DE102018121668A1 - Automated system for remote inline concentration of extremely low concentrations in pure chemicals - Google Patents

Abstract

Systems and methods for concentrating a remote sample for analysis are described. One embodiment of the sample concentration system includes, but is not limited to: a plurality of valves including at least a first valve, a second valve, and a third valve; a plurality of columns including at least a first column and a second column, the first column fluidly coupled to the first valve, the second column fluidly coupled to the second valve; and a flow meter coupled to the third valve, wherein the flow meter is fluidly coupled to each of the first column and the second column when the plurality of valves are in a first flow path arrangement to measure an amount of the liquid sample passing through the first column and the second column have flowed, wherein the plurality of valves includes a second flow path arrangement and a third flow path arrangement.

Description

CROSS-REFERENCE TO RELATED

PATENT APPLICATIONS

The present application claims priority over 35 U.S.C. Section 119 (e) of the provisional US application, serial no. No. 62 / 555,337, filed September 7, 2017, entitled "AUTOMATED SYSTEM FOR REMOTE INLINE CONCENTRATION OF ULTRA-LOW CONCENTRATIONS IN PURE CHEMICALS" (Automated system for remote in-line concentration of extremely low concentrations in pure chemicals). The provisional US application serial no. 62 / 555,337 is hereby incorporated by reference in its entirety.

BACKGROUND

In many laboratory setups, it is often necessary to analyze a large number of chemical or biological samples simultaneously. To streamline such procedures, the handling of samples has been mechanized. Such mechanized sampling may be referred to as autosampling and may be performed using an automated sampling device, an autosampler.

Inductively Coupled Plasma Spectroscopy (ICP Spectroscopy) is an analytical technique widely used to determine trace element concentrations and isotopic ratios in liquid samples. ICP spectroscopy uses electromagnetically generated, partially ionized argon plasma that reaches a temperature of approximately 7000K. When a sample is introduced into the plasma, the high temperature causes sample atoms to become ionized or emit light. Since each chemical element produces a characteristic mass or emission spectrum, measurement of the spectra of the emitted mass or light allows determination of the elemental composition of the original sample.

Sample introduction systems may be used to introduce the liquid samples into the ICP spectroscopy device (eg, an inductively coupled plasma mass spectrometer (ICP / ICP-MS), an inductively coupled plasma atomic emission spectrometer (ICP-AES), or the like) or another sample detector or introduce another analyzer for analysis. For example, a sample introduction system may withdraw a sub-sample of a fluid sample from a container and thereafter transport the sub-sample to a nebulizer which converts the sub-sample into a polydisperse aerosol suitable for ionization in plasma by the ICP spectroscopy device. The aerosol is then sorted in a spray chamber to remove the larger aerosol particles. Upon exiting the spray chamber, the aerosol is introduced into the plasma through a plasma torch assembly of the ICP-MS or ICP-AES device for analysis.

SUMMARY

Systems and methods for concentrating a remote sample for analysis are described. One embodiment of the sample concentration system includes, but is not limited to: a plurality of valves including at least a first valve, a second valve, and a third valve; a plurality of columns including at least a first column and a second column, the first column fluidly coupled to the first valve, the second column fluidly coupled to the second valve; and a flowmeter coupled to the third valve, wherein the flowmeter is fluidly coupled to each of the first column and the second column when the plurality of valves are in a first flowpath arrangement to measure an amount of the fluid sample has passed through the first column and the second column, the plurality of valves including a second flow path arrangement and a third flow path arrangement.

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.

list of figures

• 1A ist ein teilweises Blockdiagramm, das ein System darstellt, das ausgestaltet ist, über weite Strecken transportierte Proben zu analysieren, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 1B ist eine Umgebungsansicht eines Probenkonzentrationssystems gemäß beispielhaften Ausführungsformen der vorliegenden Offenbarung.
• 1C ist eine Umgebungsansicht eines Probenkonzentrationssystems gemäß beispielhaften Ausführungsformen der vorliegenden Offenbarung.
• 1D ist eine Umgebungsansicht eines Probenkonzentrationssystems gemäß beispielhaften Ausführungsformen der vorliegenden Offenbarung.
• 1E ist eine Umgebungsansicht eines Probenkonzentrationssystems gemäß beispielhaften Ausführungsformen der vorliegenden Offenbarung.
• 1F ist eine Umgebungsansicht eines Probenkonzentrationssystems gemäß beispielhaften Ausführungsformen der vorliegenden Offenbarung.
• 1G ist eine Umgebungsansicht eines Probenkonzentrationssystems gemäß beispielhaften Ausführungsformen der vorliegenden Offenbarung.
• 1H ist eine Umgebungsansicht eines Probenkonzentrationssystems gemäß beispielhaften Ausführungsformen der vorliegenden Offenbarung.
• 1I ist eine Kalibrierungskurve von Zählwerten über der Konzentration von in einer Flüssigkeitsprobe vorhandenem Magnesium, die durch ein Probenkonzentrationssystem aufbereitet wurde, gemäß Ausführungsformen der vorliegenden Offenbarung.
• 2A ist eine Umgebungsansicht, die eine Fern-Probennahmevorrichtung darstellt, die in einem Fern-Probennahmesystem verwendet ist, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 2B ist eine Umgebungsansicht, die eine Fern-Probennahmevorrichtung darstellt, die in einem Fern-Probennahmesystem verwendet ist, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 3A ist eine Umgebungsansicht, die eine Analysevorrichtung darstellt, die in einem Analysesystem verwendet ist, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 3B ist eine Umgebungsansicht, die eine Analysevorrichtung darstellt, die in einem Analysesystem verwendet ist, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 4 ist ein teilweises Blockdiagramm, das ein Analysesystem in dem System darstellt, das ausgestaltet ist, über weite Strecken transportierte Proben zu analysieren, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 5 ist ein teilweises Blockdiagramm, das einen Detektor darstellt, der in dem in 4 gezeigten Analysesystem verwendet sein kann, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 6 ist eine Umgebungsansicht, die ein Analysesystem mit einer Vielzahl von Analysevorrichtungen zum Analysieren einer von einem Fern-Probennahmesystem aufgenommenen Probe darstellt, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 7 ist eine schematische Darstellung eines Systems, enthaltend eine Probenaufnahmeleitung und Detektoren, die ausgestaltet sind zu bestimmen, wann die Probenaufnahmeleitung einen fortlaufenden Flüssigkeitsabschnitt zwischen den Detektoren enthält, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 8 ist ein teilweiser Schnitt durch eine Probenübertragungsleitung, die mehrere Abschnitte einer durch ein Fern-Probennahmesystem genommenen Probe enthält, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 9 ist ein Zeitdiagramm, das mehrere einer Probenaufnahmeleitung zugeführte und durch zwei Detektoren verzeichnete Flüssigkeitsprobenabschnitte darstellt, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 10 ist ein Flussdiagramm, das ein Verfahren zum Bestimmen darstellt, wann eine Probenaufnahmeleitung einen fortlaufenden Flüssigkeitsabschnitt zwischen Detektoren enthält, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 11 ist ein Verfahrens-Flussdiagramm eines Steuerungssystems zum Überwachen und Steuern von Verfahrensvorgängen auf Grundlage chemischer Erfassungsgrenzwerte, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 12 ist ein schematisches Diagramm einer Verarbeitungsanlage, enthaltend eine Vielzahl von Fern-Probennahmesystemen, gemäß Ausführungsbeispielen der vorliegenden Offenbarung.
• 13 ist ein Diagramm, das metallische Verunreinigung eines chemischen Bades über der Zeit darstellt, mit Datenpunkten, die manuelle Probennahme darstellen, und Datenpunkten, die mit einem automatischen System gemäß Ausführungsbeispielen der vorliegenden Offenbarung erhalten wurden.

The detailed description refers to the accompanying figures. All dimensions contained in the accompanying figures are provided by way of example only and are not intended to limit the present disclosure.

