CN105784858B - Method for measuring PPCPs in environmental soil - Google Patents
Method for measuring PPCPs in environmental soil Download PDFInfo
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- CN105784858B CN105784858B CN201610109483.8A CN201610109483A CN105784858B CN 105784858 B CN105784858 B CN 105784858B CN 201610109483 A CN201610109483 A CN 201610109483A CN 105784858 B CN105784858 B CN 105784858B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01—MEASURING; TESTING
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
- G01N2030/126—Preparation by evaporation evaporating sample
Abstract
The invention relates to a method for determining PPCPs in an environmental soil sample, which comprises the steps of sample extraction, enrichment purification, separation purification and analysis detection, wherein the step of sample extraction further comprises the step of adding N isotope internal standard extracting solutions, wherein N is an integer more than 1 and less than or equal to 16, preferably 4-16, and more preferably 8-15. The invention relates to the field of PPCPs detection, in particular to a method for determining the content of 16 PPCPs in soil and sediment samples. According to the invention, the original analysis method is improved, the multi-isotope internal standard analysis method is established, most target objects have corresponding isotope markers as internal standards, corresponding target objects which cannot purchase the isotope markers are realized, and the isotope markers of substances with similar structures and properties are selected as the internal standards. And establishing an analysis method of the multi-isotope internal standard with higher sensitivity, lower detection limit and stronger stability.
Description
Technical Field
The invention relates to the field of PPCPs detection, in particular to a method for determining the content of 16 PPCPs in soil and sediment samples.
Background
Drugs and Personal Care Products (PPCPs) including human and veterinary drugs for treating diseases and ensuring health, Personal Care Products for bathing and skin Care, and daily chemicals for aromatherapy, disinfectants, and the like are emerging pollutants having potential hazards to ecological environment and human health, and research on environmental existence, risk evaluation, toxicology and the like of the pollutants attracts wide attention in the field of environmental science. The PPCPs in the environment are very widely available, and wastewater and solid waste generated in pharmaceutical factories, hospitals, livestock and poultry farms and human daily life contain a large amount of PPCPs and enter the environment in the forms of sewage, solid waste and the like. Sewage treatment plants are also an important way for PPCPs to enter the environment, and most PPCPs are removed from water bodies mainly by adsorption to sludge, which may enter soil and groundwater if used as fertilizer for soil.
In current related research, PPCPs are generally analyzed by using ultrasonic extraction, solid phase extraction and liquid chromatography tandem mass spectrometry (SPE-LC-MS/MS) methods, and the method is mainly obtained on the basis of EPA 1694 optimization. In the existing detection laws and regulations and most laboratories, a typical internal standard method is used for analyzing several or more than ten target objects, the internal standard and the target objects have structural and property differences, and the loss, the chromatographic retention behavior and the response strength in the pretreatment process have great differences, so that the detection limit of the analysis method is high, the stability is poor, and the low-concentration PPCPs cannot be accurately quantified. And some PPCPs have the characteristic of poor stability, when an internal standard method is used for measurement, the storage time of a sample is short, and the analysis and detection requirements are harsh: collected samples need to be stored in dark and low temperature, pretreatment is completed within 3 days as far as possible, and instrument analysis and detection are completed within 45 days.
Disclosure of Invention
The invention aims to provide an analysis method of 16 PPCPs in an environmental sample, which is particularly suitable for soil and muddy bottom environments and can accurately measure the content of the PPCPs in the environmental sample and effectively compensate concentration change of the PPCPs caused by degradation. Therefore, the problems that the PPCPs content in the environmental sample cannot be accurately measured and the storage time cannot be prolonged by the conventional measuring method are solved.
In order to solve the technical problems, the invention introduces more isotope internal standards, improves the original analysis method, establishes the analysis method of the multi-isotope internal standards, achieves that most target objects have corresponding isotope markers as the internal standards, correspondingly cannot purchase the target objects of the isotope markers, and selects the isotope markers of the substances with similar structures and properties as the internal standards. And establishing an analysis method of the multi-isotope internal standard with higher sensitivity, lower detection limit and stronger stability.
