Introduction to Aquatic and Marine Geochemistry
Introduction to Aquatic and Marine Geochemistry EPS 103
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April 17 2007 Adding Biology Grand Tour Sarmento and Gruber Internal Cycling in Ocean 20070413 need paper title and final chosen reference 20070413 Adding Biology lnternal Cycles of elements Simple box model representation of systems 20070417 Effects of Biology POTENTIAL TEMPERATURE CI SALINITY uu IO 3 340 542 344 346 0 u I I I I E E 239 5 5 I I I 0 0 LU Lu o a 4 I I I l I I L I OXYGEN LmDIkg NITRATE Lmolkg 100 200 3 0 20 4D I I I I I l I I I A 2 A 2 E 5 I I i I h g 4 I 4 I l I l l I I I I Figure 1 1 Plots of temperature salinity dissolved oxygen con tent and nitrate content as a function of water depth at GEOSECS station 214 in the North Pacific 32 N 176 Wgt Broecker and Peng TOTAL INORGANIC CARBON ArumKg ALKALINITYkaq 2200 2400 2300 2400 25 00 I l I I O quot2 z E E I I I I D 0 Lu In 134 54 I I I BARIUM nmolkg O 00 DEPTH km DEPTH km Figure 1 2 Plots of total dissolved inorganic carbon alkalin ity dissolved silicate and dissolved barium as a function of water depth at GEOSECS station 21A in the North Pacific 32 N 176 W Broecker and Peng The previous 2 figures can be simplified into a simple 2 box system a surface layer bounded by the strongest part of the pycnocline a deep layer below Concentrations TCO2 shallow 2000 umolkg deep 2300 umolkg Alkalinity shallow 2300 uequivkg deep 2400 uequivkg Silicate shallow 15 umolkg deep 150 umolkg Review Terms Thermocline Pycnocline Potential Temperature Potential Density Review Wind Driven Circulation Thermohaline Circulation C14 Age of Deep water 1300 y time scale Atmosphere 760 COZ 90 K POOs in P9 C Pre 1850 Atmosphere C02 540 Pg Fluxes in Pg C y391 70 70 9 DIC FCC and PIC DOC Photosynthesis Dissolved 50 Particulate Organic Par39mquot Diss Org InorganioC 4 and Inorganic Carbon Carbon Respiration 105 to 115 100m quotquotquotquotquotquotquotquotquotquotquot 39quot139539t6391395quotquotiquot I Sinking Particles quot Deep Sea quot39 700 36 000 quot NQ 01 3800 In Sediments 1 Pg 10 5g recipe for plankton light 6C02 6H20 gt C6H1206 602 More exact recepe requirements include NO3orNH3 PO4 Si Ca Fe Co Cd Zn including major nutrients Red eld Model 106CO2 122H20 16HNO3 H3PO4 gt CH20106NH316H3PO4 138 02 or 106C02 106H20 16NH3 H3PO4 gt CH20106NH316H3PO4 106 02 need to add in effects of Temperature Si Fe Co Cd Zn eg Fe39C cellular requrements 139105 for N03 xation Modified recipe for plankton includes lipid pool based on analysis of nutrients and oxygen on shallow isopycnal surfaces 300 m to 1000 m as water flows from Atlantic to Pacific 1 122002 138H20 16HNO3 H3PO4 gt CH2080CH242NH316H3PO4 175 02 or 2 122002 122H20 16NH3 H3PO4 ltgt CH20106CH242NH316H3PO4 143 02 notes 1 Respiration produces NH3 bacteria required to make NO3 Fe required for N03 xation 2 reaction can go either direction Plants will preferentialy x NH3 given the chance H used to balance NO339 may be substituted by cations Understanding Spatial Patterns of Primary Production Review Wind Driven Circulation Coriolis Effect Upwelling California Current Peru Current Canaries Current Benguela Current Equatorial Currents Downwelling GYRES Maps and Sections from Sarmiento and Gruber 60 S V 80 S 20 E 60 E 100 E 140 E 180 140 W 100 W 60 W 20 W 20 E 5 gyres effects of Atlantic amp Arctic rivers seen 20 E 60 E 100 E 140 E 180 140 W 100 W 60 W 20 W 20 E 20 E 60 E 100 E 140 E 180 140 W 100 W 60 W 20 W 20 E Ship Measurements 3 major High nutrient areas Southern Ocean Equatorial Pacific North Pacific 80 S Seasurface phosphate mmol m 3 i I i i i 20 E 60 E 100 E 140 E 180 140 W 100 W 60 W 20 W 20 E Ship Measurements PN systematics approximately 116 Seasurface SiOH4 mmol m393 i i i l i i 20 E 60 E 100 E 140 E 180 mew mew 60 W 20 w Ship Measurements Si is utilized more in southern ocean by diatoms 80 5 Seasurface chlorophyll mg Chl m393 l 20 E 60 E 100 E 140 E 180 140 w 100 W 60 W 20 W 20 E Satellite Chlorophyll NASA SeaWiFS some 100 60 N g 40 v 30 o 335 80 S NPP annual mol rn392 yrquot w 20 E 60 E 100 E 140 E 180 140 W 100 W 60 W 20 W 20 E Ocean primary net production 50 Pg Cyr patterns governed by light and nutrients Ship measured SeaAtmosphere pCO2 difference extrapoated over 30 years positive ocean water has higher pCO2 than atmosphere 40 N S 20 7 39 18 20 N 16 Eq 14 12 20 S 10 40 08 06 ems 7 04 80 3 POC export mol 0 m 2 yrquot 0392 1 00 20 E 50 E 100 E 140 E 180 140 W 100 W 60 W 20 W 20 E Empirical Fit of spare ship obs to Satellite Chl data Export100 max0042min07200078T00806lnchl0433PP From Sarmiento and Gruber key to sections Young Water OLD Water 60 W 10 W 40quotE 90 E 140 E 170 W 120 W ii 39 quot 39 7 POTENTIAL TEMPERATURE ATLANTC SOUTHERN OCT PACIFIC 60 N 30 N Eq 30 S 60 S 60quot8 30 s Eq 30 N 60quotN l Depth m Deplh m SALINITY ATMNTIC SOUTHERN 0C PACIFIC 60 s Depth m Deplh m Depth n1 Depth m CARBON44AMC ATLANTIC Eq SOUTHERN OC 60 S PACIFIC Distance km OLDEST YOUNGEST ATLANTIC SOUTHERN OC PACIFIC Eq 30 S 60 S 60 S 30 S Eq 30quotN 60 N Depth m1 Depth m V ll llllllllllll