Improving Estimates of Sulfur, Nitrogen, and Ozone Total Deposition through Multi-Model and Measurement-Model Fusion Approaches.

Earth system and environmental impact studies need high quality and up-to-date estimates of atmospheric deposition. This study demonstrates the methodological benefits of multimodel ensemble and measurement-model fusion mapping approaches for atmospheric deposition focusing on 2010, a year for which several studies were conducted. Global model-only deposition assessment can be further improved by integrating new model-measurement techniques, including expanded capabilities of satellite observations of atmospheric composition. We identify research and implementation priorities for timely estimates of deposition globally as implemented by the World Meteorological Organization.

Updated trends for atmospheric mercury in the Arctic: 1995-2018.

The Arctic region forms a unique environment with specific physical, chemical, and biological processes affecting mercury (Hg) cycles and limited anthropogenic Hg sources. However, historic global emissions and long range atmospheric transport has led to elevated Hg in Arctic wildlife and waterways. Continuous atmospheric Hg measurements, spanning 20 years, and increased monitoring sites has allowed a more comprehensive understanding of how Arctic atmospheric mercury is changing over time. Time-series trend analysis of TGM (Total Gaseous Mercury) in air was performed from 10 circumpolar air monitoring stations, comprising of high-Arctic, and sub-Arctic sites. GOM (gaseous oxidised mercury) and PHg (particulate bound mercury) measurements were also available at 2 high-Arctic sites. Seasonal mean TGM for sub-Arctic sites were lowest during fall ranging from 1.1 ng m-3 Hyytiälä to 1.3 ng m-3, Little Fox Lake. Mean TGM concentrations at high-Arctic sites showed the greatest variability, with highest daily means in spring ranging between 4.2 ng m-3 at Amderma and 2.4 ng m-3 at Zeppelin, largely driven by local chemistry. Annual TGM trend analysis was negative for 8 of the 10 sites. High-Arctic seasonal TGM trends saw smallest decline during summer. Fall trends ranged from -0.8% to -2.6% yr-1. Across the sub-Arctic sites spring showed the largest significant decreases, ranging between -7.7% to -0.36% yr-1, while fall generally had no significant trends. High-Arctic speciation of GOM and PHg at Alert and Zeppelin showed that the timing and composition of atmospheric mercury deposition events are shifting. Alert GOM trends are increasing throughout the year, while PHg trends decreased or not significant. Zeppelin saw the opposite, moving towards increasing PHg and decreasing GOM. Atmospheric mercury trends over the last 20 years indicate that Hg concentrations are decreasing across the Arctic, though not uniformly. This is potentially driven by environmental change, such as plant productivity and sea ice dynamics.

Equal abundance of summertime natural and wintertime anthropogenic Arctic organic aerosols.

Aerosols play an important yet uncertain role in modulating the radiation balance of the sensitive Arctic atmosphere. Organic aerosol is one of the most abundant, yet least understood, fractions of the Arctic aerosol mass. Here we use data from eight observatories that represent the entire Arctic to reveal the annual cycles in anthropogenic and biogenic sources of organic aerosol. We show that during winter, the organic aerosol in the Arctic is dominated by anthropogenic emissions, mainly from Eurasia, which consist of both direct combustion emissions and long-range transported, aged pollution. In summer, the decreasing anthropogenic pollution is replaced by natural emissions. These include marine secondary, biogenic secondary and primary biological emissions, which have the potential to be important to Arctic climate by modifying the cloud condensation nuclei properties and acting as ice-nucleating particles. Their source strength or atmospheric processing is sensitive to nutrient availability, solar radiation, temperature and snow cover. Our results provide a comprehensive understanding of the current pan-Arctic organic aerosol, which can be used to support modelling efforts that aim to quantify the climate impacts of emissions in this sensitive region.

European aerosol phenomenology - 8: Harmonised source apportionment of organic aerosol using 22 Year-long ACSM/AMS datasets.

