Impact of UASB reactors operation mode on the removal of estrone and 17α-ethinylestradiol from wastewaters.

This work aims to compare the performance of the continuous operation (CO) and intermittent operation (IO) of upflow anaerobic sludge blanket (UASB) reactors for the removal of estrone (E1) and 17α-ethinylestradiol (EE2) from wastewaters. Results suggest that the IO contribute to the improvement of the overall removal of estrogens (above 95% for E1 and EE2) when compared to CO (49% for E1 and 39% for EE2). For both CO and IO, biodegradation was the main removal mechanism for E1, while for EE2, adsorption to sludge was the major removal pathway. Moreover, a higher biodegradation of estrogens was obtained with the IO compared to CO (69.4% vs. 43.3% for E1 and 21.8% vs. 8.0% for EE2). The favourable effect of IO can be justified by effluent recirculation during the feedless period which promotes the adaptation of microbial biomass to estrogens' biodegradation.

Oxolinic acid in aquaculture waters: Can natural attenuation through photodegradation decrease its concentration?

Quinolones, such as oxolinic acid (OXA), are antimicrobials commonly used in aquaculture. Thus, its presence in the aquatic environment surrounding aquaculture facilities is quite easy to understand. When present in aquatic environment, pharmaceuticals may be subjected to several attenuation processes that can influence their persistence. Photodegradation, particularly for antibiotics, can have significant importance since these compounds may be resistant to microbial degradation. OXA photodegradation studies reported in literature are very scarce, especially using aquaculture waters, but are markedly important for an appropriate risk assessment. Results hereby presented showed a decrease on photodegradation rate constant from 0.70 ± 0.02 h-1 in ultrapure water to 0.42 ± 0.01 h-1 in freshwater. The decrease on photodegradation rate constant was even more pronounced when brackish water was used (0.172 ± 0.003 h-1). In order to understand which factors contributed to the observed behaviour, environmental factors, such as natural organic matter and salinity, were studied. Results demonstrated that dissolved organic matter (DOM) may explain the decrease of OXA photodegradation observed in freshwater. However, a very sharp decrease of OXA photodegradation was observed in solutions containing NaCl and in synthetic sea salts, which explained the higher decrease observed in brackish water. Moreover, under solar radiation, the use of an 1O2 scavenger allowed us to verify a pronounced retardation of OXA decay, suggesting that 1O2 plays an important role in OXA photodegradation process.

Photodegradation of sulfadiazine in different aquatic environments - Evaluation of influencing factors.

The presence of antibiotics, such as sulfadiazine (SDZ), in the aquatic environment contributes to the generation of antimicrobial resistance, which is a matter of great concern. Photolysis is known to be a major degradation pathway for SDZ in surface waters. Therefore, influencing factors affecting SDZ photodegradation in different aquatic environments were here evaluated in order to have a better knowledge about its persistence in the environment. Photodegradation of SDZ was found to be more efficient at higher pH (t1/2 = 6.76 h, at pH = 7.3; t1/2 = 12.2 h, at pH = 6.3), in the presence of humic substances (HS) (t1/2 between 1.76 and 2.42 h), as well as in the presence of NaCl (t1/2 = 1.00 h) or synthetic sea salts (t1/2 = 0.78 h). Using ˙OH and 1O2 scavengers, it was possible to infer that direct photolysis was the main pathway for SDZ photodegradation in ultrapure water. Furthermore, results under N2 purging confirmed that 1O2 was not relevant in the phototransformation of SDZ. Then, the referred observations were used for the interpretation of results obtained in environmental matrices, namely the final effluent of a sewage treatment plant (STPF), fresh and brackish water (t1/2 between 2.3 and 3.48 h), in which SDZ photodegradation was found to be much faster than in ultrapure water (t1/2 = 6.76 h).

Determination of estrone and 17α-ethinylestradiol in digested sludge by ultrasonic liquid extraction and high-performance liquid chromatography with fluorescence detection.

Estrone, 17ß-estradiol and 17α-ethinylestradiol are increasingly recognised as important micropollutants to be monitored in wastewater treatment plants. These estrogens are retained onto sludge due to their high adsorption and since they are largely used in land applications, the monitoring of these chemicals in sludge samples is of great importance. This study describes a method for the determination of estrone and 17α-ethinylestradiol in fresh sludge samples. After spiking fresh digested sludge with estrone and 17α-ethinylestradiol and maintaining in contact during 5, 30 and 60 min, the freeze-dried samples were subjected to ultrasonic liquid extraction, with methanol and acetone, and analysed by high-performance liquid chromatography with fluorescence detection. The average recoveries obtained for estrone and 17α-ethinylestradiol using the different contact times were 103 ± 3 and 97 ± 4%, respectively. Fresh sludge samples from one waste water treatment plant located in Portugal were analysed and estrone was detected in primary fresh sludge, anaerobic digested sludge and dehydrated sludge at a concentration in the range of 1-4.8 µg/g. The method here developed does not require any sample clean-up, being fast and simple, reliable and inexpensive, making possible its application for monitoring the contamination of sludge with these estrogens.

