Explore the vast range of titles available.

Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield fromisoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jetcooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn-conformers are observed; anti-conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn-MVK-oxide with SO₂ and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We determine products through complementary multiplexed photoionization mass spectrometry, observing SO₃ and identifying organic hydroperoxide formation from reaction with SO₂ and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model.

Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have show that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield from isoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester,J. Chem. Phys.149, 44309 (2018)] but suggest different conformer distributions under jet-cooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only thesyn-conformers are observed;anti-conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction ofsyn-MVK-oxide with SO2and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We further confirm products through complementary multiplexed photoionization mass spectrometry, observing SO3 and identifying organic hydroperoxide formation from reaction with SO2 and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model.

The land ice contribution to global mean sea level rise has not yet been predicted1 using ice sheet and glacier models for the latest set of socio-economic scenarios, nor using coordinated exploration of uncertainties arising from the various computer models involved. Two recent international projects generated a large suite of projections using multiple models2,3,4,5,6,7,8, but primarily used previous-generation scenarios9 and climate models10, and could not fully explore known uncertainties. Here we estimate probability distributions for these projections under the new scenarios11,12 using statistical emulation of the ice sheet and glacier models. We find that limiting global warming to 1.5 degrees Celsius would halve the land ice contribution to twenty-first-century sea level rise, relative to current emissions pledges. The median decreases from 25 to 13 centimetres sea level equivalent (SLE) by 2100, with glaciers responsible for half the sea level contribution. The projected Antarctic contribution does not show a clear response to the emissions scenario, owing to uncertainties in the competing processes of increasing ice loss and snowfall accumulation in a warming climate. However, under risk-averse (pessimistic) assumptions, Antarctic ice loss could be five times higher, increasing the median land ice contribution to 42 centimetres SLE under current policies and pledges, with the 95th percentile projection exceeding half a metre even under 1.5 degrees Celsius warming. This would severely limit the possibility of mitigating future coastal flooding. Given this large range (between 13 centimetres SLE using the main projections under 1.5 degrees Celsius warming and 42 centimetres SLE using risk-averse projections under current pledges), adaptation planning for twenty-first-century sea level rise must account for a factor-of-three uncertainty in the land ice contribution until climate policies and the Antarctic response are further constrained.

Anthropogenic aerosols (AER) and greenhouse gases (GHG)—the leading drivers of the forced historical change—produce different large‐scale climate response patterns, with correlations trending from negative to positive over the past century. To understand what caused the time‐evolving comparison between GHG and AER response patterns, we apply a low‐frequency component analysis to historical surface ocean changes from CESM1 single‐forcing large‐ensemble simulations. While GHG response is characterized by its first leading mode, AER response consists of two distinct modes. The first one, featuring long‐term global AER increase and global cooling, opposes GHG response patterns up to the mid‐twentieth century. The second one, featuring multidecadal variations in AER distributions and interhemispheric asymmetric surface ocean changes, appears to reinforce the GHG warming effect over recent decades. AER thus can have both competing and synergistic effects with GHG as their emissions change temporally and spatially. Plain Language Summary Anthropogenically forced climate change over the past century has been mainly caused by two types of emissions: greenhouse gases (GHG) and aerosols (AER). In general, sulfate aerosols from industrial sources can reflect shortwave radiation to yield a cooling effect opposite to the GHG warming effect. However, model simulations isolating GHG and AER forcings show that the large‐scale climate effect of AER does not always dampen the GHG effect. Instead, over recent decades, AER have produced surface ocean response patterns more like the GHG response. Using a novel low‐frequency statistical decomposion, we find that aerosols have driven two distinct modes of climate change patterns over the historical period. The first mode is associated with global aerosol increase, resulting in global‐wide cooling damping the GHG‐induced warming. The second mode is associated with the shift in aerosol emissions from north America/western Europe to southeast Asia, which drives regional changes enhancing the GHG effect. Our results highlight the importance of considering the temporal and spatial evolutions of AER emissions in assessing GHG and AER climate effects and attributing historical anthropogenic climate changes to GHG and AER forcings. Key Points Over the past century, GHG forced response is characterized by a single dominant mode while AER response consists of two distinct modes Monotonic global aerosol increases, mainly from Southeast Asia emissions, produce a global aerosol cooling mode opposing greenhouse warming Important in recent decades, geographic redistribution of AER emissions produces a second aerosol mode that reinforces greenhouse warming

