HYDROCARBONS REMOVAL FROM BILGE WATER BY ADSORPTION ONTO ACTIVATED BIOCHAR FROM POSIDONIA OCEANICA

The normal operations carried out on the boats during navigation generate waste waters such as oily bilge water. The latter is the aqueous mixture of potential pollutants of different origins and types: oily fluids, lubricants and greases, cleaning fluids and other wastes that accumulate in the lower part of the vessel [1,2]. The current legislation provides that they can be discharge directly into the sea if the concentrations of some components are below the expected limits. In particular, with regard to oil / hydrocarbons contamination, the current regulatory limit is 15 mg L-1 of total hydrocarbons. The present work starts from a public/private partnership funded by a grant of the Ministry of Economic Development (MiSE). Among the aims of the project, novel methods shall be tested for the reduction of hydrocarbons concentration at values below 5 mg L-1. Moreover, instrumental techniques able to quickly measure the required low hydrocarbons concentration were tested. Among the different steps of bilge water treatment in pilot plant (coagulation, flotation, centrifugation, adsorption etc.), the latter requires the use of adsorbent materials able to reduce the oily concentration below the legal limits. Here we have hosen, optimized and tested materials obtained from bio-oil production waste, a biochar obtained by pyrolysis of Posidonia oceanica, a marine plant widespread in the Mediterranean sea. means of acid or alkali treatments. Moreover, a commercial activated carbon (Filtrasorb 400) has been used for comparison purpose. Synthetic bilge waters were prepared following the reference standards [3] for the preparation of test fluids (used to test the bilge separator plant), containing DMA (distillate marine fuel) and SLS (sodium lauryl sulfate). Batch adsorption isotherms were carried out without ionic medium and at different ionic strengths in NaCl in order to evaluate the effect of salinity on the adsorption ability of dsorbent materials. The same adsorbents were tested by column experiments. In particular, a bench pilot system was built (Figure 1.) and breakthrough curves were obtained changing amount of adsorbent material in column, flow rate, initial DMA and surfactant concentrations. Several instrumental techniques (turbidimetry, TOC, HPLC-QQQ and HPLC-FLD) have been used to measure surfactant and hydrocarbon concentrations in experimental samples. The batch experimental data were fitted with the most used isotherm models (Langmuir, Freundlich, Sips) and important considerations were made on the breakthrough curves of column experiments

FUNCTIONALIZED HALLOYSITE NANOTUBES FOR ENHANCED REMOVAL OF Hg2+ IONS FROM AQUEOUS SOLUTIONS

Water is essential for humans, animals, and plants; pollutants, usually derived from anthropogenic activities, can have a serious effect on its quality. Heavy metals are significant pollutants and are often highly toxic to living organisms, even at very low concentrations. Among the numerous removal techniques proposed, adsorption onto suitable adsorbent materials is considered to be one of the most promising. The objective of the current study was to determine the effectiveness of halloysite nanotubes (HNT) functionalized with organic amino or thiol groups as adsorbent materials to decontaminate polluted waters, using the removal of Hg2+ ions, one of the most dangerous heavy metals, as the test case. The effects of pH, ionic strength (I), and temperature of the metal ion solution on the adsorption ability and affinity of both materials were evaluated. To this end, adsorption experiments were carried out with no ionic medium and in NaNO3 and NaCl at I = 0.1 mol L−1, in the pH range 3–5 and in the temperature range 283.15–313.15 K. Kinetic and thermodynamic aspects of adsorption were considered by measuring the metal ion concentrations in aqueous solution. Various equations were used to fit experimental data, and the results obtained were explained on the basis of both the adsorbent’s characterization and the Hg2+ speciation under the given experimental conditions. Thiol and amino groups enhanced the adsorption capability of halloysite for Hg2+ ions in the pH range 3–5. The pH, the ionic medium, and the ionic strength of aqueous solution all play an important role in the adsorption process. A physical adsorption mechanism enhanced by ion exchange is proposed for both functionalized materials

