CN110274991A - The evaluation method and its application in human health risk prediction that vegetables in greenhouse booth absorbs phthalic acid ester - Google Patents

The evaluation method and its application in human health risk prediction that vegetables in greenhouse booth absorbs phthalic acid ester Download PDF

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CN110274991A
CN110274991A CN201910199625.8A CN201910199625A CN110274991A CN 110274991 A CN110274991 A CN 110274991A CN 201910199625 A CN201910199625 A CN 201910199625A CN 110274991 A CN110274991 A CN 110274991A
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paes
vegetables
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冯宇希
莫测辉
冯乃宪
陈昕
涂茜颖
曾丽娟
蔡全英
李彦文
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Jinan University
University of Jinan
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Abstract

The evaluation method for absorbing phthalic acid ester the invention discloses a kind of vegetables in greenhouse booth and its application in human health risk prediction;The evaluation method is to include the following steps: that S1. sample acquires: PAEs in the soil, vegetables and air inside and outside acquisition greenhouse, sample measure the content of wherein PAEs after pre-treatment;S2. soil inside and outside the greenhouse obtained according to S1, the content of PAEs carries out simulation and forecast using content of the equilibrium equation to the PAEs of vegetables in greenhouse booth using Te Lapu mechanism of absorption model in air;S3. PAEs result is absorbed according to the crop of S2 Te Lapu mechanism of absorption model prediction and carries out evaluation analysis.The present invention is on the basis of collecting crop absorption parameter, using the concentration of Te Lapu (Trapp) mechanism of absorption model analysis simulation greenhouse phthalic acid ester, and human health risk prediction and assessment are carried out to it, reduce the analysis cost of pollutant assessment, there is biggish practical significance.

Description

Vegetables in greenhouse booth absorbs the evaluation method of phthalic acid ester and its in human health Application in risk profile
Technical field
The present invention relates to environmental quality assessment technical fields, absorb adjacent benzene more particularly, to a kind of vegetables in greenhouse booth The evaluation method of dicarboxylic acid esters and its application in human health risk prediction.
Background technique
Phthalic acid ester (PAEs) is a kind of typical plasticiser, is widely used in plastic plasticizer and (is commonly called as being plasticized Agent) and industries such as automobile, clothes, cosmetics, lubricant and pesticide, largely enter in environment, and there is half volatile and remote Distance translation becomes global environmental contaminants.The PAE of high concentration, especially DBP and DEHP are widely examined in the soil Out, have become main organic pollutant in agricultural land soil-Vegetable System.Greenhouse canopy film is PAEs important sources, PAEs can be accumulated in crop edible part, and the agricultural product containing PAEs, which are eaten for a long time, will lead to low dosage exposure, to human health Generate certain risk.Greenhouse is in semi-closed state throughout the year, have high temperature, high humidity, high evaporation capacity and without rainwater elution etc. Feature, long-term a large amount of application chemical fertilizer lead to occur after the certain time limit of farming that soil property deteriorates, to further increase vegetables PAEs residual The problems such as staying.With extensive agriculturalization of plastic film, and the rubbish of a large amount of town sewages is discharged into farmland, soil and vegetable Phthalic acid ester pollution in dish is also increasingly severe.Therefore, there is an urgent need to a kind of vegetables in greenhouse booth to absorb commenting for PAEs Valence method provides science decision foundation for further progress PAEs control technology research and environmental quality standards formulation.
