Environmental Chemistry

Chapter 11: Water and the Hydrosphere

Contents
The Fantastic Water Molecule and the Unique Properties of Water The Hydrosphere Compartments of the Hydrosphere Aquatic Chemistry Alkalinity and Acidity Metal Ions Oxidation-Reduction Complexation and Chelation Interactions with Other Phases Aquatic Life Microbially Mediated Elemental Transitions and Cycles

The Fantastic Water Molecule and the Unique Properties of Water

The Fantastic Water Molecule and the Unique Properties of Water

Region of partial negative charge

Regions of partial positive charge

Polarity

A difference in the electronegativities of the atoms in a bond creates a polar bond

Partial charges result from bond polarization

A polar covalent bond is a covalent bond in which the electrons are not equally shared, but rather displaced toward the more electronegative atom

H-Bonding
Polarized bonds allow hydrogen bonding to occur A hydrogen bond is an electrostatic attraction between an atom bearing a partial positive charge in one molecule and an atom bearing a partial negative charge in a neighboring molecule The H atom must be bonded to an O, N, or F atom Hydrogen bonds typically are only about one-tenth as strong as the covalent bonds that connect atoms together within molecules

Hbonds are intermolecular bonds Covalent bonds are intramolecular bonds

Unique Properties

Water shrinks on melting (ice floats on water) Unusually high melting point Unusually high boiling point Unusually high surface tension Unusually high viscosity Unusually high heat of vaporization Unusually high specific heat capacity And more

There is No Substitute for Water

Box 1.1 Major Properties of Water

Unique Properties

Unusually high Mpt. and Bpt.

Predicted melting point at -73 C and boiling point at -98 C.

Unique Properties
Why H-Bonding is Important

This increase in the thermal window of liquid water from a predicted 25 to its actual 100 allows aquatic life to exist over a broader range of temperatures

H-bonding leads to viscosity and surface tension

Unique Properties
Unlike other substances water is less dense in solid form than liquid form Water at different temperatures has different densities leads to layering in lakes D ~ 1/V as ice melts D inc. and V dec.
Becoming less dense

Unique Properties
Ice shrinks on melting as 15% H-bonds are lost

A certain mass of ice occupies more space than the same mass of water

The Hydrosphere

Natural Waters
The Blue Marble
0.001 % water vapor 71 % liquid water

The Blue Marble is a famous photograph of the Earth taken on 7 December 1972 by the crew of the Apollo 17 spacecraft at a distance of about 29,000 km or about 18,000 miles. It is one of the most widely distributed photographic images in existence. The image is one of the few to show a fully lit Earth, as the astronauts had the Sun behind them when they took the image. To the astronauts, Earth had the appearance of a child's glass marble (hence the name).

The Hydrosphere
Compartments Atmosphere Land Groundwater Rivers lakes Oceans

Hydrologic Cycle

Source: http://www.nasa.gov/vision/earth/environment/warm_wetworld.html

Where Does Potable (fit for consumption) Drinking Water Come From?

Sources

Less than one third of salt-free water is liquid

Surface water: from lakes, rivers, reservoirs (< 0.01 % of total) Ground water: pumped from wells drilled into underground aquifers (0.3 %)

Natural Waters
Uses of Water

World Resources 1998-99

The number of people living in countries facing severe or chronic water shortages is projected to increase more than fourfold over the next 25 years. This will be from an estimated 505 million people today to between 2.4 and 3.2 billion people by 2025.

