CN113657748A - Risk-based high-risk organic pollutant screening method for site key industry - Google Patents
Risk-based high-risk organic pollutant screening method for site key industry Download PDFInfo
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Abstract
A high-risk organic pollutant screening method for site key industry based on risks comprises the following steps: 1) screening out a high-risk organic pollutant candidate list in the field soil environment according to the contaminated field soil environment control list and the environmental pollution survey data; 2) carrying out on-site investigation and sampling on the soil environment in the area, and screening out organic pollutants existing in the field; 3) based on the whole process control concept of clean production, the organic matters used in the on-site raw and auxiliary materials of enterprises, intermediate products and by-products possibly generated in the process flow, organic pollutants in the products and the organic matters discharged under abnormal working conditions are investigated on site; 4) grading and assigning the indexes of the pollutants screened in the step 1-3 by adopting a comprehensive grading method; 5) calculating the weight of each index according to the indexes in the step 4; 6) calculating the health risk of the pollutants obtained by screening in the step 5; columns that exceed the threshold are listed as high risk organic contaminants.
Description
Technical Field
The invention belongs to the field of soil pollution treatment, and particularly relates to a method for screening high-risk organic pollutants in site key industries based on risks.
Background
China, like many developed countries, is experiencing serious environmental pollution problems, especially soil pollution, during the development of the economy. The soil environment quality is directly related to the soil environment quality and is directly related to the farmland quality, the agricultural product safety and the human living environment health. The soil pollution has the characteristics of concealment, latency, long-term property and the like. With the increasingly prominent soil environment problem, the supervision requirement on the soil environment pollution condition is gradually increased.
China starts late in the aspect of screening environment-preferred pollutants, in the last 90 th century, a semi-quantitative method is adopted to evaluate the toxicity of pollutants, the product yield, the detection condition and the like, and a Chinese environment-preferred pollutant blacklist is provided by combining expert experience, wherein the blacklist comprises 6 pollutants, and the list recommended to be implemented recently comprises 48 pollutants. And then, a screening scheme for optimizing pollutants is also provided for provinces and parts of watersheds, a preferential pollutant blacklist with local and watershed characteristics is established, and a first batch of environment preferential pollutant blacklists (43 types) are screened out.
With the rapid development of economy and the acceleration of industrialization and urbanization processes, the problem of soil environmental pollution of construction land is increasingly prominent, and the current execution standard relates to the limited types of pollutants, especially the few types of organic pollutants, and can not meet the requirement of current site soil environmental management. Therefore, the requirement of national soil environment management is combined, a high-risk organic pollutant screening technology in the field soil in key industries needs to be constructed urgently, a high-risk organic pollutant list is put forward, the industrial characteristics are clarified, risks are prevented conveniently, corresponding analysis methods and management and control measures are made, and control is achieved from the source.
At present, domestic and foreign researches mainly focus on the prior pollutant screening in the fields of atmosphere and water environment, but soil cannot simply apply the prior pollutant screening of atmosphere and water environment due to the special properties of soil.
The above prior art has the following disadvantages:
(1) at present, domestic and foreign researches mainly focus on the prior pollutant screening in the fields of atmosphere and water environment, but soil cannot simply apply the prior pollutant screening of atmosphere and water environment due to the special properties of soil.
(2) Most of current domestic and overseas researches screen pollutants which may be harmful to ecological environment and human health by evaluating potential hazards of chemicals, most screening methods are based on a dangerous system, and the conversion to a risk-based system is a hotspot and development trend of the current research.
Disclosure of Invention
The invention aims to provide a risk-based method for screening high-risk organic pollutants in site focus industries, which can effectively screen out the high-risk organic pollutants needing to be controlled in the site focus industries and provide a basis for site management.
