Automated system for remote in-line concentration and homogenization of ultra-low concentrations of pure chemicals

Abstract

Systems and methods for concentrating and homogenizing remote samples for analysis are described. Sample concentration and homogenization system embodiments include, but are not limited to: at least a first valve; at least a first column fluidly coupled to the first valve; a flow meter fluidly coupled to the first column to measure the amount of liquid sample passing through the first column when the first valve is in a first flow path configuration; and a homogenization valve including a sample homogenization circuit in which the concentrated sample is homogenized.

Description

Background Art

[0001] In many laboratory situations, it is often necessary to analyze a large number of chemical or biological samples at once. In order to streamline this process / technique, the manipulation of samples has been mechanized. This mechanized sampling may be referred to as automatic sampling and may be performed using an automated sampling device or an automatic sampler.

[0002] Inductively coupled plasma (ICP) spectrometry is an analytical technique commonly used to determine trace element concentrations and isotope ratios in liquid samples. ICP spectrometry employs an electromagnetically generated partially ionized argon plasma that reaches a temperature of about 7,000 K. When a sample is introduced into the plasma, the high temperature causes the sample atoms to become ionized or emit light. Since each chemical element produces a characteristic mass or emission spectrum, measuring the spectrum of the emitted mass or emitted light allows the elemental composition of the original sample to be determined.

[0003] The sample introduction system can be used to introduce a liquid sample into an ICP spectrometer (e.g., an inductively coupled plasma mass spectrometer (ICP / ICP-MS), an inductively coupled plasma atomic emission spectrometer (ICP-AES), or the like) or other sample detector or analytical instrument for analysis. For example, the sample introduction system can withdraw an aliquot of the liquid sample from a container and thereafter transport the aliquot to a nebulizer, which converts the aliquot into a polydisperse aerosol suitable for ionization in a plasma by an ICP spectrometer. The aerosol is then classified in a nebulizer chamber to remove larger aerosol particles. After leaving the nebulizer chamber, the aerosol is introduced into a plasma for analysis by a plasma spray gun assembly of an ICP-MS or ICP-AES instrument. Summary of the invention

[0004] Systems and methods for mixing and homogenizing a concentrated sample for analysis are described. A concentration and homogenization system for analyzing a liquid sample by an inductively coupled mass spectrometer includes, but is not limited to, a sample concentration system coupled to a concentrated sample homogenization system. The sample concentration system may include: at least a first valve; at least a first exchange column / tubing column configured to hold at least one chemical of interest and coupled to the first valve; and a liquid mass flow meter fluidly coupled to the valve and configured to measure at least one of a mass or volume of liquid passing through the first exchange column. The system further includes a homogenization valve that introduces the concentrated sample into a sample homogenizer loop that produces a homogenized concentrated sample for analysis.

[0005] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] A detailed description is provided with reference to the accompanying drawings. Any dimensions included in the drawings are provided by way of example only and are not intended to limit the invention.

[0007] Figure 1A is a partial pipeline diagram illustrating a system configured to analyze samples transported over long distances according to an example embodiment of the present invention.

[0008] Figure 1B is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0009] Figure 1C is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0010] Figure 1D is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0011] Figure 1E is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0012] Figure 1F is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0013] Figure 1G is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0014] Figure 1H is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0015] Fig. 1I is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0016] Figure 1J is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0017] Figure 1K is an environmental view of a sample concentration and homogenization system according to an example embodiment of the present invention.

[0018] Figure 1L is a calibration graph of counts versus concentration of magnesium present in a liquid sample prepared by a sample concentration and homogenization system according to an embodiment of the present invention.

[0019] Figure 2A FIG. 1 is an environmental view illustrating a remote sampling device used in a remote sampling system according to an exemplary embodiment of the present invention.

[0020] Figure 2B FIG. 1 is an environmental view illustrating a remote sampling device used in a remote sampling system according to an exemplary embodiment of the present invention.

[0021] Figure 3A is an environmental diagram illustrating an analysis device used in an analysis system according to an exemplary embodiment of the present invention.

[0022] Figure 3B is an environmental diagram illustrating an analysis device used in an analysis system according to an exemplary embodiment of the present invention.

[0023] Figure 4 FIG. 1 is a partial pipeline diagram of an analysis system within a system configured to analyze samples transported over long distances according to an exemplary embodiment of the present invention.

[0024] Figure 5 FIG. 1 is a diagram showing an exemplary embodiment of the present invention. Figure 4 Partial piping diagram of the detector utilized within the analytical system shown.

[0025] Figure 6 is an environmental diagram illustrating an analysis system having a plurality of analysis devices for analyzing samples received from a remote sampling system according to an example embodiment of the present invention.

[0026] Figure 7 is a diagrammatic depiction of a system including a sample receiving line and a detector configured to determine when the sample receiving line contains a continuous liquid segment between detectors according to an example embodiment of the invention.

[0027] Figure 8 is a partial cross-sectional view of a sample delivery line containing multiple sample segments obtained by a remote sampling system according to an exemplary embodiment of the present invention.

[0028] Fig. 9 is a timeline illustrating a plurality of liquid sample segments supplied to a sample receiving line and recorded by two detectors according to an example embodiment of the present invention.

[0029] Fig.10 is a flow chart depicting a method of determining when a sample receiving line contains a continuous liquid segment between detectors according to an example embodiment of the present invention.

[0030] Fig.11 is a process flow diagram of a control system for monitoring and controlling process operations based on chemical substance detection limits according to an example embodiment of the present invention.

[0031] Fig.12 is a schematic diagram of a processing facility incorporating multiple remote sampling systems according to an example embodiment of the present invention.

[0032] Fig.13 is a graph depicting metal contamination of a chemical bath over time, with data points representing manual sampling and data points obtained using an automated system according to an example embodiment of the present invention. DETAILED DESCRIPTION

[0033] Overview

[0034] Determining the concentration or amount of a trace element in a sample can provide an indication of the purity of the sample, or the acceptability of the sample for use as a reagent, reactive component, or the like. For example, in a particular production or manufacturing process (e.g., mining, metallurgy, semiconductor manufacturing, pharmaceuticals, etc.), the tolerance for impurities can be very strict, for example, on the order of fractions of a billion. For example, semiconductor processes can require ultra-low detection limits for impurities in process chemicals, including but not limited to ultrapure water (UPW) used to clean wafers, isopropyl alcohol (IPA) used to dry wafers, hydrogen peroxide (H2O2), ammonia solution (NH4OH), and the like. Failure to detect ultra-low concentrations of impurities in such process chemicals can destroy semiconductor wafers, such as by causing such impurities to precipitate out of solution and onto the wafer (e.g., causing metal impurities or other conductive hazards to deposit on the wafer (such as by impurities precipitating out of solution), the wafer acting as a concentrating surface for impurities, or the like). However, the detection capabilities of even highly sensitive analytical devices, such as inductively coupled plasma mass spectrometer (ICP / ICP-MS) systems, typically do not have the precise resolution to measure chemical species present at low parts per trillion (ppq) concentrations in a sample for routine analysis.

[0035] Co-pending U.S. application Ser. No. 16 / 119,253 describes systems and methods for automated, on-line concentration of chemical species (e.g., chemical elements, molecules, compounds, etc.) present in ultra-low concentrations in samples. The example system employs one or more valve assemblies and one or more columns to concentrate a group of chemical elements in one or more samples and provides high rates of analyte retention and rapid kinetics for elution of pre-concentrated analytes for subsequent analysis by an inductively coupled plasma (ICP) analysis system (such as an ICP-MS system). The sample may be pre-concentrated at a remote sample location (e.g., as part of a remote sampling system), at an analysis system located remotely from the remote sampling system (e.g., at an analysis system having an ICP-MS system that receives the remote sample), or a combination thereof.

[0036] The homogenization step currently described is a modification of the concentration system described in U.S. Application 16 / 119,253 and provides a homogenized sample that can be analyzed by several different analysis modes. For example, an analysis device is often operated in a dedicated detection mode to detect a particular chemical species of interest, where the detection mode for one chemical species of interest may not be suitable for detecting another chemical species of interest (e.g., too much background noise may be generated in one detection mode to fail to detect a different chemical species of interest). The analysis device must therefore be operated in a dedicated detection mode to analyze the particular chemical species of interest. Under typical elution conditions (e.g., of a non-homogenized sample), the chemical species has a defined peak at a specific time after the eluent is introduced into the column. If the analysis device is not operated in the detection mode for a particular chemical species during the expected time after elution, the analysis device cannot output an accurate detection of the chemical species. For systems analyzing multiple chemical species (e.g., from a single or multiple columns), coordinating the timing of the various detection modes around the expected peak time can be cumbersome, can lead to analysis errors if the timing becomes offset, or can limit the number of detection modes available for a given sample based on timing constraints. Homogenization of the concentrated sample produces a sample curve that is a plateau opposite the peak. The same amount of species may be present in both the homogenized sample and the non-homogenized sample, but distributed throughout the entire sample volume of the homogenized sample. Therefore, multiple analysis modes can be performed on the extended sample plateau.

