1. Lectures 5 Geosc 040 Chemical Properties of Water --The Wonder Substance! Inputs, Outputs and Residence Time Today’s music: Into the Ocean Blue October Thanks to Darien H. Ocean Salinity Map The Elements Lyrics by Tom Lehrer Ocean Man By Ween Thanks to David D.

2. Lecture Review Questions:Lecture Review Questions: TA Office Hours (T & W 11-12) Homework 1 due on Thurs. (30 th ) by 11pm Cell Phone Recycling A landcane over Australia Thanks to Justin D. http://earthsky.org/earth/a-landcane-over-australia …warm-core cyclones

3. Hurricane Tracks

4. Sea Surface Temperature & Latent heat are key factors in Hurricane development and sustainability.

6. Warm water is the energy source for hurricanes energy

7. Warm water is the energy source for hurricanes energy 0 200 400600800 Heat input (cal/gram) Temperature (°C) 150 100 -100 50 0 -50 Liquid water Ice Vapor Latent heat of evaporation 540cal/gm

8. Chemical Properties of Water --The Wonder Substance! Inputs, Outputs and Residence Time

9. Cl -, Na +, S0 4 -2, Mg +2, Ca +2, K + >99% of salt in sea water HC0 3 -2, Br -, Sr -2, B +2, F - (with these, 99.99%) http://www.webelements.com/ Seawater is essentially an NaCl solution (saltwater)

10. For example, exchange of Magnesium (Mg) in seawater for Ca in ocean crust supplies excess Calcium Difference in chemical compositions between rivers and ocean --reflects sedimentation (precipitation) processes --other inputs/exchanges, such as basalt-seawater reactions at midocean ridges Rivers vs. Other Sources

11. Evaporation plays a big role in Surface Water Salinity ocean chemistry: A balance of inputs and outputs 37 ppt 30 ppt Surface water salinity

12. We’ve already examined why water is a powerful Solvent, now let’s look at the whole picture Can we explain ocean chemistry using the inputs of rivers alone? ocean rivers atmosphere rock weathering

13. Outputs compete with Inputs to shape the chemistry of seawater Ocean Chemistry and the Geochemical Cycle The Ocean has Both Inputs and Outputs Outputs include: 1--sea salt aerosols 2--biogenic sediments (biological processes); deposited on ocean floor (CaCO 3, SiO 2 ) 3--inorganic sediments (precipitates, evaporites; adsorption) 4--interaction of seawater with hot basalt (Mg and SO 4 "sink”)

14. Outputs: Seawater Evaporation in isolated basins. These sediments (“evaporites”) provide a record of seawater chemistry

16. Salt from the Sea Dead Sea Salt, Evaporation! At work

17. Pay attention to the sequence, from the open sea, first calcite … and eventually Halite!

18. The Grand Geochemical Cycle: Residence time The average time that a substance remains dissolved in seawater We call this the “residence time” of an element or substance where Input rate= average concentration in rivers (kg/km 3 ) x river discharge (km 3 /yr) Let’s consider: We will see how this works: first for water, then for total salt, and, finally, for some individual elements. These calculations give us insights into how the system works Residence Time (yrs.) = Total amount in seawater (kg) Input rate (kg/yr)

19. How long does it take to cycle ocean water through rivers and back again? Residence time of water in the ocean Volume = 1.4 x 10 9 km 3 River Influx = 3.7 x 10 5 km 3 /yr t = Volume / Influx 1.4 x 10 9 km 3 3.7 x 10 5 km 3 t ≈ 4000 years t =

20. Residence Time: total amount divided by input rate For Coconuts on the beach: 10 coconuts fall on the beach each day There are generally 20 coconuts on the beach The residence time for coconuts on this beach is: A) 1 day B) 2 days C) 0.5 days D) 20 days

21. The Grand Geochemical Cycle How much time to make the ocean salty? about 5 x 10 22 grams of dissolved solids in ocean rivers bring in about 2.5 x 10 15 gm dissolved solids per year --think about it! Should only take about 2 x 10 7 years (20 million yrs.) to bring oceans to present salinity --but we know oceans are 3.8 billion yrs. old Assuming: rivers have kept approx. same input through time oceans have kept approx. same composition through time This confirms that there must be output of material from ocean!!

