scholarly journals Investigating the Atmospheric Sources and Sinks of Perfluorooctanoic Acid Using a Global Chemistry Transport Model

Atmosphere ◽  
2020 ◽  
Vol 11 (4) ◽  
pp. 407 ◽  
Author(s):  
Rayne Holland ◽  
M. Anwar H. Khan ◽  
Rabi Chhantyal-Pun ◽  
Andrew J. Orr-Ewing ◽  
Carl J. Percival ◽  
...  
Keyword(s):  
Environmental Degradation ◽  
Transport Model ◽  
Perfluorooctanoic Acid ◽  
Chemical Transport Model ◽  
Atmospheric Concentration ◽  
Loss Process ◽  
Criegee Intermediates ◽  
The Many ◽  
Phase Out ◽  
Atmospheric Loss

Perfluorooctanoic acid, PFOA, is one of the many concerning pollutants in our atmosphere; it is highly resistant to environmental degradation processes, which enables it to accumulate biologically. With direct routes of this chemical to the environment decreasing, as a consequence of the industrial phase out of PFOA, it has become more important to accurately model the effects of indirect production routes, such as environmental degradation of precursors; e.g., fluorotelomer alcohols (FTOHs). The study reported here investigates the chemistry, physical loss and transport of PFOA and its precursors, FTOHs, throughout the troposphere using a 3D global chemical transport model, STOCHEM-CRI. Moreover, this investigation includes an important loss process of PFOA in the atmosphere via the addition of the stabilised Criegee intermediates, hereby referred to as the “Criegee Field.” Whilst reaction with Criegee intermediates is a significant atmospheric loss process of PFOA, it does not result in its permanent removal from the atmosphere. The atmospheric fate of the resultant hydroperoxide product from the reaction of PFOA and Criegee intermediates resulted in a ≈0.04 Gg year−1 increase in the production flux of PFOA. Furthermore, the physical loss of the hydroperoxide product from the atmosphere (i.e., deposition), whilst decreasing the atmospheric concentration, is also likely to result in the reformation of PFOA in environmental aqueous phases, such as clouds, precipitation, oceans and lakes. As such, removal facilitated by the “Criegee Field” is likely to simply result in the acceleration of PFOA transfer to the surface (with an expected decrease in PFOA atmospheric lifetime of ≈10 h, on average from ca. 80 h without Criegee loss to 70 h with Criegee loss).

scholarly journals Do contemporary (1980–2015) emissions determine the elemental carbon deposition trend at Holtedahlfonna glacier, Svalbard?

2017 ◽  
Vol 17 (20) ◽  
pp. 12779-12795 ◽  
Author(s):  
Meri M. Ruppel ◽  
Joana Soares ◽  
Jean-Charles Gallet ◽  
Elisabeth Isaksson ◽  
Tõnu Martma ◽  
...  
Keyword(s):  
Elemental Carbon ◽  
Transport Model ◽  
Ice Core ◽  
Climate Impact ◽  
The Arctic ◽  
Chemical Transport Model ◽  
Atmospheric Measurements ◽  
Atmospheric Concentration ◽  
Scavenging Efficiency ◽  
Firn Core

Abstract. The climate impact of black carbon (BC) is notably amplified in the Arctic by its deposition, which causes albedo decrease and subsequent earlier snow and ice spring melt. To comprehensively assess the climate impact of BC in the Arctic, information on both atmospheric BC concentrations and deposition is essential. Currently, Arctic BC deposition data are very scarce, while atmospheric BC concentrations have been shown to generally decrease since the 1990s. However, a 300-year Svalbard ice core showed a distinct increase in EC (elemental carbon, proxy for BC) deposition from 1970 to 2004 contradicting atmospheric measurements and modelling studies. Here, our objective was to decipher whether this increase has continued in the 21st century and to investigate the drivers of the observed EC deposition trends. For this, a shallow firn core was collected from the same Svalbard glacier, and a regional-to-meso-scale chemical transport model (SILAM) was run from 1980 to 2015. The ice and firn core data indicate peaking EC deposition values at the end of the 1990s and lower values thereafter. The modelled BC deposition results generally support the observed glacier EC variations. However, the ice and firn core results clearly deviate from both measured and modelled atmospheric BC concentration trends, and the modelled BC deposition trend shows variations seemingly independent from BC emission or atmospheric BC concentration trends. Furthermore, according to the model ca. 99 % BC mass is wet-deposited at this Svalbard glacier, indicating that meteorological processes such as precipitation and scavenging efficiency have most likely a stronger influence on the BC deposition trend than BC emission or atmospheric concentration trends. BC emission source sectors contribute differently to the modelled atmospheric BC concentrations and BC deposition, which further supports our conclusion that different processes affect atmospheric BC concentration and deposition trends. Consequently, Arctic BC deposition trends should not directly be inferred based on atmospheric BC measurements, and more observational BC deposition data are required to assess the climate impact of BC in Arctic snow.

scholarly journals A large and ubiquitous source of atmospheric formic acid

2015 ◽  
Vol 15 (11) ◽  
pp. 6283-6304 ◽  
Author(s):  
D. B. Millet ◽  
M. Baasandorj ◽  
D. K. Farmer ◽  
J. A. Thornton ◽  
K. Baumann ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Formic Acid ◽  
Transport Model ◽  
Model Simulation ◽  
Vertical Gradient ◽  
Precipitation Chemistry ◽  
Chemical Production ◽  
Chemical Transport Model ◽  
Criegee Intermediates ◽  
Isoprene Oxidation

Abstract. Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem CTM) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2–3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx : CH3OOH. Developing better constraints on SCI and RO2 + OH chemistry is a high priority for future work. The model neither captures the large diurnal amplitude in HCOOH seen in surface air, nor its inverted vertical gradient at night. This implies a substantial bias in our current representation of deposition as modulated by boundary layer dynamics, and may indicate an HCOOH sink underestimate and thus an even larger missing source. A more robust treatment of surface deposition is a key need for improving simulations of HCOOH and related trace gases, and our understanding of their budgets.

scholarly journals A large and ubiquitous source of atmospheric formic acid

2015 ◽  
Vol 15 (4) ◽  
pp. 4537-4599 ◽  
Author(s):  
D. B. Millet ◽  
M. Baasandorj ◽  
D. K. Farmer ◽  
J. A. Thornton ◽  
K. Baumann ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Formic Acid ◽  
Transport Model ◽  
Model Simulation ◽  
Vertical Gradient ◽  
Precipitation Chemistry ◽  
Chemical Production ◽  
Chemical Transport Model ◽  
Criegee Intermediates ◽  
Isoprene Oxidation

Abstract. Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2–3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based: (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx:CH3OOH. Developing better constraints on SCI and RO2 + OH chemistry is a high priority for future work. The model does not capture the large diurnal amplitude in HCOOH seen in surface air, nor its inverted vertical gradient at night. This implies a substantial bias in our current representation of deposition as modulated by boundary layer dynamics, and may indicate an HCOOH sink underestimate and thus an even larger missing source. A more robust treatment of surface deposition is a key need for improving simulations of HCOOH and related trace gases, and our understanding of their budgets.

scholarly journals Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument

2017 ◽  
Vol 17 (12) ◽  
pp. 7807-7826 ◽  
Author(s):  
Anna Novelli ◽  
Korbinian Hens ◽  
Cheryl Tatum Ernest ◽  
Monica Martinez ◽  
Anke C. Nölscher ◽  
...  
Keyword(s):  
Boreal Forest ◽  
Lower Troposphere ◽  
Potential Effect ◽  
Atmospheric Concentration ◽  
Criegee Intermediates ◽  
Rural Environments ◽  
Volatile Organic ◽  
Order Of Magnitude ◽  
Field Campaigns ◽  
The Many

Abstract. We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of sulfur dioxide. SCIs also add to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of  ∼  5.0  ×  104 molecules cm−3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCIs, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere.

scholarly journals Do contemporary (1980–2015) emissions determine the elemental carbon deposition trend at Holtedahlfonna glacier, Svalbard?

2017 ◽  
Author(s):  
Meri M. Ruppel ◽  
Joana Soares ◽  
Jean-Charles Gallet ◽  
Elisabeth Isaksson ◽  
Tõnu Martma ◽  
...  
Keyword(s):  
Elemental Carbon ◽  
Transport Model ◽  
Ice Core ◽  
Climate Impact ◽  
The Arctic ◽  
Chemical Transport Model ◽  
Atmospheric Measurements ◽  
Atmospheric Concentration ◽  
Scavenging Efficiency ◽  
Firn Core

