Potential carcinogenic hazards of non-regulated disinfection by-products: Haloquinones, halo-cyclopentene and cyclohexene derivatives, N-halamines, halonitriles, and heterocyclic amines

Drinking water disinfectants react with natural organic material (NOM) present in source waters usedfor drinking water to produce a wide variety of by-products. Several hundred disinfections by-products(DBPs) have been identified, but none have been identified with sufficient carcinogenic potency to account for the cancer risks projected from epidemiological studies. In a search for DBPs that might fill this risk gap, the present study projected reactions of chlorine and chloramine that could occur with substructures present in NOM to produce novel by-products. A review of toxicological data on related compounds, supplemented by use of a quantitative structure toxicity relationship (QSTR) program TOPKAT identified chemicals with a high probability of being chronically toxic and/or carcinogenic among 489 established and novel DBPs. Classes of DBPs that were specifically examined were haloquinones (HQs), related halocyclopentene and cyclohexene (HCP&H) derivatives, halonitriles (HNs), organic N-chloramines (NCls), haloacetamides (HAMs), and nitrosamines (NAs). A review of toxicological data available for quinones suggested that HQs and HCP&H derivatives appeared likely to be of health concern and were predicted to have chronic lowest observed adverse effect levels (LOAELs) in the low g/kg day range. Several HQs were predicted to be carcinogenic. Some have now been identified in drinking water. The broader class of HNs was explored by considering current toxicological data on haloacetonitriles and extending this to halopropionitriles. 2,2-dichloropropionitrile has been identified in drinking water at low concentrations, as well as the more widely recognized haloacetonitriles. The occurrence of HAMs has been previously documented. The very limited toxicological data on HAMs suggests that this class would have toxicological potencies similar to the dihaloacetic acids. Organic N-halamines are also known to be produced in drinking water treatment and have biological properties of concern, but no member has ever been characterized toxicologically beyond bacterial or in vitro studies of genotoxicity. The documented formation of several nitrosamines from secondary amines from both natural and industrial sources prompted exploration of the formation of additional nitrosamines. N-diphenylnitrosamine was identified in drinking waters. Of more interest, however, was the formation of phenazine (and subsequently N-chorophenazine) in a competing reaction. These are the first heterocyclic amines that have been identified as chlorination by-products. Consideration of the amounts detected of members of these by-product classes and their probable toxicological potency suggest a prioritization for obtaining more detailed toxicological data of HQs > HCP&H derivatives > NCls > HNs. Based upon a ubiquitous occurrence and virtual lack of in vivo toxicological data, NCls are the most difficult group to assign a priority as potential carcinogenic risks. This analysis indicates that research on the general problem of DBPs requires a more systematic approach than has been pursued in the past. Utilization of predictive chemical tools to guide further research can help bring resolution to the DBP issue by identifying likely DBPs with high toxicological potency

CH4 emission estimates from an active landfill site inferred from a combined approach of CFD modelling and in situ FTIR measurements

Globally, the waste sector contributes to nearly a fifth of anthropogenic methane emitted to the atmosphere and is the second largest source of methane in the UK. In recent years great improvements to reduce those emissions have been achieved by installation of methane recovery systems at landfill sites and subsequently methane emissions reported in national emission inventories have been reduced. Nevertheless, methane emissions of landfills remain uncertain and quantification of emission fluxes is essential to verify reported emission inventories and to monitor changes in emissions. Here we present a new approach for methane emission quantification from a complex source like a landfill site by applying a Computational Fluid Dynamics (CFD) model to calibrated in situ measurements of methane as part of a field campaign at a landfill site near Ipswich, UK, in August 2014. The methane distribution for different meteorological scenarios is calculated with the CFD model and compared to methane mole fractions measured by an in situ Fourier Transform Infrared (FTIR) spectrometer downwind of the prevailing wind direction. Assuming emissions only from the active site, a mean daytime flux of 0.83 mg m−2 s−1, corresponding to 53.26 kg h−1, was estimated. The addition of a secondary source area adjacent to the active site, where some methane hotspots were observed, improved the agreement between the simulated and measured methane distribution. As a result, the flux from the active site was reduced slightly to 0.71 mg m−2 s−1 (45.56 kg h−1), at the same time an additional flux of 0.32 mg m−2 s−1 (30.41 kg h−1) was found from the secondary source area. This highlights the capability of our method to distinguish between different emission areas of the landfill site, which can provide more detailed information about emission source apportionment compared to other methods deriving bulk emissions

