Oxidative degradation of ofloxacin (OFX) by sulfate free radicals (SO₄ ⁻•) in the UV/Oxone/Co²⁺oxidation process was investigated for the first time, with a special focus upon identifying the transformation products as well as understanding the reaction pathways. Thirteen main compounds were identified after the initial transformation of OFX; the detailed structural information of which were characterized by high-performance liquid chromatography–high resolution mass spectrometry and MS fragmentation analysis. The degradation pathways mainly encompassed ring openings at both the piperazinyl substituent and the quinolone moiety, indicating that the usage of SO₄ ⁻• aided the oxidative degradation of OFX to undergo more facile routes compared to those in previous reports by using OH•/h⁺ as the oxidant, where the initial transformation attacks were mainly confined to the piperazine moiety. Moreover, in this study, smart control over the pH conditions of the oxidation system via different modes of Oxone dosage resulted in the selective degradation of the functional sites of OFX molecule, where it was shown that the SO₄ ⁻•-driven destruction of the quinolone moiety of OFX molecule favored the neutral pH conditions. This would be beneficial for the reduction of bacterial resistance against quinolones in the aqueous environment.

Dissolved organic matter (DOM) affects arsenite [As(III)] toxicity by altering its sorption equilibrium at the cell wall interface. A better understanding of such mechanism is of great importance to assess As(III) ecotoxicity in aquatic systems. Batch experiments were conducted to study the effects of DOM on the regulation of As(III) sorption and toxicity in the diatom Navicula sp. The influence of humic acid (HA) on As(III) toxicity was assessed by measuring algal growth, chlorophyll a, and reactive oxygen species (ROS), whereas As(III) mobility across the cell wall was estimated by determining the concentration of intracellular, cell-wall-bound, and free As(III) ions in cell media. Results showed that the effects of HA on arsenite toxicity varied depending on various combinations of As(III)-HA concentrations. EC₅₀had an approximate threefold increase from 8.32 (HA-free control) to 22.39 μM (at 20 mg L⁻¹HA) when Navicula sp. was exposed to 1.0–100.0 μM of As(III), compared to an overall low complexation ratio of HA-As(III) in a range of 0.91–6.00 %. The cell wall-bound and intracellular arsenic content decreased by 19.8 and 20.3 %, respectively, despite the lower arsenite complexation (2.10 ± 0.16 % of the total As). Meanwhile, intracellular ROS was decreased by 12.6 % in response to 10.0 μM As(III) and 10 mg L⁻¹HA vs. the HA-free control. The significant contrast indicated that complexation alone could not explain the HA-induced reduction in arsenite toxicity and other factors including HA–cell surface interactions may come into play. Isotherms describing adsorption of HA to the Navicula sp. cells combined with morphological data by scanning electron microscopy revealed a protective HA floccule coating on the cell walls. Additional Fourier transform infrared spectroscopic data suggested the involvement of carboxylic groups during the adsorption of both HA and As(III) on the Navicula sp. cell surface. Collective data from this study suggest that cell wall-bound HA can moderate As(III) toxicity through the formation of a protective floccule coating occupying As(III) sorption sites and decreased effective functional groups capable of binding As(III). Our findings imply that As(III) toxicity can be alleviated due to the increased hindrance to cellular internalization of As(III) in the presence of naturally abundant DOM in water.

Iron-loaded mangosteen shell powder (Fe-MSP) was found as an effective heterogeneous Fenton catalyst for the treatment of stabilized landfill leachate. Sonolytically produced catalyst has higher efficiency than other catalysts. At the optimal conditions (pH 3, catalyst concentration of 1,750 mg/L and hydrogen peroxide concentration of 0.26 M), 81 % of the chemical oxygen demand (COD) was removed effectively from the landfill leachate. But, the efficiency of Fe-MSP was reduced in the first recycling due to the poisoning of active sites. A metal leaching study indicated that the degradation of the pollutant is mainly due to solid Fe ions present in Fe-MSP rather than the leached ferrous and ferric ions. Hydroxyl radical production in the system was confirmed by the Fenton oxidation of benzoic acid. Compared to the homogeneous Fenton process, the heterogeneous Fenton process using Fe-MSP had higher COD removal efficiency, indicating the practical applicability of the prepared catalyst.

The increasing usage and the persistence of polyester polyurethane (PU) generate significant sources of environmental pollution. The effective and environmental friendly bioremediation techniques for this refractory waste are in high demand. In this study, three novel PU degrading bacteria were isolated from farm soils and activated sludge. Based upon 16S ribosomal RNA gene sequence blast, their identities were determined. Particularly robust activity was observed in Pseudomonas putida; it spent 4 days to degrade 92 % of Impranil DLNᵀᴹfor supporting its growth. The optimum temperature and pH for DLN removal by P. putida were 25 °C and 8.4, respectively. The degradation and transformation of DLN investigated by Fourier transformed infrared spectroscopy show the decrease in ester functional group and the emergence of amide group. The polyurethanolytic activities were both presented in the extracellular fraction and in the cytosol. Esterase activity was detected in the cell lysate. A 45-kDa protein bearing polyurethanolytic activity was also detected in the extracellular medium. This study presented high PU degrading activity of P. putida and demonstrated its responsible enzymes during the PU degradation process, which could be applied in the bioremediation and management of plastic wastes.

