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Lec 5: Gases (DO & CO ) and Ph Lec 5: Gases (DO & CO2) and pH •Factors affecting Oxygen Concentrations •Inorganic & Organic Carbon and the Carbonate Cycle Wednesday: Cole, J.J. et al. 1994. Carbon dioxide supersaturation in the surface waters of lakes. Science 265:1568-1570. 1 Dissolved Gases 1. Gases constitute one class of chemical impurities of water: some essential for life, some inert, others toxic 2. Properties of gases governed by both chemical and physical laws 3. Gases tend toward equilibrium between the concentration in the atmosphere and that dissolved in water 4. Equilibrium (saturation) amount of each gas dissolved in water dependent on: a. Pressure (atmospheric pressure, elevation: increasing pressure increases solubility) b. Salinity (increasing salinity reduces solubility) c. Temperature (increasing temperature reduces solubility) 5. Solubility of a gas is independent of the concentrations of other gases in solution 2 Atmospheric vs. Dissolved Gas Concentrations (% by volume) Dissolved Relative Gas Atmosphere in water Solubility Nitrogen 78.08 42 1 Oxygen 20.95 35 3 Argon 0.934 Carbon dioxide 0.033 23 2100 Others 0.003 Nitrogen and Phosphorus are important plant nutrients 3 Oxygen • 90% of water (by weight) but not biologically available or important in this form • Probably the most important single indicator of aquatic conditions for biota • Concentration in water generally expressed as PPM (Parts per million) = mg/l, or as percent saturation: Amount Present Solubility • Determination – DO Probe and meter – Chemically (Winkler method and modifications) 4 Oxygen - Forms and Transformations • 21% of atmosphere is O2 • Aerobic/anaerobic - oxic/anoxic (hypoxic) • Oxygen drives redox (next slide) • Saturation concentration of dissolved O2 depends on atmospheric pressure and temperature • Photosynthesis produces oxygen, respiration consumes it 5 Potential Energy and Redox • Which form of N is preferred by primary producers? • How to they convert to the preferred form? Oxidizing environment Reducing environment Activation energy Activation energy Ammonium Nitrate Net energy yield Net energy yield Nitrate Ammonium Potential energy Going with potential energy Going with potential energy Activation energy Activation energy Ammonium Nitrate Net energy cost Net energy cost Nitrate Ammonium Potential energy Going against potential energy Going against potential energy 6 Factors affecting Oxygen Conc. 1. Diffusion from atmosphere (Often less important than photosynthesis). Diffusion rate depends on: a. Wave action (rate increases with increasing wave action) b. Atmospheric pressure (rate increases with increasing atmospheric pressure) c. Oxygen saturation of water (rate decreases with increasing saturation) d. Salinity (rate decreases with increasing salinity) e. Moisture content of air (rate decreases with increasing humidity) 2. Photosynthesis (Often more important than atmospheric diffusion). May contribute more than 50% of the oxygen in 2 water. Photosynthesis may contribute 5mg O2/cm /day 8 Nomogram for Determining Saturation of Oxygen at Different Temperatures Elev. Pressure 010203051525 (m) (mm Hg) Factor 0 760 1.00 Temperature (degrees C) 500 714 1.06 1000 671 1.13 1500 631 1.20 2000 594 1.28 % Saturation 2500 560 1.36 140 120 100 O 80 10 mg/l O2 at 20 C = 60 123% saturation 50 40 at sea level 30 10 mg/l O at 20OC = 20 Oxygen (mg./liter) 2 10 148% (1.20 x 0 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 120) saturation at 1500 m (~5000 ft) 01 2 34 56 7 89101112 Oxygen (cc./liter) 7 9 Oxygen Losses and Fluctuations 1. Photosynthesis and respiration often result in daily fluctuations in the O2 concentration of surface water a. May reach 200% saturation in late afternoon b. May fall to 50% saturation by dawn 2. Oxygen