Patent Description:
There are several materials present around in the Earth's environment. Some of these materials are well known, while other of these materials may still need to be identified. Furthermore, some of the materials are present on the Earth's surface, while a majority of the materials are present beneath the Earth's surface. The materials that are present beneath the surface of the Earth are usually extracted by using one or more techniques such as drilling, mining and so forth. Furthermore, it is important to analyse these materials in order to determine their compositions, for example, to determine a presence of organic components, hydrocarbons, various isotopes and so forth present therein. Moreover, their analysis is susceptible to identifying various properties that these materials possess and also, their use in different applications.

Conventionally, drilling is a technique that is used to extract fossil fuels and other components from beneath the Earth's surface. While performing a drilling operation, several by-products are obtained, apart from one or more intended products, including, mud, sludge, waste drilling fluids and similar. Furthermore, an analysis of such by-products provides important information, such as, a knowledge of a geological sequence onsite of the drilling operation, and various products that can be extracted by performing the drilling operation. For example, the waste drilling fluid contains various gases mixed with liquid. Such gases can be extracted and used for analysis of composition of mud that is extracted from the drilling operation. Results of such an analysis can be crucial for various reasons, such as, for safety of humans present in a vicinity of the drilling operation, for determination of feasibility of the drilling operation and so forth.

Generally, various techniques are used for performing such analyses. Such techniques employ a device for separating gases from the drilling fluid and subsequently, and for determining a concentration of isotopes present therein. It will be appreciated that an operation of such devices onsite of the drilling operation are subjected to changes in temperature and pressure conditions. Furthermore, to obtain higher accuracy associated with use of such devices, an impact of the changes in temperature and pressure conditions is required to be reduced, such as, by arrangement of the devices in a controlled and vibration-free environment. Therefore, the analyses are commonly performed at an offsite location, such as in a laboratory after extracting gases from the fluid. However, performing offsite analyses may result in varying compositions as compared to actual compositions of the gases that can be observed onsite of the drilling operation. It will be appreciated that, to avoid such variations, there is a need for devices that are capable of performing onsite analysis of the gases.

<CIT> relates to a mobile system for in situ acquisition of carbon isotope data on both bulk hydrocarbon mixtures and individual components in natural gas during oil and gas exploration and production.

Conventionally, devices that are used for onsite analysis of the gases have various associated drawbacks. For example, such devices are generally large in size, and require a large area for installation thereof. This drawback increases a cost associated with operation of the devices and consequently, reduces profitability of the drilling operation. Furthermore, the devices require complex climate control arrangements that further increase a complexity and costs associated with the drilling operation. Additionally, such devices are fragile and are easily affected by geological variables such as mechanical vibrations, shocks experienced during the drilling operation and so forth. The fragility of the devices leads to repetitive breakdown thereof and further increases the cost associated with the analyses (and the drilling operation). Furthermore, such devices are generally associated with large analysis times.

Therefore, in light of the foregoing discussion, there exists a need to address, for example to overcome, the aforementioned drawbacks associated with conventional devices that are used for determining isotopic composition of gases, for example, onsite of drilling operations.

The present disclosure seeks to provide an improved system for determining isotopic composition of a gaseous sample.

The present disclosure also seeks to provide an improved method of determining isotopic composition of a gaseous sample.

Furthermore, the present disclosure seeks to provide a software product recordable on machine-readable data storage media, characterised in that the software product is executable upon computing hardware for implementing an improved method of determining isotopic composition of a gaseous sample.

According to a first aspect, an embodiment of the present disclosure provides a system for determining isotopic composition of a gaseous sample, the system comprises:.

wherein the isotope-ratio mass spectrometer is configured to use the determined isotopic concentrations associated with each of the ion beams to determine the isotopic composition of the gaseous sample.

The present disclosure seeks to provide an improved, compact and reliable system and method that substantially overcomes various drawbacks associated with conventional techniques of analysis of isotopic composition of gaseous samples.

The ion source and the mass analyser are arranged in a housing.

The isotope-ratio mass spectrometer is arranged with a shock absorbing arrangement.

Optionally, the mass analyser comprises:.

Optionally, the system further comprises a sample diluter operatively coupled with the at least one gas chromatograph, wherein the sample diluter is operable to dilute the gaseous sample using a carrier gas. Optionally, the system further comprises a dilution adjustment device operatively coupled to the sample diluter, wherein the dilution adjustment device is operable to employ the determined isotopic concentrations associated with each of the ion beams to modify an amount of the carrier gas employed to dilute the gaseous sample, based on threshold isotopic concentrations associated with each of the ion beams.

Optionally, the dilution adjustment device is further operable to modify the amount of the carrier gas employed to dilute the gaseous sample, iteratively and in real time.

wherein the cylindrical tube comprises an oxidation catalyst to promote oxidation of the gaseous components.

Optionally, the cylindrical tube is fabricated using stainless steel.

The oxidation catalyst is platinised copper oxide.

Optionally, the water separator comprises:.

wherein the oxidized gaseous components are operable to flow through the tube coiled around the cylindrical support.

Optionally, the tube is fabricated using Nafion polymer.

Optionally, the hollow cylindrical casing is fabricated using glass.