The effect of metal cations on the aqueous behavior of dopamine. Thermodynamic investigation of the binary and ternary interactions with cd2+, cu2+ and uo22+ in nacl at different ionic strengths and temperatures

The interactions of dopamine [2-(3,4-Dihydroxyphenyl)ethylamine, (Dop−)] with cadmium(II), copper(II) and uranyl(VI) were studied in NaCl(aq) at different ionic strengths (0 ≤ I/mol dm−3 ≤ 1.0) and temperatures (288.15 ≤ T/K ≤ 318.15). From the elaboration of the experimental data, it was found that the speciation models are featured by species of different stoichiometry and stability. In particular for cadmium, the formation of only MLH, ML and ML2 (M = Cd2+; L = dopamine) species was obtained. For uranyl(VI) (UO22+), the speciation scheme is influenced by the use of UO2(acetate)2 salt as a chemical; in this case, the formation of ML2, MLOH and the ternary MLAc (Ac = acetate) species in a wide pH range was observed. The most complex speciation model was obtained for the interaction of Cu2+ with dopamine; in this case we observed the formation of the following species: ML2, M2L, M2L2, M2L2(OH)2, M2LOH and ML2OH. These speciation models were determined at each ionic strength and temperature investigated. As a further contribution to this kind of investigation, the ternary interactions of dopamine with UO22+/Cd2+ and UO22+/Cu2+ were investigated at I = 0.15 mol dm−3 and T = 298.15K. These systems have different speciation models, with the MM’L and M2M’L2OH [M = UO22+; M’ = Cd2+ or Cu2+, L = dopamine] common species; the species of the mixed Cd2+ containing system have a higher stability with respect the Cu2+ containing one. The dependence on the ionic strength of complex formation constants was modelled by using both an extended Debye–Hückel equation that included the Van’t Hoff term for the calculation of the formation enthalpy change values and the Specific Ion Interaction Theory (SIT). The results highlighted that, in general, the entropy is the driving force of the process. The quantification of the effective sequestering ability of dopamine towards the studied cations was evaluated by using a Boltzmann-type equation and the calculation of pL0.5 parameter. The sequestering ability was quantified at different ionic strengths, temperatures and pHs, and this resulted, in general, that the pL0.5 trend was always: UO22+ > Cu2+ > Cd2+

Evaluation of the Purity of Magnesium Hydroxide Recovered from Saltwork Bitterns

Magnesium has been listed among the 30 critical raw materials by the European Union. In recent years, many green and sustainable alternative Mg2+ sources have been sought to satisfy the EU’s demand and to avoid mineral ore consumption. In this context, saltwork bitterns, the by-products of solar sea salt production, have attracted much attention thanks to their high Mg2+ concentrations (up to 80 g/L) and low Ca2+ and bicarbonate contents (<0.5 g/L). Although investigations on Mg2+ extraction from bitterns in the form of Mg(OH)2(s) have already been performed, product purity has never been properly addressed. Mg(OH)2(s) is a chemical compound of great interest and extensive utility in numerous industrial applications only if the powder’s purity is >95% (w/w). This work presents a comprehensive experimental effort of reactive precipitation tests with NaOH solutions at stoichiometric and over-stoichiometric concentrations to: (i) assess the technical feasibility of Mg2+ recovery from real bitterns collected in saltworks of the Trapani district (Italy) and, (ii) for the first time, conduct an extensive purity investigation of the precipitated magnesium hydroxide powders as brucite. This experimental investigation demonstrates the possibility of extracting highly valuable compounds from saltwork bittern waste, embracing the water valorization and resource recovery approach

8-hydroxyquinoline-2-carboxylic acid as possible molybdophore: A multi-technique approach to define its chemical speciation, coordination and sequestering ability in aqueous solution

