CN111610283A - Method for detecting isothiazolinone bactericide and triclosan bactericide in environmental water body - Google Patents
Method for detecting isothiazolinone bactericide and triclosan bactericide in environmental water body Download PDFInfo
- Publication number
- CN111610283A CN111610283A CN202010388249.XA CN202010388249A CN111610283A CN 111610283 A CN111610283 A CN 111610283A CN 202010388249 A CN202010388249 A CN 202010388249A CN 111610283 A CN111610283 A CN 111610283A
- Authority
- CN
- China
- Prior art keywords
- sample
- triclosan
- isothiazolinone
- detecting
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for detecting isothiazolinone bactericides and triclosan bactericides in an environmental water body, which simultaneously detects 5 isothiazolinone bactericides and 2 triclosan substances in the water body by a pretreatment method of solid-phase extraction and combination of a liquid chromatography-mass spectrometer. The method comprises the following steps: firstly, coarsely filtering and finely filtering a water sample, and adding an internal standard substance; then extracting and purifying 7 substances to be detected in the sample by using a solid phase extraction column; and detecting the content of the target object in the water body by using a high performance liquid chromatography-mass spectrometer. The method has the advantages of simple steps, convenience in operation and good stability, and experimental data can be obtained quickly; the sample pretreatment cost is low, and the result can be obtained by using the common consumable materials in a laboratory. The method can be used for simultaneously detecting various isothiazolinone and triclosan substances, and has the advantages of high detection speed, high automation degree and high recovery rate of 87-117%. The method of the invention improves the industrialization level and is suitable for popularization and utilization.
Description
Technical Field
The invention relates to a method for detecting bactericides, in particular to a method for quickly detecting various bactericides by using a liquid chromatography-mass spectrometer, which is applied to the technical field of trace detection of organic pollutants.
Background
Fungicides are chemical substances that have a killing or inhibitory effect on fungi or bacteria. It can kill or inhibit the growth and reproduction of pathogenic bacteria by the virulence of the agent in vitro or in vivo. Some bactericides have no toxicity to fungi, but can interfere the pathogenic process of the fungi or influence the mutual relation between pathogens and hosts, thereby improving the defense capability of plants. Internationally, bactericides are commonly referred to as a collective term for agents for controlling various types of pathogenic microorganisms. In recent years, biocides including bactericides, insect repellents, antifouling agents, antiseptics and disinfectants have received increasing attention as emerging pollutants due to their wide use and large usage amount.
These biocides are widely used in various pharmaceuticals, personal care products (PPCPs) and household products for sterilization and disinfection. Approximately 30% of the bars in the united states have been investigated to contain antibacterial compounds. It is estimated that the annual usage of triclosan-based fungicides throughout China reaches 100 tons. The bactericide remaining after use is discharged to a sewage treatment system or a sewage treatment plant. But the wastewater treatment process of the conventional sewage treatment plant cannot completely treat such environmental pollutants. Therefore, the migration and transformation process of the bactericide is terminated in the environmental water body and is left in the environmental water body for a long time. TCS and TCC are chemically more lipophilic and their logKOWValues of 4.7 and 4.9, logKOCThe values were 4.1 and 4.5, respectively. The TCS and TCC parts of the sewage treatment plant are adsorbed on biosolids, which are 31 percent and 76 percent respectively; partial biodegradation, 65% and 21% respectively; then discharged through sewage, which is 4% and 3%, respectively. Therefore, TCS and TCC are distributed in water, sediments and organisms.