[0037] Example Implementation

[0038] General reference Figures 1A to 13, describing an example system configured to analyze a sample. In an example embodiment, the sample is introduced to a sample concentration and homogenization system before, after, or both before and after being transported through a distance between a remote sampling system and an analysis system located remote from the remote sampling system. The system 100 includes an analysis system 102 at a first location. The system 100 may also include one or more remote sampling systems 104 at a second location remote from the first location. For example, the one or more remote sampling systems 104 may be located proximate to a chemical source (such as a chemical storage tank, a chemical processing tank (e.g., a chemical bath), a chemical transport line or pipeline, or the like (e.g., a second location)) for analysis by the analysis system 102, wherein the analysis system 102 may be located remote from (several) remote sampling systems 104 (such as an analysis hub of a production facility (e.g., a first location)). The system 100 may also include one or more remote sampling systems 104 at a third location, a fourth location, etc., wherein the third location and / or the fourth location are remote from the first location. In an embodiment, the third location, the fourth location, and other locations of the remote sampling system 104 may be remote from the respective other locations of the other remote sampling systems 104. For example, one remote sampling system 104 may be located at a water line (e.g., a deionized water delivery line), while one or more other remote sampling systems 104 may be located at a chemical storage tank, a chemical treatment tank (e.g., a chemical bath), a chemical delivery line or pipeline, or the like. In some embodiments, the system 100 may also include one or more remote sampling systems 104 at a first location (e.g., near the analysis system 102). For example, the sampling system 104 at the first location may include an automatic sampler coupled to the analysis system 102. One or more sampling systems 104 may be operable to receive samples from the first location, the second location, the third location, the fourth location, etc., and the system 100 may be operable to deliver the samples to the analysis system 102 for analysis.

[0039] The remote sampling system 104 may be configured to receive a sample 150 and prepare the sample 150 for delivery (e.g., to the analysis system 102) and / or analysis. In an embodiment, the remote sampling system 104 may be positioned at various distances (e.g., 1 m, 5 m, 10 m, 30 m, 50 m, 100 m, 300 m, 1000 m, etc.) from the analysis system 102. In an embodiment, the remote sampling system 104 may include a remote sampling device 106 and a sample preparation device 108. The sample preparation device 108 may further include a valve 148 (such as a flow-through valve). In an embodiment, the remote sampling device 106 may include a device configured to collect the sample 150 from a sample stream or source (e.g., a liquid (such as wastewater, rinse water, chemicals, industrial chemicals, etc.), a gas (such as an air sample to be contacted with a liquid and / or pollutants therein), or the like). The remote sampling device 106 may include components (such as pumps, valves, tubing, sensors, etc.) suitable for obtaining a sample from a sample source and delivering the sample remotely to the analysis system 102. The sample preparation device 108 may include a device configured to prepare a sample 150 collected from the remote sampling device 106 using a diluent 114, an internal standard 116, a carrier 154, etc., such as to provide a specific sample concentration, a fortified sample, a calibration curve, or the like, and may be rinsed with a rinse solution 158.

[0040] In some embodiments, the sample 150 may be prepared (e.g., prepared sample 152) for delivery and / or analysis using one or more preparation techniques, including but not necessarily limited to: dilution, pre-concentration, addition of one or more calibration standards, etc. For example, a viscous sample 150 may be diluted (e.g., by the sample preparation device 108) before being delivered to the analysis system 102 (e.g., to prevent the sample 150 from separating during delivery). As described herein, a sample that has been transmitted from the remote sampling system 104 may be referred to as a sample 150, where the sample 150 may also be referred to as a prepared sample 152. In some embodiments, sample dilution may be dynamically adjusted (e.g., automatically adjusted) to move (several) samples 150 through the system at an expected rate. For example, the diluent 114 added to a particular sample or a particular type of sample is increased when the sample 150 moves too slowly through the system 100 (e.g., as measured by the transmission time from the second location to the first location). In another example, one liter (1L) of seawater may be remotely pre-concentrated before being delivered to the analysis system 102. In a further example, electrostatic concentration is used for material from an air sample to pre-concentrate possible airborne contaminants. In some embodiments, online dilution and / or calibration is performed automatically by the system 100. For example, the sample preparation device 108 can add one or more internal standards to a sample delivered to the analysis system 102 to calibrate the analysis system 102.

[0041] exist Figure 1A In an embodiment in which an example is shown in FIG, the sample preparation device 108 includes a sample concentration and homogenization system 200 for concentrating and homogenizing one or more chemical elements present in a sample 150 received from a remote sampling device 106 before transmitting the prepared sample 152 (e.g., a concentrated and homogenized sample) to the analysis system 102.

[0042] Alternatively or additionally, the analysis system 102 may include a sample concentration and homogenization system 200 to concentrate and homogenize one or more chemical elements prior to analysis by the analysis device described herein. Although the sample concentration and homogenization system 200 is described as concentrating and homogenizing chemical elements for analysis, it should be understood that the sample concentration and homogenization system 200 can be used to concentrate and homogenize chemical species, ions, molecules, compounds, or the like for analysis by the analysis system 102.

[0043] refer to Figure 1B to Figure 1L , showing an example embodiment of a sample concentration and homogenization system 200. Figure 1B and Figure 1C The sample concentration and homogenization system 200 shown in FIG. 2 includes an exchange column 202 , a valve 204 , a liquid mass flow meter 206 , and a homogenization valve 205 including a homogenizer loop 207 .

[0044] exist Figure 1B , valve 204 is in a sample loading configuration to provide a flow path for a sample (e.g., sample 150 or prepared sample 152) through the exchange column 202 and the liquid mass flow meter 206. The sample flows through the exchange column 202, whereby chemical elements with affinity for a particular exchange column 202 are retained within the column, and unretained sample can flow through the valve 204 to the liquid mass flow meter 206 and leave the sample concentration and homogenization system 200 as waste. Although the column described herein is referred to as an "exchange column", it should be noted that the column can be any column suitable for providing a difference between an element or species of interest and an element or species of no interest. For example, the exchange column can include, but is not limited to, an anion exchange column, a cation exchange column, a chelating column, a chromatography column, or the like, or a combination thereof.

[0045] Liquid mass flow meter 206 measures the sample flow (e.g., volume flow rate or mass flow rate) that has passed through exchange column 202 for use in calculating the final concentration of a particular chemical element retained within exchange column 202. Homogenization valve 205 is in bypass mode as shown, with the wash solution flowing directly through the valve to sprayer 208 or to waste. Alternatively, the wash solution may be directed through homogenizer loop 207.

[0046] After a threshold amount of sample mass or volume has passed through the exchange column 202, the sample concentration and homogenization system 200 automatically switches the configuration of the valve 204 to Figure 1C , whereby an eluent is introduced into the exchange column 202 to provide an eluted sample (e.g., prepared sample 152) for delivery to or analysis by the analysis system 102. For example, a controller operating valve 204 may compare the sample mass or volume measured by the liquid mass flow meter 206 with a threshold value (e.g., stored in system memory, specified by a user, etc.) to determine when enough sample has passed through the exchange column 202 to concentrate the chemical element(s) of interest for analysis by the analysis system 102.

[0047] Accordingly, the sample concentration and homogenization system 200 automatically switches the configuration of the valve 205 to a homogenization configuration, wherein the concentrated sample 152 fills the homogenizer loop 207 ( Figure 1C ). After homogenization (described below), the system pushes the concentrated, homogenized sample 152 to the nebulizer 208. Figure 1C A fluid path between valve 204, homogenization valve 205, and then to nebulizer 208 is shown in an elution configuration, but it can be understood that this flow path can be a direct connection (e.g., where the sample concentration and homogenization system 200 is included at the analysis system 102 or connected to its desolvation system) or can be a remote connection (e.g., where the sample concentration and homogenization system 200 is included in the remote sampling system 104), such as through the inclusion of valve 148 and a transfer line (e.g., the transfer line 144 described herein). The analysis results at the analysis system 102 can be compared with the volume or mass measured by the liquid mass flow meter 206 and the volume of the eluent to determine the concentration of the chemical elements present in the sample obtained by the remote sampling system 104.

[0048] The operation of the homogenizing valve 205 is Figures 1D to 1F In more detail, Figure 1D The sample loading into the homogenizer loop 207 is shown, Figure 1E Plot mixing / homogenization, and Figure 1F The concentrated, homogenized sample is shown being delivered to the nebulizer. For example, the sample homogenization valve 205 includes a homogenizer loop 207 that can be connected online to receive the sample from the exchange column 202 and deliver the sample to the nebulizer 208. To initiate the homogenization step, as in Figure 1D2, for example, a concentrated sample from an exchange column 202 is directed into a homogenizer loop 207. The system may introduce a bubble 209 into the fluid line at the beginning of sample elution from the column 202, and may introduce a bubble 211 at the end of sample elution from the exchange column 202, thus marking the beginning and end of the sample. The bubbles 209, 211 may be argon, nitrogen, an inert gas, air, or the like. The system may employ a bubble sensor adjacent to the homogenizer loop 207 to detect a first bubble in the fluid line and direct the eluent into the homogenizer loop 207 or direct the sample into a separate vial for storage. The bubble sensor may detect a second bubble in the fluid line to stop the operation of the pump that pushes the eluent through the column and into the homogenizer loop 207. Fluid that does not contain the sample (other than the bubbles 209, 211) may be diverted to a waste stream.

