CN113252815B - Method for detecting triclosan and triclocarban in sludge compost - Google Patents
Method for detecting triclosan and triclocarban in sludge compost Download PDFInfo
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Abstract
The invention relates to the technical field of environmental chemical analysis, and provides a method for detecting triclosan and triclocarban in sludge compost. In the invention, the graphitized carbon black, the Florisil, the N-propyl ethylenediamine filler and the neutral alumina in the extraction tank can absorb the lipids (such as wax and fat) and the pigments in the sludge compost; meanwhile, the adsorbing material has small adsorbability to target substances triclosan and triclocarban. And then the accurate determination of triclosan and triclocarban in the sludge compost sample is realized by utilizing liquid chromatography-mass spectrometry combined detection.
Description
Technical Field
The invention relates to the technical field of environmental chemical analysis, in particular to a method for detecting triclosan and triclocarban in sludge compost.
Background
Triclosan (TCS) and Triclocarban (TCC) are highly effective broad-spectrum antimicrobial agents, and are widely used in skin care products, textiles, deodorants, wound disinfectants, and other products due to their good skin compatibility, strong lipid solubility, and high sterilization ability. However, TCS and TCC have strong biotoxicity, are novel endocrine disruptors, can be enriched in organisms through a food chain, possibly cause dysplasia, reproductive dysfunction, cancer and the like, and have strong potential influence on human health and ecosystem. At present, the important sources of TCS and TCC in the environment are sewage and bottom sludge of a sewage treatment plant, most of TCS and TCC are adsorbed and stored in the sludge due to the hydrophobicity of the TCS and TCC and the strong adsorbability of the sludge, and researches show that the concentration of TCS in the sludge is generally between 0.028 and 37.189 mg/kg, and the concentration of TCC is generally between 1.3 and 1.5 mg/kg. The urban sludge compost has high organic matter content, complete nitrogen, phosphorus, potassium and trace nutrient elements, and the organic components can increase the soil fertility after being applied to the soil, so that the sludge compost is very important for ensuring green and safe and does not cause secondary pollution. Furthermore, the method for accurately, quickly and inexpensively detecting the TCS and TCC in the sludge compost has important significance.
TCS and TCC in sludge compost are difficult to detect because the sludge compost matrix is complex and has strong adsorption effect on hydrophobic organic matters. Based on this, the pretreatment of sludge compost samples is usually divided into two steps, extraction and purification. The existing extraction methods applied to TCS and TCC in sludge compost samples comprise Soxhlet extraction, Accelerated Solvent Extraction (ASE), ultrasonic extraction and the like; purification techniques typically include column chromatography, Gel Permeation Chromatography (GPC), and Solid Phase Extraction (SPE). The accelerated solvent extraction consumes less time, consumes less solvent and has high extraction efficiency, but because the compost matrix is very complex, the urban sludge composting process needs to add additives such as straws, rice husks, hay, dried leaves, wood chips or sawdust as a conditioner; after TCS and TCC in municipal sludge compost are extracted, the obtained extract contains a large amount of pigments and lipids, and the further purification process is very difficult: if the extraction liquid is purified by using the solid-phase column, the solid-phase column is blocked.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for detecting triclosan and triclocarban in sludge compost. The detection method provided by the invention has a good purification effect on sludge compost samples, and can accurately realize the detection of triclosan and triclocarban in sludge compost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for detecting triclosan and triclocarban in sludge compost, which comprises the following steps:
pretreating a sludge compost sample to obtain a pretreated sample;
mixing the pretreatment sample, copper powder and diatomite to obtain a sample to be extracted;
placing the sample to be extracted into an extraction cell, wherein the filler of the extraction cell comprises from bottom to top:
the device comprises a glass fiber film, a drying agent, a glass fiber film, Florisil, graphitized carbon black, N-propyl ethylenediamine filler, neutral alumina, a glass fiber film and a sample to be extracted;
extracting the sample to be extracted in the extraction tank by using an extracting agent to obtain an upper computer sample;
and performing liquid chromatography-mass spectrometry detection on the computer sample to realize the detection of triclosan and triclocarban in the sludge compost.
