Techno-economical efficiency and productivity change of wastewater treatment plants: the role of internal and external factors

Efficiency and productivity are important measures for identifying best practice in businesses and optimising resource-use. This study analyses how these two measures change across the period 2003-2008 for 196 wastewater treatment plants (WWTPs) in Spain, by using the benchmarking methods of Data Envelopment Analysis and the Malmquist Productivity Index. To identify which variables contribute to the sustainability of the WWTPs, differences in efficiency scores and productivity indices for external factors are also investigated. Our results indicate that both efficiency and productivity decreased over the five years. We verify that the productivity drop is primarily explained by technical change. Furthermore, certain external variables affected WWTP efficiency, including plant size, treatment technology and energy consumption. However, plants with low energy consumption are the only ones which improve their productivity. Finally, the benchmarking analyses proved to be useful as management tools in the wastewater sector, by providing vital information for improving the sustainability of plants.     

Temperature effect of tapered element oscillating microbalance (TEOM) system measuring semi-volatile organic particulate matter

The tapered element oscillating microbalance (TEOM) system is widely used to measure continuous particle mass concentrations in air quality networks. However, the semi-volatile aerosol material is lost under normal operation conditions (50 °C). This study has evaluated the error in the organic fraction of the TEOM-measured secondary organic aerosols formed from the degradation of biogenic pollutants. Experiments were carried out under controlled, water-free conditions in a fully equipped, high volume atmospheric simulator--the European PhotoReactor (EUPHORE). The ozonolysis of α-pinene, β-pinene and limonene provided a reproducible source of organic aerosol. Particulate matter concentration profiles were registered for different TEOM operating temperatures. When these values were compared with values from a filter-based gravimetric method and a scanning mobility particle sizer (SMPS), they showed that the differences between monitoring systems increased with increasing TEOM temperature. According to our results, when the TEOM is operated at 50 °C, it fails to measure 32-46% of the organic particulate material, depending on the aerosol precursor. This study has also identified and quantified the multi-oxygenated organic compounds lost in the TEOM monitoring by using a method based on the gas chromatography-mass spectrometry technique. Important losses have been calculated for relevant ambient aerosol compounds such as pinonic acid, pinonaldehyde, norpinone and limonalic acid. In conclusion, the present study has demonstrated that a high operating temperature of the TEOM monitor reduces the humidity interference but underestimates the semi-volatile organic fraction.     

Okadaic acid induces morphological changes, apoptosis and cell cycle alterations in different human cell types

Okadaic acid (OA) is a marine toxin produced by dinoflagellate species which is frequently accumulated in molluscs usual in the human diet. The exact action mechanism of OA has not been described yet and the results of most reported studies are often conflicting. The aim of this work was to evaluate the OA effects on morphology, cell cycle and apoptosis induction by means of light microscopy and flow cytometry, in three different types of human cells (leukocytes, HepG2 cells and SHSY5Y cells). Cells were treated with a range of OA concentrations in the presence and absence of S9 fraction. OA induced morphological changes in all the cell types studied, and cell cycle disruption only in leukocytes and neuronal cells. SHSY5Y cells were the most sensitive to OA assault. Results obtained in the presence and absence of metabolic activation were similar, suggesting that OA acts both directly and indirectly. Furthermore, OA was found to increase the subG(1) region in the flow cytometry cell cycle analysis, suggesting induction of apoptosis. These results were confirmed by the employment of specific methodologies for studying apoptosis such as caspase 3 activation and annexin V staining. Increases in the apoptosis rate were obtained in all the cells treated in the absence of S9 fraction, accompanied by increases in caspase 3 activation, suggesting that apoptosis induced by OA is a caspase 3-dependent process. Nevertheless, in the presence of S9 fraction no apoptosis was detected, indicating a metabolic detoxifying activity, although necrosis was observed in neuroblastoma cells.     

Characterization of PM10-bound polycyclic aromatic hydrocarbons in the ambient air of Spanish urban and rural areas

Urban areas constitute major pollution sources due to anthropogenic activities located in these areas. Among the legislated air pollutants, the particulate matter with an aerodynamic diameter less than or equal to 10 microns (PM10) and polycyclic aromatic hydrocarbons (PAH) are controlled under Directive 2008/50/EC and Directive 2004/107/EC, respectively due to their adverse health effects. A study was carried out at four urban and rural Spanish areas during the warm and cold seasons in 2008-2009 to quantify 19 PAH associated with the atmospheric PM10 by gas chromatography-mass spectrometry-mass spectrometry detection (GC-MS-MS) with the internal standard method. The particle-bound composition of the analysed PAH was 5 and 10 times greater in industrial and urban areas, respectively when compared to those measured in rural areas. The highest PAH concentrations during the cold period were possibly due to the additional contribution of domestic heating sources and meteorological conditions such as low temperature and solar irradiation. The use of molecular diagnostic ratios indicated that the possible, major PAH pollution sources in the most polluted areas were pyrogenic sources, mainly attributed to petroleum combustion sources (motor vehicle emissions and crude oil combustion). Petrogenic sources related to evaporative emissions also seemed to contribute in the most polluted area during the warm period. Those dates with high carcinogenic character according to the benzo(a)pyrene equivalent (BaP-eq) were also possibly attributed to petroleum combustion sources.     

