Composition of Clean Marine Air and Biogenic Influences on VOCs during the MUMBA Campaign

Volatile organic compounds (VOCs) are important precursors to the formation of ozone and fine particulate matter, the two pollutants of most concern in Sydney, Australia. Despite this importance, there are very few published measurements of ambient VOC concentrations in Australia. In this paper, we present mole fractions of several important VOCs measured during the campaign known as MUMBA (Measurements of Urban, Marine and Biogenic Air) in the Australian city of Wollongong (34°S). We particularly focus on measurements made during periods when clean marine air impacted the measurement site and on VOCs of biogenic origin. Typical unpolluted marine air mole fractions during austral summer 2012-2013 at latitude 34°S were established for CO2 (391.0 ± 0.6 ppm), CH4 (1760.1 ± 0.4 ppb), N2O (325.04 ± 0.08 ppb), CO (52.4 ± 1.7 ppb), O3 (20.5 ± 1.1 ppb), acetaldehyde (190 ± 40 ppt), acetone (260 ± 30 ppt), dimethyl sulphide (50 ± 10 ppt), benzene (20 ± 10 ppt), toluene (30 ± 20 ppt), C8H10 aromatics (23 ± 6 ppt) and C9H12 aromatics (36 ± 7 ppt). The MUMBA site was frequently influenced by VOCs of biogenic origin from a nearby strip of forested parkland to the east due to the dominant north-easterly afternoon sea breeze. VOCs from the more distant densely forested escarpment to the west also impacted the site, especially during two days of extreme heat and strong westerly winds. The relative amounts of different biogenic VOCs observed for these two biomes differed, with much larger increases of isoprene than of monoterpenes or methanol during the hot westerly winds from the escarpment than with cooler winds from the east. However, whether this was due to different vegetation types or was solely the result of the extreme temperatures is not entirely clear. We conclude that the clean marine air and biogenic signatures measured during the MUMBA campaign provide useful information about the typical abundance of several key VOCs and can be used to constrain chemical transport model simulations of the atmosphere in this poorly sampled region of the world. © 2019 The Author

Role of carbon cycle observations and knowledge in carbon management

Author Posting. © Annual Reviews, 2003. This article is posted here by permission of Annual Reviews for personal use, not for redistribution. The definitive version was published in Annual Review of Environment and Resources 28 (2003): 521-558, doi:10.1146/annurev.energy.28.011503.163443.Agriculture and industrial development have led to inadvertent changes in the natural carbon cycle. As a consequence, concentrations of carbon dioxide and other greenhouse gases have increased in the atmosphere and may lead to changes in climate. The current challenge facing society is to develop options for future management of the carbon cycle. A variety of approaches has been suggested: direct reduction of emissions, deliberate manipulation of the natural carbon cycle to enhance sequestration, and capture and isolation of carbon from fossil fuel use. Policy development to date has laid out some of the general principles to which carbon management should adhere. These are summarized as: how much carbon is stored, by what means, and for how long. To successfully manage carbon for climate purposes requires increased understanding of carbon cycle dynamics and improvement in the scientific capabilities available for measurement as well as for policy needs. The specific needs for scientific information to underpin carbon cycle management decisions are not yet broadly known. A stronger dialogue between decision makers and scientists must be developed to foster improved application of scientific knowledge to decisions. This review focuses on the current knowledge of the carbon cycle, carbon measurement capabilities (with an emphasis on the continental scale) and the relevance of carbon cycle science to carbon sequestration goals.The National Center for Atmospheric Research is supported by the National Science Foundation

A revised 1000 year atmospheric delta C-13-CO2 record from Law Dome and South Pole, Antarctica