Preferably, the mass ratio of the pretreatment sample to the copper powder is (0.5-1.0): (0.2 to 0.5); the particle size of the pretreatment sample is 10-100 meshes; the particle size of the copper powder is 100-200 meshes.
Preferably, the mass ratio of the pretreated sample to the diatomite is (0.5-1.0): (0.1 to 2.0); the particle size of the diatomite is 1-3 mm.
Preferably, the mass ratio of the pretreatment sample to the Florisil is (0.5-1.0): (2-3); the particle size of the Florisil is 100-200 meshes.
Preferably, the mass ratio of the pretreated sample to the graphitized carbon black is (0.5-1.0): (0.5 to 1); the particle size of the graphitized carbon black is 120-400 meshes.
Preferably, the mass ratio of the pretreated sample to the N-propyl ethylene diamine filler is (0.5-1.0): (1-2); the particle size of the N-propyl ethylenediamine filler is 100-200 meshes.
Preferably, the mass ratio of the pretreated sample to the neutral alumina is (0.5-1.0): (3-4); the particle size of the neutral alumina is 50-100 meshes.
Preferably, the filling rate of the filler in the extraction tank is 80-90%.
Preferably, the volume ratio of the extracting agent to the acetone and the dichloromethane is 1: (1-2) a mixed solvent; the extraction conditions include: the temperature is 80-110 ℃, the pressure is 1000-2000 psi, and the times are 1-2; the process of each extraction: the time is 2-15 min, and the volume of the extracting agent is 20-50% of the volume of the extraction pool.
Preferably, the parameters of the liquid chromatography-mass spectrometry detection include chromatographic conditions and mass spectrometry conditions:
the chromatographic conditions include:
the chromatographic column is Shim-pack GIST-HP C18Column, 3.0 μm, 2.1mm i.d. × 50mm L, Shimadzu;
the mobile phase is methanol and water in a volume ratio of 75: 25 of a mixed solution;
the flow rate is 0.3 mL/min;
the sample injection amount is 5 mu L;
the column temperature was 40 ℃;
the mass spectrometry conditions include:
the ionization mode is ESI-；
The ion spray voltage is the default tuning voltage;
the atomization gas is nitrogen with the flow rate of 3.0L/min;
the heating gas is air with the flow rate of 10.0L/min;
the drying gas is nitrogen with the flow rate of 10.0L/min;
the collision gas is argon;
the interface temperature is 300 ℃;
the DL temperature is 250 ℃;
the heating module temperature was 400 ℃.
The invention provides a method for detecting triclosan and triclocarban in sludge compost, which comprises the following steps: pretreating a sludge compost sample to obtain a pretreated sample; mixing the pretreatment sample, copper powder and diatomite to obtain a sample to be extracted; placing the sample to be extracted into an extraction cell, wherein the filler of the extraction cell comprises from bottom to top: the device comprises a glass fiber film, a drying agent, a glass fiber film, Florisil, graphitized carbon black, N-propyl ethylenediamine filler, neutral alumina, a glass fiber film and a sample to be extracted; extracting the sample to be extracted in the extraction tank by using an extracting agent to obtain an upper computer sample; and performing liquid chromatography-mass spectrometry detection on the computer sample to realize the detection of triclosan and triclocarban in the sludge compost.
In the invention, the graphitized carbon black, the Florisil, the N-propyl ethylenediamine filler and the neutral alumina in the extraction tank can absorb the lipids (such as wax and fat) and the pigments in the sludge compost; meanwhile, the adsorbing material has small adsorbability to target substances triclosan and triclocarban. And then the accurate determination of triclosan and triclocarban in the sludge compost sample is realized by utilizing liquid chromatography-mass spectrometry combined detection.
Drawings
FIG. 1 is a liquid chromatogram of TCS at a concentration of 5 ppb;
FIG. 2 is a liquid chromatogram of TCC at a concentration of 1 ppb.