It include the CLEA model of Britain in the model assessed at present for chemicals, the CETOX model of Denmark is Dutch CSOIL model, the CalTOX model of California, USA, the EUSES model of German UMS model and European Union, but China Lack the model of evaluating chemical product analysis.In these models, plant absorption model is the important models of evaluating chemical product risk, Including Briggs crop absorption factor model, Paterson and Mackay fugacity model, partition-limited model, neural network model Deng.Deng Shaopo etc. (2010) is disclosed for typical pollutant PCBs existing for certain electronic waste dismantling ground, using Trapp crop Mechanism of absorption model contains PCBs in this area's leaf vegetables according to PCBs content in the soil of factual survey acquisition, atmosphere Amount is simulated prediction, and is compared with measured value, to inquire into superiority and inferiority (Deng Shaopo, Luo Yongming, Song Jing, the Teng of the model It answers, application [J] environment section of the Chen Yongshan .Trapp model in the absorption of Typical Areas PCBs vegetables and human healthy risk assessment Learn, 2010,31 (12): 3018-3027.), but its evaluation for being directed to the pollution by polychlorinated biphenyles object in the environment of crop field, and Fitting effect is simultaneously bad, is not particularly suited for vegetables in greenhouse booth and absorbs in the evaluation of PAEs;It yet there are no for based on steady Vegetables absorb the evaluation model and evaluation method that PAEs is established in fixed closed system (such as greenhouse).
Meanwhile the human healthy risk assessment in China's contaminated site and region is in the starting stage, it is many in recent years to learn Person carried out some human healthy risk assessment's work in the trial of typical contaminated area, but mostly to investigate surrounding medium pollution condition Based on, the content of pollutant in the human healthy risk assessment of the progress mostly surrounding medium based on factual survey, this will lead to consumption Take a large amount of manpower and material resources, and carry out human healthy risk assessment can not place one's entire reliance upon sample detecting analysis.How will The prediction techniques such as mathematical model are introduced into risk assessment, the development that can effectively push human healthy risk assessment to work.
Summary of the invention
The purpose of the invention is to be to overcome existing vegetables in greenhouse booth to absorb phthalic acid ester evaluation method to exist Defect and deficiency, on the basis of collecting crop absorption parameter, using Te Lapu (Trapp) mechanism of absorption model analysis simulate The concentration of greenhouse phthalic acid ester, and human health risk prediction and assessment are carried out to it, reduce pollutant assessment Analysis cost, have biggish practical significance.
The first purpose of the invention is to provide the evaluation methods that a kind of vegetables in greenhouse booth absorbs phthalic acid ester.
A second object of the present invention is to provide application of the above-mentioned evaluation method in human health risk prediction.
Above-mentioned purpose of the invention is to give realization by the following technical programs:
A kind of vegetables in greenhouse booth absorbs the evaluation method of phthalic acid ester, includes the following steps:
S1. sample acquires: PAEs in the soil, vegetables and air inside and outside acquisition greenhouse, sample are surveyed after pre-treatment The content of fixed wherein PAEs;
S2. soil inside and outside the greenhouse obtained according to S1, in air PAEs content, using Te Lapu mechanism of absorption mould Type carries out simulation and forecast using content of the following equilibrium equation to the PAEs of vegetables in greenhouse booth:
dmL/ dt=d (CLVL)/dt=QTSCFCw+Ag(CA-CL/KLA)-λEmL(1),
It is exponential type when increasing, ratio A/VLAnd Q/VLWhen being assumed to be constant, concentration dC at any timeLThe variation of/dt:
dCL/ dt=- [Ag/ (KLAVL)+λEG]CL+CW·TSCF·Q/VL+CAgA/VL (2)
(2) formula can be considered as:
dCL/ dt=-aCL+ b (3),
Wherein a=Ag/ (KLAVL)+λEG, b=CW·TSCF·Q/VL+CAgA/VL
(3) solution of formula are as follows:
CL(t)=CL(0)exp(-at)+b/a[1-exp(-at)]
With the growth of crop, aboveground vegetation part internal pollution object and periphery pollutant reach balance and growth time When infinitely great, the content of pollutant in plant are as follows:
CL(∞)=b/a
Pollutant reaches the time required for the 95% of stable state in plant are as follows:
T (95%)=- 0.05/a;
S3. PAEs result is absorbed according to the crop of S2 Te Lapu mechanism of absorption model prediction and carries out evaluation analysis.
Parameter in above-mentioned equilibrium equation is as shown in table 1.
Preferably, the PAEs is DBP and/or DEHP.
Preferably, measuring method described in step S1 is GC-MS.
The method is also claimed in PAEs to the application in human health risk prediction in the present invention.
