Multivariate spatial analysis for the identification of criticalities and of the subtended causes in river ecosystems.

In statistics, the identification of environmental criticalities, one of the primary goals of environmental monitoring and management, translates into the detection of spatial outliers. Detected in relation to purposely defined sets of indicators, both global and local outliers are pivotal in the identification not only of the severity and spread of criticalities, but also of their nature and causes. The present research exemplifies a procedural framework to identify environmental criticalities, using two different approaches for the detection of spatial outliers in river ecosystems related to several sets of parameters (organic C, inorganic C, Ca, Co, Cr, Fe, K, Mg, Mn, N, Na, P, S, Si, V, Zn, Cl-, F-, NO3-, SO42-, chlorophyll a, chlorophyll b, pheophytin a, pheophytin b, total carotenoids, pH, and electrical conductivity), including emerging contaminants. To this end, indicator sets diagnostic for specific criticalities, derived from an empirical dataset of water quality parameters, were employed, using detection techniques based on geographically weighted principal component analysis and a modified pairwise Mahalanobis distance-based algorithm. Clear and accurate criticality scenarios were derived, highlighting both the strengths and the limitations of the proposed approach, especially in relation to the classic threshold-based methods.

Role of different microorganisms in remediating PAH-contaminated soils treated with compost or fungi.

Microbial degradation is the main responsible for polycyclic aromatic hydrocarbons (PAHs) removal from contaminated soils, and the understanding of this process is pivotal to define effective bioremediation approaches. To evaluate the contribution of several microbial groups in soil anthracene and benzo[a]pyrene degradation, the analysis of phospholipid fatty acid (PLFA) profiles and machine learning techniques were employed. To this end, PLFAs and PAH concentrations were analysed, along 274 days of incubation in mesocosms, in soils artificially contaminated with anthracene and benzo[a]pyrene, subjected to different treatments: untreated soil and soils treated with biowaste compost or fungal consortium. Random forest models, figuring anthracene or benzo[a]pyrene concentrations as dependent variables and PLFAs as predictors, were then built to evaluate the contribution of each variable in PAH degradation. PLFA profiles varied substantially among soil treatments and along time, with the increase of Actinomycetes in soils added with fungi and other Gram+ bacteria in compost amended soils. The former, together with fungi, are primarily responsible for anthracene and benzo[a]pyrene degradation in both treated soils, a process in which also metanotrophs and other Gram+ and Gram- bacteria participate. In untreated soil, the cooperation of a multitude of different microorganisms was, instead, responsible for PAH removal, a process with lower efficiency in respect to treated soils.

Nutrients and non-essential elements in edible crops following long-term mineral and compost fertilization of a Mediterranean agricultural soil.

The effects of long-term soil fertilizations on nutrient and non-essential element concentrations in edible parts of three crops important in human diet were investigated repeating four treatments (biowaste compost, biowaste compost plus mineral nitrogen, mineral NPK, unfertilized control) for seven consecutive years (2007-2014). Fruits of Solanum lycopersicum cv San Marzano collected in 2011 and 2012, bulbs of Allium cepa cv Bianca di Pompei collected in 2012 and 2013, and bulbs of Foeniculum vulgare cv Orbit collected in 2014 were analyzed. Wide variations in element concentrations were observed along time and among species, with Ca, K, Mg, and Na higher in fennel bulbs and Cd, Cr, Mn, Ni, Pb, and Zn higher in tomato fruits, where Cd reached concentrations up to ninefold higher than the permitted values (EU Regulation n. 488/2014). Despite the enrichments in soil total Cu and available Cd, Fe, K, Mn, and Zn concentrations due to long-term fertilization with biowaste compost (alone or with mineral fertilizers), plants showed lower micronutrient and non-essential element concentrations in respect to those on unfertilized soils. Considering the potential toxicity for human beings of these mobile and persistent elements, the obtained findings reassure on the safe use of biowaste compost in agriculture. Overall, this study suggests the use of compost as the most advisable fertilization practice and highlights the need of multiple crops analysis in evaluating the effects of long-term soil fertilization on their chemical composition.