Organic aerosol (OA) is a key component of total submicron particulate matter (PM1), and comprehensive knowledge of OA sources across Europe is crucial to mitigate PM1 levels. Europe has a well-established air quality research infrastructure from which yearlong datasets using 21 aerosol chemical speciation monitors (ACSMs) and 1 aerosol mass spectrometer (AMS) were gathered during 2013-2019. It includes 9 non-urban and 13 urban sites. This study developed a state-of-the-art source apportionment protocol to analyse long-term OA mass spectrum data by applying the most advanced source apportionment strategies (i.e., rolling PMF, ME-2, and bootstrap). This harmonised protocol was followed strictly for all 22 datasets, making the source apportionment results more comparable. In addition, it enables quantification of the most common OA components such as hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking-like OA (COA), more oxidised-oxygenated OA (MO-OOA), and less oxidised-oxygenated OA (LO-OOA). Other components such as coal combustion OA (CCOA), solid fuel OA (SFOA: mainly mixture of coal and peat combustion), cigarette smoke OA (CSOA), sea salt (mostly inorganic but part of the OA mass spectrum), coffee OA, and ship industry OA could also be separated at a few specific sites. Oxygenated OA (OOA) components make up most of the submicron OA mass (average = 71.1%, range from 43.7 to 100%). Solid fuel combustion-related OA components (i.e., BBOA, CCOA, and SFOA) are still considerable with in total 16.0% yearly contribution to the OA, yet mainly during winter months (21.4%). Overall, this comprehensive protocol works effectively across all sites governed by different sources and generates robust and consistent source apportionment results. Our work presents a comprehensive overview of OA sources in Europe with a unique combination of high time resolution (30-240 min) and long-term data coverage (9-36 months), providing essential information to improve/validate air quality, health impact, and climate models.

Time trends of persistent organic pollutants (POPs) and Chemicals of Emerging Arctic Concern (CEAC) in Arctic air from 25 years of monitoring.

The long-term time trends of atmospheric pollutants at eight Arctic monitoring stations are reported. The work was conducted under the Arctic Monitoring and Assessment Programme (AMAP) of the Arctic Council. The monitoring stations were: Alert, Canada; Zeppelin, Svalbard; Stórhöfði, Iceland; Pallas, Finland; Andøya, Norway; Villum Research Station, Greenland; Tiksi and Amderma, Russia. Persistent organic pollutants (POPs) such as α- and γ-hexachlorocyclohexane (HCH), polychlorinated biphenyls (PCBs), α-endosulfan, chlordane, dichlorodiphenyltrichloroethane (DDT) and polybrominated diphenyl ethers (PBDEs) showed declining trends in air at all stations. However, hexachlorobenzene (HCB), one of the initial twelve POPs listed in the Stockholm Convention in 2004, showed either increasing or non-changing trends at the stations. Many POPs demonstrated seasonality but the patterns were not consistent among the chemicals and stations. Some chemicals showed winter minimum and summer maximum concentrations at one station but not another, and vice versa. The ratios of chlordane isomers and DDT species showed that they were aged residues. Time trends of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were showing decreasing concentrations at Alert, Zeppelin and Andøya. The Chemicals of Emerging Arctic Concern (CEAC) were either showing stable or increasing trends. These include methoxychlor, perfluorohexane sulfonic acid (PFHxS), 6:2 fluorotelomer alcohol, and C9-C11 perfluorocarboxylic acids (PFCAs). We have demonstrated the importance of monitoring CEAC before they are being regulated because model calculations to predict their transport mechanisms and fate cannot be made due to the lack of emission inventories. We should maintain long-term monitoring programmes with consistent data quality in order to evaluate the effectiveness of chemical control efforts taken by countries worldwide.

Author Correction: Global and regional trends of atmospheric sulfur.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Comparison of methods for measuring atmospheric deposition of arsenic, cadmium, nickel and lead.

