The disclosure relates to chemical analysis and, more particularly, the collection of a gas sample and recovery of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) for analysis by a GC or GCMS. Some embodiments of the disclosure relate to systems designed for being capable of gas sampling and compound recovery in applications containing high humidity levels, or even steam.
Systems and processes for determining the levels of VOCs through SVOCs in gas phase matrices, such as indoor air, ambient air, workplace air, fenceline monitoring, refinery gas streams, and stack gas emissions, have been performed for decades. Such systems and processes have demonstrated numerous limitations in accurately measuring all compounds of interest at a wide range of concentrations.
In some examples, either permanent or portable real time analyzers have been used to perform these measurements, but virtually none of these “on-site” analyzers can handle high humidity samples while covering the large range of compound detection needed to measure all VOC through SVOC compounds present (which can include thousands, or even hundreds of thousands of compounds). In addition, prices for such analyzers can be prohibitive for many applications. In general, virtually all chemical analyzers demonstrate interferences when water reaches high PPM to percent levels in the sample. As an example, an excess of water in a sample for testing by GCMS can cause damage to the testing equipment (e.g., damage to the GC column) or suppressed response (e.g., due to lowered sensitivity of the MS).
Whole gas sampling devices can manage excess water by allowing it to condense out in the device—however, these approaches are accompanied by various shortcomings. First, many of the collected chemicals can react with condensed water if they are allowed to remain exposed to the water for prolonged durations of time awaiting analysis. Further, many SVOCs will stick to the walls of the container unless the containers are heated to higher temperatures to drive the low volatility compounds back into the gas phase. However, heating the container walls in this way can in turn also increase the amount of water vapor introduced back into the gas phase, again creating a problem with GCMS analysis. For many SVOCs, a relatively high temperature would be needed to transfer them substantially back into the gas phase, which would not only transfer far too much water into the analytical system but would cause many compounds to react in the presence of both a higher temperature and high water concentrations. Therefore, this problem with managing the temperature of the gas during sampling, the reduction of water before delivery to a GCMS, and the need to recover both VOCs and SVOCs have caused all prior sampling devices to fail at quantitative measurement under the sampling conditions ranging from ambient temperatures to 300 degrees Celsius, and moisture concentrations from 0 to 50 percent.
The disclosure relates to chemical analysis and, more particularly, the collection of a gas sample and recovery of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) from the gas sample at low humidity levels through high humidity levels, as well as techniques for preparing the recovered compounds for analysis by a GC or GCMS (e.g., by enrichment, dehydration, concentration, and other techniques described below). In some examples, during the initial evacuation of a sample vessel after the sample has been collected, an “active sampling,” or Dynamic Headspace Sampling (DHS) method can be used. After the vacuum is formed and the vacuum source has been removed, any remaining transfer of the heavier SVOCs is done diffusively. Therefore, in some examples, a hybrid sampling system can operate in both active and passive (diffusive) modes, whereas other sampling systems can only operate in the active sampling mode, or DHS. In some examples a gas sampling system for recovering VOCs and SVOCs can describe an assembly of a sample vessel, vacuum sleeve, and sample extraction device. In some examples, a gas sampling system for recovering VOCs and SVOCs can describe an assembly without a sample extraction device. In such examples, a vacuum sleeve or other attachment can be used to couple a sample extraction device to the sample vessel (e.g., at a laboratory). In some examples, compound recovery from the gas phase matrix samples collected in the sample vessel can require a first sample extraction device that has sorbent element(s) optimized for VOCs through light SVOCs, and a second sample extraction device that has sorbent element(s) optimized for SVOCs.
In some examples, a breath sampling system is described, in which a breath sampler inlet has a high flow port that can be selectively used to evacuate a sample vessel, and to fill it with a final fraction of a patient's exhalation, to recover various chemicals and compounds both contained in the gas phase, and in the aerosols and/or droplets in a patient's breath.
In the following description, reference is made to the accompanying drawings which form a part hereof, and in which it is shown by way of illustration specific examples that can be practiced. It is to be understood that other examples can be used, and structural changes can be made without departing from the scope of the examples of the disclosure.
The disclosure relates to chemical analysis and, more particularly, the collection of a gas sample that may or may not contain condensing droplets of moisture in the gas stream, and subsequent recovery of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) from the gas sample across a wide range of moisture or humidity levels, and at any initial gas phase sample temperature from 0 to 300 degrees Celsius, as well as techniques for preparing the recovered compounds for analysis by a GC or GCMS (e.g., by enrichment, dehydration, concentration, and other techniques described below. Embodiments of the present disclosure allow for sampling and recovery of VOCs and SVOCs at a field or site of interest (e.g., refinery gas streams, process gas streams, stack gas emissions, work place air, fenceline monitoring, ambient air, indoor air, and other gas phase matrices). Embodiments of a sampling process according to the present disclosure can include active collection of a gas phase matrix samples at a site of interest, using a pre-evacuated sample vessel (e.g., a vessel in which a vacuum has been drawn), in some examples. The pre-evacuated sample vessel can have a volume, corresponding to the required detection limits for the particular application of any given example or embodiment. At the time and/or location of sample collection, a sample extraction device can be optionally integrated into a sampler to allow for at least a portion of samples collected in a vessel to be recovered onto the sample extraction device (e.g., while additional samples continue to be collected, or during transfer to the analysis laboratory), in some examples. In some examples, a sample vessel can be used to collect samples without any sample extraction device(s) present at the collection site/field, and is later coupled to the sample extraction device(s) at a later time when the sample vessel is returned to a lab environment for analysis of its contents.
The current approach described by embodiments of the disclosure allows VOCs, SVOCs, organic compounds, and any number of compounds to be collected onsite (often referred to as “in the field”), without the need for a co-present analyzer (thereby reducing cost and complexity, and improving the range and bandwidth of compounds at the site that can be analyzed off-site). Specifically, embodiments of the disclosure allow all VOCs and SVOCs of interest to be recovered, while minimizing water content of the final extracted sample prior to GCMS analysis. Virtually all gas phase matrices can be sampled by the approach described by embodiments of the disclosure, although the approach described below is particularly well-suited towards collecting light VOCs thru heavy SVOCs in either elevated temperature gas streams, or in high moisture content streams (e.g., streams at 50% or more water vapor). The sampler described by embodiments of the disclosure is uniquely capable in collecting stack gas for analysis of a wider range of compounds than alternative approaches.
The sampler can also handle small aqueous droplets and aerosols, making it ideal for collecting breath samples for GCMS analysis. Aerosols in breath samples have created problems with other alternative sampling techniques, both because the chemicals of interest in the aerosols have difficulty reaching the analyzer and/or can cause undesirable contamination of the sampling device(s) meant only for volatile chemical adsorption and desorption. Aerosols in breath samples can contain proteins, carbohydrates, lipids, bacteria, and other non-volatiles that when thermally desorbed (e.g., at temperatures in the range of 200-300 degrees Celsius) would break apart into artifact compounds that were never present in the original sample. These artifact compounds that can be generated by decomposition caused by the thermal desorption will nonetheless show up in the GCMS analysis, thereby complicating the question as to the actual contents and/or identities of the compounds present in the actual, original sample (e.g., the sample collected by the sample vessel in the field).