The water separator is arranged with a shock absorbing arrangement.

According to a non-claimed second aspect, an embodiment of the present disclosure provides a method of determining isotopic composition of a gaseous sample, the method comprises:.

Optionally, the method further comprises diluting the gaseous sample using a carrier gas.

More optionally, the method includes diluting the gaseous sample by using the carrier gas under flow conditions. More optionally, the carrier gas as a diluter gas is injected at a sample port, for example where the sample port is included upstream of the at least one gas chromatograph.

Optionally, the method further comprises using a feedback loop to modify an amount of the carrier gas that is used for diluting the gaseous sample, by employing the determined isotopic concentrations associated with each of the ion beams, based on threshold isotopic concentrations associated with each of the ion beams.

Optionally, the method further comprises generating at least one chromatogram associated with the at least one gas chromatograph after separating the gaseous sample into the gaseous components.

Optionally, a first gas chromatograph and a second gas chromatograph of the at least one gas chromatograph are used together for separating the gaseous sample into gaseous components.

Optionally, the method further comprises correlating a first chromatogram associated with the first gas chromatograph and a second chromatogram associated with the second gas chromatograph to obtain an elution order of the gaseous components.

Optionally, the method further comprises comprising:.

According to a non-claimed third aspect, an embodiment of the present disclosure provides a software product recording on machine-readable data storage media, characterised in that the software product is executable upon computing hardware for implementing a method of determining isotopic composition of a gaseous sample.

In overview, embodiments of the present disclosure are concerned with systems for determining isotopic compositions of gaseous samples. Furthermore, embodiments of the present disclosure are concerned with methods of determining isotopic compositions of gaseous samples. Moreover, embodiments of the present disclosure are concerned with software product recordable on machine-readable data storage media and executable upon computing hardware, for implementing the aforementioned methods of determining isotopic composition of gaseous samples.

Referring to <FIG>, there is shown a schematic illustration of a system <NUM> for determining an isotopic composition of a gaseous sample, in accordance with an embodiment of the present disclosure. As shown, the system comprises an inlet <NUM>. The inlet <NUM> is operatively coupled with a valve <NUM> that is operable, namely configured, to be in a first position OA and a second position OB. The valve <NUM>, when maintained in the first position OA, enables the inlet <NUM> to be connected with a carrier gas container 106A. In an example, the carrier gas container is operable, namely configured, to store an inert and/or an unreactive gas (such as a gas known to be unreactive with the gaseous sample). In another example, the carrier gas is Helium or similar noble gas. In yet another example, the carrier gas is Nitrogen. Furthermore, when the valve <NUM> is switched to the second position OB, a connection is established between the inlet <NUM> and a gaseous sample container 106B. Moreover, maintaining the valve <NUM> in the second position OB enables a flow of the gaseous sample stored in the gaseous sample container 106B to occur into the inlet <NUM>. In one example, the gaseous sample is a mud gas that is obtained during a drilling operation, such as, an oil well drilling operation or an offshore drilling operation. Furthermore, such a mud gas can be extracted by performing a degassing operation of a drilling fluid that is obtained during the drilling operation.

In an embodiment, the inlet <NUM> is operatively coupled with a flow restricting arrangement (not shown). The flow restricting arrangement enables an amount of the gaseous sample flowing from the gaseous sample container 106B into the inlet <NUM> to be adjusted, for example reduced. Optionally, the flow restricting arrangement enables a manual control (such as, by an on-site technician) of flow of the gaseous sample into the inlet <NUM>.

The system <NUM> comprises at least one gas chromatograph <NUM> for separating the gaseous sample into gaseous components. For example, when the gaseous sample is mud gas that is extracted during a well drilling operation, the gaseous sample may comprise a plurality of gaseous components including organic gases such as methane (CH<NUM>), ethane (C<NUM>H<NUM>), propane (C<NUM>H<NUM>), inorganic gases such as carbon dioxide (CO<NUM>) and suchlike. In such an example, the gas chromatograph <NUM> enables the mud gas to be separated into the plurality of gaseous components. In operation, each of the plurality of gaseous components will be retained within the gas chromatograph <NUM> for a corresponding different duration of time (associated with a retention time). In such an example, in operation, the gaseous components flow out of the gas chromatograph in a specific order (or elution order) based upon their individual retention times. Moreover, in operation, the gas chromatograph <NUM> generates a chromatogram subsequent to separation of the gaseous sample into the gaseous components; a chromatogram is a graphical representation of concentrations of each the gaseous components, for example as a function of molecular weight or atomic weight. When the concentrations are relatively higher of certain of the gas components, the relatively higher concentrations give rise to peaks in the chromatogram. Thus, for example, such a chromatogram comprises peaks associated with each of the gaseous components separated from the gaseous sample.

According to an embodiment, the at least one gas chromatograph <NUM> is implemented using a first gas chromatograph and a second gas chromatograph. Furthermore, the first and the second gas chromatographs are used in conjunction with each other. For example, the inlet <NUM> is connected to both the first and the second gas chromatographs at a same time. In such an example, both the first and the second gas chromatographs are operable, namely are configured, to separate the gaseous sample into its gaseous constituents (namely, for example, gaseous components). Moreover, the first and the second gas chromatographs are operable, namely are configured, to generate a first chromatogram and a second chromatogram, respectively. It will be appreciated that employing the two gas chromatographs together enables a time required for separation of the gaseous sample into the gaseous constituents to be reduced.

