Spatiotemporal modelling of ozone distribution in the State of California

This paper is concerned with the spatiotemporal mapping of monthly 8-h average ozone (O₃) concentrations over California during a 15-years period. The basic methodology of our analysis is based on the spatiotemporal random field (S/TRF) theory. We use a S/TRF decomposition model with a dominant seasonal O₃ component that may change significantly from site to site. O₃ seasonal patterns are estimated and separated from stochastic fluctuations. By means of Bayesian Maximum Entropy (BME) analysis, physically meaningful and sufficiently detailed space–time maps of the seasonal O₃ patterns are generated across space and time. During the summer and winter months the seasonal O₃ concentration maps exhibit clear and progressively changing geographical patterns over time, suggesting the existence of relationships in accordance with the typical physiographic and climatologic features of California. BME mapping accuracy can be superior to that of other techniques commonly used by EPA; its framework can rigorously assimilate useful data sources that were previously unaccounted for; the generated maps offer valuable assessments of the spatiotemporal O₃ patterns that can be helpful in the identification of physical mechanisms and their interrelations, the design of human exposure and population health models, and in risk assessment. As they focus on the seasonal patterns, the maps are not contingent on short-time and locally prevalent weather conditions, which are of no interest in a global and non-forecasting framework. Moreover, the maps offer valuable insight about the space–time O₃ concentration patterns and are, thus, helpful for disentangling the influence of explanatory factors or even for identifying some influential ones that could have been otherwise overlooked.     

Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.     

Quantifying road dust resuspension in urban environment by Multilinear Engine: A comparison with PMF2

Atmospheric PM pollution from traffic comprises not only direct emissions but also non-exhaust emissions because resuspension of road dust that can produce high human exposure to heavy metals, metalloids, and mineral matter. A key task for establishing mitigation or preventive measures is estimating the contribution of road dust resuspension to the atmospheric PM mixture. Several source apportionment studies, applying receptor modeling at urban background sites, have shown the difficulty in identifying a road dust source separately from other mineral sources or vehicular exhausts. The Multilinear Engine (ME-2) is a computer program that can solve the Positive Matrix Factorization (PMF) problem. ME-2 uses a programming language permitting the solution to be guided toward some possible targets that can be derived from a priori knowledge of sources (chemical profile, ratios, etc.). This feature makes it especially suitable for source apportionment studies where partial knowledge of the sources is available.In the present study ME-2 was applied to data from an urban background site of Barcelona (Spain) to quantify the contribution of road dust resuspension to PM₁₀ and PM_2.5 concentrations. Given that recently the emission profile of local resuspended road dust was obtained (Amato, F., Pandolfi, M., Viana, M., Querol, X., Alastuey, A., Moreno, T., 2009. Spatial and chemical patterns of PM₁₀ in road dust deposited in urban environment. Atmospheric Environment 43 (9), 1650–1659), such a priori information was introduced in the model as auxiliary terms of the object function to be minimized by the implementation of the so-called “pulling equations”.ME-2 permitted to enhance the basic PMF solution (obtained by PMF2) identifying, beside the seven sources of PMF2, the road dust source which accounted for 6.9 μg m^?3 (17%) in PM₁₀, 2.2 μg m^?3 (8%) of PM_2.5 and 0.3 μg m^?3 (2%) of PM₁. This reveals that resuspension was responsible of the 37%, 15% and 3% of total traffic emissions respectively in PM₁₀, PM_2.5 and PM₁. Therefore the overall traffic contribution resulted in 18 μg m^?3 (46%) in PM₁₀, 14 μg m^?3 (51%) in PM_2.5 and 8 μg m^?3 (48%) in PM₁. In PMF2 this mass explained by road dust resuspension was redistributed among the rest of sources, increasing mostly the mineral, secondary nitrate and aged sea salt contributions.     

Analysis of cloud and precipitation chemistry at Whiteface Mountain,NY

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

Assessment of source apportionment by Positive Matrix Factorization analysis on fine and coarse urban aerosol size fractions

This study was conducted in order to investigate the differences observed in source profiles in the urban environment, when chemical composition parameters from different aerosol size fractions are subjected to factor analysis. Source apportionment was performed in an urban area where representative types of emission sources are present. PM₁₀ and PM₂ samples were collected within the Athens Metropolitan area and analysed for trace elements, inorganic ions and black carbon. Analysis by two-way and three-way Positive Matrix Factorization was performed, in order to resolve sources from data obtained for the fine and coarse aerosol fractions. A difference was observed: seven factors describe the best solution in PMF3 while six factors in PMF2. Six factors derived from PMF3 analysis correspond to those described by the PMF2 solution for the fine and coarse particles separately. These sources were attributed to road dust, marine aerosol, soil, motor vehicles, biomass burning, and oil combustion. The additional source resolved by PMF3 was attributed to a different type of road dust. Combustion sources (oil combustion and biomass burning) were correctly attributed by PMF3 solely to the fine fraction and the soil source to the coarse fraction. However, a motor vehicle's contribution to the coarse fraction was found only by three-way PMF. When PMF2 was employed in PM₁₀ concentrations the optimum solution included six factors. Four source profiles corresponded to the previously identified as vehicles, road dust, biomass burning and marine aerosol, while two could not be clearly identified. Source apportionment by PMF2 analysis based solely on PM₁₀ aerosol composition data, yielded unclear results, compared to results from PMF2 and PMF3 analyses on fine and coarse aerosol composition data.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

Converging hydrostatic and hydromechanic concepts of preferential flow definitions

The boundary between preferential flow and Richards-type flow is a priori set at a volumetric soil water content θ at which soil water diffusivity D (θ) = η (= 10^− 6 m² s^− 1), where η is the kinematic viscosity. First we estimated with a hydrostatic approach from soil water retention curves the boundary, θ^K, between the structural pore domain, in which preferential flow occurs, and the matrix pore domain, in which Richards-type flow occurs. We then compared θ^K with θ that was derived from the respective soil hydrological property functions of same soil sample. Second, from in situ investigations we determined 96 values of θ^G as the terminal soil water contents that established themselves when the corresponding water-content waves of preferential flow have practically ceased. We compared the frequency distribution of θ^G with the one of θ that was calculated from the respective soil hydrological property functions of 32 soil samples that were determined with pressure plate apparatuses in the laboratory. There is support of the notion that θ^K ≈ θ^G ≈ θ, thus indicating the potential of θ to explain more generally what constitutes preferential flow. However, the support is assessed as working hypothesis on which to base further research rather than a procedure to a clear-cut identification of preferential flow and associated flow paths.