In some embodiments, environmental gas phase matrix samples can be collected into sample vessel over a time period (e.g., a sampling period), based on an adjustable flow restrictor or controller coupled to an inlet attached to the sample vessel, as described in greater detail below. In some embodiments, high flow breath samples can be collected on the order of just a few seconds (e.g., 8-10 seconds, 10-12 seconds, etc.) by using an alternate design with a sample inlet that can be pushed into, and pulled out of the sample vessel, as described in greater detail below.
Sample extraction device 150, described in greater detail below in connection with
Vacuum sleeve 102, in some examples, can have a shaft portion 106, which is configured to hold or position a portion of sample extraction device 150 (e.g., the portion of the device 150 corresponding to height H1) at a specific position relative to an opening of sample vessel 132 and/or inlet 114 of side port 112. As illustrated by system 100 (and
This approach can be used when performing classical dynamic headspace sampling to pull a known volume from sample vessel 132 through sample extraction device 150 (which is introduced in the lab). This approach can also be applied when extraction device 150 is added in the lab, followed by creation of a vacuum to extract both VOCs and SVOCs from both the gas phase and off the interior walls of vessel 132. System 170 of
The configuration of system 170 illustrated by
In such configurations of system 100, the gas phase matrix sampling by sample vessel 132, and VOC/SVOC recovery by the sample extraction device 150 can occur during non-overlapping intervals (e.g., compounds can be recovered by device 150, at a later time from when samples are collected by vessel 132). In some embodiments, vacuum sleeve 104 has side port 112 corresponding to a valve that allows gases to travel in and out of sample vessel 132, through inlet 114. In some embodiments, an inner chamber of sample vessel 132 can be evacuated of any gases, through side port 112, to form a vacuum prior to collection of samples from a gas phase matrix.
Sample extraction device 252 can include lower cavity 220. In some examples, the lower cavity 220 can contain one or more sorbent element(s) 202, which can include, for example, an adsorbent material. As will be described below, in some examples, sorbent element(s) 202 can be selected to collect a sample for analysis. In some examples, the sorbent element(s) 202 can be located towards an extraction end 212 of the sample extraction device 252. That is to say, sorbent element(s) 202 can be closer to the extraction end 212 of the sample extraction device 252 than it is to a valve end 214 of the diffusive extraction device. During sample extraction, extraction end 212 of the sample extraction device 252 can be open to the environment of the sample vessel (e.g., sample vessel 132 of
At the valve end 214 of the diffusive extraction device 252 (e.g., opposite extraction end 212 of the diffusive extraction device 252), the diffusive extraction device 252 can include a sealing plunger, a spring, and an internal seal, for example. In some examples, the sealing plunger and internal seal can selectively restrict fluid (e.g., gas, liquid, etc.) flow through an internal channel between the sealing plunger or internal seal, and lower cavity 220 where sorbent element(s) 202 are located. For example, when the sealing plunger is pressed up against the seal, fluid flow through sample extraction device 252 can be restricted, and when the sealing plunger is moved away or otherwise separated from the seal, fluid flow through sample extraction device 252 may be unrestricted. In some examples, sealing plunger can be tensioned via a spring against the seal such that in a default configuration, the sealing plunger can be pressed up against the seal, thereby restricting fluid flow through sample extraction device 252. Fluid flow (e.g., air being drawn into a vacuum source) through sample extraction device 252 can be allowed by causing the sealing plunger to move away from the seal (e.g., via mechanical means such as a pin from above, or other means). For example, a vacuum source can be coupled to the sample extraction device 252 at the valve end 214 to open the sealing plunger and draw a vacuum through the sealing plunger, internal channel, and lower cavity 220. Additionally, in some examples, the sealing plunger can remain open (e.g., during continuous vacuum evacuation) to evaporate unwanted matrix, such as water or alcohol, from the sample through sorbent element(s) 202. In some embodiments, sample extraction device 252 can be used to perform active sampling of a sample vessel, sometimes referred to as Dynamic Headspace Sampling (DHS), in which compounds come into contact with sorbent element(s) 202 based on a vacuum source drawing a volume of gas through device 252. In some embodiments, the entire sampling system can be chilled before performing DHS, to trap lighter compounds, and to overall reduce the amount of water in the gas phase.
As an example, during a sample extraction process in which a sample can be collected in sample extraction device 252, a vacuum can be drawn through the sealing plunger, internal channel, and lower cavity 220 to facilitate sample collection by sorbent 202 in lower cavity 220. After the sample has been collected by the dynamic/diffusive extraction device 252, the sealing plunger can be remain closed (e.g., as it can be during sample collection) and can isolate the sample from the environment, allowing the sample to be stored in the sample extraction device 252 between extraction and analysis. For example, a spring can cause the sealing plunger to remain closed in the absence of a mechanical force to open the sealing plunger.
The sample extraction device 252 can further include one or more external seals 208, for example. The external seals 208 can be made of an elastomeric material and can be fluoroelastomer seals or perfluoroelastomer seals. The external seals 208 can be located externally on sample extraction device 252 between ends 212 and 214. The external seals 208 can include one or more gaskets or O-rings fitted around the outside of the sample extraction device 252, for example. In some examples, the external seals 208 can be used to form a seal between sample extraction device 252 and a sample vessel/vial into which sample extraction device 252 can be inserted during a sample extraction process, and/or to form a seal between sample extraction device 252 and a desorption device into which sample extraction device 252 can be inserted during a sample desorption process (e.g., while directing a desorb gas flow through the internal sorbent 106 during thermal desorption to an analyzer such as a GC or GCMS), such as part of the sample recovery processes described below with reference to
A notable difference between sample extraction device 252 and sample extraction device 254 can be the length of the sorbent bed (e.g., the regions within cavity 220 and cavity 222 containing sorbent element(s)). In some examples, the longer adsorbent bed of sample extraction device 254 can accommodate a plurality of sorbent element(s) 256a-c, accessible via an opening 214. In some embodiments, where sample extraction device 254 is used in conjunction with active sampling processes, channeling can be a bigger problem, requiring a longer adsorbent bed being used in sample extraction device 254, relative to sample extraction device 252, to prevent breakthrough losses of some compounds. In some embodiments, an opening 214 of an extraction end of sample extraction device 254 shown in
In some embodiments, sorbent element(s) 256a-c can be arranged in order of increasing chemical affinity to one or more compounds of interest in a sample. For example, sorbent 256a can have a relatively low chemical affinity, sorbent 256b can have a higher chemical affinity than sorbent 256a, and sorbent 256c can have the highest chemical affinity of the sorbent element(s). Sample extraction devices 252 and/or 254 can collect the sample using an active flow of gas, a static diffusive flow, and/or by sealing the sample extraction devices 252 and/or 254 inside of a vessel/vial under vacuum. In some embodiments, pulling a vacuum on the sample while the sample extraction device 252 and/or 254 is sealed in the sample vessel/vial containing the sample can improve the rate of extraction, especially for the extraction of the higher boiling point compounds. In some embodiments, sample extraction device 252 is connectively coupled to a sample vessel/vial throughout a gas matrix sampling interval, during which air/gas samples are collected directly into a sample collection vial, and indirectly collected/concentrated onto the sorbent(s) of the sample extraction device by a static diffusive flow caused by the random movement of molecules within a sample vial (or other suitable vessel for collecting a sample of a gas matrix). In some embodiments, sample extraction device 254 can be inserted into a vacuum sleeve just after sample collection. In some embodiments, sample extraction devices 252 and 254 are kept separate from a sample-collection vessel, sometimes referred to as simply a “sample vessel,” until after a gas phase matrix has been sampled by the sample vessel during the gas matrix, and prior to testing the compounds (e.g., at a testing site that is different than the sampling site or gas collection site).
