CN111257457A - Analysis method for determining metal sulfide nanoparticles in water - Google Patents
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Abstract
The invention discloses an analysis method for measuring metal sulfide nano-particles in water. The method comprises the following steps: processing the sample solution by adopting a cloud point extraction method, and collecting a TX-114 phase enriched with metal nanoparticles; adding aqueous solution of bis (p-sulfophenyl) phenylphosphine dipotassium dehydrate to the TX-114 phase, and selectively dissolving Non-MS-NPs; the contents of M-NPs and Non-MS-NPs are detected by combining liquid chromatography with inductively coupled plasma mass spectrometry, so that the metal sulfide nanoparticles are rapidly and accurately separated and determined in a water environment. By adopting the method, the separation and the determination of the metal sulfide nano-particles as low as ng/L can be realized, and the method is used for the separation and the determination of the nano silver sulfide and the nano zinc sulfide in the water environment body, so that the result is satisfactory. The method has the advantages of simple operation steps, high selectivity, high sensitivity, protection of the morphology and particle size distribution of MS-NPs and the like.
Description
Technical Field
The invention belongs to the field of environmental analytical chemistry, and relates to a method for determining metal sulfide nanoparticles in a water environment based on cloud point extraction separation.
Background
Metal nanoparticles (M-NPs) have been widely used in the fields of drug delivery, composite materials, electronic products, and the like, due to their excellent physicochemical properties. With the increase of the production amount and the use amount of the metal nanoparticles, the metal nanoparticles are inevitably released into the environment, and potential harm is caused to human health, ecological environment, social safety and the like. Numerous studies have shown that the toxicity and migratory transformation of M-NPs depends to a large extent on their morphology. The types of M-NPs are variable and generally include metal sulfide nanoparticles (MS-NPs), metal oxide nanoparticles (MO-NPs) and zero-valent metals (Z-NPs), while MS-NPs are the predominant forms of M-NPs in a water-soluble environment. Therefore, in order to accurately assess the risk of MS-NPs to the environment and human health, a rapid and accurate analytical method is required to isolate and quantitatively analyze MS-NPs in environmental samples.
Currently, common methods for analyzing M-NPs in aquatic environments include ultrafiltration separation and preconcentration, Solid Phase Extraction (SPE), and ion exchange resin method (IER), followed by quantitative analysis using detectors of specific elements, such as Inductively Coupled Plasma Mass Spectrometry (ICPMS). Meanwhile, in order to further obtain detailed information on the size distribution of M-NPs, on-line coupling based on chromatographic or electrophoretic techniques, such as Liquid Chromatography (LC), Thin Layer Chromatography (TLC), Field Flow Fractionation (FFF), Capillary Electrophoresis (CE), and Gel Electrophoresis (GE), are also common in the field of nano-analysis in combination with (ICP-MS). However, these techniques only allow the determination of M-NPs, but do not allow the determination of MS-NPs. Although X-ray near-edge absorption spectroscopy (XANES) can overcome this bottleneck, it suffers from low sensitivity, high cost and instrument rarity. In addition, due to the low concentration of M-NPs in environmental water, the complex matrix of the sample and the diversity of physicochemical properties, the routine analysis of M-NPs in the environment still faces huge challenges. Therefore, there is an urgent need to establish a method for accurately and rapidly separating and measuring MS-NPs in a complex matrix.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention provides a method for separating and determining MS-NPs in a water environment by combining Cloud Point Extraction (CPE) with liquid chromatography and inductively coupled plasma mass spectrometry (LC-ICPMS).
The invention realizes the extraction and enrichment of all forms of M-NPs based on CPE technology, and then selectively dissolves Non-metal sulfide nano particles (Non-MS-NPs) by adding aqueous solution of bis (p-sulfophenyl) phenylphosphine dehydrated dipotassium (BSPP); and finally, jointly measuring by adopting LC-ICPMS to obtain the contents of M-NPs and Non-MS-NPs, and subtracting the content of Non-MS-NPs from the content of M-NPs to realize the quantitative measurement of MS-NPs.
