Anthropogenic and natural CO2 emission sources in an arid urban environment

Recent research has shown the Phoenix, AZ metropolitan region to be characterized by a CO2 dome that peaks near the urban center. The CO2 levels, 50% greater than the surrounding non-urban areas, have been attributed to anthropogenic sources and the physical geography of the area. We quantified sources of CO2 emissions across the metropolitan region. Anthropogenic CO2 emission data were obtained from a variety of government and NGO sources. Soil CO2 efflux from the dominant land-use types was measured over the year. Humans and automobile activity produced more than 80% input of CO2 into the urban environment. Soil CO2 efflux from the natural desert ecosystems showed minimal emissions during hot and dry periods, but responded rapidly to moisture. Conversely, human maintained vegetation types (e.g. golf courses, lawns, irrigated agriculture) have greater efflux and are both temperature and soil moisture dependent. Landfills exhibited the most consistent rates, but were temperature and moisture independent. We estimate the annual CO2 released from the predominant land-use types in the Phoenix region and present a graphical portrayal of soil CO2 emissions and the total natural and anthropogenic CO2 emissions in the metropolitan region using a GIS-based approach. The results presented here do not mimic the spatial pattern shown in previous studies. Only, with sophisticated mixing models will we be able to address the total effect of urbanization on CO2 levels and the contribution to regional patterns.     

Occurrence and source characterization of perfluorochemicals in an urban watershed

Perfluorochemicals (PFCs) are used in numerous applications, mainly as surfactants, and occur ubiquitously in the environment as complex mixtures. This study was undertaken to characterize the occurrence and sources of commonly detected PFC compounds in surface waters of the Marina catchment, a watershed that drains an urbanized section of Singapore. Of the 19 target PFCs, 13 were detected with perfluorooctanoic acid (PFOA) (5-31 ng L⁻¹) and perfluorooctane sulfonate (PFOS) (1-156 ng L⁻¹) being the dominant components. Other compounds detected included perfluoroalkyl carboxylates (C7-C12) and perfluoroalkyl sulfonates (C6 and C8). Sulfonamide compounds detected 2-(N-ethylperfluorooctanesulfonamido) acetic acid (N-EtFOSAA), 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA), perfluorooctanesulfonamido acetic acid (FOSAA) and perfluorooctanesulfonamide (FOSA) were putative transformation products of N-EtFOSE and N-MeFOSE, the N-ethylated and N-methylated ethyl alcohol derivatives, respectively. Surface water concentrations were generally higher during dry weather than during storm water flow: the median concentrations of total PFCs in dry and wet weather were 57 and 138 ng L⁻¹ compared to 42 and 79 ng L⁻¹, respectively, at Stamford and Alexandra canal, suggesting the presence of a continuous source(s) which is subject to dilution during storm events. In rain water, median concentrations were 6.4 ng L⁻¹, suggesting rain contributed from 12-25% to the total PFC load for non-point source sites. The longitudinal concentration profile along one of the canals revealed a point source of sulfonated PFCs (PFOS), believed to originate from aqueous film-forming foam (AFFF). Sources were characterized using principal component analysis (PCA) and by plotting PFHxS/PFOA against PFOS/PFOA. Typical surface waters exhibit PFOS/PFOA and PFHxS/PFOA ratios below 0.9 and 0.5, respectively. PCA plots reveal waters impacted by “non-typical” PFC sources in Alexandra canal.     

Elevated atmospheric CO2 concentration and temperature across an urban–rural transect