W SDIC SALINITY NORMALIZED DIC 2002 DICmeas 35 Salmeas EvaporationPrecip effects removed 5 variation salinity normalization not needed for nutrients since pools are much lower Depth m1 Depth m ATLANTIC SOUTHERN oo PACIFIC 6 O N 30 N Eq 30 s eons 60 S sons Eq 30w 60 N o J l r39 I 39 IJ fl l I l I I I J I 39 A x 39 8 J W LI 8 39i H quotx quoti 400 g 1quot W r 3 m M f m C r WKquot r L VN P 3 i ii fj f UVA 39 Lf39 w J m NW j o 4 1 x Y A v V w Jquot f xv 4 T f V W sAlk SALINITY NORMALIZED ALKALINITY 60 N 30 N Eq 30 S SOUS 60 S 30 S Eq 30quotN 60quotN J J Depth m Depth m ATLANTIC SOUTHERN OC PACIFIC 60 N Eq 30quot3 60 S 60 S 30 S Eq 30 N 60 N V Ii V l 7 J Depth m Depth m N and P almost the same Depth m Depth m ATLANTIC SOUTHERN OC PACIFIC Eq 30 S 60 S 60 S 30 S Eq 30quotN 60 N 4i i 1000 2000 7 3000 4000 5000 7 MM 39 g 10 6000 Antarctic Imprint on Deep water of N Pacific is significant Depth m Depth m 800 ATLANTIC 5 1 10000 SOUTHERN OC 60quot5 60 s 15000 Distance km 30 S 20000 PACIFIC Eq 25000 60 N ATLANTIC SOUTHERN OC PACIFIC Eq 30 S 60 S 60 S L J 1 Depth m O 5000 10000 15000 20000 25000 30000 Distance km AOU O2SAT 39 O2 Take home messages from this quick tour 1 Biological effects on the chemistry of the ocean are easily discerned Important to the global C Cycle 2 Correlative analysis of nutrient fields and O2 have given a useful first order view of primary production and remineralization 3 Ocean circulation can mask local effects We study local biological effects by looking at the chemistry and dynamic of particles directly Oceanic DIC 2000 gt 2300 uM 15 range Oceanic POC 01 gt 10 uM factor of 100 range Tour LBNL Building 70A 4405 Friday 1145 and 1245 Mar 20 2007 Carbon System simple to salty lecture notes Ocean detail Sarmineto and Gruber CH 8 or Pilson CH 7 exams term paper topic evals returned Today 20070316 Mid Term Overview Q3 Open System CO2 calculations Q7 C14 question The DELTA notation check web site for refined info from last lecture Today Closed System CO2 calculations Graphical Representation Log C pH diagram Numerical Example F day Titration curve for carbonate system Buffering Open System 002 calculation QB on midterm 102 M solution NaOH a strong base in an open beaker of distilled water pCO2 1035 atm We know pH likely below 10 and above 56 CHARGE BALANCE Na H OH HCO339 2CO3239 substitution of components of 3 in terms of H and HZCO3 using MLE s gt 1O 2 H KWH K1H2CO3H 1003K1K2 H2003H2 consider likely pH range and magnitude of terms on LHS and RHS of equation 102 y 101 10113H 1003x1053x10103x1O5H2 a b c d a ltlt 102b lt1O4 so ignore Can solve quadratic or use a guess guess HCO3 dominates since pH lt K2 102 10113H gt H 1093 check if right guess 102 1O1131O93 1003X1063X10103X10510186 102 1O2131O186 1O2 103927 so pH is a little higher than 93 What would pH be if NaOH added 104 M Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M LogConcentration versus pH Diagram for Carbon log C Source Morel and Herring Principles of Aquatic Chemistry Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M LogConcentrmtipg ygd guis plL mgg gqor Carbon OH 14 pH gt line slope 1 O I I I l I I I I I 2 Hzco3 HCO3 c032 Cll C o 4 quot I I O l 2 I I 6 a H OHquot I b d I I 8 l I I I I I I I I 10 l I l I O 2 4 6 8 10 12 14 OH Source Morel and Herring Principles of Aquatic Chemistry Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 10393 M 10268 M LogConcenh39a smvermasepHpBiagmm or Carbon Case B points aampb Case C 63ltpHlt103 Case D points campd Case E pH gt 103 K2 l l l 2 l I l l 1 C03 Hco log C OH DH Source Morel and Herring Principles of Aquatic Chemistry Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 10393 M 10268 M LogConcenh39a smversusepHpBiagmm or Carbon Case B points aampb Case C 63ltpHlt103 Case D points campd Case E pH gt 103 K2 l l l 2 l I l l 1 C03 Hco log C OH DH Source Morel and Herring Principles of Aquatic Chemistry Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M STEP 1 draw log C pH graph with equal X and Y scaling 0 l l l l l I log C pH Fast Non Mathematical Method for Carbonate System Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M STEP 2 draw log H pH OH pH lines 0 Hl 1 l l l I OH39 2 o quot4quot 07 o 6 8 10 l L l l l O 2 4 6 8 10 12 14 pH Fast Non Mathematical Method for Carbonate System Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M STEP 3 draw vertical lines at log K1 and log K2 63 103 0 W l 1 l l l l 0H 2 I o quot4 39 07 o 6 w 8 10 l L 1 O 2 4 12 14 Fast Non Mathematical Method for Carbonate System Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M STEP 4 draw line at log10CTOTAL l log C Fast Non Mathematical Method for Carbonate System Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M STEP 5 label domains of dominant species 63 103 0 W l 1 l l l I OH39 2 HZCO3 Hco3 303 o quot4 39 ow o 6 8 10 l L 1 O 2 4 12 14 Fast Non Mathematical Method for Carbonate System Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M STEP 6 locate points at pH logK1 and pHlogK2 where HCO3 H2CO3 and HCO3 HCO32 points a and c 03 log units lower than CTline and points b and