WATER QUALITY IN STREAMS AND RIVERS IS THE END PRODUCT OF ALL PROCESSES IN THE BASIN

WATERSHEDS ARE THE KIDNEYS OF AN ECOSYSTEM

KIDNEY ANALOGOUS TO A WATERSHED

NITRATE EXAMPLE

Fingerprint water
Isotopes

Geochemical content
Nutrients

Rock Weathering
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LITHOSPHERE
Linkage between the atmosphere and the crust. Weathering results in: Igneous rocks + acid volatiles = sedimentary rocks + salty oceans

IMPORTANCE OF ROCK WEATHERING

[1] Bioavailability of nutrients that have no gaseous form:
P, Ca, K, Fe

Forms the basis of biological diversity, soil fertility, and agricultural productivity The quality and quantity of lifeforms and food is dependent on these nutrients

IMPORTANCE OF ROCK WEATHERING

[2] Buffering of aquatic systems
-Maintains pH levels -regulates availability of Al, Fe, PO4

Example: human blood. -pH highly buffered -similar to oceans

IMPORTANCE OF ROCK WEATHERING

[3] Forms soil [4] Regulates Earths climate [5] Makes beach sand!

NATURAL ACIDS that WEATHER ROCK

Produced from C, N, and S gases in the atmosphere H2CO3 Carbonic Acid HNO3 Nitric Acid H2SO4 Sulfuric Acid HCl Hydrochloric Acid

Stoichiometry
Stoichiometry is the accounting, or math, behind chemistry. Given enough information, one can use stoichiometry to calculate masses, moles, and percents within a chemical equation. Keep track of atoms, molecules, and charge
Calcite

dissolution CaCO3 + CO2 + H2O Ca2+ + 2 HCO3reactants products

TYPES OF CHEMICAL WEATHERING

Carbonate weathering Dehydration Oxidation Hydrolysis

CARBONIC ACID

Carbonic acid is produced in rainwater by Reaction of the water with carbon dioxide Gas in the atmosphere.

CARBONATE (DISSOLUTION)

All of the mineral is completely Dissolved by the water. Congruent weathering.

DEHYDRATION

Removal of water from a mineral.

OXIDATION

Reaction of minerals with oxidation. An ion in the mineral is oxidized.

OXIDATION: REDOX REACTIONS

Loss of electrons = Oxidation

Gain of electrons = Reduction
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For example, rusting

* Oxidation of elemental iron to iron(III) oxide by oxygen 4 Fe + 3 O2 2 Fe2O3

Occurs in nature as the mineral hematite, and is the principal ore for iron

HYDROLYSIS

H+ replaces an ion in the mineral. Generally incongruent weathering.

HYDROLYSIS
Silicate rock + acid + water = base cations + alkalinity + clay + reactive silicate (SiO2)

HYDROLYSIS
Base cations are
Ca2+, Mg2+, Na+, K+

Alkalinity = HCO3 Clay = kaolinite (Al2Si2O5(OH)4) Si = H4SiO4; no charge, dimer, trimer

Mineral Solubility
Solubility - relative capability of being dissolved Salt dissolution - solids break down in solution to yield ions Example: Barium chloride BaCl2 BaCl2 (s) = Ba2+ + 2 Cl

 Define K using the Law of Mass Action (activity in brackets):

[Ba ] [Cl ] K BaCl 2 (s)

Inside the [] are the measured concentrations Multiply [] by number of atoms

Solubility constant Ksp

Because the activity of the solid is 1, the equation becomes Ksp = [Ba2+] [Cl]2 The equilibrium constant for the dissolution reaction is called the solubility product constant or Ksp.

Measurements of Disequilibrium
It can be important to know whether a solution is saturated or undersaturated with respect to a mineral Consider: AaBb = aA + bB At equilibrium: Ksp = [A]a [B]b How do we know the solution is in equilibrium with the mineral? Measure [A] and [B] in solution (activity product or ion activity product) and compare to Ksp

Degree of saturation W

[A ] [B] W Ksp

where [A] and [B] are for the solution, which may or may not be in equilibrium with the mineral W > 1 Supersaturated W = 1 Saturated W < 1 Undersaturated

Problem: What is the degree of saturation of anhydrite in College Station tap water?
(Ca2+) = 3 mg/L = 0.003 gL-1/40 g Camol-1 = 0.000075 M (SO42-) = 10 mg/L = 0.010 gL-1/96 g SO42-mol-1 =

0.00010 M T = 25C Assume ideal behavior (g = 1)

Write the reaction in terms of dissolution and make use of Ksp values CaSO4 = Ca2+ + SO42-

 We calculate the ion activity product in solution: IAP = [Ca2+][SO42-] = 0.000075 0.00010 = 7.5 x 109 = 108.1 Degree of saturation

IAP 10 3.74 W 4.36 10 K sp, anh 10

Water is undersaturated with respect to annhydrite

8.1

Calcite dissolution: CaCO3 = Ca2+ + CO32

Ksp,calcite [Ca 2 ][CO 2 3 ]

Is water undersaturated or oversaturated with respect to calcite? Get stalagmites/stalagtites? Or dissolve them? Tea pots: where does mineral deposits come from?

