Annual variation of source contributions to PM10 and oxidative potential in a mountainous area with traffic, biomass burning, cement-plant and biogenic influences.

Toxicity of particulate matter (PM) depends on its sources, size and composition. We identified PM10 sources and determined their contribution to oxidative potential (OP) as a health proxy for PM exposure in an Alpine valley influenced by cement industry. PM10 filter sample chemical analysis and equivalent black carbon (eBC) were measured at an urban background site from November 2020 to November 2021. Using an optimized Positive Matrix Factorization (PMF) model, the source chemical fingerprints and contributions to PM10 were determined. The OP assessed through two assays, ascorbic acid (AA) and dithiothreitol (DTT), was attributed to the PM sources from the PMF model with a multiple linear regression (MLR) model. Ten factors were found at the site, including biomass burning (34, 40 and 38% contribution to annual PM10, OPAA and OPDDT, respectively), traffic (14, 19 and 7%), nitrate- and sulphate-rich (together: 16, 5 and 8%), aged sea salt (2, 2 and 0%) and mineral dust (10, 12 and 17%). The introduction of innovative organic tracers allowed the quantification of the PM primary and secondary biogenic fractions (together: 13, 8 and 21%). In addition, two unusual factors due to local features, a chloride-rich factor and a second mineral dust-rich factor (named the cement dust factor) were found, contributing together 10, 14 and 8%. We associate these two factors to different processes in the cement plant. Despite their rather low contribution to PM10 mass, these sources have one of the highest OPs per µg of source. The results of the study provide vital information about the influence of particular sources on PM10 and OP in complex environments and are thus useful for PM control strategies and actions.

Aerosol source apportionment uncertainty linked to the choice of input chemical components.

For a Positive Matrix Factorization (PMF) aerosol source apportionment (SA) studies there is no standard procedure to select the most appropriate chemical components to be included in the input dataset for a given site typology, nor specific recommendations in this direction. However, these choices are crucial for the final SA outputs not only in terms of number of sources identified but also, and consequently, in the source contributions estimates. In fact, PMF tends to reproduce most of PM mass measured independently and introduced as a total variable in the input data, regardless of the percentage of PM mass which has been chemically characterized, so that the lack of some specific source tracers (e.g. levoglucosan) can potentially affect the results of the whole source apportionment study. The present study elaborates further on the same concept, evaluating quantitatively the impact of lacking specific sources' tracers on the whole source apportionment, both in terms of identified sources and source contributions. This work aims to provide first recommendations on the most suitable and critical components to be included in PMF analyses in order to reduce PMF output uncertainty as much as possible, and better represent the most commons PM sources observed in many sites in Western countries. To this aim, we performed three sensitivity analyses on three different datasets across EU, including extended sets of organic tracers, in order to cover different types of urban conditions (Mediterranean, Continental, and Alpine), source types, and PM fractions. Our findings reveal that the vehicle exhaust source resulted to be less sensitive to the choice of analytes, although source contributions estimates can deviate significantly up to 44 %. On the other hand, for the detection of the non-exhaust one is clearly necessary to analyze specific inorganic elements. The choice of not analysing non-polar organics likely causes the loss of separation of exhaust and non-exhaust factors, thus obtaining a unique road traffic source, which provokes a significant bias of total contribution. Levoglucosan was, in most cases, crucial to identify biomass burning contributions in Milan and in Barcelona, in spite of the presence of PAHs in Barcelona, while for the case of Grenoble, even discarding levoglucosan, the presence of PAHs allowed identifying the BB factor. Modifying the rest of analytes provoke a systematic underestimation of biomass burning source contributions. SIA factors resulted to be generally overestimated with respect to the base case analysis, also in the case that ions were not included in the PMF analysis. Trace elements were crucial to identify shipping emissions (V and Ni) and industrial sources (Pb, Ni, Br, Zn, Mn, Cd and As). When changing the rest of input variables, the uncertainty was narrow for shipping but large for industrial processes. Major and trace elements were also crucial to identify the mineral/soil factor at all cities. Biogenic SOA and Anthropogenic SOA factors were sensitive to the presence of their molecular tracers, since the availability of OC alone is unable to separate a SOA factor. Arabitol and sorbitol were crucial to detecting fungal spores while odd number of higher alkanes (C27 to C31) for plant debris.