Detailed Description
The invention provides a method for detecting triclosan and triclocarban in sludge compost, which comprises the following steps:
pretreating a sludge compost sample to obtain a pretreated sample;
mixing the pretreatment sample, copper powder and diatomite to obtain a sample to be extracted;
placing the sample to be extracted into an extraction cell, wherein the filler of the extraction cell comprises from bottom to top:
the device comprises a glass fiber film, a drying agent, a glass fiber film, Florisil, graphitized carbon black, N-propyl ethylenediamine filler (PSA), neutral alumina, a glass fiber film and a sample to be extracted;
extracting the sample to be extracted in the extraction tank by using an extracting agent to obtain an upper computer sample;
and performing liquid chromatography-mass spectrometry detection on the computer sample to realize the detection of triclosan and triclocarban in the sludge compost.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The method comprises the step of pretreating a sludge compost sample to obtain a pretreated sample.
In the invention, the particle size of the pretreatment sample is preferably 10-100 meshes, and more preferably 50-100 meshes.
In the present invention, the pretreatment preferably includes freeze-drying, sieving and grinding in this order.
In the present invention, the freeze-drying preferably comprises the steps of: freezing at-18 deg.C for 10 h, and drying at-60 deg.C for 72 h. In the present invention, the screened screen is preferably a 1mm screen; in the invention, the sieving can remove large solids such as branches and the like in the sludge compost. The parameters and conditions of the grinding are not particularly limited as long as the particle size of the obtained pretreated sample is 10 to 100 mesh.
After the pretreatment sample is obtained, the pretreatment sample, the copper powder and the diatomite are mixed to obtain a sample to be extracted.
In the present invention, the particle size of the copper powder is preferably 100 to 200 mesh. In the invention, the particle size of the diatomite is preferably 1-3 mm; the diatomaceous earth is preferably in the form of spheres. According to the invention, the diatomite is set to be spherical with the particle size of 1-3 mm, so that the dispersion of a pretreated sample is facilitated.
In the invention, the mass ratio of the pretreatment sample to the copper powder is preferably (0.5-1.0): (0.2 to 0.5), and more preferably 0.6: 0.2. in the invention, the mass ratio of the pretreated sample to the diatomite is preferably (0.5-1.0): (0.1 to 2.0), more preferably 0.6: 1.0.
the operation of the mixing is not particularly limited in the present invention as long as the pretreated sample, the copper powder and the diatomaceous earth can be mixed.
After the sample to be extracted is obtained, the sample to be extracted is placed in an extraction tank, and the filler of the extraction tank comprises from bottom to top: the device comprises a glass fiber film, a drying agent, a glass fiber film, Florisil, graphitized carbon black, N-propyl ethylenediamine filler, neutral alumina, a glass fiber film and a sample to be extracted.
In the present invention, a glass fiber membrane is preferably provided between the florisil, the graphitized carbon black, the N-propyl ethylenediamine filler and the neutral alumina.
In the present invention, the glass fiber membrane is preferably available from thermoelectric corporation of america. In the present invention, the drying agent is preferably anhydrous sodium sulfate. In the invention, the particle size of the Florisil is preferably 100-200 meshes. In the present invention, the particle size of the graphitized carbon black is preferably 120 to 400 mesh. In the invention, the particle size of the N-propyl ethylenediamine filler is preferably 100-200 meshes. In the present invention, the particle size of the neutral alumina is preferably 50 to 100 mesh.
In the invention, the mass ratio of the pretreatment sample to the Florisil is preferably (0.5-1.0): (2-3), more preferably 0.6: 3.0. in the invention, the mass ratio of the pretreated sample to the graphitized carbon black is preferably (0.5-1.0): (0.5 to 1), and more preferably 0.6: 0.8. in the invention, the mass ratio of the pretreated sample to the N-propyl ethylenediamine filler is preferably (0.5-1.0): (1-2), more preferably 0.6: 1.5. in the invention, the mass ratio of the pretreated sample to the neutral alumina is preferably (0.5-1.0): (3-4), more preferably 0.6: 4.0.
in the invention, the filling rate of the filler in the extraction tank is preferably 80-90%.
In the invention, the volume of the extraction pool is preferably 22-66 mL, and more preferably 34 mL.
In the invention, the graphitized carbon black, the Florisil, the N-propyl ethylenediamine filler and the neutral alumina in the extraction tank can absorb the lipids (such as wax and fat) and the pigments in the sludge compost; meanwhile, the adsorbing material has small adsorbability to target substances triclosan and triclocarban.