Sources

< 1000 m3 per person per year

Engelman et al., 2000

Access to Water

Access to Water

Uneven distribution of water

Region

Total Renewable Water Resources (km3 yr-1) 43,249 11,321 6,590 518 4,850

Total Water Withdrawals (m3 yr-1) 3,414,000 1,516,247 367,449 303,977 512,440

Per Capita (m3 person-1 yr-1)

Average % of Renewable Resources 29 9 423 14

Average % Used by Agriculture

Average % Used by Industry 20 10 48 5 58

World Asia Europe Middle East/N. Africa N. America

650 1,028 503 754 1,720

71 79 25 80 27

Subject to contamination Using water at a rate faster than it can be supplied (>100 due to use of sea water)

Natural Waters
Role of Water in the Environment Water is an important constituent in our body and our survival depends on natural waters transports substances into, within, and out of living organisms distributes soluble substances (e.g. pesticides, lead, mercury) reduces concentrations via dilution and dispersion

e.g. rainwater carries substances (e.g. acids) down to earths surface, washes out (cleanses) the air but pollutes waterways

Withdrawls (2000)

Precipitation CONUS

Fastest growing areas are most water deficient: S. CA, AZ, NV, CO

Provides electricity from hydroelectric plants for 30 million people (1/10th of the U.S. population)

Glen Canyon Dam

Hoover Dam

Ogallawa (High Plains) Aquifer

Worlds largest aquifer Composed of fossil water from last ice age Rapidly dropping water table supports $32 billion agriculture most areas water withdrawn much faster than recharge

Transport medium volumes, residence times, Water Cycle fluxes Largest reservoir oceans = 40,000 yr

Liquid Medium

Compartments of the Hydrosphere

Compartments of the Hydrosphere

Surface waters (watersheds) streams, lakes reservoirs, wetlands, estuaries
Standing surface water vs. flowing surface water

Compartments of the Hydrosphere

Temperature-density relationship leads to layering in lakes

Warmer water floats on colder = thermal stratification

Compartments of the Hydrosphere

Groundwater most from precipitation and infiltration
Composition depends on surrounding rock formations (porosity and permeability)

Aquatic Chemistry

Aquatic Chemistry
Algal photosynthesis: Converts inorganic C (2HCO3-) to organic form (CH2O, emp. formula for sugars)

CO32- is either converted back to HCO3-, or ppts as limestone

Biomass (CH2O) produced

Aquatic Chemistry
Most redox reactions in water are catalyzed by bacteria e.g. N compounds to NH4+ in anoxic conditions e.g. N to NO3- in oxic conditions Chelation of metals Gas exchange with atmosphere Solute exchange between aquesous and solid phases (sediments)

Alkalinity and Acidity

Alkalinity and Acidity

Alkalinity the capacity of water to accept H+ Measure of the ability of a water body to neutralize acidity Serves as a pH buffer and reservoir for inorganic C Helps determine ability of water to support algal growth and aquatic life, used as a measure of water fertility

Dissolution of limestone and other minerals produces alkalinity e.g. CaCO3 Ca2+ + CO32CO32- + H2O HCO3- + OHWater supply with high total alkalinity is resistant to pH change (>> buffering capacity) Two samples with identical pH but different alkalinity behave differently on addition of acid Different capacity to neutralize acid pH is an intensity factor whilst alkalinity is a capacity factor

Alkalinity
Measurement of the buffer capacity (resistance to pH change) e.g. Carbonate neutralization reaction CO32- + H+ HCO3Bicarbonate neutralization reaction HCO3- + H+ H2O.CO2 H2O + CO2 Hydroxide neutralization reaction H+ + OH- H2O Alkalinity = [OH-] + [HCO3-] + 2[CO32-] [H+] Units are mg L-1 CaCO3 or mEq L-1 (regardless of species) Acid titration to change the pH to 4.5 (methyl orange end-point) If pH < 4.5 there is no acid neutralizing capacity i.e. no need to measure alkalinity

Acidity
pH = - log [H+]

H+ usually surrounded by water of hydration, written H3O+ Master Variable controls parameters e.g. speciation Ranges 5.5 - 9

Acidity
Acidity results from presence of weak acids: H2PO4-, CO2, H2S, proteins, fatty acids, metal ions (e.g. Al3+, Fe3+) e.g. [Al(H2O)6]3+ + H2O simplifies as [Al(H2O)6]3+ [Al(H2O)5OH]2+ + H3O+ [Al(H2O)5OH]2+ + H+

Difficult to measure due to volatility of gases Total acidity is determined by titration with base to pH 8.2

Metal Ions and Calcium in Water

Metal Ions and Calcium in Water

Metal Ions
Mn+ exists in various forms in water (species) Cannot exist as free ion, seeks max stability of outer e- shells, does this by accepting lone pairs from donor molecules Exist as hydrated cations [M(H2O)x]n+ coordinate bonded to water molecules or other bases (e- donors)

Metal Ions and Calcium in Water

Metal Ions
The hydrogen atoms attached to the water ligands are sufficiently positive that they can be pulled off in a reaction involving water molecules in the solution.

