High spatial resolution analysis of polybrominated diphenyl ethers (PBDEs) using transplanted lichen Evernia prunastri: A case study in central Italy.

The ability of transplanted lichen Evernia (E.) prunastri (L.) to act as a high spatial biomonitoring tool for 14 polybrominated diphenyl ethers (PBDEs) was evaluated at 23 monitoring sites in a very polluted area in central Italy. The selected area is characterized by the presence of numerous emission sources, such as waste-to-energy plant, steel plant, vehicular traffic, and domestic heating. Transplanted E. prunastri proved to be a useful tool to biomonitor PBDEs, due to its ability to bioaccumulate individual congeners in varying concentrations in relation to the strength of the emission sources present over the territory. PBDEs levels widely ranged from 132 to 24,237 ng kg-1 dry weight, according to the sources of emission located around the monitoring sites. The highest concentrations were detected at the sites close to the municipal solid waste incinerator, steel plant, and high busy roads, confirming their important role as PBDEs emissions sources.

Combined magnetic, chemical and morphoscopic analyses on lichens from a complex anthropic context in Rome, Italy.

Native and transplanted lichens were analyzed as bioaccumulators of airborne particulate matter (PM) in an eastern district of Rome, Italy, where frequent fraudulent fires are set to recover metals, mostly copper, from waste electrical and electronic equipment (WEEE). The presence of native lichens was scarce, due to the drought of spring-summer 2017, thus, sampling was extended to a neighboring area for toughening the dataset to a similar context. The magnetic analyses revealed intense properties connected to the anthropic complexity of the zone, where industrial, traffic and arson-related dusts are emitted and bio-accumulated. Magnetic and chemical analyses were compared, leading to significant linear correlations between the concentration dependent magnetic parameters (susceptibility, saturation magnetization and saturation remanence) and the concentration of heavy metals, among which copper, chrome, lead and zinc. Moreover, selected magnetic particles were chemically and morphologically characterized by Scanning Electron Microscope and Energy Dispersion System microanalyses. Magnetic particles resulted incorporated into the lichens' tissues and their composition, morphology and grain size strongly supported their anthropogenic, mostly combustion-related, origin. Even if, given the complexity of the area, it was not feasible to fully discriminate the multiple anthropogenic sources, magnetic biomonitoring of lichens, especially when combined with microtextural and compositional analyses, confirmed to be an excellent methodology for a rapid characterization of environmental pollution.

Air quality assessment in different environmental scenarios by the determination of typical heavy metals and Persistent Organic Pollutants in native lichen Xanthoria parietina.

The study was aimed to evaluate the ability of native lichen Xanthoria (X.) parietina to biomonitor and bioaccumulate some heavy metals (As, Cd, Co, Cr, Ni, Pb), PAHs, PCDDs, PCDFs, PCBs and PBDEs and to evaluate the use of the native X. parietina as a multi-tracer tool for scenarios characterized by different anthropogenic pressures. Samples of native X. parietina were collected in six different sites (two green, two residential and two industrial areas, respectively) and analyzed for the target compounds. The results show that X. parietina was a useful tool for the biomonitoring of air quality in the selected areas, and was able to bioaccumulate all the studied metals and POPs. In particular, the total concentrations dry weight (dw) ranged between 8.1 and 103.4 mg kg-1 for metals, from 113 × 103 to 183 × 103 ng kg-1 for PAHs, from 868 to 7685 ng kg-1 for PCBs, from 14.3 to 113.8 ng kg-1 for PCDDs/Fs (∑TEq = 0.9-7.1), and from 194 to 554 ng kg-1 for PBDEs. Besides, in general, the levels of analytes recovered in the different samples of lichen show an increasing trend from green to industrial sites, especially for PCBs (mean values equal to 1218, 4253 and 7192 ng kg-1 respectively for green, residential and industrial areas). The statistical approach, based on Pearson's correlation and principal component analysis tests, showed that one of the industrial sites was well-separated from the others, that resulted grouped due to some similarities.

