Analysis of cloud and precipitation chemistry at Whiteface Mountain,NY

Federal and state programs over the past two decades have resulted in the reduction of emissions of precursors of acid rain. Concomitant with these changes, measured concentrations of acidity in precipitation and in watersheds have shown a downward trend or improvement. However, another pathway for these precursors is through cloud and fog events that often tend to occur at high-elevation regions affecting the fauna and flora as well. In this study we report on long-term measurements of cloud water and precipitation chemistry made from 1994 onwards at a high-elevation location, Whiteface Mountain NY, in the northeastern United States. Trends and inter-relationship between the ions were examined along with ambient SO₂ measurements and Adirondack lakes chemistry data.     

Night-time radical chemistry during the TORCH campaign

We present one of the most comprehensive studies of night-time radical chemistry to date, from the Tropospheric ORganic CHemistry experiment (TORCH) in the summer of 2003. TORCH provided a wealth of measurements with which to study the oxidizing capacity of the atmosphere. The measurements provided input to a zero-dimensional box model which has been used to study night-time radical chemistry during the campaign. Average night-time predicted concentrations of OH (2.6 × 10⁵ molecule cm^?3), HO₂ (2.9 × 10⁷ molecule cm^?3) and [HO₂+ΣRO₂] radicals (2.2 × 10⁸ molecule cm^?3) were an order of magnitude smaller than those predicted during the daytime. The model under-predicted the night-time measurements of OH, HO₂ and [HO₂+ΣRO₂] radicals, on average by 41%, 16% and 8% respectively. Whilst the model captured the broad features of night-time radical behaviour, some of the specific features that were observed are hard to explain. A rate of radical production assessment was carried out for the whole campaign between the hours of 00:00 and 04:00. Whilst radical production was limited owing to the absence of photolytic reactions, production routes via the reactions of alkenes with O₃ provided an effective night-time radical source. Nitrate radical concentrations were predicted to be 0.6 ppt on average with a peak of 18 ppt on August 9th during a polluted heat wave period. Overall, the nitrate radical contributes about a third of the total initiation via RO₂, mostly through reaction with alkenes.     

Near roadway concentrations of organic source markers

Concentrations of elemental carbon (EC), organic carbon (OC), and 33 organic source markers (12 alkanes, 18 polycyclic aromatic hydrocarbons and ketones, and 3 hopanes) are reported near a highway in Raleigh, NC with an annual average daily traffic count of approximately 125,000 vehicles. Daily samples (24-h) were collected at two locations, one approximately 10 m and the other 275 m perpendicular from the road. Concentrations of OC were similar between near (mean = 7.6 μg m^?3) and far (8.0 μg m^?3) locations, but concentrations of most organic species at the near site were between 1.5 and 2 times higher than those at the far site.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Temperature dependence of secondary organic aerosol

Temperature was found to have a dramatic effect on secondary organic aerosol formation from two ozonolysis systems, cyclohexene and α-pinene. Isothermal experiments were conducted for both systems where the lowest temperature, 278 K, formed approximately 2.5–3 times and 5–6 times the SOA formed at 300 K and 318 K, respectively. Changing the cyclohexene system temperature to a different isothermal experimental set point after completion of SOA formation did not lead to sufficient condensation/evaporation to reproduce the SOA formation at other temperature set points. When the system temperature was cycled between two set points at the end of an experiment, the α-pinene system showed reversibility between the initial temperature 318 K and 300 K. For temperature cycles between the initial temperature of 300 K–318 K, an irreversible loss of mass is observed after the first heating cycle with reversibility observed between subsequent temperature cycles. The SOA formed at 278 K was reversible over a 22 K range but was unable to evaporate sufficiently to match the SOA mass formed at 300 K. Hygroscopicity measurements, taken after the completion of SOA formation, indicate that hygroscopicity of the aerosol is also a function of temperature and that the aerosol does not continue to be oxidized after initial growth is complete. The differing hygroscopicity of the semi-volatile component of the aerosol is evident during system temperature changes after completion of the experiment.     

