Survey of phthalates, alkylphenols, bisphenol A and herbicides in Spanish source waters intended for bottling

Background, aim and scope

Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination.

Materials and methods

Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed.

Results and discussion

Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77?C124?%) and limits of quantification were between 0.0004 and 0.029???g/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018???g/L for octylphenol to 0.970???g/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115???g/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds.

Conclusions

Target compounds were detected in a very low concentration and only in very few samples. This indicates the good quality of source waters intended for bottling and the effectiveness of the protection measures adopted in Spain. None of the samples analysed exceeded the maximum legislated levels for drinking water both in Spain and in the European Union.     

Influence of sugar cane vinasse on the sorption and degradation of herbicides in soil under controlled conditions

This study reports the influence of sugar cane vinasse on the persistence, sorption and leaching potential of diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), hexazinone (3-cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) in both a clay and sandy soil from a tropical area of Brazil. The experiments were conducted out under controlled laboratory conditions. The addition of sugarcane vinasse to soil influenced the persistence and sorption of the herbicides in both the studied clay and sandy soils, with a considerable decrease in the diuron DT(50) values in clay soil. The Ground Water Ubiquity Score (GUS) Index classifies the herbicides as leachers in both soils and treatments, with the exception of diuron, which is classified as a non-leacher in clay soil-vinasse and as a transient herbicide in sandy soil. These results suggest that special attention should be given to areas such as those where the sandy soil was collected in this study, which is a recharge area of the Guarani Aquifer and is likely to experience groundwater contamination due to the high leaching potential of the applied pesticides.     

Adapting a geographical information system-based water resource management to the needs of the Romanian water authorities

Background, aim, and scope

The need for global and integrated approaches to water resources management, both from the quantitative and the qualitative point of view, has long been recognized. Water quality management is a major issue for sustainable development and a mandatory task with respect to the implementation of the European Water Framework Directive as well as the Swiss legislation. However, data modelling to develop relational databases and subsequent geographic information system (GIS)-based water management instruments are a rather recent and not that widespread trend. The publication of overall guidelines for data modelling along with the EU Water Framework Directive is an important milestone in this area. Improving overall water quality requires better and more easily accessible data, but also the possibility to link data to simulation models. Models are to be used to derive indicators that will in turn support decision-making processes. For this whole chain to become effective at a river basin scale, all its components have to become part of the current daily practice of the local water administration. Any system, tool, or instrument that is not designed to meet, first of all, the fundamental needs of its primary end-users has almost no chance to be successful in the longer term.

Materials and methods

Although based on a pre-existing water resources management system developed in Switzerland, the methodological approach applied to develop a GIS-based water quality management system adapted to the Romanian context followed a set of well-defined steps: the first and very important step is the assessment of needs (on the basis of a careful analysis of the various activities and missions of the water administration and other relevant stakeholders in water management related issues). On that basis, a conceptual data model (CDM) can be developed, to be later on turned into a physical database. Finally, the specifically requested additional functionalities (i.e. functionalities not provided by classical commercial GIS software), also identified during the assessment of needs, are developed. This methodology was applied, on an experimental basin, in the Ialomita River basin.

Results

The results obtained from this action-research project consist of a set of tangible elements, among which (1) a conceptual data model adapted to the Romanian specificities regarding water resources management (needs, data availability, etc.), (2) a related spatial relational database (objects and attributes in tables, links, etc.), that can be used to store the data collected, among others, by the water administration, and later on exploited with geographical information systems, (3) a toolbar (in the ESRI environment) offering the requested data processing and visualizing functionalities. Lessons learned from this whole process can be considered as additional, although less tangible, results.

Discussion

The applied methodology is fairly classical and did not come up with revolutionary results. Actually, the interesting aspects of this work are, on the one hand, and obviously, the fact that it produced tools matching the needs of the local (if not national) water administration (i.e. with a good chance of being effectively used in the day-to-day practice), and, on the other hand, the adaptations and adjustments that were needed both at the staff level and in technical terms.

Conclusions

This research showed that a GIS-based water management system needs to be backed by some basic data management tools that form the necessary support upon which a GIS can be deployed. The main lesson gained is that technology transfer has to pay much attention to the differences in existing situations and backgrounds in general, and therefore must be able to show much flexibility. The fact that the original objectives could be adapted to meet the real needs of the local end-users is considered as a major aspect in achieving a successful adaptation and development of water resources management tools. Time needed to setup things in real life was probably the most underestimated aspect in this technology transfer process.

