CN108226003B - Calculation method of stratum adsorption retardation factor - Google Patents
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- 230000015572 biosynthetic process Effects 0.000 claims description 20
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000002156 adsorbate Substances 0.000 claims description 3
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- 238000007865 diluting Methods 0.000 claims description 3
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention discloses a method for calculating stratum adsorption retardation factors, which belongs to the field of underground water and soil pollution and comprises the following steps: 1) sampling the stratum soil material, and measuring the particle size distribution of the stratum soil material to obtain the characteristic particle size D10、D50And D90(ii) a 2) Determining particles of earth material in a formationA specific surface area S; 3) carrying out Batch test on the stratum soil material to obtain an adsorption curve of typical pollutants on the soil material 4) taking the average slope of the adsorption curve as the distribution coefficient K of the pollutants on the soil materiald(ii) a 5) Calculating the adsorption retardation factor R of the stratumd(ii) a The method comprises the steps of calculating and obtaining an adsorption retardation factor of the stratum by determining the characteristic particle size, the specific surface area and the distribution coefficient of the stratum material; meanwhile, the method does not need a large amount of on-site monitoring, does not need long-time scale indoor tests, has low cost, is simple, feasible, quick and effective, can be widely applied to the works of prediction, restoration and the like of underground water and soil pollution, and has good practicability.
Description
Technical Field
The invention belongs to the field of underground water and soil pollution, and particularly relates to a calculation method of a stratum adsorption retardation factor.
Background
Groundwater pollution refers to a phenomenon in which the quality of groundwater deteriorates due to human activity. Soil pollution is an important source of shallow groundwater pollution, and some pollutants in soil are easy to eluviate or enter groundwater along with seepage, so that the water quality of shallow groundwater deteriorates after the soil accumulates day by day and month, and finally pollution is caused.
Groundwater and soil pollution is often closely related to convection, dispersion, diffusion, adsorption of pollutants in the formation, for example, landfill leachate breaks down an antifouling barrier to contaminate groundwater, pollutants in contaminated sites diffuse into the ground, and the like. In many cases, the adsorption of the stratum to the pollutants has a very important influence relative to convection, dispersion and diffusion, and therefore, most of the problems of groundwater and soil pollution involve the evaluation of the adsorption performance of the pollutants by artificial clay layers or natural stratums.
Currently, the results of the Batch test are mostly used to evaluate the adsorption performance of the formation material. However, the adsorption parameters of the same soil material to the same pollutant are different in the powder and soil states, the Batch test obtains the adsorption characteristics of loose soil particle powder, and the adsorption parameters obtained by the Batch test are directly used for evaluating the adsorption of the stratum to the pollutant, so that the prediction result of the pollution of the underground water and the soil is unsafe. The adsorption of the artificial clay layer or the natural stratum to the pollutants occurs in soil body pores, and the actual situation of the adsorption test is closer to that of an earth pillar adsorption test.
However, the diffusion and adsorption process of pollutants in the soil column is very slow, and the soil column test consumes long time, often for several months; and the diffusion effect and the adsorption effect are carried out simultaneously, and the diffusion coefficient is difficult to accurately determine, so that the soil column test has long test period, and the accuracy of obtaining the adsorption parameter is influenced by the diffusion coefficient.
In fact, the adsorption difference of the same soil material in the powder and soil states is mainly caused by the difference of the contact areas of the soil material and the pollutants, namely the specific surface area of the soil body pores is smaller than the specific surface area of the powder particles, which is the main reason for the difference of the adsorption parameters of the powder and the soil.
Therefore, the adsorption parameter obtained by the Batch test is corrected according to the difference between the specific surface area of the pores of the soil body and the specific surface area of the powder particles, so that the adsorption retardation factor of the stratum material can be obtained, and a new method can be provided for calculation of pollution of underground water and soil.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a calculation method of a stratum adsorption retardation factor, which solves the problem of evaluating the adsorption performance of artificial clay layers or natural stratums on pollutants in the current problems of underground water and soil pollution.
