CN110658327B - River basin surface source heavy metal silt enrichment ratio calculation method based on sediment analysis - Google Patents
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Abstract
The invention discloses a basin surface source heavy metal silt enrichment ratio calculation method based on sediment analysis, which comprises the steps of selecting a typical small basin; collecting the column core of the sediment, and determining the heavy metal content and total phosphorus content of different sediment depth layers210PbexAn activity value; measuring mass deposition rate values of layers with different depths and deposition flux values of heavy metal and total phosphorus; establishing the heavy metal and total phosphorus deposition flux of the drainage basinLong-term quantitative relationships between values; collecting background soil of a drainage basin and measuring heavy metal and total phosphorus content values in the background soil; and establishing a long-term quantitative relation between the concentration ratios of the heavy metals in the drainage basin and the total phosphorus silt. The method has the advantages that the relation can be applied to other similar drainage basins by only establishing the long-term quantitative relation between the non-point source heavy metal and the total phosphorus silt enrichment ratio in a typical drainage basin based on sediment analysis, and the non-point source heavy metal silt enrichment ratio of the applied drainage basin can be quickly obtained.
Description
Technical Field
The invention belongs to the technical field of drainage basin non-point source pollution prevention and control, and relates to a drainage basin non-point source heavy metal sediment enrichment ratio calculation method based on sediment analysis.
Background
Agricultural non-point source pollution gradually becomes a key factor for restricting the improvement of water environment quality in China. Various chemical substances remained in farmland soil are main non-point source pollutants, and the chemical substances can finally enter water bodies such as rivers, lakes and the like along with eroded soil under the rainfall condition, so that a series of water environment quality problems are caused. At present, most of agricultural non-point source pollution researches developed in China are concentrated on nutrient substances such as carbon, nitrogen, phosphorus and the like, the problem of eutrophication of watershed water is solved, and much attention is not paid to toxic heavy metals with huge ecological safety and human health threats. The research on agricultural non-point source pollution needs to define the loss characteristics of the watershed non-point source pollutants, so that technical support is provided for the subsequent effective prevention and control measures. Soil erosion caused by surface runoff is an important form of agricultural non-point source pollution. Soil erosion processes tend to transport fine particulate matter more so that the silt in surface runoff is generally more concentrated in pollutants than the source soil. Therefore, the silt enrichment ratio is considered as an important parameter for researching the loss characteristics of the watershed non-point source pollutants and constructing a water quality model of the watershed non-point source pollutants. Because of the high attention paid to the problem of water eutrophication in the early stage, the research on the loss characteristics of the non-point source nitrogen and phosphorus of the drainage basin at home and abroad is mature at present, and an empirical formula for calculating the silt enrichment ratio is established. However, research on this aspect of heavy metals is relatively delayed. Different heavy metals have different silt enrichment ratios and are influenced by conditions such as basin climate, terrain, hydrology and the like. By establishing a runoff plot to carry out a long-term positioning observation test, foreign scholars have carried out research work on different heavy metal silt enrichment ratios. In contrast, agricultural non-point source pollution research in China starts to be overall late, and a database of a comprehensive system is not established yet. Meanwhile, as many areas do not have conditions for carrying out on-site long-term observation tests, most of the scholars directly refer to the foreign existing silt enrichment ratio research results when carrying out watershed non-point source heavy metal loss characteristic research, thereby increasing the research uncertainty. The sediment acts as the final "sink" of the watershed material and may reflect the non-point source contaminant loss characteristics over the entire watershed scale. Therefore, the quantitative relation between the heavy metal and the total phosphorus sediment enrichment ratio is established in a typical small watershed based on sediment analysis, and the heavy metal sediment enrichment ratio can be calculated in a similar watershed according to the total phosphorus sediment enrichment ratio. The collection and analysis of the sediment are simple and easy, so that the workload of establishing a runoff plot in a flow area to carry out a long-term positioning observation test is greatly saved. In view of the background, in order to calculate the enrichment ratio of the agricultural non-point source heavy metal silt of different watersheds more quickly and efficiently, the method for calculating the enrichment ratio of the heavy metal silt of the watersheds non-point source based on sediment analysis is established in the application of the patent. And selecting a typical basin to establish a long-term quantitative relation between the non-point source heavy metal and the total phosphorus sediment enrichment ratio, applying the obtained quantitative relation to other similar basins, and quickly obtaining the heavy metal sediment enrichment ratio of the application basin from the total phosphorus sediment enrichment ratio by only collecting sediment in the application basin to determine.
Disclosure of Invention
The invention aims to provide a basin non-point source heavy metal silt enrichment ratio calculation method based on sediment analysis.