Removal of tricaine methanesulfonate from aquaculture wastewater by adsorption onto pyrolysed paper mill sludge.

Tricaine methanesulfonate (MS-222) has been widely used in intensive aquaculture systems to control stress during handling and confinement operations. This compound is dissolved in the water tanks and, once it is present in the Recirculating Aquaculture Systems (RASs), MS-222 can reach the environment by the discharge of contaminated effluents. The present work proposes the implementation of the adsorption process in the RASs, using pyrolysed biological paper mill sludge as adsorbent, to remove MS-222 from aquaculture wastewater. Adsorption experiments were performed under extreme operating conditions, simulating those corresponding to different farmed fish species: temperature (from 8 to 30 °C), salinity (from 0.8 to 35‰) and different contents of organic and inorganic matter in the aquaculture wastewater. Furthermore, the MS-222 adsorption from a real aquaculture effluent was compared with that from ultrapure water. Under the studied conditions, the performance of the produced adsorbent remained mostly the same, removing satisfactorily MS-222 from water. Therefore, it may be concluded that the produced adsorbent can be employed in intensive aquaculture wastewater treatment with the same performance independently of the farmed fish species.

Comparative valorisation of agricultural and industrial biowastes by combustion and pyrolysis.

Combustion and pyrolysis processes were assessed and compared for two types of lignocellulosic biowastes: agricultural (Eucalyptus bark, grape seeds, peach stones, walnut shells, olive waste and peanut shells) and industrial (primary and biological paper mill sludge) biowastes. They were characterized by elemental, proximate and thermal analyses; the pyrolysis behaviour was studied by thermogravimetric analysis and the gases produced were identified using mass spectrometry. Agricultural biowastes showed the highest calorific values, close to the fossil fuel values (20-30MJkg(-1)) and, in general, emission of gases containing the carbon element (CH4, C2H2, CO and CO2) was higher than that of the tested industrial biowastes, making the agricultural biowastes highly competitive for combustion applications such as gas fuel. Further, the solid product which resulted from the pyrolysis of industrial biowastes is a material with large specific surface area, which is a good characteristic for possible applications as adsorbent in water remediation.

A new methodology combining PCR, cloning, and sequencing of clones discriminated by RFLP for the study of microbial populations: application to an UASB reactor sample.

This work describes a methodology combining DNA extraction, polymerase chain reaction amplification with primers targeting 16S ribosomal RNA genes, cloning, and sequencing of clones previously analyzed by restriction fragment length polymorphism (RFLP), which can be applied to study the microbial diversity in a given habitat. The methodology allows the minimization of the sequencing effort, which is particularly relevant when analyzing large numbers of clones. The methodology does not require particularly skilled personnel and can easily be adaptable to the molecular characterization of virtually any particular microbial population, provided that both adequate primers and suitable restriction enzymes for RFLP analysis of the clone library have been chosen. An example of application is presented, in which a sample taken from a continuously operating upflow anaerobic sludge blanket reactor was analyzed. RFLP analysis of the initial 162 clones with HaeIII allowed the identification of only 28 distinct profiles. As expected, identical RFLP profiles corresponded to identical nucleotide sequences.

Molasses as an external carbon source for anaerobic treatment of sulphite evaporator condensate.

Failures in stability and COD removal performance often occurred in full-scale anaerobic reactors treating the evaporator condensate from a sulphite pulp mill due to substrate inhibition and occasional contaminations with red liquor (wood cooking liquor). With this work, the beneficial effect provided by the continuous addition of an external carbon source (sugarcane molasses) on the overall performance and stability of the biological process was evaluated. With a moderate addition of molasses the inhibition was mitigated which led to an increase of the COD removal rate from 52% to 77% and a methane production increase from 460 to 1650mld(-1) at an organic loading rate of 2.61g CODl(-1)d(-1). A similar conclusion can be drawn for the case when contamination with red liquor occurs. These results suggest that sugarcane molasses addition may be regarded as a low-cost operational strategy for the anaerobic treatment of sulphite evaporator condensate.