CN107064367A - The analyzing detecting method of four kinds of heterocyclic pesticides in a kind of environmental water sample - Google Patents
The analyzing detecting method of four kinds of heterocyclic pesticides in a kind of environmental water sample Download PDFInfo
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Abstract
The invention belongs to field of pesticide detection, it is related to a kind of analysis determining method of four kinds of heterocyclic pesticides in water sample, four kinds of heterocyclic pesticides are bacterium spirit, triazolone, chlorfenapyr, fenpyroximate, using Iron(III) chloride hexahydrate as raw material, it is aided with ethylene glycol again, sodium acetate, monoethanolamine prepares amino ferroso-ferric oxide, magnetic metal organic framework material MOF 5 is prepared by obtained amino ferroso-ferric oxide again, magnetic solid phase extraction material is used as using the magnetic MOF 5 prepared again, high performance liquid chromatography determines four kinds of heterocyclic pesticides as determining instrument, set up the analysis method of four kinds of heterocyclic pesticides in water sample, the invention is easy to operate, raw material is easily obtained, measurement result accuracy is high, average recovery rate is 80.30% 108.33%, relative standard deviation is 2.96% 7.94%, effect of extracting is good, analysis result is accurate, favorable reproducibility, wide market.
Description
Technical field：
The invention belongs to field of pesticide detection, it is related to a kind of analysis determining method of four kinds of heterocyclic pesticides in water sample, profit
With magnetic solid phase extraction (MSPE) technology, using magnetic metal organic framework material MOF-5 Solid phase extraction-HPLCs come
Carbendazim, triazolone, four kinds of heterocyclic pesticides of chlorfenapyr and fenpyroximate in determination of the environment water sample.
Background technology：
Farmland weed, pest and disease damage cause very big loss to agricultural production, and the administration of agricultural chemicals is greatly reduced and manually removed
The intensity and cost of careless and pre- preventing disease and pest, improve the modernization level of agricultural.However, the water resource that the use of agricultural chemicals is caused
Pollution is to influence one of significant challenge of environment sustainable development, a large amount of uses and industrial production of the agricultural chemicals in agricultural production
In discharge cause agricultural chemicals and their metabolite is remained among crops, soil and water body.When soil applying pesticides with
Afterwards, remaining agricultural chemicals can enter water body by rainwash and interflow subsurface drainage, so as to threaten human health.Therefore, environment is strengthened
The residue detection of water body Pesticides is very necessary.
Heterocyclic organic agricultural chemicals is a class agricultural chemicals with the fastest developing speed in recent years, and it is mainly used as Insecticides (tech) ＆ Herbicides (tech)
And bactericide, also have as acaricide, rat poison and plant growth regulator etc., because of its efficient, low toxicity, residual quantity Di Er cities
Occupy very high share on field.However, it is irrational to such agricultural chemicals using can also be polluted to environment, shadow is produced to the mankind
Ring.It is commonly used in the prior art analysis detection heterocyclic organic agricultural chemicals method for Sample Pretreatment Technique combination chromatographic isolation-
Spectrum detection technique, determining the Sample Pretreatment Technique of heterocyclic organic agricultural chemicals mainly includes SPE, SPME, divides
Dissipate liquid-liquid micro-extraction, magnetic solid phase extraction etc..Conventional method for separating and detecting has gas-chromatography (GC), gas chromatography-mass spectrography
(GC-MS), high performance liquid chromatography (HPLC), HPLC-MS (HPLC-MS) and Capillary Electrophoresis (CE).Mesh
Before, it there is extraction time all over the Sample Pretreatment Technique solid phase extraction used long, extraction column blocking easily occur, need special
The defects such as equipment；There is the problem of extracting fiber service life is low in Solid-phase Microextraction；Dispersive liquid-liquid microextraction operation needs make
With expensive centrifuge.Martins etc. discloses a kind of SPE and is combined with gas chromatography tandem mass spectrometry while determining earth's surface
The method that Multiple Pesticides are remained in water and industrial wastewater, Multiple Pesticides can be remained in Accurate Determining water sample, but in the method before
Processing procedure is time-consuming relatively long using solid phase column extracting, and post is easily blocked and service life is limited, and gas chromatography-mass spectrum used
It is high with use and maintenance cost, it is difficult to large-scale application.
