A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS)

A gas-phase kinetics study of the atmospherically important reaction between Cl2 and dimethyl sulfide (DMS)Cl2 + CH3SCH3 → products has been made using a flow-tube interfaced to a photoelectron spectrometer. The rate constant for this reaction has been measured at 1.6 and 3.0 torr at T = (294 ± 2) K as (3.4 ± 0.7) × 10–14 cm3 molecule–1 s–1. Reaction (1) has been found to proceed via an intermediate, (CH3)2SCl2, to give CH3SCH2Cl and HCl as the products. The mechanism of this reaction and the structure of the intermediate were investigated using electronic structure calculations. A comparison of the mechanisms of the reactions between Cl atoms and DMS, and Cl2 and DMS has been made and the relevance of the results to atmospheric chemistry is discussed

Adaptive Divergence Versus Gene Flow in the Wild: Evaluation in Trinidadian Guppy Populations

This research investigates the impact of gene flow (genetic exchange among populations) on the evolution of biological diversity. The investigators will first document background patterns of diversity in adaptive traits (e.g., morphology, color pattern, life history) and gene flow for wild populations of Trinidadian guppies that face different environmental conditions (high vs. low predation). The investigators will then perform an experimental manipulation of the rate of gene flow between selected populations in order to evaluate theoretical predictions about the impact of gene flow on variation in adaptive traits. Gene flow is pervasive in the wild, but the activities of humans have extensively altered natural patterns of gene flow and adaptation. A growing body of theory suggests that gene flow may have substantial implications for the persistence of adaptation and hence for the evolution and preservation of biological diversity. Unfortunately, most current theory relating gene flow to adaptive trait variation remains largely untested in natural populations (particularly for the traits most closely related to fitness). The proposed research will test this theory and thus help develop robust strategies for managing gene flow in disturbed systems. It will also build on an increasingly popular case study for teaching evolution in classrooms

Historical tropospheric and stratospheric ozone radiative forcing using the CMIP6 database

We calculate ozone radiative forcing (RF) and stratospheric temperature adjustments for the period 1850-2014 using the newly availableCMIP6 ozone dataset. The CMIP6 total ozone RF (1850s-2000s) is 0.28+/-0.17 W m-2 (which is 80% higher than our CMIP5 estimation), and 0.30+/-0.17 W m-2 out to the present day (2014). The total ozone RF grows rapidly until the 1970s, slows towards the 2000s, and shows a renewed growth thereafter. Since the 1990s the shortwave RF exceeds the longwave RF. Global stratospheric ozone RF is positive between 1930 and 1970 and then turns negative, but remains positive in the Northern Hemisphere throughout. Derived stratospheric temperature changes show a localized cooling in the subtropical lower stratosphere due to tropospheric ozone increases, and cooling in the upper stratosphere due to ozone depletion by more than 1K already prior to the satellite era (1980), and by more than 2K out to the present day(2014)

Adaptive Changes in Life History and Survival following a New Guppy Introduction

Numerous studies of wild populations have shown that phenotypic traits can change adaptively on short timescales, but very few studies have considered coincident changes in major fitness components. We here examine adaptive changes in life-history traits and survival rates for wild guppies introduced into new environments. Female life-history traits in the derived (Damier River) populations diverged from the ancestral (Yarra River) population, as a result of adaptation to predation regime (high vs. low) and other aspects of the local river. Moreover, some components of the derived Damier populations, particularly juveniles, now show higher survival in the Damier than do contemporary representatives from the ancestral Yarra population. These results suggest that adaptive change can improve survival rates after fewer than 10 years (fewer than 30 guppy generations) in a new environment

Large-Scale Transport into the Arctic: The Roles of the Midlatitude Jet and the Hadley Cell

Transport from the Northern Hemisphere (NH) midlatitudes to the Arctic plays a crucial role in determining the abundance of trace gases and aerosols that are important to Arctic climate via impacts on radiation and chemistry. Here we examine this transport using an idealized tracer with a fixed lifetime and predominantly midlatitude land-based sources in models participating in the Chemistry Climate Model Initiative (CCMI). We show that there is a 25%-45% difference in the Arctic concentrations of this tracer among the models. This spread is correlated with the spread in the location of the Pacific jet, as well as the spread in the location of the Hadley Cell (HC) edge, which varies consistently with jet latitude. Our results suggest that it is likely that the HC-related zonal-mean meridional transport rather than the jet-related eddy mixing is the major contributor to the inter-model spread in the transport of land-based tracers into the Arctic. Specifically, in models with a more northern jet, the HC generally extends further north and the tracer source region is mostly covered by surface southward flow associated with the lower branch of the HC, resulting in less efficient transport poleward to the Arctic. During boreal summer, there are poleward biases in jet location in free-running models, and these models likely underestimate the rate of transport into the Arctic. Models using specified dynamics do not have biases in the jet location, but do have biases in the surface meridional flow, which may result in differences in transport into the Arctic. In addition to the land-based tracer, the midlatitude-to-Arctic transport is further examined by another idealized tracer with zonally uniform sources. With equal sources from both land and ocean, the inter-model spread of this zonally uniform tracer is more related to variations in parameterized convection over oceans rather than variations in HC extent, particularly during boreal winter. This suggests that transport of land-based and oceanic tracers or aerosols towards the Arctic differs in pathways and therefore their corresponding inter-model variabilities result from different physical processes

