CN107064367B - 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, ethanol amine prepares amino ferroso-ferric oxide, magnetic metal organic framework material MOF-5 is prepared by amino ferroso-ferric oxide obtained again, again using the magnetic MOF-5 of preparation as magnetic solid phase extraction material, high performance liquid chromatography measures 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 easily obtains, 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, and 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, benefit
With magnetic solid phase extraction (MSPE) technology, using magnetic metal organic framework material MOF-5 Solid phase extraction-HPLC come
Four kinds of carbendazim, triazolone, chlorfenapyr and fenpyroximate heterocyclic pesticides in determination of the environment water sample.
Background technique:
Farmland weed, pest and disease damage cause very big loss to agricultural production, and the application of pesticide 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, water resource caused by the use of pesticide
Pollution is one of the significant challenge for influencing environment sustainable development, a large amount of uses and industrial production of pesticide in agricultural production
In discharge cause pesticide and their metabolite to remain in crops, soil and water body.When soil applying pesticides with
Afterwards, remaining pesticide can enter water body by rainwash and interflow subsurface drainage, to threaten human health.Therefore, reinforce environment
The residue detection of pesticide is very necessary in water body.
Heterocyclic organic agricultural chemicals is a kind of pesticide with the fastest developing speed in recent years, is mainly used as Insecticides (tech) & Herbicides (tech)
And fungicide, also have as acaricide, rat poison and plant growth regulator etc., because it is efficient, low toxicity, the city residual quantity Di Er
Occupy very high share on.However, the use unreasonable to such pesticide also can cause environmental pollution, shadow is generated to the mankind
It rings.The method of analysis detection heterocyclic organic agricultural chemicals commonly used in the prior art is Sample Pretreatment Technique combination chromatographic isolation-
Spectrum detection technique, the Sample Pretreatment Technique of measurement heterocyclic organic agricultural chemicals mainly include Solid Phase Extraction, solid phase microextraction, divide
Dissipate liquid-liquid micro-extraction, magnetic solid phase extraction etc..Common method for separating and detecting has gas-chromatography (GC), gas chromatography-mass spectrography
(GC-MS), high performance liquid chromatography (HPLC), high performance liquid chromatography-mass spectrometry (HPLC-MS) and Capillary Electrophoresis (CE).Mesh
Before, all over the Sample Pretreatment Technique solid phase extraction used, that there is extraction times is long, extraction column blocking easily occurs, needs special
The defects of equipment；Solid-phase Microextraction has that extracting fiber service life is low；Dispersive liquid-liquid microextraction operation needs to make
With expensive centrifuge.Martins etc. discloses a kind of Solid Phase Extraction and gas chromatography tandem mass spectrometry combination measures earth's surface simultaneously
The remaining method of Multiple Pesticides in water and industrial wastewater, can Multiple Pesticides residual in Accurate Determining water sample, but in the method before
Treatment process is more long using solid phase column extracting time-consuming, and column easily blocks and service life is limited, and gas chromatography-mass spectrum used
With using and maintenance cost is high, it is difficult to large-scale application.
Magnetic solid phase extraction (MSPE) is a kind of novel sample pretreatment to be grown up based on magnetic Nano material,
Magnetic solid phase extraction mainly has the advantage that magnetic solid phase extraction makes solid phase extraction procedure simple compared with traditional solid phase extraction techniques
Dan Hua, it does not need expensive equipment, only can be realized by one external magnetic field of application and mutually separates；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 after rinse appropriate through that can be recycled；Magnetic solid phase extraction is in processing complexity
The problem of being blocked when sample there is no the column encountered in Solid Phase Extraction etc..
Metal-organic framework materials (metal-organic frameworks, MOFs) are class I organic-inorganic hybridized shapes
At nano-porous materials, be currently one of research hotspot and forward position of field of new materials.Metal-organic framework materials mainly by
The dimensional network structure formed containing nitrogen, the aromatic acid of the multiple tooth organic ligand of oxygen or alkali and inorganic metal center coordination bonding is brilliant
Body.Since inorganic component and organic component are combined together by MOFs material, therefore have compared to conventional porous materials many excellent
Point, if type is more, function is strong, porosity and large specific surface area, pore size Modulatory character are strong and with certain biocompatibility,
Therefore it can be applied in various modern Sample Pretreatment Technique.There has been no by magnetic metal organic framework material MOF- at present
5 report for heterocyclic pesticide enrichment 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 as magnetic solid phase extraction material, and high to the adsorption efficiency of four kinds of heterocyclic pesticides, analysis result is sensitive
Degree is high, easy to operate, and method is easy to spread universal.