Isolation sleeve 302 not only protects the samples collected with the sorbent(s) of sample extraction device 252 after device 252 has been used to collect compounds from sampled gases in a sample vessel (e.g., a “post-sampling” state), but sleeve 262 also keeps the device 252 clean after thermal desorption or thermal conditioning (e.g., a “clean,” or “post-desorption” state). After desorption or cleaning, the device 252 can be returned to sleeve 262 with minimal exposure to air, because exposure to air can cause appreciable collect organic compounds from the air to collect onto the sorbent element(s) of device 252. Sleeve 262 therefore keeps devices 252 and/or 254 clean after desorption or cleaning (e.g., in the “clean” or “post-desorption” state), and maintains the integrity of compound samples collected on the sorbent element(s) of the devices (e.g., in the “post-sampling” state).
For simplicity of illustration, sample extraction device 252 is illustrated as being inserted into vacuum sleeve 402, and held in place within the vacuum sleeve 402 by retention cap 404 (which is attached to, and separable from vacuum sleeve 402 by compatible threading on contacting surfaces of the two components). In additional embodiments, hybrid sampling system 400 can be operated to sample gas phase matrices from the surrounding or ambient environment, or any other gas source provided at side port 412 by an adapter (e.g., an adapter to couple side port 412 to a refinery stack, an adapter to couple side port 412 to a ventilator to collect breath samples without a patient's direct participation, etc.), whether or not sample extraction device 252 and/or 252 are placed in vacuum sleeve 402. In other words, hybrid sampling system 400 can be operated to collect samples of complex gas phase matrices, without requiring sample extraction device 252 to be inserted in vacuum sleeve 302, or even present at the sampling site/location. Additionally or alternatively in some situations, hybrid sampling system 400 can be operated to recover compounds using more than one sample extraction device 252, as described in further detail below in connection with
In the embodiment illustrated by
Vacuum sleeve 402 can pneumatically couple or connect sample extraction device 252 to sample vessel 432 in some embodiments. Both vacuum sleeve 402 and sample vessel 432 can be formed from inert, non-absorptive, and non-adsorptive material in some embodiments (e.g., glass, stainless steel, ceramic coated stainless steel, etc.), ensuring that collected or sampled compounds will not interact or react with their respective surfaces. In some embodiments, certain compounds may potentially adsorb to surfaces of vacuum sleeve 402 and/or sample vessel 432 at lower temperatures in the range of 10 to 40 degrees Celsius. However, in such embodiments, such compounds are reintroduced into the gas phase during vacuum processing in a lab setting (e.g., at elevated temperatures). In some embodiments, both vacuum sleeve 402 and sample vessel 432 are formed from stainless steel. However, as mentioned above, any inert, non-absorptive, and non-adsorptive material that can form an inner cavity capable of maintaining a vacuum can be used to form vacuum sleeve 402 and/or sample vessel 432 in some embodiments. The cross-sectional side view of
Retention cap 404 can further secure sample extraction device 252 within vacuum sleeve 402, and further seal parts of the body of the sample extraction device to the ambient environment/air around the hybrid sampling system 400. Retention cap 404 prevents the sample extraction devices 252 from coming out of vacuum sleeve 402 until the cap is removed, in some embodiments. In embodiments that involve operations in the lab, cap 404 is not used, because it interferes with the operation of automated rail sampling devices (e.g., an autosampler) that automatically removes sample extraction devices 252 and 254 from their respective isolation sleeves 302, illustrated by
In embodiments where retention cap 404 is a solid sampling cap (e.g., without a sample extraction device 252 as illustrated, similar to cap 160 of
Then, both the VOC and the SVOC devices can be analyzed using a GC with the ideally suited column, which may be necessary when trying to achieve the very highest dynamic range in compound volatility. In most cases, required monitoring levels for SVOCs are lower than VOCs, as many are more dangerous, and they are typically at lower concentrations in stack gas and in human breath than are VOCs, so required analytical volumes needed are typically greater for SVOCs in order to reach required detection limits. Embodiments similar to the approach detailed above in which two sample extraction devices are used are described in greater detail below, in connection with
A shaft portion of vacuum sleeve 402 can either be occupied by a sample extraction device 252 (as illustrated), or vacant from any sample extraction devices (e.g., in embodiments where hybrid sampling system 400 is sometimes operated without such devices inserted into the vacuum sleeve). In some embodiments, the shaft portion of vacuum sleeve 402 has an inner surface with dimensions sized to accommodate the body of sample extraction device 252. In some embodiments, the inner surface of the shaft of sleeve 402 has dimensions that are separated from the body of sample extraction device 252 by a small gap.
Side port 412 can be an inlet port to the sample vessel 432 (similar to a sample vial), through which samples of a gas phase matrix can be collected into the sample vessel in some embodiments. Additionally, side port 412 can be an outlet port for drawing a vacuum into the inner chamber of sample vessel 432 (e.g., cavity defined by an inner sidewall 436 of the vessel), or any other evacuation of the contents of the sample vessel in other embodiments. As an example, side port 412 can sometimes be utilized to draw a vacuum into the inner chamber of sample vessel 432, by evacuating any gases within the inner sidewall 436 of the vessel (e.g., prior to a sampling period of the system 400).
In some embodiments, side port 412 can include a microvalve that can be selectively opened to allow for gases to travel from any gas source connected or coupled to the side port (e.g., the environmental/ambient air surrounding system 300, or a gas source otherwise coupled to the side port). In some embodiments, side port 412 can be in a closed state by default (which blocks the travel of gases in/out of sample vessel 432), or in an open state (allowing gases to travel in/out of sample vessel 432). In embodiments where samples of environmental or ambient gas phase matrices surrounding hybrid sampling system 400 are collected into sample vessel 432, side port 412 can be used to collect the samples by setting it to the open state for a duration of a collection or sampling interval.
Side port 412 can also be used to receive injections of standard gas phase matrices (e.g., samples of gases and VOCs/SVOCs in known concentrations/quantities) in some embodiments. As an example, 1 cc of a gas standard with known concentrations of certain given recovery compounds (or, known proportions of recovery compounds to gases), can be injected into sample vessel 432 via side port 412. In some embodiments, samples collected by a sample extraction device (e.g., devices 252-256) subsequent to the gas standard injection can be analyzed for the presence of the given recovery compounds, in addition to their concentrations. Analysis of the sample collected subsequent to the gas standard injection can be used to confirm (or alternatively, call into question) the proper sampling, proper storage, and proper recovery of compounds in the sample (e.g., the pre-existing sample within sample vessel 432, prior to the gas standard injection via side port 412). Liquid phase surrogate compounds for SVOC recovery validation can be added to the sampling system 400 after sampling has been completed, by momentarily removing extraction device 252 prior to performing evacuation and diffusive extraction at elevated temperatures.