d 4 log units in this case log K2 log K1 below points a and c 63 103 0 W l 1 l l l I OH 2 HZCO3 Hco3 303 quotquotquotquotquotquotquotquotquotquotquotquot quotlt3quot39quotquotquotquotquotquot3quotquotquotquotquotquotquotquot o quot4 39 m 4log units 0 6 w 8 10 l L 1 O 2 4 12 14 Fast Non Mathematical Method for Carbonate System Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M STEP 7 draw lines with slopes 21012 as appropriate for H2CO3 HCO3 and CO32 63 O 103 log C Fast Non Mathematical Method for Carbonate System Graphical Representation of Closed System at Equilibrium Total Carbon 21 x 103 M 10268 M LogConcentration versus pH Diagram for Carbon Computer generated graph log C OH OH I did the previous graph using powerpoint A pencil and ruler would be as useful Came outpretly close EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry 0 Introduction to light stable isotope geochemistry 0 De nition of isotope Table 1 Commonly studied light stable isotopes their relative nuclide abundances and their approximate ranges in nature Element Nuclides Abundance N Range of isotopic variations Hydrogen 1H 99985 350 to 200 0 2H 0015 Carbon 12C 9889 40 to 0 o 13C 111 Nitrogen 14N 9963 49 to 49 0 1 N 037 Oxygen 160 99759 1 O 0037 30 to 30 0 1 0 0204 Sulfur 32 95081 333 0750 34s 4215 45 to 40 0 363 0017 o Isotope notation Rsam 12 3 5 p l r10 1nun1tsofo Rstd R A 2 6A 1000 RB 63 1000 Q fl Rayleigh fractionation Mm lgt 6 6 AiB A B 10001noca3i2 T T o Isotope standards Element Standard material EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry o Isotope fractionation o What governs isotope fractionation 0 Difference in vibrational energy between a molecule with the heavy nuclide and one with the light nuclide o 339 mm can and the ha1monic approximation l u 539 Molecular potential energy curve Harmonic approximation Em 13Ulw1 012 E nuang R Tquot 39 J atoms Exaggerated spliting in energy levels due to isotopic mass differences I T l V H o Equilibrium vs kinetic isotope effects 0 Equilibrium effects have to do with exchange reactions between different phases or substances at equilibrium C02g H C0aqltgt C02gH13C03 aq 10092 00C 10068 300C 0 Kinetic effects are isotope fractionations that occur when the relative rates of reactions between different nuclides depend on mass 0 Examples of kinetic isotope effects include evaporation diffusion and unidirectional reactions such as photosynthesis o The rate of the organic reaction below is different depending on which nuclide of carbon 12 or 13 occupies the 2 carbon position The ratio of the rates is EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry NAD NADH H H H Hgi WCOOH H SCOA C02 H O H O COASH 12k k Cil Thus with 12C in the 2 position the reaction proceeds to the right at a faster rate than with 13C in the 2 position Generally the difference between equilibrium and kinetic isotope effects can be understood by considering the following diagram 0 O A 000 3A kinetic barrier HO Reactants Energy AH I 00 Products gt Reaction path 0 Equilibrium effects relate to AH the difference in energy between the final and initial states To first order kinetic effects are related to the relative size of the potential or kinetic barrier of a reaction between nuclides with different masses oTr eJrJ of quotquot o uantum mechanical explanation for temperature dependence EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry 5 P Population fraction a 539 10 HT 0 The population fraction depends on temperature in the manner depicted for this simple twostate system This gure illustrates a system which contains two energy states a ground p0 and a single excited state pl 0 At temperatures which make kTltlt80 there are Virtually no particles in the excited state As kTgt80 the distribution of particles between the ground and excited state equalizes Vacuum permitiVity so 8854191012 J39lczm391 I Boltzmann constant k 1380661023 JK391 EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry 0 Topic 1 The oxvgen and hvdrogen isotope svstems in the studv of the 39 39 39 and paleotemperature o What fractionates water in the h dros here How do these processes manifest themselves in nature Craig 1961 gt the meteoric water line 61 86180 10 Cat 1981 gt close to meteoric water line 61 817 i 0086180 1056 i 064 o What other processes affect the composition of water 0 How do oxygen isotopes in rainwater correlate with temperature 0 First measure precipitation and surface temperature and make some sort of correlation Dansgaard 1964 gt mean annual precipitation global correlation 6130quot 0695T l36 Yurtsever 1975 gt Europe and Greenland 880 0521i 0014T 1496 i 021 o If you are interested in the ocean for example you can apply the principles learned above to examine the temperature variance of seawater over time I But where is the paleoseawater you are to measure 0 Examinin ice cores from hi latitude ice sheets 0 Isotopically snow is heavily depleted lt0 relative to seawater I This is a ftemperature altitude latitude o What are the issues with ice core data 0 Seasonal temperature effects where summer