US20050059157A1 - Systems and methods for measuring nitrate levels - Google Patents

Systems and methods for measuring nitrate levels Download PDF

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US20050059157A1
US20050059157A1 US10/895,240 US89524004A US2005059157A1 US 20050059157 A1 US20050059157 A1 US 20050059157A1 US 89524004 A US89524004 A US 89524004A US 2005059157 A1 US2005059157 A1 US 2005059157A1
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gas
sample
coupled
particles
nitrate
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George Allen
Petros Koutrakis
Yiming Ding
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/005—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods investigating the presence of an element by oxidation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
    • G01N1/2205—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling with filters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0037—NOx
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
    • G01N2001/222—Other features
    • G01N2001/2223—Other features aerosol sampling devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/173076—Nitrite or nitrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/176152—Total nitrogen determined
    • Y10T436/176921—As part of an elemental analysis

Definitions

  • Particulates are tiny clumps of soot, dirt, and various chemicals that have been linked to a wide variety of health problems—asthma, and higher rates of disease affecting the cardiovascular system or lungs. Since 1987, EPA standards have governed all particulates under 10 micrometers in diameter. This category of particulate matter is called PM10. Recently, however, studies have suggested that the most dangerous particles are actually the smaller ones, which penetrate deeper in the lungs' aereoles. Thus, new regulations will build in a separate standard for particles less than 2.5 micrometers in diameter—PM2.5.
  • PM2.5 While PM10 contains a lot of wind-blown soil, PM2.5 is derived mainly from burning fossil fuels. PM2.5 typically contains a mixture of elemental carbon, organic carbon, sulfate and nitrate particles, and acid droplets. It is unlikely that all components of PM2.5 contribute equally to the observed health effects, yet the present lack of sufficient data quantifying the individual components prevents the EPA from separately regulating these components. Because regulating PM2.5 collectively is not a cost-effective solution, the agency is under great scientific, industrial, and political pressure to specifically identify sources of the observed particle health-effects. Thus, interest in measuring the individual components of PM2.5 has increased dramatically over the last few years.
  • Koutrakis et al., Environ. Sci. Technol. 22:1463, 1988 disclose an integrated sampling method (Harvard/EPA Annular Denuder System (HEADS)) which is designed to measure various atmospheric components including particulate nitrate.
  • the method provides a non-quantitative conversion of particulate nitrate to nitric acid vapor by collection of atmospheric fine particles on a Teflon filter, with a sodium carbonate-coated filter downstream to collect nitric acid vapor produced by volatization of ammonium nitrate and by the reaction of ammonium nitrate with acidic sulfate particles.
  • Brauer et al., Environ. Sci. Technol. 24:1521, 1990 disclose a method for the continuous measurement of nitrous acid and nitric acid vapors which does not distinguish between the two species.
  • Klockow et al., Atmospheric Environment, 1989, 23, 1131-1138 disclose thermodenuder systems for the discontinuous measurement of nitric acid vapor and ammonium nitrate.
  • Buhr et al., Atmospheric Environment, 1995, 29, 2609-2624 teach a denuder for sampling nitric acid, nitrate, and sulfate.
  • Wolfson et al., U.S. Pat. No. 5,854,077 present a continuous differential nitrate measurement method.
  • the invention provides a system for measuring nitrate levels having a sample inlet for receiving a sample of gas, a collection body coupled to said sample inlet, a filter mounted within said body to collect particles from said sample of gas, a heater coupled to the body to heat the body, a gas inlet coupled to said body to provide a flow of gas through said body, and a detector coupled to said body to measure an NO x concentration.
  • the system further comprises a source of gas coupled to said gas inlet.
  • the gas may be nitrogen or another gas which is substantially free of oxygen.
  • the system also includes a catalyst, coupled to said body and to said detector, capable of reducing NO 2 to NO.
  • the catalyst may comprise molybdenum, carbon, or ferrous sulfate.
  • the detector included in the system has a light sensor, and may further include an ozone generator, for example, for the detection of the chemiluminescent oxidation of NO.
  • the detector includes an infrared sensor.
  • the detector includes a material which reversibly binds NO.
  • the filter comprises quartz fibers.
  • the system includes an extractor coupled to the sample inlet and to the collection body to substantially remove NO 2 from the gas sample.
  • the extractor may comprise a hydroxyl-bearing solvent and a base, e.g., glycerol and an organic base, e.g., an amine, such as triethanolamine.
  • the system also includes a selection platform, situated between the sample inlet and the extractor, to substantially remove particles larger than about 2.5 microns.
  • the selection platform may be a filter, an inertial impactor, or any other suitable device.
  • the system further includes a cooling system to cool the collection body.
  • the invention relates to a method for measuring a level of nitrate by receiving a gas sample, collecting nitrate particles from the gas sample on a filter, passing a stream of gas substantially free of oxygen over the collected particles, volatilizing the collected particles by heating to generate NO x , and measuring a level of NO x .
  • the method further includes substantially removing NO 2 prior to collecting nitrate particles, e.g., by passing the received sample over a hydroxyl-bearing solvent and a base, e.g., an organic base such as triethanolamine.
  • a base e.g., an organic base such as triethanolamine.
  • the method further includes removing particles larger than about 2.5 microns from the received gas sample, e.g., by passing the received sample through an inertial impactor or by passing the received sample through a filter.
  • passing a stream of gas includes passing a stream of nitrogen over the collected particles.
