and detection method for organophosphates and their conversion products.

[0010] The technical solution adopted by the present invention is: a passive sampler for organophosphates and their conversion products, comprising:

[0011] The nylon glass fiber shell comprises an upper shell and a lower shell which are interlocked with each other, and a plurality of through holes are arranged on the surface of the shell;

[0012] A polyethylene sieve plate, comprising an upper sieve plate and a lower sieve plate, wherein the polyethylene sieve plate can be embedded in the nylon fiberglass shell;

[0013] A perfluoro rubber gasket is arranged between the upper sieve plate and the lower sieve plate;

[0014] The HC-C18 / CN composite filler is accommodated in the space formed by the upper sieve plate, the lower sieve plate and the perfluororubber gasket.

[0015] The silicone ring is sleeved on the outer side of the nylon glass fiber shell.

[0016] Preferably, the nylon glass fiber shell is prepared by glass microbeads composite nylon powder through 3D printing technology.

[0017] Preferably, the through holes are square holes with a side length of 1 mm, and the interval between adjacent through holes is 1 mm.

[0018] Preferably, the HC-C18 / CN composite filler is a mixture of HC-C18 filler and CN filler in equal proportions, with a density of 1.5-1.7 mm 3 / mg.

[0019] The invention discloses a passive sampler for organophosphates and their transformation products for collecting organophosphates or organophosphate diesters.

[0020] Preferably, the organic phosphate includes 2-ethylhexyl diphenyl phosphate (EHDPP), tris(2-butoxyethyl) phosphate (TBOEP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloropropyl) phosphate (TCIPP), tricresyl phosphate (TCRP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(2-ethylhexyl) phosphate (TEHP), triethyl phosphate (TEP), tri-n-butyl phosphate (TNBP), triisobutyl phosphate (TIBP), triphenyl phosphate (TPHP), triphenyl phosphate (TPP), di(1-chloro-2-propyl) 1-hydroxy-2-propyl phosphate (BCIPHIPP), di(2-butoxyethyl) 2-hydroxyethyl phosphate (BBOEHEP), di(3-hydroxybutyl) dibutyl phosphate (3-OH-TNBP), di(2- The organic phosphoric acid diester includes one or more of di(2-butoxyethyl) phosphate (BBOEP), (2-butoxy)ethyl phosphate (BOEP), di(2-chloroethyl) phosphate (BCEP), di(2-chloropropyl) phosphate (BCIPP), di(1,3-dichloro)isopropyl phosphate (BDCIPP), di(2-ethylhexyl) phosphate (BEHP), dibutyl phosphate (DNBP), diphenyl phosphate (DPHP), di-o-cresyl phosphate (DoCP), di-p-cresyl phosphate (DpCP), dibenzyl phosphate (DBzP), diphenylmethyl phosphate (MDPP) and tert-butylphenyl phenyl phosphate (tb-PPP).

[0021] A passive sampler detection method for organophosphates and their transformation products comprises the following steps:

[0022] Step 1: construct the components of the passive sampler, clean the components with water, methanol, and ethyl acetate in turn, and assemble them after drying to obtain the passive sampler;

[0023] Step 2: Place the passive sampler in an environment suspected of containing OPEs and / or di-OPEs;

[0024] Step 3: After the collection is completed, the passive sampler is disassembled, and the nylon glass fiber shell and the silicone ring are eluted respectively, and the OPEs and / or di-OPEs contents in the eluates of the nylon glass fiber shell and the silicone ring are analyzed respectively.

[0025] Preferably, for the nylon glass fiber housing, EtAc and MeOH are used for elution in sequence, and the eluates are collected and combined into eluate A;

[0026] The silica gel ring is added to acetone, and the supernatant is collected by sonication. The supernatant obtained by sonication once or the combined supernatant obtained by multiple sonications is the eluent B.

[0027] Preferably, the OPEs internal standard mixture is added to the obtained eluate, shaken and mixed, the volume of the eluate is concentrated under a nitrogen flow, the concentrated solution is passed through a nylon syringe filter with a pore size of 0.22 microns, the filtered liquid is centrifuged at a speed of 15000g, and then the OPEs and di-OPEs in the supernatant are analyzed.