Summary of the invention:
It is an object of the invention to overcome disadvantage of the existing technology, seek to design four kinds of heterocycles in a kind of environmental water sample
The analyzing detecting method of class pesticide, this method utilizes magnetic solid phase extraction (MSPE) technology, while using magnetic metal organic framework
For material MOF-5 as magnetic solid phase extraction material, this method has the characteristics that 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 the goals above, the analyzing detecting method of four kinds of heterocyclic pesticides has in environmental water sample of the present invention
Body the following steps are included:
Step 1: preparation magnetic metal organic framework material MOF-5:
(1) Iron(III) chloride hexahydrate of 1.0g is dissolved in the pure organic solvent of 20mL ethylene glycol, adds the sodium acetate of 3g
With 10mL ethanol amine, dissolution is sufficiently stirred；
(2) mixture obtained in step (1) is reacted into 8h under the conditions of 200 DEG C in solvent thermal reaction kettle, by solvent heat
Amino ferroso-ferric oxide (NH is made with milli-Q water in mixture obtained in reaction kettle2-Fe3O4), by NH obtained2-
Fe3O412h is dried in vacuo under the conditions of 60 DEG C；
(3) 0.5065g terephthalic acid (TPA) is dissolved in 40mL N, in N dimethyl amide pure (DMF), the hydration of 2.302g six 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) after finely dispersed reaction system obtained in step (4) being reacted 10h under the conditions of 120 DEG C, product
It is washed for several times with DMF, it is spare that 12h obtained magnetic metal organic framework material MOF-5 is dried in vacuo under the conditions of 80 DEG C；
Step 2: magnetic metal organic framework material MOF-5 Solid Phase Extraction is utilized, in conjunction with high performance liquid chromatography in water sample
Four kinds of heterocyclic pesticides are analyzed, the specific steps are as follows:
(1) it takes the magnetic metal organic framework material MOF-5 of 7mg in beaker, 20mL water sample (water sample is added into beaker
In the concentration of four kinds of heterocyclic pesticides be 0.25mg/L), ultrasonic 10min keeps 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
Eluent is dried up by nitrogen is made compound, then compound obtained 0.5mL methanol is redissolved and is made finely dispersed anti-
System is answered, by finely dispersed reaction system obtained into high performance liquid chromatography detection, the high performance liquid chromatography surveys condition such as
Under:
The testing conditions of high performance liquid chromatography: Agilent ZORBAX SB-C18 performance liquid chromatographic column, specification are selected
The following length is 150mm, and internal diameter 4.6mm, filler particles diameter is 5 μm；Detector be diode array UV detector and
Fluorescence detector, the measurement wavelength of the diode array UV detector are 215nm, the excitation wavelength of the fluorescence detector
270nm, launch wavelength 315nm；Autosampler sample introduction, sample volume: 10 μ L, the gradient elution program of 4 kinds of compounds such as following formula
It is shown:
The present invention investigates the principal element for influencing four kinds of heterocyclic pesticide recovery of extraction, calculates extraction and recovery
The optimum value of each factor when rate highest, then under conditions of each factor optimum value measure four kinds of heterocyclic pesticides working curve phase
Close parameter and method detection limit and precision, concrete technology the following steps are included:
Step 1: the optimum value of each factor when four kinds of heterocyclic pesticide recovery of extraction highests is calculated:
(1) investigation of the adsorbent amount to recovery of extraction
The present invention investigates influence of the adsorbent amount to recovery of extraction, and invention weighs 4,6,7,8, the magnetic gold of 10mg respectively
Belong to organic framework material MOF-5 in 20mL simulated water sample, four kinds of heterocyclic pesticide concentration are 0.25mg/L in water sample, work as magnetic
Property metal-organic framework materials MOF-5 dosage by 4mg increase be 7mg when, recovery of extraction with adsorbent amount increase and increase,
Illustrate to increase with magnetic metal organic framework material MOF-5 dosage, adsorption site increases, adsorbance increases；But when adsorbent
When dosage is greater than 7mg, it is further continued for increasing magnetic metal organic framework material MOF-5 dosage, carbendazim, triazolone recovery of extraction
Almost unchanged, chlorfenapyr, fenpyroximate are declined, so Solvent quantity chooses 7mg in the present invention.