losses due to: a. Respiration b. Decomposition 3. Oxygen distributed in the water column mostly by currents 4. Summer stratification may limit amount of dissolved oxygen in the hypolimnion 10 0 O O Mid-Summer 1 2 2 2 Oxygen Profiles 3 4 Orthograde 1. Orthograde 5 Clinograde 6 Low productivity Depth (m) 7 2. Clinograde 8 T T High productivity 9 3. Positive Heterograde 10 Increased solubility in the 0 metalimnion due to O O 1 * 2 2 temperature 2 Concentrations of algae in 3 the metalimnion 4 4. Negative Heterograde 5 6 Positive Negative High metalimnetic Depth (m) Heterograde Heterograde respiration and/or 7 8 decomposition T T 9 10 0 5 10 15 0 5 10 15 11 O2 mg/l O2 mg/l O2 Profiles for Shallow Dimictic Lakes • Crystal Lake: Temperature OC unproductive, 0 2 4 6 8 10 12 14 16 18 20 22 24 26 2 4 6 8 10 12 14 16 18 20 22 24 26 28 0 transparent, with 2 Akagi deep photosynthesis 4 Crystal Lake, Wisc. Okono, • Other Lakes - range 6 Japan 8 from moderately 10 productive to highly 12 14 O productive T C [O2]S [O2]S 16 TOC • All lakes except 18 [O2] Adelaide show 0 2 metalimnetic Silver Lake, Depth (m) 4 Wisc. oxygen maxima 6 8 [O2] 10 Note areas of 12 TOC Adelaide Lake, 14 Wisc. DO deficit [O2] 16 [O2]S 18 [O2]S TOC 20 0 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Dissolved Oxygen (mg/l) 12 Development of a Clinograde Oxygen Curve Processes responsible for this pattern? 0 2 Lake Mendota, 4 Wisc. 6 8 Depth 10 (m) 12 IV 14 Aug. 16 18 III II I 20 July June May 22 0 1 2 3 4 5 6 7 8 9 10 11 12 Dissolved Oxygen (mg/l) 13 Productive and Consumptive Aspects of Lake Morphology High volume to surface area ratio lakes Low volume to surface area ratio lakes Productive Aspect Consumptive Aspect What other factors might affect this balance? 14 Carbon • Forms of Carbon • Transformations of Carbon • A General Introduction to Nutrient Cycling and the Carbon Cycle 15 Carbon Dioxide • Generally, the most important source of carbon for photosynthesis • Involved in buffering the pH of neutral and alkaline lakes • The measurement of CO2 in all of its forms is called “Alkalinity” 16 Lake Nyos Disaster • 1700 people and many livestock died near Lake Nyos in Cameroon in 1986 • A survivor reported a 25m high water surge and odor of rotten eggs • Caused by catastrophic release of supersaturated CO2 from the hypolimnion •CO2 probably came from volcanic activity • Landslide or cool weather released the gas • Building up again, using pipes to release pressurized water 17 Carbon dioxide in Solution The O2 Carbon O2 (photosynthesis) Plants respiratory CO Dioxide 2 Plants (respiration) Cycle O2 respiratory CO 2 Animals O2 respiratory CO 2 dissolved Bacteria organic material CO2 non-biological oxidation Organic Carbon Inorganic Carbon (mainly CO 2 ) 18 Forms of Carbon • Inorganic Carbon-bicarbonate equilibrium – Carbon dioxide: CO2 – Carbonic acid: H2CO3 - – Bicarbonate: HCO3 2- – Carbonate: CO3 - + 2- + CO2 + H2O↔ H2CO3 ↔HCO3 + H ↔CO3 + 2H -In which direction will PP drive these reactions? • Organic Carbon 19 Carbon Dioxide Cycle in Lakes CO2 – + = H2O+CO2<—>H2CO3<—>HCO3 + H <—>2HCO< 3<—>CO3 + Phytoplankton (Euphotic Zone) Ca++ H2O CaCO3 Sediments 20 Proportions of the forms of CO2 in Relation to pH Free Bicarbonate Carbonate – = pHCO2 HCO3 CO3 4 0.996 0.004 1.26 x 10-9 5 0.962 0.038 1.20 x 10-7 6 0.725 0.275 0.91 x 10-5 7 0.208 0.792 2.60 x 10-4 8 0.025 0.972 3.20 x 10-3 9 0.003 0.966 0.031 10 0.000 0.757 0.243 21 Proportion of total inorganic C 0.0 0.2 0.4 0.6 0.8 1.0 3456789101112 Forms of CO of Forms CO 2 (H 2 CO 3 Relation to to Relation ) pH HCO 2 in Water in in Water in 3 - p H CO 3 2- 22 Daily Fluctuations in Epilimnetic O2 and CO2 60 360 Sunset Sunrise 50 350 40 340 CO2 CO2 30 330 O2 O (µm) 2 (µm) 20 320 10 310 0 300 1800 2400 600 1200 1800 Time 2318 .
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