CN110726684A - Method for determining dredging depth of river sediment based on polycyclic aromatic hydrocarbon and heavy metal pollution - Google Patents
Method for determining dredging depth of river sediment based on polycyclic aromatic hydrocarbon and heavy metal pollution Download PDFInfo
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Abstract
The invention relates to a method for determining the dredging depth of river sediment based on polycyclic aromatic hydrocarbon and heavy metal pollution, which mainly comprises the following three steps: the method comprises the steps of sample collection and analysis, pollutant ecological risk analysis, calculation of the dredging depth of the sediment based on the ecological risks of the polycyclic aromatic hydrocarbon and the heavy metal, and calculation of the optimal dredging depth of the sediment. The river sediment dredging mainly aims to reduce the accumulation of polycyclic aromatic hydrocarbons and heavy metals in river sediment so as to reduce the quantity of the polycyclic aromatic hydrocarbons and the heavy metals released into an upper water body and further avoid the damage to the ecological environment. The key of sediment dredging is the determination of the dredging depth, and the critical dredging depth method provided by the invention can quickly and accurately obtain the dredging depth of the sediment in the river channel.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a method for determining the dredging depth of river sediment based on polycyclic aromatic hydrocarbon and heavy metal pollution.
Background
Polycyclic aromatic hydrocarbons and heavy metals are important pollutants to be controlled in the dredging of river sediment, and harm the ecological system of a water body and the health of residents. Polycyclic aromatic hydrocarbons typically contain up to 10 aromatic ring organic compounds, which are produced by high temperature reactions such as incomplete combustion and pyrolysis of fossil fuels and other organic materials, and the release of petroleum and petroleum products. The sediment is used as a pollutant enrichment place and can absorb pollutants in the water body, so that PAHs and heavy metals are usually removed from the water body through sedimentation. Contaminants in sediment can affect fresh water quality and induce accumulation of the food chain of the upper and lower layers leading to long-term changes in the biota. In recent years, extensive research on polycyclic aromatic hydrocarbons and heavy metals in sediments such as lakes, rivers, oceans and the like is carried out at home and abroad, and certain progress is made in the evaluation of distribution characteristics and ecological risks.
However, the sediment is a potential pollution source, and corresponding measures must be taken to control the sediment in order to prevent secondary pollution. At present, the method for removing organic pollutants in sediments mainly comprises traditional repair technologies such as dredging and capping, and biological technologies such as biological enhancement and phytoremediation. Dredging is widely applied in all countries of the world because of the capability of permanently removing pollutants, and related technologies are mature. Wherein the dredging depth is an important parameter. The dredging technology is large in cost and investment, the required cost can be reduced by using a small dredging depth, and the aim of reducing the toxicity of polycyclic aromatic hydrocarbon and heavy metal is fulfilled, so that the establishment of the reasonable dredging depth is very important. However, at the present stage, no clear scheme exists for determining the dredging depth for reducing the concentration of the polycyclic aromatic hydrocarbon and the heavy metal.
The river sediment dredging mainly aims to reduce the accumulation of polycyclic aromatic hydrocarbons and heavy metals in river sediment so as to reduce the quantity of the polycyclic aromatic hydrocarbons and the heavy metals released into an upper water body, thereby avoiding the damage to the ecological environment. The key of sediment dredging is the determination of the dredging depth, and the critical dredging depth method provided by the invention can quickly and accurately obtain the dredging depth of the sediment in the river channel.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for determining the dredging depth of river sediment based on polycyclic aromatic hydrocarbon and heavy metal pollution.
