CN109365498A - A kind of formula and soil treatment device reducing P in soil AHs biological effectiveness - Google Patents
A kind of formula and soil treatment device reducing P in soil AHs biological effectiveness Download PDFInfo
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- CN109365498A CN109365498A CN201811560855.4A CN201811560855A CN109365498A CN 109365498 A CN109365498 A CN 109365498A CN 201811560855 A CN201811560855 A CN 201811560855A CN 109365498 A CN109365498 A CN 109365498A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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Abstract
The invention discloses a kind of formulas and soil treatment device for reducing P in soil AHs biological effectiveness, belong to soil pollution recovery technique field.Formula of the invention is that active carbon (1%-5%) and biological nonionic surfactant saponin (0.1%-1.2%) are added to PAHs contaminated soil by a certain percentage, in the presence of active carbon, surfactant can promote the desorption of organic pollutant in soil media and finally be tightly held by activated carbon fixation, enhance the adsorption efficiency of active carbon, the formula is intended to reduce PAHs biological effectiveness and toxicity in soil, it is at low cost, high-efficient and environmental-friendly, wide prospect is provided for in-situ immobilization high concentration PAHs contaminated soil；Method proposed by the present invention based on PDMS fiber measurement P in soil AHs biological effectiveness can effectively survey the biological effectiveness of PAHs in soil, and overcoming conventional physical chemical method, time-consuming, is influenced by extraction conditions, the problem that test result is unstable.
Description
Technical field
The present invention relates to soil pollution recovery technique fields more particularly to a kind of P in soil AHs biological effectiveness of reducing to match
Side and soil treatment device.
Background technique
The aromatic hydrocarbons that polycyclic aromatic hydrocarbon (abbreviation PAHs) is made of two or more fused benzene rings, tool
There are strong mutagenesis, carcinogenic and teratogenesis, soil is the final whereabouts of PAHs in environment, and coking, petroleum, coal gas, timber add
PAHs pollution is the most universal in the industrial sites such as work, therefore, particularly important to the reparation of PAHs contaminated soil.It is adsorbed using carbonaceous
It is a kind of relatively new restorative procedure that material, which reduces pollutant method of migration in soil or bed mud, and this method utilizes work
Noxious pollutant in medium is transformed into the substance of low-solubility, hypotoxicity and Hypomobility by property charcoal, is had to reduce its biology
Effect property.Transition process of the pollutant from soil matrix to active carbon is the pollution that pollutant is desorbed from soil media, desorbed
Object migrates to active carbon, pollutant from liquid phase and is tightly held by activated carbon isolation.Surfactant is a kind of while having hydrophilic-parent
The surface reactive material of rouge characteristic, can by activation, solubilising, enhancing absorption, the effects of regulate and control organic pollutant in native water termination
Adsorption-desorption behavior, adding a certain amount of surfactant in the presence of active carbon in soil can promote in soil media
The desorption of organic pollutant, since the suction-operated of active carbon is much higher than soil media, the pollutant desorbed is finally active
Charcoal absorption is fixed.
Currently, the appraisal procedure of common soil pollutant biological effectiveness mainly includes physico-chemical process and biology
Method, for example mild solvent extraction of traditional physico-chemical process, Tenax extraction, cyclodextrin extraction etc. are former using " bionics "
Reason is extracted by the organic pollutant of adsorption by soil, and to simulate absorption of the organism to pollutant, but these methods can not will have by oneself
Solubilised state and the organic pollutant being adsorbed on dissolved organic carbon are kept completely separate, and the biological effectiveness for being easy to over-evaluate pollutant contains
Amount, and it is unstable with test result to be affected by extraction conditions.Object method is to be exposed to contaminated soil by directly testing
The content of pollutant is assessed in the organisms such as middle invertebrate, zoobenthos, and this method can more intuitively characterize pollution
The biological effectiveness of object, but time-consuming, and assessment result is affected by species and exposure duration etc..
PDMS(dimethyl silicone polymer) fiber is a kind of typical hydrophobic silicones material, has to hydrophobic organic compound
Stronger adsorption capacity, PDMS fiber are the quartz fibres that surface is coated with certain thickness dimethyl silicone polymer coating.PDMS is fine
Organic pollutant when dimension is contacted with pedotheque in soil pore water can be entered in PDMS polymer by diffusion to be inhaled
It receives, reaching can be desorbed after balancing by solvent elution quick and completely, further measured pollution concentration in eluent and be based on flat
The theory of distribution that weighs surveys the content of free dissolved pollutant in soil pore water, i.e. biological effectiveness concentration.The sampling of this method collection,
One is extracted and is enriched in, easy to operate, balance is quickly and amount of samples is less, can effectively assess PAHs biologically effective in soil
Property.