In order to achieve the purpose, the method for screening the high-risk organic pollutants in the site key industry based on the risks comprises the following steps:
1) screening out a high-risk organic pollutant candidate list in the field soil environment according to the field soil environment control directory of the polluted field and the environmental pollution investigation data;
2) carrying out on-site investigation and sampling on the soil environment in the area, and screening out organic pollutants existing in the field;
3) based on the whole process control concept of clean production, the organic matters used in the on-site raw and auxiliary materials of enterprises, intermediate products and by-products possibly generated in the process flow, organic pollutants in the products and the organic matters discharged under abnormal working conditions are investigated on site;
4) grading and assigning the hazard index, the exposure index and the persistent accumulation index of the pollutants screened in the steps 1-3 by adopting a comprehensive grading method;
5) calculating the weights of each index of the harmfulness index, the exposition index and the persistent accumulation by adopting an analytic hierarchy process according to the index in the step 4, and calculating the pollutant with higher comprehensive score as a secondary list of the high-risk organic pollutant according to the assignment condition of each index;
6) calculating the health risk of the pollutants obtained by screening in the step 5 under the condition that the exposure way of the field soil environment to the crowd is determined; columns that exceed the threshold are listed as high risk organic contaminants.
The high-risk organic pollutant screening method based on the risk in the site key industry is characterized in that step 2 is to use a gas chromatography-quadrupole time-of-flight mass spectrometer and a liquid chromatography-quadrupole time-of-flight mass spectrometer (GC-QTOF-MS and LC-QTOF-MS) to carry out non-target screening on a sample.
The risk-based site key industry high-risk organic pollutant screening method comprises the following steps of (1) screening high-risk organic pollutants, wherein the hazard indexes in the step 4 comprise carcinogenicity, mutagenicity, reproductive toxicity and biohazard of the pollutants;
the exposure index refers to the detection rate of pollutants in a field soil environment sample, the control condition in the soil environment standard/guide rule, and physical indexes such as vapor pressure, soil-water distribution coefficient and the like;
persistent accumulation indicators include half-life and bioaccumulation.
The method for screening the high-risk organic pollutants in the risk-based site key industry comprises the following three ways of exposing people to human groups in step 6, namely, passing through the alimentary canal, breathing and contacting the skin.
The risk-based site key industry high-risk organic pollutant screening method comprises the step 6 of calculating the health risk according to the pollution site risk assessment technical guide (HJ 25.3-2014).
The invention has the beneficial effects that:
1. compared with the traditional pollutant screening method based on hazard assessment, the method introduces the exposure risk of people, constructs a high-risk pollutant screening method based on risk analysis, and has more scientific and reasonable screening result.
2. The high-risk pollutant list of the site key industry determined by the method has important significance for finding out the pollution background of the site and determining the soil supervision key.
3. The method combines non-targeted screening monitoring data of the site of the polluted site and investigation data of the whole process of the clean production, constructs a pollutant candidate list from the source to the tail end, and is more comprehensive.
4. Compared with other technologies, the method is based on the cleaning production whole process control concept when screening the candidate pollutants, carries out detailed investigation on the original auxiliary materials, the production process, the pollution discharge link and the like, and puts the chemical substances, intermediate products and the like which are possibly used into the candidate pollutant list.
Drawings
FIG. 1 is a technical route diagram for screening high-risk organic pollutants in the field key industry.
Detailed Description
The invention discloses a risk-based method for screening high-risk organic pollutants in site key industry, which comprises the following steps:
1) and screening out a high-risk organic pollutant candidate list in the field soil environment according to the field soil environment control directory of the polluted field and the environmental pollution investigation data.
2) And (3) carrying out on-site investigation and sampling on the soil environment in the region, and carrying out non-target screening on the sample by using a gas chromatography-quadrupole time-of-flight mass spectrometer and a liquid chromatography-quadrupole time-of-flight mass spectrometer to screen out organic pollutants existing in the field.
3) Based on the whole process control concept of clean production, the organic matters used in the raw and auxiliary materials of the enterprise on site, intermediate products and by-products possibly generated in the process flow, organic pollutants in the products, organic matters discharged under abnormal working conditions and the like are investigated on site.
4) And (3) grading and assigning the hazard index, the exposure index and the persistent accumulation index of the pollutants screened in the steps 1-3 by adopting a comprehensive grading method.
