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.

Evaluation of the total antioxidant capacity of flavored water and electrochemical purine damage by sulfate radicals using a purine-based sensor

In this study, a method for the electrochemical quantification of the total antioxidant capacity (TAC) in beverages was developed. The method is based on the oxidative damage to the purine bases, adenine or guanine, that are immobilized on a glassy carbon electrode (GCE) surface. The oxidative lesions on the DNA bases were promoted by the sulfate radical generated by the persulfate/iron(II) system. The presence of antioxidants on the reactive system promoted the protection of the DNA bases immobilized on the GCE by scavenging the sulfate radical. Square-wave voltammetry (SWV) was the electrochemical technique used to perform this study. The efficiencies of five antioxidants (ascorbic acid, gallic acid, caffeic acid, coumaric acid and resveratrol) in scavenging the sulfate radical and, therefore, their ability to protect the purine bases immobilized on the GCE were investigated. These results demonstrated that the purine-based biosensor is suitable for the rapid assessment of the TAC in flavors and flavored water.

Influence of environmental temperature and humidity on the acute ventilatory response to exercise in asthmatic adolescents

Asthma is a chronic inflammatory disorder of the respiratory airways affecting people of all ages, and constitutes a serious public health problem worldwide (6). Such a chronic inflammation is invariably associated with injury and repair of the bronchial epithelium known as remodelling (11). Inflammation, remodelling, and altered neural control of the airways are responsible for both recurrent exacerbations of asthma and increasingly permanent airflow obstruction (11, 29, 34). Excessive airway narrowing is caused by altered smooth muscle behaviour, in close interaction with swelling of the airway walls, parenchyma retractile forces, and enhanced intraluminal secretions (29, 38). All these functional and structural changes are associated with the characteristic symptoms of asthma – cough, chest tightness, and wheezing –and have a significant impact on patients’ daily lives, on their families and also on society (1, 24, 29). Recent epidemiological studies show an increase in the prevalence of asthma, mainly in industrial countries (12, 25, 37). The reasons for this increase may depend on host factors (e.g., genetic disposition) or on environmental factors like air pollution or contact with allergens (6, 22, 29). Physical exercise is probably the most common trigger for brief episodes of symptoms, and is assumed to induce airflow limitations in most asthmatic children and young adults (16, 24, 29, 33). Exercise-induced asthma (EIA) is defined as an intermittent narrowing of the airways, generally associated with respiratory symptoms (chest tightness, cough, wheezing and dyspnoea), occurring after 3 to 10 minutes of vigorous exercise with a maximal severity during 5 to 15 minutes after the end of the exercise (9, 14, 16, 24, 33). The definitive diagnosis of EIA is confirmed by the measurement of pre- and post-exercise expiratory flows documenting either a 15% fall in the forced expiratory volume in 1 second (FEV1), or a ≥15 to 20% fall in peak expiratory flow (PEF) (9, 24, 29). Some types of physical exercise have been associated with the occurrence of bronchial symptoms and asthma (5, 15, 17). For instance, demanding activities such as basketball or soccer could cause more severe attacks than less vigorous ones such as baseball or jogging (33). The mechanisms of exercise-induced airflow limitations seem to be related to changes in the respiratory mucosa induced by hyperventilation (9, 29). The heat loss from the airways during exercise, and possibly its post-exercise rewarming may contribute to the exercise-induced bronchoconstriction (EIB) (27). Additionally, the concomitant dehydration from the respiratory mucosa during exercise leads to an increased interstitial osmolarity, which may also contribute to bronchoconstriction (4, 36). So, the risk of EIB in asthmatically predisposed subjects seems to be higher with greater ventilation rates and the cooler and drier the inspired air is (23). The incidence of EIA in physically demanding coldweather sports like competitive figure skating and ice hockey has been found to occur in up to 30 to 35% of the participants (32). In contrast, swimming is often recommended to asthmatic individuals, because it improves the functionality of respiratory muscles and, moreover, it seems to have a concomitant beneficial effect on the prevalence of asthma exacerbations (14, 26), supporting the idea that the risk of EIB would be smaller in warm and humid environments. This topic, however, remains controversial since the chlorified water of swimming pools has been suspected as a potential trigger factor for some asthmatic patients (7, 8, 20, 21). In fact, the higher asthma incidence observed in industrialised countries has recently been linked to the exposition to chloride (7, 8, 30). Although clinical and epidemiological data suggest an influence of humidity and temperature of the inspired air on the bronchial response of asthmatic subjects during exercise, some of those studies did not accurately control the intensity of the exercise (2, 13), raising speculation of whether the experienced exercise overload was comparable for all subjects. Additionally, most of the studies did not include a control group (2, 10, 19, 39), which may lead to doubts about whether asthma per se has conditioned the observed results. Moreover, since the main targeted age group of these studies has been adults (10, 19, 39), any extrapolation to childhood/adolescence might be questionable regarding the different lung maturation. Considering the higher incidence of asthma in youngsters (30) and the fact that only the works of Amirav and coworkers (2, 3) have focused on this age group, a scarcity of scientific data can be identified. Additionally, since the main environmental trigger factors, i.e., temperature and humidity, were tested separately (10, 28, 39) it would be useful to analyse these two variables simultaneously because of their synergic effect on water and heat loss by the airways (31, 33). It also appears important to estimate the airway responsiveness to exercise within moderate environmental ranges of temperature and humidity, trying to avoid extreme temperatures and humidity conditions used by others (2, 3). So, the aim of this study was to analyse the influence of moderate changes in air temperature and humidity simultaneously on the acute ventilatory response to exercise in asthmatic children. To overcome the above referred to methodological limitations, we used a 15 minute progressive exercise trial on a cycle ergometer at 3 different workload intensities, and we collected data related to heart rate, respiratory quotient, minute ventilation and oxygen uptake in order to ensure that physiological exercise repercussions were the same in both environments. The tests were done in a “normal” climatic environment (in a gymnasium) and in a hot and humid environment (swimming pool); for the latter, direct chloride exposition was avoided.