Anthracene and benzo(a)pyrene degradation in soil is favoured by compost amendment: Perspectives for a bioremediation approach.

In order to validate the use of compost in soil PAH bioremediation, the degradation of anthracene and benzo(a)pyrene was monitored in soils artificially contaminated and incubated in mesocosms under controlled conditions. The dynamics observed in compost amended soil were compared to those observed in soil added with a fungal consortium and untreated soil. At the same time, three microbial enzyme activities usually involved in PAH degradation (laccase, o-diphenol oxidase and peroxidase activities) were monitored. Both PAHs decreased along the time in the three mesocosms, with anthracene, with lower molecular weight, degrading with a higher rate and reaching lower residual values than benzo(a)pyrene. Although at the end of incubation, the residual values of investigated PAHs are similar in the three mesocosm types, PAH dynamics showed a higher degradation rate in the early stage in mesocosms added with the fungal mycelium and amended with compost. Among the three enzyme activities, only peroxidase showed higher values in treated than untreated mesocosms. Considering the ameliorating effects of compost on degraded soils, its use can be suggested in PAH bioremediation.

Heavy metal and polycyclic aromatic hydrocarbon concentrations in Quercus ilex L. leaves fit an a priori subdivision in site typologies based on human management.

Concentrations of four heavy metals (HMs) (Cd, Cr, Fe, Pb) and four polycyclic aromatic hydrocarbons (PAHs) (fluoranthene, phenanthrene, chrysene, benzo[a]pyrene) in Quercus ilex L. leaves collected at the Campania Region (Southern Italy) in previous air biomonitoring studies were employed to (1) test the correspondence with an a priori site subdivision (remote, periurban, and urban) and (2) evaluate long temporal trends of HM (approximately 20 years) and PAH (approximately 10 years) air contaminations. Overall, Q. ilex leaf HM and PAH concentrations resulted along the gradient: remote < periurban < urban sites, reflecting the a priori subdivision based on human management. Over a long time, although a clear decrease of leaf Pb, chrysene, fluoranthene, and phenanthrene concentrations occurred at the urban sites, a high contamination level persists.

Nutrient and toxic element soil concentrations during repeated mineral and compost fertilization treatments in a Mediterranean agricultural soil.

Agricultural soils of semi-arid Mediterranean areas are often subjected to depletion of their chemical, physical, and biological properties. In this context, organic fertilization, in addition to providing nutrients for a longer time in respect to mineral fertilization, improves many other characteristics related to soil fertility. Moreover, the combined use of organic and mineral fertilizers may promote a more sustainable crop production. However, a concern on the long-term use of organic fertilizers arises in relation to the possible accumulation of toxic elements in soil and their transfer to human beings. For this reason, a long-term study on nutrient and toxic element total concentrations and availabilities during fertilization treatments was carried out. In particular, mineral NPK fertilized soils, soils amended with biowaste compost, soils amended with biowaste compost plus mineral nitrogen, and unfertilized soils were analyzed for 11 chemical elements. The results highlighted that temporal variations in total and bioavailable concentrations of both nutrients and toxic elements, occurring also in unfertilized soils, are wider than those related to fertilization treatments. Anyway, soil amendments with biowaste compost, alone or in combination with mineral fertilizers, reduce Cu bioavailability but improve K, Fe, Mn, and Zn availabilities, excluding at the same time a long-term accumulation in soil. Total and bioavailable toxic element concentrations (apart from available Cd) do not vary in relation to fertilization treatments.

Usefulness of different vascular plant species for passive biomonitoring of Mediterranean rivers.

Choosing native vascular plants as nutrient and toxic element accumulators for passive biomonitoring of urban river quality is not an easy task in Mediterranean rivers, due to the particular climate determining high variations in river hydrology. To identify potential biomonitors for this area, the roots of seven species (Angelica sylvestris, Apium nodiflorum, Tradescantia fluminensis, Nasturtium officinale, Persicaria lapathifolia, Arctium lappa, Typha latifolia), growing in seven sites along the River Irno (Southern Italy), were collected in July 2010 and analyzed regarding their capability to accumulate Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, V, and Zn through atomic absorption spectrometry. Notwithstanding the expected different accumulation degree among the species, they highlighted similar spatial contamination gradients, and all of them appeared suitable, alone or in combination, for river passive biomonitoring. A. nodiflorum, in particular, appeared the best biomonitor for the River Irno, where severe anthropogenic impacts were detected: high Cu and Cd contamination from vine cultivation in the upper stretch, and Pb, Zn, and Mn contamination in the medium stretch from airborne dusts coming from a cast iron foundry.