The heat island effect and the high use of fossil fuels in large city centers are well documented, but by how much fossil fuel consumption is elevating atmospheric CO₂ concentrations and whether elevations in both atmospheric CO₂ and air temperature from rural to urban areas are consistently different from year to year are less well known. Our aim was to record atmospheric CO₂ concentrations, air temperature and other environmental variables in an urban area and compare it to suburban and rural sites to see if urban sites are experiencing climates expected globally in the future with climate change. A transect was established from Baltimore city center (Urban site), to the outer suburbs of Baltimore (suburban site) and out to an organic farm (rural site). At each site a weather station was set-up to monitor environmental variables for 5 years. Atmospheric CO₂ was consistently and significantly increased on average by 66 ppm from the rural to the urban site over the 5 years of the study. Air temperature was also consistently and significantly higher at the urban site (14.8 °C) compared to the suburban (13.6 °C) and rural (12.7 °C) sites. Relative humidity was not different between sites whereas the vapor pressure deficit (VPD) was significantly higher at the urban site compared to the suburban and rural sites. An increase in nitrogen deposition at the rural site of 0.6% and 1.0% compared to the suburban and urban sites was small enough not to affect soil nitrogen content. Dense urban areas with large populations and high vehicular traffic have significantly different microclimates compared to outlying suburban and rural areas. The increases in atmospheric CO₂ and air temperature are similar to changes predicted in the short term with global climate change, therefore providing an environment suitable for studying future effects of climate change on terrestrial ecosystems.     

Depositional flux of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in an urban setting

Dry and wet deposition fluxes of the PCDD/F substituted congeners were measured at two different sites (Clinton Drive and Lang Road) in Houston, TX between December 2003 and April 2004. Average total dry deposition fluxes of 351 and 125pgm(-2)d(-1) were found at Clinton Drive and Lang Road, respectively. A wet deposition flux of 2.873pgm(-2)d(-1) was measured at the Clinton Drive site. The results indicated that the dry deposition process exhibited spatial variability. In addition, the results also demonstrated that precipitation, although intermittent, is the most important mechanism for the removal of dioxins from atmosphere in the area of study. Combining the contributions of the dry and wet deposition processes at Clinton Drive resulted in a total bulk deposition flux of 527pg m(-2)d(-1). The total dry and wet deposition fluxes were dominated by OCDD followed by 1,2,3,4,6,7,8-HpCDD at both sites. Overall average dry deposition velocities of 0.35 and 0.15cms(-1) were calculated at Clinton Drive and Lang Road sites, respectively. While these velocities were similar to velocities observed in other geographical areas, the contribution of OCDD to the total deposition flux in Houston was significantly higher, probably reflecting the unique nature and character of Houston dioxin sources. The results also showed that lower chlorinated congeners, primarily present in the gas phase, are more likely to be removed from the atmosphere by precipitation. Relationships between the detected congeners in the dry deposition samples and other routinely measured air pollutants/meteorological parameters were found. The results showed that in general, the dry deposition of these congeners was consistently negatively correlated with SO(2) and NO(x) concentrations in the air and positively correlated with relative humidity. However, more research is needed to ascertain those correlations.     

Mercury exposure in terrestrial birds far downstream of an historical point source

Mercury (Hg) is a persistent environmental contaminant found in many freshwater and marine ecosystems. Historical Hg contamination in rivers can impact the surrounding terrestrial ecosystem, but there is little known about how far downstream this contamination persists. In 2009, we sampled terrestrial forest songbirds at five floodplain sites up to 137 km downstream of an historical source of Hg along the South and South Fork Shenandoah Rivers (Virginia, USA). We found that blood total Hg concentrations remained elevated over the entire sampling area and there was little evidence of decline with distance. While it is well known that Hg is a pervasive and long-lasting aquatic contaminant, it has only been recently recognized that it also biomagnifies effectively in floodplain forest food webs. This study extends the area of concern for terrestrial habitats near contaminated rivers for more than 100 km downstream from a waterborne Hg point source.     

Effect of point source removal on mercury bioaccumulation in an industrial pond

A one hectare pond on the headwaters of a mercury-contaminated creek in Oak Ridge, Tennessee acted as a biochemical reactor for the production of methylmercury, increasing waterborne methylmercury concentrations in the stream below the pond discharge. The flow of the creek was diverted around the pond in order to eliminate this input. Waterborne total mercury, methylmercury, and mercury in fish, were monitored in the pond and stream before and after bypass. Waterborne methylmercury concentration in the creek downstream from the pond decreased over 800% following diversion of streamflow around the pond, but mercury in redbreast sunfish in the pond tailwater did not decline similarly. Within the pond, now isolated from fresh waterborne mercury inputs from the stream, methylmercury concentrations in the water column remained similar to levels present before bypass. However, mercury concentrations in sunfish in the pond decreased approximately 75% following bypass, despite the continued presence of highly contaminated sediments (approximately 50 mg Hg/kg dry weight). We concluded that a decrease in the fraction of 'dissolved methylmercury' in the isolated pond relative to pre-bypass conditions explained the decrease in mercury in fish within the pond. That observation also indicates that mercury associated with pond sediments was relatively unavailable for eventual bioaccumulation when compared to 'fresh' mercury contributed by upstream sources. The lack of a post-bypass decrease in mercury concentrations in tailwater fish was also likely to be associated with the particle-associated nature of waterborne methylmercury exported from the pond.     

