Sea-suface microlayer (SML) and underlying water (ULW) samples focusing on CDOM spectral characteristics during METEOR cruise M91

The coastal upwelling system off the coast of Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. From 3 to 23 December 2012, R/V Meteor (M91) cruise took place in the Peruvian upwelling system between 4.59 and 15.4°S, and 82.0 to 77.5°W. During M91 we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like chromophoric dissolved organic matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. We analyzed SML and underlying water (ULW) samples at 38 stations focusing on CDOM spectral characteristics as indicator of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and excitation-emission matrix fluorescence (EEMs), which allow us to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. Spectral slope S varied between 0.012 to 0.043 1 nm-1 and was quite similar between SML and ULW, with no significant differences between the two compartments. Higher S values were observed in the ULW of the southern stations below 15°S. By EEMs, we identified five fluorescent components (F1-5) of the CDOM pool, of which two had excitation/emission characteristics of amino-acid-like fluorophores (F1, F4) and were highly enriched in the SML, with a median ratio SML : ULW of 1.5 for both fluorophores. In the study region, values for CDOM absorption ranged from 0.07 to 1.47 m-1. CDOM was generally highly concentrated in the SML, with a median enrichment with respect to the ULW of 1.2. CDOM composition and changes in spectral slope properties suggested a local microbial release of DOM directly in the SML as a response to light exposure in this extreme environment. In a conceptual model of the sources and modifications of optically active DOM in the SML and underlying seawater (ULW), we describe processes we think may take place (Fig. 1); the production of CDOM of higher MW by microbial release through growth, exudation and lysis in the euphotic zone, includes the identified fluorophores (F1, F2, F3, F4, F5). Specific amino-acid-like fluorophores (F1, F4) accumulate in the SML with respect to the ULW, as photochemistry may enhance microbial CDOM release by (a) photoprotection mechanisms and (b) cell-lysis processes. Microbial and photochemical degradation are potential sinks of the amino-acid-like fluorophores (F1, F4), and potential sources of reworked and more refractory humic-like components (F2, F3, F5). In the highly productive upwelling region along the Peruvian coast, the interplay of microbial and photochemical processes controls the enrichment of amino-acid-like CDOM in the SML. We discuss potential implications for air-sea gas exchange in this area.

Total organic carbon, lithology and alkylthiophenes in immature sediments (Table 1)

A series of novel long-chain 3,4-dialkylthiophenes (C36-C54) was identified in a number of sediments ranging from Pleistocene to Cretaceous. The identifications were based on mass spectral characterisation, desulphurisation and mass spectral data of synthesised model compounds. These organic sulphur compounds are probably formed by sulphur incorporation into mid-chain dimethylalkadienes with two methylenic double bonds. These putative precursor lipids are unprecedented and may be considered rather unusual. The distribution of 3,4-dialkylthiophenes in sediments varies considerably with the depositional palaeoenvironment, indicating that these compounds have a potential as molecular markers reflecting changes in palaeoenvironment.

Mineralogy and inorganic geochemistry of sediments at DSDP Leg 65 Holes

During Leg 65, 15 holes were drilled at four sites located on young crust in the mouth of the Gulf of California. Quaternary to upper Pliocene hemipelagic sediments above and interlayered within the young basaltic basement were cored. The influence of hot lava, high temperature gradients, and hydrothermal activity on the mineralogy and geochemistry of the terrigenous sediments near contacts with basalts might therefore be expected. The purpose of the present study was to determine the mineralogy and inorganic geochemistry of these sediments and to analyze the nature and extent of low temperature alteration. To this end we studied the mineralogy and inorganic geochemistry of 75 sediment samples, including those immediately overlying uppermost basalts and those from layers alternating with basalts within the basement. We separated three size fractions - <2 µm (clay), 2-20 µm (intermediate), and >20 µm (coarse) - and applied the following mineralogical determinations: x-ray diffraction (XRD), infrared spectroscopy, transmission and scanning electron microscopy, and optical microscopy (for coarse fractions, using thin sections and smear slides). We calculated the percentages of clay minerals using Biscaye's (1964) method, and used routine wet chemical analyses to determine bulk composition and quantitative spectral analyses for trace elements.

