Pollution Control Policies and Natural Resource Dynamics: A Theoretical Analysis

Policies for the management of natural resources and the resources themselves interact to form complex systems. In this paper, we present a highly simplified model that can be used to study the general features of those systems. The model has three state variables, the abundance of the resource, environmental pollution, and the capital devoted to pollution control. We analyse it graphically using the singular perturbation approach. Two modes of behavior are possible; stationary and cyclic. When the abundance of the resources varies cyclically, the length of the period of resource scarcity depends on population size, economic activity, pollution per unit of output, and policy constraints. We distinguish between two classes of policies, one in which decision-makers base their investments in pollution control capital on the abundance of the resource, and another in which those decisions depend on the amount of pollution. We show that policies based on the observation of pollution are safer than those based on resource abundance, because in the latter case, small changes in policy variables can lead much more easily to a collapse of the resource. Increases in population size, even when accompanied by an equiproportional increase in the pollution control budget can lead to a change from stationary to cyclic behavior, especially where policies are based on resource abundance.     

Organochlorine pesticide air-water exchange and bioconcentration in krill in the Ross Sea

Mean hexachlorobenzene (HCB) and hexachlorocyclohexane (HCH) concentrations, measured in seawater and air samples, confirmed the decline in levels of these compounds in Antarctic air and water. However, low α/γ-HCH ratios in air at the beginning of the sampling period suggest a predominance of fresh lindane entering the Antarctic atmosphere during the Austral spring probably due to current use in the Southern Hemisphere. Water-air fugacity ratios demonstrate the potential for HCH gas deposition to coastal Antarctic seas, while the water-air fugacity ratios for HCB imply that volatilization does not account for the observed decrease of HCB in surface seawater. HCH concentrations found in krill samples were correlated with seawater concentrations indicative of bioconcentration of HCHs from seawater.     

Intermediate distributions and primary yields of phenolic products in nitrobenzene degradation by Fenton's reagent

Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.     

Cost-effective experimental design to support modeling of concentration-response functions

Modeling concentration-response function became extremely popular in ecotoxicology during the last decade. Indeed, modeling allows determining the total response pattern of a given substance. However, reliable modeling is consuming in term of data, which is in contradiction with the current trend in ecotoxicology, which aims to reduce, for cost and ethical reasons, the number of data produced during an experiment. It is therefore crucial to determine experimental design in a cost-effective manner. In this paper, we propose to use the theory of locally D-optimal designs to determine the set of concentrations to be tested so that the parameters of the concentration-response function can be estimated with high precision. We illustrated this approach by determining the locally D-optimal designs to estimate the toxicity of the herbicide dinoseb on daphnids and algae. The results show that the number of concentrations to be tested is often equal to the number of parameters and often related to the their meaning, i.e. they are located close to the parameters. Furthermore, the results show that the locally D-optimal design often has the minimal number of support points and is not much sensitive to small changes in nominal values of the parameters. In order to reduce the experimental cost and the use of test organisms, especially in case of long-term studies, reliable nominal values may therefore be fixed based on prior knowledge and literature research instead of on preliminary experiments.     

Seasonal, spatial and inter-annual variations of trace metals in mussels from the Adriatic sea: a regional gradient for arsenic and implications for monitoring the impact of off-shore activities

Mussels are widely used as bioindicator organisms for monitoring chemical pollutants including trace metals. These elements are natural constituents in the marine environment and their basal concentrations in the organisms can be influenced by several environmental and biological factors. The aim of this work was to extend our knowledge on the natural variability of trace metals in mussels tissues, focusing on seasonal and inter-annual fluctuations in a coastal reference site of the Adriatic coast (Portonovo); a total of 39 samplings were performed during 5 years, providing an extended data-set for tissue levels of As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn. Concentrations of trace metals in mussels tissues revealed marked seasonal fluctuations with significant differences between various sampling years. Such fluctuations appeared mostly related to phytoplanctonic blooms and especially to reproductive cycle which exhibited a certain inter-annual shift of the gametogenesis period. Lower concentrations were measured in summer months for the majority of elements while a different seasonal cycle was observed for arsenic, not correlated with gonadic development, neither with other elements. Chemical speciation of arsenic was characterized to distinguish compounds of natural origin from those potentially reflecting an anthropogenic impact. Arsenobetaine and arsenocholine were always the predominant forms (up to 85% of total arsenic), while a significant increase of dimethylarsine and trimethylarsine oxide in spring (24% of total arsenic) might reflect the effect of phytoplanctonic bloom on both geochemistry and trophic transfer of this element. A significant inter-annual variability was observed for both the seasonal cycle and the range of values measured for all the elements, with particularly marked differences for arsenic, ranging from less than 10 to more than 40 microg/g in summer periods of different years. Data obtained on reference mussels were used to assess the impact of 41 off-shore platforms distributed along 5 nautical districts in the Northern and Central Adriatic Sea. Organisms sampled on these structures from 2001 to 2005 exhibited a certain enrichment of cadmium and zinc, probably associated to the use of anodic electrodes. Marked annual and geographical variations were measured for concentrations of arsenic in mussels of different platforms. However, the comparison with results of Portonovo, allowed to exclude the anthropogenic impact of exploitation activities and revealed a natural regional gradient of arsenic levels in mussels tissues associated to the changing influence of the Po river runoff on seawater salinity. In particular the higher concentrations measured in organisms sampled from platforms in the Central compared to Northern Adriatic confirmed a significant relationship between salinity and arsenic bioaccumulation, consistent with a role of arsenobetaine as an acquired osmolyte for mussels. The overall results confirmed the importance of natural variability when assessing the potential impact of anthropogenic activities.     