The purpose of the invention is realized by the following technical scheme:
an analytical method for measuring metal sulfide nanoparticles in water, comprising the steps of: (1) processing the sample solution by a Cloud Point Extraction (CPE) method, and collecting a TX-114 phase enriched with metal nanoparticles; (2) adding aqueous solution of bis (p-sulfophenyl) phenylphosphine dipotassium dehydrate (BSPP) to the TX-114 phase, and selectively dissolving Non-MS-NPs; (3) the contents of M-NPs and Non-MS-NPs are detected by combining liquid chromatography with inductively coupled plasma mass spectrometry (LC-ICPMS), so that the metal sulfide nanoparticles (MS-NPs) can be rapidly and accurately separated and determined in a water environment.
Specifically, the analysis method for determining the metal sulfide nanoparticles in the water comprises the following steps:
(1) cloud point extraction: adding a sample solution containing metal nanoparticles (M-NPs) into a centrifugal tube, and then sequentially adding a TX-114 solution and NaNO3Adjusting the pH value of the solution and an EDTA solution, heating the solution in a water bath at 45 ℃ for 15min, centrifuging, removing a supernatant, and collecting a TX-114 phase;
cloud point extraction conditions: TX-114 concentration is 0.01% -0.3% (m/v), NaNO3The concentration is 2-30mM, the EDTA concentration is 5mM, and the pH is 3-9;
(2) BSPP selectively dissolves Non-MS-NPs: adding aqueous solution of bis (p-sulfophenyl) phenylphosphine dipotassium dehydrate (BSPP) into the TX-114 phase obtained in the step (1), and shaking at 300rpm for 15-120 minutes at room temperature; wherein the concentration of BSPP in the mixed solution is 0.5-10 mM;
(3) the total M-NPs and Non-MS-NPs concentrations were measured by LC-ICPMS, respectively, and the concentration of MS-NPs was obtained by subtracting the Non-MS-NPs content from the total M-NPs content.
Preferably, in step (1), the concentration of TX-114 is 0.15% (m/v), NaNO3Is 20 mM. Wherein TX-114 is used as a surfactant for quantitatively extracting M-NPs.
Preferably, the M-NPs in the step (1) comprise zero-valent metal nano materials such as nano Ag, nano Au, nano Pd and the like, and nano Ag2S, nano ZnS and other metal sulfide nano material, nano ZrO and nano Fe2O3Metal oxide nanomaterials such as nano ZnO; the concentration of the metal nanoparticles (M-NPs) in the sample solution containing the metal nanoparticles (M-NPs) is 100 mu g/L.
Preferably, the pH in step (1) is 5.
Preferably, HNO is used in the step (1)3Or NaOH to adjust the pH.
Preferably, the centrifugation in step (1) means centrifugation at 3000rpm for 5 minutes.
Preferably, in the step (2), the concentration of BSPP in the mixed solution is 5 mM. And adding aqueous solution of bis (p-sulfophenyl) phenylphosphine dehydrated dipotassium (BSPP) into the extracted M-NPs, and selectively dissolving Non-metal sulfide nanoparticles (Non-MS-NPs) in the M-NPs without changing the original form of the MS-NPs.
Preferably, in step (2), shaking is carried out at 300rpm for 15 minutes. The vibration time is the time for dissolving Non-MS-NPs by BSPP.
Preferably, step (3) is performed with reference to the prior art (Zhou, X.X.; Liu, J.F.; Jiang, G.B.ElementalMass Size Distribution for Characterization, Quantification and identification of Trace nanoparticies in Serum and environmental waters Environ. Sci.Techniol.2017, 51, 3892) 3901): connecting LC and ICPMS by using a two-way valve, and measuring the total content of metal nanoparticles (M-NPs) in the solution by using an external standard method; by using
Chromatographic column (Venusil Durashell-NH) using modified silica gel bonded with amino as stationary phase2,
poresize, 250X 4.6mm) of LC and ICPMS connection, and measuring the content of Non-metallic sulfur nano particles (Non-MS-NPs) after dissolving bis (p-sulfophenyl) phenylphosphine dehydrated dipotassium by an external standard method.
