Gg Yr Research Articles

Long-term variability of aerosol optical thickness in Eastern Europe over 2001–2014 according to the measurements at the Moscow MSU MO AERONET site with additional cloud and NO<sub>2</sub> correction

Abstract. The atmospheric aerosol properties were obtained within the framework of the AERONET program at the Moscow State University Meteorological Observatory (Moscow MSU MO) over the 2001–2014 period. The quality data control has revealed the necessity of additional cloud screening and NO2 correction. The application of additional cloud screening according to hourly visual cloud observations provides a decrease in monthly average aerosol optical thickness (AOT) at 500 nm of up to 0.03 compared with the standard data set. We also show that the additional NO2 correction of the AERONET version 2 data is needed in large megalopolis, like Moscow, with 12 million residents and NOx emission rates of about 100 kt yr−1. According to the developed method, we estimated monthly mean NO2 content, which provides an additional decrease of 0.01 for AOT at 340 nm, and of about 0.015 – for AOT at 380 and 440 nm. The ratios of NO2 optical thickness to AOT at 380 and 440 nm are about 5–6 % in summer and reach 15–20 % in winter when both factors have similar effects on UV irradiance. Seasonal cycle of AOT at 500 nm is characterized by a noticeable summer and spring maxima, and a minimum in winter conditions, changing from 0.08 in December and January up to 0.3 in August. The application of the additional cloud screening removes a local AOT maximum in February. Statistically significant negative trends in annual AOT for UV and mid-visible spectral range have been obtained both for average and 50 % quantile values. The pronounced negative changes were observed in most months with the rate of about −1–5 % yr−1 and could be attributed to the negative trends in emissions (E) of different aerosol precursors of about 135 Gg yr−2 in ESOx, 54 Gg yr−2 in ENMVOC, and slight negative changes in NOx over the European part of Russia. No significant influence of natural factors on temporal AOT variations has been revealed.

The Greenland Ice Sheet as a hot spot of phosphorus weathering and export in the Arctic

AbstractThe contribution of ice sheets to the global biogeochemical cycle of phosphorus is largely unknown, due to the lack of field data. Here we present the first comprehensive study of phosphorus export from two Greenland Ice Sheet glaciers. Our results indicate that the ice sheet is a hot spot of phosphorus export in the Arctic. Soluble reactive phosphorus (SRP) concentrations, up to 0.35 µM, are similar to those observed in Arctic rivers. Yields of SRP are among the highest in the literature, with denudation rates of 17–27 kg P km−2 yr−1. Particulate phases, as with nonglaciated catchments, dominate phosphorus export (>97% of total phosphorus flux). The labile particulate fraction differs between the two glaciers studied, with significantly higher yields found at the larger glacier (57.3 versus 8.3 kg P km−2 yr−1). Total phosphorus yields are an order of magnitude higher than riverine values reported in the literature. We estimate that the ice sheet contributes ~15% of total bioavailable phosphorus input to the Arctic oceans (~11 Gg yr−1) and dominates total phosphorus input (408 Gg yr−1), which is more than 3 times that estimated from Arctic rivers (126 Gg yr−1). We predict that these fluxes will rise with increasing ice sheet freshwater discharge in the future.

Geochemical and tectonic uplift controls on rock nitrogen inputs across terrestrial ecosystems

AbstractRock contains > 99% of Earth's reactive nitrogen (N), but questions remain over the direct importance of rock N weathering inputs to terrestrial biogeochemical cycling. Here we investigate the factors that regulate rock N abundance and develop a new model for quantifying rock N mobilization fluxes across desert to temperate rainforest ecosystems in California, USA. We analyzed the N content of 968 rock samples from 531 locations and compiled 178 cosmogenically derived denudation estimates from across the region to identify landscapes and ecosystems where rocks account for a significant fraction of terrestrial N inputs. Strong coherence between rock N content and geophysical factors, such as protolith, (i.e. parent rock), grain size, and thermal history, are observed. A spatial model that combines rock geochemistry with lithology and topography demonstrates that average rock N reservoirs range from 0.18 to 1.2 kg N m−3 (80 to 534 mg N kg−1) across the nine geomorphic provinces of California and estimates a rock N denudation flux of 20–92 Gg yr−1 across the entire study area (natural atmospheric inputs ~ 140 Gg yr−1). The model highlights regional differences in rock N mobilization and points to the Coast Ranges, Transverse Ranges, and the Klamath Mountains as regions where rock N could contribute meaningfully to ecosystem N cycling. Contrasting these data to global compilations suggests that our findings are broadly applicable beyond California and that the N abundance and variability in rock are well constrained across most of the Earth system.