Magnetic solid phase extraction (MSPE) is a kind of novel sample pretreatment grown up based on magnetic Nano material,
Magnetic solid phase extraction mainly has the advantage that compared with traditional solid phase extraction techniques：Magnetic solid phase extraction causes solid phase extraction procedure letter
Dan Hua, the equipment that it need not be expensive is that phase separation can be achieved only by applying an external magnetic field；It can divide in a short time
From the trace materials in bulk sample；Extraction process considerably increases the contact area of target analytes and adsorbing base, just
In the attachment of analyte；Magnetic adsorbent can be recycled after appropriate rinse；Magnetic solid phase extraction is in processing complexity
Be not in the problem of post run into SPE is blocked etc. during sample.
Metal-organic framework materials (metal-organic frameworks, MOFs) are class I organic-inorganic hybridized shapes
Into nano-porous materials, be currently one of study hotspot and forward position of field of new materials.Metal-organic framework materials it is main by
It is brilliant containing dimensional network structure formed by nitrogen, the aromatic acid of the multiple tooth organic ligand of oxygen or alkali and inorganic metal center coordination bonding
Body.Because inorganic component is combined together by MOFs materials with organic component, therefore have compared to conventional porous materials many excellent
Point, such as species are more, function is strong, porosity and specific surface area is big, hole size adjustable is strong and with certain biocompatibility,
Therefore it can be applied in various modern Sample Pretreatment Technique.Not yet have magnetic metal organic framework material MOF- at present
5 are used for the report that heterocyclic pesticide is enriched with analysis.Therefore, it is related to four kinds of heterocyclic pesticides (carbendazim, three in a kind of environmental water sample
Oxazolone, chlorfenapyr, fenpyroximate) analyzing detecting method, this method utilize magnetic solid phase extraction (MSPE) technology, using magnetic metal
Organic framework material MOF-5 is high to the adsorption efficiency of four kinds of heterocyclic pesticides as magnetic solid phase extraction material, and analysis result is sensitive
Degree is high, easy to operate, method popularization easy to spread.
The content of the invention：
It is an object of the invention to overcome the shortcoming that prior art is present, seek to design four kinds of heterocycles in a kind of environmental water sample
The analyzing detecting method of class agricultural chemicals, this method utilizes magnetic solid phase extraction (MSPE) technology, while using magnetic metal organic framework
Material MOF-5 is as magnetic solid phase extraction material, and this method has the characteristics of toxicity is low, reaction condition is simple, equipment cost is low, energy
It is enough that analysis detection quickly and efficiently is carried out to four kinds of heterocyclic pesticides in environmental water sample.
To achieve these goals, the analyzing detecting method of four kinds of heterocyclic pesticides has in environmental water sample of the present invention
Body comprises the following steps：
Step one：Prepare magnetic metal organic framework material MOF-5：
(1) 1.0g Iron(III) chloride hexahydrate is dissolved in the pure organic solvent of 20mL ethylene glycol, adds 3g sodium acetate
With 10mL monoethanolamines, dissolving is sufficiently stirred for；
(2) obtained mixture in step (1) is reacted into 8h in solvent thermal reaction kettle under the conditions of 200 DEG C, by solvent heat
Amino ferroso-ferric oxide (NH is made with milli-Q water in obtained mixture in reactor2-Fe3O4), by obtained NH2-
Fe3O412h is dried in vacuo under the conditions of 60 DEG C；
(3) 0.5065g terephthalic acid (TPA)s are dissolved in 40mL N, N dimethyl acid amides pure (DMF), 2.302g six hydration and
Zinc nitrate (Zn (NO3)2·6H2O) it is dissolved in 50mL DMF, and is slowly added dropwise into the DMF solution dissolved with terephthalic acid (TPA)
In；
(4) 0.8g NH will be added in gained mixed solution in step (3)2-Fe3O4, ultrasonic 30min, be made be uniformly dispersed
Reaction system；
(5) by obtained finely dispersed reaction system in step (4) after reaction 10h under the conditions of 120 DEG C, product
Washed with DMF for several times, the obtained magnetic metal organic framework material MOF-5 of 12h are dried in vacuo under the conditions of 80 DEG C standby；
Step 2：Using magnetic metal organic framework material MOF-5 SPEs, with reference to high performance liquid chromatography in water sample
Four kinds of heterocyclic pesticides are analyzed, and are comprised the following steps that：
(1) 7mg magnetic metal organic framework material MOF-5 is taken in beaker, and 20mL water sample (water samples are added into beaker
In the concentration of four kinds of heterocyclic pesticides be 0.25mg/L), ultrasonic 10min makes magnetic metal organic framework material MOF-5 uniform
It is scattered in water sample；