On the basis of the steps (1) and (2), the sensitive measurement of the metal sulfide Nanoparticles (MS-NPs) can be realized by the liquid chromatography and inductively coupled plasma Mass spectrometry (LC-ICPMS) combined technology reported in the prior literature (Zhou, X.X.; Liu, J.F.; Jiang, G.B.Electron Mass Distribution for Characterization, Quantification and differentiation of Trace Nanoparticles in Serum and environmental Water.environmental Sci.Technol.2017,51, 3892-3901). When the total content of M-NPs is measured, a chromatographic column is not used, but a two-way connection LC and an ICPMS are used, and at the moment, MS-NPs and metal ions are not separated and directly and completely enter the ICPMS; when the Non-MS-NPs are measured, a chromatographic column is used, after BSPP is added, the Non-MS-NPs are dissolved into metal ions, and the metal ions pass through an LC column and can be separated from the metal sulfide nanoparticles, so that accurate measurement is realized. It should be noted that the metal sulfide nanoparticles cannot be directly measured because if the particle size of the metal sulfide nanoparticles is larger than 50nm, a part of the metal sulfide nanoparticles remains in the column. Therefore, the MS-NPs concentration can be measured by adopting an indirect measurement method.
Preferably, the analysis method for determining metal sulfide nanoparticles in water comprises the following specific steps:
(1) 9.5mL of sample solution containing metal nanoparticles (M-NPs) was added to the centrifuge tube, followed by 0.15mL of 10% (M/v) TX-114 aqueous solution, 0.2mL of 1M NaNO3Solution and 0.25mL of 200mM EDTA solution; and adjusting the pH value to 5; then the solution is fully mixed and heated in a water bath at 45 ℃ for 15 minutes, then the mixture is placed in a centrifuge and centrifuged at 3000rpm for 5 minutes to realize two-phase separation, a pipette is used for removing supernatant, and a lower TX-114 phase is reserved;
(2) 100 μ L of 10mM BSPP in water was added to 100 μ L of the lower TX-114 phase and shaken at 300rpm for 15 minutes at room temperature;
(3) the concentrations of total M-NPs and Non-MS-NPs were determined separately using LC-ICPMS (determination methods identical to those of Zhou, X.X.; Liu, J.F.; Jiang, G.B.Electron Mass Size Distribution for characterization, Quantification and Identification of Trace nanoparticies in Senrum and Environmental Water. Environmental. Sci. technique.2017, 51,3892-3901), and the concentration of MS-NPs was obtained by subtracting the content of Non-MS-NPs from the total M-NPs content.
In the present invention, the concentration unit M is mol/L, and mM is mmol/L.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. providing a method for determining the ng/L level of MS-NPs based on the combination of CPE and LC-ICPMS;
2. the morphology and the particle size distribution of the MS-NP are maintained;
3. the method is simple, good in repeatability and high in sensitivity.
Drawings
FIG. 1 is a schematic diagram of an analytical method for measuring metal sulfide nanoparticles in water according to the present invention.
FIG. 2 shows the results of experiments for optimizing CPE extraction conditions; wherein A is the influence of TX-114 on the extraction efficiency of M-NPs, and B is NaNO3The influence on the extraction efficiency of M-NPs, and C is the influence of the pH of the sample solution on the extraction efficiency of M-NPs.
FIG. 3 is a BSPP selective lysis Non-MS-NP condition optimization; wherein A is the influence of BSPP on the dissolution of Non-MS-NPs, and B is the influence of BSPP shaking time on the dissolution of Non-MS-NPs.