Assessment of regional metal levels in ambient air by statistical regression models

The assessment of the particulate matter (PM) levels and its constituents presented in the atmosphere is an important requirement of the air quality management and air pollution abatement. The heavy metal levels in PM10 are commonly evaluated by experimental measurements; nevertheless, the EC Directives also allow the Regional Governments to estimate the regulated metal levels (Pb in Directive 2008/50/EC and As, Ni and Cd in Directive 2004/107/EC) by objective estimation and modelling techniques. These techniques are proper alternatives to the experimental determination because the required analysis and/or the number of required sampling sites are reduced. The present work aims to estimate the annual levels of regulated heavy metals by means of multivariate linear regression (MLR) and principal component regression (PCR) at four sites in the Cantabria region (Northern Spain). Since the objective estimation techniques may only be applied when the regulated metal concentrations are below to the lower assessment threshold, a previous evaluation of the determined annual levels of heavy metals is conducted to test the fulfilment of the EC Directives requirements. At the four studied sites, the results show that the objective estimations are allowed alternatives to the experimental determination. The annual average metal concentrations are well estimated by the MLR technique in all the studied sites; furthermore, the EC quality requirements for the objective estimations are fulfilled by the developed statistical MLR models. Hence these estimations may be used by Regional Governments as a proper alternative to the experimental measurements for the regulated metal levels assessment.     

Distribution and availability of trace elements in municipal solid waste composts

Trace element contamination is one of the main problems linked to the quality of compost, especially when it is produced from urban wastes, which can lead to high levels of some potentially toxic elements such as Cu, Pb or Zn. In this work, the distribution and bioavailability of five elements (Cu, Zn, Pb, Cr and Ni) were studied in five Spanish composts obtained from different feedstocks (municipal solid waste, garden trimmings, sewage sludge and mixed manure). The five composts showed high total concentrations of these elements, which in some cases limited their commercialization due to legal imperatives. First, a physical fractionation of the composts was performed, and the five elements were determined in each size fraction. Their availability was assessed by several methods of extraction (water, CaCl(2)-DTPA, the PBET extract, the TCLP extract, and sodium pyrophosphate), and their chemical distribution was assessed using the BCR sequential extraction procedure. The results showed that the finer fractions were enriched with the elements studied, and that Cu, Pb and Zn were the most potentially problematic ones, due to both their high total concentrations and availability. The partition into the BCR fractions was different for each element, but the differences between composts were scarce. Pb was evenly distributed among the four fractions defined in the BCR (soluble, oxidizable, reducible and residual); Cu was mainly found in the oxidizable fraction, linked to organic matter, and Zn was mainly associated to the reducible fraction (iron oxides), while Ni and Cr were mainly present almost exclusively in the residual fraction. It was not possible to establish a univocal relation between trace elements availability and their BCR fractionation. Given the differences existing for the availability and distribution of these elements, which not always were related to their total concentrations, we think that legal limits should consider availability, in order to achieve a more realistic assessment of the risks linked to compost use.     

Nucella lapillus L. imposex levels after legislation prohibiting TBT antifoulants: temporal trends from 2003 to 2008 along the Portuguese coast

Nucella lapillus (dog whelk) imposex levels were assessed along the mainland Portuguese coast in 2006 and 2008 and were compared with available data from 2003 for the same area. Given that specimen size has been described as a factor inducing variation in some of the imposex assessment indices, and thus resulting in less reliable results, new monitoring and data analysis procedures are described and applied to study change of imposex levels from 2003 to 2008. A significant decline in imposex intensity was observed in the study area during the study period, and the Portuguese coast ecological status (under the terms defined by the OSPAR Commission) notably improved after 2003, confirming the effectiveness of the Regulation (EC) No. 782/2003 in reducing TBT pollution. Nevertheless, N. lapillus populations are still extensively affected by imposex, and fresh TBT inputs were detected in seawater throughout the coast in 2006. These recent inputs are attributed to vessels still carrying TBT antifoulants applied before 2003, as their presence in vessels was only forbidden in 2008. Considering that Regulation (EC) No. 782/2003 is an anticipation of the IMO global ban entered into force in September 2008, a worldwide-scale decrease in TBT pollution can be expected in the near future.     

