# US 10,309,880 B2 · Preparation of fluid samples for laser induced breakdown spectroscopy and/or imaging analysis > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,309,880 B2 - Document ID: US10309880B2 - Status: Granted - Kind: B2 - Application number: 15/561,836 - Filed: 2016-03-25 - Published: 2018-05-03 - Granted: 2019-06-04 - Earliest claimed: 2015-03-26 - Assignees: Dover Photonics LLC - Applicants: Dover Photonics LLC - Inventors: Noureddine Melikechi - Web page: https://patentgrep.com/patent/US10309880B2 ## CPC - G01N 1/4077: {by other techniques involving separation of suspended solids} - G01N 1/38: Diluting, dispersing or mixing samples - G01N 21/01: Arrangements or apparatus for facilitating the optical investigation - G01N 21/63: optically excited - G01N 21/718: {Laser microanalysis, i.e. with formation of sample plasma} - G01N 2001/381: {by membrane diffusion; Permeation tubes} - G01N 2001/4038: {electric methods, e.g. electromigration, electrophoresis, ionisation} - G01N 2001/4088: {filtration} - G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q) ## Abstract A method of analyzing, preferably by laser induced breakdown spectroscopy (LIBS), fluid samples (e.g. liquids, solutions, melts or slurries) that contain soluble and insoluble components of various elemental, molecular and biological components using a pre-characterized, preferably non-magnetic, membrane or plurality of membranes each having different characteristics, such as different porosities. The fluid sample is first deposited on the one or more membranes and the components to be analyzed are retained thereon through filtration or diffusion and then analyzed, such as with LIBS. Different components, such as different sized particles, are fixed on different membranes depending on the characteristics (e.g. pore size) of the corresponding membrane, which provides pre-sorting of the components before LIBS analysis. ## Claims ### Claim 1 A method for analyzing a fluid sample containing one or more soluble or insoluble components, the method comprising the steps of: (a) providing a plurality of membranes, each membrane having one or more known characteristics in an absence of the one or more soluble or insoluble components, including at least a known LIBS spectra, at least one first membrane having at least one characteristic different from at least one second membrane; (b) filtering or diffusing the fluid sample through or into the plurality of membranes; (c) retaining one or more components of the fluid sample on or in each of the plurality of membranes and (d) analyzing each of the plurality of membranes in the presence of the retained one or components of the fluid sample using laser induced breakdown spectroscopy (LIBS) to obtain a LIBS spectrum for each membrane in the presence of the retained one or more components, and (e) reporting (i) a LIBS analysis corresponding to each membrane in the presence of the retained one or more components, along with (ii) information regarding one or more of the known characteristics of each membrane. ### Claim 2 (depends on 1) The method of claim 1, wherein the fluid sample comprises a liquid, a solution, a melt or a slurry. ### Claim 3 (depends on 1) The method of claim 1, wherein the soluble or insoluble components comprise elemental, molecular or biological components. ### Claim 4 (depends on 1) The method of claim 1, wherein at least one of the plurality of membranes is non-magnetic or weakly magnetic. ### Claim 5 (depends on 1) The method of claim 1, wherein the characteristic is selected from the group consisting of: porosity, pore size, pore shape, materials of construction, and a combination thereof. ### Claim 6 (depends on 1) The method of claim 1, wherein each of the plurality of membranes has a pore size between 10 nm and 10 mm. ### Claim 7 (depends on 1) The method of claim 1, wherein at least one of the plurality of membranes is not chemically reactive with the fluid sample. ### Claim 8 (depends on 7) The method of claim 7, wherein at least one of the plurality of membranes is a glass filter. ### Claim 9 (depends on 1) The method of claim 1, wherein step (c) comprises quantifying atomic elements present in the components retained by each of the one or more membranes using LIBS. ### Claim 10 (depends on 9) The method of claim 9, wherein the information regarding the one or more known characteristics of each membrane includes information relating to a particle size or range of particle sizes of the components retained by each membrane. ### Claim 11 (depends on 9) The method of claim 9, further comprising classifying the components retained by each membrane by analyzing the LIBS spectrum using a multi-variate analysis method. ### Claim 12 (depends on 11) The method of claim 11, wherein the multi-variate analysis method comprises a principal component analysis (PCA) method. ### Claim 13 (depends on 11) The method of claim 11, wherein the multi-variate analysis method comprises an automatic machine learning technique selected from the group consisting of: support vector machine techniques, neural networks techniques, adaptive local hyperplane techniques, K-nearest neighbors techniques, soft independent modeling class analysis techniques, and partial least square techniques. ### Claim 14 (depends on 1) The method of claim 1, further comprising the step of characterizing the plurality of membranes prior to performing step (a), wherein the characterizing comprises acquiring a LIBS spectra for the one or more membranes. ### Claim 15 (depends on 14) The method of claim 14, wherein the characterizing further comprises characterizing the one or more membranes with respect to pore size, pore shape, and elemental composition. ### Claim 16 (depends on 1) The method of claim 1, further comprising preparing the sample prior to step (a) by conducting a dissolution step or a separation step. ### Claim 17 (depends on 1) The method of claim 1, comprising diffusing the fluid sample through at least one membrane of the one or more membranes by contacting the at least one membrane with the sample in a sample-membrane-contact location