Metal Ions and Calcium in Water

Metal Ions
Allows for loss of H+, reactions:

Acid base: Ppt: Redox:

[Fe(H2O)6]3+ [Fe(H2O)6]3+ [Fe(H2O)6]2+

[FeOH(H2O)5]2+ + H+ Fe(OH)3(s) + 3H2O + 3H+ (results from A-B) Fe(OH)3(s) + 3H2O + e- + 3H+

Due to these reactions conc. of the hydrated cation, e.g. [Fe(H2O)6]3+ is very small

Metal Ions and Calcium in Water

Metal Ions
Acid-base reaction is more completely shown by H+ ion is being pulled off by a water molecule in soln: [Fe(H2O)6]3+ + H2O Successive deprotonations: [FeOH(H2O)5]2+ +H2O [Fe(OH)2(H2O)4]+ +H2O [Fe(OH)2(H2O)4]+ + H3O+ [Fe(OH)3(H2O)3](s) + H3O+ [FeOH(H2O)5]2+ + H3O+

Forms a neutral complex which does not dissolve and precipitates, Fe(OH)3

Metal Ions and Calcium in Water

Metal Ions
Hydrated Metal Ions as Acids Hydrated metals with +3 charge or more act as Bronsted acids (inc with charge, dec with radius) e.g. [Fe(H2O)6]3+ [FeOH(H2O)5]2+ + H+

Solutions containing +3 hexaaqua ions tend to have pH's in the range from 1 to 3. Solutions containing +2 ions have higher pH's - typically around 5 - 6, although they can go down to about 3. Tendency of hydrated metal ions to act as acids leads to acid mine water [Fe(H2O)6]3+ Fe(OH)3(s) + 3H2O + 3H+

Metal Ions and Calcium in Water

Metal Ions
Properties of metals dissolved in water depend upon the nature of metal species dissolved in water, called speciation In addition to hydrated [M(H2O)x]n+ and the associated hydroxo species, metals may exist as complexes (reversibly bound to inorganic anions, organic compounds) or organometallic compounds

Metal Ions and Calcium in Water

Calcium and Harness
Ca2+ generally has highest conc. and most influence on aquatic chemistry Why? Calcium is a key element in many geochemical processes Primary minerals: gypsum (CaSO4.2H2O), anhydrite (CaSO4), dolomite (CaMg(CO3)2, calcite and aragonite (CaCO3)

Metal Ions and Calcium in Water

Calcium and Harness

CO2(g) + H2O(aq) H2CO3(aq) H2CO3(aq) H+ + HCO3CaCO3(s) Ca2+ + CO32CO32- + H2O HCO3- + OHH+ + OH- H2O CaCO3(s) + CO2(g) + H2O(aq)

KH Ka Ksp Kb 1/Kw Ca2+ + 2HCO3-

Giant titration of acid from atmospheric CO2 with base from carbonate ion in rocks K = KspKbKHKa/Kw = 1.5 x 10-6 = [Ca2+][HCO3-]2 PCO2

Metal Ions and Calcium in Water

Calcium and Harness
CaCO3(s) + CO2(g) + H2O(aq) Ca2+ + 2HCO3-

K = KspKbKHKa/Kw = 1.5 x 10-6 = [Ca2+][HCO3-]2 PCO2 If [Ca2+] = S, [HCO3-] = 2S

1.5 x 10-6 = [Ca2+][HCO3-]2 = S (2S)2 PCO2 0.00037 atm S = [CO2] = 5.2 x 10-4 mol L-1 (34 x amount calculated from Henrys law) S = [Ca2+] = 5.2 x 10-4 mol L-1 (this is 4x closed system) [HCO3-] = 2S = 1.0 x 10-3 mol L-1 Acid-base reaction increases the solubility of both the gas and he solid water that contains CO2 more readily dissolves calcium carbonate