(2) investigation of the water sample pH to recovery of extraction
The present invention investigates influence 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 as a result, when pH is from 2 to 3, the rate of recovery of four kinds of heterocyclic pesticides gradually rises
It is high；PH be 3-6 when, carbendazim, triazolone, fenpyroximate the rate of recovery gradually rise, the rate of recovery of chlorfenapyr is fallen before then 6
Shi Shengzhi highest.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
Extracting most suitable pH is 6；Experiment ultrapure water pH ≈ 6, the present invention select uncomfortable pH.
(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 magnetism
Absorption between material is unable to reach balance, influences recovery of extraction, the present invention investigated extraction time be respectively 3,5,8,10,
12, when 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, and triazolone and the fenpyroximate rate of recovery increase without significant, 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 type to recovery of extraction
The present invention investigates influence of the different eluant, eluents to the determinand elution efficiency for being adsorbed in adsorbent, and the present invention investigates
The influence of methanol, acetonitrile, four kinds of acetone, ethyl acetate pure organic solvents to recovery of extraction, ethyl acetate have highest
Elution efficiency, therefore the present invention chooses ethyl acetate as eluting solvent.
(5) investigation of the salinity to recovery of extraction
The present invention investigates influence of the salinity to the diffusion rate of water ionic strength and compound, to investigate salinity to water
The influence of four kinds of heterocyclic pesticide recovery of extraction in sample, be added in the present invention make water sample salinity be 0%, 0.5%,
1%, 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 raising and impacts to elution step, 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 dosage is
The rate of recovery of four kinds of heterocyclic pesticides is maximum when 3mL, and after dosage continues increase, recovery of extraction increases without significant, therefore this hair
Bright selection single elution agent dosage is 3mL.
(7) investigation of the elution time to recovery of extraction
The present invention investigates elution 2min, 3min and 4min, and the elution effect under the conditions of elution twice, the single elution time is
The rate of recovery of four kinds of heterocyclic pesticides is maximum when 3min, therefore the present invention chooses the single elution time as 3min.
Step 2: the working curve relevant parameter and method detection limit and precision of four kinds of heterocyclic pesticides of measurement:
(1) preparing four kinds of heterocyclic pesticide concentration is 1 μ g/L, 5 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 250 μ g/
L, the 20mL water sample of 500 μ g/L carries out high performance liquid chromatography-DAD/FLD measurement, surveys under the conditions of the magnetic solid phase extraction of optimization
Working curve regression equation, the range of linearity, the related coefficient (R of fixed four kinds of heterocyclic pesticides2) instrument detection limit and method detection
Limit.
(2) basic, normal, high three concentration that four kinds of heterocyclic pesticide concentration are 5 μ g/L, 50 μ g/L, 100 μ g/L is prepared
20mL simulated water sample is measured according to magnetic solid phase extraction step, is measured in parallel 3 investigation withinday precisions in each concentration point one day
(being indicated with relative standard deviation), three concentration once a day, measure 3 days investigation day to day precision (with relative standard deviation table
Show), the withinday precision relative standard deviation of four kinds of heterocyclic pesticides is measured within the scope of 2.98%-6.68%, it is accurate in the daytime
Relative standard deviation is spent within the scope of 2.79%-8.46%, is met analysis and is required.
Ethylene glycol of the present invention and N, N dimethyl amide pure (DMF) is pure organic solvent.
Compared with prior art, the present invention having the advantage that using magnetic metal organic framework material MOF-5, to four
Kind heterocyclic pesticide has preferable adsorption efficiency；Using magnetic metal organic framework material MOF-5 as magnetic solid phase extraction material
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, average recovery rate 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 raw materials used in the present invention is inexpensively easy simultaneously
, material preparation process is simple, and reaction condition is mild, and application environment is friendly, wide market.
Detailed description of the invention
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 diagram of the adsorbent amount of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 3 is influence diagram of the water sample pH of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 4 is influence diagram of the extraction time of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 5 is influence diagram of the eluant, eluent type of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 6 is influence diagram of the salinity of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 7 is influence diagram of the eluting agent of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 8 is influence diagram of the elution time of the present invention to four kinds of heterocyclic pesticide recovery of extraction.
Fig. 9 (1) moves the city reservoir not ultraviolet color of 100 μ g/L (a) of mark-on water sample and mark-on water sample (b) to be of the present invention
Spectrogram.
