CN109725075A - A kind of measuring method of water quality phenolic compound - Google Patents
A kind of measuring method of water quality phenolic compound Download PDFInfo
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- CN109725075A CN109725075A CN201811587446.3A CN201811587446A CN109725075A CN 109725075 A CN109725075 A CN 109725075A CN 201811587446 A CN201811587446 A CN 201811587446A CN 109725075 A CN109725075 A CN 109725075A
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Abstract
The invention discloses a kind of measuring methods of water quality phenolic compound, are related to field of water quality detection, include the following steps: Step 1: acquiring the water sample of sufficient amount using vial;Step 2: reducing agent and appropriate hydrochloric acid adjusting pH < 2 is added after water sampling immediately;Step 3: the water sample of acquisition is poured into separatory funnel;Step 4: extracting to target compound, organic extractant phase liquid is obtained, and be dehydrated to organic extractant phase liquid using anhydrous sodium sulfate;Step 6: constant volume is concentrated in organic extractant phase liquid after dehydration, upper machine measurement obtains sample spectrogram;Step 7: sample spectrogram is compared with standard spectrogram, finds out each target compound and go out peak position, and calculate ρ in conjunction with calibration curveMark;Step 8: according to formula ρi=ρMark×V1×1000/V2Calculate the concentration ρ of target compound in water samplei.Since water sample is added to reducing agent in preceding processing, thus the probability of phenolic compound oxidation is significantly reduced, to improve detection precision.
Description
Technical field
The present invention relates to field of water quality detection, in particular to a kind of measuring method of water quality phenolic compound.
Background technique
As Chinese society macroeconomic is horizontally constantly promoted, country and various circles of society are for asking in terms of environmental protection
Topic is also increasingly to pay close attention to.And water resource is as our bases for the survival of mankind, along with China is exactly originally a water
The big country of shortage of resources so the protection for water resource, and becomes compatriots and the responsibility shirked is not allowed by various circles of society.
During this period, for the detection of water quality, become us to the weight adopted an effective measure during fwaater resources protection
Reference index is wanted, such as passes through amount of nitrogen oxides, microbial pathogens content, the content of beary metal etc. in detection water.
And phenolic compound is to common are machine pollutant in water body, sum has as many as several hundred kinds.Meanwhile phenolic compound
It is from a wealth of sources, during the industrial and agricultural production for generally resulting from the mankind, such as the industry such as coking, papermaking, medicine, printing and dyeing, chemical industry
Discharge, degradation of pesticide and environment itself biogeochemical cycle all there may be.And these phenolic compounds have cause
Cancer, teratogenesis and mutagenic genotoxic potential, long-term drinking by the drinking water of phenolic compounds pollution, can cause dizzy, eruption and
The symptom of the nervous systems such as itch, part phenolic substances have been put into Environment Priority detection organic pollutant.Such as world health
Organize (WHO) that 2,4,6- trichlorophenol, 2,4,6,-Ts and pentachlorophenol are classified as 2B pollutant, it is possible to there is carcinogenic effect to the mankind.Institute
With the monitoring for phenols compound in water quality is that we cannot be neglected important link.
For this purpose, China has promulgated HJ676-2013 " measurement liquid-liquid extraction/gas-chromatography of water quality phenolic compound for 2013
Method " standard, primarily directed to the measurement of main 13 kinds of seriously polluted phenols compounds in water quality.
But due to the wherein phenolic compound in 6 in phenolic compound in 13, phenol, 2-chlorophenol, 3- cresols, 2,4-
Xylenol, 4- chlorophenol and 6 kinds of substances of the chloro- 3- cresols of 4- are more unstable with respect to remaining 7 kinds of phenolic compound, are easily oxidized, institute
When doing blank water sample detection, often can not all obtain accurate peak value, thus, the mistake of water sample detection easy to increase
Difference.
Summary of the invention
It is easy to operate the object of the present invention is to provide a kind of measuring method of water quality phenolic compound, it can be effectively
Improve the accuracy of water quality detection.