8-hydroxyquinoline-2-carboxylic acid (8-HQA) has been found in high concentrations (0.5–5.0 mmol·dm−3) in the gut of Noctuid larvae (and in a few other lepidopterans), in which it is proposed to act as a siderophore. Since it is known that many natural siderophores are also involved in the uptake and metabolism of other essential elements than iron, this study reports some results on the investigation of 8-HQA interactions with molybdate (MoO42−, i.e., the main molybdenum form in aqueous environments), in order to understand the possible role of this ligand as molybdophore. A multi-technique approach has been adopted, in order to derive a comprehensive set of information necessary to assess the chemical speciation of the 8-HQA/MoO42− system, as well as the coordination behavior and the sequestering ability of 8-HQA towards molybdate. Chemical speciation studies have been performed in KCl(aq) at I = 0.2 mol·dm−3 and T = 298.15 K by ISE-H+ (glass electrode) potentiometric and UV/Vis spectrophotometric titrations. CV (Cyclic Voltammetry), DP-ASV (Differential Pulse-Anodic Stripping Voltammetry), ESI-MS experiments and quantum mechanical calculations have been also performed to derive information about the nature and possible structure of species formed. These results are also compared with those reported for the 8-HQA/Fe3+ system in terms of chemical speciation and sequestering ability of 8HQA

Extracorporeal Membrane Oxygenation for Acute Pediatric Respiratory Failure

This article is made available for unrestricted research re-use and secondary analysis in any form or by any means with acknowledgement of the original source. These permissions are granted for the duration of the World Health Organization (WHO) declaration of COVID-19 as a global pandemic.The use of extracorporeal membrane oxygenation (ECMO) to support children with acute respiratory failure has steadily increased over the past several decades, with major advancements having been made in the care of these children. There are, however, many controversies regarding indications for initiating ECMO in this setting and the appropriate management strategies thereafter. Broad indications for ECMO include hypoxia, hypercarbia, and severe air leak syndrome, with hypoxia being the most common. There are many disease-specific considerations when evaluating children for ECMO, but there are currently very few, if any, absolute contraindications. Venovenous rather than veno-arterial ECMO cannulation is the preferred configuration for ECMO support of acute respiratory failure due to its superior side-effect profile. The approach to lung management on ECMO is variable and should be individualized to the patient, with the main goal of reducing the risk of VILI. ECMO is a relatively rare intervention, and there are likely a minimum number of cases per year at a given center to maintain competency. Patients who have prolonged ECMO runs (i.e., greater than 21 days) are less likely to survive, though no absolute duration of ECMO that would mandate withdrawal of ECMO support can be currently recommended

Impact of early enteral versus parenteral nutrition on mortality in patients requiring mechanical ventilation and catecholamines: study protocol for a randomized controlled trial (NUTRIREA-2)

BACKGROUND: Nutritional support is crucial to the management of patients receiving invasive mechanical ventilation (IMV) and the most commonly prescribed treatment in intensive care units (ICUs). International guidelines consistently indicate that enteral nutrition (EN) should be preferred over parenteral nutrition (PN) whenever possible and started as early as possible. However, no adequately designed study has evaluated whether a specific nutritional modality is associated with decreased mortality. The primary goal of this trial is to assess the hypothesis that early first-line EN, as compared to early first-line PN, decreases day 28 all-cause mortality in patients receiving IMV and vasoactive drugs for shock. METHODS/DESIGN: The NUTRIREA-2 study is a multicenter, open-label, parallel-group, randomized controlled trial comparing early PN versus early EN in critically ill patients requiring IMV for an expected duration of at least 48 hours, combined with vasoactive drugs, for shock. Patients will be allocated at random to first-line PN for at least 72 hours or to first-line EN. In both groups, nutritional support will be started within 24 hours after IMV initiation. Calorie targets will be 20 to 25 kcal/kg/day during the first week, then 25 to 30 kcal/kg/day thereafter. Patients receiving PN may be switched to EN after at least 72 hours in the event of shock resolution (no vasoactive drugs for 24 consecutive hours and arterial lactic acid level below 2 mmol/L). On day 7, all patients receiving PN and having no contraindications to EN will be switched to EN. In both groups, supplemental PN may be added to EN after day 7 in patients with persistent intolerance to EN and inadequate calorie intake. We plan to recruit 2,854 patients at 44 participating ICUs. DISCUSSION: The NUTRIREA-2 study is the first large randomized controlled trial designed to assess the hypothesis that early EN improves survival compared to early PN in ICU patients. Enrollment started on 22 March 2013 and is expected to end in November 2015. TRIAL REGISTRATION: ClinicalTrials.gov Identifier: NCT01802099 (registered 27 February 2013)

