Hydrogen production by methane dry reforming is an important yet challenging process. A performing catalyst will favor the thermodynamic equilibrium while ensuring good hydrogen selectivity. We hereby report the synthesis of Co ₓ Mg₆₋ₓ Al₂ (with x = 2 and 6) mixed oxide catalysts synthesized via hydrotalcite precursors and the synthesis of a ruthenium-based catalyst on a cobalt, magnesium, and aluminum mixed oxide supports Ru/Co ₓ Mg₆₋ₓ Al₂ (with x = 2 and 6). The impregnation of ruthenium on the hydrotalcites was performed in two ways: by impregnation on the dried hydrotalcite and by memory effect on hydrotalcite calcined at 500 °C. The deposition of ruthenium by memory effect of the magnesium and cobalt support allows the generation of both metallic and basic sites which provides an active and stable catalyst for the dry reforming reaction of methane.

In this study, the photolysis behavior of commonly used anti-inflammatory drug diclofenac (DCF) was investigated using UV-C and UV-A irradiation. In that purpose, DCF conversion kinetics, mineralization of organic content, biodegradability, and toxicity were monitored and compared. The results showed different kinetics of DCF conversion regarding the type of UV source applied. However, in both cases, the mineralization extent reached upon complete DCF conversion is rather low (≤10 %), suggesting that the majority of DCF was transformed into by-products. Formation/degradation of main degradation by-products was monitored using high-performance liquid chromatography–electrospray ionization-tandem mass spectrometry (HPLC–ESI-MS/MS), whereas different profiles were obtained by UV-C and UV-A photolysis. The results of bioassays revealed that biodegradability of DCF solutions remained low through the applied treatments. The toxicity of irradiated DCF solutions was evaluated using Vibrio fischeri. A significant reduction of toxicity, especially in the case of UV-A radiation, was observed upon complete degradation of DCF. In addition to toxicity reduction, calculated Log K OW values of DCF degradation by-products indicate their low potential for bioaccumulation (Log K OW ≤ 3) in comparison to the parent substance.

A wide variety of endocrine disrupting compounds (EDCs) with semi-volatile properties are emitted to indoor air and, thus, humans might get exposed to these compounds. Pet cats spend the major part of their lifetime at home and might integrate indoor contamination so that they could mirror the human exposure. Three classes of EDCs, polybromodiphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and phthalates (PAEs), were simultaneously considered and quantified in the serum of cats (Felis silvestris catus) living in the Paris area (France). The main compound concentrations by decreasing importance order were as follows: for PAEs, di-n-butyl phthalate (79,900 ng L⁻¹) next di-iso-butyl phthalate (53,200 ng L⁻¹), di-iso-nonyl phthalate (43,800 ng L⁻¹), and di-ethylhexyl phthalate (32,830 ng L⁻¹); for PCBs, CB153 (1378 ng L⁻¹) next CB52 (509 ng L⁻¹), CB101 (355 ng L⁻¹), CB110 (264 ng L⁻¹), and CB118 (165 ng L⁻¹); and for PBDEs, BDE 153/154 (35 ng L⁻¹) next BDE47 (10.7 ng L⁻¹). Total serum concentrations as mean ± standard deviation were 107 ± 98 μg L⁻¹ for ∑9PAEs, 2799 ± 944 ng L⁻¹ for ∑19PCBs, and 56 ± 21 ng L⁻¹ for ∑9BDEs. The three chemical groups were found in cat food: 0.088 ng g⁻¹ for ∑9BDEs, 1.7 ng g⁻¹ for ∑19PCBs, and 2292 ng g⁻¹ for ∑9PAEs and in indoor air: 0.063 ng m⁻³ for ∑9BDEs, 1.5 ng m⁻³ for ∑19PCBs, and 848 ng m⁻³ for ∑9PAEs. Contaminant intake by food ingestion was approximately 100-fold higher than that by indoor air inhalation.

Perfluorooctanoic acid (PFOA), an environmentally persistent pollutant, was found to be quickly decomposed under 254 nm UV irradiation in the presence of ferric ion and oxalic acid. To understand the PFOA decomposition mechanism by this process, the effects of reaction atmosphere and concentrations of ferric ions and oxalic acids on PFOA decomposition were investigated, as well as decomposition intermediates. PFOA mainly decomposes via two pathways: (i) photochemical oxidation via Fe(III)-PFOA complexes and (ii) one-electron reduction caused by carboxylate anion radical (CO₂ •⁻), which was generated by photolysis of ferrioxalate complexes. Under excess oxalic acid, PFOA decomposition was accelerated, and its corresponding half-life was shortened from 114 to 34 min as ferric concentration increased from 7 to 80 μM. Besides fluoride ions, six shorter chain perfluorinated carboxylic acids (PFCAs) bearing C₂-C₇ were identified as main intermediates. The presence of O₂ promoted the redox recycling of Fe³⁺/Fe²⁺ and thus avoided the exhaustion of the Fe(III).