Nonpoint source pollution of urban stormwater runoff: a methodology for source analysis

The characterization and control of runoff pollution from nonpoint sources in urban areas are a major issue for the protection of aquatic environments. We propose a methodology to quantify the sources of pollutants in an urban catchment and to analyze the associated uncertainties. After describing the methodology, we illustrate it through an application to the sources of Cu, Pb, Zn, and polycyclic aromatic hydrocarbons (PAH) from a residential catchment (228 ha) in the Paris region. In this application, we suggest several procedures that can be applied for the analysis of other pollutants in different catchments, including an estimation of the total extent of roof accessories (gutters and downspouts, watertight joints and valleys) in a catchment. These accessories result as the major source of Pb and as an important source of Zn in the example catchment, while activity-related sources (traffic, heating) are dominant for Cu (brake pad wear) and PAH (tire wear, atmospheric deposition).     

Outdoor air pollution in close proximity to a continuous point source

Data are lacking on human exposure to air pollutants occurring in ground-level outdoor environments within a few meters of point sources. To better understand outdoor exposure to tobacco smoke from cigarettes or cigars, and exposure to other types of outdoor point sources, we performed more than 100 controlled outdoor monitoring experiments on a backyard residential patio in which we released pure carbon monoxide (CO) as a tracer gas for continuous time periods lasting 0.5–2 h. The CO was emitted from a single outlet at a fixed per-experiment rate of 120–400 cc min^?1 (～140–450 mg min^?1). We measured CO concentrations every 15 s at up to 36 points around the source along orthogonal axes. The CO sensors were positioned at standing or sitting breathing heights of 2–5 ft (up to 1.5 ft above and below the source) and at horizontal distances of 0.25–2 m. We simultaneously measured real-time air speed, wind direction, relative humidity, and temperature at single points on the patio. The ground-level air speeds on the patio were similar to those we measured during a survey of 26 outdoor patio locations in 5 nearby towns. The CO data exhibited a well-defined proximity effect similar to the indoor proximity effect reported in the literature. Average concentrations were approximately inversely proportional to distance. Average CO levels were approximately proportional to source strength, supporting generalization of our results to different source strengths. For example, we predict a cigarette smoker would cause average fine particle levels of approximately 70–110 μg m^?3 at horizontal distances of 0.25–0.5 m. We also found that average CO concentrations rose significantly as average air speed decreased. We fit a multiplicative regression model to the empirical data that predicts outdoor concentrations as a function of source emission rate, source–receptor distance, air speed and wind direction. The model described the data reasonably well, accounting for ～50% of the log-CO variability in 5-min CO concentrations.     

Characteristics influencing the variability of urban CO2 fluxes in Melbourne,Australia

Urban areas are significant contributors to global carbon dioxide emissions. Vehicle emissions and other anthropogenic related activities are a frequent source of CO₂ to the atmosphere, contributing to global warming. Micrometeorological techniques used for observations in Northern Hemisphere cities have found that urban CO₂ fluxes are consistently a source. This study investigates CO₂ fluxes in an Australian city, adding to the global database of CO₂ fluxes in a bid to aid in future development of planning policies concerning reductions in CO₂ emissions. Using the eddy covariance approach, fluxes of CO₂ were measured at a suburban site (Preston) in Melbourne, Australia from February 2004 to June 2005 to investigate temporal variability. A second site (Surrey Hills) with differing surface characteristics (in particular, greater vegetation cover) was also established in Melbourne and ran simultaneously for 6 months (February 2004–July 2004). Results showed that both sites were a net source of CO₂ to the atmosphere. Diurnal patterns of fluxes were largely influenced by traffic volumes, with two distinct peaks occurring at the morning and evening traffic peak hours, with the winter morning peak averaging 10.9 μmol m⁻² s⁻¹ at Preston. Summer time fluxes were lower than during winter due to greater vegetative influence and reduced natural gas combustion. Vegetation limited the source of CO₂ in the afternoon, yet was not enough to combat the strong local anthropogenic emissions. Surrey Hills showed higher fluxes of CO₂ despite greater vegetation cover because of higher local traffic volumes. Annual emissions from Preston were estimated at 84.9 t CO₂ ha⁻¹ yr⁻¹. Magnitudes and patterns of suburban CO₂ fluxes in Melbourne were similar to those observed in Northern Hemisphere suburban areas.     

