Observational constraints on the chemistry of isoprene nitrates over the eastern United States

The formation of organic nitrates during the oxidation of the biogenic hydrocarbon isoprene can strongly affect boundary layer concentrations of ozone and nitrogen oxides (NOx = NO + NO2). We constrain uncertainties in the chemistry of these isoprene nitrates using chemical transport model simulations in conjunction with observations over the eastern United States from the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) field campaign during summer 2004. The model best captures the observed boundary layer concentrations of organic nitrates and their correlation with ozone using a 4% yield of isoprene nitrate production from the reaction of isoprene hydroxyperoxy radicals with NO, a recycling of 40% NOx when isoprene nitrates react with OH and ozone, and a fast dry deposition rate of isoprene nitrates. Simulated boundary layer concentrations are only weakly sensitive to the rate of photochemical loss of the isoprene nitrates. An 8% yield of isoprene nitrates degrades agreement with the observations somewhat, but concentrations are still within 50% of observations and thus cannot be ruled out by this study. Our results indicate that complete recycling of NOx from the reactions of isoprene nitrates and slow rates of isoprene nitrate deposition are incompatible with the observations. We find that ∼50% of the isoprene nitrate production in the model occurs via reactions of isoprene (or its oxidation products) with the NO3 radical, but note that the isoprene nitrate yield from this pathway is highly uncertain. Using recent estimates of rapid reaction rates with ozone, 20–24% of isoprene nitrates are lost via this pathway, implying that ozonolysis is an important loss process for isoprene nitrates. Isoprene nitrates are shown to have a major impact on the nitrogen oxide (NOx = NO + NO2) budget in the summertime U.S. continental boundary layer, consuming 15–19% of the emitted NOx, of which 4–6% is recycled back to NOx and the remainder is exported as isoprene nitrates (2–3%) or deposited (8–10%). Our constraints on reaction rates, branching ratios, and deposition rates need to be confirmed through further laboratory and field measurements. The model systematically underestimates free tropospheric concentrations of organic nitrates, indicating a need for future investigation of the processes controlling the observed distribution

The essential value of long-term experimental data for hydrology and water management

We would like to thank the European Research Council ERC for funding the VeWa project and most of Tetzlaff's time (project GA 335910 VeWa). No data were used in producing this manuscript.Peer reviewedPublisher PD

Interactive ozone and methane chemistry in GISS-E2 historical and future climate simulations

The new generation GISS climate model includes fully interactive chemistry related to ozone in historical and future simulations, and interactive methane in future simulations. Evaluation of ozone, its tropospheric precursors, and methane shows that the model captures much of the largescale spatial structure seen in recent observations. While the model is much improved compared with the previous chemistry-climate model, especially for ozone seasonality in the stratosphere, there is still slightly too rapid stratospheric circulation, too little stratosphere-to-troposphere ozone flux in the Southern Hemisphere and an Antarctic ozone hole that is too large and persists too long. Quantitative metrics of spatial and temporal correlations with satellite datasets as well as spatial autocorrelation to examine transport and mixing are presented to document improvements in model skill and provide a benchmark for future evaluations. The difference in radiative forcing (RF) calculated using modeled tropospheric ozone versus tropospheric ozone observed by TES is only 0.016Wm⁻². Historical 20th Century simulations show a steady increase in whole atmosphere ozone RF through 1970 after which there is a decrease through 2000 due to stratospheric ozone depletion. Ozone forcing increases throughout the 21st century under RCP8.5 owing to a projected recovery of stratospheric ozone depletion and increases in methane, but decreases under RCP4.5 and 2.6 due to reductions in emissions of other ozone precursors. RF from methane is 0.05 to 0.18Wm⁻² higher in our model calculations than in the RCP RF estimates. The surface temperature response to ozone through 1970 follows the increase in forcing due to tropospheric ozone. After that time, surface temperatures decrease as ozone RF declines due to stratospheric depletion. The stratospheric ozone depletion also induces substantial changes in surface winds and the Southern Ocean circulation, which may play a role in a slightly stronger response per unit forcing during later decades. Tropical precipitation shifts south during boreal summer from 1850 to 1970, but then shifts northward from 1970 to 2000, following upper tropospheric temperature gradients more strongly than those at the surfac

Dose–Volume Constraints fOr oRganS At risk In Radiotherapy (CORSAIR): An “All-in-One” Multicenter–Multidisciplinary Practical Summary

BACKGROUND: The safe use of radiotherapy (RT) requires compliance with dose/volume constraints (DVCs) for organs at risk (OaRs). However, the available recommendations are sometimes conflicting and scattered across a number of different documents. Therefore, the aim of this work is to provide, in a single document, practical indications on DVCs for OaRs in external beam RT available in the literature.MATERIAL AND METHODS: A multidisciplinary team collected bibliographic information on the anatomical definition of OaRs, on the imaging methods needed for their definition, and on DVCs in general and in specific settings (curative RT of Hodgkin's lymphomas, postoperative RT of breast tumors, curative RT of pediatric cancers, stereotactic ablative RT of ventricular arrythmia). The information provided in terms of DVCs was graded based on levels of evidence.RESULTS: Over 650 papers/documents/websites were examined. The search results, together with the levels of evidence, are presented in tabular form.CONCLUSIONS: A working tool, based on collected guidelines on DVCs in different settings, is provided to help in daily clinical practice of RT departments. This could be a first step for further optimizations