The technical scheme adopted by the invention is carried out according to the following steps:
step 1: selecting a typical small watershed;
step 2: collecting the column core of the sediment, and determining the heavy metal content and total phosphorus content of different sediment depth layers210PbexAn activity value;
and step 3: measuring mass deposition rate values of layers with different depths and deposition flux values of heavy metal and total phosphorus;
and 4, step 4: establishing a long-term quantitative relation between the basin heavy metal and the total phosphorus deposition flux value;
and 5: collecting background soil of a drainage basin and measuring heavy metal and total phosphorus content values in the background soil;
and 6: and establishing a long-term quantitative relation between the concentration ratio of the heavy metals in the watershed and the total phosphorus and silt.
Further, in the step 1, a typical small watershed is selected as a research area, and in order to ensure smooth collection of sediments, a relatively stable deposition environment convenient for sediment collection is required at an outlet of the watershed; secondly, in order to popularize the calculation formula obtained by research into other similar watersheds to calculate the enrichment ratio of the heavy metals of the non-point sources of other watersheds, the selected watersheds must be representative, and the climate, the terrain, the hydrology, the covered land utilization type, the soil type and the background value of the selected watersheds need to be representative.
Further, step 2, a column sampler is used for obtaining a sediment column core at the outlet of the flow field, and the sediment column core is carefully divided and bagged according to the thickness of 1cm on site. The sample is taken back to the laboratory and naturally dried, and the agate is ground through a 100-mesh nylon sieve and then subjected to HNO3-HF-HClO4After the method is digested, the content values of heavy metal and total phosphorus are measured by adopting an inductively coupled plasma emission spectrometer, and the content values of heavy metal and total phosphorus are measured by adopting a high-purity germanium low-background gamma energy spectrometer210Pbex(atmospheric sources)210Pb) activity value.
Further, step 3 is based on the different deposition depth layers obtained in step 2210PbexThe activity value is calculated by applying a CRS (constant Rate supply) model to the mass deposition Rate value of each layer. The mass deposition rate calculation formula is:
wherein R (Z) is the mass deposition rate (mg/cm) of the Z depth layer2A); i (Z) for deposition layers below depth Z210PbexCumulative amount (Bq/cm)2) (ii) a A (Z) is a Z depth layer210PbexActivity (Bq/kg); λ is210Pb decay constant (0.03114/a).
And (3) multiplying the mass deposition rate value of each deposition depth layer by the heavy metal and total phosphorus content values measured in the step (2) respectively, and calculating the watershed deposition flux values of the heavy metals and the total phosphorus content values. The deposition flux calculation formula is as follows:
S(Z)＝R(Z)×C(Z)
wherein S (Z) is the deposition flux (ug/cm) of the Z depth layer2A); r (Z) is the mass deposition rate (mg/cm) of the Z depth layer2A); c (Z) is the concentration content (mg/kg) of the Z depth layer.
Further, step 4, establishing a long-term quantitative relation between the heavy metals in different depth layers and the total phosphorus deposition flux value by applying regression analysis based on the heavy metals in different depth layers and the total phosphorus deposition flux value obtained in step 3. The formula of the quantitative relationship is in the form of y ═ ax + b, wherein y is the heavy metal deposition flux value, x is the total phosphorus deposition flux value, and a and b are constants in the formula.
Further, step 5 collects several background soil samples throughout the basin. Air-drying in laboratory, grinding, sieving, and HNO3-HF-HClO4And (4) after the method digestion, measuring the heavy metal and total phosphorus content value by using an inductively coupled plasma emission spectrometer.
Further, step 6 is to establish a long-term quantitative relationship between the river basin surface source heavy metal and the total phosphorus sediment enrichment ratio by applying an adsorption state pollutant migration empirical model based on the long-term quantitative relationship between the river basin heavy metal and the total phosphorus sediment flux value obtained in step 4 and the river basin soil background value obtained in step 5.
The empirical model for migration of adsorbed pollutants is as follows:
L＝C×Q×η
wherein L is the load of loss in adsorption state (g/km)2) (ii) a C is a watershed soil background value (mg/kg); q is basinAmount of soil erosion (t/km)2) And eta is the silt concentration ratio (dimensionless).