Evaluation of wetland CH4 in the Joint UK Land Environment Simulator (JULES) land surface model using satellite observations

Wetlands are the largest natural source of methane. The ability to model the emissions of methane from natural wetlands accurately is critical to our understanding of the global methane budget and how it may change under future climate scenarios. The simulation of wetland methane emissions involves a complicated system of meteorological drivers coupled to hydrological and biogeochemical processes. The Joint UK Land Environment Simulator (JULES) is a process-based land surface model that underpins the UK Earth System Model (UKESM) and is capable of generating estimates of wetland methane emissions. In this study, we use GOSAT satellite observations of atmospheric methane along with the TOMCAT global 3-D chemistry transport model to evaluate the performance of JULES in reproducing the seasonal cycle of methane over a wide range of tropical wetlands. By using an ensemble of JULES simulations with differing input data and process configurations, we investigate the relative importance of the meteorological driving data, the vegetation, the temperature dependency of wetland methane production and the wetland extent. We find that JULES typically performs well in replicating the observed methane seasonal cycle. We calculate correlation coefficients to the observed seasonal cycle of between 0.58 and 0.88 for most regions; however, the seasonal cycle amplitude is typically underestimated (by between 1.8 and 19.5 ppb). This level of performance is comparable to that typically provided by state-of-the-art data-driven wetland CH4 emission inventories. The meteorological driving data are found to be the most significant factor in determining the ensemble performance, with temperature dependency and vegetation having moderate effects. We find that neither wetland extent configuration outperforms the other, but this does lead to poor performance in some regions. We focus in detail on three African wetland regions (Sudd, Southern Africa and Congo) where we find the performance of JULES to be poor and explore the reasons for this in detail. We find that neither wetland extent configuration used is sufficient in representing the wetland distribution in these regions (underestimating the wetland seasonal cycle amplitude by 11.1, 19.5 and 10.1 ppb respectively, with correlation coefficients of 0.23, 0.01 and 0.31). We employ the Catchment-based Macro-scale Floodplain (CaMa-Flood) model to explicitly represent river and floodplain water dynamics and find that these JULES-CaMa-Flood simulations are capable of providing a wetland extent that is more consistent with observations in this regions, highlighting this as an important area for future model development.</p

TransitFit: an exoplanet transit fitting package for multi-telescope datasets and its application to WASP-127~b, WASP-91~b, and WASP-126~b

We present TransitFit, an open-source Python~3 package designed to fit exoplanetary transit light-curves for transmission spectroscopy studies (Available at https://github.com/joshjchayes/TransitFit and https://github.com/spearnet/TransitFit, with documentation at https://transitfit.readthedocs.io/). TransitFit employs nested sampling to offer efficient and robust multi-epoch, multi-wavelength fitting of transit data obtained from one or more telescopes. TransitFit allows per-telescope detrending to be performed simultaneously with parameter fitting, including the use of user-supplied detrending alogorithms. Host limb darkening can be fitted either independently ("uncoupled") for each filter or combined ("coupled") using prior conditioning from the PHOENIX stellar atmosphere models. For this TransitFit uses the Limb Darkening Toolkit (LDTk) together with filter profiles, including user-supplied filter profiles. We demonstrate the application of TransitFit in three different contexts. First, we model SPEARNET broadband optical data of the low-density hot-Neptune WASP-127~b. The data were obtained from a globally-distributed network of 0.5m--2.4m telescopes. We find clear improvement in our broadband results using the coupled mode over uncoupled mode, when compared against the higher spectral resolution GTC/OSIRIS transmission spectrum obtained by Chen et al. (2018). Using TransitFit, we fit 26 transit observations by TESS to recover improved ephemerides of the hot-Jupiter WASP-91~b and a transit depth determined to a precision of 170~ppm. Finally, we use TransitFit to conduct an investigation into the contested presence of TTV signatures in WASP-126~b using 126 transits observed by TESS, concluding that there is no statistically significant evidence for such signatures from observations spanning 31 TESS sectors.Comment: 14 pages, 5 figures, 5 tables, submitted to MNRAS. Temporary data address at https://cdsarc.u-strasbg.fr/ftp/vizier.submit/wasp-127b/ (Final address to be included in accepted paper