In one embodiment, the first chromatogram and the second chromatogram are correlated to obtain an elution order of the gaseous components. For example, the first chromatogram obtained after separation of the gaseous sample from the first gas chromatograph, is superimposed with the second chromatogram obtained after separation of the gaseous sample from the second gas chromatograph; for example, a strong correlation occurs when peaks of chromatograms of the first and second gas chromatographs are mutually coincident. Furthermore, the determined elution order of the gaseous constituents is associated with readings obtained by both the first and the second chromatograms, respectively. It will be appreciated that such an elution order obtained by using the two chromatograms increases an accuracy associated with measuring the determined elution order. Furthermore, a time required for determination of the elution order is reduced.

In an embodiment, the system <NUM> comprises a sample diluter that is operatively coupled with the at least one gas chromatograph <NUM>, wherein the sample diluter is operable, namely configured, to dilute the gaseous sample using a carrier gas. The sample diluter (not shown) is arranged, namely connected, between the inlet <NUM> and the at least one gas chromatograph <NUM>. Furthermore, the sample diluter is operable, namely configured, to receive the carrier gas from the carrier gas container 106A. Subsequently, the sample diluter enables a mixture of the carrier gas with the gaseous sample to be achieved, before a flow of the gaseous sample occurs into the at least one gas chromatograph <NUM>. In one example, the sample diluter operates at a pressure of <NUM> atmosphere (atm) and a volumetric flow rate, for example, in a range of <NUM> to <NUM> millilitres per minute. Such an operating pressure and volumetric flow rate of the sample diluter reduces isotopic fractionation of the gaseous sample before separation thereof using the at least one gas chromatograph <NUM>.

The system <NUM> comprises a combustion furnace <NUM> that is operatively coupled with the at least one gas chromatograph <NUM> for oxidizing the gaseous components. The combustion furnace <NUM> (shown in detail in <FIG>) is operable, namely configured, to oxidize the gaseous components flowing from the gas chromatograph <NUM>, by combustion thereof. For example, the gaseous components separated from the mud gas comprise methane (CH<NUM>), ethane (C<NUM>H<NUM>), propane (C<NUM>H<NUM>), carbon dioxide (CO<NUM>), Ethene (Ethylene) and Propene (Propylene). In such an example, the combustion furnace <NUM> is operable, namely configured, to oxidize the gaseous components to yield carbon dioxide (CO<NUM>) for Methane, Ethane and Propane.

In one example, the combustion furnace <NUM> operates at a working temperature in a range of <NUM> to <NUM>. Furthermore, the combustion furnace <NUM> is operable, namely is configured, to use an oxidation catalyst to promote oxidation of the gaseous components. In an embodiment, the oxidation catalyst is platinised copper oxide.

The system <NUM> comprises a water separator <NUM> that is operatively coupled with the combustion furnace <NUM> for removing water from the oxidized gaseous components. The water separator <NUM> (shown in detail in <FIG>) is operable, namely configured, to dehydrate the oxidised gaseous components flowing out of the combustion furnace <NUM> by removing moisture therefrom. As shown, the water separator <NUM> comprises an inlet 114A that is operatively coupled, namely operatively connected, with the combustion furnace <NUM> for receiving the oxidized gaseous components therefrom. Furthermore, the water separator <NUM> comprises an outlet 114B for providing for a flow of dehydrated oxidised gaseous components from the water separator <NUM>. In an example, the dehydrated, oxidised gaseous components flow, in operation, at a flow rate, for example, in a range of <NUM> to <NUM> millilitres per minute. In another example, the outlet 114B is coupled to a capillary tube having a radius, for example, in a range of <NUM> to <NUM> micrometres. Moreover, as shown, the water separator <NUM> comprises an inlet 116A for receiving a carrier gas, for removing moisture from the oxidised gaseous components in the water separator <NUM>. The carrier gas, subsequent to removing moisture from the oxidised gaseous components, is removed from the outlet 116B. In one example, the carrier gas is associated with a volumetric flow rate, for example, in a range of <NUM> to <NUM> millilitres per minute through the water separator <NUM>.

The system comprises an isotope-ratio mass spectrometer <NUM> that is operatively coupled with the water separator <NUM>. As shown, the outlet 114B of the water separator <NUM> is operatively coupled with the isotope-ratio mass spectrometer <NUM>, to enable a flow of the dehydrated oxidised gaseous components into the isotope-ratio mass spectrometer <NUM>. As shown, the isotope-ratio mass spectrometer <NUM> comprises an ion source <NUM> for generating ion beams associated with each of the oxidized gaseous components. For example, when the oxidized gaseous components comprise carbon dioxide (CO<NUM>), ethylene dione (C<NUM>O<NUM>), and carbon suboxide (C<NUM>O<NUM>), the ion source <NUM> is operable to produce ion beams associated with each of carbon dioxide (CO<NUM>), ethylene dione (C<NUM>O<NUM>), and carbon suboxide (C<NUM>O<NUM>), respectively. Furthermore, the ion source <NUM> is enclosed in a vacuum chamber <NUM> that is operatively coupled with a pump arrangement <NUM>. The pump arrangement <NUM> comprises a vacuum gauge <NUM>, a turbo pump <NUM> and an oil free diaphragm pump <NUM>. It will be appreciated that the turbo pump <NUM> and the diaphragm pump <NUM> enable air to be removed from the vacuum chamber <NUM>, for generating of vacuum therein.

