On the sources and sinks of atmospheric VOCs: an integrated analysis of recent aircraft campaigns over North America.

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2x larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R 2 = 0:36) and reactivity (R 2 = 0:54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (~ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL: FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene C oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

Observing atmospheric formaldehyde (HCHO) from space: validation and intercomparison of six retrievals from four satellites (OMI, GOME2A, GOME2B, OMPS) with SEAC4RS aircraft observations over the Southeast US.

Formaldehyde (HCHO) column data from satellites are widely used as a proxy for emissions of volatile organic compounds (VOCs) but validation of the data has been extremely limited. Here we use highly accurate HCHO aircraft observations from the NASA SEAC4RS campaign over the Southeast US in August-September 2013 to validate and intercompare six retrievals of HCHO columns from four different satellite instruments (OMI, GOME2A, GOME2B and OMPS) and three different research groups. The GEOS-Chem chemical transport model is used as a common intercomparison platform. All retrievals feature a HCHO maximum over Arkansas and Louisiana, consistent with the aircraft observations and reflecting high emissions of biogenic isoprene. The retrievals are also interconsistent in their spatial variability over the Southeast US (r=0.4-0.8 on a 0.5°×0.5° grid) and in their day-to-day variability (r=0.5-0.8). However, all retrievals are biased low in the mean by 20-51%, which would lead to corresponding bias in estimates of isoprene emissions from the satellite data. The smallest bias is for OMI-BIRA, which has high corrected slant columns relative to the other retrievals and low scattering weights in its air mass factor (AMF) calculation. OMI-BIRA has systematic error in its assumed vertical HCHO shape profiles for the AMF calculation and correcting this would eliminate its bias relative to the SEAC4RS data. Our results support the use of satellite HCHO data as a quantitative proxy for isoprene emission after correction of the low mean bias. There is no evident pattern in the bias, suggesting that a uniform correction factor may be applied to the data until better understanding is achieved.

Formaldehyde columns from the Ozone Monitoring Instrument: Urban versus background levels and evaluation using aircraft data and a global model.

[1] We combine aircraft measurements (Second Texas Air Quality Study, Megacity Initiative: Local and Global Research Observations, Intercontinental Chemical Transport Experiment: Phase B) over the United States, Mexico, and the Pacific with a 3-D model (GEOS-Chem) to evaluate formaldehyde column (ΩHCHO) retrievals from the Ozone Monitoring Instrument (OMI) and assess the information they provide on HCHO across local to regional scales and urban to background regimes. OMI ΩHCHO correlates well with columns derived from aircraft measurements and GEOS-Chem (R = 0.80). For the full data ensemble, OMI's mean bias is -3% relative to aircraft-derived ΩHCHO (-17% where ΩHCHO > 5 × 1015 molecules cm-2) and -8% relative to GEOS-Chem, within expected uncertainty for the retrieval. Some negative bias is expected for the satellite and model, given the plume sampling of many flights and averaging over the satellite and model footprints. Major axis regression for OMI versus aircraft and model columns yields slopes (95% confidence intervals) of 0.80 (0.62-1.03) and 0.98 (0.73-1.35), respectively, with no significant intercept. Aircraft measurements indicate that the normalized vertical HCHO distribution, required by the satellite retrieval, is well captured by GEOS-Chem, except near Mexico City. Using measured HCHO profiles in the retrieval algorithm does not improve satellite-aircraft agreement, suggesting that use of a global model to specify shape factors does not substantially degrade retrievals over polluted areas. While the OMI measurements show that biogenic volatile organic compounds dominate intra-annual and regional ΩHCHO variability across the United States, smaller anthropogenic ΩHCHO gradients are detectable at finer spatial scales (∼20-200 km) near many urban areas.

Difference frequency generation spectrometer for simultaneous multispecies detection.

A difference-frequency generation based spectrometer system for simultaneous ultra-sensitive measurements of formaldehyde (CH2O) and Methane (CH4) is presented. A new multiplexing approach using collinear quasi-phase-matching in a single grating period of periodically poled lithium niobate (PPLN) is discussed and demonstrated for two pairs of pump and signal lasers to generate mid-infrared frequencies at 2831.64 cm(-1) and 2916.32 cm(-1), respectively. The corresponding absorption signals are discriminated by modulating the DFB diode lasers at modulation frequencies of 40 kHz and 50 kHz, respectively, and using a computer based modulation and de-modulation scheme. In addition, simultaneous measurements of CH2O, CH4 and H2O are demonstrated utilizing both collinear and non-collinear quasi-phase-matching.

High-precision CO2 isotopologue spectrometer with a difference-frequency-generation laser source.

A precision laser spectrometer for the detection of CO(2) isotopes is reported. The spectrometer measures the fundamental absorption signatures of (13)C and (12)C isotopes in CO(2) at 4.32 microm using a tunable mid-IR laser source based on difference-frequency generation. The spectrometer attains a precision of up to 0.02 per thousand for 150 s of averaging. An overall accuracy of 0.05 per thousand was obtained when sampling various calibrated reference gases.