The invention aims to provide a method for measuring PPCPs in an environmental soil sample, which is characterized by comprising a sample extraction step, an enrichment purification step, a separation purification step and an analysis detection step, wherein the sample extraction step comprises a step of adding n isotope extraction internal standards, wherein n is an integer more than 1 and less than 16, preferably 4-16, and more preferably 8-15.
The determination method is characterized in that the sample extraction step comprises the steps of adding phosphate buffer salt into a sample, adjusting pH, adding an extraction internal standard solution, adding acetonitrile, repeating ultrasonic extraction, combining the extracting solutions, and performing rotary evaporation and concentration.
The determination method is characterized in that the enrichment purification step is to dilute the extracting solution with ultrapure water, filter the extracting solution with glass fiber filter paper and then enrich the extracting solution with a solid phase extraction column, preferably a hydrophilic and lipophilic solid phase extraction column.
The determination method is characterized in that in the enrichment purification step, the small column is rinsed by methanol, high-purity water and high-purity water with the pH value of 4-5 before enrichment.
The determination method of the present invention is characterized in that the analytical detection step employs an HPLC-MS/MS instrument to perform analytical detection on the purified sample.
The measurement method according to the present invention is characterized in that the analyzing and detecting step further comprises: concentrating the purified sample, diluting with 1:4 methanol/water to 500 μ L, adding13C-Atrazine sample injection internal standard, vortex mixing uniformly, filtering with 0.22 μm nylon syringe filter, and purifying sample to be detected by the instrument.
The determination method is characterized in that the analysis and detection step further comprises the step of respectively analyzing and determining the purified samples by adopting an HPLC-MS/MS instrument, and the adopted determination parameters are as follows:
HPLC detection conditions are that the sample injection volume is 10 mu L; the column temperature is 30 ℃, the chromatographic column is a C18 liquid chromatographic column, the specification is 3.5 mu m multiplied by 3.0mm multiplied by 150mm, the mobile phase in the POS mode is high-purity water containing 0.01 percent formic acid and methanol, and the flow rate is 0.30 mL/min; the mobile phase in the NEG mode is high-purity water containing 10mMol/L ammonium acetate and methanol, and the flow rate is 0.35 mL/min; the mass spectrum conditions are electrospray ionization source ESI and multi-reaction monitoring mode MRM.
The determination method is characterized in that the PPCPs are selected from more than one of quinolones, sulfanilamide synergists, antihypertensive drugs, antiepileptic drugs, anthelmintics, antidepressants, antihypertensive drugs, stimulants, chloromycetins, anti-inflammatory analgesics and blood lipid regulators.
The method for measuring PPCPs is characterized in that the PPCPs are nalidixic acid, trimethoprim, propranolol, carbamazepine, deet, sulpiride, metoprolol, caffeine, chloramphenicol, diclofenac, indomethacin, mefenamic acid, ketoprofen, bezafibrate, clofibric acid and gemfibrozil.
The measuring method according to the present invention is characterized in that the environmental sample is any one of a soil sample and a sediment sample.
In detail, the specific operation steps of the invention are as follows:
(1) a sample extraction step: weighing a certain amount of freeze-dried and ground sample, adding 15mL of phosphate buffer salt, adjusting the pH to 4-5 by using NaOH or HCl solution, and adding 13C-labeled extraction internal standard solution; adding 20mL of acetonitrile, repeatedly extracting for three times by ultrasonic waves, combining extracting solutions, and carrying out rotary evaporation and concentration.