Development and Validation of the Teacher Career-Related Support Self-Efficacy (TCSSE) Questionnaire

Background: Career-related teacher support self-efficacy refers to the teacher’s confidence in his/her own ability to support students’ career choices. To our knowledge, there are neither studies that focus on this topic nor instruments to measure it. Therefore, the current study aimed at developing and validating an instrument to assess teacher career-related support self-efficacy (TCSSE). Methods: In a multi-step process, items were developed and three studies that involved Italian in-service teachers were conducted. In Study 1 (n = 232), the TCSSE was developed and exploratory factor analysis on the 51 initial items was performed. In Study 2 (n = 294), six factors—Get Ready, Empower Self, Get Curious, Empower Skills, Emotional Support and Instrumental Support (α = 0.885)—across 36 items were tested through confirmatory factor analysis (CFA). In Study 3 (n = 100), the reliability of TCSSE was tested. Results: The EFA performed in Study 1 suggested a six-factor solution with 36 items. The results of Study 2 confirmed the six-factor structure (χ2 (579) = 1387.965, p < 0.001, CFI = 0.964, TLI = 0.961, RMSEA = 0.069), the internal consistency (α = 0.863 for Get Ready, α = 0.857 for Empower Self; α = 0.864 for Get Curious; α = 0.909 for Empower Skills; α = 0.881 for Emotional Support; α = 0.885 for Instrumental Support) and validity of the TCSSE. Finally, in Study 3, the reliability of TCSSE was also confirmed. Conclusion: The TCSSE questionnaire can provide researchers and practitioners with a new and reliable measure to assess teacher career-related support self-efficacy. Suggestions for future studies and practice are also provided

Sequestration of organometallic compounds by natural organic matter. Binding of trimethyltin(IV) by fulvic and alginic acids

The binding capacity of fulvic and alginic acids towards trimethyl tin(IV) cation was quantitatively determined in order to evaluate the sequestering ability of toxic organometallic compounds by natural organic matter. Investigations were performed in the pH range of natural waters (5\u20138.5) where the carboxylate groups, largely present in both sequestering agents, are the main binding sites. A chemical interaction model, according to which both the protonation of polyelectrolyte ligands and the hydrolysis of the organotin cation in NaCl aqueous solution were considered, was used to define the speciation of the systems under investigation. Measurements performed at different ionic strength values (0.1, 0.25, 0.5 and 0.7 mol L 121,NaCl) allowed us to consider the dependence of stability constants on the ionic strength, and to calculate the formation constants at infinite dilution. Results obtained show the formation of the complex species TMT(L), TMT(L)2 and TMT(L)(OH) for L=fulvic acid and TMT(L) for L = alginic acid, respectively. In order to compare the strength of interaction of these natural poly electrolytes with other analogous synthetic polyelectrolytes, measurements were also carried out on the trimethyltin(IV)\u2013polyacrylate (5.1 kDa) system, and in this case the formation of TMT(L), TMT(L)2 and TMT(L)(OH) species was found. Results show the following trend of stability for the species TMT(L) in the systems investigated: TMT\u2013fulvate 48 TMT\u2013polyacrylate > TMT\u2013alginate. On the basis of the stability data obtained, the lowest concentration of fulvic and alginic acids, able to act as sequestering agents towards triorganotin(IV) cation in the conditions of natural waters, was also calculated