Juan C. Durán-Álvarez

The analysis of a group of acidic pharmaceuticals, carbamazepine, and potential endocrine disrupting compounds in wastewater irrigated soils by gas chromatography-mass spectrometry.

The analysis of pharmaceuticals and potential endocrine disruptors in the environment has rightly concentrated on their presence in wastewaters and possible contamination of receiving bodies, such as groundwaters. However, wastewater is increasingly being reused for irrigation and in order to fully understand the environmental fate of these compounds, reliable methods for their analysis in soil are required, of which there are relatively few available. This article reports a method for a range of acidic pharmaceuticals, carbamazepine, and endocrine disrupting compounds in soils with final analysis by gas chromatography-mass spectrometry. Two soil types (Phaeozom and Leptosol) and three fortification levels were used to validate the method. Recoveries of acidic pharmaceuticals varied between 62 and 102%, carbamazepine from 75 to 118%, and potential endocrine disruptors between 54 and 109%; most recoveries were between 75 and 95% and relative standard deviations were generally less than 10%. Detection limits were between 0.25 and 2.5 ng/g except for phthalates and 4-nonylphenols (25 ng/g). The method was used to analyze soils where untreated wastewaters have been used to irrigate crops for approximately 90 years. Concentrations of acidic pharmaceuticals in the soil were <1 ng/g and potential endocrine disruptors varied from below the limit of detection (estrone, 17beta-estradiol, and 17alpha-ethinylestradiol) to 2079 ng/L (bis-diethylhexyl phthalate). This data indicated that despite the continuous application of the contaminants over many years, concentrations were generally lower than those expected to be contributed by a single irrigation event. Only carbamazepine, at concentrations of 6.48 ng/g (in Phaeozem) and 5.14 ng/g (in Leptosol), showed any evidence of persistence in the soils analyzed.

Accumulation and leaching potential of some pharmaceuticals and potential endocrine disruptors in soils irrigated with wastewater in the Tula Valley, Mexico.

The reuse of wastewater for irrigation of agricultural land is a well established practice but introduces many contaminants into the terrestrial environment including pharmaceuticals and personal care products. This study reports the persistence and leaching potential of a group of acidic pharmaceuticals, carbamazepine, and three endocrine disruptors in soils from the Tula Valley in Mexico, one of the largest irrigation districts in the world that uses untreated wastewater. After irrigation of soil columns with fortified wastewater over the equivalent of one crop cycle, between 0% and 7% of the total added amounts of ibuprofen, naproxen, and diclofenac and between 0% and 25% of 4-nonylphenol, triclosan, and bisphenol-A were recovered from the soil profiles. Carbamazepine was more persistent, between 55% and 107% being recovered. Amounts in leachates suggested that movement through the soil was possible for all of the analytes, particularly in profiles of low organic matter and clay content. Analysis of soil samples from the Tula Valley confirmed the general lack of accumulation of the acidic pharmaceuticals (concentrations from below the limit of detection to 0.61 μgkg(-1)) and endocrine disruptors (concentrations from below the limit of detection to 109 μgkg(-1)) despite continual addition through regular irrigation with untreated wastewater; there was little evidence of movement through the soil profiles. In contrast, carbamazepine was present in horizon A of the soil at concentrations equivalent to several years of additions by irrigation (2.6-7.5 μgkg(-1)) and was also present in the deeper horizons. The persistence and mobility of carbamazepine suggested a potential to contaminate groundwater.

Environmental fate of naproxen, carbamazepine and triclosan in wastewater, surface water and wastewater irrigated soil — Results of laboratory scale experiments

Lab-scale photolysis, biodegradation and transport experiments were carried out for naproxen, carbamazepine and triclosan in soil, wastewater and surface water from a region where untreated wastewater is used for agricultural irrigation. Results showed that both photolysis and biodegradation occurred for the three emerging pollutants in the tested matrices as follows: triclosan>naproxen>carbamazepine. The highest photolysis rate for the three pollutants was obtained in experiments using surface water, while biodegradation rates were higher in wastewater and soil than in surface water. Carbamazepine showed to be recalcitrant to biodegradation both in soil and water; although photolysis occurred at a higher level than biodegradation, this compound was poorly degraded by natural processes. Transport experiments showed that naproxen was the most mobile compound through the first 30cm of the soil profile; conversely, the mobility of carbamazepine and triclosan through the soil was delayed. Biodegradation of target pollutants occurred within soil columns during transport experiments. Triclosan was not detected either in leachates or the soil in columns, suggesting its complete biodegradation. Data of these experiments can be used to develop more reliable fate-on-the-field and environmental risk assessment studies.