  • the method further comprises reducing generated NO 2 to NO using a metal catalyst, e.g., by contacting the NO 2 with a molybdenum catalyst.
  • measuring a level of NO x includes reacting NO with ozone. In yet another embodiment, measuring a level of NO x includes detecting infrared absorption. In certain other embodiments, measuring a level of NO x includes adsorbing NO x on a conductive material.
  • collecting nitrate particles comprises collecting nitrate particles on a filter comprising quartz fibers.
  • volatilizing the collected particles includes rapidly heating the collected particles to at least 300° C.
  • the invention provides a system for measuring nitrate levels, including a'sample inlet to receive a sample of gas, an extractor coupled to said sample inlet to substantially remove NO 2 from the gas sample, a collection body coupled to said sample inlet, an inertial impactor mounted within said body to collect particles from the gas sample, a current source coupled to the inertial impactor to heat the inertial impactor and generate NO x , and a detector coupled to said catalyst to measure an NO x concentration.
  • the invention relates to a method for measuring a level of nitrate by receiving a gas sample, substantially removing NO 2 from the gas sample, collecting nitrate particles from the gas sample with an inertial impactor, passing a stream of gas substantially free of oxygen over the collected particles, volatilizing the collected particles by heating to generate NO x , and measuring a level of NO x generated by the heated particles.
  • the invention provides a system for measuring nitrate levels having means for receiving a sample of gas, support means coupled to the means for receiving, means for collecting particles coupled to the support means, means coupled to the support means, for heating the support means to generate NO x , means, coupled to the support means, for flowing a stream of gas through the support means, and means for measuring an NO x concentration coupled to the support means.
  • such a system also includes means for substantially removing NO 2 from the sample of gas, coupled to said means for receiving and said support means.
  • such a system further includes means for reducing NO 2 to NO, coupled to the support means and to the means for measuring.
  • the invention relates to a method of manufacturing a nitrate measurement apparatus by providing a sample inlet for receiving a sample of gas, coupling a collection body to the sample inlet, disposing a filter within the body, coupling a heater to the body, coupling a gas inlet to the body, and coupling an NO x detector to the body.
  • the method further comprises disposing an NO 2 extractor between said sample inlet and said collection body.
  • the invention further comprises disposing a catalyst capable of reducing NO 2 to NO between said collection body and said NO x detector.
  • FIG. 1 depicts a system for measuring nitrate levels as described herein.
  • FIG. 2 illustrates the accuracy of a method for measuring nitrate levels as described herein.
  • FIG. 3 shows the effect of atmospheric conditions on the method described herein.
  • FIG. 4 demonstrates a method of distinguishing between nitrate and NO 2 in a sample of gas using the systems and methods described herein.
  • FIGS. 5A and B present nitrate measurement results obtained over a 72-hour period.
  • the systems and methods disclosed herein are useful for measuring nitrate levels, for example, in the atmosphere, and may be capable of performing sample collection and analysis within about ten minutes.
  • variability of nitrate levels can be determined over relatively short intervals, e.g., for use in epidemiological studies, regulatory monitoring, or other research.
  • the system can be assembled or manufactured using convenient, commercially available components.
  • FIG. 1 An exemplary system 100 for measuring nitrate levels is depicted in FIG. 1 .
  • the system 100 includes a sample inlet 105 , an extractor 110 , a collection body 115 , a filter 120 , a heater 125 , a cooling system 130 , a catalyst 135 , a detector 140 , a gas inlet 145 , and a gas source 150 .
  • Other components such as a control system, a data acquisition and recording system, or a second independent heater may optionally be included. Variations on the depicted system which are capable of functioning as described herein will be apparent to those of ordinary skill in the art and are intended to be encompassed by this disclosure.
  • a sample of gas such as a sample of air or exhaust, may be received by the system using sample inlet 105 .
  • the sample of gas may be forced into the system 100 , for example, by passing an exhaust stream through the system 100 .
  • the sample of gas may be drawn into the system 100 by a vacuum, e.g., by providing a vacuum beyond the detector 140 , or by utilizing the Bernoulli effect, e.g., by passing a stream of gas rapidly past the inlet 105 , e.g., using the gas inlet 145 .
  • the sample inlet 105 may include a selection platform for removing particles larger than about 2.5 microns, such as an inertial impactor or a filter, as is well known in the art.
  • the sample of gas may then pass into the extractor 110 to remove contaminant gases.
  • the extractor 110 may be a denuder, such as the honeycomb denuder described in U.S. Pat. No. 5,302,191 or an annular denuder, another diffusion denuder, or any other system known in the art for removing gases from a sample of gas.
  • the extractor 110 may include an acidic material, such as citric acid or sulfiric acid, to trap basic compounds, such as ammonia.
  • the extractor 110 is selected to remove at least 50%, or at least 90%, or even at least 95% of the gaseous NO 2 from the sample of gas, as gaseous NO 2 may introduce error into the nitrate measurement.
  • Such an extractor may include a hydroxyl-bearing solvent, such as ethylene glycol, propylene glycol, glycerol, benzyl alcohol, or another hydroxylic solvent, and a base, including an inorganic base, such as a metal carbonate, bicarbonate, hydroxide, or phosphate, e.g., sodium hydroxide or potassium carbonate, and/or an organic base, such as an amine, e.g., 1,8-bis(dimethylamino)-naphthalene, diazabicyclooctane, diazabicyclononane, triethanolamine, diethanolamine, N,N-dimethyl-2-hydroxymethylaniline, or another organic base.
