BIODEEP (EVK3-2000-00042) Second year Scientific Report (April 1st 2002 – March 31st 2003) Annex to WP2 Contribution from partner 10 - University of Utrecht Introduction During the Urania 2002 cruise (BiodeepIII), a mooring of 3 sediment traps from the Bannock basin was successfully recovered (Tab. 1). Also from the Urania basin the sediment trap mooring was recovered, but it appeared that none of the traps had functioned properly, all for different reasons. This is the first time in the long history of this type of traps that non-functioning is observed. Sediment trap samples from the lowest trap at 3500 m (within anoxic brine) and from the middle trap at 2500 m (in oxic seawater) were analysed for elemental composition. Additionally, C and N contents were measured for the anoxic samples of the the Bannock basin. From these data, average yearly fluxes of different elements could be calculated for each the oxic and the anoxic trap. Tab. 1: Depths of sediment traps deployed in Bannock September 1999- May 2000. Bannock basin Urania basin Station BD03 Depth (m) Station PS 027 ST1 1500 ST1 ST2 2500 ST2 ST3 3500 ST3 ST4 Basin during May 2001-June 2002 and in Urania basin during Depth (m) 460 1500 2800 3500 In order to compare the data from Bannock basin with Urania basin, an earlier sample set (from a sediment trap mooring 1999-2000) from Urania basin was investigated for elemental analysis as well. Again, samples from the lowest trap (3500 m, within anoxic brine) and one upper trap (2800 m) were analysed for elemental composition. Also, suspended matter samples from the 4 different basins (L´Atalante, Urania, Bannock and Discovery basins) were investigated. However, the analysis proved to be very difficult because of a) the very little amount of material on the filters and b) the high salt content on the filters. For this reasons, it is agreed with the partners that the sampling of suspended matter will be done again during the June/July Biodeep cruise. It is essential that the filters are washed after filtration on board ship to remove the salt load in order to have reliable results during later analysis. However, a salt correction was applied for the data available on suspended matter from unwashed filters (see below). Methodology: For total elemental analysis the sediment trap and suspended matter cellulose acetate filters including the sample were dried at 40C and weighed. Subsequently, the filters were sealed in a Teflon bomb with 2.5 ml HF and 2.5 ml HClO4/HNO3 and dissolved by oven heating at 90C for 5 hours. The solutions were evaporated to dryness and redissolved in 7.5 ml 1 M HNO 3, and analysed with an inductively coupled plasma atomic emission spectrometer (ICP/AES; Perkin Elmer Optima 3000). Filter blanks as well as a calibration series of an in-house standard sediment (MM91) were simultaneously processed and used to calculate separate calibration lines for each element. Before evaporation of HF during total dissolution of the sample, a subsample was taken out and was analysed photospectrometically for Si according to the method described in Rutten et al. (2000). C/N analysis was done with an Elemental Analyser (Fisons NA 1500). BIODEEP (EVK3-2000-00042) Second year Scientific Report (April 1st 2002 – March 31st 2003) Results and Discussion Sediment traps One important result is the striking difference of total mass accumulation in the different traps, both in the different basins and in the oxic vs. anoxic traps at the same site. The average fluxes for the analysed elements from September to May for the respective sampling years are plotted in Fig. 1. In the Bannock basin, the anoxic trap accumulated about 30x more material than the oxic one (4 mg*m-2*d-1), in the Urania basin, the value is about 100x higher in the anoxic trap than the oxic trap (15 mg*m-2*d-1). -2 mg*m *d -1 2000 1000 0 BB oxic BB anoxic UB oxic UB anoxic Fig. 1: Average (sept.-may) total mass fluxes to the different sediment traps. From this data it is apparent that the fluxes in the anoxic basins are highly exaggerated due to resuspension of material within the basins due to slumping of material from the flanks of the basins and, additionally in the Urania basin, resuspension due to gas expulsions. The oxic traps which are deployed above the brine basin interface instead show reliable data on what is reaching the anoxic basins from above. Total mass fluxes differ by a factor of about 4 between Urania and Bannock basin. This difference is not caused completely by a different amount of biogenic (opal, carbonate) or by enhanced dust deposition in the basins, because extra-Si and carbonate fluxes (calculated from Ca fluxes) vary by a factor of 1.25 and 3 between the basins (Tab. 2). The enhanced input of material is thus caused additionally by higher terrigenous input into the Urania basin area. Looking at the concentrations of extra Si (Extra Si is the excess silicon above the silicon concentration of the clay (terrigenous) matrix in the sample) it appears that it is much higher in the high-flux samples than in the other samples. This additional input of Si may originate from two sources: biogenic Si due to a plankton bloom or quartz input due to storms from the Sahara. Enhanced Si-input is observed in summer and that is the time of severe wind-driven Saharan dust input in the whole Mediterranean Sea (Güllü et al., 1996). This indicates that the dust input, which also drags down biogenic and other particles through the water column, is the dominating factor for mass flux varibilities in the oxic traps. BIODEEP (EVK3-2000-00042) Second year Scientific Report (April 1st 2002 – March 31st 2003) Tab. 2: Average (sept.