Occurrence of multiclass UV filters in treated sewage sludge from wastewater treatment plants

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. So far, there is only one extensive survey on the occurrence of UV filter residues in sewage sludge. However, more data are required to draw a reliable picture of the fate and effects of these compounds in the environment. This study attempts to fill this gap through the determination of selected UV filters and derivatives namely 4-methylbenzylidenecamphor, benzophenone-3, octocrylene, ethylhexylmethoxycinnamate, ethylhexyldimethyl PABA, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 4,4′-dihydroxybenzophenone in treated sewage sludge.The target compounds were extracted using pressurized liquid extraction and after this, determined by ultra high resolution liquid chromatography-tandem mass spectrometry. The determination was fast and sensitive, affording limits of detection lower than 19 ng g⁻¹ dry weight (dw) except for 2,4-dihydroxybenzophenone (60 ng g⁻¹ dw). Good recovery rates, especially given the high complexity of sludge matrix (between 70% and 102% except for 2,4-dihydroxybenzophenone (30%)) were achieved.The application of developed method allowed reporting for the first time the occurrence of two major degradation products of benzophenone-3 that have estrogenic activity in sewage sludge: 4,4′-dihydroxybenzophenone (in 5/15 WWTPs) and 4-hydroxybenzophenone (in 1/15 WWTPs). Results revealed the presence of UV filters in 15 wastewater treatment plants in Catalonia (Spain) at concentrations ranging from 0.04 to 9.17 μg g⁻¹ dw.     

Phototransformation of ibuprofen and ketoprofen in aqueous solutions

The UV (254 nm) and UV/VUV (254/185 nm) photolysis of two anti-inflammatory drugs, ibuprofen and ketoprofen, have been studied in aqueous solutions as a possible process for the removal of non-biodegradable compounds.We have examined the effects of dissolved oxygen and initial target concentration. Upon irradiation at 254 nm, the decomposition rate of ketoprofen is almost forty times higher as it of ibuprofen whilst VUV irradiation only increased the ibuprofen decomposition rate. The presence of dissolved oxygen accelerated the photodegradation of ibuprofen, whereas no effect was observed on the degradation of ketoprofen. The maximum quantum yield for the phototransformation was 0.2. The rate of mineralization in both cases was ∼60%, even after 1 h of treatment and this suggests the formation of stable by-products which were identified using GC-MS and HPLC-MS, respectively.     

Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

Lichens as an integrating tool for monitoring PAH atmospheric deposition: A comparison with soil, air and pine needles

The aim of this study was to validate lichens as biomonitors of PAH atmospheric deposition; for that, an inter-comparison between the PAH profile and concentrations intercepted in lichens with those of air, soil and pine needles was performed. The study was conducted in a petro-industrial area and the results showed that PAH profiles in lichens were similar to those of the air and pine needles, but completely different from those of soils. Lichens accumulated higher PAH concentrations when compared to the other environmental compartments and its concentrations were significantly and linearly correlated with concentrations of PAHs in soil; we showed that a translation of the lichen PAHs concentrations into regulatory standards is possible, fulfilling one of the most important requirements of using lichens as biomonitors. With lichens we were then able to characterize the air PAHs profile of urban, petro-industrial and background areas.     

Kinetic of carbonaceous substrate in an upflow anaerobic sludge sludge blanket (UASB) reactor treating 2,4 dichlorophenol (2,4 DCP)