After the extraction tank is installed, the invention adopts an extracting agent to extract the sample to be extracted in the extraction tank, and the upper machine sample is obtained.
In the present invention, the volume ratio of the extracting agent to the dichloromethane is preferably 1: the mixed solvent of (1-2), more preferably 1: 1. in the present invention, the extraction conditions include: the temperature is preferably 80-110 ℃, and more preferably 90-100 ℃; the pressure is preferably 1000-2000 psi, and more preferably 1500 psi; the frequency is preferably 1-2 times; the process of each extraction: the time is preferably 2-15 min, and more preferably 10 min; the volume of the extracting agent is preferably 20-50% of the volume of the extraction pool, and particularly preferably 50%.
In the present invention, the extraction is preferably carried out in an accelerated solvent extractor.
After the extraction, the invention also comprises the steps of concentrating, blowing nitrogen, redissolving and filtering the obtained extract liquor to obtain the upper computer sample. In the invention, the concentration temperature is preferably 40-60 ℃; the concentration is preferably carried out on a rotary evaporator. In the present invention, the nitrogen blowing is preferably performed on a nitrogen blower, and the time for the nitrogen blowing is preferably 90 seconds. In the present invention, the redissolving agent is preferably methanol. In the present invention, the pore size of the filtration membrane for filtration is preferably 0.22. mu.m.
After the upper computer sample is obtained, the liquid chromatography-mass spectrometry combined detection is carried out on the upper computer sample, so that the detection of triclosan and triclocarban in sludge compost is realized.
In the invention, the parameters of the liquid chromatography-mass spectrometry detection comprise chromatographic conditions and mass spectrometry conditions.
In the present invention, the chromatographic conditions preferably include:
the chromatographic column is Shim-pack GIST-HP C18Column, 3.0 μm, 2.1mm i.d. × 50mm L, Shimadzu;
the mobile phase is methanol and water in a volume ratio of 75: 25 of a mixed solution;
the flow rate is 0.3 mL/min;
the sample injection amount is 5 mu L;
the column temperature was 40 ℃.
In the present invention, the mass spectrometry conditions preferably include:
the ionization mode is ESI-；
The ion spray voltage is the default tuning voltage; the default tuning voltage is an instrument default voltage, and is particularly preferably-3 kV;
the atomization gas is nitrogen with the flow rate of 3.0L/min;
the heating gas is air with the flow rate of 10.0L/min;
the drying gas is nitrogen with the flow rate of 10.0L/min;
the collision gas is argon;
the interface temperature is 300 ℃;
the DL temperature is 250 ℃;
the heating module temperature was 400 ℃.
In the present invention, the qualitative parameters of TCC and TCS mass spectra are shown in Table 1.
TABLE 1 TCC and TCS Mass Spectrometry qualitative parameters
And after the detection, obtaining the chromatographic peak areas of the triclosan and the triclocarban in the sludge compost, preferably substituting the chromatographic peak areas of the triclosan and the triclocarban in the sludge compost into a standard curve of the concentration-chromatographic peak areas of the triclosan and the triclocarban to obtain the content of the triclosan and the triclocarban in the sludge compost.
The acquisition of the standard curve of the concentration-chromatographic peak area of the triclosan and the triclocarban is not particularly limited, and a standard curve acquisition mode which is well known by a person skilled in the art can be adopted.
The following examples are provided to describe the method for detecting triclosan and triclocarban in sludge compost according to the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Description of the instruments and reagents used in the following examples
The instrument comprises the following steps: ASE350 accelerated solvent extractor (Dionex, germany); liquid chromatography coupled with mass spectrometry (shimadzu, japan).
Reagent: copper powder (100-200 meshes); diatomite (1-3 mm, spherical); graphitized carbon black (120-400 meshes); florisil (100-200 meshes); n-propyl ethylenediamine filler (100-200 meshes); neutral alumina (50-100 mesh); dichloromethane, acetone and methanol are used as chromatographic purity; glass fiber membranes (available from U.S. thermoelectric corporation).
