CN116990379A - Method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry - Google Patents
Method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry Download PDFInfo
- Publication number
- CN116990379A CN116990379A CN202310879826.9A CN202310879826A CN116990379A CN 116990379 A CN116990379 A CN 116990379A CN 202310879826 A CN202310879826 A CN 202310879826A CN 116990379 A CN116990379 A CN 116990379A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- palladium
- soil
- platinum
- helium
- 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000010948 rhodium Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 60
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 55
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 52
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 48
- 239000000428 dust Substances 0.000 title claims abstract description 43
- 239000002689 soil Substances 0.000 title claims abstract description 38
- 238000004885 tandem mass spectrometry Methods 0.000 title claims abstract description 33
- 238000009616 inductively coupled plasma Methods 0.000 title claims abstract description 31
- 230000029087 digestion Effects 0.000 claims abstract description 36
- 239000001307 helium Substances 0.000 claims abstract description 30
- 229910052734 helium Inorganic materials 0.000 claims abstract description 30
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- IHTRHZMXELXCEJ-UHFFFAOYSA-N azane;helium Chemical compound [He].N IHTRHZMXELXCEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 30
- 239000012495 reaction gas Substances 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000000120 microwave digestion Methods 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 11
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004949 mass spectrometry Methods 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 238000000889 atomisation Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000010812 external standard method Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005259 measurement Methods 0.000 abstract description 16
- 238000001819 mass spectrum Methods 0.000 abstract description 5
- 239000000523 sample Substances 0.000 description 25
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000013558 reference substance Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012491 analyte Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000002133 sample digestion Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for rapidly determining platinum, palladium and rhodium in road dust or soil by using an inductively coupled plasma tandem mass spectrometry, which comprises the following steps: step (1), carrying out digestion treatment on road dust or soil to obtain a sample treatment solution; step (2), quantitatively detecting platinum, palladium and rhodium in the sample treatment fluid by utilizing an inductively coupled plasma tandem mass spectrometry; during detection, introducing oxygen, ammonia-helium and high-energy helium into a collision/reaction tank as reaction gases; the ammonia-helium is formed by mixing ammonia and helium according to a volume ratio of 1:9; the high-energy helium gas has the purity of more than 99.999 percent. The method can solve the problems that in the prior art, the ultra-trace PGE is severely interfered by mass spectrum overlapping in the measurement environment.
Description
Technical Field
The invention relates to the technical field of determination of platinum group elements in dust or soil. In particular to a method for rapidly determining platinum, palladium and rhodium in road dust or soil by using an inductively coupled plasma tandem mass spectrometry.
Background
Platinum group elements (PGE, mainly platinum, palladium and rhodium) have good catalytic performance, and are widely used as catalysts for automobile exhaust catalytic conversion devices; while purifying the tail gas, the platinum group element particles are continuously released into the environment along with the tail gas and accumulate in the atmosphere to a certain extent, so that a potential novel environmental pollutant is formed. Recent researches find that PGE and its compounds are a class of sensitizers with high incidence rate, and part of PGE compounds have cancerogenic effect.
Inductively coupled plasma mass spectrometry (ICP-MS) has extremely low detection limit, extremely wide dynamic linear range, and can analyze a plurality of elements simultaneously and accurately provide analysis characteristics such as isotope information, and thus is widely used for noble metal measurement and monitoring. However, ultra-trace PGEs in the environment are subject to severe mass spectrometry overlap interference during the assay, and the existing mass spectrometry interference is still a great difficulty in affecting accurate ICP-MS determination, so that noble metal analysis is very challenging. The potential for collision/reaction cells in conventional ICP-QMS has been reduced in the absence of separate ions for selective reactions when using highly reactive gases. In order to deal with spectral interference, common methods are analyte/matrix separation, and mathematical equations, etc. However, the pre-sample processing of the above method is very complex and spectral interference still exists.
