CN106202925A - A kind of health risk assessment method based on fugacity model - Google Patents

Abstract

The present invention relates to environmental science and health risk assessment field, relate to prediction and the method for health risk assessment thereof of a kind of chemical pollutant concentration in multi-environment medium based on fugacity model；(1) Level III fugacity model is used, it is considered to choose air, water body, soil, four principal phases of deposit；In the case of supposing whole ecosystem balance, the environmental quality in binding district, set up the environment multimedia fugacity model of chemical pollutant；(2) process of fugacity model and parameter: described process includes chemical pollutant input in surrounding medium and output；And return to become to being predicted to the migration of the pollution compound of study area by Level III fugacity model；The inventive method has advance, comprehensive；According to features of regional environment setting model parameter, can improve model sensitivity, the analog result making regional pollution thing home to return to is more accurate.The method Environment features and the detection advantages such as the cycle is short, cost-effective simultaneously.

Description

A kind of health risk assessment method based on fugacity model

Technical field

The present invention relates to environmental science and health risk assessment field, relate to a kind of chemical pollutant based on fugacity model The prediction of concentration and the method for health risk assessment thereof in multi-environment medium.

Background technology

During Environmental Health Study on Risk Assessment, the impact on health of the multiple route of exposure need to be considered.Mostly Number research, frequently with the pollutant levels in detection varying environment medium, predicts its shadow to population health by assessment models The degree of sound and environmental risk.In real work, it is seen that use this research method to carry out Environment features, detection cycle Long, relatively costly, and testing result can be caused to there is many uncertainties owing to the detection method of environmental sample is various etc..

Have both at home and abroad many scientific research personnel use fugacity model to compound in hypermedia environmental transport and transfer, return the expansion that becomes to grind Study carefully, due to its there is simple in construction, result represents that the advantage such as directly perceived is used widely.Wherein to domestic typical urban, feature Pollutant have more research report in the migration of multi-interfacial feature, such as (2009,2013) and Tian Hui etc. (2013) fortune such as Dong Jiyuan With region, Lanzhou DDT, PAHs and the multi-interfacial feature fate behavior of 5a,6,9,9a-hexahydro-6,9-methano-2,4 under fugacity model simulation limit, it is indicated that it is main Bank is soils and sediments, and the concentration calculated according to model is the most identical with the measured concentration same period.Li Jings etc. (2008) adopt With fugacity model sunykatuib analysis benzo (a) pyrene Efficiency in Buildings in Tianjin Area gas and water, soil and deposit multimedium alternate concentration distribution move, Mobile Communication's amount and accumulation tendency, result shows that soils and sediments is the bank of its maximum, demonstrates the reliability of model equally.Ease Degree model, according to features of regional environment setting model parameter, can improve model sensitivity, make the simulation at regional pollution thing home to return to tie Fruit is more accurate.

At present by the most rare with the research that health risk model combines for fugacity model, the health risk assessment of this patent Method is based on fugacity model, on the basis of fugacity model, calculates the predictive value of chemical pollutant, so calculate right The health risk of human body, determines its venture influence size, pollutant is carried out priority control.With the patent phase having at present Ratio, the screening technique set up has practicality.

Summary of the invention

It is an object of the invention to: a kind of practical based on fugacity model a kind of health risk assessment method is provided.

For solving above-mentioned technical problem, the technical solution used in the present invention is as follows:

A kind of a kind of health risk assessment method based on fugacity model, said method comprising the steps of:

(1) Level III fugacity model is used, it is considered to choose air, water body, soil, four principal phases of deposit；Whole in supposition In the case of individual ecosystem balance, the environmental quality in binding district, set up the environment multimedium fugacity mould of chemical pollutant Type；

(2) process of fugacity model and parameter: described process includes chemical pollutant input in surrounding medium and defeated Going out, input process is: compound is directly entered principal phase and the input of gas water advection；Output procedure is: the degraded between each medium and The advection output of big gas water；By Level III fugacity model to the migration of the pollution compound of study area and return become to carrying out pre- Survey；

(3) show that chemical pollutant after concentration, utilizes four step rule to study area crowd in each surrounding medium in step (2) Health risk is estimated, and described four step rule includes: harm qualification, dose-response relationship, Exposure Assessment, risk characterization.