Metal Ions and Calcium in Water

Calcium and Harness
CO32-, H+ and OH- can be derived Ksp = [Ca2+][CO32-] Kb = [HCO3-][OH-] [CO32-] Kw = [H+][OH-] [CO32-] = 8.8 x 10-6 mol L-1 [OH-] = 1.8 x 10-6 mol L-1

[H+] = 5.6 x 10-9 mol L-1

Conclude natural water at 25 C with a pH determined by saturation with CO2 and CaCO3 should be alkaline (pH = 8.3) Actual value of calcereous waters is around 7-9 why the difference?

Metal Ions and Calcium in Water

Calcium and Harness Simple model does not include CO2 from respiration of MOs! MOs directly affect conc. of Ca2+ in water

Metal Ions and Calcium in Water

Calcium and Harness

Ca2+ Fe2+

Mg2+

Common cations of high enough concentration to be readily monitored are good indicators of pollution events

Metal Ions and Calcium in Water

Calcium and Harness
Hard water contains high concentrations of dissolved calcium and magnesium ions Soft water contains few of these dissolved ions. Counter ions of alkalinity ions

Hardness = [Ca2+] + [Mg2+]

Alkalinity is a good indicator of hardness and vice-versa

Carbonate minerals: limestone - CaCO3 dolomite - CaCO3.MgCO3 sulfates - CaSO4

(also Al3+, Fe3+, Mn2+ and Zn2+)

Metal Ions and Calcium in Water

Calcium and Harness
Deposition of white solid CaCO3 or MgCO3 when water is heated furring-up blocks pipes and lowers efficiency of industrial processes Formation of scum (insoluble ppt) with soap and water Ca2+(aq) + 2Na(C17H33COO- )(aq) detergent action is blocked Staining (due to transition metals) 2Na+ + Ca(C17H33COO- )2(s)

A pipe with hard-water scale build up

Metal Ions and Calcium in Water

Calcium and Harness
Solid deposit = carbonate hardness or temporary hardness
Ca2+ + 2HCO3CaCO3(s) + CO2(g) + H2O(aq) (removed via boiling)

Causes deposit in pipes and scales in boilers Temporary hard water has to be softened before it enters the boiler, hot-water tank, or a cooling system No solid = non-carbonate or permanent hardness Amount of metal ions that can not be removed by boiling Total hardness = temporary hardness + permanent hardness

Oxidation-Reduction

Oxidation-Reduction
Most important oxidizing agent is dissolved O2 (atmospheric) Acidic solution O2 + 4H+ + 4eBasic solution O2 + 2H2O + 4e2H2O 4OH O2 is reduced from 0 to -2 state in H2O or OH

Concentration of O2 in water is low (10 ppm average), governed by Henrys law:

O2(g)

O2(aq)

KH = [O2 (aq)] PO2

At 25 C, KH = 1.3 x10-3 mol L-1 atm-1 Dissolved O2 influences chemical speciation of elements in natural and polluted waters

Oxidation-Reduction
Show that (a) O2 + 2H2O + 4eIs the same as (b) 2H2O + 2eDouble (b): 2(2H2O + 2e- H2(g) + 2OH4H2O + 4e- 4H2(g) + 4OHAdd O2 + 2H2 2H2O O2 + 2H2O + 4e4OH (from above) H2(g) + 2OH- (from Manahan)

4OH

Question
P9-1: Confirm by calculation the value of 8.7 mg L-1 for the solubility of oxygen in water at 25 C