Above-mentioned technical purpose of the invention has the technical scheme that a kind of water quality phenolic compound
Measuring method includes the following steps:
Step 1: utilizing the water sample of vial acquisition sufficient amount;
Step 2: reducing agent and appropriate hydrochloric acid adjusting pH < 2 is added after water sampling immediately;
Step 3: the water sample of acquisition is poured into separatory funnel;
Step 4: extracting to target compound, organic extractant phase liquid is obtained, and using anhydrous sodium sulfate to organic extractant phase
Liquid is dehydrated;
Step 6: constant volume is concentrated in organic extractant phase liquid after dehydration, upper machine measurement obtains sample spectrogram;
Step 7: sample spectrogram is compared with standard spectrogram, finds out each target compound and go out peak position, and combine calibration curve
Calculate ρMark;
Step 8: according to formula ρi=ρMark×V1×1000/V2Calculate the concentration ρ of target compound in water samplei, in formula: ρiWater
The concentration of target compound in sample, μ g/L;ρMarkResulting target compound concentration, mg/L are calculated by calibration curve;V1Extraction
Constant volume after liquid concentration, mL;V2The sample volume of water sample, mL.
By using above-mentioned technical proposal, reducing agent is added in water sample, can consume the dissolved oxygen in water in this way, thus
The probability that the phenolic compound in water sample is aoxidized by water oxygen is reduced, and then is also advantageous for improving returning phenolic compound
Yield.
Preferably, the reducing agent is ascorbic acid.
By using above-mentioned technical proposal, since ascorbic acid is strong reductant, and this reducing agent is soluble easily in water, and
It will not be chemically reacted with phenolic compound to be measured, meanwhile, it is also not easy by solvent extraction.Thus, in the mistake of upper machine testing
It is smaller to the test result interference of phenolic compound to be measured in journey, meanwhile, reduction also can be fully played, phenol is avoided
The probability that class compound is oxidized.
Preferably, the quality of the ascorbic acid of addition and the volume ratio of water sample are 18.45~22.33mg/L.
By using above-mentioned technical proposal, since under room temperature, the dissolved oxygen concentration in water is 8.38mg/L, and according to anti-bad
The quality of hematic acid and the volume ratio of water sample are that 18.45~22.33mg/L adds ascorbic acid, can be greatly lowered in water and dissolve
The content of oxygen, to also just further reduced the probability that phenolic compound is oxidized.
Preferably, the quality of the ascorbic acid of addition and the volume ratio of water sample are 20.39mg/L.
It is molten in water when the amount of the ascorbic acid of addition is 20.39mg/ water L by using above-mentioned technical proposal
The concentration of oxygen is solved already close to zero, to guarantee to test in effective situation again, can also reduce the usage amount of ascorbic acid.
Preferably, step 1 is before sampling, the water sample of first mild agitation sample point.
By using above-mentioned technical proposal, the accuracy during water sampling is helped to improve in this way.
Preferably, during the water sampling of step 1, Brown Glass Brown glass bottles and jars only must be filled gas of not leaving a blank.
By using above-mentioned technical proposal, oxygen content whole in Brown Glass Brown glass bottles and jars only can be reduced in this way, and then also
Advantageously reduce the probability that phenolic compound is oxidized.
Preferably, it needs to deflate in time in extraction process again in step 4.
By using above-mentioned technical proposal, it on the one hand can be improved safety in this way, on the other hand also help to avoid
Bubble is mixed into machine test process, and influences the accuracy of test result.
In conclusion the invention has the following advantages:
1, by adding reducing agent into water sample, it can be effectively reduced the probability that phenolic compound is oxidized in this way;
2, select ascorbic acid as reducing agent, this is because ascorbic acid is soluble easily in water, and is not easy to be come out by solvent extraction, because
And the test of target compound is interfered smaller;
3, Brown Glass Brown glass bottles and jars only is selected during water sampling, and guarantees that vial expires bottle and do not leave a blank gas, can then reduce water in this way
Oxygen affects target compound test in sample.
Detailed description of the invention
Fig. 1 is that mixed be marked in after dichloromethane/ethyl acetate in the mixed solvent dilutes 500 times of 13 kinds of phenolic compounds is marked
Quasi- spectrogram;
Fig. 2 is the relational graph for adding the content of ascorbic acid quality and volume of water sample ratio and dissolved oxygen;
Fig. 3 is the gas phase spectrogram for controlling sample 1;
Fig. 4 is the gas phase spectrogram of comparative example.
Specific embodiment
Embodiment:
A kind of measuring method of water quality phenolic compound, comprising the following steps:
S1: standard production and test,
Step a: the mixed mark of 13 kinds of phenolic compounds is diluted into 500 times, 200 respectively at dichloromethane/ethyl acetate in the mixed solvent
Again, 100 times, 40 times, 20 times and 10 times, obtain six groups of standard specimens;
Step b: by six groups of standard specimens and one group of blank sample examination with computer, obtaining standard spectrogram, as shown in Fig. 1 and each phenol generalization
The calibration curve of object is closed, as shown in table 1.