Assessing indoor air quality of school environments: transplanted lichen Pseudovernia furfuracea as a new tool for biomonitoring and bioaccumulation.

The aim of this research is to evaluate the ability of transplanted lichen Pseudovernia (P). furfuracea to biomonitor and bioaccumulate in urban indoor environments. The elements As, Cd, Cr, Cu, Hg, Ni and Pb and 12 selected polycyclic aromatic hydrocarbons (PAHs) were used to assess P. furfuracea as a biomonitoring tool for the indoor air quality of school environments. To achieve this purpose, lichen samples were exposed for 2 months in the outdoor and indoor environments of five school settings located in urban and rural areas. The results demonstrated that transplanted lichen P. furfuracea is a suitable biomonitoring tool for metals and PAHs in indoor settings and can discriminate between different levels of air pollution related to urbanisation and indoor conditions, such as those characterised by school environments. A transplanted lichen biomonitoring strategy is cost-effective, "green", educational for attending children and less "invasive" than traditional air sampling methods. The feasibility of indoor monitoring by P. furfuracea is a relevant finding and could be a key tool to improve air quality monitoring programmes in school scenarios and thus focus on health prevention interventions for children, who are one of the most susceptible groups in the population.

Evaluation of Molecular Markers and Analytical Methods Documenting the Occurrence of Mustard Gas and Arsenical Warfare Agents in Soil.

The chemicals warfare agents (CWAs) are an extremely toxic class of molecules widely produced in many industrialized countries for decades, these compounds frequently contained arsenic. The plants where the CWAs have been produced or the plants where they have been demilitarized after the Second World War with unacceptable techniques can represent a serious environmental problem. CWAs standards are difficult to find on market so in present work an environmental assessment method based on markers has been proposed. Triphenylarsine, phenylarsine oxide and thiodiglycol have been selected as markers. Three reliable analytical methods based on gaschromatography and mass detection have been proposed and tested for quantitative analysis of markers. Methods performance have been evaluated testing uncertainty, linearity, recovery and detection limits and also comparing detection limits with exposure limits of reference CWAs. Proposed assessment methods have been applied to a case study of a former industrial plant sited in an area characterized by a high background of mineral arsenic.

Transplanted Lichen Pseudovernia furfuracea as a Multi-Tracer Monitoring Tool Near a Solid Waste Incinerator in Italy: Assessment of Airborne Incinerator-Related Pollutants.

The ability of a transplanted lichen, Pseudovernia (P.) furfuracea, to act as a multi-tracer biomonitoring tool for As, Cd, Ni, Pb, 12 PAHs, 17 polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and 27 polychlorinated biphenyls (PCBs) was evaluated at six areas of varying risk (high, medium, negligible) of pollutant fallout from a municipal waste incinerator in central Italy. Transplanted P. furfuracea proved to be an useful tool to biomonitor PCDDs/Fs and PCBs. Concentrations of As, heavy metals, PAHs, PCDDs/Fs resulted similar for all monitored stations. Small differences in total PCBs (4378 and 4631 pg/g dw vs 3298, 4123, 3676 and 4022 pg/g dw) and dioxin-like PCBs (1235 and 1265 pg/g dw vs 794, 1069, 1106 and 1188 pg/g dw) were observed. Air concentrations of monitored compounds appear to be more related to general air pollution than point emissions from the incinerator.

Determination of selected polychlorinated dibenzo-p-dioxins/furans in marine sediments by the application of gas-chromatography-triple quadrupole mass spectrometry.

Selected polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were detected by gas-chromatography coupled to triple quadrupole mass spectrometry (GC-QqQ-MS/MS) in marine sediments collected in central Italy. Total PCDD/Fs concentrations ranged from 11.58 to 193.29 pg/g d.w., with PCDFs as the major contributors in most cases. The congener profiles were characterized by high OCDD (70.7%-91.4%). The PCDD/Fs values are within or close to the Environmental Canada sediment reference values (0.85 pg TEQ/g d.w.). GC-QqQ-MS/MS can be a suitable alternative to standard methods for PCDD/Fs determination in environmental samples. The measured PCDD/Fs amounts could be considered as a basis for future monitoring programs.

