Toxicity assessment of common xenobiotic compounds on municipal activated sludge: comparison between respirometry and Microtox

The toxicity of four xenobiotic compounds 3,5-dichlorophenol, formaldehyde, 4-nitrophenol and dichloromethane, representative of industrial wastewater contaminants was evaluated by a simple respirometric procedure set up on the basis of OECD Method 209 and by the Microtox bioassay. Very good reproducibility was observed for both methods, the variation coefficients being in the range of 2-10% for the respirometric procedure and 6-15% for Microtox, values that can be considered very good for a biological method. Comparison of EC(50) data obtained with the two methods shows that in both cases 3,5-dichlorophenol is more toxic than other compounds investigated and dichloromethane has a very low toxicity value. Intermediate EC(50) values were found for the two other chemicals, formaldehyde and 4-nitrophenol. Moreover, the Microtox EC(50) values are generally lower (except for dichloromethane) than the respirometric ones: these differences could be explained by the fact that the Microtox method uses a pure culture of marine species and, therefore, should not necessarily be expected to behave like a community of activated sludge bacteria. In conclusion, both methods can be usefully applied for toxicity detection in wastewater treatment plants but it is advisable to take into account that Microtox is more sensitive than respirometry in estimating the acute toxicity effect on the biomass operating in the plant.     

In situ growth of well-dispersed CdS nanocrystals in semiconducting polymers

A straight synthetic route to fabricate hybrid nanocomposite films of well-dispersed CdS nanocrystals (NCs) in poly[2-methoxy-5-(2''-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) is reported. A soluble cadmium complex [Cd(SBz)₂]₂·MI, obtained by incorporating a Lewis base (1-methylimidazole, MI) on the cadmium bis(benzyl)thiol, is used as starting reagent in an in situ thermolytic process. CdS NCs with spherical shape nucleate and grow well below 200°C in a relatively short time (30 min). Photoluminescence spectroscopy measurements performed on CdS/MEH-PPV nanocomposites show that CdS photoluminescence peaks are totally quenched inside MEH-PPV, if compared to CdS/PMMA nanocomposites, as expected due to overlapping of the polymer absorption and CdS emission spectra. The CdS NCs are well-dispersed in size and homogeneously distributed within MEH-PPV matrix as proved by transmission electron microscopy. Nanocomposites with different precursor/polymer weight ratios were prepared in the range from 1:4 to 4:1. Highly dense materials, without NCs clustering, were obtained for a weight/weight ratio of 2:3 between precursor and polymer, making these nanocomposites particularly suitable for optoelectronic and solar energy conversion applications.     

Physical characteristics of the sludge in a complete retention membrane bioreactor

Sludge physical characteristics play an important role in the operation of membrane bioreactors (MBR) due to their influence on filtration and their effects on handling of excess sludge. These systems are designed to maintain high solid concentrations, thus limiting sludge production and the related operational costs of the process. In this study, the sludge from a bench scale MBR operated for about 1 year with complete solid retention was investigated to assess its physical and rheological properties. Concentrations of mixed liquor suspended solids (MLSS) up to 24 gTSSL(-1) affected the diluted sludge volume index (DSVI), the capillary suction time (CST), the specific resistance to filtration (SRF) and the compressibility (s). The MBR sludge displayed similar dewatering properties of conventional waste activated sludge, suggesting that the upgrade of wastewater treatment plants with the MBR technology would not affect the behaviour of the dewatering equipment. The apparent viscosity was expressed as a function of the MLSS and the experimental data were interpreted by comparing different models. Ostwald model was chosen, and two equations for viscosity were proposed. The thixotropy of MBR sludge was also evaluated by measuring the reduced hysteresis area (rHa) and relating this parameter to the characteristics of the sludge. The evaluation of energy consumption for mixing evidenced that, under the tested conditions, the increase of solid concentration from 3 to 30 gTSSL(-1) resulted in a limited increase of energy requirements (25-30%).     

Optimal sludge retention time for a bench scale MBR treating municipal sewage.

Membrane bioreactors allow for higher sludge concentrations and improved degradation efficiencies with respect to conventional activated sludge. However, in the current practice these systems are often operated under sub-optimal conditions, since so far no precise indications have yet been issued on the optimal operating conditions of MBR for municipal wastewater treatment. This paper reports some results of four years of operation of a bench scale membrane bioreactor where steady state conditions were investigated under different sludge retention times. The whole experimental campaign was oriented towards the investigation of optimal process conditions in terms of COD removal and nitrification, biomass activity and growth, and sludge characteristics. The membrane bioreactor treated real municipal sewage, and four different sludge ages were tested (20, 40, 60, and 80 days) and compared with previous data on complete sludge retention. The results showed that the the biology of the system, as assessed by the oxygen uptake rate, is less affected than the sludge physical parameters. In particular, although the growth yield was observed to dramatically drop for SRT higher than 80 days, the biological activity was maintained under all the tested conditions. These considerations suggest that high SRT are convenient in terms of limited excess sludge production without losses of the treatment capacity. Physical characteristics such as the viscosity and the filterability appear to be negatively affected by prolonged sludge retention times, but their values remain within the ranges normally reported for conventional activated sludge.     

