CN110658327B - River basin surface source heavy metal silt enrichment ratio calculation method based on sediment analysis - Google Patents

River basin surface source heavy metal silt enrichment ratio calculation method based on sediment analysis Download PDF

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CN110658327B
CN110658327B CN201910983467.5A CN201910983467A CN110658327B CN 110658327 B CN110658327 B CN 110658327B CN 201910983467 A CN201910983467 A CN 201910983467A CN 110658327 B CN110658327 B CN 110658327B
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焦伟
李宝
赵敏
姜永见
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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

基于沉积物分析的流域面源重金属泥沙富集比率计算方法Calculation method of sediment enrichment ratio of non-point source heavy metals in watershed based on sediment analysis

技术领域technical field

本发明属于流域面源污染防控技术领域,涉及基于沉积物分析的流域面源重金属泥沙富集比率计算方法。The invention belongs to the technical field of non-point source pollution prevention and control in a watershed, and relates to a method for calculating the enrichment ratio of heavy metal sediment in a non-point source of a watershed based on sediment analysis.

背景技术Background technique

农业面源污染逐渐成为制约我国水环境质量改善的关键因素。农田土壤中残留的各种化学物质是主要的面源污染物,它们在降雨条件下会随侵蚀土壤最终进入河流、湖泊等水体,从而引发一系列水环境质量问题。目前,我国已开展的农业面源污染研究大都集中在碳、氮、磷等营养物质,解决的是流域水体富营养化问题,而对于有着巨大生态安全和人体健康威胁的有毒重金属关注仍不是很多。开展农业面源污染研究,需要明确流域面源污染物的流失特征,从而为后续实施有效的防控措施提供技术支持。由地表径流引发的土壤侵蚀是农业面源污染发生的重要形式。土壤侵蚀过程更倾向于运移细颗粒物质,导致地表径流中泥沙通常要比源土壤富集更多的污染物。因此,泥沙富集比率被认为是流域面源污染物流失特征研究及其水质模型构建的重要参数。由于早期对水体富营养化问题的高度重视,目前国内外对流域面源氮、磷流失特征的研究已比较成熟,并建立了泥沙富集比率计算的经验公式。然而,针对重金属这方面的研究相对滞后。不同重金属具有不同的泥沙富集比率,且受流域气候、地形、水文等条件影响。通过建立径流小区开展长期定位观测试验,国外学者已开展了不同重金属泥沙富集比率的研究工作。相比之下,我国的农业面源污染研究起步总体较晚,至今尚没有建立全面系统的数据库。同时,由于很多地区不具备开展现场长期观测试验的条件,部分学者在进行流域面源重金属流失特征研究时大都直接参考国外已有的泥沙富集比率研究成果,从而增加了研究的不确定性。沉积物作为流域物质的最终“汇”,可以反映整个流域尺度上的面源污染物流失特征。因此,基于沉积物分析在典型小流域建立重金属与总磷泥沙富集比率间的定量关系,则可在相似流域根据总磷泥沙富集比率进行重金属泥沙富集比率的推算。由于沉积物的采集与分析都十分简单易行,大大节省了在流域内建立径流小区开展长期定位观测试验的工作量。鉴于上述背景,为了更快速、高效地计算不同流域的农业面源重金属泥沙富集比率,本专利申请建立一种基于沉积物分析的流域面源重金属泥沙富集比率计算方法。选取典型流域建立面源重金属与总磷泥沙富集比率间的长期定量关系,将所得定量关系式应用于其他相似流域,在应用流域只需采集沉积物进行测定,即可由总磷泥沙富集比率快速获得应用流域的重金属泥沙富集比率。Agricultural non-point source pollution has gradually become a key factor restricting the improvement of my country's water environment quality. Various chemical substances remaining in farmland soil are the main non-point source pollutants. They will eventually enter rivers, lakes and other water bodies with the erosion of soil under rainfall conditions, thus causing a series of water environment quality problems. At present, most of the agricultural non-point source pollution research carried out in my country focuses on carbon, nitrogen, phosphorus and other nutrients, and solves the problem of eutrophication of water bodies in the river basin. However, there is still not much attention to toxic heavy metals that pose a huge threat to ecological security and human health. . To carry out research on agricultural non-point source pollution, it is necessary to clarify the characteristics of the loss of non-point source pollutants in the river basin, so as to provide technical support for the subsequent implementation of 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-grained matter, resulting in surface runoff typically enriched with more contaminants than source soil. Therefore, the sediment enrichment ratio is considered to be an important