CN107991405A - The assay method of phthalate ester in soil - Google Patents
The assay method of phthalate ester in soil Download PDFInfo
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- CN107991405A CN107991405A CN201711181328.8A CN201711181328A CN107991405A CN 107991405 A CN107991405 A CN 107991405A CN 201711181328 A CN201711181328 A CN 201711181328A CN 107991405 A CN107991405 A CN 107991405A
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- phthalate ester
- assay method
- hexane
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
- G01N2030/126—Preparation by evaporation evaporating sample
Abstract
The present invention provides a kind of assay method of phthalate ester in soil, belong to Material Testing Technology field.The assay method of the phthalate ester in soil comprises the following steps, and soil to be detected and the diatomite toasted is compacted after mixing, and wrapped up with quartz sand, be compacted obtain detection block；Detection block is subjected to Accelerate solvent extraction using dichloromethane as extracting solution and obtains extracting solution；Extracting solution progress first time rotary evaporation is concentrated into 1~2mL, 5~8mL n-hexanes is added and mixes, then carries out second of rotary evaporation and obtains concentrate to 1~2mL, concentrate is used into column chromatography purification.The assay method of phthalate ester in soil provided by the invention can accurately measure the phthalandione ester content in soil, the easy phthalate ester detection reliably and suitable for Different Soil of this method.
Description
Technical field
The present invention relates to Material Testing Technology field, in particular to a kind of assay method of phthalate ester in soil.
Background technology
Phthalate ester is also known as phthalic acid ester, it is the general designation for the ester that phthalic acid is formed, and is mainly used as modifying plastics
Additive is a kind of with carcinogenicity, mutagenicity, teratogenesis, genotoxicity, neurotoxicity, endocrine disrupting environment
Hormone.In recent years, with the extensive production and use of plastic products, some rivers and lakes, reservoir, drinking water and the bottom in China
The pollution of phthalate compound has been showed in mud.It is therefore desirable to establish related detecting method to realize to the phthalate ester in soil
It is detected to determine.
The assay method of phthalate ester is mainly having colorimetric method, titration and spectrophotometry etc. in early days, but these methods
Sensitivity is low, and poor selectivity, measuring result error are larger.With the continuous development of analytical technology, chromatography is applied to by people
Phthalate ester detects, although the sensitivity of red, orange, green, blue, yellow (ROGBY) and precision are improved, they before sample in the prevalence of locating
Reason is complicated, efficiency is low, time-consuming, the shortcomings of needing to consume a large amount of organic solvents, has both easily caused the injury to experimenter, at the same time
It can not meet the requirement of quick advanced analysis technology, greatly hinder the progress of phthalate ester pollutant generaI investigation.
It is simple and convenient to operate therefore, it is necessary to a kind of method, measures accurate soil phthalate ester assay method.
The content of the invention
The present invention provides a kind of assay method of phthalate ester in soil, the phthalate ester that can accurately measure in soil contains
Amount, the easy phthalate ester detection reliably and suitable for Different Soil of this method.
What the present invention was realized in：
A kind of assay method of phthalate ester in soil, it comprises the following steps：
Soil to be detected and the diatomite toasted are compacted after mixing, and is wrapped up, is compacted with quartz sand
To detection block；
Detection block is subjected to Accelerate solvent extraction using dichloromethane as extracting solution and obtains extracting solution；
Extracting solution progress first time rotary evaporation is concentrated into 1~2mL, 5~8mL n-hexanes is added and mixes, then carries out the
Secondary rotating is evaporated to 1~2mL and obtains concentrate, and concentrate is used the laggard promoting the circulation of qi analysis of hplc of column chromatography purification.
In preferred embodiments of the present invention, the above-mentioned diatomite toasted is to toast diatomite at 500~600 DEG C
6~8h.
In preferred embodiments of the present invention, above-mentioned soil to be detected and the diatomaceous mass ratio toasted are 1~2g：
4~6g.
In preferred embodiments of the present invention, mixed after further including the diatomite modified that will be toasted with soil to be detected,
Modification is the diatomite, chitosan and acetic acid solution that will be toasted by 2~4g：1~2g：The ratio mixed configuration of 50~100ml
Into colloid, colloid is instilled into the sodium hydrate aqueous solution of mass concentration 10~20% and is stirred evenly, is added after filtration washing
55~70 DEG C are heated in the liquor potassic permanganate of mass concentration 3~10% and stirs 2~3h, after instillation hydrochloric acid to pH is neutrality
Filtering.
In preferred embodiments of the present invention, the condition of above-mentioned Accelerate solvent extraction is：Preheat 5min；Heat 5min；It is quiet
State extracts 5min；Pressure 1500psi；100 DEG C of Extracting temperature；Nitrogen purges 120s；Leacheate volume 36mL；Circulation is twice.
In preferred embodiments of the present invention, above-mentioned first time rotary evaporation be 40 DEG C of water-baths, 410mbar pressure and
Carried out under 80rpm rotating speeds.
In preferred embodiments of the present invention, above-mentioned second of rotary evaporation be 40 DEG C of water-baths, 350mbar pressure and
Carried out under 80rpm rotating speeds.
It is above-mentioned when concentrate is used column chromatography purification in preferred embodiments of the present invention, filler sieve for silica gel or not
In tripoli, eluted in advance using n-hexane, it is 1 to add after sample concentration liquid using ethyl acetate or volume ratio：4 n-hexane, third
Ketone mixed liquor.