• 1A FIG. 10 is a partial block diagram illustrating a system configured to analyze long-distance transported samples in accordance with embodiments of the present disclosure. FIG.
• 1B FIG. 10 is an environmental view of a sample concentration system according to example embodiments of the present disclosure. FIG.
• 1C FIG. 10 is an environmental view of a sample concentration system according to example embodiments of the present disclosure. FIG.
• 1D FIG. 10 is an environmental view of a sample concentration system according to example embodiments of the present disclosure. FIG.
• 1E FIG. 10 is an environmental view of a sample concentration system according to example embodiments of the present disclosure. FIG.
• 1F FIG. 10 is an environmental view of a sample concentration system according to example embodiments of the present disclosure. FIG.
• 1G FIG. 10 is an environmental view of a sample concentration system according to example embodiments of the present disclosure. FIG.
• 1H FIG. 10 is an environmental view of a sample concentration system according to example embodiments of the present disclosure. FIG.
• 1I FIG. 12 is a calibration curve of counts versus the concentration of magnesium present in a fluid sample prepared by a sample concentration system according to embodiments of the present disclosure. FIG.
• 2A FIG. 12 is an environmental view illustrating a remote sampling device used in a remote sampling system according to embodiments of the present disclosure. FIG.
• 2 B FIG. 12 is an environmental view illustrating a remote sampling device used in a remote sampling system according to embodiments of the present disclosure. FIG.
• 3A FIG. 11 is an environmental view illustrating an analysis device used in an analysis system according to embodiments of the present disclosure. FIG.
• 3B FIG. 11 is an environmental view illustrating an analysis device used in an analysis system according to embodiments of the present disclosure. FIG.
• 4 FIG. 10 is a partial block diagram illustrating an analysis system in the system configured to analyze long distance transported samples in accordance with embodiments of the present disclosure. FIG.
• 5 FIG. 12 is a partial block diagram illustrating a detector included in the in 4 may be used according to embodiments of the present disclosure.
• 6 FIG. 11 is an environmental view illustrating an analysis system having a plurality of analyzers for analyzing a sample taken from a remote sampling system, in accordance with embodiments of the present disclosure. FIG.
• 7 FIG. 3 is a schematic illustration of a system including a sample receiving line and detectors configured to determine when the sample receiving line contains a continuous liquid portion between the detectors according to embodiments of the present disclosure. FIG.
• 8th FIG. 13 is a partial cross-sectional view of a sample transfer line containing multiple sections of a sample taken by a remote sampling system, in accordance with embodiments of the present disclosure. FIG.
• 9 FIG. 5 is a timing diagram illustrating a plurality of liquid sample sections supplied to a sample receiving line and plotted by two detectors according to embodiments of the present disclosure. FIG.
• 10 FIG. 11 is a flowchart illustrating a method for determining when a sample receiving line contains a continuous liquid portion between detectors, according to embodiments of the present disclosure.
• 11 FIG. 10 is a process flow diagram of a control system for monitoring and controlling chemical based detection procedures in accordance with embodiments of the present disclosure. FIG.
• 12 FIG. 10 is a schematic diagram of a processing plant including a plurality of remote sampling systems, in accordance with embodiments of the present disclosure. FIG.
• 13 FIG. 12 is a graph illustrating metallic chemical bath contamination over time, with data points representing manual sampling and data points obtained with an automated system according to embodiments of the present disclosure. FIG.

PRECISE DESCRIPTION

Overview

The determination of trace element concentrations or amounts in a sample may provide an indication of the purity of the sample or the suitability of the sample for use as a reagent, reactive component, or the like. For example, in certain production or manufacturing processes (eg, mining, metallurgy, semiconductor manufacturing, pharmaceutical processing, etc.), the tolerances for impurities may be very strict, for example, on the order of fractions of parts per billion (ppb). For example, semiconductor processes may require extremely low detection limits for impurities in process chemicals, including, but not limited to, ultrapure water for washing wafers, isopropyl alcohol for drying wafers, hydrogen peroxide (H ₂ O ₂ ), ammonia water (NH ₄ OH), and the like. Failure to detect extremely low levels of contaminants in such process chemicals can ruin a semiconductor wafer, such as by precipitating such contaminants from solution and onto the wafer (eg, depositing a metallic contaminant or other conductivity risk onto the wafer, such as by precipitation of the contaminant from solution by acting as a concentrator surface for the contaminant, or the like). However, the detection capabilities of even highly sensitive analytical devices, such as inductively coupled plasma mass spectrometer systems (ICP / ICP-MS systems), typically do not have accurate resolution to measure concentrations of chemicals in the low part per billion (ppq) range found in a sample for a routine analysis.

Accordingly, the present disclosure is directed to systems and methods for automated in-line concentration of extremely low concentrations of chemicals (eg, chemical elements, molecules, compounds, etc.) in pure chemicals. Exemplary systems use valve assemblies and one or more columns to concentrate groups of chemical elements in one or more samples and see a high rate of analyte retention and rapid kinetics for elution of preconcentrated analytes for subsequent analysis by inductively coupled plasma analysis systems (ICP-MS). Systems). The samples may be preconcentrated at a remote sampling location (eg, as part of a remote sampling system) in an analysis system remote from remote sampling systems (eg, in an analysis system with an ICP-MS system containing samples of receiving television) or combinations thereof.

Exemplary embodiments

General with reference to 1A to 13 exemplary systems are described configured to analyze samples transported over long distances. In exemplary embodiments, the samples are introduced into the sample concentration system before, after, or both before and after transport over the distance between a remote sampling system and an analysis system remote from the remote sampling system. A system 100 contains an analysis system 102 in a first place. The system 100 can also have one or more remote sampling systems 104 contained in a second location removed from the first location. For example, the one or multiple remote sampling systems 104 located near a source of chemicals, such as a chemical storage container, a chemical treatment container (eg, a chemical bath), a chemical transport line or piping, or the like (e.g. analysis system 102 to analyze, with the analysis system 102 away from the remote sampling system (s) 104 may be arranged, such as a central analysis point for a production facility (eg, at the first location). The system 100 may also include one or more remote sampling system (s) 104 at a third location, a fourth location, and so on, with the third location and / or the fourth location remote from the first location. In implementations may be the third place, the fourth place and other places of remote sampling systems 104 away from other locations of other remote sampling systems 104 be. For example, a remote sampling system 104 on a water line (eg, a deionized water transport line) while one or more other remote sampling systems are being 104 may be disposed on a chemical storage container, a chemical treatment container (eg, a chemical bath), a chemical transportation line or piping, or the like. In some embodiments, the system may 100 also one or more remote sampling system (s) 104 contained in the first location (eg near the analysis system 102 ). For example, a sampling system 104 at the first place one with the analysis system 102 included coupled autosampler. One or multiple sampling systems 104 may be operable to receive samples from the first location, the second location, the third location, the fourth location, and so on, and the system 100 can be operable, the samples to the analysis system 102 for analysis.

A remote sampling system 104 can be configured, a sample 150 record and the sample 150 for delivery (eg to the analysis system 102 ) and / or analysis. In Embodiments may be the remote sampling system 104 at different distances from the analysis system 102 be arranged (eg 1 m, 5 m, 10 m, 30 m, 50 m, 100 m, 300 m, 1000 m, etc.). In embodiments, the remote sampling system 104 a remote sampling device 106 and a sample conditioning device 108 contain. The sample preparation device 108 can continue a valve 148 included, such as a flow valve. In embodiments, the remote sampling device 106 contain a device, designed, a sample 150 from a sample stream or sample source (eg, a liquid, such as sewage, rinse water, chemicals, industrial chemicals, etc.), a gas, such as an air sample and / or contaminants therein, that should come in contact with a liquid, or similar). The remote sampling device 106 may include components such as pumps, valves, piping, sensors, etc. that are capable of removing the sample from the sample source and dispensing the sample across the distance to the analysis system 102 , The sample preparation device 108 may include a device configured, a sample taken 150 from the remote sampling device 106 using a diluent 114 , an internal standard 116 , a vehicle 154 etc., to provide certain sample concentrations, spiked samples, calibration curves or the like, and may be treated with a rinse solution 158 do the washing up.

In some embodiments, a sample may 150 (eg a prepared sample 152 ) for delivery and / or analysis using one or more treatment techniques, including, but not limited to, dilution, pre-concentration, addition of one or more calibration standards, and so forth. For example, a viscous sample 150 be diluted in the distance (eg by the sample conditioning device 108 ) before going to the analysis system 102 is supplied (for example, to prevent the sample 150 while the feed is separated). As described here, a sample may be taken from the remote sampling system 104 was transmitted as a sample 150 be referred to, wherein "sample 150" on a prepared sample 152 can relate. In some embodiments, the sample dilution may be dynamically adjusted (eg, automatically adjusted) to move the sample (s) 150 through the system at a desired flow rate. For example, the diluent added to a particular sample or sample type becomes 114 increases when a sample 150 too slow through the system 100 moved (eg measured by the transmission time from the first location to the second location). In another example, one liter ( 1 L) seawater before feeding to the analysis system 102 be preconcentrated in the distance. In another example, an electrostatic concentration of material from an air sample is used to pre-concentrate possible air pollutants. In some embodiments, in the process flow, dilution and / or calibration is automatically performed by the system 100 carried out. For example, a sample conditioning device 108 add one or more internal standards to a sample belonging to the analytical system 102 is fed to the analysis system 102 to calibrate.

