CN110361467A - Multipath exposure assessment method of the human body to fire retardant - Google Patents
Multipath exposure assessment method of the human body to fire retardant Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 231100000727 exposure assessment Toxicity 0.000 title claims abstract description 34
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 238000005070 sampling Methods 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 10
- 230000001360 synchronised effect Effects 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 230000037396 body weight Effects 0.000 claims description 20
- 210000001061 forehead Anatomy 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 230000003116 impacting effect Effects 0.000 claims description 9
- 230000029058 respiratory gaseous exchange Effects 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000003915 air pollution Methods 0.000 claims description 8
- 239000012757 flame retardant agent Substances 0.000 claims description 8
- 239000005427 atmospheric aerosol Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- ONXPZLFXDMAPRO-UHFFFAOYSA-N decachlorobiphenyl Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl ONXPZLFXDMAPRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 210000002345 respiratory system Anatomy 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000036387 respiratory rate Effects 0.000 claims description 3
- 230000037384 skin absorption Effects 0.000 claims description 3
- 231100000274 skin absorption Toxicity 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000002137 ultrasound extraction Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 239000000443 aerosol Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 4
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- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000011156 evaluation Methods 0.000 abstract description 3
- 210000003491 skin Anatomy 0.000 description 10
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 210000003128 head Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
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- 238000002390 rotary evaporation Methods 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/02—Investigating particle size or size distribution
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F30/00—Computer-aided design [CAD]
- G06F30/20—Design optimisation, verification or simulation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The present invention relates to exposure assessment method and technology fields, more particularly to it is a kind of based on human body associated with atmosphere cascade sampling and skin wiping to the multipath exposure assessment method of fire retardant, this method is monitored according to air conditions on the spot, it carries out Atmospheric particulates and corium exposure synchronizes sampling, the acquisition of interim Atmospheric particulates is using andersen sampler, diameter grade can be divided to acquire sample, and the exposed features of accurate evaluation different diameter airborne particle, synchronize detection, it realizes and the synchronous of multipath exposure is assessed, exposed features of the full appreciation human body to pollutant.
Description
Technical field:
The invention belongs to fire retardant exposure assessment method and technology fields, and in particular to one kind is based on atmosphere cascade sampling and skin
Multipath exposure assessment method of the human body to fire retardant associated with skin wiping.
Background technique:
With the continuous development of science and technology, problem of environmental pollution caused by industrialization and urbanization causes the extensive pass of people
Note.Wherein air environmental pollution is increasingly becoming more serious one of the problem of environmental pollution in China, and in recent years, China frequently occurs
The air environmental pollution phenomenon that range is wide, the duration is long cause the extensive concern of people；The reason of Atmospheric particulates itself
Change the hot spot that the influence of property and the persistence organic pollutant being attached on particulate matter to environmental and human health impacts is research,
Partial size is the key parameter for influencing Atmospheric particulates property, and the physicochemical properties of Atmospheric particulates itself, Atmospheric particulates exist
The transport reaction mechanism of residence time, Atmospheric particulates in atmospheric environment and the poisonous and harmful pollution being adsorbed on particulate matter
Environmental behaviour of object etc. is influenced by its particle size, and the particulate matter of different-grain diameter can be sucked and can be reached by human body
The different parts of human respiratory, such as the lesser particulate matter of partial size can reach deeper respiratory system (such as lung of human body
Bubble)；The ratio that the different Atmospheric particulates of particle size enter each position of human respiratory has significant otherness；It is different
The content of environmental contaminants entrained by particles things also has significant difference, and compared with large particle, partial size is lesser
Particulate matter is bigger to the harm of human body, the grain diameter influence of particulate matter the assessment result of human body respiration exposed amount；Wherein fire retardant
It is the persistence organic pollutant in a kind of artificial source；Most of organic fire-retardant has volatility and genotoxic potential, and extensively
It is distributed in atmosphere, endangers ecological environment and human health；Showing about the exposure of particulate form organic pollutant human body respiration at present
There is research to concentrate merely on single or certain several partial size section, is related to the research of particulate form pollutant in more partial size section but relatively
It is few；Therefore, the research of the particle diameter distribution of the fire retardant of different-grain diameter particle state and human body respiration exposure needs to further elucidate.
Human body can be exposed to the pollutant in surrounding medium by breathing, skin, the paths such as ingest.These processes are sent out simultaneously
Raw, if wanting exposure of comprehensive accurate evaluation human body to pollutant in environment, need to establish complete set covers a variety of exposures
The research method in path；But research common at present, only for a certain path, still shortage can cover a variety of simultaneously
The system evaluation method in exposure path.