(2) the magnetic metal organic framework material MOF- of target compound will be adsorbed with using the effect of rubidium iron boron strong magnet
5 separate with water sample；
(3) magnetic Nano material, each 3mL are eluted in two times with 6mL ethyl acetate, each wash time is 3min, will
Compound is made by nitrogen drying in eluent, then obtained compound is obtained finely dispersed anti-with the redissolution of 0.5mL methanol
System is answered, obtained finely dispersed reaction system is entered into high performance liquid chromatography detection, the high performance liquid chromatography surveys condition such as
Under：
The testing conditions of high performance liquid chromatography：From Agilent ZORBAX SB-C18 performance liquid chromatographic columns, its specification
Following length is 150mm, and internal diameter is 4.6mm, a diameter of 5 μm of filler particles；Detector be diode array UV-detector and
Fluorescence detector, the measure wavelength of the diode array UV-detector is 215nm, the excitation wavelength of the fluorescence detector
270nm, launch wavelength 315nm；Automatic sampler sample introduction, sample size：10 μ L, the gradient elution program such as following formula of 4 kinds of compounds
It is shown：
The present invention is investigated to the principal element for influenceing four kinds of heterocyclic pesticide recovery of extraction, calculates extraction and recovery
The optimum value of each factor during rate highest, then under conditions of each factor optimum value determine four kinds of heterocyclic pesticides working curve phase
Related parameter and method detection limit and precision, concrete technology comprise the following steps：
Step one：The optimum value of each factor when calculating four kinds of heterocyclic pesticide recovery of extraction highests：
(1) investigation of the adsorbent amount to recovery of extraction
The present invention investigates influence of the adsorbent amount to recovery of extraction, invention weighs 4 respectively, 6,7,8,10mg magnetic gold
Belong to organic framework material MOF-5 in 20mL simulated water samples, four kinds of heterocyclic pesticide concentration are 0.25mg/L in water sample, work as magnetic
Property metal-organic framework materials MOF-5 consumptions by 4mg increase be 7mg when, recovery of extraction with adsorbent amount increase and increase,
Illustrate that adsorption site increases, adsorbance increases with the increase of magnetic metal organic framework material MOF-5 consumptions；But when adsorbent
When consumption is more than 7mg, it is further continued for increasing magnetic metal organic framework material MOF-5 consumptions, carbendazim, triazolone recovery of extraction
Almost unchanged, chlorfenapyr, fenpyroximate have declined, so Solvent quantity chooses 7mg in the present invention.
(2) investigations of the water sample pH to recovery of extraction
The present invention investigates influences of the water sample pH to the adsorption site activity of fiber material, and water sample has been investigated in invention respectively
PH be 2,3,4,5,6,7 under the conditions of recovery of extraction result, pH from 2 to 3 when, the rate of recovery of four kinds of heterocyclic pesticides gradually rises
It is high；When pH is 3-6, carbendazim, triazolone, the rate of recovery of fenpyroximate are gradually risen, and the rate of recovery of chlorfenapyr is fallen before then 6
Shi Shengzhi highests.After pH is higher than 6, four kinds of heterocyclic pesticide rate of recovery are all begun to decline, and illustrate material to four kinds of heterocyclic pesticides
It is 6 to extract most suitable pH；Experiment ultra-pure water pH ≈ 6, the uncomfortable pH of present invention selection.
(3) investigation of the extraction time to recovery of extraction
The present invention investigates influence of the extraction time to recovery of extraction, and extraction time deficiency can make target compound and magnetic
Absorption between material is unable to reach balance, influences recovery of extraction, the present invention investigated extraction time be respectively 3,5,8,10,
12nd, during 15min four kinds of heterocyclic pesticides rate of recovery situation, when extraction time increases to 10min by 5min, recovery of extraction liter
Height, continues to extend extraction time, triazolone and the fenpyroximate rate of recovery without notable growth, carbendazim and the chlorfenapyr rate of recovery slightly under
Drop, illustrates that absorption has reached balance, therefore it is 10min that the present invention, which chooses extraction time,.
(4) investigation of the eluant, eluent species to recovery of extraction
The present invention investigates different eluant, eluents and investigated to being adsorbed in the influence of the determinand elution efficiency of adsorbent, the present invention
The influence of methanol, acetonitrile, acetone, four kinds of pure organic solvents of ethyl acetate to recovery of extraction, ethyl acetate has highest
Elution efficiency, therefore present invention selection ethyl acetate is used as eluting solvent.