Example 1
A method for detecting triclosan and triclocarban in sludge compost comprises the following steps:
(1) collecting sludge compost samples: a sludge compost sample is taken from a composting workshop of a certain sewage treatment plant, and the composting process is an automatic control oxygen fermentation process.
(2) Obtaining a pretreatment sample: freezing and storing the collected sludge compost sample at-20 ℃, freezing for 10 h at-18 ℃, drying for 72 h at-60 ℃, sieving by a 1mm sieve, and grinding to obtain a pretreatment sample with the particle size of 50-100 meshes.
(3) Obtaining a sample to be extracted: 0.2 g of copper powder, 0.6 g of the pretreated sample and 1g of diatomaceous earth were mixed to obtain a sample to be extracted.
(4) Filling an extraction tank: the volume of the extraction cell selected in this example is 34 mL, and the packing from bottom to top of the extraction cell comprises: the sample extraction method comprises the following steps of (1) preparing a glass fiber membrane, 0.2 g of anhydrous sodium sulfate, a glass fiber membrane, 3 g of Florisil, 0.8 g of graphitized carbon black, 1.5g N-propyl ethylenediamine filler, 4 g of neutral alumina, a glass fiber membrane and a sample to be extracted; the filling rate of the filler to the extraction tank is 85%.
(5) And (3) extraction: extracting with accelerated solvent extractor (DAAN ASE 350); the extraction conditions include: the volume ratio of the extracting agent is 1: 1, the temperature is 100 ℃, the pressure is 1500 psi, and the time is 2 min; the volume of the extracting agent is 50 percent of the volume of the extraction pool; concentrating the obtained extractive solution at 50 deg.C with rotary evaporation instrument to volume of 0.5 mL, blowing on nitrogen blower for 90 s, diluting with methanol to volume of 1.0 mL, passing through 0.22 μm membrane, and collecting the supernatant as the sample.
(6) Detecting the sample on the computer by a liquid chromatogram-mass spectrum combined instrument,
the chromatographic conditions include: the chromatographic column is Shim-pack GIST-HP C18Columns (3.0 μm, 2.1mm i.d. × 50mm L, Shimadzu); the mobile phase is methanol and water in a volume ratio of 75: 25 of a mixed solution; the flow rate is 0.3 mL/min; the sample injection amount is 5 mu L; the column temperature was 40 ℃.
The mass spectrometry conditions include: the ionization mode is ESI-(ii) a The ion spray voltage is the default tuning voltage; the atomization gas is nitrogen with the flow rate of 3.0L/min; the heating gas is air with the flow rate of 10.0L/min; the drying gas is nitrogen with the flow rate of 10.0L/min; the collision gas is argon; the interface temperature is 300 ℃; the DL temperature is 250 ℃; the heating module temperature was 400 ℃.
The range of TCS and TCC standard curves is within 0.1-100 ppb:
the standard curve of TCS, using methanol as a solvent, was prepared at concentrations of 0.5 ppb, 5 ppb, 25 ppb, 50 ppb, 100 ppb, 250 ppb and 500 ppb, respectively, and the standard curve was: y =3282x +13613, r2=0.9996。
The standard curve of TCC uses methanol as solvent,prepared at concentrations of 0.1 ppb, 1 ppb, 5 ppb, 10 ppb, 20 ppb, 50 ppb and 100 ppb, respectively, and the standard curves are: y =112822x + 45623; r is2=0.9998。
FIG. 1 is a liquid chromatogram of TCS at a concentration of 5 ppb; FIG. 2 is a liquid chromatogram of TCC at a concentration of 1 ppb. As can be seen from fig. 1 and 2: the liquid chromatogram and mass spectrum combined parameter provided by the invention can realize the detection of low-concentration TCS and TCC.
And (3) performing a standard addition recovery rate experiment on the sludge compost sample according to the steps of the steps (1) to (6), wherein the standard addition is respectively 2 mu g/g and 10 mu g/g, repeating the standard addition for 3 times, the recovery rates of the TCS and the TCC are in the range of 81-102%, the relative standard deviation is less than 10%, and the detection requirements are completely met.
Example 2
According to the detection result of actual TCS and TCC in certain sludge compost in Shanghai, the concentration of triclosan is 0.6-0.8 mu g/g, and the concentration of triclocarban is 1.3-1.5 mu g/g.