世界化石能源部门CO2排放源状况及案例分析

能源部门是CO2排放的主要来源,1990-2005年,电力和热力是能源部门CO2排放的主要排放源,其次是交通运输业.从2005年经济合作与发展组织(OECD)和非OECD国家主要地区的能源部门各排放源对人均CO2排放的贡献率的情况看,北美OECD地区是电力和热力人均CO2排放量最高的地区,其他各排放源不同程度地高出世界平均水平;整体上,非OECD国家主要地区的能源部门各排放源对人均CO2排放的贡献率差异较大,各地区的经济结构、能源结构和生活水平影响能源部门各排放源对人均CO2排放的贡献率.从2005年主要国家的能源部门各排放源对人均CO2排放的贡献率的情况看,除印度外,电力和热力是大多数国家能源部门的CO2主要排放源.中国的电力和热力对能源部门人均CO2排放的贡献率最大.各国对能源部门人均CO2排放的贡献率的次排放源情况相差较大,美国和欧盟(27)主要是交通运输业等服务型产业,中国主要是制造业和建筑业等第二产业,其他国家的次排放源分布相对均衡.     

A passive sampling method for radiocarbon analysis of atmospheric CO2 using molecular sieve

Radiocarbon (¹⁴C) analysis of atmospheric CO₂ can provide information on CO₂ sources and is potentially valuable for validating inventories of fossil fuel-derived CO₂ emissions to the atmosphere. We tested zeolite molecular sieve cartridges, in both field and laboratory experiments, for passively collecting atmospheric CO₂. Cartridges were exposed to the free atmosphere in two configurations which controlled CO₂ trapping rate, allowing collection of sufficient CO₂ in between 1.5 and 10 months at current levels. ¹⁴C results for passive samples were within measurement uncertainty of samples collected using a pump-based system, showing that the method collected samples with ¹⁴C contents representative of the atmosphere. δ¹³C analysis confirmed that the cartridges collected representative CO₂ samples, however, fractionation during passive trapping means that δ¹³C values need to be adjusted by an amount which we have quantified. Trapping rate was proportional to atmospheric CO₂ concentration, and was not affected by exposure time unless this exceeded a threshold. Passive sampling using molecular sieve cartridges provides an easy and reliable method to collect atmospheric CO₂ for ¹⁴C analysis.     

Identification of a potential source of chloroform in urban air: Preliminary Communication

A new potential source of elevated chloroform (CHCl₃) concentrations in urban air is reported. The exhaust gases from gasoline internal combustion engines operated on conventional “leaded” fuel and not equipped with catalytic converters contain parts-per-billion concentrations of chloroform which can, in congested urban areas, contribute significantly to the ambient concentration of chloroform. Exhaust gases from engines burning conventional “leaded” gasoline contain much higher levels of chloroform than do exhaust gases from engines equipped with catalytic converters and operating on “nonleaded” gasoline.     

Residential runoff as a source of pyrethroid pesticides to urban creeks

Pyrethroid pesticides occur in urban creek sediments at concentrations acutely toxic to sensitive aquatic life. To better understand the source of these residues, runoff from residential neighborhoods around Sacramento, California was monitored over the course of a year. Pyrethroids were present in every sample. Bifenthrin, found at up to 73 ng/L in the water and 1211 ng/g on suspended sediment, was the pyrethroid of greatest toxicological concern, with cypermethrin and cyfluthrin of secondary concern. The bifenthrin could have originated either from use by consumers or professional pest controllers, though the seasonal pattern of discharge from the drain was more consistent with professional use as the dominant source. Stormwater runoff was more important than dry season irrigation runoff in transporting pyrethroids to urban creeks. A single intense storm was capable of discharging as much bifenthrin to an urban creek in 3 h as that discharged over 6 months of irrigation runoff.     