Soil compost amendment enhances tomato (Solanum lycopersicum L.) quality.

BACKGROUND: Tomato (Solanum lycopersicum L.) is one of the most important crops in the world and represents a key crop in southern Italy. With the aim to evaluate the nutritional characteristics of tomato fruits in relation to NPK and compost fertilisation, the concentrations of the main nutrients, toxic elements, primary metabolites and total phenols were determined in two varieties (Lido and San Marzano). Each variety was cultivated in a different experimental field, subjected to different agronomic techniques. RESULTS: Concentrations of toxic elements (Cd and Pb) were below the limits indicated by the EU Regulation (2011) in all the fruits analysed. Moreover, fruits obtained from San Marzano plants grown on organic amended soils showed a better overall quality than those obtained on mineral fertilised soil, being characterised by lower N (attributed to lower nitrate and nitrite concentrations), lower Cd, and higher soluble sugar concentrations. Higher concentrations of soluble sugars in fruits from organic amended soils were also observed in the Lido variety. CONCLUSIONS: The agricultural use of quality compost represents an effective strategy to obtain high quality products in an economically and environmentally sustainable way. © 2016 Society of Chemical Industry.

Cadmium accumulation in leaves of leafy vegetables.

Leafy vegetables have a relatively high potential for Cd uptake and translocation, and are thus considered Cd accumulators. For this reason, leaves and roots of lettuce (Lactuca sativa L.) and endive (Cichorium endivia L.) plants, grown on different agricultural soils in Campania region (southern Italy), subjected to different fertilisation treatments (unfertilisation, compost amendment and mineral fertilisation), were analysed for Cd concentrations. Moreover, to clarify if the highest concentrations found are linked to older and inedible or to younger and edible leaves, external and internal endive leaves were separately analysed. All the leafy vegetables analysed showed on average 2-fold higher Cd concentrations in leaves than in roots. Leaf Cd concentrations in both lettuce and endive plants significantly differed among fertilisation treatments, with values highest in the plants grown on mineral fertilised soils. Apart from the soil fertilisation treatments, however, Cd leaf concentrations were often higher (up to 4-fold) than the threshold deduced by the EU 420/2011 Regulation, although the plants grew on unpolluted soils. Anyway, external leaves of endive plants showed significantly higher concentrations than internal leaves (in some cases the values were 3-fold higher), partly reassuring on the consumption of the younger leaves. Moreover, this study points out two major drawbacks in the Italian and European regulatory frameworks: (1) metal concentration (as total and/or available fraction) limits in agricultural soils are lacking; (2) metal concentration thresholds (currently existing only for Cd and Pb in crops) reported in the EU 420/2011 Regulation, expressed on the fresh weight basis rather than on the dry weight basis, appear not suitable.

Compost Amendment Enhances Natural Revegetation of a Mediterranean Degraded Agricultural Soil.

A vegetation analysis was carried out on a degraded agricultural soil of the Mediterranean area (Campania region, southern Italy) in order to study the effects of different fertilization practices (quality compost, mineral fertilizers, mixed fertilization, and no fertilization) on the whole spontaneous vegetation community. The study was performed for two consecutive years at three different scales (species level, community structure, and community properties), using three different units of abundance (number of individuals, biomass, and cover of each species). The observations were carried out in spring, after 5 and 6 years of soil treatments, on a total area of 4 m(2) for each soil treatment and in each year. The different fertilization practices did not determine changes in species composition; however, the relative abundance of dominant species increased in compost and mixed fertilized soils, particularly in the second year of observation. Although the dominance and diversity were unaffected by the different fertilization practices, the total biomass and total number of individuals increased in compost-amended soils. These results indicate the effectiveness of soil quality compost amendments to enhance natural revegetation, a key step in the recovery of degraded areas.