Recommendations and perspectives

The whole material produced (conceptual data model, database and GIS tools) was disseminated among all river basin authorities in Romania on the behalf of the national water administration (ANAR). The fact that further developments, for example, to address water quantity issues more precisely, as envisaged by ANAR, can be seen as an indication that this project succeeded in providing an appropriate input to improve water quality in Romania on the long term.

     

Influence of natural events on the concentration and composition of atmospheric particulate matter

A ten-month field study aimed to determine the contribution of natural events (i.e. sea-salt and mineral dust events) to urban PM concentration was carried out at six sampling sites in Central Italy (Lazio region). Four indicators have been used to identify natural events during the period of the study. The first one is constituted by the ratio between number of particles in the coarse to the accumulation mode. It is simple, cheap, and the information are given in quasi-real time, but the nature of the event (sea-salt or mineral dust) is not detectable. The second indicator relies on the chemical analysis of the collected PM by X-ray fluorescence (XRF) and allows a robust identification of sea-salt and crustal components. The third one is based on diagnostic ratios of elemental fractions: Mg_extractable/Ti_residue for sea-salt and Ti_residue/Sb_residue for mineral dust. It requires skilled staff but it is most accurate and sensible. The last indicator, constructed on the basis of natural radioactivity data, is not diagnostic for the nature of the event but it is able to estimate the increase in PM concentration with respect to the expected concentration in the absence of natural events.The relevance of natural events and the variations in PM concentration and composition during the study are discussed. The joined use of the four indicators allowed the identification of about 20 natural PM episodes. In general, sea-salt aerosol events did not cause exceedance of the daily EU limit value for PM₁₀. Saharan dust events, instead, were in most cases responsible for the exceedance of the limit value at all stations.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.     

Epiphytische Flechten im Wandel von Immissionen und Klima ? Ergebnisse einer Vergleichskartierung 1989/2007 in Nordwestdeutschland

Zusammenfassung   Hintergrund, Ziel und Zweck Borkenbewohnende (epiphytische) Flechten reagieren sehr empfindlich auf verschiedene Umwelteinflüsse wie Stoffgehalte in der Atmosph?re und Temperaturen. Sie haben als Bioindikatoren für Luftverunreinigungen einen hohen Stellenwert bei Umweltuntersuchungen. Basierend auf einer 1989 durchgeführten Kartierung borkenbewohnender (epiphytischer) Flechten in einem landwirtschaftlich intensiv genutzten Raum Nordwestdeutschlands erfolgte 2007 eine Wiederholungsuntersuchung. Dabei galt es, m?gliche Ver?nderungen der Immissionssituation und des Klimas zu erkennen. Material und Methoden Die Studie basiert auf einer vergleichenden Kartierung epiphytischer Flechten von 355 Tr?gerb?umen an 45 Monitoringpunkten. Die angewandte Methode orientiert sich an der 1989 angewandten halb-quantitativen Erfassung. Ergebnisse Es stellten sich gravierende Ver?nderungen in der Vegetation rindenbewohnender Flechten heraus. Insgesamt war eine Erh?hung der Artenzahl an nahezu allen Monitoringpunkten festzustellen. Es wurde eine sehr starke Abnahme s?uretoleranter Arten und eine deutliche Zunahme basen- und n?hrstofffordernder Flechtenarten festgestellt. Darüber hinaus zeigte sich eine deutliche Zunahme w?rmeliebender Flechtenarten mit einem Verbreitungsschwerpunkt in Südeuropa bei gleichzeitigem Rückgang von Arten mit einem boreal-montanem Verbreitungsschwerpunkt. Diskussion Die festgestellte Entwicklung steht im Einklang mit überregionalen Beobachtungen. Sie wird im Wesentlichen auf eine gro?r?umig ver?nderte Immissionssituation, d. h. einer Abnahme der atmosph?rischen SO₂-Belastung und Zunahme der Ammoniakbelastung zurückgeführt. Ebenso treten deutliche Auswirkungen der Klimaerw?rmung hervor. Schlussfolgerungen Mit relativ geringem Untersuchungsaufwand lie?en sich Ver?nderungen bei den epiphytischen Flechten in den letzten 18 Jahren aufzeigen. Diese sind relevant für die Beurteilung regional und kleinr?umig ver?nderter Umweltbedingungen, die auch für andere Organismen und ?kosysteme l?ngerfristig von gro?er Bedeutung sind. Empfehlungen und Ausblick Unter Verwendung standardisierter Methoden vermitteln epiphytische Flechten ein differenziertes Bild der Luftbelastungssituation in Ballungsr?umen und in landwirtschaftlich genutzten Regionen. Darüber hinaus sind sie offensichtlich gute Indikatoren für Temperatur?nderungen ihrer Umgebung. Weiterer Forschungsbedarf besteht für die Verwendung epiphytischer Flechten zum Biomonitoring von Klimaver?nderungen.      

