Reviewing chemical and biological risks in urban agriculture: A comprehensive framework for a food safety assessment of city region food systems.

Attention to urban agriculture (UA) has recently grown among practitioners, scientists, and the public, resulting in several initiatives worldwide. Despite the positive perception of modern UA and locally grown, fresh produce, the potential food safety risks connected to these practices may be underestimated, leading to regulatory gaps. Thus, there is a need for assessment tools to evaluate the food safety risks connected to specific UA initiatives, to assist practitioners in self-evaluation and control, and to provide policy makers and scholars a means to pursue and assess food safety in city regions, avoiding either a lack or an excess of regulation that could ultimately hinder the sector. To address this aim, this paper reviews the most recent and relevant literature on UA food safety assessments. Food safety indicators were identified first. Then, a food safety assessment framework for UA initiatives was developed. The framework uses business surveys and food analyses (if available) as a data source for calculating a food safety index for single UA businesses and the whole UA landscape of a given city region. The proposed framework was designed to allow its integration into the CRFS (City Region Food System) toolkit developed by FAO (Food and Agriculture Organization of the United Nations), RUAF foundation (Resource Centres on Urban Agriculture and Food Security) and Wilfrid Laurier University.

Physicochemical regeneration of high silica zeolite Y used to clean-up water polluted with sulfonamide antibiotics.

High silica zeolite Y has been positively evaluated to clean-up water polluted with sulfonamides, an antibiotic family which is known to be involved in the antibiotic resistance evolution. To define possible strategies for the exhausted zeolite regeneration, the efficacy of some chemico-physical treatments on the zeolite loaded with four different sulfonamides was evaluated. The evolution of photolysis, Fenton-like reaction, thermal treatments, and solvent extractions and the occurrence in the zeolite pores of organic residues eventually entrapped was elucidated by a combined thermogravimetric (TGA-DTA), diffractometric (XRPD), and spectroscopic (FT-IR) approach. The chemical processes were not able to remove the organic guest from zeolite pores and a limited transformation on embedded molecules was observed. On the contrary, both thermal treatment and solvent extraction succeeded in the regeneration of the zeolite loaded from deionized and natural fresh water. The recyclability of regenerated zeolite was evaluated over several adsorption/regeneration cycles, due to the treatment efficacy and its stability as well as the ability to regain the structural features of the unloaded material.

Detection of potato brown rot and ring rot by electronic nose: from laboratory to real scale.

A commercial electronic nose (e-nose) equipped with a metal oxide sensor array was trained to recognize volatile compounds emitted by potatoes experimentally infected with Ralstonia solanacearum or Clavibacter michiganensis subsp. sepedonicus, which are bacterial agents of potato brown and ring rot, respectively. Two sampling procedures for volatile compounds were tested on pooled tubers sealed in 0.5-1 L jars at room temperature (laboratory conditions): an enrichment unit containing different adsorbent materials (namely, Tenax(®) TA, Carbotrap, Tenax(®) GR, and Carboxen 569) directly coupled with the e-nose (active sampling) and a Radiello(™) cartridge (passive sampling) containing a generic Carbograph fiber. Tenax(®) TA resulted the most suitable adsorbent material for active sampling. Linear discriminant analysis (LDA) correctly classified 57.4 and 81.3% total samples as healthy or diseased, when using active and passive sampling, respectively. These results suggested the use of passive sampling to discriminate healthy from diseased tubers under intermediate and real scale conditions. 80 and 90% total samples were correctly classified by LDA under intermediate (100 tubers stored at 4°C in net bag passively sampled) and real scale conditions (tubers stored at 4°C in 1.25 t bags passively sampled). Principal component analysis (PCA) of sensorial analysis data under laboratory conditions highlighted a strict relationship between the disease severity and the responses of the e-nose sensors, whose sensitivity threshold was linked to the presence of at least one tuber per sample showing medium disease symptoms. At intermediate and real scale conditions, data distribution agreed with disease incidence (percentage of diseased tubers), owing to the low storage temperature and volatile compounds unconfinement conditions adopted.

The interactions of methyl tert-butyl ether on high silica zeolites: a combined experimental and computational study.

