Degradation of Post-consumer PLA: Hydrolysis of Polymeric Matrix and Oligomers Stabilization in Aqueous Phase

Degradation of post-consumer PLA to lactic acid was analysed in order to assess the economic feasibility of the PLA chemical recycling process. Hydrolysis of PLA, in batch reactor, was analysed in the temperature range of 443–473 K, under autogenous pressure and a constant PLA to water ratio (equal to approximately 0.11 by weight), without the use of a catalyst. The experimental results suggest that the complete degradation of PLA can be obtained using relatively low reaction-times with the production of a mixture containing the monomer and traces of the dimer of lactic acid. The overall process was modelled using a two-step process: bulk degradation of PLA (in the solid or molten phase) with the solubilisation of low molecular weight oligomers, and their subsequent hydrolysis in water (stabilization). The model describes the trend of oligomer concentrations in the aqueous phase and PLA conversion as a function of time with both high accuracy and agreement with experimental results.     

PBDE,HBCD, and novel brominated flame retardant contamination in sediments from Lake Maggiore (Northern Italy)

The reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) has opened the way for the introduction of novel brominated flame retardants (NBFRs) in place of the banned formulations. Important representatives of this group are decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB). In this study, the contamination due to NBRFs was investigated for the first time in Italy in the sediments of Lake Maggiore. The aim of the research was to characterize in detail the possible presence of temporal trends and/or to identify potential sources of contamination. The study also considered the PBDE and HBCD lake sediment’s current contamination. The analytical results showed that sediments in Lake Maggiore and its tributary rivers had weak concentrations of PBEB, HBB, and BTBPE, but they did not have a negligible/insignificant contamination of HBCD (up to 23.7 ng/g dry weight (d.w.)). The determination of PBDEs in sediments showed that BDE-209 was the predominant congener (up to 217 and 28 ng/g d.w. in river and lake sediments, respectively). DBDPE was detected in the sediments with relevant concentrations (up to 280 ng/g d.w in the River Boesio sediments). The positive correlation of DBDPE with BDE-209 confirmed the wide and important use of this compound in the Lake Maggiore basin and the hypothesis that this compound will soon become one of the most important NBFRs used in Northern Italy. The contamination of Lake Maggiore sediments due to PBDEs, HBCD, and NBFRs were comparable to other worldwide situations.     

Analysis of indoor gaseous formic and acetic acid, using radial diffusive samplers

A diffusive sampling method for the determination of gaseous acetic and formic acids, using a radial symmetry diffusive sampler, has been optimised for a 7-day exposure time in this study. Sampling rate determinations were performed on data obtained from a dynamic exposure chamber, simulating the indoor conditions of an empty, closed, room, at room temperature and minimal wind speed. Analysis has been performed by means of ion chromatography. The sampling rates for formic acid concentrations of 128 microg m(-3) and 1248 microg m(-3) were determined to be 91.2 +/- 3.9 ml min(-1) and 111.6 +/- 2.8 ml min(-1), respectively. The acetic acid sampling rate was independent of the concentration in the range 160 microg m(-3)-1564 microg m(-3), and amounted to 97.3 +/- 3.1 ml min(-1). Experimentally determined sampling rates showed deviations of 3% for acetic acid, and 3-21% for formic acid, in relation to theoretically derived values. The blank values were as low as 1.69 +/- 0.07 microg for formic acid and 1.21 +/- 0.14 microg for acetic acid, and detection limits lower than 0.5 microg m(-3) could be achieved, which is an improvement of 98-99% compared to previously validated diffusive sampling methods. This study describes the first step of an extended validation program in which the applicability of these types of samplers for the measurement of organic acids will be validated and optimised for the environmental conditions typical for museum showcases.     

