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Biogeochemistry – Chemistry for understanding natural environment
Most important elements to life: CHONPS
Nutrient cations: Ca, K, Mg
Si is important to rock weathering and aquatic systems
Metals and micronutrients: Fe, Mn, B, Na
H2O is a universal solvent – highly reactive, strong dipole moment
Water exists in equilibrium between the polar molecule form and its two ionic components.
H2O H+ + OH‐
Pure water not in contact with atmosphere: [H+] = [OH‐] = 10‐7 mol/L
pH = ‐log10[H+]
Water with high [H+] relative to the [OH‐] is said to be acidic (low pH). If [OH‐] is high relative to
[H+], the solution is said to be basic (high pH). A solution can be made more acidic by adding an
acid, which donates H+. A solution can be made more basic by adding a base, which either
donates OH‐ or grabs a H+ already in solution.
The tendency of an acid to donate a H+ is called its acid dissociation constant (Ka)
For ammonium in water
NH4+ H+ + NH3
For the Ka equation shown above to work, make sure that your acid is on the left side, and is
dissociating in water to its conjugate base.
pKa = ‐log10[Ka]
When pKa = pH we get [acid] = [conjugate base]
As pH exceeds pKa the deprotonated form (i.e. conjugate base) dominates.
As pH gets lower than pKa the protonated form (i.e. acid) dominates.
The carbonate complex forms when carbon dioxide dissolves in water, forming an aqueous
acidic solution. This happens in soda (or “pop” as you Midwesterners like to call it).
CO2(g) + H2O(l) H2CO3(aq)
Once in solution, the H2CO3 exists in equilibrium as three different forms.
H2CO3 H+ + HCO3‐ H+ + H+ + CO32‐
carbonic acid bicarbonate carbonate
\______________ carbonate complex ______________/
Water can hold far more bicarbonate than CO2
Which form dominates depends on the pH of the water. If the water is already acidic (low pH),
carbonic acid dominates. If the water is basic (high pH), carbonate dominates.
This is why CO2 is considered an acid:
1. CO2 dissolves in water, combines with a single H2O molecule, forming H2CO3 (bicarb).
2. H2CO3 dissociates, forming HCO3‐ (carbonate) by releasing a single H+ back into solution,
3. This leaves us with an extra H+ floating around in the water, while the carbonate is still
holding onto the OH‐. Net result is an extra H+ in solution.
4. If the pH is high enough, the bicarbonate could dissociate again, releasing a second H+
into solution.
Stare at this figure until the
trends make intuitive sense to
you.
Salts are ionic compounds that dissolve in water.
Water can also dissolve many organic compounds, particularly polar compounds, and
those with a hydrophilic functional group.
Solubility of many compounds depend on pH.
Acid deposition (which now includes NOX) a major environmental issue since 1980s
Ocean acidification – Oceans becoming less basic (pH 8.21 pH 8.1 since start of Ind.
Rev.)
Ocean acidification caused by [CO2] is causing problems for sea creatures that make
calcareous shells (esp coral reefs), since the solubility of Ca increases as the water
becomes more acidic. Refer to mass oceanic extinction 65 million years ago.
Nitrogen and Sulfur Emissions and Deposition
Combustion causes N and O to combine, forming NOx (e.g. NO, NO2)
NOx(g) + moisture HNO3 (metal etching acid, very strong)
SO2 emissions are also problematic
SO2(g) + moisture H2SO4 (car battery acid, very strong)
NOX and SO2 increased since Ind. Rev. Clean Air Act has helped lower atmospheric SO2 and H+.
Mineral Weathering, Soil Exchange, Acid Neutralizing
Weathering of clay produces a negative intrinsic charge, which attracts metallic cations+
These cations exchange easily with other cations. This is called cation exchange.
Acidic cations: H+, Al3+
Basic cations: Ca2+, K+, Mg2+, Na+
More base cations in the clay means more base saturation
Acid Neutralizing Capability (ANC)
The more base cations in the soil (alkalinity), the more acid rain can be neutralized.
Watershed
A watershed is an area of land where all the water falling on it eventually goes to the same
place.
What matters to us is the ANC of the watershed. That is, how much rain acidity can be reduced
by ANC in soil, and carbonate complex buffering in rivers and streams.