This study is part of the Global Mercury Observation System (GMOS), a European FP7 project dedicated to the improvement and validation of mercury models to assist in establishing a global monitoring network and to support political decisions. One key question about the global mercury cycle is the efficiency of its removal out of the atmosphere into other environmental compartments. So far, the evaluation of modeled wet deposition of mercury was difficult because of a lack of long-term measurements of oxidized and elemental mercury. The oxidized mercury species gaseous oxidized mercury (GOM) and particle-bound mercury (PBM) which are found in the atmosphere in typical concentrations of a few to a few tens pg/m³are the relevant components for the wet deposition of mercury. In this study, the first European long-term dataset of speciated mercury taken at Waldhof/Germany was used to evaluate deposition fields modeled with the chemistry transport model (CTM) Community Multiscale Air Quality (CMAQ) and to analyze the influence of the governing parameters. The influence of the parameters precipitation and atmospheric concentration was evaluated using different input datasets for a variety of CMAQ simulations for the year 2009. It was found that on the basis of daily and weekly measurement data, the bias of modeled depositions could be explained by the bias of precipitation fields and atmospheric concentrations of GOM and PBM. A correction of the modeled wet deposition using observed daily precipitation increased the correlation, on average, from 0.17 to 0.78. An additional correction based on the daily average GOM and PBM concentration lead to a 50 % decrease of the model error for all CMAQ scenarios. Monthly deposition measurements were found to have a too low temporal resolution to adequately analyze model deficiencies in wet deposition processes due to the nonlinear nature of the scavenging process. Moreover, the general overestimation of atmospheric GOM by the CTM in combination with an underestimation of low precipitation events in the meteorological models lead to a good agreement of total annual wet deposition besides the large error in weekly deposition estimates. Moreover, it was found that the current speciation profiles for GOM emissions are the main factor for the overestimation of atmospheric GOM concentrations and might need to be revised in the future. The assumption of zero emissions of GOM lead to an improvement of the mean normalized bias for three-hourly observations of atmospheric GOM from 9.7 to 0.5, Furthermore, the diurnal correlation between model and observation increased from 0.01 to 0.64. This is a strong indicator that GOM is not directly emitted from primary sources but is mainly created by oxidation of GEM.

After reductions of fugitive and diffuse emissions by an industrial complex, a follow-up study was performed to determine the time variability of volatile organic compounds (VOCs) and the lifetime cancer risk (LCR). Passive samplers (3 M monitors) were placed outdoors (n = 179) and indoors (n = 75) in industrial, urban, and control areas for 4 weeks. Twenty-five compounds including n-alkanes, cycloalkanes, aromatics, chlorinated hydrocarbons, and terpenes were determined by GC/MS. The results show a significant decrease of all VOCs, especially in the industrial area and to a lesser extent in the urban area. The median outdoor concentration of benzene in the industrial area declined compared to the former study, around 85 % and about 50 % in the urban area, which in the past was strongly influenced by industrial emissions. Other carcinogenic compounds like styrene and tetrachloroethylene were reduced to approximately 60 %. VOC concentrations in control areas remained nearly unchanged. According to the determined BTEX ratios and interspecies correlations, in contrast to the previous study, traffic was identified as the main emission source in the urban and control areas and showed an increased influence in the industrial area. The LCR, calculated for benzene, styrene, and tetrachloroethylene, shows a decrease of one order of magnitude in accordance to the decreased total VOC concentrations and is now acceptable according to values proposed by the World Health Organization.

Applied research programs in the remediation of contaminated areas can be used also for gaining insights in the physiological and ecological mechanisms supporting the resistance of plant communities in stress conditions due to toxic elements. The research hypothesis of this study was that in the heavily contaminated but nutrient-poor substrate of mine tailing dams, the beneficial effect of inoculation with arbuscular mychorrizal fungi (AMF) is due to an improvement of phosphorus nutrition rather than to a reduction of toxic element transfer to plants. A concept model assuming a causal chain from root colonization to element uptake, oxidative stress variables, and overall plant development was used. The methodological novelty lies in coupling in a single research program experiments conducted at three scales: pot, lysimeter, and field plot, with different ages of plants at the sampling moment (six subsets of samples in all). The inoculation with AMF in expanded clay carrier had a beneficial effect on the development of plants in the amended tailing substrate heavily contaminated with toxic elements. The effect of inoculation was stronger when the quantity of expanded carrier was smaller (1 % vs. 7 % inoculum), probably because of changes in substrate features. The improvement of plant growth was due mainly to an improvement in phosphorus nutrition leading to an increase of protein concentration and decrease of oxidative stress enzyme activity (superoxide dismutase and peroxidase). In a single data subset, an effect of inoculation on the uptake of several toxic elements could be proved (decrease of As concentration in plant roots correlated with a decrease of oxidative stress independent from the effect of P concentration increase). The multi-scale approach allowed us to find differences between the patterns characterising the data subsets. These subset-specific patterns point out the existence of physiological differences between plants in different development states (as a result of sampling at different plant ages). From an applied perspective, conclusions are drawn with respect to the use of plants in the monitoring programs of contaminated areas and the use of inoculation with AMF in the remediation of tailing dams.