Above-mentioned when concentrate is used column chromatography purification in preferred embodiments of the present invention, filler is from top to bottom successively
It is 1~2 for mass ratio：4~6：10~12：1~2 anhydrous sodium sulfate, aluminium oxide, silica gel and anhydrous sodium sulfate, use just oneself
Alkane and volume ratio are 1~4：1 n-hexane, acetone mixture elute in advance, and it is 1~4 to add after sample concentration liquid using volume ratio：
1 n-hexane, acetone mixture.
Above-mentioned when concentrate is used column chromatography purification in preferred embodiments of the present invention, filler is from top to bottom successively
It is 1~2 for mass ratio：2~4：0.5~1.5：0.5~1.5 anhydrous sodium sulfate, florisil silica, activated carbon and anhydrous slufuric acid
Sodium, is 1~4 using n-hexane and volume ratio：1 n-hexane, acetone mixture elute in advance, and body is used after adding sample concentration liquid
Product is than being 1~4：1 n-hexane, acetone mixture.
The beneficial effects of the invention are as follows：The assay method of phthalate ester in soil provided by the invention comprises the following steps, will
Compacting obtains detection block after soil to be detected and the diatomite toasted are compacted and are wrapped up with quartz sand after mixing；Will
Detection block carries out Accelerate solvent extraction using dichloromethane as extracting solution and obtains extracting solution；Extracting solution is subjected to first time rotation
It is concentrated by evaporation to 1~2mL, adds 5~8mL n-hexanes and mix, then carries out second of rotary evaporation and obtain concentrate to 1~2mL,
Concentrate is used into column chromatography purification.The assay method of phthalate ester in soil provided by the invention can be measured accurately in soil
Phthalandione ester content, this method is easy reliable and phthalate ester suitable for Different Soil detects.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair
The restriction of scope, for those of ordinary skill in the art, without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the chromatography of the standard sample of six kinds of phthalate ester target contaminants that concentration is 1mg/L and standard substitution
Figure；
Fig. 2 is to be provided using the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6
The assay method of phthalate ester carries out column chromatography purification to the soil of 6 kinds of phthalate ester target contaminants of the 1mg/L containing 1mL respectively
The phthalate ester rate of recovery after processing；
Fig. 3 is that the assay method of the phthalate ester provided using the embodiment of the present invention 1 is dirty to containing 6 kinds of phthalate ester targets respectively
The elution curve that the soil of dye thing is handled；
Fig. 4 is that the assay method of the phthalate ester provided using the embodiment of the present invention 2 is dirty to containing 6 kinds of phthalate ester targets respectively
The elution curve that the soil of dye thing is handled；
Fig. 5 is that the assay method of the phthalate ester provided using the embodiment of the present invention 3 is dirty to containing 6 kinds of phthalate ester targets respectively
The elution curve that the soil of dye thing is handled；
Fig. 6 is that the assay method of the phthalate ester provided using the embodiment of the present invention 4 is dirty to containing 6 kinds of phthalate ester targets respectively
The elution curve that the soil of dye thing is handled；
Fig. 7 is that the assay method of the phthalate ester provided using the embodiment of the present invention 5 is dirty to containing 6 kinds of phthalate ester targets respectively
The elution curve that the soil of dye thing is handled；
Fig. 8 is that the assay method of the phthalate ester provided using the embodiment of the present invention 6 is dirty to containing 6 kinds of phthalate ester targets respectively
The elution curve that the soil of dye thing is handled；
Fig. 9 is that the assay method of the phthalate ester provided using the embodiment of the present invention 4 to blank soil matrix handle
The detection structure arrived.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer, is the conventional production that can be obtained by commercially available purchase
Product.
The embodiment of the present invention is specifically described below.
A kind of assay method of phthalate ester in soil is present embodiments provided, it comprises the following steps：
Soil to be detected and the diatomite toasted, be compacted and be compacted after being wrapped up with quartz sand by S1 after mixing
Obtain detection block；Wherein, the diatomite toasted is that diatomite is toasted 6~8h at 500~600 DEG C；It is preferable to be detected
Soil and the diatomaceous mass ratio toasted are 1~2g：4~6g；It is further preferred that further include the diatomite that will be toasted
Modified to be mixed with soil to be detected, modification is the diatomite, chitosan and acetic acid solution that will be toasted by 2~4g：1~2g：
The ratio of 50~100ml is mixedly configured into colloid, and colloid is instilled into the sodium hydrate aqueous solution of mass concentration 10~20%
Stir evenly, after filtration washing add mass concentration 3~10% liquor potassic permanganate in be heated to 55~70 DEG C and stir 2~
3h, instills after hydrochloric acid is neutrality to pH and filters.
S2, carry out Accelerate solvent extraction using dichloromethane as extracting solution using detection block and obtain extracting solution；Wherein, quickly
Solvent-extracted condition is：Preheat 5min；Heat 5min；Static state extraction 5min；Pressure 1500psi；100 DEG C of Extracting temperature；Nitrogen
120s is swept in air-blowing；Leacheate volume 36mL；Circulation is twice.