Evaluation by TCAM Model of Physical–Chemical Properties of Aerosol in Northern Italy

The chemical and size characterisation of aerosol in northern Italy was investigated by means of transport chemical aerosol model (TCAM) multiphase model long-term simulations performed within the frame of the CityDelta-CAFE exercise. The results show a high contribution of secondary inorganic compounds, in particular far from the Milan metropolitan area and in the large rural area of the Po valley where the major chemical fractions are ammonium and nitrates. The sulphate contribution is quite similar throughout this region, with the exception of areas close to SOx point emissions. Primary PM and organic compounds fractions, on the other hand, are greater close to major urban areas, in particular the Milan metropolitan zone. This work also presents a seasonal characterisation analysis of physical and chemical aerosol features. The results show that in winter, due to domestic heating emission of NOx and low temperatures, which favour the formation of secondary nitrate and organic aerosol, the PM10 and PM2.5 concentrations are higher than those in summer, in agreement with experimental data presented in several studies focussing on the same region.     

The evaluation of stability during the composting of different starting materials: comparison of chemical and biological parameters

Three blends formed by: (i) food processing waste (CP(FP)), (ii) waste water sewage sludge (CP(WW)), and (iii) their mixture (CP(FP+WW)), blended with tree pruning as bulking agent, were composted over 3 months. During composting the blends were monitored for the main physical-chemical characteristics: temperature, oxygen saturation level (O(2)%), pH, total and volatile solids, total organic carbon, and organic nitrogen (N(org)). In addition to the main parameters, the dissolved organic carbon (DOC), the inorganic nitrogen and the Oxygen Uptake Rate (OUR) were monitored. All the mixtures easily reached a peak temperature around 70°C, related to the lowest O(2)%. After 90 d, CP(FP), CP(FP+WW), and CP(WW) showed an organic matter mineralization of 43%, 35% and 33%, respectively; CP(FP) fitted an exponential model while both CP(FP+WW), and CP(WW) fitted a logistic model. During composting an OUR reduction of 79%, 78% and 73% was registered in CP(FP), CP(FP+WW), and CP(WW), respectively; the OUR successfully fitted the adopted exponential model and well reflected the stabilization process in time. The N(org) recovery at the end of the process was positive only in CP(WW) (11.6%). The DOC significantly decreased during the composting process but did not successfully fit any model. The mineral nitrogen did not follow the typical pattern with NH(4)(+) disappearance and NO(3)(-) accumulation. Strong NO(3)(-) losses were evident in all blends, while NH(4)(+) accumulations were detectable only in CP(FP), and CP(FP+WW). The NH(4)(+)/NO(3)(-) ratio did not satisfactorily reflect the composting process over time. The comparison of the first order (exponential) and logistic (sigmoidal) models applied to the OUR and OM course highlights the role of mineral nitrogen as limiting factor during composting of the more stabilized sludge.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption-desorption processes. Four soils from Melozal (35° 43' S; 71° 41' W), Parral (36° 08' S; 71° 52' W), San Carlos (36° 24' S; 71° 57' W), and Panimavida (35° 44' S; 71° 24' W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g?1) and were related to soil pH. Molinate showed K(d) values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g?1 and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K(d) values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g?1. MCPA K(d) ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Dimensions and models of contemporary public space management in England

This article discusses the concept of public space management and its evolution in a context of wider changes to urban governance. Public space management is taken as a sphere of urban governance in which conflicting societal demands on, and aspirations for, public space are interpreted through a set of processes and practices. Four interlinked dimensions for public space management are proposed: the co-ordination of interventions; the regulation of uses and conflicts between uses; the definition and deployment of maintenance routines; and investment in public spaces and their services. Within this conceptual framework, the paper looks at recent changes in public space management in England to suggest the emergence of alternative models of management. These are based on the roles ascribed to the state, to private agents and to user organisations, and on different approaches to dealing with the four management dimensions. Although the discussion shows that these models are more than just abstract formulations, and have been used to deal with a variety of public space problems, an important purpose for the paper is to provide an analytical framework through which to examine emergent practices in the management of public space and their potential consequences.     