Recent studies identified polychlorinated biphenyl (PCB) sulfate esters as a major product of PCB metabolism. Since hydroxy-PCBs (HO-PCBs), the immediate precursors of PCB sulfates and important contributors to PCB toxicity, were shown to have estrogenic activity, we investigated the estrogenicity/androgenicty of a series of PCB sulfate metabolites. We synthesized the five possible structural sulfate monoester metabolites of PCB 3, a congener shown to be biotransformed to sulfates, a sulfate ester of the paint-specific congener PCB 11, and sulfate monoesters of two HO-PCBs reported to interact with sulfotransferases (PCB 39, no ortho chlorines, and PCB 53, 3 ortho chlorines). We tested these PCB sulfates and 4′-HO-PCB 3 as positive control for estrogenic, androgenic, anti-estrogenic, and anti-androgenic activity in the E- and A-screen with human breast cancer MCF7-derived cells at 100 μM–1 pM concentrations. Only 4′-HO-PCB 3 was highly cytotoxic at 100 μM. We observed structure-activity relationships: compounds with a sulfate group in the chlorine-containing ring of PCB 3 (2PCB 3 and 3PCB 3 sulfate) showed no interaction with the estrogen (ER) and androgen (AR) receptor. The 4′-HO-PCB 3 and its sulfate ester had the highest estrogenic effect, but at 100-fold different concentrations, i.e., 1 and 100 μM, respectively. Four of the PCB sulfates were estrogenic (2′PCB 3, 4′PCB 3, 4′PCB 39, and 4′PCB 53 sulfates; at 100 μM). These sulfates and 3′PCB 3 sulfate also exhibited anti-estrogenic activity, but at nM and pM concentrations. The 4′PCB 3 sulfate (para-para′ substituted) had the strongest androgenic activity, followed by 3′PCB 3, 4′PCB 53, 4PCB11, and 4PCB 39 sulfates and the 4′HO-PCB 3. In contrast, anti-androgenicity was only observed with the two compounds that have the sulfate group in ortho- or meta- position in the second ring (2′PCB 3 and 3′PCB 3 sulfate). No dose–response was observed in any screen, but, with exception of estrogenic activity (only seen at 100 μM), endocrine activity was often displayed at several concentrations and even at 1 pM concentration. These data suggest that sulfation of HO-PCBs is indeed reducing their cytotoxicity and estrogenicity, but may produce other endocrine disruptive activities at very low concentrations.

In this study, the seasonal difference and the observable presence/absence of human adenovirus (HAdV) in the Puzih River basin in Taiwan was investigated. A total of 288 water samples were collected from 24 sites from March 2014 to February 2015. Human AdV analysis of sample was subjected to viral concentration using a GN-6 Metricel® filter, followed by DNA extraction, nested-PCR, and qPCR. Human AdV was detected in 34.3 % (99/288) of the entire river water sample. A higher percentage of HAdV (76.4 %) was obtained during the winter. The HAdV median concentration was relatively high in fall (1.4 × 10³ copies/L) and winter (2.8 × 10³ copies/L). Significant difference and correlation were found between the seasonal variation of HAdV and water quality parameters, including heterotrophic plate count, total coliform, water temperature, and turbidity. The most frequently identified HAdV (subgenus F) serotype was 41. Human AdV-41 is the main cause of gastroenteritis and should be considered for associated human health risk potential in the Puzih River basin.

Vinyl chloride (VC) is a frequent groundwater contaminant and a known human carcinogen. Bioremediation is a potential cleanup strategy for contaminated sites; however, little is known about the bacteria responsible for aerobic VC degradation in mixed microbial communities. In attempts to address this knowledge gap, the microorganisms able to assimilate labeled carbon (¹³C) from VC within a mixed culture capable of rapid VC degradation (120 μmol in 7 days) were identified using stable isotope probing (SIP). For this, at two time points during VC degradation (days 3 and 7), DNA was extracted from replicate cultures initially supplied with labeled or unlabeled VC. The extracted DNA was ultracentrifuged, fractioned, and the fractions of greater buoyant density (heavy fractions, 1.758 to 1.780 g mL⁻¹) were subject to high-throughput sequencing. Following this, specific primers were designed for the most abundant phylotypes in the heavy fractions. Then, quantitative PCR (qPCR) was used across the buoyant density gradient to confirm label uptake by these phylotypes. From qPCR and/or sequencing data, five phylotypes were found to be dominant in the heavy fractions, including Nocardioides (∼40 %), Sediminibacterium (∼25 %), Aquabacterium (∼17 %), Variovorax (∼6 %), and Pseudomonas (∼1 %). The abundance of two functional genes (etnC and etnE) associated with VC degradation was also investigated in the SIP fractions. Peak shifts of etnC and etnE gene abundance toward heavier fractions were observed, indicating uptake of ¹³C into the microorganisms harboring these genes. Analysis of the total microbial community indicated a significant dominance of Nocardioides over the other label-enriched phylotypes. Overall, the data indicate Nocardioides is primarily responsible for VC degradation in this mixed culture, with the other putative VC degraders generating a small growth benefit from VC degradation. The specific primers designed toward the putative VC degraders may be of use for investigating VC degradation potential at contaminated sites.

