Comportamento degli agrofarmaci nei corpi idrici. In: Agrofarmaci, conoscenze per un uso sostenibile, Gennari M. e Trevisan M. curatori

Capitolo 8 Comportamento degli agrofarmaci nei corpi idrici 8.1. - Definizione di corpi idrici 8.1.1. – Definizione 8.1.2. - Normativa per la tutela dei corpi idrici 8.2. - Vie di contaminazione, deriva, runoff, drenaggio 8.3. - Trasporto nei corpi idrici 8.4. - Destino nell’acqua, accumulo nei sedimenti e negli organismi acquatici, degradazione. 8.4.1. - Destino nell’acqua 8.4.2. - Sedimenti e ‘biota’ 8.4.3. - Degradazione 8.5. - Riduzione della contaminazione 8.5.1. – Generalità 8.5.2. - Bio-remediation 8.5.3. - Phyto-remediation 8.5.4. - Uso di tensioattivi, ciclodestrine e zeoliti 8.5.5. - Processi avanzati di degradazione per ossidazion

Mobility of potassium and phosphorus in soil as determined by electro-ultrafiltration (EUF)

An investigation on the desorption rates of K and P from an Italian Vertisol was carried out using an electro-ultrafiltration system (EUF). Desorption rate parameters as maximum desorbable quantity, half-time and rate constant were determined, when possible, using different extraction procedures. The buffer power of the soil and the effects of K and P applications on kinetics factors were evaluated. Potassium release from soil was described by either zero or second order reaction kinetics, depending on selected EUF procedure, and the effects of K applications were almost always negligible. Phosphorus desorption was better described in all cases by zero order reaction kinetics. A set of equations was reported to characterize the soil with respect to the kinetics of nutrient release

Modified clay minerals for water cleaning and re-cycling

A new technology for purification of organic-contaminated water employs a complex between micelles, or vesicles, of an organic cation and a clay mineral, such as montmorillonite (MMT). Micelles of octadecyltrimethylammonium (ODTMA), and benzyldimethylhexadecylammonium (BDMHDA) bromide were mostly used [1, 2]. Vesicles used were composed of didodecyldimethylammonium (DDAB) [3]. Both types of complexes have a very large surface area, large hydrophobic domains, and typically are designed to have a large excess of positive charge. They can be effective in the removal from water of anionic and neutral pollutants such as herbicides (anionic and hydrophobic ones), anionic detergents, antibiotics and other anionic drugs, and components of DOM (dissolved organic matter) such as fulvic and humic acids. DOM is not a pollutant per se, but treatment of water, e.g., by chlorination, results in production of trihalomethanes, which are carcinogenic. Noteworthy, DOM also promotes the migration of herbicides to ground water. The nature of the head group of the organic cation was shown to be critical [1]. In our work, we compared the behaviour of two micellar organoclays realized by using natural MMT and ODTMA and bovine serum albumin (BSA) as surfactants. The herbicides atrazine, and tribenuron-methyl, together with its main degradation product 2-methoxy-4-methylamino-6-methyl-1,3,5-triazine, and the non-steroidal anti-inflammatory (NSAID) drug diclofenac potassium were used as sorption models. The micelle-clay complexes were prepared as suggested by Polubesova et al. [1, 2]. Column filters (about 20 cm) made of a mixture of quartz sand and micelle-clay complexes at 50:1 w/w ratio removed 80% to 98% of the herbicides and up to 99.9% of 2-methoxy-4-methylamino-6-methyl-1,3,5-triazine and diclofenac from initial solutions. Efficiency of removal with micelle-clay filtering was significantly enhanced comparing to results obtained by using activated carbon. A quartz-clay layer placed into the bottom of the filter was able to capture almost all the released surfactants from micelle-clay complexes avoiding their leaking out the filter. The adsorption of contaminants studied was more efficient on ODTMA-MMT and BSA-MMT than natural MMT, since the surfaces of the modified micelle clay are more hydrophobic than the natural MMT. The effectiveness of atrazine and tribenuron-methyl adsorption coupled with the complete removal of the tribenuron-methyl derivative and diclofenac potassium gives account of the usefulness of organoclay systems for the elimination of this kind of pollutant from water in cleaning processes

