Outdoor air pollution fundamentals Air pollutants Air pollution standards and measurement Air pollution problems Air pollution in Hong Kong Air pollution meteorology 1. Definition of air pollutants Air pollution may be defined as the presence in the atmosphere of substance(s) added directly or indirectly in such amounts as to affect living and non-living things adversely. What is classified as a pollutant therefore depends upon recognition of which substances cause adverse effects. It is an ever-changing definition. Centuries ago only soot or odoured gases may have been considered air pollutant. Now we recognize that pollutants can cause more subtle effects than producing unpleasants smells. Even CO2 is now considered a pollutant. Air Pollution ? The key points of air pollution: i) substance; ii) man-made or naturally produced; iii) with adverse effects to living and non-living things; and iv) high concentrations or large amount. Questions arise: How do we define the above vague points? How is adversity defined? At what concentration should a pollutant be considered high? What are the substance that should be considered as pollutants? 2. Common air pollutants Particulate matter: – total suspended particulate (TSP) (typical size < 100 mm) – respirable suspended particulate (RSP) (typical size < 10 mm) (PM10, particulate matter of size < 10 mm) Gaseous pollutants: – Primary gaseous pollutants: SOx, NOx, CO, volatile organic compound (VOC), Pb; – Secondary gaseous pollutants: peroxyacetylnitrate (PAN), ozone (O3) Photochemical pollutants: – VOC, O3, PAN, CFC, greenhouse gases (CO2, H2O) 2.1 Air pollutants sources and properties Natural pollutant sources Volcano eruption: emitting smoke, particulate matter, SO2, H2S, CH4… Fires: emitting smoke, unburnt hydrocarbons, CO, CO2, NOx... Dust or sand storms dispersing dust Oceans are emitting corrosive salt aerosols Lightning produces NOx and O3 Normal human respiration produces CO2 Artificial or anthropogenic sources Stationary sources: combustion, fuel usage, waste incineration, industrial processes… Mobile sources: all emissions and exhausts from transportation 2.2 Sources of air pollutants in Hong Kong Particulate matter Pow er generation 36.7% Aircraft Marine 0.5% Fuel combustion 4.3% 3.7% Vehicle 54.8% Sulphur dioxide Pow er generation 86.4% Fuel combustion Vehicle Marine 6.6% 1.7% 5.0% Aircraft 0.3% Nitrogen oxides Vehicle 35.8% Pow er generation 42.9% Aircraft 3.6% Marine 13.1% Fuel combustion 4.6% Carbon monoxide Vehicle 89.3% Fuel combustion 3.2% Marine Aircraft 2.1% 2.5% Pow er generation 2.9% 2.2 Particulate matter typical size varies: gravel 2000µ, sand 20 ~ 1000µ, hair, 50µ, RSP with health effects 0.1 ~ 10µ Sizes that cause significant air pollution problems are 0.01 ~ 50µ, as larger particles tend to settle Sources of PM: Natural: wind, sandstorm, forest fires, volcano eruption; Anthropogenic: industry, automobiles Size of particles Large particles (2.5 ~ 250µ): produced in mechanical, crushing, crashing, milling or grinding processes. Most mechanical processes cannot produce particles of size smaller than 10µ Fine particles (0.1 ~ 10µ): produced in combustion, evaporation, condensation, settling, e.g. tobacco smoke contains particles of condensed hydrocarbons at 0.01 ~ 1µ. As usual the finer the size, the more volatile the material. Agglomeration of fine particles: Fine particles tend to stick together when they get close together due to electrostatic and Van Der Waal’s forces. Aerosols: Particles small enough to remain suspended in the atmosphere for a long time are referred to as aerosols Effects of particulate matter pollutions Visibility: Particles are able to scatter lights with wavelengths close to the particle size. Because of this particulate matter pollutions usually yield hazy days and visible smog. Since visible lights have wavelength between 0.4 ~ 0.8µ, hazy days are caused by secondary particles. Health: Inhalable lung-damaging dust ranges from 0.5 ~ 5µ; asthma, respiratory syndromes, bronchitis, decreased lung functions. Climate: Fine particles can be called condensation nuclei in meteorology. When wet air reaches saturation condition, the existence of fine particles makes it easier for water vapour to condense and form tiny droplets, forming fog and mist. It also leads to formation of clouds. 