The isotope-ratio mass spectrometer <NUM> comprises a magnetic sector mass analyser <NUM> for receiving the generated ion beams from the ion source <NUM>, wherein the mass analyser <NUM> is operable to determine isotopic concentrations associated with each of the ion beams; it will be appreciated that magnetic sector analysers are significantly more stable than other mass spectrometers, for example quadrupole analysers. The mass analyser <NUM> is operable, namely configured, to separate isotopes of each of the ion beams and subsequently, to determine an isotopic concentration thereof. For example, the ion beams are associated with oxidized gaseous components of Methane (CO<NUM>), Ethane (C<NUM>O<NUM>), and Propane (C<NUM>O<NUM>). In such an example, the mass analyser <NUM> is operable to separate carbon dioxide (CO<NUM>) into its isotopes associated with <NUM>C (associated with carbon atoms having an atomic number of <NUM> and/or mass number of <NUM>) and <NUM>C (associated with carbon atoms having an atomic number of <NUM> and/or mass number of <NUM>). Similarly, when the gaseous component is ethylene dione (C<NUM>O<NUM>), the mass analyser <NUM> is operable, namely configured, to separate the ethylene dione (C<NUM>O<NUM>) into its isotopes associated with <NUM>C<NUM> and <NUM>C<NUM>. Moreover, the mass analyser <NUM> is operable, namely configured, to separate the carbon suboxide (C<NUM>O<NUM>) into its isotopes, such as <NUM>C<NUM> and <NUM>C<NUM>.

According to the invention, the ion source <NUM> and the mass analyser <NUM> are arranged in a housing. The ion source <NUM> and the mass analyser <NUM> are arranged in the housing implemented as a vertical cabinet. The ion source <NUM>, the mass analyser <NUM> and the cabinet form a single unit. Optionally, the mass analyser <NUM> is arranged spatially under the ion source <NUM> within the cabinet when the mass analyser <NUM> is being operated. It will be appreciated that when the system <NUM> is used on-site, for example, on-site of a drilling operation, the system <NUM> is operable to experience vibrations and/or shock. According to the invention, the ion source <NUM>, the mass analyser <NUM> and the housing are arranged to be movable as a single unit, namely as a unitary apparatus arrangement. Such an arrangement provides for increased operating robustness, by reducing a risk of damage due to individual movement of each of the ion source <NUM> and the mass analyser <NUM> when experiencing the vibrations and/or shock. According to the invention, the isotope-ratio mass spectrometer <NUM> is arranged with a shock absorbing arrangement to absorb shocks and vibration being coupled to the isotope-ratio mass spectrometer <NUM> when in operation.

The isotope-ratio mass spectrometer <NUM> is mounted on the shock absorbing arrangement. The shock absorbing arrangement enables, as an aforementioned, to absorb the aforementioned vibrations and/or shock experienced by the isotope-ratio mass spectrometer <NUM> (and therefore, the ion source <NUM> and the mass analyser <NUM>), thereby, further reducing damage and wear experienced by the isotope-ratio mass spectrometer <NUM> during operation of the system <NUM>.

A magnetic material, for example Hycomax <NUM>, that is stable at high temperatures, for example at temperatures greater than <NUM>, for example at temperatures greater than <NUM>, is used for implementing a mass spectrometer analyser magnet <NUM> for the mass analyser <NUM>, thereby reduces mass position drift when ambient conditions vary in operation.

In an embodiment, the mass analyser <NUM> comprises the aforesaid mass analysing magnet <NUM> for deflecting the ion beams received from the ion source <NUM>. The mass analysing magnet <NUM> is operable to deflect ions of isotopes associated with each of the ion beams along corresponding different paths, based upon a mass-to-charge ratio of the isotope ions. For example, isotopes ions having a lower mass-to-charge ratio (such as the isotope <NUM>C) experience lesser deflection as compared to isotope ions having a higher mass-to-charge ratio (such as the isotope <NUM>C), for each isotope associated with each of the ion beams. In the same embodiment, the mass analyser <NUM> comprises a plurality of detectors <NUM> for detecting isotopic concentrations associated with each of the deflected ion beams. In one example, the plurality of detectors <NUM> is implemented using Faraday cups that are operable, namely configured, to receive the deflected ion beams. In such an example, a signal (such as a current pulse) is generated when a given ion is detected at a corresponding one of the Faraday cups, thereby, enabling determination of the isotopic concentrations associated with each of the ion beams.