Zero net growth in a membrane bioreactor with complete sludge retention

A bench-scale membrane bioreactor was operated with complete sludge retention in order to evaluate biological processes and biomass characteristics over the long term. The investigation was carried out by feeding a bench-scale plant with real sewage under constant volumetric loading rate (VLR=1.2 gCOD L_react⁻¹ h⁻¹). Biological processes were monitored by measuring substrate removal efficiencies and biomass-related parameters. The latter included bacterial activity as determined through respirometric tests specifically aimed at investigating long term heterotrophic and nitrifying activity. After about 180 days under the imposed operating conditions, the system reached equilibrium conditions with constant VSS concentration of 16–18 g L⁻¹, organic loading rate (OLR) below 0.1 gCOD gVSS⁻¹ d⁻¹ and specific respiration rates of 2–3 mgO₂ gVSS⁻¹ h⁻¹. These conditions were maintained for more than 150 days, confirming that an equilibrium had been achieved between biomass growth, endogenous metabolism, and solubilization of inorganic materials.     

Light-emitting nanocomposite CdS-polymer electrospun fibres via in situ nanoparticle generation

We report on the simple, in situ generation of CdS nanocrystals inside electrospun polymer fibres by thermal decomposition of a cadmium thiolate precursor, leading to nanocomposite light-emitting fibres. The modifications induced in the precursor by the thermal decomposition are investigated by a morphological, structural and spectroscopic analysis of the resulting nanocomposite fibres. This approach allows us to overcome nanofabrication difficulties related to disfavoured micro- or nanofluidic molecular flow as given by the direct incorporation of particles in the electrospinning solution. This method therefore enables the synthesis of luminescent, CdS-based composite fibres with emission peaked in the visible range, suitable as building blocks for nanophotonic devices based on light-emitting nanomaterials.     

Membrane bioreactor sludge rheology at different solid retention times

Rheological characterization is of crucial importance in sludge management both in terms of biomass dewatering and stabilization properties and in terms of design parameters for sludge handling operations. The sludge retention time (SRT) has a significant influence on biomass properties in biological wastewater treatment systems and in particular in membrane bioreactors (MBRs). The aim of this work is to compare the rheological behaviour of the biomass in a MBR operated under different SRTs. A bench-scale MBR was operated for 4 years under the same conditions except for the SRT, which ranged from 20 days to complete sludge retention. The rheological properties were measured over time and the apparent viscosity was correlated with the concentration of solid material when equilibrium conditions were reached and maintained. The three models most commonly adopted for rheological simulations were evaluated and compared in terms of their parameters. Then, steady-state average values of these parameters were related to the equilibrium biomass concentration (MLSS). The models were tested to select the one better fitting the experimental data in terms of mean root square error (MRSE). The relationship between the apparent viscosity and the shear rate, as a function of solid concentration, was determined and is proposed here. Statistical analysis showed that, in general, the Bingham model provided slightly better results than the Ostwald one. However, considering that a strong correlation between the two parameters of the Ostwald model was found for all the SRTs tested, both in the transient growth phases and under steady-state conditions, this model might be used more conveniently. This feature suggests that the latter model is easier to be used for the determination of the sludge apparent viscosity.     

Measuring protein structure and stability of protein-nanoparticle systems with synchrotron radiation circular dichroism

We measure the structural and stability changes of proteins at nanomolar concentration upon interaction with nanoparticles. Using synchrotron radiation circular dichroism (SRCD), we measure a decrease of 6 °C in the thermal unfolding of human serum albumin upon interaction with silver nanoparticles while this does not happen with gold. The use of SRCD allows measuring critical parameters on protein-nanoparticle interactions, and it will provide experimental data on the relative stability of key biological proteins for nanotoxicology.     

Tertiary filtered municipal wastewater as alternative water source in agriculture: a field investigation in Southern Italy

Results are reported concerning a 2-year field investigation on municipal wastewater reclamation for the irrigation of two experimental crops: tomato and fennel. Throughout the investigation, approximately 500 m(3) of tertiary membrane filtered wastewater without further disinfection was supplied to one of two parcels (500 m(2) each) of a test field located in Southern Italy. The second parcel was comparatively irrigated with 500 m(3) of conventional well water. Objectives of the investigation were (i) the evaluation of the performance of a membrane filtration pilot plant (productivity=0.7 m(3)h(-1)) for tertiary treatment and (ii) the comparison between agronomic results (features of soil and crops) after irrigation with reclaimed wastewater versus conventional groundwater. Over long term operation, the pilot plant performance resulted very good in terms of suspended solids and bacterial removal. Referring to the agronomic results, no substantial differences were observed after 2 years, both in terms of microbiological quality of the crops and characteristics of the soil. The whole results indicate membrane filtered municipal effluent as a viable alternative water resource for irrigation.