Research shows that in the present society, the wide application range of the usage amount of two types of bactericides, namely isothiazolinone bactericides and triclosan bactericides, is undeniable, and the two types of bactericides have certain toxicity, and most personal care products are flushed into a sewer after being used to become a part of domestic sewage and then are treated in an urban sewage treatment facility or directly discharged into a river environment. Has certain influence on both environment and human body. Therefore, the research on the content of the compound in the environment and the migration and transformation path in the environment is very necessary.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide a method for detecting isothiazolinone bactericides and triclosan bactericides in environmental water bodies so as to solve the technical problems of complex process and higher cost of the existing treatment method. Meanwhile, the invention also provides a high performance liquid chromatography-mass spectrometry detection method of the isothiazolinone bactericide and the triclosan bactericide, and the detection method can simultaneously detect 7 bactericide substances (MI, CMI, BIT, OIT, DCOIT, TCC and TCS). The detection process is rapid, efficient, low in cost, highly automated and convenient for industrial application.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a method for detecting isothiazolinone bactericides and triclosan bactericides in environmental water comprises the following steps:
a. taking a water sample from an environmental water body, and filtering the water sample; after at least three times of coarse filtration and at least three times of fine filtration, adding an internal standard substance TCS-d3, and waiting for pretreatment;
b. b, pretreating the water sample added with the internal standard substance in the step a by using a solid phase extraction column:
the pretreatment process comprises the following specific steps: activating the solid phase extraction column by using 10mL of methanol and 10mL of ultrapure water; loading a water sample to be treated on a solid-phase extraction column; rinsing with 5mL of ultrapure water and draining; elution was performed with 3X 4mL of methanol; blowing nitrogen to the eluted solution, fixing the volume to 1mL by using methanol when the solution is blown to be nearly dry, transferring the solution into a high performance liquid chromatography small bottle to be used as a sample to be detected for later use;
c. determining the content of a target object in a sample by using a high performance liquid chromatography-mass spectrometer:
establishing a target pollutant standard curve, taking the concentration as a horizontal coordinate and taking a peak area as a vertical coordinate; and (c) quantitatively detecting the concentration of the target object to be detected in the sample pretreated in the step b on a high performance liquid chromatography-mass spectrometer by adopting an internal standard method.
As a preferred technical scheme of the invention, in the step a, the concentration of the internal standard substance TCS-d3 is 20 mug/L.
As a preferred technical solution of the present invention, in the step b, the specific pretreatment process comprises:
activating the solid phase extraction column with 10ml methanol and 10ml ultrapure water at a flow rate of about 1-3L/min; adding a water sample to be detected to a solid phase extraction column at a flow rate of 1-3L/min; leaching with 5mL of ultrapure water and draining the ultrapure water at the flow rate of 1-3L/min; elution was performed with 3X 4mL of methanol; elution was performed with 3X 4mL of methanol; and (3) blowing nitrogen to the eluted solution, fixing the volume to 1mL by using methanol when the solution is blown to be nearly dry, and transferring the solution into a high performance liquid chromatography small bottle to be used as a sample to be detected for later use.
As a preferred technical solution of the present invention, in the step c, the detection conditions of the hplc-ms are as follows:
the column temperature is 25 ℃, the sample injection volume is 10 mu L, and the flow rate is 0.3 mL/min; HPLC-grade methanol (A) and ultrapure water (B) are adopted as mobile phases; the gradient is as follows: 0min, 50%; 5min, 80%; 5.5min, 90%; 11min, 100%; flow rate of drying gas: 8L/min, drying gas temperature: 300 ℃, sheath gas temperature: 350 ℃, sheath gas flow: 11L/min, atomizer pressure: 45psi, nozzle voltage (-): 1500V, nozzle voltage (+): 1500V, capillary Voltage (-): 4500.
in the preferred embodiment of the present invention, in step c, the target to be detected is 7 bactericide substances of MI, CMI, BIT, OIT, DCOIT, TCC, and TCS.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the invention adopts the solid-phase extraction tandem high performance liquid chromatography-mass spectrometry technology, has higher stability, better repeatability and more accurate result;
2. the result verification shows that the standard curve linear correlation degree of the isothiazolinone substances and the triclosan substances in the water body detected by the method is good, and R is2Are all larger than 0.99; the recovery rate of the added standard is between 63 and 120 percent; quantification ofThe limit range is between 0.02 and 0.05 ng/mL; the precision in the day and the precision in the day meet the requirements, and the relative deviation (RSDs) is respectively less than 8.7 percent;
3. the method has the advantages of good precision, high repeatability, accurate, sensitive and reliable result and wide application range.
