ALBERT

Description: Low-level water measurements of geological materials are fundamental in understanding the volatile inventories of the Earth from the mantle to crustal reservoirs. Here we describe the development of microanalytical techniques using the new SHRIMP SI ion microprobe to measure the abundances of OH− (as a proxy for water) in volcanic glass and nominally anhydrous minerals (NAMs). Samples were first analysed at the Carnegie Institute of Washington (CIW) on their Cameca ims-6f with calibrations based on previous FTIR and manometry analyses. SHRIMP SI is a large geometry ion microprobe and is currently mainly used for O and S isotope analyses. The analytical protocol used here incorporates multiple collection of 16O− and 16O1H− allowing rapid measurements. A single calibration line incorporating all glasses and NAMs for the SHRIMP SI allows calibration of 16O1H−/16O− to H2O over a wide range in concentration (50 to 15 000 ppm H2O). This calibration line has around a 10% uncertainty, which appears to be limited only by sample heterogeneity. The current background for SHRIMP analysis is between 20–40 ppm but this is expected to improve with improved pumping on the source chamber. A current limitation to water analysis of NAM samples, by any technique, is having a range of standard materials to enable OH− calibration to absolute H2O concentrations. Data are presented for 7 NAM samples (2 olivines, 2 orthopyroxenes and 3 clinopyroxenes) that appear to be promising as potential standards for international laboratory H2O measurements. These NAM samples have been analysed and characterised here by SHRIMP SI, FTIR, EMP and the Cameca ims-6f ion microprobe at CIW. Four of these samples have previously been measured by manometry to determine absolute H2O concentrations.

Description: In this work, we demonstrate for the first time the feasibility of stand-off laser induced breakdown spectroscopy (ST-LIBS) for the analysis of distant submerged objects. The applicability of underwater stand-off LIBS is highly challenging since it involves the delivery of a focused laser pulse toward the distant target through the aqueous media and then the transmission of the light emitted by the laserinduced plasma back to the detection system. Experiments were designed to gain fundamental knowledge regarding LIBS analysis in an underwater open-path configuration. Samples were analyzed at distances up to 80 cm from the sensor at a solid–water interface. Effective plasma formation was achieved using dual pulse excitation with Nd:YAG laser pulses at 532 nm. Intense and well resolved emission signals were observed with interpulse delay times close to 500 ms, whereas the lifetime of the laser-induced plasma was only a few ms. The effect of water temperature and the influence of the underwater optical path on the LIBS signal have also been evaluated.

Description: The Water and Global Change (WATCH) forcing datasets have been created to support the use of hydrological and land surface models for the assessment of the water cycle within climate change studies. They are based on 40-yr ECMWF Re-Analysis (ERA-40) or ECMWF interim reanalysis (ERA-Interim) with temperatures (among other variables) adjusted such that their monthly means match the monthly temperature dataset from the Climatic Research Unit. To this end, daily minimum, maximum, and mean temperatures within one calendar month have been subjected to a correction involving monthly means of the respective month. As these corrections can be largely different for adjacent months, this procedure potentially leads to implausible differences in daily temperatures across the boundaries of calendar months. We analyze day-to-day temperature fluctuations within and across months and find that across-months differences are significantly larger, mostly in the tropics and frigid zones. Average across-months differences in daily mean temperature are typically between 10% and 40% larger than their corresponding within-months average temperature differences. However, regions with differences up to 200% can be found in tropical Africa. Particularly in regions where snowmelt is a relevant player for hydrology, a few degrees Celsius difference can be decisive for triggering this process. Daily maximum and minimum temperatures are affected in the same regions, but in a less severe way.

Description: Correct assignment of the stereogenic centers of highly flexible linear diterpenes (LDs) is challenging. Herein we report the first application of VCD spectroscopy for the absolute configuration determination of LDs of algal origin and provide experimental and computational procedures, such as a fragmentation approach, which will facilitate the use of VCD spectroscopy for configuration assignments of LDs.

Description: A new class of pH-sensitive indicator dyes for optical carbon dioxide sensors based on di-OH-aza-BODIPYs is presented. These colorimetric indicators show absorption maxima in the near infrared range (λmax 670–700 nm for the neutral form, λmax 725–760 nm for the mono-anionic form, λmax 785–830 nm for the di-anionic form), high molar absorption coefficients of up to 77 000 M−1 cm−1 and unmatched photostability. Depending on the electron-withdrawing or electron-donating effect of the substituents the pKa values are tunable (8.7–10.7). Therefore, optical carbon dioxide sensors based on the presented dyes cover diverse dynamic ranges (0.007–2 kPa; 0.18–20 kPa and 0.2–100 kPa), which enables different applications varying from marine science and environmental monitoring to food packaging. The sensors are outstandingly photostable in the absence and presence of carbon dioxide and can be read out via absorption or via the luminescence-based ratiometric scheme using the absorption-modulated inner-filter effect. Monitoring of the carbon dioxide production/consumption of a Hebe plant is demonstrated.