Seasonal and spatial variation in suspended matter, organic carbon, nitrogen, and nutrient concentrations of the Senegal River in West Africa

The Senegal River is of intermediate size accommodating at present about 3.5 million inhabitants in its catchment. Its upstream tributaries flow through different climatic zones from the wet tropics in the source area in Guinea to the dry Sahel region at the border between Senegal and Mauritania. Total suspended matter, particulate and dissolved organic carbon and nitrogen as well as nutrient concentrations were determined during the dry and wet seasons at 19 locations from the up- to downstream river basin. The aims of the study were to evaluate the degree of human interference, to determine the dissolved and particulate river discharges into the coastal sea and to supply data to validate model results. Statistical analyses showed that samples from the wet and dry season are significantly different in composition and that the upstream tributaries differ mainly in their silicate and suspended matter contents. Nutrient concentrations are relatively low in the river basin, indicating low human impact. Increasing nitrate concentrations, however, show the growing agriculture in the irrigated downstream areas. Particulate organic matter is dominated by C4 plants during the wet season and by aquatic plankton during the dry season. The total suspended matter (TSM) discharge at the main gauging station Bakel was about 1.93 Tg yr −1 which is in the range of the only available literature data from the 1980s. The calculated annual discharges of particulate organic carbon (POC), dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) are 55.8 Gg yr −1 , 54.1 Gg yr −1 , and 5.3 Gg yr −1 , respectively. These first estimates from the Senegal River need to be verified by further studies.

Global and regional emissions estimates of 1,1-difluoroethane (HFC-152a, CH<sub>3</sub>CHF<sub>2</sub>) from in situ and air archive observations

Abstract. High frequency, in situ observations from 11 globally distributed sites for the period 1994–2014 and archived air measurements dating from 1978 onward have been used to determine the global growth rate of 1,1-difluoroethane (HFC-152a, CH3CHF2). These observations have been combined with a range of atmospheric transport models to derive global emission estimates in a top-down approach. HFC-152a is a greenhouse gas with a short atmospheric lifetime of about 1.5 years. Since it does not contain chlorine or bromine, HFC-152a makes no direct contribution to the destruction of stratospheric ozone and is therefore used as a substitute for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The concentration of HFC-152a has grown substantially since the first direct measurements in 1994, reaching a maximum annual global growth rate of 0.84 ± 0.05 ppt yr−1 in 2006, implying a substantial increase in emissions up to 2006. However, since 2007, the annual rate of growth has slowed to 0.38 ± 0.04 ppt yr−1 in 2010 with a further decline to an annual average rate of growth in 2013–2014 of −0.06 ± 0.05 ppt yr−1. The annual average Northern Hemisphere (NH) mole fraction in 1994 was 1.2 ppt rising to an annual average mole fraction of 10.1 ppt in 2014. Average annual mole fractions in the Southern Hemisphere (SH) in 1998 and 2014 were 0.84 and 4.5 ppt, respectively. We estimate global emissions of HFC-152a have risen from 7.3 ± 5.6 Gg yr−1 in 1994 to a maximum of 54.4 ± 17.1 Gg yr−1 in 2011, declining to 52.5 ± 20.1 Gg yr−1 in 2014 or 7.2 ± 2.8 Tg-CO2 eq yr−1. Analysis of mole fraction enhancements above regional background atmospheric levels suggests substantial emissions from North America, Asia, and Europe. Global HFC emissions (so called “bottom up” emissions) reported by the United Nations Framework Convention on Climate Change (UNFCCC) are based on cumulative national emission data reported to the UNFCCC, which in turn are based on national consumption data. There appears to be a significant underestimate ( > 20 Gg) of “bottom-up” reported emissions of HFC-152a, possibly arising from largely underestimated USA emissions and undeclared Asian emissions.