  • a hydroxyl-bearing solvent such as ethylene glycol, propylene glycol, glycerol, benzyl alcohol, or another hydroxylic solvent
  • a base including an inorganic base, such as a metal carbonate, bicarbonate, hydroxide,
  • the hydroxyl-bearing solvent and the organic base are selected to have low vapor pressures at atmospheric pressure, e.g., less than 50 Torr, or less than 10 Torr.
  • Other systems for removing NO 2 or other selected contaminants are known in the art, and may be used alone or in any combination to remove any such compounds from the sample of gas.
  • the sample of gas may then pass into the collection body 115 and through filter 120 .
  • the filter 120 may then trap nitrate particles, in addition to other particles of similar size, e.g., about 2.5 microns or less, while allowing gaseous compounds to pass through.
  • the collection body may be composed of any material capable of withstanding sufficient heat to perform the method as described herein, such as metal, ceramic, glass, quartz, or other heat-resistant material.
  • the collection body may be composed of steel, molybdenum, or an alloy comprising either material.
  • the filter may be composed of any suitable material, e.g., quartz fibers, glass fibers, metal, or other material capable of withstanding temperatures sufficient to volatilize the trapped particles.
  • a stream of gas substantially free of oxygen e.g., including less than about 5% or less than about 1% oxygen, such as nitrogen gas, helium, or argon, may then be passed over the trapped particles. This procedure helps to reduce unwanted oxidation of ammonia or other low oxidation state nitrogen-containing compounds, such as ammonium sulfate, during heating.
  • the gas may be introduced using gas inlet 145 from gas source 150 .
  • the heater 125 may then heat the filter 120 or the collection body 115 to volatilize the trapped particles.
  • the heater may perform this function by any means known in the art.
  • the heater 125 may generate heat itself, such as with a heating element, e.g., a nichrome wire or a heat lamp, used to heat the collection body or filter, or it may apply current to the filter 120 or the collection body 115 to heat that element by resistance, or it may heat the sample by any other means known in the art.
  • the heater 125 or a second heater may heat all or a portion of the path between the collection body 115 and the catalyst 135 .
  • nitrate may be converted to species such as HNO 3 , NO 2 , and NO which are carried by the stream of gas to the catalyst 135 .
  • a portion of the gaseous NO 2 in the sample of gas may be adsorbed by material on the filter, such as soot or other particulate matter, rather than passing through the filter. Upon heating such NO 2 may be desorbed at a temperature below that at which nitrate begins to substantially volatilize. In such embodiments, it may be advantageous to heat the collection body 115 and filter 120 gradually in order to release this unwanted NO 2 prior to detection and measurement of the NO x species liberated by volatilization of nitrate.
  • NO x refers generally to NO and NO 2 . By this method, more accurate nitrate determinations may be measured.
  • cooling system 130 may cool the collection body 115 and/or filter 120 by any means, such as by passing an unheated fluid, e.g., air or water, over the exterior surface of the apparatus, to further enable more rapid cycling between collection and analysis phases.
  • an unheated fluid e.g., air or water
  • the speed of heating may be adjusted to balance cycling time with measurement accuracy, depending on the needs of a particular situation and the relative importance of accounting for NO 2 in the sample of gas.
  • the catalyst 135 may be any material, such as a molybdenum or carbon converter, ferrous sulfate, or any other material capable of reducing NO 2 to NO, as is known in the art.
  • a catalyst 135 need not be included in the system, and the stream of gas may flow directly from the collection body 115 and filter 120 to the detector 140 .
  • the detector 140 may be any component capable of detecting the amount of NO, in the stream of gas.
  • a number of methods are known for detecting NO x in flowing gas streams. Perhaps the most well known and widely used process involves instruments using the chemiluminescent reaction of nitric oxide (NO) and ozone. The process operates by the reaction of ozone and nitric oxide within a reaction chamber having a transmissive window, allowing light produced by the chemiluminescent reaction to be monitored by a detector. Typical components using this process may be found in U.S. Pat. Nos.
  • a semiconductor NO, sensor is described in U.S. Pat. No. 5,863,503.
  • the resistance of this sensor is altered by the absorption of NO and NO 2 .
  • Such a detector 140 may thus simultaneously measure NO and NO 2 levels, and therefore may function accurately in the absence of a catalyst 135 .
  • detector 140 may be employed as detector 140 .
  • a detector which is capable of detection NO 2 but not NO it may be advantageous to oxidize NO in the stream of gas to NO 2 , for example, using an ozone generator or other source of oxidant.
  • the detector 140 may include or may be coupled to a processor, plotter, or other recording apparatus for displaying, recording, or storing data collected by the detector 140 .
  • the filter 120 may be replaced by an inertial impactor, which is also known to be useful for collecting particulate matter from a stream of gas.
  • the inertial impactor may be heated directly, or indirectly, as described above for a filter embodiment. Otherwise, the system is analogous to the system described above.
  • an inertial impactor is used in a system as described above which uses an NO 2 extractor, such as a diffusion denuder, as described above.
  • a system 100 as described above may be manufactured by coupling a sample inlet to a collection body, disposing a filter in said collection body, coupling said collection body to an NO x detector, and coupling a gas inlet to said body.
  • the method may further include coupling an extractor, such as an NO 2 extractor as described above, between said sample inlet and said filter.
  • an extractor such as an NO 2 extractor as described above
  • a catalyst may be disposed between said detector and said collection body to reduce NO 2 to NO.