Summary of the invention:
For at present to fire retardant still without the appraisal procedure that can cover a variety of exposed paths simultaneously, the present invention provides one
Kind is based on human body associated with atmospheric sampling and skin wiping to the multipath exposure assessment method of fire retardant.
The present invention solves scheme used by its technical problem: a kind of multipath exposure assessment side of human body to fire retardant
Method, comprising the following steps:
S1: selection sampling area monitors the air pollution situation of sampling area, records air pollution index；
S2: acquisition sample: according to the weather class of pollution of sample region, determining the sampling time, synchronous acquisition sampling area
The human skin skin granulate object sample of movable crowd in atmospheric aerosol samples and sample region；
S3: flame retardant agent content in measurement sample: the content of GC-MS/MS measurement FRs is utilized；
S4: the exposure according to the content of fire retardant in the sample measured, using exposure assessment model to human body to fire retardant
Situation is assessed.
A kind of above-mentioned human body is to the multipath exposure assessment method of fire retardant, sample collection method in the step S2
Are as follows: the sampling time is determined according to the state of air pollution, with the airborne particulate of eight grades of samplers sample gradation diameters of Anderson impacting type
Object sample；While atmospheric aerosol samples acquisition, several names are chosen with the time in the movable male and female will in same region
Hope person prepares the sample boxes of different area according to the different position to be collected of volunteer, by sample boxes be placed on subject wait wipe
Wet tissue is taken out when sampling from clean brown bottle with clean tweezers, then wears disposable glove by operator and wipe by position
The position to be collected of volunteer is wiped, the two sides for the non-woven fabrics being impregnated with isopropanol wipes three times, the wet tissue wiped across is saved
To the brown bottle of 50mL.
A kind of above-mentioned human body is to the multipath exposure assessment method of fire retardant, using eight grades of samplers of Anderson impacting type
The time of acquisition is in severe gray haze pollution situation down-sampling 36h, in slight gray haze pollution situation down-sampling 48h, weather condition
72h is sampled when being good.
For a kind of above-mentioned human body to the multipath exposure assessment method of fire retardant, exposure assessment model includes that breath exposure is commented
Estimate model and corium exposure assessment model, the breath exposure assessment models are as follows:
IFi=0.5 × (1+exp (- 0.06 × Dp,i))
DCj,i=∑ (DFj,i×Ci)；(j；HA,TB and AR)
Wherein, Dp,i(μm) is the average grain diameter of Andersen sampler the i-th partial size section；IF(inhalable fraction)
It is the inhalable efficiency (%) of different diameter airborne particle；CiIt is concentration of the FRs in the i-th partial size section；Total deposition fraction of FRs
(DFTotal) be three respiratory systems the sum of deposition fraction；DCj,iBe the i-th partial size section FRs it is inner at the position j (HA, TB and AR)
Deposited concentration (deposition concentration, unit: ng/m3)；FRs breath exposure amount (daily
Inhalation dose, DID) calculation formula it is as follows:
It is calculated according to deposited concentration: DID=(C × V)/BW
Wherein, DID is day breathing soakage (daily inhalation dose, the unit: pg/day or ng/ of FRs
kg BW/day)；C is the deposited concentration of the FRs in Atmospheric particulates；V is that respiratory rate is (adult: 15m3/day；Children:
7.6m3/day)；BW (body weight) is weight (adult and children weight are respectively 70kg and 15kg)；ET
(exposure time) is exposure duration, and ET is set as 24 hours under slight and severe gray haze pollution situation, ET points of indoor and outdoors
It Wei not 18h and 6h；
The corium exposure assessment model are as follows:Wherein, DAD (dermal
absorption dose；Unit: ng/kg BW/day) it is corium exposed amount；CFRsIt is concentration of the FRs in human skin surface
(ng/cm2)；SA (surface area) is area (the unit cm of forehead2, the area of adult forehead is 50cm2, children's forehead
Area is 36cm2)；ED (exposure duration) is exposed duration (24/ day)；When ET (exposure time) is sampling
The time (8h) to wash one's face last time apart from subject；AF (absorption factor) is the absorption fraction of FRs, BW (body
It weight) is that weight is (adult: 70kg；Children: 15kg).
