This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂ + monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5 × 10⁻³ min⁻¹ for caffeine, 12.5 and 9.0 × 10⁻³ min⁻¹ for carbamazepine, and 10.9 and 5.8 × 10⁻³ min⁻¹ for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.

In order to screen dioxin pollution in sediment of Three Gorges Dam (TGD) area, three sediment cores were obtained from two sites in 2010~2011; each core was divided into different samples with every 10 cm depth. Sediment dating determined by radiometry (¹³⁷Cs, ²¹⁰Pb) and concentrations of dioxins were analyzed by high-resolution gas chromatography/mass spectrometry. The results indicated: Sediment dating showed no significant difference among all the samples from the same core and the two locations (ANOVA, p > 0.05). The total amount of polychlorinated dibenzo-p-dioxins (PCDD)/Fs in all sample ranged from 30.7 to 371 pg/g dry weight (d.w.), with the mean value of 66.2 pg/g d.w. PCDDs occupied 60.33~85.22 % of dioxins in each sample, and PCDFs contributed to a very small extend. There was no significant difference in the dioxin concentration between 2010 and 2011 and in the two locations (t test, p > 0.05), but the vertical distribution of dioxins showed significant different in different depths. Toxic equivalent (TEQ) (WHO 2005, Humans) of samples ranged from 0.15 to 1.60 pg/g d.w.; the mean was 0.41 pg/g d.w. No significant difference was found in TEQ between 2010 and 2011(t test, p > 0.05). It could be concluded that the distribution of dioxins showed the spatial heterogeneous which resulted from the strong mixing and sediment deposition characteristics. Dioxin concentration in sediment cores was low with very low environmental risk potential. Dioxins at the two sites had the same origin, and exogenous input was the main source. It is the first report on the dioxins concentrations in sediment cores in the TGD area.

The tissue and organs (muscle, brain, liver, and gill) of four species of freshwater fish from Lake Baiyangdian were analyzed for hexachlorocyclohexanes (HCHs) and dichloro-diphenyl-trichloroethanes (DDTs). The distribution characteristics were analyzed for HCHs and DDTs in various tissue and organs, which determined the health risks for humans. The research results showed that the wet weight content of all HCHs (∑HCHs) ranged from 0.05 ∼ 14.53 ng g(-1), with a mean of 3.47 ng g(-1). The wet weight content of all DDTs (∑DDTs) ranged from ND to 8.51 ng g(-1), with a mean of 2.41 ng g(-1). For the various species of fish, the residual level of ∑HCHs was relatively higher in chub and grass carp and lowest in snakehead. The residual level of ∑DDTs was the highest in snakehead and did not exhibit a significant variance in the other three species. For the various tissues and organs, the contents of HCHs and DDTs were both highest in the fish liver, second highest in the fish gill, and lowest in the fish brain and muscle. Among the four types of isomers, the residual level of γ-HCH was relatively higher, while the residual level of α-HCH was the lowest. The content of p,p'-DDE was significantly greater to other forms of DDT and its isomer. The residual levels of HCHs and DDTs in fish were both below the national standard. However, the carcinogenic risk from the HCHs in parts of the tissue and organs of four fish species in Lake Baiyangdian exceeded the screen value threshold set by USEPA.

In the present study, the photocatalytic degradation of Reactive Red 195 (RR195) from aqueous samples under UV-A irradiation by using anatase/brookite TiO₂ (A/B TiO₂) mesoporous nanoparticles has been investigated. Batch experiments were conducted to study the effects of the main parameters affecting the photocatalytic process. The effects and interactions of most influenced parameters, such as substrate concentration and catalyst load, were evaluated and optimized by using a central composite design model and a response surface methodology. The results indicated that the dye degradation efficiency in the experimental domain investigated was mainly affected by the tested variables, as well as their interaction effects. Analysis of variance showed a high coefficient of determination value (R ² = 0.9947), thus ensuring a satisfactory adjustment of the first-order regression model (2FI model) with the experimental data. The obtained results also indicate that catalyst loading plays an important role in determining the removal efficiency of RR195 attributable to both photodegradation and adsorption process. Under optimal conditions (initial dye concentration (50 mg/L) and catalyst loading (2,000 mg/L), A/B TiO₂ showed similar removal efficiency compared to that of commercial titania (Degussa P25). Also, at these conditions, complete degradation of RR195 can be achieved by both catalysts within 15 min under UV-A irradiation. The experiments demonstrated that dye removal on the prepared A/B TiO₂ was facilitated by the synergistic effects between adsorption and photocatalysis. Photocatalytic mineralization of RR195 was monitored by total organic carbon. The recycling experiments confirmed the stability of the catalyst.