Distribution of heavy metals and polycyclic aromatic hydrocarbons in holm oak plant-soil system evaluated along urbanization gradients.

Heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) were analysed in topsoil and in Quercus ilex L. leaves from holm oak woodlands located along urbanization gradients (urban, periurban and extraurban sites) in two Italian regions (Campania and Tuscany). In each sampling site, the metal bioavailability factors (MBFs) and the pollutant bioaccumulation factors (BAFs) were calculated to estimate the fraction of each total metal concentration in soil potentially available to root uptake and to know the fate of both HMs and PAHs in the plant-soil system. In general, the results indicated a low atmospheric deposition of pollutants and, in some cases, leaves and soils accumulated higher HM and PAH concentrations in the most urbanized areas. Correlation analyses showed that in each sampling site topsoil and leaves were exposed to the same atmospheric inputs of HMs and PAHs, although to a different extent. Notwithstanding the MBFs and BAFs differed between the two regions for the most HMs, they did not show a clear pattern in relation to the urbanization gradient. However, some information could be deduced by these ratios: the high BAF calculated for Mn shows that the foliar uptake plays an important role in accumulation of this metal. Moreover, for PAHs the different values of BAFs among low and high molecular weight compounds suggest their different fate, the first accumulated in leaves by stomata and the latter preferentially deposited on topsoil.

Persistent pollutants and the patchiness of urban green areas as drivers of genetic richness in the epiphytic moss Leptodon smithii.

We determined genetic variation and metal and polycyclic aromatic hydrocarbon concentrations in Leptodon smithii moss collected in holm oak stands at cities, outskirts and remote areas of Campania and Tuscany (Italy) to investigate if anthropogenic pressure (pollutant emissions and land use change) affects moss genetic richness. In both regions, metal and polycyclic aromatic hydrocarbon concentrations reflected the trend urban>outskirts>remote areas, excepting Tuscany remote site. In both regions, the moss gene diversity increased from urban to remote areas. The findings suggest the extent and the fragmentation of urban green areas, as drivers of moss genetic richness.

Genetically biodiverse potato cultivars grown on a suitable agricultural soil under compost amendment or mineral fertilization: yield, quality, genetic and epigenetic variations, soil properties.

The use of compost for soil amendment is a promising agricultural practice environmentally and economically viable. In the framework of a wide research project designed to evaluate the effects of soil amendment with municipal solid waste compost in comparison with traditional mineral fertilization practices, 54 different cultivars (Cvs) of potatoes were AFLP (amplified fragment length polymorphism) molecularly fingerprinted. The seven most genetically biodiverse potato Cvs were used to establish an experimental field in southern Italy. The field area was divided into two portions fertilized with compost (20 Mg ha(-1)) or with ammonium sulphate (200 kg ha(-1)). No significant differences in productivity, organoleptic characteristics and element concentrations were observed between the potato tubers obtained with both kinds of soil fertilization, while the tubers grown on compost amended soil showed, on average, higher K concentrations with respect to those grown on mineral fertilised soil. cDNA-AFLP (complementary DNA-AFLP) and MSAP (methylation sensitive amplified polymorphism) analyses were carried out on both leaves and tubers of one selected Cv to estimate if any transcriptome alterations or epigenetic modifications were induced by the two kinds of fertilization, however no variations were detected. Chemical and biological soil qualities (i.e., microbial respiration, FDA hydrolysis, alkaline and acid phosphatase) were assessed on soil samples at the start of the experiment and at the end of potato crop cycle. No significant differences in soil pH and limited ones, in the available fraction of some trace elements, were observed; while conductivity was much higher for the compost amended portion of the experimental field. Microbial respiration, FDA hydrolysis and acid phosphatase activities were significantly increased by compost amendment, in comparison with mineral fertilization. Finally, a sensory panel of potato Cvs detected no significant differences among qualitative descriptors and among potatoes coming from the two differently fertilized soils.

Nutritional regulation in mixotrophic plants: new insights from Limodorum abortivum.

