Reconsidérer les flux continent-océan

Revisiting land to ocean fluxes

Reconsidrer les flux continent-ocanCatherine Jeandel& Eric Oelkers (2014)CNRS, LEGOS, Observatoire Midi-Pyrnes, Toulouse UniversityCNRS, GET, Observatoire Midi-Pyrnes, Toulouse University

Seminaire LEGOS, 7 novembre 2013Thank you to: K. Tachikawa, F. Lacan, B. Peucker-Ehrenbrink, M. Jones, C. Pearce, M. Grenier

With this talk, I will propose you our recent thoughts regarding L to O fluxesBefore starting, thanks; This issue is Geotraces /IMBER and LOICZ relevant1Weathering Processes.Chemical Weathering

OceanDissolved loadMechanical Weathering or Denudation

Particulate TransportTwo main processes are weathering the earth surface: chemical and mechanical..2Global mass fluxes to the ocean

Solid flux = 30 times the dissolved one= 50 times the atmospheric oneWeathering processes yield a dissolved flux of 1 GT/Y , bedload 10, Suspended one 20all together the solid fux annually discharged to the ocean is 30 times the liquid one3eNd oceanic distribution follows the general circulation(in the modern ocean as in the sediment)But its concentration doubles onlyAlong the general oceanic circulation

-15Lacan et al., Chem. Geol., 2012Nd paradoxField Observations (1)

-3.8Nd concentration isonly doubling Lets start with the tracer which clearly revealed that land to ocean fluxes had to be reconsidered. Here is represented (purple arrow) the simplified scheme of the general oceanic circulationepsNd values are superimposed, they represent the average atlantic and average north pacificalso the gradient is less strong than on the continent, there is a gradient. Explaining it requires to add a huge amount of Nd to the seawaterwhich is not reflected in the concentration variation which only double between here & here4Field Observations (2)Imbalanced Nd oceanic budgetDust + river inputs : not sufficient

Missing term: river solid load and/or sediments deposited on the marginsLacan&Jeandel, 2001;Tachikawa et al, 2003

This map here shows the distribution..along the margins, represented as epsNd (a dfinir) . It shows that values around north atlantic.So, when weathered one can easiliy imagine that they will not introduce the same coulour in the ocean5Field Observations (4)BOUNDARY EXCHANGE- quantifiable using Nd IC- invisible with concentrations only

FRFAFBEBE is THE major source term (>95% of the total : 1.1 1010 g(Nd)/an).

Continental inputs & margins: major for Nd(only 3% dissolution)And for the other chemical elements?

Lacan &J eandel, 2001, 2005Van der Flierdt et al, 2004Carter et al, 2012Rickli et al, 2009, 2011Grasse et al, 2012Wilson et al, 2012Grenier et al, 2013/Arsouze et al, 2009Nd paradox+ several observations as the one observed for AAIW at different oceanic places conducted us toi propose that process controlling Nd at the continent/ocean interface is BE6StrontiumOcean 87Sr/86Sr is homogenous at 0.70916

The primary controls were accepted as dissolved riverine input (87Sr/86Sr 0.7136) and hydrothermal exchange (87Sr/86Sr 0.7029)

However, the unradiogenic flux is a factor of 3 too low to balance the inputs

Therefore, part of the story is missing (as for Nd oceanic budget)Field Observations (5)Lets now discuss Sr oceanic budget. Because Sr is definitely more soluble than Nd, we can expect a different pictureFirst of all, it is clearlky moer homogeneously distributed. HOWEVER.7Strontium Imbalance: hypothesesCurrent riverine fluxes may be elevated due to a recent glaciation (Vance et al., 2009)

Subsurface weathering of volcanic islands are not included (Allgre et al., 2010)

Volcanic particulate riverine material could also contribute unradiogenic SrField Observations (6)What are the hypotheses that could explain this Sr missing term?8Sampling in Borgarfjrur estuary(Morgan Jones current work)

Field Observations (7)I will show you now results from field observation(again). Here we are in an icelandic estuary. Samples for Sr isotopes were collected at all these points9Field evidence of particulate dissolution in the ocean: Borgarfjordur Estuary (1)

Estuary water as a function of salinitySr87/Sr86 as a function of salinityField Observations (8)Results are reported now. Left: Cl concentration = f(km from the river). The salinity front occurs between 6 and 8 kmRight: Thats also where the Sr 7/6 ratio strongly increases!10Field evidence of particulate dissolution in the ocean: Borgarfjordur Estuary (2)

Sr87/Sr86 in estuary water as a function of river water fractionSr87/Sr86 attributable to particulate dissolution

50% of Sr from dissolution of particulatesField Observations (9)As for Nd, dissolution of lithogenic material is occuring at the land/ocean interfaceLefts: distribition of the 7/6 as a function of the river content in sw.right, comparison between the fluid mixing model and what is observed in the estuary: the excess of Sr is hudge and could be attributed to the dissolution of basaltic particles11

Silica budget (Mediterranean Sea) 106 Moles/y

Durrieu de Madron et al, 200951,000-127,000288,000- 424,000Siout = 2 to 8 x (Si in)Total ext. inputs = 25,000-126,000Si missing = 35,000-348,000Total dissolved river input = 24,300-118,700Total Atmospheric input =709-7,350Field Observations (11)Still in the Med Sea, more puzzling perhaps is the Si budgetGibraltar12Source of the Si missing?Range required: 3.5 1010 3.4*1011 moles/y

Total river solid discharge = 0.73 109 T/y (Ludwig et al , 2003)

Dissolution of only 1% of this flux 8.3 1010 mol/y SiO2Same result considering

Release from 1% of the first 10 cm of sediment deposited on the margins (consistent with Trguer and de la Rocha, 2012)

Field Observations (12)What could be the source of this missing Si?13Fe Particulate/Dissolved fluxParticulate transport dominatesthe flux of most metals to the ocean(Oelkers et al, 2011)

The release in seawater of even a tiny fraction (~1%) of this material deposited on the shelf/margins mayimpact oceanic isotopic & element budgets (Jeandel et al, 2011, Jeandel&Oelkers, 2014)

Fe

NdSiSrField Observations (14)First Intermediate conclusionThParticulate/dissolved fluxI am now over with the field observations and this graph resumes that 14QuestionsProcessus: Desorption or Dissolution?

