Environmental risk induced by TiO2 dispersions in waters and sediments: a case study

A southern Italian area that is characterized by large outcrops of rocks that are rich in titanium oxide (TiO₂) phases were investigated to determine the mineralogical risk induced by the natural dispersion of TiO₂ minerals. Rock, sediment and surface water samples were collected to determine the physicochemical and mineralogical factors (i.e., size distribution, morphology and alteration) indicative of potential TiO₂ toxicity. X-ray diffraction data suggested that titanium oxides were present as rutile and anatase. Scanning electron microscopy images showed elongated TiO₂ morphologies; fibres were found as either isolated or embedded/enclosed in flake-like phyllosilicates. The concentration of fibres in stream water ranged from 1.7 to 4.6 million fibres per litre. The highest fibre amounts in the sediments were in the <8-µm fraction, while single fibres were primarily concentrated in the <2-µm fraction. The results indicate that titanium oxide minerals represent a natural source of environmental risk and that the geomineralogical characterization of rich TiO₂ areas is indispensable for understanding their geoavailability, dispersion and distribution.

     

Altitude profiles of total chlorinated paraffins in humus and spruce needles from the Alps (MONARPOP)

Chlorinated paraffins (CPs) are toxic, bioaccumulative, persistent, and ubiquitously present in the environment. CPs were analyzed in humus and needle samples, which were taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) at sampling sites of 7 different altitude profiles in the Alps. Gas chromatography combined with electron ionization tandem mass spectrometry (EI-MS/MS) was used for the determination of total CPs (sum of short, medium and long chain CPs). CPs were found in all samples; the concentrations varied between 7 and 199 ng g⁻¹ dry weight (dw) and within 26 and 460 ng g⁻¹ dw in humus and needle samples, respectively. A clear vertical tendency within the individual altitude profiles could not be ascertained. Within all altitude profiles, elevated concentrations were observed in humus samples taken between 700 and 900 m and between 1300 and 1500 m. In the needle samples no similar correlation could be observed due to higher variation of the data.     

Environmental ozone exposure and oxidative DNA damage in adult residents of Florence, Italy

In 71 adults residing in Florence, Italy, enrolled in a prospective study, we investigated the correlation between individual levels of oxidative DNA damage detected by the Comet assay in circulating lymphocytes, and a specific ozone exposure score calculated in 10 different time-windows (0-5 to 0-90 days) before blood drawing, based on daily measurements provided by the local environmental monitoring system.Overall, statistically significant positive correlations between average ozone concentrations and DNA damage emerged in almost all time-windows considered; correlations were more evident among males, non-smokers, and traffic-exposed workers. Multivariate regression analyses taking into account selected individual characteristics, showed an independent effect on DNA damage of average ozone concentrations in the last 60-90 days before blood drawing. Local residents showed a divergent pattern with correlations restricted to shorter time-windows.Our results suggest that ozone concentrations at ground levels modulate oxidative DNA damage in circulating lymphocytes of residents of polluted areas.     

Synthesis of zeolite from Italian coal fly ash: Differences in crystallization temperature using seawater instead of distilled water

In this study Italian coal fly ash was converted into several types of zeolite in laboratory experiments with temperatures of crystallization ranging from 35 up to 90 °C. Distilled and seawater were used during the hydrothermal synthesis process in separate experiments, after a pre-treatment fusion with NaOH.The results indicate that zeolites could be formed from different kind of Italian coal fly ash at low temperature of crystallization using both distilled and seawater. SEM data and the powder patterns of X-ray diffraction analysis show that faujasite, zeolite ZK-5 and sodalite were synthesized when using both distilled and seawater; zeolite A crystallized only using distilled water. In particular the experiments indicate that the synthesis of zeolite X and zeolite ZK-5 takes place at lower temperatures when using seawater (35 and 45 °C, respectively). The formation of sodalite is always competitive with zeolite X which shows a metastable behaviour at higher temperatures (70–90 °C).The chemical composition of the fly ash source could be responsible of the differences on the starting time of synthesized zeolite with distilled water, in any case our data show that the formation of specific zeolites takes place always at lower temperatures when using seawater.     

Analytical characterization of movements of the spinal column and risk assessment due to repeated movements of the upper limbs of building painters

Manual activities of construction workers may induce musculoskeletal disorders. This study on a group of painters aimed to analytically characterize movements of the spinal column by both lumbar motion monitor and television cameras and to determine, using the Occupational Repetitive Actions (OCRA) Index method, the risk exerted by repeated movements of the upper limbs. The main results are: painting with a roller generally exposes workers to a lesser risk for upper limbs than painting with a brush; a roller-stick fixed at the wrong length can lead to stretching of the back at lumbar and cervical levels; to remain within the range of ‘acceptable risk’ (OCRA Index evaluation), a worker should not paint a vertical wall for over 3 h if using a roller and 2.5 h if painting with a brush; and, on average, a painter who paints for 5 h in a day lifts the bucket about 120,140 times.     