  • an oxidizer may be disposed between said detector and said collection body.
  • the components included in such a system may be any of the components set forth above or components that function equivalently or analogously.
  • FIG. 2 shows that as nitrate concentration in the gas sample increases, instrument response increases in turn. Furthermore, the very linear fit indicates that the instrument provides a linear response and should measure nitrate levels accurately over a broad range of concentrations.
  • FIG. 3 shows that the introduction of species, such as water (relative humidity (RH) saturated) or ammonia, into the sample of gas does not significantly affect the nitrate level readings of the instrument. In all cases, the peak area is relatively similar.
  • species such as water (relative humidity (RH) saturated) or ammonia
  • FIG. 4 illustrates how NO 2 in the gas sample as collected and NO 2 released from volatilization of nitrate particles can be distinguished using the present method, even in the absence of an extractor.
  • FIGS. 5A and 5B present data collected from atmospheric air samples over three-day periods. Considerable variation can be seen within a given 24-hour period, and these variations can be elucidated because of the relatively short collection-analysis cycles possible using the systems and methods disclosed above.

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Abstract

The systems and methods described herein relate to the measurement of nitrate levels in a sample of gas, for example, air, exhaust, or other sources of gas. Moreover, the systems and methods described herein are capable of operating using short sample collection periods, permitting rapid data collection and finely time-resolved nitrate monitoring over a span of time. Additionally, ambient nitrate can effectively be distinguished from other airborne particles, such as sulfate and carbon.

Description

  • This application is based on U.S. Provisional Application No. 60/158861, filed Oct. 12, 1999, the specification of which is hereby incorporated by reference.
    • BACKGROUND OF THE INVENTION
  • Particulates are tiny clumps of soot, dirt, and various chemicals that have been linked to a wide variety of health problems—asthma, and higher rates of disease affecting the cardiovascular system or lungs. Since 1987, EPA standards have governed all particulates under 10 micrometers in diameter. This category of particulate matter is called PM10. Recently, however, studies have suggested that the most dangerous particles are actually the smaller ones, which penetrate deeper in the lungs' aereoles. Thus, new regulations will build in a separate standard for particles less than 2.5 micrometers in diameter—PM2.5.
  • While PM10 contains a lot of wind-blown soil, PM2.5 is derived mainly from burning fossil fuels. PM2.5 typically contains a mixture of elemental carbon, organic carbon, sulfate and nitrate particles, and acid droplets. It is unlikely that all components of PM2.5 contribute equally to the observed health effects, yet the present lack of sufficient data quantifying the individual components prevents the EPA from separately regulating these components. Because regulating PM2.5 collectively is not a cost-effective solution, the agency is under great scientific, industrial, and political pressure to specifically identify sources of the observed particle health-effects. Thus, interest in measuring the individual components of PM2.5 has increased dramatically over the last few years.
  • A number of methods are known for measuring atmospheric nitrate levels. Koutrakis et al., Environ. Sci. Technol. 22:1463, 1988 disclose an integrated sampling method (Harvard/EPA Annular Denuder System (HEADS)) which is designed to measure various atmospheric components including particulate nitrate. The method provides a non-quantitative conversion of particulate nitrate to nitric acid vapor by collection of atmospheric fine particles on a Teflon filter, with a sodium carbonate-coated filter downstream to collect nitric acid vapor produced by volatization of ammonium nitrate and by the reaction of ammonium nitrate with acidic sulfate particles.
  • Wendt et al., “Continuous monitoring of atmospheric nitric oxide and nitrogen dioxide by chemiluminescence” in Methods of Air Sampling and Analysis, editor, J. P. Lodge Jr., Lewis Publishers, Chelsea, Mich., pp 415-421 (1989), disclose a continuous chemiluminescent NOx detection method. Yamamoto et al., Anal. Chem., 1994, 66, 362-367, describe a nitrate analysis method relying on chemiluminescent NOx detection. NOx generally refers to NO2 and NO taken together.
  • Brauer et al., Environ. Sci. Technol. 24:1521, 1990 disclose a method for the continuous measurement of nitrous acid and nitric acid vapors which does not distinguish between the two species. Klockow et al., Atmospheric Environment, 1989, 23, 1131-1138, disclose thermodenuder systems for the discontinuous measurement of nitric acid vapor and ammonium nitrate. Buhr et al., Atmospheric Environment, 1995, 29, 2609-2624, teach a denuder for sampling nitric acid, nitrate, and sulfate. Wolfson et al., U.S. Pat. No. 5,854,077, present a continuous differential nitrate measurement method.
  • Many of these and other existing methods for nitrate measurement require labor-intensive, manual collection of 24-hour integrated samples and laboratory analysis of the collected components. Not only are such samples expensive to collect, but the lengthy collection period prevents the detection of cycles and patterns which occur over the course of a day. Convenient techniques which offer improved temporal resolution and are capable of unifying the collection and analysis processes are badly needed now to reveal these daily patterns, both for epidemiological research and for regulatory monitoring.
    • SUMMARY OF THE INVENTION
  • The systems and methods described herein relate to the measurement of nitrate in gas samples by collection and analyzing samples by a technique which permits a short cycling time. Thus, in one aspect, the invention provides a system for measuring nitrate levels having a sample inlet for receiving a sample of gas, a collection body coupled to said sample inlet, a filter mounted within said body to collect particles from said sample of gas, a heater coupled to the body to heat the body, a gas inlet coupled to said body to provide a flow of gas through said body, and a detector coupled to said body to measure an NOx concentration.