Therefore, the establishment of a rapid and reliable detection method for platinum, palladium and rhodium in road dust/soil has important significance for monitoring the distribution of platinum group elements in urban environments and preventing and controlling urban traffic pollution, and is a real requirement in the practical work of environmental science.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for rapidly determining platinum, palladium and rhodium in road dust or soil by using an inductively coupled plasma tandem mass spectrometry with the advantages of simplicity, convenience, rapidness, high sensitivity, good reproducibility and accurate and reliable result, so as to solve the problems of serious mass spectrum overlapping interference and the like in the determination of ultra-trace PGE in the environment in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for rapidly determining platinum, palladium and rhodium in road dust or soil by using an inductively coupled plasma tandem mass spectrometry method comprises the following steps:
step (1), carrying out digestion treatment on road dust or soil to obtain a sample treatment solution;
step (2), quantitatively detecting platinum, palladium and rhodium in the sample treatment fluid by utilizing an inductively coupled plasma tandem mass spectrometry; during detection, introducing oxygen, ammonia-helium and high-energy helium into a collision/reaction tank as reaction gases; the ammonia-helium is formed by mixing ammonia and helium according to a volume ratio of 1:9; the high energy helium is helium with purity of more than 99.999 percent.
In the method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry, in the step (2), rh is determined by using an oxygen mass transfer method during detection; the high-energy helium mode is adopted to measure palladium, and the ammonia in-situ mass method is adopted to measure rhodium and platinum.
In the method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry, in the step (2), the flow rate of oxygen of a reaction gas is 0.1-0.5 mL/min, the flow rate of ammonia-helium of the reaction gas is 3.0-5.0 mL/min, and the flow rate of high-energy helium of the reaction gas is 7.0-12.0 mL/min.
In the method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry, in the step (2), the flow rate of oxygen of a reaction gas is 0.25mL/min, the flow rate of ammonia-helium of the reaction gas is 3.0mL/min, and the flow rate of high-energy helium of the reaction gas is 10.0mL/min.
In the method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry, in the step (2), mass spectrometry conditions during detection are as follows: radio frequency power: 1550W; plasma gas flow rate: 15L/min; carrier gas flow rate: 1.0L/min; compensating air flow rate: 0.15L/min; sampling depth: 8mm; sample lift rate: 0.33mL/min; atomization chamber temperature: -5 ℃;
mass of Q1-Q2 ions: rhodium: 103 to 119;103 to 120; palladium: 105 to 105; platinum: 195→212.
The method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry comprises the following steps:
step (1-1), putting road dust or soil samples into a digestion system for pre-digestion;
step (1-2), placing the pre-digested sample into a microwave digestion instrument, and setting a digestion program to perform heating digestion;
step (1-3), heating the digested and cooled sample in a heater until the digested sample is evaporated to near dryness, adding concentrated hydrochloric acid, then evaporating to near dryness, and repeating the steps three times to ensure that hydrofluoric acid is completely removed to obtain the digested sample;
and (3) adding ultrapure water into the digested sample for dilution and volume fixing to obtain the sample treatment liquid.
In the method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry, in the step (1-1), a digestion system is a aqua regia-hydrofluoric acid mixed system, the aqua regia-hydrofluoric acid mixed system is formed by mixing a nitric acid solution, a hydrochloric acid solution and a hydrofluoric acid solution according to the volume ratio of 2:6:1, the mass concentration of the nitric acid solution is 65-68wt%, the mass concentration of the hydrochloric acid solution is 36-38wt%, and the mass concentration of the hydrofluoric acid solution is 35-40wt%; or the digestion system is an aqua regia system, the aqua regia system is formed by mixing a nitric acid solution and a hydrochloric acid solution according to the volume ratio of 1:3, the mass concentration of the nitric acid solution is 65-68wt% and the mass concentration of the hydrochloric acid solution is 36-38wt%.
In the method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry, in the step (1-1), the ratio of the volume of a digestion system to the mass of a road dust or soil sample is 20-40 mL/g; the pre-digestion time is 35-50 min;
in the step (1-2), the digestion program of the microwave digestion instrument is as follows: raising the temperature to 120 ℃ for 6 minutes, and keeping for 5 minutes; then raising the temperature from 120 ℃ to 150 ℃ for 5 minutes, and keeping for 5 minutes; finally, raising the temperature from 150 ℃ to 190 ℃ for 6 minutes, and keeping for 40 minutes;
in the step (1-3), the heating temperature of the heater is 120-160 ℃ (the too low temperature can lead to the volatilization time to be too long, the too high temperature can easily lead to the volatilization of the element to be detected), and the mass concentration of the added concentrated hydrochloric acid is 36-38 wt%; the ratio of the adding amount of the concentrated hydrochloric acid to the volume of the digestion system is 2:8-9;
in the step (1-4), the obtained sample treatment solution is preserved at the temperature of 4 ℃ for less than or equal to 6 months.
