•The drugs removal is quite affected by water matrix characteristics.•EO technology achieved more than 90 % of degradation.•PEO was the most efficient technology; but the energy cost is ...higher.•Ibuprofen is the most recalcitrant drug studied.•Diclofenac and ketoprofen are the more oxidizable drugs.
This study is focused on the evaluation of the performance of electrochemical advanced oxidation processes in the treatment of a mixture of five pharmaceuticals contained in low concentration (1 ppm) in two different actual groundwater matrices with very different ionic conductivities. The five drugs selected were sulfadiazine, naproxen, diclofenac, ketoprofen and ibuprofen. Three types of technologies were compared: photolysis, electrolysis and photo-electrolysis. Results pointed out very important differences between the oxidazability of the five drugs with the three technologies. Also, a strong influence of the water matrix on the efficiency of the process. Although the resulting cell voltages were larger during the electrochemical treatments of the low conductivity groundwater, the removal of drugs was found to be faster and more efficient than that obtained when drugs are contained in the high-conductivity groundwaters. The most recalcitrant drug studied was ibuprofen for all processes evaluated, while diclofenac and ketoprofen were found to be the easiest drugs for being degraded. Differences observed are discussed at the light of the mechanisms proposed in the literature.
We establish the double perovskite Ba2CeIrO6 as a nearly ideal model system for j=1/2 moments, with resonant inelastic x-ray scattering indicating that the ideal j=1/2 state contributes by more than ...99% to the ground-state wave function. The local j=1/2 moments form an fcc lattice and are found to order antiferromagnetically at TN=14K, more than an order of magnitude below the Curie-Weiss temperature. Model calculations show that the geometric frustration of the fcc Heisenberg antiferromagnet is further enhanced by a next-nearest neighbor exchange, and a significant size of the latter is indicated by ab initio theory. Our theoretical analysis shows that magnetic order is driven by a bond-directional Kitaev exchange and by local distortions via a strong magnetoelastic effect. Both, the suppression of frustration by Kitaev exchange and the strong magnetoelastic effect are typically not expected for j=1/2 compounds making Ba2CeIrO6 a riveting example for the rich physics of spin-orbit entangled Mott insulators.
Wisconsin's Central Sand Plain east of the Wisconsin River is composed of eolian sand forming high-relief dunes surrounded by sand sheets and scattered low-relief dunes. To establish a maximum age ...for dune formation, three samples for optical dating were taken from glacial Lake Wisconsin lacustrine sediment that underlies eolian sand. These age estimates range from 19.3 to 13.6ka. Age estimates taken from within or at the base of the dunes range from 14.0 to 10.6ka. Samples taken from < 2m of the ground surface were slightly younger, indicating dunes were stabilized between 11.8 and 5.5ka. The younger ages near the surface of some dunes were most likely the result of pedoturbation or localized problems with applying the optical dating method. The majority of the optical age estimates from dunes (18 of 21) indicated that most of the dunes were active between 14 and 10ka and that most dune activity ended by 10ka. These ages suggest that localized activity on dune crests may have occurred in the Holocene but would have been limited to < 1m of sand accumulation. The timing of dune activity and the lack of any significant Holocene reactivation suggest that dune activation in this setting cannot be attributed solely to changes in aridity. Instead, we attribute dune formation to changes in sediment availability from either sand inputs from the Wisconsin River or the melting of permafrost.
The North American Ice Sheet Complex (NAISC; consisting of the Laurentide, Cordilleran and Innuitian ice sheets) was the largest ice mass to repeatedly grow and decay in the Northern Hemisphere ...during the Quaternary. Understanding its pattern of retreat following the Last Glacial Maximum is critical for studying many facets of the Late Quaternary, including ice sheet behaviour, the evolution of Holocene landscapes, sea level, atmospheric circulation, and the peopling of the Americas. Currently, the most up-to-date and authoritative margin chronology for the entire ice sheet complex is featured in two publications (Geological Survey of Canada Open File 1574 Dyke et al., 2003; ‘Quaternary Glaciations – Extent and Chronology, Part II’ Dyke, 2004). These often-cited datasets track ice margin recession in 36 time slices spanning 18 ka to 1 ka (all ages in uncalibrated radiocarbon years) using a combination of geomorphology, stratigraphy and radiocarbon dating. However, by virtue of being over 15 years old, the ice margin chronology requires updating to reflect new work and important revisions. This paper updates the aforementioned 36 ice margin maps to reflect new data from regional studies. We also update the original radiocarbon dataset from the 2003/2004 papers with 1541 new ages to reflect work up to and including 2018. A major revision is made to the 18 ka ice margin, where Banks and Eglinton islands (once considered to be glacial refugia) are now shown to be fully glaciated. Our updated 18 ka ice sheet increased in areal extent from 17.81 to 18.37 million km2, which is an increase of 3.1% in spatial coverage of the NAISC at that time. Elsewhere, we also summarize, region-by-region, significant changes to the deglaciation sequence. This paper integrates new information provided by regional experts and radiocarbon data into the deglaciation sequence while maintaining consistency with the original ice margin positions of Dyke et al. (2003) and Dyke (2004) where new information is lacking; this is a pragmatic solution to satisfy the needs of a Quaternary research community that requires up-to-date knowledge of the pattern of ice margin recession of what was once the world’s largest ice mass. The 36 updated isochrones are available in PDF and shapefile format, together with a spreadsheet of the expanded radiocarbon dataset (n = 5195 ages) and estimates of uncertainty for each interval.
