NOx
In
NOx gases are usually produced from the reaction between
NOx does not include nitrous oxide (N2O),[1] a fairly inert oxide of nitrogen that contributes less severely to air pollution, notwithstanding its involvement in ozone depletion[4] and high global warming potential.
NOy is defined as the sum of NOx plus the NOz compounds produced from the oxidation of NOx which include nitric acid, nitrous acid (HONO), dinitrogen pentoxide (N2O5), peroxyacetyl nitrate (PAN), alkyl nitrates (RONO2), peroxyalkyl nitrates (ROONO2), the nitrate radical (NO3), and peroxynitric acid (HNO4).[5][6]: 30
Formation and reactions
Because of energy limitations, oxygen and nitrogen do not react at ambient temperatures. But at high temperatures, they undergo an
In
In other words, the concentration of ozone in the atmosphere is determined by the ratio of these two species.
-
(1)
-
(2)
-
(3)
-
(4)
The symbol represents a "third body", a molecular species that is required to carry away energy from the exothermic reaction 2. Equation 4 relates the concentrations of NOx and ozone, and is known as the Leighton relationship.
The time that is needed to reach a steady state among NOx and ozone is dominated by reaction (3), which reverses reactions (1)+(2):
-
(5)
for mixing ratio of NO, [NO] = 10 part per billion (ppb), the time constant is 40 minutes; for [NO] = 1 ppb, 4 minutes.[8]: 211
Formation of smog
When NOx and volatile organic compounds (VOCs) react in the presence of sunlight, they form photochemical smog, a significant form of air pollution. The presence of photochemical smog increases during the summer when the incident solar radiation is higher. The emitted hydrocarbons from industrial activities and transportation react with NOx quickly and increase the concentration of ozone and peroxide compounds, especially peroxyacetyl nitrate (PAN).[9]
Children, people with lung diseases such as asthma, and people who work or exercise outside are particularly susceptible to adverse effects of smog such as damage to lung tissue and reduction in lung function.[10]
Formation of nitric acid and acid rain
NO2 is further oxidized in the gas phase during daytime by reaction with OH
- NO2 + OH (+M) → HNO3 (+M),
where M denotes a third molecule required to stabilize the addition product. Nitric acid (HNO3) is highly soluble in liquid water in aerosol particles or cloud drops.
NO2 also reacts with ozone to form nitrate radical
- NO2 + O3 → NO3 + O2.
During the daytime, NO3 is quickly
.- NO2 + NO3 (+M) → N2O5 (+M).
N2O5 reacts rapidly with liquid water (in aerosol particles or cloud drops, but not in the gas phase) to form HNO3,
- N2O5 + H2O(liq) → 2 HNO3(aq)
These are thought to be the principal pathways for formation of nitric acid in the atmosphere.[8]: 224–225 This nitric acid contributes to acid rain or may deposit to soil, where it makes nitrate, which is of use to growing plants. The aqueous phase reaction
- 2 NO2 + H2O → HNO2 + HNO3
is too slow to be of any significance in the atmosphere.[8]: 336
Sources
Natural sources
Nitric oxide is produced during thunderstorms due to the extreme heating and cooling within a lightning strike. This causes stable molecules such as N2 and O2 to convert into significant amounts of NO similar to the process that occurs during high temperature fuel combustion.[11] NOx from lightning can become oxidized to produce nitric acid (HNO3), this can be precipitated out as acid rain or deposited onto particles in the air. Elevated production of NOx from lightning depends on the season and geographic location. The occurrence of lightning is more common over land near the equator in the inter-tropical convergence zone (ITCZ) during summer months.[12] This area migrates slightly as seasons change. NOx production from lightning can be observed through satellite observations.
Scientists Ott et al.[13] estimated that each flash of lightning on average in the several mid-latitude and subtropical thunderstorms studied turned 7 kg (15 lb) of nitrogen into chemically reactive NOx. With 1.4 billion lightning flashes per year, multiplied by 7 kilograms per lightning strike, they estimated the total amount of NOx produced by lightning per year is 8.6 million tonnes. However, NOx emissions resulting from fossil fuel combustion are estimated at 28.5 million tonnes.[14]
A recent discovery indicated that cosmic ray and solar flares can significantly influence the number of lightning strikes occurring on Earth. Therefore, space weather can be a major driving force of lightning-produced atmospheric NOx.[3] Atmospheric constituents such as nitrogen oxides can be stratified vertically in the atmosphere. Ott noted that the lightning-produced NOx is typically found at altitudes greater than 5 km, while combustion and biogenic (soil) NOx are typically found near the sources at near surface elevation (where it can cause the most significant health effects).[13]
Biogenic sources
A recent study conducted by the University of California Davis found that adding nitrogen fertilizer to soil in California is contributing 25 percent or more to state-wide NOx pollution levels.[18] When nitrogen fertilizer is added to the soil, excess ammonium and nitrate not used by plants can be converted to NO by microorganisms in the soil, which escapes into the air. NOx is a precursor for smog formation which is already a known issue for the state of California. In addition to contributing to smog, when nitrogen fertilizer is added to the soil and the excess is released in the form of NO, or leached as nitrate this can be a costly process for the farming industry.
A 2018 study by the Indiana University determined that forests in the eastern United States can expect to see increases in NOx and in turn, changes in the types of trees which predominate. Due to human activity and
Industrial sources (anthropogenic sources)
The three primary sources of NOx in combustion processes:[20][21]
- thermal NOx
- fuel NOx
- prompt NOx
Thermal NOx formation, which is highly temperature dependent, is recognized as the most relevant source when combusting natural gas. Fuel NOx tends to dominate during the combustion of fuels, such as coal, which have a significant nitrogen content, particularly when burned in combustors designed to minimise thermal NOx. The contribution of prompt NOx is normally considered negligible. A fourth source, called feed NOx is associated with the combustion of nitrogen present in the feed material of cement rotary kilns, at between 300 °C and 800 °C, where it is considered a minor contributor.
