Interlaboratory development and proposition for a new quality control sample for chemical forensics analysis of chemical warfare agents

A new quality control (QC) test sample for gas chromatography–mass spectrometry (GC–MS) was created and analysed to test the comparability and repeatability of chemical forensics results within the Organisation for the Prohibition of Chemical Weapons (OPCW)–designated laboratories. The QC test sample was designed in collaboration between four laboratories and consists of 27 compounds which evaluate the performance of GC–MS instruments. This solution was analysed with GC–MS(EI) in 11 laboratories, seven of which were OPCW designated. The participating laboratories analysed the sample multiple times on consecutive days, as well as after the analysis of a set of complex matrix samples. Retention times, retention indices, peak areas, peak tailing values, signal-to-noise ratios, and isotope ratios were extracted from the GC–MS data, and statistical multivariate analyses with principal component analysis and Hotelling's T2-tests were conducted. The results from these analyses indicate that differences between GC–MS analyses by multiple laboratories were not statistically significant at the 5% level, as the approximate p-value for the null hypothesis of “no differences between the runs” was 0.69. However, similar data processing methods and data normalisation are essential for enabling the reliable comparison of chemical fingerprints between laboratories. A composition for the QC sample and criteria for acceptable GC–MS performance for chemical forensics are proposed. The composition and criteria differ from the currently used chemical weapons verification analysis QC sample by e.g. broadening the range for retention index calculations by addition of new alkane compounds, including new chemicals with concentrations close to the limit of detection (10–100 ng/ml), and including compounds with higher polarity to emulate real-life forensic samples. The proposed criteria include monitoring of retention indices, isotope ratios, peak tailing, signal-to-noise ratios, peak height, mass spectra, and sensitivity of the instrument. The new compounds and criteria will be the subject of future confidence building exercises to validate their relevancy on a large scale.</p

Response of phytoplankton to enhanced atmospheric and riverine nutrient inputs in a coastal upwelling embayment

Original research paperOver the past decades, as a consequence of human activity, there was an increase in nutrient inputs to the ocean and they are expected to enhance even more in the future. Coastal areas, accounting for a significant proportion of marine primary productivity, are the most vulnerable zones to anthropogenic impacts. The response of phytoplankton communities to an increase in organic and inorganic nutrients levels from natural allochthonous sources was assessed in microcosm experiments conducted in a coastal system affected by intermittent upwelling events (Ría de Vigo, NW Iberia). Three nutrient addition experiments were performed in spring, summer and autumn, when surface water was supplemented with 5 and 10% of atmospheric and riverine matter. Pico-, nano- and microphytoplankton abundances, chlorophyll a concentration (Chl a) and primary production rates (PP) were measured and compared with those in the control seawater sample (without additions) after 48 h of incubation. Simultaneous experiments with controlled additions of inorganic and organic nutrients were also performed in order to describe the limiting nutrient for phytoplankton growth at each experiment. The composition of the matter inputs and the structure of the phytoplankton communities determined the type of response observed. Phytoplankton responses varied among seasons, being positively correlated with dissolved inorganic nitrogen (DIN) concentrations. As expected, the phytoplankton responses to external nutrient inputs were stronger under low nutrient levels (summer) than when phytoplankton was already growing in nutrient replete conditions (spring). Null and negative responses to the natural inputs were observed in autumn, which suggests that the oceanic phytoplankton advected to this coastal system during downwelling events could be occasionally inhibited by these nutrient inputs. In a future global change scenario, characterized by enhanced nutrient inputs from riverine and atmospheric origin, the response of phytoplankton communities will strongly depend on the concentration and chemical composition of these inputs and on the structure of phytoplankton communities able to respond to themSpanish Ministry of Science and Innovation (project REIMAGE CTM2011-30155); Spanish Ministry of Economy and Competitiviness (project iSmall, reference CTM2014-56119-R); Portuguese Foundation for Science and Technology (reference SFRH/BPD/188485/2015); ESF (reference JAE DOC 040) and MINECO (project FERMIO reference CTM2014-57334-JIN)Versión del edito

Carbon dioxide fluxes increase from day to night across European streams

Globally, inland waters emit over 2 Pg of carbon per year as carbon dioxide, of which the majority originates from streams and rivers. Despite the global significance of fluvial carbon dioxide emissions, little is known about their diel dynamics. Here we present a large-scale assessment of day- and night-time carbon dioxide fluxes at the water-air interface across 34 European streams. We directly measured fluxes four times between October 2016 and July 2017 using drifting chambers. Median fluxes are 1.4 and 2.1 mmol m−2 h−1 at midday and midnight, respectively, with night fluxes exceeding those during the day by 39%. We attribute diel carbon dioxide flux variability mainly to changes in the water partial pressure of carbon dioxide. However, no consistent drivers could be identified across sites. Our findings highlight widespread day-night changes in fluvial carbon dioxide fluxes and suggest that the time of day greatly influences measured carbon dioxide fluxes across European streams

pH opposite effects on synthesis of dinucleoside polyphosphates and on oxidation reactions catalyzed by firefly luciferase

AbstractPrevious results have shown that an oxidizing product of firefly luciferin, dehydroluciferyl-adenylate, is the main intermediate in the process of synthesis of dinucleoside polyphosphates catalyzed by firefly luciferase (EC 1.13.12.7). However, we have found that the pH effects on the luciferase oxidizing processes and on the synthesis of dinucleoside polyphosphate are opposite: acidic assay media enhance the synthesis of dinucleoside polyphosphate and inhibit the oxidizing processes. The reason for this apparent contradiction lies on the activation effect of low pH on the adenylate transfer reaction from dehydroluciferyl-adenylate to the acceptor nucleotide