In one embodiment, the determined isotopic concentrations associated with each of the ion beams are employed in a feedback loop to modify an amount of the carrier gas that is used for diluting the gasesous sample, based on threshold isotopic concentrations associated with each of the ion beams. For example, during operation of the system, isotopic concentrations associated with the gaseous sample may increase beyond a working dynamic range of one or more components of the system, such as gas chromatograph, the combustion furnace and the mass spectrometer. In such an example, a sample diluter is employed in a feedback loop, such that the sample diluter controls a flow of the carrier gas to the inlet, to dilute the gaseous sample using the carrier gas to the threshold isotropic concentration. The term "threshold isotopic concentration" as used herein, refers to a predetermined isotopic concentration of isotopes associated with the gaseous sample, such that the predetermined isotopic concentration lies within the working dynamic range of the one or more components of the system. In one embodiment, the system further comprises a dilution adjustment device operatively coupled to the sample diluter. The dilution adjustment device is further operatively coupled to the mass analyser <NUM>, wherein the dilution adjustment device is operable to receive the determined isotopic concentrations associated with each of the ion beams (for example, as a digital signal therefrom). Subsequently, the dilution adjustment device is operable to employ the determined isotopic concentrations associated with each of the ion beams to modify an amount of the carrier gas employed to dilute the gaseous sample, based on threshold isotopic concentrations associated with each of the ion beams. For example, the dilution adjustment device is operable to receive the determined isotopic concentrations associated with each of the ion beams from the mass analyser <NUM> and consequently, the dilution adjustment device is operable to provide a signal to the sample diluter to increase or decrease the amount of the carrier gas used to dilute the gaseous sample, such that the isotopic concentrations associated with each of the ion beams is determined to be less than or equal to the threshold isotopic concentrations associated with each of the ion beams in a subsequent cycle. Thus, the feedback loop is established between the dilution adjustment device, the sample diluter and the mass analyzer <NUM>. In one embodiment, the dilution adjustment device is operable to adjust the amount of the carrier gas employed to dilute the gaseous sample, iteratively and in real time. For example, the dilution adjustment device, upon receiving the determined isotopic concentrations associated with each of the ion beams from the mass analyzer <NUM>, is operable, namely configured, to increase or decrease the amount of the carrier gas instantaneously, such that the isotopic concentrations associated with each of the ion beams is determined to be below the threshold isotopic concentrations. Furthermore, upon determining a change in the determined isotopic concentrations associated with each of the ion beams, the dilution adjustment device is operable, namely configured to instantaneously adjust the amount of carrier gas employed to dilute the gaseous sample, to iteratively modify the amount of carrier gas employed to dilute the gaseous sample. Such a system employing the dilution adjustment device enables the gaseous sample provided at the input to be associated with constant isotopic concentrations (such as, below the threshold isotopic concentrations) and is further, continuously adjusted at high speed (or instantaneously) giving real time gaseous sample auto ranging. The feedback loop is used to provide the diluted sample having a substantially constant ("substantially constant" is to be construed to be in a range of <NUM>% to <NUM>%, more optionally in a range of <NUM>% to <NUM>%) dilution of the gaseous sample. For example, upon determination of high isotopic concentrations in one or more of the ion beams, an amount of the carrier gas that is used to dilute the gaseous sample is increased. Alternatively, upon determination of low isotopic concentrations in one or more of the ion beams, the amount of the carrier gas that is used to dilute the gaseous sample is decreased. In one example, the feedback loop is used to achieve a constant <NUM>% dilution of the gaseous sample flowing into the at least one gas chromatograph <NUM>. Furthermore, by providing such a constant dilution of the gaseous sample, improved reproducibility is measurements associated with determination of isotopic composition of various gaseous samples is achievable during operation of the system <NUM> (such as, due to the combustion furnace <NUM> and the mass analyser <NUM> being associated with linear ranges of operation, respectively).

The isotope-ratio mass spectrometer <NUM> is operable, namely configured, to use the determined isotopic concentrations associated with each of the ion beams to determine the isotopic composition of the gaseous sample. For example, the isotope-ratio mass spectrometer <NUM> comprises a current sensor <NUM> that is communicably coupled in operation with analogue-to-digital (ADC) converters <NUM>. The current sensor <NUM> is operable, namely configured, to sense amperage (namely, magnitude) associated with the current pulses generated by the plurality of detectors <NUM>. Furthermore, the analogue-to-digital converters <NUM> are operable, namely configured, to convert the analogue signals obtained from the current sensor <NUM> to corresponding digital signals. As shown, the isotope-ratio mass spectrometer <NUM> comprises a data processing arrangement <NUM> that is communicably coupled with the analogue-to-digital converters <NUM>. In one example, the data processing arrangement <NUM> is implemented using a PIC microcontroller. The data processing arrangement <NUM> is operable, namely configured, to receive the digital signals associated with detected isotopic concentrations from the analogue-to-digital converters <NUM> and perform analysis thereof, to determine the isotopic composition of the gaseous sample (as described herein below).

