Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain)

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ng L⁻¹ range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals > alkylphenols > pesticides > illicit drugs ? estrogens.     

Degradation of phenols in olive oil mill wastewater by biological,enzymatic, and photo-Fenton oxidation

Background, aim, and scope  

Olive oil mill wastewater (OOMW) environmental impacts minimization have been attempted by developing more effective processes, but no chemical or biological treatments were found to be totally effective to mitigate their impact on receiving systems. This work is the first that reports simultaneously the efficiency of three different approaches: biological treatment by two fungal species (Trametes versicolor or Pleurotus sajor caju), enzymatic treatment by laccase, and chemical treatment by photo-Fenton oxidation on phenols removal.     

Strength and workability of masonry mortars manufactured with ladle furnace slag

Ladle furnace basic slag (LFS) is a by-product of the steelmaking process. It has rarely been recovered in the past and is usually disposed of in landfill sites. Despite containing stable chemical substances of great quality, some of which are potentially hydraulic, its practical applications have been limited. This paper discusses the attractive option of using LFS in the manufacture of masonry mortars for use in the construction industry, which requires an analysis of the principal characteristics of such mortars, i.e. workability and mechanical strength. It reports on a comparative study, using standard commercial admixtures, between conventional masonry mortars and mortars manufactured with LFS as a partial replacement for sand and cement, the results of which imply considerable economic savings in sand and cement, improvements in the properties of the mortars and in overall sustainability, by avoiding disposal and conserving natural resources.     

Early Responses to Acute Ozone Exposure in Two Fagus Sylvatica Clones Differing in Xeromorphic Adaptations: Photosynthetic and Stomatal Processes, Membrane and Epicuticular Characteristics

Two Fagus sylvatica L. clones were used to investigate the early responses to acute O₃ exposure (150 nL L⁻¹, i.e., 1.35× ambient hourly peak in rural Italy) and whether xeromorphic adaptations affect gas exchange, membrane, and epicuticular responses. One clone originated in a wet and temperate climate in Central Italy (Tuscany); the other clone originated in a warmer and drier climate in the southern-most part of the F. sylvatica distribution (Sicily). Because of higher base gas exchange rates, the most negative effects of O₃ exposure (gas exchange impairment, uncoupling between net photosynthesis and stomatal conductance, increased membrane lipid peroxidation) were found in the southern clone. Xeromorphic adaptations (higher epicuticular waxes and stomatal density, lower leaf wettability and size) were found in this clone. Our results suggest that xeromorphism may increase O₃ sensitivity in species not adapted to face water stress, like the mesophilic F. sylvatica, when experiments are carried out with full irrigation. We present evidence describing the relationship between gas exchange and number and status of stomata. Stomatal density and the structural damage to stomata resulting from O₃ exposure did not affect gas exchange: In fact, non-stomatal limitations to photosynthesis prevailed over stomatal limitations.     

Monitoring Pollution in River MureŞ, Romania, Part III: biochemical effect markers in fish and integrative reflection

Along a downstream stretch of River Mureş, Romania, adult males of two feral fish species, European chub (Leuciscus cephalus) and sneep (Chondrostoma nasus) were sampled at four sites with different levels of contamination. Fish were analysed for the biochemical markers hsp70 (in liver and gills) and hepatic EROD activity, as well as several biometrical parameters (age, length, wet weight, condition factor). None of the biochemical markers correlated with any biometrical parameter, thus biomarker reactions were related to site-specific criteria. While the hepatic hsp70 level did not differ among the sites, significant elevation of the hsp70 level in the gills revealed proteotoxic damage in chub at the most upstream site, where we recorded the highest heavy metal contamination of the investigated stretch, and in both chub and sneep at the site right downstream of the city of Arad. In both species, significantly elevated hepatic EROD activity downstream of Arad indicated that fish from these sites are also exposed to organic chemicals. The results were indicative of impaired fish health at least at three of the four investigated sites. The approach to relate biomarker responses to analytical data on pollution was shown to fit well the recent EU demands on further enhanced efforts in the monitoring of Romanian water quality.     

Biomonitoring with Gammarus pulex at the Meuse (NL), Aller (GER) and Rhine (F) rivers with the online Multispecies Freshwater Biomonitor

Biological early warning systems represent a set of tools that may be able to respond to certain chemical monitoring requirements of recent European legislation, the Water Framework Directive (WFD2000/60/EC), that aims to improve and protect water quality across Europe. In situ biomonitoring was performed along the rivers Meuse (NL), Aller (GER) and Rhine (F) within the frame of the European Union-funded Project SWIFT-WFD. Gammarus pulex was used as a test organism during the evaluation of the Multispecies Freshwater Biomonitor(R) (MFB), an online biomonitor to quantitatively record different behaviour patterns of animals. At the river Meuse G. pulex reacted to pulse exposure of either a mixture of trace metals or of several organic xenobiotics, by showing up to 20% decreased locomotory activity (already at the 1st pulse) and increased mortality (at 2nd or 3rd pulse only). G. pulex deployed within the MFB system were observed to survive well at the monitoring station on the Aller (100%) and monitoring did not result in the measurement of chemical irregularities. In contrast, deployment at the monitoring station on the Rhine river demonstrated that the test organism was able to detect chemical irregularities by up to 20% decreased locomotory activity in the animals. The MFB proved to be an alert system for water quality monitoring at sensitive sites and sites with accidental pollution.     

