Gaseous and Particulate Pollutants Pollutants

BIO4301 Pollutions Sources & Impact
Gaseous and particulate pollutants

Impact and trends
10/11/11
Dr Dirk Wildeboer
Key topics today

Describe current quality of UK air and its implications for human and environmental health Emission trends of key air pollutants Environmental and health impacts of gaseous air pollutants Environmental and health impacts of particulate air pollutants Access and use air quality data collection networks
BIO4301 Air pollution 2
UK air pollution: current status

estimated to reduce the life expectancy of every person in the UK by an average of 7-8 months estimated equivalent health costs of up to 20 billion each year. detrimental effect on ecosystems and vegetation
The Air Quality Strategy for England, Scotland, Wales and Northern Ireland (2007): Air Quality Strategy: volume 1 http://www.defra.gov.uk/environment/ quality/air/air-quality/approach/
Impact of UK air quality policies from 1990-2001

UK air quality policies have led to: marked decline in concentrations of air pollutants estimated reduction of >4,200 premature deaths per year estimated reduction of 3,500 hospital admissions per year benefits equivalent to 68 billion (cost 6 billion to implement)
BIO4301 Air pollution
UK lead emissions 1970-2009

National Emissions Inventory at http://uk-air.defra.gov.uk/
UK sulphur dioxide emission trends; 1970-2009
Explanation of SO2 trends
Since 1970 there has been a substantial overall reduction of more than 91% in SO2 emissions. Harsh winters produced small peaks in 1973 and 1979 and there was a flattening off of overall downward trend in the late 1980s. The two main contributors are solid fuel and petroleum products. Emissions from solid fuel use have declined by 86% since 1970 and those from petroleum by 77%. The most important factors in the fall in emissions from petroleum use are the decline in fuel oil use and the reduction in the sulphur content of gas oil and DERV 99% between 1994 and 2007). The reduction in the sulphur content of gas oil is particularly significant in sectors such as domestic heating, commercial heating and off-road sources where gas oil is used extensively.
Environmental effects of SO2

HEALTH EFFECTS: Aggravation of respiratory tract ECOLOGICAL EFFECTS: Impoverishment of soils EFFECTS ON MATERIALS: Corrosion of building fabrics
Schematic diagram of acid rain formation
UK background SO2 concentrations: 2010
1ppb SO2 = 2.8 g/m3
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Example of available sulphur dioxide statistics (for 2005)

Annual mean (g/m3) 50th percentile (g/m3); hourly values 3 99th percentile (g/m3); hourly values 14 Annual maximum Low air pollution band
London Brent Barnsley Gawber
96
363 days; 32,784 measurements 340 days; 30,859 measurements
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13
29
98
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UK Air Quality Monitoring Network (1)

> 300 sites across the UK automatic networks hourly (or less) pollutant concentrations data collected by modem non-automatic networks daily, weekly or monthly samples collected by physical means e.g. diffusion tube or filter samples chemical analysed and final pollutant concentrations calculated
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UK Air Quality Monitoring Networks
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UK air quality automatic monitoring sites

Automatic Urban and Rural Network (AURN) Automatic Hydrocarbon Network
http://uk-air.defra.gov.uk/
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Automatic Urban and Rural Network (AURN)

133 sites - 111 urban (24 in London) and 22 rural, (sub-) hourly measuring of NOx, SO2, O3, CO. PM10 and PM2.5 role of network determine compliance with UK/EU legislation informing the public about air quality identify long-term trends in air pollution concentrations assessing the effectiveness of policies to control pollution
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Automatic Hydrocarbon Network hourly measuring of 26 types of hydrocarbons 13 sites (urban, industrial, rural) assess ambient concentrations of VOCs re: UK standards and ozone formation potential
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Air monitoring stations
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40 year trends in SO2 and smoke in the UK
Decrease in annual average levels of SO2 and smoke since 1962 when monitoring began. The trends show that the overall levels of sulphur dioxide have fallen nearly 10-fold, and smoke levels 20-fold. Corresponding measurements from later automatic measurements since 1970 tell the same story, with urban background SO2 levels now barely distinguishable from those in rural areas
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UK Governments air quality headline indicator of sustainable development since 1987

