Polylactic-Containing Hyperbranched Polymers through the CuAAC Polymerization of Aromatic AB2 Monomers.

We report on the synthesis and characterization of a novel class of hyperbranched polymers, in which a copper(I)-catalyzed alkyne azide cycloaddition (CuAAC) reaction (the prototypical "click" reaction) is used as the polymerization step. The AB2 monomers bear two azide functionalities and one alkyne functionality, which have been installed onto a 1,3,5 trisubstituted benzene aromatic skeleton. This synthesis has been optimized in terms of its purification strategies, with an eye on its scalability for the potential industrial applications of hyperbranched polymers as viscosity modifiers. By taking advantage of the modularity of the synthesis, we have been able to install short polylactic acid fragments as the spacing units between the complementary reactive azide and alkyne functionalities, aiming to introduce elements of biodegradability into the final products. The hyperbranched polymers have been obtained with good molecular weights and degrees of polymerization and branching, testifying to the effectiveness of the synthetic design. Simple experiments on glass surfaces have highlighted the possibility of conducting the polymerizations and the formation of the hyperbranched polymers directly in thin films at room temperature.

Effects of climate change on the distribution of Fusarium spp. in Italy.

This work studies the incidence of Fusarium spp. on wheat kernels about current and future climatic conditions in Italy. Epidemiological analyses were performed from 2007 to 2013 and the resulting dataset was used to find correlations between the disease incidence of five important Fusarium species monitored in Italy (Fusarium graminearum, F. langsethiae, F. sporotrichioides, F. poae and F. avenaceum) and climatic and geographical parameters. Probabilistic-based modelling of the actual distribution of Fusarium spp. was achieved by using the Zero-inflated Poisson regression. The probabilistic geographical distribution of the Fusarium species was assessed by applying future climatic scenarios (RCPs 4.5 and 8.5). The shift from current to future climatic scenarios highlighted changes on a national and regional scale. The tightening of environmental conditions from the RCP4.5 to 8.5 scenarios resulted in a sporadic presence of F. avenaceum only in the northern region of Italy. Fusarium graminearum was plentifully present in the current climate, but the tightening of minimum and maximum temperatures and the decrease of precipitation between May-June in the RCP8.5 no longer represents the optimum conditions for it. Fusarium langsethiae was currently distributed in all of Italy, showing an increase in the probability of detecting it by moving from high to low latitudes and from low to high longitudes in the RCP8.5. Fusarium poae, unlike other Fusarium species, grows and develops in arid climatic conditions. High values of F. poae were recorded at low latitudes and longitudes. Under the RCP scenarios, it showed high incidence probabilities in the southeast and northeast areas of Italy. Fusarium sporotrichioides is scarcely present in Italy, found at high latitudes and in the central areas. Climate change altered this distribution, and the chances of discovering it increased significantly moving to southern Italy. Overall, the study shows that climate change conditions are likely to lead to an increase in the incidence of Fusarium species on wheat kernels in Italy, highlighting the importance of developing strategies to mitigate the effects of climate change on wheat production, quality, and safety.

Ozone modelling and mapping for risk assessment: An overview of different approaches for human and ecosystems health.

Tropospheric ozone (O3) is one of the most concernedair pollutants dueto its widespread impacts on land vegetated ecosystems and human health. Ozone is also the third greenhouse gas for radiative forcing. Consequently, it should be carefully and continuously monitored to estimate its potential adverse impacts especially inthose regions where concentrations are high. Continuous large-scale O3 concentrations measurement is crucial but may be unfeasible because of economic and practical limitations; therefore, quantifying the real impact of O3over large areas is currently an open challenge. Thus, one of the final objectives of O3 modelling is to reproduce maps of continuous concentrations (both spatially and temporally) and risk assessment for human and ecosystem health. We here reviewedthe most relevant approaches used for O3 modelling and mapping starting from the simplest geo-statistical approaches andincreasing in complexity up to simulations embedded into the global/regional circulation models and pro and cons of each mode are highlighted. The analysis showed that a simpler approach (mostly statistical models) is suitable for mappingO3concentrationsat the local scale, where enough O3concentration data are available. The associated error in mapping can be reduced by using more complex methodologies, based on co-variables. The models available at the regional or global level are used depending on the needed resolution and the domain where they are applied to. Increasing the resolution corresponds to an increase in the prediction but only up to a certain limit. However, with any approach, the ensemble models should be preferred.

Legislative and functional aspects of different metrics used for ozone risk assessment to forests.