  • In a certain embodiment, the system further comprises a source of gas coupled to said gas inlet. The gas may be nitrogen or another gas which is substantially free of oxygen.
  • In another embodiment, the system also includes a catalyst, coupled to said body and to said detector, capable of reducing NO2 to NO. The catalyst may comprise molybdenum, carbon, or ferrous sulfate.
  • In certain embodiments, the detector included in the system has a light sensor, and may further include an ozone generator, for example, for the detection of the chemiluminescent oxidation of NO. In another embodiment, the detector includes an infrared sensor. In yet another embodiment, the detector includes a material which reversibly binds NO.
  • In one embodiment, the filter comprises quartz fibers.
  • In yet another embodiment, the system includes an extractor coupled to the sample inlet and to the collection body to substantially remove NO2 from the gas sample. The extractor may comprise a hydroxyl-bearing solvent and a base, e.g., glycerol and an organic base, e.g., an amine, such as triethanolamine.
  • In yet another embodiment, the system also includes a selection platform, situated between the sample inlet and the extractor, to substantially remove particles larger than about 2.5 microns. The selection platform may be a filter, an inertial impactor, or any other suitable device.
  • In one embodiment, the system further includes a cooling system to cool the collection body.
  • In yet another aspect, the invention relates to a method for measuring a level of nitrate by receiving a gas sample, collecting nitrate particles from the gas sample on a filter, passing a stream of gas substantially free of oxygen over the collected particles, volatilizing the collected particles by heating to generate NOx, and measuring a level of NOx.
  • In one embodiment, the method further includes substantially removing NO2 prior to collecting nitrate particles, e.g., by passing the received sample over a hydroxyl-bearing solvent and a base, e.g., an organic base such as triethanolamine.
  • In another embodiment, the method further includes removing particles larger than about 2.5 microns from the received gas sample, e.g., by passing the received sample through an inertial impactor or by passing the received sample through a filter.
  • In one embodiment of the method, passing a stream of gas includes passing a stream of nitrogen over the collected particles.
  • In yet another embodiment, the method further comprises reducing generated NO2 to NO using a metal catalyst, e.g., by contacting the NO2 with a molybdenum catalyst.
  • In certain embodiments, measuring a level of NOx includes reacting NO with ozone. In yet another embodiment, measuring a level of NOx includes detecting infrared absorption. In certain other embodiments, measuring a level of NOx includes adsorbing NOx on a conductive material.
  • In one embodiment, collecting nitrate particles comprises collecting nitrate particles on a filter comprising quartz fibers.
  • In another embodiment, volatilizing the collected particles includes rapidly heating the collected particles to at least 300° C.
  • In yet another aspect, the invention provides a system for measuring nitrate levels, including a'sample inlet to receive a sample of gas, an extractor coupled to said sample inlet to substantially remove NO2 from the gas sample, a collection body coupled to said sample inlet, an inertial impactor mounted within said body to collect particles from the gas sample, a current source coupled to the inertial impactor to heat the inertial impactor and generate NOx, and a detector coupled to said catalyst to measure an NOx concentration.
  • In yet another aspect, the invention relates to a method for measuring a level of nitrate by receiving a gas sample, substantially removing NO2 from the gas sample, collecting nitrate particles from the gas sample with an inertial impactor, passing a stream of gas substantially free of oxygen over the collected particles, volatilizing the collected particles by heating to generate NOx, and measuring a level of NOx generated by the heated particles.
  • In yet another aspect, the invention provides a system for measuring nitrate levels having means for receiving a sample of gas, support means coupled to the means for receiving, means for collecting particles coupled to the support means, means coupled to the support means, for heating the support means to generate NOx, means, coupled to the support means, for flowing a stream of gas through the support means, and means for measuring an NOx concentration coupled to the support means.
  • In one embodiment, such a system also includes means for substantially removing NO2 from the sample of gas, coupled to said means for receiving and said support means.
  • In another embodiment, such a system further includes means for reducing NO2 to NO, coupled to the support means and to the means for measuring.
  • In yet another aspect, the invention relates to a method of manufacturing a nitrate measurement apparatus by providing a sample inlet for receiving a sample of gas, coupling a collection body to the sample inlet, disposing a filter within the body, coupling a heater to the body, coupling a gas inlet to the body, and coupling an NOx detector to the body.
  • In one embodiment, the method further comprises disposing an NO2 extractor between said sample inlet and said collection body.
  • In another embodiment, the invention further comprises disposing a catalyst capable of reducing NO2 to NO between said collection body and said NOx detector.
    • BRIEF DESCRIPTION OF THE FIGURES
  • The following figures depict certain illustrative embodiments of the invention in which like reference numerals refer to like elements. These depicted embodiments are to be understood as illustrative of the invention and not as limiting in any way.
  • FIG. 1 depicts a system for measuring nitrate levels as described herein.
  • FIG. 2 illustrates the accuracy of a method for measuring nitrate levels as described herein.
  • FIG. 3 shows the effect of atmospheric conditions on the method described herein.
  • FIG. 4 demonstrates a method of distinguishing between nitrate and NO2 in a sample of gas using the systems and methods described herein.
  • FIGS. 5A and B present nitrate measurement results obtained over a 72-hour period.
    • DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS
  • The description below pertains to several illustrative embodiments of the invention. Although many variations of the invention may be envisioned by one skilled in the art, such variations and improvements are intended to fall within the compass of this disclosure. Thus, the scope of the invention is not to be limited in any way by the disclosure below.