The invention content is as follows: in order to achieve the above purpose, the invention provides the following technical scheme:
a method for calculating a formation adsorption retardation factor comprises the following steps:
1) sampling the stratum soil material, and measuring the particle size distribution of the stratum soil material to obtain the characteristic particle size D10、D50And D90；D10、D50And D90Respectively representing the mass of the soil particles smaller than the particle size accounting for 10%, 50% and 90% of the total soil mass, and the unit is mum;
2) determining the specific surface area S of the particles of the earth material in m2/g；
3) Carrying out Batch test on the stratum soil material to obtain an adsorption curve of a typical pollutant on the soil material, wherein the adsorption curve is a curve formed by different qualities of adsorbing pollutants by a unit mass of soil material under different pollutant concentrations, the horizontal coordinate is the concentration of the pollutant in a solution before adsorption, and the vertical coordinate is the quality of the pollutant adsorbed by the unit mass of soil material after adsorption;
4) taking the average slope of the adsorption curve as the distribution coefficient K of the pollutants on the soil materialdThe unit is mL/g;
5) calculating the adsorption retardation factor R of the stratumd(-)：
The sampling was performed on the earth formation material according to standard SL 237-1999, and the particle size distribution was determined by one of the sieve analysis method, densitometer method, pipette method and laser granulometer test method.
In step 2), the specific surface area of the particles is determined according to the label GB/T19587-2004 by one of a gravimetric method, a gravimetric method and a gas chromatography method.
In step 3), the Batch test was performed according to American society for testing and materials Standard D4646-87, as follows:
a) firstly, placing the air-dried kaolin soil sample in an oven for drying, then taking out, cooling to room temperature, grinding into powder, sieving, and storing in a sealed bag for later use;
b) preparing a pollutant solution with a certain initial concentration, diluting to different times to obtain pollutant solutions with different concentrations, and storing for later use;
c) mixing the adsorbent with volume V and initial concentration C0Mixing the adsorbate solution;
d) in order to make the pollutants fully contact with the soil particles and make the soil particles reach adsorption saturation, placing the centrifugal tube in a constant-temperature oscillator for oscillation;
e) taking out the centrifugal tube, and centrifuging in a centrifuge to separate soil particles from the pollutant solution;
f) finally, sampling the clear solution at the middle upper part of the centrifugal tube, and determining the equilibrium concentration C of the pollutants in the solutioneThe amount C of the pollutant adsorbed per unit mass of the soil material is calculated by the following formulas：
In step 5), a formation adsorption retardation factor RdDerived from the following calculations:
the adsorption capacity of the unit surface area of the powder is equal to that of the unit surface area of the pore of the soil body, and the powder distribution coefficient K can be obtaineddDistribution coefficient to soil body KdcThe relationship of (1):
wherein S is the specific surface area of soil particles and the unit m2/g，ScIs the specific surface area of soil pores in the unit of m2(ii) in terms of/g. Soil mass distribution coefficient KdcIt can be expressed as:
obtaining a formation retardation factor R from the formula (5)dExpression (c):
assuming that the pores in the earth pillar are all round thin tubes, the diameter of the round tube, namely the equivalent aperture is d, the unit mum, the number of the round tubes is m (-), and the length of the round tube is L, the unit m, thereby calculating the specific surface area S of the porescUnit is m2/g：
Simplifying the aperture cumulative distribution curve into three lines of an inverted S shape, wherein the aperture range of each section is d0～d20、d20～d80And d80～d100Assuming that the average pore diameter of each segment is d10、d50And d90Then we get a simplified expression of the equivalent aperture d, in μm:
assuming that the soil particles are all spheres, obtaining the relation between the aperture D and the particle size D according to the sphere accumulation principle:
the formula (9) is introduced into formula (8) to obtain:
the formula (10) is brought into the formula (7), and the specific surface area S of porescThe expression of (c) can be simplified as:
then the formula (11) is brought into the formula (6), and the formation adsorption retardation factor R can be obtainedd：
The invention principle is as follows: according to the method, the adsorption parameters obtained by the Batch test are corrected according to the difference between the specific surface area of the pores of the soil body and the specific surface area of the powder particles, and the adsorption retardation factor of the stratum material can be obtained.