[0049] To homogenize the eluted and concentrated samples, the system pushes the samples back and forth in the homogenization loop 207, once or multiple times in each direction ( Figure 1D , Figure 1F ). Each pass within the homogenization loop 207 mixes the sample so that the chemical species of interest are more evenly dispersed throughout the sample portion. The homogenization loop 207 may be spiral as shown in the figure or may be a straight section of tubing. It may have features that promote mixing (such as baffles or the like). For example, mixing may be promoted by means of uneven speed / force of the fluid inside the fluid line traveling through the homogenization loop (e.g., higher speed toward the center of the fluid line; higher force applied to the fluid closer to the fluid line wall). In an embodiment, the homogenization loop 207 has a volume that exceeds the volume of the eluent to provide space within the homogenization loop 207 to move the sample to provide mixing. Alternatively or additionally, the volume of the homogenization loop 207 is selected so that sufficient mixing of the sample is completed by means of a single pass of the sample through the homogenization loop 207.

[0050] After the sample is mixed in the homogenization loop 107, the system introduces the mixed sample 152 to the analysis device, such as via the nebulizer 208. Figure 1F The sample may alternatively be captured in a vial or the like.

[0051] Homogenization of the sample results in a broad distribution of all species in the sample throughout the eluted sample, rather than one or more peaks of species. The analysis device can operate the homogenized sample 152 according to different detection modes to analyze for each chemical species of interest. Because each chemical species of interest has a homogenized distribution throughout the sample, the system can use multiple different detection modes on the same sample to simultaneously detect each species of interest independently of the typical peak time after elution. For example, the detection mode can include a cold plasma mode and a hot plasma mode, each mode having an optional introduction of additional gases (e.g., NH3, He, O2, combinations thereof).

[0052] refer to Figure 1G to Figure 1K , the sample concentration and homogenization system 200 may include multiple exchange columns to concentrate various chemical elements for analysis by the analysis system 102. For example, the sample concentration and homogenization system 200 is shown with a first exchange column 210 and a second exchange column 212, a plurality of valves (valves 214, 216, 218, 205 are shown), and a liquid mass flow meter 206. The exchange columns may be selected to hold chemical elements that are different from the other exchange columns of the sample concentration and homogenization system 200. For example, the first exchange column 210 may be configured to hold transition metal chemical elements (e.g., a chelating column) while allowing other chemical elements to pass (e.g., sodium, potassium, etc. that are allowed to pass to valve 216), while the second exchange column 212 may be configured to hold Group I and II chemical elements (e.g., a cation exchange column). By utilizing two or more selective exchange columns, the sample concentration and homogenization system 200 can allow for rapid elution of retained chemical species in each exchange column, rather than having affinity differences between multiple chemical elements in a single column, which can require longer elution cycles and reduce sample analysis resolution.

[0053] May include one or more homogenizing valves; Figure 1G There is only one homogenizing valve in the apparatus and it is placed in line before the sprayer 208. Other placements are possible. Figure 1G , the sample concentration and homogenization system 200 is shown in a sample loading configuration whereby valve 214 provides a flow path between the sample (e.g., sample 150 or prepared sample 152) and optional standard solution and the first exchange column 210 to retain chemical elements (e.g., transition metals) having an affinity for the exchange medium in the first exchange column 210 while passing all other chemical elements (e.g., Group I and II metals). Valve 216 is fluidly coupled to valve 214 to receive the sample and pass the sample into the second exchange column 212 to retain chemical elements (e.g., Group I and II metals) having an affinity for the exchange medium in the second exchange column 212 in a loading configuration. Valve 218 is fluidly coupled to valve 216 to receive the sample and pass the sample into the liquid mass flow meter 206 and out of the sample concentration and homogenization system 200 as waste. The homogenization valve 205 is in a bypass mode such that no sample flows through the homogenizer loop 207. Liquid mass flow meter 206 measures the sample flow (eg, volume flow rate or mass flow rate) that has passed through first exchange column 210 and second exchange column 212 to provide specific chemical elements retained within the respective exchange columns.

[0054] After a threshold amount of mass or volume of sample has passed through the first exchange column 210 and the second exchange column 212, the sample concentration and homogenization system 200 changes the configuration of valves 216 and 218 from the loading configuration ( Figure 1G Display) automatically switches to Figure 1H , whereby the eluent is introduced into the first exchange column 210 and passes through valve 216 (e.g., bypassing the second exchange column 212) to provide an eluted sample (e.g., prepared sample 152) for homogenization in the homogenization valve 205 and the homogenizer loop 207.

[0055] Next, the concentrated, homogenized sample is transmitted for analysis by the analysis system 102 to measure the chemical species of interest (e.g., transition metals) retained by the first exchange column 210. For example, the controller(s) operating the valves 214, 216, 218 may compare the mass or volume of the sample measured by the liquid mass flow meter 206 to a threshold value (e.g., stored in system memory, specified by a user, etc.) to determine when enough sample has passed through the first exchange column 210 and the second exchange column to concentrate the chemical element(s) of interest for analysis by the analysis system 102.

[0056] After eluting the chemical element(s) of interest from the first exchange column 210, the sample concentration and homogenization system 200 switches the configuration of the valve 216 from the injection configuration to the elution configuration ( Fig. 1I ) to provide a fluid path for an eluent that elutes the chemical element(s) of interest from the second exchange column 212, and switches the configuration of the valve 205 from the bypass mode to the homogenization mode. After concentration and homogenization, the eluted sample (e.g., prepared sample 152) is provided to be transmitted to the analysis system 102 or analyzed by the analysis system 102 to measure the chemical species of interest (e.g., Group I and II chemical elements) retained by the second exchange column 212.

[0057] refer to Figure 1J , the sample concentration and homogenization system 200 is shown in a flush configuration whereby the flush solution passes through valves 214 and 216, bypassing the first exchange column 210 and the second exchange column 212 to flow through the liquid mass flow meter 206 and out as waste. The homogenization valve 205 and the homogenizer loop 207 can be bypassed to form a cleaning path.

[0058] refer to Figure 1K , the sample concentration and homogenization system 200 is shown in a direct injection configuration, whereby the sample bypasses each of the first exchange column 210 and the second exchange column 212 to pass out of the valve 218 (eg, via the nebulizer 208) to be analyzed by the analysis system 102. Figure 1G to Figure 1JThe fluid path between valve 218 and nebulizer 208 is shown, but it can be appreciated that this flow path can be a direct connection (e.g., where the sample concentration and homogenization system 200 is included at the analysis system 102 or connected to the desolvation system of the analysis system) or can be a remote connection (e.g., where the sample concentration and homogenization system 200 is included at a remote sampling system 104), such as by including valve 148 and a transfer line (e.g., transfer line 144 described herein). The analysis results at the analysis system 102 can be compared to the volume or mass measured by the liquid mass flow meter 206 to determine the concentration of chemical elements present in the sample obtained by the remote sampling system 104. Although the sample concentration and homogenization system 200 is shown as having one and two exchange column configurations, it can be appreciated that more than two exchange columns can be implemented within the sample concentration and homogenization system 200 to provide additional chemical element retention, different groups of chemical elements retained, or the like.

[0059] refer to Fig. 1I , according to an embodiment of the present invention shows a calibration graph of counts versus concentration of magnesium present in a liquid sample prepared by sample concentration and homogenization system 200. The calibration graph includes an R value of 0.9993 for a concentration of magnesium present at 100 parts per trillion (ppq).

[0060] In an embodiment of the present invention, the analysis system 102 may include a sample collector 110 and / or a sample detector 130 configured to collect a sample 150 from a sample transfer line 144 coupled between the analysis system 102 and one or more remote sampling systems 104. The sample collector 110 and / or the sample detector 130 may include components such as pumps, valves, tubing, ports, sensors, etc. to receive the sample 150 from the one or more remote sampling systems 104 (e.g., via one or more sample transfer lines 144). For example, where the system 100 includes multiple remote sampling systems 104, each remote sampling system may include a dedicated sample transfer line 144 to couple to a separate portion of the sample collector 110 or a separate sample collector 110 of the analysis system 102. Additionally, the analysis system 102 may include a sampling device 160 (e.g., a local autosampler) local to the analysis system 102 configured to collect the sample 150.