(2) Enrichment and purification steps: diluting the extracting solution with ultrapure water, filtering the extracting solution by using glass fiber filter paper (firing for 4 hours at 450 ℃), and enriching the extracting solution by using a hydrophilic and lipophilic solid phase extraction column to obtain a small extraction column containing PPCPs; before the enrichment, the extraction column is washed by 10mL of methanol, 6mL of high-purity water and 6mL of high-purity water (pH is 4-5) in sequence before use, so that the purposes of activating the filler and removing impurities are achieved, and the specification of the enrichment small column is 200mg and 6 mL.
(3) A separation and purification step: cleaning the extraction column containing the PPCPs with 10mL of high-purity water, vacuumizing until the filler is completely dried (about 1-2 hours), adding 8mL of methanol for elution, collecting eluent in a 10mL glass centrifuge tube, and concentrating and fixing the volume to obtain a purified sample; concentrating the purified sample, diluting with methanol/water (volume ratio of 1:4) to 500 μ L, and adding13C-Atrazine sample injection internal standard, vortex mixing uniformly, filtering with 0.22 μm nylon syringe filter, and purifying sample to be detected by the instrument. The concentration is carried out by adopting nitrogen blowing concentration until the concentration is just dried, and the dry bath temperature is preferably 35 ℃.
(4) And (3) analyzing and detecting: analyzing and detecting the purified sample by adopting an HPLC-MS/MS instrument, wherein the adopted measurement parameters are as follows: HPLC detection conditions are that the sample injection volume is 10 mu L; the column temperature is 30 ℃, the chromatographic column is a C18 liquid chromatographic column, the specification is 3.5 mu m multiplied by 3.0mm multiplied by 150mm, the mobile phase in the POS mode is high-purity water containing 0.01 percent formic acid and methanol, and the flow rate is 0.30 mL/min; the mobile phase in the NEG mode is high-purity water containing 10mmol/L ammonium acetate and methanol, and the flow rate is 0.35 mL/min; the mass spectrum conditions are electrospray ionization source ESI and multi-reaction monitoring mode MRM. Performing qualitative analysis through retention time and qualitative ion pairs of all the target objects; and carrying out quantitative analysis through the peak area ratio of the isotope to obtain the determination result of the PPCPs content in the purified sample.
The invention has the beneficial effects that:
(1) because the target and the corresponding isotope internal standard have almost completely same chemical properties and states, the isotope markers and the target have the same loss characteristics in the pretreatment processes of sample filtration, purification, concentration and the like, the concentration change of PPCPs caused by degradation can be effectively compensated, and the storage time of the sample is prolonged;
(2) when the instrument is used for measuring, the adsorption behavior of the two in a chromatographic column and the response intensity of the two in a mass spectrum have good consistency, and particularly when a low-concentration sample is measured, even if higher instrument noise or background interference exists, the response intensity and the concentration of the two instruments still have good corresponding relation, so that the influence of the instrument and matrix interference on a measurement result is effectively reduced, the detection accuracy of the low-concentration sample is improved, and the detection limit of the method is reduced.
(3) By adopting an HPLC-MS/MS instrument, one or more of 16 PPCPs in soil and muddy bottom, namely nalidixic acid, trimethoprim, propranolol, carbamazepine, deet, sulpiride, metoprolol, caffeine, chloramphenicol, diclofenac, indomethacin, mefenamic acid, ketoprofen, bezafibrate, clofibric acid and gemfibrozil can be simultaneously measured, and the quantitative accuracy and the sensitivity are high.
Drawings
FIG. 1 is a flow chart of the assay method;
FIGS. 2a-2b are chromatograms of purified samples measured in positive and negative ion mode.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a method for measuring PPCPs (pharmaceutical and personal care products) in an environmental sample, which is a method for measuring the content of PPCPs in soil and bottom mud, and is shown in figure 1, and the method comprises the following steps:
(1) a sample extraction step: weighing a certain amount of freeze-dried and ground sample, placing the sample into a 50mL PP centrifugal tube, adding 15mL phosphate buffer salt, adjusting the pH to 4-5 by using NaOH or HCl solution, adding 50ng of 13C-labeled extraction internal standard solution, uniformly mixing, and aging for 30 min; adding 20mL of acetonitrile, performing vortex and ultrasonic treatment for 30min, and centrifuging to obtain a supernatant; extracting for three times, mixing extractive solutions, and rotary steaming at 35 deg.C to 20-30 mL.