Concentrations of 22 polycyclic aromatic hydrocarbons (PAHs) were estimated for individual particle-size distributions at the airport apron of the Taipei International Airport, Taiwan, on 48 days in July, September, October, and December of 2011. In total, 672 integrated air samples were collected using a micro-orifice uniform deposition impactor (MOUDI) and a nano-MOUDI. Particle-bound PAHs (P-PAHs) were analyzed by gas chromatography with mass selective detector (GC/MSD). The five most abundant species of P-PAHs on all sampling days were naphthalene (NaP), phenanthrene (PA), fluoranthene (FL), acenaphthene (AcP), and pyrene (Pyr). Total P-PAHs concentrations were 152.21, 184.83, and 188.94 ng/m³ in summer, autumn, and winter, respectively. On average, the most abundant fractions of benzo[a]pyrene equivalent concentration (BaPeq) in different molecular weights were high-weight PAHs (79.29 %), followed by medium-weight PAHs (11.57 %) and low-weight PAHs (9.14 %). The mean BaPeq concentrations were 1.25 and 0.94 (ng/m³) in ultrafine particles (<0.1 μm) and nano-particles (<0.032 μm), respectively. The percentages of total BaPeq in nano- and ultrafine particulate size ranges were 52.4 % and 70.15 %, respectively.

Six antibiotics, tetracyclines (TCs), and quinolones (QNs) in farmland soils from four coastal cities in Fujian Province of China were investigated. Oxytetracycline was most frequently detected, followed by enrofloxacin, ciprofloxacin, chlorotetracycline, ofloxacin, and tetracycline, with maximum concentrations of 613.2, 637.3, 237.3, 2668.9, 205.7, and 189.8 μg kg(-1), respectively. Samples from Putian City contained the highest maximum concentration of ∑TCs (3,064.2 μg kg(-1)), whereas those from Fuzhou City contained the highest maximum concentration of ∑QNs (897.8 μg kg(-1)). It is noteworthy that the ∑TCs and ∑QNs in 46.4 and 28.6 % of samples exceeded the ecotoxic effect trigger value (100 μg kg(-1)), respectively. The concentrations of these antibiotics and five tetracycline resistance genes in four soil plots at depth profiles were quantified thereafter. In most cases, both antibiotics and resistance genes decreased with the increase of depth. Some antibiotics can be detected at a depth of 60-80 cm where the abundance of tetO, tetM, and tetX reached up to 10(7) copies g(-1). Additionally, the sum of all tet genes (normalized to 16S rRNA genes) correlated with ∑TCs significantly (r = 0.676). Our results suggest that resistance determinants can migrate to deeper soil layers and would probably contaminate groundwater by vertical transport.

The aim of this study is to investigate how the presence of Cu influences tebuconazole (Teb) sorption onto contrasting soil types and two important constituents of the soil sorption complex: hydrated Fe oxide and humic substances. Tebuconazole was used in commercial form and as an analytical-grade chemical at different Teb/Cu molar ratios (1:4, 1:1, 4:1, and Teb alone). Increased Cu concentrations had a positive effect on tebuconazole sorption onto most soils and humic substances, probably as a result of Cu−Teb tertiary complexes on the soil surfaces. Tebuconazole sorption increased in the following order of different Teb/Cu ratios 1:4 > 1:1 > 4:1 > without Cu addition, with the only exception for the Leptosol and ferrihydrite. The highest K f value was observed for humic substances followed by ferrihydrite, the Cambisol, the Arenosol, and the Leptosol. The sorption of analytical-grade tebuconazole onto all matrices was lower, but the addition of Cu supported again tebuconazole sorption. The Teb/Cu ratio with the highest Cu addition (1:4) exhibited the highest K f values in all matrices with the exception of ferrihydrite. The differences in tebuconazole sorption can be attributed to the additives present in the commercial product. This work proved the importance of soil characteristics and composition of the commercially available pesticides together with the presence of Cu on the behavior of tebuconazole in soils.