A method for determining the dredging depth of river sediment based on polycyclic aromatic hydrocarbon and heavy metal pollution mainly comprises the following three steps: collecting samples, analyzing ecological risks of pollutants, calculating the dredging depth of the sediment based on the ecological risks of the polycyclic aromatic hydrocarbon and the heavy metal, and calculating the optimal dredging depth of the sediment. Wherein the step 1 of sample collection comprises the following steps:
step 1(a) carrying out layered sampling on the bottom mud of a river channel at a specified place, and taking a mud sample from the surface layer of the bottom mud downwards at each sampling point at intervals of 10cm to obtain a plurality of sediment samples;
step 1(b) spreading the collected bottom mud sample on a glass ware in time, naturally drying the bottom mud sample in a shade place with strong air fluidity, removing foreign matters such as gravels, garbage wastes, animal and plant residues and the like in the sample, crushing the bottom mud sample by using a wood stick, sieving the bottom mud sample to remove sand and stones with the particle size of more than 2mm, mixing the bottom mud sample and the foreign matters, grinding the mixture by using a mortar and a ring sieve (100 meshes) to obtain a finer soil sample, and then sealing and storing the soil sample.
Step 1(c) the sample is laid on clean A4 paper and is naturally dried in the place where the sunlight can not be directly emitted. Air-drying, removing grass roots and small stones in the samples, grinding by using a mortar, weighing 2g of soil samples (surface soil samples are mixed into one sample by equal mass of 4 samples collected in the same region), adding 15mL of dichloromethane, carrying out ultrasonic extraction for 1h in ultrasonic water bath, centrifuging for 5 minutes at 2500rpm, purifying 2mL of supernate by using 2.5g of silica gel column, eluting twice by using dichloromethane and n-hexane (v/v,1/1) eluent, collecting the eluent into a 50mL round-bottom flask, adding 30 mu L of dimethyl sulfoxide, concentrating to be dry at constant temperature of 40 ℃ on a rotary evaporator, keeping the volume to be 2mL by using acetonitrile, and finally analyzing PAHs by using a high performance liquid chromatography after passing through a 0.22 mu L filter membrane.
Step 1(d) weighing 0.4g of soil sample in a 50mL polytetrafluoroethylene crucible, sequentially adding 6mL of hydrochloric acid, 5mL of nitric acid, 5mL of hydrofluoric acid and 3mL of perchloric acid, and digesting on an electric hot plate. After digestion, 3mL of 1+1 hydrochloric acid is added, the volume is adjusted to 50mL, and heavy metal is detected by an atomic absorption spectrophotometry after filtration.
The quotient method in the average benefits in the step 2(a) is widely applied to risk analysis for predicting the joint toxicity of various pollutants (such as PAHs, heavy metals and the like) in the ocean and river sediments. Solving the MERM of the PAHs through the value of the single-component PAH, analyzing the comprehensive ecological risk of the PAHs, wherein the risk analysis refers to the following formula:
wherein C isiIs the concentration of the ith PAH; n represents the number of PAHs; ERMi represents the ERM value corresponding to the ith PAH, the specific value is shown in figure 1, and the comprehensive ecological risk of the riverway is calculated by the formula (1).
And (b) applying the potential ecological hazard index method in the step 2(b) to the evaluation of the heavy metal pollution degree in soil or sediment and the evaluation of the potential ecological hazard thereof. The calculation formula of the potential ecological risk coefficient of the single heavy metal is as follows:
in the formula (I), the compound is shown in the specification,is the potential ecological risk index of the ith heavy metal;the specific numerical value is shown in figure 2, and reflects the toxicity level and the sensitivity of organisms to pollution;the pollution coefficient of the ith heavy metal is;the measured value of the heavy metal of the bottom mud at the depth h is shown;in order to calculate the required reference value, a soil environment background value is adopted, and specific numerical values are shown in the attached figure 2, so that the pollution degree of the sediment at each sampling point can be relatively reflected.
The comprehensive potential ecological risk index RI calculation formula of various heavy metals is as follows:
and 3, calculating the optimal dredging depth of the sediment based on the PAHs according to the formula (4-5) based on the MERM comprehensive ecological risk in the step 2(a) and the distribution condition of the PAHs in the researched area in the vertical direction of the sediment, wherein the optimal dredging depth of the sediment is called as the critical dredging depth.