precipitation is less negative than winter precipitation o 5180 changes at drill site due to I Changes in latitude temperature and altitude ie as ice builds up or tectonic effects Increaseddecreased storage of 16O in ice sheets as global climate changes I Changes in atmospheric circulation patterns that affect precipitation patterns and sourcespaths of atmospheric moisture I Rehomogenization of snowice due to EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry 0 Meltingrefreezing 0 Vertical air movement 0 Water diffusion as vapor along temperature gradient 0 Thinning of layers due to plastic deformation of ice 0 Cores are difficult to date I Mainly done with ice ow models and correlation of shortterm climatic events in the ice core record with other records o The can39 quot 39 39 ualeothe in the marine 0 Let s examine the ocean and see what effects the isotopic composition of seawater over time o Seawater 5180 and 5D close to zero narrow range of values 0 16OH preferentially enriched in the vapor phase evaporation o Freezing seawater Xicmeawmer N 1002 equilibrium 0 Sea ice has 5180 N 2 0 0 Now ask what can you measure in the geologic record which will preserve the signature of the water you are interested in o The answer biogenic calcite aragonite and phosphate 0 Can write an equation for equilibrium exchange between calcite and water at equilibrium 1010603 H2180 ltgt 1010803 H2160 3 3 Cac 80 K H 180 CaC 0 arw fecalth 10286 ZSOC O r o In order to know the paleotemperature you need to know the ratios of the calcite and the water from which the calcite precipitated You could then fit a fractionation factor and assuming you know the temperature dependence of 0c calculate a temperature 0 This temperature dependence has the general form Ta 1365 6Wc65 6W2 0 Epstein and Mayeda 1953 were the first to come up with a calibrated temperature scale These authors followed up their own work with a revised scale Epstein et al 1953 which was later revised by Craig1965 Epstein and Mayeda 1953 gt oxygen isotopes in oceanic carbonate T 165 4365 6W01465 6W2 EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry Craig 1965 gt revised Epstein and Mayeda T 169 426 6W0136 6W2 Kahn et al 1981 using Horibe and Owa 1972 s calibration T 1704 4346PF 6G 65 0166PF 66 652 where SPF is the 5180 of planktonic forams 5G is the glaciation correction and SE is the watermass effect correction Once we gure out what this dependence is we should be able to measure the isotopic composition of the calcite and come up with a paleotemperature right 0 What about any changes in the 5180 of the seawater from which the calcite precipitated Other factors that affect the 5180 of the sample Salinity which is probably another way of looking at evaporation in more restricted basins is related to 5180 of seawater Nonequilibrium precipitation of carbonate tests I Species dependent Seasonality of shell growth Habitat changes of organism Preservation of shells over time I Rec stallization of aragonite to calcite 39 O O O OO TMWIMCC 1385 45465 6W 00465 6W 2 TWWCC 1704 43465 6W 01665 6W 2 I Decay of organic fraction of shell I Changes in trace element chemistry 0 Also continental glaciations could lock up enough 160 to significantly change seawater 5180 Table 2 The effect of continental glaciation on the 5180 of seawater 8180 0 Present ocean 008 If all continental glaciers melted 060 Maximum continental glaciation 090 MThis range corresponds to a Ni 3 C uncertainty in interpreted mean temperature EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry O O O 0 Table 3 Some oxygen isotope values for various Emiliani 1955 rst applied a correction to the SW value of 7030 for nonglacial times and 04o for glacial times He also suggested that geographic location be used to determine other correction factors such as evapprecip ratios etc The solution to this problem according to marine geochemists is to analyze the 5180 of both benthic bottom dwellers and pelagic surface dwellers foraminifera Kahn et al 1981 o The assumption is that the bottom water temperature is constant during a particular time and that changes to the bottom water purely re ect changes due to continental glaciations since bottomwater temperatures are near a the minimum possible already Thus if you choose a particular temperature to relate to 51 Obemhic you can normalize out any in uence from continental glaciations on 5180563 er I Therefore 818Obenthic 518Owater 818Opelagic 818Ocalcite The other possibility is to analyze mineral phases that equilibrated with each other at the same temperature such as biogenic silica and phosphate 0 The same problems of preservation still apply In the end we have some basic needs for using the calcite geothermometer 0 Continuity of the sedimentary record 0 Welldated intervals or known rates of sedimentation 0 Variation of the 5180563 over time ofthe 39 and39 r Parameter oxygen oxygen C02 EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry m 11h 39 o Isotope fractionation between various equilibrium and kinetic pathways see table 3 0 Carbon isotopes in