• Energy Research

Polycyclic aromatic hydrocarbons (PAHs) are airborne pollutants that are deposited on soils. As climate change is already altering temperature and solar radiation, the global warming is suggested to impact the environmental fate of PAHs. This study was aimed at evaluating the effect of climate change on the PAH photodegradation in soils. Samples of Mediterranean soils were subjected to different temperature and light radiation conditions in a climate chamber. Two climate scenarios were considered according to IPCC projections: 1) a base (B) scenario, being temperature and light intensity 20°C and 9.6W/m(2), respectively, and 2) a climate change (CC) scenario, working at 24°C and 24W/m(2), respectively. As expected, low molecular weight PAHs were rapidly volatilized when increasing both temperature and light intensity. In contrast, medium and high molecular weight PAHs presented different photodegradation rates in soils with different texture, which was likely related to the amount of photocatalysts contained in both soils. In turn, the hydrogen isotopic composition of some of the PAHs under study was also investigated to verify any degradation process. Hydrogen isotopes confirmed that benzo(a)pyrene is degraded in both B and CC scenarios, not only under light but also in the darkness, revealing unknown degradation processes occurring when light is lacking. Potential generation pathways of PAH photodegradation by-products were also suggested, being a higher number of metabolites formed in the CC scenario. Consequently, in a more or less near future, although humans might be less exposed to PAHs, they could be exposed to new metabolites of these pollutants, which might be even more toxic.

In cement plants, the substitution of traditional fossil fuels not only allows a reduction of CO(2), but it also means to check-out residual materials, such as sewage sludge or municipal solid wastes (MSW), which should otherwise be disposed somehow/somewhere. In recent months, a cement plant placed in Alcanar (Catalonia, Spain) has been conducting tests to replace fossil fuel by refuse-derived fuel (RDF) from MSW. In July 2009, an operational test was progressively initiated by reaching a maximum of partial substitution of 20% of the required energy. In order to study the influence of the new process, environmental monitoring surveys were performed before and after the RDF implementation. Metals and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in soil, herbage, and air samples collected around the facility. In soils, significant decreases of PCDD/F levels, as well as in some metal concentrations were found, while no significant increases in the concentrations of these pollutants were observed. In turn, PM(10) levels remained constant, with a value of 16μgm(-3). In both surveys, the carcinogenic and non-carcinogenic risks derived from exposure to metals and PCDD/Fs for the population living in the vicinity of the facility were within the ranges considered as acceptable according to national and international standards. This means that RDF may be a successful choice in front of classical fossil fuels, being in accordance with the new EU environmental policies, which entail the reduction of CO(2) emissions and the energetic valorization of MSW. However, further long-term environmental studies are necessary to corroborate the harmlessness of RDF, in terms of human health risks.

In 2009, a cement plant located in Alcanar (South Catalonia, Spain) started co-processing a special kind of refuse-derived fuel (RDF) called ENERFUEL™. In April 2014 and 2017, 5 and 8 years after RDF co-processing, the concentrations of metals and metalloids (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Tl, V and Zn) and PCDD/Fs were measured in samples of soils, herbage and air collected in the vicinity of the facility. The comparison of the current concentrations with those obtained in a baseline study (2008), when fossil fuels were used solely, has shown that the environmental concentrations of metals, metalloids and PCDD/Fs were not significantly modified. The concentrations of metals, metalloids and PCDD/Fs in soil, vegetation and air of Alcanar are in the low part of the ranges found around other cement plants in Catalonia (in general, below 50th percentile). Non-carcinogenic risks due to exposure to metals, metalloids and PCDD/Fs were lower than the safety value (HQ<1). In turn, carcinogenic risks were below the 10-5 Spanish threshold. The present results corroborate that, from an environmental point of view, the use of wastes as alternative fuels (AF) in a cement plant, which is operating with suitable technical conditions, is a good option for waste management. It contributes towards overcoming challenges such as climate change and fossil fuel depletion, while utilizing principles of circular economy.

