RESUMO
Sulfide species may be present in groundwater due to natural processes or due to anthropogenic activity. H2S contamination poses odor nuisance and may also lead to adverse health effects. Advanced oxidation processes (AOPs) are considered promising treatments for hydrogen-sulfide removal from water, but conventional AOPs usually require continuous chemical dosing, as well as post-treatment, when solid catalysts are applied. Vacuum-UV (VUV) radiation can generate ·OH in situ via water photolysis, initiating chemical-free AOP. The present study investigated the applicability of VUV-based AOP for removal of H2S both in synthetic solutions and in real groundwater, comparing combined UV-C/VUV and UV-C only radiation in a continuous-flow reactor. In deionized water, H2S degradation was much faster under the combined radiation, dominated by indirect photolysis, and indicated the formation of sulfite intermediates that convert to sulfate at high radiation doses. Sulfide was efficiently removed from natural groundwater by the two examined lamps, with no clear preference between them. However, in anoxic conditions, common in sulfide-containing groundwater, a small advantage for the combined lamp was observed. These results demonstrate the potential of utilizing VUV-based AOP for treating H2S contamination in groundwater as a chemical-free treatment, which can be especially attractive to remote small treatment facilities.
RESUMO
Advanced oxidation processes (AOPs) augment traditional water treatment methods, enhancing the removal of persistent contaminants. Efficiency of AOPs that utilize UV radiation for oxidants generation (e.g., ·OH) is reduced in water matrices that contain substants that may act as inner UV filters and/or scavengers for the generated radicals. Among such interfering compounds are major inorganic ions and dissolved organic matter that are naturally present in realistic waters. Thus, to improve AOPs efficiency it is desirable to separate the target pollutants from these natural species before treatment. Here the potential of electrodialysis as such pretreatment was investigated. The impact of this pretreatment on photo-oxidation of the pharmaceutical carbamazepine (CBZ) under VUV (λ<200 nm) irradiation, which yields ·OH generation via water homolysis, was tested in different water matrices. The obtained results indicate that in all tested solutions: Deionized water, groundwater, surface water, and treated wastewater, the addition of electrodialysis pretreatment successfully separated the target micropollutant CBZ from the major natural ions and to some extend the NOM, resulting faster degradation rates of CBZ and its transformation products in the following VUV-based AOP. Energy cost calculations indicated that addition of this pretreatment step reduces the overall energy demand of the system (i.e., energy consumption for the electrodialysis step was smaller than the energy gained by reducing the required VUV irradiation dose).
Assuntos
Poluentes Químicos da Água , Purificação da Água , Poluentes Químicos da Água/análise , Raios Ultravioleta , Vácuo , Oxidantes , Oxirredução , Purificação da Água/métodos , Carbamazepina , Íons , Peróxido de HidrogênioRESUMO
Surface degradation of profenofos (PF), a VX nerve gas surrogate, was investigated using in situ photo-oxidation that combines simple instrumentation and ambient gases (O2 and H2O) as a function of exposure conditions ([O3], [OH], UV light λ = 185 and/or 254 nm, relative humidity) and PF film surface density (0.38-3.8 g m(-2)). PF film 0.38 g m(-2) fully degraded after 60 min of exposure to both 254 and 185 nm UV light in humidified air and high ozone. The observed pseudo-first-order surface reaction rate constant (kobs = 0.075 ± 0.004 min(-1)) and calculated hydroxyl concentration near the film surface ([OH]g = (9 ± 2) × 10(7) molecules cm(-3)) were used to determine the second-order rate constant for heterogeneous reaction of PF and OH (k(OH)PF = (5 ± 1) × 10(-12) cm(3) molec(-1) s(-1)). PF degradation in the absence of 185 nm light or without humidity was lower (70% or 90% degradation, respectively). With denser PF films ranging from 2.3 to 3.8 g m(-2), only 80% degradation was achieved until the PF droplet was redissolved in acetonitrile which allowed >95% PF degradation. Surface product analysis indicated limited formation of the nontoxic phosphoric acid ester but the formation of nonvolatile chemicals with increased hydrophilicity and addition of OH.
