From 2007 to 2013, the globally averaged mole fraction of methane in the atmosphere increased by 5.7 ± 1.2 ppb yr À1. Simultaneously, δ 13 C CH4 (a measure of the 13 C/ 12 C isotope ratio in methane) has shifted to significantly more negative values since 2007. Growth was extreme in 2014, at 12.5 ± 0.4 ppb, with a further shift to more negative values being observed at most latitudes. The isotopic evidence presented here suggests that the methane rise was dominated by significant increases in biogenic methane emissions, particularly in the tropics, for example, from expansion of tropical wetlands in years with strongly positive rainfall anomalies or emissions from increased agricultural sources such as ruminants and rice paddies. Changes in the removal rate of methane by the OH radical have not been seen in other tracers of atmospheric chemistry and do not appear to explain short-term variations in methane. Fossil fuel emissions may also have grown, but the sustained shift to more 13 C-depleted values and its significant interannual variability, and the tropical and Southern Hemisphere loci of post-2007 growth, both indicate that fossil fuel emissions have not been the dominant factor driving the increase. A major cause of increased tropical wetland and tropical agricultural methane emissions, the likely major contributors to growth, may be their responses to meteorological change.

Abstract. The energy budget and the photochemistry of a snowpack depend greatly on the penetration of solar radiation in snow. Below the snow surface, spectral irradiance decreases exponentially with depth with a decay constant called the asymptotic flux extinction coefficient. As with the albedo of the snowpack, the asymptotic flux extinction coefficient depends on snow grain shape. While representing snow by a collection of spherical particles has been successful in the numerical computation of albedo, such a description poorly explains the decrease of irradiance in snow with depth. Here we explore the limits of the spherical representation. Under the assumption of geometric optics and weak absorption by snow, the grain shape can be simply described by two parameters: the absorption enhancement parameter B and the geometric asymmetry factor g G . Theoretical calculations show that the albedo depends on the ratio B/(1−g G ) and the asymptotic flux extinction coefficient depends on the product B(1 − g G ). To understand the influence of grain shape, the values of B and g G are calculated for a variety of simple geometric shapes using ray tracing simulations. The results show that B and (1 − g G ) generally covary so that the asymptotic flux extinction coefficient exhibits larger sensitivity to the grain shape than albedo. In particular it is found that spherical grains propagate light deeper than any other investigated shape. In a second step, we developed a method to estimate B from optical measurements in snow. A multi-layer, two-stream, radiative transfer model, with explicit grain shape dependence, is used to retrieve values of the B parameter of snow by comparing the model to joint measurements of reflectance and irradiance profiles. Such measurements were performed in Antarctica and in the Alps yielding estimates of B between 0.8 and 2.0. In addition, values of B were estimated from various measurements found in the literature, leading to a wider range of values (1.0-9.9) which may be partially explained by the limited accuracy of the data. This work highlights the large variety of snow microstructure and experimentally demonstrates that spherical grains, with B = 1.25, are inappropriate to model irradiance profiles in snow, an important result that should be considered in further studies dedicated to subsurface absorption of short-wave radiation and snow photochemistry.

Abstract.Measurements of e-folding depth, nadir reflectivity and stratigraphy of the snowpack around Concordia station (Dome C, 75.10 • S, 123.31 • E) were undertaken to determine wavelength dependent coefficients (350 nm to 550 nm) for light scattering and absorption and to calculate potential fluxes (depth-integrated production rates) of nitrogen dioxide (NO 2 ) from the snowpack due to nitrate photolysis within the snowpack. The stratigraphy of the top 80 cm of Dome C snowpack generally consists of three main layers:-a surface of soft windpack (not ubiquitous), a hard windpack, and a hoar-like layer beneath the windpack(s). The e-folding depths are ∼10 cm for the two windpack layers and ∼20 cm for the hoar-like layer for solar radiation at a wavelength of 400 nm; about a factor 2-4 larger than previous model estimates for South Pole. The absorption cross-section due to impurities in each snowpack layer are consistent with a combination of absorption due to black carbon and HULIS (HUmic LIke Substances), with amounts of 1-2 ng g −1 of black carbon for the surface snow layers. Depth-integrated photochemical production rates of NO 2 in the Dome C snowpack were calculated as 5. using the TUV-snow radiative-transfer model. Depending upon the snowpack stratigraphy, a minimum of 85 % of the NO 2 may originate from the top 20 cm of the Dome C snowpack. It is found that on a multi-annual time-scale photolysis can remove up to 80 % of nitrate from surface snow, confirming independent isotopic evidence that photolysis is an important driver of nitrate loss occurring in the EAIS (East Antarctic Ice Sheet) snowpack. However, the model cannot completely account for the total observed nitrate loss of 90-95 % or the shape of the observed nitrate concentration depth profile. A more complete model will need to include also physical processes such as evaporation, re-deposition or diffusion between the quasi-liquid layer on snow grains and firn air to account for the discrepancies.

The atmospheric methane burden is increasing rapidly, contrary to pathways compatible with the goals of the 2015 United Nations Framework Convention on Climate Change Paris Agreement. Urgent action is required to bring methane back to a pathway more in line with the Paris goals. Emission reduction from “tractable” (easier to mitigate) anthropogenic sources such as the fossil fuel industries and landfills is being much facilitated by technical advances in the past decade, which have radically improved our ability to locate, identify, quantify, and reduce emissions. Measures to reduce emissions from “intractable” (harder to mitigate) anthropogenic sources such as agriculture and biomass burning have received less attention and are also becoming more feasible, including removal from elevated‐methane ambient air near to sources. The wider effort to use microbiological and dietary intervention to reduce emissions from cattle (and humans) is not addressed in detail in this essentially geophysical review. Though they cannot replace the need to reach “net‐zero” emissions of CO2, significant reductions in the methane burden will ease the timescales needed to reach required CO2 reduction targets for any particular future temperature limit. There is no single magic bullet, but implementation of a wide array of mitigation and emission reduction strategies could substantially cut the global methane burden, at a cost that is relatively low compared to the parallel and necessary measures to reduce CO2, and thereby reduce the atmospheric methane burden back toward pathways consistent with the goals of the Paris Agreement.