A comprehensive field intercomparison at four different types of European sites (two rural, one urban and one industrial) comparing three different collectors (wet only, bulk and Bergerhoff samplers) was conducted in the framework of the European Committee for Standardization (CEN) to create an European standard for the deposition of the four elements As, Cd, Ni and Pb. The purpose was to determine whether the proposed methods lead to results within the uncertainty required by the EU's daughter directive (70%). The main conclusion is that a different sampling strategy is needed for rural and industrial sites. Thus, the conclusions on uncertainties and sample approach are presented separately for the different approaches. The wet only and bulk collector ("bulk bottle method") are comparable at wet rural sites where the total deposition arises mainly from precipitation, the expanded uncertainty when comparing these two types of sampler are below 45% for As, Cd and Pb, 67% for Ni. At industrial sites and possibly very dry rural and urban sites it is necessary to use Bergerhoff samplers or a "bulk bottle+funnel method". It is not possible to address the total deposition estimation with these methods, but they will give the lowest estimate of the total deposition. The expanded uncertainties when comparing the Bergerhoff and the bulk bottle+funnel methods are below 50% for As and Cd, and 63% for Pb. The uncertainty for Ni was not addressed since the bulk bottle+funnel method did not include a full digestion procedure which is necessary for sites with high loads of undissolved metals. The lowest estimate can however be calculated by comparing parallel Bergerhoff samplers where the expanded uncertainty for Ni was 24%. The reproducibility is comparable to the between sampler/method uncertainties. Sampling and sample preparation were proved to be the main factors in the uncertainty budget of deposition measurements.

Global and regional trends of atmospheric sulfur.

The profound changes in global SO2 emissions over the last decades have affected atmospheric composition on a regional and global scale with large impact on air quality, atmospheric deposition and the radiative forcing of sulfate aerosols. Reproduction of historical atmospheric pollution levels based on global aerosol models and emission changes is crucial to prove that such models are able to predict future scenarios. Here, we analyze consistency of trends in observations of sulfur components in air and precipitation from major regional networks and estimates from six different global aerosol models from 1990 until 2015. There are large interregional differences in the sulfur trends consistently captured by the models and observations, especially for North America and Europe. Europe had the largest reductions in sulfur emissions in the first part of the period while the highest reduction came later in North America and East Asia. The uncertainties in both the emissions and the representativity of the observations are larger in Asia. However, emissions from East Asia clearly increased from 2000 to 2005 followed by a decrease, while in India a steady increase over the whole period has been observed and modelled. The agreement between a bottom-up approach, which uses emissions and process-based chemical transport models, with independent observations gives an improved confidence in the understanding of the atmospheric sulfur budget.

Trends of nitrogen in air and precipitation: model results and observations at EMEP sites in Europe, 1980--2003.

We analyze trends of some nitrogen compounds using long-term measurements and results from the EMEP (co-operative programme for monitoring and evaluation of the long-range transmissions of air pollutants in Europe) chemical transport model at EMEP sites. We find statistically significant declines at the majority of sites for NH(x) (sum of ammonia and ammonium) in air and for nitrate and ammonium in precipitation, but only at a few sites for xNO3 (sum of nitrate and nitric acid) in air. Model calculations and measurements give similar results. We demonstrate that the lack of trends for xNO3 in air at least partly can be attributed to a shift in the equilibrium between nitric acid and ammonium nitrate towards particulate phase, caused by reductions in the sulfur dioxide emissions.

Modeled deposition of nitrogen and sulfur in Europe estimated by 14 air quality model systems: evaluation, effects of changes in emissions and implications for habitat protection.