(5) investigation of the salinity to recovery of extraction
The present invention investigates influence of the salinity to water ionic strength and the diffusion rate of compound, to investigate salinity to water
Added in the influence of four kinds of heterocyclic pesticide recovery of extraction in sample, the present invention make water sample salinity be respectively for 0%, 0.5%,
1%th, 5%, 10% sodium chloride (NaCl), is added after NaCl, and ascendant trend is presented in the rate of recovery of four kinds of heterocyclic pesticides, says
The addition of bright salt is conducive to the extraction of target substance, but salinity continues rise and elution step is impacted, present invention selection
Salinity is 10%.
(6) investigation of the eluting agent to recovery of extraction
The present invention investigates elution 2mL, 3mL and 4mL, the elution effect under the conditions of elution twice, and single elution agent consumption is
The rate of recovery of four kinds of heterocyclic pesticides is maximum during 3mL, and consumption continues after increasing, and recovery of extraction increases without notable, therefore this hair
Bright selection single elution agent consumption is 3mL.
(7) investigation of the elution time to recovery of extraction
The present invention investigates elution 2min, 3min and 4min, the elution effect under the conditions of elution twice, and the single elution time is
The rate of recovery of four kinds of heterocyclic pesticides is maximum during 3min, therefore the present invention chooses the single elution time for 3min.
Step 2：The working curve relevant parameter and method detection limit and precision of four kinds of heterocyclic pesticides of measure：
(1) it is 1 μ g/L, 5 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 250 μ g/ to prepare four kinds of heterocyclic pesticide concentration
L, 500 μ g/L 20mL water samples, under the conditions of the magnetic solid phase extraction of optimization, carry out high performance liquid chromatography-DAD/FLD and determine, survey
Working curve regression equation, the range of linearity, the coefficient correlation (R of fixed four kinds of heterocyclic pesticides2) instrument detection limit and method detection
Limit.
(2) it is 5 μ g/L, 50 μ g/L, 100 μ g/L basic, normal, high three concentration to prepare four kinds of heterocyclic pesticide concentration
20mL simulated water samples, according to magnetic solid phase extraction step measurements, 3 investigation withinday precisions of parallel determination in each concentration point one day
(being represented with relative standard deviation), three concentration once a day, are determined and investigate within 3 days day to day precision (with relative standard deviation table
Show), the withinday precision relative standard deviation of four kinds of heterocyclic pesticides is measured in the range of 2.98%-6.68%, it is accurate in the daytime
Relative standard deviation is spent in the range of 2.79%-8.46%, is met analysis and is required.
Ethylene glycol of the present invention and N, N dimethyl acid amides pure (DMF) is pure organic solvent.
The present invention compared with prior art, with advantages below：Using magnetic metal organic framework material MOF-5, to four
Planting heterocyclic pesticide has preferable adsorption efficiency；Magnetic solid phase extraction material is used as using magnetic metal organic framework material MOF-5
Material, using high performance liquid chromatography-ultraviolet fluorescent detector, establishes the analysis method of four kinds of heterocyclic pesticides in water sample,
This method is easy to operate, greatlys save analysis time and cost, and average recovery rate is 80.30%-108.33%, and relative standard is inclined
Difference is 2.96%-7.94%, and effect of extracting is good, and analysis result is accurate, favorable reproducibility；The present invention is raw materials used cheap easy simultaneously
, material preparation process is simple, and reaction condition is gentle, and application environment is friendly, wide market.
Brief description of the drawings
Fig. 1 is the red of amino ferroso-ferric oxide (a) of the present invention and magnetic metal organic framework material MOF-5 (b)
External spectrum figure.
Fig. 2 is influence figure of the adsorbent amount of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 3 is influence figures of the water sample pH of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 4 is influence figure of the extraction time of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 5 is influence figure of the eluant, eluent species of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 6 is influence figure of the salinity of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 7 is influence figure of the eluting agent of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 8 is influence figure of the elution time of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 9 (1) is the ultraviolet color of the present invention for moving city reservoir not the μ g/L (a) of mark-on water sample 100 and mark-on water sample (b)
Spectrogram.
Fig. 9 (2) is the iridescent of the present invention for moving city reservoir not the μ g/L (a) of mark-on water sample 100 and mark-on water sample (b)
Spectrogram
Figure 10 (1) is the ultraviolet of preceding Han Shuiku of the present invention not the μ g/L (a) of mark-on water sample 100 and mark-on water sample (b)
Chromatogram.
