BIODEEP WP 2 Chemical characterization of seawater/brine/ sediments and related fluxes. A. watercolumn/brine analyses (UU) A. watercolumn/brine analyses.

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BIODEEP WP 2 Chemical characterization of seawater/brine/ sediments and related fluxes. A. watercolumn/brine analyses (UU) A. watercolumn/brine analyses (UU) B. susp.mat. major/minor elements; C,N (UU) B. susp.mat. major/minor elements; C,N (UU) key trace elements (Pb,Co,Zn,Cu,Cd) (UP) key trace elements (Pb,Co,Zn,Cu,Cd) (UP) C. sed.traps major/minor elements; C,N (UU) C. sed.traps major/minor elements; C,N (UU) microfossils / biogenic components (UM) microfossils / biogenic components (UM) radiotracers ( 210 Pb, 230 Th) (SOC) radiotracers ( 210 Pb, 230 Th) (SOC) D. sediments (major/minor elements; C,N) (SOC/UU) D. sediments (major/minor elements; C,N) (SOC/UU) key trace elements (Pb,Co,Cu,Zn,Cd) (UP) key trace elements (Pb,Co,Cu,Zn,Cd) (UP) E. pore water extraction/analysis (UU) E. pore water extraction/analysis (UU) WP2.1 CRETE- yr2

Aspects related to brine redox chemistry o N-species o S-species o Mn 2+ - MnO 2 cycling o Fe 2+ - Fe 2 O 3 - Fe,S cycling o SO HS - cycling

N-species At interface seawater/brine: nitrate jumps from 5 to 0 uM, whereas ammonia goes from ~ 0.2 to 3600 uM In oxic seawater: org.mat. + O 2  106 HCO NO 3 - HPO 4 2- In anoxic brine: org.mat. + SO42-  106 HCO NH 4 + HPO HS -

S-species: examplified by the most extreme case: URANIA Brine CH 4 + SO  HCO HS - + H 2 O Likely dominant reaction in Urania :

Atalante Basin phosphate and DIC data (BD10CT); seawater/brine interface oyxgen en sulphide data (UM08CT)

WP2-CTD1

Bannock brines I/II (BD34CT): density and alkalinity Note rapid increase in alkalinity at seawater/brine I interface, and the rapid decrease at the brine I/II transition

Orca/AB interface comparison

Orca/AB- 2

Orca/Med.brines Major difference in interface thickness Major difference in interface thickness (~ 100 m vs ~ 100 cm) (~ 100 m vs ~ 100 cm) Major difference in redox-chemistry Major difference in redox-chemistry (Fe, S a.o.; see below) (Fe, S a.o.; see below) Orca relative to Mediterranean brine basins:

Manganese cycling: observations in other redox-dominated environment : o Tyro Basin

TB Tyro basin, eastern Mediterranean

Manganese cycling at seawater/brine Interface : (replotting data De Lange et al.)

At interface seawater/brine, Mn2+ concentration jumps from ~ to 5 umole/kg, whereas HS- goes from 0.03 to 1800 umole/l BB-Mn/HS

Bannock and Orca brines dissolved Fe 2+, HS - (UU, Saager et al.; after Trefry et al.; Wiesenburg et al.) (note different scales !

2004 Mn 2+ (uM) HS - (uM) Fe 2+ (nM) BannockOrca BBvsOB Fe,S Major importance of: S > Mn > Fe

Brines average major elements

Interface Brine basin interfaces

Interface Conservative behaviour of Ca, Sr, K Diss. Mn and HS- may only be done if sampled and stored properly Bannock basin interface

Suspended matter How much material in suspension Composition of material: major and trace elements as well as C and N concentrations Major analytical problems because of very little sample material, and also because of extremely high salt contents of samples, …. Salt corretions are only very rough, so the results are high in error. Samples should be washed just after filtreation to remove the salt, this is vital for a reliable analysis

