Photochemistry and photoinduced toxicity of acifluorfen, a diphenyl-ether herbicide

Photochemistry studies can be helpful in assessing the environmental fate of chemicals. Photochemical reactions lead to the formation of by-products that can exhibit different toxicological properties from the original compound. For this reason the photochemical behavior of the herbicide acifluorfen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in the presence of different solvents was studied. Photochemical reactions were carried out using a high-pressure mercury arc and a solar simulator. Kinetic parameters and quantum yields were determined. The identification of photoproducts was performed by mass spectrometry and [1H] nuclear magnetic resonance (NMR). Nitrofluorfen, hydroxy-nitrofluorfen, 2-chloro-4-(trifluoromethyl)phenol, 5-trifluoromethyl-5'-nitrodibenzofuran, and other derivatives were identified. The photochemical reactions were also carried out in the presence of either a singlet or a triplet quencher, and in the presence of either a radical initiator or a radical inhibitor. Substances used as inhibitors of the excited levels T1 and S1 showed that photodegradation of acifluorfen begins from a singlet state S1 through a pi,pi* transition. The role of free radicals in the photodegradation of acifluorfen was determined and a radical mechanism was proposed. Toxicity tests against Daphnia magna Strauss showed that acifluorfen was not toxic at a concentration of 0.1 mM; however, photoproducts formed after 36 h of UV exposure of the herbicide induced a remarkable toxicity to the test organism.     

On the detoxification of benthic bivalves contaminated by POPs: insights from experimental and modelling approaches

Rearing benthic bivalves that are contaminated by persistent organic pollutants (POPs) in areas with low pollution levels permits their natural detoxification. Here, we present the results of novel detoxification experiments conducted with the Manila clam (Tapes philippinarum) in the Venice Lagoon; these experiments were conducted both in summer and winter. Measurements of dioxins (PCDD), furans (PCDF), polychlorinated biphenyl (PCB) and hexachlorobenzene (HCB) concentrations in clam flesh over time after their resettlement in cleaner areas allowed for determining the minimum time required to reach safe toxicity levels. Moreover, dioxin fingerprint dynamics demonstrated successful detoxification from industrial contaminants. A simple bioaccumulation/detoxification model applied to the collected data provided for the first time estimation of detoxification rates and half-lives for POP congeners in clam flesh. This work provides a basis for considering natural detoxification as a viable solution for safely exploiting resources otherwise restricted from human consumption due to associated health risks.     

Organic Farming Benefits Local Plant Diversity in Vineyard Farms Located in Intensive Agricultural Landscapes

The majority of research on organic farming has considered arable and grassland farming systems in Central and Northern Europe, whilst only a few studies have been carried out in Mediterranean agro-systems, such as vineyards, despite their economic importance. The main aim of the study was to test whether organic farming enhances local plant species richness in both crop and non-crop areas of vineyard farms located in intensive conventional landscapes. Nine conventional and nine organic farms were selected in an intensively cultivated region (i.e. no gradient in landscape composition) in northern Italy. In each farm, vascular plants were sampled in one vineyard and in two non-crop linear habitats, grass strips and hedgerows, adjacent to vineyards and therefore potentially influenced by farming. We used linear mixed models to test the effect of farming, and species longevity (annual vs. perennial) separately for the three habitat types. In our intensive agricultural landscapes organic farming promoted local plant species richness in vineyard fields, and grassland strips while we found no effect for linear hedgerows. Differences in species richness were not associated to differences in species composition, indicating that similar plant communities were hosted in vineyard farms independently of the management type. This negative effect of conventional farming was probably due to the use of herbicides, while mechanical operations and mowing regime did not differ between organic and conventional farms. In grassland strips, and only marginally in vineyards, we found that the positive effect of organic farming was more pronounced for perennial than annual species.     

Dynamic of submicrometer particles in urban environment

Many studies show that particle toxicity increases with decreasing their size, emphasizing the role of submicrometric particles, in particular of ultrafine particles (<100 nm). In fact, particles greater than 2.5 μm are quickly removed through dry and wet deposition on the timescale of hours whereas submicrometer particles may reside in atmosphere for weeks, penetrate in indoor environment, and be long-range transported. High aerosol size resolution measurements are important for a correct assessment of the deposition efficiency in the human respiratory system, and time resolution is another important requisite. Starting from such considerations, time-resolved aerosol particle number size distributions have been measured in downtown Rome. Fast Mobility Particle Sizer (FMPS) and Scanning Mobility Particle Sizer (SMPS) measurements have been carried out at the INAIL’s Pilot Station, located in downtown Rome, in an area characterized by high density of autovehicular traffic. The two instruments have allowed to investigate deeply the urban aerosol in the range of 5.6–560 and 3.5–117 nm, respectively. In particular, the FMPS measurements have confirmed the interpretation about the transition phenomena in the time interval of few seconds, timescale typically associated with the emission of gasoline and diesel engines. In downtown Rome, the hourly average size distribution is bimodal or trimodal with maxima at about 5–15, 20–30, and 70–100 nm. Particle formation in the nucleation mode was associated to freshly emitted autovehicular exhaust.     

BMP tests of source selected OFMSW to evaluate anaerobic codigestion with sewage sludge

The aim of this study is to characterize different types of source selected organic fraction of municipal solid waste (SS-OFMSW) in order to optimize the upgrade of a sewage sludge anaerobic digestion unit by codigestion. Various SS-OFMSW samples were collected from canteens, supermarkets, restaurants, households, fruit–vegetable markets and bakery shops. The substrates characterization was carried out getting traditional chemical–physical parameters, performing elemental analysis and measuring fundamental anaerobic digestion macromolecular compounds such as carbohydrates, proteins, lipids and volatile fatty acids. Biochemical methane potential (BMP) tests were conducted at mesophilic temperature both on single substrates and in codigestion regime with different substrates mixing ratios. The maximum methane yield was observed for restaurant (675 NmlCH₄/gVS) and canteens organic wastes (571 and 645 NmlCH₄/gVS). The best codigestion BMP test has highlighted an increase of 47% in methane production respect sewage sludge digestion.     

Novel synthesis blends between bacterial polyesters and acrylic rubber: A study on enzymatic biodegradation

The biodegradability of a multicomponent system based on biotechnological occurring polyester (poly(-hydroxybutyrate-co--hydroxyvalerate) (PHBV)) with inclusion of acrylate elastomer (polybutylacrylate) (PBA) was investigated. A bacterium which produced extracellular enzymes that degrades PHBV even when blended with PBA was isolated and tentatively designated asAureobacterium saperdae. It was observed, by morphological investigation, that, while the bacterial degradation was permitted for PBA content of 20% by weight, it was inhibited for PBA content of 30%, owing to the occurrence of a rubbery layer that prevents to the bacteria an easy accessibility in the PHBV-rich regions. In fact, owing the bacterial growth, only PHBV was metabolized, whereas no degradation of PBA was detected for blend samples. It was confirmed that the degradation proceeded via surface erosion of PHBV also in the blends. Finally, mechanical tests on PHBV/PBA specimens as a function of degradation extent have shown different behavior of the blends at different the PBA content. Thermal analysis of blends and PHBV has been reported, too