Figure 10 (2) is the fluorescence of preceding Han Shuiku of the present invention not the μ g/L (a) of mark-on water sample 100 and mark-on water sample (b)
Chromatogram
Figure 11 (1) is the ultraviolet color of Huanghe water of the present invention not the μ g/L (a) of mark-on water sample 100 and mark-on water sample (b)
Spectrogram.
Figure 11 (2) is the iridescent of Huanghe water of the present invention not the μ g/L (a) of mark-on water sample 100 and mark-on water sample (b)
Spectrogram.
Embodiment：
Below by embodiment and the invention will be further described with reference to accompanying drawing.
Embodiment 1：
The analyzing detecting method of four kinds of heterocyclic pesticides specifically includes following steps in the environmental water sample that embodiment is related to：
Step one：Prepare magnetic metal organic framework material MOF-5：
(1) 1.0g Iron(III) chloride hexahydrate is dissolved in 20mL ethylene glycol, adds 3g sodium acetate and 10mL ethanol
Amine, is sufficiently stirred for dissolving；
(2) obtained mixture in step (1) is reacted into 8h in solvent thermal reaction kettle under the conditions of 200 DEG C, by solvent heat
Amino ferroso-ferric oxide (NH is made with milli-Q water in obtained mixture in reactor2-Fe3O4), by obtained NH2-
Fe3O412h is dried in vacuo under the conditions of 60 DEG C；
(3) 0.5065g terephthalic acid (TPA)s are dissolved in 40mL N, N dimethyl acid amides (DMF), 2.302g six is hydrated and nitre
Sour zinc (Zn (NO3)2·6H2O) it is dissolved in 50mL DMF, and is slowly added dropwise into the DMF solution dissolved with terephthalic acid (TPA)；
(4) 0.8g NH will be added in gained mixed solution in step (3)2-Fe3O4, ultrasonic 30min, be made be uniformly dispersed
Reaction system；
(5) by obtained finely dispersed reaction system in step (4) after reaction 10h under the conditions of 120 DEG C, product
Washed with DMF for several times, the obtained magnetic metal organic framework material MOF-5 of 12h are dried in vacuo under the conditions of 80 DEG C standby；
Step 2：Using magnetic metal organic framework material MOF-5 SPEs, with reference to high performance liquid chromatography in water sample
Four kinds of heterocyclic pesticides are analyzed, and are comprised the following steps that：
(1) 7mg magnetic metal organic framework material MOF-5 is taken in beaker, and 20mL water sample (water samples are added into beaker
In the concentration of four kinds of heterocyclic pesticides be 0.25mg/L), ultrasonic 10min makes magnetic metal organic framework material MOF-5 uniform
It is scattered in water sample；
(2) the magnetic metal organic framework material MOF- of target compound will be adsorbed with using the effect of rubidium iron boron strong magnet
5 separate with water sample；
(3) magnetic Nano material, each 3mL are eluted in two times with 6mL ethyl acetate, each wash time is 3min, will
Compound is made by nitrogen drying in eluent, then obtained compound is obtained finely dispersed anti-with the redissolution of 0.5mL methanol
System is answered, obtained finely dispersed reaction system is entered into high performance liquid chromatography detection, the high performance liquid chromatography surveys condition such as
Under：
The testing conditions of high performance liquid chromatography：From Agilent ZORBAX SB-C18 performance liquid chromatographic columns, its specification
Following length is 150mm, and internal diameter is 4.6mm, a diameter of 5 μm of filler particles；Detector be diode array UV-detector and
Fluorescence detector, the measure wavelength of the diode array UV-detector is 215nm, the excitation wavelength of the fluorescence detector
270nm, launch wavelength 315nm；Automatic sampler sample introduction, sample size：10 μ L, the gradient elution program such as following formula of 4 kinds of compounds
It is shown：
Embodiment 2：
The present embodiment is investigated to the principal element for influenceing four kinds of heterocyclic pesticide recovery of extraction, is calculated and is extracted back
The optimum value of each factor during yield highest, then under conditions of each factor optimum value determine four kinds of heterocyclic pesticides working curve
Relevant parameter and method detection limit and precision, concrete technology comprise the following steps：
Step one：The optimum value of each factor when calculating four kinds of heterocyclic pesticide recovery of extraction highests：
(1) investigation of the adsorbent amount to recovery of extraction
The present embodiment investigates influence of the adsorbent amount to recovery of extraction, weigh 4 respectively, 6,7,8,10mg magnetic metals
Organic framework material MOF-5 is in 20mL simulated water samples, and four kinds of heterocyclic pesticide concentration are 0.25mg/L in water sample, as a result such as
Shown in Fig. 2, when magnetic metal organic framework material MOF-5 consumptions are 7mg by 4mg increases, recovery of extraction is used with adsorbent
Amount increases and increased, and illustrates that adsorption site increases, adsorbance increases with the increase of magnetic metal organic framework material MOF-5 consumptions；
But when the consumption of adsorbent is more than 7mg, it is further continued for increasing magnetic metal organic framework material MOF-5 consumptions, carbendazim, triazole
Ketone recovery of extraction is almost unchanged, and chlorfenapyr, fenpyroximate have declined, so Solvent quantity chooses 7mg in the present embodiment.