[0028] The advantages and positive effects of the present invention are: compared with single silica gel material, the composite passive sampler prepared by the present invention improves the adsorption curve of OPEs and di-OPEs; in particular, it has the effect of significantly increasing the adsorption rate and capacity for aromatic OPEs such as TPHP and TCRP, indicating that the new composite filler passive sampler can effectively expand the enrichment of different types of non-polar aromatic OPEs in the air;

[0029] In addition, the new passive sampler also has good adsorption rate and capacity for TBP, TCEP, TCIPP and BCIPHIPP. Especially among them, Cl-OPEs have a higher exposure risk. Therefore, the passive sampling can effectively increase the enrichment performance of the existing silica gel material and effectively take into account the air enrichment of compounds with different polarities. For di-OPEs, the addition of nylon body also shows better enrichment performance than a single silica gel ring, including DPHP, BEHP, etc.

[0030] The passive sampler of the present invention has a good enrichment effect on both OPEs and di-OPEs, and can be applied to actual sampling in complex environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a schematic diagram of the structure of a passive sampler after assembly according to an embodiment of the present invention;

[0032] Figure 2 This is a schematic diagram of the structure of a nylon glass fiber housing according to an embodiment of the present invention;

[0033] Figure 3 It is a schematic diagram of the cross-sectional structure of a nylon glass fiber shell after partial assembly according to an embodiment of the present invention.

[0034] In the figure:

[0035] 1. Silicone ring 2. Nylon fiberglass shell 21. Upper shell

[0036] 22, lower shell 23, through hole 31, upper sieve plate

[0037] 32. Lower sieve plate 4. Perfluoro rubber gasket 5. HC-C18 / CN composite packing DETAILED DESCRIPTION

[0038] The embodiments of the present invention are described below with reference to the accompanying drawings.

[0039] The present invention relates to a passive sampler and detection method for organophosphates and their conversion products. On the basis of an organic silicone wristband, it is combined with a solid phase extraction (SPE) filler technology to design a new passive sampler, which has the advantages of both technologies at the same time, and uses the SPE filler as a sampling medium for OPEs in the air, making up for the shortcomings of a single silicone wristband, and better serving the monitoring of human exposure levels of OPEs. The passive sampler includes a nylon glass fiber shell 2, a polyethylene sieve plate, a perfluororubber gasket 4, an HC-C18 / CN composite filler 5 and a silicone ring 1. The nylon glass fiber shell 2 includes an upper shell 21 and a lower shell 22 which are interlocked with each other, and a plurality of through holes 23 are provided on the surface of the shell; the polyethylene sieve plate includes an upper sieve plate 31 and a lower sieve plate 32, and the polyethylene sieve plate can be embedded in the nylon glass fiber shell 2; the perfluoro rubber gasket 4 is arranged between the upper sieve plate 31 and the lower sieve plate 32; the HC-C18 / CN composite filler 5 is accommodated in the space formed by the upper sieve plate 31, the lower sieve plate 32 and the perfluoro rubber gasket 4. The silicone ring 1 is sleeved on the outside of the nylon glass fiber shell 2.

[0040] The nylon glass fiber shell 2 is produced by 3D printing technology, and its structure is as follows Figure 2 As shown, it includes an upper shell 21 and a lower shell 22 that can be interlocked, and the nylon glass fiber shell 2 is covered with through holes 23 to facilitate air circulation. Preferably, the upper and lower surfaces of the shell are covered with square holes with a side length and interval of 1 mm. The material used for the nylon glass fiber shell 2 is glass microbead composite nylon powder (FS 3400GF, Huashu High-Tech, China), which has a certain structural strength and relatively low cost, and has better performance than nylon (as shown in Table 1).

[0041] Table 1 Performance parameters of nylon and nylon glass fiber

[0042]

[0043] A PE sieve plate that can be placed in a nylon glass fiber shell 2 is made. The PE sieve plate in the sampler is consistent with the PE sieve plate material technology used in the mainstream SPE columns on the market. The PE sieve plate structure in the sampler is cylindrical. While the PE sieve plate has a certain effect of enriching OPEs in the air, it can prevent the leakage of fillers. The pore size of the PE sieve plate is selected to be 16-40μm, which ensures that the filler does not leak directly from the pore size (the filler particle size is 40-63μm) while maximizing the air permeability of the sampler.