Comparative example 1
The dichloromethane in the extractant of example 1 was omitted and acetone alone was substituted as the extractant.
The detection method in the embodiment 1 and the comparative example 1 is adopted to carry out the standard recovery rate detection on certain sludge compost in Shanghai, and the result is as follows: the average recovery rate of the triclosan in the sludge compost is 85 percent and the relative standard deviation is 5 percent by utilizing the measurement of example 1; the average recovery of triclocarban was 95% with a relative standard deviation of 6%. The triclosan concentration in the sludge compost measured by the detection method of the comparative example 1 is 75 percent of the average recovery rate and 8 percent of the relative standard deviation; the triclocarban was 85% with a relative standard deviation of 11%. The detection method provided by the invention has high detection accuracy.
Comparative example 2
The extraction reagents dichloromethane and acetone in example 1 were replaced with methanol alone.
The detection method in the example 1 and the comparative example 2 is adopted to extract certain sludge compost in Shanghai, and the result is as follows: with the detection method of comparative example 2, the obtained extract was dark brown, and could not be directly analyzed by an instrument, requiring an additional purification step. By adopting the detection method of the embodiment 1, the obtained extract is clear, and after being filtered by a membrane, the extract can be directly analyzed by a liquid chromatogram and a mass spectrometer. It is shown that the detection method provided by the invention has higher efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A method for detecting triclosan and triclocarban in sludge compost is characterized by comprising the following steps:
(1) collecting sludge compost samples: taking a sludge compost sample from a composting workshop of a certain sewage treatment plant, wherein the composting process is an automatic aerobic fermentation control process;
(2) obtaining a pretreatment sample: freezing and storing the collected sludge compost sample at-20 ℃, freezing for 10 h at-18 ℃, then drying for 72 h at-60 ℃, sieving by a 1mm sieve, and grinding to obtain a pretreatment sample with the particle size of 50-100 meshes;
(3) obtaining a sample to be extracted: mixing 0.2 g of copper powder, 0.6 g of the pretreated sample and 1g of diatomite to obtain a sample to be extracted;
(4) filling an extraction tank: the volume of extraction pond is 34 mL, and the filler from bottom to top of extraction pond includes: the sample extraction method comprises the following steps of (1) preparing a glass fiber membrane, 0.2 g of anhydrous sodium sulfate, a glass fiber membrane, 3 g of Florisil, 0.8 g of graphitized carbon black, 1.5g N-propyl ethylenediamine filler, 4 g of neutral alumina, a glass fiber membrane and a sample to be extracted; the filling rate of the filler to the extraction tank is 85 percent;
(5) and (3) extraction: extracting by adopting an accelerated solvent extractor; the extraction conditions include: the volume ratio of the extracting agent is 1: 1, the temperature is 100 ℃, the pressure is 1500 psi, and the time is 2 min; the volume of the extracting agent is 50 percent of the volume of the extraction pool; concentrating the obtained extract at 50 deg.C by rotary evaporation instrument to volume of 0.5 mL, blowing on nitrogen blowing instrument for 90 s, diluting with methanol to volume of 1.0 mL, passing through 0.22 μm membrane, and collecting the clear solution as the sample; the accelerated solvent extractor is a dean ASE 350;
(6) detecting the sample on the computer by adopting a liquid chromatogram-mass spectrometer:
the chromatographic conditions include: the chromatographic column is Shim-pack GIST-HP C18Column, 3.0 μm, 2.1mm i.d. × 50mm L, Shimadzu; the mobile phase is methanol and water in a volume ratio of 75: 25 of a mixed solution; the flow rate is 0.3 mL/min; the sample injection amount is 5 mu L; the column temperature was 40 ℃;
the mass spectrometry conditions include: the ionization mode is ESI-(ii) a The ion spray voltage is the default tuning voltage; the atomization gas is nitrogen with the flow rate of 3.0L/min; the heating gas is air with the flow rate of 10.0L/min; the drying gas is nitrogen with the flow rate of 10.0L/min; the collision gas is argon; the interface temperature is 300 ℃; the DL temperature is 250 ℃; the heating module temperature was 400 ℃.
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