Microplastic contamination of lettuces grown in urban vegetable gardens in Lisbon (Portugal).

Urban vegetable gardens are very often a feature of cities that want to offer their citizens a more sustainable lifestyle by producing their own food products. However, cities can have significant pollution levels (or pollution hotspots) due to specific sources of pollution, such as traffic. Among the various pollutants, microplastics (MPs) are emerging as a consensual concern due to the awareness of the environmental contamination, their bioaccumulation potential and human intake, and, consequently unknown human health impacts. The present study compared the content of MPs in lettuce plants cultivated in Lisbon urban gardens with those cultivated in a rural area, as well as samples bought in supermarkets. Microplastics were detected in all washed leaves, with mean levels ranging from 6.3 ± 6.2 to 29.4 ± 18.2 MPs/g. Lettuce grown in urban gardens from areas with high traffic density showed higher MPs levels. Weak positive Spearman's rank correlations were found between MPs content and concentrations of Cu and S (determined by Particle Induced X-Ray Emission, PIXE), suggesting a possible role of traffic contribution to MPs levels, as both elements are considered traffic-source tracers. These results contribute to shed light on the MP contamination of vegetables grown in such urban environments, that may represent a potential MP exposure route through the dietary intake, corresponding to a 70% increase in annual MP intake compared to lettuces bought in supermarkets.

Source apportionment of PM2.5 before and after COVID-19 lockdown in an urban-industrial area of the Lisbon metropolitan area, Portugal.

The lockdowns held due to the COVID-19 pandemic conducted to changes in air quality. This study aimed to understand the variability of PM2.5 levels and composition in an urban-industrial area of the Lisbon Metropolitan Area and to identify the contribution of the different sources. The composition of PM2.5 was assessed for 24 elements (by PIXE), secondary inorganic ions and black carbon. The PM2.5 mean concentration for the period (December 2019 to November 2020) was 13 ± 11 µg.m-3. The most abundant species in PM2.5 were BC (19.9%), SO4 2- (15.4%), NO3 - (11.6%) and NH4 + (5.3%). The impact of the restrictions imposed by the COVID-19 pandemic on the PM levels was found by comparison with the previous six years. The concentrations of all the PM2.5 components, except Al, Ba, Ca, Si and SO4 2-, were significantly higher in the winter/pre-confinement than in post-confinement period. A total of seven sources were identified by Positive Matrix Factorisation (PMF): soil, secondary sulphate, fuel-oil combustion, sea, vehicle non-exhaust, vehicle exhaust, and industry. Sources were greatly influenced by the restrictions imposed by the COVID-19 pandemic, with vehicle exhaust showing the sharpest decrease. Secondary sulphate predominated in summer/post-confinement. PM2.5 levels and composition also varied with the types of air mass trajectories.

Citizens' Perception on Air Quality in Portugal-How Concern Motivates Awareness.

This study aimed to understand the knowledge of Portuguese citizens about air quality and the extent to which the concerns about specific environmental problems can motivate their acquaintance of information. Moreover, this study also allowed to understand which information about air quality needs further dissemination to provide the citizens with all the available tools and the correct knowledge. For this, a national online survey about air quality perception was conducted, where 1131 answers were obtained and two different populations were compared: the general population and a sub-population from an urban-industrial area of Lisbon metropolitan area that had experienced frequent air pollution events in the past. Air pollution was considered the environmental topic of higher concern among this sub-population (61.4%), while in the general population it ranked thirdly (27.4%). Generally, the sub-population showed higher knowledge about air quality than the general population, with 61% being able to identify at least one air pollutant. The perception of the local air quality was also very different between populations, with 61% of the sub-population considering it poor or very poor, while only 14% of the general population had the same perception, which highlights the different levels of concern between populations. A weak knowledge about air pollutants (50% of the general population could not identify any air pollutant) and an erroneous perception of the contribution of the different pollution sources to air quality levels were found. More than 50% of the respondents of both populations were considered to not have enough information regarding the air quality in their area of residence, with the national air quality database being unknown to almost everyone. Overall, strong efforts should be made to increase the awareness about the importance of air quality, which may promote a higher acceptance of the implementation of future actions to improve air quality.

Spatial Distribution of Air Pollution, Hotspots and Sources in an Urban-Industrial Area in the Lisbon Metropolitan Area, Portugal-A Biomonitoring Approach.