Summary of the invention
The purpose of the present invention is to solve at high cost, processes present in traditional " source removal " soil pollution recovery technique
It is complicated and to present in the big problem of soil disturbance and conventional soil pollution biological effectiveness appraisal procedure by extracting item
Part, species, exposure duration influence the problem of limitations such as big and test result is unstable, and a kind of reduction soil proposed
The formula and soil treatment device of PAHs biological effectiveness.
To achieve the goals above, present invention employs following technical solutions:
A kind of formula reducing P in soil AHs biological effectiveness, comprising the following steps:
S1, from coke-oven plant acquire PAHs contaminated soil, by contaminated soil sample it is In Shade carry out it is air-dried, using a kind of drop
The soil treatment device of low P in soil AHs biological effectiveness by soil root system of plant and the impurity such as chad reject, smash it through
200-300 mesh is packed into be placed under 4 DEG C of environment in valve bag and be kept in dark place；
S2, PDMS fiber is taken out, is cut into the PDMS segment of fiber of 2-5cm length, PDMS segment of fiber methanol solution is impregnated into 24-
25h is cleaned by ultrasonic 2-3 times, each 10-20min with the deionized water after sterilizing after immersion, is dried rear spare；
S3, using the brown chromatogram bottle of 20-25mL as reaction vessel, and the PAHs pollution that weighs in a certain amount of S1 that treated
Soil is placed in reaction vessel, uses active carbon and surfactant as reducing matching for PAHs biological effectiveness in contaminated soil
Side, is added to reaction vessel respectively by active carbon and surfactant with the ratio of the 1%-5% of soil quality and 0.1%-1.2%
In, it stirs evenly；
S4, the deionized water after suitable sterilizing is added in mixture into S3 according to the ratio that solid-to-liquid ratio is 1:3-1:4, matches
It is set to slurry liquid, and is separately added into suitable sodium azide (NaN into mud2) and calcium chloride (CaCl2), make the concentration be respectively
25mg/L and 0.01mol/L；
Treated in S5, taking-up S2, and PDMS fiber is put into reaction vessel, is tightened reaction vessel bottle cap, is placed in turnover oscillator
On, temperature setting is 25 ± 1 DEG C in turnover oscillator, and revolving speed is set as 30-35rpm, and be protected from light concussion terminates for 28-30 days；
S6, PDMS fiber is taken out out of vial, the particulate matter for being attached to PDMS fiber surface is wiped with hygenic towelette, is cut into 1-
The PDMS segment of fiber of 1.5cm long is put into glass interpolation pipe of the 150-250 μ L with polymer support, then with glass interpolation pipe
It is put into the brown chromatography column feed materials bottle of 2mL together, 100-200 μ L acetonitrile and 1-2 μ L internal standard solution is added in interpolation pipe, tightens bottle
Lid, be vortexed concussion, and the liquid after concussion crosses 0.22 μm of glass fiber filter, carries out PAHs using high performance liquid chromatography after filtering
Concentration determination；
S7, finally further according to the test result of PAHs concentration in S6, calculate free solubilised state PAHs concentration in soil, i.e., in soil
PAHs biologically effective concentration.
It advanced optimizes, 110 μm of PDMS fibrous glass core diameter in the S2, outer diameter is 170 μm, PDMS coating layer thickness
30 μm, 13.5 μ L/m of PDMS coating density.
It advanced optimizes, the diameter range of active carbon granule is 25-75 μm in the S3, and moisture content 1.44%, ash contains
Amount 18.77%, specific surface area are 1095.99 ㎡/g, and pore volume is 0.59 cm3/g, average pore diameter 2.17nm.
It advanced optimizes, surfactant is nonionic biosurfactant saponin in the S3, and saponin contains
Amount is 20%-35%, and powdery is water-soluble, and the solubility in deionized water is 50mg/ml.
It advanced optimizes, the internal standard solution in the S6 is the decafluorobiphenyl of 100ppm.
It advanced optimizes, the S6 mesoscale eddies concussion setting speed is 3000rpm, and the concussion time is 3min.
It advanced optimizes, PAHs concentration in vortex leaching liquor is surveyed in the S6, calculate PAHs concentration in PDMS fiber, it is public
Formula is as follows:
。
In formula, CPDMSFor PAHs concentration in PDMS fiber, μ g/mL；C1To be surveyed PAHs concentration in vortex leaching liquor, μ g/
mL；V1For the total volume of vortex leaching liquor, μ L；ρPDMSFor the density μ L/cm of PDMS coating；LPDMSFor the total length of PDMS fiber,
cm。
It advanced optimizes, PAHs biologically effective concentration, calculation formula are as follows in soil in the S7:
。
In formula, CbioFor PAHs biologically effective concentration in soil, μ g/mL；KPDMS-waterFor PDMS coating-water partition coefficient,
ML- water/mL-PDMS coating.