Side port 412 can be coupled to attachments, such as a flow restrictor, flow regulator, or flow controller that attaches to the side port in some embodiments. When coupled to a flow restrictor, side port 412 can be in the “open state” to allow gases to travel in/out of sample vessel 432, while flow restrictor can be independently adjusted to change a rate at which gases are allowed to travel into the sample vessel. In some embodiments, side port 412 can be coupled to a flow restrictor, which is in turn connected to a gas source to be sampled by sample vessel 432 (e.g., a refinery gas stream, a process gas stream, a stack gas emission source, work place air, fenceline monitoring, ambient air, indoor air, an exhaled breath line of a ventilator system, and other gas phase matrices). As an example, a flow restrictor can be used to specify a rate at which samples from a gas source are collected into sample vessel 432 over a sampling interval in some embodiments. In some examples, a rate of vacuum pulled through a valve portion 214 of a sample extraction device 252 and/or 254 can be set to a relatively slow flow rate, to reduce the channeling effects that are exacerbated at relatively fast vacuum flow rates.
A threading region 416 of vacuum sleeve 402 can represent a lower portion of the vacuum sleeve that allows for the vacuum sleeve to be screwed into and fastened to any compatible threads, such as a threaded connector 408 (shown in
Sample vessel 432 can have a portion 442 corresponding to a neck portion or an upper portion of the sample vessel, in some embodiments. Portion 442 can be tapered relative to other dimensions of sample vessel 432 (as illustrated), or can have any suitable geometry relative to the remainder of the sample vessel. Portion 444 can correspond to a lower portion or bottom portion of the sample vessel in some embodiments. Sample vessel 432 can have an inner sidewall 436 and an outer sidewall 434. Inner sidewall 436 can form a cavity into which gas samples from a gas phase matrix outside of sample vessel 432 can be collected. Water 350 within inner sidewall 436 can represent condensed water that is collected during the sampling process. Water taken into sample vessel 432 during sampling will saturate to 100% relative humidity within the sample vessel, and any excess will be liquid (e.g., as represented by water 350). In certain embodiments, liquid water may react with certain VOCs, and in such embodiments a sample extraction device 252 may have to be added to device system 400 prior to sampling, so the water reactive compounds can have a chance to be adsorbed by the sorbent element(s) of device 252 with reduced exposure time to the condensed water. In embodiments where compounds are known to not react with water (e.g., most compounds at ambient temperatures), as long as the compounds have a binding affinity with the sorbent that is stronger than their binding affinity with the water, near complete recovery into the sorbent is still possible when a sample extraction device 252 is added after the sampling period, given a reasonable amount of time for the compounds to find the sorbent element(s) of device 252 (e.g., via passive diffusive motion).
Process 500 begins at step 501, where sampling system 400 (sometimes referred to as a “sampler,” for simplicity) is assembled, the sampler including a sample extraction device (e.g., device 252), a sample vessel (e.g., vessel 432), and a vacuum sleeve (e.g., sleeve 402) that are all cleaned in a laboratory, and then assembled (e.g., according to the arrangements illustrated by
After step 501, process 500 can proceed to step 502, which can occur after the hybrid sampling system is assembled, and prior to the system being sent to a sampling or collection site (e.g., a location where gas phase matrices of interest will be sampled by the system). At step 502, a vacuum can be drawn through sample extraction device 252 into a vacuum source via side port 412, to form a vacuum within the sample vessel 432. In some embodiments, after sample vessel 432 has been evacuated, a weight of the sample vessel 432 can be measured and recorded, to provide a baseline reference weight by which the weight of sampled gases and/or compounds can be determined after a sampling period at a sampling or collection site. Recording the sampler weight before and after sampling can also provide indications about the amount of water that condensed in the sampler, as the condensed water will not be a part of the gas phase sample, thereby increasing the relative concentrations of compounds still remaining in the gas phase. Moreover, a volume of the sample vessel can be changed and/or selected based on the required detection limits for a particular application, in some embodiments. As an example, for stack gas analysis where concentrations are expected to be at high parts-per-billion (PPB) through parts-per-million (PPM) levels, sample vessel 432 can have a 250 cc volume, and a sample collected by sample extracting device 252 can then be provided into the GCMS using a 50:1 split upon injection.
As described above, step 502 can be performed prior to the hybrid sampling system being sent to a sampling or collection site. Once the system arrives at the sampling or collection site, step 504 can be performed in some embodiments. At step 504, air samples containing bulk gases and compounds such as VOCs, SVOCs, etc. can be collected into sample vessel 432 over a time period (e.g., a sampling interval). At step 504, side port 412 of the sampling system is connected to a gas stream, after which a sample is introduced either rapidly (e.g., by opening the valve associated with the side port), or slowly using a flow restrictor or controller (e.g., in embodiments where a time integrated sample collection is required or desired). In some embodiments, when collection of heavier SVOCs is desired, or in order to keep steam from condensing prior to reaching the inside of sample vessel 432 a line providing the gas stream to be sampled, as well as side port 412 can be heated during the sampling time period or interval.
After the sampling time period or interval described in connection with step 504, the hybrid sampling system 400/450 can be returned to the laboratory for processing. In some embodiments, system 400/450 can be weighed and compared to the original evacuated weight (e.g., the weight measured after step 502) to determine the amount of liquid water collected, which in turn confirms that total amount of gas sampled when collecting from a high water containing sources at elevated temperatures. In some embodiments, this gravimetric determination can be used to verify whether 500 cc, 1000 cc, or even higher volumes were collected into a 500 cc reservoir, simply because some water may condense during the sampling process and before closing inlet 412, allowing more gas to be introduced. Once the sampling stops (e.g., by closing valve 412), any additional condensation of water only results in a reduction of the pressure in the vessel, and a final pressure measurement can reveal this occurrence, although gravimetric determination by looking at the weight gain of the sampler would be the best determination of the total mass collected, in some embodiments. In some embodiments, the actual volume sampled at the temperatures of the gas at the sampling point can then be easily calculated from the determined weight gain.
