Characteristics of ambient C2–C11 non-methane hydrocarbons in metropolitan Nagoya,Japan

To understand the characteristics of non-methane hydrocarbon (NMHC) abundance in an urban air of Nagoya, one of the metropolitan areas of Japan, 48 species of C₂–C₁₁ NMHCs were measured with a measurement system, developed in this study, by using gas chromatography with flame ionization detection (GC/FID) continuously for one year from December 2003 to November 2004.Annual mean concentration of NMHCs in normal and propylene equivalent (PE) in Nagoya was compared with those in four urban areas of Seoul, London, Lille, and Dallas to extract characteristics of urban air. While the absolute values of the normal and PE concentrations of alkanes, alkenes, alkyne, and aromatics were significantly different among these urban areas, the proportions of each chemical group to the total NMHC were not so different.In Nagoya, the total normal concentration was high from November to February and low from June to August. The pattern of the seasonal variation was influenced mainly by that of alkanes. On the other hand, the total PE concentration was high from July to December and low from January to June. The pattern of the seasonal variation was influenced mainly by those of alkenes and aromatics. Particularly the normal concentration of isoprene was high from May to September because of large emission associated with activity of plants. As the results, in summer, the PE concentration of isoprene was especially high, and its contribution to the total NMHCs measured in this study was approximately 40%. The total PE concentrations were high in summer when the concentration of OH radicals is also high, suggesting that the productions of ozone and secondary organic aerosol (SOA) are likely to be promoted in summer of Nagoya.     

The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.     

C2–C5 Hydrocarbon measurements in the Netherlands 1981–1991

Measurements of C₂–C₅ hydrocarbons on an hourly basis at the TNO site in Delft from 1982 to 1984 and at Moerdijk over the period 1981–1991 are presented. In combination with meteorological data (wind direction and wind speed) the Delft and Moerdijk series are evaluated to identify source categories, annual variations, background concentrations and trends. The C₂–C₅ hydrocarbon concentrations at Delft and Moerdijk are determined mainly by emission characteristics and meteorological dispersion; the dominant sources are relatively nearby and atmospheric degradation is not of much importance. Under conditions of high wind speed the concentrations measured at Moerdijk in the marine sector are close to the Atlantic background concentrations in winter and somewhat above this in summer. The continental background concentrations are higher than the marine background concentrations by a factor of almost two. The annual variation of acetylene is more pronounced than that of the other hydrocarbons, most likely due to a different seasonal variation in acetylene emissions. The annual variation of propene is smoother, indicating stronger sources in summer than in winter. This feature of propene is observed in continental as well as in marine sectors. The observations show that at Moerdijk C₂–C₄ concentrations measured in Rijnmond sector have decreased considerably since the early 1980s, corresponding with changes in emissions in that area. Averaged over all wind directions the trend of all species is downward, but for acetylene the trend is significant at a 95% confidence interval. The acetylene concentrations show an annual downward trend of 3% during the 1980s, supporting other estimates of decreasing hydrocarbon emissions from traffic over this period at the same rate.     

Production of OH radicals from the reactions of C4–C6 internal alkenes and styrenes with ozone in the gas phase

OH formation from the ozonolysis reactions of seven internal alkenes with 4–6 carbons, styrene, trans-β-methyl styrene, and α-methyl styrene was studied using complementary techniques. A small-ratio relative-rate technique in which small quantities of OH tracers are added to monitor OH formation yields provided the following results: trans-2-butene, 0.64±0.12; cis-2-butene, 0.33±0.05; trans-2-pentene, 0.46±0.08; cis-2-pentene, 0.29±0.06; trans-3-hexene, 0.53±0.08; cis-3-hexene, 0.36±0.07; and 2-methyl-2-butene, 0.98±0.24. For styrene, trans-β-methyl styrene, and α-methyl styrene, OH yields of 0.07±0.04, 0.22±0.09, and 0.23±0.12 were measured, respectively. A second method, which monitors product formation from the OH reaction with 2-butanol was used to derive OH formation yields from 2,3-dimethyl-2-butene, 2-methyl-2-butene and cis-2-pentene, and provided yields of 0.91±0.14, 0.80±0.12, and 0.27±0.07, respectively. The results are briefly discussed in terms of the relationship between structures of these alkenes and OH formation.     

Concentrations of C2–C5 hydrocarbons in atmospheric air at Deonar,Bombay, in relation to possible sources

Atmospheric C₂–C₅ hydrocarbons were determined at Deonar, an industrial suburb north of Bombay, India, during 1985. Samples were pre-concentrated on silica gel at −78°C and subsequently desorbed on to a gaschromatographic column for separation and flame ionization detection. The seasonal pattern of the monthly geometric mean hydrocarbon concentrations are used to show that refinery emissions in addition to auto exhaust are a major source of hydrocarbons at Deonar.     