In embodiments, an example of which is shown in FIG 1A is shown containing the sample conditioning device 108 a sample concentration system 200 to one or more chemical elements in the sample 150 present from the remote sampling device 106 is received, before transmitting the processed sample 152 (eg a concentrated sample) to the analytical system 102 to concentrate. Alternatively or additionally, the analysis system 102 the sample concentration system 200 to concentrate one or more chemical elements prior to analysis by the analytical devices described herein. While it is described that the sample concentration system 200 concentrated chemical elements for analysis, it is understood that the sample concentration system 200 can be used to chemical species, ions, molecules, compounds or the like through the analysis system 102 to concentrate. With reference to 1B to 1I are exemplary embodiments of the sample concentration system 200 shown. This in 1B and 1C shown sample concentration system 200 contains an exchange column 202 , a valve 204 and a liquid mass flowmeter 206 , In 1B is the valve 204 In a sample loading arrangement, a flow path between a sample (eg, a sample 150 or a prepared sample 152 ), the exchange column 202 and the liquid mass flowmeter 206 provided. The sample flows through the exchanger column 202 , creating chemical elements with an affinity to the relevant exchange column 202 Retained in the column, and the sample can pass through the valve 204 to the liquid mass flowmeter 206 flow and the sample concentration system 200 leave as wastewater. While the columns described herein are referred to as "exchange columns", it is to be understood that the columns may be any columns capable of discriminating between members of interest and species of interest and not of interest. For example, the exchange columns may include, but are not limited to, anion exchange columns, cation exchange columns, chelation columns, chromatography columns, or the like, or combinations thereof. The liquid mass flowmeter 206 measures the flow rate of the sample (eg the volumetric flow rate or mass flow rate), which is the exchanger column 202 has flowed through to the respective in the exchanger column 202 Provide retained chemical element. After a threshold amount of mass or volume of sample the exchanger column 202 has passed through the sample concentration system 200 the arrangement of the valve 204 automatically into an in 1C The eluate shown in order, whereby an eluent in the exchange column 202 to initiate an eluted sample (eg, processed sample 152 ) for transmission to or analysis by the analysis system 102 provided. For example, a control device that controls the valve 204 Presses the mass or volume of the sample through the mass flowmeter 206 Compare with a threshold value (eg, stored in system memory, specified by a user, etc.) to determine when enough sample passes through the exchanger column 202 has flowed to the / for analysis by the analysis system 102 to focus on interesting chemical element (s). While 1C a fluid path between the valve 204 in the elution system and a nebulizer 208 It will be appreciated that such a flow path may be a direct connection (where, for example, the sample concentration system 200 at the analysis system 102 or associated with a desolvation system thereof) or a remote connection (where, for example, the sample concentration system 200 in a remote sampling system 104 contained), such as by containing the valve 148 and a transmission line (eg, a transmission line described herein) 144 ). The results of the analysis on the analysis system 102 can with the volume or the mass passing through the liquid mass flow meter 206 are compared to determine a concentration of chemical elements in the remote sampling system 104 obtained sample are present.

With reference to 1D to 1H can the sample concentration system 200 contain a variety of exchange columns to a variety of chemical elements for analysis by the analysis system 102 to concentrate. For example, the sample concentration system is 200 with a first exchange column 210 and a second exchange column 212 , a variety of valves (the valves 214 . 216 and 218 are shown) and the liquid mass flowmeter 206 shown. The exchange columns can be selected to contain other chemical elements than other exchange columns of the sample concentration system 200 to retire. For example, the first exchanger column 210 be designed to retain chemical elements from the transition metals (eg, a chelation column) while allowing other chemical elements to pass through (eg, sodium, potassium, etc. become the valve 216 let through) while the second exchange column 212 may be designed to retain chemical elements of Groups I and II (eg, a cation exchange column). By using two or more selective exchange columns, the sample concentration system can 200 allow rapid elution of the chemicals retained in each exchanger column, rather than having differences in affinity between multiple chemical elements in a single column, which may require longer elution times and reduce sample analysis resolution.

With reference to 1D is the sample concentration system 200 shown in a sample loading arrangement through which the valve 214 a flow path between a sample (eg, a sample 150 or a prepared sample 152 ) as well as an optional standard solution and the first exchange column 210 provides for chemical elements with an affinity for the exchange medium in the first exchange column 210 (eg, transition metals), while all other chemical elements are allowed to pass through (eg, metals of groups I and II). The valve 216 is fluidic with the valve 214 coupled to receive the sample and the sample into the second exchange column 212 to transfer chemical elements having an affinity for the exchange medium in the second exchange column 212 (eg, Group I and II metals) while in a charging configuration. The valve 218 is fluidic with the valve 216 coupled to receive the sample and the sample into the liquid mass flowmeter 206 and from the sample concentration system 200 as wastewater. The liquid mass flowmeter 206 measures the flow rate of the sample (eg volumetric flow rate or mass flow rate) that is the first exchanger column 210 and the second exchange column 212 has flowed through to the respective in the exchanger column 212 Provide retarded chemical elements. After the threshold amount of mass or volume of the sample, the first exchange column 210 and the second exchange column 212 has passed through the sample concentration system 200 automatically the arrangement of the valve 216 and the valve 218 from one (in 1D shown) charging arrangement to a in 1E shown injection assembly, whereby an eluent in the first exchange column 210 initiated and through the valve 216 (eg bypassing the second exchanger column 212 ) is passed to an eluted sample (eg, a processed sample 152 ) for transmission to or analysis by the analysis system 102 to measure the chemical species of interest by the first exchange column 210 are retarded (eg transition metals). For example, the control device (s) containing the valves 214 . 216 . 218 Press the mass or volume of the sample passing through the fluid mass flowmeter 206 Compare with a threshold value (eg, stored in system memory, specified by a user, etc.) to determine when enough sample passes through the first exchanger column 210 and the second exchange column has flowed to the one for analysis by the analysis system 102 focus on the chemical element (s) of interest. After eluting the chemical element (s, e) of interest from the first exchange column 210 switches the sample concentration system 200 the arrangement of the valve 216 from the injection assembly into the charging assembly to form a fluid path for an eluent for eluting the chemical element (s, e) of interest from the second exchange column 212 to provide, as in 1F whereby the eluted sample (eg the processed sample 152 ) for transmission to or analysis by the analysis system 102 is provided to measure the chemical species of interest passing through the second exchange column 212 are retarded (eg chemical elements of groups I and II).

With reference to 1G is the sample concentration system 200 shown in a flushing arrangement, whereby a rinse solution through the valves 214 and 216 flows, the first exchange column 210 and the second exchange column 212 bypasses to pass through the liquid mass flow meter 206 to flow and drain as wastewater. With reference to 1H is the sample concentration system 200 shown in a direct injection arrangement, whereby a sample from each of the first exchange column 210 and the second exchange column 212 bypasses to get out of the valve 218 for analysis by the analysis system 102 exit (eg via the atomizer 208 ). While 1E . 1F and 1H a fluid path between the valve 218 and the atomizer 208 It can be seen that such a flow path can be a direct connection (where, for example, the sample concentration system 200 at the analysis system 102 or associated with a desolvation system thereof) or a remote connection (where, for example, the sample concentration system 200 in a remote sampling system 104 contained), such as by containing the valve 148 and a transmission line (eg, a transmission line described herein) 144 ). The results of the analysis on the analysis system 102 can match the volume or mass of the sample passing through the liquid mass flow meter 206 are compared to determine a concentration of the chemical elements in the remote sampling system 104 obtained sample are present. While the sample concentration system 200 With one and two exchanger column arrangements shown, it can be seen that more than two exchanger columns enter the sample concentration system 200 may be included to provide additional retention of chemical elements, different groups of retained chemical elements or the like.

With reference to 1I FIG. 3 is a calibration curve of counts versus concentration of magnesium present in a fluid sample through a sample concentration system. FIG 200 in accordance with embodiments of the present disclosure.

The calibration curve contains an R value of 0.9993 for concentrations of magnesium present at about 100 parts per quadrillion (ppq).

In embodiments of the disclosure, the analysis system 102 a sampler 110 and / or sample detector 130 contain, designed, a sample 150 from one between the analytical system 102 and one or more remote sampling systems 104 coupled sample transfer line 144 to take. The sampler 110 and / or the sample detector 130 may contain components, such as pumps, valves, piping, connectors, sensors, etc. to the sample 150 from one or more of the remote sampling systems 104 (eg via one or more sample transmission lines) 144 ). Where the system 100 for example, multiple remote sampling systems 104 Each remote sampling system may have its own sample transfer line 144 included to a separate part of the sampler 110 or to a separate sampler 110 of the analysis system 102 to join. In addition, the analysis system 102 a sampling device 160 contain, designed, a sample 150 to take that locally to the analysis system 102 is (eg a local autosampler).

The analysis system 102 also contains at least one analyzer 112 , designed to analyze samples to determine trace element concentrations, isotopic ratios and so on (eg in fluid samples). For example, the analyzer 112 an ICP spectroscopy device including, but 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 embodiments, the analysis system includes 102 a variety of analysis devices 112 (ie more than one analyzer). For example, the system 100 and / or the analysis system 102 contain multiple sampling loops, each one Sampling loop a portion of the sample into the plurality of analyzers 112 introduces. As another example, the system 100 and / or the analysis system 102 be equipped with a multi-way valve, so that a single sample quickly and serially in the variety of analysis devices 112 can be introduced. For example, shows 6 a remote sampling system 104 in fluid communication with the analysis system 102 , where the analytical system 102 a multi-way valve 600 coupled with three analyzers (shown as ICPMS 602 , Ion Chromatograph Column (IC Column) 604 and Fourier Transform Infrared Spectroscopy (FTIR) 606 ) for analysis of the remote sampling system 104 recorded sample. While 6 an embodiment shows where the analysis system 102 contains three analysis devices, the analysis system 102 less (eg, less than three) or more (eg, more than three) analytical devices 112 contain. In embodiments, the analysis devices 112 include, but are not limited to: ICPMS (eg, for trace metal determinations), ICPOES (eg, for trace metal determinations), ion chromatographs (eg, for anion and cation determinations), liquid chromatograph (LC) (e.g. for determinations of organic contaminants), FTIR infrared (eg for the determination of chemical composition and structural information), particle counter (eg for detecting undissolved particles), moisture analyzer (eg for detecting water in samples), gas chromatograph (GC) (eg, for detecting volatiles) or the like. In embodiments, the plurality of analyzers 112 in the same location as the remote sampling device 104 while the system 100 one or more additional analyzers 112 may be located away from the remote sampling system 104 for additional or other sample analysis than the analysis (s) performed by the variety of analytical devices 112 be performed. Alternatively or additionally, the plurality of analysis devices 112 at a location other than the remote sampling system 104 are located.