DETERMINATION OF PHARMACEUTICALS’ RESIDUES IN WASTEWATER OBTAINED WITH AN OPTIMIZED LC-FTICR MS METHOD

The presence of pharmacologically active molecules or their derivatives found in wastewater is a problem of wide interest (1,2). Pharmaceutical compounds (PhCs) and their metabolites, even if present in the order of µg/L and ng/L, can affect the bioconcentration factor, and then be subject to bioaccumulation and biomagnification showing toxic effects for both flora and fauna and mankind. The high resolution liquid chromatography mass spectrometry (LC-MS) coupled to tandem mass spectrometry MS/MS has gained popularity in recent decades thanks to its versatility, specificity and selectivity, finding application as the preferred method for the analysis of PhCs in complex matrices such as waste and/or discharge water. (3,4) Most methods developed in the past have focused on specific therapeutic classes, such as antibiotics for their potential resistance to biotic degradation. In this work we focus on the development of an analytical multi-residual method by using LC-FT/ICR-MS and IRMPD for a particular class of pharmaceuticals chosen according to the 10 mostly diffused and consumed products in the Mediterranean area (4-8). A solid phase extraction from spiked tap water followed by LC-FTICR MS determination has been proposed for the simultaneous analysis of these pharmaceuticals as in Figure 1: (peak 1) metformin hydrochloride (exact m/z 130.10872), (peak 2) amoxicillin (exact m/z 366.11182), (peak 3) caffeine (exact m/z 195.08765), (peak 4) erythromycin (exact m/z 734.46852), (peak 5) clarithromycin (exact m/z 748.48417), (peak 6) carbamazepine (exact m/z 237.10224), (peak 7) naproxen (exact m/z 231.10157), (peak 8) diclofenac sodium (exact m/z 294.00941), (peak 9) ibuprofen (exact m/z 205.12340), (10) aspirin (exact m/z 181.04954). In order to ascertain the identity of all chromatographic peaks, the measurements and interpretation of IRMPD-FTICR data was accomplished. All precursor ions were photon irradiated for 200 ms at 100% laser power by a 20 W continuous CO2 laser source at a wavelength of 10.6 μm. The method optimized was applied to samples collected from influent and effluent from a Wastewater Treatment Plants (WWTP) in order to assess the efficiency of the plant for removing this kind of recalcitrant compounds. Among the PhCs considered in this study, only carbamazepine and clarithromycin were found in the effluent of the WWTP

Analysis of tomato glycoalkaloids by liquid chromatography coupled with electrospray ionization tandem mass spectrometry

Steroidal glycoalkaloids (SGAs) extracted from tomato leaves and berries (Lycopersicon esculentum Mill.) were separated and identified using optimized reversed-phase liquid chromatography with electrospray ionization (ESI) and ion trap mass spectrometry (ITMS). The ESI source polarity and chromatographic conditions were evaluated. The ESI spectra contain valuable information, which includes the mass of SGAs, the mass of the aglycones, and several characteristic fragment ions. Cleavage at the interglycosidic bonds proximal to the aglycones is the most prominent process in the ESI process. A protonated molecule, [M+H](+), accompanied by a mixed adduct ion, [M+H+Na](2+), was observed for a-tomatine (i.e., m/z 1034.7 and 528.9) and dehydrotomatine (i.e., m/z 1032.6 and 527.9) in positive ion mode spectra. The structures of these tomato glycoalkaloids were confirmed using tandem mass spectrometry. The identification of a new alpha-tomatine isomer glycoalkaloid, named filotomatine (MW 1033), which shares a common tetrasaccharide structure (i.e., lycotretraose) with alpha-tomatine and dehydrotomatine, and soladulcidine as an aglycone, is described for the first time. It occurs in significant amounts in the extracts of wild tomato foliage. Multistage mass spectrometry both of the protonated molecules and of the doubly charged ions was used for detailed structural elucidation of SGAs. Key fragmentations and regularities in fragmentation pathways are described and the fragmentation mechanisms involved are proposed

IMPACT OF AIR POLLUTION ON CALCARENITE STONE

Landscape change is driven by weathering, or the in-situ breakdown of material and its removal through erosion. Weathering affects the degradation and deterioration of stone that is originally part of the landscape and covered with soil and sediments. Weathering causes changes in historical buildings and other structures, such as soiling and decay through color change and various associated features of decay (e.g., crusts, blisters, pitting). The main components of the weathering process are mechanical or physical, chemical, and biological. Damage caused to materials exposed in the atmosphere constitutes one of the most important direct effects of acidifying air pollutants. Systematic field and laboratory investigations performed in the recent decade in many countries have contributed to a considerable increase in the knowledge on the mechanisms of the effects of pollutants, on the quantification of damage and on the assessment of the cost of damage. Beside the very important role of SO2 for several materials also studies of the direct or synergistic effect of NOx and O3 have contributed to the understanding of the complex pollution effects [1,23]. Also the effect of microclimate on corrosion of building materials in different positions on buildings and locations within an urban area, has been subject to systematic studies [4]. This paper examines a case study regarding a building placed between an archaeological site of Lavello, a little town located in the Basilicata Region(southern Italy), a cultivated fields and the industrial area surrounding this town where, in the course of time, anthropogenic activity has caused significant damage. We investigated the presence of xenobiotic substances (caused by agricultural activity) and pollution (SO2, CO, NO2, Ozone, heavy metals) caused by industrial activity on the surface of building. All parameters were correlated studying the influence and synergistic effects with climatic parameters and prevailing wind