A kind of above-mentioned human body is to the multipath exposure assessment method of fire retardant, sample flame retardant agent content in the step S3
Measurement the following steps are included:
(1) sample treatment and concentration: the internal standard of 100 μ L is added in sample to be processed, is then with 20mL volume ratio
The mixed liquor ultrasonic extraction of the n-hexane and acetone of 3:1 three times, each 30min；Extract liquor three times is transferred to round-bottomed flask
And it is concentrated into about 1mL with Rotary Evaporators, then concentrate is transferred in clean teat glass, is concentrated with soft nitrogen
1mL n-hexane is added to realize that solvent is replaced after to close do, and being vortexed dissolves it sufficiently；
(2) sample purification and transfer: the sample of concentration is subjected to purified treatment with Florey silica column, with 10mL volume ratio
It is eluted for the n-hexane of 2:1 and the mixed liquor of methylene chloride, to obtain the first component containing HFRs, then the second with 8mL
Acetoacetic ester is eluted, to obtain the second component containing OPFRs；The second component containing OPFRs is blown with soft nitrogen
It is done to close, the rate of recovery indicant PCB-209 of 100 μ L is then added, be transferred in sample injection bottle after being vortexed；
(3) sample further purifies: the first component containing HFRs being blown to 1mL or so with soft nitrogen, later peracid
Property silicagel column further purifies, and the mixed liquor of the n-hexane and methylene chloride that are 1:1 with 10mL volume ratio is eluted, leacheate
It is blown to through soft nitrogen and closely does, the rate of recovery indicant PCB-209 of 100 μ L is then added, sample injection bottle is transferred to after being vortexed
In；
(4) it measures flame retardant agent content: utilizing the content of GC-MS/MS measurement FRs.
For a kind of above-mentioned human body to the multipath exposure assessment method of fire retardant, the wet tissue is medical disinfection nonwoven
Cloth, the acquisition position are the forehead of human body, and the sample boxes area is 5 × 10cm of adult forehead2, 4 × 9cm of children's forehead2。
A kind of above-mentioned human body is to the multipath exposure assessment method of fire retardant, Florey silicon used in the step S3
Earth pillar is successively activated with 8mL ethyl acetate and 6mL n-hexane in advance using preceding.
Beneficial effects of the present invention: human body of the invention is sudden and violent using breathing to the multipath exposure assessment method of fire retardant
Dew assesses the exposure of fire retardant with mode associated with corium exposure, by two kinds of paths of breath exposure and corium exposure
The synchronous detection of synchronized sampling, obtained sample can be uniformly processed, quantitative detection, compared with assessment mode single at present
Closer to the true exposure of human body；And eight grades of samplers of Anderson impacting type and the method for wet tissue wiping are this field
The exposure in two kinds of paths is assessed available human body in the multipath exposure knot of same period by the newest method of sampling simultaneously
Fruit can carry out comprehensive multipath exposure to human body simultaneously with this and assess, have extensive research application prospect.
Detailed description of the invention:
Fig. 1 is the adult exposed amount under two states measured using appraisal procedure of the present invention；
Fig. 2 is the exposed amount of the children that are measured using appraisal procedure of the present invention under two states；
Fig. 3 is the adult breath exposure amount measured under two states；
Fig. 4 is the breath exposure amount that children measure under two states；
Fig. 5 is the adult corium exposed amount measured under two states；
Fig. 6 is the corium exposed amount that children measure under two states.
Specific embodiment:
Present invention will be further explained below with reference to the attached drawings and examples, and the present embodiment is by taking OPFR as an example.