Wherein:
the harmfulness index mainly comprises carcinogenicity, mutagenicity, reproductive toxicity and biology of pollutants. Various expression forms of the acute and chronic effects of pollutants on human health and toxic effects on soil organisms are comprehensively considered, carcinogenicity, mutagenicity, reproductive toxicity and the like can be temporarily used as screening indexes of the health hazards of people, and the toxicity of the soil pollutants on earthworms is used as a screening index of the biological hazards.
The exposure index refers to the detection rate of pollutants in a field soil environment sample; and the condition of controlling pollutants in soil environment standards/guidelines at home and abroad.
Persistent accumulation indicators include half-life and bioaccumulation.
5) And (4) calculating the weight of each index by adopting an analytic hierarchy process according to the indexes in the step (4), and calculating the pollutant with higher comprehensive score as a secondary list of the high-risk organic pollutant according to the assignment condition of each index.
6) And (5) calculating the health risk of the pollutants obtained by screening in the step (5) under the condition that the exposure way of the field soil environment to the population is determined. Columns that exceed the threshold are listed as high risk organic contaminants.
Considering that the main exposure routes of soil pollutants to the human body are three routes of digestive tract, respiration and skin contact. And (4) calculating the health risk, wherein the calculation method refers to the technical guide for evaluating the risk of the pollution site (HJ 25.3-2014).
The invention is further described below with reference to the following figures and examples.
As shown in figure 1, the invention relates to a risk-based method for screening high-risk organic pollutants in field soil key industry.
Examples
Screening of candidate list of high-risk organic pollutants in site soil of certain coking enterprise in Shanxi province
1. Overview of the study region
A certain coking enterprise is located in Shanxi province and mainly engages in coke production and coal processing, the enterprise carries out zero discharge of wastewater, the outlet wastewater of a coking enterprise substation is used for refining, flushing and dedusting a workshop terrace and the like and coal supplementing water, and waste residues are completely recycled for coking production or used as hazardous substances for safety disposal and are not discharged to the environment. The pollutant emission is mainly atmospheric emission.
2. Sampling distribution point
According to the technical specification of soil environment monitoring, 7 soil samples are distributed and collected by adopting a random distribution method. Collecting soil on 0-20cm surface layer with soil sampler, collecting 1-2kg each, and filling soil into polyethylene plastic bag.
3. Enterprise investigation
And investigating and collecting the pollution source data of the basic condition, the operation time, the yield of raw and auxiliary material products, the production process, pollution treatment facilities, the emission and the like of the enterprise. The pollution source investigation mode mainly takes data collection and forms as main points, and mainly considers the migration and diffusion ways of characteristic pollutants in an air environment medium.
4. First stage candidate contaminant screening
According to ' soil pollution risk management and control standard (trial) for soil environment quality construction land ' (GB 36600) 2018 ', ' soil pollution risk assessment technology guide for construction land ' (HJ 25.3-2019) and ' book of preferentially controlled chemicals ' (first batch) ' book of preferentially controlled chemicals (second batch) ', 111 organic pollutants are involved.
And (3) analyzing and detecting soil samples collected around the enterprise by using a gas chromatography-quadrupole time-of-flight mass spectrometer and a liquid chromatography-quadrupole time-of-flight mass spectrometer, and detecting 16 pollutants.
The raw and auxiliary materials and the production process of the enterprise are investigated, and 57 organic pollutants are involved. Combining the control list, sample detection and investigation results, and finally screening 16 high-risk candidate pollutants meeting the real situation of the site environment: 1, 4-dichlorobenzene, 2-methylphenol, nitrobenzene, naphthalene, 4-chloroaniline, dimethyl phthalate, acenaphthylene, dibenzofuran, phthalic acidDiethyl ester, phenanthrene, di-n-butyl phthalate, fluoranthene, pyrene, benzo [ a ]]Anthracene,
Di (2-diethylhexyl) phthalate.
5. Second stage high risk organic pollutant screening
And establishing a comprehensive grading method to grade and assign the harmfulness, the exposition, the persistent accumulation, the health risk, the public attention and the like of the pollutants, and selecting the pollutants with higher grades.