Thermal
Thermal NOx refers to NOx formed through high temperature oxidation of the diatomic nitrogen found in combustion air.
The three principal reactions (the extended
- N2 + O ⇌ NO + N
- N + O2 ⇌ NO + O
- N + OH· ⇌ NO + H·
All three reactions are reversible.
Fuel
It is estimated that transportation fuels cause 54% of the anthropogenic (i.e. human-caused) NOx. The major source of NOx production from nitrogen-bearing fuels such as certain coals and oil, is the conversion of fuel bound nitrogen to NOx during combustion.[22] During combustion, the nitrogen bound in the fuel is released as a free radical and ultimately forms free N2, or NO. Fuel can contribute as much as 50% of total NOx emissions through the combusting oil and as much as 80% through the combusting of coal [25]
Although the complete mechanism is not fully understood, there are two primary pathways of formation. The first involves the oxidation of volatile nitrogen species during the initial stages of combustion. During the release and before the oxidation of the volatiles, nitrogen reacts to form several intermediaries which are then oxidized into NO. If the volatiles evolve into a reducing atmosphere, the nitrogen evolved can readily be made to form nitrogen gas, rather than NOx. The second pathway involves the combustion of nitrogen contained in the char matrix during the combustion of the char portion of the fuels. This reaction occurs much more slowly than the volatile phase. Only around 20% of the char nitrogen is ultimately emitted as NOx, since much of the NOx that forms during this process is reduced to nitrogen by the char, which is nearly pure carbon.
Prompt
Nitrogen oxides are released during manufacturing of nitrogen fertilizers. Though nitrous oxide is emitted during its application, it is then reacted in atmosphere to form nitrogen oxides. This third source is attributed to the reaction of atmospheric nitrogen, N2, with radicals such as C, CH, and CH2 fragments derived from fuel,
Health and environment effects
There is strong evidence that NOx respiratory exposure can trigger and exacerbate existing asthma symptoms, and may even lead to the development of asthma over longer periods of time. It has also been associated with heart disease, diabetes, birth outcomes, and all-cause mortality, but these nonrespiratory effects are less well-established.[29]
NOx reacts with ammonia, moisture, and other compounds to form nitric acid vapor and related particles.
NOx reacts with
NOx also readily reacts with common organic chemicals, and even ozone, to form a wide variety of toxic products:
The direct effect of the emission of NOx has positive contribution to the greenhouse effect.[33] Instead of reacting with ozone in Reaction 3, NO can also react with HO2. Once the concentration of NOx exceeds a certain level, atmospheric reactions result in net ozone formation. Since tropospheric ozone can absorb infrared radiation, this indirect effect of NOx is intensifying global warming.
There are also other indirect effects of NOx that can either increase or decrease the greenhouse effect. First of all, through the reaction of NO with HO2 radicals, •OH radicals are recycled, which oxidize methane molecules, meaning NOx emissions can counter the effect of greenhouse gases. For instance, ship traffic emits a great amount of NOx which provides a source of NOx over the ocean. Then, photolysis of NO2 leads to the formation of ozone and the further formation of hydroxyl radicals (·OH) through ozone photolysis. Since the major sink of methane in the atmosphere is by reaction with •OH radicals, the NOx emissions from ship travel may lead to a net global cooling.[34] However, NOx in the atmosphere may undergo dry or wet deposition and return to land in the form of HNO3/NO−3. Through this way, the deposition leads to nitrogen fertilization and the subsequent formation of nitrous oxide (N2O) in soil, which is another greenhouse gas. In conclusion, considering several direct and indirect effects, NOx emissions have a negative contribution to global warming.[35]
NOx in the atmosphere is removed through several pathways. During daytime, NO2 reacts with hydroxyl radicals (·OH) and forms
Biodiesel and NOx
Biodiesel and its blends in general are known to reduce harmful tailpipe emissions such as: carbon monoxide; particulate matter (PM), otherwise known as soot; and unburned hydrocarbon emissions.[37] While earlier studies suggested biodiesel could sometimes decrease NOx and sometimes increase NOx emissions, subsequent investigation has shown that blends of up to 20% biodiesel in USEPA-approved diesel fuel have no significant impact on NOx emissions compared with regular diesel.[38] The state of California uses a special formulation of diesel fuel to produce less NOx relative to diesel fuel used in the other 49 states. This has been deemed necessary by the California Air Resources Board (CARB) to offset the combination of vehicle congestion, warm temperatures, extensive sunlight, PM, and topography that all contribute to the formation of ozone and smog. CARB has established a special regulation for Alternative Diesel Fuels to ensure that any new fuels, including biodiesel, coming into the market do not substantially increase NOx emissions. The reduction of NOx emissions is one of the most important challenges for advances in vehicle technology. While diesel vehicles sold in the US since 2010 are dramatically cleaner than previous diesel vehicles, urban areas continue to seek more ways to reduce the formation of smog and ozone. NOx formation during combustion is associated with a number of factors such as combustion temperature. As such, it can be observed that the vehicle drive cycle, or the load on the engine have more significant impact on NOx emissions than the type of fuel used. This may be especially true for modern, clean diesel vehicles that continuously monitor engine operation electronically and actively control engine parameters and exhaust system operations to limit NOx emission to less than 0.2 g/km. Low-temperature combustion or LTC technology[2] may help reduce thermal formation of NOx during combustion, however a tradeoff exists as high temperature combustion produces less PM or soot and results in greater power and fuel efficiency.
Regulation and emission control technologies
Other technologies such as
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