Determination of cyclic and linear siloxanes in wastewater samples by ultrasound-assisted dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry

A fast, simple and environmentally friendly ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) procedure has been developed to preconcentrate eight cyclic and linear siloxanes from wastewater samples prior to quantification by gas chromatography-mass spectrometry (GC-MS). A two-stage multivariate optimization approach has been developed employing a Plackett-Burman design for screening and selecting the significant factors involved in the USA-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were: extractant solvent volume, 13 µL; solvent type, chlorobenzene; sample volume, 13 mL; centrifugation speed, 2300 rpm; centrifugation time, 5 min; and sonication time, 2 min. Under the optimized experimental conditions the method gave levels of repeatability with coefficients of variation between 10 and 24% (n=7). Limits of detection were between 0.002 and 1.4 µg L−1. Calculated calibration curves gave high levels of linearity with correlation coefficient values between 0.991 and 0.9997. Finally, the proposed method was applied for the analysis of wastewater samples. Relative recovery values ranged between 71–116% showing that the matrix had a negligible effect upon extraction. To our knowledge, this is the first time that combines LLME and GC-MS for the analysis of methylsiloxanes in wastewater samples.

Fate and Transport of Naproxen in a Sandy Aquifer Material: Saturated Column Studies and Model Evaluation

Naproxen-C14H14O3 is a nonsteroidal anti-inflammatory drug which has been found at detectable concentrations in wastewater, surface water, and groundwater. Naproxen is relatively hydrophilic and is in anionic form at pH between 6 and 8. In this study, column experiments were performed using an unconsolidated aquifer material from an area near Barcelona (Spain) to assess transport and reaction mechanisms of Naproxen in the aquifer matrix under different pore water fluxes. Results were evaluated using HYDRUS-1D, which was used to estimate transport parameters. Batch sorption isotherms for Naproxen conformed with the linear model with a sorption coefficient of 0.42 (cm3 g−1), suggesting a low sorption affinity. Naproxen breakthrough curves (BTCs) measured in soil columns under steady-state, saturated water flow conditions displayed similar behavior, with no apparent hysteresis in sorption or dependence of retardation (R, 3.85-4.24) on pore water velocities. Soil sorption did not show any significant decrease for increasing flow rates, as observed from Naproxen recovery in the effluent. Sorption parameters estimated by the model suggest that Naproxen has a low sorption affinity to aquifer matrix. Most sorption of Naproxen occurred on the instantaneous sorption sites, with the kinetic sorption sites representing only about 10 to 40% of total sorption.

Removal of paracetamol on biomass-derived activated carbon: Modeling the fixed bed breakthrough curves using batch adsorption experiments

The remediation of paracetamol (PA), an emerging contaminant frequently found in wastewater treatment plants, has been studied in the low concentration range (0.3–10 mg L−1) using as adsorbent a biomass-derived activated carbon. PA uptake of up to 100 mg g−1 over the activated carbon has been obtained, with the adsorption isotherms being fairly explained by the Langmuir model. The application of Reichemberg and the Vermeulen equations to the batch kinetics experiments allowed estimating homogeneous and heterogeneous diffusion coefficients, reflecting the dependence of diffusion with the surface coverage of PA. A series of rapid small-scale column tests were carried out to determine the breakthrough curves under different operational conditions (temperature, PA concentration, flow rate, bed length). The suitability of the proposed adsorbent for the remediation of PA in fixed-bed adsorption was proven by the high PA adsorption capacity along with the fast adsorption and the reduced height of the mass transfer zone of the columns. We have demonstrated that, thanks to the use of the heterogeneous diffusion coefficient, the proposed mathematical approach for the numerical solution to the mass balance of the column provides a reliable description of the breakthrough profiles and the design parameters, being much more accurate than models based in the classical linear driving force.

Energy consumption in an urban wastewater treatment plant: the case of Murcia Region (Spain)

Of all the costs associated with the operation and maintenance of wastewater treatment plants (WWTPs), those associated with energy use tend to be the most significant. From this point of view, it is hence logical that energy efficiency and saving strategies should be one of the current focuses of debate amongst those involved with the management of WWTPs. The present study's objective is to determine the correlation between size and energy consumption for a WWTP. To this end, 90 WWTPs currently in service were analysed and their energetic impact quantified in terms of kWh/m3 of water treated. The results obtained demonstrate that energy consumption ratio increases as the size of WWTPs decreases, either in terms of treatment volume or population equivalent served.