The system 100 and / or the analysis system 102 may be configured to report an analyte concentration at a location over time (discussed below with reference to FIG 13 shown). In some embodiments, the analyzer 112 be configured, one or more trace metals in a sample 150 capture. In other embodiments, the analyzer 112 be designed for ion chromatography. For example, ions and / or cations may be present in a sample 150 collected and a chromatographic analyzer 112 be supplied. In further embodiments, organic molecules, proteins, and so on may be sampled and delivered to a high resolution time-of-flight (HR-ToF) mass spectrometer analyzer 112 (eg, using a nebulizer 156 ). Thus, systems as described herein can be used for a variety of applications, including but not necessarily limited to: pharmaceutical applications (eg, a central mass spectrometer analyzer coupled to multiple pharmaceutical reactors), wastewater monitoring of one or more wastewater streams, semiconductor manufacturing equipment and so on. For example, a wastewater stream may be constantly monitored for contaminants and diverted to a tank when contamination has been detected. As another example, one or more streams of chemicals may be continuously monitored via analysis of the samples by one or more of the analysis system 102 connected remote sampling systems 104 can be taken, whereby an impurity limit for each of the chemical streams can be specified. When detecting an impurity that exceeds the impurity limit for a particular flow, the system may 100 to provide an alarm.

The remote sampling system 104 may be configured to selectively communicate with at least one sample transfer line 144 to couple, so the remote sampling system 104 is operable in fluid communication with the sample transfer line 144 to stand by the sample transfer line 144 a continuous fluid sample section 150 supply. For example, the remote sampling system 104 be designed, a sample 150 to take and the sample 150 the sample transfer line 144 for example, using a flow valve 148 that the remote sampling system 104 with the sample transfer line 144 coupled. The supply of the sample 150 to the sample transfer line 144 can be referred to as a "throw". The sample transfer line 144 can with a gas supply 146 coupled and may be configured to transport gas from the second location (and possibly the third location, the fourth location, etc.) to the first location. This is done by the remote sampling system 104 supplied liquid sample sections collected in a gas stream and to the location of the analysis system 102 transported using a gas pressure sample transfer.

In some embodiments, the gas in the sample transfer line 144 an inert gas, including, but not limited to: nitrogen gas, argon gas and so on. In some embodiments, the sample transfer line 144 an unsegmented or minimally segmented tube with an inside diameter of eight-tenths of a millimeter ( 0 , 8 mm) contain. However, an inner diameter of eight-tenths of a millimeter is given by way of example only and is not intended to limit the present disclosure. In other embodiments, the sample transfer line 144 contain an inside diameter greater than eight-tenths of a millimeter and / or a smaller inside diameter than eight-tenths of a millimeter. In some embodiments, the pressure in the sample transfer line 144 in a range of at least about four (4) bar to ten (10) bar. However, this scope is provided by way of example only and is not intended to limit the present disclosure. In other embodiments, the pressure in the sample transfer line 144 greater than ten bar and / or less than four bar. Further, in some particular embodiments, the pressure in the sample transfer line 144 be set up so that samples 150 in a generally upward direction (eg vertical). Such vertical alignment may facilitate the transfer of a sample taken at a location lower than the analysis system 102 (where, for example, sample source (s) and remote sampling system (s) are "on a lower floor" than the analysis system 102 are located).

In some examples, the sample transfer line 144 with a remote sampling system 104 in fluid communication with a first liquid bath (or chemical bath) and an analysis system 102 in fluid communication with a second liquid bath (or chemical bath). In embodiments of the disclosure, the system 100 include one or more leak sensors (eg, mounted in a tub) to overflow the first location and / or one or more remote locations (eg, the second location, the third location, the fourth location, and so on) to prevent or minimize. A pump, such as a syringe pump or a vacuum pump, may be used to sample into the sampling device 106 to load. A valve 148 Can be used to sample 150 at the remote sampling system 104 select, and the sample 150 can the sample transfer line 144 be fed to the sample 150 to the analysis system 102 leave at the first place. Another pump, such as a diaphragm pump, may be used to drain the analyzer 102 to pump and the sample 150 from the sample transfer line 144 to pump.

The system 100 may be embodied as an enclosed sampling system where the gas and the samples in the sample transfer line 144 not exposed to the surrounding environment. For example, a housing and / or shell may include one or more components of the system 100 enclose. In some embodiments, one or more sample lines of the remote sampling system 104 be cleaned between sample deliveries. Further, the sample transfer line 144 between samples 150 be cleaned (eg using a cleaning solution).

The sample transfer line 144 may be configured to selectively communicate with the sample receiving line 162 (eg a sample loop 164 ) in the first place, so that the sample loop 164 is operable to be in fluid communication with the sample transfer line 144 is to receive a continuous liquid sample section. The delivery of the continuous fluid sample section to the sample loop 164 may be referred to as a "catch." The sample loop 164 is also designed to be selective with the analyzer 112 to couple, so the sample loop 164 is operable to be in fluid communication with the analyzer 112 to the continuous liquid sample portion of the analyzer 112 to feed (if the system 100 z. B. has determined that a sufficient fluid sample portion for analysis by the analysis system 102 is available). In embodiments of the disclosure, the analysis system 102 include one or more detectors configured to determine that the sample loop 164 a sufficient amount of the continuous fluid sample section for analysis by the analysis system 102 contains. In one example, a sufficient amount of the continuous fluid sample section may contain enough liquid sample to deliver to the analyzer 112 to send. Another example of a sufficient amount of the continuous fluid sample section may be a continuous fluid sample in the sample collection line 162 between a first detector 126 and a second detector 128 included (such as in 7 shown). In embodiments, the first detector may be 126 and / or the second detector 128 a light analyzer 132 , an optical sensor 134 , a conductivity sensor 136 , a metal sensor 138 , a conductive sensor 140 and / or a pressure sensor 142 contain. It is to be considered that the first detector 126 and / or the second detector 128 may contain other sensors. For example, the first detector 126 a light analyzer 132 included, which detects when the sample 150 into the sample loop 164 enters, and the second detector may be another light analyzer 132 included, which detects when the sample loop 164 is filled. This example may be referred to as a "successful catch." It should be noted that the light analyzers 132 are provided by way of example only and are not intended to limit the present disclosure. Other exemplary detectors include, but are not limited to: optical sensors, Conductivity sensors, metal sensors, conductive sensors, pressure sensors and so on.

Regarding 7 are systems 100 which may determine when a continuous fluid sample section in the sample receiving line 162 is included, and / or if a sample loop 164 a sufficient amount of the continuous fluid sample section for analysis (eg, by the analysis system 102 ) contains. In exemplary embodiments, a first detector may be included 126 be configured to determine two or more conditions that indicate the presence of fluid (eg, a fluid sample portion) at a first location in the sample receiving conduit 162 , the absence of liquid at the first location in the sample receiving line 162 and so on. For example, a first state (eg, represented by a first logic level, such as a high state) may be used to indicate the presence of a fluid sample portion at the first location in the sample receiving line 162 (eg near the first detector 126 ), and a second state (eg, represented by a second logic level, such as a low state) may be used to detect the absence of a fluid sample portion at the first location in the sample receiving line 162 (eg, a void or gas in the sample receiving line 162 ).

In some embodiments, a first detector may be included 126 that has a pressure sensor 142 includes, be used to detect the presence of liquid at the first location in the sample receiving line 162 (for example, by detecting a pressure rise in the sample receiving line 162 near the first location if there is liquid). The first detector 126 may also be used to detect the absence of liquid at the first location in the sample receiving line 162 (for example, by detecting a pressure drop in the sample receiving line 162 near the first place). However, a pressure sensor is provided by way of example and is not intended to limit the present disclosure. In other embodiments, a first detector may be included 126 , which is an optical sensor 134 includes, be used to detect the presence of liquid at the first location in the sample receiving line 162 (for example, by detecting a reduction in light passing through the sample receiving line 162 passing near the first location if there is liquid). The first detector 126 may also be used to detect the absence of liquid at the first location in the sample receiving line 162 (For example, by detecting an increase in light passing through the sample receiving line 162 passes near the first place). In these examples, the first detector 126 reporting the presence of the liquid sample at the first location as a high state and the absence of the liquid sample at the first location as a low state.