In the method for rapidly determining the platinum, the palladium and the rhodium in the road dust or the soil by the inductively coupled plasma tandem mass spectrometry, in the step (2), the standard working curves of the palladium, the platinum and the rhodium are respectively determined and drawn by adopting an external standard method during detection, and a regression equation of the palladium, the platinum and the rhodium is obtained.
According to the method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry, a regression equation for determining platinum by using an ammonia gas in-situ mass method is y= 3.0559E-005 x+9.1779E-008, and R=1.0000;
the regression equation for rhodium determination by oxygen mass transfer method is: y=0.0085x+4.8646 e-005, r=1.0000;
the regression equation for measuring rhodium by adopting an ammonia in-situ mass method is as follows: y=0.0023x+3.7032e-005, r=1.0000;
the regression equation for palladium determination using the high energy helium mode was y=0.0016x+0.0000e+000, r=0.9994.
The technical scheme of the invention has the following beneficial technical effects:
the invention adopts a microwave digestion method as a pretreatment method of road dust or soil samples, and utilizes the mass transfer mode and in-situ mass mode of ICP-MS/MS to rapidly determine platinum, palladium and rhodium; compared with the prior art, the method has the following advantages:
1. the method is simple to operate, and can eliminate serious mass spectrum interference without complex analyte/matrix separation after sample digestion, such as 105 Pd is subjected to measurement 88 Sr 16 OH + 、 89 Y 16 O + Interference; 195 Pt + is subjected to 179 Hf 16 O + 、 178 Hf 17 O + 、 177 Hf 18 O + And the like, 103 Rh + then is subjected to 87 Sr 16 O + ， 86 Sr 17 O + And 40 Ar 63 Cu + interference, etc.; the invention is realized by introducing the reaction gas O into an ICP-MS/MS collision/reaction cell (CRC) 2 、NH 3 And collision gas high energy helium (HEHe) for mass spectral interference cancellation, wherein the high helium gas is first reported and O is adopted 2 Mass transfer method for Rh: 103- & gt 119, pd was measured in high helium (HEHe) mode, NH 3 Rh and Pt are measured by an in-situ mass method, so that lower detection limit and background equivalent concentration can be obtained. The detection limits of platinum, palladium and rhodium in road dust or soil are 1.5ng/g, 0.225ng/g and 0.5ng/g respectively, and the background equivalent concentrations are 0.003ng/mL, 0.0069ng/mL and 0.016ng/mL respectively.
2. The magnitude of the flow velocity of the reaction gas directly determines the elimination degree of mass spectrum interference, and influences the generation type and concentration of reaction product ions and the sensitivity of analysis. In the detection mode, the high ion reaction efficiency is achieved by controlling the flow rates of three reaction gases, namely oxygen, ammonia and high-energy helium, so that the energy loss of target ions is reduced. Compared with the traditional ICP-MS, the method has the advantages of remarkably improved sensitivity, simplicity in operation, short analysis flow, reliable analysis result accuracy and capability of meeting the analysis requirement of measuring PGE in a complex environment sample.
Drawings
FIG. 1 shows graphs of Rh operation in the examples of the invention (Rh ion masses: 103.fwdarw.119, O) 2 )；
FIG. 2 shows graphs of Rh operation (Rh ion mass: 103.fwdarw.103, NH) in an embodiment of the invention 3 )；
FIG. 3 is a graph of Pd on an example of the invention (Pd ion mass: 105→105, HEHe);
FIG. 4 is a graph showing the working of Pt in the example of the present invention (Pd ion mass: 195 to 195, NH) 3 )；
Detailed Description
1. Experimental materials
1.1 pharmaceutical products and reagents
Quality control standard substance: BCR-723 (road dust, belgium); standard solutions of palladium, platinum and rhodium, respectively, 1000mg/L (national institutes of metrology, china); internal standard solution: 10 μg/mL of a multi-element standard solution containing scandium, yttrium, rhodium, lutetium, and bismuth (agilent technology, usa); tuning solution: 1ng/mL of lithium, cobalt, yttrium, cerium, thallium mixed standard solution (Agilent technology, USA); ultrapure water (18.2 mΩ, boer, usa), prepared from an ultrapure water system, was used to prepare all standard solutions and sample solutions; nitric acid, hydrochloric acid and hydrofluoric acid are all analytically pure (merck, germany).