Has the advantages that: compared with the prior art, the method for calculating the stratum adsorption retardation factor comprises the steps of calculating the adsorption retardation factor of the stratum by determining the characteristic particle size, the specific surface area and the distribution coefficient of the stratum material; meanwhile, the method does not need a large amount of on-site monitoring, does not need long-time scale indoor tests, has low cost, is simple, feasible, quick and effective, can be widely applied to the works of prediction, restoration and the like of underground water and soil pollution, and has good practicability.
Drawings
FIG. 1 is a graph comparing the results of finite element calculations for retardation factors with geotechnical centrifuge test results;
FIG. 2 is a flow chart of a method of calculating formation adsorption retardation factors.
Detailed Description
The invention will be further described with reference to the following drawings and specific embodiments.
As shown in fig. 2, a method for estimating formation adsorption retardation factors includes the following steps:
1) sampling the stratum soil material according to the industrial standard 'geotechnical test regulation' SL 237-1999, measuring the particle size distribution of the stratum soil material, and obtaining the characteristic particle size D10(μm)、D50(. mu.m) and D90(μm)；D10(μm)、D50(. mu.m) and D90(μm) represents the mass of the soil particles smaller than the particle diameter in 10%, 50% and 90% of the total soil mass, respectively. The particle size distribution of the particles can be determined by a sieve analysis method, a densitometer method, a pipette method and a laser particle sizer test method;
2) the particle specific surface area S (m) of the stratum soil material is measured according to the national standard GB/T19587-2004 of the determination of the specific surface area of the solid substance by the gas adsorption BET method2(iv)/g); of specific surface area of the particlesThe determination can be performed by a volumetric method, a gravimetric method and a gas chromatography method;
3) carrying out a Batch test on a formation soil material according to the Standard test method for 24-hbatch-type pollutant absorption by solids and differences D4646-87 of the American Society for Testing and Materials (ASTM) Standard to obtain an adsorption curve of a typical pollutant on the soil material, wherein the adsorption curve is a curve formed by different masses of the unit mass of the soil material adsorbing the pollutant under different pollutant concentrations, the abscissa is the concentration of the pollutant in a solution before adsorption, and the ordinate is the mass of the pollutant adsorbed by the unit mass of the soil material after adsorption;
the Batch test comprises the following main test steps:
a) firstly, placing the air-dried kaolin soil sample in a 105 ℃ oven for 24 hours, then taking out, cooling to room temperature, grinding into powder, sieving, and storing in a sealing bag for later use;
b) preparing a pollutant solution with a certain initial concentration, diluting to different times to obtain pollutant solutions with different concentrations, and storing for later use;
c) mixing a certain mass m of adsorbent with a certain volume V and initial concentration C0The adsorbate solutions are mixed, and the soil-water ratio of 1:10(g/mL) is adopted in the experiment and mixed in a centrifuge tube;
d) in order to ensure that the pollutants are fully contacted with the soil particles and the soil particles reach adsorption saturation, placing the centrifugal tube in a constant-temperature oscillator, and oscillating for 24 hours at the rotating speed of 140rpm and the temperature of 25 ℃;
e) taking out the centrifugal tube, and centrifuging the centrifugal tube in a centrifuge at the rotating speed of 3000rpm for 20 minutes to separate soil particles from the pollutant solution;
f) finally, sampling the clear solution at the middle upper part of the centrifugal tube, and determining the equilibrium concentration C of the pollutants in the solutioneThe amount C of the pollutant adsorbed per unit mass of the soil material is calculated by the following formulas：
4) Taking the average slope of the adsorption curve as the foulingDistribution coefficient K of the dyeing material on the soil materiald(mL/g)；
5) Calculating the adsorption retardation factor R of the stratum according to the formula (2)d(-)：
Derivation of a calculation formula:
at present, the following formula is commonly used to obtain the adsorption retardation factor R due to calculationd(-)：
In the formula, ρdIs the dry density (g/cm) of the soil body3) N is the porosity (-) of the soil body, KdIs the partition coefficient (mL/g). Partition coefficient K obtained by Batch testdThe distribution coefficient K is obtained by directly using the Batch testdCalculating the blocking factor will yield a less secure result. Therefore, the partition coefficient K obtained by the Batch test is requireddAnd (6) correcting.
