A systematic grid sampling method and geostatistics were employed to investigate the spatial distribution, inventory, and potential ecological and human health risks of the residues of hexachlorobenzene (HCB) and chlorinated cyclodiene pesticides in soils of the Campanian Plain, Italy, and explore their relationship with the soils properties. The geometric mean (Gmean) concentrations of HCB and cyclodiene compounds followed the order CHLs (heptachlor, heptachlor epoxide, trans-chlordane, and cis-chlordane) > DRINs (aldrin, dieldrin, and endrin) > SULPHs (α-endosulfan, β-endosulfan, and endosulfan sulfate) > HCB. The residual levels of most cyclodienes in agricultural soils were generally higher than those of corresponding counterparts in the other land uses. Significant differences in the concentration of HCB and cyclodienes in the soils across the region are observed, and the Acerra-Marigliano conurbation (AMC) and Sarno River Basin (SRB) areas exhibit particularly high residual concentrations. Some legacy cyclodienes in the Campanian Plain may be attributed to a secondary distribution. The Gmean inventory of HCB, SULPHs, CHLs, and DRINs in the soil is estimated to be 0.081, 0.41, 0.36, and 0.41 metric tons, respectively. The non-cancer and cancer risks of HCB and cyclodienes for exposed populations are deemed essentially negligible, however, endosulfan poses significant ecological risks to some terrestrial species.

Nanomaterials are increasingly being used to improve the properties and functions of common building materials. A new type of self-cleaning cement incorporating TiO2 nanomaterials (TiO2-NMs) with photocatalytic properties is now marketed. This promising cement might provide air pollution-reducing properties but its environmental impact must be validated. During cement use and aging, an altered surface layer is formed that exhibits increased porosity. The surface layer thickness alteration and porosity increase with the cement degradation rate. The hardened cement paste leaching behavior has been fully documented, but the fate of incorporated TiO2-NMs and their state during/after potential release is currently unknown. In this study, photocatalytic cement pastes with increasing initial porosity were leached at a lab-scale to produce a range of degradation rates concerning the altered layer porosity and thickness. No dissolved Ti was released during leaching, only particulate TiO2-NM release was detected. The extent of release from this batch test simulating accelerated worst-case scenario was limited and ranged from 18.7 ± 2.1 to 33.5 ± 5.1 mg of Ti/m2 of cement after 168 h of leaching. TiO2-NMs released into neutral aquatic media (simulate pH of surface water) were not associated or coated by cement minerals. The TiO2-NM release mechanism is suspected to start from freeing of TiO2-NMs in the altered layer pore network due to partial cement paste dissolution followed by diffusion into the bulk pore solution to the surface. The extent of TiO2-NM release was not solely related to the cement degradation rate.

Pharmaceuticals and personal care products are released into aquatic environments, largely as a result of ineffectual removal during wastewater treatment. Here we present a screening strategy based on the use of three commercially available mass spectral databases, combined into a single searchable entity and parallelized by cluster computing. In addition to this, a targeted solid phase extraction method with Ultra High Pressure Liquid Chromatography coupled to quadrupole time of flight mass spectrometry (UHPLC-QTOF) was used to quantify 99 pharmaceuticals in South African surface water on a national level. Limits of quantification were in the low ng/L range for the majority of the compounds and it was found that nationally both Lamotrigine and Nevirapine occurred most often. Prednisolone and Ritonavir were present at the highest average concentration; 623 and 489 ng/L respectively. It is however shown that more than 50% of the targets chosen for analysis are not detectable in any of the samples, which highlights the utility of untargeted, database driven screening; prior to the use of costly analytical standards. Untargeted screening detected 45% of the compounds detected in targeted mode, and furthermore tentatively identified a total of 4273 unique compounds across the samples. Automatically triggered MS/MS analyses yielded 92 unique hits with greater than 95% confidence. It is therefore suggested that untargeted screening should precede the targeted approach as a matter of economy and to guide the selection of targets for quantification. There is however great room for improvement in current commercial database search methodologies as a large bottleneck exists due to processing time.