Surface ozone (O3) is a threat to forests by decreasing photosynthesis and, consequently, influencing the strength of land carbon sink. However, due to the lack of continuous surface O3 measurements, observational-based assessments of O3 impacts on forests are largely missing at hemispheric to global scales. Currently, some metrics are used for regulatory purposes by governments or national agencies to protect forests against the negative impacts of ozone: in particular, both Europe and United States (US) makes use of two different exposure-based metrics, i.e. AOT40 and W126, respectively. However, because of some limitations in these metrics, a new standard is under consideration by the European Union (EU) to replace the current exposure metric. We analyse here the different air quality standards set or proposed for use in Europe and in the US to protect forests from O3 and to evaluate their spatial and temporal consistency while assessing their effectiveness in protecting northern-hemisphere forests. Then, we compare their results with the information obtained from a complex land surface model (ORCHIDEE). We find that present O3 uptake decreases gross primary production (GPP) in 37.7% of the NH forested area of northern hemisphere with a mean loss of 2.4% year-1. We show how the proposed US (W126) and the currently used European (AOT40) air quality standards substantially overestimate the extension of potential vulnerable regions, predicting that 46% and 61% of the Northern Hemisphere (NH) forested area are at risk of O3 pollution. Conversely, the new proposed European standard (POD1) identifies lower extension of vulnerability regions (39.6%).

Impact of ground-level ozone on Mediterranean forest ecosystems health.

Given the high ozone concentrations observed in the Mediterranean region during summer, it is crucial to extend our knowledge on the potential ozone impacts on forest health with in situ studies, especially to protect typical endemic forests of the Mediterranean basin. This study is focused on ozone measurements and exposures over the Eastern Adriatic coast and on the calculation of different O3 metrics, i.e., accumulated exposure AOT40 (AOT40dir, AOT40ICP, AOT40pheno) and stomatal O3 fluxes with an hourly threshold of uptake (Y) to represent the detoxification capacity of trees (PODY, with Y = 0, 1, 2 nmol O3 m-2 s-1) used for forest protection. Finally, we provide an assessment of the relationships between the forest response indicators and environmental variables. Passive ozone measurements and monitoring of forest health indicators, namely growth and crown defoliation, were performed for Quercus ilex, Quercus pubescens, Pinus halepensis, and Pinus nigra forests. Results showed that, for all the analysed species, ozone levels were close to reached the upper plausibility limits for passive monitoring of air quality at forest sites (100 ppb), with the highest values found on P. halepensis in the summer period. O3 metrics based on exposure were found to be higher in pine plots than in oak plots, while the highest values of uptake-based metrics were found on P. nigra. Regarding relationships between environmental variables and forest-health response indicators, the crown defoliation was significantly correlated with the soil water content at various depth while the tree growth was correlated with the different O3 metrics. The most important predictors affecting tree growth of Q. pubescens and Q. ilex were AOT40pheno and AOT40dir and POD0 for P. nigra.

Ozone affects plant, insect, and soil microbial communities: A threat to terrestrial ecosystems and biodiversity.

Elevated tropospheric ozone concentrations induce adverse effects in plants. We reviewed how ozone affects (i) the composition and diversity of plant communities by affecting key physiological traits; (ii) foliar chemistry and the emission of volatiles, thereby affecting plant-plant competition, plant-insect interactions, and the composition of insect communities; and (iii) plant-soil-microbe interactions and the composition of soil communities by disrupting plant litterfall and altering root exudation, soil enzymatic activities, decomposition, and nutrient cycling. The community composition of soil microbes is consequently changed, and alpha diversity is often reduced. The effects depend on the environment and vary across space and time. We suggest that Atlantic islands in the Northern Hemisphere, the Mediterranean Basin, equatorial Africa, Ethiopia, the Indian coastline, the Himalayan region, southern Asia, and Japan have high endemic richness at high ozone risk by 2100.

Growing season extension affects ozone uptake by European forests.