2.3 Gaseous pollutants Both N and S are essential to our bodies. However N and S oxides are strong irritants that cause health damage at high concentrations. They also undergo atmospheric reactions to form PM10 in urban areas. N and S oxides react with water and O2 to form nitric and sulphuric acid, which are principal contributors to acid rain. Both N and S have many sources, the main of them being combustion or chemical plants. S oxides are formed from the sulphur contaminants in fuels or incomplete combustion in sulphur ores. N oxides come mainly from atmospheric nitrogen due to lightning. Effects of NOx pollutions smog problems: respiratory problems, visibility issues acid rain nutrient overload in water: decreasing water quality toxic atmosphere global warming Since 1970, all air pollutants have shown a decreasing trend except NOx, which has increased around 10%. Anthropgenic sources of NOx and SOx Effects of SOx pollutions PM formation acid rain respiratory problems 2.4 VOC VOCs are those organic compounds whose room temperature vapour pressures are greater than about 0.0007 atm. It usually contains carbon bonded with H, N or S and can vaporise at significant rates VOCs are contributors to the problem of photochemical oxidants (smogs, ozone): NOx + O2 + VOC O3 + smog sunlight Some VOCs are infrared absorbers and thus contribute to greenhouse effects. Other are known to be toxic or carcinogenic. Most VOCs are emitted from smaller sources like automobiles, paints, solvent usage, nail polish and vanish, correcting fluids. Plants, due to stringent laws, produce comparatively less VOC as emissions 2.5 Ozone O3 layer absorbs ~3% of UV radiation. It controls the amount of incoming and outgoing solar radiation to and from the Earth surface, thus maintaining a normal evolution of global climate. • Ozone occurs in two layers of the atmosphere. • The layer surrounding the earth's surface is the troposphere. • Here, ground-level or "bad" ozone is an air pollutant • that damages human health, vegetation, and many common materials. It is a key ingredient of urban smog. • The stratospheric or "good" ozone layer extends upward from about 10 to 30 miles and protects life on earth from the sun's harmful ultraviolet rays (UV-b). Any chlorofluorocarbon (CFC) molecule in the upper atmosphere tends to become stripped of a chlorine atom photochemically, by bombardment with radiation. That loose atom combines readily with any nearby ozone molecule, to form normal oxygen and chloro-monoxide: Cl + O3 ClO + O2 The monoxide then combines with any available atom of oxygen in the atmosphere to form normal oxygen and chlorine: ClO + O Cl + O2 So the outcome is a chlorine atom, as at the beginning, once again available to destroy more ozone. The chlorine thus acts as a catalyst. This catalytic process occurs most effectively on a foreign surface, for instance on an ice crystal. Since the lower stratosphere is cold over Antarctica in winter, the little water vapour there is forced to condense in polar stratospheric clouds. There is good evidence that every winter the catalytic process of CFCs virtually totally consumes the ozone between 15~25 km over Antarctica. Any CFC has a lifetime in the troposphere of ~100 years, so it can remain available to destroy ozone for a long time. Even if CFC production were stopped today, what is in the atmosphere already would damage the ozone layer for decades. Nitric oxide, NO, is a catalyst in the same way. First it reacts with ozone to form oxygen and nitrogen oxide NO2, and then that reacts with loose atoms of oxygen to create O2 and NO once more: NO + O3 NO2 + O2 NO2 + O NO + O2 The reactions occur most readily on the surface of ice particles found in the winter stratosphere above Antarctica, where temperatures are ~ -80 °C. One common misconception: O3 is poisonous. Its only function is to block radiation. O3 is also a pollutant itself, it is the chief reason for smog In 1985, a team led by British scientists J. Farman (1985) shocked the scientific community by reporting massive annual decreases of stratospheric ozone over Antarctica in the polar spring. In fact such phenomenon has been detected as early as 1977 aboard Nimbus-7 satellite, only that the observations were being discarded as wrong data. Same thing actually happen in Arctic. However, since temperature