parameter for the study of the characteristics of the loss of non-point source pollutants in the basin and the construction of water quality models. Due to the high attention paid to the eutrophication of water bodies in the early days, the research on the loss characteristics of non-point source nitrogen and phosphorus in the watershed has been relatively mature at home and abroad, and an empirical formula for the calculation of the sediment enrichment ratio has been established. However, research on this aspect of heavy metals is relatively lagging behind. Different heavy metals have different sediment enrichment ratios, and are affected by the basin climate, topography, hydrology and other conditions. Through the establishment of runoff plots to carry out long-term positioning observation experiments, foreign scholars have carried out research work on the enrichment ratio of different heavy metal sediments. In contrast, the research on agricultural non-point source pollution in my country started relatively late, and a comprehensive and systematic database has not yet been established. At the same time, since many areas do not have the conditions for carrying out long-term field observation experiments, some scholars directly refer to the existing research results of sediment enrichment ratio abroad when conducting research on the loss characteristics of heavy metals from non-point sources in the basin, which increases the uncertainty of the research. . As the final "sink" of watershed materials, sediments can reflect the loss characteristics of non-point source pollutants on the whole watershed scale. Therefore, by establishing a quantitative relationship between heavy metals and total phosphorus sediment enrichment ratios in typical small watersheds based on sediment analysis, the heavy metal sediment enrichment ratios can be estimated based on the total phosphorus sediment enrichment ratios in similar watersheds. Since the collection and analysis of sediments are very simple and easy, the workload of establishing runoff plots in the basin to carry out long-term positioning observation experiments is greatly saved. In view of the above background, in order to calculate the agricultural non-point source heavy metal sediment enrichment ratio in different watersheds more quickly and efficiently, this patent application establishes a method for calculating the basin non-point source heavy metal sediment enrichment ratio based on sediment analysis. Select typical watersheds to establish a long-term quantitative relationship between non-point source heavy metals and total phosphorus sediment enrichment ratio, and apply the obtained quantitative relationship to other similar watersheds. Accumulation ratio to quickly obtain the heavy metal sediment enrichment ratio of the application watershed.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供基于沉积物分析的流域面源重金属泥沙富集比率计算方法,本发明的有益效果是只需在一个典型流域基于沉积物分析建立面源重金属与总磷泥沙富集比率间的长期定量关系,就能将关系式应用到其它相似流域,快速获取应用流域的面源重金属泥沙富集比率。The purpose of the present invention is to provide a method for calculating the enrichment ratio of non-point source heavy metals and sediments in a river basin based on sediment analysis. The long-term quantitative relationship between the ratios can be applied to other similar watersheds, and the enrichment ratio of non-point source heavy metal sediments in the applied watershed can be quickly obtained.

