Endocrine disruptors compounds, pharmaceuticals and personal care products in urban wastewater: implications for agricultural reuse and their removal by adsorption process

In the last years, a lot of emerging contaminants, such as, endocrine disruptors compounds (EDCs), pharmaceuticals, and personal care products (PPCPs) have been detected in wastewater. Because of their toxicity and possible adverse effects on the environment and humans, their release from urban wastewater treatment plants (UWWTPs) effluents should be minimized, particularly when a wastewater reuse for crops irrigation is expected. Many processes have been investigated for advanced treatment of UWWTP effluents as well as for emerging contaminant degradation; among these, adsorption process was successfully used to remove EDCs and PPCPs from wastewater. This article shortly reviews EDCs and PPCPs removal from UWWTP effluents by adsorption process using conventional and non-conventional adsorbents. The fate of EDCs and PPCPs in UWWTPs and the implications for agricultural wastewater reuse has been addressed too. In spite of the adsorption process looking to be a valuable alternative to other advanced technologies for the removal of emerging contaminants from wastewater, some gaps still remain to evaluate the actual feasibility at full scale. However, according to a few studies available in scientific literature on the use of both powdered activated carbon and granular activated carbon at full scale, adsorption process by activated carbon is a promising, potentially effective, and economically feasible solution for producing safe wastewater for agricultural reuse.     

Use of ecosystem information to improve soil organic carbon mapping of a Mediterranean island

Detailed maps of soil C are needed to guide sustainable soil uses and management decisions. The quality of soil C maps of Italian Mediterranean areas may be improved and the sampling density reduced using secondary data related to the nature of the ecosystem. The current study was conducted to determine: (i) the improvements obtainable in mapping soil C over a Mediterranean island by using ecosystem features and (ii) the effect of different sampling densities on the map accuracy. This work relied on field sampling (n=164) of soil properties measured over the island of Pianosa (Central Italy). Statistical analysis assessing the relationship between soil properties and ecosystem features revealed that the conceptual model of ecosystems defined on the basis of environmental features such as vegetation cover, land use, and soil type was mainly related to the variation of soil organic carbon (OC) content and to the type of Mediterranean environment. The distribution of ecosystems was used to improve the accuracy of soil OC maps obtainable by a simple interpolation approach (ordinary kriging). Substantial improvement was obtained by: (i) stratification into ecosystem types and (ii) applying locally calibrated regressions to satellite imagery that introduced both inter-ecosystem and intra-ecosystem information linked to vegetation features. This study showed that interpolation methods using information on ecosystem distribution can produce accurate maps of soil OC in Mediterranean environments, mostly because of the linkage between soil OC and vegetation types, which are spatially fragmented and heterogeneous.     

Non-electrostatic surface complexation models for protons and lead(II) sorption onto single minerals and their mixture

Potentiometric titrations and lead sorption tests were conducted using muscovite, clinochlore, hematite, goethite, quartz, and a mixture of these same minerals. Mechanistic models were developed to represent and interpret these data. The aim was isolating the specific contribution of each mineral in proton and lead binding. Acid-base properties of each single mineral as well as their mixture were represented by discrete models, which consider the dissociation of n monoprotic sites (n-site/n-K(H) models). A one-site/one-K(H) model (logK(H1) = 10.69) was chosen for quartz (dissociation of SiOH edge hydroxyl groups). Goethite and hematite (FeOH groups) were represented by the same one-site/one-K(H) model (logK(H1) = 10.35). Three-site/three-K(H) models were used for muscovite (logK(H1) = 4.18; logK(H2) = 6.65; logK(H3) = 9.67) and clinochlore (logK(H1) = 3.84; logK(H2) = 6.57; logK(H3) = 9.71) assuming that SiOH and AlOH of the aluminosilicate matrix dissociate in the acid-neutral pH range while SiOH groups of quartz inclusions dissociate in the basic range. Similarly, the mixture of these minerals was represented by a three-site/three-K(H) model (logK(H1) = 3.39; logK(H2) = 6.72; logK(H3) = 10.82). According to crossed comparisons with single minerals, the first two sites of the mixture were associated with the aluminosilicate matrix (SiOH and AlOH respectively) and the third site with iron oxides (FeOH) and quartz groups. Additivity of proton binding in the mixture was demonstrated by simulating the mixture's titration curve. A unified model for the entire set of titration curves (single minerals and mixture) was also developed introducing a three-peak distribution function for proton affinity constants. Experimental data for lead sorption onto the mixture and individual minerals in 3-5 pH range denoted the competition between protons and metallic ions. The entire set of lead isotherms (individual mineral and mixture data) was represented adequately by a unified model taking into account both monodentate and bidentate complexes with the three active sites (additivity of lead binding). Experimental data of metal distribution in solid and liquid phases were successfully simulated by implementing the protonation and the surface complexation constants into the database of a dedicated software for chemical equilibria.     

Influence of salinity and temperature on the activity of biosurfactants by polychaete-associated isolates

Influence of different parameters on biosurfactant (BS) activity was carried out on strains that were isolated from the polychaetes Megalomma claparedei, Sabella spallanzanii and Branchiomma luctuosum and additional 30 strains that were previously identified as potential BS producers from crude oil enrichments of the same polychaete specimens. The selection of BS-producing strains from polychaete natural samples was carried out by using standard screening tests. The BS activity by each isolate was evaluated for the effect of salinity and temperature on emulsion production and surface tension reduction, during incubation in mineral medium supplemented with tetradecane or diesel oil. All isolates showed a similar time course of BS activity, and the latter was more influenced by salinity rather than temperature. Some of the BS producers belonged to genera that have not (i.e. Citricoccus, Cellulophaga, Tenacibaculum and Maribacter) or have poorly been (Psychrobacter, Vibrio, and Pseudoalteromonas) reported as able to produce BSs. This is remarkable as some of them have previously been detected in hydrocarbon-enriched samples. Results confirm that filter-feeding polychaetes are an efficient source for the isolation of BS producers.     

Development of low-cost ammonia gas sensors and data analysis algorithms to implement a monitoring grid of urban environmental pollutants

The present study is focused on the implementation of a novel, low cost, urban grid of nanostructured chemresistor gas sensors for ammonia concentration ([NH(3)]) monitoring, with NH(3) being one of the main precursors of secondary fine particulate. Low-cost chemresistor gas sensors based on carbon nanotubes have been developed, their response to [NH(3)] in the 0.17-5.0 ppm range has been tested, and the devices have been properly calibrated under different relative humidity conditions in the 33-63% range. In order to improve the chemresistor selectivity towards [NH(3)], an Expert System, based on fuzzy logic and genetic algorithms, has been developed to extract the atmospheric [NH(3)] (with a sensitivity of a few ppb) from the output signal of a model chemresistor gas sensor exposed to an NO(2), NO(X) and O(3) gas mixture. The concentration of these pollutants that are known to be the most significant interfering compounds during ammonia detection with carbon nanotube gas sensors has been tracked by the ARPA monitoring network in the city of Milan and the historical dataset collected over one year has been used to train the Expert System.     

Application of photocatalysis as a post treatment method of a heterotrophic-autotrophic denitrification reactor effluent

The aim of this study is the application of photocatalysis as an effective post treatment scheme for the removal of the organic matter and bacteria released by an innovative biological denitrification process referred to as heterotrophic-autotrophic denitrification, which combines heterotrophic and autotrophic denitrification processes. Photocatalytic treatment was applied using TiO2 as a photocatalyst in the loading range of 0.25-2.00 g l(-1) for irradiation periods up to 60 min using a black light fluorescent lamp with an intensity of I(0)=1309 microW cm(-2). The photocatalytic inactivation data were modelled to pseudo first order kinetics as well as by the areal rates to evaluate the photocatalyst loading effect. Chlorination was used as a final disinfection step to attain an overall inactivation of total coliforms as well as to the formation of very low level of trihalomethanes.     

Estrogenicity profile and estrogenic compounds determined in river sediments by chemical analysis, ELISA and yeast assays

An effects-directed strategy was applied to bed sediments of a polluted tributary in order to isolate and identify the major estrogenic chemicals it discharges into the River Po, the principal Italian watercourse. Sediment extract was concentrated by solid phase extraction and then fractioned into 10 fractions by reversed phase high performance liquid chromatography (RP-HPLC). Estrogenic activity of whole extract and fractions were determined using a recombinant yeast assay containing the human estrogen receptor (YES). The 10 fractions and whole extract were analysed for target compounds, e.g. estrone (E1), 17beta-estradiol (E2), estriol (E3), 4-nonylphenol (NP), 4-tert-octylphenol (t-OP), bisphenol A (BPA), using both liquid chromatography-tandem mass spectrometry (LC-MS/MS) and non-competitive enzyme-linked immunosorbent assays (ELISA). The YES assay determined high estrogenic activity in whole sediment (15.6 ng/g EE2 equivalents), and positive results for fractions nr 1, 2, 6, 7 and 8. E1, E3 and NP were the main estrogenic chemicals, however, other unidentified compounds contributed to sediment estrogenicity, particularly for polar fractions nr 1 and 2. A GC-MS screening performed in scan mode identified other potential contributors such as phthalates (DBP, BBP), and OP isomers. A next sampling campaign extended to other tributaries and receiving stretches of the River Po confirmed E1, E3 and NP as major estrogenic chemicals potentially threatening other sites of the main river. In general, target compound ELISAs have been shown to be suitable tools for a rapid screening of wide areas or large numbers of environmental samples for estrogenic risk. The potential for interferences suggests however to use cautiously the concentration values obtained from some of the immunoassays.     

A mixed integer linear programming model for optimisation of organics management in an integrated solid waste system

In this paper, the authors propose a mixed integer linear programming model for designing an Integrated Solid Waste Management System (ISWMS) to meet specific economic goals. The model refers to a set of municipalities, known as ‘local basin’, which have to share a common waste management system. At the municipal level the model allows for an identification of the optimal collection service option; at the local basin level, the model provides the optimal waste flow appropriate to the collection service option of each municipality. The model has been applied to a full-scale case study of an area located in southeast Italy. A scenario analysis was carried out to investigate alternative municipal solid waste management options, which fundamentally differ in the organic flow mass rate to be either collected and composted or landfilled. Findings show that an increase in the cost of landfilling determines the optimal collection scenario and the configuration plants tend to recover higher rates of organics in separate collection and thus higher refuse derived fuel productions. The results obtained validate the application of the model in both the strategic planning and operational phases, by supporting public administrators at both municipality and local basin level in decision making and evaluation of technical and economic performances of ISWMSs.