Combined approaches to determine the impact of wood fire on PCDD/F and PCB contamination of the environment: a case study

Fires might be the source of persistent organic pollutants (POPs) such as dioxins, furans (PCDD/Fs) and/or polychlorobiphenyls (PCBs) in the environment. In the perspective of defining legal responsibilities a thorough characterization of the impact of such an event should be carried out. However, such characterization is not easy as the environment integrates both local and diffuse sources of such molecules. Thus, a combined approach, which includes gathering field surveys, modeling and laboratory experiments, should be conducted. The objective of this work is to illustrate different approaches to give sufficient insight to determine the actual impact of wood fire on the environment. The work was carried out at the vicinity of a burnt down parcel. The fired material was a mixture of wood and PCB-contaminated soils as the site was a former pyralene-disposal site. Modeling, soil and lichen sampling and experimental combustion were carried out to delineate the contamination for each chemical and to define the area within the fire that was responsible for the environmental contamination. Concentrations of PCDD/F and PCBs were very high on the burnt plot. The combined approach determined that the furans were the predominant compounds in the smoke emitted by the fire. Based on this tracer, it was possible to demonstrate that in terms of environmental contamination of PCDD/F, the impact of the fire was restricted to a 2 km radius from the burnt down plot. For PCBs, no specific tracer was identified. In this case, the delineation of the impact could only be empirical, based on the total concentration of the chemicals.     

Is the freshwater gammarid, Dikerogammarus villosus, a suitable sentinel species for the implementation of histochemical biomarkers?

In order to enlarge the range of potential sentinel species for the implementation of a multiple biomarker approach, spatial and monthly morphological variations of four cellular compartments and contents were assessed during two years in the hepatopancreatic caeca of the freshwater gammarid, Dikerogammarus villosus (Crustacea, Amphipoda), using histochemistry coupled to image analysis. Among the three study sites, the second one, located in a reservoir receiving the overheated and copper-contaminated waters of a nuclear power plant, was the most anthropised. During this passive biomonitoring survey, unsaturated neutral lipids were more abundant, the surface densities of the lysosomal and peroxisomal systems were, respectively less and more important, and lipofuscin granules tended to accumulate in the amphipods from the second site compared to both others. Nonetheless, in this context, the present cellular biomarker suite, analysed through an integrative approach, was not powerful enough to highlight spatial heterogeneity significantly. This may partly result from particularities in the patterns of metal accumulation and copper physiological requirements of amphipods (haemocyanin synthesis). Nevertheless, we think that the use of this Ponto-Caspian non-indigenous species in biomonitoring surveys deserves further investigation, owing to its current position in freshwater and brackish European ecosystems, considering both biomass and functioning. Cellular responses could be studied in parallel with endpoints at other levels of the biological organization to compose a more powerful biomarker suite. Furthermore, comparing biological responses to environmental stress in this invasive species and less competitive autochthonous gammarids could be of great interest.     

Iron isotopic fractionation in industrial emissions and urban aerosols

A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM–EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO₃) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08‰ < δ⁵⁶Fe < +0.80‰) of enriched ores processed by the manufacturer (−0.16‰ < δ⁵⁶Fe < +1.19‰). No significant evolution of Fe fractionation during steelworks processes is observed. At the industrial source, Fe is mainly present as oxide particles, to some extent in 3–4 μm aggregates. In the close urban area, 5 km away from the steel plant, individual particle analysis of collected aerosols presents, in addition to the industrial particle type, aluminosilicates and related natural particles (gypsum, quartz, calcite and reacted sea salt). The Fe isotopic composition (δ⁵⁶Fe = 0.14 ± 0.11‰) measured in the close urban environment of the steel metallurgy plant appears coherent with an external mixing of industrial and continental Fe-containing tropospheric aerosols, as evidenced by individual particle chemical analysis. Our isotopic data provide a first estimation of an anthropogenic source term as part of the study of photochemically promoted dissolution processes and related Fe fractionations in tropospheric aerosols.     

The role of perceived government style in the facilitation of self-determined and non self-determined motivation for pro-environmental behavior

Most North Americans are concerned about the environment and feel that responsibility for its protection lies primarily with government; however, no research to date has examined the influence of the government's approach toward environmental regulation on the motivation of individual citizens. According to self-determination theory, social contexts that support one's autonomy should facilitate self-determined motivation and social contexts that thwart autonomy should lead to non self-determined motivation and a sense of apathy or amotivation. In this study (n = 283), we examined the influence of perceptions of the government's approach toward environmental regulation on motivation toward the environment and frequency of self-reported pro-environmental behavior (PEB). Using structural equation modeling, we tested the hypothesis that frequency of PEB is predicted by motivation toward the environment and that motivation is predicted by the extent to which individuals perceive the government to be autonomy-supportive versus controlling in the implementation of environmental policies. The analysis revealed that perception of government autonomy-support contributed positively to autonomous motivation and negatively to amotivation, while perception of government control was positively related to both controlled motivation and amotivation. As predicted, autonomous motivation was positively, and amotivation was negatively, associated with frequency of PEB.     