-may) elemental fluxes to different sediment traps. Extra Si is the excess silicon above the silicon of the clay (terrigenous) matrix in the sample and represents mainly eolian input of quartz from the saharan dust. nd: no data. Units: Ca, Fe, S, Si and extra Si: mg*m-2*d-1, all other: µg*m-2*d-1. Ba Bannock basin oxic anoxic Urania basin oxic anoxic Ca Fe Mn S Si extra Si 2.8 51.5 1.0 18.9 0.3 3.2 3.8 73.0 nd 1.0 0.8 24.7 0.4 nd 9.0 84.4 3.1 134.8 0.5 36.6 23.9 1000.9 nd 353.7 1.2 154.4 0.5 nd Cd Bannock basin oxic anoxic Urania basin oxic anoxic Co Cu Ni Pb Zn 0.01 nd 0.2 2.0 0.5 9.2 0.3 4.6 0.26 nd 1.7 nd 0.02 nd 0.8 29.4 2.5 62.5 1.0 228.2 1.39 nd 3.0 nd Data on carbonate concentrations in the Bannock basin anoxic trap (BD003 ST3) are reported in Tab. 3. These data are calculated from the difference of total C and organic C measurements and give more accurate values of carbonate than recalculation from Ca data because the usual assumption that the Ca in carbonate-rich sediments almost entirely is related to CaCO3 is not valid in the anoxic basins due to the formation of gypsum. The average C/N ratio of the material is 19.3 and is considerably higher than the Redfield ratio of about 6.6. Tab. 3. Total concentrations and fluxes (averages from May 01-June 02) of Bannock basin anoxic trap (BD003 ST3). average CaCO3 (wt%) CaCO3 (mg*m-2*d-1) C org (wt%) C org (mg*m-2*d-1) N (wt%) N flux (mg*m-2*d-1) 33.03 84.81 2.21 4.86 0.11 0.3 The determination of biogenic (CaCO3, Corg) components and extra Si (mainly dust with possible contribution of opal) of the sediment from the anoxic Bannock basin trap allows to describe the total composition of the material as 56.1% terrigenous, 33% Carbonate, 8.7% extra Si and 2.2% Corg (Fig. 2). From the carbonate determination the amount of excess Ca may be estimated which is not incorporated into carbonate, but may be present mainly as Gypsum. This amounts to about 10% which is included in the terrigenous fraction. 56.1 33 2.2 CaCO3 extra Si Corg Terr. 8.7 Fig. 2: Average total composition of anoxic Bannock basin sediment trap material. BIODEEP (EVK3-2000-00042) Second year Scientific Report (April 1st 2002 – March 31st 2003) In order to get further insights into variations of elemental fluxes into the Bannock basin which might be related to seasonal changes, flux data are plotted according to the four seasons. From these plots it becomes obvious that the major part of about 50% of elements and carbonate is transported in the summer to the anoxic Bannock basin trap. The remaining fraction is transported preferentially in spring, followed by less input during autumn and minimum input in winter times. The high average fluxes in summer are due to an exceptional high flux in the July-August sample. This high flux might be caused by a major resuspension event within the basin, because such high flux is not recorded in the oxic trap above the basin. CaCO3 flux Si flux spring 20% summer 49% winter 13% autumn 18% spring 22% winter 11% autumn 14% S flux Mn flux spring 20% winter 12% autumn 16% summer 53% summer 52% spring 17% winter 14% summer 50% autumn 19% Fig. 3: Average fluxes for carbonate, total Si, S and Mn for Bannock basin anoxic trap recalculated on a seasonal basis. Suspended matter Suspended matter analysis is important in order to know how much material is suspension and also of what composition this material is. However, during the analysis of the filters containing the suspended matter, severe problems were encountered. Apart from the very little amount of sample on the filter is was a major problem that the filters were not washed after filtration in order to remove the remaining brine. So the data produced are highly influenced by salt contents which results in high errors in the analysis. A salt correction was applied to the data assuming all Na in Bannock, Urania and L´Atalante basins samples is present as NaCl and all Mg in Discovery basin samples is present as MgCl2. The results show that the highest amount of suspended matter is encountered in the Discovery basin, whereas Bannock and L´Atalante basin brines show similar suspended matter loads. Urania brine has the least amount of suspended matter (Fig. 4). Although the chemical analysis shows high errors due to the salt influence, the overall trends for the different brines are considered to be meaningful. The concentrations of e.g. K show similar values for all the brines except for Discovery basin brine. The same trend is observed for S. Contrasting this, Ca concentrations are high in Urania basin brine, followed by approx half the concentration in Bannock brine. L´Atalante and Discovery brines are much more depleted in Ca than the others. These data indicate that there are major differences in the brine suspended matter compositions. These differences may have an important impact on microbiological activity and therefore should be analysed more precisely with carefully washed samples. BIODEEP (EVK3-2000-00042) Second year Scientific Report (April 1st 2002 – March 31st 2003) 30 total mass (mg/l) 25 20 15 10 5 0 AB UB DB BB 50000 12000 40000 10000 Ca (ppm) K (ppm) Fig.4: Suspended matter average total mass concentrations. 30000 20000 8000 6000 4000 10000 2000 bdl 0 0 AB UB DB BB AB UB DB BB Fig.4: K and Ca average concentrations of suspended matter from the different brines. bdl: below detection limit. References: Rutten, G. J. de Lange, P. Ziveri, J. Thomson, P. J. M. van Santvoort, S. Colley and C. Corselli (2000): Recent terrestrial and carbonate fluxes in the pelagic eastern Mediterranean; a comparison between sediment trap and surface sediment. Palaeogeography, Palaeoclimatology, Palaeoecology, 158, 197-213 Güllü G.H., Ölmez I. & Tuncel G. (1996) Chemical concentrations and elements size distributions of aerosols in the eastern Mediterranean during strong dust storms. In: Guerzoni S. & Chester R. (eds.) The impact of desert dust across the Mediterranean. Environm. Sci. Technol. Libr. 11, 339347. Kluwer Academic Publishers, Dordrecht.