Patent Grant
8395776
Ozone is a toxic gas produced in photochemical air pollution as a result of a complex sequence of reactions involving oxides of nitrogen, hydrocarbons and sunlight. The Clean Air Act in the U.S. and similar laws in other countries set limits on ozone concentrations in ambient air. Enforcement of compliance with the U.S. National Air Quality Standard requires continuous monitoring of ozone concentrations. Compliance monitoring is done almost exclusively by the method of UV absorbance of the Hg emission line at 254 nm. Low pressure mercury lamps provide an intense, stable and inexpensive source of radiation very near the maximum in the ozone absorption spectrum.
It is well known that ozone monitors based on UV absorbance suffer from interferences from other species that absorb at 254 nm. Volatile organic compounds (VOCs) that interfere are generally aromatic compounds. Some VOCs have a larger response at 254 nm than ozone itself. For example, Kleindienst et al. (1993) reported that the response of 2-methyl-4-nitrophenol is about 40% higher than ozone. Mercury provides a particularly strong interference because the electronic energy levels of Hg atoms are resonant with the Hg emission line of the low pressure Hg lamp used in ozone monitors. The relative response to Hg as compared to ozone depends on the temperature and pressure of the lamp and on the efficiency with which the instrument's internal ozone scrubber removes mercury, but is usually in the range 100-1000. The U.S. EPA (1999) reported that at a baseline ozone concentration of approximately 75 parts per billion (ppb), the presence of 0.04 ppb Hg (300 ng/m3 at room temperature) caused an increase in measured ozone concentration of 12.8% at low humidity (RH=20-30%) and 6.4% at high humidity (RH=70-80%) using a UV photometric ozone monitor. For dry air, Li et al. (2006) found that 1 ppb of mercury gave a response equal to approximately 875 ppb of ozone in the same model of Thermo Electron Corporation photometric ozone monitor used in the EPA study. This mercury interference can be quite large inside buildings where mercury vapor may be present as a result of past mercury spills (broken thermometers, fluorescent light fixtures, electrical switches, etc.), near mining operations and near various industrial facilities.
Another way in which mercury interferes in the measurement of ozone using ozone photometers is by adsorption and desorption from the instrument's internal ozone scrubber. These scrubbers are typically composed of manganese dioxide, charcoal, hopcalite or heated silver wool. Mercury atoms will adsorb to and accumulate on the surfaces of the scrubber material. If the temperature of the scrubber increases, or if the humidity changes, the mercury atoms may be released from the scrubber and enter the gas stream. While removal of mercury vapor from the sample stream by the scrubber will cause a positive interference, release of mercury from the scrubber will cause a negative interference. Since mercury is present at some level in all outdoor and indoor air, this interference may be responsible for much of the baseline drift that occurs in photometric ozone monitors.
A water vapor interference in the measurement of ozone by UV absorption has been described by several investigators (Meyer et al., 1991; Kleindienst et al., 1993; Leston and Ollison, 1993; Leston et al., 2005; Hudgens et al., 1994; Kleindienst et al., 1997; Maddy, 1998; Maddy, 1999; U.S. Environmental Protection Agency, 1998; Wilson and Birks, 2006). Recent studies have shown that this interference, which may amount to up to several tens of ppb of ozone, is caused by physical effects by water vapor on the transmission of light through the detection cell (Wilson and Birks, 2006). Depending on the humidity history, the solid-phase ozone scrubber can either add or remove water vapor from the flow stream during the measurement of reference lamp intensity, thereby affecting the calculated ozone concentration. Consistent with this hypothesis, it was found that reducing the mass of the ozone scrubber material greatly reduced the degree of interference (Wilson and Birks, 2006).
This invention provides a means of reducing interferences from Hg, UV-absorbing organic compounds, particles and water vapor to negligible levels by replacing the solid-phase ozone scrubber used in UV-absorbance-based ozone monitors with a gas-phase ozone scrubber. In particular, nitric oxide (NO) can be added to the sample stream to serve as the gas-phase scrubber.
The foregoing example of the related art and limitations related therewith are intended to be illustrative and not exclusive. Other limitations of the related art will become apparent to those of skill in the art upon a reading of the specification and a study of the drawings.
One aspect of this invention is the measurement of ozone concentrations by UV absorbance in which the solid-phase ozone scrubber is replaced by a gas-phase scrubber.
Another aspect of this invention is the use of nitric oxide gas in combination with a reaction volume as a gas-phase ozone scrubber for photometric ozone monitors.
Another aspect of this invention is the use of bromine atoms produced in the photolysis of diatomic bromine in combination with a reaction volume as a gas-phase ozone scrubber for photometric ozone monitors.
The following embodiments and aspects thereof are described and illustrated in conjunction with systems, tool and methods which are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above described problems have been reduced or eliminated, while other embodiments are directed to other improvements.
Disclosed herein is a method for measuring ozone by UV absorbance in which the solid phase scrubber is replaced by a gas-phase scrubber in order to reduce interferences of Hg, UV-absorbing compounds, particulate matter and water vapor to negligible levels.
In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the accompanying drawings forming a part of this specification wherein like reference characters designate corresponding parts in the several views.