Extracting solution progress first time rotary evaporation, is concentrated into 1~2mL, 5~8mL of addition n-hexane mixings by S3, then is carried out
Second of rotary evaporation obtains concentrate to 1~2mL, and concentrate is used the laggard promoting the circulation of qi analysis of hplc of column chromatography purification；The
One time rotary evaporation preferably carries out under 40 DEG C of water-baths, 410mbar pressure and 80rpm rotating speeds；Second of rotary evaporation is preferred
It is to be carried out under 40 DEG C of water-baths, 350mbar pressure and 80rpm rotating speeds.Preferably, when concentrate being used column chromatography purification, fill out
Expect for silica gel or florisil silica, to elute in advance using n-hexane, add after sample concentration liquid and be using ethyl acetate or volume ratio
1：4 n-hexane, acetone mixture；It is further preferred that when concentrate is used column chromatography purification, filler is from top to bottom successively
It is 1~2 for mass ratio：4~6：10~12：1~2 anhydrous sodium sulfate, aluminium oxide, silica gel and anhydrous sodium sulfate, use just oneself
Alkane and volume ratio are 1~4：1 n-hexane, acetone mixture elute in advance, and it is 1~4 to add after sample concentration liquid using volume ratio：
1 n-hexane, acetone mixture；It is further preferred that when concentrate is used column chromatography purification, filler is followed successively by from top to bottom
Mass ratio is 1~2：2~4：0.5~1.5：0.5~1.5 anhydrous sodium sulfate, florisil silica, activated carbon and anhydrous slufuric acid
Sodium, is 1~4 using n-hexane and volume ratio：1 n-hexane, acetone mixture elute in advance, and body is used after adding sample concentration liquid
Product is than being 1~4：1 n-hexane, acetone mixture.
The assay method of phthalate ester in soil provided in an embodiment of the present invention is using the diatomite toasted or modified diatom
Native and soil mixed compaction to be monitored, and obtain detection block using quartz sand parcel compacting and carry out Accelerate solvent extraction, use stone
Sand, which wraps up soil to be monitored, can ensure that extraction is complete, and extracting pressure is reduced after avoiding looseness of soil, in addition using toasting
Diatomite or modification infusorial earth extract can be enriched with and be purified in extraction process, improve soil extract in phthalein
The enriching quantity of acid esters, then using column chromatography purification is carried out after the concentration of rotary evaporation twice, can effectively remove in concentrate
Impurity carried out chromatography, the assay method of the phthalate ester in soil is simple and convenient to operate with technique, organic solvent use
The advantages that amount is few, and rate of extraction is fast, impurity disturbs less, sample recovery rate is high, the phthalate ester inspection suitable for Different Soil
Survey.
The feature and performance of the method for the present invention are described in further detail with reference to embodiments.
Embodiment 1
Embodiment 1 provides a kind of assay method of phthalate ester in soil, its specific determination step is as follows：
S101, take the supporting clean abstraction pools of ASE200, is 1 with volume ratio：1 acetone, n-hexane mixed liquor rinse
Three times, dried up using nitrogen stream.The nut of abstraction pool one end is twisted into reality, adds 2~3 appropriately sized filter papers and in bottom
Compacting, adds 5g quartz sands, and soil is mixed in preparation.
2g, be put into the beaker of 100ml by S201 by 60 purposes soil to be detected, is then added at 600 DEG C and is toasted 6h
Diatomite 5g be compacted and wrapped up with quartz sand after mixing after compacting obtain detection block；
S301, carry out Accelerate solvent extraction using dichloromethane as extracting solution using detection block and obtain extracting solution；Wherein, soon
Quick-dissolving agent extraction condition be：Preheat 5min；Heat 5min；Static state extraction 5min；Pressure 1500psi；100 DEG C of Extracting temperature；
Nitrogen purges 120s；Leacheate volume 36mL；Circulation is twice；
S401, that extracting solution is carried out under 40 DEG C of water-baths, 410mbar pressure and 80rpm rotating speeds to first time rotary evaporation is dense
1mL is reduced to, 5mL n-hexanes is added and mixes, then carries out second under 40 DEG C of water-baths, 350mbar pressure and 80rpm rotating speeds and rotates
It is evaporated to 1mL and obtains concentrate, concentrate is used into the laggard promoting the circulation of qi analysis of hplc of column chromatography purification；Concentrate is used into column layer
During analysis purification, filler is 5g silica gel and 1g anhydrous sodium sulfates, is eluted in advance using 15ml n-hexanes, is used after adding sample concentration liquid
Ethyl acetate elutes.
Embodiment 2
Embodiment 2 provides a kind of assay method of phthalate ester in soil, its specific determination step is as follows：
S201, take the supporting clean abstraction pools of ASE200, is 1 with volume ratio：1 acetone, n-hexane mixed liquor rinse
Three times, dried up using nitrogen stream.The nut of abstraction pool one end is twisted into reality, adds 2~3 appropriately sized filter papers and in bottom
Compacting, adds 5g quartz sands, and soil is mixed in preparation.
2g, be put into the beaker of 100ml by S202 by 60 purposes soil to be detected, is then added at 600 DEG C and is toasted 6h
Diatomite 5g be compacted and wrapped up with quartz sand after mixing after compacting obtain detection block；
S203, carry out Accelerate solvent extraction using dichloromethane as extracting solution using detection block and obtain extracting solution；Wherein, soon
Quick-dissolving agent extraction condition be：Preheat 5min；Heat 5min；Static state extraction 5min；Pressure 1500psi；100 DEG C of Extracting temperature；
Nitrogen purges 120s；Leacheate volume 36mL；Circulation is twice；
S204, that extracting solution is carried out under 40 DEG C of water-baths, 410mbar pressure and 80rpm rotating speeds to first time rotary evaporation is dense
1mL is reduced to, 5mL n-hexanes is added and mixes, then carries out second under 40 DEG C of water-baths, 350mbar pressure and 80rpm rotating speeds and rotates
It is evaporated to 1mL and obtains concentrate, concentrate is used into the laggard promoting the circulation of qi analysis of hplc of column chromatography purification；Concentrate is used into column layer
During analysis purification, filler is 5g florisil silicas, is eluted in advance using 10ml n-hexanes, is using volume ratio after addition sample concentration liquid
1：4 n-hexane, acetone mixture elution.