[0061] The analysis system 102 also includes at least one analysis device 112 configured to analyze a sample to determine (e.g., in a liquid sample) trace element concentration, isotope ratio, etc. For example, the analysis device 112 may include an ICP spectrometer, which includes but is not limited to an inductively coupled plasma mass spectrometer (ICP / ICP-MS), an inductively coupled plasma atomic emission spectrometer (ICP-AES), or the like. In an embodiment, the analysis system 102 includes a plurality of analysis devices 112 (i.e., more than one analysis device). For example, the system 100 and / or the analysis system 102 may include a plurality of sampling loops, wherein each sampling loop introduces a portion of the sample into a plurality of analysis devices 112. As another example, the system 100 and / or the analysis system 102 may be configured to have a multi-position valve so that a single sample can be quickly and sequentially introduced into a plurality of analysis devices 112. For example, Figure 6 A remote sampling system 104 is shown in fluid communication with an analysis system 102, wherein the analysis system 102 includes a multi-position valve 600 coupled to three analysis devices (shown as an ICPMS 602, an ion chromatography (IC) column 604, and a Fourier transform infrared spectrometer (FTIR) 606) for analyzing samples received from the remote sampling system 104. Figure 6 An embodiment is shown in which the analysis system 102 includes three analysis devices, but the analysis system 102 may include fewer (e.g., less than three) or more (e.g., more than three) analysis devices 112. In an embodiment, the analysis device 112 may include, but is not limited to, ICPMS (e.g., for trace metal determination), ICPOES (e.g., for trace metal determination), ion chromatography (e.g., for anion and cation determination), liquid chromatography (LC) (e.g., for organic pollutant determination), FTIR infrared (e.g., for chemical composition and structural information determination), particle counter (e.g., for detecting undissolved particles), moisture analyzer (e.g., for detecting water in a sample), gas chromatography (GC) (e.g., for detecting volatile components), or the like. In embodiments, the plurality of analysis devices 112 may be located at the same location as the remote sampling system 104, while the system 100 may include one or more additional analysis devices 112 located remotely from the remote sampling system 104 for sample analysis additional to or different from those performed by the plurality of analysis devices 112. Alternatively or additionally, the plurality of analysis devices 112 may be located at a location different from the remote sampling system 104.

[0062] System 100 and / or analysis system 102 may be configured to report the concentration of an analyte at a location over time (hereinafter referred to as Fig.13Further shown). In some embodiments, the analysis device 112 may be configured to detect one or more trace metals in the sample 150. In other embodiments, the analysis device 112 may be configured for ion chromatography. For example, ions and / or cations in the sample 150 may be collected and delivered to the chromatography analysis device 112. In further embodiments, organic molecules, proteins, etc. in the sample may be collected and delivered to a high-resolution time-of-flight (HR-ToF) mass spectrometer analysis device 112 (e.g., using a nebulizer 156). Therefore, the system described herein can be used for a variety of applications, including but not necessarily limited to: pharmaceutical applications (e.g., using a central mass spectrometer analysis device connected to multiple pharmaceutical reactors), waste monitoring of one or more waste streams, semiconductor manufacturing facilities, etc. For example, a waste stream may be continuously monitored for contaminants and diverted to a tank when a contaminant is detected. As another example, one or more chemical streams may be continuously monitored via analysis of samples obtained by one or more of the remote sampling systems 104 connected to the analysis system 102, whereby contamination limits for each chemical stream may be set. After a contaminant exceeding a contamination limit is detected for a particular stream, the system 100 may provide an alert.

[0063] The remote sampling system 104 may be configured to selectively couple with at least one sample transfer line 144 such that the remote sampling system 104 is operable to be in fluid communication with the sample transfer line 144 for supplying a continuous liquid sample segment 150 to the sample transfer line 144. For example, the remote sampling system 104 may be configured to collect the sample 150 and supply the sample 150 to the sample transfer line 144 using, for example, a flow-through valve 148 that couples the remote sampling system 104 to the sample transfer line 144. Supplying the sample 150 to the sample transfer line 144 may be referred to as "pitch". The sample transfer line 144 may be coupled with a gas supply 146 and may be configured to deliver gas from a second location (and possibly a third location, a fourth location, etc.) to a first location. In this manner, the liquid sample segments supplied by the remote sampling system 104 are collected in a gas stream and delivered to a location of the analysis system 102 using gas pressure sample delivery.

[0064] In some embodiments, the gas in the sample delivery line 144 may include an inert gas, including but not necessarily limited to: nitrogen, argon, etc. In some embodiments, the sample delivery line 144 may include an unsegmented or minimally segmented pipe having an inner diameter of eight tenths of a millimeter (0.8 mm). However, the inner diameter of eight tenths of a millimeter is provided by way of example only and is not intended to limit the present invention. In other embodiments, the sample delivery line 144 may include an inner diameter greater than eight tenths of a millimeter and / or an inner diameter less than eight tenths of a millimeter. In some embodiments, the pressure in the sample delivery line 144 may range from at least about four (4) bars to ten (10) bars. However, this range is provided by way of example only and is not intended to limit the present invention. In other embodiments, the pressure in the sample delivery line 144 may be greater than ten bars and / or less than four bars. In addition, in some specific embodiments, the pressure in the sample delivery line 144 may be adjusted so that the sample 150 is distributed in a generally upward direction (e.g., vertically). This vertical orientation may facilitate the transfer of samples collected at a location below the analysis system 102 (eg, where the sample source(s) and remote sampling system(s) are positioned “downstairs” relative to the analysis system 102 ).

[0065] In some examples, the sample delivery line 144 may be coupled to a remote sampling system 104 in fluid communication with a first liquid bath (or chemical bath) and to an analysis system 102 in fluid communication with a second liquid bath (or chemical bath). In an embodiment of the present invention, the system 100 may include one or more leak sensors (e.g., mounted in a recess) to prevent or minimize overflow at a first location and / or one or more remote locations (e.g., a second location, a third location, a fourth location, etc.). A pump (such as a syringe pump or a vacuum pump) may be used to load the sample into the sampling device 106. A valve 148 may be used to select a sample 150 at the remote sampling system 104, and the sample 150 may be supplied to the sample delivery line 144, which may deliver the sample 150 to the analysis system 102 at the first location. Another pump (such as a diaphragm pump) may be used to pump a discharge port on the analysis system 102 and draw the sample 150 from the sample delivery line 144.

[0066] The system 100 can be implemented as a closed sampling system, where the gas and sample in the sample delivery line 144 are not exposed to the surrounding environment. For example, a housing and / or a sheath can enclose one or more components of the system 100. In some embodiments, one or more sample lines of the remote sampling system 104 can be cleaned between sample deliveries. In addition, the sample delivery line 144 can be cleaned between samples 150 (e.g., using a cleaning solution).

[0067] The sample delivery line 144 may be configured to selectively couple with the sample receiving line 162 (e.g., sample loop 164) at a first position, such that the sample loop 164 is operable to be in fluid communication with the sample delivery line 144 to receive a continuous liquid sample segment. Delivering the continuous liquid sample segment to the sample loop 164 may be referred to as "capturing". The sample loop 164 is also configured to selectively couple with the analysis device 112, such that the sample loop 164 is operable to be in fluid communication with the analysis device 112 to supply the continuous liquid sample segment to the analysis device 112 (e.g., when the system 100 has determined that enough liquid sample segments are available for analysis by the analysis system 102). In an embodiment of the present invention, the analysis system 102 may include one or more detectors configured to determine that the sample loop 164 contains a sufficient amount of continuous liquid sample segments for analysis by the analysis system 102. In one example, the sufficient amount of continuous liquid sample may include enough liquid sample to be sent to the analysis device 112. Another example of a continuous liquid sample of sufficient volume may include a continuous liquid sample in the sample receiving line 162 between the first detector 126 and the second detector 128 (e.g., as in Figure 7 ). In an embodiment, the first detector 126 and / or the second detector 128 may include an optical analyzer 132, an optical sensor 134, a conductivity sensor 136, a metal sensor 138, a conductivity sensor 140, and / or a pressure sensor 142. It is contemplated that the first detector 126 and / or the second detector 128 may include other sensors. For example, the first detector 126 may include an optical analyzer 132 that detects when the sample 150 enters the sample loop 164, and the second detector 128 may include another optical analyzer 132 that detects when the sample loop 164 is full. This example may be referred to as "successful capture". It should be noted that the optical analyzer 132 is provided by way of example only and is not intended to limit the present invention. Other example detectors include, but are not necessarily limited to: optical sensors, conductivity sensors, metal sensors, conductivity sensors, pressure sensors, etc.

[0068] refer to Figure 7, describing a system 100 that can determine when a continuous liquid sample segment is contained in a sample receiving line 162 and / or when a sample loop 164 contains a sufficient amount of the continuous liquid sample segment for analysis (e.g., by the analysis system 102). In an example embodiment, the first detector 126 can be configured to determine two or more states that can indicate the presence of liquid (e.g., a liquid sample segment) at a first location in the sample receiving line 162, the absence of liquid at the first location in the sample receiving line 162, and the like. For example, a first state (e.g., represented by a first logic level, such as a high state) can be used to indicate the presence of a liquid sample segment at a first location in the sample receiving line 162 (e.g., near the first detector 126), and a second state (e.g., represented by a second logic level, such as a low state) can be used to indicate the absence of a liquid sample segment at the first location in the sample receiving line 162 (e.g., a void or gas in the sample receiving line 162).

[0069] In some embodiments, the first detector 126 including the pressure sensor 142 can be used to detect the presence of liquid at a first location in the sample receiving line 162 (e.g., by detecting an increase in pressure in the sample receiving line 162 near the first location when the liquid is present). The first detector 126 can also be used to detect the absence of liquid at the first location in the sample receiving line 162 (e.g., by detecting a decrease in pressure in the sample receiving line 162 near the first location). However, the pressure sensor is provided by way of example only and is not intended to limit the present invention. In other embodiments, the first detector 126 including the optical sensor 134 can be used to detect the presence of liquid at a first location in the sample receiving line 162 (e.g., by detecting a decrease in light passing through the sample receiving line 162 near the first location when the liquid is present). The first detector 126 can also be used to detect the absence of liquid at the first location in the sample receiving line 162 (e.g., by detecting an increase in light passing through the sample receiving line 162 near the first location). In these examples, the first detector 126 can report the presence of a liquid sample at the first location as a high state and the absence of a liquid sample at the first location as a low state.