5.1 hazard of contaminants
Various expression forms of the acute and chronic effects of pollutants on human health and toxic effects on soil organisms are comprehensively considered, carcinogenicity, mutagenicity, reproductive toxicity and the like can be temporarily used as screening indexes of the health hazards of people, and the toxicity of the soil pollutants on earthworms is used as a screening index of the biological hazards. The Classification result of carcinogenicity of the substance adopts the Classification result of International agency for cancer (IARC), and the Classification result of harm of other people adopts the Classification result of Global unified Classification and labeling System of Chemicals (GHS for short). The biohazard classification adopts a part 15 of chemical pesticide environmental safety evaluation test criteria: grading results of toxicity in earthworm acute toxicity test (GB/T31270.15-2014).
5.2 Exposure to contaminants
And (4) grading and assigning the pollutant detection rate index and the domestic and foreign control standard quantity by referring to the foreign research condition.
5.3 persistent accumulation of contaminants
The environmental behavior is persistent and bioaccumulative. The longer the pollutant exists in the environment, the greater the accumulation degree, and the more serious the harm to human health and environment, therefore, the persistence and biological accumulation of the pollutant are used as the exposure screening index.
And 5.4, respectively searching for the parameter values of the pollutants according to a screening system established by the comprehensive grading method. And assigning values to each index of the pollutants according to the grading assignment and scoring principles of the tables 1 and 2.
TABLE 1 pollutant Multi-index parameter grading assignment rule
TABLE 2 Multi-index screening index scoring principle
5.5, calculating the weight of each index of the pollutants, calculating the weight of each index parameter of the pollutants by adopting an analytic hierarchy process, and grading each index.
5.5.1, establishing a hierarchical model: establishing a hierarchical structure for screening high-risk pollutants in field soil key industry, determining factors of each hierarchy, and setting a level 3 according to requirements.
5.5.2, constructing a judgment matrix: the hierarchical structure reflects the relationship between the factors, but the proportion of each criterion in the criterion layer in the target measurement is not necessarily the same in the mind of different decision makers. It is appropriate to express the difference between them on a scale of 1-9. And in comparison, it is necessary to make n (n-1)/2 pairwise judgments, so that more information can be provided, and a more reasonable sequence can be obtained through repeated comparison in various aspects.
5.5.3, level list ordering and consistency checking: the hierarchical single ordering refers to calculating a weight of an importance order of the factors connected with the hierarchical single ordering in the previous hierarchical level for a certain factor in the previous hierarchical level according to the obtained judgment matrix, and the process is called hierarchical single ordering. The main purpose of this process is to calculate the eigenvalue and eigenvector of each decision matrix, and to calculate these two values, the formula AW ═ λ is usedmaxW is added. Where A is a decision matrix, λmaxIn order to judge the maximum eigenvalue of the matrix, W is the corresponding eigenvector, and each element Wi constituting the eigenvector is the weight value of the required hierarchical single order. Solving the eigenvector W and the maximum eigenvalue lambda of the judgment matrixmaxThe calculation may be performed using a sum method, a normalized sum method, and a root method. Here, the calculation is performed by a normalization summation method, and the calculation steps are as follows:
(1) firstly, each column of the judgment matrix is normalized, namely:
after normalization, the sum of each column element is 1.
In the formula, aijIs a decision matrix element, bijIs a normalized decision matrix.
(2) Adding the normalized judgment matrixes of all the columns according to rows, namely:
(3) for vector V ═ V1,V2,…,Vn]TNormalization was performed:
the vector w thus obtained1,w2,…,wn]TI.e. the weight vector.
(4) Finally, calculating the maximum characteristic root lambda of the judgment matrixmax：
In the above formula (AW)iDenotes the ith element of AW, n being the order. The possibility of comparing the factors by experts isThe phenomenon of self-contradiction occurs, so in order to avoid the phenomenon when carrying out the hierarchical single ordering, the consistency must be checked. The test procedure was as follows:
1) calculating a consistency index CI:
the consistency index CI is a scale for measuring the deviation degree of the judgment matrix A from the matrix originally formed in the main characteristic vector W.