[0044] The PE sieve plates include two, and a perfluoro rubber gasket 4 is arranged between the two PE sieve plates. The perfluoro rubber gasket 4 and the two PE sieve plates form a columnar space for accommodating the HC-C18 / CN composite filler 5. The material of the perfluoro rubber gasket 4 is selected as perfluoro rubber to avoid deformation of the sampler components caused by the increase in volume of silica gel due to swelling effect during later elution. HC-C18 and CN fillers are mixed in equal amounts and placed in the space formed by the two PE sieve plates and the perfluoro rubber ring.

[0045] HC-C18 / CN composite filler 5 has a good enrichment effect on both OPEs and di-OPEs in the air. The relevant data and description can be found in the invention "A sampler for organophosphates and their conversion products in indoor air and its sampling and determination method" (publication number CN116718681A); however, the patent uses a layered combination method with HC-C18 on the top and CN on the bottom, separated by a PE sieve plate, while the present invention uses HC-C18 / CN composite filler 5, and the filler is not in a compacted state, and has good mobility. In comparison, it has a larger enrichment specific surface area and unit adsorption capacity. The layered filler SPE column is an active sampler, compared with which the passive sampler emphasizes the passive adsorption process. In the active collection process of the active sampler, the orderly layered arrangement can reduce the load pressure and ensure the sustainable efficiency of the sampling. In the passive sampler, the dispersed and movable filler state can increase the filler specific surface area, so that it can fully contact the target compound in the air.

[0046] The shape and size of the silicone ring 1 are independently designed and customized, and its production material is common polydimethylsiloxane. The sampler is different from the silicone wristband and is similar to a pendant. It can be worn on clothes, school bags, mobile phones, etc. When assembling Figure 3 As shown, the PE sieve plate and the perfluororubber gasket 4 are assembled, and the HC-C18 / CN composite filler 5 is added thereto. The upper and lower parts are fastened by the nylon glass fiber shell 2, and the outer side of the nylon glass fiber shell 2 is fixed by the silicone ring 1 to form a wearable passive sampler. The addition of the remaining components outside the silicone ring 1 not only improves the enrichment efficiency, but also greatly improves the enrichment capacity of some aromatic OPEs and improves the adsorption curve of the single silica gel.

[0047] The prepared wearable passive sampler can be used to adsorb di-OPEs and OPEs. Organophosphates include 2-ethylhexyl diphenyl phosphate (EHDPP), tris(2-butoxyethyl) phosphate (TBOEP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloropropyl) phosphate (TCIPP), tricresyl phosphate (TCRP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(2-ethylhexyl) phosphate (TEHP), triethyl phosphate (TEP), tri-n-butyl phosphate (TNBP), tri-isobutyl phosphate (TIBP), phosphoric acid One or more of triphenyl ester (TPHP), triphenyl phosphate (TPP), di(1-chloro-2-propyl) 1-hydroxy-2-propyl phosphate (BCIPHIPP), di(2-butoxyethyl) 2-hydroxyethyl phosphate (BBOEHEP), (3-hydroxybutyl) dibutyl phosphate (3-OH-TNBP), di(2-butoxyethyl) 2-(3-hydroxybutoxy) ethyl phosphate (3-OH-TBOEP) and (2-ethyl-5-hydroxyhexyl) diphenyl phosphate (5-OH-EHDPHP). In the present invention, the organic phosphoric acid diester includes one or more of di(2-butoxyethyl) phosphate (BBOEP), (2-butoxy)ethyl phosphate (BOEP), di(2-chloroethyl) phosphate (BCEP), di(2-chloropropyl) phosphate (BCIPP), di(1,3-dichloro)isopropyl phosphate (BDCIPP), di(2-ethylhexyl) phosphate (BEHP), dibutyl phosphate (DNBP), diphenyl phosphate (DPHP), di-o-cresyl phosphate (DoCP), di-p-cresyl phosphate (DpCP), dibenzyl phosphate (DBzP), diphenylmethyl phosphate (MDPP) and tert-butylphenyl phenyl phosphate (tb-PPP).