In the formulaRepresents the optimal dredging depth based on the ecological risk of PAHs; doRepresenting the risk control level of the river sediment PAHs; d (h)i) Representing the river depth (h) corresponding to the ecological risk (D)i) (ii) a ε represents an infinitesimal positive real number; h isiThe ith sediment depth satisfying the formula (3) is expressed. In the invention, D isoThe value is 0.1, namely the ecological risk is controlled to be low or medium toxicity.
And 3, calculating the environment-friendly dredging depth based on the potential ecological risk of the single heavy metal pollutant according to a formula (6-7) by combining the distribution condition of the heavy metal of the researched area in the vertical direction of the river sediment based on the potential ecological risk of the single heavy metal pollutant in the step 2 (b).
In the formulaThe dredging depth is calculated according to the potential ecological risk coefficient of the single heavy metal pollutant;critical risk depth for ith heavy metal; n is the number of heavy metal elements;is the potential ecological risk coefficient of the ith heavy metal at the bottom mud depth h; c0
For controlling the grade value of the potential risk of single heavy metal, C is used in the invention0A value of 80, i.e. about
Ecological risk control is at medium to low risk.
Step 3(c) is based on the potential ecological wind of various heavy metal pollutants in step 2(b)
Danger is generated by combining the distribution condition of heavy metals in the vertical direction of the bottom mud of the river channel in the researched area according to a formula
(8-9) calculating the environment-friendly dredging depth based on the potential ecological risks of various heavy metal pollutants.
In the formulaCalculating the environment-friendly dredging depth according to the potential ecological risk coefficients of various heavy metal pollutants; h is0Critical risk depth; RI (h) is heavy metal at depth h of bottom mud
Synthesizing potential ecological risk indexes; c0Comprehensive risk control level for multiple heavy metalsBook, book
In the invention, C0The value is 300, namely the ecological risk is controlled to be low or medium.
Step 4, based on the three environmental-friendly dredging depths in step 3, calculating according to a formula (10)
Producing the best base based on potential ecological risks of polycyclic aromatic hydrocarbon, single heavy metal and multiple heavy metals
The dredging depth H.
The invention has the beneficial effects that:
1. based on the average benefit median quotient method and the potential ecological hazard index method, the critical dredging depth method is provided and constructed, and is detailed and practical.
2. The reasonable sediment dredging depth can be rapidly and accurately determined by using the method.
3. It is convenient to determine recommended values for the sediment dredging depth with various target pollutants.
4. Wide application range and is suitable for various polycyclic aromatic hydrocarbons and heavy metals.
5. The method for determining the dredging depth of the river sediment based on the pollution of the polycyclic aromatic hydrocarbon and the heavy metal makes up for the defects of a commonly used inflection point method in the current engineering practice. At present, the environment-friendly dredging depth determination in engineering practice mostly adopts an inflection point method, namely, an inflection point (a point at which the concentration of pollutants is suddenly reduced) is found out from the vertical distribution characteristics of the pollutants along the thickness direction of the sediment, and the thickness above the inflection point is taken as the dredging depth. However, the "inflection point method" is greatly influenced by human subjectivity. The method provided by the invention can quantitatively calculate the environment-friendly dredging depth of the river sediment, and overcomes the problem of subjectivity of the existing 'inflection point method'.
Drawings
FIG. 1 is a risk assessment value for sediment polycyclic aromatics;
FIG. 2 is a background value and a toxicity response parameter of the sediment heavy metal soil;
FIG. 3 is a graph showing the concentration distribution of PAHs in the bottom sediment of the river reach of Han bridge;
FIG. 4 is a graph showing a distribution of heavy metal concentration in bottom mud of a river section of a Han bridge;
FIG. 5 is a graph of potential ecological risks of heavy metals in the riverway of Han Jia bridge;
fig. 6 is an ecological risk map of PAHs in a bridge river.