This study aimed to understand the influence of industries (including steelworks, lime factories, and industry of metal waste management and treatment) on the air quality of the urban-industrial area of Seixal (Portugal), where the local population has often expressed concerns regarding the air quality. The adopted strategy was based on biomonitoring of air pollution using transplanted lichens distributed over a grid to cover the study area. Moreover, the study was conducted during the first period of national lockdown due to COVID-19, whereas local industries kept their normal working schedule. Using a set of different statistical analysis approaches (such as enrichment and contamination factors, Spearman correlations, and evaluation of spatial patterns) to the chemical content of the exposed transplanted lichens, it was possible to assess hotspots of air pollution and to identify five sources affecting the local air quality: (i) a soil source of natural origin (based on Al, Si, and Ti), (ii) a soil source of natural and anthropogenic origins (based on Fe and Mg), (iii) a source from the local industrial activity, namely steelworks (based on Co, Cr, Mn, Pb, and Zn); (iv) a source from the road traffic (based on Cr, Cu, and Zn), and (v) a source of biomass burning (based on Br and K). The impact of the industries located in the study area on the local air quality was identified (namely, the steelworks), confirming the concerns of the local population. This valuable information is essential to improve future planning and optimize the assessment of particulate matter levels by reference methods, which will allow a quantitative analysis of the issue, based on national and European legislation, and to define the quantitative contribution of pollution sources and to design target mitigation measures to improve local air quality.

Intercalation of a molybdenum η3-allyl dicarbonyl complex in a layered double hydroxide and catalytic performance in olefin epoxidation.

A Zn-Al layered double hydroxide (LDH) intercalated by [Mo(η(3)-C3H5)Cl(CO)2(bpdc)](2-) anions (bpdc = 2,2'-bipyridine-5,5'-dicarboxylate) has been prepared by coprecipitation from aqueous solution and characterised by various techniques. The one-pot method gives rise to a highly organised intercalate with an interlayer spacing of 18.3 Šand up to six (00l) basal reflections in the powder X-ray diffraction pattern. Spectroscopic studies (FT-IR, FT-Raman, (13)C CP MAS NMR and UV-Vis) confirm the presence of structurally intact [Mo(η(3)-C3H5)Cl(CO)2(bpdc)](2-) anions. The interlayer spacing of 18.3 Šindicates that the material contains a monolayer of guest anions positioned in such a way that the bpdc ligands are arranged with their longest dimension roughly perpendicular to the hydroxide layers of the host. Thermal properties were studied by thermogravimetric analysis and differential scanning calorimetry. The intracrystalline reactivity of intercalated dicarbonyl complexes was probed by using the hybrid nanocomposite as a precatalyst in the liquid phase epoxidation of cis-cyclooctene with tert-butylhydroperoxide as oxidant. Under the reaction conditions used, oxidative decarbonylation of the guest molecules takes place (with release of CO and CO2 as confirmed by on-line gas chromatography experiments) to give intercalated molybdenum oxide/bipyridine species that selectively catalyse the epoxidation reaction. The intracrystalline oxidative decarbonylation reaction is topotactic in nature.

Molybdenum(VI) catalysts obtained from η3-allyl dicarbonyl precursors: synthesis, characterization and catalytic performance in cyclooctene epoxidation.

The oxidative decarbonylation of the η(3)-allyl dicarbonyl complexes [Mo(η(3)-C(3)H(5))Cl(CO)(2)(L)] (L = 2,2'-bipyridine (bipy) (1), 4,4'-di-tert-butyl-2,2'-bipyridine (di-tBu-bipy) (2)) by reaction with aqueous tert-butylhydroperoxide (TBHP) or H(2)O(2) gave the following compounds in good to excellent yields: the oxo-bridged dimers [MoO(2)Cl(L)](2)O (L = bipy (3), di-tBu-bipy (6)) using TBHP(10 equiv.)/CH(3)CN/r.t.; the molybdenum oxide/bipyridine hybrid material {[MoO(3)(bipy)][MoO(3)(H(2)O)]}(n) (4) and the octanuclear complex [Mo(8)O(24)(di-tBu-bipy)(4)] (7) using TBHP(50 equiv.)/H(2)O/70 °C; the oxodiperoxo complexes MoO(O(2))(2)(L) (L = bipy (5), di-tBu-bipy (8)) using H(2)O(2)(10 equiv.)/CH(3)CN/r.t. The structure of 7·x(solvent) (where solvent = CH(2)Cl(2) and/or diethyl ether) was determined by single crystal X-ray diffraction. Despite possessing the same windmill-type complex as that described previously for 7·10CH(2)Cl(2), the crystal structure of 7·x(solvent) is unique due to differences in the crystal packing. Compounds 1-8 were examined as catalysts or catalyst precursors for the epoxidation of cyclooctene using aqueous TBHP or H(2)O(2) as oxidant at 55 or 70 °C. Reactions were performed without co-solvent or with the addition of water, ethanol or acetonitrile. Cyclooctene oxide was always the only reaction product. Solids recovered after 24 h reaction at 70 °C were identified by FT-IR spectroscopy as the hybrid 4 from (1,3-5)/TBHP, complex 5 from (1,3-5)/H(2)O(2), and complex 8 from (2,6-8)/H(2)O(2). With TBHP as oxidant, the highest epoxide yields (for 24 h reaction at 70 °C) were obtained using excess H(2)O as solvent (28-38% for 1,3-5; 87-98% for 2,6-8), while with H(2)O(2) as oxidant, the highest epoxide yields were obtained using CH(3)CN as solvent (54-81% for 3-8).

