Description: Three new metabolites, 5-hydroxy-3,7-dimethoxyflavone-4′-O-β-glucopyranoside (1), 2β,19-epoxy-3β,14β-dihydroxy-19-methoxy-5α-card-20(22)-enolide (4) and β-anhydroepidigitoxigenin-3β-O-glucopyranoside (5), along with two known compounds, uzarigenine (2) and β-anhydroepidigitoxigenin (3), were isolated from Calotropis procera (Asclepiadaceae). The structure elucidation was accomplished mainly by nuclear magnetic resonance (NMR) spectroscopic and mass spectrometric methods. To examine putative antimicrobial or cytotoxic activities, various bioassays were performed. Uzarigenine (2) demonstrated moderate cytotoxicity.

Description: A new system is presented that allows the continuous measurement of methane and carbon dioxide concentrations in surface waters autonomously using ships of opportunity. The analytical setup consists of a methane carbon dioxide-Analyzer (MCA, Los Gatos Research) joined to an established equilibrator setup. The analyzer uses off-axis integrated cavity output spectroscopy (ICOS) and combines a highly specific infrared band laser with a set of strongly reflective mirrors to obtain an effective laser path length of several kilometers. This allows detecting methane and carbon dioxide in the equilibrated gas phase with high recision (less than 0.1%) and frequency. The system was installed on the cargo ship Finnmaid (Finnlines) in November 2009, which commutes regularly in the Baltic Sea between Travemünde (Germany), Gdynia (Poland), and Helsinki (Finland). Methane concentrations of the equilibrated gas phase measured by gas chromatography and by the MCA during lab tests are in excellent agreement. The comparison of carbon dioxide data measured by the MCA system to CO2 values gathered from the same type of equilibrator in combination with a LICOR CO2 detector (Schneider et al. 1992) during onboard operation show concordant results. The time constant for the system in freshwater at room temperature was determined to be 676 s for CH4 and 226 s for CO2. Additional performance tests are presented. First field results show large regional differences with remarkable features, especially in shallow regions, demonstrating the need for the high spatiotemporal data coverage provided by the instrument.

Description: Borates are the third most important component of total alkalinity (AT) in the oxic waters. Their concentrations are a function of the dissociation constant of boric acid and total boron (TB) concentration. The latter is approximated from salinity (S) as boron behave conservatively in the seawater. The linear dependencies between TB and S developed for the open ocean contain no intercept suggesting that river water contains no boron. Based on the historical data and our own measurements we identified a TB vs. S relationship specific for the Baltic Sea: TB [μmol kg−1] = 10.838 ∗ S + 13.821. In the series of the sensitivity tests we analysed what effect can have this anomaly on the determination of borate alkalinity (AB) and on the calculations within the CO2 system performed with AT as an input variable. Due to the high pKa for boric acid the influence of TB anomaly on AB exists only for pH 〉 8. The highest deviation in AB appears at low salinities. When salinity increases the effect becomes smaller and at salinities 〉 14, due to lower slope in TB vs. S dependency in the Baltic than in the open ocean, the effect on AB turns to negative and decreases further with the S increase. These uncertainties in AB influence calculations of pCO2 (CO2 partial pressure) and pH, when CT (total CO2 concentration) and AT are used as input parameters (the combination used in biogeochemical models). For pCO2 the discrepancies in calculations are not very much dependent on the AT. The highest are observed for low salinities and pH of 8.2–8.4, however they do not exceed 10 μatm. This relatively low influence of TB anomaly on pCO2 calculations is a result of the high distance on the pH scale between high pCO2 conditions (low pH) and the highest AB anomaly (high pH). In case of pH calculations the highest influence of TB anomaly is observed for the low AT and low S waters. For three different AT considered in our study the highest pH errors (up to 0.05 pH unit) were observed for AT = 500 μmol kg−1, while the lowest (up to 0.01 pH unit) were observed for highly buffered waters (AT = 3000 μmol kg−1). Irrespective of the AT the highest errors were found for low CT simulating low pCO2 (and thus high pH) conditions. This is due to the high pKa for boric acid that shifts the effects of the TB anomaly to high pH values. Although the observed discrepancies in pH and pCO2 calculations due to TB anomaly manifest themselves only at the specific environmental conditions the use of experimentally obtained TB vs. S dependency will increase the accuracy of the CO2 system calculations for the Baltic Sea and likely for other brackish systems.

Description: Two newly designed underway systems for the measurement of CO2 partial pressure (pCO2) in seawater and the atmosphere are described. Results of an intercomparison experiment carried out in the North Sea are presented. A remarkable agreement between the two simultaneously measured (pCO2) data sets was observed even though the spatial variability in surface pCO2 was high. The average difference of all l -min averages of the seawater pCO2 was as low as 0.15 μatm with a standard deviation of 1.2 μatm indicating that no systematic difference is present. A closer examination of the profiles shows that differences tend to be highest during maxima of the pCO2 gradient (up to 14 μatm/min). The time constants of both systems were estimated from laboratory experiments to 45 s, respectively, 75 s thus quantitatively underlining their capability of a fast response to pCO2 changes