According to the test, the adsorption capacity of the unit surface area of the powder is equal to the adsorption capacity of the unit surface area of the soil pore, and the powder distribution coefficient K can be obtaineddDistribution coefficient to soil body KdcThe relationship of (1):
wherein S is the specific surface area (m) of the soil particles2/g)，ScIs the specific surface area (m) of the pores of the soil body2In terms of/g). Soil mass distribution coefficient KdcIt can be expressed as:
bringing formula (5) into formula (3) to obtain a formation retardation factor RdExpression (c):
assuming that the pores in the earth pillar are all round thin tubes, the diameter (equivalent pore diameter) of each round tube is d (mum), the number of the round tubes is m (-), and the length of each round tube is L (m), the specific surface area S of each pore can be calculatedc(m2/g)：
Simplifying the cumulative distribution curve of the aperture into three lines of an inverted 'S' shape, wherein the aperture range of each section is d0～d20、d20～d80And d80～d100Assuming that the average pore diameter of each segment is d10、d50And d90Then a simplified expression of the equivalent aperture d (μm) can be obtained:
assuming that the soil particles are all spheres, the relationship between the pore diameter D (mum) and the particle diameter D (mum) is obtained according to the sphere stacking principle:
the formula (9) is introduced into formula (8) to obtain:
the formula (10) is brought into the formula (7), and the specific surface area S of poresc(m2The expression,/g) can be simplified as:
then the formula (11) is brought into the formula (6), and the formation retardation factor R can be obtaineddIs simplifiedCalculating the formula:
stratum adsorption retardation factor R obtained by using the methodd(-) the process of heavy metal Cd breakdown 2m compacted clay liner was calculated and compared to the geotechnical centrifuge test simulation results for this process. Calculating formation adsorption retardation factor RdAnd calculating the actual measurement parameters required by the process of puncturing the 2m compacted clay liner by the heavy metal Cd, as shown in Table 1.
Table 1 model pad parameters and adsorption parameters
In the figure 1, each point takes time as a horizontal coordinate, the seepage concentration of heavy metal Cd at the bottom of a 2m compacted clay liner is a vertical coordinate, and two working conditions that the heavy metal Cd exists independently (liner 1) and is mixed with COD (chemical oxygen demand) and DDT (liner 2) are considered. Under the working condition of the liner 1, the Cd concentration calculated by finite elements changes along with time by taking a solid line as a mark, and the test result of the centrifuge takes a solid square as a mark; under the working condition of the gasket 2, the change of Cd concentration calculated by finite elements along with time is marked by a dotted line, and the test result of the centrifuge is marked by a solid circle. The comparison shows that the compacted clay retardation factor R obtained by the inventiondThe results of the finite element calculations are very close to the results of the geotechnical centrifuge tests, and the reasonability and accuracy of the formula (1) are also illustrated.