A kind of soil treatment device reducing P in soil AHs biological effectiveness, has applied to a kind of reduction P in soil AHs biology
The formula of effect property, including body and separating screen device are crushed, it is fixedly connected at left and right sides of the crushing organism bottom with supporting leg top,
The pulverizer body inner lower is provided with crushing chamber, is provided with card slot on wall at left and right sides of the crushing internal body upper end,
It is flexibly connected at left and right sides of the crushing internal body upper end and separating screen device, is provided at left and right sides of the separating screen device upper end
Strip, the strip match with card slot, and the separating screen device top middle portion is fixedly installed with sub-sieve net, in the separating screen device
Impurity collecting tank is provided at left and right sides of portion, front and rear sides are provided with dirt scraping equipment slot, the scraping dirt inside the separating screen device
Device slot is internally provided with dirt scraping equipment.
Preferably, the dirt scraping equipment includes motor, is fixedly connected on the left of the motor right side central and worm screw, the snail
Bar lower surface engages connection with worm gear upper surface, and the worm gear shaft core position is fixedly connected with drive shaft one end, the drive shaft
The other end is flexibly connected with drive rod lower end, is fixedly connected on the right side of the interlocking lever upper end and connecting rod, on the left of the connecting rod
It is flexibly connected with scraping dirt bar lower end, is fixedly connected in the middle part of scraping dirt bar upper end and scraping dirt piece.
Compared with prior art, the present invention provides at a kind of formula and its soil for reducing P in soil AHs biological effectiveness
Manage device, have it is following the utility model has the advantages that
(1) present invention proposes that a certain amount of surfactant is added during activated carbon adsorption fixing soil PAHs, promotes soil
The PAHs desorption of earth medium absorption is accelerated P in soil AHs to the migration of active carbon and is finally adsorbed admittedly by strong activated carbon of sorbent
It is fixed, the limitation of single-activity charcoal adsorption technology is breached, the absorption fixed efficiency to P in soil AHs is improved, in addition, comparing
In chemical surfactant, biosurfactant has many good qualities, as hypotoxicity, high biological degradability, good environment are simultaneous
Capacitive etc., therefore with active carbon-surfactant formula secondary pollution will not be caused to soil；
(2) a kind of soil treatment device for reducing P in soil AHs biological effectiveness, the PAHs fetched from coke-oven plant is arranged in the present invention
Contaminated soil is all mostly untreated soil, and the impurity such as root system of plant and chad are often contaminated in soil, is being carried out in fact
It needs to handle contaminated soil before testing, by being provided with soil sub-sieve grinding device, while carrying out soil crushing
Impurity can be removed, by the way that dirt scraping equipment is arranged in soil sub-sieve grinding device inner upper end, be arranged in dirt scraping equipment side miscellaneous
Matter collecting tank can effectively be scraped root system of plant and chad during carrying out the filtering crushing of soil sub-sieve using scraping dirt piece
Enter in impurity collecting tank, part fine earth earth is entered in crushing chamber by sub-sieve net to be crushed, and the present invention can effectively save soil
The time of processing improves conventional efficient；
(3) method proposed by the present invention based on hydrophobic silicones coating material measurement P in soil AHs biological effectiveness, it is hydrophobic
Property Silicone Coatings Materials using easily obtain, disposable PDMS fiber at low cost.Pedotheque and PDMS fiber shake through overturning
The mode swung comes into full contact with, and the organic pollutant in soil pore water can be entered in PDMS polymer by diffusion to be inhaled
It receives, the PAHs that PDMS fiber absorbs quickly fully is desorbed by the way of being vortexed concussion solvent elution after reaching balance, is led to
The concentration for crossing pollutant in measurement PDMS fiber surveys the content of free dissolved pollutant in soil pore water, i.e. biological effectiveness
Concentration.The sampling of this method collection extracts and is enriched in one, and easy to operate, balance is quickly and amount of samples is less, overcomes tradition
Physico-chemical process is influenced by extraction conditions, test result is unstable and biological method time-consuming, by species,
The problem of exposure duration etc. is affected；
(4) formula composition that the present invention reduces PAHs biological effectiveness in contaminated soil is active carbon and surfactant, wherein
The surfactant used dissolves in for nonionic biosurfactant saponin, saponin content 20%-35%, powdery
Water, the solubility in deionized water are 50mg/ml, during addition formula, are separately added into active carbon and surfactant soap
Angle glycosides, while setting is not added with active carbon-surfactant formula blank control group, and is not added with active carbon-surface-active
The test result of agent prescription is compared, and 16 kinds of PAHs biological effectiveness concentration significantly reduce in the soil after addition formula, utilizes height
Effect liquid phase chromatogram method carries out PAHs concentration mensuration, and it is excellent that the method has that detection sensitivity is high, easy to operate and solvent usage is small etc.