bulk natural materials 0 General ranges o L A i39 Wm H quot m i r Delaware Bay estuary and the blue crab s feeding habits o Distinguishing photosynthetic pathways in plants Table 4 Carbon isotope fractionation during equilibrium and kinetic processes Compiled from a series of sources Positive A means the heavier isotope is favored in the reaction while negative A signifies an isotopicallylighter product Equilibrium or process AWBC 0 C02 g C02 aq 09 ll C02 aq HC0339 25 C equilibrium 70 90 C02 g C02 1 03 Net diffusive transport of C02 g 44 Net diffusive transport of C02 aq or HC0339 07 Net C02 xation by RUBISCO C3 pathway 30 Net C02 xation by PEP C4 pathway 50 Net C02 production by decarboxylation during respiration large pools 33 to 99 of substrates Net C02 production by decarboxylation during respiration small pools 0 of substrates RubisCO Ribulose biphosphate carboxylase PEP phosphoenolpyruvate carboxylase Some plants have developed a preliminary step to the Calvin Cycle or C3 pathway known as the C4 pathway While most C xation begins with RubisCO C4 begins with a new molecule phosphoenolpyruvate PEP a 3C chemical that is converted into oxaloacetic acid 0AA a 4C chemical when carbon dioxide is combined with PEP The 0AA is converted to malic acid and then transported from the mesophyll cell into the bundlesheath cell where 0AA is broken down into PEP plus carbon dioxide The carbon dioxide then enters the Calvin Cycle with PEP returning to the mesophyll cell The resulting sugars are now adjacent to the leaf veins and can readily be transported throughout the plant The capture of carbon dioxide by PEP is mediated by the enzyme PEP carboxylase which has a stronger af nity for carbon dioxide than does RubisCO carboxylase When carbon dioxide levels decline below the threshold for RubisCO carboxylase RubisCO is catalyzed with oxygen instead of carbon dioxide C4 plants which often grow close EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry together have had to adjust to decreased levels of carbon dioxide by arti cially raising the carbon dioxide concentration in certain cells to prevent photorespiration Common C 4 plants include crabgrass corn and sugar cane Table 5 Nitrogen isotope fractionations during biologicallyrelated reactions From Handley and h n39 enerl emcmarir nnz A39 quot SlRTORVHY 1 Shtm1 Products to vein 7 tel 1s igl Raven 1992 Fractionation factors are composites from a variety of organisms cultured in laboratory or field experiments Process Reaction 0L fractionation factor N2 xation N2 gt NH4 gt organic N 0991 to 10041 N20 reduction N20 gt NH4 gt organic N 100343 Denitri cation NO3 2 N20 1028 1033 N0339 assimilation N0339 gt NH4 gt organic N 10027 to 103 NH4 assimilation NH4 gt organic N 10091 to 102 NO239 assimilation NO239 gt NH4 gt organic N 1007 Nitri cation NH4 gt NO239 1025 to 1035 Diffusion NH4 NH3 or N0339 in solution N 100 NH3 diffusion in gas phase 1018 39 level 0 This is due primarily to excretion processes that deplete the organism ere is believ in light nitrogen 0 Compound speci c analyses can make ner determinations of an organisms food sources and nutritional status 0 Examine the carbon in amino acids in particular the difference between essential and nonessential amino acids 1 ed to be a bulk 2 to 30 enrichment in 15N with increasing trophic EPS 103203 Nov 7 Lecture Stable Isotopes in Marine Geochemistry o Nitrogen represents nutritional state amount of nitrogen recycling or catabolism of proteins for energy in high stress environments 0 Example ofthe Hare et al 1991 pig study 0 Example of the blue crab in the Delaware Bay estuary Fantle et al 1999 For Further Information and the sources for this information 0 O 00 Craig H 1965 Isotopic Variations in Meteoric Waters Science 13317021703 Dansgaard W 1964 Stable isotopes in precipitation Tellus 4 437468 Epstein S and Mayeda T 1953 Variation of 180 content of waters from natural sources Geochim Cosmochim Acta 4 213224 Epstein S Buchsbaum R Lowenstam H Urey HC 1951 CarbonateWater Isotopic Temperature Scale Bulletin of the Geologcal Society of America 62 417 426 Epstein S Buchsbaum R Lowenstam H Urey HC 1953 Revised Carbonate Water Isotopic Temperature Scale Bulletin of the Geologcal Society ofAmerica 64 13 1 5 1326 Emiliani C 1955 Pleistocene Temperatures Journal ofGeology 63 538578 Fantle MS Dittel AI Schwalm SM Epifanio CE Fogel ML 1999 A food web analysis of the juvenile blue crab Callinectes sapidus using stable isotopes in whole animals and individual amino acids Oecologia 120 416426 Faure G 1986 Principles of Stable Isotope Geology John Wiley amp Sons New York Hare PE Fogel ML Stafford Jr TW Mitchell AD Hoering TC 1991 The Isotopic Composition of Carbon and Nitrogen in Individual Amino Acids Isolated from Modern and Fossil Proteins J Arch Sci 18 277292 Kahn MI Tadamichi 0 Ku T 1981 Paleotemperatures and the glacially induced changes in the oxygenisotope composition of sea water during late Pleistocene and Holocene time in Tanner Basin California Geology 9 485490 April 24 2007 Adding Biology Internal Element