Temporal variation of pesticide mixtures in rivers of three agricultural watersheds during a major drought in the Western Cape, South Africa

South Africa is the leading pesticide user in Sub-Saharan Africa. However, little is known about the occurrence of pesticide mixtures in surface water and potential environmental risks in Africa. This study investigated the occurrence of pesticides mixtures in three watersheds during a drought year in South Africa. The study was conducted in the Krom River, Berg River and Hex River watersheds within larger agriculture systems in the Western Cape. Pesticide spray records were collected from 38 farms. A total of 21 passive water samplers (styrenedivinylbenzene disks (SDB)) were deployed, each for two weeks per month, over seven sampling rounds during the main pesticide application period between July 2017 and January 2018. Samples were analyzed for 248 pesticide compounds using LC-HR-MS/MS. Pesticide occurrence was analyzed for temporal agreement with pesticide spraying events (Cohen's kappa) and correlation with rainfall patterns and river discharge (Pearson correlation (r p )). Pesticide time-weighted average concentrations were estimated and compared to environmental quality standards (EQS). According to the farm spray records, 96 different pesticides were sprayed during the sampling period and differed considerably between the three study areas, seasons and crops grown. In total, 53 compounds were detected in river water. We detected 39% of compounds from the spraying records and demonstrated close temporal correlations of seasonal patterns for 11 pesticide compounds between reported on spraying records and observations in the streams (kappa = 0.90). However, 23 detected pesticides were not found on spray records, many of them being herbicides. Most of the estimated two-week average pesticide concentrations were below 40 ng/L. The insecticides imidacloprid, thiacloprid, chlorpyrifos and acetamiprid and the herbicide terbuthylazine exceeded at least once their EQS 58-fold (EQS 13 ng/L), 12-fold (EQS 10 ng/L), 9-fold (EQS 0.46 ng/L), 5-fold (EQS 24 ng/L) and 3-fold (EQS 220 ng/L), respectively. Our study substantially widens the view on pesticide pollution in surface water compared to previous studies in Sub-Saharan Africa by targeting more than 200 pesticides using passive sampling systems. This broad assessment revealed the presence of 53 compounds, some of them in high concentrations, indicating possible adverse effects on biota and the quality of the ecosystem. Whether the observed concentration levels in the year 2017 were exceptional due to the lowest ever recorded rainfall and river discharge needs to be tested with additional data to better understand how pesticide pollution levels manifest under average rainfall and river discharge conditions

Transformación de la enseñanza como consecuencia del paso de la presencialidad a la virtualidad – experiencia pedagógica basada en teoría reticular

Fil: Cortaberria, Sofía C. Universidad Nacional de Córdoba. Facultad de Ciencias Económicas; Argentina.Fil: Curchod, Miguel Ángel. Universidad Nacional de Córdoba. Facultad de Ciencias Económicas; Argentina.En definitiva, el objetivo de esta ponencia es narrar el abordaje y tratamiento de la problemática del paso de la presencialidad a la virtualidad en una cátedra masiva de aproximadamente 300 alumnos, con la finalidad de: compartir la experiencia, explicitar el enfoque de formulación y gestión de proyectos complejos, comentar los logros y aprendizajes, explicar las dificultades que se presentaron, cómo se gestionó el cambio y el estrés asociado a la nueva modalidad y, principalmente distinguir los trabajos que se realizaron de manera significativamente diferente en ambos contextos.Fil: Cortaberria, Sofía C. Universidad Nacional de Córdoba. Facultad de Ciencias Económicas; Argentina.Fil: Curchod, Miguel Ángel. Universidad Nacional de Córdoba. Facultad de Ciencias Económicas; Argentina

Working for an algorithm:Power asymmetries and agency in online work settings

Drawing on interviews with 77 high-performing eBay business sellers, this article investigates the power asymmetries generated by customer evaluations in online work settings. Sellers' accounts revealed a high degree of sensitivity to negative reviews, which, while infrequent, triggered feelings of anxiety and vulnerability. These accounts exposed power asymmetries at two levels: the transactional level between sellers and customers, and the governance level between sellers and eBay. Our findings highlight three main mechanisms underlying power asymmetries in this context. First, online customer evaluations have created a new form of employee monitoring in which power is exercised through the construction of visibility gaps between buyers and sellers, and through an implicit coalition between buyers and the platform owner, who join together in the evaluation procedures. Second, by mediating and objectifying relations, algorithms reproduce power asymmetries among the different categories of actor, thereby constraining human agency. Third, online customer evaluations prompt sellers to exploit their practical knowledge of the algorithm to increase their agency. Through the lived experience of working for an algorithm, our findings contribute new understandings of power and agency in online work settings