Point can effectively improve detection efficiency and save experimental cost.
Detailed description of the invention
Fig. 1 is a kind of experiment flow figure of formula for reducing P in soil AHs biological effectiveness proposed by the present invention；
Fig. 2 is a kind of overall structure signal of soil treatment device for reducing P in soil AHs biological effectiveness proposed by the present invention
Figure；
Fig. 3 is a kind of plan structure signal of soil treatment device for reducing P in soil AHs biological effectiveness proposed by the present invention
Figure；
Fig. 4 is that a kind of dirt scraping equipment structure of soil treatment device for reducing P in soil AHs biological effectiveness proposed by the present invention is shown
It is intended to.
Figure label explanation:
1 crushes body, 2 supporting legs, 3 crushing chambers, 4 card slots, 5 sub-sieve nets, 6 separating screen devices, 7 strips, 8 impurity collecting tanks, 9 scraping dirts dress
It sets slot, 10 dirt scraping equipments, 11 scraping dirt pieces, 12 motors, 13 worm gears, 14 drive shafts, 15 worm screws, 16 drive rods, 17 connecting rods, 18 scrape
Dirty bar.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.
In the description of the present invention, it is to be understood that, term " on ", "lower", "front", "rear", "left", "right", "top",
The orientation or positional relationship of the instructions such as "bottom", "inner", "outside" is to be based on the orientation or positional relationship shown in the drawings, merely to just
In description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation, with
Specific orientation construction and operation, therefore be not considered as limiting the invention.
A kind of embodiment 1: formula reducing P in soil AHs biological effectiveness, which comprises the following steps:
S1, from coke-oven plant acquire PAHs contaminated soil, by contaminated soil sample it is In Shade carry out it is air-dried, using a kind of drop
The soil treatment device of low P in soil AHs biological effectiveness by soil root system of plant and the impurity such as chad reject, smash it through
200-300 mesh is packed into be placed under 4 DEG C of environment in valve bag and be kept in dark place；
S2, PDMS fiber is taken out, is cut into the PDMS segment of fiber of 2-5cm length, PDMS segment of fiber methanol solution is impregnated into 24-
25h is cleaned by ultrasonic 2-3 times, each 10-20min with the deionized water after sterilizing after immersion, is dried rear spare；
S3, using the brown chromatogram bottle of 20-25mL as reaction vessel, and the PAHs pollution that weighs in a certain amount of S1 that treated
Soil is placed in reaction vessel, uses active carbon and surfactant as reducing matching for PAHs biological effectiveness in contaminated soil
Side, is added to reaction vessel respectively by active carbon and surfactant with the ratio of the 1%-5% of soil quality and 0.1%-1.2%
In, it stirs evenly；
S4, the deionized water after suitable sterilizing is added in mixture into S3 according to the ratio that solid-to-liquid ratio is 1:3-1:4, matches
It is set to slurry liquid, and is separately added into suitable sodium azide (NaN into mud2) and calcium chloride (CaCl2), make the concentration be respectively
25mg/L and 0.01mol/L；
Treated in S5, taking-up S2, and PDMS fiber is put into reaction vessel, is tightened reaction vessel bottle cap, is placed in turnover oscillator
On, temperature setting is 25 ± 1 DEG C in turnover oscillator, and revolving speed is set as 30-35rpm, and be protected from light concussion terminates for 28-30 days；
S6, PDMS fiber is taken out out of vial, the particulate matter for being attached to PDMS fiber surface is wiped with hygenic towelette, is cut into 1-
The PDMS segment of fiber of 1.5cm long is put into glass interpolation pipe of the 150-250 μ L with polymer support, then with glass interpolation pipe
It is put into the brown chromatography column feed materials bottle of 2mL together, 100-200 μ L acetonitrile and 1-2 μ L internal standard solution is added in interpolation pipe, tightens bottle
Lid, be vortexed concussion, and the liquid after concussion crosses 0.22 μm of glass fiber filter, carries out PAHs using high performance liquid chromatography after filtering
Concentration determination；
S7, finally further according to the test result of PAHs concentration in S6, calculate free solubilised state PAHs concentration in soil, i.e., in soil
PAHs biologically effective concentration.