Description: Red blood cell (RBC)-based micromotors containing both therapeutic and diagnostic modalities are described as a means for potential theranostic applications. In this natural RBC-based multicargo-loaded micromotor system, quantum dots (QDs), anti-cancer drug doxorubicin (DOX), and magnetic nanoparticles (MNPs), were co-encapsulated into RBC micromotors. The fluorescent emission of both QDs and DOX provides direct visualization of their loading inside the RBC motors at two distinct wavelengths. The presence of MNPs within the RBCs allows for efficient magnetic guidance under ultrasound propulsion along with providing the potential for magnetic resonance imaging. The simultaneous encapsulation of the imaging nanoparticles and therapeutic payloads within the same RBC micromotor has a minimal effect upon its propulsion behavior. The ability of the RBC micromotors to transport imaging and therapeutic agents at high speed and spatial precision through a complex microchannel network is also demonstrated. Such ability to load and transport diagnostic imaging agents and therapeutic drugs within a single cell-based motor, in addition to a lower toxicity observed once the drug is encapsulated within the multicargo RBC motor, opens the door to the development of theranostic micromotors that may simultaneously treat and monitor diseases.

Description: We present a double-spike technique for precise determination of mass-dependent fractionation of tungsten (W) stable isotopes. Instrumental mass bias effects and isotope fractionation during W separation are corrected for by means of a W-180-W-183 double-spike added prior to sample dissolution. The separation of W from the matrix is achieved via three-step anion-exchange chromatography. Tungsten stable isotopic compositions were determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Results are expressed relative to the NIST SRM 3136 W standard as the permil difference in W-186/W-184 (delta W-186). The external reproducibility of the NIST SRM 3163 W standard is +/- 0.05 parts per thousand with an average composition of -0.01 parts per thousand on W-186/W-184 (2s.d., n = 171). Tungsten stable isotope compositions for USGS standard reference materials are as follows: AGV-2 (andesite; delta W-186 +/- 0.18 +/- 0.05 parts per thousand, 2s.d., n = 6), SDC-1 (mica schist; delta W-186 = 0.36 +/- 0.05 parts per thousand, 2s.d., n = 6), SDO-1 (shale; delta W-186 = 0.26 +/- 0.06 parts per thousand, 2s.d., n = 6), and manganese nodules NOD-A-1 (delta W-186 = 0.07 +/- 0.05 parts per thousand, 2s.d., n = 10) and NOD-P-1 (delta W-186 = 0.31 +/- 0.04 parts per thousand, 2s.d., n = 7). The long-term external reproducibility (2s.d.) for these rock standards is +/- 0.05 parts per thousand.

Description: Fungi are widespread in nature and have conquered nearly every ecological niche. Fungi occur not only in terrestrial but also in freshwater and marine environments. Moreover, fungi are known as a rich source of secondary metabolites. Despite these facts, the ecological role of many of these metabolites is still unknown and the chemical ecology of fungi has not been investigated systematically so far. This review intends to present examples of the various chemical interactions of fungi with other fungi, plants, bacteria and animals and to give an overview of the current knowledge of fungal chemical ecology.

Description: Out of the many bioactive compounds described from the oceans, only a small fraction have been studied for their ecological significance. Similarly, most chemically mediated interactions are not well understood, because the molecules involved remain unrevealed. In Antarctica, this gap in knowledge is even more acute in comparison to tropical or temperate regions, even though polar organisms are also prolific producers of chemical defenses, and pharmacologically relevant products are being reported from the Southern Ocean. The extreme and unique marine environments surrounding Antarctica along with the numerous unusual interactions taking place in benthic communities are expected to select for novel functional secondary metabolites. There is an urgent need to comprehend the evolutionary role of marine derived substances in general, and particularly at the Poles, since molecules of keystone significance are vital in species survival, and therefore, in structuring the communities. Here we provide a mini-review on the identified marine natural products proven to have an ecological function in Antarctic ecosystems. This report recapitulates some of the bibliography from original Antarctic reviews, and updates the new literature in the field from 2009 to the present.

Description: This review covers the literature published in 2013 for marine natural products (MNPs), with 982 citations (644 for the period January to December 2013) referring to compounds isolated from marine microorganisms and phytoplankton, green, brown and red algae, sponges, cnidarians, bryozoans, molluscs, tunicates, echinoderms, mangroves and other intertidal plants and microorganisms. The emphasis is on new compounds (1163 for 2013), together with the relevant biological activities, source organisms and country of origin. Reviews, biosynthetic studies, first syntheses, and syntheses that lead to the revision of structures or stereochemistries, have been included.