AU2020444034B2 - Nanoliter spray-FTICR-MS analysis method and device for organic matter dissolved in environmental solid sample - Google Patents
Nanoliter spray-FTICR-MS analysis method and device for organic matter dissolved in environmental solid sample Download PDFInfo
- Publication number
- AU2020444034B2 AU2020444034B2 AU2020444034A AU2020444034A AU2020444034B2 AU 2020444034 B2 AU2020444034 B2 AU 2020444034B2 AU 2020444034 A AU2020444034 A AU 2020444034A AU 2020444034 A AU2020444034 A AU 2020444034A AU 2020444034 B2 AU2020444034 B2 AU 2020444034B2
- Authority
- AU
- Australia
- Prior art keywords
- spray
- fticr
- nano
- dissolved organic
- organic matter
- 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.)
- Active
Links
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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
i N j 9(- WJP? I IN -Ef |EP $ l
(19)
P d PIT, R. ~(10) M a KTii V Y
(43) d VTWO 2021/212920 A1
2021 4 10 ) 28 (28.10.2021) W IPO T PWC0T
(51) tpI]$tJ - : 510070 (CN)o IS M (GUO, Pengran);
G01N 2 7/62 (202 1. 01) 3T N F_ )+ r A9 A X § § 100 - 34 9
(21)j3 PCT/CN2020/141981 Guangdong510070 (CN) o hS'1(XUN,He); +[
F 3T Z F +1 A AE + 100 9 34
(22) p $i H: 2020 * 12 f] 31 H (31.12.2020) t, Guangdong 510070 (CN) o 9 fi (LIANG,
(25) $jig : Weixin); + l - T N r [ + M M
(26) Q, tgg#: 100349k, Guangdong 510070 (CN)o
(74) jtig A : f- 1)tl f§4 fi M1]-6 $, it TT2 PR 5 (30)Vrit. ( 7 4 ) {A5t kp]
202011442452.7 2020 4 12A9 8 H (08.12.2020) CN (GUANGZIIOUKEVUEI.P.LAWOFFICE); [
(71)$iMA: f- 4 p ij id t $6162, Guangdong 510070 (CN)o
*V Uf 5 PFT (t * F 1#l 9 *V _10 (81)) ]
li * L) (INSTITUTE OF ANALYSIS, GUANG- ) A E, A
DONG ACADEMY OF SCIENCES (CHINA NATIO- fB,) AE, AG, , A, A, A , H, , , O, CBG,
NAL ANALYTICAL CENTER, GUANGZHOU)) [CN/ BH,BN,BR,BW,BY,BZCA,CH,CL,CN,CO,CR,CU,
CN]; l NA YT CA 100NTRGA NGZIIO CZ, DE, DJ, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB,
CN ,Guangdong 510070 (CN) oGD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IR, IS, IT,
JO, JP, KE, KG, KH, KN, KP, KR, KW, KZ, LA, LC, LK,
(72) &fRkA-| Z(GAN, Shuchai); + P W f 3 LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX,
[ %iI A A X iL F+ 100 34 , Guangdong MY, MZ, NA, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL,
(54) Title: NANOLITER SPRAY-FTICR-MS ANALYSIS METHOD AND DEVICE FOR ORGANIC MATTER DISSOLVED IN
ENVIRONMENTAL SOLID SAMPLE
(54)& : *$ # W$tL [JD-FTICR-MS$tfrt
30
(57) Abstract: A nanoliter spray-FTICR-MS analysis method and device for organic matter dissolved in an environmental solid sample.
The device comprises a nanoliter spray device and a Fourier transform ion cyclotron resonance mass spectrometer, wherein the nanoliter
spray device comprises a glass spray head (1), a conductive needle (2), a switching rubber head (4), a duplex pressurizing ball (5), and
a gas storage bag (6). The sample solution loaded by the glass spray head (1) is a mixed solution composed of interstitial water and
an organic solvent, and a nozzle is aligned with a sample inlet of the Fourier transform ion cyclotron resonance mass spectrometer.
The nanoliter spray device is used in combination with the Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS),
which does not purify and enrich samples by means of solid phase extraction, but instead improves the ionization efficiency and reduces
ion selective inhibition by means of changing the matrix formula and the nanoliter spray. Direct analysis of interstitial water in an
C environmental solid sample can be realized, and the key problems that, in the prior art, bioactive molecule signals need to be lost by
means of a solid-phase extraction pretreatment, and common electrospray source selective signal inhibition is needed are solved.
W O 2021/212920 A11111||||l||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
PT, QA, RO, RS, RU, RW, SA, SC, SD, SE, SG, SK, SL,
ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US,
UZ, VC, VN, WS, ZA, ZM, ZWc
(84) 31 (|i M hr]A, V V-$ jt Jtutflttk
MP): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ,
NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), kil (AM,
AZ, BY, KG, KZ, RU, TJ, TM), [III (AL, AT, BE, BG,
CH, CY, CZ, DE, DK, EE, ES, Fl, FR, GB, GR, HR, HU,
IE, IS, IT, LT, LU, LV, MC, MK, MT, NL, NO, PL, PT,
RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI,
CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG).