Importance of Oceanian small mountainous rivers (SMRs) in global land-to-ocean output of lignin and modern biospheric carbon.

The land-to-ocean export of particulate organic carbon (POC) connects carbon flow from the atmosphere through land to the ocean, of which the contemporary fraction that reaches the deep sea for burial may effectively affect atmospheric CO2. In this regard, small mountainous rivers (SMRs) in Oceania, a global erosion hotspot driven by torrential typhoon rain and active earthquakes are potentially important. Here we measured typhoon lignin discharges for Taiwan SMRs. We found that the particulate lignin export in 96 hours by a single SMR amounting to ~20% of the annual export by Mississippi River. The yearly particulate lignin discharge from Taiwan Island (35,980 km2) is governed by the frequency and magnitude of typhoon; thus, the historical lignin export ranged widely from 1.5 to 99.7 Gg yr−1, which resulted in a 10–100 times higher areal yield relative to non-Oceanian rivers. The lignin-derived modern POC output from Oceania region is 37 ± 21 Tg C yr−1, account for approximately 20% of the annual modern POC export from global rivers. Coupled with the hyperpycnal pathway, the forested watersheds of SMRs in Oceania may serve as a giant factory to rapidly produce and efficiently convey modern POC into deep sea for sequestration.

Terrestrial pyrogenic carbon export to fluvial ecosystems: Lessons learned from the White Nile watershed of East Africa

AbstractPyrogenic carbon (PyC) is important because of its role in the global organic C (OC) cycle and in modifying soil properties. However, our understanding of PyC movement from terrestrial to fluvial ecosystems is not robust. This study examined (i) whether erosion or subsurface transport was more important for PyC export from headwaters, (ii) whether PyC was exported preferentially to total OC (TOC), and (iii) whether the movement of PyC from terrestrial to aquatic ecosystems provides an explanation for the coupling of PyC and non‐PyC observed in rivers at a global scale. In the Guineo‐Congolian highland forest region of western Kenya, duplicate catchments with sizes of 1–12 ha were equipped with stream gauges in primary forest and adjacent mixed agricultural landscapes that were cleared by fire 10, 16, or 62 years before. Stream water samples were taken weekly throughout 1 year and compared with runoff to assess PyC movement. Additional stream samples were taken from all major tributaries of the White Nile watershed of Lake Victoria. PyC was not found to be preferentially eroded relative to TOC or non‐PyC, as topsoil (0–0.15 m) PyC concentrations (6.3 ± 0.3% of TOC; means and standard errors) were greater than runoff sediment (1.9 ± 0.4%) and dissolved PyC concentrations (2.0 ± 0.4%, n = 252). In addition, PyC proportions in eroded sediment were lower than and uncorrelated (r2 = 0.04; P = 0.14) with topsoil PyC. An enrichment of PyC was found with depth in the soil, from 6.3 ± 0.3% of TOC in the topsoil (0–0.15 m) to 12.3 ± 0.3% of TOC at 1–2 m. Base flow PyC proportions of TOC correlated well with subsoil PyC (r2 = 0.57; P < 0.05) but not with topsoil PyC (r2 = 0.18; P > 0.05). Similar PyC proportions were found in the studied headwater streams (2.7 ± 0.2%), their downstream inflow into Lake Victoria (3.7%), the other nine major rivers into Lake Victoria (4.9 ± 0.8%), and its outflow into the White Nile (1.1%). A strong positive correlation between dissolved PyC and non‐PyC (r2 = 0.91; P < 0.0001) in the headwater streams reflect relationships previously seen for a range of globally important rivers, and contrasts with a negative relationship for suspended sediments (r2 = −0.5; P < 0.0001). The estimated PyC export from the Lake Victoria watershed of 11 Gg yr−1 may therefore originate to a large extent from subsoil pathways in dissolved form that appeared to be an important source of PyC in aquatic environments and may explain the coupling of PyC and non‐PyC at a global scale.