Before explaining the disclosed embodiment of the present invention in detail, it is to be understood that the invention is not limited in its application to the details of the particular arrangement shown, since the invention is capable of other embodiments. Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting. Also, the terminology used herein is for the purpose of description and not of limitation.
A schematic diagram of a typical single-beam UV-absorbance photometer for measuring ozone is provided as
where l is the path length (typically 5-50 cm) and a is the absorption cross section for ozone at 254 nm (1.15×10−17 cm2 molecule−1 or 308 atm−1 cm−1), which is known with an accuracy of approximately 1%.
The pressure and temperature within the absorption cell are measured using a pressure sensor 4 and a temperature sensor 6 so that the ozone concentration can be expressed as a mixing ratio in parts-per-billion by volume (ppb). In principle, the measurement of ozone by UV absorption requires no external calibration; it is an absolute method. However, non-linearity of the photodiode response and electronics can result in a small measurement error. Therefore, ozone monitors are typically calibrated relative to an ozone standard such as one of the reference photometers maintained by the U.S. National Institute of Science and Technology (NIST).
Dual beam instruments for ozone measurements also are common. In a dual beam instrument, ozone-scrubbed air passes through one detection cell while sample air passes through the second detection cell. The flow path is periodically changed using switchable valves so that I and Io are alternately measured in each cell. Compared to a single-beam instrument, dual beam instruments provide faster measurements than single-beam instruments, and precision may be improved due to cancellation of lamp fluctuations. Typically, dual beam instruments have better precision for the same data averaging time and better baseline stability. Various plumbing variations for dual beam ozone monitors are known; for example, rather than using parallel flow paths through the two detection cells, a single sample flow may pass through one detection cell followed by an ozone scrubber followed by the second detection cell and valves used to periodically reverse the direction of flow.
Both single beam and dual beam ozone monitors suffer from interferences from mercury vapor, various organic compounds, particles such as smoke and dust, and water vapor. If a UV-absorbing, gas-phase or particulate species is present at equal concentrations during I and Io measurements, then I=Io and according to equation 1 the measured contribution to absorbance will be zero and that species will not interfere. However, nearly all chemical species are at least partially removed by the internal ozone scrubber 3 of
In the present invention, the solid-phase ozone scrubber of
X+O3→XO+O2 (2)
Examples of X include nitric oxide (NO) and the halogen atoms F, Cl, Br and I. Flow through the reaction volume 13 allows sufficient time for the reaction to be substantially complete. A nearly complete reaction is desirable, but not necessary if the flow rates of gases are held constant. The extent of reaction can be calculated from the reaction volume, V, total volumetric flow rate, F, reagent gas concentration, [X], and second order reaction rate constant, k. For example, if NO is the reagent gas X and the reaction is made pseudo-first order with [NO]>>[O3], the fraction of ozone unreacted after passing through the reaction volume is given by
where [O]o is the ozone concentration prior to reaction. For example, for a NO mixing ratio of 4 parts-per-million, a reaction volume of 50 cm3, flow rate of 1 L/min, rate constant for the NO+O3 reaction of 1.8×10−14 cm3 molec−1 s−1, ambient pressure and temperature of 25° C., [O3]o is calculated to be 0.005. In other words, the reaction is 99.5% complete. For this example, the reaction time, V/F, is 3 seconds. Thus, reaction conditions can be adjusted to achieve nearly or substantially complete destruction of ozone when NO is used as the reagent gas.
Ozone is measured by alternating opening and closing valve 12. When the valve is open (NO allowed to flow), ozone is substantially destroyed and the analytical signal Io is measured. When the valve is closed, no ozone is destroyed and the analytical signal I is measured. The concentration of ozone may then be calculated using equation 1 and applying appropriate calibration factors.
Because of the dilution effect of the added reagent gas, the contributions to absorbance by interfering compounds will be different during scrubbed (Io) and unscrubbed (I) measurements. Thus, the contribution to absorbance by an interference will be reduced by the factor R as follows:
In other words, if the reagent flow makes up 1% of the total flow, the absorbance from interferences is reduced by a factor of 100. Interferences can be completely cancelled if the reagent flow is matched by a flow of ozone-scrubber air or other inert gas during the period that the reagent flow is turned off. In that case valve 12 may be a 3-way valve that switches between reagent gas from source 11 and ozone-depleted gas from another source. Of course, the dilution factor must be accounted for in computing the ozone concentration. This is conveniently done if the reagent gas is generated photochemically since the photolysis lamp may be modulated to add and remove the reagent gas as shown in
Alternatively, NO may be produced from NO2 by photolysis using a black lamp with emissions centered at 366 nm or by use of a near UV light emitting diode:
NO2+hν→NO+O (8)
This reaction must be carried out in the absence of oxygen; otherwise ozone will be produced from combination of the O atom produced in reaction 8 with oxygen. The use of NO2 as a source of NO has the advantage that it can be supplied by a permeation tube. Nitrous oxide (N2O) has the advantage of being much less toxic. Nitrous oxide is available in small cartridges used for making whipped cream and is a consumer product.