Which phase (Fe-Mn coating) or mineral (primary or secondary)?

Kinetic?

The question now is related to the processus yielding this releaseIn order to face this issue, we realised some batch experiments15Batch experiments(Jones et al, 2012a,b; Pearce et al, 2013)Sediment samples were mixed with open ocean seawater (water of southern origin, eNd = -9.6)Marine top core from Kerguelen plateau (station C1, eNd = -1.4)Estuarine sediment from SW Iceland (eNd = +7.2)Riverine bedload Sediment from SW Iceland (eNd = +7.5)

30 l SW1g/l4 monthsSr, REE, Si aliquots taken weeklyNd IC aliquots taken every 2 weeksBatch reactors-9.6-1.4 to +7.5

Experiments (1)The principle of our experiments is resumed here16Jeandel et al; Traces and tracers, Lige, 2011Hours

1 monthInitial Sw value = -9.6-1.4KerguelenIceland Riv. 7.2

HoursIceland Est.ISOTOPENd results (Pearce et al, 2013)

CONCENTRATIONIC: Nd rapid release (0.2 to 2% of Nd contained in the KER basalt)

Cc: Nd scavenging after release: secondary phases =

REE phosphatemineral rhabdophane (REE(PO4)nH2O) ?Experiments (4)Lets now have a look with what we obtained for Nd parameters17Silica release?5CSi(OH)4 x 1025CSi(OH)4 x 20Experiments (6)Moreover, here are the results obtained for silica(temperature dependent!)18

Experiments (7)In the framework of these experiments, we settled different means to observe the particles (and not only the seawater) here are EDS/EDAX results19

Experiments (8)OlivinePlagioclaseXRD spectra are represented here, as well as elemental cartographiesSpectra: black, before, red after and the difference in blue..slight changes in the Fe and Mg content (more before than after)20Second Intermediate conclusion* Particulate material is chemically reactive, olivine & plagioclase being most susceptible to alteration* Dissolution of lithogenic material followed by precipitation of secondary phases, is strongly suspected* Trace elements (Nd, Sr, Mn, Ba, Ni ) & major ones (Si, Mg) are implied* Kinetic is rapid (weekly to monthly scale)In order to broaden our observations, made on a local and laboratory scales, we propose you now some global calculationswe focused these on Si cycle only, because Si is of prime importance for the ocean life and climate modelling 21Jeandel et al; Traces and tracers, Lige, 2011Other elements that are released(similar experiments not shown here)Relative concentration in seawaterSiBaNiMnConclusions & Consequences (1)ConclusionsWeathering of the particulate load (suspended, bedload, margin sediments)can significantly affect the oceanic budget of isotopes & elements

This processus -previously unconsidered- might help to balancethe marine Sr, Nd, Si cycles and likely Th, Ba, MgNi, Cu, Zn, Mn: Cameron, Little, Vance (all published in 2014)The weathered fraction includes a significant lithogenic component (feldspath and olivine being among the most sensitive)Kinetic of this process is rapid (within a month)Followed by secondary phase precipitation: might affect more the isotopic than the concentration budgetsConclusions & Consequences (2)ConsequencesMarine Sr cycle: differences in the reactivity of basalticand crustal particles suggest that solid load weatheringmight help account for part of the missing Sr fluxto the ocean. Impact on the geological reconstitutions?Marine Nd, REE cycles: consistent with the Boundary Exchange hypothesis. Impact on its use as paleo-tracer?

Marine Th isotopes: solid load weathering likely perturbates the coastal 232Th/230Th. Impact on its use as particle dynamic tracer?

Conclusions & Consequences (3)ConsequencesMarine Si concentrations and isotopes: This additional flux increases the Si input term, diminishes the Si residence time by 35 to 50% (at steady-state; Jeandel et al, 2011; Trguer & de la Rocha, 2012)

Impact on the biological pumpImpact on the CO2 modern cycleImpact on the climatic models

Conclusions & Consequences (4)(many) Remaining QuestionsOther elements?Clearly, one should reconsider the land to ocean fluxes of all the elements, mostly those of the essential marine micro-nutrient

Particle speciation effect?Working on this will allow the best modelling of the impact ofsuch release on a global scale, taking into account the geochemical particularities of watersheds and margins

These questions can be gathered into 2 main axis..26

Thank you!Chart111020

Mass flux to the oceans (GT/yr)

Sheet1Temp.pHAlkalinity87Sr/86SrFClCl%water from riverCmeq/Lmg/kgmg/kgmg/kg7.78.080.39033327790.70458970.00172363010.15659102625.255847.68.080.38482736780.7045890.00169881340.15135239844.42394100.7045897.58.080.3925883310.70463190.00159016630.15334131564.434060.99771766730.00228233270.7045994919-0.00003150818.67.810.44976923760.70623390.00160726490.26863447167.433440.59514033880.40485966120.70645013990.00021713999.57.80.40179126220.7080690.00173075451.115502055230.73780.14392506950.85607493050.70852437650.00046437659.87.810.40632824870.70777680.00161581420.782527479221.93590.20167579170.79832420830.70825889640.00048289649.57.780.40708731270.70830980.00171175611.51285041641.61340.10631046730.89368953270.70869729080.00038829089.57.810.39571964330.70775180.0016414620.753253937220.62630.21448054180.78551945820.70820003290.00044903299.97.820.45963659360.70816770.00168040871.227583169433.99020.13015339720.86984660280.70858768480.00042068489.87.780.40119984080.70791290.00166141030.884313042220.14670.21958633420.78041366580.70817656160.00026456169.67.770.40038353150.70770580.00165001130.726008306620.07370.22038488170.77961511830.70817289070.00046789079.67.780.45303877050.70817990.00166995961.22638485827.162350.16287029660.83712970340.70843728520.00025828529.67.770.43106387690.7090190.068993466189.0649983434247.62892835820.01786519870.98213480130.70910387370.00009387379.37.810.49159291850.70908380.0675238829311.0931687291843.53411194030.00524453010.99475546990.70916189090.00007889099.57.840.50188414230.70909570.0688157874363.3091952711954.8263480.00463324040.99536675960.7091647010.0000697019.57.980.77047748760.7091870.5455305233371.10685008032861.22183382350.00154617160.99845382840.7091788922-0.00000110789.980.90100980670.70916180.59388041955462.48778144564498.18987192120.00098349340.99901650660.70918147890.000020478910.18.111.38936342770.70918690.693414860310266.2063317828084.84805882350.0005471890.9994528110.7091834846-0.000002515410.68.121.62313382220.7091860.807866548314429.030240570810460.85216666670.00042290440.99957709560.7091840559-0.000001944110.58.081.83643832861.052574469918755.777901634311402.82038834950.000387968900HvA0.7032940HvB1.5695067265Bo10.7038555.5426008969Bo25.8206278027Bo30.703965.7264573991Bo45.5964125561Bo50.703945.4260089686Bo60.703435.7219730942Bo70.7043095.8295964126Bo80.7039875.8295964126Bo8b0.7037956.0403587444Bo90.7041356.2600896861Bo100.7049666.4484304933Bo110.7053536.735426009Bo120.70537.0538116592Bo130.7063157.4080717489Bo140.7064418.3632286996Bo150.70764710.7399103139Bo160.70810411.5695067265Bo170.708359

