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).     

Effect of herbicide and soil amendment on growth and photosynthetic responses in olive crops

Diuron [3-(3,4-dichlorophenyl)- = 1,1-dimethylurea] and simazine (6-chloro-N(2), N(4)-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the combined effect of these herbicides and the amendment of soil with an organic waste (OW) from the olive oil production industry on the growth and photosynthetic apparatus of adult olive trees and to compare the results with those obtained by Redondo-Gómez et al. for two-year-old trees. For this purpose, growth rate, gas exchange and chlorophyll fluorescence parameters were measured in 38-year-old olive trees, after one and two months of soil herbicide treatment and/or OW amendment. Soil co-application of OW and herbicide increases the quantum efficiency of Photosystem II (PSII) and the assimilation of CO(2) in olive trees, which led to a higher relative growth rate of the branches and leaves in length. Herbicide treatment reduced the photosynthetic efficiency in olive trees after two months of soil application, while this reduction is evident from week one in younger trees.     

Evaluation of GC-ion trap-MS/MS methodology for monitoring PCDD/Fs in infant formulas

The application of high resolution gas chromatography in combination with low resolution mass spectrometry with electron ionization and MS/MS detection (HRGC-MS/MS) is tested for its use in the analysis of PCDD/Fs in infant formulas. Development of the analytical method was based upon EPA directrices and international recommendations. Calibration linearity was tested and average relative response for any native and labelled compound over the five-point calibration range below 14% was found. The precision and accuracy of the proposed analytical procedure are also presented. Results obtained are in agreement with EPA criteria. The method is applied to the analysis of a number of initial and follow-on milk based infant formulas. In general, HRGC-MS/MS constitutes an interesting method for the analysis of dioxins in such matrices.     

Monitoring PCDD/Fs and other organic substances in workers of a hazardous waste incinerator: a case study

The aim of this study was to measure, 6 years after regular operations, the concentrations of a number of organic substances in blood and urine of 19 workers employed at a hazardous waste incinerator (HWI) in Spain, and to establish the temporal variation with respect to baseline data and previously performed surveys. This facility was the first, and so far the only HWI in that country. The levels of hexachlorobenzene (HCB), polychlorinated biphenyls (PCB 28, 52, 101, 138, 153 and 180) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in six composite plasma samples, while concentrations of di-, tri, and pentachlorophenols, as well those of 1-hydroxypyrene were measured in the urine of these workers. The current mean PCDD/F concentration, 10.4 ng I-TEQ/kg lipid, was significantly lower than that found in the baseline survey, 26.7 ng I-TEQ/kg lipid and similar to that found in the previous (2004) study (7.7 ng I-TEQ/kg lipid). PCDD/F levels in plasma were similar or even lower than those recently reported for various non-exposed populations. For the remaining analyzed substances in plasma and urine, there was not any significant increase in comparison with the levels found in the baseline survey. On the other hand, no marked differences between the concentrations of organic substances in plasma or urine were found according to the respective workplace (plant, laboratory and administration). The results of the present survey indicate that after 6 years of regular operation, the workers at the HWI are not occupationally exposed to PCDD/Fs and other organic substances in their workplaces.     

Simulation of stomatal conductance for Aleppo pine to estimate its ozone uptake

The data from a previous experiment carried out in open-top chambers to assess the effects of ozone (O3) exposure on growth and physiology of Aleppo pine (Pinus halepensis Mill.) were re-assessed to test the performance of the EMEP O3 stomatal conductance model used to estimate tree O3 uptake at a European scale. Aleppo pine seedlings were exposed during three consecutive years to three different O3 treatments: charcoal filtered air, non-filtered air and non-filtered air supplemented with 40 nl l(-1). The results of the model using the default parameterisation already published for Mediterranean conifers showed a poor performance when compared to measured data. Therefore, modifications of g(max), f(min), and new f(VPD), f(temp) and f(phen) functions were developed according to the observed data. This re-parameterisation resulted in a significant improvement of the performance of the model when compared to its original version.     