本发明所采用的技术方案是按照以下步骤进行:The technical scheme adopted in the present invention is to carry out according to the following steps:

步骤1:选取典型小流域;Step 1: Select a typical small watershed;

步骤2:采集沉积物柱芯,测定不同沉积深度层重金属、总磷含量值以及210Pbex活度值;Step 2: Collect sediment cores, and measure heavy metals, total phosphorus content and 210 Pb ex activity values in layers with different deposition depths;

步骤3:测定不同深度层质量沉积速率值以及重金属、总磷的沉积通量值;Step 3: Determine the quality deposition rate value of different depth layers and the deposition flux value of heavy metals and total phosphorus;

步骤4:建立流域重金属与总磷沉积通量值间的长期定量关系;Step 4: Establish a long-term quantitative relationship between heavy metals and total phosphorus deposition flux values in the basin;

步骤5:采集流域背景土壤并测定其中重金属、总磷含量值;Step 5: Collect the background soil of the watershed and determine the content of heavy metals and total phosphorus in it;

步骤6:建立流域重金属与总磷泥沙富集比率间的长期定量关系。Step 6: Establish a long-term quantitative relationship between heavy metals in the basin and the enrichment ratio of total phosphorus and sediment.

进一步,步骤1选取典型小流域作为研究区,为了保证沉积物采集的顺利进行,流域出口需要具有便于沉积物采集的相对稳定的沉积环境;其次,为将研究得到的计算公式推广到其他相似流域以进行其他流域面源重金属富集比率的计算,所选取流域还必须具有代表性,其所具备的气候、地形、水文以及所涵盖的土地利用类型、土壤类型与背景值都需具备代表性。Further, step 1 selects a typical small watershed as the study area. In order to ensure the smooth progress of sediment collection, the outlet of the watershed needs to have a relatively stable sedimentary environment that is convenient for sediment collection; secondly, in order to extend the calculation formula obtained in the study to other similar watersheds In order to calculate the heavy metal enrichment ratio of non-point sources in other watersheds, the selected watershed must also be representative, and its climate, topography, hydrology, as well as the land use types, soil types and background values covered must be representative.

进一步,步骤2使用柱状采样器在流域出口获取沉积物柱芯,现场按1cm厚度小心分割装袋。样品带回实验室后自然风干,玛瑙研磨过100目尼龙筛,经HNO3-HF-HClO4法消解后采用电感耦合等离子发射光谱仪测定重金属与总磷含量值,采用高纯锗低本底γ能谱仪测定210Pbex(大气来源210Pb)活度值。Further, in step 2, a columnar sampler was used to obtain the sediment core at the outlet of the watershed, and it was carefully divided and bagged at a thickness of 1 cm on site. After the samples were brought back to the laboratory, they were naturally air-dried, and the agate was ground through a 100-mesh nylon sieve. After being digested by the HNO 3 -HF-HClO 4 method, inductively coupled plasma emission spectrometer was used to determine the content of heavy metals and total phosphorus. The activity value of 210 Pb ex (atmospheric source 210 Pb) was determined by energy spectrometer.

进一步,步骤3基于步骤2中得到的不同沉积深度层210Pbex活度值,应用CRS(Constant Rate Supply)模型计算各层的质量沉积速率值。质量沉积速率计算公式为:Further, in step 3, based on the 210 Pb ex activity values of the layers with different deposition depths obtained in step 2, the CRS (Constant Rate Supply) model is applied to calculate the mass deposition rate values of each layer. The formula for calculating the mass deposition rate is:

Figure GDA0003625273760000031
Figure GDA0003625273760000031

其中R(Z)为Z深度层的质量沉积速率(mg/cm2·a);I(Z)为深度Z以下各沉积层的210Pbex累积量(Bq/cm2);A(Z)为Z深度层的210Pbex活度(Bq/kg);λ为210Pb衰变常数(0.03114/a)。where R(Z) is the mass deposition rate of the Z depth layer (mg/cm 2 ·a); I(Z) is the cumulative amount of 210 Pb ex (Bq/cm 2 ) of each deposited layer below the depth Z; A(Z) is the 210 Pb ex activity (Bq/kg) in the Z-depth layer; λ is the 210 Pb decay constant (0.03114/a).

将各沉积深度层的质量沉积速率值与步骤2中测定的重金属与总磷含量值分别相乘,计算它们的流域沉积通量值。沉积通量计算公式为:Multiply the mass deposition rate value of each deposition depth layer and the heavy metal and total phosphorus content values determined in step 2, respectively, to calculate their drainage flux values. The formula for calculating the deposition flux is:

S(Z)=R(Z)×C(Z)S(Z)=R(Z)×C(Z)

其中S(Z)为Z深度层的沉积通量(ug/cm2·a);R(Z)为Z深度层的质量沉积速率(mg/cm2·a);C(Z)为Z深度层的浓度含量(mg/kg)。where S(Z) is the deposition flux of the Z-depth layer (ug/cm 2 ·a); R(Z) is the mass deposition rate of the Z-depth layer (mg/cm 2 ·a); C(Z) is the Z-depth layer Concentration content of the layer (mg/kg).

进一步,步骤4基于步骤3中得到的不同深度层重金属与总磷沉积通量值,应用回归分析建立它们之间的长期定量关系。定量关系的公式形式为y=ax+b,其中y为重金属沉积通量值,x为总磷沉积通量值,a和b为公式中的常数。Further, in step 4, based on the deposition flux values of heavy metals and total phosphorus at different depths obtained in step 3, regression analysis is applied to establish a long-term quantitative relationship between them. The formula for the quantitative relationship is y=ax+b, where 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.

