Non Criteria Atmospheric Pollutants International Perspectives

1
NATURAL POLLUTERS VOLCANOES FORESTS COASTS DESERTS
Free Flowering MakinMagic
2
19thC ENVIRONMENTAL SETTING

• Fogs, cholera, sewage
• Krakatoa 1883
• Blood Rain 1903
• Tunguska 1908
• Halleys comet 1910
• End of guano

• Dramatic sunsets world-wide Ascroft sketches for
  Symons Report

3
TUNGUSKA 1908
High temperatures at the head of the Meteor
cause a Zeldovic type reaction N O2 ? NO O

• Widespread atmospheric observations of night-
  glow
• O3 loss

The nitric oxide then destroys ozone layer NO
O3 ? NO2 O2 Acid Rain!
4
HALLEY'S COMET (1910)

• Spectra of comet tail showed hydrogen, water
• In addition poisonous CO and CN which caused
  public concern as the Earth would pass through
  Halley's tail!

5
DMS
nM

• Seasonal cycles of DMS production from
  phyto-planktonic blooms
• Southern Ocean an important region
• Acid rain in coastal regions? Data Andrea et
  al

12
JAN
6
JUL
0
6
CLAW Hypothesis

• CCN from marine DMS increases albedo
  and lowers temperature. This in turn might
  feedback by lowering planktonic growth and
  lessening DMS and CCN production
• Gaia hypothesis postulates such
  geo-physiological control

7
SEASALT

• Large amounts of sea spray but mostly from bubble
  bursting not spume
• Microlayer enrichment of metals
• Reactions with acids e.g. H2SO4 2NaCl
  ? Na2SO4 2HCl?
• Asthmatic effects?

8
AGRICULTURAL EFFECTS

• Aeolian erosion of sulfate containing
  dusts
• Grazing increased in last few millennia
• Ploughing
• River-diversion
• Forest fires

9
AGRICULTURE

• Grazing increased in last few millennia
• Ploughing
• River-diversion
• Forest fires
• Dispersive sources
• Ploughing
• Pesticides
• Pollen dispersal

Aeolian erosion of sulfate containing dusts
10
LIGHTNING

• Shock
• N2 O2 ? 2NO
• NO3- in rain
• Artificial fertilizers

11
Mary Shellys Frankenstein

• Tambora Eruption1815 and the year without a
  summer

12
RATE OF ACID RAIN FORMATION

• Different rates of conversion of HCl, HF and SO2
  to soluble acids affects rainfall acidity
• Mercury also important

1000 km
13
VOG

• Volcanic fog (or vog) can be hazardous to human
  health and crops

Threats in HawaiI, Costa Rica etc
Vog from Pu'u O'o www.geosci.unc.edu/.../VolcanicH
azards.html
14
DUST VEIL INDEX

• Climate may be affected by volcanic dust, but
  sulfur may be more important
• Residence time

15
AIRCRAFT IN FLIGHT

• Volcanic ash particles can severely damage
  aircraft and lead to engine failure.

16
GALUNGGUNG VOLCANO INDONESIA, 1982.

• BA 747 on a flight from Kuala Lumpur, Malaysia,
  to Perth, Australia encountered ash from this
  eruption and lost thrust from all four engines
  and descended from 36,000 ft to 12,500 ft before
  all four engines were restarted.
• All four engines replaced

17
DUST CHEMISTRY
Typically treated as an inert matrix, but rare to
include inorganic or rarer organic chemistry
NEUTRALIZATION
OZONE INTERACTIONS
SOLUBILZATION
DUST EMISSION
18
TAIWAN DUST RECORD SEDIMENTS FROM LAKE

• Notable increase in flux
• dry periods since 1340
• Cold/dry and frequent dust storms 500, 700,
  900 1350, 1500... Lou JY et al, Science in
  China D (1997)