Fig. 9 (2) is the iridescent of the present invention for moving city reservoir not 100 μ g/L (a) of mark-on water sample and mark-on water sample (b)
Spectrogram
Figure 10 (1) is the ultraviolet of preceding Han Shuiku of the present invention not 100 μ g/L (a) of mark-on water sample and mark-on water sample (b)
Chromatogram.
Figure 10 (2) is the preceding Han Shuiku of the present invention not fluorescence of 100 μ g/L (a) of mark-on water sample and mark-on water sample (b)
Chromatogram
Figure 11 (1) is the Huanghe water of the present invention not ultraviolet color of 100 μ g/L (a) of mark-on water sample and mark-on water sample (b)
Spectrogram.
Figure 11 (2) is the iridescent of Huanghe water of the present invention not 100 μ g/L (a) of mark-on water sample and mark-on water sample (b)
Spectrogram.
Specific embodiment:
The invention will be further described by way of example and in conjunction with the accompanying drawings.
Embodiment 1:
In the environmental water sample that embodiment is related to four kinds of heterocyclic pesticides analyzing detecting method specifically includes the following steps:
Step 1: preparation magnetic metal organic framework material MOF-5:
(1) Iron(III) chloride hexahydrate of 1.0g is dissolved in 20mL ethylene glycol, adds the sodium acetate and 10mL ethyl alcohol of 3g
Dissolution is sufficiently stirred in amine；
(2) mixture obtained in step (1) is reacted into 8h under the conditions of 200 DEG C in solvent thermal reaction kettle, by solvent heat
Amino ferroso-ferric oxide (NH is made with milli-Q water in mixture obtained in reaction kettle2-Fe3O4), by NH obtained2-
Fe3O412h is dried in vacuo under the conditions of 60 DEG C；
(3) 0.5065g terephthalic acid (TPA) is dissolved in 40mL N, in N dimethyl amide (DMF), the hydration of 2.302g six 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) after finely dispersed reaction system obtained in step (4) being reacted 10h under the conditions of 120 DEG C, product
It is washed for several times with DMF, it is spare that 12h obtained magnetic metal organic framework material MOF-5 is dried in vacuo under the conditions of 80 DEG C；
Step 2: magnetic metal organic framework material MOF-5 Solid Phase Extraction is utilized, in conjunction with high performance liquid chromatography in water sample
Four kinds of heterocyclic pesticides are analyzed, the specific steps are as follows:
(1) it takes the magnetic metal organic framework material MOF-5 of 7mg in beaker, 20mL water sample (water sample is added into beaker
In the concentration of four kinds of heterocyclic pesticides be 0.25mg/L), ultrasonic 10min keeps 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
Eluent is dried up by nitrogen is made compound, then compound obtained 0.5mL methanol is redissolved and is made finely dispersed anti-
System is answered, by finely dispersed reaction system obtained into high performance liquid chromatography detection, the high performance liquid chromatography surveys condition such as
Under:
The testing conditions of high performance liquid chromatography: Agilent ZORBAX SB-C18 performance liquid chromatographic column, specification are selected
The following length is 150mm, and internal diameter 4.6mm, filler particles diameter is 5 μm；Detector be diode array UV detector and
Fluorescence detector, the measurement wavelength of the diode array UV detector are 215nm, the excitation wavelength of the fluorescence detector
270nm, launch wavelength 315nm；Autosampler sample introduction, sample volume: 10 μ L, the gradient elution program of 4 kinds of compounds such as following formula
It is shown:
Embodiment 2:
The present embodiment investigates the principal element for influencing four kinds of heterocyclic pesticide recovery of extraction, calculates and extracts back
The optimum value of each factor when yield highest, then under conditions of each factor optimum value measure four kinds of heterocyclic pesticides working curve
Relevant parameter and method detection limit and precision, concrete technology the following steps are included:
Step 1: the optimum value of each factor when four kinds of heterocyclic pesticide recovery of extraction highests is calculated:
(1) investigation of the adsorbent amount to recovery of extraction
The present embodiment investigates influence of the adsorbent amount to recovery of extraction, weighs 4,6,7,8,10mg magnetic metal respectively
Organic framework material MOF-5 is in 20mL simulated water sample, 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 dosage is 7mg by 4mg increase, recovery of extraction is used with adsorbent
Amount increases and increases, and illustrates to increase with magnetic metal organic framework material MOF-5 dosage, adsorption site increases, adsorbance increases；
But when the dosage of adsorbent is greater than 7mg, it is further continued for increasing magnetic metal organic framework material MOF-5 dosage, carbendazim, triazole
Ketone recovery of extraction is almost unchanged, and chlorfenapyr, fenpyroximate are declined, so Solvent quantity chooses 7mg in the present embodiment.
