Long-term environmental monitoring of persistent organic pollutants and metals in a chemical/petrochemical area: human health risks

Organic pollutants such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polycyclic aromatic hydrocarbons (PAHs), as well as some metals are periodically monitored in soil and vegetation samples collected in Tarragona County (Spain). We here report the temporal trends of the concentrations of the above pollutants between the initial survey (2002) and that recently (2009) performed. The area under evaluation was divided into 4 sections (chemical, petrochemical, urban/residential and unpolluted). In general terms, urban soils presented the highest concentrations of PCDD/Fs, PCNs and PAHs, confirming that traffic is a very important emission source of these pollutants. In addition, substantially higher levels of PAHs and some metals were found in vegetation samples from the petrochemical complex. The assessment of health risks of these contaminants indicated that the current concentrations of micropollutants did not mean additional non-carcinogenic or cancer risks for the population living in the zone.     

Evaluation of soil contamination in intensive agricultural areas by pesticides and organic pollutants: south-eastern Spain as a case study

A comprehensive survey of the occurrence and fate of pesticides and organic contaminants in soils from an intensive agricultural area devoted to horticultural production in plastic-based greenhouses has been performed to determine if the operation under integrated pest management practices has contributed to reduce the levels of these compounds. Almería province (south-eastern Spain) was selected for the case study. 38 agricultural soil samples (each sample corresponds to an independent private greenhouse) of areas working under integrated pest management (IPM) programs have been analyzed in order to evaluate their contamination fate. Sampling was designed to cover an area of about 400 km(2). Pesticides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phenolic compounds and di-(2-ethylhexyl)phthalate (DEHP) were monitored. The obtained results were compared to other studies reported in Spain and Europe. Among relevant persistent pesticides, DDTs and endosulfans were mainly found and the results indicated historical application, although recent application of endosulfan was rarely detected. PAHs were also found but to a lesser extent and derived from pyrogenic sources. DEHP levels were considerably higher in comparison to the other monitored analytes. The evaluation revealed that despite the use of IPM programs, pesticide and organic contaminants are still being detected in this type of agricultural soil, although at relatively low concentration levels. In general, the contamination rate was similar or lower in comparison to other agricultural areas from nearby regions or countries. However, further monitoring studies should be carried out to establish the possible reduction in contamination by the selected compounds.     

Tolerance to agricultural pesticides of strains belonging to four genera of Rhizobiaceae

In order to determine their tolerance to pesticides, 122 strains of rhizobia isolated from different geographical regions, and belonging to the genera Rhizobium, Mesorhizobium, Sinorhizobium and Bradyrhizobium were tested against eight herbicides, four fungicides and five insecticides. Sensitivity to the pesticides was measured by using the filter paper disk method at four concentrations, 0.45, 4.5, 45 and 450 μg per disk. When the pesticides were used at 0.45 μg per disk, a concentration similar to that found when pesticides are applied under field conditions, no inhibition was observed. Strains growth was affected at concentrations of 45 and 450 μg pesticide per disk. These higher concentrations can be encountered when seeds are treated with pesticides. Pesticides tolerance level was correlated to pesticide function, i.e rhizobial strains were more tolerant to insecticides, followed by herbicides and then fungicides. Two fungicides, captan and mancozeb, inhibited the highest number of strains. Only one insecticide, carbaryl, affected the growth of some rhizobial strains. Strains isolated from the arctic (Mesorhizobium spp. and R. leguminosarum bv. viciae), a putative pesticides-free environment, were either less or equally affected by pesticides compared to strains isolated from agricultural regions.     

Effectiveness in the Use of Natural Gas for the Reduction of Atmospheric Emissions: Case Study—Industrial Sector in the Metropolitan Region of Santiago,Chile

Abstract

The purpose of this investigation was to quantify the potential of natural gas to reduce emissions from stationary combustion sources by analyzing the case study of the metropolitan region of Santiago, Chile. For such purposes, referential base scenarios have been defined that represent with and without natural gas settings. The method to be applied is an emission estimate based on emission factors. The results for this case study reveal that stationary combustion sources that replaced their fuel reduced particulate matter (PM) emissions by 61%, sulfur oxides (SO_x) by 91%, nitrogen oxides (NO_x) by 40%, and volatile organic compounds (VOC) by 10%. Carbon mon-oxide (CO) emissions were reduced by 1%. As a result of this emission reduction, in addition to reductions caused by other factors, such as a shift to cleaner fuels other than natural gas, technological improvements, and sources which are not operative, emission reduction goals set forth by the environmental authorities were broadly exceeded.     