Removal and fate of emerging contaminants combining biological, flocculation and membrane treatments

An experimental study combining biological treatment with flocculation (F) and ultrafiltration (UF) membrane technology was conducted, separately and in combination, seeking to increase insight into the capability of such treatment processes to remove emerging contaminants (ECs). The occurrence and removal efficiencies of 17 ECs are reported for wastewater from Mexico City. Results showed that activated sludge (AS) is the predominant process for removing acidic pharmaceutical compounds, and the use of a cationic flocculant increases the biodegradability of these compounds as well as that of 4-nonylphenol. The UF process alone showed greater removal of phenolic compounds than AS. However, the contribution of flocculation to EC removal by the UF unit was fairly limited. In general, the F + AS + UF processes yielded better results than their separate use, leading to the highest removal rates of 15 of the 17 compounds. In the case of some phenolic compounds and the phthalic acid esters, a competitive sorption process between the membrane and the sludge steps seemed to take place. Bis-2-ethylhexylphthalate (DEHP) was found to be significantly sorbed onto sludge. The F + AS + UF process operated as a membrane bioreactor (MBR) using 16 gL(-1) of suspended solids in the mixed liquor (MLSS) yielded the highest removal efficiencies for the ECs tested.

Enhanced photocatalytic degradation of sulfamethoxazole by deposition of Au, Ag and Cu metallic nanoparticles on TiO2

ABSTRACT Mono- (Au, Ag and Cu) and bi-metallic (Au–Ag and Au–Cu) nanoparticles were deposited on TiO2 and tested for the photocatalytic degradation of sulfamethoxazole using either UV-C or simulated sunlight. The optimal loading of metallic nanoparticles was determined as 1.5 wt% for Au and Ag, and 1.0 wt% for Cu. In the case of bi-metallic nanoparticles, only the ratio 1:0.5 wt% for both Au–Ag and Au–Cu was tested. In experiments using UV-C light, the highest degradation performance was found for Ag/TiO2, while bi-metallic nanoparticles supported on TiO2 also showed increased photocatalytic activity compared with unmodified TiO2. In simulated sunlight irradiation tests, Au/TiO2 showed to be the most efficient material. Complete mineralization of sulfamethoxazole was achieved when surface-modified materials were tested in both UV-C and simulated sunlight experiments. Photolysis was efficient to fully degrade sulfamethoxazole, although mineralization was lower than 10% for both luminic sources. The main by-products of sulfamethoxazole were determined in photolysis and photocatalysis tests using UV-C light, and degradation paths were proposed. By-products showed non-toxicity and low antibiotic activity. Reuse of the catalysts upon three reaction cycles did not result in the loss of activity.

Mobility of 4-nonylphenol and di(2-ethylhexyl) phthalate in three agricultural soils irrigated with untreated wastewater

Agricultural irrigation using raw wastewater is a popular practice in developing countries. However, as endocrine disrupting chemicals have been found in this water, the potential pollution of soil and water sources has become a source of concern. Such pollutants may be removed during the passage of wastewater through the soil by degradation and/or sorption. In this study the sorption and mobility of bis-2-ethyl(hexyl)phthalate (DEHP) and 4-nonylphenol (4-NP) in three different soils (Leptosol, Phaeozem and Vertisol) was compared. The distribution coefficients showed that DEHP is rapidly sorbed onto the three tested soils (K(d) between 1.8 × 10(4) and 4.2 × 0(4) L/kg), while sorption of 4-NP (K(d) between 15 and 80 L/kg) was weaker. In batch experiments the soil sorption capacity observed was as follows: Vertisol > Phaeozem > Leptosol for both compounds. However, in column experiments the retardation factor (R(F)) for 4-NP was higher than for the DEHP in the three soils. This suggests the possible migration of DEHP through the soil via colloids. The column results were found consistent with those observed in the field. It was concluded that the risk of groundwater contamination is higher for Leptosol soil than for Phaeozem and Vertisol soils and that DEHP can reach the aquifer prior to 4-NP.

CHAPTER 7:Superficial Modification of Semiconductors with Gold Nanoparticles for Photocatalytic Applications

This chapter reviews the work related to surface modification of semiconductors with gold nanoparticles to cause plasmon-enhanced photocatalytic degradation of organic molecules, water splitting, the removal of air pollutants and the enhancement of the photocatalytic production of fine chemicals. Gold nanoparticles possess the ability to absorb visible light, because of the surface plasmon resonance, and to increase the separation of electron–hole pairs by acting as a sink of electrons thus reducing the possibility of recombination. The two main mechanisms discussed in the literature regarding plasmonic enhancement of photoactivity under visible illumination, charge transfer and local electric field enhancement, are discussed.