Characteristic study of particulates and metallic elements at an urban sampling site in Taichung, central Taiwan

Atmospheric total suspended particulate concentrations and metallic element concentrations were measured at three locations, characteristic of urban, suburban and rural sites. The sampling period was from July 2000 to August 2000. The results indicated that the urban sampling site had the highest total suspended particulate concentrations (average 108.61μ1m3), followed by the suburban site (average 60.11μ1m3) and the rural site (average 53.31μ1m3). The average PM_2.5 concentrations (24.11μ1m3) were higher than the PM_2.5-10 concentrations (12.81μ1m3) at the urban site. The average distributed ratios for PM_2.5/PM_2.5-10 were about 1.29, 1.53, 0.12, 1.12 and 2.31 for Pb, Zn, Fe, Ni and Cr, respectively. The average total suspended particulate mass ratios for daytime and nighttime were about 1.72. As for the elements Cu, Pb, Zn, Fe, Ni and Cr, these ratios were about 0.63, 0.97, 0.54, 1.66, 0.53 and 1.12, respectively. The total suspended particulate daytime concentrations of Pb and Zn were positively correlated (R = 0.925) at the urban sampling site. The elements Ni and Cr were positively correlated both during the daytime (R = 0.648) and the nighttime (R = 0.511), revealing that they came from the same emission source during daytime and nighttime, at the urban sampling site.     

Analysis of point source emissions in the Texas-Mexico border region

Pollutant emissions in the Texas-Mexico border were investigated using an emission database that covers 25 Texas counties and the states of Coahuila, Chihuahua, Nuevo Leon and Tamaulipas in Mexico. Major emissions are from energy generation, mainly from two coal-fired facilities in Coahuila, which also generate most of carbon dioxide. Texas exhibits a larger concentration of sources; around Laredo and the Lower Rio Grande Valley and a sugarcane mill is a significant contributor to particles emissions. In Mexico the minerals and metals industries are the second major contributors to emissions, especially particles. Fossil fuel production is the main source of VOCs.     

Global comparison of VOC and CO observations in urban areas

Speciated volatile organic compound (VOC) and carbon monoxide (CO) measurements from the Marylebone Road site in central London from 1998 through 2008 are presented. Long-term trends show statistically significant decreases for all the VOCs considered, ranging from ?3% to ?26% per year. Carbon monoxide decreased by ?12% per year over the measurement period. The VOC trends observed at the kerbside site in London showed greater rates of decline relative to trends from monitoring sites in rural England (Harwell) and a remote high-altitude site (Hohenpeissenberg), which showed decreases for individual VOCs from ?2% to ?13% per year. Over the same 1998 through 2008 period VOC to CO ratios for London remained steady, an indication that emissions reduction measures affected the measured compounds equally. Relative trends comparing VOC to CO ratios between Marylebone Road and Hohenpeissenberg showed greater similarities than absolute trends, indicating that emissions reductions measures in urban areas are reflected by regional background locations. A comparison of VOC mixing ratios and VOC to CO ratios was undertaken for London and other global cities. Carbon monoxide and VOCs (alkanes greater than C₅, alkenes, and aromatics) were found to be strongly correlated (>0.8) in the Annex I countries, whereas only ethene and ethyne were strongly correlated with CO in the non-Annex I countries. The correlation results indicate significant emissions from traffic-related sources in Annex I countries, and a much larger influence of other sources, such as industry and LPG-related sources in non-Annex I countries. Yearly benzene to ethyne ratios for London from 2000 to 2008 ranged from 0.17 to 0.29 and compared well with previous results from US cities and three global megacities.     

