1. Soil / Groundwater Pollution & Remediation 1 Soil Environmental Chemistry Chapter 15 & 16* Why soil environmental chemistry is important? –The place where food and energy source are produced (agriculture/mining) –The dumping ground of municipal refuse, hazardous waste (landfill) and radioactive waste (Section 15.21) –Source of drinking water (groundwater) (Section 15.9) –Soil pollution is related to air pollution and water quality (Section 15.19, 15.20 ) ***Skip Sections 15.3 -15.5, 15.10 - 15.17 & Sections 16.9-16.11

2. Soil / Groundwater Pollution & Remediation 2 Scope of Soil Chemistry Geosphere, or solid earth, is that part of earth upon which humans live and from which they extract most of their food, minerals, and fuels Lithosphere is part of the geosphere that is directly involved with environmental processes through contact with the atmosphere, the hydrosphere, and living things (p. 2-3) Sediments: dissolved load (1/4) + suspended load (2/3) + bed load (1/12) (Section 15.6) Soil chemistry, sediment (aquatic) chemistry and geochemistry (Section 15.8) are related

3. Soil / Groundwater Pollution & Remediation 3 Composition of Soil Inorganics (> 95%): minerals –O, Si, Al, Fe, Ca, Na, K, Mn, trace heavy metals Organics (< 5%) –Protein, fat, CH 2 O (10-15% of soil organics) –Humus (85-90% of soil organics) –Pesticide, PAH (trace contaminants) Water (soil solution) (p. 483) –Cation, anions, ions in hydrolyzed / complexed form Air (35% of soil volume,  =0.35) –21% O 2, 0.03% CO 2 Solid Liquid Gas

4. Soil / Groundwater Pollution & Remediation 4 Important Soil Properties Physical properties –Particle size –Density & porosity –Texture (clay, silt, sand) –Permeability (hydraulic conductivity) Chemical properties –Total vs. extractable elements –CEC and soil charge (soil is commonly considered to have negative charges) –Soil pH, organic matter –Soil inorganic ions and chelates (functional groups) in soil organics: NH 2, -OH, -COO-, -C=O, Cl -, SO 4 2-, HCO 3 -, OH -

5. Soil / Groundwater Pollution & Remediation 5 Soil Particle Size Non-soilSoil Gravel FineCoarse Sand Silt Clay 2  m 20  m 200  m 2.0 mm Soil particle size classification according to the International Society of Soil Science

6. Soil / Groundwater Pollution & Remediation 6 Soil Density & Porosity Soil particle density –Density of individual particles – 5 g/mL for some metals oxides, > 7 g/mL for metal sulfide; average 2.5 ~ 2.8 g/mL Bulk density –Include the pore spaces between particles –Smaller than particle density; average 1.2 ~1.8 g/mL Porosity –Pore space (%) = 100 - (bulk density/particle density)*100 –Example: A silt loam soil with particle density = 2.65 and bulk density = 1.5  Pore space = 100- (1.5/2.65)*100 = 43%

7. Soil / Groundwater Pollution & Remediation 7 Soil CEC (Cation Exchange Capacity) Origins –CEC of clay minerals is due to the presence of negatively charged sites on the minerals –CEC of organic matters is due to the presence of carboxylate group and other functional groups Typical soil CEC = 10 - 30 meq/100 g soil

8. Soil / Groundwater Pollution & Remediation 8 Soil pH (Section 16.3) Terminology commonly used to describe the acid- base status of soils: –Strongly acid (pH 10) Origin of soil acidity –FeS 2 + 7/2O 2 + H 2 O  Fe 2+ + 2H + + 2SO 4 2- Adjustment of acidic soil with lime –Soil}(H + ) 2 + CaCO 3  Soil}Ca 2+ + CO 2 + H 2 O Adjustment of alkaline soils by Al or Fe sulfate –2Fe 3+ + 3SO 4 2- + H 2 O  2H + + SO 4 2-