Flux to anoxic lake mg cm-2 y-1
Chen-Tung Chen et al
19
SIZE
BEFORE
Coarse mode increases during dust storms
18 to 20 March 2002
DURING
Lee, C.-T et al. Atmospheric Environment (2006)
20
SUDANDUST
Initially bulk composition reflects soil Little
evidence of chemistry
21
URBAN INTERACTIONSUPTAKE OF ORGANIC MATERIALS

• oleic acid and linoleic acid in the aerosols
  suggested cooking main source of fatty acids in
  urban areas
• PAHs and fatty acids decreased sharply after the
  dust storm

Hou, X. et al. Atmospheric Environment (2006)
22
PAH ONSILICA
Perraudin et al (2007)
23
INORGANIC REACTIONS

• affect pH
• calcium is a dominant soluble ion
• secondary transformation of sulfate and nitrate
  on dust

Rodhe H. EST (2002) Wang, Y. et al.
Atmospheric Environment (2005)
24
HUMICACIDS

• high molecular weight compounds
• carboxylic and phenolic functional groups

http//www.hagroup.neu.edu/aboutha.htm
25
PHOTODEGRADATION OF HUMIC ACID
Yousef Otaibi UEA
26
SUNLIGHT PHOTOLYSIS OF HULIS
Yousef Otaibi UEA
27
BROWN COLOUR
Abs at ? 400 nm
Surface active material (pmol/m3)
28
AEROSOL SURFACTANTS

• Physical effects
• reduce surface tension
• smaller drops
• numerous drops
• longer life-times
• increased albedo
• lower temperatures

• Chemical effects
• solubilzation
• micellization
• lung interactions

Brimblecombe and Latif Env. Chem. 1, 11-12 2004
Facchini et al, Nature 401, 257-259 1999
29
FORESTS

• Forests as a source not only in rural areas,
  but also on cities such as at Atlanta
• Choice or urban trees

30
BIOGENIC EMISSIONS AND AIR QUALITY NORTHERN ITALY

• Isoprene and oxidation products
• Source of VOC for photochemical smog Duane et al

Averaged mixing ratios
Averaged OH reactivity indices
31
FOREST AEROSOLS

• BIOGENIC EMISSIONS reactive chemistry that
  generates ozone but also uses it

Cross in the Mountains Caspar David Friedrich
32
da VINCI CODE
Virgin of the Rocks
33
FOREST FIRES

• Historical and anthropological
• Ecological
• Health
• Atmospheric

E.A. Johnson and Kiyoko Miyanishi Forest Fires -
Behaviour and Ecological Effects
34
FIRES OF 1877-1878
Coast lined with thick fog
Padang thick fog
Palembang enveloped in smoke
Fires also in Ambon and Timor
VERY STRONG ENSO
Potter, 2001
35
FIRES OF 1902 and 1910
ONLY MODERATE ENSO

• 1902Severe drought and widespread haze, but
  thought as volcanic, duststorms...
• 1910 An expansion of rubber plantations in
  Malaya

sky with a black pall of smoke.
Potter, 2001
36
FIRES OF 1914
Fires destroyed 200 km2
Two months of fog on Lake Toba
Ships complain smoke caused poor visibility
MODERATE-STRONG ENSO
Potter, 2001
37
ECOLOGICAL IMPACTS of HAZE

• Acid rain type issues - soil nutrients
• Ozone phytotoxicity
• Lower sunlight so haze decreases leaf carbon gain
  Tang YH et al Forest Ecology and
  Management 89205-211 (1996)

38
AIR TRAFFIC

• Developing the early air routes required an
  interest in smoke and visibility.
• 1972 event - severe disruption of air traffic
  e.g. at Palembang.
• 1997 Garuda Airbus crash

39
FOREST FIRE CHEMISTRY

• Rain may not be acidic
• Ammonia and organic acids important

HCl, HCOOH K2CO3, NH3
HNO3
H2SO4
Balasubramanian et al JGR 104,26881
40
CLIMATE CHANGE and GLOBAL DIMMING

• Particles in the atmosphere can both increase and
  decrease global temperature.
• Direct effects e.g. carbon
• Indirect effects - e.g. clouds