FIG. 4 is a selective investigation of BSPP dissolving Non-MS-NPs; a is untreated Ag-containing M-NPs, C is a chromatogram of an untreated Zn-containing M-NPs aqueous solution, B is treated Ag-containing M-NPs, and D is a chromatogram of a treated Zn-containing M-NPs aqueous solution.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The invention provides an analysis method for measuring metal sulfide nano-particles in water, which comprises the following steps: (1) processing the sample solution by a Cloud Point Extraction (CPE) method, and collecting a TX-114 phase enriched with metal nanoparticles; (2) adding bis (p-rs) to TX-114 phase-sulfophenyl) phenylphosphine dipotassium dehydrate (BSPP) in aqueous solution, selective for Non-MS-NPs; (3) the contents of M-NPs and Non-MS-NPs are detected by combining liquid chromatography with inductively coupled plasma mass spectrometry (LC-ICPMS), so that the metal sulfide nanoparticles (MS-NPs) can be rapidly and accurately separated and determined in a water environment. The principle of the method is as shown in figure 1: the metal nanoparticles in the water include metal sulfide nanoparticles and non-metal sulfide nanoparticles. During cloud point extraction, the metal sulfide nanoparticles and the nonmetal sulfide nanoparticles can be extracted into a TX-114 phase, and then a BSPP reagent is added into the TX-114 phase to selectively dissolve the nonmetal sulfide nanoparticles into metal ions without dissolving the metal sulfide nanoparticles. And the particle diameters of the nano particles and the ions are greatly different, so that the separation can be carried out by adopting LC-ICPMS. The inventor optimizes the conditions of cloud point extraction and BSPP selective dissolution Non-MS-NPs through experiments to obtain the conditions of cloud point extraction: TX-114 concentration is 0.01% -0.3% (m/v), NaNO3The concentration is 2-30mM, the EDTA concentration is 5mM, and the pH is 3-9; the optimal cloud point extraction conditions were as follows: TX-114 concentration 0.15% (m/v), NaNO3The concentration is 20mM, the EDTA concentration is 5mM, and the pH value is 5; in the step of selectively dissolving Non-MS-NPs by BSPP, the concentration of BSPP is 0.5-10mM, preferably 5mM, and the dissolving time is 15-120min, preferably 15 min.
Optimizing the LC-ICPMS determination method in the experiment and the document Zhou, X.X; liu, j.f.; jiang, G.B.Electron Mass Size Distribution for Characterisation, Quantification and differentiation of Trace nanoparticies in Serum and environmental waters Environ.Sci.Technol.2017,51,3892-,
(1) cloud point extraction condition optimization;
selection of tx-114 concentration: to 9.5mL of M-NPs (100. mu.g/L), 20mM NaNO was added3And TX-114 (0.01% -0.3%, m/v) in various concentrations, with dilute HNO3Or NaOH to adjust pH to 5. And then, heating the solution in a water bath at 45 ℃ for 15min, taking out, centrifuging at 3000rpm for 5min in a centrifuge, separating and removing a supernatant by using a pipette, diluting and uniformly mixing a TX-114 concentrated phase with 0.2mL of ultrapure water, and measuring M-NPs by using LC-ICPMS.
B.NaNO3Selection of concentration: to 9.5mL of M-NPs (100. mu.g/L), 2-30mM of NaNO was added3And 0.15% TX-114(m/v), diluted HNO3Or NaOH to adjust pH to 5. And then, heating the solution in a water bath at 45 ℃ for 15min, taking out, centrifuging at 3000rpm for 5min in a centrifuge, separating and removing a supernatant by using a pipette, diluting and uniformly mixing a TX-114 concentrated phase with 0.1mL of ultrapure water, and measuring M-NPs by using LC-ICPMS.
C. Selection of sample pH: to 9.5mL of M-NPs (100. mu.g/L), 20mM NaNO was added3And 0.15% TX-114(m/v), diluted HNO3Or NaOH to adjust the pH to 3-9. And then, heating the solution in a water bath at 45 ℃ for 15min, taking out, centrifuging at 3000rpm for 5min in a centrifuge, separating and removing a supernatant by using a pipette, diluting and uniformly mixing a TX-114 concentrated phase with 0.2mL of ultrapure water, and measuring M-NPs by using LC-ICPMS.