Drawings
FIG. 1 is an ion flow diagram of a liquid chromatography-mass spectrometer obtained by the third method in the embodiment of the invention.
FIG. 2 is a standard curve equation of TCS-d3 as an internal standard substance in a method according to an embodiment of the invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example one
In this embodiment, a method for detecting isothiazolinone bactericides and triclosan bactericides in an environmental water body is characterized by comprising the following steps:
a. taking a water sample from an environmental water body, and filtering the water sample; after at least three times of coarse filtration and at least three times of fine filtration, adding an internal standard substance TCS-d3, and waiting for pretreatment;
b. b, pretreating the water sample added with the internal standard substance in the step a by using a solid phase extraction column:
the pretreatment process comprises the following specific steps: activating the solid phase extraction column by using 10mL of methanol and 10mL of ultrapure water; loading a water sample to be treated on a solid-phase extraction column; rinsing with 5mL of ultrapure water and draining; elution was performed with 3X 4mL of methanol; blowing nitrogen to the eluted solution, fixing the volume to 1mL by using methanol when the solution is blown to be nearly dry, transferring the solution into a high performance liquid chromatography small bottle to be used as a sample to be detected for later use;
c. determining the content of a target object in a sample by using a high performance liquid chromatography-mass spectrometer:
establishing a target pollutant standard curve, taking the concentration as a horizontal coordinate and taking a peak area as a vertical coordinate; and (c) quantitatively detecting the concentration of the target object to be detected in the sample pretreated in the step b on a high performance liquid chromatography-mass spectrometer by adopting an internal standard method.
In this example, a standard curve of the internal standard substance TCS-d3 was plotted, and fig. 2 is a standard curve graph of the internal standard substance TCS-d3, where the standard curve equation is y 3514.43x +5503.82, and the correlation coefficient is R2＝0.9994。
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this example, a spiking recovery experiment was performed.
The recovery rate of 7 isothiazolinone bactericides and triclosan bactericides in an environmental water body is detected by adopting an internal standard method, and the experimental steps are as follows:
(1) sample pretreatment: after water samples are subjected to three times of rough filtration and three times of fine filtration, dividing the water samples into three groups of parallel samples, wherein each group of water samples is 500 milliliters, TCS-d31ml with the concentration of 20 micrograms/L is added into the first group and the second group, and the third group of samples are not added with mixed standard solution;
(2) the method comprises the following steps of (1) enriching and purifying by using a solid phase extraction column, wherein the specific process comprises the following steps: activating the solid phase extraction column with 10ml methanol and 10ml ultrapure water at a flow rate of about 1-3 l/min; adding a water sample to be detected to a solid phase extraction column at a flow rate of 1-3 l/min; leaching with 5ml of ultrapure water and draining, wherein the flow rate is 1-3 l/min; elution was carried out with 3X 4ml of methanol; blowing nitrogen to the eluted solution, fixing the volume to 1ml by using methanol when the solution is blown to be nearly dry, and transferring the solution to a small bottle of a high performance liquid chromatography for detection;
(3) determining the content of a target object in a sample by using a high performance liquid chromatography-mass spectrometer:
the method comprises the following steps of carrying out quantitative detection on the concentration of a target object in a sample on a high performance liquid chromatography-mass spectrometer, wherein the detection conditions of the liquid chromatography-mass spectrometer are as follows: the column temperature is 25 ℃, the sample injection volume is 10 mu L, and the flow rate is 0.3 mL/min; HPLC-grade methanol (A) and ultrapure water (B) are adopted as mobile phases; the gradient is as follows: 0min, 50%; 5min, 80%; 5.5min, 90%; 11min, 100%; flow rate of drying gas: 8L/min, drying gas temperature: 300 ℃, sheath gas temperature: 350 ℃, sheath gas flow: 11L/min, atomizer pressure: 45psi, nozzle voltage (-): 1500V, nozzle voltage (+): 1500V, capillary Voltage (-): 4500;
(4) and (5) calculating the recovery rate of the added standard. Calculation formula of normalized recovery (RE%):
wherein:
RE- - -recovery by adding standard,%;
c0- -concentration of mixed standard solution, ng/mL; (ii) a
V0- -volume of mixed standard solution, mL;
c1- -detection concentration of blank sample, ng/mL;
v1- -volume of blank sample at constant volume, mL;
c2- -detection concentration of sample in mixed standard solution, ng/mL;
v2- -volume when the sample added with the mixed standard solution is constant volume, mL;
(5) the observed result was 78.45 μ g/L, the recovery rate from spiking was 78.45%, and the relative standard deviation (n-3) was 3.26. Therefore, the method has better detection accuracy. The embodiment can correct the detection result through a standard recovery rate experiment, eliminate the operation error and reduce the matrix interference effect.