[0048] The prepared passive sampler needs to be pretreated before use and placed in the environment to be detected to adsorb di-OPEs and OPEs in the environment; after the collection is completed, the various components of the passive sampler are disassembled and eluted separately. The specific steps are as follows.

[0049] Step 1: Build the components of the passive sampler, clean each component with water, methanol, and ethyl acetate ultrasonically, and dry them in a vacuum dryer. Figure 3 Assemble the nylon fiberglass shell 2 parts of the sampler in the same manner. After assembly, use 8 ml of methanol and ethyl acetate to elute and dry again, and then combine with the silica gel ring 1 to form a passive sampler. After assembly, immediately wrap it with aluminum foil and seal it in a clean polypropylene bag, and store it in a -20°C refrigerator until use.

[0050] Step 2: Place the passive sampler in an environment suspected of containing OPEs and / or di-OPEs; after retrieving the sampler, immediately wrap it in aluminum foil and put it in a polypropylene bag, transfer it to the laboratory immediately, and store it in a -20℃ refrigerator until processing;

[0051] Step 3: After the collection is completed, the passive sampler is disassembled, and the nylon glass fiber shell 2 and the silicone ring 1 are eluted respectively, and the OPEs and di-OPEs contents in the eluates of the nylon glass fiber shell 2 and the silicone ring 1 are analyzed respectively;

[0052] For the assembled nylon glass fiber shell (including the PE sieve plate, perfluororubber gasket and composite filler contained therein), a rubber ring capable of completely wrapping the nylon glass fiber shell is customized, the nylon glass fiber shell is wrapped with the rubber ring, and then fixed to the filter, 8 mL of EtAc and 8 mL of MeOH are used for elution, and the eluent is collected and combined into eluent A;

[0053] Place the silica gel ring in a 50 mL PP tube, add 8 mL acetone and sonicate for 30 minutes and collect the supernatant, then add 8 mL methanol and sonicate for 30 minutes and collect the supernatant, combine the supernatants obtained twice as eluent B;

[0054] The obtained eluent A and eluent B were detected separately, and the specific steps were as follows: 10 ng of the OPEs internal standard mixture was added to the obtained eluent. The eluent was oscillated using a vortex oscillator, and then the eluent volume was concentrated to 500 μL under a gentle nitrogen flow. The concentrated solution was passed through a nylon syringe filter with a pore size of 0.22 μm, and the filtered liquid was centrifuged at a speed of 15000 g for 10 minutes. The OPEs and di-OPEs in the supernatant (supernatant A / supernatant B) were then analyzed. The supernatant was placed in a 300 μl brown glass injection vial with an inner liner, and water and methanol containing 0.1% acetic acid were used as mobile phases. The target analytes were quantitatively analyzed using Agilent 1260HPLC-G6460 MS / MS (Agilent Technologies, USA) in positive and negative ion electrospray modes. The target chemicals were separated using a Hypersil GOLD™ aQ column (150 mm×4.6 mm, 3 μm; ThermoFisher Scientific, USA) and analyzed in the multi-response monitoring (MRM) mode.

[0055] The new wearable passive sampler designed by the present invention adds other types of adsorption carriers compared to single silica gel material, thereby improving the adsorption curves of OPEs and di-OPEs, and compensating for the problem that silica gel has poor adsorption effect on some substances. In particular, it has the effect of significantly increasing the adsorption rate and capacity for aromatic OPEs such as TPHP and TCRP, indicating that the new composite filler passive sampler can effectively expand the enrichment of different types of non-polar aromatic OPEs in the air. In addition, the new passive sampler also has good adsorption rate and capacity for TBP, TCEP, TCIPP and BCIPHIPP, especially Cl-OPEs have a higher exposure risk, so the new passive sampling can effectively increase the enrichment performance of existing silica gel materials and effectively take into account the air enrichment of different polar compounds. For di-OPEs, the addition of nylon body also shows better enrichment performance than a single silica gel ring, including DPHP, BEHP, etc. The above results show that the passive sampler of the present invention has a good enrichment effect on both OPEs and di-OPEs, and can be applied to actual sampling in complex environments.