Detailed Description
Example 1:
description of implementation site: the Yangtze river delta in the plain lake region is located in the northern part of the Hangjia lake plain, and the river channels in the plain lake region are densely distributed, and the river channels have more than 3000 river channels, the total length is about 2259km, and the water area is about 45.01km2. In recent years, with the development of industry and agriculture, a large amount of industrial and agricultural wastewater and domestic sewage are directly discharged into a water body without being treated, and the wastewater contains a large amount of heavy metals and organic pollutants, so that river water and surface sediments are polluted to different degrees.
Step 1 (a): in combination with the characteristics of the flowing area of the flat lake, the bottom mud sampler is used for sampling the bottom mud of the river channel of the Han bridge in a layered mode, each sampling point is downwards sampled from the surface layer of the bottom mud at intervals of 10cm, and the sampling points downwards sample 90cm to obtain 10 sediment samples.
Step 1(b) spreading the collected bottom mud sample on a glass ware in time, naturally drying the bottom mud sample in a shade place with strong air fluidity, removing foreign matters such as gravels, garbage wastes, animal and plant residues and the like in the sample, crushing the bottom mud sample by using a wood stick, sieving the bottom mud sample to remove sand and stones with the particle size of more than 2mm, mixing the bottom mud sample and the foreign matters, grinding the mixture by using a mortar and a ring sieve (100 meshes) to obtain a finer soil sample, and then sealing and storing the soil sample.
Step 1(c) the sample is laid on clean A4 paper and is naturally dried in the place where the sunlight can not be directly emitted. Air-drying, removing grass roots and small stones in the samples, grinding the grass roots and small stones in the samples by using a mortar, weighing 2g of soil samples (surface soil samples are mixed into one sample by adopting equal mass of 4 samples collected in the same region), adding 15mL of dichloromethane, carrying out ultrasonic extraction for 1h in ultrasonic water bath, centrifuging the mixture for 5 minutes at 2500rpm, purifying 2mL of supernate by using 2.5g of silica gel column, eluting the supernate twice by using 15mL of dichloromethane and n-hexane (v/v,1/1) eluent, collecting the eluent into a 50mL round-bottom flask, adding 30 mu L of dimethyl sulfoxide, concentrating the eluent to be dry at constant temperature of 40 ℃ on a rotary evaporator, keeping the volume to be 2mL by using acetonitrile, and finally analyzing the eluent by using a high performance liquid chromatograph after passing through a 0.22 mu L filter membrane.
Step 1(d) weighing 0.4g of soil sample in a 50mL polytetrafluoroethylene crucible, sequentially adding 6mL of hydrochloric acid, 5mL of nitric acid, 5mL of hydrofluoric acid and 3mL of perchloric acid, and digesting on an electric hot plate. After digestion, 3mL of 1+1 hydrochloric acid is added, the volume is adjusted to 50mL, and heavy metal is detected by an atomic absorption spectrophotometry after filtration.
Step 2, vertical distribution characteristics of PAHs and heavy metals in the river sediment are explored according to the samples collected in the step 1, and concentration changes of different polycyclic aromatic hydrocarbons and heavy metals in Korean bridges at different depths are shown in fig. 3 and 4. The average value of the total amount of polycyclic aromatic hydrocarbon in the Han Jiaoqiang is about 3845.99ng/g, the polycyclic aromatic hydrocarbon shows fluctuation in the vertical direction, naphthalene, acenaphthene, fluorene, benzo [ a ] anthracene and benzo [ k ] fluoranthene have extremely high content on the surface layer at the depth of 50cm and 90cm, phenanthrene also has higher content at the depth of 50cm, 70cm and 90cm, therefore, the specific pollutant emission can be inferred in the sediment deposited in the corresponding time period, and perhaps the serious pollution accident happens on the river channel at that time.