4RAtQ 1J4. 1701FlR :
4.17(iii))
-~~~ ~~ Af3a E (#%1 *-(3))
MBA)R2%fr%(294 8. 2 (h))
- *RtM$iAl2i1%1, (2) (a)it ()()
(57)1I%: -$d4 t54tt#MtTW t G9Fi#F-FTCR-MS 3#?ltfrtR+, t5+qDRMM4
Mil2%%~n22R di; fD$$2 f6)l@MA(1) 4*2t (2) , $%$%(4) ,A
lUHJQLf$ (5) R'CAI*Y-R (6) ,JAAPMq (1 nGt M MJf]'7f $R j~ ti
j, L4T{4Ft1[ tM'fl t#(12) M )T PI AML t
TL ilU'(FTICR-MS))TJIT, T M4Hll{[4M C IR!%f t#e, iRlwMl 1t o 9EffIa atm,%
{h4k~t~li~In _' AtHtt +~18 fl 3tfr, IkATAI - Mil
Description
[0001] The present invention relates to the technical field of dissolved organic matter (DOM) analysis, and specifically, to an analysis method and an analysis apparatus shared by a nano spray and a Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS).
[0002] Soil and sediment are the largest carbon pools in the terrestrial system of the earth. Most of carbon exists in minerals in a coating manner or exists in the form of a solid phase after long term mineralization and stabilization. The solid phase (soil and sediment) contains a small amount of interstitial water. Dissolved organic matter in the interstitial water has hyper reactivity, plays a key role in the formation of an aggregate of soil and sediment, carbon storage, and global carbon cycling, and is also a source of nitrogen and phosphorus in microbial energy and plant nutrient elements. In addition, because the dissolved organic matter has high mobility and species diversity, existing researches prove that it also plays a key role in transmission of metal ions and organic pollutants. Due to rapid response to the environment and a source of organic matter, the dissolved organic matter in soil and sediment can also indicate changes in land use and vegetation types. Therefore, research of dissolved organic matters in geochemistry, environmental science, and other fields is an emerging and important parameter. However, types of dissolved organic matter are very complex. Existing reports show that less than 5% of types of dissolved organic matter are known at the molecular level (Jeffrey A. Hawkes, Pamela E. Rossel, Aron Stubbins, David Butterfield, Douglas P. Connelly, Eric P. Achterberg, and others, Efficient Removal of Recalcitrant Deep-Ocean Dissolved Organic Matter during Hydrothermal Circulation, Nature Geoscience, 8 (2015), 856-60).
[0003] At present, soil dissolved organic matter may be tested via a Fourier transform ion cyclotron resonance mass spectrometer, which is one of existing mass spectrometers having the highest resolution. A sample needs to be solid phase extraction pretreated with purification and enrichment. However, the test method has the following technical problems:
[0004] (1) At present, a general pretreatment method is extracting organic matter via a PPL column (Thorsten Dittmar, Boris Koch, Norbert Hertkorn, and Gerhard Kattner, A Simple and Efficient Method for the Solid-Phase Extraction of Dissolved Organic Matter (SPE-DOM) from
Seawater, Limnology and Oceanography, 6 (2008), 230-35). Because the quantity of types of dissolved organic matter may be as many as 100,000, such as peptides, carbohydrates, and amorphous polymer humic acids whose structures cannot be confirmed, a column extraction pretreatment method leads to selective loss of characteristic organic signals (Raeke Julia, Lechtenfeld Oliver J, Wagner Martin, et al. Selectivity of solid-phase extraction of freshwater dissolved organic matter and its effect on ultrahigh resolution mass spectra. Environmental Science Processes & Impacts, 2016, 18(7):918-27.). Particularly, for biological sources, bioavailable molecules, black carbon, lipids, polyphenols, and the like, these lost signals are very important for understanding the biogeochemical process of dissolved organic matter, and represent constituents that may be used by soil organisms or converted into nutrient elements and may affect retention and migration of pollutants in soil. The extraction loss is about 10% to 90%, which depends on sources of samples (Yan Li, Mourad Harir, Jenny Uhl, Basem Kanawati, Marianna Lucio, Kirill S. Smirnov, et al., How Representative Are Dissolved Organic Matter (DOM) Extracts? A Comprehensive Study of Sorbent Selectivity for DOM Isolation, Water Research, 116 (2017), 316-23). Because the extraction loss may be up to 90%, the quantitative significance of the method is also reduced. Differences between different samples are reduced due to the same extraction selectivity.
