Temporal variations in atmospheric CO2 concentrations in Kuwait City,Kuwait with comparisons to Phoenix,Arizona, USA

Hourly atmospheric carbon dioxide (CO2) concentration measurements are available from 1996 to present for a suburban site within the growing metropolitan area of Kuwait City. Analyses of this record reveal (a) an annual cycle with highest values in February and lowest values in September reflecting the growth and decay of vegetation in the Northern Hemisphere as well as fluctuations in motor traffic, (b) a weekly cycle with highest values during the weekdays and lowest values during weekends, and (c) a diurnal cycle with highest values after sunset when the local atmosphere becomes more stable following vehicular emission of CO2 throughout the day and lowest values in late afternoon following several hours of relatively unstable conditions. During the daytime, CO2 concentrations are related to wind direction, with westerly winds (coming from the desert) promoting lowest CO2 concentrations. At night, lowest CO2 levels are associated with higher wind speeds and winds from the north. The findings from the Kuwait City area, particularly when contrasted with the situation in Phoenix, further our understanding of the dynamics of CO2 levels in urban environments.     

Climatology and forecast modeling of ambient carbon monoxide in Phoenix, Arizona

We perform a climatology of factors influencing ambient carbon monoxide (CO), in which we examine the relationships between meteorology, traffic patterns, and CO at seasonal, weekly, and diurnal time scales in Phoenix, Arizona. From this analysis we identify a range of potentially important variables for statistical CO modeling. Using stepwise multivariate regression, we create a suite of models for hourly and 8-h ambient CO designed for daily operational forecasting purposes. The resulting models include variables and interaction terms related to anticipated nocturnal atmospheric stability as well as antecedent and climatological CO behavior. The models are evaluated using a range of error statistics and skill measures. The most successful approach employs a two-stage modeling strategy in which an initial prediction is made that may, depending on the forecast value, be followed by a second prediction that improves upon the first. The best models provide accurate daily forecasts of CO, with explained variances approaching 0.9 and errors under 1 ppm.     

Ammonium Nitrate,Nitric Acid,and Ammonia Equilibrium in Wintertime Phoenix,Arizona

A secondary aerosol equilibrium model, SEQUILIB, is applied to evaluate the effects of emissions reductions from precursor species on ambient concentrations during the winter in Phoenix, Arizona. The model partitions total nitrate and total ammonia to gas-phase nitric acid and ammonia and to particle-phase ammonium nitrate. Agreement between these partitions and ambient measures of these species was found to be satisfactory. Equilibrium isopleths were generated for various ammonium nitrate concentrations corresponding to high and low humidity periods which occurred during sampling. These diagrams show that ammonia is so abundant in Phoenix that massive reductions in its ambient concentrations would be needed before significant reductions in particulate ammonium nitrate would be observed. When total nitrate is reduced by reductions in its nitrogen oxides precursor, proportional reductions in particulate nitrate are expected. Many of the complex reactions in SEQUILIB do not apply to Phoenix, and its ability to reproduce ambient data in this study does not guarantee that it will be as effective in areas with more complex chemistry. Nevertheless, the nitrate chemistry in SEQUILIB appears to be sound, and it is a useful model for addressing the difficult apportionment of secondary aerosol to its precursors.     

Threshold dependence of mortality effects for fine and coarse particles in Phoenix, Arizona