Embodiment 3
Embodiment 3 provides a kind of assay method of phthalate ester in soil, its specific determination step is as follows：
S301, take the supporting clean abstraction pools of ASE200, is 1 with volume ratio：1 acetone, n-hexane mixed liquor rinse
Three times, dried up using nitrogen stream.The nut of abstraction pool one end is twisted into reality, adds 2~3 appropriately sized filter papers and in bottom
Compacting, adds 5g quartz sands, and soil is mixed in preparation.
2g, be put into the beaker of 100ml by S302 by 60 purposes soil to be detected, is then added at 600 DEG C and is toasted 6h
Diatomite 5g be compacted and wrapped up with quartz sand after mixing after compacting obtain detection block；
S303, carry out Accelerate solvent extraction using dichloromethane as extracting solution using detection block and obtain extracting solution；Wherein, soon
Quick-dissolving agent extraction condition be：Preheat 5min；Heat 5min；Static state extraction 5min；Pressure 1500psi；100 DEG C of Extracting temperature；
Nitrogen purges 120s；Leacheate volume 36mL；Circulation is twice；
S304, that extracting solution is carried out under 40 DEG C of water-baths, 410mbar pressure and 80rpm rotating speeds to first time rotary evaporation is dense
1mL is reduced to, 5mL n-hexanes is added and mixes, then carries out second under 40 DEG C of water-baths, 350mbar pressure and 80rpm rotating speeds and rotates
It is evaporated to 1mL and obtains concentrate, concentrate is used into the laggard promoting the circulation of qi analysis of hplc of column chromatography purification；It is further preferred that will
When concentrate uses column chromatography purification, filler be followed successively by from top to bottom 2g anhydrous sodium sulfates, 6g aluminium oxide, 12g silica gel and 1g without
Aqueous sodium persulfate, is 1 using 15ml n-hexanes and 15ml volume ratios：1 n-hexane, acetone mixture elute in advance, and addition sample is dense
It is 1 that volume ratio is used after contracting liquid：1 n-hexane, acetone mixture elution.
Embodiment 4
Embodiment 4 provides a kind of assay method of phthalate ester in soil, its specific determination step is as follows：
S401, take the supporting clean abstraction pools of ASE200, is 1 with volume ratio：1 acetone, n-hexane mixed liquor rinse
Three times, dried up using nitrogen stream.The nut of abstraction pool one end is twisted into reality, adds 2~3 appropriately sized filter papers and in bottom
Compacting, adds 5g quartz sands, and soil is mixed in preparation.
2g, be put into the beaker of 100ml by S402 by 60 purposes soil to be detected, is then added 5g modification infusorial earths and is mixed
Compacting obtains detection block after being compacted after closing uniformly and being wrapped up with quartz sand；The preparation method of modification infusorial earth is, by diatom
Soil toasts 6h at 600 DEG C, by the diatomite toasted, chitosan and acetic acid solution by 4g：2g：The ratio mixing of 100ml is matched somebody with somebody
Colloid is set to, colloid is instilled into the sodium hydrate aqueous solution of mass concentration 10% and is stirred evenly, matter is added after filtration washing
Measure and be heated to 70 DEG C in the liquor potassic permanganate of concentration 5% and stir 2h, instill after hydrochloric acid is neutrality to pH and be obtained by filtration；
S403, carry out Accelerate solvent extraction using dichloromethane as extracting solution using detection block and obtain extracting solution；Wherein, soon
Quick-dissolving agent extraction condition be：Preheat 5min；Heat 5min；Static state extraction 5min；Pressure 1500psi；100 DEG C of Extracting temperature；
Nitrogen purges 120s；Leacheate volume 36mL；Circulation is twice.
S404, that extracting solution is carried out under 40 DEG C of water-baths, 410mbar pressure and 80rpm rotating speeds to first time rotary evaporation is dense
1mL is reduced to, 5mL n-hexanes is added and mixes, then carries out second under 40 DEG C of water-baths, 350mbar pressure and 80rpm rotating speeds and rotates
It is evaporated to 1mL and obtains concentrate, concentrate is used into the laggard promoting the circulation of qi analysis of hplc of column chromatography purification；Concentrate is used into column layer
During analysis purification, filler is followed successively by 1g anhydrous sodium sulfates, 5g aluminium oxide, 10g silica gel and 1g anhydrous sodium sulfates from top to bottom, uses
15ml n-hexanes and 15ml volume ratios are 4：1 n-hexane, acetone mixture elute in advance, and volume is used after adding sample concentration liquid
Than for 4：1 n-hexane, acetone mixture elution.
Embodiment 5
Embodiment 5 provides a kind of assay method of phthalate ester in soil, its specific determination step is as follows：
S501, take the supporting clean abstraction pools of ASE200, is 1 with volume ratio：1 acetone, n-hexane mixed liquor rinse
Three times, dried up using nitrogen stream.The nut of abstraction pool one end is twisted into reality, adds 2~3 appropriately sized filter papers and in bottom
Compacting, adds 5g quartz sands, and soil is mixed in preparation.