Fig. 2 shows the results of CPE extraction condition optimization experiments: wherein A is the influence of TX-114 on the extraction efficiency of M-NPs, and B is NaNO3The influence on the extraction efficiency of M-NPs, and C is the influence of the pH of the sample on the extraction efficiency of M-NPs. As can be seen from graph A, as the concentration of TX-114 increases, the extraction efficiency of M-NPs increases, reaching a maximum at 0.15% (M/v); as can be seen from Panel B, it follows NaNO3The concentration is increased, the extraction rate of M-NPs is increased, and the extraction efficiency reaches the balance when the concentration is 20 mM; as shown in the C diagram, Ag2The extraction efficiency of S-NPs and ZnS-NPs is not obviously changed in the range of pH3-9, AgNPs and ZnO-NPs are the highest in the range of pH3-5, and are slightly reduced in the range of pH 6-9. The pH of the sample was selected to be 5 for extraction, considering that M-NPs are partially dissolved under strongly acidic conditions.
(2) Optimizing BSPP selective dissolving Non-MS-NPs conditions;
selection of BSPP concentration: to 10mL of Non-MS-NPs at 100. mu.g/L, 0.5-10mM BSPP was added, followed by shaking at 300rpm for 30min at room temperature. Subsequently, the content of metal ions after dissolution was measured by LC-ICPMS.
B, selection of BSPP dissolution time: 5mM BSPP was added to 10mL of Non-MS-NPs at 100. mu.g/L, and shaken at 300rpm for 15-120min at room temperature. Subsequently, the content of metal ions after dissolution was measured by LC-ICPMS.
The results of the BSPP selective lysis Non-MS-NP condition optimization experiment are shown in FIG. 3. Wherein A is the influence of BSPP on the dissolution of Non-MS-NPs, and B is the influence of BSPP shaking time on the dissolution of Non-MS-NPs. As shown in graph A, the dissolution rate of Non-MS-NP increased with the increase of the concentration of BSPP, and the equilibrium was reached at a BSPP concentration of 5 mM; as can be seen from the graph B, the dissolution rate of Non-MS-NP did not change significantly with shaking time within 15-120min, so the shaking time after adding BSPP solution was selected to be 15 min.
Selective investigation of BSPP dissolved Non-MS-NPs. 0.15% (M/v) TX-114, 20mM NaNO were added to the Ag-containing M-NPs and Zn-containing M-NPs solutions3With dilute HNO3Or NaOH to adjust pH to 5. Subsequently, the solution was heated in a water bath at 45 ℃ for 15min, centrifuged at 3000rpm for 5min in a centrifuge after being taken out, the supernatant was removed by a pipette, and 0.1mL of 5mM BSPP solution was added to the concentrated phase of TX-114 and shaken at 300rpm for 15min, respectively, and compared with the chromatograms of untreated Ag-containing M-NPs and Zn-containing M-NPs in aqueous solution.
The comparison results are shown in fig. 4. Wherein A is M-NPs and Ag containing Ag when no BSPP solution is added+LC-ICPMS diagram of aqueous solution; b is Ag-containing M-NPs and Ag when adding BSPP solution+LC-ICPMS diagram of aqueous solution; c is Zn-containing M-NPs and Zn without adding BSPP solution2+LC-ICPMS diagram of aqueous solution; d is the M-NPs of Zn and Zn when BSPP solution is added2+LC-ICPMS diagram of aqueous solution. Comparison of A and B shows that Ag is present after addition of BSPP+And Ag2The spectrogram of S-NPs is unchanged, the M-NPs peak area of AgNPs disappears, and Ag+The peak area increases. And AgNPs and Ag2After the mixture of S-NPs is added with BSPP, the peak area of M-NPs is reduced, and Ag+The peak increases, and the peak pattern and retention time of M-NPs with Ag2The S-NPs are consistent. Comparison of C and D shows that Zn is added after BSPP is added2+And the spectrum of ZnS-NPs, Zn of ZnO-NPs2+The peak area increases. Meanwhile, the mixture of ZnO-NPs and ZnS-NPs after adding BSPP, Zn2+The peak also increased and substantially coincided with the peak pattern and peak area of the ZnO-NPs. The above results demonstrate the selective dissolution of BSPP in Non-MS-NPs.