Climate change significantly modifies terrestrial ecosystems and vegetation activity, yet little is known about how climate change and ozone pollution interact to affect forest health. Here we compared the trends of two metrics widely used to protect forests against negative impacts of ozone pollution, the AOT40 (Accumulated Ozone over Threshold of 40 ppb) which only depends on surface air ozone concentrations, and the POD (Phytotoxic Ozone Dose) which relies on the amount of ozone uptaken by plants through stomata. Using a chemistry transport model, driven by anthropogenic emission inventories, we found that European-averaged ground-level ozone concentrations significantly declined (-1.6%) over the time period 2000-2014, following successful control strategies to reduce the ozone precursors emission; as a consequence, the AOT40 metric declined (-22%). In contrast, climate change increased both growing season length (~7 days/decade) and stomatal conductance and thus enhanced the stomatal ozone uptake by forests (5.9%), leading to an overall increase of potential ozone damage on plants, despite the reduction in ozone concentrations. Our results suggest that stomatal-flux based strategies of forest protection against ozone in a changing climate require a proper consideration of the duration of the growing season with a better estimation of start and end of the growing season.

Impacts of air pollution on human and ecosystem health, and implications for the National Emission Ceilings Directive: Insights from Italy.

Across the 28 EU member states there were nearly half a million premature deaths in 2015 as a result of exposure to PM2.5, O3 and NO2. To set the target for air quality levels and avoid negative impacts for human and ecosystems health, the National Emission Ceilings Directive (NECD, 2016/2284/EU) sets objectives for emission reduction for SO2, NOx, NMVOCs, NH3 and PM2.5 for each Member State as percentages of reduction to be reached in 2020 and 2030 compared to the emission levels into 2005. One of the innovations of NECD is Article 9, that mentions the issue of "monitoring air pollution impacts" on ecosystems. We provide a clear picture of what is available in term of monitoring network for air pollution impacts on Italian ecosystems, summarizing what has been done to control air pollution and its effects on different ecosystems in Italy. We provide an overview of the impacts of air pollution on health of the Italian population and evaluate opportunities and implementation of Article 9 in the Italian context, as a case study beneficial for all Member States. The results showed that SO42- deposition strongly decreased in all monitoring sites in Italy over the period 1999-2017, while NO3- and NH4+ decreased more slightly. As a consequence, most of the acid-sensitive sites which underwent acidification in the 1980s partially recovered. The O3 concentration at forest sites showed a decreasing trend. Consequently, AOT40 (the metric identified to protect vegetation from ozone pollution) showed a decrease, even if values were still above the limit for forest protection (5000 ppb h-1), while PODy (flux-based metric under discussion as new European legislative standard for forest protection) showed an increase. National scale studies pointed out that PM10 and NO2 induced about 58,000 premature deaths (year 2005), due to cardiovascular and respiratory diseases. The network identified for Italy contains a good number of monitoring sites (6 for terrestrial ecosystem monitoring, 4 for water bodies monitoring and 11 for ozone impact monitoring) distributed over the territory and will produce a high number of monitored parameters for the implementation of the NECD.

Commentary: EPA's proposed expansion of dose-response analysis is a positive step towards improving its ecological risk assessment.

The United States Environmental Protection Agency (US EPA) has recently proposed changes to strengthen the transparency of its pivotal regulatory science policy and procedures. In this context, the US EPA aims to enhance the transparency of dose-response data and models, proposing to consider for the first time non-linear biphasic dose-response models. While the proposed changes have the potential to lead to markedly improved ecological risk assessment compared to past and current approaches, we believe there remain open issues for improving the quality of ecological risk assessment, such as the consideration of adaptive, dynamic and interactive effects. Improved risk assessment including adaptive and dynamic non-linear models (beyond classic threshold models) can enhance the quality of regulatory decisions and the protection of ecological health. We suggest that other countries consider adopting a similar scientific-regulatory posture with respect to dose-response modeling via the inclusion of non-linear biphasic models, that incorporate the dynamic potential of biological systems to adapt (i.e., enhancing positive biological endpoints) or maladapt to low levels of stressor agents.

Ozone exposure affects tree defoliation in a continental climate.

Ground-level ozone (O3) affects trees through visible leaf injury, accelerating leaf senescence, declining foliar chlorophyll content, photosynthetic activity, growth, carbon sequestration, predisposing to pests attack and a variety of other physiological effects. Tree crown defoliation is one of the most important parameters that is representative of forest health and vitality. Effects of air pollution on forests have been investigated through manipulative experiments that are not representative of the real environmental conditions observed in the field. In this work we investigated the role of O3 concentration and other metrics (AOT40 and POD0) in affecting crown defoliation in temperate Romanian forests. The impacts of O3 were estimated in combination with nitrogen pollutants, climatic factors and orographic conditions, by applying a non-linear modelling approach (Random Forest and Generalised Regression Models). Ozone concentration and AOT40 under Romanian conditions were more important than meteorological parameters in affecting crown defoliation. In these particular conditions, POD0 never exceeded the critical level suggested by previous literature for forest protection, and thus was not important in affecting crown defoliation.