Bayesian inference for source determination with applications to a complex urban environment

The problem of determining the source of an emission from the limited information provided by a finite and noisy set of concentration measurements obtained from real-time sensors is an ill-posed inverse problem. In general, this problem cannot be solved uniquely without additional information. A Bayesian probabilistic inferential framework, which provides a natural means for incorporating both errors (model and observational) and prior (additional) information about the source, is presented. Here, Bayesian inference is applied to find the posterior probability density function of the source parameters (location and strength) given a set of concentration measurements. It is shown how the source–receptor relationship required in the determination of the likelihood function can be efficiently calculated using the adjoint of the transport equation for the scalar concentration. The posterior distribution of the source parameters is sampled using a Markov chain Monte Carlo method. The inverse source determination method is validated against real data sets acquired in a highly disturbed flow field in an urban environment. The data sets used to validate the proposed methodology include a water-channel simulation of the near-field dispersion of contaminant plumes in a large array of building-like obstacles (Mock Urban Setting Trial) and a full-scale field experiment (Joint Urban 2003) in Oklahoma City. These two examples demonstrate the utility of the proposed approach for inverse source determination.     

Denitrification controls in urban riparian soils: implications for reducing urban nonpoint source nitrogen pollution

The purpose of this research was to thoroughly analyze the influences of environmental factors on denitrification processes in urban riparian soils. Besides, the study was also carried out to identify whether the denitrification processes in urban riparian soils could control nonpoint source nitrogen pollution in urban areas. The denitrification rates (DR) over 1 year were measured using an acetylene inhibition technique during the incubation of intact soil cores from six urban riparian sites, which could be divided into three types according to their vegetation. The soil samples were analyzed to determine the soil organic carbon (SOC), soil total nitrogen (STN), C/N ratio, extractable NO₃ ^?-N and NH₄ ⁺-N, pH value, soil water content (SWC), and the soil nitrification potential to evaluate which of these factors determined the final outcome of denitrification. A nitrate amendment experiment further indicated that the riparian DR was responsive to added nitrate. Although the DRs were very low (0.099?~?33.23 ng N₂O-N g^?1 h^?1) due to the small amount of nitrogen moving into the urban riparian zone, the spatial and temporal patterns of denitrification differed significantly. The extractable NO₃ ^?-N proved to be the dominant factor influencing the spatial distribution of denitrification, whereas the soil temperature was a determinant of the seasonal DR variation. The six riparian sites could also be divided into two types (a nitrate-abundant and a nitrate-stressed riparian system) according to the soil NO₃ ^?-N concentration. The DR in nitrate-abundant riparian systems was significantly higher than that in the nitrate-stressed riparian systems. The DR in riparian zones that were covered with bushes and had adjacent cropland was higher than in grass-covered riparian sites. Furthermore, the riparian DR decreased with soil depth, which was mainly attributed to the concentrated nitrate in surface soils. The DR was not associated with the SOC, STN, C/N ratio, and pH. Nitrate supply and temperature finally decided the spatiotemporal distribution patterns of urban riparian denitrification. Considering both the low DR of existing riparian soils and the significance of nonpoint source nitrogen pollution, the substantial denitrification potential of urban riparian soils should be utilized to reduce nitrogen pollution using proper engineering measures that would collect the polluted urban rainfall runoff and make it flow through the riparian zones.     

An Analysis of Michigan and California CO Remote Sensing Measurements

Abstract

Remote sensing measurements of CO emissions from on-road vehicles were made in California in 1991 and in Michigan in 1992. It was determined that both fleets had a small linear increase in the high emitter frequency (vehicles emitting more than 4% CO) as a function of vehicle age for 1986 and newer model vehicles. Although high emitting vehicles were only a small minority of the fleet, they had a dominant impact on the mean CO and total CO emitted by the fleet. In Michigan, the highest emitting 5% of passenger cars generated 45% of the CO from cars. In California, the highest emitting 5% of passenger cars generated 38% of the CO from cars. There was a high correlation between the mean CO emitted by each model year of vehicle and the frequency of high emitting vehicles within the model year for both the Michigan and California fleets. The frequency of high emitters within any model year had no obvious relation to that model year’s certification standards. The high emitter frequencies for vehicles less than nine years old were very similar for the California and Michigan fleets. An increase in the high emitter frequency in the ten-year-old and older Michigan passenger car fleet (relative to the California passenger car fleet), suggests, but does not conclusively demonstrate, that the rate of high emitters in Michigan and California is reduced by the inspection and maintenance (I/M) programs.