110 μm of PDMS fibrous glass core diameter in S2, outer diameter be 170 μm, 30 μm of PDMS coating layer thickness, PDMS coating density
13.5μL/m。
The diameter range of active carbon granule is 25-75 μm in S3, moisture content 1.44%, the ash content of coal 18.77%, specific surface area
For 1095.99 ㎡/g, pore volume is 0.59 cm3/g, average pore diameter 2.17nm.
In S3 surfactant be nonionic biosurfactant saponin, saponin content 20%-35%, powdery,
Water-soluble, the solubility in deionized water is 50mg/ml.
The decafluorobiphenyl that internal standard solution in S6 is 100ppm.
It is 3000rpm that S6 mesoscale eddies, which shakes setting speed, and the concussion time is 3min.
PAHs concentration in vortex leaching liquor is surveyed in S6, calculates PAHs concentration in PDMS fiber, and formula is as follows:
。
In formula, CPDMSFor PAHs concentration in PDMS fiber, μ g/mL；C1To be surveyed PAHs concentration in vortex leaching liquor, μ g/
mL；V1For the total volume of vortex leaching liquor, μ L；ρPDMSFor the density μ L/cm of PDMS coating；LPDMSFor the total length of PDMS fiber,
cm。
PAHs biologically effective concentration, calculation formula are as follows in soil in S7:
。
In formula, CbioFor PAHs biologically effective concentration in soil, μ g/mL；KPDMS-waterFor PDMS coating-water partition coefficient,
ML- water/mL-PDMS coating.
A certain amount of surfactant is added in the present invention proposition during activated carbon adsorption fixing soil PAHs, promotes soil
The PAHs desorption of earth medium absorption is accelerated P in soil AHs to the migration of active carbon and is finally adsorbed admittedly by strong activated carbon of sorbent
It is fixed, the limitation of single-activity charcoal adsorption technology is breached, the absorption fixed efficiency to P in soil AHs is improved, in addition, comparing
In chemical surfactant, biosurfactant has many good qualities, as hypotoxicity, high biological degradability, good environment are simultaneous
Capacitive etc., therefore with active carbon-surfactant formula secondary pollution will not be caused to soil.
Embodiment 2: based on embodiment 1 but different, taking out that treated, PDMS fiber is put into reaction vessel,
Reaction vessel bottle cap is tightened, is placed on turnover oscillator, temperature setting is 25 ± 1 DEG C in turnover oscillator, and revolving speed is set as 30-
35rpm, be protected from light concussion terminates for 28-30 days, and PDMS fiber is taken out out of vial, is wiped with hygenic towelette and is attached to PDMS fiber table
The particulate matter in face is cut into the PDMS segment of fiber of 1-1.5cm long, is put into glass interpolation pipe of the 150-250 μ L with polymer support,
It is then put into together with glass interpolation pipe in the brown chromatography column feed materials bottle of 2mL, 100-200 μ L acetonitrile and 1-2 μ is added in interpolation pipe
L internal standard solution tightens bottle cap, and be vortexed concussion, and the concussion setting speed that is vortexed is 3000rpm, and the concussion time is the liquid after 3min concussion
Body crosses 0.22 μm of glass fiber filter, after filtering using high performance liquid chromatography carry out PAHs concentration determination, finally further according to
The test result of PAHs concentration calculates PAHs biologically effective concentration in the free phase of soil.
Method proposed by the present invention based on hydrophobic silicones coating material measurement P in soil AHs biological effectiveness, it is hydrophobic
Property Silicone Coatings Materials using easily obtain, disposable PDMS fiber at low cost.Pedotheque and PDMS fiber shake through overturning
The mode swung comes into full contact with, and the organic pollutant in soil pore water can be entered in PDMS polymer by diffusion to be inhaled
It receives, the PAHs that PDMS fiber absorbs quickly fully is desorbed by the way of being vortexed concussion solvent elution after reaching balance, is led to
The concentration for crossing pollutant in measurement PDMS fiber surveys the content of free dissolved pollutant in soil pore water, i.e. biological effectiveness
Concentration.The sampling of this method collection extracts and is enriched in one, and easy to operate, balance is quickly and amount of samples is less, overcomes tradition
Physico-chemical process is influenced by extraction conditions, test result is unstable and biological method time-consuming, by species,
The problem of exposure duration etc. is affected.
It is active carbon and surfactant that the present invention, which is reduced to the formula composition of PAHs biological effectiveness in contaminated soil,
The middle surfactant used is nonionic biosurfactant saponin, saponin content 20%-35%, and powdery is solvable
Yu Shui, the solubility in deionized water is 50mg/ml, and during adding formula, active carbon and surface are added in formula
Activating agent saponin, while setting is not added with active carbon-surfactant formula blank control group, and is not added with active carbon-
The test result of surfactant formula is compared, and 16 kinds of PAHs biological effectiveness concentration significantly drop in the soil after addition formula
It is low, PAHs concentration mensuration is carried out using high performance liquid chromatography, the method with detection sensitivity use by high, easy to operate and solvent
The advantages that small is measured, detection efficiency can be effectively improved and saves experimental cost.
