Nonparametric functional data estimation applied to ozone data: prediction and extreme value analysis

The study of extreme values and prediction of ozone data is an important topic of research when dealing with environmental problems. Classical extreme value theory is usually used in air-pollution studies. It consists in fitting a parametric generalised extreme value (GEV) distribution to a data set of extreme values, and using the estimated distribution to compute return levels and other quantities of interest. Here, we propose to estimate these values using nonparametric functional data methods. Functional data analysis is a relatively new statistical methodology that generally deals with data consisting of curves or multi-dimensional variables. In this paper, we use this technique, jointly with nonparametric curve estimation, to provide alternatives to the usual parametric statistical tools. The nonparametric estimators are applied to real samples of maximum ozone values obtained from several monitoring stations belonging to the Automatic Urban and Rural Network (AURN) in the UK. The results show that nonparametric estimators work satisfactorily, outperforming the behaviour of classical parametric estimators. Functional data analysis is also used to predict stratospheric ozone concentrations. We show an application, using the data set of mean monthly ozone concentrations in Arosa, Switzerland, and the results are compared with those obtained by classical time series (ARIMA) analysis.     

The economic benefits of fulfilling the World Health Organization’s limits for particulates: A case study in Algeciras Bay (Spain)

Algeciras Bay is an important industrial and port zone in the south of Spain whose pollution by particulate matter surpasses the threshold levels recommended by the World Health Organization (WHO) in its 2005 Guide on Air Quality. This study analyses the mortality avoided and the economic benefit which would be derived from a reduction of the pollution of PM2.5 and PM10 to the levels recommended by the WHO in Algeciras Bay in the period 2005-2015. The analysis carried out shows that the industrial zones, such as Los Barrios and San Roque, are those which have greater levels of pollution and in which the relative risk is greater. The calculations for Algeciras Bay between 2000 and 2015 show 182 deaths which would be avoided if the particulate matter pollution were reduced to the levels recommended by the WHO. Likewise, the economic valuation which this impact has on health is carried out through two concepts: the cost of illness and the Value of Statistical Life (VSL). The result shows that the economic benefit that would come out with the cost of illness valuation is 5,329,110€ and from the VSL is 414,787,113€.

Implications: PM_2.5 has a greater concentration in industrial localities and is linked to the industrial activity. When the particulate matter pollution is reduced to the levels recommended by the WHO in an industrialised area such as Algeciras (Spain), 182 deaths which would be avoided. The result shows that the economic benefit that would come out with the cost of illness valuation is 5,329,110€ and from the value of statistical life is 414,787,113€.     

Occurrence of alkylphenol polyethoxylates in the St. Lawrence River and their bioconcentration by mussels (Elliptio complanata)

A study was conducted in 1999 to determine the occurrence of alkylphenol polyethoxylates in the St. Lawrence River and their bioconcentration by mussels (Elliptio complanata). Concentrations of selected contaminants were measured in surface water, municipal effluent, sediments and mussels. Analyses were performed on 4-tert-octylphenol (4-t-OP), 4-n-nonylphenol (4-n-NP), nonylphenol polyethoxylates (NP(1-16)EO), nonylphenol-mono and di-ethoxycarboxylic acids (NP(1)EC and NP(2)EC), and octylphenol-mono and di-ethoxycarboxylic acids (OP(1)EC and OP(2)EC). Mussels (Elliptio complanata) taken from a reference lake were placed in cages and submerged for 62 days at two sites in the St. Lawrence River, 1.5 km upstream and 5 km downstream of the outfall of a municipal wastewater treatment plant. The results showed that many of the target chemicals were present in all matrices studied: in water, at ppt and ppb levels, and reaching ppm levels in sediments and mussels. Concentrations of these contaminants were higher in matrices sampled at the downstream site than in those drawn at the site upstream of the Montreal effluent outfall, especially in sediments. Likewise, the slight, but not significant, bioconcentration of certain alkylphenol polyethoxylates (AP(n)EO) in the mussels was more noticeable at the downstream site than at the upstream site.     