(2) Enrichment and purification steps: diluting the extractive solution with ultrapure water to 500mL, placing in a brown glass or High Density Polyethylene (HDPE) water bottle (cleaned with high purity water and methanol and air dried before use), and filtering with glass fiber filter paper (burned at 450 deg.C for 4 hr); adjusting the pH value to 4-5 by using NaOH or HCl solution; washing the solid phase extraction column with 10mL of methanol, 6mL of high-purity water and 6mL of high-purity water (pH is 4-5) in sequence to achieve the purposes of activating the filler and removing impurities; enabling the filtered diluent to pass through a small column, and controlling the flow rate to be 5-10 mL/min; the column was then rinsed with 10mL of high purity water and evacuated until the packing was completely dry (about 1-2 hours).
(3) Concentration and purification steps: eluting the small column twice by using 4mL of methanol, and collecting eluent in a 10mL glass centrifuge tube; finally, the elution liquid nitrogen is blown and concentrated (the dry bath temperature is 35 ℃) to be just dried, 500 mu L of methanol/water (the volume ratio is 1:1) containing 0.025 percent formic acid and 50ng of sample injection internal standard liquid are added, vortex mixing is carried out evenly, after being filtered by a syringe filter with the diameter of 0.22 mu m, the mixture is stored in an automatic sample injection sample bottle for instrument analysis;
(4) and (3) analyzing and detecting: and analyzing and detecting the purified sample by adopting an HPLC-MS/MS instrument to obtain a determination result of the PPCPs content in the purified sample. The measuring steps in the measuring method include:
analyzing and detecting the purified sample by adopting an HPLC-MS/MS instrument, wherein the adopted MRM conditions are as follows: electrospray ionization source (ESI), multiple reaction monitoring mode (MRM), respectively, using positive ionization mode (POS) and negative ionization mode (NEG) for analysis.
The HPLC conditions were as follows: the chromatographic column is C18 liquid chromatographic column with specification of 3.5 μm × 3.0mm × 150mm, and sample injection volume of 10 μ L; the column temperature is 30 ℃; the mobile phase in POS mode is high purity water (containing 0.01% formic acid) and methanol, and the flow rate is 0.30 mL/min; the mobile phase in NEG mode was high purity water (containing 10mmol/L ammonium acetate) and methanol at a flow rate of 0.35mL/min, and the gradient elution procedure is shown in the following table.
According to the method, impurities are removed in the sample enrichment process, PPCPs in the sample are adsorbed on an SPE column, a target object is eluted by using an eluent, and then a high-sensitivity HPLC-MS/MS detector is used for quantification by an isotope internal standard method, so that the method for accurately determining the content of the PPCPs in the sample with high accuracy and high sensitivity is established. At present, the content of PPCPs in general environmental media except special polluted sites is extremely low, the quantitative mode of an internal standard method cannot meet the quantitative requirement of the substances, and after the unimaginable labor is paid, the applicant finally discovers an unexpectedly good determination parameter, so that 16 kinds of trace PPCPs existing in environmental soil can be simultaneously detected after the internal standard of various isotopes is added. .
The measurement method of the embodiment of the present invention will be described in further detail with reference to specific examples. The invention provides a method for measuring PPCPs in soil and bottom mud, which comprises the following steps:
(1) a sample extraction step: weighing a certain amount of freeze-dried and ground sample, adding 15mL of phosphate buffer salt, adjusting the pH to 4-5 by using NaOH or HCl solution, and adding 13C-labeled extraction internal standard solution; adding 20mL of acetonitrile, repeatedly extracting for three times by ultrasonic waves, combining extracting solutions, and carrying out rotary evaporation and concentration.