Assuntos
Inseticidas/química , Organotiofosfatos/química , Processos Fotoquímicos , Cinética , Oxirredução , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície , Raios UltravioletaRESUMO
The COVID-19 pandemic created a global crisis impacting not only healthcare systems, but also economics and society. Therefore, it is important to find novel methods for monitoring disease activity. Recent data have indicated that fecal shedding of SARS-CoV-2 is common, and that viral RNA can be detected in wastewater. This suggests that wastewater monitoring is a potentially efficient tool for both epidemiological surveillance, and early warning for SARS-CoV-2 circulation at the population level. In this study we sampled an urban wastewater infrastructure in the city of Ashkelon (Ì´ 150,000 population), Israel, during the end of the first COVID-19 wave in May 2020 when the number of infections seemed to be waning. We were able to show varying presence of SARS-CoV-2 RNA in wastewater from several locations in the city during two sampling periods, before the resurgence was clinically apparent. This was expressed with a new index, Normalized Viral Load (NVL) which can be used in different area scales to define levels of virus activity such as red (high) or green (no), and to follow morbidity in the population at the tested area. The rise in viral load between the two sampling periods (one week apart) indicated an increase in morbidity that was evident two weeks to a month later in the population. Thus, this methodology may provide an early indication for SARS-CoV-2 infection outbreak in a population before an outbreak is clinically apparent.
Assuntos
COVID-19 , Esgotos , Humanos , Pandemias , RNA Viral , SARS-CoV-2 , Águas ResiduáriasRESUMO
Nicotine dynamics in an indoor environment can be greatly affected by building parameters (e.g. relative humidity (RH), air exchange rate (AER), and presence of ozone), as well as surface parameters (e.g. surface area (SA) and polarity). To better understand the indoor fate of nicotine, these parameter effects on its sorption, desorption, and oxidation rates were investigated on model indoor surfaces that included fabrics, wallboard paper, and wood materials. Nicotine sorption under dry conditions was enhanced by higher SA and higher polarity of the substrate. Interestingly, nicotine sorption to cotton and nylon was facilitated by increased RH, while sorption to polyester was hindered by it. Desorption was affected by RH, AER, and surface type. Heterogeneous nicotine-ozone reaction was investigated by Fourier transform infrared spectrometry with attenuated total reflection (FTIR-ATR), and revealed a pseudo first-order surface reaction rate of 0.035 +/- 0.015 min(-1) (at [O(3)] = 6 +/- 0.3 x 10(15) molecules cm(-3)) that was partially inhibited at high RH. Extrapolation to a lower ozone level ([O(3)] = 42 ppb) showed oxidation on the order of 10(-5) min(-1) corresponding to a half-life of 1 week. In addition, similar surface products were identified in dry and high RH using gas chromatography-mass spectrometry (GC-MS). However, FTIR analysis revealed different product spectra for these conditions, suggesting additional unidentified products and association with surface water. Knowing the indoor fate of condensed and gas phase nicotine and its oxidation products will provide a better understanding of nicotine's impact on personal exposures as well as overall indoor air quality.