Embodiment 1: the conduct of same region is chosen in November, 2016 to selection Xinxiang City Muye District during in January, 2017
Sample region is chosen two days and is monitored to the air pollution situation in the region, records air pollution index, monitoring result is air
Performance figure AQI numerical value is respectively 70 and 350, and respectively slight gray haze and severe haze weather, mild or moderate haze weather are adopted
Sample 48h, severe haze weather sample 36h, acquire atmospheric aerosol samples respectively with eight grades of samplers of Anderson impacting type；
While atmospheric aerosol samples acquisition, 20 volunteers are recruited in the region and carry out adopting for epidermis wipe samples
Collect work, there are male 10 respectively in 20 volunteers, wherein children there are 5；Women has 10, and wherein children have 5；For
Reduce the influence of sampling sites factor, the unified forehead for choosing volunteer is as wiping area, wherein adult forehead sample boxes face
Product is 5 × 10cm2, children's forehead sample boxes area is 4 × 9cm2；Researcher wear disposable glove, by sample boxes be placed on by
The forehead of examination person is taken the clean medical non-woven fabrics wet tissue impregnated through isopropanol with clean tweezers from Brown Glass Brown glass bottles and jars only
Out, it is wiped repeatedly three times on the two sides of the forehead of subject wet tissue, the wet tissue of wiping is saved to the clean brown of 50ml
In bottle；
Sample treatment: the internal standard of 100 μ L is separately added into sample to be processed, is then 3:1's with 20mL volume ratio
The mixed liquor ultrasonic extraction of n-hexane and acetone three times, each ultrasound 30min；
Sample concentrated by rotary evaporation: extract liquor will be transferred in round-bottomed flask three times and be carried out being concentrated into 1mL with Rotary Evaporators,
Then concentrate is transferred in clean teat glass, with soft nitrogen be concentrated into it is close dry after be added the n-hexane of 1mL into
The displacement of row solvent, and being vortexed dissolves it sufficiently；
Solid Phase Extraction: by the sample of concentration with the Fu Luo that is successively activated in advance with 8mL ethyl acetate and 6mL n-hexane in advance
In silica column carry out purified treatment, the mixed liquor of the n-hexane and methylene chloride that are 2:1 with 10mL volume ratio eluted, with
To the first component containing HFRs；It is eluted again with the ethyl acetate of 8mL later, to obtain the second component containing OPFRs；
Sample nitrogen blows transfer: the second component containing OPFRs being blown to soft nitrogen and is closely done, 100 μ L are then added
Rate of recovery indicant PCB-209 (500ng/mL), be vortexed after be transferred in the sample injection bottle containing interpolation pipe；
Sample further purifies: the first component containing HFRs being blown to 1mL or so with soft nitrogen, later peracidity silicon
Rubber column gel column (mass ratio 44%, pillar loading are 600mg) further purification, the n-hexane and two for being 1:1 with 10mL volume ratio
The mixed liquor of chloromethanes is eluted, and leacheate is blown to through soft nitrogen and closely does, and the rate of recovery indicant of 100 μ L is then added
PCB-209 (50ng/mL) is transferred to after being vortexed containing in interpolation pipe sample injection bottle；
FRs content in measurement sample: the content of FRs in two groups of samples is measured respectively using GC-MS/MS.
The present embodiment is disappeared using eight grades of samplers sample atmospheric aerosol samples of Anderson impacting type and using medical
Malicious non-woven fabrics wipes human epidermal, the outgoing sampling easy to carry of eight grades of sampler small volumes of Anderson impacting type, produces
In the acceptable scope of human body, the medical non-woven fabrics that isopropanol is impregnated with is slightly odorous for raw noise, but to human body without appoint
What is endangered, and can be wiped to the multiple positions of human body, carries out flame retardant agent content measurement to privileged site, the method for sampling simplifies
Sample preparation, it is simple and convenient, it is easily operated；And wet tissue tool, instrument with used in the process of are free of flame retardant constituent, are surveyed
Flame retardant agent content is entirely to come from the exposure of human body corium；Reagent used in experiment detection process is chromatographically pure, and sample
Keep stringent quality to control in the overall process of product processing, it is ensured that measurement method and data it is accurate and reliable.
Calculate breath exposure amount: sudden and violent as human body respiration using the sample of Anderson Anderson eight grades of samplers samples of impacting type
Reveal situation, and then breath exposure situation of the human body to fire retardant is assessed using breath exposure amount assessment models, assesses mould
Type is as follows:
IFi=0.5 × (1+exp (- 0.06 × Dp,i))
DCj,i=∑ (DFj,i×Ci)；(j；HA,TB and AR)
Wherein, Dp,i(μm) is the average grain diameter of Andersen sampler the i-th partial size section；IF(inhalable fraction)
It is the inhalable efficiency (%) of different diameter airborne particle；CiIt is concentration of the FRs in the i-th partial size section；Total deposition fraction of FRs
(DFTotal) be three respiratory systems the sum of deposition fraction；DCj,iBe the i-th partial size section FRs it is inner at the position j (HA, TB and AR)
Deposited concentration (deposition concentration, unit: ng/m3)；
The calculation formula of OPFRs breath exposure amount (daily inhalation dose, DID) is as follows:
It is calculated according to deposited concentration: DID=(C × V)/BW
Wherein, DID be OPFRs day breathing soakage (daily inhalation dose, unit: pg/day or
ng/kg BW/day)；C is the deposited concentration of the FRs in Atmospheric particulates；V is that respiratory rate is (adult: 15m3/day；Children:
7.6m3/day)；BW (body weight) is weight (adult and children weight are respectively 70kg and 15kg)；ET
(exposure time) is exposure duration, and ET is set as 24 hours under slight and severe gray haze pollution situation, ET points of indoor and outdoors
It Wei not 18h and 6h.