A tobacco-related carcinogen: assessing the impact of smoking behaviours of cohabitants on benzene exposure in children.

BACKGROUND: Secondhand smoke (SHS) represents a major preventable cause of morbidity for communities, especially for children, who are more susceptible than adults to the adverse effects of passive smoking. SHS contains several carcinogens, including benzene. OBJECTIVE: To investigate the role of household characteristics and the smoking behaviours of cohabitants in predicting SHS-derived benzene exposure levels. Methods In this cross-sectional study, 122 children (aged 5-11 years old) were selected from a school in rural Italy. Characteristics of their home environment and the smoking habits of the children's cohabitants were obtained via questionnaire, and urinary unmodified benzene (u-UB) and cotinine (a specific nicotine metabolite) levels were determined from spot urine samples. RESULTS: Significant differences between SHS-exposed and SHS-unexposed children were found with respect to u-UB levels (median values 359.50 and 92.50 ng/litre, respectively; p<0.001). The excretion of u-UB increased significantly in parallel to increased SHS exposure as follows: unexposed to SHS (median value 92.50 ng/litre)

Benzene exposure in childhood: Role of living environments and assessment of available tools.

Benzene is a widespread air pollutant and a well-known human carcinogen. Evidence is needed regarding benzene intake in the pediatric age group. We investigated the use of urinary (u) trans,trans-muconic acid (t,t-MA), S-phenylmercapturic acid (SPMA), and unmodified benzene (UB) for assessing exposure to low concentrations of environmental benzene and the role of living environment on benzene exposure in childhood. u-t,t-MA, u-SPMA, u-UB and u-cotinine were measured in urine samples of 243 Italian children (5-11 years) recruited in a cross-sectional study. Analytical results were compared with data obtained from questionnaires about participants' main potential exposure factors. u-UB, u-t,t-MA and u-SPMA concentrations were about 1.5-fold higher in children living in urban areas than in those in the rural group. Univariate analyses showed that u-UB was the only biomarker able to discriminate secondhand smoke (SHS) exposure in urban and rural children (medians=411.50 and 210.50 ng/L, respectively); these results were confirmed by the strong correlation between u-UB and u-cotinine in the SHS-exposed group and by multivariate analyses. A regression model on u-SPMA showed that the metabolite is related to residence area (p<0.001), SHS exposure (p=0.048) and gender (p=0.027). u-UB is the best marker of benzene exposure in children in the present study, and it can be used as a good carcinogen-derived biomarker of exposure to passive smoking, especially related to benzene, when urine sample is collected at the end of the day. In addition, it is important to highlight that SHS resulted the most important contributor to benzene exposure, underlining the need for an information campaign against passive smoking exposure.

Performance of different work clothing types for reducing skin exposure to pesticides during open field treatment.

The aim of this study was to estimate the performance of different work clothing types for reducing skin exposure to five pesticides (azinphos-methyl, terbutylazine, alachlor, dimethoate, and dicamba) in field distribution by tractor equipped with boom sprayer. Performance was assessed by measuring the penetration factors of different types of work clothing. The results show that the protection offered by personal protective equipment (PPE) was always >97%, whereas the performance of cotton garments ranged from 84.1% to 92.5%. The different cotton garments differed significantly in their permeability, and the upper part of the body was the anatomical region showing the greatest values of the penetration factors. These results confirm the necessity of using PPE properly to minimise dermal exposure to pesticides.

Monitoring of traffic-related pollution in a province of central Italy with transplanted lichen Pseudovernia furfuracea.

The ability of transplanted lichen Pseudevernia furfuracea to biomonitor specific airborne pollutants (heavy metals and polycyclic aromatic hydrocarbons­PAHs) was investigated at five stations with different traffic densities in Viterbo, Italy. Exposed lichen showed high levels of all analysed pollutants; greatest values were for Zn (147­252 µg/g dw), Pb (24.9­34.6 µg/g dw), fluoranthene (37­107 ng/g dw), pyrene (23­124 ng/g dw). Comparison between contaminants concentration in lichens before and after exposure showed "accumulation" or "severe accumulation" rates in more than 90% of each substance. Besides, Pseudevernia furfuracea accumulated airborne PAHs in a manner that was proportional to traffic density.