Accelerated carbonation of municipal solid waste incineration fly ashes

As a result of the EU Landfill Directive, the disposal of municipal solid waste incineration (MSWI) fly ash is restricted to only a few landfill sites in the UK. Alternative options for the management of fly ash, such as sintering, vitrification or stabilization/solidification, are either costly or not fully developed. In this paper an accelerated carbonation step is investigated for use with fly ash. The carbonation reaction involving fly ash was found to be optimum at a water/solid ratio of 0.3 under ambient temperature conditions. The study of ash mineralogy showed the disappearance of lime/portlandite/calcium chloride hydroxide and the formation of calcite as carbonation proceeded. The leaching properties of carbonated ash were examined. Release of soluble salts, such as SO4, Cl, was reduced after carbonation, but is still higher than the landfill acceptance limits for hazardous waste. It was also found that carbonation had a significant influence on lead leachability. The lead release from carbonated ash, with the exception of one of the fly ashes studied, was reduced by 2-3 orders of magnitude.     

Levels of metals, PCBs, PCNs and PAHs in soils of a highly industrialized chemical/petrochemical area: temporal trend

In 2005, the concentrations of various metals and organic pollutants were analyzed in soils collected in different areas of Tarragona (Catalonia, Spain), where an important chemical/petrochemical complex is located. The levels of seven elements (As, Cd, Cr, Hg, Mn, Pb and V), as well as those of polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polycyclic aromatic hydrocarbons (PAHs) were determined in soils, and compared with those obtained in a background study carried out in 2002. Only Cd and Pb showed significant higher concentrations in the petrochemical zone, while no significant differences were found for the remaining elements. In turn, vanadium was the only element showing a significant increase in the concentration between 2002 and 2005. With regard to the organic pollutants, no significant differences were found according to the area of sampling. However, an increase in naphthalene levels was observed during the period 2002-2005 in soils of the chemical and petrochemical areas. According to the present results, it is suggested that the levels of vanadium must be periodically monitored to assure that the important industrialization of Tarragona does not mean health risks for the population living near the complex.     

A neural-fuzzy approach to classify the ecological status in surface waters

A methodology based on a hybrid approach that combines fuzzy inference systems and artificial neural networks has been used to classify ecological status in surface waters. This methodology has been proposed to deal efficiently with the non-linearity and highly subjective nature of variables involved in this serious problem. Ecological status has been assessed with biological, hydro-morphological, and physicochemical indicators. A data set collected from 378 sampling sites in the Ebro river basin has been used to train and validate the hybrid model. Up to 97.6% of sampling sites have been correctly classified with neural-fuzzy models. Such performance resulted very competitive when compared with other classification algorithms. With non-parametric classification-regression trees and probabilistic neural networks, the predictive capacities were 90.7% and 97.0%, respectively. The proposed methodology can support decision-makers in evaluation and classification of ecological status, as required by the EU Water Framework Directive.     

Waste foundry sand used to cover organic waste in landfills

Journal of Material Cycles and Waste Management - Waste foundry sand (WFS) is a waste generated during the molding of metal parts and primarily discarded in landfills, which generates environmental...     

Water demand of central pivot-irrigated areas in Bahia,Brazil: management of water resources applied to sustainable production

When performed without technical criteria, the rapid expansion of irrigated agricultural frontiers can result in overexploitation of water, causing worrying impacts on the balance of agroecosystems. This study proposes a model applied to the state of Bahia, to estimate the water demand of areas irrigated by a central pivot, in order to contribute to information that will subsidize the inspection and planning of water resources in the promotion of sustainable agriculture. The irrigated areas were identified and measured by photointerpretation using orbital images from the Landsat-8 satellite. With a historical series of data, the reference evapotranspiration was calculated and monthly water balance was elaborated. The data obtained were spatialized by kriging, and with punctual values of water deficit (mm), the water demand of the irrigated perimeter of the equipment was estimated. The results were described considering strategic planning units, proposed from municipalities, hydrographic basins and biomes. A total of 4075 pivots were quantified, covering an irrigated area of 265,896.30 ha and with an average annual consumption of 1,333,473,208.02 m³ of water. Areas of high demand were identified, especially in the western region of Bahia, which includes the hydrographic basin of the São Francisco River and the Cerrado biome, concentrating 80.85% and 75.47% of the state water demand for pivots, respectively. Considering possible points of water vulnerability and continuity of this expansion, the results provide the primary information needed to encourage the adoption of public policies aimed at the management of water resources. The study method proposes guidelines that condition the application in any region of interest in the world.

Graphical abstract