And (3) calculating the PAHs ecological risk in the vertical direction of the river sediment according to a formula (1), drawing a graph 6 according to the ecological risk value, and then calculating the critical dredging depth of the river sediment according to a formula (4-5). As can be seen from the observation of FIG. 6, the range of the vertical MERM value of Korean bridge is 0.01-0.52, which is a medium-low toxicity, and the toxicity is 30%. Calculating potential ecological risks in the vertical direction of heavy metal in the river sediment according to a formula (2-3), and drawing a graph 5 according to an ecological risk value, wherein the potential risk of heavy metal cadmium in a research area of Han Jia bridge is the largest, and the ecological risk coefficient is larger than 320, which is a very high risk; the ecological risk coefficient of the rest heavy metals is less than 40, and the potential risk level is low; the comprehensive potential risk index RI of the river channel in the research area is 400-600, and the comprehensive potential risk grade is higher risk.
And 3, determining the dredging depth of the river channel according to the ecological risk value obtained in the step 2. The dotted line in FIG. 6 is the risk control level (D)0) On the premise of monitoring the depth range and meeting the requirement of formula (4), when D is0When the dredging depth is 0.1, the dredging depth is about 60 cm; when D is present0The dredging depth is about 50cm when the depth is 0.5. Through calculation, the recommended sediment dredging depth value of the Korean bridge basin with PAHs as target pollutants is 50-60 cm. In fig. 5, two dotted lines are a single heavy metal potential risk control level value and a multiple heavy metal potential risk control level value, respectively. When C is present0When the critical risk depth of cadmium is 80, the maximum sampling depth is 90cm considering the limitation of sampling conditions, so the critical risk depth of cadmium is 90 cm; when C is present0At 300 f, the dredging depth is about 90cm, also considering the maximum depth.
And 4, determining the optimal dredging depth of the river according to the PAHs, the single heavy metal and the recommended values of the dredging depths of the heavy metal bottom mud obtained in the step 3. Through calculation, the optimal dredging depth of the bottom sediment of the Korean bridge basin with PAHs and heavy metals as target pollutants is 90 cm.
Claims (6)
1. The invention provides a method for determining the environment-friendly dredging depth of river sediment based on ecological risks of polycyclic aromatic hydrocarbon and heavy metal, which mainly comprises the three steps of river sediment sample collection, sediment pollutant ecological risk analysis, calculation of the dredging depth of the sediment based on the ecological risks of polycyclic aromatic hydrocarbon and heavy metal and calculation of the optimal dredging depth of the sediment, and is characterized in that the optimal dredging depth of the sediment is determined by calculating the critical dredging depth, and the calculation formula is as follows:
in the formulaRepresenting an optimal dredging depth; doRepresenting the risk control level of the river sediment PAHs; d (h)i) Representing the river depth (h) corresponding to the ecological risk (D)i) (ii) a ε represents an infinitesimal positive real number; h isiThe ith sediment depth satisfying the formula (2) is expressed. In the invention, D isoThe value is 0.1, namely the ecological risk is controlled to be low or medium toxicity.
In the formulaThe dredging depth is calculated according to the potential ecological risk coefficient of the single heavy metal pollutant;critical risk depth for ith heavy metal; n is the number of heavy metal elements;is the potential ecological risk coefficient of the ith heavy metal at the bottom mud depth h; c0For controlling the grade value of the potential risk of single heavy metal, C is used in the invention0And the value is 80, namely the ecological risk is controlled to be low or medium.
In the formulaCalculating the environment-friendly dredging depth according to the potential ecological risk coefficients of various heavy metal pollutants; h is0Critical risk depth; RI (h) is the comprehensive potential ecological risk index of heavy metals at the bottom mud depth h; c0For controlling the comprehensive potential risk level of various heavy metals, the invention uses C0The value is 300, namely the ecological risk is controlled to be low or medium.
Wherein H is the optimal sediment dredging depth based on polycyclic aromatic hydrocarbon, single heavy metal and potential ecological risks of multiple heavy metals.