This graph shows the average number of days on which levels of any one of a basket of five pollutants (carbon monoxide, nitrogen dioxide, ozone, fine particles and sulphur dioxide) were moderate or higher according to the Air Pollution Information Service bandings. These five pollutants are recognised as the most important for causing short term health effects.
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The average number of days of pollution at urban sites caused by individual pollutants
Figure shows the average number of days of pollution at urban sites since 1993 caused by each individual pollutant. Although the headline indicator had been showing an overall downward trend in UK urban areas since the early 1990s, 2003 showed a sharp rise, due primarily to an increased number of poor ozone days. In urban areas, ozone accounted for approximately 70% of the increase over previous years, with the remainder due to PM10 particles. The main causes of days of moderate or higher air pollution at urban sites are now ozone and fine particles (PM10).
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UK Nitrogen Dioxide emission trends; 19702008
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Explanation of NO2 trends
The road transport sector is the largest source of NOx (approx 33%) with stationary combustion and power generation also being significant sources. Since 1970, overall NOx emissions have decreased by 47%, although this decrease has not been constant. Up to 1984 the NOx emission profile was relatively flat with small peaks in 1973 and 1979 which were largely due to cold winters. From 1984, emissions rose markedly as a result of the growth in road traffic, reaching a peak in 1989. Since 1989, total NOx emissions have declined by 46% as a result of a 59% decrease from road transport, due to the introduction of catalytic converters and stricter regulations and a 54% reduction from power stations.
Environmental effects of NO2

HEALTH EFFECTS: Aggravation of respiratory tract; Promotion of asthmatic attacks EFFECTS ON MATERIALS: Corrosion of building fabrics (Via Acid Rain) ECOLOGICAL EFFECTS: Impoverishment of soils (Via Acid Rain); Inhibition of plant growth CLIMATE EFFECTS: Participation in photochemical smog formation
View of Canary Wharf in August 2003
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Background NO2 annual averages (g/m3) in the UK; 2002
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UK carbon monoxide emission trends; 1970-2008
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Explanation of CO trends
Carbon monoxide arises from incomplete fuel-combustion and is of concern mainly because of its effect on human health and its role in tropospheric ozone formation. It leads to a decreased uptake of oxygen by the lungs and can lead to a range of symptoms as the concentration increases. The UK emissions of carbon monoxide are dominated by road transport activities. Over the period 1970-2003 emissions decreased by 76% reflecting significant reduction in emissions from road transport, domestic and agricultural sectors.
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Environmental effects of CO
70
HEALTH EFFECTS: Cardio-vascular effects
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Death
Saturation of blood (%COHb)
50
40
Loss of consciousness
60 mg/m3 300 mg/m3 900 mg/m3
30
20
10
Observable effects e.g.physical coordination impairment

1 2 3 4 5 6 7
0 Duration of e xposure at heavy w ork (hours); tim es are tripled for at rest conditions
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UK non-methane VOC emission trends; 1970-2008
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Explanation of non-methane VOC trends

NMVOCs are organic compounds which differ widely in their chemical composition and which are grouped together as they display similar behaviours in the atmosphere. NMVOCs are emitted to air as combustion products, as vapour arising from petrol and solvent use and from numerous other sources. Processes which emit NMVOCs include many branches of industry, transport, agriculture and domestic sources. Only 20% of the NMVOC emissions arise from combustion sources with the transport sector dominating. Other major sources of NMVOC emissions are the use of solvents and production processes. There was an increase from 1970 to 1990 followed by a steady reduction due to more stringent emission limits across a range of sectors Interest in NMVOC emissions has grown as their role in the photochemical production of ozone has been appreciated. BIO4301 Air pollution 29
Environmental effects of O3
HEALTH EFFECTS: Promotion of asthmatic attacks EFFECTS ON MATERIALS: Embrittlement of plastics ECOLOGICAL EFFECTS: Inhibition of plant growth CLIMATE EFFECTS: [Component of photochemical smog]
Diurnal production of ozone/photochemical smog
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Ozone/photochemical smog formation

Photochemical smog is produced in bright sunlight when nitrogen oxides hydrocarbons and oxygen interact chemically to produce powerful oxidants like ozone (O3) and peroxyacetyl nitrate (PAN).
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Atmospheric Particulate Terminology

Particles Aggregations of matter, either solid or liquid, which are larger than individual molecules. Particle sizes are expressed as diameters, unless otherwise stated. A general term embracing all airborne particles.
Suspended Particulate Matter (SPM) Aerosol
A suspension of particles in a gas. These particles can be solid or liquid. In atmospheric science, aerosols are often classified by regional type for example, background, polar, desert, marine, urban, etc. The term used to describe particles that are able to pass through a size selective inlet with a 50% efficiency cut-off at 10 m aerodynamic diameter. The aerodynamic diameter refers to unit density spherical particles with the same aerodynamic properties (such as falling speed).
PM10
Atmospheric Particulate Terminology