Trifluoroacetic acid (TFA) in the atmosphere is produced by degradation of hydrochlorofluorocarbons and hydrofluorocarbons. In recent years, TFA has attracted global attention because of increased environmental concentrations, biological toxicity and accumulation in aqueous environments. This study focused on the mechanisms underlying the adsorption of TFA by particulate matter to identify the appropriate descriptive model for this process and thus improve estimation of TFA adsorption in future environmental monitoring. Onsite gas and particle phase sampling in Beijing, China, and subsequent measurement of TFA concentrations indicated that the TFA concentration in the gas phase (1396 ± 225 pg m−3) was much higher than that in the particle phase (62 ± 8 pg m−3) and that monthly concentrations varied seasonally with temperature. Based on the field results and analysis, an adsorption experiment of TFA on soot was then conducted at three different temperatures (293, 303, and 313 K) to provide parameters for kinetic and thermodynamic modelling. The proportion of atmospheric TFA concentration in the gas phase increased with temperature, indicating that temperature affected the phase distribution of TFA. The subsequent kinetic and thermodynamic modelling showed that the adsorption of TFA by soot could be described well by the Bangham kinetic model. The adsorption was controlled by diffusion, and the key mechanism was physical adsorption. The adsorption behavior can be well described by the Langmuir isotherm model. The calculated thermodynamic parameters ΔG° (−2.34, −1.25, and −0.15 kJ mol−1 at 293, 303, and 313 K, respectively), ΔH° (−34.34 kJ mol−1), and ΔS° (−109.22 J mol−1 K−1) for TFA adsorption by soot were negative, indicating that adsorption was a spontaneous, exothermic process.

In agricultural lowland landscapes, intensive agricultural is accompanied by a wide use of agrochemical application, like pesticides and fertilizers. The latter often causes serious environmental threats such as N compounds leaching and surface water eutrophication; additionally, since perchlorate can be present as impurities in many fertilizers, the potential presence of perchlorates and their by-products like chlorates and chlorites in shallow groundwater could be a reason of concern. In this light, the present manuscript reports the first temporal and spatial variation of chlorates, chlorites and major anions concentrations in the shallow unconfined aquifer belonging to Ferrara province (in the Po River plain). The study was made in 56 different locations to obtain insight on groundwater chemical composition and its sediment matrix interactions.During the monitoring period from 2010 to 2011, in June 2011 a nonpoint pollution of chlorates was found in the shallow unconfined aquifer belonging to Ferrara province. Detected chlorates concentrations ranged between 0.01 and 38 mg/l with an average value of 2.9 mg/l. Chlorates were found in 49 wells out of 56 and in all types of lithology constituting the shallow aquifer. Chlorates concentrations appeared to be linked to NO3−, volatile fatty acids (VFA) and oxygen reduction potential (ORP) variations. Chlorates behaviour was related to the biodegradation of perchlorates, since perchlorates are favourable electron acceptors for the oxidation of labile dissolved organic carbon (DOC) in groundwater. Further studies must take into consideration to monitor ClO4− in pore waters and groundwater to better elucidate the mass flux of ClO4− in shallow aquifers belonging to agricultural landscapes.

In this study, ZnAlTi layered double hydroxide (ZnAlTi-LDH) combined with fullerene (C60) was fabricated by the urea method, and calcined under vacuum atmosphere to obtain nanocomposites of C60-modified ZnAlTi layered double oxide (ZnAlTi-LDO). The morphology, structure and composition of the nanocomposites were analyzed by Scanning Electron Microscopy, High-resolution transmission electron microscopy, X-ray diffraction patterns, Fourier transform infrared and specific surface area. The UV-vis diffuse reflectance spectra indicated that the incorporation of C60 expanded the absorption of ZnAlTi-LDO to visible-light region. The photo-degradation experiment was conducted by using a series of C60 modified ZnAlTi-LDO with different C60 weight percentage to degrade Bisphenol A (BPA) under simulated visible light irradiation. In this experiment, the degradation rate of C60 modified ZnAlTi-LDO in photo-degradation of BPA under simulated visible light irradiation was over 80%. The intermediates formed in the degradation of BPA process by using LDO/C60-5% were 4-hydroxyphenyl-2-propanol, 4-isopropenylphenol and Phenol. Photogenerated holes, superoxide radical species, ·OH and singlet oxygen were considered to be responsible for the photodegradation process, among which superoxide radical species and ·OH played a predominant role in the photocatalytic reaction system. C60 modified ZnAlTi-LDO catalysts for photocatalytic reduction shows great potential in degradation of organic pollutants and environmental remediation.

4-nitrophenol (PNP), isolated from diesel exhaust particles, has estrogenic and anti-androgenic activities, and affects the hypothalamus-pituitary-gonad axis in male rats. However, the effect of PNP on the reproduction of the female rats is still unknown. The aim of the study was to investigate the effect of neonatal PNP exposure on the ovarian function of female rats. The neonatal female rats were exposed to PNP (10 mg/kg, subcutaneously injection), the ovary and serum samples were collected at postnatal day (PND) 7, 14 and 21. The results showed that the ratio of primordial and primary follicles increased whereas the ratio of antral follicles decreased in the PNP treated ovaries at PND21. Even though no abnormality was observed in cyclicity, there was a significantly delayed timing of vaginal opening in PNP treated rats. The ovarian expressions of steroidogenic enzymes including StAR, P450scc, P450c17 and P450arom increased at PND14 in the PNP treated rats compared with the control rats. In consistent with the gene expressions, the concentration of estradiol-17β showed the similar pattern. However, PNP exposure failed to cause any significant change in the expressions of steroidogenic enzymes in cultured neonatal ovaries. Furthermore, PNP suppressed the expression of estrogen receptor β (ERβ), but not estrogen receptor α (ERα), in cultured ovaries or developmental ovaries. These results suggested that PNP might directly affect the expression of ERβ in the rat ovaries, resulting in the disrupted steroidogenesis during ovarian development and the delayed puberty.