Presence of Siloxanes in the Biogas of a Wastewater Treatment Plant Separation in Condensates and Influence of the Dose of Iron Chloride on its Elimination

The siloxanes present in the biogas produced during anaerobic digestion damage the mechanism of cogeneration equipment and, consequently, negatively affect the energy valorization process. For this reason, the detection and elimination of these silicon-derived chemical compounds are a priority in the management of cogeneration facilities. In this regard, the objectives of this paper are, firstly, to characterize the siloxanes in the biogas and, secondly, to qualitatively evaluate the influence of the dose of iron chloride on its elimination. The research was performed at the Rincón de León Wastewater Treatment Plant (Alicante, Spain). The outflow biogas of the digesters and of the pressurized gasometers was sampled and analyzed. The results obtained made it possible to demonstrate, firstly, the absence of linear siloxanes and that, of the cyclic siloxanes, the predominant type was decamethylcyclopentasiloxane, and, secondly, that the addition of iron chloride in the digesters significantly reduces the siloxane content in the biogas. Additionally, it was demonstrated that the process of compression of the biogas, with the elimination of condensates, also produces significant reductions in the concentration of siloxanes in the biogas.

Removal of endocrine disrupting compounds from wastewater: a comparison between a conventional activated sludge with tertiary treatment and membrane bioreactors

Póster presentado en 19th International Congress of Chemical and Process Engineering, Prague, Czech Republic August 28th-September 1st, 2010.

Beyond megaprojects?. Water alternatives for mass tourism in coastal Mediterranean Spain

Water availability in adequate quantities and qualities is a fundamental requirement for tourism. In the Mediterranean, one of the world’s leading tourist destinations, water availability is subject to modest and erratic precipitation figures which may decline with climate change. The tourist industry therefore may have to assure future supplies by either recurring to new technologies such as desalination or increasing efficiency in water use. A third and yet little explored alternative would be to seek for complementary of uses with irrigation, the traditional user in many coastal Mediterranean areas and holder of substantial amounts of water. In this paper we present the example of the Consorcio de Aguas de la Marina Baja to show how Benidorm, in Mediterranean Spain and one of the most important tourist centers of the Mediterranean, obtains part of its water through agreements with farmers by which these trade their water with Benidorm and other towns’ treated wastewater of enough quality to be used for irrigation, and obtain several compensations in return. The advantages and disadvantages of the water trade between farmers and tourist interests in the Benidorm area are discussed and we argue that solutions to the pending water crisis of many coastal Mediterranean tourist areas may not need to rely uniquely on expensive technologies to generate new resources but may attempt other alternatives.

Role of the denitrifying Haloarchaea in the treatment of nitrite-brines

Haloferax mediterranei is a denitrifying halophilic archaeon able to reduce nitrate and nitrite under oxic and anoxic conditions. In the presence of oxygen, nitrate and nitrite are used as nitrogen sources for growth. Under oxygen scarcity,this haloarchaeon uses both ions as electron acceptors via a denitrification pathway. In the present work, the maximal nitriteconcentration tolerated by this organism was determined by studying the growth of H. mediterranei in minimal medium containing30, 40 and 50 mM nitrite as sole nitrogen source and under initial oxic conditions at 42 °C. The results showed theability of H. mediterranei to withstand nitrite concentrations up to 50 mM. At the beginning of the incubation, nitrate wasdetected in the medium, probably due to the spontaneous oxidation of nitrite under the initial oxic conditions. The completeremoval of nitrite and nitrate was accomplished in most of the tested conditions, except in culture medium containing 50 mMnitrite, suggesting that this concentration compromised the denitrification capacity of the cells. Nitrite and nitrate reductases activities were analyzed at different growth stages of H. mediterranei. In all cases, the activities of the respiratory enzymeswere higher than their assimilative counterparts; this was especially the case for NirK. The denitrifying and possibly detoxifyingrole of this enzyme might explain the high nitrite tolerance of H. mediterranei. This archaeon was also able to remove60 % of the nitrate and 75 % of the nitrite initially present in brine samples collected from a wastewater treatment facility.These results suggest that H. mediterranei, and probably other halophilic denitrifying Archaea, are suitable candidates for thebioremediation of brines with high nitrite and nitrate concentrations.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Biodiesel production by transesterification of sludge in supercritical conditions