Age models for ODP Leg 172 sites

Ten ODP sites drilled in a depth transect (2164-4775 m water depth) during Leg 172 recovered high-deposition rate (>20 cm/kyr) sedimentary sections from sediment drifts in the western North Atlantic. For each site an age model covering the past 0.8-0.9 Ma has been developed. The time scales have a resolution of 10-20 kyr and are derived by tuning variations of estimated carbonate content to the orbital parameters precession and obliquity. Based on the similarity in the signature of proxy records and the spectral character of the time series, the sites are divided into two groups: precession cycles are better developed in carbonate records from a group of shallow sites (2164-2975 m water depth, Sites 1055-1058) while the deeper sites (2995-4775 m water depth, Sites 1060-1063) are characterized by higher spectral density in the obliquity band. The resulting time scales show excellent coherence with other dated carbonate and isotope records from low latitudes. Besides the typical Milankovitch cyclicity significant variance of the resulting carbonate time series is concentrated at millennial-scale changes with periods of about 12, 6, 4, 2.5, and 1.5 kyr. Comparisons of carbonate records from the Blake Bahama Outer Ridge and the Bermuda Rise reveal a remarkable similarity in the time and frequency domain indicating a basin-wide uniform sedimentation pattern during the last 0.9 Ma.

Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

Lucky Strike records of hydrothermal outflow temperatures

We deployed autonomous temperature sensors at black smoker chimneys, cracks, and diffuse flow areas at the Lucky Strike hydrothermal field (Mid-Atlantic Ridge, ~37°17'N) between summer 2009 and summer 2012 and contemporaneously measured tidal pressures and currents as part of the long-term MoMAR experiment to monitor hydrothermal activity. We classify the temperature data according to the hydrogeologic setting of the measurement sites: a high-temperature regime (>190°C) representing discharge of essentially unmixed, primary hydrothermal fluids through chimneys, an intermediate-temperature regime (10-100°C) associated with mixing of primary fluids with cold pore fluids discharging through cracks, and a low-temperature regime (<10°C) associated with a thermal boundary layer forming over bacterial mats associated with diffuse outflow of warm fluids. Temperature records from all the regimes exhibit variations at semi-diurnal tidal periods, and cross-spectral analyses reveal that high-temperature discharge correlates to tidal pressure while low-temperature discharge correlates to tidal currents. Intermediate-temperature discharge exhibits a transitional behavior correlating to both tidal pressure and currents. Episodic perturbations, with transient temperature drops of up to ~150°C, which occur in the high-temperature and intermediate-temperature records, are not observed on multiple probes (including nearby probes at the same site), and they are not correlated with microearthquake activity, indicating that the perturbation mechanism is highly localized at the measurement sites within the hydrothermal structures. The average temperature at a given site may increase or decrease at annual time scales, but the average temperature of the hydrothermal field, as a whole, appears to be stable over our 3 year observation period.

Calcium carbonate stratigraphy of ODP Site 177-1090

A total of 776 sediment samples were measured for percent CaCO3 using a coulometer. These data are compared with percent blue reflectance (450-550 nm) measured with the Oregon State University split-core analysis track. In previous studies percent blue reflectance has been an excellent proxy for percent CaCO3 and in this study shows many of the main depositional trends (i.e., a 100-k.y. cycle, with a 55% reflectance range is evident in the upper 900 k.y., underlain by sediments exhibiting a 40-k.y. cycle with only a 30% reflectance range). Between ~21 and 5 Ma the average percent reflectance decreases from ~35% to ~8%. A similar decrease is also recorded between ~24 and 22 Ma. Percent CaCO3 trends closely match those of the percent blue spectral reflectance. This is especially well shown in the 100-k.y. cyclicity and in the interval between 24.5 and 21.5 Ma. In both intervals CaCO3 analyses are abundant. An exception occurs in the interval between 2 and 5 meters composite depth (~193 and 240 k.y.). There, percent CaCO3 and percent reflectance are out of phase. The lack of agreement is not likely to be due to a very wet core, in which water would dominate the spectral reflectance instead of sediment, or to problems with the composite depth slice. The discrepancy remains unexplained and provides clear evidence that when noninvasive measurements are used as proxies for chemical measurements they must be substantiated by the actual chemical or physical measurements.

