Evaluation of a diode laser based photoacoustic instrument combined with preconcentration sampling for measuring surface–atmosphere exchange of ammonia with the aerodynamic gradient method

We present here a novel instrument for measuring surface–atmosphere exchange fluxes of ammonia. The instrument is the upgraded version of a recently developed near-infrared diode laser based photoacoustic ammonia concentration monitoring instrument, i.e. the original instrument is supplemented with two additional sampling lines, an appropriate gas handling system and an advanced software controlling gradient measurements. As a result of these developments, ammonia concentration can be measured simultaneously at three different heights above the ground and ammonia fluxes can be calculated from these data using the aerodynamic gradient method. The instrument operates fully automatically, requires minimal maintenance and has a temperature controlled, waterproof housing which makes it suitable for measurements even under harsh field conditions. Preliminary tests on stability and accuracy were carried out during two two-week field measurement campaigns, with the three sampling inlets being placed at the same height together with the inlet of a reference instrument. The readings of the three channels agreed well (with correlation coefficients above 0.96). Comparison to reference instruments showed good stability of the photoacoustic instrument, there was no measurable zero-drift or change in sensitivity during the tests. Flux measurements were carried out during a three-week field campaign in southern Scotland over fertilized grassland with reference to a wet-chemical AMANDA instrument in gradient configuration. Ammonia fluxes calculated from the data of the two instruments agreed well. Fluxes up to 2500 ng m^?2 s^?1 were observed after fertilization. The minimum detectable ammonia flux was calculated on the basis of “virtual ammonia fluxes”, from measurements carried out with all inlets at the same height and was found to be ±60 ng m^?2 s^?1 which ensures reliable measurements above intensively managed grasslands or agricultural fields.     

Short Term Air Quality Standards for Suspended Particulate Matter in New York State

The Clean Air Act of 1970 requires each state to submit plans for implementation, maintenance, and enforcement of national ambient air quality standards subsequent to promulgation. Such plans have been geared to meet annual averages and maximum values. Based on experience in implementing the abatement plan it was found that air quality standards for averaging times shorter than one year are needed to shorten the time required to show contravention and to provide a basis for early corrective measures to regulate specific sources. This paper reports on the need and procedures used by New York State to develop such standards for suspended particulates. Daily suspended particulate data were analyzed by the Kolmogorov-Smirnov method goodness of fit technique to determine that the form of the distribution was log normal. A method developed by Larsen for predicting short term maximum concentrations for log normally distributed data was used to determine numerical values for one, two, and three month standards. Monthly, bi-monthly, and tri-monthly suspended particulate standards of 130, 110, and 100 µg/m³, respectively are proposed for the most extensively developed areas of New York State and correspondingly lower values for other areas. The methods used in this development are generally applicable to other air contaminants.     

The Fate of Aromatic Hydrocarbons in Photochemical Smog Systems: Toluene

The economic impact of various ozone concentrations on California agriculture is examined using an economic model of crop production that accounts for interdependence among crops. Such interdependence recognizes that net economic effects are determined not only by yield sensitivity to ozone but also by market conditions that affect relative crop prices and profitability. Changes in crop yields due to alternations in ambient ozone concentrations are used to drive the economic model. The predicted yield changes are derived from NCLAN data under a range of assumptions concerning functional form and yield effects. The results indicate that the economic effects of ozone are substantial for 13 included crops. The economic estimates display varying sensitivity to the functional form of the response relationship. The need for additional experimental data to more precisely define the relationship depends on the range of policy actions being considered.     

Runoff transport of pyrethroids from a residential lawn in central California

An irrigation runoff study on a residential lawn was conducted in California, northeast of Sacramento, during the summer and fall of 2008 to investigate the contribution of turf uses of pyrethroids to residues in Californian urban creek sediments. This study examined how over irrigation (i.e., irrigation that produces runoff) in the summer season may transport recently applied pyrethroids. The study included liquid and granular applications of both bifenthrin [(2-methyl-3-phenyl-phenyl) methyl 3-(2-chloro-3,3,3-trifluoro-prop-1-enyl)-2,2-dimethyl-cyclopropane-1-carboxylate] and beta-cyfluthrin [Cyano(4-fluoro-3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethyl-cyclopropanecarboxylate]. Generally, runoff did not occur at irrigation rates of 2.03 cm/h (0.8 in/h) but did occur when the irrigation rates were increased to about 3.81 cm/h (1.5 in/h), generating chemical losses in the first runoff event of up to 0.58 and 0.08% of applied for beta-cyfluthrin and bifenthrin, respectively. Chemical runoff losses dropped significantly between over-irrigation events with the third over-irrigation event chemical runoff losses representing 0.026 and 0.015% of applied for beta-cyfluthrin and bifenthrin, respectively. Runoff losses were generally less for liquid formulations than granular formulations but within a factor of three. Additionally, the study included a simulated winter rainstorm 8 wk after application. The low runoff losses from turf seen in this study suggest that other sources could be contributing to observed residues in urban streams. Other sources could include pyrethroids ending up on impervious surfaces, such as concrete driveways from off-target applications to turf, spills, and other poor handling practices, or pyrechroids applied directly to impervious surfaces for insect control.     