Rising critical emission of air pollutants from renewable biomass based cogeneration from the sugar industry in India

In the recent past, the emerging India economy is highly dependent on conventional as well as renewable energy to deal with energy security. Keeping the potential of biomass and its plentiful availability, the Indian government has been encouraging various industrial sectors to generate their own energy from it. The Indian sugar industry has adopted and made impressive growth in bagasse (a renewable biomass, i.e. left after sugercane is crushed) based cogeneration power to fulfil their energy need, as well as to export a big chunk of energy to grid power. Like fossil fuel, bagasse combustion also generates various critical pollutants. This article provides the first ever estimation, current status and overview of magnitude of air pollutant emissions from rapidly growing bagasse based cogeneration technology in Indian sugar mills. The estimated emission from the world’s second largest sugar industry in India for particulate matter, NOX, SO2, CO and CO2 is estimated to be 444 ± 225 Gg yr−1, 188 ± 95 Gg yr−1, 43 ± 22 Gg yr−1, 463 ± 240 Gg yr−1 and 47.4 ± 9 Tg yr−1, respectively in 2014. The studies also analyze and identify potential hot spot regions across the country and explore the possible further potential growth for this sector. This first ever estimation not only improves the existing national emission inventory, but is also useful in chemical transport modeling studies, as well as for policy makers.

Spatial and temporal variation of dissolved organic matter in the Changjiang: Fluvial transport and flux estimation

AbstractThe Changjiang is the most important source of freshwater and dissolved organic matter (DOM) for the East China Sea. However, knowledge regarding the sources, seasonal fluxes, and fluvial transport of terrigenous DOM (tDOM) in the Changjiang is lacking. To fill this knowledge gap, we measured dissolved organic carbon (DOC) and dissolved lignin in water samples collected in the middle and lower Changjiang under different hydrological conditions. Additional samples were collected biweekly in the lower Changjiang. Through comparisons with other rivers, we found that the DOC in the Changjiang is mainly from soil organic matter and has a higher fraction of tDOM during flood. Mass balance model results indicate that approximately 33% of the dissolved lignin discharged into the middle and lower Changjiang is removed during its transport to the lower reach during both low‐discharge and flood periods. Based on a comparison of the removal rates under these two contrasting hydrological conditions and considering the lower organic carbon content and fine grain size of the Changjiang's suspended particles, we speculate that the major process for the removal of dissolved lignin is sorption, and potentially flocculation by suspended particles. Changjiang discharges 1.4 ± 0.10 Tg yr−1 and 8.6 ± 0.30 Gg yr−1 DOC and dissolved lignin to the estuary during the period of July 2010 to June 2011, respectively. Seasonal distributions of DOC and dissolved lignin fluxes are controlled by water discharge, which will be affected by future climate change and the Three Gorges Dam.

Top-down constraints on atmospheric mercury emissions and implications for global biogeochemical cycling

Abstract. 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.

Spatial and topographic trends in forest expansion and biomass change, from regional to local scales.

Natural forest growth and expansion are important carbon sequestration processes globally. Climate change is likely to increase forest growth in some regions via CO2 fertilization, increased temperatures, and altered precipitation; however, altered disturbance regimes and climate stress (e.g. drought) will act to reduce carbon stocks in forests as well. Observations of asynchrony in forest change is useful in determining current trends in forest carbon stocks, both in terms of forest density (e.g. Mg ha(-1) ) and spatially (extent and location). Monitoring change in natural (unmanaged) areas is particularly useful, as while afforestation and recovery from historic land use are currently large carbon sinks, the long-term viability of those sinks depends on climate change and disturbance dynamics at their particular location. We utilize a large, unmanaged biome (>135 000 km(2) ) which spans a broad latitudinal gradient to explore how variation in location affects forest density and spatial patterning: the forests of the North American temperate rainforests in Alaska, which store >2.8 Pg C in biomass and soil, equivalent to >8% of the C in contiguous US forests. We demonstrate that the regional biome is shifting; gains exceed losses and are located in different spatio-topographic contexts. Forest gains are concentrated on northerly aspects, lower elevations, and higher latitudes, especially in sheltered areas, whereas loss is skewed toward southerly aspects and lower latitudes. Repeat plot-scale biomass data (n = 759) indicate that within-forest biomass gains outpace losses (live trees >12.7 cm diameter, 986 Gg yr(-1) ) on gentler slopes and in higher latitudes. This work demonstrates that while temperate rainforest dynamics occur at fine spatial scales (<1000 m(2) ), the net result of thousands of individual events is regionally patterned change. Correlations between the disturbance/establishment imbalance and biomass accumulation suggest the potential for relatively rapid biome shifts and biomass changes.