The copper production in Bor (East Serbia) during the last 100 years presents an important source of the pollution of environment. Dust, waste waters, tailing, and air pollutants influence the quality of soil, water, and air. Over 2,000 ha of fertile soil have been damaged by the flotation tailing from Bor’s facilities. The goal of the present work has been to determine the content of Pb, Cu, and Fe in wild plants (17 species) naturally growing in the damaged soil and in fodder crops (nine species) planted at the same place. The content of Pb, Cu, and Fe has been analyzed in damaged soil as well. This study has also searched for native (wild) and cultivated plants which are able to grow in contaminated soil in the area of the intense industrial activity of copper production in Bor, which means that they can accumulate and tolerate heavy metals in their above-ground tissues. It has been found out that the content of all metals in contaminated soil decreases considerably at the end of the experiment. As it has been expected, all plant species could accumulate investigated metals. All tested plants, both wild-growing and cultivated plants, seem to be quite healthy on the substrate which contained extremely high concentrations of copper.

The aim of this research was to determine and compare the quantitative and qualitative characteristics of dissolved organic matters (DOM) from eight aquatic macrophytes in a eutrophic lake. C, H, N, and P in ground dry leaves and C, N, and P in DOM of the species were determined, and C/N, C/P, C/H, DOC/C, TDN/N, TDP/P, DOC/TDN, and DOC/TDP were calculated. Chemical structures of the DOM were characterized by the use of multiple techniques including UV-visible, FT-IR, and (13)C CP/MAS spectra. The results showed subtle differences in quantity and quality of DOM among species and life-forms. Except oriental pepper which had a C/H of 0.7, C/H of all the other species was 0.6. C/N and C/P of ground leaves was 10.5-17.3 and 79.4-225.3, respectively, which were greater in floating and submerged species than in the others. Parrot feather also had a small C/P (102.8). DOC/C, TDN/N, and TDP/P were 7.6-16.8, 5.5-22.6, and 22.9-45.6 %, respectively. Except C/N in emergent and riparian species, C/N in the other species and C/P in all the species were lower in their DOM than in the ground leaves. DOM of the macrophytes had a SUVA254 value of 0.83-1.80. The FT-IR and (13)C NMR spectra indicated that the DOM mainly contained polysaccharides and/or amino acids/proteins. Percent of carbohydrates in the DOM was 37.3-66.5 % and was highest in parrot feather (66.5 %) and crofton weed (61.5 %). DOM of water hyacinth, water lettuce, and sago pondweed may have the greatest content of proteins. Aromaticity of the DOM was from 6.9 % in water lettuce to 17.8 % in oriental pepper. DOM of the macrophytes was also different in polarity and percent of Ar-OH. Distinguished characteristics in quantity and quality of the macrophyte-derived DOM may induce unique environmental consequences in the lake systems.

Because sponges are promising bioindicators, we present here a multispecies comparison of the bioconcentration capacity for copper, zinc and the hydrocarbon fluoranthene. The spatial distribution of sponge populations was studied in 17 areas in intertidal zones on the Lower Normandy coast (France) to determine the most common species with the highest bioaccumulation capacity. Results are compared with published data on blue mussels Mytilus edulis from the Réseau d'Observation de la Contamination Chimique biomonitoring network. A total of 720 sponge samples were collected to assess species richness. Samples were analysed for metal concentrations by flame-mode atomic absorption spectrometry. Analyses of polycyclic aromatic hydrocarbon were sub-contracted. Species richness varies according to the water mass concerned. The most common species in the study area showing the highest bioconcentration in its soft tissues is Hymeniacidon perlevis, which contains about 20 times the zinc, 44 times the copper and 16 times the fluoranthene levels found in mussels. The variability of contaminant concentrations in H. perlevis is also systematically higher than those in mussels. The results obtained for this sponge closely reflect the heterogeneous distribution of contaminants. This study demonstrates that H. perlevis has a much higher capacity to accumulate in situ contaminants than the blue mussel M. edulis. H. perlevis meets all the requirements of a good bioindicator suitable for use in an integrated monitoring programme. In the near future, controlled cultivation of H. perlevis will allow us to produce sufficient quantities of this species to carry out ecotoxicological tests and in situ biomonitoring by caging.