At 25 C, KH = 1.3 x10-3 mol L-1 atm-1 KH = [O2 (aq)] / PO2 [O2 (aq)] = KH x PO2 [O2 (aq)] = (1.3 x10-3 mol L-1 atm-1 ) x 0.21 atm = 2.7 x 10-4 mol L-1 [O2 (aq)] = 2.7 x 10-4 mol L-1 x 32.00 g mol-1 = 8.7x 10-3 g L-1 = 8.7 mg L-1 = 8.7 ppm

Oxidation-Reduction
Depletion of O2 Temperature (inc) Pressure (dec) Salts (inc) Organic matter (inc)

Dissolved O2 decreases with increasing temperature

Oxidation-Reduction
Oxygen Demand
The most common substance oxidized by DO in water is organic matter (plant debris, dead animals etc.)
0 to -2

CH2O(aq) + O2(aq)
0 to +4

CO2(g) + H2O(aq)

Similarly DO is consumed by NH3 and NH4+ in the nitrification process Water in streams and rivers are constantly replenished with oxygen Stagnant water and deep lakes can have depleted oxygen

Oxidation-Reduction
Oxygen Demand
Half reactions Oxidation: Reduction:

CH2O + H2O CO2 + 4e- + 4H+ 4H+ + O2 + 4e2H2O CH2O(aq) + O2(aq) CO2(g) + H2O(aq)

In basic conditions? O2 + 4H+ + 4e- p 2 H2O React with hydroxide O2 + 4H+ + 4OH- + 4e- p 2H2O + 4OHO2 + 4H2O + 4e- p 2H2O + 4OHO2 + 2H2O + 4e- p 4OH-

Same overall

Question
P9-4: Determine the balanced redox reaction for the oxidation of ammonia to nitrate ion by O2 in alkaline solution (basic) Does this reaction make the water more basic or less? NH3 + O2 p NO3- + H2O Using standard redox balancing techniques: NH3 + 2O2 + OH- p NO3- + 2H2O The water becomes less basic since OH- is removed

Measures of amount of organics/biological species in water

Biochemical Oxygen Demand (BOD) Chemical Oxygen Demand (COD) Total Organic Carbon (TOC) Dissolved Organic Carbon (DOC) (TOC)-(DOC) = Suspended carbon in water

Oxidation-Reduction
Biological Oxygen Demand
The capacity of the organic and biological matter in a sample of natural water to consume oxygen, a process usually catalyzed by bacteria, is called BOD Procedure: measure O2 in the stream or lake. Take a sample and store at 25oC for five days and remeasure O2 content. The difference is the BOD BOD5 corresponds to about 80% of the actual value. It is not practical to measure the BOD for an infinite period of time Surface waters have a BOD of about 0.7 mg L-1 significantly lower than the solubility of O2 in water (8.7 mg L-1) Sewage has BOD of ~100 mg L-1

Oxidation-Reduction
Chemical Oxygen Demand
O2 + 4H+ + 4e 2H2O

Dichromate ion, Cr2O72- dissolved in sulfuric acid is a powerful oxidizing agent. It is used as an oxidant to determine COD Cr2O72- + 14H+ + 6e2Cr3+ + 7 H2O

Excess dichromate is added to achieve complete oxidation Back titration with Fe2+ gives the desired endpoint value # moles of O2 consumed = 6/4 x (#moles Cr2O7 consumed)

Note: Cr2O72- is a powerful oxidizing agent and can oxidize species that are not usually oxidized by O2 - hence gives an upper limit

Question
P9-5: A 25 mL sample of river water was titrated with 0.0010 M Na2Cr2O7 and required 8.7 mL to reach the endpoint. What is the COD (mg O2/L)?