Inhalable particles Respirable particles Particles which can enter the human nose or mouth during normal breathing. Those inhalable particles that are able to penetrate to the unciliated regions of the deep lung (the alveolar region). Suspended particulate air pollutants with a diameter of less than 15 m, arising from the incomplete combustion of fossil fuels.There are two types of smoke, depending on the measurement technique utilised: dark smoke which is measured by reflectance; and gravimetric smoke (or Total Suspended Particulates, TSP) which is measured in terms of mass.
Smoke
Physical properties of particulate matter

Particle size, shape and density
These parameters influence the terminal settling velocity (speed at which it drops out of the atmosphere), likelihood of re-suspension, diffusion to a surface and, thus, the behaviour of the particle in the atmosphere. The parameter aerodynamic diameter (AD) has been defined to classify all particles >0.5 m AD in terms of the above properties. The AD of a particle is the diameter of a sphere of unit density 0 (where 0 = 1 x 103 kg m-3) having the same settling velocity as the particle in question. The AD defines the aerodynamic properties of a particle and consequently its potential health and environmental impacts (such as the availability of particles for inhalation or the rate of deposition to a surface). Particle size is important when evaluating potential human health impacts. For example, not all particles that are inhaled are deposited in the lung almost all particles larger than 7 m are deposited in the nose or throat, whereas up to 60% of particles below 0.1 m are deposited in the lungs alveoli (air spaces).
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Physical properties of particulate matter (continued)

Shape and morphology (structure) influence the adhesion properties of a particle its ability to stick to a surface; its atmospheric behaviour e.g. the long and thin shape of asbestos fibres allows them to be inhaled and subsequently deposited in the human lung. Particles from different sources often have characteristic shapes that aid source identification e.g. diesel engine particles are reported as chain-like agglomerates of sub-micron particles, whereas petrol engine exhaust particles are characterised by larger smooth and pitted particles, oil-fired particles are porous, near-spherical particles, and coal particles are perfectly smooth spherical particles.
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Average particle diameter of selected atmospheric particles

Sea salt nuclei Fly ash Carbon black Paint pigments Tobacco smoke Cement dust Milled flour Combustion nuclei Oil smoke Metallurgical dust and fumes Photochemical smog Insecticide dusts 0.001 0.01 0.1 1.0 10.0 100.0 Coal dust Pollens
Average particle diameter (m)
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Modal distributions Three modal size distributions of particles in the ambient atmosphere can be identified, each behaving independently :
the nuclei mode (<0.05 m AD) particles formed by condensation from the gaseous phase, as a result of recent combustion, and having extensive atmospheric lifetimes the accumulation mode (0.05 - 2 m AD) particles formed by the coagulation of particles from the nuclei mode and condensation on existing material, and having an atmospheric lifetime of days the coarse particle mode (>2 m AD) particles generally produced by mechanical processes such as comminution. They are few in number and usually have very short atmospheric lifetimes of a couple of hours before rainfall and sedimentation remove them.
The three modal distributions of atmospheric particulate matter

Hot vapour Chemical route of gases to low volatility vapour Condensation
Primary particles Nucleation Coagulation
Mechanical generation
Chain agglomerates
Condensation growth Windblown dust Sea spray Volcanoes Plant particles Emissions
Droplets Coagulation Coagulation Coagulation Rainout and washout
Sedimentation 1 2 10 100
0.002
0.01
0.1
Particle diameter (m) Nuclei range Accumulation range Coarse particles
Fine particles
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Atmospheric lifetime and transport

The atmospheric lifetime of a particle is the length of time it remains suspended in air. The ability of a particle to remain suspended in air depends upon its aerodynamic properties size, shape and density. The different size groupings, therefore, exhibit different lifetime and transport characteristics.
Characteristics of the different size groupings

Coarse mode particles are rapidly removed from the atmosphere and become important soiling agents within a short distance of the emission point. The deposition of coarse particles from industry and mining activities was a major cause of local soiling problems, although it has now been reduced by stricter legislation. Accumulation mode particles are the most stable and long-lived of atmospheric particles with lifetimes of 7 - 30 days. Fine particles have relatively long atmospheric lifetimes and often exhibit a high spatial uniformity over large urban areas. They may be transported long distances before removal occurs.
Removal mechanisms: wet and dry deposition
Dry deposition This is the continuous transfer of particles (and gases) by impaction, sedimentation (removal by gravity) and Brownian motion (erratic movement due to the movement of air molecules). The rate of dry deposition is generally expressed as the deposition velocity (Vd), which is given by the following equation:
Flux density towards surface (g m -2 s -1 ) Vd (ms ) = Concentration at reference height (g m -3 )