Pesticide by-products in the Rhône delta (Southern France). The case of 4-chloro-2-methylphenol and of its nitroderivative

A field monitoring campaign for pesticides and their transformation intermediates was carried out in the Rh?ne delta (Southern France). It was evidenced the following transformation sequence: MCPA-->4-chloro-2-methylphenol (CMP)-->4-chloro-2-methyl-6-nitrophenol (CMNP). Interestingly CMP disappeared about as quickly as MCPA, while CMNP was environmentally more persistent than the parent molecules. This is very relevant to the environmental risk associated with the occurrence of these compounds, because the nitration of chlorophenols reduces their acute toxicity but the nitroderivatives could have more marked long-term effects, associated with their genotoxicity. Irradiation experiments suggested that the photonitration of CMP into CMNP involves nitrogen dioxide, generated from the photolysis of nitrate and from the photooxidation of nitrite by ()OH. The photochemistry of Fe(III) species could also play a significant role, but its contribution is still difficult to be quantified. Another important intermediate of CMP transformation is methylnitrophenol (MNP), produced via a dechlorination/nitration pathway, with ortho-cresol as the most likely reaction intermediate.     

Serum concentrations of persistent organic pollutants (POPs) in the inhabitants of a Sicilian city

Background

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are common environmental contaminants that have been associated with human health problems.

Objectives

To assess serum concentrations of several organochlorine contaminants in general population living in a city with an ancient agricultural tradition and to identify possible exposure sources in Sicily.

Methods

A cross-sectional study was conducted on 101 individuals. Each participant answered a face-to-face questionnaire submitted by well-trained personnel and provided a serum sample which was analyzed for the concentrations of PCBs, HCB, HCHs and DDTs by using gas-chromatography coupled with mass spectrometry.

Results

HCB, p,p′-DDE, PCB 138, PCB 153 and PCB 180 were detected in more than 80% of the study participants. The ng g⁻¹ lipid median concentrations were: 18.6 for HCB; 175.1 for p,p′-DDE; 22. for PCB 138; 32.5 for PCB 153 and 23.0 for PCB 180. PCB 153 and PCB 138, PCB 138 and PCB 180, PCB 153 and PCB 180, and p,p′-DDE and HCB showed a high correlation each other (p < 0.05). HCB and p,p′-DDE concentrations were significantly higher in subjects >49 years old (adj-p = 0.03 in 50-69 years old and adj-p < 0.001 in >69 years old, respectively) whereas PCB 138, PCB 153 and PCB 180 concentrations were higher in males (adj-p = 0.03), in subjects >69 years old (adj-p = 0.04) and in current smokers (adj-p = 0.04).

Conclusions

The present study shows that serum concentrations of organochlorine compounds detected in subjects living in a small Sicilian city with ancient agricultural tradition are similar to those found in subjects living in urban areas of other countries. However, further investigations are needed to compare data from rural/urban areas in the same country, assessing correlations between serum concentrations of several chemical compounds and potential health effects in general population.     

Photochemical production of organic matter triplet states in water samples from mountain lakes, located below or above the tree line

The production of triplet states (T(*)) of chromophoric dissolved organic matter (CDOM), reacting with the probe molecule 2,4,6-trimethylphenol (TMP) was measured upon irradiation of water samples, taken from lakes located in a mountain area (NW Italy) between 1450 and 2750 m above sea level. The lakes are located below or above the tree line and surrounded by different vegetation types (trees, alpine meadows or exposed rocks). The most photoactive samples belonged to lakes below the tree line and their fluorescence spectra and CDOM optical features suggested the presence of a relatively elevated amount of humic (allochthonous) material. The lowest (negligible) photoactivity was found for a lake surrounded by exposed rocks. Its CDOM showed an important autochthonous contribution (due to in-lake productivity) and considerably higher spectral slope compared to the other samples, suggesting low CDOM molecular weight and/or aromaticity. Among the samples, CDOM photoactivity (measured as the rate of TMP-reactive T(*) photoproduction) decreased with changing vegetation type in the order: trees, meadows, rocks. It could be connected with decreasing contribution from catchment runoff and increasing contribution from autochthonous processes and possibly precipitation.