No. moles Cr2O72- = 0.0010 mol L-1 x (8.7 x 10-3 L) = 8.7 x 10-6 mols No. moles O2 = 1.5 moles Cr2O72- = 1.5 x (8.7 x 10-6 mols) = 1.3 x 10-5 mols O2 1.3 x 10-5 mol x 32.00 g mol-1 = 4.2 x 10-4 g 0.42 mg / 0.025 L = 17 mg L-1

Oxidation-Reduction
The pE Scale
Oxidation and reduction are controlled by the concentrations of electrons which are present: pE = - log10[e-] Low pE means electrons are available (reducing environment) High pE means electrons are unavailable (oxidizing environment) pE is calculated from electrode potential (E) by the relationship: pE = E 2.303 RT/F

Oxidation-Reduction
The pE Scale
When a significant amount of O2 is dissolved, the reduction of O2 is the dominant reaction determining e- availability: O2 + H+ + e H2O

Under such circumstances, the pE of the water is related to its acidity and to the partial pressure as follows: pE = 20.75 + log([H+] PO2) OR pE = 20.75 pH + log(PO2 )

Oxidation-Reduction
The pE Scale
A convenient approach is to use Nernst Equation of electrochemistry E = E0 (RT/F) (log 4[products] / 4[reactants]) for 1 electron redox process E = E0 - 0.0591(log 4[products] / 4[reactants])
where E0 is the standard electrode potential for a one electron reduction

One can equate pE to the Electrode Potential E pE = E/0.0591 or pE0= E0/0.0591 Dividing throughout by 0.0591: pE = pE0 - (log 4[products] / 4[reactants])

Redox Chemistry in Natural Waters

The pE-pH Diagram
Nature of a chemical species Is usually a function of pH and pE Move from pE = pE0 - (log 4[products] / 4[reactants]) to an equation relating pE to pH

Redox Chemistry in Natural Waters

The pE Scale
O2 + H+ + e H2O E0 = 1.23 V pE0 = 1.23/0.0591

pE = pE0 - (log 4[products] / 4[reactants]) pE = 20.75 - log 1/ 4[reactants] = 20.75 + log (4[reactants]) pE = 20.75 + log([H+] PO2) = = 20.75 + log([H+] + log (PO2) pE = 20.75 pH + log(PO2 ) pE = 20.75 pH + log(PO2 ) For a neutral sample of water that is saturated with oxygen from air (PO2 = 0.21 atm) that is free from CO2 (pH = 7) the pE value corresponds to 13.9 pE value decreases with decrease in O2 and increase in pH Dominant redox equilibrium reaction determines pE of water (O2 may not be dominant redox species!)

Question
What is the most oxidizing conditions possible in water?

PO2 cannot exceed 1, log(1) = 0 pE = 20.75 pH pE = 20.75 - pH This can be drawn on a pE/pH diagram as a boundary line, When pE > 20.75 pH water will be oxidized A similar analysis gives boundary below which water will be reduced pH pE

pE = - pH

Redox Chemistry in Natural Waters

The pE Scale
Example 1/8NO3 + 5/4H+ + e1/8NH4+ + 3/8H2O E0 = +0.836 V

pE0 = E0/0.0591 = 0.836/0.0591 = +14.15 ax = x log a log(1/b) = -log b

pE

pE0

log

[NH4+]1/8 [NO3-]1/8[H+]5/4)

= 14.15 - 5/4pH -1/8log([NH4+]/[NO3-]) Note: Express the reactions as one electron reduction process .. Follow the examples given on page 435

Question
9-7: Deduce the equilibrium ratio of concentrations of NH4+ to NO3- at a pH of 6.0 (a) for aerobic water having a pE = +11, and (b) for anaerobic water with pE = -3 pE = 14.15 (5/4)pH (1/8)log([NH4+] / [NO3-]) 11 = 14.15 (5/4) x 6 (1/8)log([NH4+] / [NO3-]) log([NH4+] / [NO3-]) = -8(4.35) = -34.8 [NH4+] / [NO3-] = 1.6 x 10-35 pE = 14.15 (5/4)pH (1/8)log([NH4+] / [NO3-]) -3 = 14.15 (5/4) x 6 (1/8)log([NH4+] / [NO3-]) log([NH4+] / [NO3-]) = 8(9.65) = 77.2 [NH4+] / [NO3-] = 1.6 x 1077

Problem 9-7

pH = 6, pE = 11,

pH = 6, pE = -3,

Redox Chemistry in Natural Waters

The pE-pH Diagram
Fe3+ + e For this reaction, pE0 = 13.2 pE = 13.2 + log([Fe3+] / [Fe2+]) Fe2+