A kind of evaluation method of PAEs human health risk, first to measure or predicting concentration of the DBP and DEHP in vegetables, It is calculated further according to following calculation formula:
Wherein, DI is content (the μ g.kg for being orally ingested PAEs-1d-1);CDBPAnd CDEHPIndicate DBP and DEHP in vegetables Concentration (mg.kg-1dw);W indicates the water content (92.31%) in vegetables;IR is vegetables daily intaking amount (314.47g.d-1), R The ratio (winter 61%) of the total vegetable consumption amount of booth vegetable Zhan, bw be people average weight (children (5~11 years old): 26.15kg, adult (> 18 years old): 65.56kg), rDBPAnd rDEHPIndicate that gastrointestinal tract absorbs the rate of DBP and DEHP from food (DBP:0.685, DEHP:0.552).
Compared with prior art, the invention has the following advantages:
It is (1) of the invention for the first time by Te Lapu mechanism of absorption model use in the evaluation that vegetables in greenhouse booth absorbs PAEs, A kind of evaluation method for organic pollutant in stable closed system is established, simulated conditions are sufficiently stable, and evaluate As a result accurate, reduce the analysis cost of pollutant assessment, there is biggish practical significance.
(2) present invention introduces the prediction techniques such as mathematical model when carrying out PAEs to human health risk forecast assessment In risk assessment, and formula is corrected, keeps result more accurate.
Detailed description of the invention
Fig. 1 is that crop absorbing model of the present invention and human health risk evaluate associated diagram.
Fig. 2 is that crop absorbs PAEs model schematic.
Satellite mapping near Fig. 3 sampling site.
Fig. 4 is the content of PAEs in sampling position periphery plastic shed soil-vegetables-air.
Fig. 5 is PAEs overall content in China's soil and vegetables (S indicates that soil, V indicate vegetables).
Fig. 6 is that predicted value and actual value compare (vegetables 1- balsam pear, vegetables 2- corn).
Fig. 7 is that blade absorbed for 95% stable time (d).
Fig. 8 is that leaf area and PAEs absorb relationship.
Fig. 9 is contribution rate of the separate sources to PAEs in vegetables.
Figure 10 is children and adult exposure actual value and predicted value.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
The evaluation method that vegetables in greenhouse booth of the invention absorbs phthalic acid ester mainly includes the following steps: from potential Crop absorbing model parameter is obtained in risk farming land, then absorbs pollutant model using the parameter building crop obtained, then It carries out model result to calculate and verify, carries out human healthy risk assessment using model result, carry out risk verifying, process is as schemed Shown in 1.
The evaluation method of 1 vegetables in greenhouse booth of embodiment absorption phthalic acid ester
One, method
1, model hypothesis
Assuming that it is that (most of organic matter enters the intracorporal mode of plant to Passive intake that PAEs, which enters the intracorporal mode of plant, Passive intake), the process is as shown in Fig. 2, can be described as:
(1) root absorption: root absorption is that PAEs enters one of intracorporal approach of plant;
(2) transported under ground portion to aerial part: plant can be shifted PAEs under ground portion by transpiration pull To aerial part;
(3) blade absorbs: PAEs is a kind of organic pollutant (SVOCs) of half volatile, and plant can be inhaled by blade Receive PAEs
(4) it volatilizees from blade: PAEs can be evaporated into air while plant absorption PAEs;
(5) some metabolism or degradation process: PAEs can carry out some incomplete metabolism in plant;
(6) biological diluting effect: with the growth of plant, the increase of biomass, PAEs can go out in the intracorporal concentration of plant Now certain variation.
2, experimental data is collected, data in literature is collected and analysis
Early period, inventor sample the greenhouse near the academy of agricultural sciences of Guangzhou, as shown in Figure 3.It acquires respectively The sample of soil and vegetables in 5 greenhouses, balsam pear (5 samples including balsam pear (5 samples) in greenhouse, outside greenhouse Product), corn (6 samples) and corresponding soil (16 samples) outside greenhouse.In addition, also acquiring in greenhouse (5 samples Product) outside in (3 samples) air PAEs concentration.PAEs concentration analysis is measured according to the literature method before us.Knot Fruit is as shown in figure 4, different types of PAEs has detection in soils-vegetables-air, as the content of DiBP in balsam pear reaches 6.5mg/kgDW, DEHP content reaches 1.68mg/kgDW in soil.The statistical result showed (Fig. 5) of inventor early period, DiBP and DEHP is generally detected in agricultural land soil-Vegetable System, and concentration highest, PAEs maximum to Health Impact, have compared with High carcinogenic risk, therefore prediction and risk assessment are carried out mainly for DiBP and DEHP below.