Fresh submarine groundwater discharge (FSGD) can deliver significant fluxes of water and solutes from land to sea. In the Arctic, which accounts for ∼34% of coastlines globally, direct observations and knowledge of FSGD are scarce. Through integration of observations and process‐based models, we found that regardless of ice‐bonded permafrost depth at the shore, summer SGD flow dynamics along portions of the Beaufort Sea coast of Alaska are similar to those in lower latitudes. Calculated summer FSGD fluxes in the Arctic are generally higher relative to low latitudes. The FSGD organic carbon and nitrogen fluxes are likely larger than summer riverine input. The FSGD also has very high CO2 making it a potentially significant source of inorganic carbon. Thus, the biogeochemistry of Arctic coastal waters is potentially influenced by groundwater inputs during summer. These water and solute fluxes will likely increase as coastal permafrost across the Arctic thaws. Plain Language Summary Groundwater flows from land to sea, transporting freshwater, organic matter, nutrients, and other solutes that impact coastal ecosystems. However, along coasts of the rapidly‐warming Arctic, there is limited knowledge regarding how much fresh groundwater enters the ocean. Using field observations and numerical models, we show that groundwater flowing from tundra in northern coastal Alaska carries large amounts of freshwater, organic matter, and carbon dioxide to the Arctic lagoons during summer. These inputs are likely significant to coastal biogeochemical cycling and marine food webs. Groundwater discharge and the associated transport of dissolved materials are expected to increase due to longer periods of above‐zero temperatures that thaw frozen soils below the tundra. Key Points Summer fresh submarine groundwater discharge (FSGD) to the Alaskan Beaufort Sea is only 3%–7% of rivers but carries as much organic matter Summer FSGD delivers a median of 116 (interquartile range: 35–405) and 6 (2–21) kg/d per km dissolved organic carbon and nitrogen Fresh groundwater at the beach of Simpson Lagoon (SL) has a median PCO2 of ∼33,000 μatm implying substantial CO2 flux