This study evaluates the elemental (W, Mo, Zn, Fe, Cu, Cd, Mn, Pb, Cr, Co, B, and Bi) composition of Marrubium astracanicum Jacq. (Lamiaceae), around the abandoned tungsten mine on Uludağ Mountain, Turkey, to determine if it is an appropriate candidate for phytomonitoring and/or phytoremediation purposes. Three sample sites were selected around the mine for soil and plant sampling. Two sites approximately 500 m from the mine were assumed to be unpolluted sites. The other site was selected from a waste removal pool (WRP) and was assumed to be a polluted site. The soil and different organs (roots, leaves, and flowers) of plant samples were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) to determine the elemental content. The classic open wet digestion procedure was applied to the samples with 5 mL HNO₃ and 3 mL H₂O₂ in a borosilicate glass vessel for the roots, leaves, and the flowers of the plants. Kjeldahl digestion was used for the soil samples. The W, Zn, Fe, Cu, Cd, Mn, Pb, B, and Bi contents were found to be higher in the soil samples from the waste removal pools compared with the samples from the unpolluted sites. We also found that the elemental composition of M. astracanicum has generally been increased by the activity of the tungsten mine, and there were significant correlations between the elemental contents of the soil samples and plant parts, except for Mo and Cr. The high level of many elements in the soil samples indicates the presence of contamination related to tungsten-mining activity on Uludağ Mountain. Assessing the elemental contents of M. astracanicum, we can suggest this species as a candidate for phytoremediation purposes of W-contaminated sites due to its high W-accumulation capacity.

The aim of this descriptive-analytical study was to measure the concentration of heavy metals (HMs) in the leaf and bark of Ulmus carpinifolia as new biological indicators, and the ecological risk assessment of these metals in the ambient air. To achieve these goals, 48 sampling locations were selected in the city and concentration of four HMs—zinc (Zn), copper (Cu), lead (Pb), and cadmium (Cd)—was measured in the mentioned indicator using atomic absorption spectroscopy method. After this, ecological risk assessment, source appointment, and spatial distribution were conducted. In this regard, the enrichment factor (EF), potential ecological risk factor (E ᵣ), potential ecological risk index (RI), correlation coefficient (r), and other indices were calculated. The results showed that the concentration of HMs in the leaf and bark in ascending order is as Cd<Cu<Pb<Zn and Cd<Pb<Cu<Zn, respectively. The EF results indicated that the main origin of all measured HMs except Zn is anthropogenic sources. Also, the principal component analysis (PCA) and spatial distribution proved that the concentration of HMs is mainly originated from the traffic and other human activities. On the other hand, the results RI presented that the majority of locations sampled in the study area was exposed to serious ecological risk in terms of surveyed HMs. The leaf and bark of U. carpinifolia can be applied as bio-indicators of the presence of heavy metals in the ambient air and ecological risk imposed by them.

This article reports for the first time a facile, green synthesis of 2D CuO nanoleaves (NLs) using the amino acid, namely aspartic acid, and NaOH by a microwave heating method. The amino acid acts as a complexing/capping agent in the synthesis of CuO NLs. This method resulted in the formation of self-assembled 2D CuO NLs with an average length and width of ~300–400 and ~50–82 nm, respectively. The as-synthesized 2D CuO NLs were built up from the primary CuO nanoparticles by oriented attachment growth mechanism. The CuO NLs were characterized by an X-ray diffraction (XRD) method, transmission electron microscopy (TEM), selected-area electron diffraction (SAED) pattern, and Fourier transform infrared spectroscopy (FT-IR). The optical properties were investigated using UV-visible spectroscopy. For the first time, rose bengal and eosin Y dyes were degraded photochemically by solar irradiation using CuO NLs as a photocatalyst. The synthesized CuO NLs act as an efficient photocatalyst in the degradation of rose bengal and eosin Y dye under direct sunlight. The degradation of both the dyes, namely rose bengal and eosin Y, took place within 120 and 45 min, respectively, using CuO NLs as a photocatalyst, whereas commercial CuO, SnO₂ quantum dots (QDs), and commercial SnO₂ took more than 120 and 45 min for the degradation of rose bengal and eosin Y, respectively. The synthesized CuO NLs showed a superior photocatalytic activity as compared to that of commercial CuO, SnO₂ QDs, and commercial SnO₂. The reusability of the CuO NLs as a photocatalyst in the degradation of dyes was investigated, and it was evident that the catalytic efficiency decreases to a small extent (5–6 %) after the fifth cycle of operation.