(2) Enrichment and purification steps: diluting the above extractive solution with ultrapure water, filtering with glass fiber filter paper (firing at 450 deg.C for 4 hr), and enriching with hydrophilic and lipophilic solid phase extraction column; a separation and purification step: eluting the small column twice by using 4mL of methanol, and collecting eluent in a 10mL glass centrifuge tube; finally, the elution liquid nitrogen is blown and concentrated (the dry bath temperature is 35 ℃) to be just dried, 500 mu L of methanol/water (the volume ratio is 1:1) containing 0.025 percent formic acid and 50ng of sample injection internal standard liquid are added, vortex mixing is carried out evenly, after being filtered by a syringe filter with the diameter of 0.22 mu m, the mixture is stored in an automatic sample injection sample bottle and is used as a purified sample of an instrument;
(3) HPLC-MS/MS determination: the measurement is carried out by using a high performance liquid chromatograph Ultimate 3000 of Dionex and an AB triple quadrupole tandem mass spectrometer API 3200, the chromatographic column is a C18 liquid chromatographic column, the specification is 3.5 mu m multiplied by 3.0mm multiplied by 150mm, and the mass spectrum condition is as follows: electrospray ionization source (ESI), multiple reaction monitoring mode (MRM), HPLC conditions: the sample injection volume is 10 mu L; the column temperature is 30 ℃; the mobile phase in POS mode is high purity water (containing 0.01% formic acid) and methanol, and the flow rate is 0.30 mL/min; the mobile phase in NEG mode was high purity water (containing 10mmol/L ammonium acetate) and methanol at a flow rate of 0.35 mL/min. Performing qualitative analysis through retention time and qualitative ion pairs of all the target objects; and carrying out quantitative analysis through the peak area ratio of the isotope to obtain the measurement result of the purified sample.
Examples
The embodiment of the invention provides a method for determining PPCPs in a soil sample, which comprises the following steps:
a sample extraction step: weighing a certain amount of freeze-dried and ground sample, placing the sample into a 50mL PP centrifugal tube, adding 15mL phosphate buffer salt, adjusting the pH to 4-5 by using NaOH or HCl solution, adding 50ng of 13C-labeled extraction internal standard solution, uniformly mixing, and aging for 30 min; adding 20mL of acetonitrile, performing vortex and ultrasonic treatment for 30min, and centrifuging to obtain a supernatant; extracting for three times, mixing extractive solutions, and rotary steaming at 35 deg.C to 20-30 mL.
Enrichment and purification steps: diluting the extractive solution with ultrapure water to 500mL, placing in a brown glass or High Density Polyethylene (HDPE) water bottle (cleaned with high purity water and methanol and air dried before use), and filtering with glass fiber filter paper (burned at 450 deg.C for 4 hr); adjusting the pH value to 4-5 by using NaOH or HCl solution; washing the solid phase extraction column with 10mL of methanol, 6mL of high-purity water and 6mL of high-purity water (pH is 4-5) in sequence to achieve the purposes of activating the filler and removing impurities; passing the filtered diluent through a small column, and controlling the flow rate at 5-10 mL/min; the column was then rinsed with 10mL of high purity water and evacuated until the packing was completely dry (about 1-2 hours).
A concentration step: eluting the small column twice by using 4mL of methanol, and collecting eluent in a 10mL glass centrifuge tube; and finally, carrying out blowing concentration on the elution liquid nitrogen (the dry bath temperature is 35 ℃) until the elution liquid nitrogen is just blown dry, adding 500 mu L of methanol/water (the volume ratio is 1:1) containing 0.025% formic acid and 50ng of sample injection internal standard solution, carrying out vortex mixing uniformly, filtering by using a 0.22 mu m syringe filter, storing in an automatic sample injection sample bottle, and carrying out instrument analysis.