9. Soil / Groundwater Pollution & Remediation 9 Total Elements The composition of major elements (%) and minor elements (mg/kg) of the mineral component in soils Most common elements in soil: O, Si, Al, Fe, Ca, Na, K, Mg

10. Soil / Groundwater Pollution & Remediation 10 Bioavailable Elements Except for geological time, the “insoluble fraction” of total elements will not play a significant role with respect to plant growth or in terms of most environmental processes The “bioavailable” or “extractable” elements is the portion of the total element that can take part in a range of chemical and biological reactions Percentage (%) of total metal extracted from soil using two extractants (DTPA=diethylenetriaminepentaacetic acid)

11. Soil / Groundwater Pollution & Remediation 11 Macronutrients vs. Micronutrients (Sections 16.4-16.7) Macronutrients –C,H,O  from atmosphere –N, P, K  from fertilizer –Ca –Mg –S Micronutrients –B –Cl –Cu –Fe –Mn –Mo

12. Soil / Groundwater Pollution & Remediation 12 Soil Organic Matter (OM) Major classes of soil OM (Table 16.1, p.481) –Humus (humic acid, fulvic acid, and humin) (p. 482) –Fats, resin, and waxes –Saccharides –N-containing organics –Phosphorus compounds

13. Soil / Groundwater Pollution & Remediation 13 Soil Minerals (Inorganic Fractions) Primary minerals (rock-forming minerals)(Table 15.1, p. 434) –Silicates, oxides, carbonates, sulfides, sulfates, halides, native elements Secondary minerals  Clay (Section 15.7) –Secondary minerals are formed by alteration of parent mineral matter. Clays are silicate minerals, usually containing Al, are one of the most significant classes of secondary minerals

14. Soil / Groundwater Pollution & Remediation 14 Soil Minerals (Inorganic Fractions) ClaysA group of microcrystalline secondary minerals consisting of hydrous aluminum silicates that have sheet-like structure (Si 4+ -O tetrahedral sheet : Al 3+ -O octahedral sheet = 1:1 or 2:1) –Kaolinite, Al 2 Si 2 O 5 (OH) 4  1:1 –Montmorillonite, Al 2 (OH) 2 Si 4 O 10  2:1 –Illite, K 0-2 Al 4 (Si 8-6 Al 0-2 )O 20 (OH) 4  2:1 Hydroxides –Fe 2 O 3 ·nH 2 O, 2Fe 2 O 3 ·H 2 O, Fe 2 O 3 ·H 2 O –Al 2 O 3 ·H 2 O, Al 2 O 3 ·3H 2 O –SiO 2 ·nH 2 O

15. Soil / Groundwater Pollution & Remediation 15 Soil Clay (Sections 15.7; 5.5) Structure (p. 445) –Tetrahedral sheet (Si-4O) –Octahedral sheet (Al-6O) Importance of clay –Holding water –Protect plant nutrient from leaching (Ca 2+, K +, Mg 2+ ) (soil clay is negatively charged due to ion replacement of Si 4+ and Al 3+ by metal ions of similar size but less charge): [SiO 2 ] + Al 3+  [AlO 2 - ] + Si 4+ (p. 131)  the reason why soil has cation exchange capacity (CEC) –Can be a pollutant carrier in water (e.g., clay adsorbs metals)

16. Soil / Groundwater Pollution & Remediation 16 Soil Pollution Major soil pollutants –Heavy metals –Pesticides –Fertilizers (N, P) Major sources –Pesticides & fertilizers –Solid waste & sludge disposal –Wastewater irrigation

17. Soil / Groundwater Pollution & Remediation 17 Important Soil Environmental Processes Heavy metals Pesticides Redox Hydrolysis Acid-Base reaction Complexation/chelation Precipitation Sorption Biological degradation Physical process (volatilization) Photochemical processes

18. Soil / Groundwater Pollution & Remediation 18 Soil Chemistry of Metals: Mercury (Hg) Redox –2Hg + == Hg 2+ + Hg 0 Precipitation –Hg 2+  HgS (reduced) Adsorption –Cationic Hg 2+ –Anionic HgCl 3 -, HgCl 4 2- Biological –Methylation to form Hg(CH 3 ) 2

