A passive sampler and detection method for organophosphates and their conversion products

Abstract

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 solid phase extraction filler technology to design a new passive sampler, using SPE filler as a sampling medium for OPEs in the air, making up for the shortcomings of a single silicone wristband and better serving OPEs monitoring; the passive sampler includes a nylon glass fiber shell, which is provided with a polyethylene sieve plate and a perfluororubber gasket, and the space formed is filled with HC-C18 / CN composite filler, and the silicone ring can be sleeved on the outside of the nylon glass fiber shell. The beneficial effect of the present invention is that compared with a single silicone 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.

Description

Technical Field

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

[0002] Organophosphate esters (OPEs) are a class of triester compounds whose side chains are substituted with alkyl, aromatic, or chloroalkyl groups. Due to their excellent properties in reducing the flammability of polymers and increasing their plasticity, OPEs are widely used as flame retardants or plasticizers in a variety of household and industrial products. 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, while TDCIPP is added to polyurethane foam. Alkyl organophosphate esters (Alkyl-OPEs) such as tris(2-butoxyethyl)phosphate (TBOEP) and 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 urgently needs new alternatives, and thus OPEs have attracted great environmental attention.

[0003] OPEs are high-volume 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, making them easily released into the environment during product production, use, and disposal through volatilization, abrasion, or leaching. A large number of OPEs, particularly some chlorinated OPEs, are relatively persistent in the environment and difficult to fully degrade. The commonly used TBOEP, TPHP, and TDCIPP even have similar environmental persistence to the PBDEs they replaced. Although insufficient research data are available worldwide to support the risks of low-dose, long-term exposure to OPEs, toxicological and epidemiological studies have shown that exposure to some OPEs can lead to various adverse health effects, such as lipidome homeostasis disturbances, endocrine disruption, serum hypertriglyceridemia, and reproductive impairment. At high occupational exposure doses, tris(2-chloroethyl)phosphate (TCEP), TDCIPP, and TCIPP are potentially carcinogenic. Di-OPE diesters have greater endocrine disrupting potential than their parent triesters and may produce comparable or even greater endocrine-disrupting effects. 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] Based on recent research on OPEs, passive sampling technology is now increasingly being used to monitor OPE concentrations in indoor ambient air, reflecting changes in medium- and long-term average OPE concentrations. Traditional passive samplers typically use PUF disks as the enrichment medium, simultaneously collecting OPEs in both the gaseous and particulate phases of the air, reflecting the total concentration of OPEs in the air. However, due to low enrichment efficiency and generally long sampling cycles, this cannot reflect changes in air concentration. Furthermore, the sampling volume must be calculated using mathematical models, which are affected by air circulation rate, temperature, and humidity. This introduces uncertainty in estimating and comparing concentrations between different indoor environments.

[0006] Silicone wristbands offer a powerful quantitative tool that is extremely useful for exposure assessment. Commercially available silicone wristbands can be modified to function as personal samplers that individuals wear on their wrists and then return 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 how researchers characterize personal chemical exposures. Chemical classes measured using silicone wristbands include polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalate and non-phthalate plasticizers, dioxins and furans, environmental phenols, pharmaceuticals (i.e., nicotine), pesticides, and flame retardants. These silicone wristbands, defined as passive sampling devices (PSDs), consist solely of PDMS and are worn on an individual or organism during the sampling period, typically in a wristband format. Experiments with silicone wristbands have involved sampling periods ranging from 4 hours to 30 days, with 5 and 7 days being the most common sampling lengths. The ideal sampling time length will depend on the physicochemical properties of the target analyte and the absorption profile of the wristband. The silicone wristband can be easily integrated into an exposure assessment tool for a variety of unique study populations.