Sedimentary data from the Semlac loess-paleosol sequence

The volumetric magnetic susceptibility was measured at frequencies of 300 and 3000 Hz in a static field of 300 mA/m using a Magnon International VSFM in the Laboratory for Environmental- and Palaeomagnetism at the University of Bayreuth. The magnetic susceptibility was mass-normalised. The frequency dependence was calculated as MSfd = (MSlf - MShf) / MSlf *100 [%]. A spectrophotometer (Konica Minolta CM-5) was used to determine the colour of dried and homogenised sediment samples by detecting the diffused reflected light under standardised observation conditions (2° Standard Observer, Illuminant C). Colour spectra were obtained in the visible range (360 to 740 nm), in 10 nm increments, and the spectral data was converted into the Munsell colour system and the CIELAB Colour Space (L*a*b*, CIE 1976) using the Software SpectraMagic NX (Konica Minolta). The measurement of the particle size was conducted by using a Laser Diffraction Particle Size Analyzer (Beckman Coulter LS 13 320 PIDS) and by calculating the mean diameters of the particles within a size range of 0.04 - 2000 µm. Each sample was measured two times in two different concentrations to increase accuracy. Finally all measurements with reliable obscuration (8 - 12 %) were averaged.

Mineralogy of ODP Hole 117-722B (Appendix)

Bulk mineralogy of the terrigenous fraction of 99 samples from ODP Site 722 on the Owen Ridge, western Arabian Sea, has been determined by x-ray diffraction, using an internal standard method. The sampling interval, approximately 4.3 k.y., provides a detailed mineralogic record for the past 500 k.y. Previous studies have identified important modern continental sediment sources and the mineral assemblages presently derived from each. These studies have also demonstrated that most of this material is supplied by southwest and northwest winds during the summer monsoon. A variety of marine and terrestrial records and general circulation model (GCM) simulations have indicated the importance of monsoonal circulation during the Pleistocene and Holocene and have demonstrated increased aridity during glacial times and increased humidity during inter glacials. The mineralogic data generated here were used to investigate variations in source area weathering conditions during these environmental changes. Terrigenous minerals present include smectite, illite, palygorskite, kaolinite, chlorite, quartz, plagioclase feldspar, and dolomite. This mineralogy is consistent with the compositions of source areas presently supplying sediment to the Arabian Sea. An R-mode factor analysis has identified four mineral assemblages present throughout the past 500 k.y.: quartz/chlorite/dolomite (Factor 1), kaolinite/plagioclase/illite (Factor 2), smectite (Factor 3), and palygorskite/dolomite (Factor 4). Chlorite, illite, and palygorskite are extremely susceptible to chemical weathering, and a spectral comparison of these factors with the eolian mass accumulation rate (MAR) record from Hole 722B (an index of dust source area aridity) indicates that Factors 1, 2, and 4 are directly related to changes in aridity. Because of these characteristics, Factors 1,2, and 4 are interpreted to originate from arid source regions. Factor 3 is interpreted to record more humid source conditions. Time-series of scores for the four factors are dominated by short-term (10-100 k.y.) variability, and do not correlate well to glacial/interglacial fluctuations in the time domain. These characteristics suggest that local climatic shifts were complex, and that equilibrium weathering assemblages did not develop immediately after climatic change. Spectral analysis of factor scores identifies peaks at or near the primary Milankovitch frequencies for all factors. Factor 1 (quartz/chlorite/dolomite), Factor 2 (kaolinite/plagioclase/illite), and Factor 4 (illite/palygorskite) are coherent and in phase with the MAR record over the 23, 41, and 100 k.y. bands, respectively. The reasons for coherency at single Milankovitch frequencies are not known, but may include differences in the susceptibilities of minerals to varying time scales of weathering and/or preferential development of suitable continental source environments by climatic changes at the various Milankovitch frequencies.