  • The systems and methods disclosed herein are useful for measuring nitrate levels, for example, in the atmosphere, and may be capable of performing sample collection and analysis within about ten minutes. Thus, variability of nitrate levels can be determined over relatively short intervals, e.g., for use in epidemiological studies, regulatory monitoring, or other research. Furthermore, the system can be assembled or manufactured using convenient, commercially available components.
  • An exemplary system 100 for measuring nitrate levels is depicted in FIG. 1. The system 100 includes a sample inlet 105, an extractor 110, a collection body 115, a filter 120, a heater 125, a cooling system 130, a catalyst 135, a detector 140, a gas inlet 145, and a gas source 150. Other components, such as a control system, a data acquisition and recording system, or a second independent heater may optionally be included. Variations on the depicted system which are capable of functioning as described herein will be apparent to those of ordinary skill in the art and are intended to be encompassed by this disclosure.
  • A sample of gas, such as a sample of air or exhaust, may be received by the system using sample inlet 105. The sample of gas may be forced into the system 100, for example, by passing an exhaust stream through the system 100. Alternatively, the sample of gas may be drawn into the system 100 by a vacuum, e.g., by providing a vacuum beyond the detector 140, or by utilizing the Bernoulli effect, e.g., by passing a stream of gas rapidly past the inlet 105, e.g., using the gas inlet 145. The sample inlet 105 may include a selection platform for removing particles larger than about 2.5 microns, such as an inertial impactor or a filter, as is well known in the art. The sample of gas may then pass into the extractor 110 to remove contaminant gases. The extractor 110 may be a denuder, such as the honeycomb denuder described in U.S. Pat. No. 5,302,191 or an annular denuder, another diffusion denuder, or any other system known in the art for removing gases from a sample of gas. For example, the extractor 110 may include an acidic material, such as citric acid or sulfiric acid, to trap basic compounds, such as ammonia. In one embodiment, the extractor 110 is selected to remove at least 50%, or at least 90%, or even at least 95% of the gaseous NO2 from the sample of gas, as gaseous NO2 may introduce error into the nitrate measurement. Such an extractor may include a hydroxyl-bearing solvent, such as ethylene glycol, propylene glycol, glycerol, benzyl alcohol, or another hydroxylic solvent, and a base, including an inorganic base, such as a metal carbonate, bicarbonate, hydroxide, or phosphate, e.g., sodium hydroxide or potassium carbonate, and/or an organic base, such as an amine, e.g., 1,8-bis(dimethylamino)-naphthalene, diazabicyclooctane, diazabicyclononane, triethanolamine, diethanolamine, N,N-dimethyl-2-hydroxymethylaniline, or another organic base. In certain embodiments, the hydroxyl-bearing solvent and the organic base are selected to have low vapor pressures at atmospheric pressure, e.g., less than 50 Torr, or less than 10 Torr. Other systems for removing NO2 or other selected contaminants are known in the art, and may be used alone or in any combination to remove any such compounds from the sample of gas.
  • The sample of gas may then pass into the collection body 115 and through filter 120. The filter 120 may then trap nitrate particles, in addition to other particles of similar size, e.g., about 2.5 microns or less, while allowing gaseous compounds to pass through. The collection body may be composed of any material capable of withstanding sufficient heat to perform the method as described herein, such as metal, ceramic, glass, quartz, or other heat-resistant material. For example, the collection body may be composed of steel, molybdenum, or an alloy comprising either material. The filter may be composed of any suitable material, e.g., quartz fibers, glass fibers, metal, or other material capable of withstanding temperatures sufficient to volatilize the trapped particles. A stream of gas substantially free of oxygen, e.g., including less than about 5% or less than about 1% oxygen, such as nitrogen gas, helium, or argon, may then be passed over the trapped particles. This procedure helps to reduce unwanted oxidation of ammonia or other low oxidation state nitrogen-containing compounds, such as ammonium sulfate, during heating. The gas may be introduced using gas inlet 145 from gas source 150.
  • The heater 125 may then heat the filter 120 or the collection body 115 to volatilize the trapped particles. The heater may perform this function by any means known in the art. For example, the heater 125 may generate heat itself, such as with a heating element, e.g., a nichrome wire or a heat lamp, used to heat the collection body or filter, or it may apply current to the filter 120 or the collection body 115 to heat that element by resistance, or it may heat the sample by any other means known in the art. In addition to heating the collection body 115 and/or the filter 120, the heater 125 or a second heater may heat all or a portion of the path between the collection body 115 and the catalyst 135. Upon volatilization, nitrate may be converted to species such as HNO3, NO2, and NO which are carried by the stream of gas to the catalyst 135.
  • In certain embodiments, for example, wherein an extractor 110 is not used to remove NO2 from the gas sample, a portion of the gaseous NO2 in the sample of gas may be adsorbed by material on the filter, such as soot or other particulate matter, rather than passing through the filter. Upon heating such NO2 may be desorbed at a temperature below that at which nitrate begins to substantially volatilize. In such embodiments, it may be advantageous to heat the collection body 115 and filter 120 gradually in order to release this unwanted NO2 prior to detection and measurement of the NOx species liberated by volatilization of nitrate. NOx, as used herein, refers generally to NO and NO2. By this method, more accurate nitrate determinations may be measured. Rapid heating, however, may permit more rapid cycling between collection and analysis phases. Similarly, cooling system 130 may cool the collection body 115 and/or filter 120 by any means, such as by passing an unheated fluid, e.g., air or water, over the exterior surface of the apparatus, to further enable more rapid cycling between collection and analysis phases. Thus, the speed of heating may be adjusted to balance cycling time with measurement accuracy, depending on the needs of a particular situation and the relative importance of accounting for NO2 in the sample of gas.
