Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

The Contribution of Marsh Zones to Water Quality in Dutch Shallow Lakes: A Modeling Study

Many lakes have experienced a transition from a clear into a turbid state without macrophyte growth due to eutrophication. There are several measures by which nitrogen (N) and phosphorus (P) concentrations in the surface water can be reduced. We used the shallow lake model PCLake to evaluate the effects of three measures (reducing external nutrient loading, increasing relative marsh area, and increasing exchange rate between open water and marsh) on water quality improvement. Furthermore, the contribution of different retention processes was calculated. Settling and burial contributed more to nutrient retention than denitrification. The model runs for a typical shallow lake in The Netherlands showed that after increasing relative marsh area to 50%, total phosphorous (TP) concentration in the surface water was lower than the Maximum Admissible Risk (MAR, a Dutch government water quality standard) level, in contrast to total nitrogen (TN) concentration. The MAR levels could also be achieved by reducing N and P load. However, reduction of nutrient concentrations to MAR levels did not result in a clear lake state with submerged vegetation. Only a combination of a more drastic reduction of the present nutrient loading, in combination with a relatively large marsh cover (approximately 50%) would lead to such a clear state. We therefore concluded that littoral marsh areas can make a small but significant contribution to lake recovery.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

Multiscale analysis of heavy metal contents in Spanish agricultural topsoils

This study characterized and mapped the spatial variability patterns of seven topsoil heavy metals (Cr, Ni, Pb, Cu, Zn, Hg and Cd) within the Ebro river basin (9.3 million ha) by Multivariate Factorial Kriging. The variograms and cross-variograms of heavy metal concentrations showed the presence of multiscale variation that was modeled using three variogram models with ranges of 20km (short-range), 100km (medium-range) and 225km (long-range). Our results indicate that the heavy metal concentration is influenced by bedrock composition and dynamics at all the spatial scales, while human activities have a notorious effect only at the short- and medium-range scale of variation. Sources of Cu, Pb and Zn (and secondary Cd) are associated with agricultural practices (at the short-range scale of variation), whereas Hg variation at the short- and medium-range scale of variation is related to atmospheric deposition.     

Traffic and catalytic converter - related atmospheric contamination in the metropolitan region of the city of Rio de Janeiro, Brazil

In this work, 24-h PM10 samples were collected in Rio de Janeiro, Brazil, and analysed for trace elements (Cd, Ce, Cu, La, Mo, Ni, Pb, Pd, Rh, Sb and Sn). The sampling was carried out at five locations (Bonsucesso; Centro, downtown city; Copacabana; Nova Igua?u and Sumaré) with different traffic densities and anthropogenic activities. An analytical method based on the EPA method for the determination of trace elements in airborne particulate matter (PM), using ultrasonic-assisted extraction and inductively coupled plasma mass spectrometry (ICP-MS) was applied. Our results suggest that vehicular traffic is the most important source of environmental pollution at the studied sites. The presence of Mo, Pd and Rh in the analysed filters reflects an additional source of pollution caused by the erosion and deterioration of automotive catalytic converters.     

Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.     

Mineralization of the biocide chloroxylenol by electrochemical advanced oxidation processes

Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.     

Polymer biodegradation: mechanisms and estimation techniques

Within the frame of the sustainable development, new materials are being conceived in order to increase their biodegradability properties. Biodegradation is considered to take place throughout three stages: biodeterioration, biofragmentation and assimilation, without neglect the participation of abiotic factors. However, most of the techniques used by researchers in this area are inadequate to provide evidence of the final stage: assimilation. In this review, we describe the different stages of biodegradation and we state several techniques used by some authors working in this domain. Validate assimilation (including mineralisation) is an important aspect to guarantee the real biodegradability of items of consumption (in particular friendly environmental new materials). The aim of this review is to emphasise the importance of measure as well as possible, the last stage of the biodegradation, in order to certify the integration of new materials into the biogeochemical cycles. Finally, we give a perspective to use the natural labelling of stable isotopes in the environment, by means of a new methodology based on the isotopic fractionation to validate assimilation by microorganisms.     

Monitoring PCDD/Fs, PCBs and metals in the ambient air of an industrial area of Catalonia, Spain

In 2005 and 2006, the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and metals (As, Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sn, Tl and V) were measured in air samples collected in an industrial area of Sant Adrià del Besòs (Barcelona, Catalonia, Spain) where a municipal solid waste incinerator (MSWI) is placed, and in a background/control area. In general terms, concentrations of all environmental pollutants were higher at the industrial site. No significant seasonal/temporal variations were observed in any of the areas. No Pearson correlation was found between the PCDD/F concentrations and the environmental conditions of the two sampling periods considered. Principal component analyses (PCA) were performed to get information on the relationship among samples, pollutants, and emission sources. The results indicate that the MSWI of S. Adrià de Besòs is not a significant emission source of the above compounds for the area under its direct influence. Moreover, a notable difference in the PCDD/F congener profiles was found between ambient air and stack gas emissions, indicating that the current levels of PCDD/Fs are more related to other potential emissions sources rather than to those from the MSWI.     

Construction demolition wastes, Waelz slag and MSWI bottom ash: a comparative technical analysis as material for road construction

The objective of the study is to analyze the technical suitability of using secondary materials from three waste flows (construction and demolition waste (CDW), Waelz slag and municipal solid waste incineration (MSWI) bottom ash), under the regulations and standards governing the use of materials for road construction. A detailed technical characterization of the materials was carried out according to Spanish General Technical Specifications for Road Construction (PG3). The results show that Waelz slag can be adequate for using in granular structural layers, while CDW fits better as granular material in roadbeds. Likewise, fresh MSWI bottom ash can be used as roadbed material as long as it does not contain a high concentration of soluble salts. This paper also discusses the adequacy of using certain traditional test methods for natural soils when characterizing secondary materials for use as aggregates in road construction.