Sequential application of soil vapor extraction and bioremediation processes for the remediation of ethylbenzene-contaminated soils

Soil vapor extraction (SVE) is an efficient, well-known and widely applied soil remediation technology. However, under certain conditions it cannot achieve the defined cleanup goals, requiring further treatment, for example, through bioremediation (BR). The sequential application of these technologies is presented as a valid option but is not yet entirely studied. This work presents the study of the remediation of ethylbenzene (EB)-contaminated soils, with different soil water and natural organic matter (NOMC) contents, using sequential SVE and BR. The obtained results allow the conclusion that: (1) SVE was sufficient to reach the cleanup goals in 63% of the experiments (all the soils with NOMC below 4%), (2) higher NOMCs led to longer SVE remediation times, (3) BR showed to be a possible and cost-effective option when EB concentrations were lower than 335 mg kgsoil −1, and (4) concentrations of EB above 438 mg kgsoil −1 showed to be inhibitory for microbial activity.

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.

Remediation of soils combining soil vapor extraction and bioremediation: benzene

This work reports the study of the combination of soil vapor extraction (SVE) with bioremediation (BR) to remediate soils contaminated with benzene. Soils contaminated with benzene with different water and natural organic matter contents were studied. The main goals were: (i) evaluate the performance of SVE regarding the remediation time and the process efficiency; (ii) study the combination of both technologies in order to identify the best option capable to achieve the legal clean up goals; and (iii) evaluate the influence of soil water content (SWC) and natural organic matter (NOM) on SVE and BR. The remediation experiments performed in soils contaminated with benzene allowed concluding that: (i) SVE presented (a) efficiencies above 92% for sandy soils and above 78% for humic soils; (b) and remediation times from 2 to 45 h, depending on the soil; (ii) BR showed to be an efficient technology to complement SVE; (iii) (a) SWC showed minimum impact on SVE when high airflow rates were used and led to higher remediation times for lower flow rates; (b) NOM as source of microorganisms and nutrients enhanced BR but hindered the SVE due the limitation on the mass transfer of benzene from the soil to the gas phase.