In this work, the interactions of methyl tert-butyl ether (MTBE) on different dealuminated high silica zeolites were studied by means of both experimental and computational approaches. Zeolites with different textural and surface features were selected as adsorbents and the effect of their physico-chemical properties (i.e. pore size architecture and type and amount of surface OH sites) on sorption capacity were studied. High silica mordenite (MOR) and Y zeolites (both with a SiO2/Al2O3 ratio of 200) and ZSM-5 solid (SiO2/Al2O3 ratio of 500) were selected as model sorbents. By combining FTIR and SS-NMR (both (1)H and (13)C CPMAS NMR) spectroscopy it was possible to follow accurately the MTBE adsorption process on highly defective MOR characterized by a high concentration of surface SiOH groups. The adsorption process is found to occur in different steps and to involve isolated silanol sites, weakly interacting silanols, and the siloxane network of the zeolite, respectively. H-bonding and van der Waals interactions occurring between the mordenite surface and MTBE molecules were modeled by DFT calculations using a large cluster of the MOR structure where two adjacent side-pockets were fused in a large micropore to simulate a dealumination process leading to silanol groups. This is the locus where MTBE molecules are more strongly bound and stabilized. FTIR spectroscopy and gravimetric measurements allowed determination of the interaction strength and sorption capacities of all three zeolites. In the case of both Y and MOR zeolites, medium-weak H-bonding with isolated silanols (both on internal and external zeolite surfaces) and van der Waals interactions are responsible for MTBE adsorption, whereas ZSM-5, in which a negligible amount of surface silanol species is present, displays a much lower amount of adsorbed MTBE retained mainly through van der Waals interactions with zeolite siloxane network.

Persistence and degradation of new ß-lactam antibiotics in the soil and water environment.

The development of new antibiotics with low environmental persistence is of utmost importance in contrasting phenomena of antibiotic resistance. In this study, the persistence of two newly synthesized monocyclic ß-lactam antibiotics: (2R)-1-(methylthio)-4-oxoazetidin-2-yl acetate, P1, and (2R,3R)-3-((1R)-1-(tert-butyldimethylsilanyloxy)ethyl)-1-(methylthio)-4-oxoazetidin-2-yl acetate, P2, has been investigated in water in the pH range 3-9 and in two (calcareous and forest) soils, then compared to amoxicillin, a ß-lactam antibiotic used in human and veterinary medicine. P1 and P2 persistence in water was lower than that of amoxicillin with only a few exceptions. P1 hydrolysis was catalyzed at an acidic pH whereas P2 hydrolysis takes place at both acidic and alkaline pH values. P1 persistence in soils depended mainly on their water potential (t1/2: 35.0-70.7d at wilting point; <1d at field capacity) whereas for P2 it was shorter and unaffected by soil water content (t1/2 0.13-2.5d). Several degradation products were detected in soils at both water potentials, deriving partly from hydrolytic pathways and partly from microbial transformation. The higher LogKow value for P2 compared with P1 seemingly confers P2 with high permeability to microbial membranes regardless of soil water content. P1 and P2 persistence in soils at wilting point was shorter than that of amoxicillin, whereas it had the same extent at field capacity.

Migration kinetics of mineral oil hydrocarbons from recycled paperboard to dry food: monitoring of two real cases.

Mineral oil hydrocarbons present in printing inks and recycled paper migrate from paper-based food packaging to foods primarily through the gas phase. Migration from two commercial products packed in recycled paperboard, i.e. muesli and egg pasta, was monitored up to the end of their shelf life (1 year) to study the influence of time, storage conditions, food packaging structure and temperature. Mineral oil saturated and aromatic hydrocarbons (MOSH and MOAH, respectively), and diisopropyl naphthalenes (DIPN) were monitored using online HPLC-GC/FID. Storage conditions were: free standing, shelved, and packed in transport boxes of corrugated board, to represent domestic, supermarket and warehouse storage, respectively. Migration to food whose packs were kept in transport boxes was the highest, especially after prolonged storage, followed by shelved and free-standing packs. Tested temperatures were representative of refrigeration, room temperature, storage in summer months and accelerated migration testing. Migration was strongly influenced by temperature: for egg pasta directly packed in paperboard, around 30 mg kg⁻¹ of MOSH migrated in 8 months at 20°C, but in only 1 week at 40°C. Muesli was contained into an internal polyethylene bag, which firstly adsorbed hydrocarbons and later released them partly towards the food. Differently, the external polypropylene bag, containing pasta and recycled paper tray, strongly limited the migration towards the atmosphere and gave rise to the highest level of food contamination. Tests at increased temperatures not only accelerated migration, but also widened the migration of hydrocarbons to higher molecular masses, highlighting thus a difficult interpretation of data from accelerated simulation.