2. The method for determining the environmental dredging depth of the river sediment based on the ecological risk of the polycyclic aromatic hydrocarbons and the heavy metals, as claimed in claim 1, is characterized in that the sample collection comprises the following steps:
(1) the method comprises the steps of sampling river sediment at a specified place in a layered mode, and taking a sediment sample from the surface layer of the sediment downwards at each sampling point at intervals of 10cm to obtain a sediment sample;
(2) spreading the collected bottom mud sample on a glass ware in time, naturally drying in the shade with strong air fluidity, removing foreign matters such as gravel, garbage wastes, animal and plant residues and the like in the sample, crushing by using a wood stick, sieving to remove sand and stone with the particle size of more than 2mm, mixing, grinding by using a mortar and a ring sieve (100 meshes) to obtain a finer soil sample, and then sealing and storing the soil sample.
(3) The samples were laid flat on clean A4 paper and allowed to air dry in sunlight. Air-drying, removing grass roots and small stones in the samples, grinding the materials in a mortar, weighing 2g of soil samples (surface soil samples are mixed into a sample by equal mass of 4 samples collected in the same region), adding 15mL of dichloromethane, carrying out ultrasonic extraction for 1h in ultrasonic water bath, centrifuging the mixture for 5 minutes at 2500rpm, purifying 2mL of supernate with 2.5g of silica gel column, eluting the mixture twice with 15mL of dichloromethane and n-hexane (v/v,1/1) eluent, collecting the eluent into a 50mL round-bottom flask, adding 30 mu L of dimethyl sulfoxide, concentrating the eluent to be dry at constant temperature of 40 ℃ on a rotary evaporator, keeping the volume to be 2mL with acetonitrile, and finally carrying out quantitative analysis on the polycyclic aromatic hydrocarbons by a high performance liquid chromatograph after passing through a 0.22 mu L filter membrane.
(4) Weighing 0.4g of soil sample in a 50mL polytetrafluoroethylene crucible, adding 6mL of hydrochloric acid, 5mL of nitric acid, 5mL of hydrofluoric acid and 3mL of perchloric acid in sequence, and digesting on an electric hot plate. After digestion, 3mL of 1+1 hydrochloric acid is added, the volume is adjusted to 50mL, and heavy metal is detected by an atomic absorption spectrophotometry after filtration.
3. The method for determining the environmental dredging depth of the river sediment based on the ecological risks of the polycyclic aromatic hydrocarbons and the heavy metals, as recited in claim 2, is characterized in that the ecological risk analysis of the sediment pollutants, namely the polycyclic aromatic hydrocarbons, adopts an average benefit median quotient method, the MERM of the PAHs is obtained through the value of the PAH of the single component, and the comprehensive ecological risk of the PAHs is analyzed.
4. The method for determining the environmental-friendly dredging depth of the river sediment based on the ecological risks of the polycyclic aromatic hydrocarbons and the heavy metals, as claimed in claim 2, is characterized in that the ecological risk analysis of the heavy metals in the sediment pollutants adopts a potential ecological hazard index method, the potential risk index is obtained through single and multiple heavy metal values, and the potential ecological risk of the heavy metals is analyzed.
5. The method as claimed in claim 3, wherein the method for determining the environment-friendly dredging depth of the river sediment based on the ecological risk of polycyclic aromatic hydrocarbons and heavy metals is characterized in that the optimal dredging depth of the river sediment is calculated according to the MERM and the following formulas (1) and (2) by combining the distribution of PAHs in the studied area in the vertical direction of the river sediment.
6. The method for determining the environmental-friendly dredging depth of the river sediment based on the ecological risks of the polycyclic aromatic hydrocarbons and the heavy metals is characterized in that the optimal dredging depth of the river sediment is calculated according to the potential risk index of the heavy metals and the distribution conditions of the heavy metals in the studied area in the vertical direction of the river sediment according to the formulas (3), (4), (5), (6) and (7).
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