[0007] Wristbands were first used to assess asphalt use by roofers and were later expanded to sample a variety of populations that may be exposed to environmental pollutants for occupational reasons, including firefighters, workers at electronic waste recycling facilities, fishermen, aircraft maintenance workers, and others. Using wristbands in occupational settings allows for easy characterization of potential acute exposures 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 pollutants. Wristbands eliminate the need for researchers to be present when collecting samples, such as when collecting indoor dust, paper 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 washing hands affect the concentration of SVOCs in the wristbands. 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 wristbands. Since the wristbands may be in direct contact with the surface of the objects, the human exposure results obtained by the wristbands are a combination of multiple exposure pathways, which makes it impossible to accurately determine the contribution of the respiratory exposure pathway and confound the exposure pathway results. In addition, in existing studies, the enrichment effect of silicone wristbands on di-OPEs and some OPEs is relatively poor. Summary of the Invention

[0009] 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 provided 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 perfluororubber gasket, disposed 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 outside 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 1.5-1.7mm 3 / mg.

[0019] The invention relates to an application of a passive sampler for organophosphates and their conversion products in 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), (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 conversion products comprises the following steps:

[0022] Step 1: Construct the components of the passive sampler, clean each component 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 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 shell, EtAc and MeOH are used for elution in sequence, and the eluates are collected and combined into eluate A;

[0026] The silica gel ring was added to acetone, and the supernatant was collected by ultrasonication. The supernatant obtained by one ultrasonication or the combined supernatant obtained by multiple ultrasonications was used as eluent B.

[0027] Preferably, the OPEs internal standard mixture is added to the obtained eluate, shaken and mixed, the eluate volume is concentrated under a nitrogen flow, the concentrated solution is passed through a nylon syringe filter with a pore size of 0.22 μm, the filtered liquid is centrifuged at 15,000 g, 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 of 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. In particular, Cl-OPEs have a higher exposure risk. Therefore, this passive sampling can effectively enhance the enrichment performance of existing silica gel materials 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 and BEHP.

[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 assembled structure of a passive sampler according to one embodiment of the present invention;

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

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

[0034] In the picture:

[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. Perfluororubber 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 transformation products. Based on an organic silicone wristband, this design combines it with solid phase extraction (SPE) packing technology to create a new passive sampler that combines the advantages of both technologies. The SPE packing serves as the sampling medium for OPEs in the air, overcoming the shortcomings of a single silicone wristband and better serving the monitoring of human exposure to OPEs. The passive sampler comprises a nylon fiberglass housing 2, a polyethylene sieve plate, a perfluoroelastomer gasket 4, an HC-C18 / CN composite packing 5, and a silicone ring 1. The nylon fiberglass shell 2 comprises an upper shell 21 and a lower shell 22 that fit together, each with multiple through-holes 23 formed on its surface. The polyethylene sieve plate comprises an upper sieve plate 31 and a lower sieve plate 32, which can be inserted into the nylon fiberglass shell 2. A perfluoroelastomer gasket 4 is positioned between the upper and lower sieve plates 31, 32. An HC-C18 / CN composite filler 5 is housed within the space formed by the upper and lower sieve plates 31, 32, and the perfluoroelastomer gasket 4. A silicone ring 1 is sleeved onto the exterior of the nylon fiberglass shell 2.

[0040] The nylon glass fiber shell 2 is produced using 3D printing technology, and its structure is as follows Figure 2 As shown, the nylon fiberglass shell 2 comprises an upper shell 21 and a lower shell 22 that can be interlocked. The nylon fiberglass shell 2 is perforated 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 spacing of 1 mm. The nylon fiberglass shell 2 is made of glass microbeads composited with nylon powder (FS 3400GF, Farsoon High-Tech, China). While offering a certain level of structural strength and relatively low cost, it also possesses superior performance compared to nylon (as shown in Table 1).

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

[0042]

[0043] A PE sieve plate is manufactured to fit within a nylon fiberglass housing 2. The PE sieve plate in the sampler is made using the same material technology as that used in mainstream SPE cartridges on the market. The PE sieve plate in the sampler is cylindrical in structure. While enriching OPEs in the air, the PE sieve plate prevents packing from leaking. The pore size of the PE sieve plate is selected to be 16-40 μm, ensuring that the packing does not leak directly from the pores (the packing particle size is 40-63 μm) while maximizing the sampler's air permeability.

