Maurizio Carotenuto

Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview.

Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives.

Photocatalytic degradation of the antibiotic chloramphenicol and effluent toxicity effects

Chloramphenicol sodium succinate (CAP, C15H15Cl2N2 Na2O8) is a broad-spectrum antibiotic exhibiting activity against both Gram-positive and Gram-negative bacteria as well as other groups of microorganisms only partially removed by conventional activated sludge wastewater treatment plants. Thus, CAP and its metabolites can be found in effluents. The present work deals with the photocatalytic degradation of CAP using TiO2 as photocatalyst. We investigated the optimization of reaction contact time and concentration of TiO2 considering CAP and its by-products removal as well as effluent ecotoxicity elimination. Considering a CAP real concentration of 25mgL(-1), kinetic degradation curves were determined at 0.1, 0.2, 0.4, 0.8, 1.6 and 3.2gL(-1) TiO2 after 5, 10, 30, 60 and 120min reaction time. Treated samples were checked for the presence of by-products and residual toxicity (V. fischeri, P. subcapitata, L. sativum and D. magna). Results evidenced that the best combination for CAP and its by-products removal could be set at 1.6gL(-1) of TiO2 for 120min with an average residual toxicity of approximately 10%, that is the threshold set for negative controls in most toxicity tests for blank and general toxicity test acceptability.

Advanced Oxidation Processes for Antibiotics Removal: A Review

DOI: 10.2174/1385272821666170103162 813 Abstract: Year-by-year, the amount of antibiotics for human and veterinary use increases. Their presence in both treated and untreated wastewater was highlighted in several studies, suggesting that traditional activated sludge processes are unsuitable for their efficient removal. In this review paper, we summarized the role of advanced oxidation processes (AOPs) in antibiotics removal evidencing their pros, cons and limitations. In most cases, they are still applied at laboratory or pilot scale, with just few examples of full-scale applications. Main constraints are related to energy cost, catalyst management and potential residual toxicity in treated effluents. The main advantages are related to the full mineralization of target compounds or the ability to increase their relative biodegradability. Future challenges include nano-based green synthetized catalysts maximizing the use of solar radiation for energy saving. Generally, AOPs application is part of a more structured wastewater treatment process including operating units at various technological contents.

An integrated chemical and ecotoxicological assessment for the photocatalytic degradation of vancomycin

The photocatalytic degradation of an antibiotic, vancomycin B hydrochloride (VAN-B), has been investigated in aqueous suspensions of titanium dioxide (TiO2) by monitoring the change in its concentration as well as the production of ammonia and chlorides as a function of irradiation time. The removal of 50 mg L−1 VAN-B solution yields maximum concentrations of 2.45 and 2.53 mg N-NH3 L−1 after 120 min of photocatalytic oxidation using 0.1 and 0.2 g TiO2 L−1, respectively. When 0.2 g TiO2 L−1 were applied up to 87% of the stoichiometric amount of chloride was reached within 120 min of irradiation, corresponding to 0.087 mmol L−1. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Ceriodaphnia dubia) was performed to evaluate the potential detoxification of VAN-B and its by-products of oxidation under chronic and acute tests. The toxicity of the treated VAN-B samples varied during the oxidation, due to the formation of some intermediate products more toxic than VAN-B. Despite almost total removal of VAN-B that was achieved within 120 min of irradiation, a significant increase in toxicity was observed in chronic tests proving that the chronic assays are more appropriate than acute ones to detect the impact of by-products formed during the photocatalytic degradation of antibiotics.