Rodent sperm analysis in field-based ecological risk assessment: pilot study at Ravenna army ammunition plant,Ravenna, Ohio

Ecological risk assessment (ERA) guidance recommends that field-truthing efforts proceed when modeled hazard quotients (HQs) suggest that toxicological effects are occurring to site receptors. To date, no field methods have been proposed by the regulatory community that can lead to definitive determinations of acceptable or unacceptable risk for birds and mammals, the two terrestrial classes of receptors that are commonly assessed using the HQ method. This paper describes rodent sperm analysis (RSA) as a viable method to be applied in the field at sites with historical contamination. RSA is capable of detecting biological differences that bear on reproduction, a highly regarded toxicological endpoint of concern in USEPA Superfund-type ERAs. The results of RSA's first application at a study site are reported and discussed. The paper also provides the rationale for RSA's efficacy in the context of Superfund and other environmental cleanup programs, where limited time and money are available to determine and evaluate the field condition.     

Dehalogenation Potential of Municipal Waste Incineration Fly Ash

BACKGROUND, AIMS AND SCOPE: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novo synthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. RESULTS AND DISCUSSION: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300 degrees C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene --> pentachlorobenzene --> 1,2,3,5-tetrachlorobenzene --> 1,3,5-trichlorobenzene --> 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2 as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer CONCLUSIONS: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3 to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. RECOMMENDATIONS AND OUTLOOK: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study.     

A microcosm approach to assessing the effects of earthworm inoculation and oat cover cropping on CO2 fluxes and biological properties in an amended semiarid soil

We designed a microcosm experiment to assess the influence of inoculation with Eisenia foetida earthworms and the establishment of an Avena sativa cover crop on biological (enzyme activities and labile carbon fractions) soil quality indicators in a soil treated with a composted organic residue, and to determine the contribution of these treatments to carbon dioxide emissions from the soil to the atmosphere of the microcosm. The microcosms were incubated for 53 days under 28 °C/18 °C day/night temperatures. The addition of earthworms and the planting of A. sativa increased dehydrogenase activity of compost amended soil by about 44% after 23 days of incubation. The metabolic potential, calculated as the ratio dehydrogenase activity/water soluble C, was higher in the compost amended soil planted with A. sativa. The highest total amount of CO₂–C evolved occurred in the soil treated with composted residue and earthworms (about 40% of the total amount of CO₂ evolved came from earthworm activity). The planting of A. sativa increased the decomposition rate constant of organic matter in the amended soil but decreased the potentially mineralizable C pool. In conclusion, the establishment of an A. sativa cover crop and the addition of E. foetida to a degraded agricultural soil treated with composted residue were effective treatments for improving the biological and biochemical quality and the metabolic potential of the soil.     

Manganese toxicity thresholds for restoration grass species

Manganese toxicity thresholds for restoration plants have not been established. As a result, ecological risk assessments rely on toxicity thresholds for agronomic species, which may differ from those of restoration species. Our objective was to provide Mn toxicity thresholds for grasses commonly used in restoration. We used a greenhouse screening study where seedlings of redtop, slender wheatgrass, tufted hairgrass, big bluegrass, basin wildrye, and common wheat were grown in sand culture and exposed to increasing concentrations of Mn. The LC50, EC50-plant, EC50-shoot, EC50-root, PT50-shoot, and the PT50-root were then determined. Phytotoxicity thresholds and effective concentrations for the restoration species were generally higher than values reported for agronomic species. Our estimates of PT50-shoot for the five restoration grasses range from 41,528 to 120,082 mg Mn kg(-1). Measures of EC50-plant for these restoration grasses ranged from 877 to >6,000 mg Mn l(-1). These thresholds might be more useful for risk assessors than those based on crop plants that are widely used.