The long-term quantitative relation formula between the concentration ratio of the heavy metal in the drainage basin and the total phosphorus silt is as follows:
wherein etaiThe silt enrichment ratio (dimensionless) of the heavy metal i in the drainage basin is obtained; etaTotal phosphorusThe silt enrichment ratio (dimensionless) of the total phosphorus in the basin is shown; l is a radical of an alcoholiThe load (g/km) of the drainage basin heavy metal i in the adsorption state is lost2)；LTotal phosphorusThe load (g/km) of the adsorption state loss of total phosphorus in the drainage basin2)；AiThe soil background value ratio (dimensionless) of heavy metal i in the drainage basin to total phosphorus; a and b are constants in a quantitative relation formula of the heavy metal in the watershed and the total phosphorus deposition flux value; x is total phosphorus deposition flux value (ug/cm)2·a)。
Wherein, x of the watershed to be calculated is obtained through the steps 2 and 3, etaTotal phosphorusAccording to the empirical formula proposed by Menzel R.G. EtaTotal phosphorusThe empirical formula of (2) is:
lnηtotal phosphorus＝2-0.2×lnQ
Wherein etaTotal phosphorusThe silt enrichment ratio (dimensionless) of the total phosphorus in the drainage basin is adopted; q is the erosion amount (t/km) of the soil in the drainage basin2)。
Drawings
FIG. 1 is a flow chart of a method for calculating the concentration ratio of heavy metal silt in a watershed non-point source based on sediment analysis;
FIG. 2 is a schematic diagram showing the change of the deposition flux of heavy metals and total phosphorus in a basin;
FIG. 3 is a schematic diagram showing the dependence of the heavy metals in the watershed on the total phosphorus deposition flux.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Fig. 1 shows a flow chart of a method for calculating the concentration ratio of heavy metal silt in a watershed non-point source based on sediment analysis, which comprises the following implementation steps:
step 1
In this case, a small flow field located upstream of the Yimeng river in the Yimeng mountain area of China was selected as an example for analysis. The agricultural small watershed is representative in the Yimeng mountain area, the area of the forest land and the cultivated land accounts for more than 70% of the area of the whole watershed, and no obvious industrial pollution source exists.
Step 2
After early field investigation, a column sampler is used for obtaining a 25cm deep deposition column core at about 1km upstream of the outlet of the drainage basin, and the column core is carefully divided and bagged according to the thickness of 1cm on the field. The sample is taken back to the laboratory and naturally dried, and the agate is ground through a 100-mesh nylon sieve and then subjected to HNO3–HF–HClO4After the digestion, the heavy metal and total phosphorus content values are measured by adopting an inductively coupled plasma emission spectrometer, and the heavy metal and total phosphorus content values are measured by adopting a high-purity germanium low-background gamma energy spectrometer210Pbex(atmospheric sources)210Pb) activity value. Taking Pb and Cu as examples, the results of the different deposition depth layer measurements are shown in Table 1. As can be seen from the table, the Pb content ranged from 29.86 to 37.98mg/kg, the Cu content ranged from 34.84 to 47.07mg/kg, the total phosphorus content ranged from 398.02 to 1381.28mg/kg,210Pbexthe activity range is 4.15-12.12 Bq/kg. The method is not limited to the two heavy metals, and is also applicable to other heavy metals for sediment determination.
TABLE 1 heavy metals, Total phosphorus content values and210Pbexvalue of activity
Step 3
Based on the different deposition depth layers obtained in step 2210PbexAnd calculating the activity value by using a CRS model to obtain the mass deposition rate value of each layer. The mass deposition rate calculation formula is:
wherein R (Z) is the mass deposition rate (mg/cm) of the Z depth layer2A); i (Z) for deposition layers below depth Z210PbexCumulative amount (Bq/cm)2) (ii) a A (Z) is a Z depth layer210PbexActivity (Bq/kg); λ is210Pb decay constant (0.03114/a).
And (3) multiplying the mass deposition rate value of each deposition depth layer by the Pb, Cu and total phosphorus content value measured in the step (2) respectively to obtain the watershed deposition flux values of the deposition depth layers. The deposition flux calculation formula is:
S(Z)＝R(Z)×C(Z)
wherein S (Z) is the deposition flux (ug/cm) of the Z depth layer2A); r (Z) is the mass deposition rate (mg/cm) of the Z depth layer2A); c (Z) is the concentration content (mg/kg) of the Z depth layer.
As shown in FIG. 2, the Pb deposition flux was 13.93-23.10ug/cm2A, Cu deposition flux is 16.73-26.36ug/cm2A, total phosphorus deposition flux is 191.03-814.23ug/cm2A. According to the chronological sequence reflected by the sediment column core, the historical change trend of the deposition flux of two heavy metals of the basin Pb and the Cu and the total phosphorus is generally consistent, the lowest value of the two heavy metals appears in 1978, and the highest value appears near 2008.