Metals and tributyltin sediment contamination along the Southeastern Tyrrhenian Sea coast

Anthropogenic pressures can adversely affect the quality of coastal sediment posing at risk human health and the ecosystem. The Southeastern Tyrrhenian Sea (STS) coast (Italy) is still largely unexplored under this point of view. This study investigated for the first time in the area the seasonal variation and potential impact of selected metals (Cd, Cr, Cu, Ni, and Pb) and tributyltin (TBT) from sediment samples collected along the STS coast (Casalvelino Marina, Casalvelino Bay, Acciaroli Marina and Acciaroli Bay) in the perspective of Water Framework Directive and Marine Strategy Framework Directive. Data were compared to the contamination background levels of Punta Licosa reference site considering elemental enrichment factors (EFs) and single substance- and mixture-based risk characterisation ratios. Further, data were discussed considering the review of Southern Tyrrhenian Sea sediment quality. Results evidenced an increase of contamination levels from March to October showing that marinas are more impacted than bays. Sediment EFs highlighted that contamination levels were always greater than the reference site like risk characterisation ratios, suggesting the presence of potential threats. The sediment quality database generated after literature review revealed a similar situation for the whole Southern Tyrrhenian Sea.

Genetically biodiverse potato cultivars grown on a suitable agricultural soil under compost amendment or mineral fertilization: yield, quality, genetic and epigenetic variations, soil properties

The use of compost for soil amendment is a promising agricultural practice environmentally and economically viable. In the framework of a wide research project designed to evaluate the effects of soil amendment with municipal solid waste compost in comparison with traditional mineral fertilization practices, 54 different cultivars (Cvs) of potatoes were AFLP (amplified fragment length polymorphism) molecularly fingerprinted. The seven most genetically biodiverse potato Cvs were used to establish an experimental field in southern Italy. The field area was divided into two portions fertilized with compost (20 Mg ha(-1)) or with ammonium sulphate (200 kg ha(-1)). No significant differences in productivity, organoleptic characteristics and element concentrations were observed between the potato tubers obtained with both kinds of soil fertilization, while the tubers grown on compost amended soil showed, on average, higher K concentrations with respect to those grown on mineral fertilised soil. cDNA-AFLP (complementary DNA-AFLP) and MSAP (methylation sensitive amplified polymorphism) analyses were carried out on both leaves and tubers of one selected Cv to estimate if any transcriptome alterations or epigenetic modifications were induced by the two kinds of fertilization, however no variations were detected. Chemical and biological soil qualities (i.e., microbial respiration, FDA hydrolysis, alkaline and acid phosphatase) were assessed on soil samples at the start of the experiment and at the end of potato crop cycle. No significant differences in soil pH and limited ones, in the available fraction of some trace elements, were observed; while conductivity was much higher for the compost amended portion of the experimental field. Microbial respiration, FDA hydrolysis and acid phosphatase activities were significantly increased by compost amendment, in comparison with mineral fertilization. Finally, a sensory panel of potato Cvs detected no significant differences among qualitative descriptors and among potatoes coming from the two differently fertilized soils.

Simulating the fate of indigenous antibiotic resistant bacteria in a mild slope wastewater polluted stream

The fate of indigenous surface-water and wastewater antibiotic resistant bacteria in a mild slope stream simulated through a hydraulic channel was investigated in outdoor experiments. The effect of (i) natural (dark) decay, (ii) sunlight, (iii) cloudy cover, (iv) adsorption to the sediment, (v) hydraulic conditions, (vi) discharge of urban wastewater treatment plant (UWTP) effluent and (vii) bacterial species (presumptive Escherichia coli and enterococci) was evaluated. Half-life time (T1/2) of E. coli under sunlight was in the range 6.48-27.7min (initial bacterial concentration of 105CFU/mL) depending on hydraulic and sunlight conditions. E. coli inactivation was quite similar in sunny and cloudy day experiments in the early 2hr, despite of the light intensity gradient was in the range of 15-59W/m2; but subsequently the inactivation rate decreased in the cloudy day experiment (T1/2=23.0min) compared to sunny day (T1/2=17.4min). The adsorption of bacterial cells to the sediment (biofilm) increased in the first hour and then was quite stable for the remaining experimental time. Finally, when the discharge of an UWTP effluent in the stream was simulated, the proportion of indigenous antibiotic resistant E. coli and enterococci was found to increase as the exposure time increased, thus showing a higher resistance to solar inactivation compared to the respective total populations.

