Chemometric studies in the Lagoon of Venice, Italy. Annual evolution of sulphur species and relationship to biogeochemical cycles in lagoon water

During the period March 1997-March 1998 dimethyl sulphide (DMS), dimethylsulphoniopropionate (DMSP) and carbon disulphide (CS2) were determined weekly in the water of the Lagoon of Venice, Italy (at three stations located in the Giudecca Canal, the San Secondo Canal and the Rio di San Nicolò). At the same time, the following hydrological and biological variables were also measured: tide height, temperature, transmittance, fluorescence, pH, salinity, chlorinity, sulphate, ammonia, nitrite, nitrate, phosphate, silicate, chlorophyll a, phaeopigments, phytoplankton (abundance and biomass). Principal component analysis (PCA), applied as a dimension reduction tool, made it possible to summarize multivariate information in a small number of components, which highlighted the relationships between the temporal evolutions of the sulphur compounds with hydrological and biological variables in the seasonal biogeochemical cycle of the lagoon. In particular the overall temporal cycle, which begins with the development of biological activity in late winter and spring, followed by the predominance of degradation processes during the late summer and the remineralization of nutrients in autumn, is clearly described in the plane of the first two principal components, together with the interrelationships between all the relevant variables.     

Temporal evolution of DMS and DMSP in Antarctic Coastal Sea water

The temporal evolution of concentrations of dimethylsulphide (DMS), its precursor dimethylsulphoniopropionate (DMSP) and chlorophyll a is surveyed weekly in the water column and in a landfast ice core at a coastal station of Gerlache Inlet (Terra Nova Bay, Antarctica) from 27 November 2000 to 14 February 2001. The DMS and DMSP profile concentrations in the water column are similar and show a clear temporal trend, with minimum values (<0.7?nM) at all depths occurring on 27 November 2000 and maximum values (4.8 × 10²?nM for DMS and 1.8 × 10²?nM for DMSP) in surface water on 27 December 2000 for DMS and on 19 December 2000 for DMSP. When the sea-ice cover is present, the temporal evolution of DMSP closely follows that of chlorophyll a in the water column, supporting the idea that DMSP, and therefore DMS, has a phytoplanktonic origin. However, when the ice cover breaks up during the late austral summer, a second phytoplankton bloom occurs, while the DMSP concentration in the sea-water column remains very low. In the ice core, the results show higher concentrations of DMSP than those of the underlying sea water, highlighting the important role of sea ice in the sulphur cycle of the Antarctic ecosystem.     

Hardware components wastes pyrolysis: energy recovery and liquid fraction valorisation

Pyrolysis of hardware components wastes consisting mainly in computers and television components was performed under nitrogen. The degradation products were separated in three fractions, solid, liquid and gaseous. Analyses of the three phases were carried out using gas chromatography (GC), mass spectrometry (MS), thermal analysis and infrared spectroscopy. The energetic content of the gas phase and the economic value of the liquid phase were also determined. The gas fraction produced was rich in light hydrocarbons and hydrogen. Consequently, its calorific value was high and widely sufficient to make the pyrolysis process self-sustained. The main products of the liquid phase were phenol and isopropylphenol (ca. 50–80 wt.%). The presence of Br-based compounds, deriving from the flame retardant employed in hardware components, were also detected. A controlled combustion of the solid phase permitted to obtain the glass fibres unaltered, which can be recycled.     

Microscopic calculation of the constitutive relations

Homogenization theory is used to calculate the macroscopic dielectric constant from the quantum microscopic dielectric function in a periodic medium. The method can be used to calculate any macroscopic constitutive relation, but it is illustrated here for the case of electrodynamics of matter. The so-called cell problem of homogenization theory is solved and an explicit expression is given for the macroscopic dielectric constant in a form akin to the Clausius-Mossotti or Lorentz-Lorenz relation. The validity of this expression is checked by showing that the standard formula is recovered for cubic materials and that the average of the microscopic energy density is the macroscopic one. Finally, the general expression is applied to Bloch eigenstates.     

First-principles calculation of 17O and 25Mg NMR shieldings in MgO at finite temperature: rovibrational effect in solids

The temperature dependence of (17)O and (25)Mg NMR chemical shifts in solid MgO have been calculated using a first-principles approach. Density functional theory, pseudopotentials, a plane-wave basis set, and periodic boundary conditions were used both to describe the motion of the nuclei and to compute the NMR chemical shifts. The chemical shifts were obtained using the gauge-including projector augmented wave method. In a crystalline solid, the temperature dependence is due to both (i) the variation of the averaged equilibrium structure and (ii) the fluctuation of the atoms around this structure. In MgO, the equilibrium structure at each temperature is uniquely defined by the cubic lattice parameters, which we take from experiment. We evaluate the effect of the fluctuations within a quasiharmonic approximation. In particular, the dynamical matrix, defining the harmonic Hamiltonian, has been computed for each equilibrium volume. This harmonic Hamiltonian was used to generate nuclear configurations that obey quantum statistical mechanics. The chemical shifts were averaged over these nuclear configurations. The results reproduce the previously published experimental NMR data measured on MgO between room temperature and 1000 degrees C. It is shown that the chemical shift behavior with temperature cannot be explained by thermal expansion alone. Vibrational corrections due to the fluctuations of atoms around their equilibrium position are crucial to reproduce the experimental results.     

