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Acid Deposition and Impacts

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acid+rain.jpg
Copyright: http://uksovannara.blogspot.co.uk/2012/07/harmful-effects-of-acid-rai
n.html

Today s lecture
Sources of acidifying pollutants in air.
Acid deposition and stages of
acidification
Effects of acid rain and their controls
Terrestrial ecosystems
Aquatic ecosystems
UK Acid Water Monitoring Network
(AWMN): Status, Recovery and
Future ..
forest-acid-rain-bg

What do we mean by

Acid rain ?

pH of unpolluted rain?
Dissolution of CO2:
Oxidation of N and S compounds in the
atmosphere to form nitric and sulphuric acid:
Other natural sources of acidity in rain.
Thus rain with acids dissolved in it.
Dynamic equilibrium of carbonic acid with CO2 at pH 5.65

Background acidification of soils by N


and S cycles
Freeman. 2007. Environmental Science: A Canadian Perspective,
Peasons Inc.

Marine originTerrestrial originPollutionSodiumSea saltSoil dustBiomass burningMa


gnesiumSea saltSoil dustBiomass burningPotassiumSea saltBiogenic aerosols, soil
dustBiomass burning,
fertilizerCalciumSea saltSoil dustCement manufacture,
Fuel burning, Biomass
burningChlorideSea saltIndustrial hydrochloric
acidSulphateSea salt, DMS
DMS, H2S etc from
biological decay,
volcanoes, soil dustFossil fuel burning,
biomass burningNitrate/NitriteAtmospheric
nitrogen, lighteningNOx from biological
decay, atmospheric
nitrogen, lighteningVehicle emissions,
fossil fuels, biomass
butrning, fertilizerAmmoniumAmmonia from
biological decayAmmonia from
biological decayAmmonia fertilizers,
human, animal waste
decomposition
Adapted from Heal, 2005, p360
SOURCES OF INDIVIDUAL IONS (Anions and cations) IN RAINWATER

Anthropogenic sources of acidifying


pollutants: NOx
Sources of reactive N in the
atmosphere:
Ammonia released from
fertilizer and manure
N2O, NO, NO2 from agriculture

Fertilizer
O2 + heat O + O
N2 + O NO + N
N + O2 NO + O

Anthropogenic sources of acidifying


pollutants: SO2
SOx:
Fossil fuel burning (particularly industrial flue
gases
Fossil use in electric utilities (60-70 % SO2
release source)
Extraction of metal from ore (chalcopyriteCuFeS2)

NOx and SOx sources in New England by 2002


Source US EPA: http://www.epa.gov/region1/eco/acidrain/causes.html
Road engine as a source
dominant here
Industry as a source dominant here

J. Galloway, 2008.
A global increase in atmospheric reactive N deposition (Oxidized and reduced for
ms).

History of

acid rain

research

Mid-nineteenth century, higher


concentrations of sulphuric acid in
precipitation near industrial towns
(Manchester) identified
Acid rain used for the first time in
1870s
1960s work by Ode
declining fish
populations in Scandinavia
link
to acid rain

acid rain
acid rain

Trends in atmospheric pollutants


Sulphur traditionally been emitted in larger
quantities than N
Canadian Example (Schindler et al., 2005)
NOx doubled 1970-1985, now remains constant
17% decrease from regulations of vehicle emissions and
smelters ~balanced by 29% increase from electrical
generation.
NH3 increase due to increasing farming intensity
SO42- in rain declined by 45-50% since 1980s due to
reduced SOx emissions from smelters and coal-fired
power plants
UK (see Monteith and Evans, 2005, Kernan et al.
2010)

SO2 and NOx Oxidation in the


atmosphere

TRANSFER OF ATMOSPHERIC SOLUTES


Dry deposition: Occurs during dry periods between
precipitation events.
Direct transfer of pollutant gases from the air (particularly
SO2) onto vegetation, water or soil surface
Gravitational settling of larger particles.
Subsequent oxidation to form H2SO4 and HNO3 takes place
on the surfaces when wetted with rain or dew
Gases may also pass into plant stomata
Acid surge during initial runoff
Increased by afforested regions since plants scavenge dry
deposits more than bare surface

TRANSFER OF ATMOSPHERIC SOLUTES:


2. Wet deposition
Wet deposition:
Absorption of pollutant into droplets in or below clouds
and removal by precipitation
Wash out: removal of solutes by falling precipitation
Rain out: acid inputs which originate within the cloud
system
Early part of rain often has highest solute concentrations

colonsay-rain

TRANSFER OF ATMOSPHERIC SOLUTES: 3.