(Table 1) Vertical distribution of relative contents of the main planktonic groups in the water column of the Kuril-Kamchatka region at Station VITYZ5635

Determinations were made of contents of carbon, lipids, nitrogen and, in some material, protein, carbohydrates, elementary composition of lipids and their spectral composition in total plankton samples from different depths (from the surface to 3000 m) and in several species of macroplanktonic deep-water crustaceans (decapods and mysids) living at different depths. Content of organic carbon and lipids in total plankton is high (40 to 60 and 35 to 70% of dry weight, respectively) and it does not change significantly with increasing depth. Deep-water macroplanktonic crustaceans have extremely high content of organic carbon and lipids, but there are no significant differences in this respect between species that live in different layers of the deep-water zone. Elementary composition of lipids indicates that they are highly saturated, with a marked predominance of unsaponifiable fraction, about 20% of which consists of methane hydrocarbons.

Time-series of snow spectral albedo and superficial snow specific surface area at Dome C in Antarctica, 2012-2015

Spectral albedo has been measured at Dome C since December 2012 in the visible and near infrared (400 - 1050 nm) at sub-hourly resolution using a home-made spectral radiometer. Superficial specific surface area (SSA) has been estimated by fitting the observed albedo spectra to the analytical Asymptotic Approximation Radiative Transfer theory (AART). The dataset includes fully-calibrated albedo and SSA that pass several quality checks as described in the companion article. Only data for solar zenith angles less than 75° have been included, which theoretically spans the period October-March. In addition, to correct for residual errors still affecting data after the calibration, especially at the solar zenith angles higher than 60°, we produced a higher quality albedo time-series as follows: In the SSA estimation process described in the companion paper, a scaling coefficient A between the observed albedo and the theoretical model predictions was introduced to cope with these errors. This coefficient thus provides a first order estimate of the residual error. By dividing the albedo by this coefficient, we produced the "scaled fully-calibrated albedo". We strongly recommend to use the latter for most applications because it generally remains in the physical range 0-1. The former albedo is provided for reference to the companion paper and because it does not depend on the SSA estimation process and its underlying assumptions.

Spectral reflectance library of selected biotic and abiotic coral reef features in Glovers Reef, Belize

Underwater spectral reflectance was measured for selected biotic and abiotic coral reef features of Glovers Reef, Belize from March 6 - 10, 2005. Spectral reflectance's of 63 different benthic types were obtained in-situ. An Ocean Optics USB2000 spectrometer was deployed in an custom made underwater housing with a 0.5 m fiber-optic probe mounted next to an artificial light source. Spectral readings were collected with the probe (bear fibre) about 5 cm from the target to ensure that the target would fill the field of view of the fiber optic (FOV diameter ~4.4 cm), as well as to reduce the attenuating effect of the intermediate water (Roelfsema et al., 2006). Spectral readings included for one target included: 1 reading of the covered spectral fibre to correct for instrument noise, 1 reading of spectralon panel mounted on divers wrist to measure incident ambient light, and 8 readings of the target. Spectral reflectance was calculated for each target by first subtracting the instrument noise reading from each other reading. The corrected target readings were then divided by the corrected spectralon reading resulting in spectral reflectance of each target reading. An average target spectral reflectance was calculated by averaging the eight individual spectral reflectance's of the target. If an individual target spectral reflectance was visual considered an outlier, it was not included in the average spectral reflectance calculation. See Roelfsema at al. (2006) for additional info on the methodology of underwater spectra collection.