Abstract. The climate impact of black carbon (BC) is notably amplified in the Arctic by its deposition that causes albedo decrease and subsequent earlier snow and ice spring melt. To comprehensively assess the climate impact of BC in the Arctic, information on both atmospheric BC concentrations and deposition are essential. Currently, Arctic BC deposition data are very scarce, while atmospheric BC concentrations have been shown to generally decrease since the 1990s. However, a 300-year Svalbard ice core showed a distinct increase in EC (elemental carbon, proxy for BC) deposition from 1970 to 2004 contradicting atmospheric measurements and modelling studies. Here, our objective was to decipher whether this increase has continued in the 21st century, and to investigate the drivers of the observed EC deposition trends. For this, a shallow firn core was collected from the same Svalbard glacier, and a regional-to-meso-scale chemical transport model (SILAM) was run from 1980 to 2015. The ice and firn core data indicate peaking EC deposition values at the end of the 1990s, and lower values thereafter. The modelled BC deposition results generally support the observed glacier EC variations. However, the ice and firn core results clearly deviate from both measured and modelled atmospheric BC concentration trends, and the modelled BC deposition trend shows variations seemingly independent from BC emission or atmospheric BC concentration trends. Furthermore, ca. 99 % BC mass is wet-deposited at this Svalbard glacier, indicating that meteorological processes such as precipitation and scavenging efficiency have most likely a stronger influence on the BC deposition trend than BC emission or atmospheric concentration trends. BC emission source sectors contribute differently to the modelled atmospheric BC concentrations and BC deposition, which further supports our conclusion that different processes affect atmospheric BC concentration and deposition trends. Consequently, Arctic BC deposition trends should not directly be inferred based on atmospheric BC measurements, and more observational BC deposition data are required to assess the climate impact of BC in Arctic snow.

scholarly journals Urban Air Quality Modeling Using Low-Cost Sensor Network and Data Assimilation in the Aburrá Valley, Colombia

Atmosphere ◽  
2021 ◽  
Vol 12 (1) ◽  
pp. 91
Author(s):  
Santiago Lopez-Restrepo ◽  
Andres Yarce ◽  
Nicolás Pinel ◽  
O.L. Quintero ◽  
Arjo Segers ◽  
...  
Keyword(s):  
Air Quality ◽  
Data Assimilation ◽  
Transport Model ◽  
Cost Model ◽  
Low Cost ◽  
Model Performance ◽  
Monitoring Network ◽  
Correlation Factor ◽  
Chemical Transport Model ◽  
High Quality

The use of low air quality networks has been increasing in recent years to study urban pollution dynamics. Here we show the evaluation of the operational Aburrá Valley’s low-cost network against the official monitoring network. The results show that the PM2.5 low-cost measurements are very close to those observed by the official network. Additionally, the low-cost allows a higher spatial representation of the concentrations across the valley. We integrate low-cost observations with the chemical transport model Long Term Ozone Simulation-European Operational Smog (LOTOS-EUROS) using data assimilation. Two different configurations of the low-cost network were assimilated: using the whole low-cost network (255 sensors), and a high-quality selection using just the sensors with a correlation factor greater than 0.8 with respect to the official network (115 sensors). The official stations were also assimilated to compare the more dense low-cost network’s impact on the model performance. Both simulations assimilating the low-cost model outperform the model without assimilation and assimilating the official network. The capability to issue warnings for pollution events is also improved by assimilating the low-cost network with respect to the other simulations. Finally, the simulation using the high-quality configuration has lower error values than using the complete low-cost network, showing that it is essential to consider the quality and location and not just the total number of sensors. Our results suggest that with the current advance in low-cost sensors, it is possible to improve model performance with low-cost network data assimilation.

scholarly journals Sunset–sunrise difference in solar occultation ozone measurements (SAGE II, HALOE, and ACE–FTS) and its relationship to tidal vertical winds

2015 ◽  
Vol 15 (2) ◽  
pp. 829-843 ◽  
Author(s):  
T. Sakazaki ◽  
M. Shiotani ◽  
M. Suzuki ◽  
D. Kinnison ◽  
J. M. Zawodny ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Seasonal Variations ◽  
Climate Model ◽  
Transport Model ◽  
Stratospheric Aerosol ◽  
Data Sets ◽  
Chemical Transport Model ◽  
Latitude Range ◽  
Solar Occultation ◽  
Vertical Winds