The novel Serratia proteamaculans isolated from a chromium-contaminated site was tolerant to a concentration of 500 mg Cr(VI)/l. The optimum pH and temperature for reduction of Cr(VI) by S. proteamaculans were found to be 7.0 and 30 °C, respectively. The Cr(VI) reduction rate decreased with the increase in Cr(VI) concentration from 100 to 400 mg/l, suggesting the enzymatic chromium reduction. Resting and permeabilised cell assays provided the better evidence that chromate reduction in S. proteamaculans is enzymatic. Reduction by cell-free filtrate shows no extracellular chromate-reducing activity, revealing that this activity may be associated to membrane fraction and/or cytosolic fraction. Assays conducted with cytosolic and particulate fraction of S. proteamaculans confirmed the role of membrane-bound proteins in Cr(VI) reduction. Furthermore, chromium reduced by heat-treated cells suggests that membrane-associated chromate reductase activity of S. proteamaculans is preceded by its adsorption on the cell surface.

A wet–dry deposition sampler was located at The Scientific and Technological Research Council of Turkey-National Metrology Institute (TUBITAK-UME) station, and a bulk deposition sampler was placed at the Kadıllı village to determine the atmospheric deposition flux of polycyclic aromatic hydrocarbons (PAHs) and pesticides (organochlorine and organophosphorus) in soluble fraction of samples in Kocaeli, Turkey. The 28 samples for each wet, dry, and total deposition were collected weekly from March 2006 to March 2007. Gas chromatography-tandem mass spectrometry was used to analyze the samples which were prepared by using solid-phase extraction (SPE) method. The sum of volume weighted mean of deposition fluxes was obtained as 7.43 μg m⁻² day⁻¹for wet deposition, 0.28 μg m⁻² day⁻¹for dry deposition and 0.54 μg m⁻² day⁻¹for bulk deposition samples for PAHs and 9.88 μg m⁻² day⁻¹for wet deposition, 4.49 μg m⁻² day⁻¹for dry deposition, and 3.29 μg m⁻² day⁻¹for bulk deposition samples for pesticides. While benzo(a)anthracene had the highest fluxes among PAH compounds for all types of depositions, guthion and phosphamidon had the highest deposition flux compared with the other pesticides. Benzo(ghi)perylene, dibenz(a,h)anthracene, indeno(1,2,3-c,d)pyrene, benzo(a)pyrene, and acenaphthene were not detected in any of the samples. Beta-HCH, gamma-HCH, and endrin aldehyde were the only compounds among 18 organochlorine pesticides to be detected in all deposition samples. The main sources of pesticides were the high number of greenhouses around the sampling stations. However, all of the organophosphorus pesticides were detected in all deposition samples. The pollution sources were identified as coal and natural gas combustion, petrogenic sources, and traffic for TUBITAK-UME station whereas coal and natural gas combustion and traffic were the main sources for Kadıllı station by considering the results of factor analysis, ratios, and wind sector analysis.

The degradation of Romandolide® ([1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxycarbonyl] methyl propanoate), a synthetic alicyclic musk, by activated sludge inocula was investigated using both the manometric respirometry test OECD 301F and the CO₂evolution test. In addition to measuring its biodegradability, key steps of the upper part of the metabolic pathway responsible for Romandolide® degradation were identified using extracts at different time points of incubation. Early metabolism of Romandolide® yielded ester hydrolysis products, including Cyclademol® (1-(3,3-dimethylcyclohexyl)ethanol). The principal metabolites after 31 days were identified as 3,3-dimethyl cyclohexanone and 3,3-dimethyl cyclohexyl acetate. Formation of 3,3-dimethyl cyclohexanone from Cyclademol® by sludge was confirmed in subsequent experiments using Cyclademol® as a substrate, indicating the involvement of an oxygen insertion reminiscent of a Baeyer–Villiger oxidation. Further mineralization of 3,3-dimethyl cyclohexanone was also confirmed in subsequent studies. Three steps were thus required for complete biodegradation of the alicyclic musk: (1) successive ester hydrolyses leading to the formation of Cyclademol® with concomitant degradation of the resulting acids, (2) conversion of Cyclademol® into 3,3-dimethyl cyclohexanone, and (3) further mineralization via ring cleavage.