European emissions of HCFC-22 based on eleven years of high frequency atmospheric measurements and a Bayesian inversion method

HCFC-22 (CHClF2), a stratospheric ozone depleting substance and a powerful greenhouse gas, is the third most abundant anthropogenic halocarbon in the atmosphere. Primarily used in refrigeration and air conditioning systems, its global production and consumption have increased during the last 60 years, with the global increases in the last decade mainly attributable to developing countries. In 2007, an adjustment to the Montreal Protocol for Substances that Deplete the Ozone Layer called for an accelerated phase out of HCFCs, implying a 75% reduction (base year 1989) of HCFC production and consumption by 2010 in developed countries against the previous 65% reduction. In Europe HCFC-22 is continuously monitored at the two sites Mace Head (Ireland) and Monte Cimone (Italy). Combining atmospheric observations with a Bayesian inversion technique, we estimated fluxes of HCFC-22 from Europe and from eight macro-areas within it, over an 11-year period from January 2002 to December 2012, during which the accelerated restrictions on HCFCs production and consumption have entered into force. According to our study, the maximum emissions over the entire domain was in 2003 (38.2 ± 4.7 Gg yr−1), and the minimum in 2012 (12.1 ± 2.0 Gg yr−1); emissions continuously decreased between these years, except for secondary maxima in the 2008 and 2010. Despite such a decrease in regional emissions, background values of HCFC-22 measured at the two European stations over 2002–2012 are still increasing as a consequence of global emissions, in part from developing countries, with an average trend of ca 7.0 ppt yr−1. However, the observations at the two European stations show also that since 2008 a decrease in the global growth rate has occurred. In general, our European emission estimates are in good agreement with those reported by previous studies that used different techniques. Since the currently dominant emission source of HCFC-22 is from banks, we assess the banks' size and their contribution to the total European emissions up to 2030, and we project a fast decrease approaching negligible emissions in the last five years of the considered period. Finally, inversions conducted over three month periods showed evidence for a seasonal cycle in emissions in regions in the Mediterranean basin but not outside it. Emissions derived from regions in the Mediterranean basin were ca. 25% higher in warmer months than in colder months.

A halocarbon survey from a seagrass dominated subtropical lagoon, Ria Formosa (Portugal): flux pattern and isotopic composition

Abstract. In this study we report fluxes of chloromethane (CH3Cl), bromomethane (CH3Br), iodomethane (CH3I), and bromoform (CHBr3) from two sampling campaigns (summer and spring) in the seagrass dominated subtropical lagoon Ria Formosa, Portugal. Dynamic flux chamber measurements were performed when seagrass patches were either air-exposed or submerged. Overall, we observed highly variable fluxes from the seagrass meadows and attributed them to diurnal cycles, tidal effects, and the variety of possible sources and sinks in the seagrass meadows. The highest emissions with up to 130 nmol m−2 h−1 for CH3Br were observed during tidal changes, from air exposure to submergence and conversely. Furthermore, during the spring campaign, the emissions of halocarbons were significantly elevated during tidal inundation as compared to air exposure. Accompanying water sampling performed during both campaigns revealed elevated concentrations of CH3Cl and CH3Br, indicating productive sources within the lagoon. Stable carbon isotopes of halocarbons from the air and water phase along with source signatures were used to allocate the distinctive sources and sinks in the lagoon. Results suggest that CH3Cl was rather originating from seagrass meadows and water column than from salt marshes. Aqueous and atmospheric CH3Br was substantially enriched in 13C in comparison to source signatures for seagrass meadows and salt marshes. This suggests a significant contribution from the water phase on the atmospheric CH3Br in the lagoon. A rough global upscaling yields annual productions from seagrass meadows of 2.3–4.5 Gg yr−1, 0.5–1.0 Gg yr−1, 0.6–1.2 Gg yr−1, and 1.9–3.7 Gg yr−1 for CH3Cl, CH3Br, CH3I, and CHBr3 respectively. This suggests a minor contribution from seagrass meadows to the global production of CH3Cl and CH3Br with about 0.1 and 0.7%, respectively. In comparison to the known marine sources for CH3I and CHBr3, seagrass meadows are rather small sources.