Development of an eye-safe solid-state tunable laser transmitter in the 1.4-1.5 microm wavelength region based on Cr4+:YAG crystal for lidar applications.

An experimental optimization of the efficiency of a gain switched tunable Cr4+:YAG laser at 10 Hz is described. The thermal lensing during pulsed operation was measured. Optimal performance occurred at a crystal temperature of 34 degrees C and resulted in an output energy of approximately 7 mJ and a pulse duration of approximately 35 ns. Tunability in the range of 1350-1500 nm, spectral linewidth of approximately 200 GHz, and M2<4 are demonstrated. The main laser material parameters are estimated. Such a laser could be employed in a laboratory-based nonscanning lidar system if a narrowband birefringent filter is installed. The tunability will permit the improvement of the Cr4+:YAG transmitter for water-vapor differential absorption lidar if injection seeding is applied.

High-power, tunable difference frequency generation source for absorption spectroscopy based on a ridge waveguide periodically poled lithium niobate crystal.

A novel waveguide for difference frequency generation in the mid-IR spectral region at 3.52 mum is characterized. High mid-IR power of 15 mW and an external conversion efficiency of up to 19 %W( -1) have been obtained. An optical beam propagation factor M(2) =1.18 was determined using the second moment method. A simple 2-f absorption spectra demonstrates the potential of this mid-IR source for high precision trace gas sensing applications.

First demonstration of a high performance difference frequency spectrometer on airborne platforms.

We discuss the first airborne deployment and performance tests of a mid-IR difference frequency spectrometer system for highly sensitive measurements of formaldehyde. The laser system is based upon difference-frequency generation (DFG) at ~3.5 mum by mixing a DFB diode laser at 1562 nm and a distributed feedback (DFB) fiber laser at 1083 nm in a periodically poled LiNbO(3) (PPLN) crystal. Advanced LabVIEW software for lock-in, dual-beam optical noise subtraction, thermal control and active wavelength stabilization, renders a sensitivity of ~20 pptv (Absorbance ~7*10(-7)) for 30s of averaging. The instrument's performance characteristics spanning more than 300 flight hours during three consecutive airborne field missions MIRAGE, IMPEX and TexAQS operating on two airborne platforms, NCAR's C-130 and NOAA's P-3 aircraft are demonstrated.

Atomic mercury flux monitoring using an optical parametric oscillator based lidar system.

A newly developed optical parametric oscillator (OPO) based differential absorption lidar (DIAL) system has been applied to the monitoring of atomic mercury emissions at several chlor-alkali plants in Europe. The versatility of the system is illustrated by measured time series of mercury flux and movies of vertical and horizontal concentration distributions, which yield important input parameters for the environmental community. Long term measurements of the resonance absorption of mercury at 253.65 nm poses special demands, i.e. long term stability, on the light source that often have been hard to fulfill, in different respects, for standard OPO and dye laser based systems. Here, approaches to meet these demands are presented.

Versatile mobile lidar system for environmental monitoring.

A mobile lidar (light detection and ranging) system for environmental monitoring is described. The optical and electronic systems are housed in a truck with a retractable rooftop transmission and receiving mirror, connected to a 40-cm-diameter vertically looking telescope. Two injection-seeded Nd:YAG lasers are employed in connection with an optical parametric oscillator-optical parametric amplification transmitter, allowing deep-UV to mid-IR wavelengths to be generated. Fast switching that employs piezoelectric drivers allows multiwavelength differential absorption lidar for simultaneous measurements of several spectrally overlapping atmospheric species. The system can also be used in an imaging multispectral laser-induced fluorescence mode on solid targets. Advanced LabVIEW computer control and multivariate data processing render the system versatile for a multitude of measuring tasks. We illustrate the monitoring of industrial atmospheric mercury and hydrocarbon emissions, volcanic sulfur dioxide plume mapping, fluorescence lidar probing of seawater, and multispectral fluorescence imaging of the facades of a historical monument.

Atmospheric mercury near a chlor-alkali plant in Sweden.

Atmospheric mercury species/fractions were measured near a chlor-alkali plant in Sweden during August 28 to September 4, 2001. The concentration of total gaseous mercury in the plume from the plant was measured using TEKRAN and GARDIS instruments. Gaseous elemental mercury was measured using a light detection and ranging (LIDAR) technique. From vertical LIDAR sweeps through the plume from the chlor-alkali plant mercury emission rates could be calculated. The concentrations of reactive gaseous mercury (RGM) in the plume and also inside the cell house were measured using annular KCl coated denuders. The RGM emission constitutes 0.5-1.0% of the total mercury emitted from the plant. The mercury concentration adsorbed on particles was measured as well as the mercury flux from soil. The data presented also include an intercomparison showing an excellent agreement between TEKRAN/GARDIS and LIDAR gaseous mercury measurements.