进一步,步骤5在整个流域范围内采集若干背景土壤样品。实验室内风干、研磨过筛后,经HNO3-HF-HClO4法消解后采用电感耦合等离子发射光谱仪测定重金属与总磷含量值。Further, step 5 collects several background soil samples in the whole watershed. After air-drying, grinding and sieving in the laboratory, after digestion by HNO 3 -HF-HClO 4 method, inductively coupled plasma emission spectrometer was used to determine the content of heavy metals and total phosphorus.

进一步,步骤6基于步骤4中得到的流域重金属与总磷沉积通量值间的长期定量关系、步骤5中得到的流域土壤背景值,应用吸附态污染物迁移经验模型建立流域面源重金属与总磷泥沙富集比率间的长期定量关系。Further, in step 6, based on the long-term quantitative relationship between heavy metals and total phosphorus deposition flux values in the watershed obtained in step 4, and the background soil value of the watershed obtained in step 5, an empirical model for the migration of adsorbed pollutants is used to establish the relationship between heavy metals in non-point sources and total phosphorus in the watershed. Long-term quantitative relationship between phosphorus and sediment enrichment ratios.

吸附态污染物迁移经验模型为:The empirical model for the migration of adsorbed pollutants is:

L=C×Q×ηL=C×Q×η

其中L为吸附态流失负荷(g/km2);C为流域土壤背景值(mg/kg);Q为流域土壤侵蚀量(t/km2),η为泥沙富集比率(无量纲)。Among them, L is the adsorption loss load (g/km 2 ); C is the background soil value of the watershed (mg/kg); Q is the soil erosion amount of the watershed (t/km 2 ), and η is the sediment enrichment ratio (dimensionless) .

流域重金属与总磷泥沙富集比率间的长期定量关系公式为:The long-term quantitative relationship between heavy metals and total phosphorus sediment enrichment ratio in the basin is as follows:

Figure GDA0003625273760000041
Figure GDA0003625273760000041

其中ηi为流域重金属i的泥沙富集比率(无量纲);η总磷为流域总磷的泥沙富集比率(无量纲);Li为流域重金属i的吸附态流失负荷(g/km2);L总磷为流域总磷的吸附态流失负荷(g/km2);Ai为流域重金属i与总磷的土壤背景值之比(无量纲);a和b为流域重金属与总磷沉积通量值定量关系公式中的常数;x为总磷沉积通量值(ug/cm2·a)。Among them, η i is the sediment enrichment ratio of heavy metal i in the basin (dimensionless); ηtotal phosphorus is the sediment enrichment ratio of total phosphorus in the basin (dimensionless); Li is the adsorption loss load of heavy metal i in the basin (g/ km 2 ); L total phosphorus is the adsorbed loss load of total phosphorus in the watershed (g/km 2 ); A i is the ratio of heavy metal i and total phosphorus in the watershed to the soil background value (dimensionless); a and b are the heavy metals and the total phosphorus in the watershed The constant in the quantitative relationship formula of total phosphorus deposition flux value; x is the total phosphorus deposition flux value (ug/cm 2 ·a).

其中,待计算流域的x通过步骤2、3得到,η总磷根据Menzel R.G提出的经验公式得到。η总磷的经验计算公式为:Among them, x of the watershed to be calculated is obtained through steps 2 and 3, and η total phosphorus is obtained according to the empirical formula proposed by Menzel RG. The empirical calculation formula of ηtotal phosphorus is:

lnη总磷=2-0.2×lnQlnηtotal phosphorus =2-0.2×lnQ

其中η总磷为流域总磷的泥沙富集比率(无量纲);Q为流域土壤侵蚀量(t/km2)。Among them, ηtotal phosphorus is the sediment enrichment ratio (dimensionless) of total phosphorus in the watershed; Q is the soil erosion amount (t/km 2 ) in the watershed.