Sheet1

Sheet2

Distance, kmSr87/86 sediments

Sheet3

Distance, km[Cl] ppm

Distance, kmSr87/86 estuary water


Fraction river content of estuary waterSr87/86 estuary water

Dissolved flux (Gaillardet et al., 2003)1Bedload Flux (Walling, 2006)10Suspended Material Flux (Syvitiski et al., 2003)20


Chart25.255844.423944.434067.4334430.737821.935941.613420.626333.990220.146720.073727.16235247.6289283582843.5341119403954.8263482861.22183382354498.18987192128084.848058823510460.852166666711402.8203883495



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Sheet3







Chart40.7045890.7045890.7046310.7062330.708060.7077760.7083090.7077510.7081670.7079120.7077050.7081790.709010.7090830.7090950.709180.7091610.7091860.70918611.5695067265



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Sheet3







Chart600-0.00003150810.00021713990.00046437650.00048289640.00038829080.00044903290.00042068480.00026456160.00046789070.00025828520.00009387370.00007889090.000069701-0.00000110780.0000204789-0.0000025154-0.00000194410

Distance, kmSr87/86( fluid mixing model - estuary water)


Sheet1

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Sheet3







Chart30.7045890.7046310.7062330.708060.7077760.7083090.7077510.7081670.7079120.7077050.7081790.709010.7090830.7090950.709180.7091610.7091860.709186



Sheet1

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Sheet3



00-0.00003150810.00021713990.00046437650.00048289640.00038829080.00044903290.00042068480.00026456160.00046789070.00025828520.00009387370.00007889090.000069701-0.00000110780.0000204789-0.0000025154-0.00000194410




11020


Graph224.568348537524.568348537523.18171487280.40562443010.51214759560.40562443010.40562443010.62266052740.62266052746.956767088411.822772843319.903898390.17172883870.51246355280.2217379320.2217379320.40561690270.40561690276.365029486319.973790040918.99471109980.13838984030.51273771710.42914768340.42914768340.39125537620.39125537626.419912184817.689271777714.8649929380.17383006480.51287951570.32017597150.32017597150.31511691070.31511691076.466481818714.863096039117.55878720510.15969434450.51289795370.2905346050.2905346050.31024099130.31024099139.118932433316.763179494225.77673790240.20686723760.51292004480.34237403710.34237403710.54337307150.5433730715

Exp AExp BExp CDuration (Hours)Nd (pmol/kg)

Seawater SolutionsContainer NumberSample NameDepth (m)Date CollectedOther InfoInitial Seawater Samples1A4 st7-J415002/10/99Acidified2ANT4 st715002/10/99Bout 20, Acidified (pH 2)3A4 st8-J435002/15/99Acidified (20ml 6N HCl)4ANT4 st85009Bout 45ANT4 st8-J415002/10/996A4 st-J425002/10/99Acidified7ANT4 st743002/10/99Bout 3, Acidified (pH 2)8ANT4 st725002/10/99Bout 15, Acidified (pH 2)9ANT4 st728002/10/99Bout 9, Acidified (pH 2)10ANT4 st820002/15/99No. 7REACTOR AA&B Solution:1,2,3,4,6,9 + half of 10Empty container weight (kg):1.12Full container weight (kg):32.00Weight of solution (kg):30.88REACTOR BA&B Solution:1,2,3,4,6,9 + half of 10Empty container weight (kg):1.13Full container weight (kg):32.00Weight of solution (kg):30.87REACTOR CC Solution:5,7,8 + half of 10Empty container weight (kg):1.11Full container weight (kg):32.20Weight of solution (kg):31.09

Seawater Solutions1

Basalt Samples166.2-0.7-127.4

Sampling Times 1166.2-0.7-127.4

Sampling Times 2166.2-0.7-127.4

Si & Al SamplesREACTOR ASample Name:BR1a (Icelandic river sand)BET (m2/g):6.358Weight (g):30.0596Date Added:2/16/09Time Added:15:52Final Reactor Weight (kg):32.4REACTOR BSample Name:BR13a (Icelandic estaurine sand)BET (m2/g):7.357Weight (g):30.094Date Added:2/16/09Time Added:15:53Final Reactor Weight (kg):32.4REACTOR CSample Name:KEPOS C1 0.5-1 (Keruglen marine sand)BET (m2/g):2.214Weight (g):30.044Date Added:2/16/09Time Added:15:54Final Reactor Weight (kg):32.4