In some embodiments, a system 100 also include one or more additional detectors, such as a second detector 126 , a third detector and so on. For example, a second detector 126 also be configured to determine two or more conditions that indicate the presence of fluid (eg, a fluid sample portion) at a second location in the sample receiving conduit 162 , the absence of liquid at the second location in the sample receiving line 162 and so on. For example, a first state (eg, represented by a first logic level, such as a high state) may be used to detect the presence of a fluid sample portion at the second location in the sample receiving line 162 (eg near the second detector 126 ), and a second state (eg, represented by a second logic level, such as a low state) may be used to detect the absence of a fluid sample portion at the second location in the sample receiving line 162 display.

In some embodiments, a second detector may be included 126 that has a pressure sensor 142 includes, be used to detect the presence of liquid at the second location in the sample receiving line 162 (for example, by detecting a pressure rise in the sample receiving line 162 near the second location if there is liquid). The second detector 126 may also be used to detect the absence of liquid at the second location in the sample receiving line 162 (for example, by detecting a pressure drop in the sample receiving line 162 near the second place). However, a pressure sensor is provided by way of example and is not intended to limit the present disclosure. In other embodiments, a first detector may be included 126 , which is an optical sensor 134 includes, be used to detect the presence of liquid at the first location in the sample receiving line 162 (for example, by detecting a reduction in light passing through the sample receiving line 162 passing near the first location if there is liquid). The second detector 126 may also be used to detect the absence of liquid at the second location in the sample receiving line 162 (For example, by detecting an increase in light passing through the sample receiving line 162 passes near the second place). In these examples, the second detector 126 reporting the presence of the fluid sample at the second location as a high state and the absence of the fluid sample at the second location as a low state.

A control device 118 can with one or more detector (s) 126 communicative be coupled and configured, liquid at the first location in the sample receiving line 162 , at the second location in the sampling line 162 at another location in the sampling line 162 and so on. For example, the controller forwards 118 a detection process using a first detector 126 and liquid at the first location in the sample receiving line 162 can through the control device 118 be recorded (eg when the control device 118 a state change from low to high, determined by the first detector 126 ). Then the first detector can 126 be monitored (eg, continuously, at least substantially continuously), and the controller 118 may then be a lack of liquid at the first location in the sample receiving line 162 (for example, when the control device 118 a change in state from high to low, determined by the first detector 126 ).

Similarly, the control device 118 also a detection process using a second detector 126 and liquid at the second location in the sample receiving line 162 can through the control device 118 be recorded (eg when the control device 118 a state change from low to high, determined by the second detector 126 ). Then the second detector 126 be monitored (eg, continuously, at least substantially continuously), and the controller 118 may subsequently lack liquid at the second location in the sample receiving line 162 (for example, when the control device 118 a change in state from high to low, determined by the second detector 126 ).

The control device 118 and / or the one or more detectors 126 may include or affect the operation of a timer to timewarp certain events (eg, presence or absence of fluids at particular times at multiple locations in the sample receiving line) 162 ) for the system 100 provided. As an example, the control device 118 monitor the times at which state changes are recorded by the various detectors to make determinations as to whether the liquid sample is to be admitted to the analytical system 102 instead of passing the fluid to the wastewater drain or holding loop, for example. As another example, the control device 118 Monitor the time the fluid in the sample collection line 162 and / or the sample loop 164 spends, based on by the control device 118 about the detector (s) 126 recorded state changes.

Liquid sample section interruption and determination of a suitable liquid section

In general, when the sample is taken near an associated analyzer (eg, by an autosampler adjacent to an analyzer), a sample can span the entire distance between the sample source and the analyzer without requiring significant amounts of sample. However, in a transmission of a sample over a long distance, the filling of the entire transmission line could 144 between the remote sampling system 104 and the analysis system 102 (eg, up to hundreds of meters of sample length) may be intolerable or undesirable, such as due to environmental concerns in disposing of unused specimen parts, viscosity of the specimen, or the like. Accordingly, in embodiments, the remote sampling system fills 104 not the entire transmission line 144 with the sample; rather, a liquid sample portion that is part of the entire volume of the transmission line 144 represents, through the transmission line 144 for analysis by the analysis system 102 cleverly. While the transmission line 144 for example, can be up to hundreds of meters long, the sample can be sampled at any given time during the passage to the analysis system 102 about one meter or less of the transmission line 144 taking. While sending liquid sample sections through the line, those from the remote sampling systems 104 can reduce skillful sample quantity, the sample in the sample transmission line 144 during the passage to the analysis system 102 Blow or fill gaps / voids. Such bubbles or voids may form due to circumstances attributable to the transmission of the sample over a long distance, such as changes in the cross-sections between pipes during the passage, due to interference with residues of the cleaning liquid used to clean the pipes between samples, due to reactions with cleaning fluid in the conduits, due to pressure difference (s) along the path of the transmission line or the like. For example, as in 8th shown a liquid sample 800 from the remote sampling system 104 through the transmission line 144 be sent to the first place where the analytical system 102 located. The volume of the whole, through the remote sampling system 104 taken sample is in 8th represented by V _GES . As shown, there may be gaps or voids 802 in the transmission line 144 during the passage from the remote sampling system 104 form. The gaps or voids 802 divide a number of sample sections 804 on, no sufficient sample volumes or volumes for analysis by the analytical system 102 contain. Such sample sections 804 can be a larger sample section 806 precede or follow with a volume (shown as V _PROBE ) sufficient for analysis by the analysis system 102 , In embodiments, the amount of sample collected by the remote sampling system 104 is taken (for example, V _GES ), adjusted so that a sufficient amount of the sample 150 for analysis by the analyzer 112 is provided. For example, the volumetric ratio is the "thrown" amount of the sample 150 to the "trapped" amount of the sample 150 (eg V _GES / V _PROBE ) at least about one quarter (1.25). However, this relationship is by way of example only and is not intended to limit the present disclosure. In some embodiments, the ratio is greater than one quarter, and in other embodiments, the ratio is less than one quarter. In one example, a sample becomes 150 (eg concentrated sulfuric acid or nitric acid) of two and a half milliliters ( 2 , 5 ml), and a sample 150 of one milliliter (1 ml) is caught. In another example, a sample 150 of one and a half milliliters (1.5 ml), and a sample 150 of one milliliter (1 ml) is caught. In embodiments of the disclosure, the "thrown" amount of sample is 150 adjusted to the distance between the first location and the second location, the extent of sample transfer tubes between the first location and the second location, the pressure in the sample transfer line 144 and so on. In general, the ratio V _GES / V _{PROBE may be} greater than one to the formation of gaps / voids 802 and sample sections 804 in the sample transfer line 144 to be considered during the passage.

The system 100 can choose which one from a variety of remote sampling systems 104 his respective sample to the analysis system 102 transmit (eg "throw"), causing the detectors 126 determining if sufficient sample to send to the analysis system 102 (eg "catch") is present (eg V _PROBE in the sample loop 164 ), or whether there is a void or gap in the line (eg, between the detectors 126 ) so that the sample is not at that particular time to the analysis system 102 should be sent. If bubbles or gaps are present (eg in the sample loop 164 ), their presence could affect the accuracy of the analysis of the sample, especially if the sample is in the analytical system 102 before insertion into the analyzer 112 had to be diluted or further diluted as the analyzer 112 could analyze an "empty" solution.

In some embodiments, a system 100 be configured to determine when a continuous fluid sample section (eg, a sample section 806 ) in a sample receiving line 162 and / or a sample loop 164 so that the system can avoid a gap or white space 802 or a smaller sample section 804 to the analyzer 112 transferred to. For example, the system 100 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 (eg, downstream of the first location). The system 100 can also do a sample loop 164 between the first detector 126 and the second detector 126 contain. In embodiments, a valve, such as a multi-way valve, which is interposed between at least two flow path arrangements (eg, a first, in 3A shown flow path arrangement of the valve 148 ; a second, in 3B shown flow path arrangement of the valve 148 , etc.) is switchable between the first detector 126 and the sample loop 164 and between the second detector 126 and the sample loop 164 be set. In embodiments of the disclosure, the system 100 determine that a continuous fluid sample section in the sample receiving line 162 and / or the sample loop 164 by recording liquid at both the first location and the second location simultaneously while there is no change in state from high to low over the first detector 126 recorded at the first place. In other words, the fluid sample is continuous from the first detector 126 to the second detector 126 without one through the first detector 126 detected state change run until the second detector 126 detects the presence of the fluid sample.