Host-Guest interaction between herbicide oxadiargyl and hydroxypropyl-β-cyclodextrin

In the face of a growing human population and increased urbanization, the demand for pesticides will simply rise. Farmers must escalate yields on increasingly fewer farm acres. However, the risks of pesticides, whether real or perceived, may force changes in the way these chemicals are used. Scientists are working toward pest control plans that are environmentally sound, effective, and profitable. In this context the development of new pesticide formulations which may improve application effectiveness, safety, handling, and storage can be pointed out as a solution. As a contribution to the area, the microencapsulation of the herbicide oxadiargyl (OXA) in (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was performed. The study was conducted in different aqueous media (ultrapure water and in different pH buffer solutions). In all cases an increment of the oxadiargyl solubility as a function of the HP-β-CD concentration that has been related to the formation of an inclusion complex was verified. UV-Vis and NMR experiments allowed concluding that the stoichiometry of the OXA/HP-β-CD complex formed is 1 : 1. The gathered results can be regarded as an important step for its removal from industrial effluents and/or to increase the stabilizing action, encapsulation, and adsorption in water treatment plants.

Optimization of HS-SPME analytical conditions using factorial design for trihalomethanes determination in swimming pool water samples

Trihalomethanes (THMs) are widely referred and studied as disinfection by-products (DBPs). The THMs that are most commonly detected are chloroform (TCM), bromodichloromethane (BDCM), chlorodibromomethane (CDBM), and bromoform (TBM). Several studies regarding the determination of THMs in swimming pool water and air samples have been published. This paper reviews the most recent work in this field, with a special focus on water and air sampling, sample preparation and analytical determination methods. An experimental study has been developed in order to optimize the headspace solid-phasemicroextraction (HS-SPME) conditions of TCM, BDCM, CDBM and TBM from water samples using a 23 factorial design. An extraction temperature of 45 °C, for 25min, and a desorption time of 5 min were found to be the best conditions. Analysis was performed by gas chromatography with an electron capture detector (GC-ECD). The method was successfully applied to a set of 27 swimming pool water samples collected in the Oporto area (Portugal). TCM was the only THM detected with levels between 4.5 and 406.5 μg L−1. Four of the samples exceeded the guideline value for total THMs in swimming pool water (100 μgL−1) indicated by the Portuguese Health Authority.

Influence of Soil Chemistry and Plant Physiology in the Phytoremediation of Cu, Mn, and Zn

Different anthropogenic sources of metals can result from agricultural, industrial, military, mining and urban activities that contribute to environmental pollution. Plants can be grown for phytoremediation to remove or stabilize contaminants in water and soil. Copper (Cu), manganese (Mn) and zinc (Zn) are trace essential metals for plants, although their role in homeostasis in plants must be strictly regulated to avoid toxicity. In this review, we summarize the processes involved in the bioavailability, uptake, transport and storage of Cu, Mn and Zn in plants. The efficiency of phytoremediation depends on several factors including metal bioavailability and plant uptake, translocation and tolerance mechanisms. Soil parameters, such as clay fraction, organic matter content, oxidation state, pH, redox potential, aeration, and the presence of specific organisms, play fundamental roles in the uptake of trace essential metals. Key processes in the metal homeostasis network in plants have been identified. Membrane transporters involved in the acquisition, transport and storage of trace essential metals are reviewed. Recent advances in understanding the biochemical and molecular mechanisms of Cu, Mn and Zn hyperaccumulation are described. The use of plant-bacteria associations, plant-fungi associations and genetic engineering has opened a new range of opportunities to improve the efficiency of phytoremediation. The main directions for future research are proposed from the investigation of published results.