The standard curve of 1 13 kinds of phenolic compounds of table
Serial number | Target compound | Standard curve function | Correlation r2 |
1 | Phenol | Y=10.67265x+2.46508 | 0.99974 |
2 | 2-chlorophenol | Y=8.05010x+1.70854 | 0.99976 |
3 | 3- cresols | Y=11.03797x+2.84950 | 0.99972 |
4 | 2- nitrophenols | Y=6.51895x+3.06530e-1 | 0.99972 |
5 | 2,4- xylenols | Y=11.72419x+2.57409 | 0.99975 |
6 | 2,4- Dichlorophenols | Y=6.37532x+1.89746 | 0.99971 |
7 | 4- chlorophenol | Y=7.79943x+2.25983 | 0.99970 |
8 | The chloro- 3- cresols of 4- | Y=8.49327x+2.25522 | 0.99970 |
9 | 2,4,6- trichlorophenols | Y=5.33086x+5.30619e-1 | 0.99965 |
10 | 2,4- dinitrophenol dinitrophenolates | Y=2.84312x-6.84649 | 0.99519 |
11 | 4- nitrophenols | Y=6.24704x-1.45286 | 0.99963 |
12 | 2- methyl -4,6- dinitrophenol dinitrophenolate | Y=4.71370x-5.77555 | 0.99857 |
13 | Pentachlorophenol | Y=3.83034x-1.00824 | 0.99964 |
Here, measuring gas phase spectrogram after 200 times, 100 times, 40 times, 20 times and 10 times of mark dilution mixed for 13 kinds of phenolic compounds
Similar to 500 times of gas phase spectrogram of dilution, only there is difference in the size of peak area, so no longer record herein.Gas phase test
It is the prior art, it is identical as standard HJ 676-2013.
In addition, 13 kinds of phenolic compounds herein mix each concentration in mark, as shown in following table two:
The concentration of each phenolic compound in the mixed mark of 2 13 kinds of phenolic compounds of table
S2, sample test:
The test of river water sample:
Step 1: by the river water mild agitation of sample point, water sample is acquired using the Brown Glass Brown glass bottles and jars only that volume is 1L, and guarantee brown
Vial fills gas of not leaving a blank;
Step 2: 20.39mg ascorbic acid being added into water sample, makes it completely dissolved, while it is 38% that mass fraction, which is added,
Water sample is adjusted pH < 2 by hydrochloric acid;
Step 3: amount shakes up water sample, measures 500mL and pours into 1000mL separatory funnel, and 30g sodium chloride, oscillation dissolution is added;
Step 4: being added 60mL dichloromethane/ethyl acetate mixed solvent, shakes, releasing gas, then shaking out 5~
10min stands 10min or more, until organic phase is sufficiently separated with water phase, collects organic phase;
Step 5: repeating extraction 1~2 time, merges organic phase.Organic phase is dehydrated through anhydrous sodium sulfate, and with q. s. methylene chloride/
Ethyl acetate mixed solvent washs anhydrous sodium sulfate, collects organic extractant phase liquid;
Step 6: being transferred to concentrate bottle for the extract liquor after dehydration and drying, is concentrated into 1.0mL at 45 DEG C or less with enrichment facility,
Dichloromethane/ethyl acetate mixed solvent 3.0mL is added, then is concentrated and is settled to 1.0mL, upper gas chromatograph for determination obtains sample
Product spectrogram;
Step 7: sample spectrogram is compared with standard spectrogram, and that finds out corresponding phenolic compound goes out peak position, and according to
Know that standard curve obtains ρMark;
Step 8: according to formula ρi=ρMark×V1×1000/V2Calculate the concentration ρ of target compound in water samplei, in formula: ρiWater
The concentration of target compound in sample, μ g/L;ρMarkResulting target compound concentration, mg/L are calculated by calibration curve;V1Extraction
Constant volume after liquid concentration, mL;V2The sample volume of water sample, mL.Wherein, the sample point of river water is located at Taizhou Jiangjiang Jiang Bin
Park section.As a result as shown in Table 3:
The content of 13 kinds of phenolic compounds in three water sample of table
Serial number | Target compound | ρMark/mg/L | ρi/mg/L |
1 | Phenol | 0 | 0 |
2 | 2-chlorophenol | 0 | 0 |
3 | 3- cresols | 0 | 0 |
4 | 2- nitrophenols | 0 | 0 |
5 | 2,4- xylenols | 0 | 0 |
6 | 2,4- Dichlorophenols | 0 | 0 |
7 | 4- chlorophenol | 0 | 0 |
8 | The chloro- 3- cresols of 4- | 0 | 0 |
9 | 2,4,6- trichlorophenols | 0 | 0 |
10 | 2,4- dinitrophenol dinitrophenolates | 0 | 0 |
11 | 4- nitrophenols | 0 | 0 |
12 | 2- methyl -4,6- dinitrophenol dinitrophenolate | 0 | 0 |
13 | Pentachlorophenol | 0 | 0 |
13 kinds of phenolic compounds are not detected from the water sample in upper table two as can be seen that river.