Partially mycoheterotrophic (mixotrophic) plants gain carbon from both photosynthesis and their mycorrhizal fungi. This is considered an ancestral state in the evolution of full mycoheterotrophy, but little is known about this nutrition, and especially about the physiological balance between photosynthesis and fungal C gain. To investigate possible compensation between photosynthesis and mycoheterotrophy in the Mediterranean mixotrophic orchid Limodorum abortivum, fungal colonization was experimentally reduced in situ by fungicide treatment. We measured photosynthetic pigments of leaves, stems, and ovaries, as well as the stable C isotope compositions (a proxy for photosynthetic C gain) of seeds and the sizes of ovaries and seeds. We demonstrate that (1) in natural conditions, photosynthetic pigments are most concentrated in ovaries; (2) pigments and photosynthetic C increase in ovaries when fungal C supply is impaired, buffering C limitations and allowing the same development of ovaries and seeds as in natural conditions; and (3) responses to light of pigment and (13)C contents in ovaries shift from null responses in natural conditions to responses typical of autotrophic plants in treated L. abortivum, demonstrating photoadaptation and enhanced use of light in the latter. L. abortivum thus preferentially feeds on fungi in natural conditions, but employs compensatory photosynthesis to buffer fungal C limitations and allow seed development.

A multi-approach monitoring of particulate matter, metals and PAHs in an urban street canyon.

For the first time until now, the results from a prediction model (Atmospheric Dispersion Modelling System (ADMS)-Road) of pollutant dispersion in a street canyon were compared to the results obtained from biomonitors. In particular, the instrumental monitoring of particulate matter (PM10) and the biomonitoring of 14 polycyclic aromatic hydrocarbons (PAHs) and 11 metals by Quercus ilex leaves and Hypnum cupressiforme moss bags, acting as long- and short-term accumulators, respectively, were carried out. For both PAHs and metals, similar bioaccumulation trends were observed, with higher concentrations in biomonitors exposed at the leeward canyon side, affected by primary air vortex. The major pollutant accumulation at the leeward side was also predicted by the ADMS-Road model, on the basis of the prevailing wind direction that determines different exposure of the street canyon sides to pollutants emitted by vehicular traffic. A clear vertical (3, 6 and 9 m) distribution gradient of pollutants was not observed, so that both the model and biomonitoring results suggested that local air turbulences in the street canyon could contribute to uniform pollutant distribution at different heights.

Assessment of the effects of Cr, Cu, Ni and Pb soil contamination by ecotoxicological tests.

This study aimed to assess soil quality by chemical and ecotoxicological investigations and to check the correspondence between soil metal concentrations and ecotoxicity. For these purposes, surface soils collected at four adjacent roadside urban parks and at a former industrial area were characterized for C/N, organic matter content, texture, and pH. Cr, Cu, Ni and Pb, chosen among the most representative soil metal contaminants, were measured as total content and as available and water soluble fractions. In addition, the total concentrations of the investigated metals were used to calculate two chemical indices: the contamination and the potential ecological risk factors. The toxicity of the investigated soils was evaluated by an ecotoxicity test battery carried out on both soil samples (Vibrio fischeri, Heterocypris incongruens and Sinapis alba) and elutriates (Vibrio fischeri, Daphnia magna and Selenastrum capricornutum). The findings, both by the chemical and ecotoxicological approaches, would suggest that the soils with high metal contamination pose ecological risks. On the other hand, moderately metal contaminated soils did not exclude soil ecotoxicity. In fact, toxic effects were also highlighted in soils with low metal content, toxicity being affected by metal availability and soil characteristics. Moreover, the results suggest the importance of using a battery of tests to assess soil ecotoxicity.

Tropospheric ozone effects on chemical composition and decomposition rate of Quercus ilex L. leaves.