2g, be put into the beaker of 100ml by S502 by 60 purposes soil to be detected, is then added 5g modification infusorial earths and is mixed
Compacting obtains detection block after being compacted after closing uniformly and being wrapped up with quartz sand；The preparation method of modification infusorial earth is, by diatom
Soil toasts 6h at 550 DEG C, by the diatomite toasted, chitosan and acetic acid solution by 2g：1g：The ratio mixing of 60ml is matched somebody with somebody
Colloid is set to, colloid is instilled into the sodium hydrate aqueous solution of mass concentration 15% and is stirred evenly, matter is added after filtration washing
Measure and be heated to 65 DEG C in the liquor potassic permanganate of concentration 8% and stir 3h, instill after hydrochloric acid is neutrality to pH and be obtained by filtration
S503, carry out Accelerate solvent extraction using dichloromethane as extracting solution using detection block and obtain extracting solution；Wherein, soon
Quick-dissolving agent extraction condition be：Preheat 5min；Heat 5min；Static state extraction 5min；Pressure 1500psi；100 DEG C of Extracting temperature；
Nitrogen purges 120s；Leacheate volume 36mL；Circulation is twice；
S504, that extracting solution is carried out under 40 DEG C of water-baths, 410mbar pressure and 80rpm rotating speeds to first time rotary evaporation is dense
1mL is reduced to, 5mL n-hexanes is added and mixes, then carries out second under 40 DEG C of water-baths, 350mbar pressure and 80rpm rotating speeds and rotates
It is evaporated to 1mL and obtains concentrate, concentrate is used into the laggard promoting the circulation of qi analysis of hplc of column chromatography purification；It is further preferred that will
When concentrate uses column chromatography purification, filler be followed successively by from top to bottom mass ratio for 2g anhydrous sodium sulfates, 4g florisil silicas,
0.5g activated carbons and 1g anhydrous sodium sulfates, are 1 using 15ml n-hexanes and 15ml volume ratios：1 n-hexane, acetone mixture are pre-
Elution, volume ratio is used as 1 after adding sample concentration liquid：1 n-hexane, acetone mixture elution.
Embodiment 6
Embodiment 6 provides a kind of assay method of phthalate ester in soil, its specific determination step is as follows：
S601, take the supporting clean abstraction pools of ASE200, is 1 with volume ratio：1 acetone, n-hexane mixed liquor rinse
Three times, dried up using nitrogen stream.The nut of abstraction pool one end is twisted into reality, adds 2~3 appropriately sized filter papers and in bottom
Compacting, adds 5g quartz sands, and soil is mixed in preparation.
2g, be put into the beaker of 100ml by S602 by 60 purposes soil to be detected, is then added 5g modification infusorial earths and is mixed
Compacting obtains detection block after being compacted after closing uniformly and being wrapped up with quartz sand；The preparation method of modification infusorial earth is, by diatom
Soil toasts 8h at 500 DEG C, by the diatomite toasted, chitosan and acetic acid solution by 3g：2g：The ratio mixing of 75ml is matched somebody with somebody
Colloid is set to, colloid is instilled into the sodium hydrate aqueous solution of mass concentration 20% and is stirred evenly, matter is added after filtration washing
Measure and be heated to 60 DEG C in the liquor potassic permanganate of concentration 3% and stir 3h, instill after hydrochloric acid is neutrality to pH and be obtained by filtration
S603, carry out Accelerate solvent extraction using dichloromethane as extracting solution using detection block and obtain extracting solution；Wherein, soon
Quick-dissolving agent extraction condition be：Preheat 5min；Heat 5min；Static state extraction 5min；Pressure 1500psi；100 DEG C of Extracting temperature；
Nitrogen purges 120s；Leacheate volume 36mL；Circulation is twice；
S604, that extracting solution is carried out under 40 DEG C of water-baths, 410mbar pressure and 80rpm rotating speeds to first time rotary evaporation is dense
1mL is reduced to, 5mL n-hexanes is added and mixes, then carries out second under 40 DEG C of water-baths, 350mbar pressure and 80rpm rotating speeds and rotates
It is evaporated to 1mL and obtains concentrate, concentrate is used into the laggard promoting the circulation of qi analysis of hplc of column chromatography purification；It is further preferred that will
When concentrate uses column chromatography purification, filler be followed successively by from top to bottom 1g anhydrous sodium sulfates, 3g florisil silicas, 1g activated carbons and
1g anhydrous sodium sulfates, are 4 using 15ml n-hexanes and 15ml volume ratios：1 n-hexane, acetone mixture elute in advance, add sample
Volume ratio is used as 4 after savoring concentrate：1 n-hexane, acetone mixture elution.
The phthalate ester in soil provided using embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6
Assay method be detected, by soil to be detected be substituted for added with 1ml concentration be 1mg/L target contaminants soil, its
Middle target contaminant is selected as repefral (DMP), diethyl phthalate (DEP), phthalic acid respectively
Di-n-butyl (DnBP), butyl benzyl phthalate (BBP), phthalic acid diethylhexyl ester (DEHP), adjacent benzene two
Formic acid di-n-octyl (DnOP) and the deuterated dibutyl phthalate (DnBP-D of standard substitution4) be detected.
First, using the chromatogram of sample during different target pollutant.
The parameter of gas chromatographic analysis is in 1.1 the present embodiment：Gas-chromatography column temperature keeps 1min at 50 DEG C, then with
The programming rate of 30 DEG C/min rises to 200 DEG C of holding 1min, then rises to 280 DEG C of holding 3min with the programming rate of 8 DEG C/min, no
Split sampling.Use selective ion detection (the Selected Ion of the ChemStation of Agilent GC-MS
Monitoring, SIM) pattern and internal standard method carry out quantitative analysis.Fig. 1 is six kinds of phthalate ester mesh that concentration is 1mg/L
Mark the chromatogram of the hybrid standard sample of pollutant and standard substitution.