Furthermore from attached drawing 2 as can be seen that the additive amount and volume of water sample ratio of ascorbic acid are in 18.45~20.33mg/L
Between when, oxygen content significantly decreases, and when ascorbic acid additive amount and volume of water sample ratio reach 20.39mg/L's
When, the content fall of dissolved oxygen very little.Comprehensive whole consideration, additive amount and the volume of water sample ratio of ascorbic acid
It is best that value reaches 20.39mg/L.
S3, quality control test:
Step I: it is separately added into the mixed mark of 13 kinds of phenolic compounds of various concentration in the separatory funnel of step 3 again in S2, obtains
Control sample 1, control sample 2 and control sample 3;
Step II: will control sample 1, and control sample 2 and control sample 3 are handled according to the processing mode of water sample in S2, then upper gas
Chromatography measurement, obtains each control sample gas phase spectrogram, as shown in Fig. 3, and is calculated according to standard curve, controls 13 in sample
The concentration of kind phenolic compound, as shown in Table 4;
Step III: it is poor that the content of calculated 13 kinds of phenolic compounds is made with 13 kinds of content of phenolic compounds in S2 water sample, it
It is compared again with the concentration of phenolic compound in practical each control sample of table five afterwards, obtains the rate of recovery, as a result as shown in Table 6.
The concentration of the calculated each control sample of table four
The concentration of the practical each control sample of table five
The rate of recovery of each phenolic compound of table six
The test method that can be seen that the application by the result of table six is higher for the recycling of the phenolic compound in water.
In addition, the gas phase spectrogram of control sample 2 and the gas phase spectrogram and control sample 1 that control sample 3 approaches, only deposited on peak area
In difference, because without showing.
Comparative example:
A kind of measuring method of water quality phenolic compound is with the difference for controlling sample 1 in embodiment one, surveys doing quality control
During examination and it is not added with ascorbic acid, obtains the gas phase spectrogram such as attached drawing 4.From spectrogram it is clear that there are many
Phenolic compound does not go out cutting edge of a knife or a sword, and then has proved amply in actual mechanical process, and the addition of ascorbic acid is for improving test
Precision plays a significant role.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (8)
1. a kind of measuring method of water quality phenolic compound, includes the following steps:
Step 1: utilizing the water sample of vial acquisition sufficient amount;
Step 2: reducing agent and appropriate hydrochloric acid adjusting pH < 2 is added after water sampling immediately;
Step 3: the water sample of acquisition is poured into separatory funnel;
Step 4: extracting to target compound, organic extractant phase liquid is obtained, and using anhydrous sodium sulfate to organic extractant phase
Liquid is dehydrated;
Step 6: constant volume is concentrated in organic extractant phase liquid after dehydration, upper machine measurement obtains sample spectrogram;
Step 7: sample spectrogram is compared with standard spectrogram, finds out each target compound and go out peak position, and combine calibration curve
Calculate ρMark;
Step 8: according to formula ρi=ρMark×V1×1000/V2Calculate the concentration ρ of target compound in water samplei, in formula: ρiWater sample
The concentration of middle target compound, μ g/L;ρMarkResulting target compound concentration, mg/L are calculated by calibration curve;V1Extract liquor
Constant volume after concentration, mL;V2The sample volume of water sample, mL.
2. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: the reducing agent is
Ascorbic acid.
3. a kind of measuring method of water quality phenolic compound according to claim 2, it is characterised in that: the Vitamin C of addition
The quality of acid and the volume ratio of water sample are 18.45~92.23mg/L.
4. a kind of measuring method of water quality phenolic compound according to claim 3, it is characterised in that: the Vitamin C of addition
The quality of acid and the volume ratio of water sample are 55.39mg/L.
5. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: step 1 is sampling
Before, the water sample of first mild agitation sample point.
6. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: the water intaking of step 1
During sample, Brown Glass Brown glass bottles and jars only must be filled gas of not leaving a blank.
7. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: the glass of step 1
Bottle is Brown Glass Brown glass bottles and jars only.
8. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: extract again in step 4
It needs to deflate in time during taking.
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