[0070] In some embodiments, the system 100 may also include one or more additional detectors, such as a second detector 126, a third detector, etc. For example, the second detector 126 may also be configured to determine two or more states, which may indicate the presence of liquid (e.g., a liquid sample segment) at a second location in the sample receiving line 162, the absence of liquid at the second location in the sample receiving line 162, etc. For example, a first state (e.g., represented by a first logic level, such as a high state) may be used to indicate the presence of a liquid sample segment at a second location in the sample receiving line 162 (e.g., near the second detector 126), and a second state (e.g., represented by a second logic level, such as a low state) may be used to indicate the absence of a liquid sample segment at the second location in the sample receiving line 162.

[0071] In some embodiments, a second detector 126 including a pressure sensor 142 may be used to detect the presence of liquid at a second location in the sample receiving line 162 (e.g., by detecting an increase in pressure in the sample receiving line 162 near the second location when liquid is present). The second detector 126 may also be used to detect the absence of liquid at a second location in the sample receiving line 162 (e.g., by detecting a decrease in pressure in the sample receiving line 162 near the second location). However, the pressure sensor is provided by way of example only and is not intended to limit the present invention. In other embodiments, a second detector 126 including an optical sensor 134 may be used to detect the presence of liquid at a second location in the sample receiving line 162 (e.g., by detecting a decrease in light passing through the sample receiving line 162 near the second location when liquid is present). The second detector 126 may also be used to detect the absence of liquid at a second location in the sample receiving line 162 (e.g., by detecting an increase in light passing through the sample receiving line 162 near the second location). In these examples, the second detector 126 may report the presence of a liquid sample at the second location as a high state and the absence of a liquid sample at the second location as a low state.

[0072] The controller 118 may be communicatively coupled to the one or more detectors 126 and configured to register liquid at a first location in the sample receiving line 162, a second location in the sample receiving line 162, another location in the sample receiving line 162, etc. For example, the controller 118 initiates a detection operation using the first detector 126, and liquid at a first location in the sample receiving line 162 may be registered by the controller 118 (e.g., when the controller 118 registers a change in state from low to high as determined by the first detector 126). The first detector 126 may then be monitored (e.g., continuously, at least substantially continuously), and the controller 118 may subsequently register the absence of liquid at the first location in the sample receiving line 162 (e.g., when the controller 118 registers a change in state from high to low as determined by the first detector 126).

[0073] Similarly, the controller 118 may also initiate a detection operation using the second detector 126, and liquid at the second location in the sample receiving line 162 may be registered by the controller 118 (e.g., when the controller 118 registers a change in state from low to high as determined by the second detector 126). The second detector 126 may then be monitored (e.g., continuously, at least substantially continuously), and the controller 118 may subsequently register the absence of liquid at the second location in the sample receiving line 162 (e.g., when the controller 118 registers a change in state from high to low as determined by the second detector 126).

[0074] The controller 118 and / or one or more detectors 126 may include or affect the operation of timers that provide the system 100 with timing of specific events (e.g., the presence or absence of liquid at a particular time at a plurality of locations in the sample receiving line 162). As an example, the controller 118 may monitor the time at which a change in state is registered by various detectors in order to determine whether to allow the liquid sample to be directed to the analysis system 102 (e.g., as opposed to directing the liquid to waste or a holding loop). As another example, the controller 118 may monitor, via the detector(s) 126, the time that liquid spends in the sample receiving line 162 and / or the sample loop 164 based on the change in state registered by the controller 118.

[0075] Liquid sample segment interruption and determination of appropriate liquid segment

[0076] Generally speaking, when obtaining a sample close to an associated analytical device (e.g., an autosampler next to the analytical device), the sample can span the entire distance between the sample source and the analytical device without requiring a large sample volume. However, for long-distance transmission of the sample, filling the entire transmission line 144 between the remote sampling system 104 and the analytical system 102 (e.g., up to hundreds of meters of sample length) may be prohibitive or undesirable, such as due to environmental concerns about disposing of unused sample portions, sample viscosity, etc. Accordingly, in an embodiment, the remote sampling system 104 does not fill the entire transmission line 144 with the sample, but rather, a liquid sample segment representing a small portion of the total transmission line 144 volume is sent through the transmission line 144 to be analyzed by the analytical system 102. For example, although the transmission line 144 may be hundreds of meters long, the sample may occupy about one meter or less of the transmission line 144 at any given time during transfer to the analytical system 102. While sending a liquid sample segment through a pipeline can reduce the amount of sample sent from the remote sampling system 104, the sample can cause bubbles or gaps / voids in the sample transfer line 144 during transfer to the analysis system 102. Such bubbles or gaps / voids can form due to conditions associated with long distance transfer of the sample (such as changes in orifices between tubing during transfer), due to interaction with residual cleaning fluid used to clean the line between samples, due to reaction with residual fluid in the line, due to pressure differential(s) along the span of the transfer line, or the like. For example, as in Figure 8 , a liquid sample 800 may be sent from the remote sampling system 104 through the transfer line 144 to a first location where the analysis system 102 is located. The volume of the total sample obtained by the remote sampling system 104 is Figure 8 V TOT As shown, gaps or voids 802 may be formed in the transfer line 144 during transfer from the remote sampling system 104. The gaps or voids 802 divide several sample sections 804 that do not contain a sufficient amount or volume of sample for analysis by the analysis system 102. Such sample sections 804 may be separated from each other by a volume (shown as V) sufficient for analysis by the analysis system 102. SAMPLE ) before and / or after the larger sample segment 806. In an embodiment, the amount of sample collected by the remote sampling system 104 (e.g., V TOT ) to provide a sufficient amount of sample 150 to be analyzed by the analysis device 112. For example, the volume ratio of the amount of sample 150 "delivered" to the amount of sample 150 "captured" (e.g., V TOT / V SAMPLE) is at least about one and one quarter (1.25). However, this ratio is provided by way of example only and is not intended to limit the present invention. In some embodiments, the ratio is greater than one and one quarter, and in other embodiments, the ratio is less than one and one quarter. In one example, two and one-half milliliters (2.5 mL) of sample 150 (e.g., concentrated sulfuric acid or nitric acid) are delivered, and one milliliter (1 mL) of sample 150 is captured. In another example, one and one-half milliliters (1.5 mL) of sample 150 are delivered, and one milliliter (1 mL) of sample 150 is captured. In embodiments of the present invention, the amount of sample 150 "delivered" is adjusted to take into account the distance between the first position and the second position, the amount of sample delivery line tubing between the first position and the second position, the pressure in the sample delivery line 144, etc. In summary, V TOT / V SAMPLE The ratio of may be greater than one to account for the formation of gaps / voids 802 and sample segments 804 in the sample delivery line 144 during transfer.

[0077] The system 100 can select which of the plurality of remote sampling systems 104 should transmit their respective samples to the analysis system 102 (e.g., “route”), whereby the detector 126 facilitates determining whether sufficient sample is present (e.g., V in the sample loop 164). SAMPLE ) to be sent to the analysis system 102 (e.g., "captured"), or whether there is a void or gap in the line (e.g., between the detectors 126) such that the sample should not be sent to the analysis system 102 at that particular time. If there were to be bubbles or gaps (e.g., in the sample loop 164), their presence could compromise the accuracy of the analysis of the sample, particularly if the sample would be diluted prior to introduction to the analysis device 112 or further diluted at the analysis device 112, as the analysis device 112 could be analyzing a "blank" solution.

[0078] In some embodiments, the system 100 may be configured to determine when a continuous liquid sample segment (e.g., sample segment 806) is contained in the sample receiving line 162 and / or the sample loop 164, so that the system 100 can avoid transmitting a gap or void 802 or a smaller sample segment 804 to the analysis device 112. For example, the system 100 may include a first detector 126 at a first location along the sample receiving line 162 and a second detector 126 at a second location along the sample receiving line 162 (e.g., downstream of the first location). The system 100 may also include a sample loop 164 between the first detector 126 and the second detector 126. In embodiments, a valve (such as may be configured in at least two flow paths (e.g., Figure 3A A first flow path configuration of valve 148 is shown in FIG. Figure 3BThe system 100 may be positioned between the first detector 126 and the sample loop 164 and between the second detector 126 and the sample loop 164. In an embodiment of the present invention, the system 100 may determine that a continuous liquid sample segment is contained in the sample receiving line 162 and / or the sample loop 164 by simultaneously registering liquid at both the first position and the second position without registering a state change from high to low by the first detector 126 at the first position. In other words, the liquid sample has been continuously transferred from the first detector 126 to the second detector 126 without the first detector 126 detecting a state change until the second detector 126 recognizes the presence of the liquid sample.