Claims (5)
1. A method for calculating stratum adsorption retardation factors is characterized by comprising the following steps: the method comprises the following steps:
1) sampling the stratum soil material, and measuring the particle size distribution of the stratum soil material to obtain the characteristic particle size D10、D50And D90；D10、D50And D90Respectively represent smallThe mass of the soil particles in the particle size accounts for 10%, 50% and 90% of the total soil mass, and the unit is mum;
2) determining the specific surface area S of the particles of the earth material in m2/g；
3) Carrying out Batch test on the stratum soil material to obtain an adsorption curve of a typical pollutant on the soil material, wherein the adsorption curve is a curve formed by different qualities of adsorbing pollutants by a unit mass of soil material under different pollutant concentrations, the horizontal coordinate is the concentration of the pollutant in a solution before adsorption, and the vertical coordinate is the quality of the pollutant adsorbed by the unit mass of soil material after adsorption;
4) taking the average slope of the adsorption curve as the distribution coefficient K of the pollutants on the soil materialdThe unit is mL/g;
5) calculating the adsorption retardation factor R of the stratumd：
2. The method for estimating the formation adsorption retardation factor according to claim 1, wherein: in step 1), the sampling is carried out on the stratum soil material according to the standard SL 237-1999, and the particle size distribution of the particles is determined by one of a screening method, a densitometer method, a pipette method and a laser particle sizer test method.
3. The method for estimating the formation adsorption retardation factor according to claim 1, wherein: in step 2), the specific surface area of the particles is determined according to the label GB/T19587-2004 by one of a gravimetric method, a gravimetric method and a gas chromatography method.
4. The method for estimating the formation adsorption retardation factor according to claim 1, wherein: in step 3), the Batch test was performed according to American society for testing and materials Standard D4646-87, as follows:
a) firstly, placing the air-dried kaolin soil sample in an oven for drying, then taking out, cooling to room temperature, grinding into powder, sieving, and storing in a sealed bag for later use;
b) preparing a pollutant solution with a certain initial concentration, diluting to different times to obtain pollutant solutions with different concentrations, and storing for later use;
c) mixing the adsorbent with volume V and initial concentration C0Mixing the adsorbate solution;
d) in order to make the pollutants fully contact with the soil particles and make the soil particles reach adsorption saturation, placing the centrifugal tube in a constant-temperature oscillator for oscillation;
e) taking out the centrifugal tube, and centrifuging in a centrifuge to separate soil particles from the pollutant solution;
f) finally, sampling the clear solution at the middle upper part of the centrifugal tube, and determining the equilibrium concentration C of the pollutants in the solutioneThe amount C of the pollutant adsorbed per unit mass of the soil material is calculated by the following formulas：
5. The method for estimating the formation adsorption retardation factor according to claim 1, wherein: in step 5), a formation adsorption retardation factor RdDerived from the following calculations:
the adsorption capacity of the unit surface area of the powder is equal to the adsorption capacity of the unit surface area of the pore of the soil body, and the powder distribution coefficient K is obtaineddDistribution coefficient to soil body KdcThe relationship of (1):
wherein S is the specific surface area of soil particles and the unit m2/g，ScIs the specific surface area of soil pores in the unit of m2G, soil mass distribution coefficient KdcThen it is expressed as:
obtaining a formation retardation factor R from the formula (5)dExpression (c):
assuming that the pores in the earth pillar are all round thin tubes, the diameter of a round tube is d, the unit of mu m, the number of the round tubes is m, the length of the round tube is L, and the unit of m and n are the porosity of the earth body, and calculating the specific surface area S of the pores according to the equivalent pore diameter d, the unit of mu m and the unit of ncUnit is m2/g：
Simplifying the aperture cumulative distribution curve into three lines of an inverted S shape, wherein the aperture range of each section is d0～d20、d20～d80And d80～d100Assuming that the average pore diameter of each segment is d10、d50And d90Then we get a simplified expression of the equivalent aperture d, in μm:
assuming that the soil particles are all spheres, obtaining the relation between the aperture D and the particle size D according to the sphere accumulation principle:
bringing formula (9) into formula (8):
the formula (10) is brought into the formula (7), and the specific surface area S of porescThe expression of (c) is simplified as:
then the formula (11) is brought into the formula (6), and the formation adsorption retardation factor R is obtainedd：
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