The performance of an upflow anaerobic sludge blanket (UASB) reactor treating 2,4 dichlorophenol (2,4 DCP) was evaluated at different hydraulic retention times (HRTs) using synthetic wastewater in order to obtain the growth substrate (glucose-COD) and 2,4 DCP removal kinetics. Treatment efficiencies of the UASB reactor were investigated at different hydraulic retention times (2-20 h) corresponding to a food to mass (F/M) ratio of 1.2-1.92 g-COD g(-1) VSS day(-1). A total of 65-83% COD removal efficiencies were obtained at HRTs of 2-20 h. In all, 83% and 99% 2,4 DCP removals were achieved at the same HRTs in the UASB reactor. Conventional Monod, Grau Second-order and Modified Stover-Kincannon models were applied to determine the substrate removal kinetics of the UASB reactor. The experimental data obtained from the kinetic models showed that the Monod kinetic model is more appropriate for correlating the substrate removals compared to the other models for the UASB reactor. The maximum specific substrate utilization rate (k) (mg-COD mg(-1) SS day(-1)), half-velocity concentration (K(s)) (mg COD l(-1)), growth yield coefficient (Y) (mg mg(-1)) and bacterial decay coefficient (b) (day(-1)) were 0.954 mg-COD mg(-1) SS day(-1), 560.29 mg-COD l(-1), 0.78 mg-SS g(-1)-COD, 0.093 day(-1) in the Conventional Monod kinetic model. The second-order kinetic coefficient (k(2)) was calculated as 0.26 day(-1) in the Grau reaction kinetic model. The maximum COD removal rate constant (U(max)) and saturation value (K(B)) were calculated as 7.502 mg CODl(-1)day(-1) and 34.56 mg l(-1)day(-1) in the Modified Stover-Kincannon Model. The (k)(mg-2,4 DCP mg(-1) SS day(-1)), (K(s)) (mg 2,4 DCPl(-1)), (Y) (mg SS mg(-1) 2,4 DCP) and (k(d)) (day(-1)) were 0.0041 mg-2,4 DCP mg(-1) SS day(-1), 2.06 mg-COD l(-1), 0.0017 mg-SS mg(-1) 2,4 DCP and 3.1 x 10(-5) day(-1) in the Conventional Monod kinetic model for 2,4 DCP degradation. The second-order kinetic coefficient (k(2)) was calculated as 0.30 day(-1) in the Grau reaction kinetic model. The maximum 2,4 DCP removal rate constant (U(max)) and saturation value (K(B)) were calculated as 0.01 mg COD l(-1) day(-1) and 9.8 x 10(-3) mg l(-1) day(-1) in the Modified Stover-Kincannon model.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Metallothionein levels in Algerian mice (Mus spretus) exposed to elemental pollution: an ecophysiological approach

The potential use of metallothioneins (MTs) as biomarkers of trace metal contamination was evaluated for the first time in the Algerian mouse (Mus spretus). Mice were collected seasonally in an abandoned mining area (Aljustrel) and in a reference area, both located in southern Portugal. MT levels were quantified in liver and kidney by differential pulse polarography and hepatic elemental concentrations (Mn, Fe, Cu, Zn, Se) were determined by particle-induced X-ray emission. Hepatic iron and selenium concentrations were elevated in mice from Aljustrel mine when compared to reference animals. MTs levels were averagely higher in mice from Aljustrel than those originated from the reference area. A season-dependent significant effect was found on the hepatic and renal MT concentrations, characterized by higher levels in winter and lower in autumn. In contaminated mice positive relationship between liver elemental contents (Cu in autumn and Fe in winter) and MTs were found. The seasonal variation of MT suggests that probably physiological and environmental factors could influence hepatic and renal MT induction. Results seem to imply that some environmental disturbance occur in the vicinity of the Aljustrel mine. Therefore, for the management purposes MT levels should be followed in liver of M. spretus, especially in winter. Furthermore, other physiological factors that could influence MT expression and turnover in Algerian mouse should also be monitored.     

Effect of sewage sludges contaminated with polybrominated diphenylethers on agricultural soils

The fate of polybrominated diphenyl ethers (PBDEs) in sewage sludge after agricultural application was analysed. This study was based on the analysis of sewage sludge and sludge amended soil samples collected during 2005. PBDE concentrations in sewage sludge ranged from 197 to 1185ng/g dry weight (dw), being deca-BDE-209 the predominant congener. PBDE levels in soils ranged between 21 and 690ng/g dw, being BDE-209 also the predominant congener in all soil samples. Sewage-sludge amendment at the research stations increased concentrations of all BDE congeners 1.2- to 45-fold, with the highest increases for BDE-209. Results obtained evidenced the cumulative effect of the sludge application rates. Moreover, high levels found at soils four years after the last sludge application indicate persistence of PBDEs in soils, including deca-BDE-209.     

Trace organic chemicals contamination in ground water recharge

Population growth and unpredictable climate changes will pose high demands on water resources in the future. Even at present, surface water is certainly not enough to cope with the water requirement for agricultural, industrial, recreational and drinking purposes. In this context, the usage of ground water has become essential, therefore, their quality and quantity has to be carefully managed. Regarding quantity, artificial recharge can guarantee a sustainable level of ground water, whilst the strict quality control of the waters intended for recharge will minimize contamination of both the ground water and aquifer area. However, all water resources in the planet are threatened by multiple sources of contamination coming from the extended use of chemicals worldwide. In this respect, the environmental occurrence of organic micropollutants such as pesticides, pharmaceuticals, industrial chemicals and their metabolites has experienced fast growing interest. In this paper an overview of the priority and emerging organic micropollutants in the different source waters used for artificial aquifer recharge purposes and in the recovered water is presented. Besides, some considerations regarding fate and removal of such compounds are also addressed.