NOT pH DEPENDENT!

e.g. Ratio of Fe3+ to Fe2+ when pE = -4.1 (reducing) -4.1 = 13.2 + log([Fe3+] / [Fe2+]) log([Fe3+] / [Fe2+]) = -17.3 [Fe3+] / [Fe2+] = 5 x 10-18 (far more Fe2+) Transition between dominance of one form over the other occurs at [Fe3+] = [Fe2+], pE = 13.2 + log(1) = 13.2 + 0 = 13.2

Redox Chemistry in Natural Waters

pE pH Stability Field Diagrams
Zone dominance of various oxidation states
pE independent pH independent

Fe3+ ion is stable in oxidizing acidic conditions, Insoluble Fe(OH)3 is predominant iron species Fe2+/Fe3+ ions can only exist under acidic conditions At higher pH Fe3+ is present as Fe(OH)3. Fe(OH)2 does not precipitate until solution becomes significantly basic Changes in redox conditions govern whether the iron will be in solution or in the sediments

pE independent

Complexation and Chelation

Complexation and Chelation

Mn+ exists in various forms in water Exist as hydrated cations [M(H2O)x]n+ coordinate bonded to water molecules or other bases (e- donors) called ligands Ligands - bond to a metal ion to form a complex ion (coordination compound) e.g. Cd2+ + CN[CdCN]+

[CdCN]+ + CN- Cd(CN)2 Cd(CN)2 + CN- [Cd(CN)3][Cd(CN)3]- + CN- Cd(CN)42(CN- is unidentate ligand)

Complexation and Chelation

Complexes with chelating agents are more important, can be more than one bonding group on a ligand e.g. nitrilotriacetate (NTA) ligand

Has 4 binding sites, stability inc. with no. of binding sites

Ligands found in natural waters contain a variety of functional groups that can donate e-

Complexation and Chelation

Ligands may undergo redox, decarboxylation, and hydrolysis Complexation may change the oxidation state of the metal, may become: (i) solubilized from an insoluble compound and enter solution, or (ii) insoluble and removed from solution e.g. complexation with negative species can convert soluble Ni2+ (cation) into [Ni(CN)4]2- (anion). Cations are readily bound by ion exchange processes in soils (exchange of H+ with another cation), whilst anionic species are not.

Complexation and Chelation

Occurrence and Importance
Chelating agents are common potential pollutants Occur in sewage and industrial wastes e.g. EDTA (ethylenediaminetetraacetic acid)

+ Mn+

Tend to solubilize heavy metals from plumbling and from waste deposits

Complexation and Chelation

Complexation by Humic Substances
Humic substances - Most important class of complexing agents Formed from decomposition of vegetation Classified based on extraction with strong base: (a) Humin nonextractable plant residue (b) Humic acid precipitates after addition of acid (c) Fulvic acid organic material remaining in acidified solution High molecular mass, polyelectrolytic macromolecules, e.g. fulvic acid

Complexation and Chelation

Complexation by Humic Substances
Binding of metal ions by humic substances:

Complexation and Chelation

Complexation by Organometallic Compounds
Organometallic compounds metal attaches to organic ligand Hg2+ (Mercury (II) ion) CH3Hg+ (Monomethylmercury ion) (CH3)2Hg (Dimethylmercuty) May enter direct as pollutants or be synthesized biologically by bacteria Common to find organometallic Hg, Sn, Se and As compounds, all highly toxic

Interactions with Other Phases

Interactions with Other Phases

Most of the important chemical phenomena do not occur in solution, but rather through interaction of solutes in water with other phases e.g. redox reactions catalyzed by bacteria, solute-particle interactions

Interactions with Other Phases

1. Organic compounds may be present as films on the surface of water, may undergo photolysis 2. Gases are exchange with the atmosphere 3. Photosynthesis and other biological processes (e.g. biodegradation of organics) in bacterial cells 4. Particles introduced by eroding streams or precipitation of insoluble salts

