Urban–rural differences in atmospheric mercury speciation

Measurements of gaseous elemental mercury (GEM), particulate mercury (Hg_p), and reactive gaseous mercury (RGM) were concurrently recorded at an urban site in Detroit and a rural site in Dexter, both in Michigan for the calendar year 2004. Their average concentrations (±standard deviation) for the urban area were 2.5 ± 1.4 ng m^?3, 18.1 ± 61.0 pg m^?3, and 15.5 ± 54.9 pg m^?3, respectively, while their rural counterparts were 1.6 ± 0.6 ng m^?3, 6.1 ± 5.5 pg m^?3, and 3.8 ± 6.6 pg m^?3, respectively. The medians of urban-to-rural ratios of Hg concentrations indicate approximately 1-fold, 2-fold, and 3-fold gradients between Detroit and Dexter for GEM, Hg_p, and RGM, respectively. The urban–rural differences in Hg also varied considerably on different temporal scales and with wind flow patterns, which was most evident in RGM. Our results show that while Hg at both sites was impacted by regional sources, meteorological conditions, and photochemical transformations, the extent of variations in the observed urban-to-rural gradients, particularly in RGM, cannot be fully accounted for by these processes. Both analyses of the annual data and case studies indicate that the more variable and episodic nature of Hg, particularly RGM, seen in Detroit compared with Dexter, was the result of direct impact from local anthropogenic sources.     

Is There a Metabolism of an Urban Ecosystem? An Ecological Critique

The energy and material flows of a city are often described as urban metabolism (UM), which is put forward as a way to link a city's ecology and economy. UM draws parallels to the biology of individual organisms, yet the analogy is misapplied. In striving to be interdisciplinary, UM makes this organismic comparison rather than identifying the city as an ecosystem, thereby ignoring developments in ecological theory. Using inappropriate rhetoric misdirects researchers, which influences scientific investigation-from problem statements to interpretations. UM is valuable in quantifying the city's use of natural resources but does not achieve a comprehensive, integrated analysis of the urban ecosystem. To realize an interdisciplinary, perhaps transdisciplinary, understanding of urban ecology, researchers need to emphasize the essential tenets of material flows analysis, view the city as an ecosystem, and use language that properly reflects current knowledge, theory, and conceptual frameworks in the foundational disciplines.     

Opportunities for Increasing Resilience and Sustainability of Urban Social–Ecological Systems: Insights from the URBES and the Cities and Biodiversity Outlook Projects

Urban futures that are more resilient and sustainable require an integrated social–ecological system approach to urban policymaking, planning, management, and governance. In this article, we introduce the Urban Biodiversity and Ecosystem Services (URBES) and the Cities and Biodiversity Outlook (CBO) Projects as new social–ecological contributions to research and practice on emerging urban resilience and ecosystem services. We provide an overview of the projects and present global urbanization trends and their effects on ecosystems and biodiversity, as a context for new knowledge generated in the URBES case-study cities, including Berlin, New York, Rotterdam, Barcelona, and Stockholm. The cities represent contrasting urbanization trends and examples of emerging science–policy linkages for improving urban landscapes for human health and well-being. In addition, we highlight 10 key messages of the global CBO assessment as a knowledge platform for urban leaders to incorporate state-of-the-art science on URBES into decision-making for sustainable and resilient urban development.     

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.     

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.     

Characterization of Naturally-occurring and Anthropogenic PAHs in Urban Sediments—Wycoff/Eagle Harbor Superfund Site

Polycyclic aromatic hydrocarbons (PAH) are ubiquitous constituents in urban sedimentary environments. The accurate characterization of their source(s) in sediments influences decisions regarding the liability for clean-up and remedial options. In this study, an extensive PAH dataset that included 50 non-alkylated (parent) and alkylated PAH groups and isomers was acquired using a modified EPA Method 8270 for the study of 5 cm intervals from 10 sediment cores (28–78 cm) obtained from the Eagle Harbor Superfund Site on Bainbridge Island, Washington. Conventional hydrocarbon “fingerprinting” and the PAH profiles in the Pb²¹⁰ age-dated cores revealed three primary PAH sources to the sediments over the past 220 years, namely (1) naturally occurring background; (2) urban runoff, and (3) creosote, the latter resulting from prior operations at the former Wyckoff wood-processing facility located on the Harbor. Naturally occurring background PAH in the pre-industrial (<1900) sediments were dominated by perylene, 1,7-dimethylphenanthrene (derived from the oxidation of abietic acid resins), and pyrogenic PAH most likely derived from historic forest fires. The concentration of PAH_total in these pre-industrial sediments was consistently less than 1 mg/kg (dry). Urban runoff in the post-industrial (>1930) sediments was dominated by low but consistent concentrations (10–20 mg/kg dry) of pyrogenic PAH derived primarily from the combustion of fossil fuel(s). The creosote-impacted sediments in the post-industrialized sediments contained high concentrations (1000–140,000 mg/kg dry) of pyrogenic PAH associated with distilled, coal-derived liquids.     

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.     

Evolution of newspaper coverage of water issues in Australia during 1843–2011

News accounts both reflect and influence public opinion through their noted ‘agenda-setting’ capability. We examined newspaper articles in Australia’s The Sydney Morning Herald from 1843 to 2011 to observe the evolution of media coverage on water issues related to water resources management. The results showed that water supply-related articles have dominated the reporting of water issues since 1843. This emphasis is reflected in the institutions involved and their related policy/management initiatives, as well as the themes of the articles. Extreme events such as flooding and drought have punctuated the historical record of reports on water issues. An economic development-driven tone was overwhelmingly predominant in newspaper articles (85 % of the total); however, there has been a marked decline in the importance of development-driven tone relative to environmental-sustainability oriented tone of articles since 1994. People from academia and NGOs were rarely quoted. Inclusion of wider range stakeholders should be considered as a strategic break-through and natural events should be considered as an “opportunity” to change public opinion on water issues for environmental sustainability.     

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.