Discovering oxidative potential (OP) drivers of atmospheric PM10, PM2.5, and PM1 simultaneously in North-Eastern Spain.

Ambient particulate matter (PM) is a major contributor to air pollution, leading to adverse health effects on the human population. It has been suggested that the oxidative potential (OP, as a tracer of oxidative stress) of PM is a possible determinant of its health impact. In this study, samples of PM10, PM2.5, and PM1 were collected roughly every four days from January 2018 until March 2019 at a Barcelona urban background site and Montseny rural background site in northeastern Spain. We determined the chemical composition of samples, allowing us to perform source apportionment using positive matrix factorization. The OP of PM was determined by measuring reactive oxygen species using dithiothreitol and ascorbic acid assays. Finally, to link the sources with the measured OP, both a Pearson's correlation and a multiple linear regression model were applied to the dataset. The results showed that in Barcelona, the OP of PM10 was much higher than those of PM2.5 and PM1, whereas in Montseny results for all PM sizes were in the same range, but significantly lower than in Barcelona. In Barcelona, several anthropogenic sources were the main drivers of OP in PM10 (Combustion + Road Dust + Heavy Oil + OC-rich) and PM2.5 (Road Dust + Combustion). In contrast, PM1 -associated OP was driven by Industry, with a much lower contribution to PM10 and PM2.5 mass. Meanwhile, Montseny exhibited no clear drivers for OP evolution, likely explaining the lack of a significant difference in OP between PM10, PM2.5, and PM1. Overall, this study indicates that size fraction matters for OP, as a function of the environment typology. In an urban context, OP is driven by the PM10 and PM1 size fractions, whereas only the PM1 fraction is involved in rural environments.

The unexpected role of bioaerosols in the Oxidative Potential of PM.

Bioaerosols represent up to 15-25% of PM by mass, but there is currently no assessment of their impact on Oxidative Potential (OP), or capacity of particulate matter (PM) to produce damaging oxidative reactions in the human lungs. Here, the OP of selected bioaerosols (bacteria cells vs fungal spores) was assessed through the cell-free DTT assay. Results show that bioaerosols induce Reactive Oxygen Species (ROS) production, varying along the microorganism type, species, and concentration. Fungal spores show up to 10 times more ROS generation than bacterial cells. At the highest concentrations, fungal spores present as much oxidative reactivity as the most redox-active airborne chemicals (Copper, Naphtoquinone). Moreover, bioaerosols substantially influence OP of ambient PM and that of its chemical constituents: in presence of A. fumigatus spores, the OP of Cu/NQ is increased by a factor of 2 to 5, whereas, 104 and 105 S. epidermidis bacterial cells.mL-1 halves the OP of Cu/NQ. Finally, viable and gamma-rays-killed model bioaerosols present similar oxidative reactivity, suggesting a metabolism-independent cellular mechanism. These results reveal the importance of bioaerosols for PM reactivity. PM toxicity can be modified due to bioaerosols contribution or by their ability to modulate the OP of toxic chemicals present in PM.

Cadmium bioaccumulation and gastric bioaccessibility in cacao: A field study in areas impacted by oil activities in Ecuador.