[0056] The scheme of the present invention is described below in conjunction with the accompanying drawings, wherein the experimental methods without specific operating steps are all carried out in accordance with the corresponding product instructions, and the instruments, reagents, and consumables used in the examples can all be purchased from commercial companies unless otherwise specified.

[0057] Example 1: Construction of a passive sampler

[0058] The nylon glass fiber shell 2 is produced by 3D printing technology, and its structure is as follows Figure 2 As shown, the designed nylon glass fiber shell 2 has a total outer diameter of 27mm, an internal space diameter of 23mm, a height of 4.5mm, and a shell wall thickness of 1mm. The upper and lower surfaces of the shell are covered with square holes with a side length and interval of 1mm to facilitate air circulation. The material used for the nylon glass fiber shell 2 is glass microbead composite nylon powder (FS 3400GF, Huashu High-Tech, China). The PE sieve plate structure in the sampler is a cylinder with an outer diameter of 22.8mm and a thickness of 1mm; the pore size of the PE sieve plate is selected to be 16-40μm, which ensures that the filler does not leak directly from the pore size (the filler particle size is 40-63μm) while maximizing the air permeability of the sampler. The outer diameter of the perfluororubber gasket 4 is 22mm, the inner diameter is 17mm, and the thickness is 2mm. The material is perfluororubber, which can be placed between two PE sieve plates. The perfluororubber ring and the PE sieve plate ultimately form a space volume of 453mm for storing fillers. 3 . Use 125 mg of HC-C18 and CN fillers. The density of the mixed filler is about 1.59 mm 3 / mg, 250mg filler is expected to have a volume of 398mm 3The silicone ring 1 is made of polydimethylsiloxane; the outer diameter of the silicone ring 1 is 25 mm, the inner diameter is 20 mm, and the height is 6 mm.

[0059] When assembling Figure 3 As shown, the PE sieve plate and the perfluororubber gasket 4 are assembled, and the HC-C18 / CN composite filler 5 is added thereto. The upper and lower parts are fastened by the nylon glass fiber shell 2, and the outer side of the nylon glass fiber shell 2 is fixed by the silicone ring 1 to form a wearable passive sampler.

[0060] Example 2: Passive sampler detection example

[0061] 2.1 Sampler assembly and pretreatment

[0062] All parts of the sampler were ultrasonically cleaned using water, methanol, and ethyl acetate in sequence, and then dried using a vacuum dryer. Figure 3 After the assembly is completed, 8 ml of methanol and ethyl acetate are used to elute and dry, and then combined with the silica gel ring. Figure 1 After assembly, wrap it with aluminum foil and seal it in a clean polypropylene bag, and store it in a -20℃ refrigerator until use.

[0063] 2.2 Sample collection

[0064] The samples were collected from multiple server rooms at Nankai University.

[0065] A total of 21 samplers that had been assembled and wrapped in advance were brought to the server room and opened. Passive sampling devices were randomly hung at the same height in the room. Three samplers (two of which were parallel controls) were randomly collected every other week as a group, for a total of 7 groups. In addition, three clean passive samplers were taken as the blank group, recorded as week 0. After the samplers were collected, they were immediately wrapped in aluminum foil and placed in a polypropylene bag, and immediately transferred to the laboratory and stored in a -20°C refrigerator awaiting processing.

[0066] 2.3 Sample processing

[0067] Different treatment methods are required for the components of the passive sampler. For the assembled nylon glass fiber housing, a custom perfluoro rubber ring and filter are used to fix it. 8mL EtAc and 8mL MeOH are used for elution and the eluents are collected and combined as eluent A. The silicone ring is placed in a 50mL PP tube, 8mL acetone is added for ultrasonication for 30 minutes and the supernatant is collected. Then 8mL methanol is used for ultrasonication for 30 minutes and the supernatant is collected. The supernatants obtained from the two times are combined as eluent B. 10ng of OPEs internal standard mixture is added to the obtained eluent. It is shaken using a vortex oscillator, and then the eluent volume is concentrated to 500μL under a gentle nitrogen flow. The concentrated solution is passed through a nylon syringe filter with a pore size of 0.22 microns, and the filtered liquid is centrifuged at 15,000g for 10 minutes. The supernatant is then analyzed for OPEs and di-OPEs.

[0068] The analysis steps are as follows: the supernatant was placed in a 300 μL brown glass injection vial with an inner liner, and water and methanol containing 0.1% acetic acid were used as the mobile phase, and the target analytes were quantitatively analyzed using an Agilent 1260HPLC-G6460MS / MS (Agilent Technologies, USA) in positive and negative ion electrospray modes. The target chemicals were separated using a Hypersil GOLD TM aQ column (150 mm×4.6 mm, 3 μm; ThermoFisher Scientific, USA) and analyzed in multi-response monitoring (MRM) mode.

[0069] The results are shown in Table 2, wherein the silicone ring refers to the adsorption of a single silicone ring, and the whole refers to the entire sampler (including the single silicone ring and the nylon glass fiber shell). The sampler can gradually enrich organic phosphates over time in the air environment. The data in Table 2 prove the pollutant adsorption curve of the sampler. During the 7-week sampling process, the sampler still did not reach the enrichment upper limit. The overall adsorption situation was different from that of the single silicone ring, which intuitively showed that the existence of other accessories of the sampler overcame the problem of the deficiency of a single silicone material, proving that the sampler prepared in this embodiment improves the adsorption rate and adsorption amount, and improves the adsorption curve; It makes up for the problem that silica gel has a poor adsorption effect on some substances.

[0070] Table 2 Enrichment of some OPEs and di-OPEs in the silica gel ring and the sampler as a whole (ng)

[0071]

[0072] Example 3: Passive sampler detection example

[0073] 3.1 Sampler assembly and pretreatment

[0074] All parts of the sampler were ultrasonically cleaned using water, methanol, and ethyl acetate in sequence, and then dried using a vacuum dryer. Figure 3 After the assembly is completed, 8 ml of methanol and ethyl acetate are used to elute and dry, and then combined with the silica gel ring. Figure 1 After assembly, wrap it with aluminum foil and seal it in a clean polypropylene bag, and store it in a -20℃ refrigerator until use.

[0075] 3.2 Sample collection

[0076] The samples came from volunteers from different provinces in China.

[0077] The packaged passive samplers will be delivered to the homes of different volunteers. The volunteers will have to wear the passive samplers for the next two weeks starting from the moment they open the package and put them on. After two weeks, the samplers will be wrapped and placed in clean polypropylene and sent back. They will then be stored in a -20℃ refrigerator awaiting processing.

[0078] 3.3 Sample processing

[0079] Different treatment methods are required for the components of the passive sampler. For the nylon glass fiber housing body, a customized perfluororubber ring and filter are used to fix it. 8mL EtAc and 8mL MeOH are used for elution and the eluents are collected and combined as eluent A. The silicone ring is placed in a 50mL PP tube, 8mL acetone is added for ultrasonication for 30 minutes and the supernatant is collected. Then 8mL methanol is used for ultrasonication for 30 minutes and the supernatant is collected. The supernatants obtained from the two times are combined as eluent B. 10ng of OPEs internal standard mixture is added to the obtained eluent. The vortex oscillator is used for oscillation, and then the eluent volume is concentrated to 500μL under a gentle nitrogen flow. The concentrated solution is passed through a nylon syringe filter with a pore size of 0.22 microns, and the filtered liquid is centrifuged at 15,000g for 10 minutes. The supernatant is then analyzed for OPEs and di-OPEs.

[0080] The results are shown in Table 3. The sampler can function normally when following a person. The main types and concentrations of OPEs of samplers of different volunteers are different, which shows that the sampling results of the sampler will show differences in different scenarios and environments, and not all sampler results tend to be consistent.

[0081] Table 3 shows the enrichment of different pollutants by the samplers worn by some volunteers (ng / day)

[0082]

[0083] The embodiments of the present invention are described in detail above, but the contents described are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A passive sampler for organophosphates and their conversion products, characterized in that: include, A nylon glass fiber shell, comprising an upper shell and a lower shell that are interlocked with each other, and a plurality of through holes are provided on the surface of the shell; a polyethylene sieve plate, comprising an upper sieve plate and a lower sieve plate, and the polyethylene sieve plate can be embedded in the nylon glass fiber shell; A perfluoro rubber gasket is arranged between the upper sieve plate and the lower sieve plate; The HC-C18 / CN composite filler is accommodated in the space formed by the upper sieve plate, the lower sieve plate and the perfluororubber gasket. The silicone ring is sleeved on the outer side of the nylon glass fiber shell.