Comparing concentration-based (AOT40) and stomatal uptake (PODY) metrics for ozone risk assessment to European forests.

Tropospheric ozone (O3) produces harmful effects to forests and crops, leading to a reduction of land carbon assimilation that, consequently, influences the land sink and the crop yield production. To assess the potential negative O3 impacts to vegetation, the European Union uses the Accumulated Ozone over Threshold of 40 ppb (AOT40). This index has been chosen for its simplicity and flexibility in handling different ecosystems as well as for its linear relationships with yield or biomass loss. However, AOT40 does not give any information on the physiological O3 uptake into the leaves since it does not include any environmental constraints to O3 uptake through stomata. Therefore, an index based on stomatal O3 uptake (i.e. PODY), which describes the amount of O3 entering into the leaves, would be more appropriate. Specifically, the PODY metric considers the effects of multiple climatic factors, vegetation characteristics and local and phenological inputs rather than the only atmospheric O3 concentration. For this reason, the use of PODY in the O3 risk assessment for vegetation is becoming recommended. We compare different potential O3 risk assessments based on two methodologies (i.e. AOT40 and stomatal O3 uptake) using a framework of mesoscale models that produces hourly meteorological and O3 data at high spatial resolution (12 km) over Europe for the time period 2000-2005. Results indicate a remarkable spatial and temporal inconsistency between the two indices, suggesting that a new definition of European legislative standard is needed in the near future. Besides, our risk assessment based on AOT40 shows a good consistency compared to both in-situ data and other model-based datasets. Conversely, risk assessment based on stomatal O3 uptake shows different spatial patterns compared to other model-based datasets. This strong inconsistency can be likely related to a different vegetation cover and its associated parameterizations.

Future impacts of nitrogen deposition and climate change scenarios on forest crown defoliation.

Defoliation is an indicator for forest health in response to several stressors including air pollutants, and one of the most important parameters monitored in the International Cooperative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP Forests). The study aims to estimate crown defoliation in 2030, under three climate and one nitrogen deposition scenarios, based on evaluation of the most important factors (meteorological, nitrogen deposition and chemical soil parameters) affecting defoliation of twelve European tree species. The combination of favourable climate and nitrogen fertilization in the more adaptive species induces a generalized decrease of defoliation. On the other hand, severe climate change and drought are main causes of increase in defoliation in Quercus ilex and Fagus sylvatica, especially in Mediterranean area. Our results provide information on regional distribution of future defoliation, an important knowledge for identifying policies to counteract negative impacts of climate change and air pollution.

Tropospheric ozone reduces carbon assimilation in trees: estimates from analysis of continuous flux measurements.

High ground-level ozone concentrations are typical of Mediterranean climates. Plant exposure to this oxidant is known to reduce carbon assimilation. Ozone damage has been traditionally measured through manipulative experiments that do not consider long-term exposure and propagate large uncertainty by up-scaling leaf-level observations to ecosystem-level interpretations. We analyzed long-term continuous measurements (>9 site-years at 30 min resolution) of environmental and eco-physiological parameters at three Mediterranean ecosystems: (i) forest site dominated by Pinus ponderosa in the Sierra Mountains in California, USA; (ii) forest site composed of a mixture of Quercus spp. and P. pinea in the Tyrrhenian sea coast near Rome, Italy; and (iii) orchard site of Citrus sinensis cultivated in the California Central Valley, USA. We hypothesized that higher levels of ozone concentration in the atmosphere result in a decrease in carbon assimilation by trees under field conditions. This hypothesis was tested using time series analysis such as wavelet coherence and spectral Granger causality, and complemented with multivariate linear and nonlinear statistical analyses. We found that reduction in carbon assimilation was more related to stomatal ozone deposition than to ozone concentration. The negative effects of ozone occurred within a day of exposure/uptake. Decoupling between carbon assimilation and stomatal aperture increased with the amount of ozone pollution. Up to 12-19% of the carbon assimilation reduction in P. ponderosa and in the Citrus plantation was explained by higher stomatal ozone deposition. In contrast, the Italian site did not show reductions in gross primary productivity either by ozone concentration or stomatal ozone deposition, mainly due to the lower ozone concentrations in the periurban site over the shorter period of investigation. These results highlight the importance of plant adaptation/sensitivity under field conditions, and the importance of continuous long-term measurements to explain ozone damage to real-world forests and calculate metrics for ozone-risk assessment.

