Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high-time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.

Organic aerosol (OA) data acquired by the Aerosol Mass Spectrometer (AMS) in 37 field campaigns were deconvolved into hydrocarbon‐like OA (HOA) and several types of oxygenated OA (OOA) components. HOA has been linked to primary combustion emissions (mainly from fossil fuel) and other primary sources such as meat cooking. OOA is ubiquitous in various atmospheric environments, on average accounting for 64%, 83% and 95% of the total OA in urban, urban downwind, and rural/remote sites, respectively. A case study analysis of a rural site shows that the OOA concentration is much greater than the advected HOA, indicating that HOA oxidation is not an important source of OOA, and that OOA increases are mainly due to SOA. Most global models lack an explicit representation of SOA which may lead to significant biases in the magnitude, spatial and temporal distributions of OA, and in aerosol hygroscopic properties.

[1] The aerosol mass spectrometer (AMS), manufactured by Aerodyne Research, Inc., has been shown to be capable of delivering quantitative information on the chemical composition and size of volatile and semivolatile fine airborne particulate matter with high time resolution. Analytical and software tools for interpreting the data from this instrument and generating meaningful, quantitative results have been developed and are presented here with a brief description of the instrument. These include the conversion of detected ion rates from the quadrupole mass spectrometer during the mass spectrum (MS) mode of operation to atmospheric mass concentrations of chemical species (in mg m À3 ) by applying calibration data. It is also necessary to correct for variations in the electron multiplier performance, and a method involving the measurement of the instrument's response to gas phase signals is also presented. The techniques for applying particle velocity calibration data and transforming signals from time of flight (TOF) mode to chemical mass distributions in terms of aerodynamic diameter (dM/dlog(D a ) distributions) are also presented. It is also possible to quantify the uncertainties in both MS and TOF data by evaluating the ion counting statistics and variability of the background signal, respectively. This paper is accompanied by part 2 of this series, in which these methods are used to process and analyze AMS results on ambient aerosol from two U.K. cities at different times of the year.

Range shifts due to climate change may cause species to move out of protected areas. Climate change could therefore result in species range dynamics that reduce the relevance of current fixed protected areas in future conservation strategies. Here, we apply species distribution modeling and conservation planning tools in three regions (Mexico, the Cape Floristic Region of South Africa, and Western Europe) to examine the need for additional protected areas in light of anticipated species range shifts caused by climate change. We set species representation targets and assessed the area required to meet those targets in the present and in the future, under a moderate climate change scenario. Our findings indicate that protected areas can be an important conservation strategy in such a scenario, and that early action may be both more effective and less costly than inaction or delayed action. According to our projections, costs may vary among regions and none of the three areas studied will fully meet all conservation targets, even under a moderate climate change scenario. This suggests that limiting climate change is an essential complement to adding protected areas for conservation of biodiversity.

Abstract. Mobility particle size spectrometers often referred to as DMPS (Differential Mobility Particle Sizers) or SMPS (Scanning Mobility Particle Sizers) have found a wide range of applications in atmospheric aerosol research. However, comparability of measurements conducted world-wide is hampered by lack of generally accepted technical standards and guidelines with respect to the instrumental setup, measurement mode, data evaluation as well as quality control. Technical standards were developed for a minimum requirement of mobility size spectrometry to perform long-term atmospheric aerosol measurements. Technical recommendations include continuous monitoring of flow rates, temperature, pressure, and relative humidity for the sheath and sample air in the differential mobility analyzer.We compared commercial and custom-made inversion routines to calculate the particle number size distributions from the measured electrical mobility distribution. All inversion routines are comparable within few per cent uncertainty for a given set of raw data.Furthermore, this work summarizes the results from several instrument intercomparison workshops conducted within the European infrastructure project EUSAAR (European Supersites for Atmospheric Aerosol Research) and AC-TRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) to determine present uncertainties especially of custom-built mobility particle size spectrometers. Under controlled laboratory conditions, the particle number size distributions from 20 to 200 nm determined by mobility particle size spectrometers of different design are within an uncertainty range of around ±10 % after correcting internal particle losses, while below and above this size range the discrepancies increased. For particles larger than 200 nm, the uncertainty range increased to 30 %, which could not be explained. The network reference mobility spectrometers with identical design agreed within ±4 % in the peak particle number concentration when all settings were done carefully. The consistency of these reference instruments to the total particle number concentration was demonstrated to be less than 5 %.Additionally, a new data structure for particle number size distributions was introduced to store and disseminate the data at EMEP (European Monitoring and Evaluation Program). This structure contains three levels: raw data, processed data, and final particle size distributions. Importantly, we recommend reporting raw measurements including all relevant instrument parameters as well as a complete documentation on all data transformation and correction steps. These technical and data structure standards aim to enhance the quality of long-term size distribution measurements, their comparability between different networks and sites, and their transparency and traceability back to raw data.