Cycling in Ocean 20070420 EXPLORING PARTICLE DYNAMICS OPTICAL INSTRUMENTATION TRANSMISSOMETER SCATTERING SENSOR PIC SENSOR AUTONOMOUS FREE PROFILING ROBOTS CARBON EXPLORER CARBON FLUX EXPLORER 20070424 some REVIEW from 20070417 20 RESULTS FROM THE SOUTHERN OCEAN 20070427 REDOX CHEMISTRY Atmosphere 760 COZ 90 J Poms in P9 C Pre 1850 Atmosphere C02 540 Pg V Fluxes in Pg C y391 70 70 9 IIIIIIIIIlII POC and PIC DOC 39 Photosynthesis Dissolved 50 Partlculate Organlc Car39mquot Dlss Org Inorganic CE N 40 and Inorganic Carbon Carbon Respiration 163953910 115 amp 100m quotquotquotquotquotquotquotquotquotquotquot 39quot1395 t6391395quotquotiquot I Sinking Par cles quot Deep Sea 700 36 000 quot NQ 01 3800 In Sediments 1 Pg 10 5g 20 E 60 E 100 E 140 E 180 140 W 100 W 60 W 20 W Ship Measurements 3 major High nutrient areas Southern Ocean Equatorial Pacific North Pacific 80 5 Seasurface chlorophyll mg Chl m393 20 E l 60 E 100 E 140 E 180 140 W 100 W 60 W Satellite Chlorophyll NASA SeaWiFS 80 N 100 50 gquot 40 397 7 77 39 q V r a 53 r V 18 16 80 S NPP annual mol rn392 yrquot w 20 E 60 E 100 E 140 E 180 140 W 100 W 60 W 20 W 20 E Ocean primary net production 50 Pg Cyr patterns governed by light and nutrients 80 3 POC export mol 0 m 2 yrquot V l 20 E 50 E 100 E 140 E 180 140 W 100 W 60 W 20 W Empirical Fit of spare ship obs to Satellite Chl data Export100 max0042min07200078T00806lnchl0433PP Main rule CaCO3 production occurs in waters warmer than 50 and when rliut irelnts are high I 30 N a I 4 80 N g 40 N 95gt 80 S CaCO3 export mol 039 m zyr391 39 0 03 I 39 I I r 1 000 20 E 60 E 100 E 140 E 180 140 w 100 w 60 W 20 W 20 E Empirical Fit to Satellite data 50 40 30 20 10 09 08 07 06 05 04 03 60 S 80 3 Opal export mol Si m392 yr l 39 l 20 E 60 E 100 E 140 E 180 140 W 100 W 60 W 20 W 20 E Empirical Fit to Satellite data HOW can we do better IMPROVED OBSERVATIONS OF BIOLOGICAL PROCESSES LEADING TO CARBON and CaCO3 and opal SEDIMENTATION are possible Views of Primary Productivity and Sedimentation based on Carbon Explorer results see attached pdf 20070424Explorerpdf Concepts that are important to the presentation 1 Light profile is exponential with depth in particle free water the attenuation coefficient Absorbance is 005 m391 for blue and 036 m391 for red I2 Ioe39kz Depth of 1 light in blue is 100 m for red 18 m This explains why chlorophyll absorption is in the blue part of the visable spectrum Maximum solar enery is also at the same wavelength that chlorophyll a absorbes 2 At some depth below the surface light will permitjust enough photosynthesis to balance respiration This is called the COMPENSATION DEPTH wavelength attenuation coefficient DEPTH 10000 10000 06065 00278 04724 00045 08679 00007 02865 00001 00821 00000 00285 00000 00067 00000 00006 00000 Views of Primary Productivity and Sedimentation based on Carbon Explorer results Concepts that are important to understanding the presentation 3 Mixing of the upper layer occurs on various timescales hourly daily and seasonally We can describe mixed layers using the difference of potential density between the surface and depth A change of 001 and 005 usually demarks the hourly and daily depth of mixing 4 Because the mixed upper layer is mixing during the day phytoplankton experience a fluctuating light regime 5 CRITICAL DEPTH is the depth of mixing where integrated phytoplankton photosynthesis just balances the respiration of the community all organisms in the layen menu Assignment 3 Today CO2 and rainwater Due in class Feb 16 2007 Term paper guide lines previously Feb 2 2007 Ocean Circulation of water BampB chapter 1 and lecture overturning aka thermohaline circulation Readings for lecture and next week BampB Ch 3 p62 99 major ions 8 cycle read not empasized N cycle and acid rain BampB 100131 BampB CH4 pp141168 Weathering reactions Feb 6 2007 Large scale differences Ocean vs River Chemistry Why Ocean Storage times majorminor ions Cyclic Salts Beginning Discussion of SourcesSinks Rainwater Chemistry ABYSSAL CIRCULATION 4539 AJ39L39 1353915 39 180 13539 9 V JS W 039 4539l Sn09 AS39E 90quotE 135 EV 180quot 39 135 w 90 w 45 w f FE 23 Schematic flow Vines for abyssa circulaiion The crossr natched areag indiuale remost or produchon or bottom water Adapted from Siomme HY Deep Sea Research 1958 49 CEc guEw g MapHm 779M 1909 MM9mm 0F 9557 M47256 GEM31661147 aw 5 M 545 07 77 6 025m c zv 74 144732 0 775 97owvrc AWE zz oeaasw Mat AW HAVE 55M nu eggsw CyL739 39c739 Lax77 ME ri TM r A Kf gy oavr sf 795 555 WWE 5 9479415 myny ru 0554 194 2094156 wasWu 19IE 552w 5914750 Fae MMM tort55K 146 Principles 0 Ocean Physics Temperature 739 C O 10 20 30 4O Salinity s psu Fig 49 Ternperature saiinity density diagram for seawater over range of normal variations of Tand s This is a crossplot of Fig 45 Adapted from Dietrich 6 Ocean ography An Introductory View 1968 Temperature Salinity Diagram for 5N 32W Atlantic Watermass analysis Concepts Potential Temperature T of water parcel raised to surface without gain or loss of heat externally Potential Density Density of Water moved to the surface wo gain