Abstract. This paper contains a comprehensive investigation of the sunset–sunrise difference (SSD, i.e., the sunset-minus-sunrise value) of the ozone mixing ratio in the latitude range of 10° S–10° N. SSD values were determined from solar occultation measurements based on data obtained from the Stratospheric Aerosol and Gas Experiment (SAGE) II, the Halogen Occultation Experiment (HALOE), and the Atmospheric Chemistry Experiment–Fourier transform spectrometer (ACE–FTS). The SSD was negative at altitudes of 20–30 km (−0.1 ppmv at 25 km) and positive at 30–50 km (+0.2 ppmv at 40–45 km) for HALOE and ACE–FTS data. SAGE II data also showed a qualitatively similar result, although the SSD in the upper stratosphere was 2 times larger than those derived from the other data sets. On the basis of an analysis of data from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) and a nudged chemical transport model (the specified dynamics version of the Whole Atmosphere Community Climate Model: SD–WACCM), we conclude that the SSD can be explained by diurnal variations in the ozone concentration, particularly those caused by vertical transport by the atmospheric tidal winds. All data sets showed significant seasonal variations in the SSD; the SSD in the upper stratosphere is greatest from December through February, while that in the lower stratosphere reaches a maximum twice: during the periods March–April and September–October. Based on an analysis of SD–WACCM results, we found that these seasonal variations follow those associated with the tidal vertical winds.

scholarly journals The UIUC three-dimensional stratospheric chemical transport model: Description and evaluation of the simulated source gases and ozone

1999 ◽  
Vol 104 (D9) ◽  
pp. 11755-11781 ◽  
Author(s):  
Eugene V. Rozanov ◽  
Vladimir A. Zubov ◽  
Michael E. Schlesinger ◽  
Fanglin Yang ◽  
Natalia G. Andronova
Keyword(s):  
Transport Model ◽  
Three Dimensional ◽  
Chemical Transport ◽  
Model Description ◽  
Chemical Transport Model ◽  
Simulated Source

scholarly journals Carbon monoxide (CO) and ethane (C<sub>2</sub>H<sub>6</sub>) trends from ground-based solar FTIR measurements at six European stations, comparison and sensitivity analysis with the EMEP model

2011 ◽  
Vol 11 (17) ◽  
pp. 9253-9269 ◽  
Author(s):  
J. Angelbratt ◽  
J. Mellqvist ◽  
D. Simpson ◽  
J. E. Jonson ◽  
T. Blumenstock ◽  
...  
Keyword(s):  
Transport Model ◽  
Global Scale ◽  
Global Model ◽  
Scale Model ◽  
Chemical Transport Model ◽  
Suitable Alternative ◽  
European Model ◽  
Time Period ◽  
Volatile Organic ◽  
Made In

Abstract. Trends in the CO andC2H6 partial columns ~0–15 km) have been estimated from four European ground-based solar FTIR (Fourier Transform InfraRed) stations for the 1996–2006 time period. The CO trends from the four stations Jungfraujoch, Zugspitze, Harestua and Kiruna have been estimated to −0.45 ± 0.16% yr−1, −1.00 ± 0.24% yr−1, −0.62 ± 0.19 % yr−1 and −0.61 ± 0.16% yr−1, respectively. The corresponding trends for C2H6 are −1.51 ± 0.23% yr−1, −2.11 ± 0.30% yr−1, −1.09 ± 0.25% yr−1 and −1.14 ± 0.18% yr−1. All trends are presented with their 2-σ confidence intervals. To find possible reasons for the CO trends, the global-scale EMEP MSC-W chemical transport model has been used in a series of sensitivity scenarios. It is shown that the trends are consistent with the combination of a 20% decrease in the anthropogenic CO emissions seen in Europe and North America during the 1996–2006 period and a 20% increase in the anthropogenic CO emissions in East Asia, during the same time period. The possible impacts of CH4 and biogenic volatile organic compounds (BVOCs) are also considered. The European and global-scale EMEP models have been evaluated against the measured CO and C2H6 partial columns from Jungfraujoch, Zugspitze, Bremen, Harestua, Kiruna and Ny-Ålesund. The European model reproduces, on average the measurements at the different sites fairly well and within 10–22% deviation for CO and 14–31% deviation for C2H6. Their seasonal amplitude is captured within 6–35% and 9–124% for CO and C2H6, respectively. However, 61–98% of the CO and C2H6 partial columns in the European model are shown to arise from the boundary conditions, making the global-scale model a more suitable alternative when modeling these two species. In the evaluation of the global model the average partial columns for 2006 are shown to be within 1–9% and 37–50% of the measurements for CO and C2H6, respectively. The global model sensitivity for assumptions made in this paper is also analyzed.

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