HPLC-MS/MS determination: the measurement was carried out using a high performance liquid chromatograph Ultimate 3000 and an AB triple quadrupole tandem mass spectrometer API 3200 from Dionex, USA, and the column was a C18 liquid chromatography column, 3.5 μm.times.3.0 mm.times.150 mm. The mass spectrum conditions are as follows: electrospray ionization source (ESI), multiple reaction monitoring mode (MRM), HPLC conditions: the sample injection volume is 10 mu L; the column temperature is 30 ℃; the mobile phase in POS mode is high purity water (containing 0.01% formic acid) and methanol, and the flow rate is 0.30 mL/min; the mobile phase in NEG mode was high purity water (containing 10mmol/L ammonium acetate) and methanol at a flow rate of 0.35 mL/min. Performing qualitative analysis through retention time and qualitative ion pairs of all the target objects; and carrying out quantitative analysis through the peak area ratio of the isotope to obtain the measurement result of the purified sample. As shown in fig. 2a-2b, which are measurement chromatograms of positive ion mode of purified sample, it can be seen that each target object on the chromatogram has no interference of other impurities, and the response is good, so that accurate quantification can be achieved.
TABLE 1 sludge substrate recovery results with addition of standard
In conclusion, the determination method disclosed by the invention determines the content of the drug in the purified sample by isotope internal standard quantification and then by an HPLC-MS/MS method, so that the problems of short sample storage time, higher detection limit, serious actual water body matrix interference and the like are avoided, and a set of detection method with high accuracy and high sensitivity is established.
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (2)
1. The method for determining the PPCPs in the environmental soil sample is characterized by comprising the steps of sample extraction, enrichment purification, separation purification and analysis detection, wherein the step of sample extraction comprises the steps of adding phosphate buffer salt into a sample, adjusting pH, adding an extraction internal standard solution, adding acetonitrile, repeating ultrasonic extraction, combining extracting solutions, performing rotary evaporation concentration, wherein the internal standard solution is n isotope purification internal standards and 13C internal standard extracting solutions, and n is 4-16;
the enrichment purification step is to dilute the extracting solution with ultrapure water, filter the extracting solution with glass fiber filter paper, and then enrich the extracting solution with hydrophilic and lipophilic solid phase extraction column;
in the enrichment purification step, before enrichment, the small column is leached by methanol, high-purity water and high-purity water with the pH value of 4-5;
the analysis and detection step adopts an HPLC-MS/MS instrument to analyze and detect the purified sample, and adopts the following determination parameters: the HPLC conditions were as follows: the sample injection volume is 10 mu L; the column temperature is 30 ℃, the chromatographic column is a C18 liquid chromatographic column, the specification is 3.5 mu m multiplied by 3.0mm multiplied by 150mm, the mobile phase in the POS mode is high-purity water containing 0.01 percent formic acid and methanol, and the flow rate is 0.30 mL/min; the mobile phase in the NEG mode is high-purity water containing 10mmol/L ammonium acetate and methanol, and the flow rate is 0.35 mL/min; the mass spectrum conditions are electrospray ionization source ESI and multi-reaction monitoring mode MRM;
concentrating the purified sample, diluting with methanol/water at volume ratio of 1:4 to 500 μ L, adding13C-Atrazine sample injection internal standard, vortex mixing uniformly, filtering with 0.22 μm nylon syringe filter, and purifying sample to be detected by the instrument;
the PPCPs are nalidixic acid, trimethoprim, propranolol, carbamazepine, deet, sulpiride, metoprolol, caffeine, chloramphenicol, diclofenac, indomethacin, mefenamic acid, ketoprofen, bezafibrate, clofibric acid and gemfibrozil.
2. The assay method according to claim 1, wherein the environmental sample is any one of a soil and a sediment sample.
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