2) Defining a random consistency index mean value RI:
for n-3-10 orders, their RI's can be obtained through calculation, and the RI's are naturally 0 in consideration of the fact that the 1 and 2 orders of the decision matrix always have complete consistency. Thus, the RI of a decision matrix of order 1-10 is shown in the following table:
RI value with matrix order of 1-10
| Order of the scale | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| RI | 0.00 | 0.00 | 0.52 | 0.89 | 1.12 | 1.26 | 1.36 | 1.41 | 1.46 | 1.49 |
In the table, RI is 0 when n is 1 and 2, because the positive reciprocal matrix of order 1 and 2 always is uniform.
3) Calculating the consistency ratio CR:
for the judgment matrix A with n >3, comparing the calculated CI with the RI of the same order (indicating that n is the same), wherein the ratio of the two is CR, and when the ratio is less than or equal to 0.1 (namely CR <0.10), the inconsistency degree of A is considered to be in an allowable range, the judgment matrix A passes the inspection; when the ratio is greater than 0.1, the judgment matrix does not pass the consistency check, and appropriate correction needs to be carried out on the judgment matrix and the check is continued until the judgment matrix passes the consistency check.
5.5.4, construction of a discrimination matrix and solving of weight: according to an index system, through an expert consulting method questionnaire survey, multiple experts in the field are selected, the importance degree of the index is respectively scored, then the scoring result is internally discussed and summarized, and pairwise judgment matrixes are obtained as follows:
| hazard screening index | Index of persistent accumulation | Exposure screening index | |
| Hazard screening index | 1 | 2 | 2 |
| Index of persistent accumulation | 1/2 | 1 | 2 |
| Exposure screening index | 1/2 | 1/2 | 1 |
Calculating and judging the maximum characteristic root lambda of the matrix S by using MATLAB softwaremax3.0536. For consistency check of the judgment matrix, consistency indexes need to be calculated:
the average random consistency index RI is 0.52. Random consistency ratio:
therefore, the results of the hierarchical analysis are considered to have satisfactory consistency, i.e. the distribution of the weight coefficients is very reasonable. And calculating the weight of the index by using matlab software.
| Index layer | Weight of |
| Hazard screening index | 0.4934 |
| Index of persistent accumulation | 0.3108 |
| Exposure screening index | 0.1958 |
The weight of the index is obtained by a hierarchical analysis method. Constructing a decision matrix S ═ u (u)ij)p×pNamely:
| index of health hazard | Index of environmental hazard | |
| Index of health hazard | 1 | 3 |
| Index of environmental hazard | 1/3 | 1 |
Calculating and judging the maximum characteristic root lambda of the matrix S by using MATLAB softwaremax2. And calculating the weight of the index by using matlab software.
| Index layer | Weight of |
| Index of health hazard | 0.75 |
| Index of environmental hazard | 0.25 |
The weight of the index is obtained by a hierarchical analysis method. Constructing a decision matrix S ═ u (u)ij)p×pNamely:
| durability | Biological accumulation property | |
| Durability | 1 | 1/4 |
| Biological accumulation property | 4 | 1 |
Calculating and judging the maximum characteristic root lambda of the matrix S by using MATLAB softwaremax2. And calculating the weight of the index by using matlab software.
| Index layer | Weight of |
| Durability | 0.2 |
| Biological accumulation property | 0.8 |
The weight of the index is obtained by a hierarchical analysis method. Constructing a decision matrix S ═ u (u)ij)p×pNamely:
| detecting the condition | Physical index | |
| Detecting the condition | 1 | 2 |
| Physical index | 1/2 | 1 |
Calculating and judging the maximum characteristic root lambda of the matrix S by using MATLAB softwaremax2. And calculating the weight of the index by using matlab software.
| Index layer | Weight of |
| Detecting the condition | 0.6667 |
| Physical index | 0.3333 |
Weighting of indicators, using hierarchical analysisThe method finds the index weight. Constructing a decision matrix S ═ u (u)ij)p×pNamely:
calculating and judging the maximum characteristic root lambda of the matrix S by using MATLAB softwaremax3.0142. For consistency check of the judgment matrix, consistency indexes need to be calculated:
the average random consistency index RI is 0.52. Random consistency ratio:
therefore, the results of the hierarchical analysis are considered to have satisfactory consistency, i.e. the distribution of the weight coefficients is very reasonable. And calculating the weight of the index by using matlab software.