附图说明Description of drawings

图1为基于沉积物分析的流域面源重金属泥沙富集比率计算方法流程框图;Fig. 1 is a flow chart of the method for calculating the enrichment ratio of heavy metal sediments from non-point sources in the basin based on sediment analysis;

图2为流域重金属与总磷沉积通量变化示意图;Figure 2 is a schematic diagram of the changes in the deposition fluxes of heavy metals and total phosphorus in the watershed;

图3为流域重金属与总磷沉积通量相关性示意图。Figure 3 is a schematic diagram of the correlation between heavy metals and total phosphorus deposition flux in the watershed.

具体实施方式Detailed ways

下面结合具体实施方式对本发明进行详细说明。The present invention will be described in detail below with reference to specific embodiments.

如图1所示为基于沉积物分析的流域面源重金属泥沙富集比率计算方法流程框图,实施步骤如下:Figure 1 shows the flow chart of the calculation method for the enrichment ratio of heavy metals in non-point sources in the basin based on sediment analysis. The implementation steps are as follows:

步骤1step 1

本案例选择位于我国沂蒙山区沂河上游的孟良崮小流域作为实例分析。该农业小流域在沂蒙山区具有代表性,林地和耕地面积占到全流域面积的70%以上,不存在明显的工业污染源。In this case, the Menglianggu small watershed located in the upper reaches of the Yihe River in the Yimeng Mountains of my country is selected as an example for analysis. This small agricultural watershed is representative in the Yimeng Mountains, with forest land and arable land accounting for more than 70% of the total watershed area, and there is no obvious source of industrial pollution.

步骤2Step 2

经前期实地调查后在该流域出口上游约1km处使用柱状采样器获取25cm深沉积物柱芯,现场按1cm厚度小心分割装袋。样品带回实验室后自然风干,玛瑙研磨过100目尼龙筛,经HNO3–HF–HClO4法消解后采用电感耦合等离子发射光谱仪测定重金属与总磷含量值,采用高纯锗低本底γ能谱仪测定210Pbex(大气来源210Pb)活度值。以Pb、Cu两种重金属为例,不同沉积深度层测定结果见表1。由表可知,Pb含量范围为29.86-37.98mg/kg,Cu含量范围为34.84-47.07mg/kg,总磷含量范围为398.02-1381.28mg/kg,210Pbex活度范围为4.15-12.12Bq/kg。本方法不局限于上述两种重金属,同样适用沉积物测定的其他重金属。After the preliminary field investigation, a columnar sampler was used to obtain a 25cm-deep sediment core at about 1km upstream of the outlet of the watershed, and it was carefully divided and bagged at a thickness of 1cm on site. After the samples were brought back to the laboratory, they were naturally air-dried, and the agate was ground through a 100-mesh nylon sieve. After being digested by the HNO 3 -HF-HClO 4 method, the content of heavy metals and total phosphorus was determined by inductively coupled plasma emission spectrometer. High-purity germanium with low background γ was used. The activity value of 210 Pb ex (atmospheric source 210 Pb) was determined by energy spectrometer. Taking Pb and Cu as an example, the measurement results of layers with different deposition depths are shown in Table 1. It can be seen from the table that the Pb content range is 29.86-37.98mg/kg, the Cu content range is 34.84-47.07mg/kg, the total phosphorus content range is 398.02-1381.28mg/kg, and the 210 Pb ex activity range is 4.15-12.12Bq/ kg. This method is not limited to the above two heavy metals, and is also applicable to other heavy metals measured in sediments.

表1不同沉积深度层重金属、总磷含量值以及210Pbex活度值Table 1 Heavy metals, total phosphorus content and 210 Pb ex activity values in layers with different deposition depths

Figure GDA0003625273760000051
Figure GDA0003625273760000051

Figure GDA0003625273760000061
Figure GDA0003625273760000061

步骤3Step 3

基于步骤2中得到的不同沉积深度层210Pbex活度值,应用CRS模型计算得到各层的质量沉积速率值。质量沉积速率计算公式为:Based on the 210 Pb ex activity values of the layers with different deposition depths obtained in step 2, the CRS model was used to calculate the mass deposition rate values of each layer. The formula for calculating the mass deposition rate is:

Figure GDA0003625273760000062
Figure GDA0003625273760000062

其中R(Z)为Z深度层的质量沉积速率(mg/cm2·a);I(Z)为深度Z以下各沉积层的210Pbex累积量(Bq/cm2);A(Z)为Z深度层的210Pbex活度(Bq/kg);λ为210Pb衰变常数(0.03114/a)。where R(Z) is the mass deposition rate of the Z depth layer (mg/cm 2 ·a); I(Z) is the cumulative amount of 210 Pb ex (Bq/cm 2 ) of each deposited layer below the depth Z; A(Z) is the 210 Pb ex activity (Bq/kg) in the Z-depth layer; λ is the 210 Pb decay constant (0.03114/a).