The effects of high HIV prevalence on orphanhood and living arrangements of children in Malawi, Tanzania, and South Africa

Using longitudinal data from three demographic surveillance systems (DSS) and a retrospective cohort study, we estimate levels and trends in the prevalence and incidence of orphanhood in South Africa, Tanzania, and Malawi in the period 1988–2004. The prevalence of maternal, paternal, and double orphans rose in all three populations. In South Africa—where the HIV epidemic started later, has been very severe, and has not yet stabilized—the incidence of orphanhood among children is double that of the other populations. The living arrangements of children vary considerably between the populations, particularly in relation to fathers. Patterns of marriage, migration, and adult mortality influence the living and care arrangements of orphans and non-orphans. DSS data provide new insights into the impact of adult mortality on children, challenging several widely held assumptions. For example, we find no evidence that the prevalence of child-headed households is significant or has increased in the three study areas

Climate proofing The Netherlands

Regional climate change should not be seen only as a threat; changes to weather patterns could generate opportunities for large-scale innovations. About the challenges the Netherlands face in times of climate change

Hillslope Hydrology in Global Change Research and Earth System Modeling

Earth System Models (ESMs) are essential tools for understanding and predicting global change, but they cannot explicitly resolve hillslope-scale terrain structures that fundamentally organize water, energy, and biogeochemical stores and fluxes at subgrid scales. Here we bring together hydrologists, Critical Zone scientists, and ESM developers, to explore how hillslope structures may modulate ESM grid-level water, energy, and biogeochemical fluxes. In contrast to the one-dimensional (1-D), 2- to 3-m deep, and free-draining soil hydrology in most ESM land models, we hypothesize that 3-D, lateral ridge-to-valley flow through shallow and deep paths and insolation contrasts between sunny and shady slopes are the top two globally quantifiable organizers of water and energy (and vegetation) within an ESM grid cell. We hypothesize that these two processes are likely to impact ESM predictions where (and when) water and/or energy are limiting. We further hypothesize that, if implemented in ESM land models, these processes will increase simulated continental water storage and residence time, buffering terrestrial ecosystems against seasonal and interannual droughts. We explore efficient ways to capture these mechanisms in ESMs and identify critical knowledge gaps preventing us from scaling up hillslope to global processes. One such gap is our extremely limited knowledge of the subsurface, where water is stored (supporting vegetation) and released to stream baseflow (supporting aquatic ecosystems). We conclude with a set of organizing hypotheses and a call for global syntheses activities and model experiments to assess the impact of hillslope hydrology on global change predictions. Plain Language Summary Hillslopes are key landscape features that organize water availability on land. Valley bottoms are wetter than hilltops, and sun-facing slopes are warmer and drier than shaded ones. This hydrologic organization leads to systematic differences in soil and vegetation between valleys and hilltops, and between sunny and shady slopes. Although these patterns are fundamental to understanding the structures and functions of water and terrestrial ecosystems, they are too fine grained to be represented in global-scale Earth System Models. Here we bring together Critical Zone scientists who study the interplay of vegetation, the porous upper layer of the continental crust from vegetation to bedrock, and moisture dynamics deep into the weathered bedrock underlying hillslopes and Earth System Model scientists who develop global models, to ask: Do hillslope-scale processes matter to predicting global change? The answers will help scientists understand where and why hillslopes matter, and to better predict how terrestrial ecosystems, including societies, may affect and be affected by our rapidly changing planet.National Science Foundation [NSF-EAR-1528298, NSF-EAR-0753521]6 month embargo; published online: 27 February 2019This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Hillslope Hydrology in Global Change Research and Earth System Modeling

Earth System Models (ESMs) are essential tools for understanding and predicting global change, but they cannot explicitly resolve hillslope‐scale terrain structures that fundamentally organize water, energy, and biogeochemical stores and fluxes at subgrid scales. Here we bring together hydrologists, Critical Zone scientists, and ESM developers, to explore how hillslope structures may modulate ESM grid‐level water, energy, and biogeochemical fluxes. In contrast to the one‐dimensional (1‐D), 2‐ to 3‐mdeep, and free‐draining soil hydrology in most ESM land models, we hypothesize that 3‐D, lateral ridge‐to‐valley flow through shallow and deep paths and insolation contrasts between sunny and shady slopes are the top two globally quantifiable organizers of water and energy (and vegetation) within an ESM grid cell. We hypothesize that these two processes are likely to impact ESM predictions where (and when) water and/or energy are limiting. We further hypothesize that, if implemented in ESM land models, these processes will increase simulated continental water storage and residence time, buffering terrestrial ecosystems against seasonal and interannual droughts. We explore efficient ways to capture these mechanisms in ESMs and identify critical knowledge gaps preventing us from scaling up hillslope to global processes. One such gap is our extremely limited knowledge of the subsurface, where water is stored (supporting vegetation) and released to stream baseflow (supporting aquatic ecosystems). We conclude with a set of organizing hypotheses and a call for global syntheses activities and model experiments to assess the impact of hillslope hydrology on global change predictions