| Index layer | Weight of |
| Carcinogenicity | 0.7396 |
| Mutagenicity | 0.1666 |
| Reproductive toxicity | 0.0938 |
The weight of the index is obtained by a hierarchical analysis method. Constructing a decision matrix S ═ u (u)ij)p×pNamely:
| detection rate | Standard quantity of | |
| Detection rate | 1 | 6 |
| Standard quantity of | 1/6 | 1 |
Calculating and judging the maximum characteristic root lambda of the matrix S by using MATLAB softwaremax2. And calculating the weight of the index by using matlab software.
| Index layer | Weight of |
| Detection rate | 0.8571 |
| Standard quantity of | 0.1429 |
The weight of the index is obtained by a hierarchical analysis method. Constructing a decision matrix S ═ u (u)ij)p×pNamely:
| vapour pressure | Boiling point | |
| Vapour pressure | 1 | 4 |
| Boiling point | 1/4 | 1 |
Calculating and judging the maximum characteristic root lambda of the matrix S by using MATLAB softwaremax2. And calculating the weight of the index by using matlab software.
| Index layer | Weight of |
| Vapour pressure | 0.8 |
| Water distribution coefficient of soil | 0.2 |
TABLE 3 comprehensive weight of each index
6. Contaminant ranking
And (4) calculating the total score of the candidate pollutants according to the assigning method, the principle and the weight of 4 (first stage candidate pollutant screening) -5 (second stage high risk organic pollutant screening), as shown in table 4.
TABLE 4 screening of the scores and Total scores of the various indexes of pollutants
TABLE 4 screening of the pollutant index scores and Total scores
7. Screening of high-risk organic pollutants in third-stage site key industry
According to the screening result of the high-risk pollutants in the second stage, the top 10 types with higher scores are selectedAnd (4) pollutant, establishing a risk-based high-risk pollutant screening system, and selecting the pollutant with high risk level for priority control. The first 10 higher scoring contaminants were: benzo [ a ]]Anthracene,
Di (2-diethyl hexyl) phthalate, phenanthrene, fluoranthene, naphthalene, nitrobenzene, 1, 4-dichlorobenzene, pyrene and 4-chloroaniline.
Exposure assessment for soil environment, three pathways via the alimentary tract, respiration and skin contact are considered. And (4) calculating the health risk, wherein the calculation method refers to the technical guide for evaluating the risk of the pollution site (HJ 25.3-2014). For non-carcinogenic health risks>1 or carcinogenic health risks>10-4List of high risk contaminants. The specific calculation method is as follows:
(1) oral soil uptake route
In an industrial manner, the population may be exposed to contaminated soil by oral ingestion. For the carcinogenic effect of a single pollutant, considering the life-long hazards of the population exposed in adulthood, the soil exposure corresponding to the oral soil intake route is calculated by formula 7:
in formula 7, OISERcaOral intake of soil exposure (carcinogenic effect), kg soil kg-1Body weight d-1；
OSIRa-daily soil intake by adults in mg. d-1;
EDa-adult exposure period, a; (ii) a
EFa-adult frequency of exposure, d.a-1; (ii) a
BWa-adult body weight, kg;
ABso-oral intake absorption efficiency factor, dimensionless;
ATca-mean time to carcinogenic effect, d;
for the non-carcinogenic effect of a single pollutant, considering the exposure hazard of the population in adulthood, the soil exposure corresponding to the oral soil intake route is calculated by the formula 8:
in formula 8, OISERnc-Exposure to soil by oral ingestion (non-carcinogenic effect), kg soil/kg-1Body weight d-1；
ATnc-mean time to non-carcinogenic effect, d.