EXAMPLE III
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, the measurement of 7 kinds of isothiazolinone bactericides and triclosan bactericides in an actual sample was carried out.
Collecting water samples of Huangpu river and Huangpu river tributary in Shanghai area, pretreating the water samples added with the internal standard substance by using a solid phase extraction column according to the embodiment, then purifying and enriching the water samples by using a solid phase extraction column according to the embodiment I, and finally analyzing and detecting the actual concentration of the substance to be detected in the samples by using a liquid chromatography-mass spectrometer according to the embodiment I, wherein the specific detection process is as follows:
a. pretreating a sample:
coarsely filtering the collected water sample for three times, finely filtering for three times, adding an internal standard substance TCS-d3, and waiting for pretreatment;
b. pretreating a water sample added with an internal standard substance by using a solid phase extraction column:
the specific process is as follows: activating the solid phase extraction column by using 10ml of methanol and 10ml of ultrapure water; loading a water sample to be treated on a solid-phase extraction column; rinsing with 5ml of ultrapure water and draining; elution was carried out with 3X 4ml of methanol; blowing nitrogen to the eluted solution, fixing the volume to 1ml by using methanol when the solution is blown to be nearly dry, and transferring the solution to a small bottle of a high performance liquid chromatography for detection;
c. determining the content of a target object in a sample by using a high performance liquid chromatography-mass spectrometer:
establishing a target pollutant standard curve, taking the concentration as a horizontal coordinate and taking a peak area as a vertical coordinate; and (3) quantitatively detecting the concentration of the target object in the sample on a high performance liquid chromatography-mass spectrometer by adopting an internal standard method.
In the detection, the monitoring conditions of the chromatograph-mass spectrometer are also as follows: the column temperature was 25 ℃, the injection volume was 10 μ L, and the flow rate was 0.3 mL/min. HPLC-grade methanol (A) and ultrapure water (B) were used as mobile phases. The gradient is as follows: 0min, 50%; 5min, 80%; 5.5min, 90%; 11min, 100%. Flow rate of drying gas: 8L/min, drying gas temperature: 300 ℃, sheath gas temperature: 350 ℃, sheath gas flow: 11L/min, atomizer pressure: 45psi, nozzle voltage (-): 1500V, nozzle voltage (+): 1500V, capillary Voltage (-): 4500.
the concentrations of isothiazolinone and 2 Chinese triclosan in 5 water samples are shown in the following table 2. The practical results show that the method can be applied to the content determination of MI, CMI, BIT, OIT, DCOIT, TCC and TCS of isothiazolinone and triclosan bactericides in water samples.