[0079] In an example embodiment where two or more detectors are used to determine when a sample receiving line contains a continuous liquid segment between the detectors, a liquid segment is received in the sample receiving line. Figure 7 , the sample receiving line 162 receives the liquid sample segment. Next, the liquid segment is registered at a first location in the sample receiving line by initiating a detection operation using a first detector, the first detector being configured to detect the presence and / or absence of the liquid segment at the first location in the sample receiving line. For example, referring to Figure 7 , the first detector 126 detects the liquid sample segment at the first location in the sample receiving line 162 as a change of state from low to high. Fig. 9 , a liquid sample segment can be detected at the first position at time t1 and t5. Then, after registering the liquid segment at the first position, the first detector is monitored. For example, referring to Figure 7 , the first detector 126 is monitored by the controller 118, and the first detector 126 detects the absence of the liquid sample segment at the first location in the sample receiving line 162 as a state change from high to low. Fig. 9 , monitoring of the first location begins (eg, continuously, at least substantially continuously) at times t1 and t5, and the absence of the liquid sample segment may be detected at the first location at t3 and t6.

[0080] Similarly, a liquid segment is registered at a second location in the sample receiving line by initiating a detection operation using a second detector configured to detect the presence and / or absence of the liquid segment at the second location in the sample receiving line. Figure 7 , the second detector 126 detects the liquid sample segment at the second location in the sample receiving line 162 as a state change from low to high. Fig. 9 , a liquid sample segment is detected at the second location at time t2 and t7. Then, after registering the liquid segment at the second location, the second detector is monitored. For example, referring to Figure 7, the second detector 126 is monitored by the controller 118, and the second detector 126 detects the absence of the liquid sample segment at the second location in the sample receiving line 162 as a state change from high to low. Fig. 9 , monitoring of the second location begins (eg, continuously, at least substantially continuously) at times t2 and t7, and the absence of the liquid sample segment may be detected at the second location at t4 and t8.

[0081] When liquid is registered at both the first location and the second location simultaneously, a continuous liquid segment is registered in the sample receiving line between the first detector and the second detector. Figure 7 , when the high state indicates that a liquid sample segment is present at each of the first detector 126 and the second detector 126, the controller 118 registers the consecutive liquid sample segment in the sample receiving line 162 (eg, present between the first detector 126 and the second detector 126). Fig. 9 , when a liquid sample segment is detected at the second position, a continuous liquid sample segment may be registered at time t2.

[0082] In some embodiments, a logical AND operation may be used to determine when a consecutive liquid segment is registered in the sample receiving line and initiate transfer of the consecutive liquid segment from the sample receiving line to the analytical device. Figure 7 , the controller 118 may use a logical AND operation on the high state at each of the first detector 126 and the second detector 126, and initiate the selective coupling of the sample loop 164 with the analysis device 112 using the valve 148, so that the sample loop 164 is operable to be in fluid communication with the analysis device 112 to supply the continuous liquid sample segment to the analysis device 112. In some embodiments, the controller 118 may determine whether to switch the valve 148 to supply the continuous liquid sample segment to the analysis device 112 only when a state change from low to high is registered at the first detector 126 or the second detector 126. In some embodiments, the system 100 requires that the high state at the second detector 126 be maintained for a period of time (e.g., 10 seconds) before initiating the selective coupling of the sample loop 164 with the analysis device. Fig. 9 t shown in Δ For example, a timer or timing functionality of the controller 118 and / or processor 120 may verify the period of time that the second detector 126 has maintained the high state, whereby once the second detector 126 has maintained the high state for time t Δ (eg, threshold time) and if the first detector is in a high state, the controller 118 may determine that a sufficient liquid sample segment (eg, Figure 8 The segment 806 in has been captured, and the valve 148 can be switched to supply a continuous liquid sample segment to the analysis device 112. Duration t ΔIt may correspond to a period of time beyond which it is not possible for the second detector to measure voids or bubbles, which period of time may vary depending on the flow rate or other delivery conditions of the sample.

[0083] In some embodiments, the controller 118 may monitor the timing of the first detector 126 in the high state and / or the low state. For example, in embodiments where the flow characteristics of the sample delivered from the remote sampling system 104 are known, in the event that the high state at the second detector 126 is confirmed or not confirmed, the first detector 126 may be monitored to determine the length of time spent in the high state to approximate whether there will be enough liquid sample in the sample receiving line 162 and / or the sample loop 164 for the controller 118 to send the sample to the analysis device 112. For example, for a given flow rate of the sample, the volume of the sample may be approximated by monitoring the length of time the first detector 126 has been in the high state. However, due to fluctuations in pump functionality, the type of sample delivered, sample viscosity, duration of delivery, delivery distance, ambient temperature conditions, delivery line 144 temperature conditions, or the like, the flow rate of the sample may not be readily known, so the functionality of the second detector 126 may be informative.

[0084] In an embodiment of the present invention, the systems and techniques described herein may be used to determine that a portion of the sample receiving line between the first detector 126 and the second detector 126 (eg, a sample loop) is full without bubbles. Fig. 9 The absence of liquid sample in the first location between times t3 and t5 described above may correspond to the presence of bubbles in the sample receiving line 162. When the system 100 has reached a state in which no bubbles will be present in the sample receiving line 162, the controller 118 switches the valve 148 to allow fluid in the sample loop 164 to pass to the analysis device 112 (for analysis or sample conditioning prior to analysis).

[0085] Example Method

[0086] Fig.10Process 810 is depicted in an example embodiment in which two detectors are used to determine when a sample receiving line contains a sufficient amount of sample in a continuous liquid sample segment for analysis by an analysis system without gaps or voids in the continuous liquid sample segment. As shown, a liquid segment is received in the sample receiving line (box 812). For example, the sample receiving line 162 may receive a sample obtained by the remote sampling system 104 and transmitted through the transfer line 144. Process 810 also includes registering a liquid segment at a first position in the sample receiving line using a first detector, the first detector being configured to detect the presence and / or absence of the liquid segment as it travels through the first position (box 814). For example, the first detector 126 may measure the presence of a liquid sample segment at a first position in the sample receiving line 162. Reference Fig. 9 , a liquid sample segment is detected at the first position at times t1 and t5.

[0087] Next, after registering the liquid segment at the first location, the first detector is monitored (block 816). For example, the first detector 126 may be monitored by the controller 118 to determine whether a liquid segment is not present at the first location in the sample receiving line 162 (e.g., whether the first detector 126 has transitioned from a high state (indicating that sample fluid is detected) to a low state, wherein sample fluid is not detected). Fig. 9 , monitoring the first location begins (e.g., continuously, at least substantially continuously) at times t1 and t5. Next, registering a continuous liquid segment in the sample receiving line when the absence of a liquid segment at the first location in the sample receiving line was not registered before registering a liquid segment at a second location in the sample receiving line downstream of the first location by performing a detection operation using a second detector, the second detector being configured to detect the presence and / or absence of a liquid segment at the second location (block 818). For example, referring to Fig. 9, the first detector 126 detects the presence of sample fluid at times t1 and t5, while the second detector 126 detects the presence of sample fluid at times t2 and t7. In the event that the first detector 126 does not detect the absence in the transition time before the second detector detects the liquid sample segment, the second detector (starting at time t2) will register the sample segment at the first detector only between times t1 and t3. At this time, the controller 118 can direct the valve 148 to switch to send the sample contained in the sample loop 164 to the analysis device 112. Although the first detector 126 registers the presence of liquid sample at t5, the first detector also detects the absence of liquid sample at t6 before the second detector 126 subsequently detects the presence of liquid sample at t7. In this way, the system 100 will recognize that a gap or void (e.g., gap / void 802) exists in the sample loop 164 and will not switch the valve 148 for analysis, but will allow insufficient sample segments (e.g., liquid segments 804) to pass to waste. As described herein, a timer (eg, implemented by controller 118) may be used to time the second detector 128 once it has been maintained in a high state for a particular period of time (eg, t Δ ) to switch valve 148.

[0088] Control System

[0089] The system 100 (including some or all of its components) can operate under computer control. For example, the processor 120 can be included with or in the system 100 to control the components and functions of the system described herein using software, firmware, hardware (e.g., fixed logic circuits), manual processing, or a combination thereof. The terms "controller," "functionality," "service," and "logic" as used herein generally represent software, firmware, hardware, or a combination of software, firmware, and hardware in conjunction with a control system. In the case of a software implementation, a module, functionality, or logic represents a program code that performs a specified task when executed on a processor (e.g., a central processing unit (CPU) or several CPUs). The program code can be stored in one or more computer-readable memory devices (e.g., internal memory and / or one or more tangible media), etc. The structures, functions, methods, and techniques described herein can be implemented on various commercial computing platforms with various processors.

[0090] For example, one or more components of the system, such as the analysis system 102, the remote sampling system 104, the valve 148, the pump, and / or the detector (e.g., the first detector 126, the second detector 126, the sample detector 130) may be coupled to a controller that controls the collection, delivery, and / or analysis of the sample 150. For example, the controller 118 may be configured to switch the valve 148 that couples the sample loop 164 to the analysis system 102 and direct the sample 150 from the sample loop 164 to the analysis system 102 when a successful "capture" is indicated by the first detector 126 and the second detector 126 (e.g., when both sensors detect liquid). In addition, the controller 118 may implement functionality to determine an "unsuccessful capture" (e.g., when the sample loop 164 is not filled with enough sample 150 for complete analysis by the analysis system 102). In some embodiments, an "unsuccessful capture" is determined based on, for example, a change in the signal strength of a signal received from a sensor (such as the first detector 126 or the second detector 126). In other embodiments, “unsuccessful capture” is determined when the first detector 126 has indicated a sample 150 in the sample receiving line 162 and a predetermined amount of time has passed where the second detector 126 has not indicated a sample 150 in the sample receiving line 162 .