Monitoring of pharmaceutically active compounds on the Guadalquivir River basin (Spain): occurrence and risk assessment

Guadalquivir River (South of Spain) is among the major freshwater sources of the European Atlantic basin. Until now scientific efforts have been focused on contamination by heavy metals and some priority pollutants in Guadalquivir River. However, the presence of "emerging contaminants", such as pharmaceutically active compounds, has not yet been studied. In this work the occurrence and risk assessment of sixteen pharmaceutically active compounds, belonging to different therapeutic groups, in Guadalquivir River during its course through Seville city are reported. Wastewater effluents from four wastewater treatment plants discharging into Guadalquivir River and river water samples were analyzed. All studied pharmaceutically active compounds, except sulfamethoxazole, trimethoprim, estrone and clofibric acid, were detected in effluent wastewaters at concentration levels up to 28.9 μg L(-1). Among the pharmaceutically active compounds found in effluent wastewater, seven were present in Guadalquivir River samples at concentration levels up to 0.75 μg L(-1), which indicated an important dilution from effluent discharge. Environmental risk assessment reveals that potential ecotoxicological risk cannot be expected on Guadalquivir River at measured concentration levels. Only, the lipid regulator gemfibrozil showed a medium risk for the environment. The risk for acute toxic effects in the environment with the current use of active pharmaceutical ingredients is unlikely. However, the results do not rule out the potential for chronic environmental effects.     

Behaviour of different lichen species as biomonitors of air pollution by PAHs in natural ecosystems

Six different species of lichens (Parmelia sulcata Tayl., Evernia prunastri (L.) Ach., Ramalina farinacea, Pseudevernia furfuracea (L.) Zopf., Usnea sp. and Lobaria pulmonaria (Schreb.) Hoffm.) were collected in two mountain valleys in Central Pyrenees: the Aspe and Aragon valleys. Two multivariate techniques have been applied with different purposes, ANOVA and Discriminant Analysis (DA), to evaluate the data. The PAHs spatial distribution was studied in the three more abundant and widespread species in the area: P. sulcata, E. prunastri (L.) Ach. and R. farinacea in terms of total PAHs, PAHs related to the combustion processes and toxicity. Different behaviour of each lichen species to trap PAHs was found, being P. sulcata the best one to monitor the most persistent PAHs of pyrogenic origin and E. prunastri the most appropriate to provide information about pyrogenic and petrogenic PAHs. Traffic was the most relevant influence in PAHs bioaccumulation in lichen species.     

Tracking sewage derived contamination in riverine settings by analysis of synthetic surfactants

A study has been made of the presence and reactivity of the most commonly used surfactants, both anionic (linear alkylbenzene sulfonates, LAS, and alkyl ethoxysulfates, AES) and non-ionic (alcohol polyethoxylates, AEOs, and nonylphenol polyethoxylates, NPEOs), in water and surface sediments from the middle stretch of the Guadalete River in SW Spain (12 stations). Average values were between 0.1 and 3.7 mg kg(-1) in sediment, and between 0.2 and 37 μg L(-1) in water. The sorption of surfactants was dominated by hydrophobic mechanisms, so those homologues having longer alkyl chains (e.g. C(18)AEO) showed higher relative percentages and concentrations in sediments compared with water. Local and sharply higher concentrations of these compounds were observed at three sampling stations (7, 9 and 12), indicating the occurrence of wastewater discharges into the river. By analysing the distributions of different surfactant homologues and their metabolites we were able to distinguish between sewage contamination from sources discharging treated and untreated wastewaters. Upstream (stations 1-2), LAS concentrations were below 30 μg L(-1) and the composition of their degradation intermediates (sulfophenyl carboxylic acids, SPCs) (160 μg L(-1)) was dominated by short-chain homologues (C(6)-C(9)SPCs), indicating that the degradation of this surfactant is at an advanced stage. The highest concentration (487 μg L(-1)) of SPCs was detected near the effluent outlet of a sewage treatment plant (STP) (station 12). Sampling stations (7 and 9) affected by untreated wastewater discharges were the only ones showing the presence of the most reactive and biodegradable SPC isomers and homologues (e.g. C(11)SPC). Here, LAS reached the highest concentration values measured (>2 mg L(-1)), and showed a homologue distribution closer to that of commercial mixtures than LAS found at the other stations.