Coordinated airborne studies in the tropics (CAST)

This is the final version of the article. It first appeared from the American Meteorological Society via http://dx.doi.org/10.1175/BAMS-D-14-00290.1Abstract The main field activities of the Coordinated Airborne Studies in the Tropics (CAST) campaign took place in the west Pacific during January–February 2014. The field campaign was based in Guam (13.5°N, 144.8°E), using the U.K. Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 atmospheric research aircraft, and was coordinated with the Airborne Tropical Tropopause Experiment (ATTREX) project with an unmanned Global Hawk and the Convective Transport of Active Species in the Tropics (CONTRAST) campaign with a Gulfstream V aircraft. Together, the three aircraft were able to make detailed measurements of atmospheric structure and composition from the ocean surface to 20 km. These measurements are providing new information about the processes influencing halogen and ozone levels in the tropical west Pacific, as well as the importance of trace-gas transport in convection for the upper troposphere and stratosphere. The FAAM aircraft made a total of 25 flights in the region between 1°S and 14°N and 130° and 155°E. It was used to sample at altitudes below 8 km, with much of the time spent in the marine boundary layer. It measured a range of chemical species and sampled extensively within the region of main inflow into the strong west Pacific convection. The CAST team also made ground-based measurements of a number of species (including daily ozonesondes) at the Atmospheric Radiation Measurement Program site on Manus Island, Papua New Guinea (2.1°S, 147.4°E). This article presents an overview of the CAST project, focusing on the design and operation of the west Pacific experiment. It additionally discusses some new developments in CAST, including flights of new instruments on board the Global Hawk in February–March 2015.CAST is funded by NERC and STFC, with grant NE/ I030054/1 (lead award), NE/J006262/1, NE/J006238/1, NE/J006181/1, NE/J006211/1, NE/J006061/1, NE/J006157/1, NE/J006203/1, NE/J00619X/1, and NE/J006173/1. N. R. P. Harris was supported by a NERC Advanced Research Fellowship (NE/G014655/1). P. I. Palmer acknowledges his Royal Society Wolfson Research Merit Award. The BAe-146-301 Atmospheric Research Aircraft is flown by Directflight Ltd and managed by the Facility for Airborne Atmospheric Measurements, which is a joint entity of the Natural Environment Research Council and the Met Office. The authors thank the staff at FAAM, Directflight and Avalon Aero who worked so hard toward the success of the aircraft deployment in Guam, especially for their untiring efforts when spending an unforeseen 9 days in Chuuk. We thank the local staff at Chuuk and Palau, as well as the authorities in the Federated States of Micronesia for their help in facilitating our research flights. Special thanks go to the personnel associated with the ARM facility at Manus, Papua New Guinea without whose help the ground-based measurements would not have been possible. Thanks to the British Atmospheric Data Centre (BADC) for hosting our data and the NCAS Atmospheric Measurement Facility for providing the radiosonde and ground-based ozone equipment. Chlorophyll-a data used in Figure 1 were extracted using the Giovanni online data system, maintained by the NASA GES DISC. We acknowledge the MODIS mission scientists and associated NASA personnel for the production of this data set. Finally we thank many individuals associated with the ATTREX and CONTRAST campaigns for their help in the logistical planning, and we would like to single out Jim Bresch for his excellent and freely provided meteorological advice

The evolution of the student as a customer in Australian higher education: a policy perspective

In 2014, the Australian Federal Government attempted to de-regulate higher education fees so as to allow universities to set their own tuition fees. The associated public debate offer critical insights into how the identity of a student as a ‘customer’ of higher education is understood and deployed when developing higher education policy. This paper uses the 2014 Australian higher education reforms as a lens through which to further scholarly research into the student-as-customer metaphor and to see how it is influenced by the perceptions and understandings of policy actors external to the higher education sector. These include politicians, special interest groups, the students and their parents and prospective employers. This study reveals that the public/private nexus—both of funding and benefit— problematizes traditional conceptualisations of students and others as higher education customers. In turn, this restricts the ability or desire of policy actors to describe how the student functions as a customer as a consequence of market reform. This inability compromises the development of effective and sustainable higher education polic