We determined the effects of tropospheric ozone on the chemical composition of Quercus ilex L. leaves and their decomposition, with a view to assessing the influence of ozone on nutrient cycling and the sustainability of Mediterranean holm oak forests. Forming one of the most widespread thermophilous vegetation communities in the area, Q. ilex is a dominant and widespread evergreen oak in the Mediterranean, where concentrations of tropospheric ozone are particularly high. The dynamics of carbon, nitrogen, lignin and cellulose concentrations were monitored for six months during the decomposition of leaves from plants subjected to controlled ozone exposure in open-top chambers. Ozone-exposed leaves, compared to unexposed leaves, showed no significant differences in C, N, lignin and cellulose concentrations prior to the incubation in mesocosms. However, during decomposition, leaves from plants exposed to ozone lost C significantly more slowly and showed a higher C/N ratio than unexposed leaves. Ozone exposure significantly slowed down the decomposition rate, indicating a negative effect of tropospheric ozone on nutrient cycling, which may reduce long-term sustainability of the holm oak forest.

Total and available soil trace element concentrations in two Mediterranean agricultural systems treated with municipal waste compost or conventional mineral fertilizers.

The temporal dynamics of some trace elements in two different types of Mediterranean soils were studied in order to evaluate the possible long-term contamination following compost amendments. Total and available (DTPA-extractable) concentrations of Cd, Cu, Pb and Zn were determined. The study was carried out on two agricultural soils in Campania region (southern Italy), a Sandy Loam Calcaric Cambisol (SG) and a Clay Gleyc Luvisol (CO), during 3 years of organic amendment with compost. The compost, produced from the organic fraction of municipal solid waste and urban yard trimmings, in accordance with the Italian law for agricultural use, was applied at annually rates of 15, 30, and 45 t ha(-1) (on dry weight basis). Wide variations in total and available Cd, Cu, Pb and Zn concentrations were observed over time, but appeared to be in many cases unrelated to the treatments, occurring also in control plots. After 3 years of compost application the amended SG soil showed the highest and significant increase in total Cd and Zn concentrations; in addition, the available Cd, Pb and Zn concentrations increased in accordance with the compost rates. The CO soil, characterized by a higher clay content, lower organic matter content and lower cation exchange capacity, exhibited a lower increase in available metal fractions. Our findings show that compost amendment affects more the available than the total metal concentrations in the two types of soils studied and thus it is important into legislation that metal "bioavailability" may be considered in defining threshold metal values.

Assessment of the effects of soil PAH accumulation by a battery of ecotoxicological tests.

Surface soils were collected at remote, urban and industrial sites in the Southern of Italy in order to evaluate PAH concentrations and assess the toxic effects by a battery of ecotoxicological tests. The tests were performed on whole soils and on both organic and aqueous extracts. Further goal of this study was to integrate the results coming from each test and matrix in a synthetic toxicity index. The highest summation sigmaPAH concentrations were measured at the industrial soil, although this one did not show an high ecotoxicological risk. Among the performed tests, the phytotoxicity tests showed the highest sensitivity. For whole soil, the worst case always has been represented by test through bacteria. Our results could represent the first step toward the selection of a proper battery to characterize the soil ecotoxicological risk.

Temporal variations in PAH concentrations in Quercus ilex L. (holm oak) leaves in an urban area.

Temporal variations of polycyclic aromatic hydrocarbon (PAH) concentrations in leaves of a Mediterranean evergreen oak, Quercus ilex L., were investigated in order to assess the suitability of this species to biomonitor PAH air contamination. Leaf samples were collected at six sites of the urban area of Naples (Italy) and at a control site in the Vesuvius National Park, in May and September 2001, and in January and May 2002. PAH extraction was conducted by sonication in dichloromethane-acetone and quantification by GC-MS. In winter, leaf total PAH concentrations showed, at all the urban sites, values 2-fold higher than in all the other samplings, reflecting the temporal trend reported for PAH air contamination in the Naples urban area. Moreover, leaf PAH concentrations showed, at all the urban sites, a decrease in May 2002 after the winter accumulation. At the control site leaf PAH concentrations showed lower values and smaller temporal variations than at the urban sites. The findings support the suitability of Q. ilex leaves to monitor temporal variations in PAH contamination. The highest winter concentrations of total PAHs were due to the medium molecular weight PAHs that increased with respect to both low and high molecular weight PAHs. The medium molecular weight PAHs showed the same temporal trend both at the urban and remote sites.