or loss of heat 3939310 4370 I i 39 Atlantic 350 Salinity 5 psu CHEbucPrL ComPosmbm Rage vs OCEAN AND 3T0 19ch 77145 warez Kvalas 05 Z 31 Eekwad LoMPDNENT M MM PFM MM 50le y e TAM Side x 10 HLD IDquot 53xqu Fhlb 5sz1gt3 8319 39quot 72 012 lip 53 18 12539 ngcu d Nod 63 0 a lo 920 S G ll 50 Mg m 01 1300 9y 2 152 59quot 1 all zggo 23 2 00 K1quot 23 00 380 0 1 3970 Ca2 zap 035 900 m o l n H503 3 094 No 2 o 010 it 8054 3 012 4 0 0 00 I E 06 00 lt006xD 3 0 000006 ME 4W1 o 920 2 94 17 5 PER WongMS 4 Mm VOLUME 0 ocsmvs 370 M04 km3 Periodic Table of Elements 3 Vertical Frames of Elements M w m 39 mm in the North Piaei ze Ocean 39 39 quot 39 r E gt2 39r i HE E figure 121 in Sarmiento and Gruber TABLE 219 Logarithms of the Elemental Oceanic Residences Times with Respect to Their River Input log TRIO H He 45 Li Be B C N O F Ne 63 2 70 49 63 45 57 Na Mg Al Si P 8 Cl Ar 77 70 2 38 4 69 79 K C21 Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 67 59 46 4 S 3 4 2 4 5 4 4 4 4 5 4 8 Rb Sr Y Zr Nb M0 Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 64 66 5 5 5 47 4 6 Cs Ba La Hf Tu W Re 05 1r PI Au Hg Tl Pb Bi P0 Al Rn 58 45 63 3 5 26 Fr R21 AC 66 Ce Pr Nd PmlSml EulsdlrleyIHol Er ITml Yb Lul Th Pa U 2 64 Source From The Cl l71iXl39 oleie AnmXpierc and Oceans H D Holland copyright 1979 by John Wiley amp Sons lnc 1979 l39or dziizi sources New York p 159 Reprinted by permission See Holland C WCLIC COM PONEAJTS MN MAIN MEcHews M L5 TgvchLE Kauasruvg 63 6amp4 V Jud I a IVAquot 1 xwaeo l J W am My WM 392 Q v M MMM nLLe EPS103 Feb 23 2007 Asst 5 hand out today Review of Marine Sediments revisit Hydrothermal Carbonate sedimentation Silical sedimentation Summary of inputs and outputs From EPS B C82 Oceans Oct 23 2006 Sediments Sediments The longest continuous memory of the Earth s climate Terrigenous deposits Biogenous deposits 1 Continental margins Calcareous oozes Glacial deposits Siliceous radiolarian oozes Presem manganese Clays Siliceous diatom oozes names H Hydrogenous deposits also How do we learn about Sediments Sounding weights 1880 s Echo Sounders 1940 s Bottom Grabs Camera Systems Gravity Cores Piston Cores Deep Ocean Drilling Ships Glomar Challenger J OIDES Resolution not the CIA boat Glomar Explorer Piston Core Longest Piston Core 30 m Marine Sediments are up to L L quot 2000 m thick b c d e Piston Cores and Deep Sea Drilling Sediment Library of the World s Oceans b H quota hquot E b K Woods Hole Glomar Challenger I Scripps J OIDES Resolution OSU 5 Lamont Core Sampling Time to Settle Type of I I Particle Diameter Settling Velocnty 4 km 25 ml Boulder 2256 mm 10 in Cobble 64 256 mm gt2 12 in Pebble 4764 mm 16 2 12 in Granule 2 4 mm 112 16 in Sand 00622 mm 25 cmsec 1 insec 18 days Sill 0004 0062 mm 0025 cmsec 1100 insec 6 months Clay lt0004 mm 000025 cmsec 50 yearsa Table 51 size counts heavier things fall out quickly Fecal Pellets Accelerate Transport of very Small Particles to the Deep Sea What are Sediments Terri ginous 44 Rivers Dust Volcanic Ash Biogenous 55 Calcium Carbonate Siliceous Hydro genous l Formed locally by Terrigenous deposits Biogenous deposits H Hydrogenous 39 39 r C Continental margins Calcareous oozes depositsalso Chemlcal reacuons I Glacial deposits Siliceous radiolarian oozes presenumanganese Clays Siliceous diatom oozes WWI e g Mn nodules Comsogenous from outer space Sources of Terriginous Sediments quot 1 Mississippi River Delta Submarine Canyons Eg Bay of Bengal Indian Ocean off Congo Atlantic lI 2lt1Cahyon 39 A n Sherneak A heads Conhna altlt 3 shmf 7 39 l A quotV A J Continental K yopey 39 Distributionquot quot channelf T arbidity Flows water sediment mixture density 13 gCC gt seawater at any depth N Atlantic 5 Saharan Dust What are Sediments Terriginous 44 Rivers 4 Dust 39 I a Volcanic Ash 39 Biogenous 55 F Aquot Calcium Carbonate quot Siliceous Hydrogenous 1 Formed locally Terrigenous deposits Biogenous deposits H Hydrogenous r r C t39 t i C depos39t l chemlcal reactlons E J1 J 39quots s iii i ii iian prese tirani ganese eg Mn nodules Clays Siliceous diatom oozes 0d 95 Comsogenous Two Vlews Taxonomlc vs Process from outer space Big news in 1977 Chemosynthesis fueled food web discovered at midocean rthermal enfgsv 1 ms pasesutlile x mlhe Science that led to discovery was based on geophisics and geochemical Bottom current Chimney Precipitation 4 4 FeOOH lInO2 PreCIpItatIon S d t t CaSO4 Has 8 Imen a ion Seawater seepage H28 in water I Z r V 1 i it Basalt Basalt x Pecipitatigt X FeSFeSzCuFe82 J V x 350 C 660 F 350 C 660 F o zucs BrooksCole 7 Thomson questions Original research questions What causes anomalously cool sediment temperatures near mid ocean ridges What explains unequal residence times for elements like Mg Hmothesis Flowing seawater cools and reacts with hot rocks at mid ocean ridges A saltwater plumbing syslem UN39TED STATES N THE GALAPAGOS RIFT a boundary l All between separating plates of oceanlc crust viogejafnl39 lava erupts cools and cracks Cold seawater AMERICAN penetrates into fractures and growing hot drops off some elements while picking up others man ganese