The evaluation and intercomparison of air quality models is key to reducing model errors and uncertainty. The projects AQMEII3 and EURODELTA-Trends, in the framework of the Task Force on Hemispheric Transport of Air Pollutants and the Task Force on Measurements and Modelling, respectively (both task forces under the UNECE Convention on the Long Range Transport of Air Pollution, LTRAP), have brought together various regional air quality models to analyze their performance in terms of air concentrations and wet deposition, as well as to address other specific objectives. This paper jointly examines the results from both project communities by intercomparing and evaluating the deposition estimates of reduced and oxidized nitrogen (N) and sulfur (S) in Europe simulated by 14 air quality model systems for the year 2010. An accurate estimate of deposition is key to an accurate simulation of atmospheric concentrations. In addition, deposition fluxes are increasingly being used to estimate ecological impacts. It is therefore important to know by how much model results differ and how well they agree with observed values, at least when comparison with observations is possible, such as in the case of wet deposition. This study reveals a large variability between the wet deposition estimates of the models, with some performing acceptably (according to previously defined criteria) and others underestimating wet deposition rates. For dry deposition, there are also considerable differences between the model estimates. An ensemble of the models with the best performance for N wet deposition was made and used to explore the implications of N deposition in the conservation of protected European habitats. Exceedances of empirical critical loads were calculated for the most common habitats at a resolution of 100 × 100 m2 within the Natura 2000 network, and the habitats with the largest areas showing exceedances are determined. Moreover, simulations with reduced emissions in selected source areas indicated a fairly linear relationship between reductions in emissions and changes in the deposition rates of N and S. An approximate 20 % reduction in N and S deposition in Europe is found when emissions at a global scale are reduced by the same amount. European emissions are by far the main contributor to deposition in Europe, whereas the reduction in deposition due to a decrease in emissions in North America is very small and confined to the western part of the domain. Reductions in European emissions led to substantial decreases in the protected habitat areas with critical load exceedances (halving the exceeded area for certain habitats), whereas no change was found, on average, when reducing North American emissions in terms of average values per habitat.

Temporal trends of Persistent Organic Pollutants (POPs) in arctic air: 20 years of monitoring under the Arctic Monitoring and Assessment Programme (AMAP).

Temporal trends of Persistent Organic Pollutants (POPs) measured in Arctic air are essential in understanding long-range transport to remote regions and to evaluate the effectiveness of national and international chemical control initiatives, such as the Stockholm Convention (SC) on POPs. Long-term air monitoring of POPs is conducted under the Arctic Monitoring and Assessment Programme (AMAP) at four Arctic stations: Alert, Canada; Stórhöfði, Iceland; Zeppelin, Svalbard; and Pallas, Finland, since the 1990s using high volume air samplers. Temporal trends observed for POPs in Arctic air are summarized in this study. Most POPs listed for control under the SC, e.g. polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs) and chlordanes, are declining slowly in Arctic air, reflecting the reduction of primary emissions during the last two decades and increasing importance of secondary emissions. Slow declining trends also signifies their persistence and slow degradation under the Arctic environment, such that they are still detectable after being banned for decades in many countries. Some POPs, e.g. hexachlorobenzene (HCB) and lighter PCBs, showed increasing trends at specific locations, which may be attributable to warming in the region and continued primary emissions at source. Polybrominated diphenyl ethers (PBDEs) do not decline in air at Canada's Alert station but are declining in European Arctic air, which may be due to influence of local sources at Alert and the much higher historical usage of PBDEs in North America. Arctic air samples are screened for chemicals of emerging concern to provide information regarding their environmental persistence (P) and long-range transport potential (LRTP), which are important criteria for classification as a POP under SC. The AMAP network provides consistent and comparable air monitoring data of POPs for trend development and acts as a bridge between national monitoring programs and SC's Global Monitoring Plan (GMP).

Biomass burning in eastern Europe during spring 2006 caused high deposition of ammonium in northern Fennoscandia.

High air concentrations of ammonium were detected at low and high altitude sites in Sweden, Finland and Norway during the spring 2006, coinciding with polluted air from biomass burning in eastern Europe passing over central and northern Fennoscandia. Unusually high values for throughfall deposition of ammonium were detected at one low altitude site and several high altitude sites in north Sweden. The occurrence of the high ammonium in throughfall differed between the summer months 2006, most likely related to the timing of precipitation events. The ammonia dry deposition may have contributed to unusual visible injuries on the tree vegetation in northern Fennoscandia that occurred during 2006, in combination with high ozone concentrations. It is concluded that long-range transport of ammonium from large-scale biomass burning may contribute substantially to the nitrogen load at northern latitudes.