Daily data for fine (< 2.5 microns) and coarse (2.5-10 microns) particles are available for 1995-1997 from the U.S. Environmental Protection Agency (EPA) research monitor in Phoenix, AZ. Mortality effects on the 65 and over population were studied for both the city of Phoenix and for a region of about 50 mi around Phoenix. Coarse particles in Phoenix are believed to be natural in origin and spatially homogeneous, whereas fine particles are primarily vehicular in origin and concentrated in the city itself. For this reason, it is natural to focus on city mortality data when considering fine particles, and on region mortality data when considering coarse particles, and most of the results reported here correspond to those assignments. After allowing for seasonality and long-term trend through a nonlinear (B-spline) trend curve, and also for meteorological effects based on temperature and specific humidity, a regression of mortality was performed on PM using several different measures for PM. Based on a linear PM effect, we found a statistically significant coefficient for coarse particles, but not for fine particles, contrary to what is widely believed about the effects of coarse and fine particles. An analysis of nonlinear pollution-mortality relationships, however, suggests that the true picture is more complicated than that. For coarse particles, the evidence for any nonlinear or threshold-based effect is slight. For fine particles, we found evidence of a threshold, most likely with values in the range of 20-25 micrograms/m3. We also found some evidence of interactions of the PM effects with season and year. The main effect here is an apparent seasonal interaction in the coarse PM effect. An attempt was made to explain this in terms of seasonal variation in the chemical composition of PM, but this led to another counterintuitive result: the PM effect is highest in spring and summer, when the anthropogenic concentration of coarse PM is lowest as determined by a principal components analysis. There was no evidence of confounding between the fine and coarse PM effects. Although these results are based on one city and should be considered tentative until replicated in other studies, they suggest that the prevailing focus on fine rather than coarse particles may be an oversimplification. The study also shows that consideration of nonlinear effects can lead to real changes of interpretation and raises the possibility of seasonal effects associated with the chemical composition of PM.     

Threshold Dependence of Mortality Effects for Fine and Coarse Particles in Phoenix,Arizona

ABSTRACT

Daily data for fine (<2.5 um) and coarse (2.5-10 um) particles are available for 1995-1997 from the U.S. Environmental Protection Agency (EPA) research monitor in Phoenix, AZ. Mortality effects on the 65 and over population were studied for both the city of Phoenix and for a region of about 50 mi around Phoenix. Coarse particles in Phoenix are believed to be natural in origin and spatially homogeneous, whereas fine particles are primarily vehicular in origin and concentrated in the city itself. For this reason, it is natural to focus on city mortality data when considering fine particles, and on region mortality data when considering coarse particles, and most of the results reported here correspond to those assignments.

After allowing for seasonality and long-term trend through a nonlinear (B-spline) trend curve, and also for meteorological effects based on temperature and specific humidity, a regression of mortality was performed on PM using several different measures for PM. Based on a linear PM effect, we found a statistically significant coefficient for coarse particles, but not for fine particles, contrary to what is widely believed about the effects of coarse and fine particles. An analysis of nonlinear pollution-mortality relationships, however, suggests that the true picture is more complicated than that. For coarse particles, the evidence for any nonlinear or threshold-based effect is slight. For fine particles, we found evidence of a threshold, most likely with values in the range of 20-25 ug/m³. We also found some evidence of interactions of the PM effects with season and year.

The main effect here is an apparent seasonal interaction in the coarse PM effect. An attempt was made to explain this in terms of seasonal variation in the chemical composition of PM, but this led to another counterintuitive result: the PM effect is highest in spring and summer, when the anthropogenic concentration of coarse PM is lowest as determined by a principal components analysis. There was no evidence of confounding between the fine and coarse PM effects. Although these results are based on one city and should be considered tentative until replicated in other studies, they suggest that the prevailing focus on fine rather than coarse particles may be an oversimplification. The study also shows that consideration of nonlinear effects can lead to real changes of interpretation and raises the possibility of seasonal effects associated with the chemical composition of PM.     

Remote sampling of a CO2 point source in an urban setting

High frequency CO₂ and wind speed measurements were used to examine the urban baseline eddy covariance CO₂ flux and analyse the CO₂ rich plume from a local power station. A reliable relationship between high frequency CO₂ maxima and the rate of CO₂ emission at the power station was established. This relationship was shown to be highly dependant on wind speed. The ensemble mean plume was found to be Gaussian in horizontal profile with a width dependant on wind speed. The relationship between peak CO₂ mixing ratio and averaging time was shown to be a simple power law with a time exponent of approximately 0.5. The large, short pulses in CO₂ mixing ratio in the power plant plume were found to have an approximately Lorentzian shape. These pulses generated negative vertical eddy flux measurements so data from the plume sector were necessarily excluded from the flux baseline results. The plume-excluded flux had a similar magnitude and variability to those reported in other urban CO₂ flux studies despite this site not being ideal due to the proximity of roughness elements to the measurement point.     

