Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Depth integrated nitrogen fixation from the northern Benguela upwelling system during Maria S. Merain cruise MSM18/5

Nitrogen fixation data from the cruise number MSM18/5 with research vessel "Maria S. Merian" from 22.08.-20.09.2011 (from Walvis Bay to Walvis Bay) in front of Angola and northern Namibia. Samples taken by CTD- rosette sampler from different depths and incubated in glass bottles (535 ml) at light intensities that resemble the in situ light intensities of the sampling depth after 15N2 gas was injected to the sample. After the incubation time of 6 hours, the complete bottle content was filtered onto a pre-combusted Whatman GF/F filter. Filters were frozen, transported to the institute on dry ice and measured in a mass spectrometer for Delta 15N. The principle of the method was described by Montoya et al. (1996) and calculation was done according to their spread sheet. From the data of the single depths, the nitrogen fixation per square meter within the upper 40 m of the water column was calculated. The methods are described in detail in a paper submitted by Wasmund et al. in 2014 to be printed in 2015. Some results are surprisingly below zero. This occurs if the Delta 15N of the blank is higher than the measurement after incubation. It indicates that no nitrogen fixation occurred. Due to natural variability, the variability of the nitrogen fixation data is high. In an overall estimate, also over several cruises, negative and positive values compensate more or less, suggesting that nitrogen fixation is insignificant in the waters in front of northern Namibia and southern Angola.

Stable Water Isotopologue data collected during HCCT-2010

Cloud samples for the isotopic analysis were collected in the framework of the Hill Cap Cloud Thuringia 2010 (HCCT-2010) campaign on Schmücke (50° 39'N/ 10° 46'E, 937 m a.s.l.; Germany) in September and October 2010 with a three-stage Caltech Active Strand Cloudwater Collector (CASCC) during 13 different cloud events with a temporal resolution of 1 to 3 hours. In a first step, we ensured that no additional fractionation occurred during sampling with the CASCC. The d values of the three sizes classes of the CASCC (4 µm to 16 µm, 16 µm to 22 µm and >22 µm) did not differ significantly, revealing that the cloud droplets of different sizes quickly equilibrate their delta value with the one of the surrounding vapor. delta values in the cloud droplets varied from -77 per mil to -15 per mil in d2H and from -12.1 per mil to -3.9 per mil in d18O and were fitted by d2H =7.8*d18O +13*10**-3. delta values decreased with temperature as well as towards the end of the campaign, representing a seasonal trend which is known from d values in precipitation. The deuterium excess of the cloud samples was generally higher than the Local Meteoric Water Line of the closest GNIP (Global Network of Isotopes in Precipitation) station. Rain decreases its deuterium excess during falling through an unsaturated air column, while the cloud droplets conserve the deuterium excess of the initial evaporation and thus have been found to be a good indicator for the airmass source region: higher deuterium excess was measured for polar air masses and lower deuterium excess for Mediterranean air masses. Changes in d values during one cloud event were up to 3.6 per mil (d2H) and 0.23 per mil (d18O), except for frontal passages, which were associated with increases of ~6 per mil per hour (d2H) and ~0.6 per mil per hour (d18O). Using a box model, we showed that the influence of condensation only was able to explain the variation in the isotope signal of two cloud passages. Consequently, we deduced that the water vapor "feeding" the cloud advected the measured changes. A trajectory analysis and moisture source diagnostic revealed that it is very likely that the variations were either related to rain out along the trajectories or to meteorological changes in the moisture source region. This was the first study using stable water isotopologues in cloud water manifesting their potential in the context of atmospheric water vapor circulation.