In an exemplary implementation in which two or more detectors are used to determine if a sample receiving line contains a continuous liquid section between the detectors, a liquid section is received in a sample receiving line. For example, with reference to 7 the sample receiving line 162 a liquid sample section. Then, the liquid portion is registered at a first location in the sample receiving line by initiating a detection operation using a first detector configured to detect presence and / or absence of the liquid portion at the first location in the sample receiving line. For example, with reference to 7 the first detector 126 a liquid sample section at the first location in the sample receiving line 162 as a state change from low to high. Regarding 9 For example, liquid sample portions at the first location may be detected at times t ₁ and t ₅ . Then, afterwards upon detecting the liquid portion at the first location, the first detector monitors. For example, with reference to 7 the first detector 126 through the control device 118 monitored, and the first detector 126 detects a lack of the liquid sample portion at the first location in the sample receiving line 162 as a state change from high to low. Regarding 9 For example, the first location is monitored (eg, continuously, at least substantially continuously) beginning at times t ₁ and t ₅ , and a lack of the fluid sample portions may be detected at the first location at times t ₃ and t ₆ .

Similarly, the liquid portion is recorded at a second location in the sample receiving conduit by initiating a detection operation using a second detector configured to detect presence and / or absence of the liquid portion at the second location in the sample receiving conduit. For example, with reference to 7 the second detector 126 a liquid sample section at the second location in the sample receiving line 162 as a state change from low to high. Regarding 9 For example, liquid sample portions may be detected at the second location at times t ₂ and t ₇ . Then, following the detection of the liquid portion at the second location, the second detector is monitored. For example, with reference to 7 the second detector 126 through the control device 118 monitored, and the second detector 126 detects a lack of the liquid sample portion at the second location in the sample receiving line 162 as a state change from high to low. Regarding 9 For example, the second location is monitored (eg, continuously, at least substantially continuously) beginning at times t ₂ and t ₇ , and a lack of the fluid sample portions may be detected at the second location at times t ₄ and t ₈ .

When liquid is recorded simultaneously at both the first location and the second location, a continuous liquid portion is recorded in the sample receiving conduit between the first detector and the second detector. For example, with reference to 7 when a high state indicates the presence of a fluid sample section at each of the first detector 126 and the second detector 126 represents the control device 118 a continuous liquid sample section in the sample receiving line 162 (eg as between the first detector 126 and the second detector 126 available). Regarding 9 For example, a continuous fluid sample portion may be recorded at time t ₂ when a fluid sample portion at the second location is detected.

In some embodiments, a logical AND operation may be used to determine when a continuous liquid portion is recorded in the sample receiving conduit and to initiate a transfer of the continuous liquid portion from the sample receiving conduit to the analyzer. For example, with reference to 7 the control device 118 a logical AND operation on a high state at each of the first detector 126 and the second detector 126 and selectively coupling the sample loop 164 with the analyzer 112 using the valve 148 initiate so that the sample loop 164 is operable in fluid communication with the analyzer 112 to stand by the continuous liquid sample section of the analyzer 112 supply. In some embodiments, the control device 118 only determine if they are the valve 148 switches so that a continuous liquid sample section of the analyzer 112 is supplied when a state change from low to high at the first detector 126 or at the second detector 126 is recorded. In some embodiments, the system requires 100 that the high state at the second detector 126 over a period of time (eg the in 9 shown t _Δ ) is maintained before there is a selective coupling of the sample loop 164 with the analyzer initiates. For example, a timer or a timer function of the control device 118 and / or the processor 120 check the period during which the second detector 126 has maintained the high state, eliminating the control device 118 as soon as the second detector 126 the high state during the time t _Δ has persisted (eg, a threshold time), and with the first detector in the high state, determines that a sufficient fluid sample portion (e.g. 806 in 8th ) was caught, and can the valve 148 switch so that the continuous liquid sample section of the analyzer 112 is supplied. The duration of t _Δ may correspond to a period beyond which the second detector is unlikely to measure a void or bubble, which time may depend on the flow rate of the sample or other conditions.

In some embodiments, the control device 118 the timing of the first detector 126 monitor in high state and / or low state. For example, in embodiments where the flow characteristics of the remote sampling system 104 transmitted sample, the first detector 126 be monitored to determine the amount of time spent in the high state to approximate whether a sufficient fluid sample in the sample receiving line 162 and / or the sample loop 164 would be present to the control device 118 to induce the sample to the analyzer 112 to send, either with or without confirmation a high state at the second detector 126 , For example, for a given flow rate of the sample, the volume of the sample may be approximated by monitoring the length of time over which the first detector 126 was in high state. However, the flow rate of a sample may not be readily apparent due to variations in pump function, type of sample transferred, duration of transfer, distance of transfer, ambient temperature conditions, temperature conditions of the transfer line 144 or similar; therefore, the function of the second detector 126 be meaningful.

In embodiments of the disclosure, the systems and techniques described herein may be used to determine that a portion of a sample receiving line (eg, a sample loop) is between the first detector 126 and the second detector 126 filled, without bubbles are present. For example, the absence of the liquid sample at the first location may be between times t ₃ and t ₅ as described with reference to FIGS 9 described the presence of a bubble in the sample receiving line 162 correspond. If the system 100 has reached a state in which no bubbles in the sample receiving line 162 are present, the control device switches 118 the valve 148 so that the fluid in the sample loop 164 to the analyzer 112 (for analysis or sample preparation prior to analysis).

Exemplary method

10 is a process 810 of an exemplary implementation in which two detectors are used to determine when a sample receiving line contains a sufficient amount of sample in a continuous liquid sample section for analysis by an analysis system, without gaps or voids in the continuous liquid sample section. As shown, a liquid portion is received in a sample receiving line (block 812 ). For example, the sample receiving line 162 by the remote sampling system 104 taken and over the transmission line 144 record the transferred sample. The procedure 810 Also includes recording the liquid portion at a first location in the sample receiving conduit with a first detector configured to detect the presence and / or absence of the liquid portion as it passes the first location (block 814 ). For example, the first detector 126 the presence of the liquid sample section at the first location in the sample receiving line 162 measure up. Regarding 9 For example, liquid sample _portions are detected at the first location at times t ₁ and t ₅ .

Next, after detecting the liquid portion at the first location, the first detector is monitored (Block 816 ). For example, the first detector 126 through the control device 118 be monitored to determine whether a lack of the liquid portion at the first location in the sample receiving line 162 is present (for example, whether the first detector 126 from a high state indicating the detection of sample fluid has gone to a low state in which no sample fluid is detected). Regarding 9 the first location, beginning at times t ₁ and t ₅ , is monitored (eg, continuously, at least substantially continuously). Then, a continuous liquid portion is recorded in the sample receiving pipe if no absence of the liquid portion at the first location in the sample receiving pipe is noted before the liquid portion at the second location in the sample receiving pipe downstream from the first location by performing a detection operation using a second detector configured to detect presence and / or absence of the liquid portion at the second location (block 818 ). For example, with reference to 9 the first detector 126 the presence of the sample fluid at times t ₁ and t ₅ , while the second detector 126 detects the presence of the sample fluid at times t ₂ and t ₇ . Only the liquid sample portion between the times t ₁ and t ₃ at the first detector would be recorded by the second detector (beginning at time t ₂ ) without the first detector 126 detecting an absence in the meantime before the second detector detected that sample portion. At this time, the control device could 118 the valve 148 instruct so switch that in the sample loop 164 contained sample to the analyzer 112 is sent. While the first detector 126 the presence of the liquid sample at t ₅ , the first detector also detects the absence of the liquid sample at t ₆ before the second detector 126 then the presence of the liquid sample is detected at t ₇ . Therefore, the system recognizes 100 that a gap or a void (eg the gap / the void 802 ) in the sample loop 164 exists and turns off the valve 148 not for analysis; instead it leaves the unsuitable sample section (eg the liquid section 804 ) to the wastewater drain. As described herein, a timer (eg, by the controller 118 implemented) to the valve 148 to switch as soon as the second detector 126 has maintained the high state for a certain period of time (eg, t _Δ ) after the first detector 126 maintained the high state in the meantime.

control systems

A system 100 , which contains some or all of its components, can work under computer control. For example, a processor 120 at or in a system 100 to control the components and functions of systems described herein using software, hardware (e.g., hardwired 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, or hardware in connection with controlling the systems. In the case of software implementation, the module, functionality, or logic is program code that performs specified tasks when executed on a processor (eg, a central processing unit (CPU) or CPUs). The program code may be stored in one or more computer-readable storage devices (eg, in internal memory and / or one or more tangible media), and so on. The structures, functions, approaches, and techniques described herein may be implemented on a variety of commercially available computing platforms having a variety of processors.

For example, one or more components of the system, such as the analysis system 102 , the remote sampling system 104 , the valves 148 , Pumps and / or detectors (eg the first detector 126 , the second detector 126 , the sample detector 130 ) with a control device for controlling the taking, the dispensing and / or the analysis of samples 150 be coupled. For example, the control device 118 be designed, a valve 148 to turn on the sample loop 164 with the analysis system 102 couples, and a sample 150 from the sample loop 164 to the analysis system 102 to steer when passing through the first detector 126 and the second detector 126 a successful "catch" is indicated (eg if both sensors detect liquid). Next, the control device 118 perform some functionality to determine "unsuccessful snapping" (for example, if the sample loop 164 not with a sufficient amount of a sample 150 is filled to an analysis by the analysis system 102 execute). For example, in some embodiments, "unsuccessful snapping" is determined based on changes 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 snatching" is determined when the first detector 126 a sample 150 in the sample receiving line 162 has indicated and a predetermined period has passed, in which the second detector 126 no sample 150 in the sample receiving line 162 has displayed.