Cacao from South America is especially used to produce premium quality chocolate. Although the European Food Safety Authority has not established a limit for cadmium (Cd) in chocolate raw material, recent studies demonstrate that Cd concentrations in cacao beans can reach levels higher than the legal limits for dark chocolate (0.8 mg kg-1, effective January 1st, 2019). Despite the fact that the presence of Cd in agricultural soils is related to contamination by fertilizers, other potential sources must be considered in Ecuador. This field study was conducted to investigate Cd content in soils and cacao cultivated on Ecuadorian farms in areas impacted by oil activities. Soils, cacao leaves, and pod husks were collected from 31 farms in the northern Amazon and Pacific coastal regions exposed to oil production and refining and compared to two control areas. Human gastric bioaccessibility was determined in raw cacao beans and cacao liquor samples in order to assess potential health risks involved. Our results show that topsoils (0-20 cm) have higher Cd concentrations than deeper layers, exceeding the Ecuadorian legislation limit in 39% of the sampling sites. Cacao leaves accumulate more Cd than pod husks or beans but, nevertheless, 50% of the sampled beans have Cd contents above 0.8 mg kg-1. Root-to-cacao transfer seems to be the main pathway of Cd uptake, which is not only regulated by physico-chemical soil properties but also agricultural practices. Additionally, natural Cd enrichment by volcanic inputs must not be neglected. Finally, Cd in cacao trees cannot be considered as a tracer of oil activities. Assuming that total Cd content and its bioaccessible fraction (up to 90%) in cacao beans and liquor is directly linked to those in chocolate, the health risk associated with Cd exposure varies from low to moderate.

Mercury contamination level and speciation inventory in Lakes Titicaca & Uru-Uru (Bolivia): Current status and future trends.

Aquatic ecosystems of the Bolivian Altiplano (∼3800 m a.s.l.) are characterized by extreme hydro-climatic constrains (e.g., high UV-radiations and low oxygen) and are under the pressure of increasing anthropogenic activities, unregulated mining, agricultural and urban development. We report here a complete inventory of mercury (Hg) levels and speciation in the water column, atmosphere, sediment and key sentinel organisms (i.e., plankton, fish and birds) of two endorheic Lakes of the same watershed differing with respect to their size, eutrophication and contamination levels. Total Hg (THg) and monomethylmercury (MMHg) concentrations in filtered water and sediment of Lake Titicaca are in the lowest range of reported levels in other large lakes worldwide. Downstream, Hg levels are 3-10 times higher in the shallow eutrophic Lake Uru-Uru than in Lake Titicaca due to high Hg inputs from the surrounding mining region. High percentages of MMHg were found in the filtered and unfiltered water rising up from <1 to ∼50% THg from the oligo/hetero-trophic Lake Titicaca to the eutrophic Lake Uru-Uru. Such high %MMHg is explained by a high in situ MMHg production in relation to the sulfate rich substrate, the low oxygen levels of the water column, and the stabilization of MMHg due to abundant ligands present in these alkaline waters. Differences in MMHg concentrations in water and sediments compartments between Lake Titicaca and Uru-Uru were found to mirror the offset in MMHg levels that also exist in their respective food webs. This suggests that in situ MMHg baseline production is likely the main factor controlling MMHg levels in fish species consumed by the local population. Finally, the increase of anthropogenic pressure in Lake Titicaca may probably enhance eutrophication processes which favor MMHg production and thus accumulation in water and biota.

Metal and metalloid foliar uptake by various plant species exposed to atmospheric industrial fallout: mechanisms involved for lead.

Fine and ultrafine metallic particulate matters (PMs) are emitted from metallurgic activities in peri-urban zones into the atmosphere and can be deposited in terrestrial ecosystems. The foliar transfer of metals and metalloids and their fate in plant leaves remain unclear, although this way of penetration may be a major contributor to the transfer of metals into plants. This study focused on the foliar uptake of various metals and metalloids from enriched PM (Cu, Zn, Cd, Sn, Sb, As, and especially lead (Pb)) resulting from the emissions of a battery-recycling factory. Metal and metalloid foliar uptake by various vegetable species, exhibiting different morphologies, use (food or fodder) and life-cycle (lettuce, parsley and rye-grass) were studied. The mechanisms involved in foliar metal transfer from atmospheric particulate matter fallout, using lead (Pb) as a model element was also investigated. Several complementary techniques (micro-X-ray fluorescence, scanning electron microscopy coupled with energy dispersive X-ray microanalysis and time-of-flight secondary ion mass spectrometry) were used to investigate the localization and the speciation of lead in their edible parts, i.e. leaves. The results showed lead-enriched PM on the surface of plant leaves. Biogeochemical transformations occurred on the leaf surfaces with the formation of lead secondary species (PbCO(3) and organic Pb). Some compounds were internalized in their primary form (PbSO(4)) underneath an organic layer. Internalization through the cuticle or penetration through stomata openings are proposed as two major mechanisms involved in foliar uptake of particulate matter.