REE SamplesDayDateDay No[Si] & [Al] SamplesREE + Si Isotope SamplesNd Isotope Samples10 ml500ml5000mlMonday2/16/090InitalInitalInitalEXPERIMENT STARTEDTuesday2/17/0911Wednesday2/18/0922Thursday2/19/0933Friday2/20/0944Saturday2/21/0955Sunday2/22/0966Monday2/23/097711Tuesday2/24/098Wednesday2/25/0998Thursday2/26/0910Friday2/27/09119Saturday2/28/0912Sunday3/1/0913Monday3/2/091410Tuesday3/3/0915Wednesday3/4/0916112Thursday3/5/0917Friday3/6/091812Saturday3/7/0919Sunday3/8/0920Monday3/9/092113Tuesday3/10/0922Wednesday3/11/0923Thursday3/12/09241432Friday3/13/0925Saturday3/14/0926Sunday3/15/0927Monday3/16/092815Tuesday3/17/0929Wednesday3/18/0930Thursday3/19/0931Friday3/20/093216Saturday3/21/0933Sunday3/22/0934Monday3/23/0935Tuesday3/24/0936Wednesday3/25/0937174Thursday3/26/0938Friday3/27/0939Saturday3/28/0940Sunday3/29/0941Monday3/30/0942Tuesday3/31/0943Wednesday4/1/094418Thursday4/2/0945Friday4/3/0946Saturday4/4/0947Sunday4/5/0948Monday4/6/0949Tuesday4/7/0950Wednesday4/8/09511953Thursday4/9/0952Friday4/10/0953Saturday4/11/0954Sunday4/12/0955Monday4/13/0956Tuesday4/14/0957Wednesday4/15/0958Thursday4/16/0959Friday4/17/0960Saturday4/18/0961Sunday4/19/0962Monday4/20/0963206Tuesday4/21/0964Wednesday4/22/0965Thursday4/23/0966Friday4/24/0967Saturday4/25/0968Sunday4/26/0969Monday4/27/0970Tuesday4/28/0971Wednesday4/29/0972Thursday4/30/0973Friday5/1/0974Saturday5/2/0975Sunday5/3/0976Monday5/4/0977Tuesday5/5/0978Wednesday5/6/0979Thursday5/7/09802174Friday5/8/0981Saturday5/9/0982Sunday5/10/0983Monday5/11/0984Tuesday5/12/0985Wednesday5/13/0986Thursday5/14/0987Friday5/15/0988Saturday5/16/0989Sunday5/17/0990Monday5/18/0991Tuesday5/19/0992Wednesday5/20/0993Thursday5/21/0994228Friday5/22/0995Saturday5/23/0996Sunday5/24/0997Monday5/25/0998Tuesday5/26/0999Wednesday5/27/09100Thursday5/28/09101Friday5/29/09102Saturday5/30/09103Sunday5/31/09104Monday6/1/09105Tuesday6/2/09106Wednesday6/3/09107Thursday6/4/09108239Friday6/5/09109Saturday6/6/09110Sunday6/7/09111Monday6/8/09112Tuesday6/9/09113Wednesday6/10/09114Thursday6/11/09115Friday6/12/09116Saturday6/13/09117Sunday6/14/09118Monday6/15/09119Tuesday6/16/09120Wednesday6/17/0912124105EXPERIMENT FINISHEDThursday6/18/09122Friday6/19/09123Saturday6/20/09124Sunday6/21/09125Total25116

Nd SamplesSample NameDate SampledDay (No.)Day (hrs)Time SampledTime DifferenceLinear Time (hrs)Expt Started2/16/09003:52:00 PM12:00:00 AM0.00A Inital 12/16/090010:27:00 AM5:25:00 AM-5.42A Inital 22/16/09002:58:00 PM12:54:00 AM-0.90A#12/17/091243:11:00 PM12:41:00 AM23.32A#22/18/092485:31:00 PM1:39:00 AM49.65A#32/19/093725:12:00 PM1:20:00 AM73.33A#42/20/094965:27:00 PM1:35:00 AM97.58A#52/21/0951204:50:00 PM12:58:00 AM120.97A#62/22/0961445:21:00 PM1:29:00 AM145.48A#72/23/0971687:32:00 PM3:40:00 AM171.67A#82/25/0992164:39:00 PM12:47:00 AM216.78A#92/27/09112644:23:00 PM12:31:00 AM264.52A#103/2/09143364:15:00 PM12:23:00 AM336.38A#113/4/09163844:10:00 PM12:18:00 AM384.30A#123/6/09184323:59:00 PM12:07:00 AM432.12A#133/9/09215043:48:00 PM12:04:00 AM503.93A#143/12/09245762:40:00 PM1:12:00 AM574.80A#153/16/09286724:06:00 PM12:14:00 AM672.23A#163/20/09327683:58:00 PM12:06:00 AM768.10A#173/25/09378883:39:00 PM12:13:00 AM887.78A#184/1/094410564:12:00 PM12:20:00 AM1056.33A#194/8/095112242:16:00 PM1:36:00 AM1222.40A#204/20/0963151210:45:00 AM5:07:00 AM1506.88A#215/7/098019202:20:00 PM1:32:00 AM1918.47A#225/21/0994225611:44:00 AM4:08:00 AM2251.87A#236/4/0910825926:33:00 PM2:41:00 AM2594.68A#246/17/09121290410:40:00 AM5:12:00 AM2898.80Expt Started2/16/09003:53:00 PM12:00:00 AM0.00B Inital 12/16/090010:29:00 AM5:24:00 AM-5.40B Inital 22/16/09002:59:00 PM12:54:00 AM-0.90B#12/17/091243:13:00 PM12:40:00 AM23.33B#22/18/092485:32:00 PM1:39:00 AM49.65B#32/19/093725:13:00 PM1:20:00 AM73.33B#42/20/094965:28:00 PM1:35:00 AM97.58B#52/21/0951204:51:00 PM12:58:00 AM120.97B#62/22/0961445:22:00 PM1:29:00 AM145.48B#72/23/0971687:34:00 PM3:41:00 AM171.68B#82/25/0992164:41:00 PM12:48:00 AM216.80B#92/27/09112644:24:00 PM12:31:00 AM264.52B#103/2/09143364:16:00 PM12:23:00 AM336.38B#113/4/09163844:11:00 PM12:18:00 AM384.30B#123/6/09184324:01:00 PM12:08:00 AM432.13B#133/9/09215043:49:00 PM12:04:00 AM503.93B#143/12/09245762:41:00 PM1:12:00 AM574.80B#153/16/09286724:07:00 PM12:14:00 AM672.23B#163/20/09327684:00:00 PM12:07:00 AM768.12B#173/25/09378883:41:00 PM12:12:00 AM887.80B#184/1/094410564:14:00 PM12:21:00 AM1056.35B#194/8/095112242:18:00 PM1:35:00 AM1222.42B#204/20/0963151211:03:00 AM4:50:00 AM1507.17B#215/7/098019202:30:00 PM1:23:00 AM1918.62B#225/21/0994225611:46:00 AM4:07:00 AM2251.88B#236/4/0910825926:34:00 PM2:41:00 AM2594.68B#246/17/09121290412:02:00 PM3:51:00 AM2900.15Expt Started2/16/09003:53:00 PM12:00:00 AM0.00C Inital 12/16/090010:30:00 AM5:23:00 AM-5.38C Inital 22/16/09003:00:00 PM12:53:00 AM-0.88C#12/17/091243:14:00 PM12:39:00 AM23.35C#22/18/092485:34:00 PM1:41:00 AM49.68C#32/19/093725:14:00 PM1:21:00 AM73.35C#42/20/094965:29:00 PM1:36:00 AM97.60C#52/21/0951204:52:00 PM12:59:00 AM120.98C#62/22/0961445:23:00 PM1:30:00 AM145.50C#72/23/0971687:35:00 PM3:42:00 AM171.70C#82/25/0992164:42:00 PM12:49:00 AM216.82C#92/27/09112644:26:00 PM12:33:00 AM264.55C#103/2/09143364:18:00 PM12:25:00 AM336.42C#113/4/09163844:12:00 PM12:19:00 AM384.32C#123/6/09184324:02:00 PM12:09:00 AM432.15C#133/9/09215043:51:00 PM12:02:00 AM503.97C#143/12/09245762:42:00 PM1:11:00 AM574.80C#153/16/09286724:09:00 PM12:16:00 AM672.27C#163/20/09327684:02:00 PM12:09:00 AM768.15C#173/25/09378883:42:00 PM12:11:00 AM887.82C#184/1/094410564:15:00 PM12:22:00 AM1056.37C#194/8/095112242:20:00 PM1:33:00 AM1222.45C#204/20/0963151211:20:00 AM4:33:00 AM1507.45C#215/7/098019202:34:00 PM1:19:00 AM1918.68C#225/21/0994225611:48:00 AM4:05:00 AM2251.92C#236/4/0910825926:36:00 PM2:43:00 AM2594.72C#246/17/0912129042:12:00 PM1:41:00 AM2902.32