TABLE 1 concentration test results of 7 kinds of isothiazolinone and triclosan in water
The solid phase extraction column in this example is the Oasis HLB column from Waters. The high performance liquid chromatography-mass spectrometer is an Agilent 1260 type liquid chromatograph, and the chromatographic column is a Poroshell 120EC-C18 reversed phase column: 3X 100mm, 2.7 μm, Agilent. In the method, 5 isothiazolinone substances (MI, CMI, BIT, OIT and DCOIT) and 2 triclosan substances (TCC and TCS) in a water body are detected simultaneously by a pretreatment method of solid phase extraction and a liquid chromatography-mass spectrometer. The method of the embodiment comprises the following steps:
(1) filtering the water sample by three times of rough filtration and three times of fine filtration, and adding an internal standard substance;
(2) extracting and purifying 7 substances to be detected in a sample by using a solid phase extraction column;
(3) and detecting the content of the target object in the water body by using a high performance liquid chromatography-mass spectrometer.
FIG. 1 is an ion flow diagram of a liquid chromatography-mass spectrometer obtained by the method of this example. According to the ion flow diagram of fig. 1, a target substance in a sample can be qualitatively detected to determine the presence of the target substance in the sample. Next, based on the area of each species peak in the ion flow graph in conjunction with the standard curve of fig. 2, the species recovery rate (as shown in example two) and the concentration level of the target species in the sample (as shown in example three) can be calculated. Further, the data of the recovery rate and concentration level in table 1 were obtained by calculation of the formulas and processing of the data in examples two and three.
The method has the advantages of simple steps, convenience in operation and good stability, and experimental data can be obtained quickly; the sample pretreatment cost is low, and the result can be obtained by using the common consumable materials in a laboratory. In addition, the method can also be used for simultaneously detecting 7 isothiazolinone and triclosan substances, the detection speed is high, the automation degree is high, and the recovery rate can reach 87% -117%. The method can improve the industrialization level to a certain extent and is suitable for popularization and utilization.
In summary, the method of the embodiment of the invention can simultaneously detect 7 bactericides in the environmental water body: MI, CMI, BIT, OIT, DCOIT, TCC, TCS. The method disclosed by the embodiment of the invention is applied to the field of trace detection of organic pollutants, and particularly relates to a method for detecting isothiazolinone bactericides and triclosan bactericides in environmental water.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, as long as the purpose of the present invention is met, and the technical principle and the inventive concept of the method for detecting isothiazolinone bactericides and triclosan bactericides in environmental water bodies of the present invention shall fall within the protection scope of the present invention.
Claims (5)
1. A method for detecting isothiazolinone bactericides and triclosan bactericides in environmental water is characterized by comprising the following steps:
a. taking a water sample from an environmental water body, and filtering the water sample; after at least three times of coarse filtration and at least three times of fine filtration, adding an internal standard substance TCS-d3, and waiting for pretreatment;
b. b, pretreating the water sample added with the internal standard substance in the step a by using a solid phase extraction column:
the pretreatment process comprises the following specific steps: activating the solid phase extraction column by using 10mL of methanol and 10mL of ultrapure water; loading a water sample to be treated on a solid-phase extraction column; rinsing with 5mL of ultrapure water and draining; elution was performed with 3X 4mL of methanol; blowing nitrogen to the eluted solution, fixing the volume to 1mL by using methanol when the solution is blown to be nearly dry, transferring the solution into a high performance liquid chromatography small bottle to be used as a sample to be detected for later use;
c. determining the content of a target object in a sample by using a high performance liquid chromatography-mass spectrometer:
establishing a target pollutant standard curve, taking the concentration as a horizontal coordinate and taking a peak area as a vertical coordinate; and (c) quantitatively detecting the concentration of the target object to be detected in the sample pretreated in the step b on a high performance liquid chromatography-mass spectrometer by adopting an internal standard method.
2. The method for detecting isothiazolinone disinfectants and triclosan disinfectants in the environmental water body according to claim 1, wherein: in said step a, the concentration of internal standard TCS-d3 was 20. mu.g/L.