3, model data is collected
It includes two partial contents that model data, which is collected: (1) Te Lapu plant absorption model parameter is as shown in table 1;(2) PAEs basic physical and chemical is as shown in table 2.
1 Te Lapu plant absorption model parameter meaning of table
1) fw indicates fresh weight;
2) pollutant concentration calculates in soil aqueous solution: Cw≈ csoil/Kd=csoil/ (OC × KOC);In formula, csoil To air-dry pollutant concentration (actual measurement) in soil, OC is soil organic carbon 0.0465 (actual measurement), KOC pollutant organic carbon point Distribution coefficient;
3)KLACalculation method: KLA=KLW/KAW, K in formulaLWFor plant-water partition coefficient, KLW=(Wp+Lpa Kbow)·ρp/ρW, in formula, Wp: water content of plant, (gg-1);Lp: rouge content in plant, (gg-1);ρp、ρW: plant and Water density, kgm-3;B: vegetable butter-octanol compensation coefficient;Kow: pollutant octanol-water partition coefficient;A: octanol-water correction system Number, a=ρw/ρo;Water density:ρW=1000kgm-3, octanol densityρO=827kgm-3;The above parameter value is shown in text;Kaw: Dimensionless Henry's constant;
4) TSCF calculation method: TSCF=0.784exp [- (lgKow-1.78) 2/2.44]
The physicochemical properties of 2 PAEs of table
DMP DEP DiBP DOP DEHP BBP
Kow 3.63 295 360000 7400000000 4100000000 3600000
M 194.19 222.24 278.35 390.56 390.56 312
Pv 0.00419 0.0035 0.00001 0.00014 0.0000002 0.00006
S 5000 896 13 3 0.4 2.9
Koa 10232930 35481339 346736850 33884415614 33884415614 602559586
Kaw 3.98E-06 9.77E-06 5.37E-05 0.00158 0.00158 8.32E-05
Koc 17.4 142 170000 3600000000 2000000000 1700
1)Kow: the octanol water partition coefficient of phthalic acid ester;
2) M: the molecular mass of phthalic acid ester;
3) Pv: the saturated vapour pressure of phthalic acid ester;
4) S: phthalic acid ester solubility μ gL-1
5)Koa: the octanol air distribution coefficient of phthalic acid ester;
6)Kaw: dimensionless Henry's constant;
7)KOCPollutant organic carbon distribution coefficient;
4, model use
It mainly include the calculating of distribution coefficient in vegetable tissue, root absorption meter according to Te Lapu model modeling process Calculation, transpiration current concentration factor calculate, gas exchanges calculate, metabolism is diluted with light degradation calculating and biology, finally public according to calculating Formula is balanced equation.Te Lapu is proposed mainly for hydrophobic contaminant to be absorbed based on growing process mechanism crop Model, it is contemplated that material absorbing and exchange process.According to equilibrium equation listed above:
dmL/ dt=d (CLVL)/dt=QTSCFCw+Ag(CA-CL/KLA)-λEmL(1), the meaning of parameter such as 1 institute of table Show.