A recipe for finding good solutions to MINLPs

Finding good (or even just feasible) solutions for Mixed-Integer Nonlinear Programming problems independently of the specific problem structure is a very hard but practically important task, especially when the objective and/or the constraints are nonconvex. With this goal in mind, we present a general-purpose heuristic based on Variable Neighborhood Search, Local Branching, a local Nonlinear Programming algorithm and Branch-and-Bound. We test the proposed approach on MINLPLib, comparing with several existing heuristic and exact methods. An implementation of the proposed heuristic is freely available and can employ all NLP/MINLP solvers with an AMPL interface as the main search tools.     

Practical strategies for generating rank-1 split cuts in mixed-integer linear programming

In this paper we propose practical strategies for generating split cuts, by considering integer linear combinations of the rows of the optimal simplex tableau, and deriving the corresponding Gomory mixed-integer cuts; potentially, we can generate a huge number of cuts. A key idea is to select subsets of variables, and cut deeply in the space of these variables. We show that variables with small reduced cost are good candidates for this purpose, yielding cuts that close a larger integrality gap. An extensive computational evaluation of these cuts points to the following two conclusions. The first is that our rank-1 cuts improve significantly on existing split cut generators (Gomory cuts from single tableau rows, MIR, Reduce-and-Split, Lift-and-Project, Flow and Knapsack cover): on MIPLIB instances, these generators close 24% of the integrality gap on average; adding our cuts yields an additional 5%. The second conclusion is that, when incorporated in a Branch-and-Cut framework, these new cuts can improve computing time on difficult instances.     

Green synthesis of para-Menthane-3,8-diol from Eucalyptus citriodora: Application for repellent products

A simple and efficient method was developed for the synthesis of para-Menthane-3,8-diol (PMD), a well-known repellent active against mosquitoes, from Eucalyptus citriodora essential oil by a treatment of citric acid in a biphasic medium (H₂O/essential oil). The E. citriodora contains as main component (+)-citronellal (74% in the present case), which cyclises (Prins reaction) to form cis/trans PMD isomers. As an example, an emulsion containing an aqueous solution of 7% citric acid and E. citriodora oil at 50°, conducted after 15 h stirring to 82% conversion of (+)-citronellal with a selectivity of 80% with the remaining presence of monoterpenes and sesquiterpenes in the medium. Investigations of lasting protection on human volunteers are carried out using a cage test bioassay protocol and Aedes aegypti mosquitoes. At 20% in ⁱPrOH, the new reaction mixture showed a complete protection of 303 min compared to 22 min with the pure essential oil. The modified oil was compared with N,N-diethyl-m-methylbenzamide (DEET), the most popular active used in repellent formulations. Thermogravimetric analyses (TGA) of E. citriodora, the modified oil, PMD, DEET, and (+)-citronellal were performed and showed a slow evaporation rate for PMD and DEET as well as for the modified oil, which may explain their long lasting protection action.     

Improved strategies for branching on general disjunctions

Within the context of solving Mixed-Integer Linear Programs by a Branch-and-Cut algorithm, we propose a new strategy for branching. Computational experiments show that, on the majority of our test instances, this approach enumerates fewer nodes than traditional branching. On average, on instances that contain both integer and continuous variables the number of nodes in the enumeration tree is reduced by more than a factor of two, and computing time is comparable. On a few instances, the improvements are of several orders of magnitude in both number of nodes and computing time.     

RBFOpt: an open-source library for black-box optimization with costly function evaluations

We consider the problem of optimizing an unknown function given as an oracle over a mixed-integer box-constrained set. We assume that the oracle is expensive to evaluate, so that estimating partial derivatives by finite differences is impractical. In the literature, this is typically called a black-box optimization problem with costly evaluation. This paper describes the solution methodology implemented in the open-source library RBFOpt, available on COIN-OR. The algorithm is based on the Radial Basis Function method originally proposed by Gutmann (J Glob Optim 19:201–227, 2001.  https://doi.org/10.1023/A:1011255519438), which builds and iteratively refines a surrogate model of the unknown objective function. The two main methodological contributions of this paper are an approach to exploit a noisy but less expensive oracle to accelerate convergence to the optimum of the exact oracle, and the introduction of an automatic model selection phase during the optimization process. Numerical experiments show that RBFOpt is highly competitive on a test set of continuous and mixed-integer nonlinear unconstrained problems taken from the literature: it outperforms the open-source solvers included in our comparison by a large amount, and performs slightly better than a commercial solver. Our empirical evaluation provides insight on which parameterizations of the algorithm are the most effective in practice. The software reviewed as part of this submission was given the Digital Object Identifier (DOI)  https://doi.org/10.5281/zenodo.597767.