Atmospheric nitrogen deposition in south-east Scotland: Quantification of the organic nitrogen fraction in wet,dry and bulk deposition

Water soluble organic nitrogen (WSON) compounds are ubiquitous in precipitation and in the planetary boundary layer, and therefore are a potential source of bioavailable reactive nitrogen. This paper examines weekly rain data over a period of 22 months from June 2005 to March 2007 collected in 2 types of rain collector (bulk deposition and “dry + wet” deposition) located in a semi-rural area 15 km southwest of Edinburgh, UK (N55°51′44″, W3°12′19″). Bulk deposition collectors are denoted in this paper as “standard rain gauges”, and they are the design used in the UK national network for monitoring precipitation composition. “Dry + wet” deposition collectors are flushing rain gauges and they are equipped with a rain detector (conductivity array), a spray nozzle, a 2-way valve and two independent bottles to collect funnel washings (dry deposition) and true wet deposition. On average, for the 27 weekly samples with 3 valid replicates for the 2 types of collectors, dissolved organic nitrogen (DON) represented 23% of the total dissolved nitrogen (TDN) in bulk deposition. Dry deposition of particles and gas on the funnel surface, rather than rain, contributed over half of all N-containing species (inorganic and organic). Some discrepancies were found between bulk rain gauges and flushing rain gauges, for deposition of both TDN and DON, suggesting biological conversion and loss of inorganic N in the flushing samplers.     

Effects of post-sampling conditions on ambient carbon aerosol filter measurements

Ambient carbonaceous material collected on quartz filters is prone to measurement artifacts due to material gained or lost during post-sampling field latency, shipping, and storage. In seventeen sampling events over a one year period, ambient PM_2.5 aerosols were collected on quartz filters (without denuders) and subjected to various filter treatments to assess the potential for and extent of artifacts. The filter treatments simulated post-sampling environments that filters may be exposed to and included: storage at 40 °C for up to 96 h, storage at ?16 °C for 48 h, and storage at room temperature (～21 °C) for 48 h. Carbon mass on the filters was measured using a thermal-optical method. The total carbon (TC), total organic carbon (TOC) and total elemental carbon (TEC) as well as carbon thermal fraction masses were obtained. Statistical analyses were performed to identify significant differences in carbon fraction concentrations between filters analyzed immediately after sampling and after being subjected to treatment.TOC and TC concentrations decreased by on average 15 ± 5% and 10 ± 4%, respectively, for filters maintained at 40 °C for 96 h but did not change for filters stored at room temperature or frozen for 48 h. TEC did not change for any of the filter treatments. The mass concentration for the organic carbon thermal fraction that evolves at the lowest temperature step (OC1) decreased with increasing storage time at 40 °C with average losses of 70 ± 7% after 96 h. Therefore, OC1 is not a stable measurement due to post-sampling conditions that may be encountered. This work demonstrates that TOC and TC can have substantial measurement artifacts on filters subjected to field latency and other non-temperature controlled post-sampling handling, compared to the carbon loadings on the filter at the end of the sampling period.     

Influence of organic waste type and soil structure on the bacterial filtration rates in unsaturated intact soil columns

