Some issues relating to the use of perfluorooctanesulfonate (PFOS) samples as reference standards

Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.     

Fe(III)–EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe²⁺ under UV irradiation of the iron complex and the photochemical formation of HO^? from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H₂O₂ concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe²⁺ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H₂O₂ concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.     

Privatisation and outsourcing in wartime: the humanitarian challenges

The tendency today to privatise many activities hitherto considered the exclusive preserve of the state has given rise to sharp debate. The specific nature of humanitarian emergencies elucidates in particularly stark contrast some of the main challenges connected to the privatisation and outsourcing of essential public services, such as the provision of drinking water and health care. Privatising the realms of defence and security, which are at the very core of state prerogative, raises several legal and humanitarian concerns. This article focuses on the roles and responsibilities of the various parties involved in armed conflicts, especially those of private companies engaged in security, intelligence and interrogation work, and in the provision of water supply and health services. It highlights the need for humanitarian and development actors to grasp better the potential risks and opportunities related to privatisation and outsourcing with a view to supplying effective protection and assistance to communities affected by war.     

Optimal Carbon Capture and Storage Policies

The IPCC recommends the use of carbon capture and sequestration (CCS) technologies in order to achieve the Kyoto environmental goals. This paper sheds light on this issue by assessing the optimal strategy regarding the long-term use of CCS technologies. The aim is to analyze the optimal CCS policy when the sequestration rate is endogenous, being therefore one specific tool of the environmental policy. We develop a simple growth model to identify the main driving forces that should determine the optimal CCS policy. We show that, under some conditions on the cost of extractions, CCS may be a long-term solution to curb carbon emissions. We also show that over time the social planner will choose to decrease the rate of capture and sequestration. We then derive the decentralized equilibrium outcome by considering the programs of the fossil resource-holder and of the representative consumer. Finally, we determine the optimal environmental policy, i.e. the carbon tax scheme, as well as the dynamics of the fossil fuel price needed to implement it.     

Water quality assessment by means of HFNI valvometry and high-frequency data modeling

The high-frequency measurements of valve activity in bivalves (e.g., valvometry) over a long period of time and in various environmental conditions allow a very accurate study of their behaviors as well as a global analysis of possible perturbations due to the environment. Valvometry uses the bivalve's ability to close its shell when exposed to a contaminant or other abnormal environmental conditions as an alarm to indicate possible perturbations in the environment. The modeling of such high-frequency serial valvometry data is statistically challenging, and here, a nonparametric approach based on kernel estimation is proposed. This method has the advantage of summarizing complex data into a simple density profile obtained from each animal at every 24-h period to ultimately make inference about time effect and external conditions on this profile. The statistical properties of the estimator are presented. Through an application to a sample of 16 oysters living in the Bay of Arcachon (France), we demonstrate that this method can be used to first estimate the normal biological rhythms of permanently immersed oysters and second to detect perturbations of these rhythms due to changes in their environment. We anticipate that this approach could have an important contribution to the survey of aquatic systems.     

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.     

Two sampling strategies for an overview of pesticide contamination in an agriculture-extensive headwater stream

Two headwaters located in southwest France were monitored for 3 and 2 years (Auvézère and Aixette watershed, respectively) with two sampling strategies: grab and passive sampling with polar organic chemical integrative sampler (POCIS). These watersheds are rural and characterized by agricultural areas with similar breeding practices, except that the Auvézère watershed contains apple production for agricultural diversification and the downstream portion of the Aixette watershed is in a peri-urban area. The agricultural activities of both are extensive, i.e., with limited supply of fertilizer and pesticides. The sampling strategies used here give specific information: grab samples for higher pesticide content and POCIS for contamination background noise and number of compounds found. Agricultural catchments in small headwater streams are characterized by a background noise of pesticide contamination in the range of 20–70 ng/L, but there may also be transient and high-peak pesticide contamination (2000–3000 ng/L) caused by rain events, poor use of pesticides, and/or the small size of the water body. This study demonstrates that between two specific runoff events, contamination was low; hence the importance of passive sampler use. While the peak pesticide concentrations seen here are a toxicity risk for aquatic life, the pesticide background noise of single compounds do not pose obvious acute nor chronic risks; however, this study did not consider the risk from synergistic “cocktail” effects. Proper tools and sampling strategies may link watershed activities (agricultural, non-agricultural) to pesticides detected in the water, and data from both grab and passive samples can contribute to discussions on environmental effects in headwaters, an area of great importance for biodiversity.     

The food-print of Paris: long-term reconstruction of the nitrogen flows imported into the city from its rural hinterland

Between the tenth and twentieth century the population of Paris city increased from a few thousand to near 10 million inhabitants. In response to the growing urban demand during this period, the agrarian systems of the surrounding rural areas tremendously increased their potential for commercial export of agricultural products, made possible by a surplus of agricultural production over local consumption by humans and livestock in these areas. Expressed in terms of nitrogen, the potential for export increased from about 60 kg N/km2/year of rural territory in the Middle Ages, to more than 5,000 kg N/km2/year from modern agriculture. As a result of the balance between urban population growth and rural productivity, the rural area required to supply Paris (i.e. its food-print) did not change substantially for several centuries, remaining at the size of the Seine watershed surrounding the city (around 60,000 km2). The theoretical estimate of the size of the supplying hinterland at the end of the eighteenth century is confirmed by the figures deduced from the analysis of the historical city toll data (octroi). During the second half of the twentieth century, the ‘food-print’ of Paris reduced in size, owing to an unprecedented increase in the potential for commercial export associated with modern agricultural systems based on chemical N fertilization. We argue that analysing the capacity of territories to satisfy the demand for nitrogen-containing food products of local or distant urban population and markets might provide new and useful insights when assessing world food resource allocation in the context of increasing population and urbanization.