Further, described big gas phase includes gas phase and the sub-phase of aerosol.

Further, described water body includes water phase, suspended particulate substance phase and roe phase mutually.

Further, the described soil phase includes gas phase, solid son phase and water phase.

Further, described deposit includes solid son phase and water phase mutually.

Further, in described step (2), process and the parameter step of fugacity model also include: fugacity model parameter quick Perceptual analysis.

Further, described step (3) also includes the sensitivity analysis of health risk assessment.

Technical scheme is used to provide the benefit that:

1, the inventive method has advance, comprehensive；Owing to chemical pollutant is prone to migrate at hypermedia environment, and Fugacity model has simple in construction, result represents directly perceived, and wherein for domestic typical urban, characteristic contamination multi-interfacial feature moves Move in research report, according to features of regional environment setting model parameter, model sensitivity can be improved, make regional pollution thing home to return to Analog result is more accurate.The method Environment features and the detection advantages such as the cycle is short, cost-effective simultaneously.

2, the inventive method has the safety of population health；Consider the exposure chamber of varying environment medium, consider Crowd's route of exposure, based on carrying out population health risk assessment on the basis of fugacity model, and then identifies chemical pollutant pair The influence degree of crowd.

3, the feature that the inventive method has operability, sustainability is strong；Chemical pollutant according to model prediction In surrounding medium, concentration can strengthen the measured value of this district's chemical pollutant and the specific aim of health risk assessment, for the ring of this area Border protection provides certain technical support.

Accompanying drawing explanation

The migration of TBBPA and return in Fig. 1 simulated environment.

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention will be further described.

Application example:

Yangtze River Delta city TBBPA health risk assessment method

(1) study area brief introduction

Study area is positioned at Yangtze River Delta Taihu Plain In Northwestern Margin, and the soil gross area is 4.39 × 105hm², wherein land Area is 3.6 × 105hm², water surface area is 7.33 × 104hm², cultivated area is 1.48 × 105hm².Genus north Asia, study area heat Band marine climate, has a moderate climate throughout the year, and rainfall is abundant, makes a clear distinction between the four seasons.The end of spring and the beginning of summer has plum rains to occur often, and summer is hot Rainy, the highest temperature often reaches more than 36 DEG C, and winter air moistens, and weather is sombre.According to 2013 year rule yearbooks, study area household register people Mouthful being about 3,700,000, gender's ratio is for 99.1:100.

(2) parameter of fugacity model

The data that model needs include the ambient parameter needed for the physical and chemical parameter of TBBPA and study area.Physical and chemical parameter passes through Consulting literatures, collection of data gained, the ambient parameter of study area is obtained by actual concrete mensuration and consulting literatures.Model Parameter is needed to be shown in Table 1,2.

The physical and chemical parameter that table 1 TBBPA is main

Ambient parameter needed for table 2 study area

(3) fugacity model predicts the outcome

And return to become to being predicted to the migration of study area TBBPA by Level III model.Water body, atmospheric advection layer TBBPA Pollution concentration use measured data (1.2ng L^-1、0.5ng·m^-3), show TBBPA in big gas phase by model prediction Concentration is 437ng m^-3, soil mutually in concentration be 61.5ng g^-1, water body mutually in concentration be 3.82mg L^-1, deposit It is 0.189mg g in mutually^-1, distribution percentage ratio is respectively 5.62%, 8.36%, 63%, 23%, sees Fig. 1.