The isotope-ratio mass spectrometer <NUM> is operable, namely, configured to determine the isotopic concentrations associated with each of the ion beams as ratios. For example, when the ion beam is associated with carbon dioxide (CO<NUM>), the isotope-ratio mass spectrometer <NUM> is operable (namely, configured) to determine a ratio of isotopic concentrations of <NUM>C and <NUM>C ions associated with the gaseous sample. Subsequently, the isotope-ratio mass spectrometer <NUM> is operable, namely configured, to use a predetermined ratio of isotopic concentrations of <NUM>C and <NUM>C ions associated with a reference gaseous sample of carbon dioxide (CO<NUM>). Furthermore, the isotope-ratio mass spectrometer <NUM> is operable, namely configured, to determine a delta value (δ) associated with measured concentrations each of the detected isotopes. Optionally, the delta value is determined in accordance with Pee Dee Belemnite (PDB) standard or Vienna PDB (VPDB) standard. For example, the delta value (δ) is determined using a formula, for example, as described below: <MAT> wherein <MAT> Sample is the determined ratio of isotopic concentrations of <NUM>C and <NUM>C associated with the gaseous sample of carbon dioxide (CO<NUM>) and <MAT>Reference is the predetermined ratio of isotopic concentrations associated with the reference gaseous sample of carbon dioxide (CO<NUM>). Furthermore, δSample is an isotopic concentration associated with the isotope <NUM>C, represented in parts per thousand (represented as δ<NUM>C).

Subsequently, the data processing arrangement <NUM> is operable to determine the isotopic composition of the gaseous sample by using isotopic concentrations of each detected isotope, associated with all of the gaseous components separated from the gaseous sample. Optionally, the determined isotopic composition of the gaseous sample is graphically represented on a user interface (shown in <FIG>), for example on a graphical user interface (GUI). For example, the data processing arrangement <NUM> is communicably coupled with a display arrangement. In such an example, the data processing arrangement <NUM> is operable to render the graphical representation of the determined isotopic composition of the gaseous sample on a user interface associated with the display arrangement.

According to one embodiment, the isotope-ratio mass spectrometer <NUM> is calibrated using the reference gaseous sample. The isotope-ratio mass spectrometer <NUM> may be required to be calibrated before initiating operation of the system <NUM> (such as, during a setup phase of the system <NUM>). Alternatively, during prolonged operation of the system <NUM>, one or more components of the system <NUM> (such as the isotope-ratio mass spectrometer <NUM>) may experience a malfunction, thereby causing an error in determined isotopic compositions of gaseous samples. In such a situation, a recalibration of the isotope-ratio mass spectrometer <NUM> using the reference gaseous sample enables such errors to be taken into account and/or corrected. The system <NUM> is beneficially used to determine a reference isotopic composition of the reference gaseous sample. The reference gaseous sample is allowed to flow into the system <NUM> using a reference gas sample inlet <NUM>. As the reference, gaseous sample is associated with a corresponding predetermined isotopic composition, the reference gaseous sample may not be required to flow through the at least one gas chromatograph <NUM> and the combustion furnace <NUM>. Furthermore, the reference isotopic composition of the reference gaseous sample is determined using the system <NUM>, specifically, using the isotope-ratio mass spectrometer <NUM>. In such a situation, the determined reference isotopic composition is compared with the predetermined isotopic composition of the reference gaseous sample to determine a correction factor. In an example, the correction factor is associated with a difference between the predetermined isotopic composition and the determined reference isotopic composition of the reference gaseous sample. Subsequently, the isotope-ratio mass spectrometer <NUM> is calibrated using the correction factor, to correct an error associated with the isotope-ratio mass spectrometer <NUM> and/or prior to starting operation of the system <NUM>. Optionally, the aforementioned steps are iterated by using a plurality of reference gaseous samples to improve an accuracy associated with the determined correction factor.

Referring to <FIG>, there is shown an illustration of a user interface <NUM> depicting a graphical representation of isotopic compositions of a gaseous sample with respect to a reference gaseous sample, in accordance with an embodiment of the present disclosure. The user interface <NUM> is rendered on a display device (not shown). As shown, the user interface <NUM> graphically depicts a determined isotopic composition <NUM> of the gaseous sample corresponding to isotopic concentrations associated with various isotopes, represented as delta values δ<NUM>C, δ<NUM>C and δ<NUM>C. Furthermore, the user interface depicts a predetermined isotopic composition <NUM> of the reference gaseous sample corresponding to isotopic concentrations of isotopes represented by delta values δ<NUM>C, δ<NUM>C and δ<NUM>C.

Referring to <FIG>, there is shown a sectional view of the combustion furnace <NUM> of <FIG>, in accordance with an embodiment of the present disclosure. The combustion furnace <NUM> comprises a furnace box <NUM> that is operable, namely configured, to incorporate various components of the combustion furnace <NUM> therein. Furthermore, the combustion furnace <NUM> comprises a cartridge heater <NUM>. The cartridge heater <NUM> is a joule heating element that is operable, namely configured, to produce heat energy when electric current is passed therethrough. In one example, an operation of the cartridge heater <NUM> is associated with a power consumption in a range of <NUM> to <NUM> Watts. In another example, the cartridge heater <NUM> is capable of producing an operating temperature in a range of <NUM> to <NUM>.