•Updated deglaciation sequence using regional studies/expertise and radiocarbon data.•Region-by-region overview of significant ice margin changes from 18 ka to 1 ka.•New 18 ka 14C (∼21.7 ka cal.) ice sheet is 3.1% larger than previous estimates.•36 updated isochrones (PDFs/shapefiles) and radiocarbon dataset (n = 5195 ages).•Ice margins of Dyke et al. (2003) retained where new information is lacking.
Quasimolecular orbitals in cluster Mott insulators provide a route to tailor exchange interactions, which may yield novel quantum phases of matter. We demonstrate the cluster Mott character of the ...lacunar spinel GaTa_{4}Se_{8} using resonant inelastic x-ray scattering (RIXS) at the Ta L_{3} edge. Electrons are fully delocalized over Ta_{4} tetrahedra, forming quasimolecular J_{tet}=3/2 moments. The modulation of the RIXS intensity as function of the transferred momentum q allows us to determine the cluster wave function, which depends on competing intracluster hopping terms that mix states with different character. This mixed wave function is decisive for the macroscopic properties since it affects intercluster hopping and exchange interactions and furthermore renormalizes the effective spin-orbit coupling constant. The versatile wave function, tunable via intracluster hopping, opens a new perspective on the large family of lacunar spinels and cluster Mott insulators in general.Quasimolecular orbitals in cluster Mott insulators provide a route to tailor exchange interactions, which may yield novel quantum phases of matter. We demonstrate the cluster Mott character of the lacunar spinel GaTa_{4}Se_{8} using resonant inelastic x-ray scattering (RIXS) at the Ta L_{3} edge. Electrons are fully delocalized over Ta_{4} tetrahedra, forming quasimolecular J_{tet}=3/2 moments. The modulation of the RIXS intensity as function of the transferred momentum q allows us to determine the cluster wave function, which depends on competing intracluster hopping terms that mix states with different character. This mixed wave function is decisive for the macroscopic properties since it affects intercluster hopping and exchange interactions and furthermore renormalizes the effective spin-orbit coupling constant. The versatile wave function, tunable via intracluster hopping, opens a new perspective on the large family of lacunar spinels and cluster Mott insulators in general.
Pleistocene permafrost had a major but generally unappreciated effect on the landscape of Wisconsin, second only to glaciation. Evidence for continuous permafrost during the last part of the ...Wisconsin Glaciation includes ice-wedge casts seen both in outcrop (generally in gravel pits) and as polygonal networks (on aerial photographs). Other important evidence includes fossil tundra organisms. Other features that are probably the result of permafrost in Wisconsin include talus cones, block streams, solifluction rubble at the base of most hillslopes, fluvial cobble gravel, gullies that are today inactive, lake-ice collapse trenches, and ice-walled-lake plains. Permafrost caused accelerated regional erosion of the landscape; most topographic features formed before the last permafrost melted have been highly modified or even destroyed, whereas those formed after are much better preserved. In addition, the presence of permafrost influenced many glacial processes and landforms. Permafrost was present until about 14 000 yr BP in the southern part of the state to about 10 000 yr BP in the northern part.
The honeycomb compound alpha-RuCl3 is widely discussed as a proximate Kitaev spin-liquid material. This scenario builds on spin-orbit entangled j = 1/2 moments arising for a t(2g)(5) electron ...configuration with strong spin-orbit coupling lambda and a large cubic crystal field. The actual low-energy electronic structure of alpha-RuCl3, however, is still puzzling. In particular, infrared absorption features at 0.30, 0.53, and 0.75 eV seem to be at odds with a j = 1/2 scenario. Also the energy of the spin-orbit exciton, the excitation from j = 1/2 to 3/2, and thus the value of lambda, are controversial. Combining infrared and Raman data, we show that the infrared features can be attributed to single, double, and triple spin-orbit excitons. We find lambda = 0.16 eV and Delta = 42(4) meV for the observed noncubic crystal-field splitting, supporting the validity of the j = 1/2 picture for alpha-RuCl3. The unusual strength of the double excitation is related to the underlying hopping interactions, which form the basis for dominant Kitaev exchange.
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