[0005] (2) After pretreatment is completed, the current internationally universal mass spectrometry detection method sequentially includes ionization via a common electro-spray source and detection via a Fourier transform ion cyclotron resonance mass spectrometer. However, because the electro-spray source has a problem of obvious selective suppression, during implementation of this method, a high-polarity compound with relatively low surface activity, especially matter containing amino acids or carbohydrates and having relatively high polarity, may be suppressed by matter with high surface activity in an ionization process. As a result, its ionization efficiency is obviously lower than that of the matter with high surface activity.
[0006] (3) In addition, a water sample required for analysis of natural dissolved organic matter via solid-phase extraction is generally more than 20 milliliters, which makes soil sampling very difficult. Therefore, in a traditional method, dissolved organic matter is acquired by adding ultra pure water or inorganic salt-containing water for elution. However, the dissolved organic matter acquired using this method cannot represent actual dissolved organic matter in soil, but can represent only matter that may be potentially eluted. Moreover, the dissolved organic matter actually acquired via elution is related to an elution method, an amount of added water, and inorganic salts, which makes results of the same sample uncertain.
[0007] In summary, currently existing methods and technologies have technical problems that need to be solved urgently in the following three aspects: pretreatment signal loss, ionization suppression in a detection process, and limitation on a sample collection amount.
[0008] To overcome deficiencies in the prior art, the objectives of the present invention are to provide a method and an apparatus for analyzing and detecting a trace of interstitial water in an environmental solid sample without solid-phase extraction.
[0009] According to a first aspect, the present invention provides a nano-spray-FTICR-MS analysis apparatus for dissolved organic matters in environmental solid samples. The analysis apparatus includes a nano-spray apparatus and an FTICR-MS;
[0010] the nano-spray apparatus includes a glass sprayer, a conductive needle, a rubber adapter, a duplex-type pressurization ball, and a gas storage bag; the rubber adapter has a hollow lumen structure; one end of the rubber adapter is sleeved on the end, distal from a nozzle, of the glass sprayer, the other end of the rubber adapter is connected to one end of the gas storage bag via a pipeline, the other end of the gas storage bag is connected to one end of the duplex-type pressurization ball via a one-way valve I, the other end of the duplex-type pressurization ball is connected to outside air via a one-way valve II, when the duplex-type pressurization ball is compressed, the one-way valve I is opened, and the one-way valve II is closed, and when the duplex-type pressurization ball is released, the one-way valve I is closed, and the one-way valve II is opened;
[0011] the conductive needle is disposed on the axis of the glass sprayer, one end of the conductive needle is proximal to the nozzle of the glass sprayer, the other end of the conductive needle extends into the rubber adapter and is connected to the end, penetrating a side wall of the rubber adapter, of a metal conductive clip, and the other end of the metal conductive clip is grounded; and
[0012] a sample solution loaded in the glass sprayer is a mixed solution of interstitial water and organic solvents; and the nozzle is aligned with an injection port of the Fourier transform ion cyclotron resonance mass spectrometer.
[0013] Preferably, the conductive needle is a gilded steel needle or a silver needle.
[0014] Preferably, the sample solution is directly injected from the rubber adapter into the glass sprayer via a micro-syringe.
[0015] Preferably, the proportion of the interstitial water to the organic solvents ranges from 1:1 to 1:100.
[0016] Preferably, the organic solvents include alcohol, and the proportion of the alcohol to the other organic solvent ranges from 1:0 to 1:10.
[0017] Preferably, the gas storage bag is provided with a pressure gauge.
[0018] According to a second aspect, the present invention provides a nano-spray-FTICR-MS analysis method for dissolved organic matters in environmental solid samples. The analysis method uses the above analysis apparatus and includes the following steps:
[0019] (1) loading a prepared sample solution into the glass sprayer, where the sample solution is a mixed solution of interstitial water, methanol, and isopropanol;
[0020] (2) aligning the glass sprayer with the injection port of the Fourier transform ion cyclotron resonance mass spectrometer via adjustment, applying a voltage on an ion source of the Fourier transform ion cyclotron resonance mass spectrometer for sucking air into the glass sprayer via the duplex-type pressurization ball to start pressurization until spraying is achieved via Coulomb explosion; and
[0021] (3) starting scanning and accumulating spectrograms by the Fourier transform ion cyclotron resonance mass spectrometer to acquire quasi-molecular ion peaks of dissolved organic matter, and performing spectrum unfolding to acquire a molecular formula.
[0022] Further, molecular ion peaks of the dissolved organic matter include various organic matter types, such as a lipid region, a protein or polypeptide region, an amino sugar region, a black carbon region, a lignin region, and a tannin/polyphenol region.
[0023] Compared with the prior art, the present invention has the following beneficial effects:
[0024] (1) The formula of a to-be-tested sample is a mixed solution of interstitial water, methanol, and isopropanol, which can greatly improve the ionization efficiency of dissolved organic matter and reduce selective suppression.
[0025] (2) The nano-spray apparatus uses the gilded steel needle having high chemical inertness and electrical conductivity, and is equipped with the pressurization ball, thereby being capable of implementing stable spraying in a case that the voltage of the ion source is relatively low.