22. Cl 80 million yrs. SO 4 9 million yrs. Na 60 million yrs. Ca 1 million yrs. Mg 10 million yrs. PO 4 100 thousand yrs. Typical Element Residence Times The Grand Geochemical Cycle Don’t worry too much about absolute numbers, but be able to explain why Cl residence time is so much longer than, say, that of phosphate

23. The Grand Geochemical Cycle Residence time is inversely related to extent of involvement in chemical reactions in the ocean Na and Cl primarily precipitate as evaporite deposits (infrequent events over geologic history). Bio-inert Ca used by organisms to make CaCO 3 (calcium carbonate) skeletons PO 4 used in biological cycle (organic matter production)--this is a nutrient element. Biolimiting

24. Was the Chemistry of the Ancient Oceans the Same as Today? We can use ancient evaporite deposits to tell us how ocean chemistry changed through time (different sequence of minerals precipitated) We also can use the chemistry of “brine” inclusions in the evaporites to constrain elemental ratios of major elements in seawater through time. New data suggest that ocean chemistry has changed a bit through time. Perhaps this reflects changes in ocean spreading rates and cycling of seawater through hydrothermal systems! We can use ancient evaporite deposits to tell us how ocean chemistry changed through time (different sequence of minerals precipitated) We also can use the chemistry of “brine” inclusions in the evaporites to constrain elemental ratios of major elements in seawater through time. New data suggest that ocean chemistry has changed a bit through time. Perhaps this reflects changes in ocean spreading rates and cycling of seawater through hydrothermal systems! Time (billions of yrs) Ocean Salinity 35 0/00

25. Phosphate has a shorter residence time than most major elements in seawater because… A. It has an atomic mass that is much less than all other elements B. It preferentially forms inorganic minerals when seawater evaporates C. It is quite volatile and goes easily into the atmosphere D. It is cycled very rapidly by organisms because it is essential to their metabolism E. None of the above

26. Ocean’s Chemistry and The hydrologic and geochemical cycles Outputs compete with Inputs to shape the chemistry of seawater

27. Ocean Chemistry is a balance between inputs and outputs: A) True or B) False

28. Seawater salinity: Which is/are True? A. The most abundant element dissolved in seawater is Cl B. The element sodium is present in table salt and it is dissolved in seawater C. The salinity of ocean surface water is generally higher than that of deepwater D. All of the above E. A and B

29. Seawater Chemistry Which of the following are true: A.Evaporation reduces the salinity of seawater B. The average salinity of seawater is 70 oo/o C. Mineral deposits, such as halite and gypsum represent outputs for chemicals in the ocean D. The geochemical cycle includes wash, spin, and rinse E. B and C

30. Gases in Seawater Nitrogen (N 2 ) 78.08 Oxygen (O 2 ) 20.95 Carbon dioxide (CO 2 ) 0.03 (365 ppm) Argon, Helium, Neon (Ar, He, Ne) 0.95 % in atmosphere

31. Gases Dissolved in Seawater Gases are soluble in seawater in proportion to their atmospheric concentration --Gas Exchange Gas exchange is enhanced by mixing and biologic processes

32. Solubility (amount that can be dissolved) 1) Depends on temperature and salinity of seawater Decreases with increasing Temperature Decreases with increasing Salinity 2) Helped by wind-mixing of surface layer Important for oxygenation of seawater and CO 2 uptake from the atmosphere Important for fishes and other aerobic critters. Gasp! They need Oxygen to Breathe! For Gases Dissolved in Seawater

33. Solubility of gases in seawater is controlled by temperature (and also by salinity) These curves reflect maximum amount that can be held in solution under these conditions

34. Cold water holds more gas in solution Pepsi

35. Solubility of Gases in Seawater A) Gases dissolve more readily in warmer water B) Cold freshwater can dissolve more gas than warm saltwater C) Fishes need oxygen to live and they get that by breaking O molecules from H 2 0 D) A and B E) B and C

36. What controls variations in oxygen and carbon dioxide with depth in the ocean?

37. What controls variations in oxygen and carbon dioxide with depth in the ocean?

38. Dissolved Gases in Seawater more oxygen in surface waters less oxygen in deep waters Indicates consumption of dissolved oxygen below surface waters less carbon dioxide in surface waters more carbon dioxide in deep waters Indicates a process that creates carbon dioxide in deep waters Depth profiles of dissolved oxygen and dissolved carbon dioxide

40. General Classification of Water Masses Why is ocean water stratified into these layers? What are the characteristics of each of these regions? Why do we care?

42. Density of Seawater Salinity (S) - Temperature (T) - Density Diagram note dual effects of S & T typical range of seawater S & T Define Sigma t :  t = (Density-1.0) x 1000 For example: seawater with a density of 1.026 would have  t = 26 We'll use this diagram to differentiate water masses Increasing Density