Raman spectroscopy was used to investigate sorption mechanisms of cephapirin (CHP), a veterinary antibiotic, onto quartz (SiO₂) and feldspar (KAlSi₃O₈) at different pH. Sorption occurs by electrostatic attraction, monodentate and bidentate complexation. The zwitterion (CHP⁰) adsorbs to a quartz(+) surface by electrostatic attraction of the carboxylate anion group (-COO-) at low pH, but adsorbs to a quartz(-) surface through electrostatic attraction of the pyridinium cation, and possibly COO- bridge complexes, at higher pH. CHP- bonds to quartz(-) surfaces by bidentate complexation between one oxygen of -COO- and oxygen from carbonyl of an acetoxymethyl group. On a feldspar(+/-) surface, CHP⁰ forms monodentate complexes between CO, and possible -COO- bridges and/or electrostatic attachments to localized edge (hydr)oxy-Al surfaces. CHP- adsorbs to feldspar(-) through monodentate CO complexation. Similar mechanisms may operate for other cephalosporins. Results demonstrate, for the first time, that Raman techniques can be effective for evaluating sorption mechanisms of antibiotics. Raman spectroscopy indicates that cephapirin, a veterinary antibiotic, sorbs to quartz and feldspar by electrostatic attraction, and monodentate and bidentate complexation.

Background, aim and scope One of the problems to affect Portland cement matrices is low resistance to aggressive agents, due principally to the presence of a high content of portlandite in the hydrated cements. Pozzolanic materials have played an important role in the improving the durability of cement-based materials for decades. This work studies the behaviour of cement mortar matrices blended with 10% calcined paper sludge (source for metakaolinite) and exposed to different environmental conditions (saline and non-saline environments) after 6 and 12 months of exposure. Materials and methods Two cements were studied: an ordinary Portland cement (CEM 1, 42.5R), acting as reference cement, and a blended cement formulated by mixing 90% (by mass) of CEM 1, 42.5R with 10% (by mass) of paper sludge calcined at 700°C for 2 h. The specimens were exposed 1 year to saline and non-saline environments. All the mineralogy samples were studied through X-ray diffraction and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray analyser. The in-depth study on ionic mobility was performed on samples subjected to natural exposure (coast and tableland) for 6 and 12 months. Results Portland cement was composed of quartz, calcite, calcium hydroxide and tobermorite gels. The pozzolanic cement (10% calcined paper sludge) is of the same composition but a high calcite concentration and barium carbonate. SEM analysis from coastline show deposits of variable composition. The deposits are identified on the surface of different mineral components. The minerals from tableland are much fractured, i.e. calcite and feldspars. Inside the fractures, the deposits and the ions are located and trapped superficially. Discussion SEM analysis of control cement Portland and 10% calcined paper sludge shows deposits on quartz and calcite with a very high concentration of Pb, Zn, Cl and barium sulphate. A very porous aspect is due to the presence of the different aggregate types. This porous configuration permits retention of the ion environment. The pozzolanic cement in environments subject to the saline mist favours the retention and transport of ions observed. Something similar also happens with the increase in exposure to outdoor weather. Non-saline samples show temperature changes (ice or thaw cycles). Barium retention is kept on the surface in fracture lines by the gelification processes. In general, it may be inferred that an increase in exposure time increases the diffusion of ions towards test piece interiors. The chemical composition profiles show that the ions present different penetration speeds. Conclusions The results indicate the better vulnerability of pozzolanic cements from calcined paper sludge in saline and non-saline environments. The cements with a 10% addition of calcined paper sludge favour retention and transport of ion has been observed. Recommendations and perspectives Today, projects are centred on a new recycling line for industrial waste of this kind, with special attention on its incorporation in cement manufacture as a pozzolanic material, setting the most appropriate activation conditions of the mineralogical compound in this waste (kaolinite and metakaolinite) and taking them as a starting point for this project. The use of pozzolanic cement with 10% addition of calcined paper sludge is a system which favours ionic retention.

Background, aim, and scope Bombing and destruction of the industrial and military targets accompanied by complete or incomplete combustion during the war conflict and NATO operation in former Yugoslavia caused the emission of persistent organic pollutants into the atmosphere, water, and soil. A total of 129 ambient air samples from 24 background, urban, and industrial sites, including hot spots, were collected to assess a gas-particle partitioning behavior of various persistent organic pollutants. Materials and methods High volume sampling technique was applied with quartz filters that collect the atmospheric particles and polyurethane foam filters (PUF) that retain the gaseous compounds. Three to ten samples were taken at each site. GFs and PUFs were analyzed separately for their content of polychlorinated biphenyls, organochlorine pesticides, and polyaromatic hydrocarbons. Results Gas phase and particle phase concentrations of selected persistent organic pollutants (POPs) in all samples were converted into the particle-bound fractions [Greek Phi symbol]. These fractions were found to be highly variable, but generally highest in Bosnia and Herzegovina due to the elevated levels of total suspended material in ambient air. Discussion Experimental values of particle-associated fraction were compared to the Junge-Pankow model. Interestingly, a model for urban/industrial environments provided a better prediction of partitioning behavior than a model for background and rural background sites. That is probably because the total amount of atmospheric particles is higher in the Balkan region than found in the previously published studies. Conclusions Even though it has been stated in previous studies that less than 5% of polychlorinated biphenyls (PCBs) are bound to the particles, up to 67% of PCBs were particle associated at several sampling sites in this study. PCB-contaminated soils are probably still one of the strong sources of particles to the atmosphere. Recommendations and perspectives Information on the particle-bound fractions of POPs is important not only for prediction of their fate but also for an estimation of risks they can pose to the environment as well as to humans. When assessing such hazards, it has to be considered that modeled values of the particle-bound fractions can be seriously underestimated at sites with elevated levels of suspended atmospheric matter or at sites with heavily contaminated soils.