Toward a robust analytical method for separating trace levels of nano-materials in natural waters: cloud point extraction of nano-copper(II) oxide

Cloud point extraction (CPE) factors, namely Triton X-114 (TX-114) concentration, pH, ionic strength, incubation time, and temperature, were optimized for the separation of nano-sized copper(II) oxide (nCuO) in aqueous matrices. The kinetics of phase transfer was studied using UV–visible spectroscopy. From the highest separation rate, the most favorable conditions were observed with 0.2 %?w/v of TX-114, pH?=?9.0, ionic strength of 10 mM NaCl, and incubation at 40 °C for 60 min, yielding an extraction efficiency of 89.2?±?3.9 % and a preconcentration factor of 86. The aggregate size distribution confirmed the formation of very large nCuO–micelle assemblies (11.9 μm) under these conditions. The surface charge of nCuO was also diminished effectively. An extraction efficiency of 91 % was achieved with a mixture of TX-100 and TX-114 containing 30 wt.% of TX-100. Natural organic and particulate matters, represented by humic acid (30 mg/L) and micron-sized silica particles (50 mg/L), respectively, did not significantly reduce the CPE efficiency (<10 %). The recovery of copper(II) ions (20 mg/L) in the presence of humic acid was low (3–10 %). The spiked natural water samples were analyzed either directly or after CPE by inductively coupled plasma mass spectrometry following acid digestion/microwave irradiation. The results indicated the influence of matrix effects and their reduction by CPE. A delay between spiking nCuO and CPE may also influence the recovery of nCuO due to aggregation and dissolution. A detection limit of 0.04 μg Cu/L was achieved for nCuO.     

Indoor air quality (IAQ) assessment in a multistorey shopping mall by high-spatial-resolution monitoring of volatile organic compounds (VOC)

In order to assess indoor air quality (IAQ), two 1-week monitoring campaigns of volatile organic compounds (VOC) were performed in different areas of a multistorey shopping mall. High-spatial-resolution monitoring was conducted at 32 indoor sites located in two storehouses and in different departments of a supermarket. At the same time, VOC concentrations were monitored in the mall and parking lot area as well as outdoors. VOC were sampled at 48-h periods using diffusive samplers suitable for thermal desorption. The samples were then analyzed with gas chromatography–mass spectrometry (GC–MS). The data analysis and chromatic maps indicated that the two storehouses had the highest VOC concentrations consisting principally of terpenes. These higher TVOC concentrations could be a result of the low efficiency of the air exchange and intake systems, as well as the large quantity of articles stored in these small spaces. Instead, inside the supermarket, the food department was the most critical area for VOC concentrations. To identify potential emission sources in this department, a continuous VOC analyzer was used. The findings indicated that the highest total VOC concentrations were present during cleaning activities and that these activities were carried out frequently in the food department. The study highlights the importance of conducting both high-spatial-resolution monitoring and high-temporal-resolution monitoring. The former was able to identify critical issues in environments with a complex emission scenario while the latter was useful in interpreting the dynamics of each emission source.     

A review of plant–pharmaceutical interactions: from uptake and effects in crop plants to phytoremediation in constructed wetlands

Pharmaceuticals are commonly found both in the aquatic and the agricultural environments as a consequence of the human activities and associated discharge of wastewater effluents to the environment. The utilization of treated effluent for crop irrigation, along with land application of manure and biosolids, accelerates the introduction of these compounds into arable lands and crops. Despite the low concentrations of pharmaceuticals usually found, the continuous introduction into the environment from different pathways makes them ‘pseudo-persistent’. Several reviews have been published regarding the potential impact of veterinary and human pharmaceuticals on arable land. However, plant uptake as well as phytotoxicity data are scarcely studied. Simultaneously, phytoremediation as a tool for pharmaceutical removal from soils, sediments and water is starting to be researched, with promising results. This review gives an in-depth overview of the phytotoxicity of pharmaceuticals, their uptake and their removal by plants. The aim of the current work was to map the present knowledge concerning pharmaceutical interactions with plants in terms of uptake and the use of plant-based systems for phytoremediation purposes.     

Road traffic impact on urban water quality: a step towards integrated traffic,air and stormwater modelling

Methods for simulating air pollution due to road traffic and the associated effects on stormwater runoff quality in an urban environment are examined with particular emphasis on the integration of the various simulation models into a consistent modelling chain. To that end, the models for traffic, pollutant emissions, atmospheric dispersion and deposition, and stormwater contamination are reviewed. The present study focuses on the implementation of a modelling chain for an actual urban case study, which is the contamination of water runoff by cadmium (Cd), lead (Pb), and zinc (Zn) in the Grigny urban catchment near Paris, France. First, traffic emissions are calculated with traffic inputs using the COPERT4 methodology. Next, the atmospheric dispersion of pollutants is simulated with the Polyphemus line source model and pollutant deposition fluxes in different subcatchment areas are calculated. Finally, the SWMM water quantity and quality model is used to estimate the concentrations of pollutants in stormwater runoff. The simulation results are compared to mass flow rates and concentrations of Cd, Pb and Zn measured at the catchment outlet. The contribution of local traffic to stormwater contamination is estimated to be significant for Pb and, to a lesser extent, for Zn and Cd; however, Pb is most likely overestimated due to outdated emissions factors. The results demonstrate the importance of treating distributed traffic emissions from major roadways explicitly since the impact of these sources on concentrations in the catchment outlet is underestimated when those traffic emissions are spatially averaged over the catchment area.     