Suspended matter Average suspended material in different basins

Suspended matter B D B U B A B ppm mg/l SrSKCa susp. matter Average total mass and composition Mass and concentrations are corrected for salt influence

Suspended matter bdl

Sediment traps 3500ST3 2500ST2 1500ST1 Depth (m)Station BD03 Bannock basin

Sediment traps 3500ST3 2500ST2 1500ST1 Depth (m)Station BD03 Bannock basin

Sediment traps 3500ST3 2500ST2 1500ST1 Depth (m)Station BD03 Bannock basin 3500ST4 2800ST3 1500ST2 460ST1 Depth (m)Station PS 027 Urania basin

Sediment traps 3500ST3 2500ST2 1500ST1 Depth (m)Station BD03 Bannock basin 3500ST4 2800ST3 1500ST2 460ST1 Depth (m)Station PS 027 Urania basin

Methodology: Total destruction of samples for ICP-OES and ICP-MS analysis Subsampling during total destruction for Si analysis with photospectrometer C-total, C-organic and N contents with CNS- analyser

Total mass flux (average september-may)

Additional Si input in sediment: evidence for dust input

Urania basin oxic Bannock basin oxic 14,73,9 average mass flux (mg/m2/d)

anoxic oxic Urania basin anoxic oxic (mg/m2/d) (µg/m2/d)(mg/m2/d) Bannock basin SiSMnFeCa Average elemental fluxes

Average chemical characterization of sediment 56,1Terr. 2,2OM 8,7SiO 2 extra 33,0CaCO 3 Wt%Comp. WP2.1 Bannock anoxic

Bannock anoxic 2001/2002

Average Si-flux Bannock anoxic

Average S-flux Bannock anoxic

Average Mn-flux Bannock anoxic

Average CaCO 3 -flux Bannock anoxic

Average C org -flux Bannock anoxic

Average N-flux Bannock anoxic

WP2-2 Chemical characterization of sediments & pore waters Chemical characterization of sediments & pore waters

WP2.1d BoxcoreSampling site BW sampleWinckler bottles PW extr. Glove- box water% samples BD19MCDBx XYES #1 BD21MCUB.ex XYES #1 BD26BCABx XYES #1 BD27BCnormalxx BD31BCnormalxx BD42BCBBx x YES #1 BIODEEP 2002 pore/water sampling

Chemical characterization of sediments Sediment preparation methods (+/- salt removal, prior to analysis; intercalibration,..) Sediment preparation methods (+/- salt removal, prior to analysis; intercalibration,..) Intercalibration (methods, Labs,…) (see Thomson) Intercalibration (methods, Labs,…) (see Thomson) Sediment composition Sediment composition

BD26BC (AB)

BD26BC (AB) Mg/Al Na/Al

BD26BC (AB) Ca/Al Mn/Al

BD41BC (BB)

BD41BC (BB) Ca/Al Mn/Al

UBcores BD07BC BD21MC Major differences occur between the core in E and W basin

BD21MC (UB east)

BD21MC (UB-east) porewater results Brine ?! Precip. ?!

BD21MC (UB-east) solid phase results

BD07BC (UB-west) sediment results

Clearly for some elements the total sediment is salt- dominated Clearly for some elements the total sediment is salt- dominated Corrections can be done from intercalibration results Corrections can be done from intercalibration results

UR2001 sed. Sediment composition (DB)

Sediment composition (DB)

BD19MC-Cl BD19MC (DB)

WP2.1e BD19MC BW

DB-sediment BD19MC porewater results

BD19MC

DBalls

Prelim. Composition: Ca 6 Mg 20 (SO 4 ) 6 Cl 13 (CO 3 2- ) x. y H 2 O

Future Perspectives Suspended matter (esp. at interfaces) Suspended matter (esp. at interfaces) Gas content of brines (pressure sampling!) Gas content of brines (pressure sampling!) Sediment traps Sediment traps Sediment work (Discovery basin) Sediment work (Discovery basin)