It is exponential type when increasing, ratio A/VLAnd Q/VLWhen being assumed to be constant, concentration dC at any timeLThe variation of/dt:
dCL/ dt=- [Ag/ (KLAVL)+λEG]CL+CW·TSCF·Q/VL+CAgA/VL (2)
(2) formula can be considered as:
dCL/ dt=-aCL+ b (3),
Wherein a=Ag/ (KLAVL)+λEG, b=CW·TSCF·Q/VL+CAgA/VL
(3) solution of formula are as follows:
CL(t)=CL(0)exp(-at)+b/a[1-exp(-at)]
With the growth of crop, aboveground vegetation part internal pollution object and periphery pollutant reach balance and growth time When infinitely great, the content of pollutant in plant are as follows:
CL(∞)=b/a
Pollutant reaches the time required for the 95% of stable state in plant are as follows:
T (95%)=- 0.05/a
Two, crop absorbs PAEs model prediction result and explains
1, vegetables-soil-air total DBP and DEHP content average value
After measured, vegetables-soil-air total DBP and DEHP content average value is as shown in table 3,
3 vegetables of table-soil-air total DBP and DEHP content average value
2, parameter calculates
Balsam pear and maize seed DBP and DEHP content prediction value are as follows, predicted value and actual value can be compared (Fig. 6), together When make time (Fig. 7) of t (95%), leaf area and PAEs absorb relationship as shown in figure 8, air source coefficient and soil source coefficient As shown in Figure 9.As can be seen that predicted value of the DBP in vegetables and measured value error are less than DEHP;Vegetables absorb PAEs and reach 95% stable time is related with PAEs physicochemical property and plant relevant parameter;The model is when predicting plant absorption pollutant, leaf Surface area parameters play decisive role;PAEs in greenhouse air is the important channel that vegetables absorb PAEs.
4 balsam pear of table and maize seed DBP and DEHP content prediction value
Model parameter Balsam pear DBP Balsam pear DEHP Corn DBP Corn DEHP
A 0.7 0.7 0.8 0.8
CL 1.69 1.24 1.31 1.13
Cw 2.2E-05 3.29E-05 3.74E-05 1.40E-04
CL(0) 0.00E+00 0.00E+00 0.00E+00 0.00E+00
CA 160000pg/m3 374000pg/m3 160000pg/m3 374000pg/m3
g 9.26E-04 9.26E-04 9.26E-04 9.26E-04
KLA 9.68E+06 3.28E+05 9.68E+06 3.28E+05
VL 2.00E-03 2.00E-03 3.00E-03 3.00E-03
Q 1.16E-08 1.16E-08 1.16E-08 1.16E-08
TSCF 6.18E-02 6.18E-02 6.18E-02 6.18E-02
t 79 24 80 29
EnterE 0 0 0 0
EnterG 4.05E-07 4.05E-07 4.05E-07 4.05E-07
A 4.65E-02 4.65E-02 4.65E-02 4.65E-02
Te Lapu Mechanism Model is mainly used for hydrophobic organic pollutant, and model is based on being situated between to environment in growing process Pollutant absorbs in matter, it is contemplated that plant absorbs pollutant, aerial part in soil pore water by root system and passes through plant leaf blade With the exchanging of Gaseous Pollutants, the dilution of pollutant and the degradation of pollutant.It is needed simultaneously when Te Lapu model is applied Measure the pollutant load in the pre- measuring plants of pollutant ability in air and soil.In addition, although Te Lapu model is plant- Atmospheric Absorption approach is taken into account, sufficiently stable in its simulated conditions, and it is organic to plant absorption not account for true nature condition Pollutant effects.Greenhouse is in semi-closed state throughout the year, smaller by Ventilation Effect, therefore is more suitable for Te Lapumo Type.