And (4) establishing a long-term quantitative relation between Pb and Cu of different depth layers and the total phosphorus deposition flux value by applying regression analysis based on the Pb and Cu of different depth layers obtained in the step (3). As shown in FIG. 3, there is a good correlation between the flux values of Pb, Cu and total phosphorus deposition, R2The values were 0.70, 0.83, respectively, indicating similar bleed characteristics between them. The obtained quantitative relation formula is respectively as follows:
Pb：y＝0.0080x+14.881
Cu：y＝0.0125x+16.057
wherein y is a heavy metal deposition flux value (ug/cm)2A); x is total phosphorus deposition flux value (ug/cm)2·a)。
A plurality of 100-120cm deep natural forest soil samples are collected in the whole range of the watershed. Air-drying in laboratory, grinding, sieving, and HNO3–HF–HClO4And (4) after digestion, measuring the heavy metal and total phosphorus content value by using an inductively coupled plasma emission spectrometer. The background content of Pb in the drainage basin soil is 20.37mg/kg, the background content of Cu is 21.82mg/kg, and the total background content of phosphorus is 664.27 mg/kg.
Step 6
And (3) establishing a long-term quantitative relation among river basin surface sources Pb, Cu and total phosphorus sediment enrichment ratios by applying an adsorption state pollutant migration empirical model based on the long-term quantitative relation among the river basin Pb, Cu and total phosphorus sediment flux values obtained in the step (4) and the soil background value obtained in the step (5). The obtained quantitative relation formula is respectively as follows:
wherein etaPbIs the silt enrichment ratio (dimensionless) of the basin Pb; etaCuThe silt enrichment ratio (dimensionless) of the basin Cu; etaTotal phosphorusThe silt enrichment ratio (dimensionless) of the total phosphorus in the drainage basin is adopted; x is the value of total phosphorus deposition flux (ug/cm) in the basin2·a)。
Collecting the deposit in the watershed to be calculated, measuring the total phosphorus concentration content value and the mass deposition rate value in the deposit, calculating to obtain the total phosphorus deposition flux value, and obtaining eta obtained by the existing empirical formulaTotal phosphorusAnd substituting the values into the relational expression to obtain the silt enrichment ratio of Pb and Cu in the current year of the basin to be calculated.
The method selects a typical small watershed; collecting the column core of the deposit, determining the heavy metal content and total phosphorus content of different deposit depth layers and210Pbexan activity value; measuring mass deposition rate values of layers with different depths and deposition flux values of heavy metal and total phosphorus; establishment of watershed heavy metalsLong term quantitative relationship to total phosphorus deposition flux values; collecting background soil of a drainage basin and measuring heavy metal and total phosphorus content values in the background soil; and establishing a long-term quantitative relation between the concentration ratios of the heavy metals in the drainage basin and the total phosphorus silt. The invention also has the advantages that: firstly, a long-term quantitative relation between the heavy metal and the total phosphorus silt enrichment ratio is established in a typical small watershed, and the formula can be applied to other similar watersheds to calculate the heavy metal silt enrichment ratio; and secondly, after a calculation formula is established, only the sediments are required to be collected and measured in the application basin, and the heavy metal sediment enrichment ratio of the basin in the current year can be calculated according to the total phosphorus sediment enrichment ratio, so that the method is simple and feasible.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the present invention in any way, and all simple modifications, equivalent variations and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the present invention.