[0026] (3) As the nano-spray apparatus is used, tolerance to salt is increased, the present invention is adapted to most soil samples in the freshwater system, so as to implement pretreatment free of solid-phase extraction. Therefore, selective loss of key signals in a pretreatment process is completely avoided.
[0027] (4) Because solid-phase extraction pretreatment is not required, waste of interstitial water is reduced. In addition, the flow rate of a used nano-spray sample is extremely low, so that the collection amount of interstitial water is greatly reduced. The need of adding pure water or salt containing water for elution of dissolved organic matter is avoided, so that the acquired organic matter is real dissolved organic matter that is in full compliance with the scene.
[0028] FIG. 1 is a schematic structural diagram of a nano-spray apparatus according to the present invention;
[0029] FIG. 2 is a schematic diagram of combined application of a nano-spray apparatus and a Fourier transform ion cyclotron resonance mass spectrometer according to the present invention;
[0030] In the drawings, parts represented by reference numerals are as follows: 1-glass sprayer; 2-gilded steel needle; 3-fixation frame; 4-rubber adapter; 5-duplex-type pressurization ball; 6-gas
storage bag; 7- one-way valve I , 8-one-way valve II; 9-spray in Coulomb explosion; 10-metal
conductive clip; 11-pressure gauge; 12-injection port; and 13-sample solution;
[0031] FIG. 3 is a diagram of comparison between different methods for a standard (natural dissolved organic carbon) of the International Humic Substance Society (IHSS), where
[0032] (a) is a Van Krevelen distribution diagram of organic matter acquired via solid-phase extraction and electro-spray ionization according to a traditional method;
[0033] (b) is a Van Krevelen distribution diagram of organic matter acquired according to a nano-spray ionization method of the present invention;
[0034] (c) is a molecular weight distribution diagram of organic matter acquired via solid-phase extraction and electro-spray ionization according to a traditional method;
[0035] (d) is a molecular weight distribution diagram of organic matter acquired according to a nano-spray ionization method of the present invention; and
[0036] (e) is a diagram showing the difference between quantities of detected molecules, where the white region denotes the quantity of molecules detected according to a traditional method, the gray region denotes the quantity of molecules detected according to a nano-spray ionization method of the present invention, and the overlapped region denotes a shared part;
[0037] FIG. 4 is a Van Krevelen distribution diagram of organic matter acquired by treating a 10 fold-diluted standard (natural dissolved organic carbon) of the IHSS according to a nano-spray ionization method of the present invention;
[0038] FIG. 5 is a diagram of comparison between different methods for DOM in forest soil interstitial water, where
[0039] (a) is a Van Krevelen distribution diagram of organic matter acquired via solid-phase extraction and electro-spray ionization according to a traditional method; and
[0040] (b) is a Van Krevelen distribution diagram of organic matter acquired according to a nano-spray ionization method of the present invention; and
[0041] FIG. 6 is a diagram showing the difference between types of dissolved organic matter in water that are detected using two methods, where the dashed box shows signal distribution of dissolved organic matter detected using the method and the apparatus of the present invention, and the dashed circle shows signal distribution of dissolved organic matter detected using a traditional method, and
[0042] in the drawings, regions represented by reference numerals are as follows: 14-lipid region, 15-protein or polypeptide region, 16-amino sugar region, 17-black carbon region, 18 lignin region, and 19-tannin/polyphenol region.
[0043] The technical solutions of the present invention will be further described below with reference to the accompanying drawings and embodiments. The following embodiments are illustrative rather than restrictive, and are not intended to limit the protection scope of the present invention. All technologies achieved based on content of the present invention fall within the scope of the present invention. In the case of no conflict, an optimal technical solution can be acquired by adjusting or combining the embodiments of the present application and characteristics in the embodiments.
[0044] Embodiment 1
[0045] As shown in FIGs. 1 and 2, this embodiment provides a nano-spray-FTICR-MS analysis apparatus for dissolved organic matters in environmental solid samples, including a nano-spray apparatus and a Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS).
[0046] The nano-spray apparatus is entirely mounted on a fixation frame 3, and mainly includes a glass sprayer 1, a conductive needle 2, a rubber adapter 4, a duplex-type pressurization ball 5, a gas storage bag 6, a one-way valve I7, a one-way valve II 8, a metal conductive clip 10, and a pressure gauge 11.
[0047] The rubber adapter 4 has a hollow lumen structure. One end of the rubber adapter 4 is sleeved on the end, distal from a nozzle, of the glass sprayer 1. The other end of the rubber adapter 4 is connected to one end of the gas storage bag 6 via a pipeline. The other end of the gas storage bag 6 is connected to one end of the duplex-type pressurization ball 5 via the one-way valve I7. The other end of the duplex-type pressurization ball 5 is connected to outside air via the one-way valve 11 (8). The pressure gauge 11 is connected to the gas storage bag 6.