将各沉积深度层的质量沉积速率值与步骤2中测定的Pb、Cu、总磷含量值分别相乘,得到它们的流域沉积通量值。沉积通量计算公式为:Multiply the mass deposition rate value of each deposition depth layer with the Pb, Cu, and total phosphorus content values determined in step 2 to obtain their drainage flux values. The formula for calculating the deposition flux is:

S(Z)=R(Z)×C(Z)S(Z)=R(Z)×C(Z)

其中S(Z)为Z深度层的沉积通量(ug/cm2·a);R(Z)为Z深度层的质量沉积速率(mg/cm2·a);C(Z)为Z深度层的浓度含量(mg/kg)。where S(Z) is the deposition flux of the Z-depth layer (ug/cm 2 ·a); R(Z) is the mass deposition rate of the Z-depth layer (mg/cm 2 ·a); C(Z) is the Z-depth layer Concentration content of the layer (mg/kg).

如图2所示,Pb沉积通量为13.93-23.10ug/cm2·a,Cu沉积通量为16.73-26.36ug/cm2·a,总磷沉积通量为191.03-814.23ug/cm2·a。根据该沉积物柱芯反映的年代时序,流域Pb、Cu两种重金属与总磷的沉积通量历史变化趋势大体一致,其最低值均出现在1978年,而最高值出现在2008年附近。As shown in Figure 2, the Pb deposition flux is 13.93-23.10ug/cm 2 ·a, the Cu deposition flux is 16.73-26.36ug/cm 2 ·a, and the total phosphorus deposition flux is 191.03-814.23ug/cm 2 ·a a. According to the chronological time series reflected by the sediment core, the historical trends of the sedimentary fluxes of Pb and Cu and total phosphorus in the basin are roughly the same.

步骤4Step 4

基于步骤3中得到的不同深度层Pb、Cu与总磷沉积通量值,应用回归分析建立它们之间的长期定量关系。如图3所示,流域Pb、Cu与总磷沉积通量值间均存在很好的相关性,其R2值分别为0.70、0.83,这表明它们之间有着相似的流失特征。获得定量关系公式分别为:Based on the deposition flux values of Pb, Cu and total phosphorus at different depth layers obtained in step 3, regression analysis was applied to establish a long-term quantitative relationship between them. As shown in Fig. 3, there is a good correlation between Pb, Cu and total phosphorus deposition flux values in the watershed, and their R 2 values are 0.70 and 0.83, respectively, indicating that they have similar loss characteristics. The quantitative relationship formulas obtained are:

Pb:y=0.0080x+14.881Pb: y=0.0080x+14.881

Cu:y=0.0125x+16.057Cu: y=0.0125x+16.057

其中y为重金属沉积通量值(ug/cm2·a);x为总磷沉积通量值(ug/cm2·a)。Wherein y is the heavy metal deposition flux value (ug/cm 2 ·a); x is the total phosphorus deposition flux value (ug/cm 2 ·a).

步骤5Step 5

在整个流域范围内采集若干100-120cm深天然林地土壤样品。实验室内风干、研磨过筛后,经HNO3–HF–HClO4法消解后采用电感耦合等离子发射光谱仪测定重金属与总磷含量值。流域Pb土壤背景含量为20.37mg/kg,Cu背景含量为21.82mg/kg,总磷背景含量为664.27mg/kg。Several 100-120 cm deep natural woodland soil samples were collected throughout the watershed. After air-drying, grinding and sieving in the laboratory, after digestion by HNO 3 -HF-HClO 4 method, the inductively coupled plasma emission spectrometer was used to determine the content of heavy metals and total phosphorus. The background content of Pb in the watershed soil was 20.37 mg/kg, the background content of Cu was 21.82 mg/kg, and the background content of total phosphorus was 664.27 mg/kg.