and silicon from crustal rocks Rising through ssures the hot water ows from the sea oor where the metal oxides precipitate or separate out M CARIBBEAN BLAKE l I I SOUTH AMERICA BASEECLILON CLAMBAKE GARDEN 39 N CLAMBAKE ll OYSTER OF EDEN 7 DEAD BED n In l39AlN INL R AND SLALL MULHL lBl39LDWv DY WILLIAM H B NAIIUNAL GLUK NAI39HH MU DWlSlUN ONDV a National Geographic Alvin Submersible sed for first vents exploration Crew Light sphere TV camera Main ballast Variable ballast Film cameras Viewing port Robot arm Sample Batteries basket Crabs led Alvin to the vents Search that may have taken weeks look only days Chemosynthetic Primary Production HZS xed by bacterial symbiont leads to Chemosynthetic pn39mary production Which feeds the host Bottom current Chimney Precipitation 39 FeOOH Mn02 PreCIpItatIon S d t t CaSO4 FeS 6 men a Ion Seawater seepage H28 in water 7 5 2 X a of XBasalt Precipitation z FeS FeSz CuFeSz J V I 350 C 660 F I 850 C quot 660 F 2005 BrooksCale Thomson Huge clams discoverd CI am Bake gt 1 quotVs Whal happens lo the community when the vents slop venting What are Sediments Terriginous 44 Rivers 4 Dust 39 I a Volcanic Ash 39 Biogenous 55 F Aquot Calcium Carbonate quot Siliceous Hydrogenous 1 Formed locally Terrigenous deposits Biogenous deposits H Hydrogenous r r C t39 t i C depos39t l chemlcal reactlons E J1 J 39quots s iii i ii iian prese tirani ganese eg Mn nodules Clays Siliceous diatom oozes 0d 95 Comsogenous Two Vlews Taxonomlc vs Process from outer space From Germain and VonDamm 2003 60 E 120 E IBUquot 120quot W ofquot W lt7 Global Metalliferous I AHFMMH 2333 10101 Sediment Distributions Al no0 Nu dam 20 S 40 S 60 S 60quot E 12039quot E 18039 120quot W 60 W 0 80 N 60quot S Figure 2 Global map of the A1 Fe MnA1 ratio for sur cial marine sediments Highest ratios mimic the trend of the global MOR axis after Bostrom et 11 1969 Analysis Reveals The Process What are Sediments Terri ginous 44 Rivers Dust Volcanic Ash Biogenous 55 Calcium Carbonate 39 Siliceous Hydrogenous 1 Formed locally Terrigenous deposits Biogenous deposits H Hydrogenous r r c r t I c I depos39t l Chemlcal reacuons g Gaizlleeorigms S izzgeuosuligzazlrian oozes Presel39lltjgassganese eg Mn nodules Clays Siliceous diatom oozes WWI Comsogenous from outer space LamontDoherty Geological Observatory yearbook 1974 Calcium Carbonate in Sediments Ocean Carbon Chemistry Depth productivity patterns of CaCO3 organisms Antarctic ATCUC CaCO3 accumulates above CCD CaCO3 dissolves below CCD Caco3 is more soluble in colder and hi her ressure water TWO Concepts Water Calcium Carbonate Saturation Depth Sediments Calcium Carbonate Compensation Depth Calcium Carbonate Compensation Depth The depth at which the rain rate of CaCO3 equals the dissolution rate of CaCO3 Easily seen in marine sediment color CCD is deeper than chemical saturation depth More supply gt deeper CCD Explains Snow line seen in sediments Photos from Face of the Deep Heezen and Hollsler 197 31 08n13 45w 27 Gen 14 36w 28 36n 15 58w 23 O1n 40 27W North Atlantic Sediments Biogenous 55 Carbonate Seds Productivity limited to waters gt5 0 Depth important Siliceous seds Coldest waters Dominated by diatoms Mid ocean ridge Mean position oi rill valley Biogenous deposits H E Calcareous oozes I Siliceous radiolarian oozes Siliceous diatom oozes a Figure 813 Distribution of taco in deepsea sediments of the Atlantic Ocean Note that Hm high shallowest dcp atop the ntrations are heated m the Ridge A cr P E Biscztyc V Kolla and K K Turekitul Distri on of Calcium Carbonate in Ieprintezl by pprmission of the p J of CaCO3 Sediment abundances reflect the topography of the seafloor and productIVIty patterns Siliceous Sediments Diatoms predominate in coldest waters Siliceous Radiolaria 2 Living Organism Siliceous Shell From 0 R Anderson Radiolaria Springer Verlag 1983 Summary of Sources and Sinks Berner and Berner CH 8 discussion T813T820 know the big picture CI TABLE 813 The Oceanic Chloride Budget Rates in T9 Cl lyr Present Day Budget Inputs Outputs Rivers natural 215 Net sea air transfer 40 Rivers pollution 93 Porewater burial 25 Total 308 Total 65 Long Term Balanced Budget Inputs Outputs Rivers 215 NaCl evaporative deposition 163 Net sea air transfer 40 Pore water burial 12 Total 215 Note Tg 1012 g Replacement time for C1 is 87 million years Longterm average Cl Concentration gt O Ff Time gt Figure 812 Schematic representation of change of chloride Cl concentration in seawater with geo logic time Sudden drops are due to the rapid precipitation of NaCl in evaporite basins IF Adkins DP Sdzmg Earth and Pianetargv Science Letters 316 quot2003 109 123 1239 Cl 9119 931 CI HIKE 934 CI 9M9 1925 1935 1945 1955 19 1941 195 196 197 1935 1955 1975 1995 D I I x I x I 6 I n I x I x I x I x I x I 4 a 1 4 0 0 39 o O n 0 1 39 1 C x I 1391 50 1 f q 3 C I 1 0 5 a o 4 O i r loo 4 439 393 4 O 5 C o 0 4 l I l 39quoti D 150 A o O a o o 4 o a o 39 O I 39 0 200 quot u C g o C O l W A o B 0 C 250 Pore water Cl reveals glacial to post glacial salinity changes
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