1.2 preparation of Standard solution
Preparation of stock solution: the standard stock solutions of platinum, palladium and rhodium were serially diluted to 0, 0.01,0.1000, 0.5000, 2.00ng/mL with 5wt% nitric acid solution to give a series of mixed standard solutions. And under the optimized experimental conditions, the acquired blank and standard solution series are automatically drawn into a standard curve through an instrument. The linear correlation coefficient r of the standard curve of the element to be detected is more than or equal to 0.999.
1.3 instruments and reference conditions
Agilent ICP-MS/MS 8800 (USA); BP210s electronic balance (Sartorius company, germany); PALL pure water purification System (USA); 10-100 mu L, 10-1000 mu L automatic pipette (Eppendorf, germany); the Mars5 microwave digestion instrument was mounted (U.S.).
2. Sample preparation method
In the embodiment, the pretreatment of the road dust sample is carried out by a microwave digestion method, and the specific operation is as follows:
placing 0.25g of road dust sample into a microwave digestion tank, and sequentially adding an aqua regia-hydrofluoric acid system: 2mL of nitric acid, 6mL of hydrochloric acid and 1mL of hydrofluoric acid are placed in a fume hood for pre-digestion for 40min, then placed in a microwave digestion instrument, and heated and digested according to a preset digestion program, wherein the specific digestion program is as follows: the temperature is risen to 120 ℃ for 6 minutes, and the temperature is kept for 5 minutes; the temperature is risen to 150 ℃ for 5 minutes, and the temperature is kept for 5 minutes; the temperature was ramped up to 190℃for 6 minutes and held for 40 minutes. After complete digestion, the digestion tank was placed in a twelve-position heater and evaporated to near dryness at 120 ℃, 2mL of hydrochloric acid was added, and repeated three times. The solution was then transferred to a 20mL PET bottle and the volume was set to 20mL with ultrapure water. The treated samples were stored in a refrigerator at constant temperature of 4 ℃. The supernatant was diluted twice before measurement, leaving it for inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) detection. Performing blank control; when the microwave digestion is carried out, the aqua regia system is adopted to replace the aqua regia-hydrofluoric acid system for pretreatment so as to be convenient for comparison with a pretreatment group of the aqua regia-hydrofluoric acid system, wherein the aqua regia system is 2mL nitric acid and 6mL hydrochloric acid. In this example, nitric acid is a 68wt% nitric acid solution, hydrochloric acid is a 37wt% hydrochloric acid solution, and hydrofluoric acid is a 36wt% hydrofluoric acid solution.
3. ICP-MS/MS detection conditions
Radio frequency power: 1550W; plasma gas flow rate: 15L/min; carrier gas flow rate: 1.0L/min; compensating air flow rate: 0.15L/min; sampling depth: 8mm; sample lift rate: 0.33mL/min;
reaction gas O 2 Flow rate: 0.25mL/min; reactant gas NH 3 (i.e. NH 3 He 1:9, V/V) flow rate: 3.0mL/min; high helium (high energy helium, helium with purity greater than 99.999%, HEHe) gas flow rate: 10.0mL/min;
atomization chamber temperature: -5 ℃; mass of Q1-Q2 ions: rh:103 to 119;103 to 120; pd:105 to 105; pt:195→212.
4. Determination of ICP-MS/MS assay methods
4.1 microwave digestion-inductively coupled plasma tandem mass spectrometry inspection method
Processing the road dust sample according to the preparation method of the sample 2 and performing instrument detection according to the detection conditions of the ICP-MS/MS; and analyzing the accuracy, the precision and the like of the sample.
4.1.1 Standard working curves
And sucking a certain amount of sample by a sample injection needle of the automatic sampler, collecting each sample three times, and linearly regressing the standard concentration (X) by using the ratio (Y) of the response signal of the element to the response signal of the internal standard element. The working curves are shown in fig. 1 to 4, and can be seen from fig. 1 to 4:
the regression equation of platinum measured by ammonia in situ mass method is y= 3.0559 ej005 x+9.1779e-008, r=1.0000;
the regression equation for rhodium determination by oxygen mass transfer method is: y=0.0085x+4.8646 e-005, r=1.0000;
the regression equation for measuring rhodium by adopting an ammonia in-situ mass method is as follows: y=0.0023x+3.7032e-005, r=1.0000;
the regression equation for palladium determination using the high energy helium mode was y=0.0016x+0.0000e+000, r=0.9994.