3. The method for detecting isothiazolinone disinfectants and triclosan disinfectants in the environmental water body according to claim 1, wherein: in the step b, the specific pretreatment process comprises the following steps:
activating the solid phase extraction column with 10ml methanol and 10ml ultrapure water at a flow rate of about 1-3L/min; adding a water sample to be detected to a solid phase extraction column at a flow rate of 1-3L/min; leaching with 5mL of ultrapure water and draining the ultrapure water at the flow rate of 1-3L/min; elution was performed with 3X 4mL of methanol; elution was performed with 3X 4mL of methanol; and (3) blowing nitrogen to the eluted solution, fixing the volume to 1mL by using methanol when the solution is blown to be nearly dry, and transferring the solution into a high performance liquid chromatography small bottle to be used as a sample to be detected for later use.
4. The method for detecting isothiazolinone disinfectants and triclosan disinfectants in the environmental water body according to claim 1, wherein: in the step c, the detection conditions of the high performance liquid chromatography-mass spectrometer are as follows:
the column temperature is 25 ℃, the sample injection volume is 10 mu L, and the flow rate is 0.3 mL/min;
HPLC-grade methanol (A) and ultrapure water (B) are adopted as mobile phases;
the gradient is as follows: 0min, 50%; 5min, 80%; 5.5min, 90%; 11min, 100%;
flow rate of drying gas: 8L/min, drying gas temperature: 300 ℃, sheath gas temperature: 350 ℃, sheath gas flow: 11L/min, atomizer pressure: 45psi, nozzle voltage (-): 1500V, nozzle voltage (+): 1500V, capillary Voltage (-): 4500.
5. the method for detecting isothiazolinone disinfectants and triclosan disinfectants in the environmental water body according to claim 1, wherein: in step c, the target substances to be detected are 7 bactericide substances of MI, CMI, BIT, OIT, DCOIT, TCC and TCS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010388249.XA CN111610283A (en) | 2020-05-09 | 2020-05-09 | Method for detecting isothiazolinone bactericide and triclosan bactericide in environmental water body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010388249.XA CN111610283A (en) | 2020-05-09 | 2020-05-09 | Method for detecting isothiazolinone bactericide and triclosan bactericide in environmental water body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111610283A true CN111610283A (en) | 2020-09-01 |
Family
ID=72204997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010388249.XA Pending CN111610283A (en) | 2020-05-09 | 2020-05-09 | Method for detecting isothiazolinone bactericide and triclosan bactericide in environmental water body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111610283A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113252815A (en) * | 2021-06-16 | 2021-08-13 | 中国科学院地理科学与资源研究所 | Method for detecting triclosan and triclocarban in sludge compost |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2604699A1 (en) * | 2010-08-11 | 2013-06-19 | Kyowa Medex CO., LTD. | Method for measuring glycosylated hemoglobin |
| CN108693262A (en) * | 2018-04-13 | 2018-10-23 | 佛山市梅雨科技有限公司 | A kind of assay method of Determination of Preservatives in Cosmetics |
-
2020
- 2020-05-09 CN CN202010388249.XA patent/CN111610283A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2604699A1 (en) * | 2010-08-11 | 2013-06-19 | Kyowa Medex CO., LTD. | Method for measuring glycosylated hemoglobin |
| CN108693262A (en) * | 2018-04-13 | 2018-10-23 | 佛山市梅雨科技有限公司 | A kind of assay method of Determination of Preservatives in Cosmetics |
Non-Patent Citations (4)
| Title |
|---|
| ARNE WICK等: "Comparison of electrospray ionization and atmospheric pressure chemical ionization for multi-residue analysis of biocides, UV-filters and benzothiazoles in aqueous matrices and activated sludge by liquid chromatography–tandem mass spectrometry", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| WANG-RONG LIU等: "Biocides in the Yangtze River of China: Spatiotemporal distribution,mass load and risk assessment", 《ENVIRONMENTAL POLLUTION》 * |