Inter-model comparison of global hydroxyl radical (OH) distributions and their impact on atmospheric methane over the 2000–2016 period

The modeling study presented here aims to estimate how uncertainties in global hydroxyl radical (OH) distributions, variability, and trends may contribute to resolving discrepancies between simulated and observed methane (CH4) changes since 2000. A multi-model ensemble of 14 OH fields was analyzed and aggregated into 64 scenarios to force the offline atmospheric chemistry transport model LMDz (Laboratoire de Meteorologie Dynamique) with a standard CH4 emission scenario over the period 2000–2016. The multi-model simulated global volume-weighted tropospheric mean OH concentration ([OH]) averaged over 2000–2010 ranges between 8:7*10^5 and 12:8*10^5 molec cm-3. The inter-model differences in tropospheric OH burden and vertical distributions are mainly determined by the differences in the nitrogen oxide (NO) distributions, while the spatial discrepancies between OH fields are mostly due to differences in natural emissions and volatile organic compound (VOC) chemistry. From 2000 to 2010, most simulated OH fields show an increase of 0.1–0:3*10^5 molec cm-3 in the tropospheric mean [OH], with year-to-year variations much smaller than during the historical period 1960–2000. Once ingested into the LMDz model, these OH changes translated into a 5 to 15 ppbv reduction in the CH4 mixing ratio in 2010, which represents 7%–20% of the model-simulated CH4 increase due to surface emissions. Between 2010 and 2016, the ensemble of simulations showed that OH changes could lead to a CH4 mixing ratio uncertainty of > 30 ppbv. Over the full 2000–2016 time period, using a common stateof- the-art but nonoptimized emission scenario, the impact of [OH] changes tested here can explain up to 54% of the gap between model simulations and observations. This result emphasizes the importance of better representing OH abundance and variations in CH4 forward simulations and emission optimizations performed by atmospheric inversions

Evaluating the relationship between interannual variations in the Antarctic ozone hole and Southern Hemisphere surface climate in chemistry-climate models

Studies have recently reported statistically significant relationships between observed year-to-year spring Antarctic ozone variability and the Southern Hemisphere Annular Mode and surface temperatures in spring-summer. This study investigates whether current chemistry-climate models (CCMs) can capture these relationships, in particular, the connection between November total column ozone (TCO) and Australian summer surface temperatures, where years with anomalously high TCO over the Antarctic polar cap tend to be followed by warmer summers. The interannual ozone-temperature teleconnection is examined over the historical period in the observations and simulations from the Whole Atmosphere Community Climate Model (WACCM) and nine other models participating in the Chemistry-Climate Model Initiative (CCMI). There is a systematic difference between the WACCM experiments forced with prescribed observed sea surface temperatures (SSTs) and those with an interactive ocean. Strong correlations between TCO and Australian temperatures are only obtained for the uncoupled experiment, suggesting that the SSTs could be important for driving both variations in Australian temperatures and the ozone hole, with no causal link between the two. Other CCMI models also tend to capture this relationship with more fidelity when driven by observed SSTs, though additional research and targeted modelling experiments are required to determine causality and further explore the role of model biases and observational uncertainty. The results indicate that CCMs can reproduce the relationship between spring ozone and summer Australian climate reported in observational studies, suggesting that incorporating ozone variability could improve seasonal predictions, however more work is required to understand the difference between the coupled and uncoupled simulations

Evaluating the relationship between interannual variations in the Antarctic ozone hole and Southern Hemisphere surface climate in chemistry-climate models

Studies have recently reported statistically significant relationships between observed year-to-year spring Antarctic ozone variability and the Southern Hemisphere Annular Mode and surface temperatures in spring-summer. This study investigates whether current chemistry-climate models (CCMs) can capture these relationships, in particular, the connection between November total column ozone (TCO) and Australian summer surface temperatures, where years with anomalously high TCO over the Antarctic polar cap tend to be followed by warmer summers. The interannual ozone-temperature teleconnection is examined over the historical period in the observations and simulations from the Whole Atmosphere Community Climate Model (WACCM) and nine other models participating in the Chemistry-Climate Model Initiative (CCMI). There is a systematic difference between the WACCM experiments forced with prescribed observed sea surface temperatures (SSTs) and those with an interactive ocean. Strong correlations between TCO and Australian temperatures are only obtained for the uncoupled experiment, suggesting that the SSTs could be important for driving both variations in Australian temperatures and the ozone hole, with no causal link between the two. Other CCMI models also tend to capture this relationship with more fidelity when driven by observed SSTs, though additional research and targeted modelling experiments are required to determine causality and further explore the role of model biases and observational uncertainty. The results indicate that CCMs can reproduce the relationship between spring ozone and summer Australian climate reported in observational studies, suggesting that incorporating ozone variability could improve seasonal predictions, however more work is required to understand the difference between the coupled and uncoupled simulations