But ions dont behave ideally . . .

Concentration related to activity using the activity coefficient g, where [z] = gz (z) The value of g depends on: Concentration of ions and charge in the solution Charge of the ion Diameter of the ion

Ionic strength I = concentration of ions and charge in solution I = 1/2 Smizi2

where mi = concentration of each ion in moles per kg, zi = charge of ion

Activity and Concentration

Activity effective concentration Ion-ion and ion-H2O interactions (hydration shell) cause number of ions available to react chemically ("free" ions) to be less than the number present Concentration can be related to activity using the activity coefficient g, where [z] = gz (z)
Activity coefficient gz 1 as concentrations 0 and tend to be <1 except for brines

Carbonate Chemistry

The Carbonate System

pH of most natural waters controlled by reactions involving the carbonate system Groundwater and seawater chemistries are often poised near calcite equilibrium, with pH buffered by calcite dissolution and precipitation Applications
Fate of CO2 from fossil fuels and other CO2 sources on the atmosphere Effect of acid rain on lakes Effect of acid mine drainage on rivers

Carbonate System
Carbonate species are necessary for all biological systems Aquatic photosynthesis is affected by the presence of dissolved carbonate species. Neutralization of strong acids and bases Effects chemistry of many reactions Effects global carbon dioxide content

PCO2

= 103.5 yields pH = 5.66 is todays PCO2? ~368 ppm = 10-3.43

What is 103.5? 316 ppm CO2

What

pH = 5.63

pH of Global Precipitation

DIPROTIC ACID SYSTEM

Carbonic Acid (H2CO3)
Can donate two protons (a weak acid)

Bicarbonate (HCO3-)
Can donate or accept one proton (can be either an acid or a base

Carbonate (CO32-)
Can accept two protons (a base)

TOTAL CARBONATE SPECIES (CT)

OPEN SYSTEM
Water is in equilibrium with the partial pressure of CO2 in the atmosphere Useful for chemistry of lakes, etc Carbonate equilibrium reactions are thus appropriate

First the CO2 dissolves according to: (1) CO2 (g) CO2 (l)

According to Henrys Law, solubility increases as water temperature decreases

Equilibrium is established between the dissolved CO2 and H2CO3, carbonic acid.

(2) CO2 (l) + H2O (l) H2CO3 (l)

Carbonic acid is a weak acid that dissociates in two steps.

(3) H2CO3 + H2O H3O+ + HCO3

pKa1 (25 C) = 6.37

(4) HCO3- + H2O H3O+ + CO32pKa2 (25 C) = 10.25

The above presen ted mor e schematically: + H 2O + H 2O

-

CO 2(g)

CO 2 (l)

H2CO 3

HCO 3 + + H 3O

+ H 2O

CO 3 + + H 3O

2-

+ Ca

2+

CaCO 3

Not e that the reverse is also true and that the scheme represents the solubility of CaC O3 in an acidic solution resulting in the liberation of CO 2 in the atmos phere.

Activity of Carbonate Species versus pH

CARBONATE SPECIES AND pH

Carbonate Buffering: Humans

We

can describe the formation and dissociation of carbonic acid through the following chemical and equilibrium equations

Carbonic

acid forms when CO2 dissolves in and reacts with water:

CO2(g) + H2O = H2CO3 Most dissolved CO2 occurs as aqueous CO2 rather than H2CO3, but we write it as carbonic acid for convenience The equilibrium constant for the reaction is:

KCO2

[H2CO3 ] [H2CO3 ] PCO2 [H2O] PCO2

Note we have a gas in the reaction and use partial pressure rather than activity

First dissociation: H2CO3 = HCO3 + H+

[H ][HCO ] K1 [H2CO 3 ]

FIRST REACTION

Second dissociation: HCO3 = CO32 + H+

[H ][CO ] K2 [HCO ]

2 3 3

SECOND REACTION

Variables and Reactions Involved in Understanding the Carbonate System

Gas Dissociation of Dissociation Cations equilibria carbonic acid of water PCO2 [H2CO3] [H+] [Ca2+] [HCO3] [CO32] [OH] Measurements DIC Alkalinity

ALKALINITY refers to water's ability, or inability, to neutralize acids.