is slightly higher in Arctic, ozone depletion is less. The effect of a compound on stratospheric ozone depletion is assessed by the unit ozone depletion potential (ODP). ODP is usually defined as the total steady-state ozone destruction, vertically integrated over the stratosphere, that results per unit mass of species i emitted per year relative to that of CFC-11. O3,i ODPi O 3,CFC11 compound CFC-11 (CFCl3) CFC-12 (CF2Cl2) CFC-113 (CFCl2CF2Cl) CFC-115 (CF2ClCF3) HCFC-22 (CF2HCl) HFC-225ca (CF3CF2CHCL2) ODP 1.00 0.82 0.92 0.40 0.04 0.02 In September 1987, Montréal Protocol on Substances that Deplete the Ozone Layer, each signer agreed to reduce the production of CFC-11 ~ CFC-114 and halons. Consumption of these FCFs was frozen at 1986 level from 1989 and is to be reduced to 80% and then 50% of these values at 1994 and 1999. For undeveloped countries, production must not exceed 110% of the 1986 levels. 2.6 Greenhouse effect The atmosphere absorbs a high fraction of long-wave radiation of the earth. Greenhouse effect Water in vapour form is the principal agent for this effect. CO2 is the next in importance only. CO2 is not as important because its concentration is much lower and its main infrared absorption is localized in a narrow band near 1.5 x 104 nm. However the amount of water in the atmosphere is fairly constant, whereas the amount of CO2 is increasing quickly due to rapid growth in industrial activities for the past century. 3. Local air pollution problems Air pollution problems appear in 3 main effects: Effects on health Smoke particles that enter and deposited on the alveoli can cause tuberculosis. Other particles might adsorb gas which causes more intensive irritation. Gases and particles might also penetrate into the bloodstream, e.g. suspended lead from vehicle exhausts can causes significant nervous problems. Ecological effects Plants and animals are also susceptible to air pollution effects. Fluorine emitted by factories can damage plants nearby and significantly lowers the value and vitality of the crop nearby Effects on materials Many acidic gases, like fluorine, chlorine, SOx, NOx can attack metals and concrete and etch glass 3.1 Some severe air pollutions London smog (1952) – Peak daily concentrations nearly 4000 µgm-3 of SOx and 6000 µgm-3 of smoke Los Angeles photochemical smog (1940s) – Huge amount of O3 found by photochemical reactions between NOx from automobile emissions, peroxyacetyl nitrate (PAN) and solar radiation Acid rain (1968) – Buildings damage and ecological changes in Scandinavia Bhopal chemical plant accident (1984) – 3300 people died and more than 200000 suffered from respiratory and eye diseases when 40 tonnes of methyl-isocyanate (MIC) were accidentally released Chernobyl radiation accident (1986) – More than 250 curies of radioactive isotopes were released in a nuclear power plant explosion. Entire Northern and Eastern Europe were affected. 30 casualties, countless radiation sickness Antarctica ozone hole (since 1983) – Ozone depletion at Antarctica due to CFC Forest fire in Indonesia (1997) – More than 30000 people suffered from respiratory problems, visibility often less than 30 m, it was reported that breathing the air was the same as smoking 100 cigarettes per day. 4. The atmosphere Average composition of dry clean air by volume N2 78.084% O2 20.946% Ar 0.934% CO2 0.036% Ne 0.002% He 0.001% ... Typical concentrations of various gases in clean air (ppm) H2O CO2 CH4 CO O3 NH3 NO2 SO2 H2S 0 ~ 70000 360 1.5 0.1 0.02 0.01 0.001 0.0002 0.0002 Concentrations are usually expressed ‘by volume’ because there is a direct relationship between the volume, partial pressure and the number of molecules present. (Dalton’s law) In ambient air at 1 atm, there are ~2.693 x 1019 molecules / cm3 (Loschmidt number) Two concentration units are commonly used in reporting atmospheric species abundance C concentrat ion of species i in ppm i 106 C where Ci and C are moles/volu me of species i and air mi mass concentrat ion mi in mgm , Ci 10-6 Mi -3 where M i is the molecular weight of species i 5. Air quality standards The legislative basis for air pollution abatement in the USA is the 1963 Clean Air Act and its amendments. The Act and its amendments provide for the establishment of two kinds of national ambient air quality standards. Primary ambient air