Individual and combined effect of ions species and organic matter on the removal of microcontaminants by Fe3+-EDDS/solar-light activated persulfate.

This work is focused on improving the understanding of the complex water matrix interactions occurring during the removal of a microcontaminants mixture (acetamiprid, carbamazepine and caffeine) by solar/Fe3+-EDDS/persulfate process. The individual and combined effects of sulfates (100-500 mg/L), nitrates (20-160 mg/L), bicarbonates (77-770 mg/L) and chlorides (300-1500 mg/L) were assessed by comparing the outcomes obtained in different synthetic and actual water matrices. In general, the results showed negligible effects of the different anions on Fe3+-EDDS concentration and PS consumption profiles, while the combination of bicarbonates and chlorides seemed to be the key for the MC removal efficiency decrease found when working with complex matrixes. Finally, the influence of dissolved organic matter on process performance was evaluated. It was concluded that there is neither any influence of this variable on Fe3+-EDDS concentration and PS consumption profiles. In contrast, there was a general negative effect on MC removal efficiency, which strongly depended on both the concentration and composition of the dissolved organic matter.

Mobility of insecticide residues and main intermediates in a clay-loam soil, and impact of leachate components on their photocatalytic degradation.

This work assesses the behavior (adsorption, degradation and leaching) of four insecticides (chlorantraniliprole, thiametoxam, imidacloprid and pirimicarb) and their main reaction intermediates in a clay-loam textured soil (1.6% OM). Following the batch equilibrium method, the KOC (as log values) ranged from 1.2 to 3.9 (thiametoxam and pirimicarb, respectively). All the insecticides were moderately persistent (t½ = 39-100 days) in the following order: thiametoxam > imidacloprid > pirimicarb > chlorantraniliprole. Two major transformation products, desmethyl-formamido pirimicarb and desmethyl pirimicarb, were formed as consequence of dealkylation of the parent compound. Using disturbed soil columns only thiametoxam (93% of the initial amount) and imidacloprid (42% of the initial amount) were recovered from leachates. In the case of pirimicarb and chlorantraniliprole, 74% and 30%, respectively, were recovered from the soil. Thiametoxam and imidacloprid can be catalogued as mobile compounds, while pirimicarb and chlorantraniliprole are classified as immobile according to the screening indices used (GUS and ELI). Leachates containing thiametoxam and imidacloprid were subjected to photocatalytic treatment for 240 min using TiO2/Na2S2O8 with the help of a photochemical reactor equipped with LED lamp. Both compounds had a very fast degradation rate (half-lives ≤ 0.5 min) in deionized water, while their half-lives were 112 min and 178 min, respectively, in leaching water. This implies a strong effect of the water matrix composition, mainly due to organic matter dissolved (quenching). Only traces of thiametoxam urea and hydroxy imidacloprid were detected during the photocatalytic experiment.

Photocatalytic degradation of four insecticides and their main generated transformation products in soil and pepper crop irrigated with reclaimed agro-wastewater under natural sunlight.

This work is the first-ever study of the concurrence of four insecticides (chlorantraniliprole, imidacloprid, pirimicarb and thiamethoxam) and their main transformation products (TPs) in soil and pepper crop irrigated with reclaimed and non-reclaimed water under agricultural field conditions. Field experiments were conducted using different irrigation supplies: control water (CW), wastewater polluted with phytosanitary commercial products containing the studied insecticides (WW) and reclaimed wastewater after a photocatalytic processing with TiO2/Na2S2O8 at pilot plant under sunlight (RWW). Photocatalytic treatments removed most of the insecticides and their TPs generated during the photoperiod. Neither target insecticides nor their TPs were detected in pepper samples when CW and RWW were used as irrigation source, whereas the four insecticides and two TPs were detected when WW was used. In the experiment carried out with WW, all insecticides and eight TPs were detected in soil samples. The impact of using reclaimed water on the quality of pepper crop was also assessed, showing barely any significant difference.

Appraisal of water matrix on the removal of fungicide residues by heterogeneous photocatalytic treatment using UV-LED lamp as light source.

In this study, the photocatalytic degradation of four fungicides, myclobutanil, penconazole and difenoconazole (triazole compounds) and boscalid (carboxamide), has been examined in different aqueous matrices (tap water, irrigation water and two WWPT effluents). Experiments were conducted at laboratory scale with different reagents-zinc oxide (ZnO), titanium dioxide (TiO2), sodium persulphate (Na2S2O8) and the combined systems ZnO/Na2S2O8 and TiO2/Na2S2O8-in water exposed to UV-LED irradiation. Previously, the effect of catalyst and oxidant loading on the disappearance kinetics of the different fungicides was assessed to know maximum degradation efficiency. The influence of water matrices and pesticide loading in removal effectiveness has been evaluated. It was observed a greater efficiency in processes conducted using the tandems ZnO/Na2S2O8 and TiO2/Na2S2O8 in irrigation and tap waters. Results showed that UV-LED are a suitable alternative for tackling the removal of organic pollutants in water.

Particle Analysis for the Detection of Gunshot Residue (GSR) in Nasal Samples Using Scanning Laser Ablation and Inductively Coupled Plasma-Mass Spectrometry (SLA-ICPMS).