In this study wastewater treatment plant (WWTP) sludge was subjected to a reactive pyrolysis treatment to produce a high quality pyro-oil. Sludge was treated in supercritical conditions in the presence of methanol using hexane as cosolvent in a high pressure lab-autoclave. The variables affecting the pyro-oil yield and the product quality, such as mass ratio of alcohol to sludge, presence of cosolvent and temperature, were investigated. It was found that the use of a non-polar cosolvent (hexane) presents advantages in the production of high quality pyro-oil from sludge: increase of the non-polar pyro-oil yield and a considerable reduction of the amount of methanol needed to carry out the transesterification of fatty acids present in the sludge.

Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction for determination of mercury in water samples

A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid–liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L−1 was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L−1, which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L−1 and 1 µg L−1, respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L−1) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained.

Water reduction in waste-activated sludge by resettling and filtration in batch. Phase (1): pilot-scale experiments to optimize performance

This article describes an effective procedure for reducing the water content of excess sludge production from a wastewater treatment plant by increasing its concentration and, as a consequence, minimizing the volume of sludge to be managed. It consists of a pre-dewatering sludge process, which is used as a preliminary step or alternative to the thickening. It is made up of two discontinuous sequential stages: the first is resettling and the second, filtration through a porous medium. The process is strictly physical, without any chemical additives or electromechanical equipment intervening. The experiment was carried out in a pilot-scale system, consisting of a column of sedimentation that incorporates a filter medium. Different sludge heights were tested over the filter to verify the influence of hydrostatic pressure on the various final concentrations of each stage. The results show that the initial sludge concentration may increase by more than 570% by the end of the process with the final volume of sludge being reduced in similar proportions and hydrostatic pressure having a limited effect on this final concentration. Moreover, the value of the hydrostatic pressure at which critical specific cake resistance is reached is established.

Brackish groundwater desalination by reverse osmosis in southeastern Spain. Presence of emerging contaminants and potential impacts on soil-aquifer media

Desalinated brackish groundwater is becoming a new source of water supply to comply with growing water demands, especially in (semi-) arid countries. Recent publications show that some chemical compounds may persist in an unaltered form after the desalination processes and that there is an associated risk of mixing waters with different salinity for irrigation. At the university of Alicante campus (Spain), a mix of desalinated brackish groundwater and water from the existing aquifer is currently applied for landscape irrigation. The presence of 209 emerging compounds, surfactants, priority substances according to the 2008/105/EC Directive, 11 heavy metals and microbiological organisms in blended water and aquifer samples was investigated. Thirty-five compounds were detected (pesticides, pharmaceuticals and surfactants) among them two priority substances α-endosulfan and Ni were found above the permitted maximum concentration. Blended water used for landscape irrigation during the summer period is supersaturated with respect to carbonates, which may ultimately lead to mineral precipitation in the soil-aquifer media and changes in hydraulic parameters.

Conditional Order-m Efficiency of Wastewater Treatment Plants: The Role of Environmental Factors

The growing economic and environmental importance of managing water resources at a global level also entails greater efforts and interest in improving the functioning and efficiency of the increasingly more numerous wastewater treatment plants (WWTPs). In this context, this study analyzes the efficiency of a uniform sample of plants of this type located in the region of Valencia (Spain). The type of efficiency measure used for this (conditional order-m efficiency) allows continuous and discrete contextual variables to be directly involved in the analysis and enables the assessment of their statistical significance and effect (positive or negative). The main findings of the study showed that the quality of the influent water and also the size and age of the plants had a significant influence on their efficiency levels. In particular, as regards the effect of such variables, the findings pointed to the existence of an inverse relationship between the quality of the influent water and the efficiency of the WWTPs. Also, a lower annual volume of treated water and more modern installations showed a positive influence. Additionally, the average efficiency levels observed turned out to be higher than those reported in previous studies.

The effect of electricity tariffs over the operating costs of the Spanish wastewater treatments plants

Given the complex structure of electricity tariffs and their steady growth in Spanish, we've studied its effect over the operating costs of the wastewater treatment plants (WWTP), concluding that in the last three years the revisions of electricity rates have meant increases in electricity costs of 64.5% in the rate 3.1.A and 79.1% in the rate 6.1. This has caused the cost of electricity, which was the most important, has increased from a 44% of total operating costs in the year 2009, to more than a 56% in the year 2012.