Assuntos
Nicotina/química , Adsorção , Ar , Fibra de Algodão , Umidade , Cinética , Oxirredução , Ozônio/química , Poliésteres/química , Propriedades de SuperfícieRESUMO
Despite growing apprehension regarding the fate of organic micropollutants (MPs) of emerging concern, little attention has been paid to their presence in domestic greywater, where they mainly originate from personal care products. Many MPs are not fully removed in conventional greywater treatments and require additional treatment. Vacuum-UV radiation (VUV) can generate ·OH in situ, via water photolysis, initiating advanced oxidation process (AOP) without any chemical addition. Despite growing interest in VUV-based AOP, its performance in real-life grey- or wastewater matrices has hardly been investigated. The present study investigates the removal of triclosan (TCS) and oxybenzone (BP3), common antibacterial and UV-filter MPs, in deionized water (DIW) and in treated greywater (TGW) using combined UVC/VUV or UVC only radiation in a continuous-flow reactor. Degradation kinetics of these MPs and their transformation products (TPs) were addressed, as well as bacterial growth inhibition of the resulting reactor's effluent. In DIW, MP degradation was much faster under the combined UVC/VUV irradiation. In TGW, the combined radiation successfully removed both MPs but at lower efficiency than in DIW, as particles and dissolved organic matter (DOM) acted as radical scavengers. Filtration and partial DOM removal prior to irradiation improved the process efficiency and reduced energy requirements under the combined radiation (from 1.6 and 167 to 1.1 and 6.0 kWh m-3·Ö¼order-1 for TCS and BP3, respectively). VUV radiation also reduced TP concentrations in the effluent. As a result, bacterial growth inhibition of triclosan solution irradiated by VUC/VUV was lower than that irradiated by UVC light alone, for UV dose > 120 mJ cm-2.
Assuntos
Raios Ultravioleta , Vácuo , Águas Residuárias , Poluentes Químicos da Água/isolamento & purificação , Purificação da Água/métodos , Benzofenonas/isolamento & purificação , Oxirredução , Fotólise , Triclosan/isolamento & purificaçãoRESUMO
Chlorpyrifos (CP) is still a commonly employed organophosphorus insecticide worldwide. In semi-arid and Mediterranean climates, applied CP is expected to remain on leaves surfaces for relatively long time due to the lack of summer rains and common use of drip irrigation. The present work examines the loss rate of CP from leaves via different surface processes: evaporation, direct photolysis and reactions with ozone and OH radicals. Laboratory experiments showed that evaporation rate constant of CP increased from 0.109 to 0.492 h-1 with the increase in wind speed up to 4 m/s. First-order rate constant of direct photolysis, measured using a solar simulator, was k'UV = 1.15 (±0.01) x 10-20 cm2 photon-1. Second-order rate constants for the reaction of CP with ozone and OH were measured as 6 × 10-20 and 6 × 10-12 cm3 molecule-1 s-1, respectively. The above rate constants were applied successfully in an outdoor experiment to predict the disappearance of chloropyrifos under specific environmental conditions. Further modeling showed that the insecticide half-life time on exposed surfaces under typical Mediterranean environment will be in the range of 0.9-6.9 h. Evaporation is expected to be the dominant removal path under most environmental conditions, followed by direct photolysis and reaction with OH.
Assuntos
Clorpirifos/farmacologia , Meio Ambiente , Inseticidas/farmacologia , Fotólise , Folhas de Planta/química , Atmosfera , Clorpirifos/análise , Cymbopogon/química , Diospyros/química , Meia-Vida , Radical Hidroxila/química , Inseticidas/análise , Malus/química , Ozônio , Folhas de Planta/efeitos dos fármacos , Luz SolarRESUMO
A new, simple and accurate method is introduced for determining H(2)CO(3)(*) alkalinity in fresh waters dominated by the carbonate weak-acid system. The method relies on a single H(3)PO(4) dosage and two pH readings (acidic pH value target: pH~4.0). The computation algorithm is based on the concept that the overall alkalinity mass of a solution does not change upon the addition of a non-proton-accepting species. The accuracy of the new method was assessed batch-wise with both synthetic and actual tap waters and the results were compared to those obtained from two widely used alkalinity analysis methods (titration to pH~4.5 and the Gran titration method). The experimental results, which were deliberately obtained with simple laboratory equipment (glass buret, general-purpose pH electrode, magnetic stirrer) proved the method to be as accurate as the conventional methods at a wide range of alkalinity values (20-400 mg L(-1) as CaCO(3)). Analysis of the relative error attained in the proposed method as a function of the target (acidic) pH showed that at the range 4.0