Wave hydrodynamics around a multi-functional artificial reef at Leirosa

This paper describes an application of the Boussinesq-type COULWAVE model to study the wave hydrodynamics in the vicinity of a multi-functional artificial reef (MFAR). This reef is under investigation and consists of a supplementary protection solution for the Leirosa sand dune system located at South of Figueira da Foz, on the Portuguese West coast. Such installation near the coastline is expected to contribute to enhance the surfing conditions in the area, protect the sand dune system in the surroundings of Leirosa beach, and increase its environmental value. Numerical calculations with the COULWAVE model were performed for four test cases, considering two reef geometries (differing in the reef angle) and two incident wave conditions (storm condition and a common wave condition). Comparisons between the results obtained, in terms of wave heights and breaking line positions allow us to assess the influence of the reef on the hydrodynamics near the beach and around the reef. Moreover, the reef performance was analysed in terms of surfability and coastal protection. The surfability parameters (breaker height, Iribarren number and peel angle) were calculated for each test case using the numerical wave heights, wave directions and wave breaking positions. Comparisons of parameters allow characterizing the most appropriate configuration of the reef to improve the surfing conditions in the study area. A methodology based on numerical free surface elevations and horizontal velocity components was developed to calculate wave directions, since this is not a direct output of the COULWAVE model. Concerning coastal protection, analyses of the mean currents around the reef were used together with observations of the velocity cells near the shoreline as an indication of the sediment transport.     

Design and first experimental results of a bubbling fluidized bed for air gasification of plastic waste

Plastic wastes have an especially high potential for use as alternative fuels, considering their high heating value and their large and stable availability. They could be used in electricity production based on gasification technologies, wherein electricity is produced in engines by means of the conversion of plastic wastes into a valuable gas. However, there are still some technical barriers to overcome before this technology can access the commercial stage, and further scientific research is needed to gain deeper understanding of the process and to be able to control and optimize it. This research presents the design and first experimental results of a bubbling fluidized bed gasifier conceived for the gasification of actual plastic residues. The experimental tests revealed that the selection and design of the reactor were adequate and proved some of the advantages of using plastic as a fuel, related in part to the absence of ashes and char. A valuable syngas over 5 MJ/m³ was generated, which contained a considerable fraction of methane as well as hydrogen and carbon monoxide as main combustible gases. The highest efficiency was achieved when the equivalence ratio was increased to 0.35, reaching 61 % in terms of cold gas efficiency and 66 % carbon conversion.     

The origin of speciation: trace metal kinetics over natural water/sediment interfaces and the consequences for bioaccumulation

The speciation of heavy metals was measured over a variety of natural and undisturbed water/sediment interfaces. Simultaneously, two benthic species (oligochaete Limnodrilus spp. and the midge Chironomus riparius) were exposed to these sediments. Under occurring redox conditions, free ion activities of trace metals Cd, Cu, Ni, Pb, and Zn were measured with a chelating exchange technique, while geochemical conditions (i.e., redox) remained in tact. Free ion activities were compared with total dissolved concentrations in pore waters and surface waters in order to relate speciation to bioaccumulation. Limnodrilus spp. and C. riparius have accumulation patterns that could be linked to time-dependent exposure concentrations, expressed as chemical speciation, in the surface water and the sediment's pore water. Concentrations of free metal ions in the overlying surface water, rather than in sediment pore water, proved to be the best predictor for uptake. For the first time, measurements are obtained from sediments without disturbing physical-chemical conditions and thus bioavailability, a major restriction of other studies so far.     

Cost–benefit analysis of using sewage sludge as alternative fuel in a cement plant: a case study