Abstract. Organic matter frequently represents the single largest fraction of fine particulates in urban environments and yet the exact contributions from different sources and processes remain uncertain, owing in part to its substantial chemical complexity. Positive Matrix Factorisation (PMF) has recently proved to be a powerful tool for the purposes of source attribution and profiling when applied to ambient organic aerosol data from the Aerodyne Aerosol Mass Spectrometer (AMS). Here we present PMF analysis applied to AMS data from UK cities for the first time. Three datasets are analysed, with the focus on objectivity and consistency. The data were collected in London during the Regent's Park and Tower Environmental Experiment (REPARTEE) intensives and Manchester. These occurred during the autumn and wintertime, such that the primary fraction would be prominent. Ambiguities associated with rotationality within sets of potential solutions are explored and the most appropriate solution sets selected based on comparisons with external data. In addition to secondary organic aerosols, three candidate sources of primary organic aerosol (POA) were identified according to mass spectral and diurnal profiles; traffic emissions, cooking and solid fuel burning (for space heating). Traffic represented, on average, 40% of POA during colder conditions and exhibited a hydrocarbon-like mass spectrum similar to those previously reported. Cooking aerosols represented 34% of POA and through laboratory work, their profile was matched with that sampled from the heating of seed oils, rather than previously-published spectra derived from charbroiling. This suggests that in these locations, oil from frying may have contributed more to the particulate than the meat itself. Solid fuel aerosols represented 26% of POA during cold weather conditions but were not discernable during the first REPARTEE campaign, when conditions were warmer than the other campaigns. This factor showed features associated with biomass burning and occurred mainly at night. Grid-scale emission factors of the combustion aerosols suitable for use in chemical transport models were derived relative to CO and NOx. The traffic aerosols were found to be 20.5 μg m−3 ppm−1 relative to CO for Manchester and 31.6 μg m−3 ppm−1 relative to NOx for London. Solid fuel emissions were derived as 24.7 μg m−3 ppm−1 relative to CO for Manchester. These correspond to mass emission ratios of 0.018, 0.026 (as NO) and 0.021 respectively and are of a similar order to previously published estimates, derived from other regions or using other approaches.