| WANG-RONG LIU等: "Biocides in wastewater treatment plants: Mass balance analysis and pollution load estimation", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| ZHI-FENG CHEN等: "Determination of biocides in different environmental matrices by use of ultra-high-performance liquid chromatography–tandem mass spectrometry", 《ANAL BIOANAL CHEM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113252815A (en) * | 2021-06-16 | 2021-08-13 | 中国科学院地理科学与资源研究所 | Method for detecting triclosan and triclocarban in sludge compost |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | Multiresidue determination of fluoroquinolone, sulfonamide, trimethoprim, and chloramphenicol antibiotics in urban waters in China | |
| Chen et al. | Determination of biocides in different environmental matrices by use of ultra-high-performance liquid chromatography–tandem mass spectrometry | |
| Bai et al. | Occurrence, distribution and bioaccumulation of antibiotics in the Liao River Basin in China | |
| Perret et al. | Sulphonamide residues in Italian surface and drinking waters: a small scale reconnaissance | |
| Mitani et al. | Determination of fluoroquinolones in environmental waters by in-tube solid-phase microextraction coupled with liquid chromatography–tandem mass spectrometry | |
| van Leerdam et al. | Determination of polar 1H-benzotriazoles and benzothiazoles in water by solid-phase extraction and liquid chromatography LTQ FT Orbitrap mass spectrometry | |
| CN103913426B (en) | A kind of method assessing antibiotic relict usefulness in waste water | |
| Turiel et al. | Determination of quinolones and fluoroquinolones in hospital sewage water by off‐line and on‐line solid‐phase extraction procedures coupled to HPLC‐UV | |
| Klein et al. | Quantitative determination of triclocarban in wastewater effluent by stir bar sorptive extraction and liquid desorption–liquid chromatography–tandem mass spectrometry | |
| CN108318613A (en) | The detection method of antibiotic in a kind of environmental sample | |
| CN105651922A (en) | Method for measuring PPCPs (pharmaceuticals and personal care products) in environmental water sample | |
| Mosse et al. | Soluble organic components of winery wastewater and implications for reuse | |
| Neng et al. | Determination of tributyltin in environmental water matrices using stir bar sorptive extraction with in-situ derivatisation and large volume injection-gas chromatography–mass spectrometry | |
| CN107941928A (en) | A kind of method of antibiotic in liquid chromatography mass Simultaneous Determination environment water | |
| Kinani et al. | Formation and determination of organohalogen by-products in water–Part II. Sample preparation techniques for analytical approaches | |
| CN111610283A (en) | Method for detecting isothiazolinone bactericide and triclosan bactericide in environmental water body | |
| Van Hoi et al. | Determination of Pharmaceutical Residues by UPLC‐MS/MS Method: Validation and Application on Surface Water and Hospital Wastewater | |
| Jhankal et al. | Quantification of antiviral drug entecavir in pharmaceutical formulation by voltammetric techniques | |
| Sun et al. | Determination of trace triclosan in environmental water by microporous bamboo‐activated charcoal solid‐phase extraction combined with HPLC‐ESI‐MS | |
| CN112684070B (en) | Method for measuring semi-volatile organic compounds in solid waste | |
| Bahri et al. | Development of solid-phase microextraction for the determination of trihalomethanes in drinking water from Bizerte, Tunisia | |
| Ma et al. | Simultaneous determination of nitroimidazoles and amphenicol antibiotics in water samples using ultrasound-assisted dispersive liquid–liquid microextraction coupled with ultra-high-performance liquid chromatography with tandem mass spectrometry | |
| Shi et al. | Simultaneous determination of 8 fluoroquinolone antibiotics in sewage treatment plants by solid-phase extraction and liquid chromatography with fluorescence detection | |
| Karlsson et al. | Influence of filtration, preservation and storing on the analysis of low molecular weight organic acids in natural waters | |
| Martínez-Barrachina et al. | Use of a solid-phase extraction disk module in a FI system for the automated preconcentration and determination of surfactants using potentiometric detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200901 |