The balance expression relating to principal phase migration amount can be set up according to Steady state hypothesis and mass balance relation:

E_i+G_AiC_Ai+f_j∑D_ij=f_i(∑D_ij+D_Ri+D_Ai)

In formula:

I, j=1 ... 4, respectively air, water body, soil, deposit phase；

R, A respectively degradation process is peaceful flows through journey；

E_iFor rate of discharge, mol/h；

G_AiFor advection rate of influx, m³/h；

C_AiConcentration, mol/m is flowed into for advection³；

D_AiFor advection output speed mol/ (Pa h)；

D_RiFor degradation rate mol/ (Pa h)；

D_ijFor migration rate mol/ (Pa h) between medium；

f_i, f_jFor fugacity, Pa.

Three grades of fugacity model are primarily adapted for use in stable state input and output, each alternate migration, and each mutually in occur each Plant course of reaction, and assume that these processes all belong to and process.

The computational methods of partial parameters, according to the volatilization bimodulus theoretical model of gas-water interface mass exchange, gas phase and liquid phase Coefficient of mass transfer K_12-AAnd K_12-WThe method that available Southworth proposes calculates.

Gas side gas water coefficient of mass transfer k_12-A(cm/h):

$k_{12-A}=1137.5(V_{WIND}+V_{RIVER})\sqrt{18/M_B}$

In formula:

V_wind: wind speed, m/s；

V_river: the speed in river, m/s；

M_B: the molecular weight of pollutant, g/mol.

Water side gas water coefficient of mass transfer k_12-W(cm/h):

Work as V_wind< during 1.9m/s:

$k_{12-W}=23.51\frac{V_{RIVER}^{0.969}}{h_W^{0.6763}}\sqrt{32/M_B}$

As 1.9 < V_wind< during 5m/s:

$k_{12-W}=23.51\frac{V_{RIVER}^{0.969}}{h_W^{0.673}}\sqrt{32/M_B}\exp \left(0.526\right(V_{WIND}-1.9\left)\right)$

In formula:

h_w: the river depth of water, unit m.

Aqueous phase coefficient of molecular diffusion B_w(m²/ h) calculating can calculate by the method for Hayduk and Laudie:

$B_W=\frac{13.26\&times;{10}^{-5}}{{\mathrm{\&eta;}}_W^{1.14}{v}_B^{0.589}}$

In formula:

η_w: the viscosity of water, cP；

V_B: the molal volume of compound, cm³/mol。

Compound volatilization process between soil with air is to be connected by by boundary layer of air and edaphic diffusion Composition, the latter is composed in parallel by the diffusion of water and air in soil again.

Air phase coefficient of mass transfer K in soil_3A(m/h):

k_3A=B_EA/yso

Aqueous phase coefficient of mass transfer K in soil_3w(m/h):

k_3W=B_EW/yso

In formula:

Yso: soil horizon diffusional pathlength (m)

B_EA: the effective diffusion cofficient (m of soil air²/h)

B_EW: the effective diffusion cofficient (m of water in soil²/h)

B_EAAnd B_EWValue can have a Millington-Quirk Equation for Calculating:

$B_{EA}=B_A{v}_A^{10/3}{(v_A+v_W)}^2$

$B_{EW}=B_W{v}_W^{10/3}/{(v_A+v_W)}^2$

In formula:

V_A: the volume fraction of soil air；

V_W: the volume fraction of water in soil；

B_A: air molecule diffusion coefficient (m²/h)；

B_W: water diffusion coefficient (m²/h)；See top to calculate.

B_ACan calculate with following formula:

$B_A=\frac{{10}^{-3}{T}^{1.75}\sqrt{M_r}}{P{(V_A^{1/3},V_B^{1/3})}^2}$

$M_r=\frac{M_A+M_B}{M_A{M}_B}$

In formula:

P: atmospheric pressure, atm；

V_A: the molal volume of air, 20.1cm³/mol；

M_A: the molecular weight of air, g/mol；

M_B: the molecular weight of compound, g/mol.

