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Air-discharged waste from commonly used trenchless technologies of sewer pipe repairs is an emerging and poorly characterized source of urban pollution.

 

Iron (Fe) is ubiquitous in nature and found as Fe II or Fe III in minerals or as dissolved ions Fe 2+ or Fe 3+ in aqueous systems. The interactions of soluble Fe have important implications for fresh water and marine biogeochemical cycles, which have impacts on global terrestrial and atmospheric environments. Upon dissolution of Fe III into natural aquatic systems, organic carboxylic acids efficiently chelate Fe III to form [Fe III –carboxylate] 2+ complexes that undergo a wide range of photochemistry-induced radical reactions. The chemical composition and photochemical transformations of these mixtures are largely unknown, making it challenging to estimate their environmental impact. To investigate the photochemical process of Fe III –carboxylates at the molecular level, we conduct a comprehensive experimental study employing UV-visible spectroscopy, liquid chromatography coupled to photodiode array and high-resolution mass spectrometry detection, and oil immersion flow microscopy. In this study, aqueous solutions of Fe III –citrate were photolyzed under 365 nm light in an experimental setup with an apparent quantum yield of ( φ ) ∼0.02, followed by chemical analyses of reacted mixtures withdrawn at increment time intervals of the experiment. The apparent photochemical reaction kinetics of Fe 3+ –citrates (aq) were expressed as two generalized consecutive reactions of with the experimental rate constants of j 1 ∼ 0.12 min −1 and j 2 ∼ 0.05 min −1 , respectively. Molecular characterization results indicate that R and I consist of both water-soluble organic and Fe–organic species, while P compounds are a mixture of water-soluble and colloidal materials. The latter were identified as Fe–carbonaceous colloids formed at long photolysis times. The carbonaceous content of these colloids was identified as unsaturated organic species with low oxygen content and carbon with a reduced oxidation state, indicative of their plausible radical recombination mechanism under oxygen-deprived conditions typical for the extensively photolyzed mixtures. Based on the molecular characterization results, we discuss the comprehensive reaction mechanism of Fe III –citrate photochemistry and report on the formation of previously unexplored colloidal reaction products, which may contribute to atmospheric and terrestrial light-absorbing materials in aquatic environments. 

Ancient greenhouse periods are useful analogs for predicting effects of anthropogenic climate change on regional and global temperature and precipitation patterns. A paucity of terrestrial data from polar regions during warm episodes challenges our understanding of polar climate responses to natural/anthropogenic change and therefore our ability to predict future changes in precipitation. Ellesmere and Axel Heiberg Islands in the Canadian Arctic preserve terrestrial deposits spanning the late Paleocene to middle Eocene (59–45 Ma). Here we expand on existing regional sedimentology and paleontology through the addition of stable (δ¹³C, δ¹⁸O) and clumped (Δ₄₇) isotope analyses on palustrine carbonates. δ¹³C isotope values range from −4.6 to +12.3‰ (VPDB), and δ¹⁸O isotope values range from −23.1 to −15.2‰ (VPDB). Both carbon and oxygen isotope averages decrease with increasing diagenetic alteration. Unusually enriched carbon isotope (δ¹³C) values suggest that analyzed carbonates experienced repeated dissolution‐precipitation enrichment cycles, potentially caused by seasonal fluctuations in water availability resulting in summer carbonate dissolution followed by winter carbonate re‐precipitation. Stable isotopes suggest some degree of precipitation seasonality or reduction in winter water availability in the Canadian Arctic during the Paleogene. Clumped (Δ₄₇) temperature estimates range from 52 to 121°C and indicate low temperature solid‐state reordering of micritic samples and diagenetic recrystallization in sparry samples. Average temperatures agree with vitrinite reflectance data for Eureka Sound Group and underlying sediments, highlighting structural complexity across the region. Broadly, combined stable and clumped isotope data from carbonates in complex systems are effective for describing both paleoclimatic and post‐burial conditions.

 

Earth's hydrological cycle is expected to intensify in response to global warming, with a “wet‐gets‐wetter, dry‐gets‐drier” response anticipated over the ocean. Subtropical regions (∼15°–30°N/S) are predicted to become drier, yet proxy evidence from past warm climates suggests these regions may be characterized by wetter conditions. Here we use an integrated data‐modeling approach to reconstruct global and zonal‐mean rainfall patterns during the early Eocene (∼56–48 million years ago). The Deep‐Time Model Intercomparison Project (DeepMIP) model ensemble indicates that the mid‐ (30°–60°N/S) and high‐latitudes (>60°N/S) are characterized by a thermodynamically dominated hydrological response to warming and overall wetter conditions. The tropical band (0°–15°N/S) is also characterized by wetter conditions, with several DeepMIP models simulating narrowing of the Inter‐Tropical Convergence Zone. However, the latter is not evident from the proxy data. The subtropics are characterized by negative precipitation‐evaporation anomalies (i.e., drier conditions) in the DeepMIP models, but there is surprisingly large inter‐model variability in mean annual precipitation (MAP). Intriguingly, we find that models with weaker meridional temperature gradients (e.g., CESM, GFDL) are characterized by a reduction in subtropical moisture divergence, leading to an increase in MAP. These model simulations agree more closely with our new proxy‐derived precipitation reconstructions and other key climate metrics and imply that the early Eocene was characterized by reduced subtropical moisture divergence. If the meridional temperature gradient was even weaker than suggested by those DeepMIP models, circulation‐induced changes may have outcompeted thermodynamic changes, leading to wetter subtropics. This highlights the importance of accurately reconstructing zonal temperature gradients when reconstructing past rainfall patterns.

 

Abstract Many measurements at the LHC require efficient identification of heavy-flavour jets, i.e. jets originating from bottom (b) or charm (c) quarks. An overview of the algorithms used to identify c jets is described and a novel method to calibrate them is presented. This new method adjusts the entire distributions of the outputs obtained when the algorithms are applied to jets of different flavours. It is based on an iterative approach exploiting three distinct control regions that are enriched with either b jets, c jets, or light-flavour and gluon jets. Results are presented in the form of correction factors evaluated using proton-proton collision data with an integrated luminosity of 41.5 fb -1 at  √s = 13 TeV, collected by the CMS experiment in 2017. The closure of the method is tested by applying the measured correction factors on simulated data sets and checking the agreement between the adjusted simulation and collision data. Furthermore, a validation is performed by testing the method on pseudodata, which emulate various mismodelling conditions. The calibrated results enable the use of the full distributions of heavy-flavour identification algorithm outputs, e.g. as inputs to machine-learning models. Thus, they are expected to increase the sensitivity of future physics analyses.