INTRODUCTION: The Turia river basin, located in the east of the Iberian Peninsula, drains into the Mediterranean Sea near the city of Valencia (population, 814,208). The predominance of sea-breeze fluxes favours the inland transport of pollutants from the city up the basin where ozone concentrations exceeding the threshold for protection of human health are systematically recorded during the summer months. METHODS: This work analyses the variability in ozone levels by examining their spatial and temporal distribution in a Mediterranean river basin downwind from a city within the period 2005–2008. Orographic determinants and atmospheric fluxes induce strong variations in ozone measurements, even on relatively close locations. CONCLUSIONS: Results show a different behaviour of the monthly means and the daily cycles depending on the season of the year and the measuring environment, with summer/winter ratios ranging from 2.4 in cities to 1.6 inland, and mean values always higher in the interior of the basin. Daily cycles show significant summer/winter differences related to the predominant situations of anticyclonic stability in winter, which limit ventilation, and the predominant breeze circulations in summer. Results also show a “weekend effect” at urban and medium-distance stations. At the most inland station, the weekend/weekday behaviour differs according to the season of the year; weekend ozone levels are higher in spring, autumn and winter, and lower in summer, coinciding with the predominance of local wind cycles that favour air mass penetration inland from the coast.

PURPOSE: Phosphorus amendments have been widely and successfully used in immobilization of one single metal (e.g., Pb) in contaminated soils. However, application of P amendments in the immobilization of multiple metals and particularly investigations about the effects of planting on the stability of the initially P-induced immobilized metals in the contaminated soils are far limited. METHODS: This study was conducted to determine the effects of phosphate rock tailing (PR), triple superphosphate fertilizer (TSP), and their combination (P+T) on mobility of Pb, Cu, and Zn in a multimetal-contaminated soil. Chinese cabbage (Brassica rapa subsp. chinensis) (metal-sensitive) and Chinese kale (Brassica alboglabra Bailey) (metal-resistant) were introduced to examine the effects of planting on leaching of Pb, Cu, and Zn in the P-amended soils. RESULTS: All three P treatments greatly reduced CaCl2-extractable Pb and Zn by 55.2–73.1% and 14.3–33.6%, respectively. The PR treatment decreased CaCl2-extractable Cu by 27.8%, while the TSP and P+T treatments increased it by 47.2% and 44.4%, respectively. All three P treatments were effective in reducing simulated rainwater leachable Pb, with dissolved and total leachable Pb decrease by 15.6–81.9% and 16.3–64.5%, respectively. The PR treatment reduced the total leachable Zn by 16.8%, while TSP and P+T treatments increased Zn leaching by 92.7% and 78.9%, respectively. However, total Cu leaching were elevated by 17.8–178% in all P treatments. Planting promoted the leaching of Pb and Cu by 98.7–127% and 23.5–170%, respectively, especially in the colloid fraction, whereas the leachable Zn was reduced by 95.3–96.5% due to planting. The P treatments reduced the uptake of Pb, Cu, and Zn in the aboveground parts of Chinese cabbage by up to 65.1%, 34.3%, and 9.59%, respectively. Though P treatments were effective in reducing Zn concentrations in the aboveground parts of the metal-resistant Chinese kale by 22.4–28.9%, they had little effect on Pb and Cu uptake. CONCLUSIONS: The results indicated that all P treatments were effective in immobilizing Pb. The effect on the immobilization of Cu and Zn varied with the different P treatments and evaluation methods. Metal-sensitive plants are more responsive to the P treatments than metal-resistant plants. Planting affects leaching of metals in the P-amended soils, specially leaching of colloid fraction. The conventional assessment on leaching risks of heavy metals by determining dissolved metals (filtered through 0.45-μm pore size membrane) in leachates could be underestimated since colloid fraction may also contribute to the leaching.

INTRODUCTION: The halophyte Halimione portulacoides collected in a polluted area of the river Sado estuary (Portugal) and obtained from hydroponic cultures was used to evaluate the compartmentation of Zn and its preferential binding sites. In parallel, we tried to assess if the minimum available Zn concentration found in marsh soil induces changes at the ultrastructural level. MATERIALS AND METHODS: A sequential extraction method was used to study the Zn compartmentation within the cell. Both dried plant samples and extracts/residues from compartmentation studies were digested by HNO₃–HClO₄ (4:1) until dryness and analyzed by atomic absorption spectrophotometry. Segments of young leaves, previously exposed to Zn were fixed in glutaraldehyde and osmium tetroxide. Ultrathin sections were stained and examined by transmission electron microscopy at 80 kV. RESULTS AND DISCUSSION: Proteins and carbohydrates of the cell walls constitute preferential binding sites of Zn, containing between 25% and 33% and between 30% and 40% of the total, respectively. Hydroponic plants accumulate Zn in their leaves up to (194 μg g⁻¹) without visible damage or changes in the protein and chlorophyll concentrations, compared with the controls. Chlorenchyma chloroplasts of Zn-treated plants exhibited an unusual number of starch grains, which can be seen as an alert mechanism. CONCLUSIONS AND PERSPECTIVES: Although so far the levels of Zn in the leaves within the studied area have not reached high values, monitoring them remains a priority. Also, issues related with starch synthesis and organic ligands must be evaluated. The understanding of the predictable behavior of this halophyte is our main goal, and the results here presented can contribute to this achievement.