Calculate corium exposed amount: the sample for using wet tissue to wipe is commented as the foundation of human body corium exposure using corium exposure
Estimate model to assess corium exposure of the human body to fire retardant, assessment models are as follows:
Wherein, DAD (dermal absorption dose；Unit: ng/kg BW/day) it is corium exposed amount；COPFRsIt is
Concentration (ng/cm of the OPFRs in human skin surface2)；SA (surface area) is area (the unit cm of forehead2, adult volume
The area of head is 50cm2, the area of children's forehead is 36cm2)；ED (exposure duration) is exposed duration (24/ day)；
ET (exposure time) is the time (8h) to wash one's face last time when sampling apart from subject；AF (absorption factor) is
The absorption fraction of OPFRs, is specifically shown in Table 1；BW (body weight) is that weight is (adult: 70kg；Children: 15kg).
The relevant parameter of 1 human body forehead surface OPFRs corium exposure model of table
As a result with analysis: method associated with atmospheric sampling of the present invention and skin wiping is respectively adopted to adult and children in weight
The exposure of OPFRs is detected under degree gray haze and slight gray haze two states, as a result as depicted in figs. 1 and 2；Using list
One appraisal procedure examines adult and children under severe gray haze and slight gray haze two states to the exposure of OPFRs
It surveys, as a result as Figure 4-Figure 6；
Under the same conditions using the present invention is based on sides associated with atmospheric sampling and skin wiping it can be seen from Fig. 1-6
The particulate form OPFRs exposed amount of adult and children that method obtains are above single breath exposure amount and single corium exposure
Amount, illustrate use appraisal procedure of the invention to the exposure assessment of human body more comprehensively, closer to true exposed state；Lead to simultaneously
Comparison is crossed it has also been found that under the same conditions, breath exposure amount illustrates through respiratory pathways much larger than corium exposed amount compared to true
Skin approach is easier to expose, the protection in terms of Ying Jiaqiang breath exposure approach.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the present invention, all in the spirit and principles in the present invention
Any modifications, equivalent replacements, and improvements done in range, should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of human body is to the multipath exposure assessment method of fire retardant, it is characterised in that: the following steps are included:
S1: selection sampling area monitors the air pollution situation of sampling area, records air pollution index；
S2: according to the weather class of pollution of sample region, sampling time, the atmosphere of synchronous acquisition sampling area sample acquisition: are determined
The human skin skin granulate object sample of movable crowd in aerosol sample and sample region；
S3: flame retardant agent content in measurement sample: the content of GC-MS/MS measurement FRs is utilized；
S4: according to the content of fire retardant in the sample measured, using exposure assessment model to human body to the exposure of fire retardant
It is assessed.
2. a kind of human body according to claim 1 is to the multipath exposure assessment method of fire retardant, it is characterised in that: described
Sample collection method in step S2 are as follows: the sampling time is determined according to the state of air pollution, with eight grades of samplers of Anderson impacting type
Acquire the atmospheric aerosol samples of gradation diameter；While atmospheric aerosol samples acquisition, several names are chosen with the time in same district
The movable male and female volunteer in domain prepares the sample boxes of different area according to the different positions to be collected of volunteer, will sample
Frame is placed on the position to be wiped of subject, and when sampling is taken out wet tissue from clean brown bottle with clean tweezers, then by grasping
Author wears the position to be collected of disposable glove wiping volunteer, and the two sides for the non-woven fabrics being impregnated with isopropanol wipes three
It is secondary, the wet tissue wiped across is saved to the brown bottle of 50mL.
3. a kind of human body according to claim 2 is to the multipath exposure assessment method of fire retardant, it is characterised in that: use
The time of eight grades of samplers samples of Anderson impacting type is to pollute in severe gray haze pollution situation down-sampling 36h in slight gray haze
Situation down-sampling 48h, weather condition sample 72h when being good.