Increasing concentrations of dichloromethane, CH&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;Cl&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, inferred from CARIBIC air samples collected 1998–2012

Abstract. Atmospheric concentrations of dichloromethane, CH2Cl2, a regulated toxic air pollutant and minor contributor to stratospheric ozone depletion, were reported to have peaked around 1990 and to be declining in the early part of the 21st century. Recent observations suggest this trend has reversed and that CH2Cl2 is once again increasing in the atmosphere. Despite the importance of ongoing monitoring and reporting of atmospheric CH2Cl2, no time series has been discussed in detail since 2006. The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) has analysed the halocarbon content of whole-air samples collected at altitudes of between ~ 10–12 km via a custom-built container installed on commercial passenger aircraft since 1998, providing a long-term record of CH2Cl2 observations. In this paper we present this unique CH2Cl2 time series, discussing key flight routes which have been used at various times over the past 15 years. Between 1998 and 2012 increases were seen in all northern hemispheric regions and at different altitudes, ranging from ~ 7–10 ppt in background air to ~ 13–15 ppt in regions with stronger emissions (equating to a 38–69% increase). Of particular interest is the rising importance of India as a source of atmospheric CH2Cl2: based on CARIBIC data we provide regional emission estimates for the Indian subcontinent and show that regional emissions have increased from 3–14 Gg yr−1 (1998–2000) to 16–25 Gg yr−1 (2008). Potential causes of the increasing atmospheric burden of CH2Cl2 are discussed. One possible source is the increased use of CH2Cl2 as a feedstock for the production of HFC-32, a chemical used predominantly as a replacement for ozone-depleting substances in a variety of applications including air conditioners and refrigeration.

First observations of the fourth generation synthetic halocarbons HFC-1234yf, HFC-1234ze(E), and HCFC-1233zd(E) in the atmosphere.

Halogenated alkenes are a class of anthropogenic substances, which replace ozone-depleting substances and long-lived greenhouse gases in the foam-blowing, refrigeration, and solvent sectors. We report the first multiyear atmospheric measurements of the hydrofluorocarbons HFC-1234yf (2,3,3,3-tetrafluoroprop-1-ene, CF3CF═CH2), and HFC-1234ze(E) (E-1,3,3,3-tetrafluoroprop-1-ene trans-CF3CH═CHF), and the hydrochlorofluorocarbon HCFC-1233zd(E) (E-1-chloro-3,3,3-trifluoroprop-1-ene trans-CF3CH═CHCl) from the high altitude observatory at Jungfraujoch and from urban Dubendorf (Switzerland). When observations started in 2011 HFC-1234yf was undetectable at Jungfraujoch (mole fractions <0.003 ppt, parts-per-trillion, 10(-12)) but since then the percentage of measurements with detectable mole fractions has steadily increased to 4.5% in 2014. By contrast, in 2014 HFC-1234ze(E) was detectable in half of our samples at Jungfraujoch and in all samples at Dubendorf demonstrating the wide use of this compound within the air mass footprints of the stations. Our back trajectory analysis for the Jungfraujoch observations suggests high emission strength of HFC-1234ze(E) in the Belgium/Netherlands region. HCFC-1233zd(E) is present at very low mole fractions (typically <0.03 ppt) at both stations, and features pronounced seasonality and a general absence of pollution events during our 2013-2014 measurements. This is indicative of the presence of significant emissions from source locations outside the footprints of the two stations. Based on a simple one-box model calculation we estimate globally increasing HCFC-1233zd(E) emissions from 0.2 Gg yr(-1) in 2013 to 0.5 Gg yr(-1) for 2014.

Long-term variations in PM2.5 emission from open biomass burning in Northeast Asia derived from satellite-derived data for 2000–2013

PM2.5 emissions from open biomass burning (BB) in Northeast Asia (NEA: China, Mongolia, Korea, and Japan) during 2000–2013 were estimated using satellite-derived data (GFASv1.0 and GFED3). The annual mean BB PM2.5 emission in NEA during the study period was 660 Gg yr−1, in which considerable inter-annual variability was observed. In general, PM2.5 emissions in NEA were the highest in spring (Mar.–May), likely due to the burning of crop residues and forest fire. The contribution of PM2.5 from open BB in Northeast Asia was less than 10% of the anthropogenic PM2.5 emission, except in Mongolia, wherein BB emission was the predominant source of PM2.5. Although the emissions calculated by GFASv1.0 were significantly higher than GFED3 by a factor of 2.66 (Mongolia) to 10.9 (South Korea) due to difficulty in small fire detection by GFED3, they generally showed consistent temporal variation on average. In general, statistically significant long-term trends of open BB PM2.5 emissions were not observed in NEA, except in South Korea.

U.S. emissions of HFC‐134a derived for 2008–2012 from an extensive flask‐air sampling network

AbstractU.S. national and regional emissions of HFC‐134a are derived for 2008–2012 based on atmospheric observations from ground and aircraft sites across the U.S. and a newly developed regional inverse model. Synthetic data experiments were first conducted to optimize the model assimilation design and to assess model‐data mismatch errors and prior flux error covariances computed using a maximum likelihood estimation technique. The synthetic data experiments also tested the sensitivity of derived national and regional emissions to a range of assumed prior emissions, with the goal of designing a system that was minimally reliant on the prior. We then explored the influence of additional sources of error in inversions with actual observations, such as those associated with background mole fractions and transport uncertainties. Estimated emissions of HFC‐134a range from 52 to 61 Gg yr−1 for the contiguous U.S. during 2008–2012 for inversions using air transport from Hybrid Single‐Particle Lagrangian Integrated Trajectory (HYSPLIT) model driven by the 12 km resolution meteorogical data from North American Mesoscale Forecast System (NAM12) and all tested combinations of prior emissions and background mole fractions. Estimated emissions for 2008–2010 were 20% lower when specifying alternative transport from Stochastic Time‐Inverted Lagrangian Transport (STILT) model driven by the Weather Research and Forecasting (WRF) meteorology. Our estimates (for HYSPLIT‐NAM12) are consistent with annual emissions reported by U.S. Environmental Protection Agency for the full study interval. The results suggest a 10–20% drop in U.S. national HFC‐134a emission in 2009 coincident with a reduction in transportation‐related fossil fuel CO2 emissions, perhaps related to the economic recession. All inversions show seasonal variation in national HFC‐134a emissions in all years, with summer emissions greater than winter emissions by 20–50%.

Phosphorus transport by the largest Amazon tributary (Madeira River, Brazil) and its sensitivity to precipitation and damming

Originating in the Bolivian and Peruvian Andes, the Madeira River is the largest tributary of the Amazon River in terms of discharge. Andean rivers transport large quantities of nutrient-rich suspended sediments and are the main source of phosphorus (P) to the Amazon basin. Here, we show the seasonal variability in concentrations and loads of different P forms (total, particulate, dissolved, and soluble reactive P) in the Madeira River through 8 field campaigns between 2009 and 2011. At our sampling reach in Porto Velho, Brazil, the Madeira River transports ~177–247 Gg yr−1 of P, mostly linked to particles (~85%). Concentrations and loads of all P forms have a maximum at rising waters and a minimum at low waters. Total P concentrations were substantially higher at a given discharge at rising water than at a similar discharge at falling water. The peak of P concentrations matched the peak of rainfall in the upper basin, suggesting an influence of precipitation-driven erosion. Projected precipitation increase in the eastern slopes of the Andes could enhance sediment yield and hence the P transport in the Madeira River. Because most of the P is particulate, however, we hypothesize that the planned proliferation of hydropower dams in the Madeira basin has the potential to reduce P loads substantially, possibly counteracting any precipitation-related increases. In the long term, this could be detrimental to highly productive downstream floodplain forests that are seasonally fertilized with P-rich deposits.