Evaluation of wetland CH4 in the Joint UK Land Environment Simulator (JULES) land surface model using satellite observations

Wetlands are the largest natural source of methane. The ability to model the emissions of methane from natural wetlands accurately is critical to our understanding of the global methane budget and how it may change under future climate scenarios. The simulation of wetland methane emissions involves a complicated system of meteorological drivers coupled to hydrological and biogeochemical processes. The Joint UK Land Environment Simulator (JULES) is a process-based land surface model that underpins the UK Earth System Model (UKESM) and is capable of generating estimates of wetland methane emissions. In this study, we use GOSAT satellite observations of atmospheric methane along with the TOMCAT global 3-D chemistry transport model to evaluate the performance of JULES in reproducing the seasonal cycle of methane over a wide range of tropical wetlands. By using an ensemble of JULES simulations with differing input data and process configurations, we investigate the relative importance of the meteorological driving data, the vegetation, the temperature dependency of wetland methane production and the wetland extent. We find that JULES typically performs well in replicating the observed methane seasonal cycle. We calculate correlation coefficients to the observed seasonal cycle of between 0.58 and 0.88 for most regions; however, the seasonal cycle amplitude is typically underestimated (by between 1.8 and 19.5 ppb). This level of performance is comparable to that typically provided by state-of-the-art data-driven wetland CH4 emission inventories. The meteorological driving data are found to be the most significant factor in determining the ensemble performance, with temperature dependency and vegetation having moderate effects. We find that neither wetland extent configuration outperforms the other, but this does lead to poor performance in some regions. We focus in detail on three African wetland regions (Sudd, Southern Africa and Congo) where we find the performance of JULES to be poor and explore the reasons for this in detail. We find that neither wetland extent configuration used is sufficient in representing the wetland distribution in these regions (underestimating the wetland seasonal cycle amplitude by 11.1, 19.5 and 10.1 ppb respectively, with correlation coefficients of 0.23, 0.01 and 0.31). We employ the Catchment-based Macro-scale Floodplain (CaMa-Flood) model to explicitly represent river and floodplain water dynamics and find that these JULES-CaMa-Flood simulations are capable of providing a wetland extent that is more consistent with observations in this regions, highlighting this as an important area for future model development

TransitFit: combined multi-instrument exoplanet transit fitting for JWST, HST and ground-based transmission spectroscopy studies

We present TRANSITFIT†, a package designed to fit exoplanetary transit light-curves. TRANSITFIT offers multi-epoch, multi-wavelength fitting of multi-telescope transit data. TRANSITFIT allows per-telescope detrending to be performed simultaneously with transit parameter fitting, including custom detrending. Host limb darkening can be fitted using prior conditioning from stellar atmosphere models. We demonstrate TRANSITFIT in a number of contexts. We model multi-telescope broadband optical data from the ground-based SPEARNET survey of the low-density hot-Neptune WASP-127 b and compare results to a previously published higher spectral resolution GTC/OSIRIS transmission spectrum. Using TRANSITFIT, we fit 26 transit epochs by TESS to recover improved ephemeris of the hot-Jupiter WASP-91 b and a transit depth determined to a precision of 111 ppm. We use TRANSITFIT to conduct an investigation into the contested presence of TTV signatures in WASP-126 b using 180 transits observed by TESS, concluding that there is no statistically significant evidence for such signatures from observations spanning 27 TESS sectors. We fit HST observations of WASP-43 b, demonstrating how TRANSITFIT can use custom detrending algorithms to remove complex baseline systematics. Lastly, we present a transmission spectrum of the atmosphere of WASP-96 b constructed from simultaneous fitting of JWST NIRISS Early Release Observations and archive HST WFC3 transit data. The transmission spectrum shows generally good correspondence between spectral features present in both datasets, despite very different detrending requirements