[0044] Two PE frits are installed, with a perfluoroelastomer gasket 4 positioned between them. This gasket and the two PE frits form a columnar space for accommodating the HC-C18 / CN composite filler 5. Perfluoroelastomer gasket 4 is made of perfluoroelastomer to prevent deformation of the sampler components due to the swelling of the silica gel during elution. An equal mixture of HC-C18 and CN fillers is placed in the space formed by the two PE frits and the perfluoroelastomer ring.

[0045] HC-C18 / CN composite filler 5 exhibits excellent enrichment of both OPEs and di-OPEs in air. Related data and descriptions can be found in the invention "A Sampler for Organophosphates and Their Transformation Products in Indoor Air and Method for Sampling and Determination Thereof" (Publication No. CN116718681A). However, that patent utilizes a layered arrangement with HC-C18 on top and CN on the bottom, separated by a PE sieve plate. The present invention, however, utilizes HC-C18 / CN composite filler 5. Furthermore, the filler is not compacted, resulting in greater mobility and, by comparison, a greater surface area for enrichment and specific adsorption capacity. Layered SPE cartridges are active samplers, whereas passive samplers emphasize the passive adsorption process. In active samplers, the orderly layered arrangement reduces load pressure and ensures sustainable sampling efficiency. In passive samplers, the dispersed, mobile filler increases the specific surface area, allowing for sufficient contact with target compounds 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, a wearable passive sampler is formed by assembling a PE sieve plate and a perfluoroelastomer gasket 4, adding an HC-C18 / CN composite filler 5, and fastening the top and bottom with a nylon fiberglass shell 2. The outer surface of the nylon fiberglass shell 2 is secured with a silicone ring 1. The addition of the remaining components beyond the silicone ring 1 not only improves the enrichment efficiency but also significantly enhances the enrichment capacity of some aromatic OPEs, improving 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), triisobutyl phosphate (TIBP), phosphoric acid One or more of triphenyl phosphate (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 tested 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 them with water, methanol, and ethyl acetate in turn, 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, elute again with 8 ml of methanol and ethyl acetate and dry, then combine with the silicone 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 place it in a polypropylene bag. Transfer it to the laboratory and store it in a -20°C freezer 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 frit, perfluoroelastomer gasket, and composite filler contained therein), a rubber ring that can completely cover the nylon glass fiber shell is customized. The nylon glass fiber shell is wrapped with the rubber ring and then fixed to the filter. Elution is performed with 8 mL of EtAc and 8 mL of MeOH, and the eluate is collected and combined as eluate A.

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

[0054] The resulting eluents A and B were assayed separately, specifically by adding 10 ng of an internal standard mixture of OPEs to the eluents. The eluents were then shaken using a vortex shaker and concentrated to 500 μL under a gentle stream of nitrogen. The concentrated solution was passed through a 0.22 μm nylon syringe filter and the filtered liquid was centrifuged at 15,000 g for 10 minutes. The supernatants (supernatant A / supernatant B) were then analyzed for OPEs and di-OPEs. The supernatants were placed in 300 μL brown glass vials with inner tubes, and the target analytes were quantified using an Agilent 1260 HPLC-G6460 MS / MS (Agilent Technologies, USA) in positive and negative ion electrospray modes using water and methanol containing 0.1% acetic acid as the mobile phase. 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 multiple-response monitoring (MRM) mode.

[0055] The new wearable passive sampler designed by the present invention improves the adsorption curves of OPEs and di-OPEs by adding other types of adsorption carriers compared to a single silica gel material, thereby compensating for the poor adsorption of some substances by silica gel. In particular, the adsorption rate and capacity of aromatic OPEs such as TPHP and TCRP were significantly increased, demonstrating that the new composite filler passive sampler can effectively expand the enrichment of different types of non-polar aromatic OPEs in the air. Furthermore, the new passive sampler also exhibited good adsorption rates and capacities for TBP, TCEP, TCIPP, and BCIPHIPP. In particular, Cl-OPEs present a higher exposure risk. Therefore, this new passive sampler can effectively enhance the enrichment performance of existing silica gel materials and effectively address the air enrichment of compounds of different polarities. For di-OPEs, the addition of a nylon body also demonstrated superior enrichment performance compared to a single silica gel ring, including DPHP and BEHP. These results demonstrate that the passive sampler of the present invention has a good enrichment effect on both OPEs and di-OPEs, making it suitable for practical sampling in complex environments.

[0056] The present invention is described below with reference to the accompanying drawings. Experimental methods without specific operating steps are carried out in accordance with the corresponding product specifications. Unless otherwise specified, the instruments, reagents, and consumables used in the examples can be purchased from commercial companies.

[0057] Example 1: Construction of a passive sampler

[0058] The nylon glass fiber shell 2 is produced using 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 intervals 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 cylindrical 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 perfluororubber gasket 4 has an outer diameter of 22mm, an inner diameter of 17mm, and a thickness of 2mm. The material is perfluororubber and 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 125mg of HC-C18 and CN fillers were used. The density of the mixed filler was about 1.59mm 3 / mg, the estimated volume of 250mg filler is 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 together 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 Assemble the nylon fiberglass shell of the sampler in the same way. After the assembly is completed, use 8 ml of methanol and ethyl acetate to elute and dry again, and then combine it with the silica gel ring. Figure 1 After assembly, immediately wrap the sampler in aluminum foil, 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 pre-assembled and wrapped samplers were brought to the server room and opened. Passive sampling devices were randomly hung at the same height in the server 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 a blank group, recorded as Week 0. After the samplers were collected, they were immediately wrapped in aluminum foil and placed in a polypropylene bag. They were immediately transferred to the laboratory and stored in a -20°C refrigerator pending processing.

[0066] 2.3 Sample processing

[0067] The components of the passive sampler require different handling methods. The assembled nylon fiberglass housing was secured with a custom perfluoroelastomer ring and filter. Elution was performed with 8 mL of EtAc and 8 mL of MeOH, and the eluents were collected and combined as eluent A. The silicone ring was placed in a 50 mL polypropylene tube, sonicated with 8 mL of acetone for 30 minutes, and the supernatant was collected. The supernatant was then sonicated with 8 mL of methanol for 30 minutes, and the supernatant was collected. The two supernatants were combined as eluent B. 10 ng of an internal standard mixture of OPEs was added to the resulting eluate. The eluate was shaken using a vortex shaker and concentrated to 500 μL under a gentle stream of nitrogen. The concentrated solution was passed through a 0.22 μm nylon syringe filter, and the filtered solution was centrifuged at 15,000 g for 10 minutes. The supernatant was then analyzed for OPEs and di-OPEs.

[0068] The analytical procedure was as follows: The supernatant was placed in a 300 μL brown glass vial with a liner. Target analytes were quantitatively analyzed using an Agilent 1260 HPLC-G6460 MS / MS (Agilent Technologies, USA) in positive and negative electrospray modes using water and methanol containing 0.1% acetic acid as the mobile phase. Target compounds were separated using a Hypersil GOLD™ aQ column (150 mm × 4.6 mm, 3 μm; ThermoFisher Scientific, USA), and analyzed in multiple-response monitoring (MRM) mode.

[0069] The results are shown in Table 2, wherein the silicone ring refers to the adsorption condition 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 condition was different from the adsorption condition of the single silicone ring, which intuitively shows that the existence of other accessories of the sampler overcomes 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 Assemble the nylon fiberglass shell of the sampler in the same way. After the assembly is completed, use 8 ml of methanol and ethyl acetate to elute and dry again, and then combine it with the silica gel ring. Figure 1 After assembly, immediately wrap the sampler in aluminum foil, 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 in different provinces of China.