1
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Removal mechanisms: wet and dry deposition

Wet deposition The transport of particles and gases to the Earths surface in aqueous form. Due to its dependence on precipitation, wet deposition is episodic. Two mechanisms of wet deposition may be identified: rain-out or in-cloud scavenging the main route for wet deposition, whereby particles are included in the developing water droplet in a cloud; and wash-out or below-cloud scavenging a much less efficient removal process whereby particles are scavenged by precipitating droplets.
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Sources and emissions of atmospheric particles

Particles may be generated in the atmosphere by a wide range of processes including
fuel combustion vehicle emissions industrial emissions material wear and tear re-suspension chemical reactions.
A basic classification of particles can be made as follows:

Primary particulate matter - comprising direct emissions from a combustion source e.g. those which arise from mobile sources, such as petrol and diesel engines and those from stationary sources e.g. chimney stack emissions and fugitive emissions from uncontrolled activities such as bonfires; Coarse particles arising from the re-suspension of soils and dusts, sea spray and construction activity, with re-suspension of road dust contributing significantly to elevated PM10 levels at roadside sites; Secondary particulate matter - formed within the atmosphere from the condensation of vapours or by the chemical reaction of gases of natural or anthropogenic origin. Secondary particulate pollutants include sulphuric acid (H2SO4), ammonium sulphate ((NH4)2SO4) and ammonium nitrate (NH4NO3).
Particulate pollutants
Particulate matter with a diameter of 10m (PM10) Inhalable particles - can enter the human nose or mouth during normal breathing. Respirable particles - inhalable particles that are able to penetrate to the un-ciliated regions of the deep lung (the alveolar region).
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Sources and emissions of atmospheric particles

Primary particulate matter direct emissions from a combustion source mobile sources (petrol and diesel engines) stationary sources (domestic and industrial chimney stacks) Coarse particles re-suspension of soils and dusts, sea spray and construction activity (re-suspension of road dust significant contribution to elevated PM10 levels at roadside sites Secondary particulate matter formed within the atmosphere by condensation of vapours chemical reaction of gases e.g. ammonium sulphate and ammonium nitrate
UK estimated emissions for PM10 for 1970 -2009
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Trends in PM10 emissions

The main sources of primary PM10 are road transport (all road transport emits PM10, but diesel vehicles emit a greater mass of particulate per vehicle kilometre), stationary combustion (domestic coal combustion has traditionally been the major source of particulate emissions in the UK) and industrial processes (including bulk handling, construction, mining and quarrying). Emissions of PM10 within the UK have declined since 1970. This is due mainly to the reduction in coal use. Domestic and commercial emissions have fallen from 245 kilotonnes (50% of the total emission) in 1970 to 19 kilotonnes (14%) in 2007.
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Environmental/health effects of PM10 Health effects respiratory problems (e.g. decreased lung function, aggravated asthma, chronic bronchitis), particularly in combination with elevated SO2 Effects on materials soiling of exposed materials Ecological effects reduced visibility, acidifying of surface waters and soils
Background PM10 annual averages (g/m3) in the UK in 2002 and 2010
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Environmental effects of atmospheric particulates (PM10) HEALTH EFFECTS: Respiratory problems (particularly in combination with SO2 (e.g. London Smogs)) EFFECTS ON MATERIALS: Soiling of exposed materials ECOLOGICAL EFFECTS: Reduced visibility
Air quality standards for particulates

Particles (PM10) (gravimetric)
All authorities
50 g m-3, not to be exceeded more than 35 times a year
Daily mean
31 December 2004
40 g m-3 Scotland Only 50 g m-3, not to be exceeded more than 7 times a year
Annual mean Daily mean
31 December 2004 31 December 2010
18 g m-3 Particles (PM2.5) (gravimetric) * 25 g m-3 (target)
Annual mean Annual mean
31 December 2010 2020
All authorities
15% cut in urban background exposure
Annual mean
2010 - 2020
Scotland Only
12 g m-3 (limit)
Annual mean
2010
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Chemical composition of particulate matter

Atmospheric particulate matter consists of both soluble and insoluble components. The insoluble material (30 - 40% of SPM) is comprised of man-made materials such as elemental and organic carbon, iron oxides (corrosion derived and natural soil constituent), manganese oxides, quartz, calcite and clay minerals. The water-soluble material (60 - 70% of the total mass) consists mainly of ionic components. The main components of particulate matter in the UK include: Particulate elemental carbon (PEC) Derived from combustion processes, PEC is the black component of smoke responsible for the soiling of materials and the absorption of light (hence its influence on the black smoke reflectance method. PEC also has strong adsorptive properties (due to a high porosity and surface area) and provides a site for catalytic reactions.
Chemical composition of particulate matter (contd)