Currently, aluminum stub with carbon adhesive devices are used to collect inorganic gunshot residues (GSR) from the hands of a shooter. In an ideal shooting case, the gunshot particles do not persist for more than 2 h in the hands of the shooter, provided that the hands have not been washed. However, for forensic analysis and inference, the extended persistence of GSR would be desirable. This study investigates a novel GSR sampling and detection protocol. Sampling was performed in the nostrils using swab devices impregnated in ethylenediaminetetraacetic acid (EDTA). The GSRs persisted for longer periods in nasal mucus than on the hands, and particles were detected 6 h after shooting occurred. The analytical determination was conducted by scanning laser ablation-inductively coupled plasma-mass spectrometry (SLA-ICPMS) which enable the identification of the number of particles and their elemental composition. Seventeen isotope signals corresponding to 13 C, 205 Tl and 15 analytes that are usually associated with the composition of GSR residues were monitored: 27 Al, 29 Si, 31 P, 33 S, 35 Cl, 39 K, 44 Ca, 57 Fe, 60 Ni, 63 Cu, 66 Zn, 118 Sn, 121 Sb, 137 Ba, and 208 Pb. The SLA technique enabled the reduction of the swab analysis time to 40 min. The effectiveness of this methodology was evaluated with two types of firearms: a pistol and a shotgun. The results indicated that the methodology proposed for the analysis of the nasal GSR was effective and that it can improve or complement the forensic analyses and inferences presented in a court.

Electrospun silk fibroin/TiO2 mats. Preparation, characterization and efficiency for the photocatalytic solar treatment of pesticide polluted water.

The photocatalytic properties of silk fibroin (SF) incorporating TiO2 nanoparticles using an electrospinning technique were examined. Electrospun SF/TiO2 mats were successfully prepared and characterized by different techniques (XRD, FE-SEM, XPS, XDS, FTIR and BET). The photocatalytic efficiency of these materials were assessed by their ability to degrade four pesticides (boscalid, hexythiazox, pyraclostrobin and trifloxystrobin) in water exposed to solar irradiation. The effect of catalyst loading on the disappearance kinetics of the different pesticides was studied in order to determine the maximum degradation efficiency. The degradation rate significantly increases upon adding the TiO2. However, no significant differences (p < 0.05) were observed when the TiO2 loading was increased from 25 to 50 mg for most compounds. Thus, SF mats with 25 mg of TiO2 were selected. Therefore, a new and simple approach to produce materials with photocatalytic activity, safety and potential application in the purification of water contaminated by pesticides has been developed.

Solar-driven photocatalytic treatment as sustainable strategy to remove pesticide residues from leaching water.

We have demonstrated the potential leaching of eight compounds, one insecticide (flonicamid) and seven fungicides (myclobutanil, penconazole, boscalid, difenoconazole, trifloxystrobin, pyraclostrobin and fenpyroximate) trough a typical Mediterranean soil (Calcaric regosol). The concentrations found in leaching water were in all cases above the limit set by the EU in groundwater (0.1 µg L-1). For this, the efficiency of different homogeneous (photo-Fenton and photo-Fenton-like) and heterogeneous (ZnO and TiO2) photocatalytic systems was tested in deionized water to choose the most appropriate treatment to remove pesticide residues from leaching water. The efficiency was in the order: ZnO + S2O82- (pH 7) > TiO2+ S2O82- (pH 7) > ZnO (pH 7) > TiO2 (pH 7) > Fe3+ (pH 3) > Fe3+ (pH 5) > Fe2+ (pH 3) > Fe2+ (pH 5). Thus, in the subsequent experiment we focus on the efficacy of solar heterogeneous photocatalysis (ZnO/Na2S2O8 and TiO2/ Na2S2O8) on their removal from leaching water. A fast removal was observed for all pesticides at the end of the photoperiod, noticeably higher in the case of ZnO system, with the exception of flonicamid, a recalcitrant pesticide where the degradation rate only reached about 20% after 240 min of solar exposure. Although the mineralisation of the initial dissolved organic carbon was not complete due to the presence of interfering substances in the leaching water, the conversion rate under ZnO/Na2S2O8 treatment was about 1.3 times higher than using TiO2/Na2S2O8.

Analysis of gunshot residues as trace in nasal mucus by GFAAS.

When a gun is fired, the majority of gunshot residues are deposited on the shooter's hands. But these residues disappear through contact with surfaces or washing. Therefore, the maximum time frame to find GSR on a suspect's hands is 8h. The mucus, inside of a nostril, forms a surface layer where they are trapped foreign particles. In this way, mucus inside of a gunshot suspect's nostrils could act like an adhesive medium to stick on it gaseous particles from a gunshot. In this study, the presence of GSR in nasal mucus and its residence time is examined. A new procedure for the sampling of possible gunshot residue accumulated in the nasal mucus is designed. Samples are taken with cotton swabs moistened with a solution of EDTA and, after an acid digestion, are analysed by graphite furnace atomic absorption spectrometry. In addition, samples of hands are taken for comparison purposes. GSR recovery has been successful. The concentration of GSR in nasal mucus is found to be lower than on the hands, but with a longer residence time. Thus, it is possible to expand the sampling time of a suspect also, as nasal mucus cannot be contaminated by handling weapons.