Fast screening procedure for antibiotics in wastewaters by direct HPLC-DAD analysis

Growing concern about the contamination of wastewaters by antibiotics demands fast but sensitive analytical methodologies, for the screening of a large number of samples. The purpose of this work was to develop a simple methodology, using direct injection of the samples, by HPLC with diode array detection (DAD), for a multiresidue analysis of five antibiotics of different classes. Wastewater from an urban water treatment plant was selected as a model to study possible coelution of interfering compounds. The linearity interval ranged from 40 to 400 µg/L for amoxicillin (Amox), metronidazole (Metro), cefazolin (Cefa), and chloramphenicol (Chloram) and from 20 to 200 µg/L for sulfamethoxazole (Sulfa), with LODs lower than 14 µg/L. Repeatability, expressed by the CV of six repeated injections, ranged from 1 to 8%, while the intermediate precision varied between 2 and 11%. The recovery ranged from 90 to 109%. This method enables the fast screening of a large number of samples, with an expanded uncertainty in the 1–22% range. The advantage of the proposed method is to significantly reduce the number of samples to be analyzed by more complex methods.

Gestão de Afluências Indevidas em Redes de Águas Residuais Urbanas

As afluências indevidas resultantes direta ou indiretamente da precipitação são um dos principais fatores que provocam graves problemas de carácter ambiental, estrutural e económico, no âmbito de um bom funcionamento dos sistemas separativos de saneamento e tratamento de águas residuais urbanas. Ao longo dos anos, com a expansão do serviço de saneamento à população, tem sido reconhecido que os caudais excedentes às redes de drenagem de águas residuais e estações de tratamento são um problema grave e para isso estão a ser criados critérios cada vez mais exigentes no domínio da gestão e operação destes sistemas de saneamento. Para uma melhor compreensão sobre a incidência das afluências indevidas nos sistemas de saneamento e nas estações de tratamento de águas residuais, é necessário realizar estudos de quantificação e caracterização no sistema de esgotos. Com a necessidade de compreender a plenitude e natureza deste problema, tornou-se necessário desenvolver metodologias com o objetivo de melhorar a eficiência e eficácia hidráulica dos sistemas de drenagem e de tratamento. Este trabalho tem como objetivo a análise quantitativa das afluências indevidas, recorrendo a um caso de estudo de uma bacia de drenagem de águas residuais. Para adquirir mais conhecimento sobre o tema foi necessário recolher várias metodologias existentes de maneira a selecionar, estudar e aplicar o método mais vantajoso. Nesta dissertação, foram utilizados dados disponibilizados pela SIMRIA, no que respeita aos caudais de bombagem da estação elevatória a que afluiu a rede em estudo, e pela INDAQUA Feira, no que respeita aos dados de precipitação.

Assessment of groundwater contamination in an agricultural peri-urban area (NW Portugal): an integrated approach

The excessive use of pesticides and fertilisers in agriculture has generated a decrease in groundwater and surface water quality in many regions of the EU, constituting a hazard for human health and the environment. Besides, on-site sewage disposal is an important source of groundwater contamination in urban and peri-urban areas. The assessment of groundwater vulnerability to contamination is an important tool to fulfil the demands of EU Directives. The purpose of this study is to assess the groundwater vulnerability to contamination related mainly to agricultural activities in a peri-urban area (Vila do Conde, NW Portugal). The hydrogeological framework is characterised mainly by fissured granitic basement and sedimentary cover. Water samples were collected and analysed for temperature, pH, electrical conductivity, chloride, phosphate, nitrate and nitrite. An evaluation of groundwater vulnerability to contamination was applied (GOD-S, Pesticide DRASTIC-Fm, SINTACS and SI) and the potential nitrate contamination risk was assessed, both on a hydrogeological GIS-based mapping. A principal component analysis was performed to characterised patterns of relationship among groundwater contamination, vulnerability, and the hydrogeological setting assessed. Levels of nitrate above legislation limits were detected in 75 % of the samples analysed. Alluvia units showed the highest nitrate concentrations and also the highest vulnerability and risk. Nitrate contamination is a serious problem affecting groundwater, particularly shallow aquifers, especially due to agriculture activities, livestock and cesspools. GIS-based cartography provided an accurate way to improve knowledge on water circulation models and global functioning of local aquifer systems. Finally, this study highlights the adequacy of an integrated approach, combining hydrogeochemical data, vulnerability assessments and multivariate analysis, to understand groundwater processes in peri-urban areas.

Electric vehicles in urban areas: test cases using a scenario simulator

Electric vehicles introduction will affect cities environment and urban mobility policies. Network system operators will have to consider the electric vehicles in planning and operation activities due to electric vehicles’ dependency on the electricity grid. The present paper presents test cases using an Electric Vehicle Scenario Simulator (EVeSSi) being developed by the authors. The test cases include two scenarios considering a 33 bus network with up to 2000 electric vehicles in the urban area. The scenarios consider a penetration of 10% of electric vehicles (200 of 2000), 30% (600) and 100% (2000). The first scenario will evaluate network impacts and the second scenario will evaluate CO2 emissions and fuel consumption.