(2) Skin contact with soil
In an industrial manner, people may be exposed to contaminated soil due to direct skin contact. The life-long hazard of human exposure during adulthood is considered for the carcinogenic effects of a single pollutant. The soil exposure of the skin-to-soil route was calculated using equation 9:
in formula 9, the soil exposure (carcinogenic effect) of DCSERca-skin contact route, kg soil. kg-1Body weight d-1；
SAEa-adult exposed skin surface area, cm2；
SSARa-coefficient of soil adhesion to adult skin surface, mg cm-2；
ABSd-skin contact absorption efficiency factor, dimensionless;
ev-daily skin contact event frequency, times d-1.
For the non-carcinogenic effect of a single pollutant, considering the exposure hazard of the human population in adulthood, the soil exposure corresponding to the skin-to-soil contact path is calculated by the formula 10:
in formula 10, DCSERnc-soil exposure to skin contact (non-carcinogenic effect), kg soil kg-1Body weight d-1。
(3) The way of sucking soil particles
In an industrial manner, people may be exposed to contaminated soil by inhaling airborne particulate matter from the soil.
For the carcinogenic effect of a single pollutant, considering the lifetime hazard of the human population during adulthood exposure, the soil exposure corresponding to the approach of inhaling soil particulate matter is calculated by formula 11:
in formula 11, PISERca-the amount of soil exposure (carcinogenic effect) to soil particulate matter imbibed in, kg soil kg-1 body weight d-1;
PM 10-the content of inhalable floating particles in the air, mg.m < -3 >;
DAIRa-daily air respiration in adults, m 3. d-1;
PIAF-the retention proportion of soil particles sucked in the body is dimensionless;
fspi-proportion of particulate matter from soil in indoor air, dimensionless;
fspo-the proportion of particulate matter from soil in the outdoor air, is dimensionless;
EFIa-indoor exposure frequency for adults, d.a-1;
EFOa-frequency of outdoor exposure to adults, d.a-1;
for the non-carcinogenic effect of a single pollutant, considering the exposure hazard of the crowd in adulthood, the soil exposure corresponding to the path of inhaling the soil particulate matter is calculated by the formula 12:
in formula 12, PISERnc-the soil exposure (non-carcinogenic effect) to soil particulate matter uptake, kg soil kg-1 body weight d-1.
(4) For a single pollutant, the recommended models for calculating the exposure pathway carcinogenic risk of orally ingested soil, skin-exposed soil, and inhaled soil particulate matter are shown in equations 13-14, respectively. And (3) calculating a recommended model of the carcinogenic risk of a single pollutant in the soil through the 3 exposure ways, and obtaining a formula 16.
The risk of carcinogenesis by oral ingestion of soil was calculated using equation 13:
CRois＝OISERca×Csur×SFo (13)
in formula 13, CRois-the carcinogenic risk of the oral uptake soil route, dimensionless;
csur-concentration of contaminant in surface soil, mg. kg-1(ii) a The parameter values must be obtained from a plot survey.
SFo-oral ingestion of carcinogenic slope factor, (mg contaminant kg)-1Body weight d-1)-1。
The risk of carcinogenesis for the skin-to-soil pathway was calculated using equation 14:
CRdcs＝DCSERca×Csur×SFd C2 (14)
in formula 14, CRdcs — the carcinogenic risk of the skin-contact soil pathway, dimensionless.
SFd-skin contact carcinogenic slope factor, (mg pollutant kg-1 body weight d-1)-1。
The carcinogenic risk of the soil particulate matter inhalation pathway is calculated using equation 15:
CRpis＝PISERca×Csur×SFi (15)
in formula 15, CRpis-the carcinogenic risk of the soil particulate matter uptake pathway, dimensionless.
SFi-respiratory inhalation carcinogenic slope factor, (mg contaminant kg-1 body weight d-1) -1.
The total carcinogenic risk of a single pollutant in the soil through all exposure pathways is calculated using equation 16:
CRn＝CRois+CRdcs+CRpis (16)
in formula 16, CRn — total carcinogenic risk of a single pollutant (nth species) in soil through all exposure pathways, dimensionless.
(5) Quotient of harm of single pollutant in soil
For a single pollutant, calculating a recommendation model of exposure path harm quotient of orally-ingested soil, skin-contacted soil and inhaled soil particulate matter, see formulas 17-19 respectively, and calculating a recommendation model of the damage index of the single pollutant in the soil through the 3 paths, see formula 20.