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.     

Elements Influencing Cost Allocation in the Pinal Creek Aquifer,Arizona, USA: An Introduction and Synopsis of Findings

This article provides context for the ensuing three-part study published in this volume that describes quantitative allocation of mass metal loading to the 20 km groundwater plume in the Pinal Creek alluvial aquifer. The plume resulted from >75 years of copper ore leaching by ferric sulfate and sulfuric acid in the Globe-Miami mining district, Arizona. Geochemical fingerprinting, followed by spatial and temporal analysis of Pinal Creek monitoring well data, identified three distinct source areas and plumes. Each exhibited a unique chlorine-copper-iron chemical signature that resulted from differences in process geochemistry, ore mineralogy, and solution handling. As the acid plume advanced, carbonate buffering capacity was consumed, with concomitant precipitation of metal oxyhydroxides that evolved into acid-bearing aluminum and iron cements. Column experiments, geochemical modeling, and empirical data indicate that dissolution of the residual acidic precipitates will result in asymptotic reductions in metal concentrations, which will affect response costs for up to 140 years after initiation of remedial pumping in the late 1980s. Finally, metal loading to the alluvial aquifer was quantified for each source area using Darcy's Law or flow data combined with the sum of aluminum, copper, iron, manganese, and zinc, which constitute >99% of the total metal mass. Based on this analysis, to date Webster Gulch contributed 94% of the loading, Upper Bloody Tanks Wash contributed 5%, and the Miami Unit contributed 1%. A sensitivity analysis that varied all parameters in the loading calculation by ±20% resulted in only small differences in allocation (±1%) because the large mass released from Webster Gulch (618 kt of metal) dominates the overall allocation.     

Chemical speciation of PM2.5 and PM10 in south Phoenix, AZ, USA

Phoenix, AZ, experiences high particulate matter (PM) episodes, especially in the wintertime. The spatial variation of the PM concentrations and resulting differences in exposure is of particular concern. In this study, PM2.s (PM with aerodynamic diameter <2.5 microm) and PM10 (PM with aerodynamic diameter <10 microm) samples were collected simultaneously from the east and west sides of South Phoenix and at a control site in Tempe and analyzed for trace elements and bulk elemental and organic carbon. Measurements showed that although PM2.5 concentrations had similar trends in temporal scale across all sites, concentrations of PM10 did not. The difference in PM10 concentrations and fluctuation across the three sites suggest effects of a local soil source as evidenced by high concentrations of Al, Ca, and Fe in PM10. K and anthropogenic elements (e.g., Cu, Pb, and Zn) in PM2.5 samples on January 1 were strikingly high, suggesting the influence of New Year's fireworks. Concentrations of toxic elements (e.g., Pb) in the study presented here are not different from similar studies in other U.S. cities. Application of principal component analysis indicated two broad categories of emission sources--soil and combustion--together accounting for 80 and 90% of variance, respectively, in PM2.5 and PM10. The soil and combustion components explained approximately 60 and 30% of the variance in PM10, respectively, whereas combustion sources dominated PM2.5 (>50% variance). Many elements associated with anthropogenic sources were highly enriched, with enrichment factors in PM2.5 an order of magnitude higher than in PM10 relative to surface soil composition in the study area.     

An Evaluation of CO2, Measurements as an Indicator of Air Pollution

Measurements of ambient carbon dioxide (CO₂), made at the Continuous Air Monitoring Program station in downtown Cincinnati, Ohio, and at a rural location near Cincinnati are presented and evaluated to determine the significance of CO₂ data in urban air quality monitoring programs. Through analysis of rural CO₂ data and evaluation of combustion-sources by means of a diffusion model, it is demonstrated that the variation of urban CO₂ concentrations around the prevailing atmosphere background level results from combustion-and noncombustion {natural) sources. The concentration from natural sources can be substantial and in fact override the combustion sources. Because it is not yet practical to predict the contribution of natural sources to urban CO₂ concentrations, data obtained for-this gas have only limited utility as an index of air quality. Significant statistical relationships between CO₂ data and air quality measurements for summer months are shown to result from similar meteorological effects rather than similar sources. A seasonal and spatial variation of ih-ese relationships is postulated and subsequently demonstrated by analysis of CO₂ and air quality measurements from New Orleans, Louisiana, and SU Louis, Missouri.     