quality standards: those measures to protect public health with an adequate margin of safety Secondary ambient air quality standards: specify a level of pollutant concentrations requisite to the public welfare from any known or anticipated adverse effects associated with the presence of such air pollutants in the air. These effects include damage to crops and vegetation, wildlife, visibility, climate and economy. Air quality standards are based solely on the effects of air pollution, not by scientific or economical standards. Three kinds of studies have been conducted: animal testing, short-term exposures to human volunteers, and epidemiological studies. National air quality standards (1997): standards not to be exceeded once a year Pollutant Averaging time Primary (µgm-3) Secondary (µgm-3) SOx annual 80 daily 365 PM10 annual 50 50 daily 150 150 PM2.5 annual 15 15 daily 65 65 CO 8 hours 10 10 1 hour 40 VOC 3 hours 160 160 NOx annual 100 100 Pb 3 months 1.5 1.5 O3 8 hours 80 80 Air quality objectives of Hong Kong (1987): daily threshold not more than once a year, hourly threshold not more than 3 times a year Concentration in Microgrammes per Cubic Metre (i) Averaging Time Pollutant 1hr 8hrs 24hrs 3mths 1yr Health Effects of Pollutant at Elevated Ambient Levels 350 80 Respiratory illness; reduced lung function; morbidity and mortality rates increase at higher levels. Total Suspended Particulates 260 80 Respirable fraction has effects on health. Respirable Suspended Particulates (v) 180 55 Respiratory illness; reduced lung function; cancer risk for certain particles; morbidity and mortality rates increase at higher levels. 150 80 Respiratory irritation; increased susceptibility to respiratory infection; lung development impairment. Sulphur Dioxide 800 Nitrogen Dioxide 300 Carbon Monoxide 30 000 Photochemical Oxidants (as ozone) (vi) Lead Impairment of co-ordination; deleterious to pregnant women and those with heart and circulatory conditions. 10 000 Eye irritation; cough; reduced athletic performance; possible chromosome damage. 240 1.5 Affects cell and body processes; likely neuropsychological effects, particularly in children; likely effects on rates of incidence of heart attacks, strokes and hypertension. 5.1 Air pollution index The Air Pollution Index (API) of USA is the compact expression of the air quality levels referring to five major pollutants: PM10, SO2, CO, O3, and NO2, based on the National Ambient Air Quality Standards (NAAQS). The Hong Kong API is based upon the Hong Kong Air Quality Objectives (HKAQO). Our API is slightly more sophisticated and is comprised of 9 sub-indices: TSP (daily average), RSP/PM10 (daily average), SO2 (daily average), SO2 (hourly average), NO2 (daily average), NO2 (hourly average), CO (8-hour average), CO (hourly average) and O3 (hourly average). Calculations of API: 1) Calculate sub-index Ii of the ith pollutant Xi observed concentration for the ith pollutant Xi,j concentration for the ith pollutant and the jth breakpoint Xi,j+1concentration for the ith pollutant and the (j+1) breakpoint Ii,j API value for the ith pollutant and the jth breakpoint Ii,j+1 API value for the ith pollutant and the (j+1)th breakpoint API values 0 50 100 200 300 400 500 TSP Daily 0 80 260 375 625 875 1000 RSP Daily 0 55 180 350 420 500 600 SO2 Daily 0 80 350 800 1600 2100 2620 SO2 Hourly 0 400 800 1600 2400 3200 4000 NO2 Daily 0 80 150 280 565 570 940 NO2 Hourly 0 150 300 1130 2260 3000 3750 CO 8-hour 0 5 10 17 34 46 57.5 CO Hourly 0 15 30 60 90 120 150 O3 Hourly 0 120 240 400 800 1000 1200 The maximum of all sub-indices are then selected as the API API Max[ I1 , I 2 ,..., I 9 ] Air Quality Status Air Pollution Level API Health Implications [1] Air quality significantly worse than both short-term and long-term AQOs. Severe 201 to 500 People with existing heart or respiratory illnesses will experience significant aggravation of their symptoms and there will be also widespread symptoms in the healthy population. These include eye irritation, wheezing, coughing, phlegm and sore throat. Air quality worse than both short-term and long-term AQOs. Very High 101 to 200 People with existing heart or respiratory illnesses will notice mild aggravation of their health conditions. Generally healthy individuals may also notice some discomfort. Air quality within the shortterm AQOs but worse than the long-term. High 51 to 100 Very few people, if any, may notice immediate health effects. Long-term effects may, however, be observed if you are exposed to such levels for a long time. Air quality within all AQOs. Medium 26 to 50 None expected for the general population. Air quality well within all AQOs. Low 0 to 25 None expected. 