2nd, using the comparison of adsorption recovery rate during different measuring methods.
The rate of recovery situation of 2.1 pairs of obtained various target contaminants counts, and the results are shown in Figure 2, the results showed that,
Analysis condition provided in this embodiment meets the requirement of the trace analysis of phthalate ester material in environment.
3rd, using the comparison of elution curve during different measuring methods.
The elution curve of 3.1 pairs of obtained various target contaminants counts, and for the ease of comparing elution curve, will drench
The cumulative volume of washing lotion is both designed as 60ml, and 1 pipe is collected per 10ml in lessivation, blows concentration using nitrogen after collection, n-hexane is fixed
Hold to 1mL, upper machine testing, blank control is set, to exclude the background contamination that solvent, filler, glass apparatus are brought.Each processing
Three repetitions are set.The rate of recovery, elution time, leacheate volume etc. are weighed by comprehensive, selects best purification mode.
Outflow information in view of accurately collecting object under the conditions of various elution, the cumulative volume of every kind of leacheate is expanded
To 60ml, the leacheate that embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 are obtained carries out respectively
Collect and measure, elution curve is drawn according to result, as a result as shown in Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8, it is clear that Ge Geshi
The target contaminant applied in example is leached out, and the method leacheate dosage that embodiment 4 provides is few, elution is fastest, most
It is adapted to the purification of six kinds of phthalate esters.
Testing result when the 4th, using actual soil.
4.1 for examination soil matrix
The agricultural land soil of the regional four kinds of common soil types of east China is selected to add matrix as soil, to determine analysis
The detection limit of method, the polluted farmland soil that simultaneous selection Taizhou electronic waste disassembles near area carry out sample as actual sample
Product measure reappearance verification；Wherein, the basic physical and chemical of soil matrix is shown in Table 1.
Basic physical and chemical of the table 1 for examination soil
Select Arid Red Soil, the Huang of Qixia Hill In Nanjing at Chinese Academy of Sciences's red soil ecological experiment station (Jiangxi Yingtan red soil station)
Brown earth, the brunisolic soil in Shandong Shouguang and Northeast Institute of Geography and Agricultural Ecology, Chinese Academy of Sc's (Heilungkiang Helen's agricultural ecological
System country field science observation study station) four kinds of soil such as black earth at Helen station are measured and add back as addition matrix
Receive verification, respectively gather 0~15cm topsoil samples, with blossom type layout method sampling after, soil sample is placed in cloth earth bag, band
Laboratory is gone back to, crosses 60 mesh sieves after air-drying, -20 DEG C save backup.Added in four kinds of matrix soils according to the concentration of 0.1mg/kg
The mixed liquor of six kinds of target contaminants, the phthalate ester assay method provided afterwards using embodiment 6 are analyzed measure, the results are shown in Table 2.
From table 2 it can be seen that the average recovery rate of six kinds of phthalate esters is in the range of 74.9%~119.2% in four kinds of soil, wherein red
It is 80.3%~119.2% in earth, yellowish soil is 75.0%~112.7%, and brunisolic soil is 80.0%~118.6%, in black earth
For 79.1%~118.6%, and standard deviation is respectively less than 10%, and the rate of recovery of each object is close to the rate of recovery of U.S. EPA
Scope, meets analysis and requires.
The TIANZHU XINGNAO Capsul of 2 four kinds of phthalate ester in soil of table
R is the rate of recovery, and RSD is relative standard deviation.
4.2 instrument detection limits determine
The mixed standard solution that 7 pin concentration are 20 μ g/L is continuously analyzed by above procedure, according to ChemStation's
Signal-to-Noise methods obtain the signal-to-noise ratio (pk-pk S/N) of sample introduction, calculate the instrument detection under this analysis condition
Limit, calculation formula are as follows：
IDLs=3Q × N/I
Wherein Q is sample introduction concentration, and N is level of noise, and I is signal value.
It is as shown in table 3 that the instrument test limit obtained under selected analysis condition is analyzed and calculated to sample introduction.It is the result shows that this
Analysis condition substantially meets the trace analysis of phthalate ester material in environment.
Table 3 is continuously into the average signal-to-noise ratio and instrument test limit of 7 pin, 20 μ g/L titers
The drafting of 4.3 standard curves
Prepare the hybrid standard liquid of six kinds of target contaminants of 7 various concentrations respectively using standard substance, carry out GC/MS
Measure, quantifying for target contaminant is carried out according to interior target response factor result, and calculates standard deviation.
4.3.1 the verification of standard curve
The mixed standard solution newly configured is subjected to GC/MS analyses, calculates the difference of compound concentration and measured concentration.
Successively prepare gradient concentration for 20 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 500 μ g/L, 1000 μ g/L and
The standard solution of six kinds of phthalate ester materials of 2000 μ g/L, standard curve is established using internal standard method, obtains the range of linearity, calculates line
Property equation and related coefficient, and will the results are shown in table 4.
The parameters such as the linear equations of 4 six kinds of phthalate esters of table, related coefficient
Six kinds of materials of the results show are linear good in the range of the μ g/L of 20 μ g/L~2000, related coefficient 0.997 with
On.Carry out qualitative and quantitative using the standard substance solution of 20 μ g/Ls of the standard curve to newly preparing and compare with actual value
Compared with calculating standard deviation, the results are shown in Table 5.20% is respectively less than by the opposite mark deviation of 5 visible six kinds of object analyses of table, it is full
Foot analysis requires.