Embodiment 3: based on Examples 1 and 2 but different, appropriate PAHs contaminated soil, total PAHs in soil are taken
Concentration be 700mg/kg, by pedotheque it is In Shade air-dry, reject the impurity such as root system of plant and chad, smash it through
200 meshes are packed into valve bag and are kept in dark place at 4 DEG C；PDMS fiber is cut into the length of 3cm, is impregnated with methanol solution
For 24 hours, it is cleaned 3 times with sterile deionized water later after drying for use, using 20mL brown chromatogram bottle as reaction vessel, weighs 5g
Soil is placed in 20mL brown chromatogram bottle, is separately added into 2% active carbon and 0.12% saponin, is stirring evenly and then adding into 15ml
Sterile deionized water is made into the slurry liquid that Tu Shui ratio is 1:3, sodium azide (NaN is added2) and calcium chloride (CaCl2), it sets simultaneously
It sets and is not added with active carbon-surfactant formula blank control group, the PDMS fiber of 2 3cm is added in each reaction vessel,
Bottle cap is tightened, is placed on turnover oscillator, 25 DEG C of temperature, revolving speed 30rpm, concussion 28 days is protected from light, PDMS is taken out after concussion
Fiber wipes the particulate matter for being attached to PDMS fiber surface with hygenic towelette, is cut into the segment of fiber of 1cm long, is put into 150 μ L band polymer
It in the glass interpolation pipe of bracket, is then put into together with glass interpolation pipe in 2mL brown chromatography column feed materials bottle, is added in interpolation pipe
100 μ L acetonitriles and 1 μ L internal standard solution tighten bottle cap, and be vortexed concussion, and the liquid after concussion crosses 0.22 μm of glass fiber filter, on
Machine test, according to the biologically effective concentration of PAHs in test result calculations soil, the results are shown in Table 1, the results showed that, and it is not added with work
Property charcoal-surfactant formula test result compare, after addition formula 1,16 kinds of PAHs biological effectiveness concentration are aobvious in soil
Writing reduces, and reduced rate is between 95.7%-100%.
Embodiment 4: based on embodiment 1,2 and 3 but different, taking appropriate PAHs contaminated soil, air-dries and remove impurity,
300 meshes are smashed it through, is packed into valve bag and is kept in dark place at 4 DEG C；PDMS fiber is cut into the length of 5cm, it is molten with methanol
Liquid impregnates 25h, clean later with sterile deionized water after drying for 3 times for use, using 25mL brown chromatogram bottle as reaction vessel,
Weigh 5g soil to be placed in 25mL brown chromatogram bottle, be separately added into 2% active carbon and 1.2% saponin, after mixing evenly plus
Enter 20ml sterile deionized water, is made into the slurry liquid that Tu Shui ratio is 1:4, sodium azide (NaN is added2) and calcium chloride (CaCl2),
Setting simultaneously is not added with active carbon-surfactant formula blank control group, is added 2 2cm's in each reaction vessel
PDMS fiber, tightens bottle cap, is placed on turnover oscillator, 26 DEG C of temperature, revolving speed 35rpm, concussion 30 days is protected from light, after concussion
PDMS fiber is taken out, the particulate matter for being attached to PDMS fiber surface is wiped with hygenic towelette, the segment of fiber of 1.5cm long is cut into, is put into 250
It in μ L glass interpolation pipe, is then put into together with glass interpolation pipe in 2mL brown chromatography column feed materials bottle, 200 μ L is added in interpolation pipe
Acetonitrile and 2 μ L internal standard solutions tighten bottle cap, and be vortexed concussion, and the liquid after concussion crosses 0.22 μm of glass fiber filter, and upper machine is surveyed
Examination, according to the biologically effective concentration of PAHs in test result calculations soil, the results are shown in Table 2, the results showed that, and it is not added with activity
Charcoal-surfactant formula test result is compared, and after addition formula 2,16 kinds of PAHs biological effectiveness concentration are significant in soil
It reduces, reduced rate is between 89.55%-100%.