Assessing ozone and nitrogen impact on net primary productivity with a Generalised non-Linear Model.

Some studies suggest that in Europe the majority of forest growth increment can be accounted for N deposition and very little by elevated CO(2). High ozone (O(3)) concentrations cause reductions in carbon fixation in native plants by offsetting the effects of elevated CO(2) or N deposition. The cause-effect relationships between primary productivity (NPP) of Quercus cerris, Q. ilex and Fagus sylvatica plant species and climate and pollutants (O(3) and N deposition) in Italy have been investigated by application of Generalised Linear/non-Linear regression model (GLZ model). The GLZ model highlighted: i) cumulative O(3) concentration-based indicator (AOT40F) did not significantly affect NPP; ii) a differential action of oxidised and reduced nitrogen depositions to NPP was linked to the geographical location; iii) the species-specific variation of NPP caused by combination of pollutants and climatic variables could be a potentially important drive-factor for the plant species' shift as response to the future climate change.

Urban ecosystem services: tree diversity and stability of tropospheric ozone removal.

Urban forests provide important ecosystem services, such as urban air quality improvement by removing pollutants. While robust evidence exists that plant physiology, abundance, and distribution within cities are basic parameters affecting the magnitude and efficiency of air pollution removal, little is known about effects of plant diversity on the stability of this ecosystem service. Here, by means of a spatial analysis integrating system dynamic modeling and geostatistics, we assessed the effects of tree diversity on the removal of tropospheric ozone (O3) in Rome, Italy, in two years (2003 and 2004) that were very different for climatic conditions and ozone levels. Different tree functional groups showed complementary uptake patterns, related to tree physiology and phenology, maintaining a stable community function across different climatic conditions. Our results, although depending on the city-specific conditions of the studied area, suggest a higher function stability at increasing diversity levels in urban ecosystems. In Rome, such ecosystem services, based on published unitary costs of externalities and of mortality associated with O3, can be prudently valued to roughly US$2 and $3 million/year, respectively.

Comparison of seasonal variations of ozone exposure and fluxes in a Mediterranean Holm oak forest between the exceptionally dry 2003 and the following year.

Ozone and energy fluxes have been measured using the eddy covariance technique, from June to December 2004 in Castelporziano near Rome (Italy), and compared to similar measurements made in the previous year. The studied ecosystem consisted in a typical Mediterranean Holm oak forest. Stomatal fluxes have been calculated using the resistance analogy and by inverting the Penmann-Monteith equation. Results showed that the average stomatal contribution accounts for 42.6% of the total fluxes. Non-stomatal deposition proved to be enhanced by increasing leaf wetness and air humidity during the autumnal months. From a comparison of the two years, it can be inferred that water supply is the most important limiting factor for ozone uptake and that prolonged droughts alter significantly the stomatal conductance, even 2 months after the soil water content is replenished. Ozone exposure, expressed as AOT40, behaves similarly to the cumulated stomatal flux in dry conditions whereas a different behaviour for the two indices appears in wet autumnal conditions. A difference also occurs between the two years.

Physiological response of Pinus halepensis needles under ozone and water stress conditions.

The aim of this study was to evaluate how physiological processes of potted Pinus halepensis plants, grown under controlled conditions, were affected by ozone (O3) and/or water stress, integrating the gas exchange and biochemical data with fluorescence OJIP polyphasic transient data. Plants submitted to only water stress (T1) and with ozone (T3) showed a strong decrease in stomatal conductance and gas exchange, coinciding with a reduction of maximum yield of photochemistry (varphipo) and very negative values of leaf water potential. Simultaneously, a great increase of both PSII antenna size, indicated by absorption per reaction centre, and electron transport per reaction centre were found. The reduction of photosynthesis in the O3-treated plants (T2) by a slowing down of the Calvin cycle was supported by the increase of related fluorescence parameters such as relative variable fluorescence, heat de-excitation constant, energy de-excitation by spillover, and the decrease of varphipo. We suggest an antagonistic effect between the two stresses to explain the delayed ozone-induced decrease of stomatal conductance values for T3 with respect to T1 plants, by an alteration of the physiological mechanisms of stomatal opening, which involve the increase of intra-cellular free-calcium induced by ABA under co-occurring water shortage. We emphasise the importance of considering the intensity of the individual stress factor in studies concerning the interaction of stresses.