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.     

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.     

The environmental Kuznets curve and CO2 emissions in the USA

Environmental Science and Pollution Research - In this paper, we analyze the existence of the environmental Kuznets curve as reported by Kuznets (Am Econ Rev 5:1–28, 1955) by using the...     

Beryllium-7 measurements in the Houston and Phoenix urban areas: an estimation of upper atmospheric ozone contributions

Natural radionuclides have been proposed as a means of assessing the transport of ozone (O3) and aerosols in the troposphere. Beryllium-7 (7Be) is produced in the upper troposphere and lower stratosphere by the interaction of cosmogenic particles with atmospheric nitrogen and oxygen. 7Be has a 53.29-day half-life (478 keV gamma) and is known to attach to fine particles in the atmosphere once it is formed. It has been suggested that O3 from aloft can be transported into rural and urban regions during stratospheric-tropospheric folding events leading to increased background levels of O3 at the surface. 7Be can be used as a tracer of upper atmospheric air parcels and the O3 associated with them. Aerosol samples with a 2.5-microm cutoff were collected during 12-hr cycles (day/night) for a 30-day period at Deer Park, TX, near Houston, in August-September of 2000, and at Waddell, AZ, near Phoenix, in June-July of 2001. A comparison of 7Be levels with 12-hr O3 averages and maxima shows little correlation. Comparison of nighttime and daytime O3 levels indicate that during the day, when mixing is anticipated to be higher, the correlation of 7Be with O3 in Houston is approximately twice that observed at night. This is consistent with mixing and with the anticipated loss of O3 by reaction with nitric oxide (NO) and dry deposition. At best, 30% of the O3 variance can be explained by the correlation with 7Be for Houston, less than that for Phoenix where no significant correlation was seen. This result is consistent with the intercept values obtained for 7Be correlations with either O3 24-hr averages or O3 12-hr maxima and is also in the range of the low O3 levels (25 ppb) observed at Deer Park during a tropical storm event where the O3 is attributable primarily to background air masses. That is, maximum background O3 level contributions from stratospheric sources aloft are estimated to be in the range of 15-30 ppb in the Houston, TX, and Phoenix, AZ, area, and levels above these are because of local tropospheric photochemical production.     

Spatial distribution of submicrometre particles and CO in an urban microscale environment

Traffic is the major source of submicrometre particles in an urban environment but the spatial distribution of particles around an urban site has not been measured. The aim of this paper was to investigate the relationship of CO and particles at a busy central urban location surrounded by buildings. This study measured the concentration and size distribution of submicrometre particles at a fixed location and concentrations of submicrometre particles and CO at 10 locations around a square site in the Brisbane Central Business District (CBD). Changes in concentration were assessed as a function of traffic volume and wind direction and speed.Fixed site measurements of submicrometre particle number concentration varied between 7.9×10² (±40) and 2.6×10⁵ (±1.3×10⁴) cm⁻³ and showed a strong positive correlation with traffic flow rate, confirming that vehicles were the major source of urban submicrometre particles. The particle concentration decreased exponentially with increasing wind speed.Average particle concentrations around the site ranged between 19.7×10³ (±8.2×10³) and 32.5×10³ (±16.6×10³) cm⁻³. Analysis of the particle measurements around the site showed that time and location both had a statistically significant effect on mean particle concentration around the square over the period of the study.Around the site, CO concentration was relatively constant (within instrument error), ranging between 2.2 (±1.9) and 4.5 (±3.0) ppm. Again both time and location had a statistically significant effect on CO concentration during the measurement period. However, CO concentration was not significantly correlated to particle number concentration around the site and examination of between-site comparisons with the two pollutants showing different spatial and temporal trends.The significant difference in the concentration trends between the locations around the square indicates that there is considerable inhomogeneity in the particle concentration around the site. One implication of this is that careful thought must be given to locations of air intakes of air-conditioning systems in urban environments.     

