Oxidation of ketone groups in transported biomass burning aerosol from the 2008 Northern California Lightning Series fires

Submicron particles were collected from June to September 2008 in La Jolla, California to investigate the composition and sources of atmospheric aerosol in an anthropogenically-influenced coastal site. Factor analysis of aerosol mass spectrometry (AMS) and Fourier transform infrared (FTIR) spectroscopy measurements revealed that the two largest sources of submicron organic mass (OM) at the sampling site were (1) fossil fuel combustion associated with ship and diesel truck emissions near the ports of Los Angeles and Long Beach and (2) aged smoke from large wildfires burning in central and northern California. During non-fire periods, fossil fuel combustion contributed up to 95% of FTIR OM, correlated to sulfur, and consisted mostly of alkane (86%) and carboxylic acid groups (9%). During fire periods, biomass burning contributed up to 74% of FTIR OM, consisted mostly of alkane (48%), ketone (25%), and carboxylic acid groups (17%), and correlated to AMS-derived factors resembling brush fire smoke, wood smoldering and flaming particles, and biogenic secondary organic aerosol. The two AMS-derived biomass burning factors were identified as oxygenated and hydrocarbon biomass burning aerosol on the basis of spectral similarities to smoldering and flaming smoke particles, respectively. In addition, the ratio of oxygenated to hydrocarbon biomass burning OM shows a clear diurnal trend with an afternoon peak, consistent with photochemical oxidation. Back trajectory analysis indicates that 2–4-day old forest fire emissions include substantial ketone groups, which have both lower O/C and lower m/z 44/OM fraction than carboxylic acid groups. Air masses with more than 4-day old emissions have higher carboxylic acid/ketone group ratios, showing that atmospheric processing of these ketone-containing organic aerosol particles results in increased m/z 44 and O/C. These observations may provide functionally-specific evidence for the type of chemical processing that is responsible for biomass burning particle composition in the atmosphere.     

Neural Network Input Selection for Hydrological Forecasting Affected by Snowmelt1

Abstract: Snowmelt largely affects runoff in watersheds in Nordic countries. Neural networks (NN) are particularly attractive for streamflow forecasting whereas they rely at least on daily streamflow and precipitation observations. The selection of pertinent model inputs is a major concern in NNs implementation. This study investigates performance of auxiliary NN inputs that allow short‐term streamflow forecasting without resorting to a deterministic snowmelt routine. A case study is presented for the Rivière des Anglais watershed (700 km²) located in Southern Québec, Canada. Streamflow (Q), precipitations (rain R and snow S, or total P), temperature (T) and snow lying (A) observations, combined with climatic and snowmelt proxy data, including snowmelt flow (Q_SM) obtained from a deterministic model, were tested. NN implemented with antecedent Q and R produced the largest gains in performance. Introducing increments of A and T to the NNs further improved the performance. Long‐term averages, seasonal data, and Q_SM failed to improve the networks.     

Do trans-Pacific air masses deliver PBDEs to coastal British Columbia, Canada?

In order to distinguish between ‘local’ and ‘background’ sources of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in coastal British Columbia (Canada) air, we collected samples from two sites: a remote site on western Vancouver Island, and a near-urban site in the Strait of Georgia. Seasonally-integrated samples of vapor, particulate, and rain were collected continuously during 365 days for analysis of 275 PCB and PBDE congeners. While deposition of the legacy PCBs was similar at both sampling sites, deposition of PBDEs at the remote site amounted to 42% (10.4 mg/ha/year) of that at the near-urban site. Additional research into atmospheric circulation in the NE Pacific Ocean will provide more insight into the transport and fate of priority pollutants in this region, but trans-Pacific delivery of PBDEs to the west coast of North America may underlie in part our observations. For example, approximately 40% of >12,000 ten-day back trajectories calculated for the remote site originated over Asia, compared to only 2% over North America.     

Automatic model calibration applying global optimization techniques

This paper summarizes a study aimed at the application of global optimization techniques for the purpose of quantitative characterization of the Wolfville formation located in Nova Scotia, Canada. Aquifer parameters (transmissivity, storativity, areal recharge and boundary flux) are calibrated in order to yield the best possible match with the available field observations. The calibration is accomplished using a global approach to the inverse procedure in “black box” systems optimization which makes possible the simultaneous fitting of several tens of parameters. This study indicates that, even for a limited number of optimized parameters, a global search procedure should be considered. Numerical results are presented and discussed to show the validity of the approach.