2. The passive sampler for organophosphates and their conversion products according to claim 1, characterized in that: The nylon glass fiber shell is made of glass microbeads and nylon powder through 3D printing technology.

3. The passive sampler for organophosphates and their conversion products according to claim 2, characterized in that: The through holes are square holes with a side length of 1 mm, and the interval between adjacent through holes is 1 mm.

4. The passive sampler for organophosphates and their conversion products according to claim 1, characterized in that: HC-C18 / CN composite filler is a mixture of HC-C18 filler and CN filler in equal proportions, with a density of 1.5-1.7mm 3 / mg.

5. Use of the passive sampler for organophosphates and their conversion products as described in any one of claims 1 to 4 in collecting organophosphates or organophosphate diesters.

6. The use according to claim 5, characterized in that: Organic phosphates include 2-ethylhexyl diphenyl phosphate (EHDPP), tris(2-butoxyethyl) phosphate (TBOEP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloropropyl) phosphate (TCIPP), tricresyl phosphate (TCRP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(2-ethylhexyl) phosphate (TEHP), triethyl phosphate (TEP), tri-n-butyl phosphate (TNBP), tri-isobutyl phosphate (TIBP), phosphoric acid One or more of triphenyl ester (TPHP), triphenyl phosphate (TPP), di(1-chloro-2-propyl) 1-hydroxy-2-propyl phosphate (BCIPHIPP), di(2-butoxyethyl) 2-hydroxyethyl phosphate (BBOEHEP), (3-hydroxybutyl) dibutyl phosphate (3-OH-TNBP), di(2-butoxyethyl) 2-(3-hydroxybutoxy) ethyl phosphate (3-OH-TBOEP) and (2-ethyl-5-hydroxyhexyl) diphenyl phosphate (5-OH-EHDPHP); The organic phosphoric acid diester includes one or more of di(2-butoxyethyl) phosphate (BBOEP), (2-butoxy)ethyl phosphate (BOEP), di(2-chloroethyl) phosphate (BCEP), di(2-chloropropyl) phosphate (BCIPP), di(1,3-dichloro)isopropyl phosphate (BDCIPP), di(2-ethylhexyl) phosphate (BEHP), dibutyl phosphate (DNBP), diphenyl phosphate (DPHP), di-o-cresyl phosphate (DoCP), di-p-cresyl phosphate (DpCP), dibenzyl phosphate (DBzP), diphenylmethyl phosphate (MDPP) and tert-butylphenyl phenyl phosphate (tb-PPP).

7. The passive sampler detection method for organophosphate and its conversion products according to any one of claims 1 to 4, characterized in that: The steps include: Step 1: construct the components of the passive sampler, clean the components with water, methanol, and ethyl acetate in turn, and assemble them after drying to obtain the passive sampler; Step 2: Place the passive sampler in an environment suspected of containing OPEs and / or di-OPEs; Step 3: After the collection is completed, the passive sampler is disassembled, and the nylon glass fiber shell and the silicone ring are eluted respectively, and the OPEs and / or di-OPEs contents in the nylon glass fiber shell and the silicone ring eluates are analyzed respectively.

8. The detection method according to claim 7, characterized in that: For the nylon glass fiber shell, EtAc and MeOH were used for elution in sequence, and the eluates were collected and combined into eluate A; The silica gel ring is added to acetone, and the supernatant is collected by sonication. The supernatant obtained by sonication once or the combined supernatant obtained by multiple sonications is the eluent B.

9. The detection method according to claim 8, characterized in that: The OPEs internal standard mixture was added to the obtained eluate, and the mixture was shaken to mix. The volume of the eluate was concentrated under a nitrogen flow, and the concentrated solution was passed through a nylon syringe filter with a pore size of 0.22 μm. The filtered liquid was centrifuged at 15,000 g, and then the OPEs and di-OPEs in the supernatant were analyzed.

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