Oxidation of Copper(I) in seawater at nanomolar levels

The oxidation and reduction of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17-8.49), temperature (5-35ºC) and ionic strength (0.1-0.7 M). The oxidation rate was fitted to an equation for sodium chloride and seawater valid at different pH and media conditions: k . . pH- . /T- . I . I k . . pH- . /T- . I . I (sw) (NaCl) log 5 036 0 514 1764 915 1101 0 233 log 5 221 0 609 1915 433 1818 0 408 = + + = + + The reduction of Cu(II) was studied in both media for different initial concentration of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) produced was 20% and 9% for NaCl and seawater, respectively. Considering the copper(I) reduced from Cu(II), the speciation and the contribution of these species to the kinetic process was studied. The Cu(I) speciation is dominated by the CuCl2 - species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range 0.1 M to 0.7 M chloride concentrations.

Assessment of the presence of pharmaceutical compounds in seawater samples from coastal area of Gran Canaria Island (Spain)

[EN]This study presents the evaluation of seven pharmaceutical compounds belonging to different commonly used therapeutic classes in seawater samples from coastal areas of Gran Canaria Island. The target compounds include atenolol (antihypertensive), acetaminophen (analgesic), norfloxacin and ciprofloxacin (antibiotics), carbamazepine (antiepileptic) and ketoprofen and diclofenac (anti-inflammatory). Solid phase extraction (SPE) was used for the extraction and preconcentration of the samples, and liquid chromatography tandem mass spectrometry (LC-MS/MS) was used for the determination of the compounds. Under optimal conditions, the recoveries obtained were in the range of 78.3% to 98.2%, and the relative standard deviations were less than 11.8%. The detection and quantification limits of the method were in the ranges of 0.1–2.8 and 0.3–9.3 ng·L−1, respectively. The developed method was applied to evaluate the presence of these pharmaceutical compounds in seawater from four outfalls in Gran Canaria Island (Spain) during one year. Ciprofloxacin and norfloxacin were found in a large number of samples in a concentration range of 9.0–3551.7 ng·L−1. Low levels of diclofenac, acetaminophen and ketoprofen were found sporadically.

Chemistry of Fe(II) in the presence of organic exudates from phytoplankton and of copper in seawater

Programa de doctorado de Oceanografía ; 2006-2008

Changes in the microbial community based on seawater pH variations

Ocean acidification is an effect of the rise in atmospheric CO2, which causes a reduction in the pH of the ocean and generates a number of changes in seawater chemistry and consequently potentially impacts seawater life. The effect of ocean acidification on metabolic processes (such as net community production and community respiration and on particulate organic carbon (POC) concentrations was investigated in summer 2012 at Cap de la Revellata in Corsica (Calvi, France). Coastal surface water was enclosed in 9 mesocosms and subjected to 6 pCO2 levels (3 replicated controls and 6 perturbations) for approximately one month. No trend was found in response to increasing pCO2 in any of the biological and particulate analyses. Community respiration was relatively stable throughout the experiment in all mesocosms, and net community production was most of the time close to zero. Similarly, POC concentrations were not affected by acidification during the whole experimental period. Such as the global ocean, the Mediterranean Sea has an oligotrophic nature. Based on present results, it seems likely that seawater acidification will not have significant effects on photosynthetic rates, microbial metabolism and carbon transport.

Characterization of major zinc containing myonecrotic and procoagulant metalloprotease 'malabarin' from non lethal trimeresurus malabaricus snake venom with thrombin like activity: its neutralization by chelating agents

A major myonecrotic zinc containing metalloprotease 'malabarin' with thrombin like activity was purified by the combination of gel permeation and anion exchange chromatography from T. malabaricus snake venom. MALDI-TOF analysis of malabarin indicated a molecular mass of 45.76 kDa and its N-terminal sequence was found to be Ile-Ile-Leu- Pro(Leu)-Ile-Gly-Val-Ile-Leu(Glu)-Thr-Thr. Atomic absorption spectral analysis of malabarin raveled the association of zinc metal ion. Malabarin is not lethal when injected i.p. or i.m. but causes extensive hemorrhage and degradation of muscle tissue within 24 hours. Sections of muscle tissue under light microscope revealed hemorrhage and congestion of blood vessel during initial stage followed by extensive muscle fiber necrosis with elevated levels of serum creatine kinase and lactate dehydrogenase activity. Malabarin also exhibited strong procoagulant action and its procoagulant action is due to thrombin like activity; it hydrolyzes fibrinogen to form fibrin clot. The enzyme preferentially hydrolyzes A? followed by B subunits of fibrinogen from the N-terminal region and the released products were identified as fibrinopeptide A and fibrinopeptide B by MALDI. The myonecrotic, fibrinogenolytic and subsequent procoagulant activities of malabarin was neutralized by specific metalloprotease inhibitors such as EDTA, EGTA and 1, 10-phenanthroline but not by PMSF a specific serine protease inhibitor. Since there is no antivenom available to neutralize local toxicity caused by T. malabaricus snakebite, EDTA chelation therapy may have more clinical relevance over conventional treatment.

