1. Water chemistry overview 4 Oct 2001 Announcements –Canoe trip!! –Exam next Wednesday –College certified drivers? Today's lecture –The idea of budgets –Factors influencing chemical composition of freshwater –Some important ions

2. Budgets Surface Inflow Wind-blown particles Evaporation Surface Outflow Groundwater discharge Groundwater recharge Sedimentation Precipitation Internal cycling

3. Internal cycling driven by Seasonal changes in biological demand Food web dynamics Seasonal changes in the chemical environment (usually oxygenated/not oxygenated) Seasonal weather changes Availability of limiting nutrients Internal cycling

4. (Aquatic) Biogeochemistry Biogeochemistry is chemistry in an environmental context that considers the biology, geology, and chemical interactions of elements. Biogeochemistry focuses on the cycling of substances between living (biotic) and non-living (abiotic) components of ecosystems. (see Schlesinger, W.H. 1997 Biochemistry for more information about biogeochemistry)

5. Salinity Salinity: summed concentrations of the major cations (+) and anions (-) in the water (mg/liter or meq/liter) Major ions = concentrations > 1mg/liter Conductivity (specific conductance): surrogate measure of salinity, measures the ease by which an electrical current passes between two electrodes submersed in the water (microSiemens (  S)/cm at 25  C) Total dissolved solids (TDS): dry a filter of the water sample; TDS= change in weight of filter containing "stuff" in the water. (not accurate)

6. Factors determining the occurrence of an element 1.Occurrence and forms of elements in water 1.Solubility 2.Disassociation 2.Major source pools 1.Atmosphere (dry/wet deposition, etc) 2.Lithosphere (rocks) 3.Biosphere (humans…) 3.Biological demand (e.g. limiting elements) Liebig's Law of the Minimum: CHOPKN Environment10050 51025 Organism5025 5120

7. Lithosphere contribution to major ions

8. Other terms "Soft water" low salinity (~conductivity) often in drainages with acidic igneous rocks (e.g. granite) "hard water" high salinity, due to large concentrations of carbonate (CO 3 = ), usually from the the drainage of calcareous deposits (e.g., limestone)

9. Proportional occurrence controlled by: Types of minerals in the area Atmospheric inputs Evaporation vs precipitation

10. Ion concentration (salinity) lake space Note: simplification that works best at global scale At small spatial scales, precipitation, evaporation, and climate are similar, so differences in geology predominate Salinity (TDS) (mg/l) Dominant ions Precipitation or runoff Low High CaHCO 3 NaCl

11. Dominant ions On average… Ca 2+ > Mg 2+ > Na + > K + HCO 3 - > SO 4 2- > Cl - Mostly rock-weathering In rich agricultural systems, NO 3 - can be important (> 1mg/liter) P,N,Fe and trace elements (micronutrients) are biologically important (although unimportant in terms of total ions)

12. Exceptions Ocean-derived spray and rain increase Na + > Mg 2+ Rock-weathering sequence is less applicable to small drainages (local precipitation) Acidification leads to H + >  Al ions > Ca 2+ > Mg 2+ Local applications of road salt (NaCl) and fertilizers increase SO 4 -, Cl -, NO 3 - and decrease HCO 3 - Inter-year variation and climatic signals (= changes in evaporation rates or precipitation)

13. Changes in ions Conservative ions: little change over time (Mg 2+, Na +, K + ) Dynamic ions: concentrations are influenced by organism metabolism (HCO 3 -, SO 4 -, Si, Fe, Ca 2+, P, N) ==> Biological demand

14. Calcium (Ca 2+ ) From rocks Critical for membrane ion exchange Can limit the distribution of organisms that use Ca 2+ in building exoskeletons or shells (e.g. crayfish uncommon at [Ca 2+ ]< 2 ppm) Interacts with CO 3 - (carbonate) to form CaCO 3 (= whiting or marl) in the presence of high levels of photosynthesis (loss of CO 2 )

15. Annual Calcium distributions

16. Silica From rocks (igneous) Found in many forms High biological demand, primarily from diatoms (to build frustule), also sponges and some macrophytes

17. Diatom (algae) frustules

18. Distribution of silica (Si) under stratified conditions

19. Annual Silica Oligotrophic hardwater lake

20. Given the above isopeth plot of calcium distributions in Wintergreen Lake, 1. plot the Ca conc. vs. depth profile for mid-August 2. relative to that Ca profile, sketch in plausible temperature and oxygen profiles (say max O 2 is 8 mg/l and max temp is 25 o C) 3. give a plausible explanation(s) as to the mechanisms that increase calcium concentration in the water column during the winter months. Question of the day: