Methane is an important greenhouse gas, and its atmospheric concentration has nearly tripled since pre-industrial times. The growth rate of atmospheric methane is determined by the balance between ...surface emissions and photochemical destruction by the hydroxyl radical, the major atmospheric oxidant. Remarkably, this growth rate has decreased markedly since the early 1990s, and the level of methane has remained relatively constant since 1999, leading to a downward revision of its projected influence on global temperatures. Large fluctuations in the growth rate of atmospheric methane are also observed from one year to the next, but their causes remain uncertain. Here we quantify the processes that controlled variations in methane emissions between 1984 and 2003 using an inversion model of atmospheric transport and chemistry. Our results indicate that wetland emissions dominated the inter-annual variability of methane sources, whereas fire emissions played a smaller role, except during the 1997-1998 El Niño event. These top-down estimates of changes in wetland and fire emissions are in good agreement with independent estimates based on remote sensing information and biogeochemical models. On longer timescales, our results show that the decrease in atmospheric methane growth during the 1990s was caused by a decline in anthropogenic emissions. Since 1999, however, they indicate that anthropogenic emissions of methane have risen again. The effect of this increase on the growth rate of atmospheric methane has been masked by a coincident decrease in wetland emissions, but atmospheric methane levels may increase in the near future if wetland emissions return to their mean 1990s levels.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Our knowledge of the distribution of mercury concentrations in air of the Southern Hemisphere was until recently based mostly on intermittent measurements made during ship cruises. In the last few ...years continuous mercury monitoring has commenced at several sites in the Southern Hemisphere, providing new and more refined information. In this paper we compare mercury measurements at several remote sites in the Southern Hemisphere made over a period of at least 1 year at each location. Averages of monthly medians show similar although small seasonal variations at both Cape Point and Amsterdam Island. A pronounced seasonal variation at Troll research station in Antarctica is due to frequent mercury depletion events in the austral spring. Due to large scatter and large standard deviations of monthly average median mercury concentrations at Cape Grim, no systematic seasonal variation could be found there. Nevertheless, the annual average mercury concentrations at all sites during the 2007-2013 period varied only between 0.85 and 1.05 ng m-3. Part of this variability is likely due to systematic measurement uncertainties which we propose can be further reduced by improved calibration procedures. We conclude that mercury is much more uniformly distributed throughout the Southern Hemisphere than the distributions suggested by measurements made onboard ships. This finding implies that smaller trends can be detected in shorter time periods. We also report a change in the trend sign at Cape Point from decreasing mercury concentrations in 1996-2004 to increasing concentrations since 2007.
From 2007 to 2013, the globally averaged mole fraction of methane in the atmosphere increased by 5.7 ± 1.2 ppb yr−1. Simultaneously, δ13CCH4 (a measure of the 13C/12C 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 13C‐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.
Plain Language Summary
Atmospheric methane, which is a powerful greenhouse gas, is increasing rapidly. In the 20th century, methane growth was primarily driven by emissions from fossil fuel sources, such as the natural gas industry and coal mining. Then, in the early years of the 21st century, came a period of stability in methane. However, since 2007, growth has resumed, with especially strong growth in 2014. Evidence from carbon isotopes implies that the primary cause of the new growth is an increase in biogenic emissions, probably from wetlands and also agricultural sources, such as rice fields and cattle. The evidence presented in this research study, from a wide range of measurement sites both in the northern and southern hemispheres, suggests increased tropical emissions, for example from tropical wetlands, may be a principal cause of the global rise in methane. Contributions to the growth may also come from agricultural sources and perhaps some fossil fuel emissions also.
Key Points
Atmospheric methane is growing rapidly
Isotopic evidence implies that the growth is driven by biogenic sources
Growth is dominated by tropical sources
We perform global-scale inverse modeling to constrain present-day atmospheric mercury emissions and relevant physiochemical parameters in the GEOS-Chem chemical transport model. We use Bayesian ...inversion methods combining simulations with GEOS-Chem and ground-based Hg0 observations from regional monitoring networks and individual sites in recent years. Using optimized emissions/parameters, GEOS-Chem better reproduces these ground-based observations and also matches regional over-water Hg0 and wet deposition measurements. The optimized global mercury emission to the atmosphere is ~ 5.8 Gg yr-1. The ocean accounts for 3.2 Gg yr-1 (55 % of the total), and the terrestrial ecosystem is neither a net source nor a net sink of Hg0. The optimized Asian anthropogenic emission of Hg0 (gas elemental mercury) is 650-1770 Mg yr-1, higher than its bottom-up estimates (550-800 Mg yr-1). The ocean parameter inversions suggest that dark oxidation of aqueous elemental mercury is faster, and less mercury is removed from the mixed layer through particle sinking, when compared with current simulations. Parameter changes affect the simulated global ocean mercury budget, particularly mass exchange between the mixed layer and subsurface waters. Based on our inversion results, we re-evaluate the long-term global biogeochemical cycle of mercury, and show that legacy mercury becomes more likely to reside in the terrestrial ecosystem than in the ocean. We estimate that primary anthropogenic mercury contributes up to 23 % of present-day atmospheric deposition.
The recent increase of atmospheric methane is investigated by using two atmospheric inversions to quantify the distribution of sources and sinks for the 2006-2008 period, and a process-based model of ...methane emissions by natural wetland ecosystems. Methane emissions derived from the two inversions are consistent at a global scale: emissions are decreased in 2006 (-7 Tg) and increased in 2007 (+21 Tg) and 2008 (+18 Tg), as compared to the 1999-2006 period. The agreement on the latitudinal partition of the flux anomalies for the two inversions is fair in 2006, good in 2007, and not good in 2008. In 2007, a positive anomaly of tropical emissions is found to be the main contributor to the global emission anomalies (~60-80%) for both inversions, with a dominant share attributed to natural wetlands (~2/3), and a significant contribution from high latitudes (~25%). The wetland ecosystem model produces smaller and more balanced positive emission anomalies between the tropics and the high latitudes for 2006, 2007 and 2008, mainly due to precipitation changes during these years. At a global scale, the agreement between the ecosystem model and the inversions is good in 2008 but not satisfying in 2006 and 2007. Tropical South America and Boreal Eurasia appear to be major contributors to variations in methane emissions consistently in the inversions and the ecosystem model. Finally, changes in OH radicals during 2006-2008 are found to be less than 1% in inversions, with only a small impact on the inferred methane emissions.
Longer-term (i.e., 20–40 years) tropospheric ozone (O3) time series obtained from surface and ozonesonde observations have been analyzed to assess possible changes with time through 2010. The time ...series have been selected to reflect relatively broad geographic regions and where possible minimize local scale influences, generally avoiding sites close to larger urban areas. Several approaches have been used to describe the changes with time, including application of a time series model, running 15-year trends, and changes in the distribution by month in the O3 mixing ratio. Changes have been investigated utilizing monthly averages, as well as exposure metrics that focus on specific parts of the distribution of hourly average concentrations (e.g., low-, mid-, and high-level concentration ranges). Many of the longer time series (∼30 years) in mid-latitudes of the Northern Hemisphere, including those in Japan, show a pattern of significant increase in the earlier portion of the record, with a flattening over the last 10–15 years. It is uncertain if the flattening of the O3 change over Japan reflects the impact of O3 transported from continental East Asia in light of reported O3 increases in China. In the Canadian Arctic, declines from the beginning of the ozonesonde record in 1980 have mostly rebounded with little overall change over the period of record. The limited data in the tropical Pacific suggest very little change over the entire record. In the southern hemisphere subtropics and mid-latitudes, the significant increase observed in the early part of the record has leveled off in the most recent decade. At the South Pole, a decline observed during the first half of the 35-year record has reversed, and O3 has recovered to levels similar to the beginning of the record. Our understanding of the causes of the longer-term changes is limited, although it appears that in the mid-latitudes of the northern hemisphere, controls on O3 precursors have likely been a factor in the leveling off or decline from earlier O3 increases.
► O3 at mid-latitudes of the N.H. is flat or declining in the last 10–15 years. ► O3 in S.H. subtropics and mid-latitudes increased earlier but has leveled off. ► 15-year moving trends reveal changes in both high and low O3 concentrations. ► Precursor (NOx) reductions in Europe and N.A. likely contribute to O3 decline.
Concern about the adverse effects of mercury on human health and ecosystems has led to tightening emission controls since the mid 1980s. But the resulting mercury emissions reductions in many parts ...of the world are believed to be offset or even surpassed by the increasing emissions in rapidly industrializing countries. Consequently, concentrations of atmospheric mercury are expected to remain roughly constant. Here we show that the worldwide atmospheric mercury concentrations have decreased by about 20 to 38 % since 1996 as indicated by long-term monitoring at stations in the Southern and Northern Hemispheres combined with intermittent measurements of latitudinal distribution over the Atlantic Ocean. The total reduction of the atmospheric mercury burden of this magnitude within 14 years is unusually large among most atmospheric trace gases and is at odds with the current mercury emission inventories with nearly constant anthropogenic emissions over this period. This suggests a major shift in the biogeochemical cycle of mercury including oceans and soil reservoirs. Decreasing reemissions from the legacy of historical mercury emissions are the most likely explanation for this decline since the hypothesis of an accelerated oxidation rate of elemental mercury in the atmosphere is not supported by the observed trends of other trace gases. Acidification of oceans, climate change, excess nutrient input and pollution may also contribute by their impact on the biogeochemistry of ocean and soils. Consequently, models of the atmospheric mercury cycle have to include soil and ocean mercury pools and their dynamics to be able to make projections of future trends.
The authors evaluated continuous high-resolution gaseous elemental mercury (GEM) data from the Cape Point Global Atmosphere Watch (CPT GAW) station with different statistical analysis techniques. GEM ...data were evaluated by cluster analysis and the results indicated that two clusters, separated at 0.904 ng m-3, existed. The air mass history for the two-cluster solution was investigated by means of back-trajectory analysis. The air mass back-trajectory net result showed lower GEM concentrations originating from the sparsely populated semi-arid interior of South Africa and the marine environment, whereas higher GEM concentrations originated predominately along the coast of South Africa that most likely coincide with trade routes and industrial activities in urban areas along the coast. Considering the net result from the air mass back-trajectories, it is evident that not all low GEM concentrations are from marine origin, and similarly, not all high GEM concentrations have a terrestrial origin. Equations were developed by means of multi-linear regression (MLR) analysis that allowed for the estimation and/or prediction of atmospheric GEM concentrations from other atmospheric parameters measured at the CPT GAW station. These equations also provided some insight into the relation and interaction of GEM with other atmospheric parameters. Both measured and MLR calculated data confirm a decline in GEM concentrations at CPT GAW over the period evaluated.
Total gaseous mercury (TGM) has been measured at the WMO Global Atmosphere Watch (GAW) station at Cape Point, South Africa, since September 1995, representing the only long term TGM measurement in ...the Southern Hemisphere (SH) so far. Annual medians suggest a small but significant decrease of TGM concentrations from 1.29 ng m−3 in 1996 to 1.19 ng m−3 in 2004. Background TGM concentrations at Cape Point varied seasonally, with a summer maximum and a winter minimum. Comparison with the seasonal variation of CO concentrations in both hemispheres calls into question the influence of mercury sink by the Hg0 + OH reaction. If confirmed at other sites in the SH, the observed TGM seasonal variation may pose an important constraint on the global models of atmospheric mercury.
A new coastal background site has been established for observations of greenhouse gases (GHGs) in the central Namib Desert at Gobabeb, Namibia. The location of the site was chosen to provide ...observations for a data-poor region in the global sampling network for GHGs. Semi-automated continuous measurements of carbon dioxide, methane, nitrous oxide, carbon monoxide, atmospheric oxygen, and basic meteorology are made at a height of 21 m a.g.l., 50 km from the coast at the northern border of the Namib Sand Sea. Atmospheric oxygen is measured with a differential fuel cell analyzer (DFCA). Carbon dioxide and methane are measured with an early-model cavity ring-down spectrometer (CRDS); nitrous oxide and carbon monoxide are measured with an off-axis integrated cavity output spectrometer (OA-ICOS). Instrument-specific water corrections are employed for both the CRDS and OA-ICOS instruments in lieu of drying. The performance and measurement uncertainties are discussed in detail. As the station is located in a remote desert environment, there are some particular challenges, namely fine dust, high diurnal temperature variability, and minimal infrastructure. The gas handling system and calibration scheme were tailored to best fit the conditions of the site. The CRDS and DFCA provide data of acceptable quality when base requirements for operation are met, specifically adequate temperature control in the laboratory and regular supply of electricity. In the case of the OA-ICOS instrument, performance is significantly improved through the implementation of a drift correction through frequent measurements of a reference cylinder.
PDF