5.2 Measurement of air pollution The air quality monitoring network in Hong Kong of the Environmental Protection Department (EPD) comprises fourteen fixed monitoring stations as of July 1999 to meet the following objectives:– To understand air pollution problems in order that cost-effective policies and solutions can be developed; – To assess how far standards and targets are being achieved or violated; – To assist the assessment of public's exposure to air pollution; and – To provide public information on current and forecast air quality. Other stations have been used in the past and there are more planned for the future. In addition to the EPD's stations, other independent monitoring units are operated, for example, those being operated by the power companies in order to assess the air quality impact of their power stations. A typical sampling urban sampling station High volume RSP and TSP samplers Solar radiation detector Acid rain collector Wind anemometer tapered element oscillating microbalance - continuous RSP Gaseous pollutants analyzer Mobile air sampler 6. Air Pollution in Hong Kong Chiefly vehicular emission related - TSP, RSP & photochemical pollution Large industrial sources are relatively under control Hong Kong is extremely mountainous. This makes trapping of air pollutants easy. Modelling and prediction of air pollutants dispersion also becomes difficult. Pollution events usually happen in hot summer or winter. OZONE (Hourly Maximum) 700 1996 600 1998 1999 1999 400 1999 1997 1999 300 1997 3 Air Quality Objective: 240 m g/m 1999 1996 1996 200 1998 1999 1996 1999 1999 100 Ci ty o ex ic M At he ns Ho us to n Te xa s Ci ty Ro m e Ko ng Ho ng Yo rk Ne w To ky o An ge le s Lo s Sy dn ey ng ap or e Si To ro nt o Lo nd on o ok Ba ng k Fr an cis c Be rli n 0 Sa n Concentration ( m g/m3) 500 7. Atmospheric stability subadiabatic z0 + dz B A z0 superadiabatic C z0 - dz adiabatic T0 - dT T0 T0 + dT 7.1 Lapse rates A lapse rate is the change of temperature with unit rise of elevation. Under adiabatic condition, the lapse rate near the Earth surface is ~-9.8 K km-1. If the numerical value of the lapse is greater in magnitude than this value, superadiabatic lapse; lower, subadiabatic lapse. For calculation purposes, meteorologists and engineers have defined a standard atmospheric lapse of about by ~-6.5 K km-1 by the approximate average of all observations. It simply indicates the the adiabatic assumption is not too appropriate. What does not the atmosphere always have an adiabatic lapse rate as its actual profile? It is because other processes such as winds and solar heating leading to the dynamic temperature behaviour is seldom adiabatic. Other processes exert an equal influence on the prevailing temperature profile than does the adiabatic rising and falling of air parcels. One common fallacy: Cold air is more dense, and therefore heavier than warm air. Therefore, when the air aloft is colder than the air near the ground, the atmosphere is unstable: the cold air will sink and the warm air will rise. 7.2 Temperature-elevation curve The temperature-elevation curve is the principal determination of atmospheric stability. Suppose an air parcel is at point A on the figure. If it is displaced suddenly upward or downward, fast enough to be considered reversible and adiabatic. It would then move to B or C. If the air parcel is displaced slowly, then it could transfer heat to or from the air around it. The process is then unadiabatic. If the surrounding air has adiabatic lapse rate, wherever the air parcel moves, it will reach the same temperature and pressure as the surrounding air. Because of this, further movement is prohibited. This condition is neutral stability: simple displacement do not lead to restoration to original position, nor do they make the parcel move further. When the sun comes up and heats the ground surface and the air above it, there will be a layer of warmed air near the ground, where the lapse rate is