Acid rain and mercury

Homework: 13-1, 13-2, and 13-4

 Natural pH of Rain
• Equilibrium with natural CO2 (280 ppmv) results in a rain pH of 5.7:


H 2O
CO2 ( g )   CO2  H 2O K H  3 102 M atm-1

 HCO3  H  K1  9 107 M
CO2  H 2O 


 CO32  H 
HCO3 
 K 2  7 1010 M

 [ H  ]  ( K1 K H PCO2 )1/ 2
• This pH can be modified by natural acids (H2SO4, HNO3, RCOOH…)
and bases (NH3, CaCO3) e natural rain has a pH in range 5-7

“Acid rain” refers to rain with pH < 5 e damage to ecosystems

 Chemical Composition of Precipitation

Neutralization by NH3 is illusory because NH4+ g NH3 + H+ in ecosystem

 Precipitation pH over Taiwan

2004-2010 2011 2012 2013

http://acidrain.epa.gov.tw/research/28.htm
 Trend in Frequency of Acid Rain (pH < 5)
Jan-May, 2014

http://acidrain.epa.gov.tw/research/28.htm
Acid rain report
PRECIPITATION PH OVER THE UNITED STATES
LONG-TERM TREND IN US SO2 EMISSIONS
Sulfate wet deposition and aerosol concentrations, 1980-2010
Circles = observations; background = model

Leibensperger et al. [2012]

 Nitrate wet deposition and aerosol concentrations, 1980-2010

Leibensperger et al. [2012]

Ammonium wet deposition and aerosol concentrations, 1980-2010

Leibensperger et al. [2012]

Trends in precipitation pH
 Electronic structure of mercury

Mass number = 80: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14 5s2 5p6 5d10 6s2

• Complete filling of subshells gives Hg(0) a low melting point, volatility

• Two stable oxidation states: Hg(0) and Hg(II)
 Biogeochemical cycle of mercury
ANTHROPOGENIC
PERTURBATION:
fuel combustion
mining WATER-SOLUBLE
VOLATILE
oxidation
Hg(0) Hg(II)
(months)

volcanoes
erosion ATMOSPHERE

OCEAN/SOIL
Hg(0) Hg(II) particulate
reduction biological Hg
uptake

uplift burial

SEDIMENTS
 RISING MERCURY IN THE ENVIRONMENT
Global mercury deposition has roughly tripled since preindustrial times

Dietz et al. [2009]

HUMAN EXPOSURE TO MERCURY IS MAINLY FROM FISH CONSUMPTION
Tuna is the #1 contributor

Mercury biomagnification factor State fish consumption advisories

EPA reference dose (RfD) is 0.1 μg kg-1 d-1 (about 2 fish meals per week)
 Atmospheric transport distributes Hg on a global scale
Implies global-scale transport of anthropogenic emissions
Anthropogenic Hg emission (2006)

Mean Hg(0) concentration in surface air:

circles = observed, background = GEOS-Chem model

Hg(0) lifetime = 0.5-1 year

Streets et al. [2009];

Soerensen et al. [2010]
 UNEP Minamata Convention on Mercury
Opened for signatures in October 2013; already signed by 128 countries

• Requires best available control technology

for coal-fired power plants
• Mercury mining to be banned in 15 years
• Many mercury-containing commercial
products to be banned by 2020

• Convention requires ratification by 50 countries to go into effect

• Only ratifying country so far has been the US (November 6, 2013)

Updated : 128 signatures and 107 ratifications (May 2019)

United Nations Environment Programme
 History of global anthropogenic Hg emissions

Large past (legacy) contribution from N. American and European emissions;

Asian dominance is a recent phenomenon

Streets et al. , 2011

Global historical Hg consumption

Horowitz et al. , 2014

 What can we hope from the Minamata Convention?

Effect of zeroing global anthropogenic

emissions by 2015

• Zeroing anthropogenic emissions would decrease ocean Hg by 30% by 2100,

while keeping emissions constant would increase it by 40%

• Elevated Hg in surface ocean will take centuries to fix; the only thing we can do
in short term is prevent it from getting worse.
Amos et al. [2013]