19. Soil / Groundwater Pollution & Remediation 19 Soil Chemistry of Metals: Cd, Pb, Cr Cd –Water soluble Cd: pH , concentration  –Adsorbed Cd: pH , adsorption  –Insoluble Cd: CdS cab be formed in reduced environment Pb (Most Pb in plant from air-borne Pb (gasoline) –Insoluble Pb (PbCO 3, Pb 3 (PO 4 ) 2, PbSO 4 ): pH , concentration  (acidic pH will release Pb) –Chelation of Pb with chelates in soil Cr –Cr 3+ can be strongly adsorbed on soil –Anionic Cr (i.e, Cr 6+ in the form of Cr 2 O 7 2- and CrO 4 2- ) exist only in weak acid/basic condition

20. Soil / Groundwater Pollution & Remediation 20 Effects of pH on Cu, Cd, Zn, Pb Reactions –Cu(OH) 2 == Cu 2+ + 2OH - Ksp = 1.6x10 -19 –Cd(OH) 2 == Cd 2+ + 2OH - Ksp = 2x10 -14 –Zn(OH) 2 == Zn 2+ + 2OH - Ksp = 4.5x10 -17 –Pb(OH) 2 == Pb 2+ + 2OH - Ksp = 4.2x10 -15 Relationship between metal concentration and pH –lg[Cu 2+ ] = 9.2 - 2pH –lg[Cd 2+ ] = 14.3 - 2pH –lg[Zn 2+ ] = 11.65-2pH –lg[Pb 2+ ] = 13.62 -2pH

21. Soil / Groundwater Pollution & Remediation 21 Soil Chemistry of Pesticides Adsorption Volatilization Leaching & solubility Degradation (p. 496) –Biodegradation –Photochemical degradation –Chemical degradation (hydrolysis)

22. Soil / Groundwater Pollution & Remediation 22 Remediate of Soil Metal Contamination: Use of Lime In certain pH range, increased pH will reduce soluble metal concentrations –use of limestone to reduce soluble metal concentration and therefore the toxicity to plants In some cases, further increase in pH will increase metal concentration in soil solution (why?)

23. Soil / Groundwater Pollution & Remediation 23 Remediation of Soil Pollution Bioremediation –In-situ or Ex-situ Natural attenuation –Use of self purification capacity –Slow, inexpensive On-going studies –Phytoremediation –Composting –Slurry reactors

24. Soil / Groundwater Pollution & Remediation 24 Bioremediation Process by which organic hazardous materials are biologically degraded, usually to innocuous materials such as carbon dioxide, water, inorganic salts and biomass (biotransformation and mineralization)

25. Soil / Groundwater Pollution & Remediation 25 Bioremediation Market Assessment 100 million tons of hazardous waste generate annually One third of over 2 million gasoline UST’s are leaking Over 50,000 historically contaminated sites All federal installations require extensive remediation action Estimated cost of $1,700,000,000,000 EPA consider bioremediation the lowest cost treatment where applicable

26. Soil / Groundwater Pollution & Remediation 26 When Does Biodegradation Occur? When proper conditions exist When appropriate metabolic activity is expressed When there is “contact” between contaminants, nutrients, and organisms When toxicity or preferential utilization does not occur

27. Soil / Groundwater Pollution & Remediation 27 Natural Attenuation Natural assimilative capacity Process by which the indigenous microflora degrades contaminants using ambient levels of nutrients and electron acceptors

28. Soil / Groundwater Pollution & Remediation 28 Phytoremediation Process by which inorganic and organic contaminants are uptaken by vegetation (plants) from contaminated soils. Plants are then removed by biomass (p.492)

29. Soil / Groundwater Pollution & Remediation 29 Soil Slurry Reactor (Zhang et al., 2000)

30. Soil / Groundwater Pollution & Remediation 30 Environmental Chemistry The study of the sources, reactions, transport, effects, and fates of chemical species in water, soil, air, and living environments, and the effects of technology thereon