Claims (6)
1. The method for calculating the concentration ratio of the heavy metal silt of the watershed non-point source based on sediment analysis is characterized by comprising the following steps of:
step 1: selecting a typical small watershed;
step 2: collecting the column core of the sediment, and determining the heavy metal content and total phosphorus content of different sediment depth layers210PbexAn activity value;
and 3, step 3: measuring mass deposition rate values of layers with different depths and deposition flux values of heavy metal and total phosphorus;
and 4, step 4: establishing a long-term quantitative relation between the watershed heavy metal and the total phosphorus deposition flux value;
and 5: collecting background soil of a drainage basin and measuring the content values of heavy metals and total phosphorus in the background soil;
step 6: establishing a long-term quantitative relation between the concentration ratios of heavy metals in the watershed and the total phosphorus sediment;
and step 6, establishing a long-term quantitative relationship between the river basin surface source heavy metal and the total phosphorus sediment concentration ratio by applying an adsorption state pollutant migration empirical model based on the long-term quantitative relationship between the river basin heavy metal and the total phosphorus deposition flux value obtained in the step 4 and the river basin soil background value obtained in the step 5, wherein the adsorption state pollutant migration empirical model is as follows:
L＝C×Q×η
wherein L is the adsorption state loss load; c is a watershed soil background value; q is the erosion amount of the soil in the watershed, and eta is the silt enrichment ratio;
the long-term quantitative relation formula between the concentration ratio of the heavy metal in the drainage basin and the total phosphorus silt is as follows:
wherein etaiThe silt concentration ratio of the heavy metal i in the drainage basin is shown; etaTotal phosphorusThe silt concentration ratio of the total phosphorus in the drainage basin is obtained; l isiThe load is the adsorption state loss load of the heavy metal i in the drainage basin; l isTotal phosphorusThe load is lost in the adsorption state of the total phosphorus in the drainage basin; a. theiThe ratio of the drainage basin heavy metal i to the soil background value of total phosphorus; a and b are constants in a quantitative relation formula of the heavy metal in the watershed and the total phosphorus deposition flux value; x is the total phosphorus deposition flux value;
wherein, x of the watershed to be calculated is obtained through the steps 2 and 3, etaTotal phosphorusEta is obtained from the empirical formula proposed by Menzel R.GTotal phosphorusThe empirical formula of (2) is:
lnηtotal phosphorus＝2-0.2×lnQ
Wherein etaTotal phosphorusThe silt enrichment ratio of the total phosphorus in the basin is obtained; q is the erosion amount of the soil in the drainage basin.
2. The method for calculating the silt enrichment ratio of the heavy metals in the watershed non-point source based on the sediment analysis of claim 1, which is characterized in that: in the step 1, a typical small watershed is selected as a research area, and in order to ensure smooth collection of sediments, a relatively stable deposition environment convenient for sediment collection is required at an outlet of the watershed; secondly, in order to popularize the calculation formula obtained by research into other similar watersheds for calculating the non-point source heavy metal enrichment ratio of other watersheds, the selected watersheds must be representative, and the climate, the terrain, the hydrology, the covered land utilization type, the soil type and the background value of the selected watersheds need to be representative.
3. The method for calculating the silt enrichment ratio of the heavy metals in the watershed non-point source based on the sediment analysis of claim 1, which is characterized in that: step 2, a sediment column core is obtained at the outlet of the fluid area by using a column-shaped sampler, the sediment column core is carefully cut and bagged according to the thickness of 1cm on site, the sample is taken back to a laboratory and then is naturally dried, and agate is ground and sieved by a 100-mesh nylon sieve and then is subjected to HNO3–HF–HClO4After the digestion, the heavy metal and total phosphorus content values are measured by adopting an inductively coupled plasma emission spectrometer, and the heavy metal and total phosphorus content values are measured by adopting a high-purity germanium low-background gamma energy spectrometer210PbexAnd (4) an activity value.
4. The method for calculating the concentration ratio of the heavy metal sediment in the watershed non-point source based on the sediment analysis as claimed in claim 1, wherein the method comprises the following steps: the step 3 is based on the layers with different deposition depths obtained in the step 2210PbexAnd (3) calculating the mass deposition rate value of each layer by using a CRS model, wherein the mass deposition rate calculation formula is as follows:
wherein R (Z) is the mass deposition rate of the Z depth layer; i (Z) for deposition layers below depth Z210Pbex(ii) an accumulated amount; a (Z) is a Z depth layer210PbexActivity; λ is210The Pb decay constant; and (3) multiplying the mass deposition rate value of each deposition depth layer by the heavy metal and total phosphorus content values measured in the step (2) respectively, and calculating the watershed deposition flux values, wherein the deposition flux calculation formula is as follows:
S(Z)＝R(Z)×C(Z)
wherein S (Z) is the deposition flux of the Z depth layer; r (Z) is the mass deposition rate of the Z depth layer; c (Z) is the concentration content of the Z depth layer.
5. The method for calculating the silt enrichment ratio of the heavy metals in the watershed non-point source based on the sediment analysis of claim 1, which is characterized in that: and 4, establishing a long-term quantitative relation between the heavy metals in different depth layers and the total phosphorus deposition flux value obtained in the step 3 by applying regression analysis, wherein the formula form of the quantitative relation is y ═ ax + b, y is the heavy metal deposition flux value, x is the total phosphorus deposition flux value, and a and b are constants in the formula.
6. The method for calculating the silt enrichment ratio of the heavy metals in the watershed non-point source based on the sediment analysis of claim 1, which is characterized in that: step 5, collecting a plurality of background soil samples in the whole watershed range, air-drying, grinding and sieving in a laboratory, and then HNO3–HF–HClO4And (4) after the method digestion, measuring the heavy metal and total phosphorus content value by using an inductively coupled plasma emission spectrometer.
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