(4) health risk assessment

1. qualification is endangered

Change generally according to IARC (IARC) and US EPA integrated risk information system (IRIS) in the world Carcinogenecity classification carries out compound threshold, the identification of non-threshold and assessment.The bio-toxicity of TBBPA is carried out by many scientific research personnel Cross systematic research.WHO etc. (1995) check the toxicity of TBBPA with rat, add 50mg kg respectively in rat chow^-1·d^-1、100mg·kg^-1·d^-1TBBPA, it was found that feed after 28d and 90d, rat, without poisoning symptom, is given in 90d The things of mice adds 7100mg kg^-1·d^-1TBBPA, mice there will be the symptom such as malnutrition and anemia.Koizumi Carry out 18d per os exposure experiment Deng (2001) with the young Mus of just birth 4～21d, find that TBBPA has severe renal toxicity.Tada Start after wean to carry out per os exposure experiment in 27d from trimester of pregnancy to pregnant mouse Deng (2006), by pregnancy period mice and The histopathology of its offspring is tested, and display TBBPA exposure can cause the Focal necrosis of hepatic parenchymal cells.The most not Having the clear and definite TBBPA of experimentation is carcinogen, and internationally recognized TBBPA is a kind of environment incretion interferent, has thyroxine Interference, immunotoxicity and cytotoxicity.So this Preliminary Study assert that TBBPA is non-threshold compound.

2. dose-effect relationship

Dose-effect relationship is to the relation between injurious factor exposure level and exposed population group's health health effect incidence rate Carry out the process of quantitative estimation, be also the quantitative basis of health risk assessment.In environment and health research field, pay close attention to pollutant Healthy health effect analysis, mainly includes concern pollutant, to human health damage character, use sucklings to move in the world Thing exposes experiment method, utilizes animal toxicology data, by deriving or epidemiologic data, threshold value safe to the human body between planting Estimate.When carrying out health risk assessment, the change recommended in general US EPA integrated risk information system of employing (IRIS) The RfD (reference dose) of compound, but in this data base, the RfD value of TBBPA is not inquired by inquiry.This research is intended by front The experimental result of people, enters the RfD value of TBBPA in conjunction with derivation between Benchmark dose analysis, non-threshold compound R fD derivation method, kind Row is derived.Holland scientist Leo etc. (2008) carry out endocrine disruption experiment, respectively to 8 groups of reconditionings to Wistar rat Carrying out the dose-effect relationship research of 28d, research finds that in 2 kinds of effects, testicular toxicity BMDL value is relatively low, for 0.5mg kg^-1·d^-1, therefore this research uses testicular toxicity effect B MDL value in its result of study to carry out RfD derivation.

The non-threshold compound R fD derivation method recommended according to US EPA, computing formula is as follows:

$RfD=\frac{BMDL}{UF\&times;MF}---\left(1\right)$

(1), in formula: UF (uncertain factor) value is 300, MF (modifying factor) value is 1.

Estimating TBBPA secure threshold in Wistar rat, RfD value is 1.6 × 10^-3mg·kg^-1·d^-1。 According to derivation between planting, the dose,equivalent of crowd is the 1/6 of rat, and the RfD value tentatively deriving crowd TBBPA is 2.6 × 10^{- 4}mg·kg^-1·d^-1。

3. Exposure Assessment

" Exposure Factors Handbook " and " the Dermal Exposure recommended in conjunction with US EPA Assessment " and early stage investigation, determine the exposure parameter of study area crowd and combine previous research, to people in study area Group carries out the TBBPA Exposure Assessment of many route of exposure.Study area crowd's exposure parameter is shown in Table 3.