In some embodiments, after making this gravimetric determination, process 500 can proceed to step 506, where a vacuum is drawn through the top valve (e.g., valve end 214) and gases that are not retained by the sorbent element(s) in the sample extraction device (e.g., bulk, fixed gases) are removed from sample vessel 432. In some embodiments, a vacuum can be slowly applied to the top of sample extraction device 252 (e.g., where an internal seal comprising a sealing plunger and a seal is located, near valve end 214) to pull gas phase chemicals collected within sample vessel 432 onto the sorbent element(s) of the sample extraction device, thereby eliminating most of the fixed gases that are not retained on the sorbent. Evacuating bulk gases carrying compounds of interest (e.g., VOCs or SVOCs in the gas phase matrix) in this manner can improve collection/recovery rates of the compounds of interest onto the sorbent element(s) of one or more sample extraction devices during subsequent process steps. As a vacuum is drawn through valve end 214, the gases carrying VOCs and some SVOCs can travel through an extraction end 212 of device 252, through an internal channel that connects a lower cavity 220 or 222 to the valve end 214. During evacuation through the lower cavity 220 or 222, VOCs as well as some lighter SVOCs can be collected and/or recovered onto sorbent element(s) located in the lower cavity 220 or 222 (e.g., sorbent 202 or 256a-c of
Process 500 can proceed to step 508, which occurs after step 506 in some embodiments. In other words, steps 506 and 508 can be considered as a sequence of steps, each associated with a respective temperature level provided for the respective sampling techniques described by those steps. As mentioned above, system 400 can be maintained at a relatively low temperature in connection with step 506. At step 508, compounds from the sampled air, or another gas phase matrix collected at step 504 (e.g., through side port 412), are adsorbed at one or more sorbent elements located in the lower cavity of a sample extraction device 252 (e.g., by entering an extraction end 212 of the device, and coming into contact with one or more sorbent elements). In some embodiments, step 508 can simply describe the adsorption of compounds collected at step 504 by one or more sorbent elements (e.g., omitting the optional heating of system 400).
In some embodiments, the entire sampling system 400 can be heated to raise vapor pressure of SVOCs within sample vessel 432, thereby promoting movement of said compounds towards the one or more sorbent elements of a sample extraction device 252 (e.g., as a vacuum is drawn through valve end 214 of the sample extraction device). In some embodiments, an extraction end 212 of the sample extraction device 252 can be heated relatively more than the overall/entire sampling system 400, to prevent or create conditions that discourage the collection of moisture in sample extraction device 252, by keeping sample vessel 432 slightly cooler than sample extraction device 252. In this way, step 508 can describe maintaining conditions that raise vapor pressure of SVOCs within sample vessel 432 that may be stuck along inner sidewall 436 of sample vessel 432, and promoting movement of SVOCs towards the one or more sorbent elements contained in sample extraction device 252. These conditions can include, in some embodiments, heating system 400 such that collected compounds within sample vessel 432 (e.g., VOCs, SVOCs) can come into contact with the sorbent element(s) of a sample extraction device 252 while a vacuum is drawn through sample extraction device 252 to collect the VOCs and SVOCs present in the air samples.
Because the compounds adsorbed by the sorbent element(s) are meant to be analyzed by GCMS and GC-MS/MS, these analysis techniques have some limitations, such as the potential for interference from excess water vapor. Many samples of complex gas phase matrices have elevated levels of water vapor, from ambient air which can be as much as 3-4% water vapor, to stack gas streams that may be 50% water vapor and at elevated temperatures. Another example of a complex gas phase matrix with elevated levels of water vapor is exhaled breath, with water vapor in exhaled breath exceeding 100% relative humidity at 37 degrees Celsius, due to aerosols and/or water droplets included in the exhaled breath. Excess water in the sample can cause damage to the GC column, and also suppression of the response in the MS. Therefore, water must be substantially reduced prior to injection into a GCMS or GC-MS/MS. Sampling and analysis techniques have been developed that can reduce water concentrations as long as the water is at non-condensing concentrations. As an example, if the dew point of the sample within sample vessel 432 is at 25 degrees Celsius and a sample extraction device 252 is at 35 degrees Celsius, then water can be kept in the gas phase thereby allowing it to pass through the one or more sorbent elements of the sample extraction device, unretained. However, in certain embodiments, sorbent element(s) cannot be generally increased in temperature to meet elevated gas stream temperatures, because doing so can prevent chemicals of interest from being trapped on the sorbent.
Process 500 can proceed to step 510, where water is extracted out of the sample extraction device and its sorbent element(s), to dehydrate the sorbent element(s). In some embodiments, step 510 can simply describe the dehydration of the sorbent element(s) (e.g., omitting the cooling of system 400). In some embodiments, a bottom portion 444 of sampling system 400 can be cooled to promote water condensation within sample vessel 432, and dehydrate the one or more sorbent elements of sample extraction device 252. In some embodiments, the sampling system 400 is placed on a cold tray to cool the bottom portion 444 of the sample vessel 432 to transfer most of the water in the closed system back to the bottom of the sample vessel (e.g., away from sample extraction device 252 and its sorbent element(s)). In some embodiments, bottom portion 444 can be cooled for between 5 and 30 minutes to transfer water in the closed system back to the bottom of the sample vessel. Moreover, at the lower temperatures, any of the very light VOCs that were not firmly maintained or adsorbed on the sorbent element(s) of device 252 can again collect onto one or more of the stronger beds of the sorbent element(s).
After step 510, process 500 can proceed to step 512, where sample extraction device 252 is removed from the vacuum sleeve by which it was coupled to sample vessel 432 (e.g., by first removing retention cap 404). Sample extraction devices with dehydrated sorbent element(s) can be removed from the hybrid sampling system 400 and can be isolated in individual sleeves (e.g., isolation sleeves 302 of
The sequence of events described above in connection with
In some embodiments, SVOCs can be collected diffusively once a vacuum has been created (e.g., after step 506). When sorbents are heated, they expand, and when they are cooled, they contract. During contraction, gaps in the sorbent or along the walls can occur, causing inconsistent carrier gas or air flow through the sorbent, and allowing compounds to penetrate further into the sorbent bed, due to a lack of exposure to the entire bed. During diffusive compound collection or trapping under vacuum (e.g., during a collection interval), chemicals are allowed to travel in random directions rather than being steered in the direction of reducing pressure gradient, such as when gas is convectively flowing through a sorbent bed, and through channels in that sorbent bed. During static, diffusive sampling, the random movement of molecules allows them to distribute onto the sorbent bed in a true “affinity distribution” profile, with the very heaviest compounds right at the beginning of the sorbent bed, where they can be recovered the fastest, and where they are unlikely to create any background or carryover during the next analysis.
During the SVOC transfer stage, it is not necessary to heat the sampler to the boiling point of desired compounds in some embodiments. Even at relatively low temperatures (50-100 deg C.), compounds with boiling points of 400-600 deg C. will have some vapor pressure. Even if the equilibrium at a relatively low temperature is 99% adsorbed on the container walls, and 1% in the gas phase, that 1% will collect onto the sample extraction device, forcing yet another 1% to go into the gas phase (that retains the 100:1 adsorbed to gas phase ratio), and then another, until most or all of the high boiling compounds are transferred to the sample extraction device. This is in stark contrast to what is necessary during classical sampling of a headspace within a vial or container, where only the compounds that are in the headspace after a given equilibration period will be included in the analysis. Also, during vacuum extraction, boiling points of compounds can be reduced, allowing recovery of compounds at lower temperatures.