A study on dynamic state information (DSI) around users for safe urban life

To select each node by devices and by contexts in urban computing, users have to put their plan information and their requests into a computing environment (ex. PDA, Smart Devices, Laptops, etc.) in advance and they will try to keep the optimized states between users and the computing environment. However, because of bad contexts, users may get the wrong decision, so, one of the users’ demands may be requesting the good server which has higher security. To take this issue, we define the structure of Dynamic State Information (DSI) which takes a process about security including the relevant factors in sending/receiving contexts, which select the best during user movement with server quality and security states from DSI. Finally, whenever some information changes, users and devices get the notices including security factors, then an automatic reaction can be possible; therefore all users can safely use all devices in urban computing.

Contexts-management strategy in considering the security in urban computing based on urban design

Urban Computing (UrC) provides users with the situation-proper information by considering context of users, devices, and social and physical environment in urban life. With social network services, UrC makes it possible for people with common interests to organize a virtual-society through exchange of context information among them. In these cases, people and personal devices are vulnerable to fake and misleading context information which is transferred from unauthorized and unauthenticated servers by attackers. So called smart devices which run automatically on some context events are more vulnerable if they are not prepared for attacks. In this paper, we illustrate some UrC service scenarios, and show important context information, possible threats, protection method, and secure context management for people.

Natural organic matter fractionation along the treatment of water for human consumption

The main objective of this study was to characterize the organic matter present in raw water and along the treatment process, as well as its seasonal variation. A natural organic matter fractionation approach has been applied to Lever water treatment plant located in Douro River, in Oporto (Portugal). The process used was based on the sorption of dissolved organic matter in different types of ion exchange resins, DAX-8, DAX-4 and IRA-958, allowing its separation into four fractions: very hydrophobic acids (VHA), slightly hydrophobic acids (SHA), charged hydrophilic (CHA) and hydrophilic neutral (NEU). The dissolved organic carbon (DOC) determination was used to quantify dissolved organic matter. Samples were collected monthly, during approximately one year, from raw water captured at the surface and under the bed of the river, and after each step of the treatment: pre-filtration in sand/anthracite filters, ozonation, coagulation/flocculation, counter current dissolved air flotation and filtration (CoCoDAFF) and chlorination. The NEU fraction showed a seasonal variation, with maximum values in autumn for the sampling points corresponding to raw water captured at the surface and under the bed of the river. It was usually the predominating fraction and did not show a significant decrease throughout the treatment. Nevertheless their low concentration, the same occurred for the CHA and VHA fractions. There was an overall decrease in the SHA fraction throughout the water treatment (especially after CoCoDAFF and ozonation) as well as in the DOC. The TSUVA254 values obtained for raw water generally varied between 2.0 and 4.0 L mgC-1 m-1 and between 0.75 and 1.78 L mgC-1 m-1 for treated water. It was observed a decrease of TSUVA values along the treatment, especially after ozonation. These results may contribute to a further optimization in the process of treating water for human consumption.

Avaliação multitécnica em hidrogeologia ambiental e suas implicações na gestão de recursos hídricos subterrâneos

Mestrado em Engenharia Geotécnica e Geoambiente

Estudo hidrogeológico e hidropedológico das áreas periurbanas de Valbom e Avintes: implicações na gestão dos recursos hídricos subterrâneos

Mestrado em Engenharia Geotécnica e Geoambiente

Sensors for the detection and quantification of bacterial contamination in water for human use

The deterioration of water quality by Cyanobacteria cause outbreaks and epidemics associated with harmful diseases in Humans and animals because of the toxins that they release. Microcystin-LR is one of the hepatotoxins most widely studied and the World Health Organization, recommend a maximum value of 1mgL 1 in drinking water. Highly specific recognition molecules, such as molecular imprinted polymers are developed to quantify microcystins in waters for human use and shown to be of great potential in the analysis of these kinds of samples. The obtained results were auspicious, the detection limit found, 1.5mgL 1, being of the same order of magnitude as the guideline limit recommended by the WHO. This technology is very promising because the sensors are stable and specific, and the technology is inexpensive and allows for rapid on-site monitoring.