  • The catalyst 135 may be any material, such as a molybdenum or carbon converter, ferrous sulfate, or any other material capable of reducing NO2 to NO, as is known in the art. In embodiments where a detector 140 is used which is capable of simultaneously detecting NO2 and NO, a catalyst 135 need not be included in the system, and the stream of gas may flow directly from the collection body 115 and filter 120 to the detector 140.
  • The detector 140 may be any component capable of detecting the amount of NO, in the stream of gas. A number of methods are known for detecting NOx in flowing gas streams. Perhaps the most well known and widely used process involves instruments using the chemiluminescent reaction of nitric oxide (NO) and ozone. The process operates by the reaction of ozone and nitric oxide within a reaction chamber having a transmissive window, allowing light produced by the chemiluminescent reaction to be monitored by a detector. Typical components using this process may be found in U.S. Pat. Nos. 3,967,933 to Etess et al.; 4,236,895 to Stahl; 4,257,777 to Dymond; 4,315,753 to Bruckenstein et al.; 4,657,744 to Howard; 4,765,961 to Schiff; and 4,822,564 to Howard. The use of a chemiluminescent nitrogen oxide monitoring device in controlling a nitrogen oxide removal unit placed on the outlet of a boiler is shown in U.S. Pat. No. 4,188,190 to Muraki et al. Because these systems are typically not capable of detecting NO2 in the gas stream, a catalyst 135 may be employed in conjunction with such a detector.
  • Another procedure involves the use of an infrared beam, detector, and a comparator chamber. In U.S. Pat. No. 4,647,777 to Meyer, a beam of infrared light is passed through a gas sample and into a selective infrared detector. The beam is split and one portion passes through a chamber containing a fluid that absorbs the spectral wavelengths of the selected gas. The two beams are compared and the difference between the two beams gives an indication of the amount of a selected gas in the sample.
  • A semiconductor NO, sensor is described in U.S. Pat. No. 5,863,503. The resistance of this sensor is altered by the absorption of NO and NO2. Such a detector 140 may thus simultaneously measure NO and NO2 levels, and therefore may function accurately in the absence of a catalyst 135.
  • One of the above detectors, or any other detector capable of measuring NO or NO2 concentrations, may be employed as detector 140. In the case of a detector which is capable of detection NO2 but not NO, it may be advantageous to oxidize NO in the stream of gas to NO2, for example, using an ozone generator or other source of oxidant. The detector 140 may include or may be coupled to a processor, plotter, or other recording apparatus for displaying, recording, or storing data collected by the detector 140.
  • In certain embodiments, the filter 120 may be replaced by an inertial impactor, which is also known to be useful for collecting particulate matter from a stream of gas. In order to volatilize the collected sample, the inertial impactor may be heated directly, or indirectly, as described above for a filter embodiment. Otherwise, the system is analogous to the system described above. Thus, in one embodiment, an inertial impactor is used in a system as described above which uses an NO2 extractor, such as a diffusion denuder, as described above.
  • A system 100 as described above may be manufactured by coupling a sample inlet to a collection body, disposing a filter in said collection body, coupling said collection body to an NOx detector, and coupling a gas inlet to said body. In certain embodiments, the method may further include coupling an extractor, such as an NO2 extractor as described above, between said sample inlet and said filter. When the detector employed does not adequately detect NO2, a catalyst may be disposed between said detector and said collection body to reduce NO2 to NO. Alternatively, if the detector employed does not adequately detect NO, an oxidizer may be disposed between said detector and said collection body. The components included in such a system may be any of the components set forth above or components that function equivalently or analogously.
  • The following examples are provided solely to further illustrate the nature and advantages of one embodiment of the present invention and are not intended to limit the scope of the invention in any way.
  • Exemplification
  • A system as described above and depicted in FIG. 1 was tested to determine the accuracy and utility of the measurements recorded thereby.
  • FIG. 2 shows that as nitrate concentration in the gas sample increases, instrument response increases in turn. Furthermore, the very linear fit indicates that the instrument provides a linear response and should measure nitrate levels accurately over a broad range of concentrations.
  • FIG. 3 shows that the introduction of species, such as water (relative humidity (RH) saturated) or ammonia, into the sample of gas does not significantly affect the nitrate level readings of the instrument. In all cases, the peak area is relatively similar.
  • FIG. 4 illustrates how NO2 in the gas sample as collected and NO2 released from volatilization of nitrate particles can be distinguished using the present method, even in the absence of an extractor.
  • FIGS. 5A and 5B present data collected from atmospheric air samples over three-day periods. Considerable variation can be seen within a given 24-hour period, and these variations can be elucidated because of the relatively short collection-analysis cycles possible using the systems and methods disclosed above.
  • All articles, patents, and other references set forth above are hereby incorporated by reference. While the invention has been disclosed in connection with the embodiments shown and described in detail, various equivalents, modifications, and improvements will be apparent to one of ordinary skill in the art from the above description. Such equivalents, modifications, and improvements are intended to be encompassed by the following claims.