BACKGROUND, AIM, AND SCOPE: According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography–high-resolution mass spectrometry (LC–Orbitrap–MS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents. MATERIALS AND METHODS: Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200 mg hydrophilic–lipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP. RESULTS AND DISCUSSION: Cyclophosphamide and epirubicin were recovered after 50 mL preconcentration on solid-phase extraction 200 mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500 mL of water. Limits of detection were of 0.35 and 2.77 ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1 μg/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85 ng L−1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8 μg L−1. CONCLUSIONS: The results obtained in this study demonstrate the capability of LC–Orbitrap–MS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.

PURPOSE: Degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) in soils by Fe3O4 nanoparticles combined with soil indigenous microbes was investigated, and the effects of Fe3O4 nanoparticles on soil microbial populations and enzyme activities were also studied. METHODS: The soils contaminated with 2,4-D were treated with Fe3O4 nanoparticles. The microbial populations and enzyme activities were analyzed by dilution plate method and chemical assay, respectively, and the concentration of 2,4-D in soil was determined by high-performance liquid chromatography (HPLC). RESULTS: The results indicated that Fe3O4 nanoparticles combined with soil indigenous microbes led to a higher degradation efficiency of 2,4-D than the treatments with Fe3O4 nanoparticles or indigenous microbes alone. The degradation of 2,4-D in soils followed the pseudo first-order kinetic. The half-lives of 2,4-D degradation (DT50) of the combined treatments were 0.9, 1.9 and 3.1 days in a Red soil, Vertisol and Alfisol, respectively, which implied that the DT50 of the combination treatments were significantly shorter than that of the treatments Fe3O4 nanoparticles or indigenous microbes alone. The effects of Fe3O4 nanoparticles on soil microbial populations and enzyme activities were also investigated and compared with the α-Fe2O3 nanoparticles. The results suggested that the α-Fe2O3 nanoparticles had only comparatively small effects on degradation of 2,4-D in soils, while the Fe3O4 nanoparticles not only degraded 2,4-D in soils but also increased the soil microbial populations and enzyme activities; the maximum increase in enzyme activities were 67.8% (amylase), 53.8% (acid phosphatase), 26.5% (catalase) and 38.0% (urease), compared with the untreated soil. Moreover, the introduction of Fe3O4 nanoparticles at the different dosage resulted in a variable degradation efficiency of 2,4-D in soil. CONCLUSION: The method of combining Fe3O4 nanoparticles with indigenous soil microbes may offer great benefits for the application of nanotechnology in remediation of herbicide contaminated soil.

Residues of tetracyclines reach soils as a result of animal waste application. Sorption is a key process in transport, fate, and effects of contaminants in the environment. In this work, we have attempted to predict the sorption of four widely used tetracyclines (oxytetracycline, tetracycline, chlortetracycline, and doxycycline) from soil physicochemical properties. Batch sorption experiments were performed on 15 natural soils with a broad range of physicochemical properties, and the data were fitted to several isotherm models. Multivariate analysis methods were conducted to identify the main factors affecting the sorption distribution coefficients (K d) of the tetracyclines at two aqueous concentration levels (100 and 400 μg L−1). All four tetracycline sorption isotherms in alkaline and acidic soils were well described by the Freundlich and Langmuir equation, respectively. At intermediate soil pH (from 5.3 to 7), oxytetracycline and tetracycline exhibited Freundlich behavior, whereas chlortetracycline and doxycycline followed a Langmuir model. Two partial least squares (PLS) models were developed. The first one uses five soil descriptors as input variables; the second uses, pH, cation exchange capacity (CEC), and log K d,OTC. Both models satisfactorily predicted distribution coefficients within a factor of 1.5. Sorption of tetracyclines in soil is governed by several factors, in the following order of importance: solution speciation, CEC (dominant at acidic–neutral soil pH), transition metal content, and texture. The PLS models indicated that tetracycline sorption can be predicted using a minimal set of soil descriptors including oxytetracycline sorption data.