Electrochemical study of butylate: application to the analysis of water

The electroactivity of butylate (BTL) is studied by cyclic voltammetry (CV) and square wave voltammetry (SWV) at a glassy carbon electrode (GCE) and a hanging mercury drop electrode (HMDE). Britton–Robinson buffer solutions of pH 1.9–11.5 are used as supporting electrolyte. CV voltammograms using GCE show a single anodic peak regarding the oxidation of BTL at +1.7V versus AgCl/ Ag, an irreversible process controlled by diffusion. Using a HMDE, a single cathodic peak is observed, at 1.0V versus AgCl/Ag. The reduction of BTL is irreversible and controlled by adsorption. Mechanism proposals are presented for these redox transformations. Optimisation is carried out univaryingly. Linearity ranges were 0.10–0.50 mmol L-1 and 2.0–9.0 µmolL-1 for anodic and cathodic peaks, respectively. The proposed method is applied to the determination of BTL in waters. Analytical results compare well with those obtained by an HPLC method.

Use and reuse of SPE disks for the determination of pyrethroids in water by GC-ECD

Seven pyrethroids (bifenthrin, fenpropathrin, k-cyhalothrin, permethrin, a-cypermethrin, fenvalerate, and deltamethrin) were extracted from water using C18 solid-phase extraction disks, followed by gas chromatography with an electron capture detector (GC-ECD) analysis. The limits of detection in water samples ranged from 0.5 ng L-1 (fenpropathrin) to 110 ng L- 1 (permethrin), applying the calibration graph. The effects of different numbers of (re)utilizations of the same disks (up to four times with several concentrations) on the recoveries of the pyrethroids were considered. The recoveries were all between 70 and 120% after four utilizations of the same disk. There was no difference between these recoveries at a confidence level of 95%.

Soil remediation time to achieve clean-up goals I: influence of soil water content

The current models are not simple enough to allow a quick estimation of the remediation time. This work reports the development of an easy and relatively rapid procedure for the forecasting of the remediation time using vapour extraction. Sandy soils contaminated with cyclohexane and prepared with different water contents were studied. The remediation times estimated through the mathematical fitting of experimental results were compared with those of real soils. The main objectives were: (i) to predict, through a simple mathematical fitting, the remediation time of soils with water contents different from those used in the experiments; (ii) to analyse the influence of soil water content on the: (ii1) remediation time; (ii2) remediation efficiency; and (ii3) distribution of contaminants in the different phases present into the soil matrix after the remediation process. For sandy soils with negligible contents of clay and natural organic matter, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) if the soil water content belonged to the range considered in the experiments with the prepared soils, then the remediation time of real soils of similar characteristics could be successfully predicted, with relative differences not higher than 10%, through a simple mathematical fitting of experimental results; (ii) increasing soil water content from 0% to 6% had the following consequences: (ii1) increased remediation time (1.8–4.9 h, respectively); (ii2) decreased remediation efficiency (99–97%, respectively); and (ii3) decreased the amount of contaminant adsorbed onto the soil and in the non-aqueous liquid phase, thus increasing the amount of contaminant in the aqueous and gaseous phases.

Soil remediation time to achieve clean-up goals II: influence of natural organic matter and water contents

This work reports a relatively rapid procedure for the forecasting of the remediation time (RT) of sandy soils contaminated with cyclohexane using vapour extraction. The RT estimated through the mathematical fitting of experimental results was compared with that of real soils. The main objectives were: (i) to predict the RT of soils with natural organic matter (NOM) and water contents different from those used in experiments; and (ii) to analyse the time and efficiency of remediation, and the distribution of contaminants into the soil matrix after the remediation process, according to the soil contents of: (ii1) NOM; and (ii2) water. For sandy soils with negligible clay contents, artificially contaminated with cyclohexane before vapour extraction, it was concluded that: (i) if the NOM and water contents belonged to the range of the prepared soils, the RT of real soils could be predicted with relative differences not higher than 12%; (ii1) the increase of NOM content from 0% to 7.5% increased the RT (1.8–13 h) and decreased the remediation efficiency (RE) (99–90%) and (ii2) the increase of soil water content from 0% to 6% increased the RT (1.8–4.9 h) and decreased the RE (99–97%). NOM increases the monolayer capacity leading to a higher sorption into the solid phase. Increasing of soil water content reduces the mass transfer coefficient between phases. Concluding, NOM and water contents influence negatively the remediation process, turning it less efficient and more time consuming, and consequently more expensive.

Remediation efficiency of vapour extraction of sandy soils contaminated with cyclohexane: influence of air flow rate, water and natural organic matter content

Abstract This work reports the analysis of the efficiency and time of soil remediation using vapour extraction as well as provides comparison of results using both, prepared and real soils. The main objectives were: (i) to analyse the efficiency and time of remediation according to the water and natural organic matter content of the soil; and (ii) to assess if a previous study, performed using prepared soils, could help to preview the process viability in real conditions. For sandy soils with negligible clay content, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) the increase of soil water content and mainly of natural organic matter content influenced negatively the remediation process, making it less efficient, more time consuming, and consequently more expensive; and (ii) a previous study using prepared soils of similar characteristics has proven helpful for previewing the process viability in real conditions.