[0091] In some embodiments, the controller 118 is communicatively coupled to an indicator at a remote location (such as a second location) and provides an indication (e.g., an alert) at the second location when insufficient sample 150 is received at the first location. The indication can be used to (e.g., automatically) initiate additional sample collection and delivery. In some embodiments, the indicator provides an alert to the operator (e.g., via one or more indicator lights, via a display readout, a combination thereof, etc.). In addition, the indication can be timed and / or initiated based on one or more predetermined conditions (e.g., only when multiple samples have been missed). In some embodiments, the indicator can also be activated based on conditions measured at the remote sampling location. For example, the detector 130 at the second location can be used to determine when the sample 150 is provided to the remote sampling system 104, and the indicator can be activated when the sample 150 is not collected.

[0092] In some embodiments, the collector 118 may be operable to provide different timings for collecting samples from different remote locations and / or for different types of samples 150. For example, the controller 118 may be alerted when the remote sampling system 104 is ready to deliver the sample 150 to the sample delivery line 144, and may initiate the delivery of the sample 150 into the sample delivery line 144. The controller 118 may also be communicatively coupled to one or more remote sampling systems 102 to receive (and possibly log / record) identification information associated with the sample 150, and / or control the order in which the samples 150 are delivered within the system 100. For example, the controller 118 may queue multiple samples 150 remotely and coordinate the delivery of the samples through one or more sample delivery lines 144. In this manner, the delivery of samples 150 may be coordinated along multiple simultaneous flow paths (e.g., through multiple sample delivery lines 144), one or more samples 150 may be in transit while one or more additional samples 150 are being acquired, and the like. For example, Fig.11 An example control flow diagram of the system 100 is shown, wherein the analysis system 102 is shown in fluid communication with two remote sample locations (shown as sample location 900 and sample location 902) via two remote sampling systems 104a and 104b and associated transfer lines 144a and 144b. In the embodiment shown, the analysis system 102 sends commands (shown as 904a and 904b) to each of the remote sampling systems 104a and 104b, respectively. The remote sampling systems 104a and 104b each transfer samples obtained at the corresponding sampling locations (sampling location 900 for the remote sampling system 104a, sampling location 902 for the remote sampling system 104b) to the analysis system 102 via transfer lines 144a and 144b, respectively. The analysis system 102 then processes the samples to determine the amounts of various chemical species contained therein. The analysis system 102 then determines whether any amount of the chemical species exceeds an element-specific limit (e.g., a limit for a specific contaminant in the sample). In an embodiment, the system 100 may independently set contamination limits for each sampling location and independently set contamination limits for a specific chemical species at each sampling location. For example, the tolerance for a specific metal contaminant may be reduced during processing, so a downstream chemical sample may have a lower limit for a specific chemical species than a chemical sample taken upstream. Fig.11, the analysis system 102 determines that no chemical species exceeds any element-specific limit of the sample obtained by the remote sampling system 104a at the sampling location 900. The analysis system 102 then sends an indication, shown as 908a, to the CIM host 906 to allow continuation of the process application at the sampling location 900 due to the operation of the process application below the element-specific limit. The analysis system 102 has determined that at least one chemical species present in the sample obtained by the remote sampling system 104b at the sampling location 902 exceeds the element-specific limit (e.g., the limit of a contaminant in the sample). The analysis system 102 then sends an indication, shown as 908b, to the CIM host 906 to send an alert directed to the process application at the sampling location 902 due to the operation of the process application above the element-specific limit. The CIM host 906 then directs the process at the sampling location 902 to stop operation via a stop process command 910 based on the analysis of the sample obtained by the remote sampling system 104b at the sampling location 902. In an embodiment, communication between the CIM host 906 and components of the system 100 may be facilitated by the SECS / GEM protocol. In an embodiment, the system 100 may include context-specific actions when an element is determined to be above an element-specific limit in a sample at a particular sample location, wherein such context-specific actions may include, but are not limited to, ignoring the alert and continuing process operation, stopping process operation, running a system calibration and then rerunning the out-of-limit sample, or the like. For example, after a first alert, the analysis system 102 may perform a calibration (or another calibration) and then rerun the sample, while a subsequent alert (e.g., a second alert) will cause the CIM host 906 to command the process at the violating sample location to pause operation.

[0093] The controller 118 may include a processor 120, a memory 122, and a communication interface 124. The processor 120 provides the processing functions of the controller 118 and may include any number of processors, microcontrollers, or other processing systems, and resident or external memory for storing data and other information accessed or generated by the controller 118. The processor 120 may execute one or more software programs that implement the techniques described herein. The processor 120 is not limited by the materials from which it is formed or the processing mechanisms employed therein, and as such, may be implemented via semiconductor(s) and / or transistors (e.g., using electronic integrated circuit (IC) components), etc.

[0094] The memory 122 is an example of a tangible, computer-readable storage medium that provides storage functionality to store various data associated with the operation of the controller 118 (such as software programs and / or program code segments or other data that instruct the processor 120 and possibly other components of the controller 118 to perform the functions described herein). Thus, the memory 122 can store data such as a program of instructions for operating the system 100 (including its components), etc. It should be noted that although a single memory is described, a wide variety of types and combinations of memories (e.g., tangible, non-transitory memories) may be employed. The memory 122 may be integrated with the processor 120, may include independent memories, or may be a combination of both.

[0095] The memory 122 may include, but is not necessarily limited to, removable and non-removable memory components such as random access memory (RAM), read-only memory (ROM), flash memory (e.g., secure digital (SD) memory card, mini SD memory card, and / or micro SD memory card), magnetic memory, optical memory, universal serial bus (USB) memory device, hard disk memory, external memory, etc. In an embodiment, the system 100 and / or the memory 122 may include a removable integrated circuit card (ICC) memory, such as the memory 122 provided by a subscriber identity module (SIM) card, a universal subscriber identity module (USIM) card, a universal integrated circuit card (UICC), etc.

[0096] The communication interface 124 is operably configured to communicate with components of the system. For example, the communication interface 124 may be configured to transmit data for storage in the system 100, retrieve data from a memory in the system 100, etc. The communication interface 124 is also communicatively coupled to the processor 120 to facilitate data transfer between components of the system 100 and the processor 120 (e.g., for transferring input received from a device communicatively coupled to the controller 118 to the processor 120). It should be noted that while the communication interface 124 is described as a component of the controller 118, one or more components of the communication interface 124 may be implemented as external components communicatively coupled to the system 100 via a wired and / or wireless connection. The system 100 may also include and / or be connected to one or more input / output (I / O) devices (e.g., via the communication interface 124), which include but are not necessarily limited to: a display, a mouse, a touchpad, a keyboard, etc.

[0097] The communication interface 124 and / or the processor 120 may be configured to communicate with a variety of different networks, including but not necessarily limited to: a wide area cellular telephone network, such as a 3G cellular network, a 4G cellular network, or a Global System for Mobile Communications (GSM) network; a wireless computer communication network, such as a Wi-Fi network (e.g., a wireless local area network (WLAN) operating using the IEEE 802.11 network standard); the Internet; a wide area network (WAN); a local area network (LAN); a personal area network (PAN) (e.g., a wireless personal area network (WPAN) operating using the IEEE 802.15 network standard); a public telephone network; an external network; an internal network, etc. However, this list is provided by way of example only and is not intended to limit the present invention. In addition, the communication interface 124 may be configured to communicate with a single network or multiple networks across different access points.

[0098] Example 1 - Example Monitoring System

[0099] In general, the system 100 described herein may incorporate any number of remote sampling systems 104 to acquire samples from any number of sampling locations. Fig.12In the embodiment shown in , the system 100 includes five remote sampling systems 104 (shown as 104A, 104B, 104C, 104D, 104E) located at five different locations of a processing facility that utilizes chemical baths, bulk chemicals, environmental effluents, and other liquid samples. The remote sampling systems 104 obtain samples at different locations for transmission to an analysis system 102 located remote from each of the five remote sampling systems 104. The first remote sampling system 104A is located near the deionized water pipeline 1000 and is spaced apart from the analysis system 102 by a distance of about forty meters (40m) (shown as d5). The second remote sampling system 104B is located near the distribution valve point 1002 and is spaced apart from the analysis system 102 by a distance of about eighty meters (80m) (shown as d4). The third remote sampling system 104C is located near the chemical supply tank 1004 and is spaced apart from the analysis system 102 by a distance of about eighty meters (80m) (shown as d3). The chemical supply tank 1004 is located remotely from the chemical storage tank 1008 and is supplied with chemicals from the chemical storage tank 1008. A fourth remote sampling system 104D is located proximate to the chemical supply tank 1006 and is spaced apart from the analysis system 102 by a distance of about eighty meters (80 m) (shown as d2). The chemical supply tank 1006 is located remotely from the chemical storage tank 1008 and is supplied with chemicals from the chemical storage tank 1008. A fifth remote sampling system 104E is located proximate to the chemical storage tank 1004 and is spaced apart from the analysis system 102 by a distance of about three hundred meters (300 m) (shown as d1). Although five remote sampling systems 104 are shown, the system 100 may utilize more than five remote sampling systems 104 to monitor ultra-trace impurities throughout the process facility, such as at other process streams, chemical baths, bulk chemical storage, environmental effluents, and other liquid samples. In one embodiment, sample delivery from the remote sampling system 104 to the analysis system is provided at a rate of approximately one and a half meters per second (1.2 m / s), thereby providing near instantaneous analysis (eg, ICPMS analysis) of ultra-trace impurities throughout the processing facility.