The terms alkalinity and total alkalinity are often used to define the same thing.

Total

alkalinity - sum of the bases in equivalents that are titratable with strong acid (the ability of a solution to neutralize strong acids)
Bases

which can neutralize acids in natural waters: HCO3, CO32, B(OH)4, H3SiO4, HS, organic acids (e.g., acetate CH3COO, formate HCOO)

Carbonate alkalinity
Alkalinity (HCO3) + 2(CO32) Reason is that in most natural waters, ionized silicic acid and organic acids are present in only small concentrations If pH around 7, then
Alkalinity HCO3

Bicarbonate dominates alkalinity of sea water

Alk = OH + HCO3 + 2CO32 + B(OH)4- - H+

Gran Titration for Acid Neutralizing Capacity (total alkalinity)

This method determines ANC by titration with 0.1 N Hydrochloric Acid between the pH range of 4.5 and 3.5 at which the contributions of organic acids, carbonate and bicarbonate are neutralized. Explicitly accounts for most organic acids

Charge Balance
Fundamental principle of solution chemistry is that solutions are electronically neutral Sum of positive charges must equal the sum of negative charges in any sample
+ = -

+ > -, there is an unmeasured anion Equivalents: moles/L x valence

ION Percent Difference Quality Control

+ - - / + + Normalizes the charge balance NADP guidelines for allowable error Error should be random and equal zero If error always positive, means there is an unmeasured anion (negative charge)

 Alkalinity is routinely measured in natural water samples. By measuring only two parameters, such as alkalinity and pH, the remaining parameters that define the carbonate chemistry of the solution (PCO2, [HCO3], [CO32], [H2CO3]) can be determined.

Alkalinity and hardness.

Calcium (Ca++) and Magnesium (Mg++) are primarily responsible for hardness. However, in most waters, alkalinity and hardness have similar values because the carbonates and bicarbonates responsible for total alkalinity are usually in the form of Calcium carbonate or Magnesium carbonate. However, waters with high total alkalinity are not always hard, since the carbonates can be in the form of Sodium or Potassium carbonate.

CLOSED CARBONATE SYSTEM

Carbon dioxide is not lost or gained to the atmosphere Total carbonate species (CT) is constant regardless of the pH of the system Occurs when acid-base reactions much faster than gas dissolution reactions Equilibrium with atmosphere ignored

How does [CO32] respond to changes in Alk or DIC? CT = [H2CO3*] + [ HCO3] + [CO32] ~ [ HCO3] + [CO32] (an approximation) Alk = [OH] + [HCO3] + 2[CO32] + [B(OH)4-] [H+] ~ [HCO3] + 2[CO32] (a.k.a. carbonate alkalinity) So (roughly): [CO32] ~ Alk CT CT , [CO32] Alk , [CO32]

Diurnal changes in DO and pH Whats up?

Photosynthesis is the biochemical process in which plants and algae

harness the energy of sunlight to produce food. Photosynthesis of aquatic plants and algae in the water occurs when sunlight acts on the chlorophyll in the plants. Here is the general equation: 6 H20 + 6 CO2 + light energy > C6H12O6 + 6 O2 Note that photosynthesis consumes dissolved CO2 and produces dissolved oxygen (DO). we can see that a decrease in dissolved CO2 results in a lower concentration of carbonic acid (H2CO3), according to: CO2 + H20 <=> H2CO3 (carbonic acid)

As the concentration of H2CO3 decreases so does the concentration of H+, and thus the pH increases.

Cellular Respiration
Cellular respiration is the process in which organisms, including plants, convert the chemical bonds of energy-rich molecules such as glucose into energy usable for life processes.
The equation for the oxidation of glucose is: C6H12O6 + 6 O2 > 6 H20 + 6 CO2 + energy As CO2 increases, so does H+, and pH decreases. Cellular respiration occurs in plants and algae during the day and night, whereas photosynthesis occurs only during daylight.

Rock Cycle

Hydrolysis

Carbonate weathering

Classic reference on geochemical weathering

%A R. M. Garrels %A F. T. MacKenzie %T Origin of the chemical composition of some springs and lakes %B Equilibrium Concepts in Natural Water Systems %E R. G. Gould %S Am. Chem. Soc. Adv. Chem. Ser. %V 67 %P 222-242 %D 1967