Mapping and quantifying habitat fragmentation in small coastal areas: a case study of three protected wetlands in Apulia (Italy)

In the Mediterranean Region, habitat loss and fragmentation severely affect coastal wetlands, due to the rapid expansion of anthropogenic activities that has occurred in the last decades. Landscape metrics are commonly used to define landscape patterns and to evaluate fragmentation processes. This investigation focuses on the performance of a set of landscape pattern indices within landscapes characterized by coastal environments and extent below 1,000 ha. The aim is to assess the degree of habitat fragmentation for the monitoring of protected areas and to learn whether values of landscape metrics can characterize fine-resolution landscape patterns. The study areas are three coastal wetlands belonging to the Natura 2000 network and sited on the Adriatic side of Apulia (Southern Italy). The Habitat Maps were derived from the Vegetation Maps generated integrating phytosociological relevés and Earth Observation data. In the three sites, a total of 16 habitat types were detected. A selected set of landscape metrics was applied in order to investigate their performance in assessing fragmentation and spatial patterns of habitats. The final results showed that the most significant landscape patterns are related to highly specialized habitat types closely linked to coastal environments. In interpreting the landscape patterns of these highly specialized habitats, some specific ecological factors were taken into account. The shape indices were the most useful in assessing the degree of fragmentation of habitat types that usually have elongated morphology along the shoreline or the coastal lagoons. In all the cases, to be meaningful, data obtained from the application of the selected indices were jointly assessed, especially at the class level.     

Organic pollutants in compost and digestate. Part 2. Polychlorinated dibenzo-p-dioxins, and -furans, dioxin-like polychlorinated biphenyls, brominated flame retardants, perfluorinated alkyl substances, pesticides, and other compounds

Compost and digestate are important recycling fertilizers and have beneficial effects on soil parameters. However, they can contain significant amounts of organic pollutants. Here, the first comprehensive data set on dibenzo-p-dioxins and -furans (PCDD/F), dioxin-like polychlorinated biphenyls (DL-PCB), brominated flame retardants, perfluorinated alkyl substances (PFAS), pesticides, phthalates, nonylphenol and chlorinated paraffins (CP) in source-separated compost and digestate from Switzerland is presented (n = 3-18). The median summation 17PCDD/F and summation 12DL-PCB concentrations were at 3.2 ng I-TEQ kg(-1)dry weight (dw) and 3.0 ng WHO-TEQ kg(-1)dw, respectively. Brominated diphenyl ether 209 (BDE 209) accounted for 72% of the total polyBDE content (10 microg kg(-1)dw). Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) levels were at 100 and 0.51 microg kg(-1)dw, respectively. PFAS were identified for the first time in compost and digestate (median concentration 6.3 microg kg(-1)dw, summation 21compounds). Out of 269 pesticides analysed, 30 fungicides, 14 herbicides, eight insecticides and one acaricide were detected. Di-(2-ethylhexyl)phthalate (DEHP) median concentration accounted for 280 microg kg(-1)dw and nonylphenol was below the detection limit of 1 mg kg(-1)dw. The sum of short and medium chain CP was between 90 and 390 microg kg(-1)dw. The concentrations observed were at or above the levels found in background soils, which are the main recipient of compost and digestate. Where actually applied, compost can contribute considerably to the total input of organic pollutants to the soil. However, on a total Swiss agricultural area base, inputs seem to be limited.     

Urinary biomarkers and low-level environmental benzene concentration: assessing occupational and general exposure

The categories of urban workers undergoing prolonged exposure to gasoline due to vehicle emissions, evaporation and traffic fumes are considered occupationally exposed to benzene, even if at low concentrations. The aim of this study was to evaluate the specificity of unmetabolized benzene excreted in urine (UBz) and S-phenylmercapturic acid (SPMA) as biomarkers of exposure to very low levels of benzene, and to study the impact of putative individual confounders like smoking and alcohol habits, co-exposure to other toxicants and body mass index on the exposure assessment. Environmental and biological monitoring of exposure to benzene were performed in 114 Urban Policemen. The mean value of UBz in non-smokers was significantly lower than in either groups of light to moderate smokers and heavy smokers (0.24, 1.82 and 2.82 microg L(-1), respectively). On the contrary, SPMA values did not discriminate exposure resulting from smoking habits. Moreover, the concentration of UBz in non-smokers appears to be correlated with environmental benzene concentration (BenzA) (R(2)=0.13, beta=0.37, p=0.002). On the other hand, no significant correlation was found between SPMA concentration (corrected for creatinine excretion and log transformed, LogSPMA) and LogBenzA (R(2)=0.003, beta=0.05, p=0.6). Our findings reinforce previous research on the use of unmetabolized urinary benzene as a specific and sensitive biomarker of low-level exposure to benzene and confirm that smoking habits strongly influence the excretion of UBz.     

Development of a comprehensive analytical method for the determination of chlorinated paraffins in spruce needles applied in passive air sampling

Conifer needles are used for the monitoring of atmospheric persistent organic pollutants. The objective of the present study was to develop a method for the detection of airborne chlorinated paraffins (CPs) using spruce needles as a passive sampler. The method is based on liquid extraction of the cuticular wax layer followed by chromatographic fractionation and detection of CPs using two different GCMS techniques. Total CP concentrations (sum of short (SCCP), medium (MCCP) and long chain CPs (LCCP)) were determined by EI-MS/MS. SCCP and MCCP levels as well as congener group patterns (n-alkane chain length, chlorine content) could be evaluated using ECNI-LRMS. For the first time, data on environmental airborne CPs on spruce needles taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) are presented providing evidence that spruce needles are a suitable passive sampling system for the monitoring of atmospheric CPs.