Interactions with Other Phases

Lipophillic pollutants in aquatic environment are associated with:
Particles; and Colloidal organic carbon (natural organic matter)

Partition coefficients are used to model particle water exchange

Aquatic Life

Aquatic Life
Autotrophic biota utilize solar or chemical energy to fix elements into complex molecules Producers autotrophs that utilize solar energy to synthesize organic matter Heterotrophic biota utilize organic substances produced by autotrophs for energy and as raw materials for synthesis of own biomass Decomposers a subclass of heterotrophs (bacteria and fungi) which break down material to form simple compounds

Aquatic Life
Microorganisms exist as single cell organisms Bacteria, fungi, algae Algae and photosynthetic bacteria: predominant producers of biomass that supports the rest of the food chain Catalyze chemical reactions Break down biomass and mineralize essential elements (N, P) Play important role in biogeochemical cycles Breakdown and detoxify many xenobiotic pollutants

Aquatic Life
Algae MOs that consume inorganic nutrients and produce OM from CO2 via photosynthesis hv CO2 + H2O {CH2O} + O2(g)

Fungi Nonphotosynthetic, aerobic organisms Important role in determining composition of natural waters since decomposition products enter water (cellulose from wood and other plant materials including humic substances)

Bacteria
Single celled MOs (rods, spheres, or spirals) Characteristics unicellular, semi-rigid cell wall, motility with flagella, multiplication via binary fission Obtain energy needed for metabolism and reproduction by mediating chemical reactions (biogeochemical cycles) Subclasses:
Heterotrophic bacteria Aerobic bacteria Anaerobic bacteria Facultative bacteria

Bacteria
Prokaryotic bacterial cell Enclosed in cell wall Capsule enclosure (slime layer) Cell membrane controls material transport Cytoplasm contains nutrients for metabolism

Bacteria
Bacterial Growth and Metabolism Reproduce rapidly, high surface-volume ratio Metabolic reactions of bacteria are mediated by enzymes

Microbially Mediated Elemental Transitions and Cycles

Microbially Mediated Elemental Transitions and Cycles

Biogeochemical cycles microbially mediated transitions between elemental species

Microbially Mediated Elemental Transitions and Cycles

Carbon Cycle Small amount is atmospheric CO2 Large amount present in minerals (carbonates) Organic fraction as hydrocarbons Manufacture of toxic xenobiotic compounds from hydrocarbons

Microbially Mediated Elemental Transitions and Cycles

Carbon Cycle Involvement of MOs Photosynthesis algae, higher plants, bacteria use light energy to fix inorganic C CO2 + H2O {CH2O} + O2(g) Respiration: Aerobic respiration OM is oxidized {CH2O} + O2(g) CO2 + H2O Anaerobic respiration uses oxidants other than O2, NO3- or SO42 Degradation of biomass by bacteria and fungi. Prevents accumulation of wastes, converts organic C, N S, P into inorganic forms for use by plants Methane production in anoxic sediments 2{CH2O} CH4 + CO2

Bacterial utilization and degradation of HCs oxidation of HCs Biodegradation of organic matter treatment of wastewater

Microbially Mediated Elemental Transitions and Cycles

Nitrogen Cycle N is interchanged among the atmosphere, OM, and inorganic compounds MOs mediate reactions

Microbially Mediated Elemental Transitions and Cycles

Nitrogen fixation binding of atmospheric N2 3{CH2O} + 2N2 + 3H2O + 4H+ 3CO2 + 4NH4+

Nitrification converts ammonium to nitrate 2O2 + NH4+ NO3- + 2H+ + H2O

Nitrate reduction N in compounds is reduced by MOs to lower oxidation states Denitrification produces N2, N2O or NO, returns to atmosphere

Microbially Mediated Elemental Transitions and Cycles

Microbial transformations of Sulfur Reduction of sulfate, oxidation of sulfide, degradation of organis S compounds Microbial transformations of Phosphorus Microbial transformations of halogens Operate on xenobiotic compounds Microbial transformations of Iron Oxidize iron (II) to iron (III)