Claims (43)

1. A system for measuring nitrate levels, comprising
a sample inlet for receiving a sample of gas,
a collection body coupled to said sample inlet,
a filter mounted within said body to collect particles from said sample of gas,
a heater coupled to the body to heat the body,
a gas inlet coupled to said body to provide a flow of gas through said body, and
a detector coupled to said body to measure an NOx concentration.
2. The system of claim 1, further comprising
a source of gas coupled to said gas inlet.
3. The system of claim 2, wherein said gas is nitrogen.
4. The system of claim 2, wherein said gas is substantially free of oxygen.
5. The system of claim 1, further comprising
a catalyst, coupled to said body and to said detector, capable of reducing NO2 to NO.
6. The system of claim 5, wherein said catalyst comprises molybdenum.
7. The system of claim 1, wherein said detector includes a light sensor.
8. The system of claim 7, wherein said detector further includes an ozone generator.
9. The system of claim 1, wherein said detector includes an infrared sensor.
10. The system of claim 1, wherein said detector includes a material which reversibly binds NO.
11. The system of claim 1, wherein said filter comprises quartz fibers.
12. The system of claim 1, further comprising
an extractor coupled to said sample inlet and to said collection body to substantially remove NO2 from the gas sample.
13. The system of claim 12, wherein the extractor comprises a hydroxyl-bearing solvent and a base.
14. The system of claim 13, wherein the hydroxyl-bearing solvent is glycerol and the base is an organic base.
15. The system of claim 14, wherein the organic base is an amine.
16. The system of claim 12, further comprising
a selection platform, situated between said sample inlet and said extractor, to substantially remove particles larger than about 2.5 microns.
17. The system of claim 16, wherein said selection platform is a filter.
18. The system of claim 16, wherein said selection platform is an inertial impactor.
19. The system of claim 1, further comprising
a cooling system to cool the collection body.
20. A method for measuring a level of nitrate, comprising
receiving a gas sample,
collecting nitrate particles from the gas sample on a filter,
passing a stream of gas substantially free of oxygen over the collected particles,
volatilizing the collected particles by heating to generate NOx, and
measuring a level of NOx.
21. The method of claim 20, further comprising
substantially removing NO2 prior to collecting nitrate particles.
22. The method of claim 21, wherein substantially removing NO2 includes passing the received sample over a hydroxyl-bearing solvent and a base.
23. The method of claim 21, wherein substantially removing NO2 includes passing the received sample over a hydroxyl-bearing solvent and an organic base.
24. The method of claim 21, wherein substantially removing NO2 includes passing the received sample over a mixture comprising glycerol and triethanolamine.
25. The method of claim 20, further comprising
removing particles larger than about 2.5 microns from the received gas sample.
26. The method of claim 25, wherein substantially removing particles larger than about 2.5 microns includes passing the received sample through an inertial impactor.
27. The method of claim 25, wherein substantially removing particles larger than about 2.5 microns includes passing the received sample through a filter.
28. The method of claim 20, wherein passing a stream of gas includes passing a stream of nitrogen over the collected particles.
29. The method of claim 20, further comprising
reducing generated NO2 to NO using a metal catalyst.
30. The method of claim 29, wherein reducing generated NO2 includes contacting said NO2 with a molybdenum catalyst.
31. The method of claim 20, wherein measuring a level of NOx includes reacting NO with ozone.
32. The method of claim 20, wherein measuring a level of NOx includes detecting infrared absorption.
33. The method of claim 20, wherein measuring a level of NOx includes adsorbing NOx on a conductive material.
34. The method of claim 20, wherein collecting nitrate particles comprises collecting nitrate particles on a filter comprising quartz fibers.
35. The method of claim 20, wherein volatilizing the collected particles includes rapidly heating the collected particles to at least 300° C.
36. A system for measuring nitrate levels, comprising
a sample inlet to receive a sample of gas,
an extractor coupled to said sample inlet to substantially remove NO2 from the gas sample,
a collection body coupled to said sample inlet,
an inertial impactor mounted within said body to collect particles from the gas sample,
a current source coupled to the inertial impactor to heat the inertial impactor and generate NOx, and
a detector coupled to said catalyst to measure an NOx concentration.
37. A method for measuring a level of nitrate, comprising
receiving a gas sample,
substantially removing NO2 from the gas sample,
collecting nitrate particles from the gas sample with an inertial impactor,
passing a stream of gas substantially free of oxygen over the collected particles,
volatilizing the collected particles by heating to generate NOx, and
measuring a level of NO, generated by the heated particles.
38. A system for measuring nitrate levels, comprising
means for receiving a sample of gas,
support means coupled to said means for receiving,
means for collecting particles coupled to said support means,
means, coupled to said support means, for heating the support means to generate NOx,
means, coupled to said support means, for flowing a stream of gas through said support means, and
means for measuring an NOx concentration coupled to said support means.
39. The system of claim 38, further comprising
means for substantially removing NO2 from the sample of gas, coupled to said means for receiving and said support means.
40. The system of claim 38, further comprising
means for reducing NO2 to NO, coupled to said support means and to said means for measuring.
41. A method of manufacturing a nitrate measurement apparatus, comprising
providing a sample inlet for receiving a sample of gas,
coupling a collection body to said sample inlet,
disposing a filter within said body,
coupling a heater to the body,
coupling a gas inlet to said body, and
coupling an NOx detector to said body.
42. The method of claim 41, further comprising
disposing an NO2 extractor between said sample inlet and said collection body.
43. The method of claim 41, further comprising
disposing a catalyst capable of reducing NO2 to NO between said collection body and said NOx detector.
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