As shown, the combustion furnace <NUM> also comprises a cylindrical tube <NUM> wound around the cartridge heater <NUM>. In an embodiment, the cylindrical tube <NUM> is fabricated using a metal or metal allow, for example stainless steel. The cylindrical tube <NUM> is operatively coupled with an inlet <NUM> wherefrom the gaseous sample is drawn into the combustion furnace <NUM>. Furthermore, the cylindrical tube <NUM> comprises an oxidation catalyst to promote oxidation of the gaseous components flowing therethrough. According to the invention, the oxidation catalyst is platinised copper oxide. For example, the oxidation catalyst is implemented as granules of platinised copper oxide that are arranged along a length of the cylindrical tube <NUM>. The oxidation catalyst enables oxidation of the gaseous components at a lower temperature as compared to conventional combustion furnaces that do not employ the oxidation catalyst therein. Furthermore, the oxidation of the gaseous components at the lower temperature increases an operating life of the combustion furnace <NUM> and consequently, the system <NUM>. Moreover, the cylindrical tube <NUM> is operatively coupled with an outlet <NUM>. The gaseous components that have undergone oxidation while passing through the cylindrical tube <NUM> are extracted from the outlet <NUM>.

Referring to <FIG>, there is shown a sectional view of the water separator <NUM> of <FIG>, in accordance with an embodiment of the present disclosure. As shown, the water separator <NUM> comprises a hollow cylindrical casing <NUM>. The hollow cylindrical casing <NUM> incorporates various components of the water separator <NUM> therein. In an embodiment, the hollow cylindrical casing <NUM> is fabricated using glass, for example silica glass. Furthermore, the water separator <NUM> comprises a cylindrical support <NUM> incorporated within the hollow cylindrical casing <NUM>. For example, the cylindrical support <NUM> is implemented as a wire that is arranged through a centre of the hollow cylindrical casing <NUM>. Moreover, the water separator <NUM> comprises an elongate wire (not shown) helically coiled around the cylindrical support <NUM> and a tube <NUM> surrounding the elongate wire. The elongate wire acts as a base for supporting the tube <NUM>. Furthermore, coiling of the tube <NUM> around the cylindrical support <NUM> increases a surface area of the tube <NUM> while enabling the water separator <NUM> to maintain a compact form factor, thereby, increasing an efficiency associated with the water separator <NUM>. According to one embodiment, the tube <NUM> is fabricated using Nafion polymer.

In operation, the oxidized gaseous components are allowed to flow into the water separator <NUM> through the inlet 114A. Subsequently, the oxidized gaseous components flow through the tube <NUM> coiled around the cylindrical support <NUM>. During such a flow of the oxidized gaseous components through the tube <NUM>, the carrier gas flows into the water separator <NUM> through the inlet 116A. Furthermore, during flow of the oxidized gaseous components helically through the tube <NUM>, the carrier gas flows along an outer surface of the tube <NUM>. Such a flow of the carrier gas enables to capture moisture that has been separated from the gaseous components through walls of the tube <NUM>. The dehydrated oxidized gaseous components flow out of the water separator <NUM> through the outlet 114B. Moreover, the carrier gas, having a higher moisture content in comparison to the carrier gas at inlet 116A, is removed from the water separator <NUM> through the outlet 116B.

According to the invention, the water separator <NUM> is arranged with a shock absorbing arrangement 408A-B. Such a shock absorbing arrangement 408A-B enables absorption of shocks and/or vibrations experienced by the water separator <NUM> during operation of the system <NUM>, for example, on-site of a drilling operation. Consequently, wear and/or damage experienced by the water separator <NUM> (and the system <NUM>) is substantially reduced and an operating life of the system <NUM> is increased.

Referring to <FIG>, there are shown steps of a method <NUM> of determining an isotopic composition of a gaseous sample, in accordance with an embodiment of the present disclosure. At a step <NUM>, the gaseous sample is separated into gaseous components using at least one gas chromatograph. At a step <NUM>, the gaseous components are oxidized in a combustion furnace. At a step <NUM>, water is removed from the oxidized gaseous components using a water separator. At a step <NUM>, ion beams associated with each of the oxidized gaseous components are generated using an ion source associated with an isotope-ratio mass spectrometer. At a step <NUM>, isotopic concentrations associated with each of the ion beams are determined using a mass analyser. At a step <NUM>, the isotopic composition of the gaseous sample is determined by the isotope-ratio mass spectrometer using the isotopic concentrations associated with each of the ion beams.

The steps <NUM> to <NUM> are only illustrative and other alternatives can also be provided where one or more steps are added, one or more steps are removed, or one or more steps are provided in a different sequence without departing from the scope of the claims herein. In an example, the method further comprises diluting the gaseous sample using a carrier gas. In another example, the method further comprises using a feedback loop to modify an amount of the carrier gas that is used for diluting the gaseous sample, based on the determined isotopic concentrations associated with each of the ion beams. In yet another example, the method further comprises generating at least one chromatogram associated with the at least one gas chromatograph after separating the gaseous sample into the gaseous components.

In one example, a first gas chromatograph and a second gas chromatograph of the at least one gas chromatograph are used together for separating the gaseous sample into gaseous components. In another example, the method further comprises correlating a first chromatogram associated with the first gas chromatograph and a second chromatogram associated with the second gas chromatograph to obtain an elution order of the gaseous components. In yet another example, the method further comprises determining a reference isotopic composition of a reference gaseous sample associated with a predetermined isotopic composition; determining a correction factor for the isotope-ratio mass spectrometer by correlating the determined reference isotopic composition with the predetermined isotopic composition associated with the reference sample; and calibrating the isotope-ratio mass spectrometer using the determined correction factor.