The sediment environment provides habitat for fauna and flora. As pollutants can interchange between water and sediments, pollution will exert a significant influence on the water environment. Previous studies on polycyclic aromatic hydrocarbon (PAHs) pollution of sediments have primarily focused on the comparison of concentrations between seasons, land uses and species. Studies on the identification of the hierarchy of factors which influence PAHs distribution and its variability in river sediments are limited. This paper discusses a comprehensive investigation into the inherent variability of PAHs in sediments and the primary factors which influence this variability. The study outcomes confirmed that key factors exerting influence on PAH distribution in sediments can be ranked in the order: land use > population > seasons. Accordingly, intensive urban land use was identified as the most important factor influencing PAHs distribution. Additionally, it was found that with increasing urban development, PAHs concentrations and their variability in sediments increase in terms of the molecular weight of different species. The study outcomes are expected to enhance management strategies to mitigate PAHs pollution of urban water environments including the prioritisation of factors requiring management and the selection of appropriate approaches in the context of cost-effectiveness.

Little is known about pollution in urban snow and how aerosol and gaseous air pollutants interact with the urban snowpack. Here we investigate interactions of exhaust pollution with snow at low ambient temperature using fresh snow in a temperature-controlled chamber. A gasoline-powered engine from a modern light duty vehicle generated the exhaust and was operated in homogeneous and stratified engine regimes. We determined that, within a timescale of 30 min, snow takes up from the exhaust a large mass of organic pollutants and aerosol particles, which were observed by electron microscopy, mass spectrometry and aerosol sizers. Specifically, the concentration of total organic carbon in the exposed snow increased from 0.948 ± 0.009 to 1.828 ± 0.001 mg/L (homogeneous engine regime) and from 0.275 ± 0.005 to 0.514 ± 0.008 mg/L (stratified engine regime). The concentrations of benzene, toluene and 13 out of 16 measured polycyclic aromatic hydrocarbons (PAHs), particularly naphthalene, benz[a]anthracene, chrysene and benzo[a]pyrene in snow increased upon exposure from near the detection limit to 0.529 ± 0.058, 1.840 ± 0.200, 0.176 ± 0.020, 0.020 ± 0.005, 0.025 ± 0.005 and 0.028 ± 0.005 ng/kg, respectively, for the homogeneous regime. After contact with snow, 50–400 nm particles were present with higher relative abundance compared to the smaller nanoparticles (<50 nm), for the homogeneous regime. The lowering of temperature from 25 ± 1 °C to (−8) – (−10) ± 1 °C decreased the median mode diameter of the exhaust aerosol particles from 69 nm to 57 nm (p < 0.1) and addition of snow to 51 nm (p < 0.1) for the stratified regime, but increased it from 20 nm to 27 nm (p < 0.1) for the homogeneous regime. Future studies should focus on cycling of exhaust-derived pollutants between the atmosphere and cryosphere. The role of the effects we discovered should be evaluated as part of assessment of pollutant loads and exposures in regions with a defined winter season.

Emission from coal-fired power plants is one of the major anthropogenic sources of mercury (Hg) in the environment, because emitted Hg can be quickly deposited nearby the source, attention is paid to the effects of coal-burning facilities on levels of toxic methyl-mercury (MeHg) in biota near such sources. Since rice is an agricultural crop that can bio-accumulate MeHg, the potential effects of a large Hg-emitting coal-fired power plant in Hunan Province, China on both inorganic Hg (Hg(II)) and MeHg distributions in rice was investigated. Relatively high MeHg (up to 3.8 μg kg−1) and Hg(II) (up to 22 μg kg−1) concentrations were observed in rice samples collected adjacent to the plant, suggesting a potential impact of Hg emission from the coal fired power plant on the accumulation of Hg in rice in the area. Concentrations of MeHg in rice were positively correlated with soil MeHg, soil S, and gaseous elemental Hg (GEM) in ambient air. Soil MeHg was the most important factor controlling MeHg concentrations in rice. The methylation of Hg in soils may be controlled by factors such as the chemical speciation of inorganic Hg, soil S, and ambient GEM.