Even when using hydrophobic sorbent element(s) in sample extraction devices 252 and 254, some water will partition into the sample extraction devices when heated to higher temperatures, where water molecules will tend to randomize within the sample vessel 432. Therefore, after the heated extraction (e.g., step 508), and while the system is still a closed system, the bottom portion 444 of the vacuum container can be chilled (e.g., step 510) to a temperature well below that of the sample extraction device 252 at upper portion 442, and under vacuum any condensed water in the sample extraction device 252 can rapidly transfer out of the sorbent element(s) and back to the bottom of the vacuum container (e.g., water 449). Ultimately, VOCs and SVOCs have been transferred to the sorbent, while almost all of the condensed water has been left in the container to be removed during a subsequent cleaning or vessel evacuation process. After the extraction described by
The sample extraction devices 252 and 254 can be cleaned enough for reuse after thermal desorption into a GCMS, without any additional cleaning in some embodiments. Sample vessel 432 and vacuum sleeve 402 can be rinsed in purified or deionized water, and then baked out either in a lab oven or heated under a vacuum to remove any additional water or chemical background. Heating the sample vessel and vacuum sleeve under a vacuum can be done prior to insertion of a sample extraction device 252, such as when optionally replacing a cap attachment 160 of
Process 600 can relate to embodiments in which two sample extraction devices are used, where a first sample extraction device containing first sorbent element(s) is optimized for adsorption of VOCs, and a second sample extraction device containing second sorbent element(s) is optimized for adsorption of SVOCs. In some embodiments, the first sample extraction device containing sorbent(s) optimized for VOC adsorption can be used in the field during air sample collection by the sample vessel 432. Since the gas phase samples and the VOCs contained within them are exposed to the first sample extraction device for an appreciable period of time (e.g., during the sampling, and subsequent transport back to a lab setting), passive and/or diffusive motion of the VOCs can occur at close to atmospheric pressure, over a prolonged period of time (e.g., 1 or more days). As described in greater detail below, vacuum assisted extraction can be performed in connection with the second sample extraction device (and optionally, with the first sample extraction device as well), so that SVOCs can be fully transferred to the second sample extraction device under a vacuum.
Process 600 begins at step 601, where sampling system 400 (sometimes referred to as a “sampler,” for simplicity) is assembled, the sampler including a sample extraction device (e.g., device 252) optimized for collection of VOCs through light SVOCs, a sample vessel (e.g., vessel 432), and a vacuum sleeve (e.g., sleeve 402) that are all cleaned in a laboratory, and then assembled (e.g., according to the arrangements illustrated by
Step 602 can occur after the hybrid sampling system is assembled at step 601, and prior to the system being sent to a sampling or collection site (e.g., a location where gas phase matrices of interest will be sampled by the system). At step 602, a vacuum can be drawn through side port 412, to form a vacuum within the sample vessel 432. In some embodiments, after sample vessel 432 has been evacuated, a weight of the sample vessel 432 can be measured and recorded, to provide a baseline reference weight by which the weight of sampled gasses and/or compounds can be determined after a sampling period at a sampling or collection site.
As described above, step 602 can be performed prior to the hybrid sampling system being sent to a sampling or collection site. Once the system arrives at the sampling or collection site, step 604 can be performed in some embodiments. At step 604, similar to step 504 of
After the sampling time period or interval described in connection with step 604, the hybrid sampling system 400 can be returned to the laboratory for processing. In some embodiments, system 400 can be weighed and compared to the original evacuated weight (e.g., the weight measured after step 602) to determine the amount of liquid water collected, which in turn confirms that total amount of gas sampled when collecting from a high water containing sources at elevated temperatures.
In some embodiments, process 600 can proceed to step 606, which describes adsorbing the compounds collected in the air samples within sample vessel 432 by passive or diffusive transfer, at the one or more sorbent elements of the sample extraction device. In some embodiments, step 606 can take place over a collection interval spanning any suitable amount of time required to transport a sample vessel coupled to sample extraction device to a laboratory for analysis (e.g., 1 day, 2 days, etc.). In connection with the first sample extraction device with first sorbent element(s) optimized for VOCs, a vacuum does not need to be drawn through valve end 214, unlike step 506 of
Process 600 can proceed to step 608, which is similar to step 510 of
Process 600 can proceed to step 610, after step 608 has been performed for the first sample extraction device. At step 610, the first sample extraction device is replaced with the second sample extraction device containing second sorbent element(s) optimized for collection/recovery of SVOCs. After replacing the first sample extraction device with the second sample extraction device, process 600 can proceed to step 612.
At step 612, which is similar to step 506 of
At step 614, compounds from the sampled air, or another gas phase matrix collected at step 604 are adsorbed at one or more sorbent elements located in the lower cavity of a sample extraction device 254 (e.g., by entering an extraction end 212 of the device, and coming into contact with one or more sorbent elements). In some embodiments, step 614 can simply describe the adsorption of compounds collected at step 504 by one or more sorbent elements (e.g., omitting the optional heating of system 400). In some embodiments, the entire sampling system 400 can be heated to raise vapor pressure of SVOCs within sample vessel 432, thereby promoting movement of said compounds towards the one or more sorbent elements of a sample extraction device 252. In some embodiments, an extraction end 212 of the sample extraction device 252 can be heated relatively more than the overall/entire sampling system 400, to particularly encourage or promote movement of SVOCs within sample vessel 432 towards the extraction end (and the one or more sorbent elements contained within the lower cavity of the sample extraction device).
Process 600 can continue to step 616, similar to step 510 of
After step 616, process 600 can proceed to step 618, where the second sample extraction device 254 is removed from the vacuum sleeve by which it was coupled to sample vessel 432 (e.g., by first removing retention cap 404). Both the first sample extraction device and the second sample extraction device discussed above in connection with
Process 700 can relate to embodiments in which two sample extraction devices are used, where a first sample extraction device containing first sorbent element(s) is optimized for adsorption of VOCs through light SVOCs, and a second sample extraction device containing second sorbent element(s) is optimized for adsorption of SVOCs. In some embodiments, neither the first sample extraction device containing sorbent(s) optimized for adsorbing VOCs through light SVOCs, nor the second extraction device containing sorbent(s) optimized for adsorbing SVOCs are used in the field, during sample collection by the sample vial 432. Instead, a sampler similar to sampling system 170 of
Process 700 begins at step 701, where sampling system 400 (sometimes referred to as a “sampler,” for simplicity) is assembled, the sampler including a sample vessel (e.g., vessel 432), and a vacuum sleeve (e.g., sleeve 402) that are all cleaned in a laboratory, and then assembled (e.g., according to the arrangements illustrated by
Step 702 can occur after the sampling system is assembled at step 701, and prior to the system being sent to a sampling or collection site (e.g., a location where gas phase matrices of interest will be sampled by the system). At step 702, a vacuum can be drawn through side port 412, to form a vacuum within the sample vessel 432.
As described above, step 702 can be performed prior to the vacuum sampling system being sent to a sampling or collection site. Once the system arrives at the sampling or collection site, step 704 can be performed in some embodiments. At step 704, similar to step 504 of
After the sampling time period or interval described in connection with step 704, the vacuum sampling system 170 can be returned to the laboratory for processing. In some embodiments, process 700 can proceed to step 706, in which pressure in sample vessel 432 is adjusted by introducing and/or adding an inert gas to the sample vessel, via side port 412. In some embodiments, the inert gas can be Ultra High Purity Nitrogen, or UHP N2. In some embodiments, an amount of Nitrogen is added to adjust pressure within sample vessel 432 to atmospheric pressure.