Furthermore, disclosed is a software product recording on machine-readable data storage media, characterised in that the software product is executable upon computing hardware for implementing the aforementioned method of determining isotopic composition of a gaseous sample.

In the foregoing, there is disclosed the system and the method of determining isotopic composition of gaseous samples, and the software product executable upon computing hardware for implementing the aforementioned method. The system comprises at least one gas chromatograph for separating the gaseous sample into gaseous components. The at least one gas chromatograph may be implemented using two or more gas chromatographs, such as the first gas chromatograph and the second gas chromatograph. Such an implementation of the at least one gas chromatograph enables reduction in time required for separation of the gaseous sample into gaseous components, thereby, enabling faster analysis thereof using the system. Furthermore, chromatograms associated with the two or more gas chromatograms may be correlated to determine the elution order of the gaseous components. Such a correlation of the chromatograms enables to increase an accuracy associated with the determined elution order. Moreover, the system comprises the combustion furnace. Such a combustion furnace is implemented using a cartridge heater associated with lower power consumption for combustion (or oxidation) of the gaseous components. It will be appreciated that such decrease in power consumption by the combustion furnace enables to increase a power efficiency associated with operation of the system. Furthermore, use of the oxidation catalyst in the combustion furnace enables oxidation of gaseous components at lower operating temperatures of the system, thereby, enabling improved operating life of the system. The system comprises the water separator. The water separator may be implemented using the coiled cylindrical tube for flow of gaseous components therethrough. Such an implementation of the water separator enables a reduction in dimensions thereof, consequently, enabling to provide the system having a more compact form factor. Additionally, the tube used in the water separator may be fabricated using Nafion polymer. Such a fabrication of the tube enables a requirement of use of hazardous chemicals (such as magnesium perchlorate) within the system to be eliminated, for dehydration of the gaseous components. In such an example, a safety associated with use of the system is increased. Moreover, the system comprises the isotope-ratio mass spectrometer operatively coupled with the water separator, to determine the isotopic composition of the gaseous sample. The isotope-ratio mass spectrometer comprises the ion source for generating ion beams associated with each of the oxidized gaseous components and the mass analyser for receiving the generated ion beams from the ion source. Such an isotope-ratio mass spectrometer is implemented by incorporating the ion source and the mass analyser within the housing. It will be appreciated that such an implementation enables the isotope-ratio mass spectrometer to act as a single unit, namely as a unitary apparatus, thereby, allowing the system to be resistant to damage from mechanical vibrations and shock. Additionally, the isotope-ratio mass spectrometer is arranged with the shock-absorbing arrangement. Such an arrangement further enables to reduce an impact associated with mechanical vibrations and/or shock experienced by the system. The reduction in the impact of mechanical vibrations and/or shock enables the system to be more damage-resistant and also, allows operation thereof on-site, such as, of a drilling operation. It will be appreciated that the on-site operation of the system enables to provide increased accuracy and reduced analysis time for the system as compared to conventional arrangements for determination of isotopic compositions of gaseous components. Therefore, the present disclosure provides a compact and reliable system and method of determining isotopic composition of gaseous samples.

Claim 1:
A system (<NUM>) that is configured to determine isotopic composition of a gaseous sample, the system comprising:
- at least one gas chromatograph (<NUM>) that is configured to separate the gaseous sample into gaseous components;
- a combustion furnace (<NUM>) operatively coupled with the at least one gas chromatograph for oxidizing the gaseous components, wherein the combustion furnace comprises a cartridge heater (<NUM>) surrounded with a cylindrical tube (<NUM>) wound comprising an oxidation catalyst to promote oxidation of the gaseous components, wherein the oxidation catalyst is platinized copper oxide;
- a water separator (<NUM>) that is operatively coupled with the combustion furnace, wherein the water separator is configured to remove water from the oxidized gaseous components;
- a first shock absorbing arrangement (408A-B) arranged with the water separator, wherein the first shock absorbing arrangement enables absorption of shocks and/or vibrations experienced by the water separator during operation of the system; and
- an isotope-ratio mass spectrometer (<NUM>) that is operatively coupled with the water separator, the isotope-ratio mass spectrometer comprising:
- an ion source (<NUM>) that is configured to generate ion beams associated with each of the oxidized gaseous components;
- a mass analyser (<NUM>) that is configured to receive the generated ion beams from the ion source, wherein the mass analyser is configured to determine isotopic concentrations associated with each of the ion beams; and
- a second shock absorbing arrangement arranged with the isotope-ratio mass spectrometer, the isotope-ratio mass spectrometer being mounted on the second shock absorbing arrangement, wherein the second shock absorbing arrangement enables to absorb the vibrations and/or shocks experienced by the isotope-ratio mass spectrometer during operation of the system,
wherein the isotope-ratio mass spectrometer is configured to use the determined isotopic concentrations associated with each of the ion beams to determine the isotopic composition of the gaseous sample, characterised in that the ion source and the mass analyser are arranged in a housing implemented as a vertical cabinet and wherein the ion source, the mass analyser and the housing are arranged to be movable as a single unit.