Seasonal drivers and risks of aquatic pesticide pollution in drought and post-drought conditions in three Mediterranean watersheds

The Western Cape in South Africa has a Mediterranean climate, which has in part led to an abundance of agriculturally productive land supporting the wheat, deciduous fruit, wine, and citrus industries. South Africa is the leading pesticide user in Sub-Saharan Africa. There is limited data on the pesticide pollution of surface water over different seasons in low- and middle-income countries. We evaluated the seasonal drivers of aquatic pesticide pollution in three river catchments (Berg, Krom, and Hex Rivers) from July 2017 to June 2018 and April to July 2019, using 48 passive samplers. Our sampling followed the most severe drought (2015-2018) over the last century. Thus, our analyses focus on how drought and post-drought conditions may affect in-stream pesticide concentrations and loads. Samples were analyzed for 101 pesticide compounds using liquid chromatography - high-resolution mass spectrometry. Environmental Quality Standards (EQS) were used to assess the risks. We detected 60 pesticide compounds across the sampling periods. Our results indicate that all samples across all three catchments contained at least three pesticides and that the majority (83%) contained five or more pesticides. Approximately half the number of pesticides were detected after the drought in 2018. High concentration sums of pesticides (>1mug/L) were detected over long time periods in the Hex River Valley (22weeks) and in Piketberg (four weeks). Terbuthylazine, imidacloprid, and metsulfuron-methyl were detected in the highest concentrations, making up most of the detected mass, and were frequently above EQS. The occurrence of some pesticides in water generally correlated with their application and rainfall events. However, those of imidacloprid and terbuthylazine did not, suggesting that non-rainfall-driven transport processes are important drivers of aquatic pesticide pollution. The implementation of specific, scientific sound, mitigation measures against aquatic pesticide pollution would require comprehensive pesticide application data as well as a targeted study identifying sources and transport processes for environmentally persistent pesticides

Seasonal variations in air concentrations of 27 organochlorine pesticides (OCPs) and 25 current-use pesticides (CUPs) across three agricultural areas of South Africa

For decades pesticides have been used in agriculture, however, the occurrence of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) is poorly understood in Africa. This study investigates air concentrations of OCPs and CUPs in three South African agricultural areas, their spatial/seasonal variations and mixture profiles. Between 2017 and 2018, 54 polyurethane foam-disks passive air-samplers (PUF-PAS) were positioned in three agricultural areas of the Western Cape, producing mainly apples, table grapes and wheat. Within areas, 25 CUPs were measured at two sites (farm and village), and 27 OCPs at one site (farm). Kruskal-Wallis tests investigated area differences in OCPs concentrations, and linear mixed-effect models studied differences in CUPs concentrations between areas, sites and sampling rounds. In total, 20 OCPs and 16 CUPs were detected. A median of 16 OCPs and 10 CUPs were detected per sample, making a total of 11 OCPs and 24 CUPs combinations. Eight OCPs (trans-chlordane, o,p'-/p,p'-dichlorodiphenyldichloroethylene (DDE)/dichlorodiphenyltrichloroethane (DDT), endosulfan sulfate, γ-hexachlorocyclohexane and mirex) and two CUPs (carbaryl and chlorpyrifos) were quantified in all samples. p,p'-DDE (median 0.14 ng/m(3)) and chlorpyrifos (median 0.70 ng/m(3)) showed the highest concentrations throughout the study. Several OCPs and CUPs showed different concentrations between areas and seasons, although CUPs concentrations did not differ between sites. OCPs ratios suggest ongoing chlordane use in the region, while DDT and endosulfan contamination result from past-use. Our study revealed spatial and seasonal variations of different OCPs and CUPs combinations detected in air. Further studies are needed to investigate the potential cumulative or synergistic risks of the detected pesticides

Tracking the ultraviolet-induced photochemistry of thiophenone during and after ultrafast ring opening

Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S–C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales