N 2, O 2 Ar CO mg/l mg/l. Carbon dioxide. Carbon dioxide 4. - Only about 0.035% of air (~350 ppm)
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1 (Carbon dioxide : CO 2 ) Carbon dioxide 4 N 2, O 2 Ar CO mg/l mg/l 30 CO 2 CO 2 carbonate ph Only about 0.035% of air (~350 ppm) Concentration in water higher than expected based on low atmospheric partial pressure of its high solubility Gas (at 10ºC) 1 atm (mg/l) N O CO Carbon dioxide CO 2 CO 2 CO 2 carbonate 5 Carbon dioxide bicarbonate carbonate ph CaCO 3 MgCO 3 ph 6
2 Carbon dioxide CO 2 ph CO 2 carbonic acid carbonate bicarbonate CO 2 carbonate bicarbonate ph Carbon dioxide reaction in water CO 2 (gas) CO 2 (dissolved) <1% CO 2 carbonic acid CO 2 + H 2 O H 2 CO Carbon dioxide reaction in water Inorganic C equilibria carbonic acid bicarbonate hydrogen ions H 2 CO 3 HCO 3 + H + ph bicarbonate 100% (ph of 8.3) ph carbonate HCO 3 CO 3 + H + 9 Note 100% CO 2 for ph< 4.5; 100% bicarbonate for ph 8 and 100% carbonate for ph> 12 10
3 CO 2 supersaturation killer Lake Nyos In the middle of an August night in 1986 in the westafrican country of Cameroon a misty cloud of carbon dioxide bubbled out of a lake and swept silently down the surrounding valleys thousands of animals and 1700 people died, many in their sleep. Gas Estimates at Lake Nyos Possible CO 2 storage 1.45 km 3 Amount of CO 2 stored in May 1987 Estimated CO 2 released in 1986 (Kling, 1989) 0.38 km km 3 (up to 1 km 3 )
4 Remediation of the Hazards Soda pop chemistry 17 18
5 CO 2 and the inorganic carbon system CO 2 CO 2 ( ) carbon carbon dioxide allocthonous (alkalinity),, ph, total inorganic carbon (Nitrogen : N 2 ) Nitrogen 79% (NH 3 N) (NO 3 ) (NO ) Total Alkalinity (Alk T ) = [HCO 3 ] + 2[CO 3 ] +[OH ] [H + ]
6 4 (Nitrogen Fixation) (Azolla) Rhizobium 23 Aerobic bacteria Azomonas, Azobactor, Beijerinckia, Berxia, Methylomonas, Mycobacterium Spirillium Facultatively anaerobic bacteria Bacillus, Enterobactor Klebsiella Anaerobic bacteria Clostridium, Desulfovibrio Desulfotomaculum Photosynthetic bacteria Nonsulfer purple bacteria Rhodomicrobium, Rhodopseudomonas Rhodospirillium Purple sulfer bacteria Chromatium Ectothiorhodospira Green sulfer bacteria Chlorobium (Bluegreen algae) Anabaena 24 Ammonificication ( ) Org. N NH 3 + H + NH 4 + Anabaena heterotroph NH 4 + nitrification 25 26
7 Nitrification NH 3 NO 2 NO 3 2 NH (1/2) O 2 NO 2 + 2H + + H 2 O Nitrisomonas, Nitrosococcus,Nitrosospira, Nitrosolobus Nitrification ph 78 ph Nitrobacter ph NO 2 + 1/2 O 2 NO 3 Nitrobacter Denitrification Denitrification (N 2 ) (N 2 O) (NO) denitrifying bacteria anaerobic bacteria 29 30
8 NH 3 NH 3 Nitrogen ph nitrification denitrification nitrate reduction nitrification nitrate reduction (S; sulfur) S CaSO 4 (gypsum), H 2 S H 2 SO 4 S S epilimnion hypolimnion, S H 2 O 2 H 2 S, FeS 2 SO 4 H 2 H 2 SO
9 S H 2 S SO 4 (pyrite; FeS 2 ) H 2 S SO 2 H 2 S Some major steps in the sulfur cycle include: 1.Assimilative reduction of sulfate (SO 4 ) into SH groups in proteins. 2.Release of SH to form H 2 S during excretion, decomposition, and desulfurylation. 3.Oxidation of H 2 S by chemolithotrophs to form sulfur (S o ) and sulfate (SO 4 ) 4.Dissimilative reduction of sulfate (SO 4 ) by anaerobic respiration of sulfatereducing bacteria. 5.Anaerobic oxidation of H 2 S and S by anoxygenic phototrophic bacteria (purple and green bacteria) Thiobacillus (Methane : CH 4 ) organic gas marsh gas bacteria multistage breakdown complex organic material organic compound of simple molecular structure CH 4 CO 2 O