Reactive Transport Models (RTMs) are essential tools for understanding and predicting intertwined ecohydrological and biogeochemical processes on land and in rivers. While traditional RTMs have focused primarily on subsurface processes, recent watershed‐scale RTMs have integrated ecohydrological and biogeochemical interactions between surface and subsurface. These emergent, watershed‐scale RTMs are often spatially explicit and require extensive data, computational power, and computational expertise. There is however a pressing need to create parsimonious models that require minimal data and are accessible to scientists with limited computational background. To that end, we have developed BioRT‐HBV 1.0, a watershed‐scale, hydro‐biogeochemical RTM that builds upon the widely used, bucket‐type HBV model known for its simplicity and minimal data requirements. BioRT‐HBV uses the conceptual structure and hydrology output of HBV to simulate processes including advective solute transport and biogeochemical reactions that depend on reaction thermodynamics and kinetics. These reactions include, for example, chemical weathering, soil respiration, and nutrient transformation. The model uses time series of weather (air temperature, precipitation, and potential evapotranspiration) and initial biogeochemical conditions of subsurface water, soils, and rocks as input, and output times series of reaction rates and solute concentrations in subsurface waters and rivers. This paper presents the model structure and governing equations and demonstrates its utility with examples simulating carbon and nitrogen processes in a headwater catchment. As shown in the examples, BioRT‐HBV can be used to illuminate the dynamics of biogeochemical reactions in the invisible, arduous‐to‐measure subsurface, and their influence on the observed stream or river chemistry and solute export. With its parsimonious structure and easy‐to‐use graphical user interface, BioRT‐HBV can be a useful research tool for users without in‐depth computational training. It can additionally serve as an educational tool that promotes pollination of ideas across disciplines and foster a diverse, equal, and inclusive user community. Plain Language Summary Reactive Transport models (RTMs) are essential tools to understand the movement of water, nutrients and other elements from land to rivers and their interactions with each other. Recent watershed scale RTMs, unlike earlier ones that primarily focus on the subsurface processes, have integrated belowground processes and above‐ground dynamics and characteristics including changing weather and vegetation cover. However, these models require large amount of data and are challenging for users with limited computational background. Here we developed BioRT‐HBV 1.0, a parsimonious, watershed‐scale RTM with a graphical user interface that is comparatively easy to learn and use and requires minimal data. BioRT‐HBV can simulate a wide variety of processes like chemical weathering, carbon and nutrient transformation, soil organic carbon decomposition, among others. Here, we introduce the model structure, its governing equations, and examples that demonstrate the use of model in simulating carbon and nitrogen processes. We put forward this model as a potential research and educational tool that can be used by students and researchers from diverse disciplines. Key Points We introduce BioRT‐HBV, a watershed scale reactive transport model that is parsimonious, flexible with reaction network, easy to use and requires minimal data BioRT‐HBV can simulate a variety of user‐defined biogeochemical processes, including carbon and nitrogen processes BioRT‐HBV is open source for any researchers interested in ecohydrological and biogeochemical reactive transport processes

A key challenge in aerosol pollution studies and climate change assessment is to understand how atmospheric aerosol particles are initially formed 1 , 2 . Although new particle formation (NPF) mechanisms have been described at specific sites 3 – 6 , in most regions, such mechanisms remain uncertain to a large extent because of the limited ability of atmospheric models to simulate critical NPF processes 1 , 7 . Here we synthesize molecular-level experiments to develop comprehensive representations of 11 NPF mechanisms and the complex chemical transformation of precursor gases in a fully coupled global climate model. Combined simulations and observations show that the dominant NPF mechanisms are distinct worldwide and vary with region and altitude. Previously neglected or underrepresented mechanisms involving organics, amines, iodine oxoacids and HNO 3 probably dominate NPF in most regions with high concentrations of aerosols or large aerosol radiative forcing; such regions include oceanic and human-polluted continental boundary layers, as well as the upper troposphere over rainforests and Asian monsoon regions. These underrepresented mechanisms also play notable roles in other areas, such as the upper troposphere of the Pacific and Atlantic oceans. Accordingly, NPF accounts for different fractions (10–80%) of the nuclei on which cloud forms at 0.5% supersaturation over various regions in the lower troposphere. The comprehensive simulation of global NPF mechanisms can help improve estimation and source attribution of the climate effects of aerosols. Molecular-level experiments are described to develop a detailed assessment of 11 new particle formation mechanisms in a global climate model and, in comparison with simulations and observations, the dominant mechanisms worldwide are mapped.

Sea level rise (SLR) is a long-lasting consequence of climate change because global anthropogenic warming takes centuries to millennia to equilibrate for the deep ocean and ice sheets. SLR projections based on climate models support policy analysis, risk assessment and adaptation planning today, despite their large uncertainties. The central range of the SLR distribution is estimated by process-based models. However, risk-averse practitioners often require information about plausible future conditions that lie in the tails of the SLR distribution, which are poorly defined by existing models. Here, a community effort combining scientists and practitioners builds on a framework of discussing physical evidence to quantify high-end global SLR for practitioners. The approach is complementary to the IPCC AR6 report and provides further physically plausible high-end scenarios. High-end estimates for the different SLR components are developed for two climate scenarios at two timescales. For global warming of +2°C in 2100 (RCP2.6/SSP1-2.6) relative to pre-industrial values our high-end global SLR estimates are up to 0.9 m in 2100 and 2.5 m in 2300. Similarly, for a (RCP8.5/SSP5-8.5), we estimate up to 1.6 m in 2100 and up to 10.4 m in 2300. The large and growing differences between the scenarios beyond 2100 emphasize the long-term benefits of mitigation. However, even a modest 2°C warming may cause multi-meter SLR on centennial time scales with profound consequences for coastal areas. Earlier high-end assessments focused on instability mechanisms in Antarctica, while here we emphasize the importance of the timing of ice shelf collapse around Antarctica. This is highly uncertain due to low understanding of the driving processes. Hence both process understanding and emission scenario control high-end SLR.