Operative modalities and exposure to pesticides during open field treatments among a group of agricultural subcontractors.

This paper reports the results of a field study of occupational pesticide exposure (respiratory and dermal) among a group of Italian agricultural subcontractors. These workers consistently use pesticides during much of the year, thus resulting in a high exposure risk. Ten complete treatments were monitored during spring/summer. Pesticides that were applied included azinphos-methyl, dicamba, dimethoate, terbuthylazine, and alachlor. Several observations were made on worker operative modalities and the use of personal protective equipment (PPE) during work. Total potential and actual exposure ranged from 14 to 5700 microg and from 0.04 to 4600 microg, respectively. Dermal exposure contributed substantially more than inhalation to the total exposure (93.9-100%). Hand contamination ranged from 0.04 to 4600 microg and was the major contributor to dermal exposure. Penetration through specific protective garments was less than 2.4% in all cases, although penetration through general work clothing was as high as 26.8%. The risk evaluation, based on comparison between acceptable daily intake and total absorbed doses, demonstrates that it is presumable to expect possible health effects for workers regularly operating without PPE and improper tractors. Comparisons between exposure levels and operative modalities highlighted that complete PPE and properly equipped tractors contributed to a significant reduction in total exposure to pesticides during agricultural activities. In conclusion, monitored agricultural subcontractors presented very different levels of pesticide exposure due to the high variability of operative modalities and use of PPE. These results indicate the need to critically evaluate the efficacy of training programs required for obtaining a pesticide license in Italy.

Exposure to organic solvents among handicraft car painters: A pilot study in Italy.

Car repair painters usually experience long-term exposure to many different solvents. In Italy, the greater part of car painting shops are "handicraft", i.e. 2-5 workers and small premises. Usually workers do not have specific duties, but everyone takes part in all different operations. Moreover, working time is not standardized but varies according to the workload, working methods tend to be traditional, and compliance to individual protection devices is poor. We have hence assessed, on a sample of 8 italian handicraft car painting shops, the exposure levels to solvents, implementing three classic exposure monitoring methods: environmental sampling with charcoal tubes, personal sampling with diffusive charcoal samplers, and urinary determination of unmetabolised solvents. A simple regression analysis was performed to evaluate relationships between the three series of data. The solvents analysed were toluene, ethylbenzene, 1, 2-dichloropropane, n-butylacetate, n-amylacetate, xylene isomers, ethylacetate, and benzene. Benzene was included due to several factors, among others its presence (1% v/v) in the italian unleaded gasoline. Benzene was found in all shops, at levels around or higher than the 8-h time-weighted average limit (8-h TLV-TWA). Other solvents were found in the different shops at various levels, 10(-2) - 10(-1) times the 8-h TLV-TWA. Air concentrations of toluene, n-butylacetate, xylenes, and benzene were positively correlated with urinary levels of the parent compounds, while a negative correlation was found for ethylbenzene. The health implications of workers' exposure level was briefly discussed.

Nonylphenols in freshwaters of the hydrologic system of an Italian district: association with human activities and evaluation of human exposure.

A sampling campaign for the determination of concentrations of nonylphenol isomers (NPs) in freshwaters and sediments of the hydrologic system of the Rieti district (central Italy) was conducted from 2002 to 2003. Eighteen sampling points, selected on the basis of the different human activities in the vicinity, were monitored; six series of water samples (from June 2002 to February 2003) and one of sediment samples (summer 2002) were analyzed by GC/MS. There was a direct relationship between concentrations of NPs and the presence of urban or industrial activities near the sampling point. However, concentrations of NPs in water were in the range of < 0.1-1.4 microg l(-1), and their presence limited to short distances from the sources of contamination. Accumulation factors in sediment samples ranged from 10(2) to 5x10(3).