Food contamination by C20–C50 mineral paraffins from the atmosphere

Most foods from plant origin usually contain 1–10 mg/kg (dry weight) of non-resolved isomeric alkanes in the range of the n-alkanes C₂₀–C₅₀ which are assumed to be residues from mineral oil products (in addition to the natural paraffins). In edible vegetable oils, concentrations may exceed 100 mg/kg. Since it was suspected that this contamination was mostly of environmental origin, particulate matter from air was analysed for the same range of paraffins. In a road tunnel, around 5 μg/m³ of such paraffins were found, corresponding to about 3% of the fine dust (PM10). The composition corresponded to that found in the particulate matter from the exhaust of diesel engines, which in turn largely corresponded to engine (lubricating) oil. In Swiss cities, the C₂₀–C₅₀ mineral paraffins in the PM10 from ambient air amounted to 0.1–1.5 μg/m³ (about 1% of the dust) and seemed to primarily originate from incomplete combustion of heating and diesel oil, lubricating oil, and road tar debris. On the countryside, the concentrations were around 0.03 μg/m³ (0.3% of the dust). Soil contained 0.5–10 mg/kg of these paraffins. The similarity of the molecular weight (volatility) distribution suggests that the food contamination with paraffins, is mostly from the air. A substantial proportion probably consists of lubricating oil. If this hypothesis is confirmed, measures should be investigated to reduce this contamination.     

Characteristics of lead geochemistry and the mobility of Pb isotopes in the system of pedogenic rock–pedosphere–irrigated riverwater–cereal–atmosphere from the Yangtze River delta region,China

Knowledge of the characteristics of Pb and its isotopic transfer in different compartments is scant, especially for the mobility of Pb isotopes in the geochemical cycle. The present study characterizes differential Pb transport mechanism and the mobility of Pb isotopes in the pedogenic parent rock–pedosphere–irrigated riverwater–cereal–atmosphere system in the Yangtze River delta region, by determining Pb concentration and Pb isotopic ratios of pedogenic parent rocks, fluvial suspended particle matter, tillage soils, soil profiles, irrigated riverwater, fertilizer, Pb ore, cereal roots and grains. The results show that Pb isotopes in the geochemical cycle generally follow the equation of ²⁰⁸Pb/²⁰⁶Pb = −1.157 × ²⁰⁶Pb/²⁰⁷Pb + 3.46 (r² = 0.941). However, Pb isotopes have different mobility in different environmental matrixes. Whereas in the pedosphere, the heavier Pb (²⁰⁸Pb) usually shows stronger mobility relative to the lighter Pb, and is more likely to transfer into soil exchangeable Pb fraction and carbonates phase. The lighter Pb shows stronger transfer ability from soil to cereal grain via root compared to the heavier Pb. However, the cereal grains have lower ²⁰⁶Pb/²⁰⁷Pb and higher ²⁰⁸Pb/²⁰⁶Pb ratios than root and tillage soil, similar to the airborne Pb and anthropogenic Pb, implying that a considerable amount of Pb in cereal grains comes from the atmosphere. The estimate model shows that 16.7–52.6% (average: 33.5%) of Pb in rice grain is the airborne Pb.     

Another explanation of pollution–income patterns

The Andreoni and Levinson (2001) theoretical framework can be used to show that the shape of the environmental Kuznets curve can be explained without considering increasing returns to scale in pollution abatement technology, but simply by making explicit that the marginal disutility of pollution increases with income.     

Use of thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) on identification of odorant emission focus by volatile organic compounds characterisation

Volatile organic compounds (VOCs) from several different municipal solid wastes’ treatment plants in Mallorca (Spain) have been analysed by thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS). Ambient (immission) air was collected during February and March 2011 by active sampling onto sorbents Tenax™ TA and Carboxen™ 1000. The study presents the chemical characterisation of 93 volatile organic compounds (VOCs) from an overall set of 84 immission air samples. 70 VOCs were positively identified.The linear fit for all 93 external standard calibration, from 10 mg L⁻¹ to 150 mg L⁻¹ (n = 4), was within the range 0.974 < r² < 0.998. Limits of detection of the method (LOD) for all the standards were within the range 1.1–4,213 pg, as the absolute standard amount spiked into sorbent tubes in 1 μL standard mixture (dissolved in methanol).Overall results stated systematic correlation between waste’s nature and VOCs’ air composition. Organic wastes show main contribution of terpenes, waste water sludge residues’ of reduced sulphured compounds (RSCs) and municipal solid wastes show contribution of a wide sort of VOCs. The use of a chemometric approach for variable’s reduction to 12 principal components enables evaluation of similarities and dissimilarities between facilities. PCA clearly related samples to its corresponding facility on the basis of their VOCs composition and the ambient temperature.     