Table 3 study area crowd's exposure parameter

Surrounding medium TBBPA each to study area carries out Exposure Assessment, owing to deposit phase contacts less with crowd, and non-principal Expose medium, therefore this research does not considers to relate to.The per os that relates to air, water body, soil mutually, skin, breath exposure approach enter Row Exposure Assessment, the results are shown in Table 4.In 3 kinds of route of exposure, study area crowd's per os reconditioning is the highest, reaches 103.51mg kg^-1·d^-1.Secondly for skin exposure, breath exposure, respectively 7.42 × 10^-2mg·kg^-1·d^-1、1.60×10^-4mg·kg^-1· d^-1.The main exposure medium of study area crowd TBBPA is drinking water, and its per os exposes contribution rate can reach 99%.

4. risk characterization

The health risk of 3 kinds of route of exposure TBBPA of study area crowd is estimated, finds the non-cause of breath exposure approach Minimum 6.1 × the 10-of cancer value-at-risk⁷, in the acceptable health risk value 1 × 10 that RS (Royal Society) is recommended^-6And U.S. environment The health risk level 1 × 10 that protection office is recommended^-4Within the scope of.Skin exposes and per os exposes all beyond acceptable health risk Value, respectively may be about 2.85 × 10-⁴、0.41.Wherein, it is the highest that drinking water per os exposes non-carcinogenic value-at-risk, is 0.40, super Cross acceptable health risk value.

Table 4 study area adult's health risk value

(3) modelling verification

1. modelling verification

To environment mutually in the migration of TBBPA and return to become to carrying out lab simulation.At 1m³Air bin, natural ventilation port is set, Simulated atmosphere phase, water body phase, soil phase, deposit equal composition your pupil's state system respectively.The wherein preparation of deposit phase: take suitable Amount deposit, carries out Air Exposure, and rear evenly laid out in the top layer of air bin, thickness is about 1cm, adds homemade simulation lake water As overlying water, the total phosphorus (TP) of primary simulation lake water, total nitrogen (TN), COD (COD) concentration are respectively 0.5mg L^-1、15mg·L^-1、50mg·L^-1.Water-volume of sediment is than for 3:1.Aqueous phase: see the preparation of deposit phase.The preparation of soil phase: Fresh for the soil of collection sample carries out high temperature sterilize, and lyophilization is pulverized, and product of being marked by TBBPA join in dichloromethane solution, join It is set to TBBPA standard solution, adds to sample, put into after being sufficiently mixed stirring in ventilating kitchen and treat that dichloromethane volatilizees, examine afterwards Survey loss concentration and moisture content, keep soil moisture content 18%～25% according to old red magnitude (2007).Soil after contaminating Tiling is placed in air bin, and soil thickness is about 5cm.Big gas phase: free gas in air bin.According to study area system in 2013 (land surface is 3.6 × 10 to control yearbook⁵hm², water surface area is 7.33 × 10⁴hm²), soil phase and water in simulated air storehouse-heavy Long-pending thing phase surface area proportion is 5:1.In storehouse, analog temperature controls between 10～15 DEG C.According to TBBPA in the environment partly The phase of declining arranges open-assembly time (60d).

2. the detection of sample

Collection, technical specification (GB/T 160.10-2004, GB/T5750.2-of preserving, analyzing according to different samples 2006, HJ/T166-2004), gather, detect, the sample size in the district that analyzes and researches.

3. modelling verification

Root set according to the literature soil mutually in TBBPA environmental exposure concentration, be respectively provided with 2 kinds of batches: low concentration (0 μ g/ Kg, 5 μ g/kg, 25 μ g/kg), high concentration (200 μ g/kg, 300 μ g/kg^[).Experimental simulation finds, TBBPA actual measurement in big gas phase Between value and the analogue value, error is 4.38%～18.23%, wherein low concentration (4.38%～14.68%), high concentration (6.82% ～18.23%).Water body mutually between TBBPA measured value and the analogue value error be 5.71%～17.96%, wherein low concentration (5.71%～12.58%), high concentration (6.03%～17.96%).The measured value of deposit middle TBBPA mutually and analogue value error It is 5.31%～18.73%, wherein low concentration (5.31%～18.17%), high concentration (6.82%～18.73%).Soil phase The measured value of middle TBBPA and the error of the analogue value are 4.69%～18.15%, wherein low concentration (4.69%～16.84%), high Concentration (6.83%～18.15%).