In some embodiments, the controller is 118 communicatively coupled to an indicator at a remote location, such as the second location, and provides an indication (eg, an alarm) at the second location if an insufficient sample 150 recorded at the first location. The display can be used to initiate additional sampling and dispensing (eg automatically). In some embodiments, the indicator provides an alarm to the operator (eg, via one or more indicator lights, an output display, a combination thereof, etc.). Further, the display may be timed and / or initiated based on one or more predetermined conditions (eg, only if multiple samples have failed). In some embodiments, an indicator may also be activated based on conditions measured at a remote sampling location. For example, a detector 130 used at the second location to determine when the sample 150 for a remote sampling system 104 is provided, and the indicator can be activated if no sample 150 is taken.

In some embodiments, the controller is 118 operable, various timers for taking samples from different locations and / or for different types of samples 150 provided. For example, the control device 118 be reported if a remote sampling system 104 ready, a sample 150 into the sample transfer line 144 and can transfer the sample 150 into the sample transfer line 144 initiate. The control device 118 can also use one or more remote sampling systems 102 be communicatively coupled to the samples 150 to receive (and possibly log) appropriate identification information, and / or to control the order in which the samples are stored 150 in the system 100 be delivered. For example, the control device 118 from a distance several samples 150 and their delivery through one or more of the sample transfer lines 144 coordinate. In this way, the delivery of samples 150 along multiple simultaneous flow paths (eg, through multiple sample transfer lines 144 ) can be one or more samples 150 are in the transfer while one or more additional samples 150 be taken, and so on. For example, shows 11 an exemplary control flowchart for the system 100 where the analysis system 102 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 related transmission lines 144a and 144b is shown. In the embodiment shown, the analysis system sends 102 Commands to each from the remote sampling system 104a and the remote sampling system 104b shown as 904a and 904b, respectively. The remote sampling system 104a and the remote sampling system 104b each transferred to the respective sample location (the sample location 900 for the remote sampling system 104a , the sample location 902 for the remote sampling system 104b) taken sample to the analysis system 102 over the transmission line 144a or the transmission line 144b , The analysis system 102 then processes the samples to determine amounts of various chemicals contained therein. The analysis system 102 then determines if any of the amounts of the chemicals exceed an element-specific limit (eg, a threshold for a particular contaminant in the sample). In embodiments, the system 100 Determine impurity limits independently for each sampling location and for specific chemicals independently at each sampling location. For example, the tolerance for a particular metallic contaminant may decrease during processing; thus, downstream chemical samples may have lower limits for the particular chemical than for upstream chemical samples. As in 11 shown, the analysis system determined 102 in that no chemical substance has any of the element-specific limits for the sampling site 900 through the remote sampling system 104b exceeds the sample taken. The analysis system 102 then sends a CIM host 906 a message shown as 908a to indicate continuation of process applications at the sampling site 900 because the operation of the process applications is below the element specific limits. The analysis system 102 has determined that at least one of the at the sampling location 902 through the remote sampling system 104b sample present exceeds the element-specific limit (eg, a contamination limit in the sample). The analysis system 102 then sends the CIM host 906 a message shown as 908b, to the process applications at the sampling site 902 send directed alarm because the operation of the process applications is above the element-specific limits. The CIM host 906 then indicates based on the analysis by the remote sampling system 104b at the sampling point 902 taken sample via a process stop command 910 the processes at the sampling site 902 to stop the operation. In embodiments, the communication between the CIM host 906 and the components of the system 100 be enabled by the SECS / GEM protocol. In embodiments, the system 100 Include context-specific actions when it is determined that an item is above an item-specific threshold in a sample for a particular sample location, where such context-specific actions may include but are not limited to: ignoring an alarm and continuing the method operation, stopping the method operation, performing system calibration and re-analyzing the cross-border sample or the like. For example, at a first alarm, the analysis system 102 perform a calibration (or another calibration) and then re-analyze the sample, while a subsequent alarm (eg, a second alarm) will analyze the CIM host 906 would command to stop the processes at the offending sampling location.

The control device 118 can be a processor 120 , a store 122 and a communication interface 124 contain. The processor 120 sees processing functionality for the controller 118 and may include any number of processors, microcontrollers or other processing systems, and resident or external memory for storing data or other information to which the controller 118 accessed or generated by it. The processor 120 can run one or more software programs that perform the techniques described here. The processor 120 is not limited by the materials from which it is formed or the processing mechanisms used therein, and therefore may be implemented using semiconductors and / or transistors (eg, using integrated circuit (IC) devices) and so on ,

The memory 122 is an example of a tangible computer-readable storage medium, the storage functionality for storing various, with the operation of the control device 118 linked data, such as software programs and / or program code segments or other data, for directing the processor 120 and possibly other components of the control device 118 provides to perform the functionality described here. Thus, the memory can 122 Storing data, such as a program with instructions for operating the system 100 (including its components) and so on. It should be noted that while a single memory is described, a wide variety of types and combinations of memories (eg, tangible, non-volatile memory) may be used. The memory 122 can be part of the processor 120 be a stand-alone store or a combination of both.

The memory 122 may include, but is not limited to: removable and non-removable memory components, such as memory cells. A Random Access Memory (RAM), a read only memory (ROM), a flash memory (eg, a Secure Digital Memory Card (SD) card, a miniSD memory card, and / or a microSD memory card), magnetic memory, optical memory, Universal Serial Bus (USB) memory devices, hard disk memory, external memory and so on. In embodiments, the system 100 and / or the memory 122 a removable smart card memory (Integrated Circuit Card, ICC) include such. B. a memory 122 which is provided by a Subscriber Identity Module (SIM) card, a Universal Subscriber Identity Module (USIM) card, a Universal Integrated Circuit Card (UICC) card and so on.

The communication interface 124 is operatively configured to communicate with components of the system. For example, the communication interface 124 be designed to store data in the system 100 to transfer data from storage in the system 100 to query and so on. The communication interface 124 is synonymous with the processor 120 communicatively coupled to a data transfer between components of the system 100 and the processor 120 (for example, to communicate inputs to the processor 120 received by a device connected to the control device 118 communicatively coupled). It should be noted that while the communication interface 124 as a component of a control device 118 is described, one or more components of the communication interface 124 can be designed as external components with the system 100 are communicatively coupled via a wired and / or wireless connection. The system 100 may also include and / or be associated with one or more input / output (I / O) devices (eg, via the communication interface 124 ), including but not limited to: a display, a mouse, a touchpad, a keyboard and so on.

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 mobile network, such as a 3G mobile network, a 4G mobile network, or a Global System For Mobile Communications (GSM) network ); a wireless computer communications network, such as a Wi-Fi network (eg, a Wireless Local Area Network (WLAN) operated using the IEEE 802.11 networking standard); an internet; the Internet; a Wide Area Network (WAN); a Local Area Network (LAN); a Personal Area Network (PAN) (eg a Wireless Personal Area Network (WPAN) operated using the IEEE 802.15 network standard); a public telephone network, an extranet, an intranet; and so on. However, this list is provided by way of example only and is not intended to limit the present disclosure. Next, the communication interface 124 be configured to communicate with a single network or with multiple networks via different access points.

Example 1 - Exemplary Monitoring System

In general, the systems described here 100 any number of remote sampling systems 104 included to take samples from any number of sampling sites. In an in 12 The implementation shown contains the system 100 five remote sampling systems 104 (shown as 104A, 104B . 104C . 104D . 104E ), located at five different locations of a processing plant, using chemical baths, bulk chemicals, environmental effluents, and other fluid samples. The remote sampling systems 104 Take samples at the various locations to take them to the far of each of the five remote sampling systems 104 arranged analysis system 102 transferred to. A first remote sampling system 104A is located near a pipe 1000 for deionized water and from the analysis system 102 over a distance (as d ₅ shown) of about forty meters (40 m) away. A second remote sampling system 104B is located near a distribution valve point 1002 and from the analysis system 102 over a distance (as d ₄ shown) of about eighty meters (80 m) away. A third remote sampling system 104C is located near a chemical feed tank 1004 and from the analysis system 102 over a distance (as d ₃ shown) of about eighty meters (80 m) away. The chemical supply container 1004 is located far from a chemical storage container 1008 and is fed with chemicals from this. A fourth remote sampling system 104D is located near a chemical feed tank 1006 and from the analysis system 102 over a distance (as d ₂ shown) of about eighty meters (80 m) away. The chemical supply container 1006 is located far from the chemical storage container 1008 and is fed with chemicals from this. A fifth remote sampling system 104E is located near the chemical storage container 1004 and from the analysis system 102 over a distance (as d ₁ shown) of about three hundred meters (300 m) away. While five remote sampling systems 104 shown, the system can 100 more than five remote sampling systems 104 use it to ultra-trace contaminants throughout Processing equipment, such as other process flows, chemical baths, storage facilities for loose chemicals, discharges into the environment, and other liquid samples to monitor. In one implementation, the sample transfer is from the remote sampling systems 104 to the analytical system at a rate of about 1.2 meters per second (1.2 m / s), which provides near-real-time analysis (eg, ICPMS analysis) of the ultra-trace contaminants throughout the processing plant.