Measurements of air–surface exchange rates of volatile organic compounds

Vertical gradients of volatile organic compounds (VOCs) were measured over a maize field and a soybean field in 1995 and 1996, respectively, in the Lower Coastal Plains of North Carolina. The measurements over the maize field were conducted in its early growth period, during May 1995, and the measurements over the soybean field were conducted in its middle and later growth periods during July through August 1996 at the same location. These measurements were combined with micrometeorological flux measurements to determine emission flux measurements for various VOCs. This measurement programme was part of project NOVA (Natural emissions of Oxidant precursors: Validation of techniques and Assessment) to estimate the flux of VOCs. Methanol was identified as the major biogenic compound for both years with the average flux of 3450 ± 1456 µg/m²/hr over maize and 3079 ± 2766 µg/m²/hr over soybean. Acetone is another compound that was identified as a biogenic compound for both years with the average flux of 425 ± 223 µg/m²/hr over maize and 2701 ± 1710 µg/m²/hr over soybean. In addition to biogenic compounds, a large number of aromatic compounds, including styrene and 1,2,4-trimethylbenzene, were also identified as emissions from the ground over the soybean field.     

The Historical Dynamics of Social–Ecological Traps

Environmental degradation is a typical unintended outcome of collective human behavior. Hardin’s metaphor of the “tragedy of the commons” has become a conceived wisdom that captures the social dynamics leading to environmental degradation. Recently, “traps” has gained currency as an alternative concept to explain the rigidity of social and ecological processes that produce environmental degradation and livelihood impoverishment. The trap metaphor is, however, a great deal more complex compared to Hardin’s insight. This paper takes stock of studies using the trap metaphor. It argues that the concept includes time and history in the analysis, but only as background conditions and not as a factor of causality. From a historical–sociological perspective this is remarkable since social–ecological traps are clearly path-dependent processes, which are causally produced through a conjunction of events. To prove this point the paper conceptualizes social–ecological traps as a process instead of a condition, and systematically compares history and timing in one classic and three recent studies of social–ecological traps. Based on this comparison it concludes that conjunction of social and environmental events contributes profoundly to the production of trap processes. The paper further discusses the implications of this conclusion for policy intervention and outlines how future research might generalize insights from historical–sociological studies of traps.     

Comparison of line– and point–source releases of tracer gases

Field measurements were made of greenhouse gas emissions from a wastewater treatment system using open path monitoring with detection by FTIR spectroscopy. Emission rates were determined by the ratio technique using a sulfur hexafluoride tracer gas released from a line source. As a quality control check, a second tracer gas – ethylene – was released from various single point locations. This paper presents a comparison of the line-source and point-source tracer releases for approximating emissions from the area source. The two types of tracer release showed excellent agreement when both release points were two hundred meters from the FTIR beam path. Data for other release points also were comparable, once differences in vertical dispersion as a function of distance are taken into account.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Degradation of rizazole in water–sediment systems

This study investigated the degradation of rizazole in water-sediment systems (West Lake system, WL; Beijing–Hangzhou Grand Canal system, BG) with two different types of sediments under aerobic and anaerobic conditions. The half-lives of rizazole in the WL water phase (14.59–15.13 d) were similar to those in the BG water phase (15.90–16.46 d). Within 3–7 d, the rizazole concentration in the sediments reached the maximum values, i.e., equilibrium. Rizazole dissipation was faster in the WL sediment phase with higher organic matter content (T_1/2 = 18.99–19.09 d) compared with the BG sediment phase (T_1/2 = 31.08–33.32 d). Rizazole degradation was slightly faster in the West Lake water-sediment system (WL system) (T_1/2 = 17.11–18.05 d) than in the Beijing–Hangzhou Grand Canal water—sediment system (BG system) (T_1/2 = 20.51–25.02 d). The aerobic degradation of rizazole was similar to its anaerobic degradation in the water-sediment system. The findings are useful to understand the behavior of pesticide in environment.     

Modeling the surface–atmosphere exchange of ammonia

New parameterizations for surface–atmosphere exchange of ammonia are presented for application in atmospheric transport models and compared with parameterizations of the literature. The new parameterizations are based on a combination of the results of three years of ammonia flux measurements over a grassland canopy (dominated by Lolium perenne and Poa trivialis) near Wageningen, the Netherlands and existing parameterizations from literature. First, a model for the surface–atmosphere exchange of ammonia that includes the concentration at the external leaf surface is derived and validated. Second, a parameterization for the stomatal compensation point (expressed as Γ_s, the ratio of [NH₄⁺]/[H⁺] in the leaf apoplast) that accounts for the observed seasonal variation is derived from the measurements. The new, temperature-dependent Γ_s describes the observed seasonal behavior very well. It is noted, however, that senescence of plants and field management practices will also influence the seasonal variation of Γ_s on a shorter timescale. Finally, a relation that links Γ_s to the atmospheric pollution level of the location through the ‘long-term’ NH₃ concentration in the air is proposed.     