步骤6Step 6

基于步骤4中得到的流域Pb、Cu与总磷沉积通量值间的长期定量关系、步骤5中得到的土壤背景值,应用吸附态污染物迁移经验模型建立流域面源Pb、Cu与总磷泥沙富集比率间的长期定量关系。获得定量关系公式分别为:Based on the long-term quantitative relationship between Pb, Cu and total phosphorus deposition flux values in the watershed obtained in step 4, and the soil background value obtained in step 5, an empirical model for the migration of adsorbed pollutants was used to establish the non-point source Pb, Cu and total phosphorus in the watershed Long-term quantitative relationship between sediment enrichment ratios. The quantitative relationship formulas obtained are:

Figure GDA0003625273760000071
Figure GDA0003625273760000071

Figure GDA0003625273760000072
Figure GDA0003625273760000072

其中ηPb为流域Pb的泥沙富集比率(无量纲);ηCu为流域Cu的泥沙富集比率(无量纲);η总磷为流域总磷的泥沙富集比率(无量纲);x为流域总磷沉积通量值(ug/cm2·a)。where η Pb is the sediment enrichment ratio of Pb in the watershed (dimensionless); η Cu is the sediment enrichment ratio of Cu in the watershed (dimensionless); ηtotal phosphorus is the sediment enrichment ratio of total phosphorus in the watershed (dimensionless) ; x is the total phosphorus deposition flux value in the basin (ug/cm 2 ·a).

在待计算流域采集沉积物,测定沉积物中总磷浓度含量值和质量沉积速率值,计算得到总磷沉积通量值,并将由已有经验公式获得的η总磷值带入上述关系式即可得到待计算流域当年的Pb、Cu泥沙富集比率。Collect sediments in the watershed to be calculated, measure the total phosphorus concentration and mass deposition rate in the sediments, calculate the total phosphorus deposition flux value, and put the η total phosphorus value obtained from the existing empirical formula into the above relationship, namely The Pb and Cu sediment enrichment ratios of the watershed to be calculated in the current year can be obtained.

本发明选取典型小流域;采集沉积物柱芯,测定不同沉积深度层重金属、总磷含量值以及210Pbex活度值;测定不同深度层质量沉积速率值以及重金属、总磷的沉积通量值;建立流域重金属与总磷沉积通量值间的长期定量关系;采集流域背景土壤并测定其中重金属与总磷含量值;建立流域重金属与总磷泥沙富集比率间的长期定量关系。本发明优点还在于:一、只需在典型小流域建立重金属与总磷泥沙富集比率间的长期定量关系,便可将公式应用于其他相似流域进行重金属泥沙富集比率的计算;二、建立计算公式后,在应用流域只需采集沉积物进行测定,即可由总磷泥沙富集比率计算该流域当年的重金属泥沙富集比率,简单易行。The present invention selects typical small watersheds; collects sediment cores, measures heavy metals, total phosphorus content values and 210 Pb ex activity values in different deposition depth layers; ; Establish the long-term quantitative relationship between heavy metals and total phosphorus deposition flux in the watershed; collect background soil in the watershed and determine the content of heavy metals and total phosphorus; establish long-term quantitative relationship between heavy metals and total phosphorus and sediment enrichment ratios in the watershed. The invention also has the following advantages: 1. only need to establish a long-term quantitative relationship between heavy metals and total phosphorus sediment enrichment ratios in typical small watersheds, and the formula can be applied to other similar watersheds to calculate the heavy metal sediment enrichment ratios; 2. . After the calculation formula is established, the sediment enrichment ratio of the current year in the basin can be calculated from the total phosphorus sediment enrichment ratio only by collecting sediments in the application basin, which is simple and easy to implement.

以上所述仅是对本发明的较佳实施方式而已,并非对本发明作任何形式上的限制,凡是依据本发明的技术实质对以上实施方式所做的任何简单修改,等同变化与修饰,均属于本发明技术方案的范围内。The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention belong to the present invention. within the scope of the technical solution of the 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:
Figure FDA0003625273750000011
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:
Figure FDA0003625273750000021
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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