Emissions from motor vehicles are a significant source of fine particulate matter (PM) and gaseous pollutants in urban environments. Few studies have characterized both gaseous and PM emissions from individual in-use vehicles under real-world driving conditions. Here we describe chase vehicle studies in which Received 27 February 2003; accepted 29 March 2004. This work was supported in part by the New York State Energy Research and Development Authority (NYSERDA), contract # 4918ERT-ERES99; the US Environmental Protection Agency (EPA), cooperative agreement # R828060010; and New York State Department of Environmental Conservation (NYS DEC), contract # C004210. Although the research described in this article has been funded in part by US EPA, it has not been subjected to the Agency's required peer and policy review and therefore does not necessary reflect the views of the Agency, and no official endorsement should be inferred. The authors thank the MTA for their cooperation, including Chris Bush for providing bus fleet information and Dana Lowell for help in organizing the logistics of the Fall 2000 campaign, the NYS DEC for providing drivers during the chase experiments, and Queens College for logistical support during the Summer 2001 campaign. The TILDAS scientists on-board the mobile laboratory, particularly Joanne Shorter and Mark Zahniser, are acknowledged for their assistance throughout the two phases of this study. Thanks also go to Jay Slowik and Leah Williams for help with laboratory soot experiments, Tim Onasch for assistance with the development of data analysis programs, and Paul Ziemann for useful discussions about organic mass spectral analysis. P. J. Silva thanks the Camille and Henry Dreyfus Foundation for Support. D. A. Ghertner thanks Robert Harriss for providing funding for his involvement in this project.Address correspondence to Manjula R. Canagaratna, Center for Aerosol and Cloud Chemistry and Center for Atmospheric and Environmental Chemistry, Aerodyne Research Inc., 45 Manning Road, Billerica, MA 01821, USA. E-mail: mrcana@aerodyne.com on-road emissions from individual vehicles were measured in real time within seconds of their emission. This work uses an Aerodyne aerosol mass spectrometer (AMS) to provide size-resolved and chemically resolved characterization of the nonrefractory portion of the emitted PM; refractory materials such as elemental carbon (EC) were not measured in this study. The AMS, together with other gas-phase and particle instrumentation, was deployed on the Aerodyne Research Inc. (ARI) mobile laboratory, which was used to "chase" the target vehicles. Tailpipe emission indices of the targeted vehicles were obtained by referencing the measured nonrefractory particulate mass loading to the instantaneous CO 2 measured simultaneously in the plume. During these studies, nonrefractory PM 1.0 (NRPM 1 ) emission indices for a representative fraction of the New York City Metropolitan Transit Authority (MTA) bus fleet were determined. Diesel bus emissions ranged from 0.10 g NRPM 1...

Atmospheric black carbon makes an important but poorly quantified contribution to the warming of the global atmosphere. Laboratory and modelling studies have shown that the addition of non-black carbon materials to black carbon particles may enhance the particles' light absorption by 50 to 60% by refracting and reflecting light. Real world experimental evidence for this 'lensing' effect is scant and conflicting, showing that absorption enhancements can be less than 5% or as large as 140%. Here we present simultaneous quantifications of the composition and optical properties of individual atmospheric black carbon particles. We show that particles with a mass ratio of non-black carbon to black carbon of less than 1.5, which is typical of fresh traffic sources, are best represented as having no absorption enhancement. In contrast, black carbon particles with a ratio greater than 3, which is typical of biomass burning emissions, are best described assuming optical lensing leading to an absorption enhancement. We introduce a generalised hybrid model approach for estimating scattering and absorption enhancements based on laboratory and atmospheric observations. We conclude that the occurrence of the absorption enhancement of black carbon particles is determined by the particles' mass ratio of non-black carbon to black carbon.Atmospheric black carbon (BC) makes the second largest single contribution after CO 2 to climate forcing in the present-day atmosphere 1 . Previous detailed modelling and laboratory studies have shown that weakly absorbing non-BC materials contained within the same particles as BC can significantly enhance the absorption per unit mass of the latter through refraction and internal reflections, sometimes referred to as the 'lensing effect' 2,3 . A "coreshell" description 4 has often been applied to describe this effect when coatings envelop the central BC core, but this oversimplifies the complex particle morphologies 5 . The non-BC components may not be evenly distributed and the BC core is not necessarily completely enclosed, and as such the absorption enhancement predicted using the core-shell approach could greatly overestimate the real value 3 . Microscopy 5,6 can examine BC microphysical properties but has limited quantitative capability and may evaporate semi-volatile materials.By detecting the remaining non-BC fragment after laser induced incandescence with a single particle soot photometer (SP2 7 , DMT inc.), Sedlacek et al. 8 and Moteki et al. 9 reported the non-core-shell structure of some BC particles, however they did not provide an appropriate model approach to estimate optical properties. Measurement of single BC particle mass ratioIn this study, for the first time we quantify the mixing state of individual BC particles using morphology-independent measurements of the total particle mass (M p ) and the mass of the refractory black carbon, rBC (M rBC ) from a variety of laboratory and field experiments. We determined the mass ratio, M R (= M non-BC /M rBC ), where M non-BC is the mas...