Example 1
Separation and determination of metal sulfide nanoparticles in environmental water sample
Three environmental waters were collected, including river water, lake water and wastewater from sewage treatment plants. Analysis three environmental waters were weakly alkaline, with a pH in the range of 7.59 to 8.74, and contained a comparable concentration of cations (4.75-108mg/L Na) as determined using a pH meter+，Mg2+，K+And Ca2+) And natural organic matter (NOM, 1.06-2.19mg C/L). The content of Ag-containing M-NPs and Zn-containing M-NP was found to be in the range of 0-15.1ng/L and 61.3-94.2ng/L, respectively, by the LC-ICPMS method (Zhou, X.X.; Liu, J.F.; Jiang, G.B.Electron Mass Size Distribution for Characterization, Quantification and Identification of Trace nanoparticies in Serum and environmental waters. environ. Sci.Technol.2017,51, 3892-3901). For lake water and wastewater from sewage treatment plants, the Ag-containing M-NPs detected by the LC-ICPMS method (Zhou, X.X.; Liu, J.F.; Jiang, G.B.Electron Mass Sizedistribution for Characterization, Quantification and Identification of trade nanoparticies in Serum and Environmental Waters.environmental Sci.Technol.2017,51,3892-3901) were Ag2S-NP, while the Zn-containing M-NPs in the sample are ZnS-NPs and other ZnNP-containing mixtures.
In order to further evaluate the applicability of the method provided by the invention, 81.2ng/L Ag is added into each water sample at the same time2S-NPs, 119ng/L AgNPs, 217ng/L ZnS-NPs and 385ng/L ZnO-NPs, and the method for measuring the M-NPs concentration comprises the following steps:
(1) cloud point extraction: adding a sample solution into a centrifuge tube, and then sequentially adding a TX-114 solution and NaNO3Adjusting the pH value of the solution and an EDTA solution, heating the solution in a water bath at 45 ℃ for 15min, centrifuging, removing a supernatant, and collecting a TX-114 phase;
cloud point extraction conditions: TX-114 concentration 0.15% (m/v), NaNO3The concentration is 20mM, the EDTA concentration is 5mM, and the pH value is 5;
(2) BSPP selectively dissolves Non-MS-NPs: adding an aqueous solution of bis (p-sulfophenyl) phenylphosphine dipotassium dehydrate (BSPP) to the TX-114 phase obtained in the step (1), and shaking at 300rpm for 15 minutes at room temperature; wherein the concentration of BSPP in the mixed solution is 5 mM;
(3) the concentrations of total M-NPs and Non-MS-NPs were determined separately using LC-ICPMS (Zhou, X.X.; Liu, J.F.; Jiang, G.B.Electron Mass Size Distribution for Characterization, Quantification and Identification of Trace nanoparticies in Serum and environmental Water. environmental. Sci. technique.2017, 51,3892-3901), and the concentration of MS-NPs was obtained by subtracting the content of Non-MS-NPs from the total M-NPs content.
The method of the invention is used for measuring the concentration ratio obtained by the method, and the recovery rate of the sample is calculated according to the actual standard concentration to obtain Ag2The recovery rates of S-NPs and ZnS-NPs were in the range of 81.3-96.6%, demonstrating the applicability of the developed method to environmental samples. The results prove that the method can realize the efficient separation and determination of MS-NPs in the water environment.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An analytical method for measuring metal sulfide nanoparticles in water, comprising the steps of: (1) processing the sample solution by adopting a cloud point extraction method, and collecting a TX-114 phase enriched with metal nanoparticles; (2) adding a bis (p-sulfophenyl) phenylphosphine dehydrated dipotassium solution into the TX-114 phase to selectively dissolve nonmetal sulfide nanoparticles; (3) the content of the metal nanoparticles and the content of the non-metal sulfide nanoparticles are detected by combining a liquid chromatography method and an inductively coupled plasma mass spectrometry method, so that the metal sulfide nanoparticles are quickly and accurately separated and determined in a water environment.