Age determination on rock samples from Svalbard

A linear, N-S-trending belt of elliptical, positive magnetic anomalies occurs in central Nordaustlandet, northeast Svalbard. They extend from the Caledonian and older complexes in the vicinity of Duvefjorden, southwards beneath the western margin of Austfonna and the offshore areas covered by Carboniferous and younger strata, to the vicinity of Edge¯ya. One of the strongest anomalies occurs in inner Duvefjorden where it coincides with a highly magnetic quartz monzonite-granite pluton at Djupkilsodden. U-Pb and Pb-Pb zircon dating of this post-tectonic pluton defines an age of c. 415 Ma, this being based on the Pb-Pb analyses of three specimens (Pb-Pb ages of 414±10 Ma, 411±10 Ma and 408±10 Ma) and a U-Pb discordia with an upper intercept at 417+18/-7 Ma. Neighbouring felsic plutons in central Nordaustlandet, including the Rijpfjorden and Winsnesbreen granites, lack magnetic signatures in their exposed parts, but have a similar Caledonian age. The central Nordaustlandet magnetic anomalies appear to be part of a circa 300 km long linear belt of late Silurian or early Devonian post-tectonic plutonism that characterizes the Caledonian basement of eastern Svalbard. Felsic intrusions of similar age further west in Spitsbergen are likewise both highly magnetic (Hornemantoppen batholith) and largely non-magnetic (Newtontoppen batholiths / Chydeniusbreen granitoid suite). They all appear to have been intruded at the end of the main period of Caledonian terrane assembly of the northwestern Barents Shelf.

Depth integrated nitrogen fixation from the northern Benguela upwelling system during Maria S. Merain cruise MSM17/3

Nitrogen fixation data from the cruise number MSM17/3 with research vessel "Maria S. Merian" from 30.01.-10.02.2011 (= "leg a" from Walvis Bay to Walvis Bay) in front of Namibia. Samples taken by CTD- rosette sampler from different depths and incubated in glass bottles (535 ml) at light intensities that resemble the in situ light intensities of the sampling depth after 15N2 gas was injected to the sample. After the incubation time of 6-8 hours, the complete bottle content was filtered onto a pre-combusted Whatman GF/F filter. Filters were frozen, transported to the institute on dry ice and measured in a mass spectrometer for Delta 15N. The principle of the method was described by Montoya et al. (1996) and calculation was done according to their spread sheet. From the data of the single depths, the nitrogen fixation per square meter within the upper 40 m of the water column was calculated. The methods are described in detail in a paper submitted by Wasmund et al. in 2014 to be printed in 2015. Some results are surprisingly below zero. This occurs if the Delta 15N of the blank is higher than the measurement after incubation. It indicates that no nitrogen fixation occurred. Due to natural variability, the variability of the nitrogen fixation data is high. In an overall estimate, also over several cruises, negative and positive values compensate more or less, suggesting that nitrogen fixation is insignificant in the waters in front of northern Namibia and southern Angola.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.

Depth integrated nitrogen fixation from the northern Benguela upwelling system during METEOR cruise M100/1

Nitrogen fixation data from the cruise number M100 with research vessel "Meteor" from 01.09.-01.10.2013 (1st leg from Walvis Bay to Walvis Bay) in front of Namibia. Samples taken by CTD- rosette sampler from different depths and incubated in glass bottles (270-1070 ml) at light intensities that resemble the in situ light intensities of the sampling depth after 15N2 gas was injected to the sample. After the incubation time of 24 hours, the complete bottle content was filtered onto a pre-combusted Whatman GF/F filter. Filters were frozen, transported to the institute on dry ice and measured in a mass spectrometer for Delta 15N. The principle of the method was described by Montoya et al. (1996) and calculation was done according to their spread sheet. From the data of the single depths, the nitrogen fixation per square meter within the upper 40 m of the water column was calculated. The methods are described in detail in a paper submitted by Wasmund et al. in 2014 to be printed in 2015. Some results are surprisingly below zero. This occurs if the Delta 15N of the blank is higher than the measurement after incubation. It indicates that no nitrogen fixation occurred. Due to natural variability, the variability of the nitrogen fixation data is high. In an overall estimate, also over several cruises, negative and positive values compensate more or less, suggesting that nitrogen fixation is insignificant in the waters in front of northern Namibia and southern Angola.