Electrical Resistance Heating of Volatile Organic Compounds in Sedimentary Rock

Electrical resistance heating (ERH) is a common method of remediation for volatile organic compounds in unconsolidated soils, both above and below the water table. In the past eight years, ERH has been used to successfully treat 10 or more contaminated sedimentary bedrock sites. Sedimentary bedrock treatment has recently expanded to greater depths and into karst limestone environments. This article describes the implementation issues for rock remediation and provides case studies of three sites remediated by ERH in Pennsylvania and Alabama. With proper design, the remediation of sedimentary bedrock can be completed as effectively as the remediation of overburden materials. © 2014 Wiley Periodicals, Inc.     

Abnormal maternal serum chorionic gonadotropin levels in pregnancies with fetal chromosome abnormalities

The alpha subunit of human chorionic gonadotropin (alpha-hCG), human chorionic gonadotropin (hCG) and alpha fetoprotein (AFP) were measured in the serum of 25 women with chromosomally abnormal fetuses between 18 and 25 weeks of gestation and in 74 normal pregnancies. AFP levels less than 0.5 multiples of the median (MoM) or greater than 2.5 MoM were observed in 24 per cent of the abnormal pregnancies and in 6.76 per cent of the normal pregnancies. A low concentration of hCG (< 0.25 MoM) was observed in 8 per cent of abnormals and in 2.7 per cent of normals while an elevated concentration of hCG (>2.5 MoM) was observed in 56 per cent of abnormals and in 1.35 per cent of normals. Elevated hCG-alpha (>2.5 MoM) was observed in 28 per cent of abnormals and in none of the normals. Determination of elevated levels of hCG-alpha or hCG resulted in detection of 68 per cent of pregnancies with chromosomally abnormal fetuses with a false positive rate of 1.35 per cent. Determination of both elevated and depressed gonadotropin levels resulted in detection of 76 per cent of abnormal pregnancies with a false positive rate of 4.05 per cent. Measurement of hCG and hCG-alpha in maternal serum samples can be used as a screening procedure for detecting pregnancies at risk for fetal chromosome abnormalities.     

Verifying emission factors and national POPs emission inventories for the UK using measurements and modelling at two rural locations

Different approaches are used to verify the adequacy of emission factors (EFs) and their use in emission inventories of persistent organic pollutants (POPs). The applicability of EFs was tested using atmospheric dispersion modelling to predict atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and resulting toxic equivalents (SigmaTEQ) and particulate matter <10 microm (PM(10)) in two rural locations in northern England (UK). The modelling was based on general assumptions of fuel composition, consumption and heating needs to simulate emissions of POPs from the domestic burning of coal and wood where ambient measurements were made in the winter of 1998. The model was used to derive the local contribution to ambient air concentrations, which were estimated independently based on comparative air measurements. The results support the hypothesis that in both villages, the majority of PAHs and the lower chlorinated PCDFs were locally released. The situation for PCBs and polychlorinated naphthalenes (PCNs) was different. While the EFs show the release of both compound groups from the domestic burning of coal and wood, the ambient levels of these "legacy POPs" in the villages were still clearly dominated by other sources. Rural areas relying mainly on fossil fuels can exceed the proposed UK ambient air quality standard for benzo[a]pyrene during winter. The measured EFs were then used to estimate the importance of the domestic burning of coal and wood to national emission inventories for these compound classes. Extrapolations to the UK suggest that the domestic burning of pure wood and coal were minor emitters for chlorinated POPs but contributed strongly to PAH and PM(10) levels in 2000. Finally, the UK's national POPs emission inventories based on source inventories and EF, as used here, were compared to estimates derived using the increase in atmospheric concentration of selected POPs.     

Polycyclic aromatic hydrocarbons (PAHs) in the air of Chinese cities

Polycyclic aromatic hydrocarbons (PAHs) were determined in the air of 37 cities and 3 rural locations across China during the winter, spring, summer and autumn of 2005, using polyurethane foam (PUF) disks as passive air samplers (PAS). Winter and autumn concentrations in cities exceeded spring and summer values. Concentrations were amongst the highest in the world; seasonally averaged autumn/winter values in some cities in the north and north-west of China exceeded proposed European Union air quality standards. Several factors, acting in combination, influenced air concentrations. A significant negative correlation was found between average annual city concentrations and the annual average temperature, while winter time PAH concentrations correlated with estimated coal consumption. The highest total PAH concentrations and loadings of high molecular weight compounds generally occurred in major cities located on higher land (500-2000 m), where relatively cold winters and higher coal consumption occurs. Lower values occurred in cities located in the south and east China and along the coastal regions. Molecular markers indicated incomplete combustion of fossil fuels dominated the urban air and gave evidence for photo-decomposition of selected compounds.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.