Sample NameDateTimeWeight empty sample pot (g)Weight empty syringe (g)Weight full sample pot (g)Weight full syringe (g)Weight of sample (g)Amount removed from container (g)4.016.869.18SampleSample pHA Initial 12/16/0910:27:00 AM10.0212.6121.0312.9811.0111.38155.9-1.9-133.8-79.38.22A Initial 22/16/092:58:00 PM10.0912.6921.1513.0411.0611.41155.9-1.9-133.8-71.08.07A#12/17/093:11:00 PM10.1012.6320.9413.0210.8411.23156.1-2.0-133.9-69.38.04A#22/18/095:31:00 PM10.0612.1620.8812.5610.8211.22156.2-1.7-134.0-69.78.05A#32/19/095:12:00 PM10.0812.0620.9012.4410.8211.20156.4-1.6-133.7-69.68.05A#42/20/095:27:00 PM10.0712.1121.0012.5510.9311.37156.0-1.7-134.0-70.18.05A#52/21/094:50:00 PM10.0812.0820.9512.4510.8711.24156.1-1.5-133.3-70.18.06A#62/22/095:21:00 PM10.0512.0920.4712.4710.4210.80156.1-1.6-133.2-69.98.06A#72/23/097:32:00 PM10.0712.1020.6412.4510.5710.92156.3-1.5-133.3-68.08.03A#82/25/094:39:00 PM10.0512.1421.0012.5110.9511.32156.4-1.5-133.6-68.48.03A#92/27/094:23:00 PM10.1812.1921.0512.5610.8711.24156.6-1.4-134.1-68.68.03A#103/2/094:15:00 PM10.0412.6620.8413.0210.8011.16156.5-1.0-132.4-68.48.05A#113/4/094:10:00 PM10.0112.1620.6912.5410.6811.06165.3-1.5-134.6-67.18.01A#123/6/093:59:00 PM10.0012.1320.5212.4610.5210.85165.1-1.4-133.7-68.08.03A#133/9/093:48:00 PM10.0612.1320.8412.5410.7811.19157.1-1.4-131.5-67.68.04A#143/12/092:40:00 PM10.0512.0620.7812.4210.7311.09156.5-0.7-131.5-66.38.02A#153/16/094:06:00 PM10.0512.1719.7912.819.7410.38156.9-0.6-131.2-65.48.01A#163/20/093:58:00 PM10.1112.2220.5312.5910.4210.79157.5-0.2-130.2-65.28.02A#173/25/093:39:00 PM10.0713.0920.2613.4810.1910.58157.10.0-130.8-65.08.01A#184/1/094:12:00 PM10.1013.2820.6013.6410.5010.86157.00.8-129.3-64.98.03A#194/8/092:16:00 PM10.0413.3220.8113.6510.7711.10155.0-0.7-131.0-66.68.03A#204/20/0910:45:00 AM10.0913.3020.6613.8710.5711.14150.2-4.5-133.5-68.48.00A#215/7/092:20:00 PM10.1113.3720.1513.9810.0410.65164.1-2.4-135.1-63.07.92A#225/21/0911:44:00 AM10.0413.2020.8613.5310.8211.15164.4-1.0-133.2-62.17.94A#236/4/096:33:00 PM10.1012.1521.2012.5411.1011.49164.8-0.2-132.1-59.77.91A#246/17/0910:40:00 AM10.2012.2138.5512.7028.3528.84167.0-8.2-140.1-62.87.84B Initial 12/16/0910:29:00 AM10.0412.6421.0413.0211.0011.38155.9-1.9-133.8-85.38.33B Initial 22/16/092:59:00 PM10.1112.6020.8413.0310.7311.16155.9-1.9-133.8-72.98.11B#12/17/093:13:00 PM10.0212.6220.6713.1410.6511.17156.1-2.0-133.9-71.58.08B#22/18/095:32:00 PM10.0412.1420.7712.5710.7311.16156.2-1.7-134.0-73.08.11B#32/19/095:13:00 PM10.1012.1820.7612.5910.6611.07156.4-1.6-133.7-73.18.11B#42/20/095:28:00 PM10.0212.1620.7212.5910.7011.13156.0-1.7-134.0-74.38.13B#52/21/094:51:00 PM10.0012.1320.8212.5310.8211.22156.1-1.5-133.3-74.68.14B#62/22/095:22:00 PM10.0912.0920.8412.4310.7511.09156.1-1.6-133.2-74.58.14B#72/23/097:34:00 PM10.1012.1520.7312.5410.6311.02156.3-1.5-133.3-73.68.13B#82/25/094:41:00 PM10.0612.1521.0012.5110.9411.30156.4-1.5-133.6-74.28.13B#92/27/094:24:00 PM10.0712.1620.8512.5110.7811.13156.6-1.4-134.1-75.58.15B#103/2/094:16:00 