µ-Oxido-bis-[chlorido(4,4'-di-tert-butyl-2,2'-bipyridine-κN,N')dioxido-molybdenum(VI)] 0.2-hydrate.

The title hydrate, [Mo(2)Cl(2)O(5)(C(18)H(24)N(2))(2)]·0.2H(2)O, has been isolated as the oxidation product of [Mo(η(3)-C(3)H(5))Cl(CO)(2)(di-t-Bu-bipy)] (where di-t-Bu-bipy is 4,4'-di-tert-butyl-2,2'-bipyridine). A µ-oxide ligand bridges two similar MoCl(di-t-Bu-bipy)O(2) units, having the terminal oxide ligands mutually cis, and the chloride and µ-oxide trans to each other. In the binuclear complex, the coordination geometries of the metal atoms can be described as highly distorted octa-hedra. Individual complexes co-crystallize with a partially occupied water mol-ecule of crystallization (occupancy factor = 0.20; H atoms not located), with the crystal packing being mediated by the need to effectively fill the available space. A number of weak C-H⋯O and C-H⋯Cl inter-actions are present.

Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C-S activation of trithiacyclononane: experimental and theoretical studies.

The macrocycle 1,4,7-trithiacyclononane (ttcn) reacts with [(η(5)-Ind)Mo(CO)(2)(NCMe)(2)](+) (or [(η(5)-Ind)Mo(CO)(2)(κ(2)-dme)](+)) to give [(η(3)-Ind)Mo(CO)(2)(κ(3)-ttcn)](+) as the BF(4)(-) salt (1), but its reaction with [(η(5)-Ind)Mo(CO)(2)(C(3)H(6))(FBF(3))] affords the C-S bond cleavage product [(η(5)-Ind)Mo(CO)(κ(3)-1,4,7-trithiaheptanate)]BF(4) (6), which has been characterised by X-ray crystallography (Ind = C(9)H(7), indenyl). In contrast to ttcn, the macrocycles 1,3,5-trithiane (tt) and 1,4,7,10-tetrathiacyclododecane (ttcd) fail to induce changes in the coordination mode of indenyl: tt and ttcd react with [(η(5)-Ind)Mo(CO)(2)(NCMe)(2)](+) (or [(η(5)-Ind)Mo(CO)(2)(κ(2)-dme)](+)) to give [(η(5)-Ind)Mo(CO)(2)(κ(2)-tt)](+) (2), characterised by X-ray crystallography, and [(η(5)-Ind)Mo(CO)(2)(κ(2)-ttcd)](+) (3), respectively. The cyclopentadienyl (Cp = C(5)H(5)) analogues [(η(5)-CpMo(CO)(2)(κ(2)-tt)](+) (4) and [(η(5)-CpMo(CO)(2)(κ(2)-ttcn)](+) (5) have also been synthesised and 5 characterised by X-ray crystallography. DFT calculations showed that the η(5)-Ind/Cp coordination mode is always the most stable. However, a molecular dynamics study of the macrocycles conformations revealed that the major conformer of ttcn was a chair, which favoured κ(3) coordination. As indenyl complexes undergo slippage with a small barrier (<10 kcal mol(-1)), the kinetically preferred species [(η(3)-Ind)Mo(CO)(2)(κ(3)-ttcn)](+) (1) is the observed one. The conversion to 6 proceeds stepwise, with loss of ethylene followed by loss of CO, as calculated by DFT, with a barrier of 38.7 kcal mol(-1), consistent with the slow uncatalysed reaction.