By the comparison to different exposure concentrations TBBPA measured values with the analogue value, find measured value and the simulation of low concentration Between value, error is less, and the error of high concentration is relatively large.It should be noted that TBBPA loss concentration is about (0 after Ran Du ±0.5)μg/kg、(5±3.38)μg/kg、(25±5.79)μg/kg、(200±10.21)μg/kg、(300±17.48)μg/ Kg, the moisture content after loss is 20% ± 7%.

Surrounding medium TBBPA each to study area returns the concentration that becomes to carry out health risk assessment.3 kinds of route of exposure are breathed sudden and violent The non-carcinogenic value-at-risk minimum 6.1 × 10 of dew approach^-7, in the acceptable health risk value 1 × 10 that RS (Royal Society) is recommended^-6And the health risk level 1 × 10 that Environmental Protection Agency USA is recommended^-4Within the scope of.Skin exposes and per os exposes all beyond can Accept health risk value, respectively may be about 2.85 × 10^-4、0.41。

By to TBBPA concentration measured value and the comparison of predictive value, find in big gas phase TBBPA measured value and the analogue value it Between error be 4.38%～18.23%, water body mutually between TBBPA measured value and the analogue value range of error be 5.71%～ 17.96%, deposit mutually in measured value and the analogue value range of error of TBBPA be 5.31%～18.73%, soil mutually in The measured value of TBBPA and the range of error of the analogue value are 4.69%～18.15%.Research finds, at each environment middle low concentration mutually Error relatively small, the error of high concentration is relatively large.

Although technical scheme is described in detail by above-described embodiment, but the technical side of the present invention Case is not limited to above example, in the case of without departing from the thought of the present invention and objective, to technical scheme institute Any change done falls within claims of the present invention limited range.

Claims (7)

1. an a kind of health risk assessment method based on fugacity model, it is characterised in that said method comprising the steps of:

(1) Level III fugacity model is used, it is considered to choose air, water body, soil, four principal phases of deposit；Whole in supposition In the case of ecosystem balance, the environmental quality in binding district, set up the environment multimedia fugacity model of chemical pollutant；

(2) process of fugacity model and parameter: described process includes chemical pollutant input in surrounding medium and output, defeated Entering process is: compound is directly entered principal phase and the input of gas water advection；Output procedure is: degraded between each medium and air/ The advection output of water；And return to become to being predicted to the migration of the pollution compound of study area by Level III fugacity model；

(3) show that chemical pollutant after concentration, utilizes four step rule to study area population health in each surrounding medium in step (2) Risk is estimated, and described four step rule includes: harm qualification, dose-response relationship, Exposure Assessment, risk characterization.

A kind of health risk assessment method based on fugacity model the most according to claim 1, it is characterised in that: described greatly Gas phase includes gas phase and the sub-phase of aerosol.

A kind of health risk assessment method based on fugacity model the most according to claim 1, it is characterised in that: described water Body includes water phase, suspended particulate substance phase and roe phase mutually.

A kind of health risk assessment method based on fugacity model the most according to claim 1, it is characterised in that: described soil Include gas phase, solid son phase and water phase mutually.

A kind of health risk assessment method based on fugacity model the most according to claim 1, it is characterised in that: described heavy Long-pending thing includes solid son phase and water phase mutually.

A kind of health risk assessment method based on fugacity model the most according to claim 1, it is characterised in that described step Suddenly in (2), process and the parameter step of fugacity model also include: the sensitivity analysis of fugacity model parameter.

A kind of health risk assessment method based on fugacity model the most according to claim 1, it is characterised in that: described step Suddenly (3) also include the sensitivity analysis of health risk assessment.