PM10.0412.6321.0112.9910.9711.33156.5-1.0-132.4-75.88.18B#113/4/094:11:00 PM10.0812.1620.6812.5510.6010.99165.3-1.5-134.6-75.08.14B#123/6/094:01:00 PM10.0812.1520.2812.6910.2010.74165.1-1.4-133.7-76.28.17B#133/9/093:49:00 PM10.0812.0520.8912.4310.8111.19157.1-1.4-131.5-75.78.18B#143/12/092:41:00 PM10.0912.1120.6412.4610.5510.90156.5-0.7-131.5-75.28.18B#153/16/094:07:00 PM10.1212.0820.8812.4810.7611.16156.9-0.6-131.2-74.88.18B#163/20/094:00:00 PM10.0412.1621.0112.5110.9711.32157.5-0.2-130.2-74.28.18B#173/25/093:41:00 PM10.1313.2220.7313.5610.6010.94157.10.0-130.8-74.38.18B#184/1/094:14:00 PM10.1013.1120.4313.4910.3310.71157.00.8-129.3-75.48.22B#194/8/092:18:00 PM10.0813.3621.0113.6810.9311.25155.0-0.7-131.0-76.68.21B#204/20/0911:03:00 AM9.9813.0519.2413.409.269.61150.2-4.5-133.5-79.18.20B#215/7/092:30:00 PM10.0613.3520.1913.7610.1310.54164.1-2.4-135.1-74.78.13B#225/21/0911:46:00 AM10.0613.3920.8313.7310.7711.11164.4-1.0-133.2-74.48.15B#236/4/096:34:00 PM10.1312.1921.8612.7711.7312.31164.8-0.2-132.1-73.08.14B#246/17/0912:02:00 PM10.2012.1544.7612.5734.5634.98167.0-8.2-140.1-76.98.08C Initial 12/16/0910:30:00 AM10.0812.6321.3213.0711.2411.68155.9-1.9-133.8-80.28.24C Initial 22/16/093:00:00 PM10.1212.6020.9812.9410.8611.20155.9-1.9-133.8-69.28.04C#12/17/093:14:00 PM10.0612.6521.0213.0310.9611.34156.1-2.0-133.9-67.08.00C#22/18/095:34:00 PM10.1012.6420.9413.0110.8411.21156.2-1.7-134.0-67.58.01C#32/19/095:14:00 PM10.0212.1320.5712.5410.5510.96156.4-1.6-133.7-67.28.01C#42/20/095:29:00 PM10.0712.1620.7312.5310.6611.03156.0-1.7-134.0-68.08.02C#52/21/094:52:00 PM10.0612.1120.8812.5110.8211.22156.1-1.5-133.3-68.18.03C#62/22/095:23:00 PM10.0812.0920.8212.5010.7411.15156.1-1.6-133.2-67.58.02C#72/23/097:35:00 PM10.0012.1420.5212.5910.5210.97156.3-1.5-133.3-66.07.99C#82/25/094:42:00 PM10.1012.1221.0112.5110.9111.30156.4-1.5-133.6-66.37.99C#92/27/094:26:00 PM10.0212.0220.5912.3910.5710.94156.6-1.4-134.1-65.87.98C#103/2/094:18:00 PM10.0712.0720.5712.4310.5010.86156.5-1.0-132.4-65.57.99C#113/4/094:12:00 PM10.1412.0620.8412.4410.7011.08165.3-1.5-134.6-65.27.97C#123/6/094:02:00 PM10.0412.1120.6712.4710.6310.99165.1-1.4-133.7-65.77.99C#133/9/093:51:00 PM10.0312.1420.8012.5210.7711.15157.1-1.4-131.5-64.97.99C#143/12/092:42:00 PM10.0712.1620.7112.4810.6410.96156.5-0.7-131.5-63.87.97C#153/16/094:09:00 PM10.0512.1520.8212.5410.7711.16156.9-0.6-131.2-62.57.96C#163/20/094:02:00 PM10.1112.1721.4412.5411.3311.70157.5-0.2-130.2-62.27.96C#173/25/093:42:00 PM10.0413.2820.6013.6410.5610.92157.10.0-130.8-60.47.93C#184/1/094:15:00 PM10.0413.2620.7213.6010.6811.02157.00.8-129.3-61.97.97C#194/8/092:20:00 PM10.0013.2920.2913.6510.2910.65155.0-0.7-131.0-62.37.95C#204/20/0911:20:00 AM10.1213.2720.7313.6210.6110.96150.2-4.5-133.5-65.47.95C#215/7/092:34:00 PM10.0813.9820.8113.3010.7310.05164.1-2.4-135.1-59.67.87C#225/21/0911:48:00 AM10.1013.1920.8413.8410.7411.39164.4-1.0-133.2-57.67.86C#236/4/096:36:00 PM10.0612.2222.4112.7012.3512.83164.8-0.2-132.1-55.77.84C#246/17/092:12:00 PM10.1512.1745.0112.6334.8635.32167.0-8.2-140.1-57.57.75