Households’ recycling efforts

Households’ recycling effort is often argued to be of an insignificant size. It is also frequently argued that this contribution, if significant, is not a cost to households, since it is voluntary. Thus households’ use of time and energy are frequently disregarded in cost-benefit analyses of stricter recycling targets. In this survey, based on 1162 interviews, we find that sorting at source involves significant extra use of time and energy in the households. On average, each of those asked reported that they use close to half an hour a week for cleaning, sorting and transporting recyclable waste. On average, 185 h is used per tonne of waste. Four out of ten reported that they use warm or hot water to clean the materials. When investigating the motives for sorting waste, we find that many perceive sorting as mandatory, while some in fact find it a pleasant activity in itself. Moral motives for sorting at source are also widespread. A majority would prefer that a company took over the sorting if this were possible, and on average, the respondents are willing to pay US$ 20/year for this service.     

Modeling survival and mark loss in molting animals: recapture, dead recoveries, and exuvia recoveries

Capture-mark-recapture (CMR) analyses aim primarily at estimating relevant life history parameters, despite the fact that some individuals are not always recaptured, even if alive on the study site. Applying such approaches to species with a complex life cycle, such as insects, remains challenging because each change of stage tends to cause mark loss through molting. We developed a multistate model based on three exclusive events ("dead", "surviving and molting", and "surviving and staying in the same larval stage") to estimate probabilities of survival and mark loss. Estimates of biologically relevant parameters were derived from those of the probabilities of transition between these states. The model was applied to data from radio-tracking diodes glued on grasshoppers. The estimates of recapture probabilities decreased throughout the season for animals remaining alive, while the detection of dead animals and lost diodes was exhaustive. The survival probability was higher for larvae than for adults (0.98 vs. 0.96), and mark loss was stronger in larvae than in adults (0.09 vs. 0.06). We show that the survival rate of a species with a high rate of mark loss can be estimated using multistate models, provided that marks can be recovered after being lost. These models are flexible enough to test for several effects that potentially affect survival and mark loss probabilities.     

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions

Introduction

This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O₂) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.

Materials and methods

A laboratory scale device consisting of a 250?ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30?g/l) at pH?4 and room temperature with bubbling of oxygen gas were investigated.

Results and conclusion

Experiments showed an observed degradation rate k _(obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5?±?0.5 and 3.5?±?0.2?min when experiments were conducted at [ZVI]?=?1 and 30?g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20?min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.     

Impact of chronic cadmium exposure at environmental dose on escape behaviour in sea bass (Dicentrarchus labrax L.; Teleostei, Moronidae)

The effect of chronic exposure to a low concentration (0.5 microg l(-1)) of cadmium ions was investigated on escape behaviour of sea bass, Dicentrarchus labrax, using video analysis. Observations were also performed on the microanatomy of lateral system neuromasts. When fish were exposed for 4h per day over 8 days to the cadmium ions, most of both types of neuromasts observed remained intact. However, some of them presented damaged sensory maculae. Whereas before cadmium exposure, fish responded positively to nearly all the lateral system stimulations, after exposure they decreased by about 10% their positive responses to stimulations. From the 15th day after the beginning of cadmium exposure, neuromasts presented progressively less damage, cadmium accumulation in gills and scales decreased significantly and fish escape behaviour had recovered. This study presents a new concept in ecotoxicology: using behavioural change to reveal the effects of pollution levels, scarcely detectable by currently used techniques (physiological responses).     

Zn isotope study of atmospheric emissions and dry depositions within a 5 km radius of a Pb–Zn refinery

The present paper examines the use of zinc isotopes as tracers of atmospheric sources and focuses on the potential fractionation of Zn isotopes through anthropogenic processes. In order to do so, Zn isotopic ratios are measured in enriched ores and airborne particles associated with pyrometallurgical activities of one of the major Pb–Zn refineries in France. Supporting the isotopic investigation, this paper also compares morphological and chemical characteristics of Zn particles collected on dry deposition plates (“environmental samples”) placed within a 5 km radius of the smelter, with those of Zn particles collected inside the plant (“process samples”), i.e. dust collected from the main exhaust system of the plant. To ensure a constant isotopic “supply”, the refinery processed a specific set of ores during the sampling campaigns, as agreed with the executive staff of the plant. Enriched ores and dust produced by the successive Zn extraction steps show strong isotope fractionation (from ?0.66 to +0.22‰) mainly related to evaporation processes within the blast furnaces. Dust from the main chimney displays a δ⁶⁶Zn value of ?0.67‰. Application of the Rayleigh equation to evaluate the fractionation factor associated with the Zn vapor produced after a free evaporation gives a range of α_ore/vapor from 1.0004 to 1.0008. The dry deposits, collected on plates downwind of the refinery, display δ⁶⁶Zn variations of up to +0.7‰. However, it is to be noted that between 190 and 1250 m from the main chimney of the refinery, the dry deposits show a high level of large (>10 μm) Zn, S, Fe and O bearing aggregates characterized by positive δ⁶⁶Zn values (+0.02 to +0.19‰). These airborne particles probably derive from the re-suspension of slag heaps and local emissions from the working-units. In contrast, from 1720 to 4560 m, the dry deposits are comprised of small (PM10) particles, including spherical Zn-bearing aggregates, showing negative δ⁶⁶Zn values (?0.52 to ?0.02‰). Our results suggest that the source of the distal dry fallouts is the main chimney plume, whose light Zn isotopic signature they preserve. Based on Zn isotopic analysis in combination with morphological and chemical characteristics of airborne particles, the present study suggests the traceability of smelter dusts by Zn isotopes.