[0048] The one-way valve I7 and the one-way valve II8 are disposed in the following manners: When the duplex-type pressurization ball 5 is compressed, the one-way valve I7 is opened, the one-way valve II8 is closed, and air in the duplex-type pressurization ball 5 is squeezed into the gas storage bag 6. When the duplex-type pressurization ball 5 is released, the one-way valve I7 is closed, the one-way valve II8 is opened, and outside air is supplemented into the duplex-type pressurization ball 5 for next pressurization.
[0049] The conductive needle 2 is disposed on the axis of the glass sprayer 1. One end of the conductive needle 2 is proximal to the nozzle of the glass sprayer 1. The other end of the conductive needle 2 extends into the rubber adapter 4 and is connected to the end, penetrating a side wall of the rubber adapter 4, of the metal conductive clip 10. The other end of the metal conductive clip 10 is grounded. Preferably, the conductive needle 2 uses the gilded steel needle or the silver needle that has high chemical inertness and electrical conductivity, thereby being capable of implementing stable spraying in a case that the voltage of the ion source is relatively low.
[0050] A sample solution 13 loaded in the glass sprayer 1 is a mixed solution of interstitial water and organic solvents. The nozzle is aligned with an injection port 12 of the Fourier transform ion cyclotron resonance mass spectrometer. Preferably, the proportion of the interstitial water to the organic solvents ranges from 1:1 to 1:100. The organic solvents at least include methanol, and may further include other organic solvents, such as isopropanol. The proportion of the alcohol to the other organic solvent ranges from 1:0 to 1:10.
[0051] During use, a prepared sample solution 13 is loaded into the glass sprayer 1 first. Then, the glass sprayer 1 is aligned with the injection port 12 of the Fourier transform ion cyclotron resonance mass spectrometer via adjustment. A voltage is applied on an ion source of the Fourier transform ion cyclotron resonance mass spectrometer for sucking air into the glass sprayer 1 via the duplex-type pressurization ball 5 to start pressurization until spraying is achieved via Coulomb explosion. The Fourier transform ion cyclotron resonance mass spectrometer starts scanning and accumulates spectrograms to acquire quasi-molecular ion peaks of dissolved organic matter. Then, spectrum unfolding is performed to acquire a molecular formula.
[0052] Embodiment 2
[0053] This embodiment provides a nano-spray-FTICR-MS analysis method for dissolved organic matters in environmental solid samples. The analysis method uses the analysis apparatus of embodiment 1 and specifically includes the following steps:
[0054] First, add 1 microliter of sample interstitial water into methanol to prepare a sample solution 13 in which the proportion of the interstitial water to the organic solvent is 1:10. Load 5 microliter of the sample solution 13 into a glass sprayer 1. Then, insert a conductive needle 2 into a tip of the glass sprayer 1, connect a duplex-type pressurization ball 5 and a gas storage bag 6 to a rubber adapter 4, and connect a pressure gauge 11 to the gas storage bag 6. Fix on a fixation frame 3 the above apparatus in which the sample solution 13 is loaded. Align the glass sprayer 1 with an injection port 12 of the Fourier transform ion cyclotron resonance mass spectrometer by adjusting the direction and the position of the glass sprayer 1. Make sure that a metal conductive clip 10 is grounded. Boost a voltage on an ion source of the Fourier transform ion cyclotron resonance mass spectrometer for sucking air into the glass sprayer 1 via the duplex-type pressurization ball 5 to start pressurization until spraying is achieved via Coulomb explosion. The Fourier transform ion cyclotron resonance mass spectrometer starts testing and accumulates scans to acquire a mass spectrogram.
[0055] FIG. 3 is a molecular distribution diagram of a natural dissolved organic carbon standard of the IHSS. Molecular weight distribution in c and that in d are similar. After spectrum unfolding, it is found that the H/C ratio of a molecular formula acquired according to a traditional test method is mainly distributed between 0.5 and 1.5, and the O/C ratio thereof is mainly distributed between 0.1 to 0.9 (a of FIG. 3). The substances presented in Fig. 3a are mainly lignin-like and some polyphenol-like compounds. Actually, the quantity of detected molecules is 1827, which is far less than the quantity 2636 (e of FIG. 3) detected using the method of the present invention. In addition, distribution of molecular types is relatively narrow. The diversity of molecules detected using the method of the present invention is significantly great (b in FIG. 3), and covers a lipid region 14, a protein or polypeptide region 15, an amino sugar region 16, a black carbon region 17, a lignin region 18, and a tannin/polyphenol region 19 (FIG. 6).
[0056] It can be learned that at the same sample concentration, the analysis method of the present invention effectively increases types and the amount of detectable dissolved organic matter.
[0057] Embodiment 3
[0058] FIG. 4 shows a distribution diagram of types of molecules detected using a 10 fold diluted sample solution according to a process and a method similar to embodiment 2. It can be learned that, molecular formulae that can be acquired for the 10 fold-diluted sample solution according to this method are also richer and more complete than those can be acquired according to a traditional method (a in FIG. 3).