166.2-0.7-127.4

166.2-0.7-127.4

166.2-0.7-127.4

000

000

000

Sample NameDateTimeWeight empty sample container (g)Weight full sample container (g)Weight of sample (g)Weight of sub-sample (white pot) (g)Weight of remaining sample (g)Spike weight before (g)Spike weight after (g)Actual spike weight (g)A&B Initial2/9/095:26:00 PM54.21592.04537.83121.8477415.9823135.5141134.47871.0354A#12/23/094:12:00 PM55.26578.14522.88119.9208402.9592133.4437132.40361.0401A#23/4/094:30:00 PM53.95593.38539.43123.5789415.8511130.3247129.28571.0390A#33/12/093:10:00 PM54.63572.66518.03128.3322389.6978127.2087126.17011.0386A#43/25/094:05:00 PM54.65594.95540.30117.2519423.0481124.0927123.05421.0385A#54/8/0910:53:00 AM54.80599.98545.18121.7173423.4627120.9772119.93991.0373A#64/21/0910:43:00 AM55.35582.78527.43117.4044410.0256117.8637116.83151.0322A#75/7/0910:10:00 AM55.20572.52517.32118.0940399.2260114.7590113.72461.0344A#85/21/0911:03:00 AM55.26554.66499.40119.0380380.3620111.6531110.61761.0355A#96/4/095:47:00 PM55.00562.05507.05126.7888380.2612108.5462107.50781.0384A#106/17/099:57:00 AM54.73589.11534.38121.4027412.9773105.4356104.40061.0350A&B Initial2/9/095:26:00 PM54.21592.04537.83121.8477415.9823135.5141134.47871.0354B#12/23/095:38:00 PM54.85590.44535.59118.2488417.3412132.4034131.36351.0399B#23/4/094:41:00 PM55.26605.79550.53124.0573426.4727129.2854128.24671.0387B#33/12/093:54:00 PM54.30589.48535.18120.0964415.0836126.1698125.13241.0374B#43/25/094:17:00 PM54.91584.21529.30118.2101411.0899123.0542122.01541.0388B#54/8/0911:35:00 AM53.29563.76510.47119.8344390.6356119.9397118.90161.0381B#64/21/0911:01:00 AM55.02583.37528.35115.9238412.4262116.8313115.79531.0360B#75/7/0911:03:00 AM54.55583.64529.09118.4701410.6199113.7247112.68891.0358B#85/21/0911:13:00 AM55.14582.24527.10119.9941407.1059110.6176109.58251.0351B#96/4/095:57:00 PM54.68566.28511.60115.2681396.3319107.5077106.47211.0356B#106/17/0911:15:00 AM55.46587.74532.28112.9703419.3097104.4006103.36521.0354C Initial2/10/0910:14:00 AM53.76606.22552.46122.3924430.0676134.4783133.44441.0339C#12/23/096:42:00 PM53.95609.90555.95121.1564434.7936131.3634130.32481.0386C#23/4/094:52:00 PM54.81593.81539.00116.2476422.7524128.2467127.20891.0378C#33/12/095:00:00 PM54.86598.80543.94112.4080431.5320125.1323124.09271.0396C#43/25/094:05:00 PM54.29601.10546.81117.0209429.7891122.0154120.97741.0380C#54/8/091:12:00 PM54.38591.11536.73120.0539416.6761118.9012117.86421.0370C#64/21/0911:18:00 AM53.42590.47537.05118.8230418.2270115.7951114.75971.0354C#75/7/091:26:00 PM55.23582.61527.38121.0422406.3378112.6890111.65311.0359C#85/21/0911:22:00 AM55.28573.67518.39119.2532399.1368109.5825108.54641.0361C#96/4/096:09:00 PM55.45580.82525.37120.9431404.4269106.4721105.43631.0358C#106/17/091:15:00 PM54.98596.93541.95129.8181412.1319103.3653102.32941.0359

Sample NameDateTimeWeight empty sample container (kg)Weight full sample container (kg)Weight of sample (kg)A&B Initial2/9/095:50:00 PM0.215.645.43A#12/23/095:09:00 PM0.215.245.03A#23/12/093:32:00 PM0.215.315.10A#34/8/0911:20:00 AM0.215.174.96A#45/7/0910:43:00 AM0.205.325.12A#56/17/0910:32:00 AM0.215.204.99A&B Initial2/9/095:26:00 PM0.215.645.43B#12/23/096:06:00 PM0.215.235.02B#23/12/094:29:00 PM0.215.265.05B#34/8/0912:11:00 PM0.225.204.98B#45/7/0912:00:00 PM0.225.245.02B#56/17/0911:51:00 AM0.205.275.07C Initial2/10/0912:30:00 PM0.195.615.42C#12/23/097:15:00 PM0.215.275.06C#23/12/095:40:00 PM0.205.315.11C#34/8/091:58:00 PM0.205.255.05C#45/7/092:00:00 PM0.215.345.13C#56/17/092:06:00 PM0.204.984.78

Graph3-9.5662896053-9.5662896053-9.56515104290.14923699350.14923699350.14923699350.14923699350.13909545480.1390954548-3.40293150764.3279631336-6.85185336940.20204135050.20204135050.16592538930.16592538930.14226098260.14226098261.94517495195.671693084-4.2765757740.20482222040.20482222040.17495934160.17495934160.18514894250.18514894254.71123315875.7446076819-3.04883233930.20445658940.20445658940.12002939380.12002939380.14407513970.14407513975.07090222835.7863191599-2.25713267340.23921924520.23921924520.18062645880.18062645880.15153692990.15153692995.50183248615.9974186631-2.61114738290.25593178770.25593178770.16874357020.16874357020.13165743260.1316574326