Occult deposition:
Deposition of acidic
pollutants (SO2 and NOx)
onto surface by impaction
of fog and cloud droplets
Influenced by climatic
factors.
Concentration of pollutants
can be much higher than in
rain. Why?
Important where low
rainfall but high relative
humidity.

imageEUG
pine_needle_ice

Occult deposition

Dry vs wet deposition


In the UK averaged over a year the:

Dry deposition = wet deposition


Relative importance of wet or dry deposition varies
with geographic location and season
difference in the amount of rainfall and emissions
Dry deposition dominates close to emission source normally occurs in 2 or 3 days
If pollutants stay in atmosphere for longer, then
gets oxidised to acids followed by wet deposition.
Wet deposition more important with distance from
the source.

Spatial trends .
Regional rather than global problem.
Sulphur compounds in the atmosphere have a residence
time of a few days, therefore, they are not well mixed
and have regional effects
Areas with high rainfall amounts may have higher acid
loading even though less acidic precipitation.
Rate and distance of movement also associated with
height of pollutant emissions i.e. tall stacks enhance
long-distance transfer
Atmospheric circulation patterns also important

acid rain
Acid
precipitation in
Europe
Elsom, 1992, p85
Sweden more acidity
from wet deposition
further from source general circulation

Stages of acidification
3 stages of
acidification
3 stages of acidification

1) natural buffering capacity provides resistance to pH


change
2) all buffering capacity utilized leading to variation in
pH
3) New stable system with lower pH
H. Zhang. Oklahoma State University

Natural buffering against acidification


If not well buffered, then catchments are
highly sensitive to acid inputs
What is buffering?
Capacity to assimilate a limited number of H+
ions without an appreciable change in pH
Usually H+ absorbed by soils or freshwater
systems until a buffering threshold is
exceeded, then have rapid decrease in pH

Impacts of acidity on terrestrial


and aquatic ecosystems

effects of acid rain


Kemp, 2004, p353
Effects: Terrestrial and aquatic ecosystems
The Impact Cascade

acid rain
Effects: Terrestrial ecosystems
See: Vrba, J. et al (2003) Long term studies (1871-2000) on acidification and rec
overy of lakes
in the Bohemian Forest (central Europe). Science of the Total Environment, 310,
73-85.
The effects of acid rain on a
spruce forest in the Czech
Republic.
Suggested relationship to forest
decline (although possibly other
effects e.g. O3 in air).
Direct acid deposition on leaves
of plant can cause lesions, only
where pH 3.4 or below
Leaches Ca, Mg, K from leaves
and needles
Depletion of Ca in needles affects
susceptibility to freezing

acid conifers
-Conifers are
efficient
scavengers of
cloud
droplets

Heal, 2005, p376


Acid inputs initially neutralized by exchange of H+ ions with Ca2+ and Mg2+ in
soils at cation exchange sites
Acidification occurs if acid inputs continue faster than base cations released
into soil from mineral weathering

Geological sensitivity
granite-xpl_pm18-23
sandstone2_pm13-19
Sandstone: grains of quartz, cemented
together by calcium carbonate.
Granite: feldspars, quartz, mica,
tourmaline.
limestone-xpl_pm14-09
Limestone: fossils, and calcite crystals
http://www.earth.ox.ac.uk/~oesis/micro/index.html
The type of underlying bedrock
will control the catchment s
susceptibility to acidification as
HCO
3
concentrations influenced
by catchment geology
The type of underlying bedrock
will control the catchment s
susceptibility to acidification as
HCO3- concentrations influenced
by catchment geology