[0059] Embodiment 4
[0060] FIG. 5 shows a distribution diagram of forest soil dissolved organic matter acquired according to this method, and uses a distribution diagram of types of molecules detected using a fold-diluted sample solution according to a process and a method similar to embodiment 2. It can be learned that the same effect as embodiment 1 is achieved, that is, this method can detect more types of organic matter in interstitial water of forest soil. These types cover a lipid region 14, a protein or polypeptide region 15, an amino sugar region 16, a black carbon region 17, a lignin region 18, and a tannin/polyphenol region 19 (FIG. 6). It may be found via observation on the detected organic matter that, this method can detect more types of nitrogen-containing organic matter, and the detected organic matter may have higher bioavailability. This indicates that soil dissolved organic carbon plays a greater role in soil carbon and nitrogen cycling than previously recognized.
[0061] Because the sample amount (1 microliter) suitable for this method is 1/10,000 or less than 1/10,000 of the sample amount (10 milliliters) for a conventional method, for a soil sample from which interstitial water is difficult to acquire, types of dissolved organic matter that can be detected are greatly increased using this method. This method plays an important role in understanding the geochemical role of dissolved organic carbon in interstitial water, cycling of soil nutrient elements, and migration and transformation of soil environmental pollutants.
[0062] In addition, especially for the study of a root micro-region, the amount of samples required for this method is much lower than that for a traditional method. In addition, protein like and polysaccharide-like substances that can be detected according to this method are key targets for the study of a plant root micro-region. Therefore, this method is especially suitable for soil and sediment samples that require a high-resolution profile composed of organic matter. In addition to soil, this method can also be applied to other environmental sample types with similar concentration ranges and matrix characteristics.
[0063] In conclusion, according to the nano-spray-FTICR-MS analysis method and apparatus for dissolved organic matters in environmental solid samples, the nano-spray apparatus and the Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) are combined for use; a sample is purified and enriched without solid-phase extraction; and the ionization efficiency is improved while ion selective suppression is reduced by changing a formula of a matrix and using nano-spraying. Therefore, direct analysis of interstitial water in an environmental solid sample can be achieved, and thousands of quasi-molecular ion peaks can be acquired at a time. The quasi-molecular ion peaks are displayed in a Van Krevelen distribution diagram of organic matter. In addition to molecules, of organic matter, in a lignin region that is mainly tested in a traditional method, molecules, of organic matter, in a lipid region, a protein or polypeptide region, an amino sugar region, a black carbon region, and a tannin/polyphenol region can be acquired, which resolves key problems in the prior art that biologically active molecular signals are lost because solid-phase extraction pretreatment is required and that signals are selectively suppressed in common electro-spray ionization. In addition, the sample amount of this method is 1/10,000 of the sample amount of a traditional method, which can meet requirements for analysis of in-situ dissolved organic matter, such as environmental solid samples (for example, soil and sediment), from which an interstitial water sample is difficult to acquire, and resolves a problem that elution/water-extractable dissolved organic matter that cannot reflect a real environment is used in the past.
[0064] The above embodiments are merely used to illustrate the technical concept and characteristics of the present invention, are intended to make those of ordinary skill in the art understand the content of the present invention and implement the present invention based on the content, and should not limit the protection scope of the present invention. Any equivalent change or modification figured out based on the essence of the content of the present invention shall fall within the protection scope of the present invention.
Claims (8)
- l1CLAIMS What is claimed is: 1. A nano-spray-FTICR-MS analysis apparatus for dissolved organic matters in environmental solid samples, wherein comprising a nano-spray apparatus and a Fourier transform ion cyclotron resonance mass spectrometer; the nano-spray apparatus comprises a glass sprayer (1), a conductive needle (2), a rubber adapter (4), a duplex-type pressurization ball (5), and a gas storage bag (6), wherein the rubber adapter (4) has a hollow lumen structure; one end of the rubber adapter (4) is sleeved on the end, distal from a nozzle, of the glass sprayer (1); the other end of the rubber adapter (4) is connected to one end of the gas storage bag (6) via a pipeline; the other end of the gas storage bag (6) is connected to one end of the duplex-type pressurization ball (5) via a one-way valve I (7); the other end of the duplex-type pressurization ball (5) is connected to outside air via a one-way valve 11 (8); when the duplex-type pressurization ball (5) is compressed, the one-way valve I (7) is opened, and the one-way valve 11 (8) is closed; and when the duplex-type pressurization ball (5) is released, the one-way valve 1 (7) is closed, and the one-way valve 11 (8) is opened; the conductive needle (2) is disposed on an axis of the glass sprayer (1); one end of the conductive needle (2) is proximal to the nozzle of the glass sprayer (1); the other end of the conductive needle (2) extends into the rubber adapter (4) and is connected to the end, penetrating a side wall of the rubber adapter (4), of a metal conductive clip (10); and the other end of the metal conductive clip (10) is grounded; and a sample solution (13) loaded in the glass sprayer (1) is a mixed solution of interstitial water and organic solvents; and the nozzle is aligned with an injection port (12) of the Fourier transform ion cyclotron resonance mass spectrometer.