Background, aim, and scope  To enforce the implementation of the Kyoto Protocol targets, a number of governmental/international institutions have launched emission trade schemes as an approach to specify CO₂ caps and to regulate the emission trade in recent years. These schemes have been basically applied for large industrial sectors, including energy producers and energy-intensive users. Among them, cement plants are included among the big greenhouse gas (GHG) emitters. The use of waste as secondary fuel in clinker kilns is currently an intensive practice worldwide. However, people living in the vicinity of cement plants, where alternative fuels are being used, are frequently concerned about the potential increase in health risks. In the present study, a cost–benefit analysis was applied after substituting classical fuel for sewage sludge as an alternative fuel in a clinker kiln in Catalonia, Spain. Materials and methods  The economical benefits resulting in the reduction of CO₂ emissions were compared with the changes in human health risks due to exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and carcinogenic metals (As, Cd, Co, and Cr) before and after using sewage sludge to generate 20% of the thermal energy needed for pyro-processing. The exposure to PCDD/Fs and metals through air inhalation, soil ingestion and dermal absorption was calculated according to the environmental levels in soil. The carcinogenic risks were assessed, and the associated cost for the population was estimated by considering the DG Environment’s recommended value for preventing a statistical fatality (VPF). In turn, the amount of CO₂ emitted was calculated, and the economical saving, according to the market prices, was evaluated. Results  The use of sewage sludge as a substitute of conventional energy meant a probability cancer decrease of 4.60 for metals and a cancer risk increase of 0.04 for PCDD/Fs. Overall, a net reduction of 4.56 cancers for one million people can be estimated. The associated economical evaluation due to the decreasing cancer for 60,000 people, the current population living near the cement plant, would be of 0.56 million euros (US$ 0.83 million). In turn, a reduction of 144,000 tons of CO₂ emitted between 2003 and 2006 was estimated. Considering a cost of 20 euros per ton of CO₂, the global saving would be 2.88 million euros (US$ 4.26 million). Discussion  After the partial substitution of the fuel, the current environmental exposure to metals and PCDD/Fs would even mean a potential decrease of health risks for the individuals living in the vicinity of the cement plant. The total benefit of using sewage sludge as an alternative fuel was calculated in 3.44 million euros (US$ 5.09 million). Environmental economics is becoming an interesting research field to convert environmental benefits (i.e., reduction of health risks, emission of pollutants, etc.) into economical value. Conclusions  The results show, that while the use of sewage sludge as secondary fuel is beneficial for the reduction in GHG emissions, no additional health risks for the population derived from PCDD/F and metal emissions are estimated. Recommendations and perspectives  Cost–benefit analysis seems to be a suitable tool to estimate the environmental damage and benefit associated to industrial processes. Therefore, this should become a generalized practice, mainly for those more impacting sectors such as power industries. On the other hand, the extension of the study could vastly be enlarged by taking into account other potentially emitted GHGs, such as CH₄ and N₂O, as well as other carcinogenic and non-carcinogenic micropollutants.     

Influence of temperature on the chemical removal of 3-methylbutanal,trans-2-methyl-2-butenal,and 3-methyl-2-butenal by OH radicals in the troposphere

Absolute rate coefficients for the gas-phase reactions of OH radical with 3-methylbutanal (k₁), trans-2-methyl-2-butenal (k₂), and 3-methyl-2-butenal (k₃) have been obtained with the pulsed laser photolysis/laser-induced fluorescence technique. Gas-phase concentration of aldehydes was measured by UV absorption spectroscopy at 185 nm. Experiments were performed over the temperature range of 263–353 K at total pressures of helium between 46.2 and 100 Torr. No pressure dependence of all k_i (i = 1–3) was observed at all temperatures. In contrast, a negative temperature dependence of k_i (i.e., k_i increases when temperature decreases) was observed in that T range. The resulting Arrhenius expressions (±2σ) are: k₁(T) = (5.8 ± 1.7)×10^?12 exp{(499 ± 94)/T} cm³ molecule^?1 s^?1, k₂(T)=(6.9 ± 0.9)×10^?12 exp{(526 ± 42)/T} cm³ molecule^?1 s^?1, k₃(T)=(5.6 ± 1.2)×10^?12 exp{(666 ± 54)/T} cm³ molecule^?1 s^?1.The tropospheric lifetimes derived from the above OH-reactivity trend are estimated to be higher for 3-methylbutanal than those for the unsaturated aldehydes. A comparison of the tropospheric removal of these aldehydes by OH radicals with other homogeneous degradation routes leads to the conclusion that this reaction can be the main homogeneous removal pathway. However, photolysis of these aldehydes in the actinic region (λ > 290 nm) could play an important role along the troposphere, particularly for 3-methyl-2-butenal. This process could compete with the OH reaction for 3-methylbutanal or be negligible for trans-2-methyl-2-butenal in the troposphere.     

Composition changes in the cuticular surface lipids of the helophytes <Emphasis Type="Italic">Phragmites australis</Emphasis> and <Emphasis Type="Italic">Juncus effusus</Emphasis> as result of pollutant exposure

Aim of the study  

Helophytes like rush and reed are increasingly used for phytoremediation of contaminated water. This study characterises the response of rush and reed plants to chemical stressors such as chlorobenzene, benzene and methyl-tert-butyl ether. The extractable wax layer of the cuticle was chosen for detailed investigations due to its multiple, particularly, protective functions for plants and its easy availability for analysis.