Thought-Action Fusion and Neutralization Behavior

This study presents a new inventory to assess thought-action fusion (TAF). 160 college students ages 18 to 22 (M = 19.17, SD = 1.11) completed the new Modified Thought Action Scale (MTAFS). Results indicated high internal consistency in the MTAFS (Cronbach’s α = .95). A principal component analysis suggested a three factor solution of TAF-Moral (TAFM), TAFLikelihood (TAFL), and TAF-Harm avoidance-Positive (TAFHP) all with eigenvalues above 1, and factor loadings above .4. A second study examined the association between TAF, obsessivecompulsive and anxiety tendencies after the activation of TAF-like thought processes in a nonclinical sample (n=76). Subjects were randomly assigned to one of three treatment groups intended to provoke TAFL-self, TAFL-other, and TAF moral thought processes. Stepwise regression analyses revealed: 1) the Obsessive-Compulsive Inventory subscales Neutralizing and Ordering significantly predicted instructed neutralization behavior (INB) in non-clinical participants; 2) TAF-Likelihood contributed significant unique variance in INB. These findings suggest that the provocation of neutralization behavior may be mediated by specific subsets of TAF and obsessive-compulsive tendencies.

Sensitivity of Nd isotopic composition in seawater to changes in Nd sources and paleoceanographic implications

It has been argued that past changes in the sources of Nd could hamper the use of the Nd isotopic composition (ϵNd) as a proxy for past changes in the overturning of deep water masses. Here we reconsider uncertainties associated with ϵNd in seawater due to potential regional to global scale changes in the sources of Nd by applying a modeling approach. For illustrative purposes we describe rather extreme changes in the magnitude of source fluxes, their isotopic composition or both. We find that the largest effects on ϵNd result from changes in the boundary source. Considerable changes also result from variations in the magnitude or ϵNd of dust and rivers but are largely constrained to depths shallower than 1 km, except if they occur in or upstream of regions where deep water masses are formed. From these results we conclude that changes in Nd sources have the potential to affect ϵNd. However, substantial changes are required to generate large-scale changes inϵNd in deep water that are similar in magnitude to those that have been reconstructed from sediment cores or result from changes in meridional overturning circulation in model experiments. Hence, it appears that a shift in ϵNdcomparable to glacial-interglacial variations is difficult to obtain by changes in Nd sources alone, but that more subtle variations can be caused by such changes and must be interpreted with caution.

Descaling Injury Impairs the Osmoregulatory Ability of Atlantic Salmon Smolts Entering Seawater

The effect of descaling injury on the osmoregulatory ability of hatchery Atlantic salmon Salmo salar smolts in seawater was investigated. Experimental series were initiated during early, middle, and late periods of the spring smolt migration (April 25, May 11, and May 31, respectively). For each time series, descaled smolts (subjected to descaling on 10% of the body surface area) and control smolts (held out of water for 15 s) were transferred to seawater at 0, 1, 3, or 7 d posttreatment. After fish were held in 35% seawater for 24 h, gill and blood samples were collected and analyzed for Na(+),K(+)-ATPase activity and plasma osmolyte levels. Based on gill Na(+),K(+)-ATPase activity, the three series spanned the period from early smolting (increasing activity) to de-smolting (decreasing activity). In each series, descaled fish transferred to seawater at 0 and 1 d posttreatment had greater plasma osmolality than control fish; descaled fish transferred to seawater at 3 d posttreatment did not differ from controls. The greatest perturbation in osmolality (70 milliosmoles) was observed at the peak of smolting (middle series), whereas lesser increases were seen for early and late-series smolts. The observed osmotic perturbations in descaled fish would probably reduce performance and decrease survival during smolt migration.