(2) investigations of the water sample pH to recovery of extraction
The present embodiment investigates influences of the water sample pH to the adsorption site activity of fiber material, and water sample pH has been investigated respectively
For the recovery of extraction result under the conditions of 2,3,4,5,6,7, from the figure 3, it may be seen that pH from 2 to 3 when, the recovery of four kinds of heterocyclic pesticides
Rate gradually rises；When pH is 3-6, carbendazim, triazolone, the rate of recovery of fenpyroximate gradually rise, and the recovery of chlorfenapyr takes the lead in down
Drop then rises to highest at 6.After pH is higher than 6, four kinds of heterocyclic pesticide rate of recovery are all begun to decline, and illustrate that material is miscellaneous to four kinds
It is 6 that ring class agricultural chemicals, which extracts most suitable pH,；Experiment ultra-pure water pH ≈ 6, the present embodiment selects uncomfortable pH.
(3) investigation of the extraction time to recovery of extraction
The present embodiment investigates influence of the extraction time to recovery of extraction, and extraction time deficiency can make target compound and magnetic
Property material between absorption be unable to reach balance, influence recovery of extraction, the present embodiment investigated extraction time be respectively 3,5,
8th, 10,12, during 15min four kinds of heterocyclic pesticides rate of recovery situation, as a result as shown in figure 4, extraction time is increased to by 5min
During 10min, recovery of extraction rise continues to extend extraction time, triazolone and the fenpyroximate rate of recovery are without notable growth, carbendazim
It is slightly decreased with the chlorfenapyr rate of recovery, illustrates that absorption has reached balance, therefore it is 10min that the present embodiment, which chooses extraction time,.
(4) investigation of the eluant, eluent species to recovery of extraction
The present embodiment investigates different eluant, eluents to being adsorbed in the influence of the determinand elution efficiency of adsorbent, the present embodiment
Investigated the influence of methanol, acetonitrile, acetone, four kinds of pure organic solvents of ethyl acetate to recovery of extraction, as a result as shown in figure 5,
Ethyl acetate has highest elution efficiency, therefore the present embodiment chooses ethyl acetate and is used as eluting solvent.
(5) investigation of the salinity to recovery of extraction
The present embodiment investigates influence of the salinity to water ionic strength and the diffusion rate of compound, to investigate salinity pair
Added in water sample in the influence of four kinds of heterocyclic pesticide recovery of extraction, the present embodiment make water sample salinity be respectively for 0%,
0.5%th, 1%, 5%, 10% sodium chloride (NaCl), as a result as shown in fig. 6, adding after NaCl, four kinds of heterocyclic pesticides
Ascendant trend is presented in the rate of recovery, illustrates that the addition of salt is conducive to the extraction of target substance, but salinity continues to raise to elution step
Suddenly impact, the present embodiment selection salinity is 10%.
(6) investigation of the eluting agent to recovery of extraction
The present embodiment investigates elution 2mL, 3mL and 4mL, the elution effect under the conditions of elution twice, as shown in fig. 7, single
The rate of recovery of four kinds of heterocyclic pesticides is maximum when eluting agent is 3mL, and consumption continues after increasing, and recovery of extraction is without notable increasing
It is long, therefore it is 3mL that the present embodiment, which chooses single elution agent consumption,.
(7) investigation of the elution time to recovery of extraction
The present embodiment investigates elution 2min, 3min and 4min, the elution effect under the conditions of elution twice, as shown in figure 8, single
The rate of recovery of four kinds of heterocyclic pesticides is maximum when secondary elution time is 3min, therefore the present embodiment selection single elution time is
3min。
Step 2：The working curve relevant parameter and method detection limit and precision of four kinds of heterocyclic pesticides of measure：
(1) it is 1 μ g/L, 5 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 250 μ g/ to prepare four kinds of heterocyclic pesticide concentration
L, 500 μ g/L 20mL water samples, under the conditions of the magnetic solid phase extraction of optimization, carry out high performance liquid chromatography-DAD/FLD and determine, and four
Plant working curve regression equation, the range of linearity, the coefficient correlation (R of heterocyclic pesticide2) instrument detection limit and method detection limit are such as
Shown in table 1.