Micropollutants in urban stormwater: occurrence,concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments

This study aimed at: (a) providing information on the occurrence and concentration ranges in urban stormwater for a wide array of pollutants (n?=?77); (b) assessing whether despite the differences between various catchments (land use, climatic conditions, etc.), the trends in terms of contamination level are similar; and (c) analyzing the contribution of total atmospheric fallout (TAF) with respect to sources endogenous to this contamination. The studied contaminants include conventional stormwater contaminants (polycyclic aromatic hydrocarbons (PAHs), Zn, Cu, Pb, etc.), in addition to poorly or undocumented pollutants such as nonylphenol and octylphenol ethoxylates (NPnEO and OPnEO), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs), a wide variety of pesticides, and various metals of relevance (As, Ti, Sr, V). Sampling and analysis were performed using homogeneous methods on three urban catchments with different land use patterns located in three distinct French towns. For many of these pollutants, the results do not allow highlighting a significant difference in stormwater quality at the scale of the three urban catchments considered. Significant differences were, however, observed for several metals (As, Cr, Cu, Ni, Sr and Zn), PAHs, and PBDEs, though this assessment would need to be confirmed by further experiments. The pollutant distributions between dissolved and particulate phases were found to be similar across the three experimental sites, thus suggesting no site dependence. Lastly, the contributions of TAF to stormwater contamination for micropollutants were quite low. This finding held true not only for PAHs, as previously demonstrated in the literature, but also for a broader range of molecules such as BPA, NPnEO, OPnEO, and PBDEs, whose high local production is correlated with the leaching of urban surfaces, buildings, and vehicles.     

Cytogenetic biomonitoring of oral mucosa cells of crack cocaine users

The aim of the present study was to comparatively evaluate genomic damage (micronucleus) and cellular death (pyknosis, karyolysis, and karyorrhexis) in exfoliated oral mucosa cells from crack cocaine users by micronucleus test. A total of 30 crack cocaine users and 30 health controls (non-exposed individuals) were included in this setting. Individuals had epithelial cells from cheek mechanically exfoliated, placed in fixative, and dropped in clean slides, which were checked for the above nuclear phenotypes. The results pointed out significant statistical differences (p?<?0.05) of micronucleated oral mucosa cells from crack cocaine users. Exposure to crack cocaine caused an increase of other nuclear alterations closely related to cytotoxicity such as karyolysis in oral cells as well. In summary, these data indicate that crack cocaine is able to induce chromosomal breakage and cellular death in oral mucosa cells of users.     

The amorphous Zn biomineralization at Naracauli stream,Sardinia: electron microscopy and X-ray absorption spectroscopy

An amorphous Zn biomineralization (“white mud”), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.     

Photodegradation of gaseous acetaldehyde and methylene blue in aqueous solution with titanium dioxide-loaded activated carbon fiber polymer materials and aquatic plant ecotoxicity tests

TiO₂-supported activated carbon felts (TiO₂–ACFTs) were prepared by dip coating of felts composed of activated carbon fibers (ACFs) with either polyester fibers (PS-A20) and/or a polyethylene pulp (PE-W15) in a TiO₂ aqueous suspension followed by calcination at 250 °C for 1 h. The as-prepared TiO₂–ACFTs with 29–35 wt.% TiO₂ were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and N₂ adsorption. The TiO₂–ACFT(PS-A20) samples with 0 and 29 wt.% TiO₂ were microporous with specific surface areas (S _BET) of 996 and 738 m²/g, respectively, whereas the TiO₂–ACFT(PE-W15) samples with 0 and 35 wt.% TiO₂ were mesoporous with S _BET of 826 and 586 m²/g, respectively. Adsorption and photocatalytic activity of the as-prepared samples were evaluated by measuring adsorption in the dark and photodegradation of gaseous acetaldehyde (AcH) and methylene blue (MB) in aqueous solution under UV light. The TiO₂ loading caused a considerable decrease in the S _BET and MB adsorption capacity along with an increase in MB photodegradation and AcH mineralization. Lemna minor was chosen as a representative aquatic plant for ecotoxicity tests measuring detoxification of water obtained from the MB photodegradation reaction with the TiO₂–ACFT samples under UV light.     

Degree of phosphorus saturation of an Oxisol amended with biosolids in a long-term field experiment

When applied to agricultural soils, phosphate fertilizers and the mineral or organic compounds present in solid and/or liquid waste may raise phosphorus (P) content and increase soil P saturation. The degree of phosphorus saturation (DPS) is a good indicator of potential P loss from agricultural soils. The purpose of this study was to calculate the DPS of samples from an Oxisol amended for 5 years with biosolids and mineral fertilizer. DPS was calculated based on P, iron, and aluminum extracted by ammonium oxalate and oxalic acid (DPS_ox) or by Mehlich-1 solution (DPS_M1). Treatments included NPK mineral fertilization (175 kg ha^?1 of P), B1?=?19.02 t ha^?1 of biosolids (350 kg ha^?1 of P), B2?=?38.17 t ha^?1 of biosolids (703 kg ha^?1 of P), B3?=?76.26 t ha^–1 of biosolids (1,405 kg ha^?1 of P), and a control (no P added). Water-extractable P (WEP) was also measured. Critical levels of DPS_ox and DPS_M1 (21 and 24 %, respectively) were only achieved in the topsoil (0–0.1 m) at the highest biosolid dose. Concentration of WEP was positively correlated to DPS_ox and DPS_M1. The DPS_M1 method may be an alternative to DPS_ox for assessing the environmental risk of P loss from soil into surface runoff.