[0100] Example 2 - Reproducibility

[0101] In one embodiment, the analysis system 102 is located one hundred meters (100 m) from the remote sampling system 104. The remote sampling system 104 obtains twenty discrete samples and transports them to the analysis system 102 for determining the signal intensity of each chemical species present in each of the twenty discrete samples. Each discrete sample includes the following chemical species: lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al), calcium (Ca), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), germanium (Ge), strontium (Sr), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), barium (Ba), cerium (Ce), hafnium (Hf), tungsten (W), and lead (Pb). After analysis by the analysis system 102, it is determined that the relative standard deviation (RSD) is less than three percent (<3%) for all chemical species across all twenty discrete samples. Accordingly, the example system 100 at one hundred meters between the analysis system 102 and the remote sampling system 104 provides reliable reproducibility from obtaining a sample, transferring the sample one hundred meters to the analysis system 102 (eg, via transfer line 144 ), and analyzing the sample with the analysis system 102 .

[0102] Example 3 - Comparison with Manual Sampling - Semiconductor Process Example

[0103] refer to Fig.13, a graph showing metal contamination of a chemical bath (SC-1 bath) of a semiconductor manufacturing process over time is provided. The graph includes a portion 1100 showing data points of metal contamination measured from manual samples taken at three time points. The graph also includes a portion 1102, which shows data points of metal contamination measured from manual samples from portion 1100 superimposed on data points of metal contamination measured from samples taken from system 100 (e.g., from remote sampling system 104) at a sampling frequency that exceeds the sampling frequency of the manual sampling method (e.g., at least sixteen to seventeen times more frequently). As shown in portion 1102, a gradual increase in contaminants occurs over time during the semiconductor manufacturing process. Lifetime or life counting methods (e.g., manual sampling techniques from portion 1100) that determine when to swap chemicals in a particular semiconductor process are generally unable to account for the specificity of metal contamination over time. As such, chemicals are typically swapped without knowing the metal contaminants in the bath. This can result in over-exchanges, where the chemical bath may actually provide additional wafer processing but is replaced anyway (e.g., resulting in a loss of process availability time), or under-exchanges, where the chemical bath actually has unacceptable metal contamination but is not replaced until a later time (e.g., possibly damaging wafers produced by the process). As can be seen in section 1102, metal contamination can be automatically tracked at a higher frequency with the system 100. A contamination limit 1104 is set to alert the CIM host 906 when a contamination limit is reached for a chemical bath. Thus, the system 100 can automatically cause process operation to cease when the contamination limit 1104 is reached (e.g., to avoid under-exchanges), while allowing the process to continue when the contamination limit 1104 is not reached, thereby increasing process availability time when feasible (e.g., to avoid over-exchanges).

[0104] in conclusion

[0105] In embodiments, various analytical devices may utilize the structures, techniques, methods, etc. described herein. Thus, although a system is described herein, various analytical instruments may utilize the described techniques, methods, structures, etc. These devices may be configured to have limited functionality (e.g., a thin device) or to have robust functionality (e.g., a thick device). Thus, the functionality of a device may be related to the software or hardware resources of the device (e.g., processing power, memory (e.g., data storage capacity), analytical capabilities, etc.).

[0106] Generally speaking, any function described herein can be implemented using hardware (e.g., fixed logic circuitry, such as integrated circuits), software, firmware, manual processing, or a combination thereof. Therefore, the blocks discussed in the above disclosure generally represent hardware (e.g., fixed logic circuits, such as integrated circuits), software, firmware, or a combination thereof. In the case of a hardware configuration, the various blocks discussed in the above disclosure can be implemented as integrated circuits together with other functionalities. Such an integrated circuit may include all functions of a given block, system, or circuit, or a portion of the functions of the block, system, or circuit. In addition, the elements of a block, system, or circuit may be implemented across multiple integrated circuits. Such an integrated circuit may include various integrated circuits, including (but not necessarily limited to) monolithic integrated circuits, flip-chip integrated circuits, multi-chip module integrated circuits, and / or mixed signal integrated circuits. In the case of a software implementation, the various blocks discussed in the above disclosure represent executable instructions (e.g., program codes) that perform a specified task when executed on a processor. These executable instructions may be stored in one or more tangible computer-readable media. In some such cases, the entire system, block, or circuit may be implemented using its software or firmware equivalents. In other cases, portions of a given system, block, or circuit may be implemented in software or firmware, while other portions are implemented in hardware.

[0107] Although the subject matter has been described in language specific to structural features and / or process operations, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as example forms of implementing the claims.

Claims

1. A sample concentration and homogenization system for analyzing a liquid sample by an analysis system, the sample concentration and homogenization system comprising: at least a first valve switchable between different flow path configurations; at least a first column configured to hold at least one chemical of interest from a liquid sample, the first column fluidly coupled to the first valve; a flow meter coupled to the first column in a first flow path configuration to measure an amount of liquid sample passing through the first column; wherein the system comprises a second flow path configuration in which the flow meter is not in fluid communication with the first column; and The system further comprises a homogenization valve and a homogenizer circuit, wherein the homogenization valve is operable to place the homogenizer circuit in fluid communication with the first column in a second flow path configuration.

2. The sample concentration and homogenization system of claim 1, wherein the homogenizer circuit is adapted to capture and homogenize the liquid sample.

3. The sample concentration and homogenization system of claim 2, further comprising a gas valve configured to inject gas bubbles into the system when the homogenization valve places the homogenizer loop in fluid communication with the first column.

4. The sample concentration and homogenization system of claim 3, further comprising a bubble sensor adjacent to the homogenizer loop.

5. The sample concentration and homogenization system according to claim 1, further comprising: A controller is operably coupled to the flow meter and the first valve, the controller being configured to compare an amount of liquid sample passing through the first column measured by the flow meter with a sample threshold value.

6. The sample concentration and homogenization system of claim 5, wherein the controller switches the first valve from the first flow path configuration to the second flow path configuration when the amount of liquid sample passed through the first column measured by the flow meter at least meets the sample threshold.

7. The sample concentration and homogenization system of claim 5, further comprising: A computer memory is accessible by the controller, the computer memory storing the sample threshold value.

8. The sample concentration and homogenization system of claim 5, further comprising: A user interface is accessible by the controller, the user interface being configured to receive the sample threshold value from a user.

9. The sample concentration and homogenization system of claim 1, further comprising a second column, and wherein the first column is a different column type than the second column.

10. The sample concentration and homogenization system of claim 9, wherein at least one of the first column or the second column comprises an anion exchange column, a cation exchange column, a chelating column or a chromatography column.

11. The sample concentration and homogenization system of claim 1, further comprising: A sprayer is in fluid communication with the first column and the homogenizer circuit when the plurality of valves are in the second flow path configuration.

12. The sample concentration and homogenization system of claim 1, further comprising: A transfer line is coupled between the third valve and the analysis system, and when the plurality of valves are in the second flow path configuration, the transfer line is in fluid communication with the first column.

13. A sample concentration and homogenization system for analyzing a liquid sample by an analysis system, the sample concentration and homogenization system comprising: a valve configured to switch between at least a first flow path configuration and a second flow path configuration; a column configured to separate one or more analytes of interest from a liquid sample, the column being in fluid communication with the valve in each of the first flow path configuration and the second flow path configuration; a flow meter fluidly coupled to each of the valve and the column when the valve is in the first flow path configuration, the flow meter not fluidly coupled to the column when the valve is in the second flow path configuration, the flow meter configured to measure an amount of liquid sample passing through the column when the valve is in the first flow path configuration; as well as A homogenizer circuit is fluidly connected to the column in the second flow path configuration and is adapted to hold and homogenize the liquid sample.

14. The sample concentration and homogenization system of claim 13, further comprising: A controller is operably coupled to the flow meter and the valve, the controller being configured to compare an amount of liquid sample passing through the column measured by the flow meter to a sample threshold value.

15. The sample concentration and homogenization system of claim 14, further comprising: A computer memory is accessible by the controller, the computer memory storing the sample threshold value.

16. The sample concentration and homogenization system of claim 14, further comprising: A user interface is accessible by the controller, the user interface being configured to receive the sample threshold value from a user.

17. The sample concentration and homogenization system of claim 14, wherein the controller switches the valve from the first flow path configuration to the second flow path configuration when the amount of liquid sample passed through the column measured by the flow meter at least meets the sample threshold.

18. A sample concentration and homogenization system as described in claim 13, wherein when the valve is in the second flow path configuration, the column and the valve are connected to the eluent fluid, and wherein when the valve is in the second flow path configuration, the flow meter is not connected to the eluent fluid.

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