Other reagent gases may be used to effectively scrub ozone. The rates of reactions of halogen atoms with ozone, for example, are much larger than that of NO so that the reaction times required are much shorter. At 25° C. the reaction rate coefficients are 1.0×10−11, 1.2×10−11, 1.2×10−12 and 1.2×10−12 cm3 molec−1 s−1 for the reactions of F, Cl, Br and I atoms with ozone, respectively (NASA, 2006). In addition, halogens are catalytic in their reactions with ozone via the sequence of reactions,
thus reducing the concentration of halogen atom required to efficiently destroy ozone within a given reaction time. Halogen atoms are easily produced by photolysis of the corresponding diatomic halogen molecules, F2, Cl2, Br2 and I2 as follows:
X2+hν→2 X (14)
Although any of the diatomic halogens could be used as a source of halogen atoms, Br2 is considered the most suitable for use as a gas-phase scrubber. Fluorine is the most corrosive of the halogens and is difficult and even dangerous to handle. It is a gas at room temperature and atmospheric pressure and thus cannot be supplied by a permeation tube. Iodine is a solid at room temperature and atmospheric pressure. Sufficient vapor pressure could be obtained by heating, but because of its low vapor pressure it will condense onto cooler surfaces throughout the apparatus unless the entire flow path is heated. Permeation tubes may be produced that contain either chlorine or bromine in liquid form. The ClO product formed in the reaction of Cl atoms with O3 absorbs strongly at 254 nm, the same wavelength used for ozone detection. This absorption by the ClO product is calculated to reduce the sensitivity to ozone by up to 37% and introduce uncertainty since some of the ClO would be lost to its disproportionation reaction and possibly other reactions. Bromine has a much larger absorption cross section than chlorine in the near UV where inexpensive light sources such as black lamps and UV LEDs are readily available, and BrO does not absorb significantly at 254 nm. Also, the catalytic reaction sequence described by reactions 11-13 is much faster for bromine atoms than for chlorine atoms. The rate determining step, reaction 12, has a rate coefficient of 2.7×10−12 cm3 molec−1 s−1 for the BrO+BrO reaction and 8.5×10−15 cm3 molec−1 s−1 for the ClO+ClO reaction (NASA, 2006). Thus, the BrO+BrO reaction is more than 300 times faster. Both reactions form products other than 2X+O2 that don't propagate the chain. In the case of bromine, the branching ratio to the products 2Br+O2 is 85% compared to 49% for the products 2 Cl+O2 in the case of chlorine (NASA, 2006). Clearly, bromine is a better catalyst than chlorine for ozone destruction, a fact well known with respect to relative effects of chlorine and bromine on ozone depletion in the stratosphere.
Other reagents for ozone destruction may be derived from photolysis of relatively stable compounds. Some examples include H2O2 and HNO2 (HONO, nitrous acid). Hydrogen peroxide, which may be supplied by a permeation tube, photolyzes to produce two hydroxyl radicals, which undergo a relatively fast reaction with ozone:
H2O2+hν→2 OH (8)
OH+O3→HO2+O2 (9)
Nitrous acid photolyzes to produce OH and NO, both of which react with ozone, as discussed above:
HONO+hν→OH+NO (10)
Alkenes and aromatic compounds also are known for their reactions with ozone, although the gas-phase reaction rates are relatively slow. One skilled in the art would be aware of many other species that react with ozone that may potentially serve as the reagent for a gas-phase scrubber.
Of the reagents discussed above, the preferred reagents are NO and Br atoms. An advantage of NO is that it has no known reactions with any potentially interfering compounds in ambient air. Although the vapor pressure of NO is too high for a permeation tube, it can be produced by photolysis of N2O or NO2, as discussed earlier. Bromine may be supplied in-line from a permeation tube and photolyzed to produce Br atoms.
An UV ozone monitor was modified according to
While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub-combinations therefore. It is therefore intended that the following appended claims hereinafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations are within their true spirit and scope. Each apparatus embodiment described herein has numerous equivalents.
The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. Whenever a range is given in the specification, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure.
In general the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The above definitions are provided to clarify their specific use in the context of the invention.
All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. All references cited herein are hereby incorporated by reference to the extent that there is no inconsistency with the disclosure of this specification. Some references provided herein are incorporated by reference herein to provide details concerning additional starting materials, additional methods of synthesis, additional methods of analysis and additional uses of the invention.
This application is a non-provisional application claiming the benefits of provisional application No. 61/084,892 filed Jul. 30, 2008.
| Number | Name | Date | Kind |
|---|---|---|---|
| 4018562 | Parks et al. | Apr 1977 | A |
| 5571724 | Johnson | Nov 1996 | A |
| 7045359 | Birks et al. | May 2006 | B2 |
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| U.S. Appl. No. 12/595,930, filed Oct. 14, 2009, First Named Inventor: Peter C. Andersen. |
| U.S. Appl. No. 12/480,544, filed Jun. 8, 2009, First Named Inventor: John W. Birks. |
| Number | Date | Country | |
|---|---|---|---|
| 20100027016 A1 | Feb 2010 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61084892 | Jul 2008 | US |