Characterization of lead-recycling facility emissions at various workplaces: major insights for sanitary risks assessment.

Most available studies on lead smelter emissions deal with the environmental impact of outdoor particles, but only a few focus on air quality at workplaces. The objective of this study is to physically and chemically characterize the Pb-rich particles emitted at different workplaces in a lead recycling plant. A multi-scale characterization was conducted from bulk analysis to the level of individual particles, to assess the particles properties in relation with Pb speciation and availability. Process PM from various origins were sampled and then compared; namely Furnace and Refining PM respectively present in the smelter and at refinery workplaces, Emissions PM present in channeled emissions. These particles first differed by their morphology and size distribution, with finer particles found in emissions. Differences observed in chemical composition could be explained by the industrial processes. All PM contained the same major phases (Pb, PbS, PbO, PbSO(4) and PbO·PbSO(4)) but differed on the nature and amount of minor phases. Due to high content in PM, Pb concentrations in the CaCl(2) extractant reached relatively high values (40 mg L(-1)). However, the ratios (soluble/total) of CaCl(2) exchangeable Pb were relatively low (<0.02%) in comparison with Cd (up to 18%). These results highlight the interest to assess the soluble fractions of all metals (minor and major) and discuss both total metal concentrations and ratios for risk evaluations. In most cases metal extractability increased with decreasing size of particles, in particular, lead exchangeability was highest for channeled emissions. Such type of study could help in the choice of targeted sanitary protection procedures and for further toxicological investigations. In the present context, particular attention is given to Emissions and Furnace PM. Moreover, exposure to other metals than Pb should be considered.

Study of lead phytoavailability for atmospheric industrial micronic and sub-micronic particles in relation with lead speciation.

Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650+/-20mg Pb kg(-1)) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO(4), PbSO(4) x PbO, alpha-PbO and Pb(0). Morphology investigations revealed that PM(2.5) (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 microm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01M CaCl(2) extraction.

Self-selection among diets differing in methionine content by chickens of different lines.

Two trials were conducted to compare the ability of chickens from different genetic lines to select among diets differing in methionine. In Trial 1, chicks from White Plymouth Rock (HW) and White Leghorn (HA) lines were offered a choice of diets containing .85, .58, or .44% methionine from 1 through 7 days of age. In Trial 2, a slow-growing line of White Plymouth Rocks (LW) was used in addition to the same lines used in Trial 1. A choice of the three diets was offered from 1 through 13 and from 20 through 23 days of age. During the period from 14 through 19 days of age, all chicks were fed the .44% methionine diet. In both trials, Line HW chicks first exhibited a dietary preference at 5 days of age. Line HA chicks did not discriminate among diets in either trial when given a choice from 1 day posthatch. They did, however, exhibit a preference starting on Day 20 in Trial 2 (after being fed the deficient diet). No dietary preferences were exhibited by chicks from Line LW. Results of these trials showed that selection among diets varying in methionine content was influenced by genotype, age, nutritional state of the chick, and their interactions.

Food intake adjustments of chicks: short term reactions of genetic stocks to deficiencies in lysine, methionine or tryptophan.

1. Growth, food intake, and food preference were measured in two experimental lines (White Rocks and White Leghorns) of chickens fed diets varying in content of lysine, methionine, or tryptophan. Diet A was balanced in all amino acids, while the remaining 6 diets were moderately (approximately 30%) or slightly (approximately 15%) deficient in either lysine, methionine, or tryptophan relative to NRC recommendations for broiler diets. 2. Body weight and food utilisation efficiency of White Leghorns at 10 d of age were not affected by diet, whereas the lower concentrations of lysine and methionine depressed these traits in White Rocks. 3. Tryptophan deficiency reduced food intake of White Leghorns, but not White Rocks. 4. With choice feeding of balanced and deficient diets from day 10 to 16, preferences between the diets were minimal for White Leghorns, whereas for White Rocks there was an almost immediate preference for the balanced diet, followed by lack of preference or preference for the deficient diet. 5. Apparently for some genetic stocks there is rapid adjustment to deficiencies in these amino acids with overconsumption, followed by compensation for preference of the balanced diet. The response, however, will vary depending on the deficient amino acid.