4. a kind of human body according to claim 1 is to the multipath exposure assessment method of fire retardant, it is characterised in that: exposure
Assessment models include breath exposure assessment models and corium exposure assessment model, the breath exposure assessment models are as follows:
IFi=0.5 × (1+exp (- 0.06 × Dp,i))
DCj,i=∑ (DFj,i×Ci)；(j；HA,TB and AR)
Wherein, Dp,i(μm) is the average grain diameter of Andersen sampler the i-th partial size section；IF (inhalable fraction) is not
With the inhalable efficiency (%) of particles things；CiIt is concentration of the FRs in the i-th partial size section；Total deposition fraction of FRs
(DFTotal) be three respiratory systems the sum of deposition fraction；DCj,iBe the i-th partial size section FRs it is inner at the position j (HA, TB and AR)
Deposited concentration (deposition concentration, unit: ng/m3)；
The calculation formula of FRs breath exposure amount (daily inhalation dose, DID) is as follows:
It is calculated according to deposited concentration: DID=(C × V)/BW
Wherein, DID is day breathing soakage (daily inhalation dose, the unit: pg/day or ng/kg of FRs
BW/day)；C is the deposited concentration of the FRs in Atmospheric particulates；
V is that respiratory rate is (adult: 15m3/day；Children: 7.6m3/day)；BW (body weight) is weight (adult and children
Weight be respectively 70kg and 15kg)；ET (exposure time) is exposure duration, under slight and severe gray haze pollution situation
ET is set as 24 hours, and the ET of indoor and outdoors is respectively 18h and 6h；
The corium exposure assessment model are as follows:
Wherein, DAD (dermal absorption dose；Unit: ng/kg BW/day) it is corium exposed amount；CFRsIt is that FRs exists
Concentration (the ng/cm of human skin surface2)；SA (surface area) is area (the unit cm of forehead2, the area of adult forehead
For 50cm2, the area of children's forehead is set as 36cm2)；ED (exposure duration) is exposed duration (24/ day)；ET
(exposure time) is the time (8h) to wash one's face last time when sampling apart from subject；AF (absorption factor) is
The absorption fraction of FRs, BW (body weight) are that weight is (adult: 70kg；Children: 15kg).
5. a kind of human body according to claim 1 is to the multipath exposure assessment method of fire retardant, it is characterised in that: described
In step S3 sample flame retardant agent content measurement the following steps are included:
(1) sample treatment and concentration: the internal standard of 100 μ L is added in sample to be processed, is then 3:1's with 20mL volume ratio
The mixed liquor ultrasonic extraction of n-hexane and acetone three times, each 30min；By extract liquor three times be transferred to round-bottomed flask and with rotation
Turn evaporimeter and be concentrated into about 1mL, be then transferred to concentrate in clean teat glass, is concentrated into soft nitrogen close dry
1mL n-hexane is added afterwards to realize that solvent is replaced, and being vortexed dissolves it sufficiently；
(2) sample purification and transfer: the sample of concentration is subjected to purified treatment with Florey silica column, is 2 with 10mL volume ratio:
1 n-hexane and the mixed liquor of methylene chloride are eluted, to obtain the first component containing HFRs, then the acetic acid second with 8mL
Ester is eluted, to obtain the second component containing OPFRs；The second component containing OPFRs is blown to closely with soft nitrogen
It is dry, the rate of recovery indicant PCB-209 of 100 μ L is then added, is transferred in sample injection bottle after being vortexed；
(3) sample further purifies: the first component containing HFRs being blown to 1mL or so with soft nitrogen, later peracidity silicon
Rubber column gel column further purifies, and the mixed liquor of the n-hexane and methylene chloride that are 1:1 with 10mL volume ratio is eluted, and leacheate is through soft
The nitrogen of sum, which is blown to, closely to be done, and the rate of recovery indicant PCB-209 of 100 μ L is then added, is transferred in sample injection bottle after being vortexed；
(4) it measures flame retardant agent content: utilizing the content of GC-MS/MS measurement FRs.
6. a kind of human body according to claim 2 is to the multipath exposure assessment method of fire retardant, it is characterised in that: described
Wet tissue is medical disinfection non-woven fabrics, and the wiping position is the forehead of people's body, the sample boxes area be adult forehead 5 ×
10cm2, 4 × 9cm of children's forehead2。
7. a kind of human body according to claim 5 is to the multipath exposure assessment method of fire retardant, it is characterised in that: described
Florey silica column used in step S3 is successively activated with 8mL ethyl acetate and 6mL n-hexane in advance using preceding.
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