Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Activated sludge systems removal efficiency of veterinary pharmaceuticals from slaughterhouse wastewater

The knowledge on the efficiency of wastewater treatment plants (WWTPs) from animal food production industry for the removal of both hormones and antibiotics of veterinary application is still very limited. These compounds have already been reported in different environmental compartments at levels that could have potential impacts on the ecosystems. This work aimed to evaluate the role of activated sludge in the removal of commonly used veterinary drugs, enrofloxacin (ENR), tetracycline (TET), and ceftiofur, from wastewater during a conventional treatment process. For that, a series of laboratory-controlled experiments using activated sludge were carried out in batch reactors. Sludge reactors with 100 μg/L initial drug charge presented removal rates of 68 % for ENR and 77 % for TET from the aqueous phase. Results indicated that sorption to sludge and to the wastewater organic matter was responsible for a significant percentage of drugs removal. Nevertheless, these removal rates still result in considerable concentrations in the aqueous phase that will pass through the WWTP to the receiving environment. Measuring only the dissolved fraction of pharmaceuticals in the WWTP effluents may underestimate the loading and risks to the aquatic environment.     

Homegardens as a Multi-functional Land-Use Strategy in Sri Lanka with Focus on Carbon Sequestration

This paper explores the concept of homegardens and their potential functions as strategic elements in land-use planning, and adaptation and mitigation to climate change in Sri Lanka. The ancient and locally adapted agroforestry system of homegardens is presently estimated to occupy nearly 15 % of the land area in Sri Lanka and is described in the scientific literature to offer several ecosystem services to its users; such as climate regulation, protection against natural hazards, enhanced land productivity and biological diversity, increased crop diversity and food security for rural poor and hence reduced vulnerability to climate change. Our results, based on a limited sample size, indicate that the homegardens also store significant amount of carbon, with above ground biomass carbon stocks in dry zone homegardens (n = 8) ranging from 10 to 55 megagrams of carbon per hectare (Mg C ha⁻¹) with a mean value of 35 Mg C ha⁻¹, whereas carbon stocks in wet zone homegardens (n = 4) range from 48 to 145 Mg C ha⁻¹ with a mean value of 87 Mg C ha⁻¹. This implies that homegardens may contain a significant fraction of the total above ground biomass carbon stock in the terrestrial system in Sri Lanka, and from our estimates its share has increased from almost one-sixth in 1992 to nearly one-fifth in 2010. In the light of current discussions on reducing emissions from deforestation and forest degradation (REDD+), the concept of homegardens in Sri Lanka provides interesting aspects to the debate and future research in terms of forest definitions, setting reference levels, and general sustainability.     

Insights into the dissolution and the three-dimensional structure of insensitive munitions formulations

Two compounds, 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO) are the main ingredients in a suite of explosive formulations that are being, or soon will be, fielded at military training ranges. We aim to understand the dissolution characteristics of DNAN and NTO and three insensitive muntions (IM) formulations that contain them. This information is needed to accurately predict the environmental fate of IM constituents, some of which may be toxic to people and the environment. We used Raman spectroscopy to identify the different constituents in the IM formulations and micro computed tomography to image their three-dimensional structure. These are the first three-dimensional images of detonated explosive particles.     

Sexual difference in PCB congener distributions of burbot (Lota lota) from Lake Erie

Concentrations of 86 congeners of polychlorinated biphenyls (PCBs) were determined for 25 adult female and 25 adult male burbot (Lota lota) from Lake Erie. Significant differences in mean proportions of total PCB concentration between males and females ages 14–17 were found for 26 congeners. Males generally had higher mean proportions of hexachloro congeners, whereas females had higher mean proportions of more highly chlorinated congeners. In contrast, only four congeners exhibited differences between males and females ages 6–13 in mean proportions of total PCB. Therefore, the sexual difference in PCB congener distribution widened for older burbot. Males ages 14–17 also had higher proportions of certain hexachloro congeners than the other three demographic groups (males ages 6–13, females ages 6–13, and females ages 14–17) we examined. The reverse was true for more highly chlorinated congeners. The results supported a previous hypothesis that older male burbot spent a substantial amount of time feeding in the vicinity of mouths of rivers with sediment contaminated with PCBs. However, additional studies are needed to clarify and corroborate this apparent “hot spot” effect, such as seasonal movements, spatial distributions, and diet of burbot; and PCB congener distributions of various species of prey fishes captured at various locations throughout the eastern basin of Lake Erie and at different locations in the contaminated rivers.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Effect of fatty acids and oils on photodegradation of azadirachtin‐A

Abstract

Azadirachtin‐A on exposure to UV‐light (254 nm) as a thin film on glass surface gave a isomerised (Z)‐2‐ methylbut‐2‐enoate product. Half‐life of azadirachtin‐A as thin film under UV light was found to be 48 min. Azadirachtin ‐A was irradiated along with saturated and unsaturated fatty acids, and fatty oils under ultra‐violet light as thin film. Saturated fatty acid increased the rate of photodegradation of azadirachtin‐A, whereas unsaturated fatty acids such as oleic, linoleic and elaidic acid reduced the rate of degradation. Castor, linseed and olive oil accelerated the rate of degradation, whereas neem oil showed no or little change in the rate of degradation of azadirachtin‐A. None of these fatty acids and fatty oils were effective in controlling the rate of degradation of azadirachtin‐A under UV‐light as thin film.     

Long Range Cloud Diffusion in the Lower Atmosphere

Previous attempts to measure heavy metals in air are discussed with particular reference to lead. A polarographic method was developed for lead in air samples taken on glass fiber sheet. Using this method, the distribution of lead across the glass fiber sheet was investigated, and within experimental error, found to be uniform. Air samples from 18 Ontario cities, previously analyzed for benzo [a]pyrene content were analyzed.