Organic wastes are considered to be a source for the potentially pathogenic microorganisms found in surface and sub-surface water resources. Following their release from the organic waste matrix, bacteria often infiltrate into soil and may be transported to significant depths contaminating aquifers. We investigated the influence of soil texture and structure and most importantly the organic waste properties on the transport and filtration coefficients of Escherichia coli and total bacteria in undisturbed soil columns. Intact soil columns (diameter 16 cm and height 25 cm) were collected from two soils: sandy clay loam (SCL) and loamy sand (LS) in Hamadan, western Iran. The cores were amended with cow manure, poultry manure and sewage sludge at a rate of 10 Mg ha(-1) (dry basis). The amended soil cores were leached at a steady-state flux of 4.8 cm h(-1) (i.e. 0.12 of saturated hydraulic conductivity of the SCL) to a total volume of up to 4 times the pore volume of the columns. The influent (C(0)) and effluent (C) were sampled at similar time intervals during the experiments and bacterial concentrations were measured by the plate count method. Cumulative numbers of the leached bacteria, filtration coefficient (lambda(f)), and relative adsorption index (S(R)) were calculated. The preferential pathways and stable structure of the SCL facilitated the rapid transport and early appearance of the bacteria in the effluent. The LS filtered more bacteria when compared with the SCL. The effluent contamination of poultry manure-treated columns was greater than the cow manure- and sewage sludge-treated ones. The difference between cow manure and sewage sludge was negligible. The lambda(f) and S(R) values for E. coli and total bacteria were greater in the LS than in the SCL. This indicates a predominant role for the physical pore-obstruction filtration mechanisms as present in the poorly structured LS vs. the retention at adsorptive sites (chemical filtration) more likely in the better structured SCL. While the results confirmed the significant role of soil structure and preferential (macroporous) pathways, manure type was proven to have a major role in determining the maximum penetration risk of bacteria by governing filtration of bacteria. Thus while the numbers of bacteria in waste may be of significance for shallow aquifers, the type of waste may determine the risk for microbial contamination of deep aquifers.     

The potential of public engagement in sustainable waste management: designing the future for biosolids in New Zealand

Strategies for beneficial use of biosolids in New Zealand and elsewhere are currently focused primarily on land application. The long-term success of these and other strategies is dependent not only on technical factors, but also on their environmental, economic, social and cultural sustainability. This paper briefly reviews the situation with respect to biosolids management in New Zealand, where land application is not yet widespread; the rise in public opposition to land application in the United States; and the biosolids industry's approach to public engagement. We argue that, at least until recently, the industry has misinterpreted the nature and meaning of public opposition and thus substituted public relations for public engagement. We argue that genuine public engagement is necessary and that its purpose cannot be to gain public acceptance for an already-decided-upon strategy. It therefore calls for humility among biosolids managers, including a willingness to open up the framing of 'the problem', to acknowledge areas of uncertainty, and to recognise the role of values in 'technical' decision-making. We then present and analyse an example of the use of the scenario workshop process for public participation in biosolids management policy in Christchurch, New Zealand, and conclude that scenario workshops and related methods represent an opportunity to enhance sustainable waste management when certain conditions are met.     

Lorenz Curve and Gini Coefficient: Novel tools for analysing seasonal variation of environmental radon gas

Using a methodology derived from Economics, the Lorenz Curve and Gini Coefficient are introduced as tools for investigating and quantifying seasonal variability in environmental radon gas concentration. While the Lorenz Curve presents a graphical view of the cumulative exposure during the course of the time-frame of interest, typically one year, the Gini Coefficient distils this data still further, to provide a single-parameter measure of temporal clustering. Using the assumption that domestic indoor radon concentrations show annual cyclic behaviour, generally higher in the winter months than in summer, published data on seasonal variability of domestic radon concentration levels, in various areas of the UK, Europe, Asia and North America, are analysed. The results demonstrate significantly different annual variation profiles between domestic radon concentrations in different countries and between regions within a country, highlighting the need for caution in ascribing seasonal correction factors to extended geographical areas. The underlying geography, geology and meteorology of a region have defining influences on the seasonal variability of domestic radon concentration, and some examples of potential associations between the Gini Coefficient and regional geological and geographical characteristics are proposed. Similar differences in annual variation profiles are found for soil-gas radon measured as a function of depth at a common site, and among the activity levels of certain radon progeny species, specifically ²¹⁴Bi deposited preferentially in human body-fat by decay of inhaled radon gas. Conclusions on the association between these observed measures of variation and potential underlying defining parameters are presented.