(2) it is 5 μ g/L, 50 μ g/L, 100 μ g/L basic, normal, high three concentration to prepare four kinds of heterocyclic pesticide concentration
20mL simulated water samples, according to magnetic solid phase extraction step measurements, 3 investigation withinday precisions of parallel determination in each concentration point one day
(being represented with relative standard deviation), three concentration once a day, are determined and investigate within 3 days day to day precision (with relative standard deviation table
Show), as a result as shown in table 2, the withinday precision relative standard deviation of four kinds of heterocyclic pesticides is in 2.98%-6.68% scopes
Interior, day to day precision relative standard deviation meets analysis and required in the range of 2.79%-8.46%.
The working curve relevant parameter and method detection limit of 1 four kinds of heterocyclic pesticides of table
The precision of 2 four kinds of heterocyclic pesticides of table is determined
Embodiment 3：
The residual quantity that four kinds of heterocyclic pesticides in Han Shuiku, Huanghe water before city reservoir, Qingdao City move in Qingdao City is determined, collection
First filtered after 3 kinds of water samples with fast qualitative filter paper that aperture is 80-120 μm, then with 0.45 μm of membrane filtration；After filtering
Water sample is measured using the methods described of embodiment 1, and carries out degree of accuracy test with the methods described of embodiment 2, and four are prepared respectively
It is 5 μ g/L, 50 μ g/L, the actual water sample progress mark-on time of 100 μ g/L basic, normal, high three concentration to plant heterocyclic pesticide concentration
Yield is tested, and each concentration point is determined 3 times, calculates average value, relative standard deviation and the recovery of standard addition of 3 measure；Wherein,
Four kinds of heterocyclic pesticides are not detected in three kinds of water sample blank；Move city reservoir gravimetry experiment and the results are shown in Table 3, preceding Korea Spro's reservoir water experimental result
4 are shown in Table, Huanghe water experimental result is shown in Table 5；Actual water sample blank and mark-on chromatogram are shown in Fig. 9-11 respectively；Can from table
Go out, the recovery of standard addition of the present embodiment is 80.30%-108.33%, and relative standard deviation is 2.96%-7.94%, therefore, this
The effect of extracting of embodiment is good, and analysis result is accurate, favorable reproducibility.
Table 3 moves the preci-sion and accuracy result (n=3, μ g/L) of four kinds of heterocyclic pesticides of city reservoir mark-on
The preci-sion and accuracy result (n=3, μ g/L) of the four kinds of heterocyclic pesticides of preceding Korea Spro's reservoir water mark-on of table 4
The preci-sion and accuracy result (n=3, μ g/L) of table 5 Huanghe water mark-on, four kinds of heterocyclic pesticides
。
Claims (9)
1. a kind of analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample, it is characterised in that four kinds of heterocyclic pesticides
Including carbendazim, triazolone, chlorfenapyr and fenpyroximate, concrete technology operating procedure is as follows：
Step one：Prepare magnetic metal organic framework material MOF-5：
(1) 1.0g Iron(III) chloride hexahydrate is dissolved in 20mL ethylene glycol, adds 3g sodium acetate and 10mL monoethanolamines, fill
Divide stirring and dissolving；
(2) obtained mixture in step (1) is reacted into 8h in solvent thermal reaction kettle under the conditions of 200 DEG C, by solvent thermal reaction
Amino ferroso-ferric oxide (NH is made with milli-Q water in obtained mixture in kettle2-Fe3O4), by obtained NH2-Fe3O4
12h is dried in vacuo under the conditions of 60 DEG C；
(3) 0.5065g terephthalic acid (TPA)s are dissolved in 40mL N, N dimethyl acid amides (DMF), 2.302g six is hydrated and zinc nitrate
(Zn(NO3)2·6H2O) it is dissolved in 50mL DMF, and is slowly added dropwise into the DMF solution dissolved with terephthalic acid (TPA)；
(4) 0.8g NH will be added in gained mixed solution in step (3)2-Fe3O4, ultrasonic 30min is made finely dispersed anti-
Answer system；
(5) by obtained finely dispersed reaction system in step (4) after reaction 10h under the conditions of 120 DEG C, the product use of institute
DMF is washed for several times, the obtained magnetic metal organic framework material MOF-5 of 12h is dried in vacuo under the conditions of 80 DEG C standby；
Step 2：Using magnetic metal organic framework material MOF-5 SPEs, with reference to high performance liquid chromatography to four kinds in water sample
Heterocyclic pesticide is analyzed, and is comprised the following steps that：
(1) 7mg magnetic metal organic framework material MOF-5 is taken in beaker, and 20mL water samples are added into beaker (four in water sample
The concentration for planting heterocyclic pesticide is 0.25mg/L), ultrasonic 10min makes magnetic metal organic framework material MOF-5 dispersed
In water sample；
(2) using the effect of rubidium iron boron strong magnet will be adsorbed with the magnetic metal organic framework material MOF-5 of target compound with
Water sample is separated；
(3) magnetic Nano material is eluted in two times with 6mL ethyl acetate, each 3mL, each wash time is 3min, will be eluted
Compound is made by nitrogen drying in liquid, then obtained compound 0.5mL methanol is redissolved into obtained finely dispersed reactant
System, high performance liquid chromatography detection is entered by obtained finely dispersed reaction system.