- 2. The nano-spray-FTICR-MS analysis apparatus for dissolved organic matters in environmental solid samples according to claim 1, wherein the conductive needle (2) is a gilded steel needle or a silver needle.
- 3. The nano-spray-FTICR-MS analysis apparatus for dissolved organic matters in environmental solid samples according to claim 1, wherein the sample solution (13) is directly injected from the rubber adapter (4) into the glass sprayer (1) via a micro-syringe.
- 4. The nano-spray-FTICR-MS analysis apparatus for dissolved organic matters in environmental solid samples according to claim 1, wherein a proportion of the interstitial water to the organic solvents ranges from 1:1 to 1:100.
- 5. The nano-spray-FTICR-MS analysis apparatus for dissolved organic matters in environmental solid samples according to claim 1, wherein the organic solvents comprise alcohol, and a proportion of the alcohol to the other organic solvent ranges from 1:0 to 1:10.
- 6. The nano-spray-FTICR-MS analysis apparatus for dissolved organic matters in environmental solid samples according to claim 1, wherein the gas storage bag (6) is provided with a pressure gauge (11).
- 7. A nano-spray-FTICR-MS analysis method for dissolved organic matters in environmental solid samples, using the analysis apparatus according to any one of claims 1 to 6 and comprising the following steps: (1) loading a prepared sample solution into the glass sprayer, wherein the sample solution is a mixed solution of interstitial water, methanol, and isopropanol; (2) aligning the glass sprayer with the injection port of the Fourier transform ion cyclotron resonance mass spectrometer via adjustment, applying a voltage on an ion source of the Fourier transform ion cyclotron resonance mass spectrometer for sucking air into the glass sprayer via the duplex-type pressurization ball to start pressurization until spraying is achieved via Coulomb explosion; and (3) starting scanning and accumulating spectrograms by the Fourier transform ion cyclotron resonance mass spectrometer to acquire quasi-molecular ion peaks of dissolved organic matter, and performing spectrum unfolding to acquire a molecular formula.
- 8. The nano-spray-FTICR-MS analysis method for dissolved organic matters in environmental solid samples according to claim 7, wherein molecular ion peaks of the dissolved organic matters comprise various organic matter types, such as a lipid region, a protein or polypeptide region, an amino sugar region, a black carbon region, a lignin region, and a tannin/polyphenol region.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011442452.7A CN112630289B (en) | 2020-12-08 | 2020-12-08 | Nanoliter spray-FTICR-MS analysis method and device for dissolved organic matters in environmental solid sample |
| CN202011442452.7 | 2020-12-08 | ||
| PCT/CN2020/141981 WO2021212920A1 (en) | 2020-12-08 | 2020-12-31 | Nanoliter spray-fticr-ms analysis method and device for organic matter dissolved in environmental solid sample |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2020444034A1 AU2020444034A1 (en) | 2022-06-23 |
| AU2020444034B2 true AU2020444034B2 (en) | 2022-12-01 |
Family
ID=75309598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2020444034A Active AU2020444034B2 (en) | 2020-12-08 | 2020-12-31 | Nanoliter spray-FTICR-MS analysis method and device for organic matter dissolved in environmental solid sample |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN112630289B (en) |
| AU (1) | AU2020444034B2 (en) |
| WO (1) | WO2021212920A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115480022B (en) * | 2022-10-21 | 2023-10-24 | 贵州大学 | Method for tracing analysis of dissolved black carbon and granular black carbon in plateau lake water body |
| CN117849158B (en) * | 2024-03-08 | 2024-06-25 | 清华大学 | Direct ionization mass spectrometry system based on micro-sampling probe |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1558230A (en) * | 2004-02-03 | 2004-12-29 | 复旦大学 | Nano-liter spraying device |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060255261A1 (en) * | 2005-04-04 | 2006-11-16 | Craig Whitehouse | Atmospheric pressure ion source for mass spectrometry |
| US8378294B2 (en) * | 2008-05-20 | 2013-02-19 | Shimadzu Corporation | Method of atmospheric pressure ionization for mass spectrometer |
| CN106384705B (en) * | 2016-08-29 | 2019-02-19 | 山东省分析测试中心 | A kind of high-throughput Nanoliter electrospray analysis system and its application based on miniature array |
| CN106783511B (en) * | 2017-02-27 | 2018-07-13 | 中国计量科学研究院 | Esi ion source and its operating method are received based on polarity reversal voltage strategy |
| CN210294180U (en) * | 2019-05-31 | 2020-04-10 | 中国石油天然气股份有限公司 | Full two-dimensional gas chromatography and Fourier transform ion cyclotron resonance mass spectrum coupling system |
| CN210982351U (en) * | 2019-10-14 | 2020-07-10 | 浙江汇泽医药科技有限公司 | Multiple milliliter electrospray mass spectrometry coupling device and system thereof |