The risk quotient for the oral soil uptake route was calculated using equation 17:
in formula 17, HQois, a risk quotient of the soil intake route by mouth, is dimensionless;
SAF-reference dose distribution coefficient exposed to soil, dimensionless.
RfDo-oral intake reference dose, mg contaminant kg-1 body weight d-1;
the risk quotient for the skin contact soil approach is calculated using equation 18:
in formula 18, HQdcs, a damage quotient for the skin contact soil route, is dimensionless.
RfDd-skin contact reference dose, mg contaminants kg-1Body weight d-1；
The risk quotient for the way of sucking soil particles is calculated using equation 19:
in formula 19, Hqpis, a hazard quotient of a way of sucking soil particulate matter, and is dimensionless.
RfDi-reference dose for respiratory inhalation, mg contaminant kg-1Body weight d-1；
The hazard index of a single contaminant in the soil through all exposure routes is calculated using equation 20:
HIn＝HQois+HQdcs+HQpis (20)
formula 20, HIn — hazard index for a single contaminant in soil (nth) through all exposure routes, dimensionless.
(2) According to the pollutant risk calculation formula, the exposure parameters of the soil in the research area are searched, and the parameters are shown in table 5.
Table 5 exposure parameters in risk assessment
(3) The total exposure risk of the contaminant to the population was assessed based on the detected concentration of the contaminant, see table 6. The total carcinogenic risk of di (2-diethylhexyl) phthalate is higher than 10-4The method is listed as a high-risk organic pollutant list in the site key industry.
TABLE 6 Risk assessment results
Claims (5)
1. A high-risk organic pollutant screening method for site key industry based on risks comprises the following steps:
1) screening out a high-risk organic pollutant candidate list in the field soil environment according to the field soil environment control directory of the polluted field and the environmental pollution investigation data;
2) carrying out on-site investigation and sampling on the soil environment in the area, and screening out organic pollutants existing in the field;
3) based on the whole process control concept of clean production, the organic matters used in the on-site raw and auxiliary materials of enterprises, intermediate products and by-products possibly generated in the process flow, organic pollutants in the products and the organic matters discharged under abnormal working conditions are investigated on site;
4) grading and assigning the hazard index, the exposure index and the persistent accumulation index of the pollutants screened in the steps 1-3 by adopting a comprehensive grading method;
5) calculating the weights of each index of the harmfulness index, the exposition index and the persistent accumulation by adopting an analytic hierarchy process according to the index in the step 4, and calculating the pollutant with higher comprehensive score as a secondary list of the high-risk organic pollutant according to the assignment condition of each index;
6) calculating the health risk of the pollutants obtained by screening in the step 5 under the condition that the exposure way of the field soil environment to the crowd is determined; columns that exceed the threshold are listed as high risk organic contaminants.
2. The risk-based site-focused industrial high-risk organic pollutant screening method according to claim 1, wherein the step 2 is to perform non-target screening on the sample by using a gas chromatography quadrupole time-of-flight mass spectrometer and a liquid chromatography quadrupole time-of-flight mass spectrometer.
3. The risk-based site-focused industrial high-risk organic pollutant screening method according to claim 1, wherein the hazard indexes in the step 4 comprise carcinogenicity, mutagenicity, reproductive toxicity and biohazard of pollutants;
the exposure index refers to the detection rate of pollutants in a field soil environment sample, the control condition in the soil environment standard/guide rule, and physical indexes such as vapor pressure, soil-water distribution coefficient and the like;
persistent accumulation indicators include half-life and bioaccumulation.
4. The risk-based screening method for high-risk organic pollutants in the field emphasis industry according to claim 1, wherein the exposure routes to human groups in the step 6 comprise three routes of digestive tract, respiration and skin contact.
5. The risk-based site-focused industrial high-risk organic pollutant screening method according to claim 1, wherein the calculation method for calculating the health risk in the step 6 is according to the pollution site risk assessment technical guide (HJ 25.3-2014).
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