Appendix A. Whole-rock major, trace and rare earth element analyses of the Ulubey volcanics, Appendix B. Analytical standards and detection limits for analyses

Collisional and post-collisional volcanic rocks in the Ulubey (Ordu) area at the western edge of the Eastern Pontide Tertiary Volcanic Province (EPTVP) in NE Turkey are divided into four suites; Middle Eocene (49.4-44.6 Ma) aged Andesite-Trachyandesite (AT), Trachyandesite-Trachydacite-Rhyolite (TTR), Trachydacite-Dacite (TD) suites, and Middle Miocene (15.1 Ma) aged Trachybasalt (TB) suite. Local stratigraphy in the Ulubey area starts with shallow marine environment sediments of the Paleocene-Eocene time and then continues extensively with sub-aerial andesitic to rhyolitic and rare basaltic volcanism during Eocene and Miocene time, respectively. Petrographically, the volcanic rocks are composed primarily of andesites/trachyandesites, with minor trachydacites/rhyolites, basalts/trachybasalts and pyroclastics, and show porphyric, hyalo-microlitic porphyric and rarely glomeroporphyric, intersertal, intergranular, fluidal and sieve textures. The Ulubey (Ordu) volcanic rocks indicate magma evolution from tholeiitic-alkaline to calc-alkaline with medium-K contents. Primitive mantle normalized trace element and chondrite normalized rare earth element (REE) patterns show that the volcanic rocks have moderate light rare earth element (LREE)/heavy rare earth element (HREE) ratios relative to E-Type MORB and depletion in Nb, Ta and Ti. High Th/Yb ratios indicate parental magma(s) derived from an enriched source formed by mixing of slab and asthenospheric melts previously modified by fluids and sediments from a subduction zone. All of the volcanic rocks share similar incompatible element ratios (e.g., La/Sm, Zr/Nb, La/Nb) and chondrite-normalized REE patterns, indicating that the basic to acidic rocks originated from the same source. The volcanic rocks were produced by the slab dehydration-induced melting of an existing metasomatized mantle source, and the fluids from the slab dehydration introduced significant large ion lithophile element (LILE) and LREE to the source, masking its inherent HFSE-enriched characteristics. The initial 87Sr/86Sr (0.7044-0.7050) and eNd (-0.3 to +3.4) ratios of the volcanics suggest that they originated from an enriched lithospheric mantle source with low Sm/Nd ratios. Integration of the geochemical, petrological and isotopical with regional and local geological data suggest that the Tertiary volcanic rocks from the Ulubey (Ordu) area were derived from an enriched mantle, which had been previously metasomatized by fluids derived from subducted slab during Eocene to Miocene in collisional and post-collisional extension-related geodynamic setting following Late Mesozoic continental collision between the Eurasian plate and the Tauride-Anatolide platform.

XCO2 and XCH4 total column measurement during POLARSTERN cruise PS83 (ANT-XXIX/10), north-south gradient

A portable Fourier transform spectrometer (FTS), model EM27/SUN, was deployed onboard the research vessel Polarstern to measure the column-average dry air mole fractions of carbon dioxide (XCO2) and methane (XCH4) by means of direct sunlight absorption spectrometry. We report on technical developments as well as data calibration and reduction measures required to achieve the targeted accuracy of fractions of a percent in retrieved XCO2 and XCH4 while operating the instrument under field conditions onboard the moving platform during a 6-week cruise on the Atlantic from Cape Town (South Africa, 34° S, 18° E; 5 March 2014) to Bremerhaven (Germany, 54° N, 19° E; 14 April 2014). We demonstrate that our solar tracker typically achieved a tracking precision of better than 0.05° toward the center of the sun throughout the ship cruise which facilitates accurate XCO2 and XCH4 retrievals even under harsh ambient wind conditions. We define several quality filters that screen spectra, e.g., when the field of view was partially obstructed by ship structures or when the lines-of-sight crossed the ship exhaust plume. The measurements in clean oceanic air, can be used to characterize a spurious air-mass dependency. After the campaign, deployment of the spectrometer alongside the TCCON (Total Carbon Column Observing Network) instrument at Karlsruhe, Germany, allowed for determining a calibration factor that makes the entire campaign record traceable to World Meteorological Organization (WMO) standards. Comparisons to observations of the GOSAT satellite and concentration fields modeled by the European Centre for Medium-Range Weather Forecasts (ECMWF) Copernicus Atmosphere Monitoring Service (CAMS) demonstrate that the observational setup is well suited to provide validation opportunities above the ocean and along interhemispheric transects.

Calibration of tracer concentration measurement and results

A reliable assessment of relevant substance flows is very important for environmental risk assessments and efficiency analysis of measures to reduce or avoid emissions of micropollutants like drugs to water systems. Accordingly, a detailed preparation of monitoring campaigns should include an accuracy check for the sampling configuration to prove the reliability of the monitoring results and the subsequent data processing. The accuracy of substance flow analyses is expected to be particularly weak for substances having high short-term variations of concentrations in sewage. This is especially the case linked to the observation of substance flows close to source in waste water systems. The verification of a monitoring configuration in a hospital sewer in Luxembourg is in the centre of interest of the case study presented here. A tracer test in the sewer system under observation is an essential element of the suggested accuracy check and provides valuable information for an uncertainty analysis. The results illustrate the importance of accuracy checks as an essential element of the preparation of monitoring campaigns. Moreover the study shows that continuous flow proportional sampling enables a representative observation of short-term peak loads of the iodinated x-ray contrast media iobitridol close to source.

Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

Contiunous surface water uncorrected and quench-corrected active fluorescence and derived chlorophyll a concentration using calibration by HPLC pigments during POLARSTERN cruise ANT-XXV/1

The relationship between phytoplankton assemblages and the associated optical properties of the water body is important for the further development of algorithms for large-scale remote sensing of phytoplankton biomass and the identification of phytoplankton functional types (PFTs), which are often representative for different biogeochemical export scenarios. Optical in-situ measurements aid in the identification of phytoplankton groups with differing pigment compositions and are widely used to validate remote sensing data. In this study we present results from an interdisciplinary cruise aboard the RV Polarstern along a north-to-south transect in the eastern Atlantic Ocean in November 2008. Phytoplankton community composition was identified using a broad set of in-situ measurements. Water samples from the surface and the depth of maximum chlorophyll concentration were analyzed by high performance liquid chromatography (HPLC), flow cytometry, spectrophotometry and microscopy. Simultaneously, the above- and underwater light field was measured by a set of high spectral resolution (hyperspectral) radiometers. An unsupervised cluster algorithm applied to the measured parameters allowed us to define bio-optical provinces, which we compared to ecological provinces proposed elsewhere in the literature. As could be expected, picophytoplankton was responsible for most of the variability of PFTs in the eastern Atlantic Ocean. Our bio-optical clusters agreed well with established provinces and thus can be used to classify areas of similar biogeography. This method has the potential to become an automated approach where satellite data could be used to identify shifting boundaries of established ecological provinces or to track exceptions from the rule to improve our understanding of the biogeochemical cycles in the ocean.

Revised calibration of the MBT-CBT paleotemperature proxy

The MBT-CBT proxy for the reconstruction of paleotemperatures and past soil pH is based on the distribution of branched glycerol dialkyl glycerol tetraether (brGDGT) membrane lipids. The Methylation of Branched Tetraether (MBT) and the Cyclisation of Branched Tetraether (CBT) indices were developed to quantify these distributions, and significant empirical relations between these indices and annual mean air temperature (MAT) and/or soil pH were found in a large data set of soils. In this study, we extended this soil dataset to 278 globally distributed surface soils. Of these soils, 26% contains all nine brGDGTs, while in 63% of the soils the seven most common brGDGTs were detected, and the latter were selected for calibration purposes. This resulted in new transfer functions for the reconstruction of pH based on the CBT index: pH = 7.90-1.97 × CBT (r**2 = 0.70; RMSE = 0.8; n = 176), as well as for MAT based on the CBT index and methylation index based on the seven most abundant GDGTs (defined as MBT'): MAT = 0.81-5.67 × CBT + 31.0 × MBT' (r**2 = 0.59; RMSE = 5.0 °C; n = 176). The new transfer function for MAT has a substantially lower correlation coefficient than the original equation (r**2 = 0.77). To investigate possible improvement of the correlation, we used our extended global surface soil dataset to statistically derive the indices that best describe the relations of brGDGT composition with MAT and soil pH. These new indices, however, resulted in only a relatively minor increase in correlation coefficients, while they cannot be explained straightforwardly by physiological mechanisms. The large scatter in the calibration cannot be fully explained by local factors or by seasonality, but MAT for soils from arid regions are generally substantially (up to 20 °C) underestimated, suggesting that absolute brGDGT-based temperature records for these areas should be interpreted with caution. The applicability of the new MBT'-CBT calibration function was tested using previously published MBT-CBT-derived paleotemperature records covering the last deglaciation in Central Africa and East Asia, the Eocene-Oligocene boundary and the Paleocene-Eocene thermal maximum. The results show that trends remain similar in all records, but that absolute temperature estimates and the amplitude of temperature changes are lower for most records, and generally in better agreement with independent proxy data.

Metallic Fluence Monitors and J-value standards

Utilizing the neutron-irradiation parameter J is one of the major uncertainties in 40Ar/39Ar dating. The associated error of the individual J-value for a sample of unknown age depends on the accuracy of the age of the geological standards, the fast-neutron fluence distribution in the reactor and the distances between standards and samples during irradiation. While it is generally assumed that rotating irradiation evens out radial neutron fluence gradients, we observed axial and radial variations of the J-values in sample irradiations in the rotating channels of two reactors. To quantify them, we included three-dimensionally distributed metallic fast- (Ni) and thermal- (Co) neutron fluence monitors in three irradiations and geological age standards in three more. Two irradiations were carried out under Cd-shielding in the FRG1 reactor in Geesthacht, Germany, and four without Cd-shielding in the LVR-15 reactor in Rez, Czech Republic. The 58Ni(nf,p)58Co activation reaction and ?-spectrometry of the 811 keV peak associated with the subsequent decay of 58Co to 58Fe allow to calculate the fast-neutron fluence. The fast-neutron fluences at known positions in the irradiation container correlate with the J-values determined by mass-spectrometric 40Ar/39Ar measurements of the geological age standards. Ra-dial neutron fluence gradients are up to 1.8 %/cm in FRG1 and up to 2.2 %/cm in LVR-15; the corre-sponding axial gradients are up to 5.9 and 2.1 %/cm. We conclude that sample rotation might not al-ways suffice to meet the needs of high-precision dating and gradient monitoring can be crucial.