Field observations of regional and urban impacts on NO2, ozone,UVB, and nitrate radical production rates in the Phoenix air basin

In the May and June of 1998, field measurements were taken at a site near the Usery Pass Recreation Area, ∼27 miles from the downtown Phoenix area, overlooking Phoenix and Mesa, Arizona. This site was selected to examine the impacts of the Phoenix urban plume on the Usery Pass Recreation Area and surrounding regions. Data were obtained for ultraviolet-B (UVB) radiation, nitrogen dioxide (NO₂), peroxyacetyl nitrate (PAN), ozone (O₃), and carbon monoxide (CO). Nocturnal plumes of NO₂ (in tens of ppb), observed near midnight, were correlated with CO and anti-correlated with O₃. This behavior was consistent with the titration of locally generated NO by boundary layer O₃ to form the nighttime NO₂ plumes that were subsequently transported into the Usery Pass Recreation area. Nitrate radical (NO₃) production rates were calculated to be very high on the edges of these nocturnal plumes. Examination of O₃ and PAN data also indicates that Phoenix is being affected by long-range transport of pollutants from the Los Angeles to San Diego areas. A regional smoke episode was observed in May, accompanied by a decrease in UVB of factor of two and a decrease in O₃ and an increase in methyl chloride. Low level back trajectories and chemical evidence confirm that the smoke event originated in northern Mexico and that the reduced O₃ levels observed at Usery Pass could be partially due to reduced photolysis rates caused by carbonaceous soot aerosols transported in the smoke plume. The results are discussed with regard to potential effects of local pollution transport from the Phoenix air basin as well as an assessment of the contributions from long-range transport of pollutants to the background levels in the Phoenix-Usery Pass area.     

SO2 dosages in an urban area

Five winter-semesters of data of SO₂ concentration at three sites in the urban area of Milan were analyzed to generate statistics of dosage which describe the dosage distributions, the temporal structure, the dependence upon concentration thresholds and the six-month-average concentration. By considering the joint distributions of dosages and their durations it is found that the basic ambiguity between dosages and their durations can be resolved since for each dosage value only a limited range of durations is observed. It is also found that the six-month-average concentration has a dominating role on the statistics of dosages; previous works have reported a similar influence on concentration statistics, durations and extreme values. For most of the statistics it has been possible to develop simple and accurate empirical models.     

An aerosol flow tube study of the interaction of N2O5 with calcite, Arizona dust and quartz

The interaction of N₂O₅ with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO₃) and quartz (SiO₂) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10⁻³ for CaCO₃, (8.6 ± 0.6) × 10⁻³ for Quartz and (9.8 ± 1.0) × 10⁻³ for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.     

An Urban Airshed Model for Predicting Carbon Monoxide Concentrations in Tucson,Arizona

ABSTRACT

The Electric Power Research Institute (EPRI) is conducting research to investigate mercury removal in utility flue gas using sorbents. Bench-scale and pilot-scale tests have been conducted to determine the abilities of different sor-bents to remove mercury in simulated and actual flue gas streams. Bench-scale tests have investigated the effects of various sorbent and flue gas parameters on sorbent performance. These data are being used to develop a theoretical model for predicting mercury removal by sorbents at different conditions. This paper describes the results of parametric bench-scale tests investigating the removal of mercuric chloride and elemental mercury by activated carbon.

Results obtained to date indicate that the adsorption capacity of a given sorbent is dependent on many factors, including the type of mercury being adsorbed, flue gas composition, and adsorption temperature. These data provide insight into potential mercury adsorption mechanisms and suggest that the removal of mercury involves both physical and chemical mechanisms. Understanding these effects is important since the performance of a given sorbent could vary significantly from site to site depending on the coal- or gas-matrix composition.