2. the analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample according to claim 1, it is characterised in that high
Effect liquid phase chromatogram surveys condition：From Agilent ZORBAX SB-C18 performance liquid chromatographic columns, its specification is length 150mm,
Internal diameter is 4.6mm, a diameter of 5 μm of filler particles；Detector is diode array UV-detector and fluorescence detector, described two
The measure wavelength of pole pipe array UV-detector is 215nm, the excitation wavelength 270nm of the fluorescence detector, launch wavelength
315nm；Automatic sampler sample introduction, sample size：10 μ L, the gradient elution program of 4 kinds of compounds is as shown in the table：
3. the analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample according to claim 1, it is characterised in that be
Ensure that Solvent quantity is 7mg in testing result accuracy, detection method of the present invention.
4. the analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample according to claim 1, it is characterised in that be
The pH value for ensureing water sample used in testing result accuracy, detection method of the present invention is 6.
5. the analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample according to claim 1, it is characterised in that be
Ensure that extraction time chooses 10min in testing result accuracy, detection method of the present invention.
6. the analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample according to claim 1, it is characterised in that be
Ensure that eluting solvent used chooses ethyl acetate, single elution agent in testing result accuracy, detection method of the present invention
Consumption chooses 3mL.
7. the analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample according to claim 1, it is characterised in that should
The withinday precision relative standard deviation for four kinds of heterocyclic pesticides that analyzing detecting method is measured is 2.98%-6.68%, in the daytime
Precision relative standard deviation is 2.79%-8.46%.
8. the analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample according to claim 1, it is characterised in that many
Bacterium spirit, triazolone, the working curve relevant parameter of four kinds of heterocyclic pesticides of chlorfenapyr and fenpyroximate and method detection limit and precision
The computational methods of degree are that four kinds of heterocyclic pesticide concentration of preparation are 1 μ g/L, 5 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 250 μ
G/L, 500 μ g/L 20mL water samples, under the conditions of the magnetic solid phase extraction of optimization, carry out high performance liquid chromatography-DAD/FLD and determine,
Working curve regression equation, the range of linearity, the coefficient correlation (R of four kinds of heterocyclic pesticides2) instrument detection limit and method detection limit
Such as following table：
9. the analyzing detecting method of four kinds of heterocyclic pesticides in environmental water sample according to claim 1, it is characterised in that logical
Spend checking carbendazim, triazolone, the withinday precision relative standard deviation of four kinds of heterocyclic pesticides of chlorfenapyr and fenpyroximate and day
Between precision relative standard deviation verify the accuracy of the analysis method, the withinday precision of four kinds of heterocyclic pesticides
The computational methods of relative standard deviation and day to day precision relative standard deviation are that first four kinds of heterocyclic pesticide concentration of preparation are 5 μ
G/L, 50 μ g/L, the 20mL simulated water samples of 100 μ g/L basic, normal, high three concentration, according still further to magnetic solid phase extraction step measurements,
Parallel determination is investigated withinday precisions and represented with relative standard deviation, three concentration daily one for 3 times in each concentration point one day
It is secondary, determine and investigate within 3 days day to day precision and represented with relative standard deviation, be as a result the withinday precision of four kinds of heterocyclic pesticides
Relative standard deviation is in the range of 2.98%-6.68%, and day to day precision relative standard deviation is in 2.79%-8.46% scopes
It is interior, meet precision of analysis requirement.
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