[0077] The packaged passive samplers will be delivered to the homes of different volunteers. From the moment the sampler is opened and put on, the volunteer must wear it with him / her for the next two weeks. After two weeks, the sampler will be wrapped and placed in clean polypropylene and sent back. It will then be stored in a -20℃ refrigerator awaiting processing.

[0078] 3.3 Sample processing

[0079] The components of the passive sampler require different handling methods. The nylon fiberglass housing was secured with a custom perfluoroelastomer ring and filter. Elution was performed with 8 mL of EtAc and 8 mL of MeOH, and the eluents were collected and combined as eluent A. The silicone ring was placed in a 50 mL PP tube, sonicated with 8 mL of acetone for 30 minutes, and the supernatant was collected. The supernatant was then sonicated with 8 mL of methanol for 30 minutes, and the two supernatants were combined as eluent B. 10 ng of an internal standard mixture of OPEs was added to the resulting eluate. The solution was shaken using a vortex shaker and concentrated to 500 μL under a gentle stream of nitrogen. The concentrated solution was passed through a 0.22 μm nylon syringe filter, and the filtered solution was centrifuged at 15,000 g for 10 minutes. The supernatant was then analyzed for OPEs and di-OPEs.

[0080] The results are shown in Table 3. The sampler can function normally when following people. The main OPEs types and concentrations 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 should not be considered to limit the scope 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 by: include, 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 provided on the surface of the shell; 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; a perfluororubber gasket, disposed between the upper sieve plate and the lower sieve plate; 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 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; A silicone ring, which is sleeved on the outside of the nylon glass fiber shell and is made of polydimethylsiloxane; The detection method includes the following steps: Step 1: Construct the components of the passive sampler, clean each component 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 body and the silicone ring are eluted respectively, and the OPEs and / or di-OPEs content in the nylon glass fiber shell body and the silicone ring eluate are analyzed respectively, wherein the nylon glass fiber shell body includes a nylon glass fiber shell, a polyethylene sieve plate, a perfluororubber gasket and an HC-C18 / CN composite filler.

2. The passive sampler for organophosphates and their conversion products according to claim 1, characterized in that: The nylon fiberglass shell is made of glass microbeads and nylon powder using 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: For the nylon glass fiber shell body, 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, sonicated and the supernatant is collected. The supernatants obtained by one or more sonications are combined as eluent B.

5. The passive sampler for organophosphates and their conversion products according to claim 4, characterized in that: The OPEs internal standard mixture was added to the obtained eluate, shaken and mixed, and the eluate was concentrated under a 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 filtered at 15000 g The supernatant was centrifuged at 400 rpm and analyzed for OPEs and di-OPEs.

6. Use of the passive sampler for organophosphates and their conversion products according to any one of claims 1 to 3 in collecting organophosphates or organophosphate diesters.

7. The use according to claim 6, characterized in that: The organic phosphates include one or more of 2-ethylhexyl diphenyl phosphate, tris(2-butoxyethyl) phosphate, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tricresyl phosphate, tris(1,3-dichloro-2-propyl) phosphate, tris(2-ethylhexyl) phosphate, triethyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, triphenyl phosphate, di(1-chloro-2-propyl)-1-hydroxy-2-propyl phosphate, di(2-butoxyethyl)-2-hydroxyethyl phosphate, (3-hydroxybutyl) dibutyl phosphate, di(2-butoxyethyl)-2-(3-hydroxybutoxy)ethyl phosphate and (2-ethyl-5-hydroxyhexyl) diphenyl phosphate; The organic phosphoric acid diester includes one or more of di(2-butoxyethyl) phosphate, (2-butoxy)ethyl phosphate, di(2-chloroethyl) phosphate, di(2-chloropropyl) phosphate, di(1,3-dichloro)isopropyl phosphate, di(2-ethylhexyl) phosphate, dibutyl phosphate, diphenyl phosphate, di-o-cresyl phosphate, di-p-cresyl phosphate, dibenzyl phosphate, diphenylmethyl phosphate and tert-butylphenyl phenyl phosphate.

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