Effects of acidifying water bodies


Acidification of lakes
Acidification of lakes
Reduced bacterial activity in
sediments
Reduced bacterial activity in
sediments
Inhibits
nutrient
Inhibits
nutrient

decomposition and
generation
decomposition and
generation

Affects aquatic food webs


Affects
aquatic food
webs
Decline in invertebrate
populations
Decline in invertebrate
populations
Decline in fish depending on
invertebrates
Decline in fish depending on
invertebrates
Decline in birds depending
on fish
Decline in birds depending
on fish
Acidification of amphibian
breeding pools (esp. from
snowmelt)
Acidification of amphibian
breeding pools (esp. from
snowmelt)
Reduction in fertilisation of
eggs
Reduction in fertilisation of
eggs
Decline in amphibian
numbers
Decline in amphibian
numbers
Loss of fish (Trout, Salmon
etc.)

acid rain
Gypsum highly soluble and occupies large volume (mechanical stress)
Gypsum highly soluble and occupies large volume (mechanical stress)
Effects: Calcareous building stone
1908
1969

Summary of effects
Harm to terrestrial ecosystems (plants and soils)
Harm to aquatic ecosystems
Mobility of toxic metals (e.g. Al)
Weathering of building material
Effects amplified where:
Trees intercept clouds/fog
High acid deposition (i.e. uplands with high rainfall)
Base poor soils

Solutions?
1.Technological:
I.Desulphurization of flue gases
II.Liming of forests, soils and lakes
2.Prevention (see Schindler et al. 2006)
3.International legislation - management of acid
deposition needs to be done internationally
(i.e. EU, Canada/USA)

Recovery of Lakes and Rivers from Acidification in the UK


UK government program to
monitor acidity trend at the
Acid Waters Monitoring
Network (AWMN) sites
Produce weekly or biweekly
monitoring data
Trends in pH, non-marine
SO4 & NO3
Key Q: Trends in bulk
deposition chemistry, UK (20
years data trend)
Kernan et al. 2010, UK
DEFRA Report
Visit the website here for relevant data
and papers.
http://awmn.defra.gov.uk/

Trends in pH of Bulk Deposition: 1985-2005


Significant increase in pH in 11 out of 12 monitoring sites

Non-marine SO4-2 deposition trends: 1985-2005


Red line: Significant decreasing trend

Recovery of Aquatic Macrophytes: The scale of ecosystem impacts

Current ANC status and reference levels to


achieve in the UK
By 2007 actual ANC still lagged behind the reference
target level

pH recovery targets: Improving but in certain


regions targets have yet to be achieved
By 2007 pH still lagged behind the reference target level

So in case of the UK
Significant recovery in chemical and biological
parameters of water bodies observed, but still lags
behind the reference levels in most sites
And (next page)

SO4 reduction led to pH improvement in the UK water, but the


future trends of NO3 could dampen this improvement

RECAP
ACID deposition due to air pollution
Impacts on ecosystems and built environment
Significant improvement in water bodies status
in the UK
Atmospheric reactive N deposition may drive
acidity in the current century.

References
Kernan, M., R.W. Battarbee, C. J. Curtis, D. T. Montieth,
and E. M. Shilland. 2010. Recovery of Lakes and
Streams in the UK from the Effects of Acid Rain. UK Acid
Water Monitoring Network 20 Year Interpretative
Report. DEFRA
(http://awmn.defra.gov.uk/resources/interpreports/20yearInterpRpt.pdf).
Monteith, D.T. and Evans, C.D. (2005) The United
Kingdom Acid Waters Monitoring Network: a review of
the first 15 years and introduction to the special issue.
Environmental Pollution, 137, 3-13.
Schindler, D.W., Dillo, P.J. and Schreier, H. (2006) A
review of anthropogenic sources of nitrogen and their
effects on Canadian ecosystems. Biogeochemistry, 79;
25-44.

General References
Arnell, N. (2002) Hydrology and Global
Environmental Change. Pearson.
Elsom, D.M (1992) Atmospheric Pollution a
Global Problem. Blackwell.
Heal, K.V. (2005) Solutes. In: Holden, J. (Ed.)
An Introduction to Physical Geography and the
Environment. Pearson.
Kemp, D.D. (2004) Exploring Environmental
Issues. An integrated approach. Routledge.