Food intake adjustments of chicks: short term reactions to deficiencies in lysine, methionine and tryptophan.

1. Two experiments were conducted to compare food intake responses of broiler chicks fed diets varying in lysine, methionine, and tryptophan. Diet D was formulated to create simultaneous deficiencies of lysine, methionine, and tryptophan. Diet A matched National Research Council (1984) recommendations for broilers, and diets B and C were, respectively, 2:1 and 1:2 mixes of diets A and D. 2. Short-term food intake can provide information on the sequences of adaptation of chicks to a diet deficient in essential amino acids. 3. Chicks consumed 26% less of diet D than A during the first 24 h posthatch. When chicks fed diet A or D to 7 d of age were then fed one of 4 diets singly, within 24 h intake was lowest for chicks fed diet D. Within 48 h, food intake of diet C was more than that of diet D and less than that of diet A, while for diet B intake was more than of diet D but not different from diet A. 4. In the second experiment, chicks were fed diet A to 8 d and then diets A or D alone or given a choice of diets A and D from 8 to 20 d of age. Within 4 to 8 h, food intake of chicks fed diet D alone decreased markedly followed by partial recovery within 24 h. In a choice setting, consistent preference of Diet A over Diet D was observed within 7 h followed by stabilisation at about 65% diet A to 35% diet D. 5. Chicks fed diet D alone from 8 to 20 d of age, then placed in the same choice situation preferred diet A to D with a delay of less than one h and stabilisation at about 85%. Chicks provided a choice of diets A and D from 8 to 20 d, and then diet D alone reduced their food intake more quickly than those not given a choice initially. 6. Broiler chicks appear to react to amino acid deficiencies within a short period (hours) by adjusting their feed intake and/or selection. The response is influenced by age and prior experience.

Feed intake adjustments by hens to feeding regimens in which dietary methionine is varied.

At 20 wk of age, 315 ISA Brown pullets were individually caged and randomly assigned to one of seven feeding regimens for the next 20 wk. In Regimen 1 Diet A was fed, in Regimen 2 Diet B was fed, Regimens 3 and 4 alternated Diets A and B weekly (the week Diet A was fed in Regimen 3, Diet B was fed in Regimen 4), Regimens 5 and 6 alternated Diets A and B monthly (reversing as with 3 and 4), and in Regimen 7 pullets were given a choice of Diets A and B. Diet A was methionine-deficient (.23%) and Diet B was balanced for methionine (.33%). Feed and nutrient consumption, egg production, egg weight, and egg mass were lower in Regimen 1 than 2. Pullets in Regimen 1 lost body weight and those in Regimen 2 gained weight. Overall feed consumption for Regimens 3 through 7 was similar to that for Regimen 2. For Regimens 3 through 6, however, consumption increased when the balanced diet was fed and decreased when the deficient diet was fed. Concomitant with these oscillations in feed consumption were changes in egg mass, so that means for these traits were intermediate and different from those for Regimens 1 and 2. For Regimen 7, in which Diets A and B were continuously available, no preference of diet was observed during the first 4 wk.(ABSTRACT TRUNCATED AT 250 WORDS)

Effect of dietary lysine level on lipogenesis in broilers.

From 3-7 weeks of age, male and female broilers were fed ad libitum on 1 of the 8 experimental diets. These diets were isoenergetic (13.6 kJ/kg) and isoproteic (186 g/kg) and provided 7 to 14 g/kg lysine. The growth performances, the abdominal fat proportion and hepatic malic enzyme activity (malate dehydrogenase with decarboxylating EC 1.1.1.40) were measured. All parameters varied when dietary lysine concentration was increased from 7 to 9 or to 11 g/kg. The lysine requirement in the finishing period for minimum abdominal fat proportion was higher than for minimum feed conversion ratio, itseful higher than for maximal growth rate. Malic enzyme activity varied with abdominal fat proportion, and this variation could explain the reduction in fatness. However, an excess of lysine did not amplify the reduction of fat deposit.