The above linear regression equation shows that three elements of platinum, rhodium and palladium have good linear relationship in the concentration range of 0.01-0.2 mug/mL.
4.1.2 testing of precision and accuracy
Six parts by mass of BCR-723 were weighed in parallel for precision testing, and the standard reference substance was repeatedly assayed six times by the method of this example. The results in table 1 show that the measurement results of 3 elements in the standard sample substantially agree with the standard values provided by the reference substance. Besides the larger change coefficient of platinum, the RSD of rhodium and platinum is less than or equal to 7.8%, which proves that the method of the embodiment has good precision and accuracy.
Table 1 test results of BCR-723 (N=6, unit μg kg -1 )
4.1.3 sensitivity of the method
Processing a road dust sample according to the preparation method of the sample 2, analyzing and detecting according to the detection conditions of the ICP-MS/MS, and calculating detection limits according to the concentration corresponding to the standard deviation of 11 signals detected by a blank solution, wherein the detection limits of platinum, palladium and rhodium in the method are respectively 1.5ng/g, 0.225ng/g and 0.5ng/g; the background equivalent concentrations were 0.003ng/mL, 0.0069ng/mL and 0.016ng/mL, respectively.
5. Results and analysis
5.1 selection of microwave digestion System
The most critical step in sample digestion is the choice of the digestion solvent system, which directly affects the digestion effect. In this example, the digestion effects of the aqua regia system and the aqua regia-hydrofluoric acid system are compared, and the results are shown in table 2, and the data in table 2 show that the digestion effect of the aqua regia-hydrofluoric acid system is better, so that the aqua regia plus hydrofluoric acid system is selected as the digestion solvent in this example.
TABLE 2 measurement results of BCR-723 under two digestion systems (μg kg) -1 )
5.2 selection of analysis conditions
5.2.1 selection of mass spectrometry modes:
this example uses the No Gas mode for the determination of BCR-723 samples, comprising O 2 Mode, he mode, HEHe mode and NH 3 And (5) measuring a mode. As can be seen from Table 3, in the MS/MS mode, O is used 2 The mass transfer method can effectively eliminate the ArCu by measuring the Rh 103-119 + Interference; as can be seen from Table 4, the use of the high helium (HEHe) mode for Pd determination effectively eliminates ArCu + Interference, from Table 5, it can be seen that NH 3 The in-situ mass method can effectively eliminate interference by measuring Rh and Pt.
Table 3 comparison of the results of Rh measurements in the different measurement modes (unit: μg kg) -1 )
Table 4 comparison of measurement results of Pd in different measurement modes (unit: μg kg) -1 )
TABLE 5 comparison of the measurement results of Pt in different measurement modes (unit: μg kg) -1 )
5.2.2 selection of reaction gas flow rate
In ORS3, the flow rate of the reaction gas affects the concentration and type of the reaction product ions, and directly determines the degree of elimination of mass spectrum interference. In order to determine the most suitable reaction gas flow rate in the MS/MS mode, the measurement results of each element of the international standard reference substance BCR-723 at different reaction gas flow rates were measured, and the results are shown in tables 6 to 8.
The experimental results show that: when the ammonia flow is 3mL/min, the high helium flow is 10mL/min and the oxygen flow is 0.25mL/min, the interference elimination effect is more obvious, and the measured data can be more accurate. Therefore, the flow rate of the ammonia gas is finally determined to be 3mL/min, the flow rate of the high helium gas is finally determined to be 10mL/min, and the flow rate of the oxygen gas is finally determined to be 0.25mL/min as the optimal reaction gas flow rate.
TABLE 6Rh in O 2 Comparison of measurement results at different flow rates
Table 7 comparison of measurement results of Pd at different flow rates of he
TABLE 8Rh in NH 3 Comparison of measurement results at different flow rates
In conclusion, the embodiment establishes a pretreatment method for digestion of palladium, platinum and rhodium in road dust/soil by an aqua regia and hydrofluoric acid system and an inductively coupled plasma tandem mass spectrometry method; the method is simple, convenient and quick, high in sensitivity, good in reproducibility and accurate and reliable in result, and can provide a technical means for further researching the distribution characteristics of platinum group elements in road dust/soil and preventing and controlling traffic pollution.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While the obvious variations or modifications which are extended therefrom remain within the scope of the claims of this patent application.