Experimental and statistical validation of SPME-GC-MS analysis of phenol and chlorophenols in raw and treated water

A procedure based on solid-phase microextraction (SPME) and gas chromatography coupled with mass spectrometry (GC-MS) was developed and validated in order to analyse 10 phenols in water samples. The optimised conditions were obtained using polyacrylate fibre (PA), 20ml of sample volume, 10% NaCl, pH 4.0 and direct extraction at 35 degrees C and 1000rpm, for 40min. The linear range and quantification limits for these compounds by SPME-GC-MS were defined. An evaluation of the main uncertainty sources of this method is included, which allows expanded uncertainties in the 9.4-35% range for the majority of the compounds. The main source of uncertainty is associated with matrix effects. The validated method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from water supply system of a large area (Lisbon and neighbour municipalities).     

Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.     

Air Quality Survey Carried Out by Schoolchildren: An Innovative Tool for Urban Planning

An educational project on biological monitoring of air quality was launched in 2004 to involve about 650 young students (age 6 to 16) from 21 schools of nine municipalities in Tuscany (Central Italy) in active detection of the crucial pollutant ozone with indicator sensitive tobacco seedlings. Results implied the reading of 9,300 raw biological figures and were fortified by the data captured by six photometric analysers. Under the guidance of their teachers, the students had several opportunities to practice with many basic and applied study areas and were initiated into the scientific method in a simple and absorbing manner. Curiosity and involvement were widespread; a sort of emotional and responsible relationship was developed by several pupils. Though primarily an educational exercise, the survey introduced a research element and the regional picture of air pollution that emerged has increased our knowledge of the air quality situation in the area. Biological monitoring of air quality is a powerful tool to improve the awareness and involvement in key topics of environmental education. In addition, it represents a crucial element for improving the awareness of problems and implies the active participation of citizens in the assessment of several indicators of the state of the environment. Its potential as a robust implement in landscape and urban planning is noteworthy.     

Biological endpoints, enzyme activities, and blood cell parameters in two anuran tadpole species in rice agroecosystems of mid-eastern Argentina

Different biological variables of tadpoles, including survival, development and growth rates, and biomarkers [cholinesterases, glutathione-S-transferases (GST), and blood cell morphology] were evaluated in two anuran species, Scinax squalirostris (Hylidae) and Leptodactylus mystacinus (Leptodactylidae), using in situ experimental chambers in a rice field (RF) sprayed with insecticide Lambda-cyhalothrin (LTC) by aircraft in Santa Fe Province, Argentina. We found a significant decrease in body weight (0.62?±?0.04 g) of L. mystacinus and an increased development rate of S. squalirostris in individuals from RF (41?±?1; Gosner) with respect to individuals from the reference site (RS: 0.93?±?0.04 g and 37?±?0; respectively). In S. squalirostris, individuals from RF mean values of butyrylcholinesterase activities decreased at 48 (4.09?±?0.32 nmol min^-1 mg^-1 of TP) and 96 h (3.74?±?0.20 nmol min^-1 mg^-1 of TP), whereas inhibition of acetylcholinesterase was observed at 96 h (47.44?±?2.78 nmol min^-1 mg^-1 of TP). In L. mystacinus from RF, an induction of acetylcholinesterase activity was observed at 96 h (36.01?±?1.09 nmol min^-1 mg^-1 of TP). Glutathione-S-transferase levels varied between species, being higher in L. mystacinus individuals but lower in S. squalirostris from RF at 48 (272.29 ±11.78 and 71.87?±?1.70 nmol min^-1 mg^-1 of TP; respectively) and 96 h (279.25?±?13.06 and 57.62?±?4.58 nmol min^-1 mg^-1 of TP, respectively). Blood cell parameters revealed a lower number of mitotic cells (MC: 0.36?±?0.31%o for S. squalirostris and 0.08?±?0.05 %o for L. mystacinus) and higher number of eosinophils (E: 3.45?±?1.75 %o for S. squalirostris and 7.64?±?0.98 %o for L. mystacinus) in individuals from the RF than in individuals from the RS (MC: 2.55?±?0.74 %o for S. squalirostris and 1.87?±?0.72%o for L. mystacinus; and E: 0.13?±?0.09 for S. squalirostris and 3.20?±?0.80 for L. mystacinus). Overall, our results demonstrate the existence of apparent differences in sensitivity between species in a series of sublethal responses to short-term exposure in RF after the application of Lambda-cyhalothrin. We suggest that the integral use of biological endpoints (development and growth) together with biomarkers (cholinesterase, GST, and blood cell parameters) may be a promising integral procedure for investigating pesticide exposure in wild frog populations.