Determination of vapor pressure-temperature relationships of current–use pesticides and transformation products

Sub-cooled liquid vapor pressures (P_L ⁰) of current–use organochlorine and organophosphate pesticides (chlorothalonil, chlorpyrifos methyl, diazinon, fipronil) and selected transformation products (chlorpyrifos oxon, heptachlor epoxide, oxychlordane, 3,5,6-trichloro-2-pyridinol) were determined at multiple temperatures using the gas chromatography retention time technique. Results were utilized to determine vapor pressure-temperature relationships and to calculate enthalpies of vaporization (ΔH_vap). While results for chlorothalonil and diazinon were comparable with published values, the measured value for fipronil (1.82 × 10^{? 6} Pa) is almost an order of magnitude higher than the reported literature value (3.7 × 10^{? 7} Pa). The availability of vapor pressure temperature relationships for these chemicals will aid in pesticide risk assessment development and improve the effectiveness of mitigation and remediation efforts.     

Estimates of global anthropogenic methane emissions 1860–1993

This paper provides the first time series estimates of global anthropogenic methane emissions from the mid-19th century to the present. Our purpose is to provide time series estimates of anthropogenic methane emissions for global climate models estimated or calibrated using historical time series data. Previous estimates of methane emissions include “top-down” (deconvolution) estimates of total emissions, estimates of global anthropogenic emissions for the 16th century, and various estimates of anthropogenic and natural emissions in the 1980s and 1990s. This study uses previously published point estimates for the 16th century and the 1980s and early 1990s and a variety of historical time series of proxy variables to estimate a time series of global anthropogenic methane emissions. We find that anthropogenic methane emissions have increased from about 80 million tonnes per annum in 1860 to about 380 million tonnes in 1990. The relative importance of various emission sources changes over time. The rate of increase now may be slowing. A comparison with the estimates generated by Khalil and Rasmussen suggests that natural sources of methane have declined over the period. There are, however, great uncertainties in these estimates which future research may be able to reduce.     

Fate of atrazine in switchgrass–soil column system

Atrazine, a broad-leaf herbicide, has been used widely to control weeds in corn and other crops for several decades and its extensive used has led to widespread contamination of soils and water bodies. Phytoremediation with switchgrass and other native prairie grasses is one strategy that has been suggested to lessen the impact of atrazine in the environment. The goal of this study is to characterize: (1) the uptake of atrazine into above-ground switchgrass biomass; and (2) the degradation and transformation of atrazine over time. A fate study was performed using mature switchgrass columns treated with an artificially-created agricultural runoff containing 16 ppm atrazine. Soil samples and above-ground biomass samples were taken from each column and analyzed for the presence of atrazine and its chlorinated metabolites. Levels of atrazine in both soil and plant material were detectable through the first 2 weeks of the experiment but were below the limit of detection by Day 21. Levels of deethylatrazine (DEA) and didealkylatrazine (DDA) were detected in soil and plant tissue intermittently over the course of the study, deisopropylatrazine (DIA) was not detected at any time point. A radiolabel study using [¹⁴C]atrazine was undertaken to observe uptake and degradation of atrazine with more sensitivity. Switchgrass columns were treated with a 4 ppm atrazine solution, and above-ground biomass samples were collected and analyzed using HPLC and liquid scintillation counting. Atrazine, DEA, and DIA were detected as soon as 1 d following treatment. Two other metabolites, DDA and cyanuric acid, were detected at later time points, while hydroxyatrazine was not detected at all. The percentage of atrazine was observed to decrease over the course of the study while the percentages of the metabolites increased. Switchgrass plants appeared to exhibit a threshold in regard to the amount of atrazine taken up by the plants; levels of atrazine in leaf material peaked between Days 3 and 4 in both studies.     

Dispersion of pollutants over land–water–land interface: Study using CALPUFF model

The CALMET/CALPUFF modeling system is used to study atmospheric dispersion of pollutant over land–water–land interface. It is shown that the default scheme used by CALMET/CALPUFF to handle inhomogeneous surfaces does not take care of the different turbulence characteristics over such surfaces. An alternative method is suggested to incorporate different turbulent characteristics over inhomogeneous surfaces by using the appropriate atmospheric stability category over different surfaces. The results show that the presence of water body can increase the ground level concentration by a factor of up to 50 for the width of water body varying from 1 km to 5 km. It is also shown that the effect of water body on the ground level concentration decreases as the distance from the water body increases. The present study showed that for land–water interface, the realistic specification of turbulence characteristics over inhomogeneous surfaces significantly changes the estimation of ground level concentration as compared to the default scheme available in the CALMET/CALPUFF modeling system and is expected to give realistic results.