Municipal wastewater spiramycin removal by conventional treatments and heterogeneous photocatalysis

This study assessed the effects and removal options of the macrolide spiramycin, currently used for both in human and veterinary medicine- with a special focus on advanced oxidation processes based on heterogeneous TiO2_assisted photocatalysis. Spiramycin real concentrations were investigated on a seasonal basis in a municipal wastewater treatment plant (up to 35μgL-1), while its removal kinetics were studied considering both aqueous solutions and real wastewater samples, including by-products toxicity assessment. High variability of spiramycin removal by activated sludge treatments (from 9% (wintertime) to >99.9% (summertime)) was observed on a seasonal basis. Preliminary results showed that a total spiramycin removal (>99.9%) is achieved with 0.1gL-1 of TiO2 in aqueous solution after 80min. Integrated toxicity showed residual slight acute effects in the photocatalytic treated solutions, independently from the amount of TiO2 used, and could be linked to the presence of intermediate compounds. Photolysis of wastewater samples collected after activated sludge treatment during summer season (SPY 5μgL-1) allowed a full SPY removal after 80min. When photocatalysis with 0.1gL-1 of TiO2 was carried out in wastewater samples collected in winter season (SPY 30μgL-1) after AS treatment, SPY removal was up to 91% after 80min.

Toxicity assessment within the application of in situ contaminated sediment remediation technologies: A review

Polluted sediment represents a great problem for aquantic environments with potential direct acute and chronic effects for the biota and can be tackled with both in situ and ex situ treatments. Once dredging activities are not compulsory, sediment can be kept in place and managed with techniques involving the use of amendment and/or capping. Before their application, the assessment of their potential impact to the target environment cannot ignore the safe-by-design approach. The role of toxicity in in situ sediment remediation was reviewed discussing about how it can be used for the selection of amendments and the monitoring of treatment technologies. Results evidenced that capping technology coupled to activated carbon (AC) is the most frequently applied approach with effects varying according to the rate of contamination in treated sediment, the amount of AC used (% v/v), and target biological models considered. Little data are available for zerovalent iron as well as other minor amending agents such as hematite, natural zeolite, biopolymers and organoclays. Current (eco-)toxicological information for in situ sediment remediation technologies is fragmentary and incomplete or entirely missing, making also the interpretation of existing data quite challenging. In situ sediment remediation represents an interesting potentially effective approach for polluted sediment recovering. As its application in some lab-based and field studies reported to induce negative effects for target organisms, amendments and capping agents must be attentively evaluated for short- and long-term environmental effects, also in the perspective of the remediated site monitoring and maintenance.

Biomonitoring of nutrient and toxic element concentrations in the Sarno River through aquatic plants

The Sarno River is considered the most polluted river in Europe and one of the ten most polluted rivers in the world. So far, its quality has been usually evaluated by water and sediment analyses of either inorganic or organic pollutants. However, a biomonitoring approach would be of paramount importance in the evaluation of river quality, since it integrates pollutant temporal fluctuations, as in the case of discontinuous inputs from urban, industrial and agricultural activities. To this end, a passive biomonitoring study of the Sarno River was carried out, using two native aquatic plants accumulators of inorganic pollutants. The spring area was monitored analysing the roots of the semi-submerged Apium nodiflorum, whereas the whole river course was monitored analysing the shoots of the submerged Potamogeton pectinatus. The information on the four macronutrient (Ca, K, Mg, P), the six micronutrient (Cu, Fe, Mn, Na, Ni, Zn) and the four toxic element (Cd, Cr, Pb, V) concentrations were separately combined in the Nemerow Pollution Index. Results evidenced a severe pollution degree of the Sarno River, attributable to toxic elements > micronutrients > macronutrients. In particular, the spring area showed high K concentrations, as well as high concentrations of several micronutrients and toxic elements. A generalized Zn contamination and a progressive macronutrient (above all Ca and P), micronutrient (above all Ni, Cu and Fe) and toxic element (above all Cr and Pb) accumulation toward the mouth was related to pollution from agricultural and urban activities. Industrial sources, especially tanneries along the Solofrana tributary, accounted for high Mn concentrations, whereas the volcanic origin of the substrate accounted for a generalized V contamination.