Sulphates Accounts for approximately 30 - 35% by mass of the soluble ionic fraction. Marine aerosols are a major source. Nitrates Accounts for around 25% by mass of the soluble ionic fraction. Ammonium salts Ammonium salts include chlorides, sulphates and nitrates formed by reactions between naturally occurring ammonia and airborne acids from pollution sources. Ammonium accounts for approximately 18 - 25% of the soluble ionic fraction. Chlorides Derive from marine sources and the application of de-icing salt on roads, pavements and runways during winter. Metals Emitted from both natural and anthropogenic sources. Sodium and magnesium predominantly come from seawater. The heavy metals found in urban areas tend to be anthropogenic in origin, especially around heavily industrialised areas. Lead has been singled out as an important heavy metal because of its sources car exhausts (due to the use of unleaded petrol), metal smelters, paints, etc. but other metals such as Cd, Be and Hg are all known to be highly toxic to man.
Cloud formation due to PM pollution
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Air Quality Management Areas

Since December 1997 each local authority in the UK has been required to carry out a review and assessment of air quality in their area. This involves measuring air pollution and trying to predict how it will change in the next few years. The aim of the review is to make sure that the national air quality objectives will be achieved throughout the UK by the relevant deadlines. If a local authority identifies sites where the objectives are not being achieved and are not likely to be achieved, it must declare an Air Quality Management Area there. This area may vary from involving one or two streets to a much larger area. The next stage is for the local authority to put together a plan to improve the air quality - a Local Air Quality Action Plan. The general progress that each local authority is making towards its air quality review can be seen by accessing the following web-site: http://www.defra.gov.uk/environment/quality/air/air-quality/laqm/
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Location of Air Quality Management Areas within the UK
KEY This Local Authority has declared an Air Quality Management Area This Local Authority currently has no Air Quality Management Areas
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Example of an AQMA
LONDON BOROUGH OF HARINGEY AQMA covers the whole borough. Pollutants declared: Nitrogen dioxide (NO2), Particulate Matter < 10 m (PM10)
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BIO4301 Pollutions Sources & Impact

Gaseous and particulate pollutants

Key topics today

UK air pollution: current status

Impact of UK air quality policies from 1990-2001

BIO4301 Air pollution

UK lead emissions 1970-2009

BIO4301 Air pollution

UK sulphur dioxide emission trends; 1970-2009

BIO4301 Air pollution

Explanation of SO2 trends

Environmental effects of SO2

BIO4301 Air pollution

Schematic diagram of acid rain formation

BIO4301 Air pollution

UK background SO2 concentrations: 2010

1ppb SO2 = 2.8 g/m3

BIO4301 Air pollution

Example of available sulphur dioxide statistics (for 2005)

London Brent Barnsley Gawber

363 days; 32,784 measurements 340 days; 30,859 measurements

BIO4301 Air pollution

UK Air Quality Monitoring Network (1)

BIO4301 Air pollution

UK Air Quality Monitoring Networks

BIO4301 Air pollution

UK air quality automatic monitoring sites

BIO4301 Air pollution

Automatic Urban and Rural Network (AURN)

BIO4301 Air pollution

BIO4301 Air pollution

Air monitoring stations

BIO4301 Air pollution

40 year trends in SO2 and smoke in the UK

BIO4301 Air pollution

UK Governments air quality headline indicator of sustainable development since 1987

BIO4301 Air pollution

BIO4301 Air pollution

UK Nitrogen Dioxide emission trends; 19702008

BIO4301 Air pollution

Explanation of NO2 trends

Environmental effects of NO2

BIO4301 Air pollution

Background NO2 annual averages (g/m3) in the UK; 2002

BIO4301 Air pollution

UK carbon monoxide emission trends; 1970-2008

BIO4301 Air pollution

BIO4301 Air pollution

HEALTH EFFECTS: Cardio-vascular effects

Saturation of blood (%COHb)

60 mg/m3 300 mg/m3 900 mg/m3

Observable effects e.g.physical coordination impairment

BIO4301 Air pollution

UK non-methane VOC emission trends; 1970-2008

BIO4301 Air pollution

Explanation of non-methane VOC trends

Diurnal production of ozone/photochemical smog

BIO4301 Air pollution

Ozone/photochemical smog formation

BIO4301 Air pollution

Atmospheric Particulate Terminology

Suspended Particulate Matter (SPM) Aerosol