| CN210897196U (en) * | 2019-11-19 | 2020-06-30 | 深圳至秦仪器有限公司 | Electrospray ion source and mass spectrum device |
-
2020
- 2020-12-08 CN CN202011442452.7A patent/CN112630289B/en active Active
- 2020-12-31 AU AU2020444034A patent/AU2020444034B2/en active Active
- 2020-12-31 WO PCT/CN2020/141981 patent/WO2021212920A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1558230A (en) * | 2004-02-03 | 2004-12-29 | 复旦大学 | Nano-liter spraying device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112630289A (en) | 2021-04-09 |
| AU2020444034A1 (en) | 2022-06-23 |
| CN112630289B (en) | 2021-11-30 |
| WO2021212920A1 (en) | 2021-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020444034B2 (en) | Nanoliter spray-FTICR-MS analysis method and device for organic matter dissolved in environmental solid sample | |
| Quilliam et al. | Ion‐spray mass spectrometry of marine neurotoxins | |
| Read et al. | Rapid screening procedures for the hydrolysis products of chemical warfare agents using positive and negative ion liquid chromatography–mass spectrometry with atmospheric pressure chemical ionisation | |
| Straub et al. | Determination of penicillin G, ampicillin, amoxicillin, cloxacillin and cephapirin by high-performance liquid chromatography—electrospray mass spectrometry | |
| Spoof et al. | Screening for cyanobacterial hepatotoxins, microcystins and nodularin in environmental water samples by reversed-phase liquid chromatography–electrospray ionisation mass spectrometry | |
| Barco et al. | Analysis of cyanobacterial hepatotoxins in water samples by microbore reversed-phase liquid chromatography–electrospray ionisation mass spectrometry | |
| Cai et al. | Elucidation of LSD in vitro metabolism by liquid chromatography and capillary electrophoresis coupled with tandem mass spectrometry | |
| Kwok et al. | Detection of bioactive peptides including gonadotrophin‐releasing factors (GnRHs) in horse urine using ultra‐high performance liquid chromatography–high resolution mass spectrometry (UHPLC/HRMS) | |
| CN105021758A (en) | Chemical derivatization-based phosphatide classification detection and quantification method | |
| Guan et al. | Identification of ex vivo catabolites of peptides with doping potential in equine plasma by HILIC‐HRMS | |
| Zhu et al. | Presence of morphine and morphine-6-glucuronide in the marine mollusk Mytilus edulis ganglia determined by GC/MS and Q–TOF–MS: Starvation increases opiate alkaloid levels | |
| Guan et al. | A comprehensive approach to detecting multitudinous bioactive peptides in equine plasma and urine using hydrophilic interaction liquid chromatography coupled to high resolution mass spectrometry | |
| Fiori et al. | Evaluation of two different clean-up steps, to minimise ion suppression phenomena in ion trap liquid chromatography–tandem mass spectrometry for the multi-residue analysis of beta agonists in calves urine | |
| CN111562302B (en) | Method for extracting and analyzing water-soluble and water-insoluble organic matters in atmospheric fine particles | |
| Zhao et al. | Qualitative and quantitative analysis of the diuretic component ergone in Polyporus umbellatus by HPLC with fluorescence detection and HPLC-APCI-MS/MS | |
| Tao et al. | Fabrication and evaluation of magnetic phosphodiesterase-5 linked nanoparticles as adsorbent for magnetic dispersive solid-phase extraction of inhibitors from Chinese herbal medicine prior to ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry analysis | |
| Draisci et al. | Confirmatory analysis of residues of stanozolol and its major metabolite in bovine urine by liquid chromatography–tandem mass spectrometry | |
| Xin et al. | Simple and fast determination of tetrodotoxin in human plasma based on hydrophilic-interaction/ion-exchange mixed-mode solid phase extraction combined with liquid chromatography-tandem mass spectroscopy | |
| Yan et al. | Analysis of proteinaceous binding media used in Tang Dynasty polychrome pottery by MALDI-TOF-MS | |
| Wang et al. | Fast and sensitive analysis of dermorphin and HYP6‐dermorphin in equine plasma using liquid chromatography tandem mass spectrometry | |
| Fang et al. | Liquid chromatography/quadrupole time-of-flight mass spectrometry for determination of saxitoxin and decarbamoylsaxitoxin in shellfish | |
| Chang et al. | Doping control analysis of small peptides in human urine using LC-HRMS with parallel reaction monitoring mode: screening and confirmation | |
| Wang et al. | Determination of paeoniflorin in rat plasma by a liquid chromatography‐tandem mass spectrometry method coupled with solid‐phase extraction | |
| Cao et al. | Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent | |
| CN106645490A (en) | Method for determining perfluorooctanesulfonic acid and perfluorohexanesulfonic acid in edible parts of crops |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) |