Embodiment 5: it is raw to be applied to a kind of reduction P in soil AHs for a kind of soil treatment device reducing P in soil AHs biological effectiveness
The formula of object validity, including body 1 and separating screen device 6 are crushed, it crushes and is fixed at left and right sides of 1 bottom of body with 2 top of supporting leg
Connection crushes 1 inner lower of body and is provided with crushing chamber 3, crushes and is provided with card slot 4 on wall at left and right sides of 1 inner upper end of body,
It crushes and is flexibly connected at left and right sides of 1 inner upper end of body and separating screen device 6, be provided with strip at left and right sides of 6 upper end of separating screen device
7, strip 7 matches with card slot 4, and 6 top middle portion of separating screen device is fixedly installed with sub-sieve net 5, the 6 inside left and right sides of separating screen device
It is provided with impurity collecting tank 8,6 inside front and rear sides of separating screen device are provided with dirt scraping equipment slot 9, are arranged inside dirt scraping equipment slot 9
There is dirt scraping equipment 10.
Dirt scraping equipment 10 includes motor 12, is fixedly connected on the left of 12 right side central of motor and worm screw 15,15 lower surface of worm screw
Connection is engaged with 13 upper surface of worm gear, 13 shaft core position of worm gear is fixedly connected with 14 one end of drive shaft, 14 other end of drive shaft with
16 lower end of drive rod is flexibly connected, and is fixedly connected on the right side of 16 upper end of interlocking lever and connecting rod 17,17 left side of connecting rod and scraping dirt bar
18 lower ends are flexibly connected, and are fixedly connected in the middle part of 18 upper end of scraping dirt bar and scraping dirt piece 11.
A kind of soil treatment device for reducing P in soil AHs biological effectiveness, the PAHs fetched from coke-oven plant is arranged in the present invention
Contaminated soil is all mostly untreated soil, and the impurity such as root system of plant and chad are often contaminated in soil, is being carried out in fact
It needs to handle contaminated soil before testing, by being provided with soil sub-sieve grinding device, while carrying out soil crushing
Impurity can be removed, by the way that dirt scraping equipment 10 is arranged in soil sub-sieve grinding device inner upper end, be set in 10 side of dirt scraping equipment
Set impurity collecting tank 8, carry out soil sub-sieve filtering crush during, using scraping dirt piece 11 can effectively by root system of plant with
Chad is scraped in impurity collecting tank 8, and part fine earth earth is entered in crushing chamber 3 by sub-sieve net 5 to be crushed, and the present invention can be effective
The time of soil treatment is saved, conventional efficient is improved.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of formula for reducing P in soil AHs biological effectiveness, which comprises the following steps:
S1, from coke-oven plant acquire PAHs contaminated soil, by contaminated soil sample it is In Shade carry out it is air-dried, using a kind of drop
The soil treatment device of low P in soil AHs biological effectiveness by soil root system of plant and the impurity such as chad reject, smash it through
200-300 mesh is packed into be placed under 4 DEG C of environment in valve bag and be kept in dark place；
S2, PDMS fiber is taken out, is cut into the PDMS segment of fiber of 2-5cm length, PDMS segment of fiber methanol solution is impregnated into 24-
25h is cleaned by ultrasonic 2-3 times, each 10-20min with the deionized water after sterilizing after immersion, is dried rear spare；
S3, using the brown chromatogram bottle of 20-25mL as reaction vessel, and the PAHs pollution that weighs in a certain amount of S1 that treated
Soil is placed in reaction vessel, uses active carbon and surfactant as reducing matching for PAHs biological effectiveness in contaminated soil
Side, is added to reaction vessel respectively by active carbon and surfactant with the ratio of the 1%-5% of soil quality and 0.1%-1.2%
In, it stirs evenly；
S4, the deionized water after suitable sterilizing is added in mixture into S3 according to the ratio that solid-to-liquid ratio is 1:3-1:4, matches
It is set to slurry liquid, and is separately added into suitable sodium azide (NaN into mud2) and calcium chloride (CaCl2), make the concentration be respectively
25mg/L and 0.01mol/L；
Treated in S5, taking-up S2, and PDMS fiber is put into reaction vessel, is tightened reaction vessel bottle cap, is placed in turnover oscillator
On, temperature setting is 25 ± 1 DEG C in turnover oscillator, and revolving speed is set as 30-35rpm, and be protected from light concussion terminates for 28-30 days；
S6, PDMS fiber is taken out out of vial, the particulate matter for being attached to PDMS fiber surface is wiped with hygenic towelette, is cut into 1-
The PDMS segment of fiber of 1.5cm long is put into glass interpolation pipe of the 150-250 μ L with polymer support, then with glass interpolation pipe
It is put into the brown chromatography column feed materials bottle of 2mL together, 100-200 μ L acetonitrile and 1-2 μ L internal standard solution is added in interpolation pipe, tightens bottle
Lid, be vortexed concussion, and the liquid after concussion crosses 0.22 μm of glass fiber filter, carries out PAHs using high performance liquid chromatography after filtering
Concentration determination；
S7, finally further according to the test result of PAHs concentration in S6, calculate free solubilised state PAHs concentration in soil, i.e., in soil
PAHs biologically effective concentration.