After adding the inert gas to adjust pressure within sample vessel 432 to atmospheric pressure, process 700 can proceed to step 708, which describes coupling a first sample extraction device with one or more sorbent elements optimized for adsorption of VOCs to the sample vessel via vacuum sleeve 402/406.
Process 700 can then proceed to step 710, where a vacuum can be drawn through the top valve (e.g., valve end 214) and a known volume of gases are removed from sample vessel 432, specifically through sample extraction device 254 of
In some embodiments, a vacuum can be slowly applied to the top of sample extraction device 254 (e.g., where an internal seal comprising a sealing plunger and a seal is located, near valve end 214) to pull gas phase chemicals collected within sample vessel 432 onto the sorbent element(s) of the sample extraction device, thereby eliminating most of the fixed gases that are not retained on the sorbent. In some embodiments, the entire sampling system 400 can be optionally heated to raise vapor pressure of SVOCs within sample vessel 432, thereby promoting movement of said compounds towards the one or more sorbent elements of a sample extraction device 254 (e.g., as a vacuum is drawn through valve end 214 of the sample extraction device).
Process 700 can then proceed to step 712, which is similar to step 706 described above. At step 712, pressure in sample vessel 432 is adjusted by introducing and/or adding an inert gas to the sample vessel, via side port 412. In some embodiments, the inert gas can be Nitrogen, or N2. In some embodiments, an amount of Nitrogen is added to adjust pressure within sample vessel 432 to atmospheric pressure. In some embodiments, step 712 can be performed so that virtually no outside air is introduced into the sampler when exchanging sample extraction devices (e.g., as described below, in connection with step 714).
Process 700 can then proceed to step 714, which describes replacing a first sample extraction device with first sorbent element(s) with a second sample extraction device with second sorbent element(s). In other words, step 714 describes removing the first sample extraction device from the vacuum sampler (and placing it in an isolation sleeve of
After replacing the first sample extraction device with the second sample extraction device, process 700 can proceed to step 716. At step 716, which is similar to step 506 of
At step 718, compounds from the sampled air, or another gas phase matrix collected at step 704 are adsorbed at one or more sorbent elements located in the lower cavity of a sample extraction device 252 (e.g., by entering an extraction end 212 of the device, and coming into contact with one or more sorbent elements).
Process 700 can proceed to step 720, which is similar to step 510 of
After step 720, process 700 can proceed to step 722, where the second sample extraction device 252 is removed from the vacuum sleeve by which it was coupled to sample vessel 432 (e.g., by first removing retention cap 404). Both the first sample extraction device and the second sample extraction device discussed above in connection with
Breath sampler inlet 802 can sometimes be referred to as being in a “flow divert” position when configured or positioned as shown in
In
Process 1300 begins at step 1302, which describes assembling an adapter 812 and breath sampler inlet 802 onto sample vessel 432, and securing the parts via a cap 822. Sampling system 800 (sometimes referred to as a “sampler,” for simplicity) is assembled, using sample vessel 432, and adapter 812, and breath sampler inlet 802 that are all cleaned in a laboratory, and then assembled (e.g., according to the arrangements illustrated by
After step 1302, process 1300 can proceed to step 1304, which describes attaching a vacuum source 902 to the top of breath sampler inlet 802, and pushing breath sampler inlet down to the “flow open” position to create a vacuum in the vessel. Sampling system 800 can be configured to have a vacuum source 902 be seated within an inner surface of inlet opening 804. A side port vacuum gauge can be connected to the vacuum source 902, and can verify that the sample vessel 432 is under vacuum, in some embodiments. In the position illustrated in
After step 1304, process 1300 can proceed to step 1306, which describes pulling up on breath sampler inlet 802 to the “divert” position to isolate and maintain the vacuum in the collection vessel. In some embodiments, the position and/or configuration of breath sampler inlet 802 described by step 1304 is illustrated by
After step 1306, the process 1300 can proceed to step 1308, which describes attaching a mouthpiece (e.g., disposable mouthpiece 1002 of
After step 1308, process 1300 can proceed to step 1310, which describes pushing breath sampling inlet 802 downwards and collect remaining fraction of breath sample from patient (e.g., deep alveolar air, as mentioned above in connection with the description of
After step 1310, process 1300 can proceed to step 1312, which describes pulling breath sampler inlet up to isolate the collected sample (e.g., “flow divert” position). In some embodiments step 1312 can be illustrated by the breath sampling system of
After step 1314, process 1300 can proceed to step 1316, which describes using dynamic headspace sampling to evacuate sample vessel 432 through a top valve of sample extraction device 252. In this manner, a known volume of sample can be drawn through the sorbent bed(s) during sample extraction, and a vacuum can be formed within sample vessel 432. In particular compounds from the deep alveolar air from a patient's exhalation, or another gas phase matrix collected at step 1310 are adsorbed at one or more sorbent elements located in the lower cavity of a sample extraction device 252 (e.g., by entering an extraction end 212 of the device, and coming into contact with one or more sorbent elements).
After step 1316, process 1300 can proceed to step 1318, which describes using second-stage diffusive sampling techniques to adsorb compounds from the deep alveolar air from a patient's exhalation, or another gas phase matrix collected at step 1310.
After step 1318, process 1300 can proceed to step 1320, which describes dehydrating the sample extraction device with at least one sorbent element, optionally cooling the system to promote dehydration of device and sorbent. In particular, at step 1318, a bottom portion 444 of sample vessel 432 can be cooled to promote water condensation within sample vessel 432, and dehydrate the one or more sorbent elements of sample extraction device 252.
After step 1318, process 1300 can proceed to step 1320, which describes analyzing compounds recovered onto device containing at least one sorbent element. In some examples, sample extraction devices with dehydrated sorbent element(s) can be analyzed by thermal desorption processes, using either a splitless injection technique, or a split injection technique.
In some embodiments, processes 500, 600, and 700, can be used in connection with the breath sampling system operations described by process 1300, except that the sample extraction device 252 may not be placed in the container during sample collection (e.g., during step 1310). In connection to steps described in connection with process 500, a single extraction device can be placed in the sample vessel 432, a vacuum can be slowly pulled on the container containing a sample of a patient's exhalation (slowly to avoid channeling), and once under vacuum, the sample vessel 432 can be heated to allow a second stage vacuum diffusive transfer of heavy compounds to the extraction device without likewise transferring the heavy, non-volatile compounds to the extraction device 252 (proteins, carbohydrates, lipids, bacteria), and without accumulating water on the sample extraction device 252.