Exp AExp BExp CDuration (Hours)E Nd

Sheet1Sample NameDateDayTimeLinear Time (Hrs)Weight empty sample container (kg)Weight full sample container (kg)Weight of sample (kg)Nd (pmol/kg)2 s.d143Nd/144NdError (2 sigma)eNd2 sigmaA&B Initial2/9/0905:50:00 PM0.000.215.645.4324.56834853750.40562443010.51214759560.0000076505-9.5660.149A#12/23/09145:09:00 PM335.320.215.245.036.95676708840.17172883870.51246355280.0000103574-3.4030.202A#23/12/09313:32:00 PM741.700.215.315.106.36502948630.13838984030.51273771710.00001051.9450.205A#34/8/095811:20:00 AM1385.500.215.174.966.41991218480.17383006480.51287951570.00001048124.7110.204A#45/7/098710:43:00 AM2080.880.205.325.126.46648181870.15969434450.51289795370.00001226335.0710.239A#56/17/0912710:32:00 AM3047.320.215.204.999.11893243330.20686723760.51292004480.000013125.5020.256A&B Initial2/9/0905:26:00 PM0.000.215.645.4324.56834853750.40562443010.51214759560.0000076505-9.5660.149B#12/23/09146:06:00 PM336.670.215.235.0211.82277284330.2217379320.51285986780.0000085064.3280.166B#23/12/09314:29:00 PM743.050.215.265.0519.97379004090.42914768340.51292875250.00000896915.6720.175B#34/8/095812:11:00 PM1386.750.225.204.9817.68927177770.32017597150.51293249040.00000615325.7450.120B#45/7/098712:00:00 PM2082.570.225.245.0214.86309603910.2905346050.51293462870.00000925965.7860.181B#56/17/0912711:51:00 AM3042.420.205.275.0716.76317949420.34237403710.51294545050.00000865045.9970.169C Initial2/10/09012:30:00 PM0.000.195.615.4223.18171487280.62266052740.5121476540.0000071306-9.5650.139C#12/23/09147:15:00 PM342.750.215.275.0619.903898390.40561690270.5122867480.0000072928-6.8520.142C#23/12/09315:40:00 PM749.170.205.315.1118.99471109980.39125537620.51241876650.0000094914-4.2770.185C#34/8/09581:58:00 PM1393.470.205.255.0514.8649929380.31511691070.51248170530.0000073858-3.0490.144C#45/7/09872:00:00 PM2089.500.215.345.1317.55878720510.31024099130.51252229080.0000077684-2.2570.152C#56/17/091272:06:00 PM3049.600.204.984.7825.77673790240.54337307150.51250414270.0000067493-2.6110.132Blank 10.51197424160.0001431027-12.9482.791Blank 20.51223834940.0001348175-7.7962.630Standard0.512638DRA14650.51255658980.000003977-1.5880.078DRA500.51255579780.0000058198-1.6040.114DRA15000.51259588530.0000064168-0.8220.125DRA2540.51262074510.0000039294-0.3370.077REACTOR ASample Name:BR1a (Icelandic river sand)BET (m2/g):6.358Weight (g):30.0596Date Added:2/16/09Time Added:15:52Final Reactor Weight (kg):32.4REACTOR BSample Name:BR13a (Icelandic estaurine sand)BET (m2/g):7.357Weight (g):30.094Date Added:2/16/09Time Added:15:53Final Reactor Weight (kg):32.4REACTOR CSample Name:KEPOS C1 0.5-1 (Keruglen marine sand)BET (m2/g):2.214Weight (g):30.044Date Added:2/16/09Time Added:15:54Final Reactor Weight (kg):32.4

Sheet10.14923699350.14923699350.14923699350.14923699350.13909545480.13909545480.20204135050.20204135050.16592538930.16592538930.14226098260.14226098260.20482222040.20482222040.17495934160.17495934160.18514894250.18514894250.20445658940.20445658940.12002939380.12002939380.14407513970.14407513970.23921924520.23921924520.18062645880.18062645880.15153692990.15153692990.25593178770.25593178770.16874357020.16874357020.13165743260.1316574326


Sheet20.40562443010.51214759560.40562443010.40562443010.62266052740.62266052740.17172883870.51246355280.2217379320.2217379320.40561690270.40561690270.13838984030.51273771710.42914768340.42914768340.39125537620.39125537620.17383006480.51287951570.32017597150.32017597150.31511691070.31511691070.15969434450.51289795370.2905346050.2905346050.31024099130.31024099130.20686723760.51292004480.34237403710.34237403710.54337307150.5433730715


Sheet3

Graph424.568348537524.568348537523.18171487280.40562443010.51214759560.40562443010.40562443010.62266052740.62266052746.956767088411.822772843319.903898390.17172883870.51246355280.2217379320.2217379320.40561690270.40561690276.365029486319.973790040918.99471109980.13838984030.51273771710.42914768340.42914768340.39125537620.39125537626.419912184817.689271777714.8649929380.17383006480.51287951570.32017597150.32017597150.31511691070.31511691076.466481818714.863096039117.55878720510.15969434450.51289795370.2905346050.2905346050.31024099130.31024099139.118932433316.763179494225.77673790240.20686723760.51292004480.34237403710.34237403710.54337307150.5433730715



Sheet10.14923699350.14923699350.14923699350.14923699350.13909545480.13909545480.20204135050.20204135050.16592538930.16592538930.14226098260.14226098260.20482222040.20482222040.17495934160.17495934160.18514894250.18514894250.20445658940.20445658940.12002939380.12002939380.14407513970.14407513970.23921924520.23921924520.18062645880.18062645880.15153692990.15153692990.25593178770.25593178770.16874357020.16874357020.13165743260.1316574326


Sheet20.40562443010.51214759560.40562443010.40562443010.62266052740.62266052740.17172883870.51246355280.2217379320.2217379320.40561690270.40561690270.13838984030.51273771710.42914768340.42914768340.39125537620.39125537620.17383006480.51287951570.32017597150.32017597150.31511691070.31511691070.15969434450.51289795370.2905346050.2905346050.31024099130.31024099130.20686723760.51292004480.34237403710.34237403710.54337307150.5433730715


Sheet3

Graph5-9.5662896053-9.5662896053-9.56515104290.14923699350.14923699350.14923699350.14923699350.13909545480.1390954548-3.40293150764.3279631336-6.85185336940.20204135050.20204135050.16592538930.16592538930.14226098260.14226098261.94517495195.671693084-4.2765757740.20482222040.20482222040.17495934160.17495934160.18514894250.18514894254.71123315875.7446076819-3.04883233930.20445658940.20445658940.12002939380.12002939380.14407513970.14407513975.07090222835.7863191599-2.25713267340.23921924520.23921924520.18062645880.18062645880.15153692990.15153692995.50183248615.9974186631-2.61114738290.25593178770.25593178770.16874357020.16874357020.13165743260.1316574326

Exp AExp BExp CDuration (Hours)e Nd


Sheet10000.14923699350.14923699350.14923699350.14923699350.13909545480.13909545480000.20204135050.20204135050.16592538930.16592538930.14226098260.14226098260000.20482222040.20482222040.17495934160.17495934160.18514894250.18514894250000.20445658940.20445658940.12002939380.12002939380.14407513970.14407513970000.23921924520.23921924520.18062645880.18062645880.15153692990.15153692990000.25593178770.25593178770.16874357020.16874357020.13165743260.1316574326


Sheet20000.40562443010.51214759560.40562443010.40562443010.62266052740.62266052740000.17172883870.51246355280.2217379320.2217379320.40561690270.40561690270000.13838984030.51273771710.42914768340.42914768340.39125537620.39125537620000.17383006480.51287951570.32017597150.32017597150.31511691070.31511691070000.15969434450.51289795370.2905346050.2905346050.31024099130.31024099130000.20686723760.51292004480.34237403710.34237403710.54337307150.5433730715


Sheet3

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