2. a kind of formula for reducing P in soil AHs biological effectiveness according to claim 1, it is characterised in that: the S2
Middle 110 μm of PDMS fibrous glass core diameter, outer diameter be 170 μm, 30 μm of PDMS coating layer thickness, 13.5 μ L/m of PDMS coating density.
3. a kind of formula for reducing P in soil AHs biological effectiveness according to claim 1, it is characterised in that: the S3
In active carbon granule diameter range be 25-75 μm, moisture content 1.44%, the ash content of coal 18.77%, specific surface area 1095.99
㎡/g, pore volume are 0.59 cm3/g, average pore diameter 2.17nm.
4. a kind of formula for reducing P in soil AHs biological effectiveness according to claim 1, it is characterised in that: the S3
Middle surfactant is nonionic biosurfactant saponin, and saponin content 20%-35%, powdery is water-soluble, goes
Solubility in ionized water is 50mg/ml.
5. a kind of formula for reducing P in soil AHs biological effectiveness according to claim 1, it is characterised in that: the S6
In internal standard solution be 100ppm decafluorobiphenyl.
6. a kind of reduction P in soil AHs biological effectiveness according to claim 1 is matched, it is characterised in that: in the S6
The concussion setting speed that is vortexed is 3000rpm, and the concussion time is 3min.
7. a kind of formula for reducing P in soil AHs biological effectiveness according to claim 1, it is characterised in that: the S6
PAHs concentration in middle survey vortex leaching liquor calculates PAHs concentration in PDMS fiber, and formula is as follows:
,
In formula, CPDMSFor PAHs concentration in PDMS fiber, μ g/mL；C1To be surveyed PAHs concentration in vortex leaching liquor, μ g/mL；V1
For the total volume of vortex leaching liquor, μ L；ρPDMSFor the density μ L/cm of PDMS coating；LPDMSFor the total length of PDMS fiber, cm.
8. a kind of formula for reducing P in soil AHs biological effectiveness according to claim 1, it is characterised in that: the S7
PAHs biologically effective concentration, calculation formula are as follows in middle soil:
,
In formula, CbioFor PAHs biologically effective concentration in soil, μ g/mL；KPDMS-waterFor PDMS coating-water partition coefficient, mL-
Water/mL-PDMS coating.
9. a kind of soil treatment device for reducing P in soil AHs biological effectiveness, it is characterised in that: be applied to a kind of reduction soil
The formula of PAHs biological effectiveness, including body (1) and separating screen device (6) are crushed, at left and right sides of crushing body (1) bottom
It is fixedly connected with supporting leg (2) top, crushing body (1) inner lower is provided with crushing chamber (3), the crushing body (1)
It is provided with card slot (4) on wall at left and right sides of inner upper end, crushing body (1) inner upper end and separating screen device (6) left and right two
Side is flexibly connected, and is provided with strip (7) at left and right sides of separating screen device (6) upper end, the strip (7) and card slot (4) phase
Match, separating screen device (6) top middle portion is fixedly installed with sub-sieve net (5), the internal left and right sides setting of the separating screen device (6)
Have impurity collecting tank (8), the internal front and rear sides of the separating screen device (6) are provided with dirt scraping equipment slot (9), the dirt scraping equipment slot
(9) dirt scraping equipment (10) are internally provided with.
10. a kind of soil treatment device for reducing P in soil AHs biological effectiveness according to claim 9, feature exist
In: the dirt scraping equipment (10) includes motor (12), is fixedly connected on the left of motor (12) right side central and worm screw (15), institute
It states worm screw (15) lower surface and engages connection, worm gear (13) shaft core position and drive shaft (14) one end with worm gear (13) upper surface
It is fixedly connected, drive shaft (14) other end is flexibly connected with drive rod (16) lower end, interlocking lever (16) upper end and company
It is fixedly connected, is flexibly connected on the left of the connecting rod (17) with scraping dirt bar (18) lower end, the scraping dirt bar on the right side of extension bar (17)
(18) it is fixedly connected in the middle part of upper end and scraping dirt piece (11).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113617813A (en) * | 2021-07-23 | 2021-11-09 | 上海同济建设科技股份有限公司 | Method for removing polycyclic aromatic hydrocarbons in soil through hydrothermal carbon enhanced washing |
| CN114018672A (en) * | 2021-11-24 | 2022-02-08 | 江苏环科检测有限公司 | Automatic desorption device of organic pretreatment |
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