Depth integrated nitrogen fixation from the northern Benguela upwelling system during METEOR cruise M103/2

Nitrogen fixation data from the cruise number M103/2 with research vessel "Meteor" from 21.01.-11.02.2014 (second leg from Walvis Bay to Walvis Bay) in front of Namibia. Samples taken by CTD- rosette sampler from different depths and incubated in glass bottles (535 ml) at light intensities that resemble the in situ light intensities of the sampling depth after 15N2 gas was injected to the sample. After the incubation time of 24 hours, the complete bottle content was filtered onto a pre-combusted Whatman GF/F filter. Filters were frozen, transported to the institute on dry ice and measured in a mass spectrometer for Delta15N. The principle of the method was described by Montoya et al. (1996) and calculation was done according to their spread sheet. From the data of the single depths, the nitrogen fixation per square meter within the upper 40 m of the water column was calculated. The methods are described in detail in a paper submitted by Wasmund et al. in 2014 to be printed in 2015. Some results are surprisingly below zero. This occurs if the Delta15N of the blank is higher than the measurement after incubation. It indicates that no nitrogen fixation occurred. Due to natural variability, the variability of the nitrogen fixation data is high. In an overall estimate, also over several cruises, negative and positive values compensate more or less, suggesting that nitrogen fixation is insignificant in the waters in front of northern Namibia and southern Angola.

C and H geochemistry of altered oceanic crus of ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with dD values from -64per mil to -25per mil. All samples are enriched in water relative to fresh basalts. The dD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with d13C values from -14.9per mil to -26.6per mil. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with d13C = -4.5per mil and (2) an organic compound with d13C = -26.6per mil. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when "fresh" oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ? -4.7per mil, similar to the d13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 * 10**12 molC/yr.

Depth integrated nitrogen fixation from the northern Benguela upwelling system during Maria S. Merain cruise MSM18/4

Nitrogen fixation data from the cruise number MSM18/4 with research vessel "Maria S. Merian" from 24.07.-20.08.2011 (from Libreville to Walvis Bay) in front of Angola and northern Namibia. Samples taken by CTD- rosette sampler from different depths and incubated in glass bottles (535 ml) at light intensities that resemble the in situ light intensities of the sampling depth after Delta 15 N2 gas was injected to the sample. After the incubation time of 6 hours, the complete bottle content was filtered onto a pre-combusted Whatman GF/F filter. Filters were frozen, transported to the institute on dry ice and measured in a mass spectrometer for Delta15N. The principle of the method was described by Montoya et al. (1996) and calculation was done according to their spread sheet. From the data of the single depths, the nitrogen fixation per square meter within the upper 40 m of the water column was calculated. The methods are described in detail in a paper submitted by Wasmund et al. in 2014 to be printed in 2015. Some results are surprisingly below zero. This occurs if the Delta15N of the blank is higher than the measurement after incubation. It indicates that no nitrogen fixation occurred. Due to natural variability, the variability of the nitrogen fixation data is high. In an overall estimate, also over several cruises, negative and positive values compensate more or less, suggesting that nitrogen fixation is insignificant in the waters in front of northern Namibia and southern Angola.

PM2.5, PM10, and PM10-associated elements in the air in Bamako, Mali (2012-2013)

Saharan dust incursions and particulates emitted from human activities degrade air quality throughout West Africa, especially in the rapidly expanding urban centers in the region. Particulate matter (PM) that can be inhaled is strongly associated with increased incidence of and mortality from cardiovascular and respiratory diseases and cancer. Air samples collected in the capital of a Saharan-Sahelian country (Bamako, Mali) between September 2012 - July 2013 were found to contain inhalable PM concentrations that exceeded World Health Organization (WHO) and US Environmental Protection Agency (USEPA) PM2.5 and PM10 24-h limits 58 - 98% of days and European Union (EU) PM10 24-h limit 98% of days. Mean concentrations were 1.2-to-4.5 fold greater than existing limits. Inhalable PM was enriched in transition metals, known to produce reactive oxygen species and initiate the inflammatory reaction, and other potentially bioactive and biotoxic metals/metalloids. Eroded mineral dust composed the bulk of inhalable PM, whereas most enriched metals/metalloids were likely emitted from oil combustion, biomass burning, refuse incineration, vehicle traffic, and mining activities. Human exposure to inhalable PM and associated metals/metalloids over 24-h was estimated. The findings indicate that inhalable PM in the Sahara-Sahel region may present a threat to human health, especially in urban areas with greater inhalable PM and transition metal exposure.