The photodegradation of polycyclic aromatic hydrocarbons (PAHs) in two typical Mediterranean soils, either coarse- or fine-textured, was here investigated. Soil samples, spiked with the 16 US EPA priority PAHs, were incubated in a climate chamber at stable conditions of temperature (20 °C) and light (9.6 W m(-2)) for 28 days, simulating a climate change base scenario. PAH concentrations in soils were analyzed throughout the experiment, and correlated with data obtained by means of Microtox(®) ecotoxicity test. Photodegradation was found to be dependent on exposure time, molecular weight of each hydrocarbon, and soil texture. Fine-textured soil was able to enhance sorption, being PAHs more photodegraded than in coarse-textured soil. According to the EC50 values reported by Microtox(®), a higher detoxification was observed in fine-textured soil, being correlated with the outcomes of the analytical study. Significant photodegradation rates were detected for a number of PAHs, namely phenanthrene, anthracene, benzo(a)pyrene, and indeno(123-cd)pyrene. Benzo(a)pyrene, commonly used as an indicator for PAH pollution, was completely removed after 7 days of light exposure. In addition to the PAH chemical analysis and the ecotoxicity tests, a hydrogen isotope analysis of benzo(a)pyrene was also carried out. The degradation of this specific compound was associated to a high enrichment in (2)H, obtaining a maximum δ(2)H isotopic shift of +232‰. This strong isotopic effect observed in benzo(a)pyrene suggests that compound-specific isotope analysis (CSIA) may be a powerful tool to monitor in situ degradation of PAHs. Moreover, hydrogen isotopes of benzo(a)pyrene evidenced a degradation process of unknown origin occurring in the darkness.

In recent years, the climate change impact on the concentrations of persistent organic pollutants (POPs) has become a topic of notable concern. Changes in environmental conditions such as the increase of the average temperature, or the UV-B radiation, are likely to influence the fate and behavior of POPs, ultimately affecting human exposure. The state of the art of the impact of climate change on environmental concentrations of POPs, as well as on human health risks, is here reviewed. Research gaps are also identified, while future studies are suggested. Climate change and POPs are a hot issue, for which wide attention should be paid not only by scientists, but also and mainly by policy makers. Most studies reported in the scientific literature are focused on legacy POPs, mainly polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and pesticides. However, the number of investigations aimed at estimating the impact of climate change on the environmental levels of polycyclic aromatic hydrocarbons (PAHs) is scarce, despite of the fact that exposure to PAHs and photodegradation byproducts may result in adverse health effects. Furthermore, no data on emerging POPs are currently available in the scientific literature. In consequence, an intensification of studies to identify and mitigate the indirect effects of the climate change on POP fate is needed to minimize the human health impact. Furthermore, being this a global problem, interactions between climate change and POPs must be addressed from an international perspective.

This paper was aimed at reviewing recent studies related with the impact on environment and human health of metals and PCDD/Fs near cement plants. It has been particularly focused on the impact of cement plants located in Catalonia, Spain, which have been monitored by our research for more than ten years. Environmental monitoring studies were performed under different cement plant conditions. While some of our studies examined temporal trends of the levels of the above indicated pollutants, the main goal of other surveys was to assess the impact of implementing alternative fuels in the facilities. Even one of the studies was performed before and after the cement plant temporally ceased its industrial activity. The impact of cement plants burning alternative fuels on the emissions of metals and PCDD/Fs elsewhere was also reviewed. Regarding the cement plants in Catalonia, no significant differences were found, neither in the long-term follow-up studies, nor when alternative fuels are used, nor when a cement plant temporally stopped its activity. These results are in agreement with those reported for several stack emissions of other cement plants working under different conditions. We conclude that emissions of metals and PCDD/Fs by cement plants working with the best available techniques (BAT), should not cause a significant negative impact neither on the surrounding environment, nor on the human health of the population living in the neighborhood.

This study aimed at evaluating the potential impact of a cement plant after 4 years of the employment of alternative fuel.