2. The analytical method for the determination of metal sulfide nanoparticles in water as set forth in claim 1, comprising the steps of:
(1) cloud point extraction: adding a metal-containing material to a centrifuge tubeAdding TX-114 solution and NaNO in sequence into sample solution of NaNO particles3Adjusting the pH value of the solution and an EDTA solution, heating the solution in a water bath at 45 ℃ for 15min, centrifuging, removing a supernatant, and collecting a TX-114 phase;
cloud point extraction conditions: TX-114 concentration is 0.01% -0.3% (m/v), NaNO3The concentration is 2-30mM, the EDTA concentration is 5mM, and the pH is 3-9;
(2) the aqueous solution of bis (p-sulfophenyl) phenylphosphine dehydrate dipotassium salt selectively dissolves the nonmetallic sulfide nanoparticles: adding a bis (p-sulfophenyl) phenylphosphine dehydrated dipotassium solution into the TX-114 phase obtained in the step (1), and shaking at 300rpm for 15-120 minutes at room temperature; wherein the concentration of the aqueous solution of bis (p-sulfophenyl) phenylphosphine dipotassium dehydrate in the mixed solution is 0.5-10 mM;
(3) the concentrations of the total metal nanoparticles and the non-metal sulfide nanoparticles are respectively determined by adopting a liquid chromatography method and an inductively coupled plasma mass spectrometry method, and the concentration of the metal sulfide nanoparticles is obtained by subtracting the content of the non-metal sulfide nanoparticles from the content of the total metal nanoparticles.
3. The analytical method for the determination of metal sulfide nanoparticles in water as set forth in claim 2, wherein the concentration of TX-114 in step (1) is 0.15% (m/v).
4. The analytical method for the determination of metal sulfide nanoparticles in water as set forth in claim 2, wherein in the step (1), NaNO is added3Is 20 mM.
5. The analytical method for the determination of metal sulfide nanoparticles in water as claimed in claim 2, wherein the metal nanoparticles of step (1) comprise zero-valent metal nanomaterial of nano-Ag, nano-Au, nano-Pd, nano-Ag2S, nano ZnS metal sulfide nano material, nano ZrO and nano Fe2O3Metal oxide nano material of nano ZnO; metal nano in the sample solution containing metal nano particlesThe concentration of rice grains is 100 mug/L.
6. The method according to claim 2, wherein the pH in step (1) is 5 and HNO is used as the component3Or NaOH to adjust the pH.
7. The analytical method for the determination of metal sulfide nanoparticles in water as set forth in claim 2, wherein the centrifugation in the step (1) is centrifugation at 3000rpm for 5 minutes.
8. The analytical method for the determination of metal sulfide nanoparticles in water according to claim 2, wherein the concentration of bis (p-sulfophenyl) phenylphosphine dipotassium dehydrate in the mixed solution in the step (2) is 5 mM.
9. The analytical method for the determination of metal sulfide nanoparticles in water as set forth in claim 2, wherein the shaking is performed at 300rpm for 15 minutes in the step (2).
10. The analytical method for measuring metal sulfide nanoparticles in water according to any one of claims 1 to 9, comprising the following steps:
(1) 9.5mL of sample solution containing metal nanoparticles was added to the centrifuge tube, followed by 0.15mL of 10% (M/v) TX-114 aqueous solution, and 0.2mL of 1M NaNO3Solution and 0.25mL of 200mM EDTA solution; and with dilute HNO3Or NaOH to adjust its pH to 5; then the solution is fully mixed and heated in a water bath at 45 ℃ for 15 minutes, then the mixture is placed in a centrifuge and centrifuged at 3000rpm for 5 minutes to realize two-phase separation, a pipette is used for removing supernatant, and a lower TX-114 phase is reserved;
(2) add 100. mu.L of 10mM aqueous solution of bis (p-sulfophenyl) phenylphosphine dipotassium dehydrate to 100. mu.L of the lower TX-114 phase, shaking at 300rpm for 15 minutes at room temperature;
(3) the total M-NPs and Non-MS-NPs concentrations were measured by LC-ICPMS, respectively, and the concentration of MS-NPs was obtained by subtracting the Non-MS-NPs content from the total M-NPs content.
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