Example 2 - Reproducibility

In one implementation was the analysis system 102 one hundred meters ( 100 m) from a remote sampling system 104 arranged. The remote sampling system 104 took twenty discrete samples and transported them to the analysis system 102 for determining the signal strength of each chemical contained in each of the twenty discrete samples. Each discrete sample contained 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 was determined that the relative standard deviation (RSD) was less than three percent (<3%) over all twenty discrete samples for all chemicals. Accordingly, the exemplary system looked 100 at one hundred meters between the analysis system 102 and the remote sampling system 104 a reliable reproducibility from taking the sample, transferring the sample over one hundred meters to the analysis system 102 (eg via the transmission line 144 ) until analyzing the samples with the analysis system 102 in front.

Example 3 - Comparison with Manual Sampling - Example

Semiconductor processing

Regarding 13 Fig. 12 is a diagram showing metallic contamination of a chemical bath for semiconductor manufacturing process (SC-1 bath) over time. The diagram contains an area 1100 showing metallic contaminant data points measured from manual samples taken at three time points. The diagram also contains an area 1102 containing the data points for metallic contamination from the range measured from manual samples 1100 shows superimposed on data points for metallic contamination, measured from samples taken from the system 100 (eg from the remote sampling systems 104 ) were taken at a sampling frequency exceeding that of the manual sampling procedure (eg, at least sixteen to seventeen times more frequently). As in the area 1102 As shown, a gradual increase in impurities occurs in the semiconductor manufacturing process over time. Lifetime or life count method for determining when to replace the chemicals in a particular semiconductor process (eg, the manual sampling technique in the field) 1100 ) are often unable to take into account the peculiarities of metallic contamination over time. Therefore, the chemicals are often changed without knowledge of the metallic contaminants in the bath. This may result in excessive replacement where the chemical bath could actually provide further wafer processing and yet be replaced (resulting, for example, in loss of process life) or insufficient replacement where the chemical bath actually has an inadmissible metallic contaminant, but not until later (which may, for example, jeopardize the wafer produced in the process). As in the area 1102 You can see the metallic contamination with the system 100 be tracked at a higher frequency automatically. An impurity limit 1104 is set to the CIM host 906 alarm when the contamination limit for the chemical bath has been reached. The system 100 Therefore, it may automatically cause the process operation to stop if the impurity limit 1104 is reached (eg to avoid inadequate replacement) while allowing the process to continue when the contaminant limit 1104 is not reached, thereby providing process time if possible (eg to avoid excessive replacement).

concluding remark

In embodiments, a variety of analytical devices may utilize the structures, techniques, approaches, and so forth described herein. Thus, although systems are described herein, a variety of analytical devices may utilize the described techniques, approaches, structures, and so on. These devices may be designed with limited functionality (eg, thin devices) or with robust functionality (eg, thick devices). Thus, the functionality of a device may relate to its software or hardware resources, e.g. Processor performance, memory (e.g., data storage capability), analytical capability, and so forth.

In general, any of the functions described herein may be performed using hardware (eg, hard-wired logic circuits, such as integrated circuits), software, firmware, manual processing, or a combination thereof. Thus, the blocks described in the above disclosure generally represent hardware (e.g., hardwired logic circuits, such as integrated circuits), software, firmware, or a combination thereof. In the case of hardware implementation, the various blocks described in the above disclosure may be referred to as integrated circuits may be implemented together with other functionality. Such integrated circuits may include all of the functions of a particular block, system or circuit, or a portion of the functions of the block, system or circuit. Further, elements of the blocks, systems, or circuits may be implemented over multiple integrated circuits. Such integrated circuits may include various integrated circuits, including but not limited to: a monolithic integrated circuit, an integrated flip-chip circuit, a multi-chip integrated circuit, and / or a mixed-signal integrated circuit. In the case of a software implementation, the various blocks described in the above disclosure represent executable instructions (eg, program code) that perform certain tasks when executed on a processor. These executable instructions may be stored in one or more tangible computer-readable media. In some cases, the entire system, block, or circuit may be implemented using its software or firmware equivalent. In other cases, a portion of a particular system, block, or circuit may be implemented in software or firmware while other portions are embodied in hardware.

Although the subject matter has been described in language specific to structural features and / or procedures, 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 exemplary embodiments of the claims.

Claims (20)

Sample concentration system for the analysis of a fluid sample by an analytical system, comprising: a plurality of valves including at least a first valve, a second valve and a third valve, the plurality of valves being switchable between different flow path arrangements; a plurality of columns including at least a first column and a second column, wherein the first column and the second column are configured to retain at least one chemical of interest from a fluid sample, the first column being fluidly coupled to the first valve, the second column Pillar is fluidly coupled to the second valve; and a flow meter coupled to the third valve, the flow meter being fluidly coupled to each of the first column and the second column when the plurality of valves are in a first flow path arrangement to measure an amount of the liquid sample passing through the first column and the second column have flowed, the plurality of valves including a second flow path arrangement in which the first column, the first valve, the second valve and the third valve are in fluid communication and the second column and the flow meter are not are in fluid communication with the first column, and the plurality of valves include a third flow path arrangement in which the first column, the first valve, the second column, the second valve and the third valve are in fluid communication and the flow meter is not is in fluid communication with the first column or the second column. Sample concentration system after Claim 1 , further comprising: a controller operatively coupled to the flow meter and the plurality of valves, the controller configured to set the amount of liquid sample that has flowed through the first column and the second column measured by the flow meter to a threshold value to compare the sample. Sample concentration system after Claim 2 wherein the controller switches the plurality of valves from the first flow path arrangement to the second flow path arrangement when the amount of liquid sample that has flowed through the first column and the second column, as measured by the flow meter, reaches at least the threshold value of the sample. Sample concentration system after Claim 2 , further comprising: a computer memory accessible to the controller, the computer memory storing the threshold value of the sample. Sample concentration system after Claim 2 , further comprising: a user interface accessible to the controller, the user interface configured to receive the threshold of the sample from a user. Sample concentration system after Claim 1 wherein the first column is a different column type than the second column. Sample concentration system after Claim 1 wherein the first column is a chelation column, and wherein the second column is a cation exchange column. Sample concentration system after Claim 1 wherein at least one of the first column or the second column contains an anion exchange column, a cation exchange column, a chelation column or a chromatography column. Sample concentration system after Claim 1 wherein the plurality of valves includes a fourth flow path arrangement in which the liquid sample introduced into the first valve bypasses each of the first column and the second column during transfer to the third valve. Sample concentration system after Claim 1 wherein the first valve includes an input for the fluid sample and for an internal standard, wherein the first valve is configured to mix the fluid sample and the internal standard prior to introducing the fluid sample into the first column. Sample concentration system after Claim 1 further comprising: a nebulizer coupled to the third valve, the nebulizer being in fluid communication with the first column when the plurality of valves are in the second flow path arrangement. Sample concentration system after Claim 1 , further comprising: an atomizer coupled to the third valve, the atomizer being in fluid communication with the second column when the plurality of valves are in the third flow path arrangement. Sample concentration system after Claim 1 further comprising: a transmission line coupled between the third valve and an analysis system, the transmission line being in fluid communication with the first column when the plurality of valves are in the second flow path arrangement. Sample concentration system after Claim 1 further comprising: a transmission line coupled between the third valve and an analysis system, wherein the transmission line is in fluid communication with the second column when the plurality of valves are in the third flow path arrangement. Sample concentration system for the analysis of a fluid sample by an analytical system, comprising: a valve configured to switch between at least a first flow path arrangement and a second flow path arrangement; a column configured to separate one or more analytes of interest from a fluid sample, the column being in fluid communication with the valve in each of the first flow path assembly and the second flow path assembly; a flow meter fluidly coupled to each of the valve and the column when the valve is in the first flow path arrangement, the flow meter not being fluidly coupled to the column when the valve is in the second flow path arrangement and the flow meter is configured to measure an amount of the liquid sample that has flowed through the column when the first valve is in the first flow path arrangement. Sample concentration system after Claim 15 , further comprising: a controller operatively coupled to the flow meter and the valve, the controller configured to compare the amount of fluid sample that has flowed through the column measured by the flow meter with a threshold value of the sample. Sample concentration system after Claim 16 , further comprising: a computer memory accessible to the controller, the computer memory storing the threshold value of the sample. Sample concentration system after Claim 16 , further comprising: a user interface accessible to the controller, the user interface configured to receive the threshold of the sample from a user. Sample concentration system after Claim 16 wherein the controller switches the valve from the first flow path arrangement to the second flow path arrangement when the amount of liquid sample that has flowed through the column measured by the flow meter reaches at least the threshold value of the sample. Sample concentration system after Claim 15 wherein the column and the valve are in fluid communication with an eluent when the valve is in the second flow path arrangement, and wherein the flow meter is not in fluid flow Connection with the eluent is when the valve is in the second flow path arrangement.

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