for a requisite amount of time to promote a degree of diffusion, and analyzing the components retained on the membrane using LIBS analysis performed at different distances from the sample-membrane contact location. ### Claim 18 (depends on 17) The method of claim 17, wherein the sample-membrane-contact location comprises a surface of the membrane and the different distances comprise different depths along a thickness of the membrane. ### Claim 19 (depends on 17) The method of claim 17, wherein the sample-membrane-contact location comprises a spot on a surface of the membrane and the different distances comprise different radial distances from the spot along the surface of the membrane. ### Claim 20 (depends on 17) The method of claim 17, wherein the one or more membranes comprises a plurality of membranes in which at least one first membrane has at least one characteristic different from at least one second membrane, wherein the at least one characteristic different comprises a degree of diffusivity relative to one or more components or classes of components of interest for analysis in the sample. ### Claim 21 A method for analyzing a fluid sample containing one or more insoluble components, the method comprising the steps of: (a) providing one or more membranes each membrane having one or more known characteristics, including at least a known LIBS spectra in the absence of the one or more soluble or insoluble components wherein at least one of the one or more membranes is a hydrophilic glass filter; (t) filtering or diffusing the fluid sample through or into the one or more membranes and retaining one or more components of the fluid sample on or in each of the one or more membranes; (c) analyzing each of the plurality of membranes using laser induced breakdown spectroscopy (LIBS) to obtain a LIDS spectrum for each membrane in the presence of the retained one or more components, and reporting (i) a LIBS analysis corresponding to each membrane in the presence of the retained one or more components, along with (ii) information regarding one or more of the known characteristics of each membrane. ### Claim 22 (depends on 21) The method of claim 21, wherein the one or more membranes comprises a plurality of membranes in which at least one first membrane has at least one characteristic different from at least one second membrane. ### Claim 23 A method for analyzing a fluid sample containing one or more soluble or insoluble components, the method comprising the steps of: (a) providing one or more membranes, each membrane having one or more known characteristics in an absence of the one or more soluble or insoluble components, including at least a known LIBS spectra; (b) filtering or diffusing the fluid sample through or into the one or more membranes and retaining one or more components of the fluid sample on or in each of the one or more membranes; (c) fixing one or more of the retained components in or on the one or more membranes; (d) analyzing each of the one or more membranes in the presence of the retained one or more components of the fluid sample using laser induced breakdown spectroscopy (LIBS) to obtain a LIBS spectrum for each membrane in the presence of the retained one or more components, and (e) reporting (i) a LIBS analysis corresponding to each membrane in the presence of the retained one or more components along with (ii) information regarding one or more of the known characteristics of each membrane. ### Claim 24 (depends on 23) The method of claim 23, wherein the fixing step comprises solidifying one or more of the retained components. ### Claim 25 (depends on 23) The method of claim 23, wherein the fixing step comprises removing moisture and hydrates from one or more of the retained components. ### Claim 26 (depends on 23) The method of claim 23, wherein the fixing step comprises subjecting the membrane with the retained components to a method selected from the group consisting of: (i) using air convection to remove moisture, (ii) using a thermo electric cooler or a thermo electric heater, (iii) fixing the liquid on the membranes using radiation; and (iv) a combination of any of (i)-(iii). ### Claim 27 (depends on 23) The method of claim 23, further comprising trapping and capturing any gases given off by retained components sample during the fixation step and independently analyzing the gaseous fraction. ### Claim 28 A method for analyzing a fluid sample containing one or more soluble or insoluble components, the method comprising the steps of: (a) magnetizing the sample; (b) magnetically physically separating the sample into a portion containing magnetic particles and a portion containing non-magnetic particles; (c) providing one or more membranes, each membrane having one or more known characteristics in an absence of the one or more soluble or insoluble components including at least a known LIBS spectra; (d) filtering or diffusing a portion of the fluid sample through or into the one or more membranes and retaining one or more components of the fluid sample on or in each of the one or more membrane; (e) analyzing each of the one or more membranes in the presence of the retained one or more components of the fluid sample using laser induced breakdown spectroscopy (LIBS) to obtain a LIBS spectrum for each membrane with the retained one or more components, and (f) reporting (i) a LIBS analysis corresponding to each membrane in the presence of the retained one or more components, along with (ii) information regarding one or more of the known characteristics of each membrane. ### Claim 29 (depends on 28) The method of claim 28, further comprising using the portion containing magnetic particles as the fluid sample in step (d). ### Claim 30 (depends on 28) The method of claim 28, further comprising using the portion containing the non-magnetic particles as the fluid sample in step (d). ### Claim 31 (depends on 28) The method of claim 28, further comprising separately performing step (d), step (e), or both steps (d) and (e) on both the portion containing magnetic particles and the portion containing the non-magnetic particles.