A new approach of coordinated global and regional climate modeling is presented. It is applied to the Canadian Centre for Climate Modelling and Analysis Regional Climate Model (CanRCM4) and its parent global climate model CanESM2. CanRCM4 was developed specifically to downscale climate predictions and climate projections made by its parent global model. The close association of a regional climate model (RCM) with a parent global climate model (GCM) offers novel avenues of model development and application that are not typically available to independent regional climate modeling centers. For example,when CanRCM4 is driven by its parent model, driving information for all of its prognostic variables is available (including aerosols and chemical species), significantly improving the quality of their simulation. Additionally, CanRCM4 can be driven by its parent model for all downscaling applications by employing a spectral nudging procedure in CanESM2 designed to constrain its evolution to follow any large-scale driving data. Coordination offers benefit to the development of physical parameterizations and provides an objective means to evaluate the scalability of such parameterizations across a range of spatial resolutions. Finally, coordinating regional and global modeling efforts helps to highlight the importance of assessing RCMs’ value added relative to their driving global models. As a first step in this direction, a framework for identifying appreciable differences in RCM versus GCM climate change results is proposed and applied to CanRCM4 and CanESM2.

Air‐sea heat and moisture fluxes modulate the surface energy balance and oceanic and atmospheric heat transport across all timescales. Spatial gradients of these fluxes, on a multitude of spatial scales, also have significant impacts on the ocean and atmosphere. Nevertheless, analysis of these gradients, and discussion regarding our ability to represent them, is relatively absent within the community. This letter discusses their importance and presents a wintertime climatology. Their sensitivity to spatiotemporal scale and choice of data set is also examined in the mid‐latitudes. A lead‐lag analysis illustrates that wintertime air‐sea heat flux gradients in the Gulf Stream can precede the North Atlantic Oscillation by ∼1 month. A lack of observations and thus validation of air‐sea heat flux gradients represents a significant gap in our understanding of how air‐sea processes affect weather and climate, and warrants increased attention from the observational and modeling communities. Plain Language Summary The oceans impact both weather and climate by heating and cooling the lower atmosphere. Surface latent (sensible) heat flux is a quantity that measures the exchange of heat associated with evaporation of seawater (an air‐sea temperature difference). In addition to the absolute exchange, the manner in which the exchange varies spatially (the heat flux gradients) is also known to be important for the development of weather systems and longer‐term climate. Despite this, relatively little attention is paid in the literature to variability in these gradients. This study provides a brief overview of their importance and provides a wintertime climatology in these gradients. It is also illustrated that when considering gradients, the importance of specifying the spatial scale over which the gradient is calculated is critical. Although many differences exist between air‐sea heat flux data products in these gradients, there are currently almost no observations to validate them in key areas of interest, which represents a significant deficiency in our understanding of ocean‐atmosphere interactions. This is emphasized by demonstrating that these gradients in the mid‐latitudes can statistically precede variability in the North Atlantic Oscillation, the most important mode of monthly atmospheric variability in the North Atlantic. Key Points Air‐sea heat and moisture flux gradients modulate important oceanic and atmospheric processes across a multitude of spatiotemporal scales Air‐sea heat flux gradient variability can statistically precede mid‐latitude atmospheric variability Notable air‐sea heat and moisture flux gradient inconsistencies exist in data products, yet the ability to validate them remains elusive