practically adiabatic. If the surrounding air has a subadiabatic lapse rate, then if it is moved upwards, it will follow the adiabatic curve, making itself colder and denser than the surrounding. Gravity will then drive it back down. If it is moved downwards, it becomes warmer and less dense, and gravity will push it upwards. For whatever disturbance, the parcel will be restored to its original position. The atmosphere is stable. When the ground cools at evening, temperature increases with height near the ground. This is called inversion. Because of the difference is temperature gradient, the situation inside the inversion is extremely stable. If the surrounding air has a superadiabatic lapse rate, then if it is moved upwards, it will follow the adiabatic curve, making itself warmer and less dense than the surrounding. Gravity will then drive it further upward. If it is moved upwards, it becomes colder and denser than the surrounding, and gravity will push it further downwards. Whatever disturbs it from its original position, the parcel will continue to move away from its original position. The atmosphere is unstable and vertical motion is spontaneous if any minute trigger exists. By afternoon, enough heat has been transferred from the warmed ground to the surrounding. The heated adiabatic air, extends to large height (~2 km) where it meets the stable air above. The air there has a standard lapse rate and thus superadiabatic. 7.3 Examples of instability Thermals : A thermal is a column of warm-air bubbles, expanding as they rise due to atmospheric instability. Thermals commonly occur on warm, calm afternoons above hot grounds. The air lifts off, entrains more air and bubbles and form a column of ~1 km vertical height. The lift is great enough to support soaring eagles without rising hot air column flapping their wings. slowly falling warm air Hot ground low pressure warm air column near ground Tornadoes : A tornado is the result of extreme instability, consisting of a violent vortical air flow and a tapering funnel of twisting cloud. Although the formation of tornadoes is similar to thermals, it depend on three conditions: 1) a sufficient amount of convective energy, 2) stable PBL to prevent thunderstorms to release instability and 3) strong increase of wind speed with respect to height. 7.4 Mixing heights Due to the thermals, there will be vigorous vertical mixing from the clouds with irregular ground at ~2 km, and then negligible vertical mixing above that. The rising tops but flat bottoms air columns provide good vertical clouds tops near mixing and induce large-scale three-mixing height dimensional turbulence, which mixing induce horizontal mixing. Pollutants height released at ground-level will be mixed uniformly up to that mixing height, but not above it. Mixing heights set a limit to air pollutants dispersions. 8. Effect of atmospheric stability on air pollutant dispersion natural adiabatic lapse Looping : The plume is formed in unstable condition. The flow pattern follows closely that of a flow past bluff body forming a turbulent wake behind it. actual temperature lapse Coning : A typical buoyant plume which grows by mixing. It is formed in neutral atmospheric condition. The plume is usually bifurcated and rises by its own buoyancy. Fanning : The plume is seen to reach its equilibrium level quickly. The plume starts off bifurcated by meets strong inversion and travels stably. It is formed in stable atmospheric condition. Fumigating : The plume is formed by being trapped by a strong stable inversion above and a well mixed unstable air below it. It occurs usually in the morning when sunshine causes the layer beneath the inversion to be mixed by convection. Lofting : If the inversion is weak, the plume may penetrate it and then continue to spread upwards but not downwards due to the inversion. Thermalling : It is formed when the thermals are well developed, and the plume is carried away by convection and is broken into lumps. Flagging : When the efflux velocity of the plume is not large enough to carry the effluent, some pollutants are trapped near the stack hole. This is then brought down by gravity. Bifurcation : The buoyancy of a hot plume generates a double vortex circulation in the plume with an updraught. This is due to internal convective motion of the plume