Species-dependent chromium accumulation, lipid peroxidation, and glutathione levels in germinating kiwifruit pollen under Cr(III) and Cr(VI) stress

The accumulation of chromium by germinating kiwifruit pollen appears to be significantly affected by Cr species, Cr concentration and calcium availability. Cr(III) accumulation always occurred in a linear manner while Cr(VI) uptake followed a logarithmic model. In the absence of exogenous calcium, Cr(III) accumulation was much higher than that of Cr(VI). It was observed that, as the Cr(III) concentration increased, there was a significant decrease in the endogenous calcium content of pollen, ultimately leading to complete calcium depletion after 90 min of incubation at 150 microM Cr(III). This loss of calcium could be responsible for the strong inhibition of tube emergence and growth following exposure of pollen to Cr(III). Indeed, when exogenous calcium was added to the kiwifruit pollen culture medium, significant growth recovery and reduced Cr(III) uptake occurred; the opposite was true in Cr(VI)-treatments. A significant rise in lipid peroxide production occurs in the presence of both Cr species; the effect was more pronounced following Cr(VI) exposure. Finally, glutathione pool dynamics appears to be differentially affected by chromium species and concentrations. In conclusion, results of the present study have provided important information regarding the different activity profiles of Cr(III) and Cr(VI) in relation to kiwifruit pollen performance, and have also demonstrated differences in some biochemical responses of pollen to metal stress.     

A new hybrid system of QSAR models for predicting bioconcentration factors (BCF)

The aim was to develop a reliable and practical quantitative structure-activity relationship (QSAR) model validated by strict conditions for predicting bioconcentration factors (BCF). We built up several QSAR models starting from a large data set of 473 heterogeneous chemicals, based on multiple linear regression (MLR), radial basis function neural network (RBFNN) and support vector machine (SVM) methods. To improve the results, we also applied a hybrid model, which gave better prediction than single models. All models were statistically analysed using strict criteria, including an external test set. The outliers were also examined to understand better in which cases large errors were to be expected and to improve the predictive models. The models offer more robust tools for regulatory purposes, on the basis of the statistical results and the quality check on the input data.     

Hydrolytic degradation of azimsulfuron, a sulfonylurea herbicide

The chemical degradation of the herbicide azimsulfuron was investigated in aqueous solutions at different pH values. The hydrolysis rate, determined by HPLC analyses, was pH dependent and was much faster in acidic than in neutral or weakly basic conditions. The metabolites formed at different pH values were compared with standards when possible or isolated and identified using ESI-LC-MS/MS, (1)H NMR and (13)C NMR. The two main products of hydrolysis in mild acidic solution were identified as 2-amino-4,6-dimethoxy-pyrimidine and 2-methyl-4-(2-methyl-2H-tetrazol-5-yl)-2H-pyrazole-3-sulfonamide, both produced as a result of the sulfonylurea bridge cleavage. Under basic conditions, a new product, a substituted 2-pyrimidinamine, deriving from the contraction of the sulfonylurea bridge, was isolated and completely characterized for the first time.     

Why Should We Calculate Complex Indices of Ozone Exposure? Results from Mediterranean Background Sites

While moving towards a flux-based approach, exposure-based ozone metrics are still a practical measure for summarising ambient air quality. Ozone hourly concentrations for the period 2000–2004 from sites in the Mediterranean Italy (≤600 m a.s.l.) were examined to define the O₃ summary statistic in the area, and to determine how O₃ exposure indices correlate to each other. Thirty-four of the most common O₃ exposure metrics were calculated. The results show that background O₃ pollution in Italy exceeds the European and North American standards. The exceedances of the target value, information and alert thresholds set by the 2002/3/CE Directive should encourage Italy to take the appropriate measures to reduce the risk. All the O₃ exposure indices, except the maximum permissible ozone concentration (MPOC) for forests, point to the potential for negative effects on vegetation and human health across Italy. As indices evaluated significantly correlated with each other, we suggest use of the most biologically meaningful metric when summarizing air quality information.