[1] We present new measurements of δ13C of CO2 extracted from a high‐resolution ice core from Law Dome (East Antarctica), together with firn measurements performed at Law Dome and South Pole, covering the last 150 years. Our analysis is motivated by the need to better understand the role and feedback of the carbon (C) cycle in climate change, by advances in measurement methods, and by apparent anomalies when comparing ice core and firn air δ13C records from Law Dome and South Pole. We demonstrate improved consistency between Law Dome ice, South Pole firn, and the Cape Grim (Tasmania) atmospheric δ13C data, providing evidence that our new record reliably extends direct atmospheric measurements back in time. We also show a revised version of early δ13C measurements covering the last 1000 years, with a mean preindustrial level of −6.50‰. Finally, we use a Kalman Filter Double Deconvolution to infer net natural CO2 fluxes between atmosphere, ocean, and land, which cause small δ13C deviations from the predominant anthropogenically induced δ13C decrease. The main features found from the previous δ13C record are confirmed, including the ocean as the dominant cause for the 1940 A.D. CO2 leveling. Our new record provides a solid basis for future investigation of the causes of decadal to centennial variations of the preindustrial atmospheric CO2 concentration. Those causes are of potential significance for predicting future CO2 levels and when attempting atmospheric verification of recent and future global carbon emission mitigation measures through Coupled Climate Carbon Cycle Models

A new pilot Australian tropical atmospheric research station (ATARS)

Baseline reports availabe at: http:/​/​www.bom.gov.au/​inside/​cgbaps/​baseline.shtml

Southern Hemisphere atmospheric history of carbon monoxide over the late Holocene reconstructed from multiple Antarctic ice archives

Abstract. Carbon monoxide (CO) is a naturally occurring atmospheric trace gas, a regulated pollutant, and one of the main components determining the oxidative capacity of the atmosphere. Evaluating climate–chemistry models under different conditions than today and constraining past CO sources requires a reliable record of atmospheric CO mixing ratios ([CO]) that includes data since preindustrial times. Here, we report the first continuous record of atmospheric [CO] for Southern Hemisphere (SH) high latitudes over the past 3 millennia. Our continuous record is a composite of three high-resolution Antarctic ice core gas records and firn air measurements from seven Antarctic locations. The ice core gas [CO] records were measured by continuous flow analysis (CFA), using an optical feedback cavity-enhanced absorption spectrometer (OF-CEAS), achieving excellent external precision (2.8–8.8 ppb; 2σ) and consistently low blanks (ranging from 4.1±1.2 to 7.4±1.4 ppb), thus enabling paleo-atmospheric interpretations. Six new firn air [CO] Antarctic datasets collected between 1993 and 2016 CE at the DE08-2, DSSW19K, DSSW20K, South Pole, Aurora Basin North (ABN), and Lock-In sites (and one previously published firn CO dataset at Berkner) were used to reconstruct the atmospheric history of CO from ∼1897 CE, using inverse modeling that incorporates the influence of gas transport in firn. Excellent consistency was observed between the youngest ice core gas [CO] and the [CO] from the base of the firn and between the recent firn [CO] and atmospheric [CO] measurements at Mawson station (eastern Antarctica), yielding a consistent and contiguous record of CO across these different archives. Our Antarctic [CO] record is relatively stable from −835 to 1500 CE, with mixing ratios within a 30–45 ppb range (2σ). There is a ∼5 ppb decrease in [CO] to a minimum at around 1700 CE during the Little Ice Age. CO mixing ratios then increase over time to reach a maximum of ∼54 ppb by ∼1985 CE. Most of the industrial period [CO] growth occurred between about 1940 to 1985 CE, after which there was an overall [CO] decrease, as observed in Greenland firn air and later at atmospheric monitoring sites and attributed partly to reduced CO emissions from combustion sources. Our Antarctic ice core gas CO observations differ from previously published records in two key aspects. First, our mixing ratios are significantly lower than reported previously, suggesting that previous studies underestimated blank contributions. Second, our new CO record does not show a maximum in the late 1800s. The absence of a [CO] peak around the turn of the century argues against there being a peak in Southern Hemisphere biomass burning at this time, which is in agreement with (i) other paleofire proxies such as ethane or acetylene and (ii) conclusions reached by paleofire modeling. The combined ice core and firn air [CO] history, spanning −835 to 1992 CE, extended to the present by the Mawson atmospheric record, provides a useful benchmark for future atmospheric chemistry modeling studies. </jats:p

A 60 yr record of atmospheric carbon monoxide reconstructed from Greenland firn air

We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140-150 nmol mol-1, which is higher than today's values. CO mole fractions rose by 10-15 nmol mol-1 from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a ≈ 30 nmol mol-1 decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe. © Author(s) 2013