The evaluation of 2 human health risk of embodiment
1, method
The method proposed according to Fig. 1, by taking Guangzhou academy of agricultural sciences periphery greenhouse as an example, survey region is with agricultural and use of living Based on ground, region resident eats the produced vegetables of the greenhouse more;Lack in agricultural land soil and vegetables in existing evaluation criterion The reference limit value of PAEs lacks chemicals exposure analysis evaluation model model.The calculation formula proposed according to USEPA:
Wherein, C is PAE concentration (mg/kg) in vegetables, and IR is vegetables daily intaking amount (μ gkg-1d-1), bw is weight (kg), wherein DBP, EDHP are 100,20 μ gkg- respectively1d-1)。
Since the formula has compared with big limitation evaluation organic pollutant, when we analyze PAEs content in vegetables again It waits, using dry weight, and the formula does not embody, in addition it is also necessary to the ratio of the total vegetable consumption amount of booth vegetable Zhan is calculated, The absorption coefficient of intestinal absorption phthalic acid ester is considered simultaneously, therefore judgement schematics should be modified, as follows:
Wherein, DI is content (the μ g.kg for being orally ingested PAEs-1d-1);CDBPAnd CDEHPIndicate DBP and DEHP in vegetables Concentration (mg.kg-1dw);W indicates the water content (92.31%) in vegetables;IR is vegetables daily intaking amount (314.47g.d-1), R The ratio (winter 61%) of the total vegetable consumption amount of booth vegetable Zhan, bw be people average weight (children (5~11 years old): 26.15kg, adult (> 18 years old): 65.56kg), rDBPAnd rDEHPIndicate that gastrointestinal tract absorbs the rate of DBP and DEHP from food (DBP:0.685, DEHP:0.552).
2, result
It is predicted according to above-mentioned formula, DEHP forecasting risk is lower than calculation risk.Evaluation result is below USEPA regulation Daily intaking amount.The accuracy of plant absorption model directly affects the accuracy of risk assessment;Human contact PAEs not only can be with , can also be by the intake of the foods such as meat, fish, milk, poultry, fruit by vegetables, therefore the day that we calculate is taken in Amount is likely lower than real value.

Claims (5)

1. the evaluation method that a kind of vegetables in greenhouse booth absorbs phthalic acid ester, which comprises the steps of:
S1. sample acquires: PAEs in the soil, vegetables and air inside and outside acquisition greenhouse, sample measure it after pre-treatment The content of middle PAEs;
S2. soil inside and outside the greenhouse obtained according to S1, in air PAEs content, using Te Lapu mechanism of absorption model, Simulation and forecast is carried out using content of the following equilibrium equation to the PAEs of vegetables in greenhouse booth:
dmL/ dt=d (CLVL)/dt=QTSCFCw+Ag(CA-CL/KLA)-λEmL,
It is exponential type when increasing, ratio A/VLAnd Q/VLWhen being assumed to be constant, concentration dC at any timeLThe variation of/dt:
CL(t)=CL(0)exp(-at)+b/a[1-exp(-at)]
Wherein a=Ag/ (KLAVL)+λEG, b=CW·TSCF·Q/VL+CAgA/VL
With the growth of crop, aboveground vegetation part internal pollution object and periphery pollutant reach balance and growth time is infinite When big, the content of pollutant in plant are as follows:
CL(∞)=b/a
Pollutant reaches the time required for the 95% of stable state in plant are as follows:
T (95%)=- 0.05/a;
S3. PAEs result is absorbed according to the crop of S2 Te Lapu mechanism of absorption model prediction and carries out evaluation analysis.
2. evaluation method according to claim 1, which is characterized in that the PAEs is DBP and/or DEHP.
3. the method according to claim 1, wherein measuring method described in step S1 is GC-MS.
4. any one of claims 1 to 3 the method is in PAEs to the application in human health risk prediction.
5. a kind of evaluation method of PAEs human health risk, which is characterized in that first measure or predict DBP and DEHP in vegetables Concentration, calculated further according to following calculation formula:
Wherein, DI is content (the μ g.kg for being orally ingested PAEs-1d-1);CDBPAnd CDEHPIndicate that DBP and DEHP is dense in vegetables Spend (mg.kg-1dw);W indicates the water content (92.31%) in vegetables;IR is vegetables daily intaking amount (314.47g.d-1), R is big The ratio (winter 61%) of the total vegetable consumption amount of canopy vegetables Zhan, bw be people average weight (children (5~11 years old): 26.15kg, Adult (> 18 years old): 65.56kg), rDBPAnd rDEHPIndicate gastrointestinal tract absorbed from food DBP and DEHP rate (DBP: 0.685, DEHP:0.552).
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CN113517068A (en) * 2021-04-20 2021-10-19 复旦大学 Method for estimating daily intake of DEHP (dehydroepiandrosterone) by using physiological toxicity metabolic kinetics model

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