In connection to steps described in connection with process 600, a sample extraction device 252 can be placed in the breath sampling system 800 (e.g., seated within adapter 812, as illustrated by
Finally, in connection to steps described in connection with process 700 an active sampling extraction device 254 can be used by withdrawing a known volume, then restoring atmospheric pressure using UHP N2 through side port 412, followed by exchanging the first extraction device for a second extraction device optimized for SVOC analysis, where a vacuum is created in breath sampling system 800 through the top of the second extraction device, followed by heating to perform a diffusive, vacuum recovery of the heavier SVOCs in the breath sample, while leaving the non-volatile compounds in vessel 432 where they will not create artifacts when the extraction devices are desorbed into a GCMS
Therefore, in some embodiments, techniques disclosed herein can be used in the analysis of chemicals in gas phase matrices sampled under conditions ranging from ambient temperatures to 300 degrees Celsius, and moisture concentrations from 0 to 50 percent. In some embodiments, a method comprises at a vessel with an attached extraction device containing sorbent, performing the following steps. In some embodiments, the method comprises creating a pre-sampling vacuum in the vessel using a vacuum inlet coupled to the vessel. In some embodiments, the method further comprises collecting, by the vessel, a gas phase sample into the vessel. In some embodiments, the method further comprises removing, through an opening of the attached extraction device, a volume of gas from the vessel while collecting one or more first compounds of the gas phase sample with the sorbent via dynamic headspace sampling technique. In some embodiments, the method further comprises disconnecting a vacuum source from the opening of the attached extraction device to create a closed system. In some embodiments, the method further comprises performing a second stage diffusive extraction under a partial to strong vacuum, to collect one or more second compounds. In some embodiments, the method further comprises heating the vessel during the second stage diffusive extraction to improve recovery of one or more low volatility compounds. In some embodiments, the method further comprises after detaching the vacuum inlet from the vessel, collecting one or more second compounds of the gas phase sample with the sorbent via a diffusive sampling technique.
In some embodiments, the opening of the attached extraction device comprises an upper opening on a first end of the attached extraction device, wherein the attached extraction device has a lower opening on a second end of the attached extraction device that is opposite the first end, wherein the first end of the attached extraction device is located outside of the vessel, and wherein the second end of the attached extraction device is located within the vessel. In some embodiments, the vessel further comprises a vacuum sleeve having an inner cavity that forms a seal with the attached extraction device such that the second end of the attached extraction device is under vacuum after the partial to strong vacuum is created in the vessel. In some embodiments, the second end of the attached extraction device is positioned above an inlet of the vacuum sleeve that allows gases to travel in and out of the vessel along a path that is separated from the extraction device.
In some embodiments, creating the pre-sampling vacuum comprises coupling the vacuum inlet to a side port valve of a vacuum sleeve that couples the attached extraction device to the vessel, and evacuating, using the vacuum inlet coupled to the side port valve, the vessel through the side port. In some embodiments, the method further comprises detaching the attached extraction device, and replacing the detached extraction device with a second extraction device. In some embodiments, the sorbent of the attached extraction device comprises at least a first sorbent element optimized to collect volatile compounds (VOCs), and wherein the second extraction device comprises at least a second sorbent element optimized to collect semi-volatile compounds (SVOCs). In some embodiments, the method further comprises adding, by a side port valve of a vacuum sleeve that couples the attached extraction device to the vessel, inert gas to the vessel, prior to replacing the detached extraction device with the another extraction device. In some embodiments, the method further comprises dehydrating the sorbent after collecting the one or more first compounds of the gas phase sample via the dynamic headspace sampling technique or after the second stage diffusive extraction to collect one or more second compounds, and before removing the attached extraction device from the vessel.
In some embodiments, the vessel has an upper portion to which the attached extraction device is coupled, and a lower portion opposite the upper portion, and wherein dehydrating the sorbent comprises cooling at least the lower portion of the vessel. In some embodiments, collecting the gas phase sample comprises opening a side port valve of a vacuum sleeve that couples the extraction device to the vessel to allow gases to enter the vessel through an inlet of the vacuum sleeve, without the gases contacting the attached extraction device while entering the vessel. In some embodiments, the method further comprises collecting the gas phase sample through the side port via a minimal path length inlet that is heated to keep moisture from over-condensing prior to reaching the vessel. In some embodiments, collecting the gas phase samples comprises receiving, at the vessel, samples of a gas phase matrix from a valve coupled to a flow restrictor when time integrated sampling is required, or when the production of gas to be sampled occurs at a low rate. In some embodiments, collecting the gas phase samples comprises receiving, at the vessel, samples of a gas phase matrix heated between 0 and 300 degrees Celsius without affecting the recovery of VOCs and SVOCs in the gas phase samples. In some embodiments, collecting the gas phase samples comprises receiving, at the vessel, samples of a gas phase matrix with a water concentration between 0 and 50 percent. In some embodiments, the extraction device is coupled to the vessel using a vacuum sleeve, and wherein the method further comprises securing, by a retention cap configured to fit around the extraction device, a coupling between the extraction device and the vacuum sleeve, such that the extraction device is not removable from the vacuum sleeve when secured by the retention cap.
In some embodiments, a method can comprise, at a vessel with an adapter having an opening, seating a breath sampler inlet within the opening, and creating a pre-sampling vacuum in the vessel using a vacuum inlet coupled to the breath sampler inlet, by pushing down the breath sampler inlet into the opening, to pneumatically couple an interior of the vessel to the vacuum inlet. In some embodiments, the method can further comprise pulling up on the breath sampler inlet, to maintain the pre-sampling vacuum in the vessel. In some embodiments, the method can further comprise receiving, at a mouthpiece coupled to the breath sampler inlet, a first fraction of a breath sample corresponding to an exhalation, and eliminating the first fraction of the breath sample, while the breath sampler inlet is pulled up. In some embodiments, the method can further comprise pushing down on the breath sampler inlet to pneumatically couple the interior of the vessel to the mouthpiece, and receiving, at the mouthpiece, a second fraction of the breath sample corresponding to the exhalation. In some embodiments, the method can further comprise collecting, by the vessel, the second fraction of the breath sample, while the breath sampler inlet is pushed down. In some embodiments, the method can further comprise pulling up on the breath sampler inlet to isolate the collected second fraction of the breath sample, removing the breath sampler inlet from the opening of the adapter, and inserting a sample extraction device into the opening of the adapter.
In some embodiments, collecting the second fraction of the breath sample comprises receiving the fraction of a breath sample from a patient's exhalation through the breath sampler inlet with minimal loss of water droplets or aerosols in the breath that contain important, diagnostically relevant SVOCs. In some embodiments, the breath sampler inlet has a divert position corresponding to when the breath sampler inlet is pulled up, wherein the first fraction of the breath sample corresponds to non-alveolar air, wherein the breath sampler inlet has a sample collection position corresponding to when the breath sampler inlet is pushed down, and wherein the second fraction of the breath sample corresponds to deep alveolar air. In some embodiments, a path between the mouthpiece and the vessel is formed when the breath sampler inlet is pushed down, and wherein the path allows for zero-loss collection of VOCs and SVOCs in breath.
Although examples have been fully described with reference to the accompanying drawings, it is to be noted that various changes and modifications will become apparent to those skilled in the art. Such changes and modifications are to be understood as being included within the scope of examples of this disclosure as defined by the appended claims.
This application claims the benefit of U.S. Provisional Patent Application No. 63/194,879, filed on May 28, 2021, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes.
Number | Date | Country | |
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63194879 | May 2021 | US |