Effect of variations in the redox potential of Gleysol on barium mobility and absorption in rice plants

Two assays were designed to obtain information about the influence of redox potential variations on barium mobility and bioavailability in soil. One assay was undertaken in leaching columns, and the other was conducted in pots cultivated with rice (Oryza sativa) using soil samples collected from the surface of Gleysol in both assays. Three doses of barium (100,300 mg kg⁻¹ and 3000 mg kg⁻¹-soil dry weight) and two redox potential values (oxidizing and reducing) were evaluated. During the incubation period, the redox potential (Eh) was monitored in columns and pots until values of −250 mV were reached. After the incubation period, geochemical partitioning was conducted on the barium using the European Communities Bureau of Reference (BCR) method. Rainfall of 200 mm d⁻¹ was simulated in the columns and in the planting of rice seedlings in the pots. The results of the geochemical partitioning demonstrated that the condition of reduction favors increased barium concentrations in the more labile chemical forms and decreased levels in the chemical forms related to oxides. The highest barium concentrations in leached extracts (3.36 mg L⁻¹) were observed at the highest dose and condition of reduction at approximately five times above the drinking water standard. The high concentrations of barium in the soil did not affect plant dry matter production. The highest levels and accumulation of barium in roots, leaves, and grains of rice were found at the highest dose and condition of reduction. These results demonstrate that reduction leads to solubilization of barium sulfate, thereby favoring greater mobility and bioavailability of this element.     

Chlorinated and brominated organic contaminants in fish from Shanghai markets: a case study of human exposure

In the present study were two favorite edible fish species for local residents, i.e., mandarin fish and crawfish, collected from the Shanghai market and analyzed for selected organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), hexabromocyclododecane (HBCDD), polybrominated diphenyl ethers (PBDEs) and methoxylated PBDEs (MeO-PBDEs). Efforts were also made to identify the potential sources of these contaminants. Comparable concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and HBCDD were found in muscle tissue of mandarin fish from Guangdong (GDF), the Pearl River Delta and from Taihu Lake (TLF), the Yangtze River Delta. Levels of chlordanes, PCBs and PBDEs were about one magnitude lower in TLF compared to GDF. The concentrations of OCPs in the butter-like gland of the crawfish (CFB) were 2-5 times of those in the crawfish muscle (CFM) while concentrations of PCBs, PBDEs and MeO-PBDEs were comparable. The different patterns and levels of chlorinated and brominated organohalogen contaminants seen in mandarin fish from GDF and TLF indicates that different types of chemicals might be used in the two delta regions. The present study also shows a good correlation between the concentrations of hexachlorobenzene (HCB) and pentachloroanisol (PCA) in fish for the first time. Fish consumption limits based on chemical contaminants with non-carcinogenic effects were calculated. The estimated maximum daily consumption limit for GDF, TLF, CFM and CFB were 1.5, 2.6, 3.7 and 0.08 kg, respectively, indicating no significant risk regarding the persistent organic pollutants measured in the present study.     

Mutagenicity of particulate matter fractions in areas under the impact of urban and industrial activities

Organisms in the environment are exposed to a mixture of pollutants. Therefore the purpose of this study was to analyze the mutagenicity of organic and inorganic responses in two fractions of particulates (TSP and PM2.5) and extracts (organic and aqueous). The mutagenicity of organic and aqueous particulate matter extracts from urban-industrial and urban-residential areas was evaluated by Salmonella/microsome assay, through the microsuspension method, using strain TA98 with and without liver metabolization. Additionally, strains YG1021 and YG1024 (nitro-sensitive) were used for organic extracts. Aqueous extracts presented negative responses for mutagenesis and cytotoxicity was detected in 50% of the samples. In these extracts the presence of potential bioavailable metals was identified. All organic extracts presented mutagens with a higher potential associated with PM2.5. This study presents a first characterization of PM2.5 in Brazil, through the Salmonella/microsome assay. The evaluation strategy detected the anthropic influence of groups of compounds characteristically found in urban and industrial areas, even in samples with PM values in accordance with quality standards. Thus, the use of a genotoxic approach in areas under different anthropic influences will favor the adoption of preventive measures in the health/environment relation.     

Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO₂ and CuO/TiO₂/Al₂O₃ by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO₂/RVC, 90% degradation was achieved in 2 h while with CuO/TiO₂/Al₂O₃/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO₂/RVC/UV and 99% with CuO/TiO₂/Al₂O₃/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.