Saturated and aromatic mineral oil hydrocarbons from paperboard food packaging: estimation of long-term migration from contents in the paperboard and data on boxes from the market.

In the absence of a functional barrier, mineral oil hydrocarbons from printing inks and recycled fibres tend to migrate from paper-based food-packaging materials through the gas phase into dry food. Concentrations easily far exceed the limit derived from the acceptable daily intake (ADI) of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). Since the estimation of long-term migration into the food by testing at 40°C for 10 days is difficult, it seems preferable (and easier) to use the mineral oil content in the paperboard. Evaporation experiments showed that hydrocarbons eluted up to about n-C24 are sufficiently volatile for relevant migration into dry food: in worst-case situations, about 80% migrate into the packed food. The extraction of the paperboard was optimised to give good recovery of the relevant hydrocarbons, but to discriminate against those of high molecular mass which tend to disturb gas chromatographic analysis in on-line coupled normal phase HPLC-GC-FID. Even though some of the relevant hydrocarbons had already evaporated, the average concentration of < C24 mineral oil saturated hydrocarbons (MOSH) in the paperboard boxes of 102 products from the Swiss and Italian market was 626 mg kg⁻¹. Nearly 15% of investigated boxes still contained more than 1000 mg kg⁻¹ < C24 MOSH up to over 3000 mg kg⁻¹ (maximum = 3500 mg kg⁻¹). This amount of MOSH in the board have the potential of contaminating the packed food at a level exceeding the limit, derived from the JECFA ADI, hundreds of times.

Electronic nose as an innovative tool for the diagnosis of grapevine crown gall.

For the first time, a portable electronic nose was used to discriminate between healthy and galled grapevines, experimentally inoculated with two tumourigenic strains of Agrobacterium vitis. The volatile profile of target cutting samples was analysed by headspace solid phase microextraction coupled with gas chromatography-mass spectrometry. Spectra from tumoured samples revealed the presence of styrene which is compatible with decarboxylation of cinnamic acid involved in secondary metabolism of plants. Principal Component Analysis confirmed the difference in volatile profiles of infected vines and their healthy controls. Linear Discriminant Analysis allowed the correct discrimination between healthy and galled grapevines (83.3%, cross-validation). Although a larger number of samples should be analysed to create a more robust model, our results give novel interesting clues to go further with research on the diagnostic potential of this innovative system associated with multi-dimensional chemometric techniques.

Degradation of primisulfuron by a combination of chemical and microbiological processes.

Microbial degradation of the herbicide primisulfuron was investigated using enrichment cultures from contaminated soils and 20 axenic cultures. At neutral pH, no disappearance of the herbicide was detected either in the enrichment cultures or in the growth media of the axenic microbial cultures. During the growth of some of the microbial strains, however, the pH of the medium dropped below 6, resulting in the hydrolysis of primisulfuron. The rate of primisulfuron hydrolysis was clearly pH dependent; primisulfuron was more persistent in neutral or weakly basic solutions than in acidic solutions. After hydrolysis of the herbicide, four products were observed. These were identified as methyl 2-(aminosulfonyl)benzoate, 2-amino-4,6-(difluoromethoxy)pyrimidine, 2-N-[[[[[4, 6-bis(difluoromethoxy)-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl ]be nzoic acid, and 2-(aminosulfonyl)benzoic acid. After hydrolysis, it was found that the fungus Phanerochaete chrysosporium mineralized 27 and 24% of (14)C-phenyl- and (14)C-pyrimidine-labeled products, respectively, after 24 days of incubation. Similarly, Trametes versicolor mineralized 13 and 11% of (14)C-phenyl- and (14)C-pyrimidine-labeled hydrolysis products, respectively. In addition, primisulfuron in a hydrolytically stable solution, at pH 7. 0, was rapidly decomposed after ultraviolet irradiation, and two photolysis products were isolated [methylbenzoate and 4, 6-(difluoromethoxy)pyrimidin-2-ylurea]. When (14)C-phenyl-labeled primisulfuron was exposed to photolysis for 24 h, 32% of the initial radioactivity was recovered as (14)CO(2), whereas no (14)CO(2) was detected if the herbicide was labeled at the (14)C-pyrimidine position. Mineralization of (14)C-pyrimidine-labeled products of photolyzed primisulfuron by P. chrysosporium was approximately 25% after 24 days. These results clearly indicate that hydrolysis and photolysis of primisulfuron facilitated microbial degradation.