Claims (10)
1. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by using the inductively coupled plasma tandem mass spectrometry is characterized by comprising the following steps of:
step (1), carrying out digestion treatment on road dust or soil to obtain a sample treatment solution;
step (2), quantitatively detecting platinum, palladium and rhodium in the sample treatment fluid by utilizing an inductively coupled plasma tandem mass spectrometry; during detection, introducing oxygen, ammonia-helium and high-energy helium into a collision/reaction tank as reaction gases; the ammonia-helium is formed by mixing ammonia and helium according to a volume ratio of 1:9; the high energy helium is helium with purity of more than 99.999 percent.
2. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to claim 1, wherein in the step (2), rh is determined by an oxygen mass transfer method; the high-energy helium mode is adopted to measure palladium, and the ammonia in-situ mass method is adopted to measure rhodium and platinum.
3. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to claim 2, wherein in the step (2), the flow rate of the reaction gas oxygen is 0.1-0.5 mL/min, the flow rate of the reaction gas ammonia-helium is 3.0-5.0 mL/min, and the flow rate of the reaction gas high-energy helium is 7.0-12.0 mL/min.
4. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to claim 3, wherein in the step (2), the flow rate of the reaction gas oxygen is 0.25mL/min, the flow rate of the reaction gas ammonia-helium is 3.0mL/min, and the flow rate of the reaction gas high-energy helium is 10.0mL/min.
5. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to any one of claims 1 to 4, wherein in the step (2), mass spectrometry conditions at the time of detection are: radio frequency power: 1550W; plasma gas flow rate: 15L/min; carrier gas flow rate: 1.0L/min; compensating air flow rate: 0.15L/min; sampling depth: 8mm; sample lift rate: 0.33mL/min; atomization chamber temperature: -5 ℃;
mass of Q1-Q2 ions: rhodium: 103 to 119;103 to 120; palladium: 105 to 105; platinum: 195→212.
6. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to claim 1, wherein in the step (1), the digestion treatment method is a microwave digestion method, comprising the steps of:
step (1-1), putting road dust or soil samples into a digestion system for pre-digestion;
step (1-2), placing the pre-digested sample into a microwave digestion instrument, and setting a digestion program to perform heating digestion;
step (1-3), heating the digested and cooled sample in a heater until the digested sample is evaporated to near dryness, adding concentrated hydrochloric acid, then evaporating to near dryness, and repeating the steps three times to ensure that hydrofluoric acid is completely removed to obtain the digested sample;
and (3) adding ultrapure water into the digested sample for dilution and volume fixing to obtain the sample treatment liquid.
7. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to claim 6, wherein in the step (1-1), the digestion system is a aqua regia-hydrofluoric acid mixed system, the aqua regia-hydrofluoric acid mixed system is formed by mixing a nitric acid solution, a hydrochloric acid solution and a hydrofluoric acid solution according to a volume ratio of 2:6:1, the mass concentration of the nitric acid solution is 65-68 wt%, the mass concentration of the hydrochloric acid solution is 36-38 wt%, and the mass concentration of the hydrofluoric acid solution is 35-40 wt%;
or the digestion system is an aqua regia system, the aqua regia system is formed by mixing a nitric acid solution and a hydrochloric acid solution according to the volume ratio of 1:3, the mass concentration of the nitric acid solution is 65-68wt% and the mass concentration of the hydrochloric acid solution is 36-38wt%.
8. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to claim 6, wherein in the step (1-1), the ratio of the volume of the digestion system to the mass of the road dust or soil sample is 20-40 mL/g; the pre-digestion time is 35-50 min;
in the step (1-2), the digestion program of the microwave digestion instrument is as follows: raising the temperature to 120 ℃ for 6 minutes, and keeping for 5 minutes; then raising the temperature from 120 ℃ to 150 ℃ for 5 minutes, and keeping for 5 minutes; finally, raising the temperature from 150 ℃ to 190 ℃ for 6 minutes, and keeping for 40 minutes;
in the step (1-3), the heating temperature of a heater is 120-160 ℃, and the mass concentration of the added concentrated hydrochloric acid is 36-38 wt%; the ratio of the adding amount of the concentrated hydrochloric acid to the volume of the digestion system is 2:8-9;
in the step (1-4), the obtained sample treatment solution is preserved at the temperature of 4 ℃ for less than or equal to 6 months.
9. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to claim 1, wherein in the step (2), an external standard method is adopted to determine and draw standard working curves of palladium, platinum and rhodium respectively during detection, so as to obtain a regression equation of palladium, platinum and rhodium.
10. The method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry according to claim 9, wherein the regression equation for determining platinum by ammonia gas in situ mass method is y= 3.0559E-005 x+9.1779e-008, r=1.0000;
the regression equation for rhodium determination by oxygen mass transfer method is: y=0.0085x+4.8646 e-005, r=1.0000;
the regression equation for measuring rhodium by adopting an ammonia in-situ mass method is as follows: y=0.0023x+3.7032e-005, r=1.0000;
the regression equation for palladium determination using the high energy helium mode was y=0.0016x+0.0000e+000, r=0.9994.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310879826.9A CN116990379A (en) | 2023-07-18 | 2023-07-18 | Method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310879826.9A CN116990379A (en) | 2023-07-18 | 2023-07-18 | Method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116990379A true CN116990379A (en) | 2023-11-03 |
Family
ID=88522444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310879826.9A Pending CN116990379A (en) | 2023-07-18 | 2023-07-18 | Method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116990379A (en) |
-
2023
- 2023-07-18 CN CN202310879826.9A patent/CN116990379A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Da Silva et al. | Application of silica gel organofunctionalized with 3 (1-imidazolyl) propyl in an on-line preconcentration system for the determination of copper by FAAS | |
| CN100498309C (en) | Method for analyzing metal content in catalytic cracking catalyst through X ray fluorescence method | |
| CN113984726B (en) | Method for detecting mercury ions by amino phenylboronic acid functionalized magnetic beads/glyoxal modified DNA | |
| Li | Studies on the determination of trace amounts of gold by chemical vapour generation non-dispersive atomic fluorescence spectrometry | |
| CN107703222B (en) | Method for determining trace organic amine in atmospheric particulates | |
| CN116990379A (en) | Method for rapidly determining platinum, palladium and rhodium in road dust or soil by inductively coupled plasma tandem mass spectrometry | |
| CN101324520B (en) | Method for rapidly detecting micro trace quantity lead in ship hull steel with graphite oven atomic absorption | |
| Feng et al. | Flow-injection spectrophotometric determination of mercury (II) in water by the catalytic decomposition of ferrocyanide | |
| CN111521668A (en) | Detection method for rapidly determining calcium content in wine product | |
| CN114609234B (en) | Method for detecting content of metal element in polyether amine solid catalyst | |
| Chang et al. | Determination of Hg and Bi by electrothermal vaporization inductively coupled plasma mass spectrometry using vapor generation with in situ preconcentration in a platinum-coated graphite furnace | |
| Tanner et al. | New instrumentation for airborne acid rain research | |
| CN113866256B (en) | Inductively coupled plasma mass spectrum detection product for 10 elements in peripheral blood and application | |
| Li et al. | Trace and ultratrace analysis of purified water samples and hydrogen peroxide solutions for phosphorus by flow-injection method | |
| CN112147209A (en) | Method for measuring arsenic in geochemical sample by ICP-MS | |
| Okamoto et al. | Determination of cadmium by inductively coupled plasma atomic emission spectrometry after suction-flow on-line preconcentration on 8-quinolinol-loaded active carbon | |
| CN112630348A (en) | Detection method for detecting selenate selenite in water by using HPLC-ICP-MS | |
| CN108982706B (en) | Method for detecting impurity cis-perhydroisoindole in mitiglinide calcium | |
| CN113391016A (en) | Analysis method of selenium form in corn | |
| CN114166920A (en) | Method and system for measuring concentration of gaseous nitrous acid in ambient atmosphere | |
| Marshall et al. | Mercury displacement detection for the determination of picogram amounts of sulfite ion or sulfur dioxide by atomic spectrometry | |
| Preetha et al. | On-line solid phase extraction preconcentration of ultratrace amounts of zinc in fractionated soil samples for determination by flow injection flame AAS | |
| CN114354579B (en) | Method for simultaneously detecting silver and palladium elements in silver and palladium mixture | |
| CN118534016A (en) | Method for rapidly and quantitatively detecting NO content in plant body | |
| CN118443865A (en) | Quantitative analysis and detection method for chlorine in different forms in solid recovery fuel |
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 |