Analyzing source apportioned methane in northern California during Discover-AQ-CA using airborne measurements and model simulations

This study analyzes source apportioned methane (CH4) emissions and atmospheric mixing ratios in northern California during the Discover-AQ-CA field campaign using airborne measurement data and model simulations. Source apportioned CH4 emissions from the Emissions Database for Global Atmospheric Research (EDGAR) version 4.2 were applied in the 3-D chemical transport model GEOS-Chem and analyzed using airborne measurements taken as part of the Alpha Jet Atmospheric eXperiment over the San Francisco Bay Area (SFBA) and northern San Joaquin Valley (SJV). During the time period of the Discover-AQ-CA field campaign EDGAR inventory CH4 emissions were ∼5.30 Gg day−1 (Gg = 1.0 × 109 g) (equating to ∼1.90 × 103 Gg yr−1) for all of California. According to EDGAR, the SFBA and northern SJV region contributes ∼30% of total CH4 emissions from California. Source apportionment analysis during this study shows that CH4 mixing ratios over this area of northern California are largely influenced by global emissions from wetlands and local/global emissions from gas and oil production and distribution, waste treatment processes, and livestock management. Model simulations, using EDGAR emissions, suggest that the model under-estimates CH4 mixing ratios in northern California (average normalized mean bias (NMB) = −5.2% and linear regression slope = 0.20). The largest negative biases in the model were calculated on days when large amounts of CH4 were measured over local emission sources and atmospheric CH4 mixing ratios reached values >2.5 parts per million. Sensitivity emission studies conducted during this research suggest that local emissions of CH4 from livestock management processes are likely the primary source of the negative model bias. These results indicate that a variety, and larger quantity, of measurement data needs to be obtained and additional research is necessary to better quantify source apportioned CH4 emissions in California.

Estimates of European emissions of methyl chloroform using a Bayesian inversion method

Abstract. Methyl chloroform (MCF) is a man-made chlorinated solvent contributing to the destruction of stratospheric ozone and is controlled under the "Montreal Protocol on Substances that Deplete the Ozone Layer" and its amendments, which called for its phase-out in 1996 in developed countries and 2015 in developing countries. Long-term, high-frequency observations of MCF carried out at three European sites show a constant decline in the background mixing ratios of MCF. However, we observe persistent non-negligible mixing ratio enhancements of MCF in pollution episodes, suggesting unexpectedly high ongoing emissions in Europe. In order to identify the source regions and to give an estimate of the magnitude of such emissions, we have used a Bayesian inversion method and a point source analysis, based on high-frequency long-term observations at the three European sites. The inversion identified southeastern France (SEF) as a region with enhanced MCF emissions. This estimate was confirmed by the point source analysis. We performed this analysis using an 11-year data set, from January 2002 to December 2012. Overall, emissions estimated for the European study domain decreased nearly exponentially from 1.1 Gg yr−1 in 2002 to 0.32 Gg yr−1 in 2012, of which the estimated emissions from the SEF region accounted for 0.49 Gg yr−1 in 2002 and 0.20 Gg yr−1 in 2012. The European estimates are a significant fraction of the total semi-hemisphere (30–90° N) emissions, contributing a minimum of 9.8% in 2004 and a maximum of 33.7% in 2011, of which on average 50% are from the SEF region. On the global scale, the SEF region is thus responsible for a minimum of 2.6% (in 2003) and a maximum of 10.3% (in 2009) of the global MCF emissions.