The measured value and standard deviation of 5 six kinds of phthalate esters of table
4.3.2 method detection limit is definite
After addition is five times in six kinds of phthalate ester pollutants of method detection limit concentration in four kinds of test matrix soil, use
The analysis method of optimization carries out pre-treatment, continuous seven sample introductions analysis, and computational methods detection limit according to the following formula：
MDLs=S × t (n-1,0.99)
Wherein, S is the standard deviation of seven results, and n-1 is the free degree, and 0.99 represents that confidential interval is 99%.
Five times of concentration addition recovery experiment result according to instrument detection limit calculates the method in various soil matrixes and detects
Limit, the results are shown in Table 6.Method detection limit can meet that phthalate ester is analyzed between 0.002~0.29mg/kg in four kinds of matrix
Requirement.
The method detection limit (mg/kg) of 6 four kinds of soil matrixes of table
4.3.4 blank sample is analyzed
The analysis of phthalate compound is easily disturbed by various contextual factors, therefore sample analysis is at the same time, various blank
The analysis of sample is very very necessary.Quality control procedure, except the analysis of sample to be tested, it is also necessary to carry out three kinds of samples
Analysis：I.e. overall process blank (i.e. using instrument and reagent identical in analytic process, is handled according to the process of sample treatment
Obtained blank value, characterizes all experimental implementations, experiment reagent, tester, artificial pollution and Instrumental Analysis etc. and is brought
Analytical error.Purpose is to ensure that the analysis of the object under the conditions of present analysis from the accurate of severe jamming and experimental implementation
Property), soil matrix blank (using soil matrix carry out analysis, it is therefore an objective to deduct different soils matrix belt come background do
Disturb), (addition decuples six kinds of phthalate ester targets of method detection limit concentration to matrix mark-on sample respectively in different soils matrix
Thing, then extraction and analysis measure is carried out, for verifying applicability of the analysis method in this kind of soil types).Use the rate of recovery, mark
The reappearance and reliability of the weighing results such as quasi- deviation.
The overall process blank value of the six kinds of phthalate esters measured using the analysis method of optimization is between 1.10 ± 0.03~37.08
Between ± 1.46ng, Fig. 9 is seen.DnBP and DEHP has a slightly higher background value as can be seen from Figure 9, and relative standard deviation also compared with
Greatly, this shows two kinds of compounds existing background value is of a relatively high in the environment, and error when sample analysis measures is also larger.This
Two kinds of compounds are most common in plasticizer, and DnBP is often used as rubber adhesive, cable sheath and various coating；And
DEHP is mainly used for producing food pack, toy for children, building materials and medical equipment.Plastics containing both compounds
Application of the product in people live is relatively broad, and their in vitro high background values also have corresponding report.Cause
Not only the recall rate of two kinds of pollutants is higher in surrounding medium for this, their background values in the environment are also higher.
The measure of blank soil mark-on sample is the influence measured for clearly different soil matrixes to target contaminant.
Concentration is that the mixed solution of six kinds of phthalate ester objects of 1mg/L is added into four kinds of soil, is carried using embodiment 4
The phthalate ester measuring method of confession carries out sample analysis, calculates the TIANZHU XINGNAO Capsul and standard deviation of object, the results are shown in Table 7.From
It is higher with the content of DnBP and DEHP in six kinds of target contaminants from the point of view of the blank value of four kinds of soil matrixes, it is secondly then DMP,
The content of three kinds of materials is respectively 49.2~142.6 μ g/kg, 152.3~427.0 μ g/kg and 27.5~50.0 μ g/kg.Such as table 8
It is shown, compared with Soil Loss safe level value in addition to the DMP in the DnBP in black earth and four kinds of soil is exceeded, Qi Tajun
In allowed band.
7 four kinds of matrix blank measure for examination soil of table
- it is not detected less than test limit.
Concentration limit (mg/kg) of the 8 six kinds of phthalate ester objects of table in Soil Loss
For the matrix of soil type, then using the total content of six kinds of target contaminants in black earth as highest.This
May be related with the property of Phthalate Esters in itself.Since in the content of organic matter higher soil or deposit, phthalate ester
Class material is easier to be adsorbed, and is not easy to shift, and black earth is that the content of organic matter is highest in four kinds of matrix, thus terephalic acid
The absorption of ester, the absorption of DEHP components especially strong to the lipophilicity of high molecular weight is the most obvious, and it is empty in matrix to result in it
Content is higher in white.
4.3.5 reference material of soil is analyzed
According to the type of the soil matrix of selection, (CRM119-100 (BNAs-Sandy Loam 6) and CRM136- are selected
100 two kinds of (BNAs-Clay 1) phthalate ester reference material of soil, carry out pre-treatment according to the method for optimization and analysis measure, meter
The difference between the reference value that simultaneously comparative measurements value and standard substance provide is calculated, so that the reliability of evaluation method.Putting as a result
It is 95% to believe section.
Since Phthalate Esters are highly prone to the interference of external analysis condition in the analysis process, experiment point every time
Analysis must include sample to be tested (14 or so), overall process blank (2~3), the matrix blank (2~3 of corresponding soils type
It is a) and Soil standard object of reference (marker for once corresponding to soil types need to be analyzed by often analyzing about 100 samples), to protect
Demonstrate,prove the reliability of experimental result.Every time the standard solution of upper machine analysis also must matching while using, to ensure the accurate of analysis result
Property.In the parallel continuous mode parallel with sample of overall process blank, blank mark-on, mark-on reclaims, mark-on sample, it is necessary to use
Internal standard compound is quantified, to ensure the quality control of process.