10 Water Chemistry (The major ions in inland water) ION BALANCE FOR TYPICAL FRESH WATER Major ion concentrations freshwater Anions mg/l Cations mg/l Anions Percent Cations Percent HCO 3 73% Ca +2 63% SO % Mg +2 17% Cl 10% Na + 15% K + 4% other < 1% other < 1% HCO Ca SO Mg Cl 7.8 Na SiO 2 13 K NO 3 ~1.0 Fe +3 ~0.7 Total = ~91.4 anions + ~28.4 cations = ~ 120 mg/l (TDS) (Source of ions),,,,, ( ) oxidation reduction 41 42
11 Carbonate (CO 3 ) anion CO 3 HCO 3 Ca 2+ evaporation Ca(HCO 3 ) 2 CaCO 3 + H 2 O + CO 2 alkalinity CO 3 CO 3 (compound of CO 3 ) CO 3 CaCO 3 CO 3 Ca 2+ calcite aragonite 30 Na 2 CO 3, K 2 CO 3, (NH 4 ) 2 CO 3, Mg(CO 3 ), BaCO 3 SrCO 3 CaCO 3 H 2 CO 3 Ca(HCO 3 ) 2 HCO 3 CO Cl (chloride) Cl halide angal cell Cl Edaphic igneous rock ( ) chloride, soda lite (Na 8 (AlSiO 4 ) 6 Cl 2 ), (magmatic water) Atmospheric volcanic gas HCl Pollution, ( 5 g/l),, NaCl CaCl
12 Ca (calcium) Ca CaCO 3 Ca(HCO 3 ) 2 Ca Silicate, anorthite (CaAl 2 Si 2 O 8 ) CaCO 3 CO 2 HCO 3 Ca Calcite (CaCO 3 ),, Marl CaCO 3 gastropod, clam shells marl Anorthite Sinter Mg (magnesium) Mg Mg silicate nonsilicate Sinter Gypsum Anhydrite Mg silicate forsterite (Mg 2 SiO 4 ) H 2 CO 3 silica, cabonate serpentine (H 4 Mg 3 Si 2 O 9 ) 5Mg 2 SiO 4 + 4H 2 O + 4CO 2 2H 4 Mg 3 Si 2 O 9 + 4MgCO 3 + SiO 2 Ca SO 4 gypsum (CaSO 4.2H 2 O) anhydrite (CaSO 4 ) SO 4 CO 3 calcium CaCl 2 49 Forsterite 50
13 Na (sodium) Na Na aluminosilicates ( ) Saltern lake; Utah Type of sodium lakes 3 1. Salterns lakes NaCl 2. Saline lakes Na 2 SO 4 Aluminosilicate Saline lake; Chile 3. Soda lakes NaHCO 3 Na 2 CO 3 Soda lake; California K (potassium) K K feldspar KAlSi 3 O 8, sodium mineral Leucite (KAlSi 2 O 6 ) Feldspar Leucite Nutrients phosphorus (sediment) 53 54
14 Phosphorus levels in the environment Major factors affecting phosphorus levels, cycling, and impacts on water quality include: Soil properties Land use and disturbance Transport associated with runoff Phosphorus Cycle phospholipid ATP (Adenosine 5' triphosphate) 5(6aminopurin9yl)3,4dihydroxyoxolanyl methoxyhydroxyphosphoryl oxyhydroxyphosphory oxyphosphonic acid phosphatizing bacteria CaHPO 4 [Ca 3 (PO 4 ) 2 ] 57 Where does phosphorus come from? 58
15 Phosphorus external sources Phosphorus internal sources Nonpoint sources ( ) (Watershed) (land use management) (urban and rural) ( ; failing septic systems), Point sources ( ) O 2 > 1 mg/l Insoluble ferric (+3) salts form that precipitate and settle out, adsorbing PO 4 3 O 2 < 1 mg/l (anoxic) ferric ion reduced to soluble ferrous ion (Fe +2 ) allowing sediment phosphate to diffuse up into the water ( ) algal blooms Phosphorus Lake budget Phosphorus cycling major sources Dissolved Particulate Particulate Particulate and dissolved 61 62
16 Phosphorus cycling internal recycling Rapid PO 4 3 recycling Bacterial Algal Zooplankton Phosphorus cycle major transformations The whole phosphorus cycle Nitrogen basic properties Nitrogen, chlorophyll Nitrogen biologically available forms N 2 major source, Blue green algae (cyanobacteria) and anaerobic bacteria Nitrate (NO 3 ) and ammonium (NH 4+ ) major forms dissolved inorganic nitrogen (DIN) Total nitrogen (TN) includes: DIN + dissolved organic nitrogen (DON) + particulate nitrogen 65 66
17 Nitrogen sources NO 3 NH 4+ (power plants, vehicle exhaust, acid rain),, (NO 3 ) (NO 3 and NH 4+ ) (NO 3 and NH 4+ ) hypoliminion (NH 4+ ) Nitrogen toxicity Methemoglobinemia blue baby syndrome > 10 mg/l NO 3 N or > 1 mg/l NO 2 N in well water NO 3 N 2 O and NO x smog,, 67 68
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