Perfluorinated compounds (PFCs) have been widely used in industrial and consumer products and frequently detected in many environmental media. Potential reproductive effects of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) have been reported in mice, rats and water birds. PFOS and PFOA were also confirmed developing toxicants towards zebrafish embryos; however, the reported effect concentrations were contradictory. Polyfluorinated alkylated phosphate ester surfactants (including FC807) are precursor of PFOS and PFOA; however, there is no published information about the effects of FC807 and PFNA on zebrafish embryos. Therefore, this study was conducted to determine the effects of these four PFCs on zebrafish embryos. Normal fertilized zebrafish embryos were selected to be exposed to several concentrations of PFOA, PFNA, PFOS or FC807 in 24-well cell culture plates. A digital camera was used to image morphological anomalies of embryos with a stereomicroscope. Embryos were observed through matching up to 96-h post-fertilization (hpf) and rates of survival and abnormalities recorded. PFCs caused lethality in a concentration-dependent manner with potential toxicity in the order of PFOS > FC807 > PFNA > PFOA based on 72-h LC₅₀. Forty-eight-hour post-fertilization pericardial edema and 72- or 96-hpf spine crooked malformation were all observed. PFOA, PFNA, PFOS and FC807 all caused structural abnormalities using early stages of development of zebrafish. The PFCs all retarded the development of zebrafish embryos. The toxicity of the PFCs was related to the length of the PFC chain and functional groups.

INTRODUCTION: Over the last few decades, the chromium-based tanning industry has shown rapid growth in Pakistan. However, the rules and regulations promulgated by the government are not strictly followed for processing the effluent discharge from the tanneries. Consequently, tannery effluents have become a great source of water pollution in surrounding areas. MATERIALS AND METHODS: In this case study, characterization of tannery effluent wastewater (TW), shallow groundwater (SW), and deep groundwater (DW) samples was carried out to determine the source of water pollution in the district of Kasur, Pakistan. RESULTS: The concentrations of calcium (Ca), chlorine (Cl), chromium (Cr), iron (Fe), potassium (K), Mg, sulfur (S), silicon (Si), and Sr in TW were significantly higher than SW and DW, which also exceeded the international limits. In addition, increased concentrations of major toxic elements (Cl, Cr, Fe, K, Ni, and Si) were also observed in SW, which were higher in comparison to DW. Strikingly, the concentrations of Cr and Si in various DW samples were also beyond World Health Organization (WHO) safe limit, which reinforced the trend that water pollution in the area is directly linked to the distance from the source (TW). The particle-induced X-ray emission (PIXE) indices also suggested that TW is a main contributory source of water-based pollution in the area, which is imposing great threat to local inhabitants due to known hazardous and carcinogenic potential of these elements. CONCLUSION: Protecting the water resources will be a formidable challenge in the study area, which requires modernization of tannery industry, thereby improving the recovery and recycling of TW. Moreover, PIXE analysis presented here as a successful tool, could serve as landmark for the contemporary research in environmental toxicology.

PURPOSE: Although the ecotoxicological effects of copper (Cu) on grapevine are of global concern due to the intensive and long-term application of Cu-based fungicides in vineyards, comparatively little is known about the phytotoxicity, accumulation, and translocation of Cu in grapevines. Therefore, this study was to conduct a hydroponic experiment to determine the influence of solution Cu concentration not only on bioaccumulation and the translocation of Cu in grapevine roots, stems, and leaves, but also on the subsequent growth inhibition of the roots. METHODS: Grapevine cuttings were grown for 30 days and then exposed to various Cu concentrations (0.1–50 μM) for 15 days. The dose–response profile was described by a sigmoid Hill equation. Optical microscopy was used to examine the cytotoxicity of Cu on the roots. In addition, bioaccumulation factors (BAFs) and translocation factors (TFs) were calculated from the results of the hydroponic experiment. RESULTS: Copper was tolerated by grapevines at a concentration ≤1 μM. The median inhibition concentration (IC50) obtained from the Hill model was 3.94 μM (95% confidence interval, 3.65–4.24). From the light micrographs of root tip cells, signs of toxicity including increased vacuolization and plasmolysis were observed at solution Cu concentrations ≥10 μM. In addition, a higher Cu concentration was found in the roots (25–12,000 mg kg−1) than in the stems (5–540 mg kg−1) and leaves (7–46 mg kg−1), indicating a very limited translocation of Cu from the roots to the aboveground parts. CONCLUSIONS: This study investigated not only the macroscopic root growth and Cu accumulation by grapevine, but also the microscopic changes in root tissue at the cell level after the exposure experiment. Based on the BAFs and TFs, the grapevine could be considered a Cu-exclusive plant. For toxic effects on the exposure of roots to Cu, this study also revealed that root growth, as well as the histological changes in rhizodermal cells, can be used as phytotoxic indicators of grapevine under Cu stress.