(2) investigation of the water sample pH to recovery of extraction
The present embodiment investigates influence of the water sample pH to the adsorption site activity of fiber material, has investigated water sample pH respectively
Recovery of extraction under the conditions of being 2,3,4,5,6,7 is as a result, from the figure 3, it may be seen that when pH is from 2 to 3, the recycling of four kinds of heterocyclic pesticides
Rate gradually rises；PH be 3-6 when, carbendazim, triazolone, fenpyroximate the rate of recovery gradually rise, the recycling 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 pesticide, which extracts most suitable pH,；Experiment ultrapure water pH ≈ 6, the present embodiment select 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
Absorption between property material is unable to reach balance, influences recovery of extraction, the present embodiment investigated extraction time be respectively 3,5,
8, when 10,12,15min four kinds of heterocyclic pesticides rate of recovery situation, as a result as shown in figure 4, extraction time is increased to by 5min
When 10min, recovery of extraction is increased, and continues to extend extraction time, triazolone and the fenpyroximate rate of recovery without significant 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 type to recovery of extraction
The present embodiment investigates influence of the different eluant, eluents to the determinand elution efficiency for being adsorbed in adsorbent, the present embodiment
Investigated the influence of methanol, acetonitrile, four kinds of acetone, ethyl acetate pure organic solvents 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 as eluting solvent.
(5) investigation of the salinity to recovery of extraction
The present embodiment investigates influence of the salinity to the diffusion rate of water ionic strength and compound, to investigate salinity pair
The influence of four kinds of heterocyclic pesticide recovery of extraction in water sample, be added in the present embodiment make water sample salinity be 0%,
0.5%, 1%, 5%, 10% sodium chloride (NaCl), as a result as shown in fig. 6, being added 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 increase to elution step
Suddenly it impacts, the present embodiment selects salinity for 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 after dosage continues increase, recovery of extraction increases without significant
It is long, therefore it is 3mL that the present embodiment, which chooses single elution agent dosage,.
(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 measurement:
(1) preparing four kinds of heterocyclic pesticide concentration is 1 μ g/L, 5 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 250 μ g/
L, the 20mL water sample of 500 μ g/L carries out high performance liquid chromatography-DAD/FLD and measures under the conditions of the magnetic solid phase extraction of optimization, and four
Working curve regression equation, the range of linearity, the related coefficient (R of kind heterocyclic pesticide2) instrument detection limit and method detection limit are such as
Shown in table 1.
(2) basic, normal, high three concentration that four kinds of heterocyclic pesticide concentration are 5 μ g/L, 50 μ g/L, 100 μ g/L is prepared
20mL simulated water sample is measured according to magnetic solid phase extraction step, is measured in parallel 3 investigation withinday precisions in each concentration point one day
(being indicated with relative standard deviation), three concentration once a day, measure 3 days investigation day to day precision (with relative standard deviation table
Show), the results are shown in Table 2, and the withinday precision relative standard deviation of four kinds of heterocyclic pesticides is in 2.98%-6.68% range
Interior, day to day precision relative standard deviation meets analysis and requires within the scope 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 measures
Embodiment 3:
Measurement Qingdao City move Han Shuiku before city reservoir, Qingdao City, in Huanghe water four kinds of heterocyclic pesticides residual quantity, acquisition
It is first filtered with the fast qualitative filter paper that aperture is 80-120 μm after 3 kinds of water samples, then with 0.45 μm of membrane filtration；It will be filtered
Water sample is measured using 1 the method for embodiment, and carries out accuracy test with 2 the method for embodiment, prepares four respectively
Kind heterocyclic pesticide concentration is that the actual water sample of basic, normal, high three concentration of 5 μ g/L, 50 μ g/L, 100 μ g/L carries out mark-on time
Yield test, each concentration point measure 3 times, calculate average value, relative standard deviation and the recovery of standard addition of 3 measurements；Wherein,
Four kinds of heterocyclic pesticides are not detected in three kinds of water sample blank；Moving city reservoir gravimetry experiment 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；It can from table
Out, the recovery of standard addition of the present embodiment is 80.30%-108.33%, relative standard deviation 2.96%-7.94%, therefore, sheet