For the reliability of verification method, qualitative and quantitative determination is carried out to certified reference material, the results are shown in Table 9.Survey
Definite value is lain substantially within given confidential interval, it was demonstrated that the phthalate ester analysis method comparison optimized herein is reliable.
Comparison (mg/kg) * of 9 reference material of soil measured value of table and reference value
*：- it is the component not contained in standard substance.
4.3.6 actual soil and contaminated soil sample analysis
The polluted farmland soil that area is disassembled using Taizhou electronic waste is analyzed as actual sample and compares correlation
Result by references, verifies the reliability of analysis method；Parallel sample is analyzed at the same time, understands analysis method in actual sample continuous mode
In reappearance.
For reappearance of the verification method when measuring actual sample, our the agricultural land soil samples to pollution have carried out point
Analysis, adds standard substitution and sets three repetitions, analysis result is shown in Table 10.Substitute is added in overall process blank sample
DnBP-D4, the TIANZHU XINGNAO Capsul for obtaining substitute is 94.8% ± 7.8%, which ensure that the optimization method of this paper first
Meet the requirement of the trace analysis of phthalate ester in soil material.And for the analysis knot of selected polluted agricultural land regional soil sample
Fruit, six kinds of phthalate ester total concentrations of display are about 4.2mg/kg, and the closest electronic waste of the sample point disassembles a distance and is about
250m.Six kinds of phthalate ester target contaminants of this result and other research reports are when electronic waste is disassembled in the range of point 100m
Total concentration is up to 9.1~50.6mg/kg, up to the result base of 2.6~17.6mg/kg (Zhang etal., 2010) during 1000m
This is consistent, as a result in credible scope.
The actual contaminated soil sample analysis of table 10
In conclusion the assay method of phthalate ester in soil provided in an embodiment of the present invention can be measured accurately in soil
Phthalandione ester content, this method is easy reliable and phthalate ester suitable for Different Soil detects.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this area
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of assay method of phthalate ester in soil, it is characterised in that it comprises the following steps：
Soil to be detected and the diatomite toasted are compacted after mixing, and wrapped up with quartz sand, are compacted be examined
Survey block；
The detection block is subjected to Accelerate solvent extraction using dichloromethane as extracting solution and obtains extracting solution；
Extracting solution progress first time rotary evaporation is concentrated into 1~2mL, 5~8mL n-hexanes is added and mixes, then carries out the
Secondary rotating is evaporated to 1~2mL and obtains concentrate, and the concentrate is used the laggard promoting the circulation of qi analysis of hplc of column chromatography purification.
2. the assay method of phthalate ester in soil according to claim 1, it is characterised in that the diatomite toasted
It is that diatomite is toasted into 6~8h at 500~600 DEG C.
3. the assay method of phthalate ester in soil according to claim 1, it is characterised in that the soil to be detected and institute
It is 1~2g to state the diatomaceous mass ratio toasted：4~6g.
4. the assay method of phthalate ester in soil according to claim 1, it is characterised in that further include and toasted described
Diatomite modified after mixed with the soil to be detected, the modification is by the diatomite toasted, chitosan and the second
Acid solution presses 2~4g：1~2g：The ratio of 50~100ml is mixedly configured into colloid, and the colloid is instilled to mass concentration 10
Stirred evenly in~20% sodium hydrate aqueous solution, the liquor potassic permanganate of mass concentration 3~10% is added after filtration washing
In be heated to 55~70 DEG C and stir 2~3h, instill hydrochloric acid to pH to filter after neutral.
5. the assay method of phthalate ester in soil according to claim 1, it is characterised in that the Accelerate solvent extraction
Condition is：Preheat 5min；Heat 5min；Static state extraction 5min；Pressure 1500psi；100 DEG C of Extracting temperature；Nitrogen purges 120s；
Leacheate volume 36mL；Circulation is twice.
6. the assay method of phthalate ester in soil according to claim 1, it is characterised in that the first time rotary evaporation
It is to be carried out under 40 DEG C of water-baths, 410mbar pressure and 80rpm rotating speeds.
7. the assay method of phthalate ester in soil according to claim 1, it is characterised in that second of rotary evaporation
It is to be carried out under 40 DEG C of water-baths, 350mbar pressure and 80rpm rotating speeds.
8. the assay method of phthalate ester in soil according to claim 1, it is characterised in that the concentrate is used into column
During chromatography purification, filler is silica gel or florisil silica, is eluted in advance using n-hexane, and acetic acid second is used after adding sample concentration liquid
Ester or volume ratio are 1：4 n-hexane, acetone mixture.
9. the assay method of phthalate ester in soil according to claim 1, it is characterised in that the concentrate is used into column
During chromatography purification, filler is followed successively by mass ratio as 1~2 from top to bottom：4~6：10~12：1~2 anhydrous sodium sulfate, aoxidize
Aluminium, silica gel and anhydrous sodium sulfate, are 1~4 using n-hexane and volume ratio：1 n-hexane, acetone mixture elute in advance, add
It is 1~4 that volume ratio is used after sample concentration liquid：1 n-hexane, acetone mixture.
10. the assay method of phthalate ester in soil according to claim 1, it is characterised in that use the concentrate
During column chromatography purification, filler is followed successively by mass ratio as 1~2 from top to bottom：2~4：0.5~1.5：0.5~1.5 anhydrous slufuric acid
Sodium, florisil silica, activated carbon and anhydrous sodium sulfate, are 1~4 using n-hexane and volume ratio：1 n-hexane, acetone mixing
Liquid elutes in advance, and volume ratio is used as 1~4 after adding sample concentration liquid：1 n-hexane, acetone mixture.
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