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 preceding four kinds of heterocyclic pesticides of 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. the analyzing detecting method of four kinds of heterocyclic pesticides in a kind of 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 1: preparation magnetic metal organic framework material MOF-5:
(1) Iron(III) chloride hexahydrate of 1.0g is dissolved in 20mL ethylene glycol, adds the sodium acetate and 10mL ethanol amine of 3g, fills
Divide stirring and dissolving；
(2) mixture obtained in step (1) is reacted into 8h under the conditions of 200 DEG C in solvent thermal reaction kettle, by solvent thermal reaction
Amino ferroso-ferric oxide is made with milli-Q water in mixture obtained in kettle, by NH obtained2-Fe3O4Under the conditions of 60 DEG C
It is dried in vacuo 12h；
(3) 0.5065g terephthalic acid (TPA) is dissolved in 40mL N, in N dimethyl amide, the hydration of 2.302g six and zinc nitrate are dissolved in
In 50mL DMF, and it 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) after finely dispersed reaction system obtained in step (4) being reacted 10h under the conditions of 120 DEG C, product use
DMF is washed for several times, and it is spare that 12h obtained magnetic metal organic framework material MOF-5 is dried in vacuo under the conditions of 80 DEG C；
Step 2: magnetic metal organic framework material MOF-5 Solid Phase Extraction is utilized, in conjunction with high performance liquid chromatography to four kinds in water sample
Heterocyclic pesticide is analyzed, the specific steps are as follows:
(1) it takes the magnetic metal organic framework material MOF-5 of 7mg in beaker, 20mL water sample is added into beaker, four in water sample
The concentration of kind heterocyclic pesticide is 0.25mg/L, and ultrasonic 10min keeps magnetic metal organic framework material MOF-5 evenly 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 separates；
(3) magnetic Nano material, each 3mL are eluted in two times with 6mL ethyl acetate, each wash time is 3min, will be eluted
Liquid is dried up by nitrogen is made compound, then compound obtained is redissolved with 0.5mL methanol, finely dispersed reactant is made
System, by finely dispersed reaction system obtained into high performance liquid chromatography detection.
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 are as follows: Agilent ZORBAX SB-C18 performance liquid chromatographic column is selected, specification is length 150mm,
Internal diameter is 4.6mm, and filler particles diameter is 5 μm；Detector be diode array UV detector and fluorescence detector, described two
The measurement wavelength of pole pipe array UV detector is 215nm, the excitation wavelength 270nm of the fluorescence detector, launch wavelength
315nm；Autosampler sample introduction, sample volume: 10 μ L, the gradient elution program of 4 kinds of compounds are 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
Guarantee testing result accuracy, Solvent quantity is 7mg in the detection method.
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
Guarantee testing result accuracy, the pH value of water sample used is 6 in the detection method.
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
Guarantee testing result accuracy, extraction time chooses 10min in the detection method.
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
Guarantee testing result accuracy, eluting solvent selection ethyl acetate used in the detection method, the choosing of single elution agent dosage
Take 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 measures 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 more
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 calculation method of degree be prepare four kinds of heterocyclic pesticide concentration be 1 μ g/L, 5 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 250 μ
The 20mL water sample of g/L, 500 μ g/L, under the conditions of the magnetic solid phase extraction of optimization, using diode array UV detector and fluorescence
Detector is measured, the working curve regression equations of four kinds of heterocyclic pesticides, the range of linearity, related coefficient instrument detection limit and
Method detection limit is as follows:
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 verifying 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 calculation method of relative standard deviation and day to day precision relative standard deviation is that first four kinds of heterocyclic pesticide concentration of preparation are 5 μ
The 20mL simulated water sample of basic, normal, high three concentration of g/L, 50 μ g/L, 100 μ g/L is measured according still further to magnetic solid phase extraction step,
It is measured in parallel 3 investigation withinday precisions in each concentration point one day and is indicated with relative standard deviation, three concentration daily one
It is secondary, it measures 3 days investigation day to day precision and is indicated with relative standard deviation, result is the withinday precision of four kinds of heterocyclic pesticides
Relative standard deviation is within the scope of 2.98%-6.68%, and day to day precision relative standard deviation is in 2.79%-8.46% range
It is interior, meet precision of analysis requirement.
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