Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium enriched from mangrove sediments

The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase microextraction (SPME) combining with gas chromatography–mass spectrometry (GC–MS) method. Seventeen metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene, methyl ester, and phthalic acid were found. The detection of various common and novel metabolites demonstrates that SPME combining with GC–MS is a quick and convenient method for identification as well as monitoring the real time changes of metabolite concentrations throughout the degradation processes. The knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.     

Copper complexation by tannic acid in aqueous solution

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon (OC)/l was investigated in a nine-step titration experiment (Cu/OC molar ratio = 0.0030–0.0567). We differentiated between soluble and insoluble Cu species by 0.45 μm filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations (‘free’ Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (>0.45 μm) was the dominant Cu species for Cu/OC = 0.0030–0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 × 10⁻⁶– 5.58 × 10⁻⁶ cm² s⁻¹).     

Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have been globally detected in impacted natural waters. The detection of trace quantities of EDCs and PPCPs in the environment is of great concern since some of these compounds have known physiological responses at low concentrations. EDCs can have a wide range of polarities, acidic and basic moieties, and exist in trace quantities, which often requires numerous complex extractions, large sample collection volumes, and multiple instrumental analyses. A comprehensive method has been developed allowing for the analysis of 58 potential EDCs in various water matrices using a single solid-phase extraction (SPE) of a 1 L sample with subsequent analyses using both gas chromatography and liquid chromatography, each coupled with tandem mass spectrometry (GC–MS/MS and LC–MS/MS). Instrument detection limits ranged between 0.12–7.5 pg with corresponding method reporting limits of 1–10 ng l⁻¹ in water. Recoveries for most compounds were between 50% and 112% with good reproducibility (RSD 6–22%).     

Rapid degradation of butachlor in wheat rhizosphere soil

The degradative characteristics of butachlor in non-rhizosphere, wheat rhizosphere, and inoculated rhizosphere soils were measured. The rate constants for the degradation of butachlor in non-rhizosphere, rhizosphere, and inoculated rhizosphere soils were measured to be 0.0385, 0.0902, 0.1091 at 1 mg/kg, 0.0348, 0.0629, 0.2355 at 10 mg/kg, and 0.0299, 0.0386, 0.0642 at 100 mg/kg, respectively. The corresponding half-lives for butachlor in the soils were calculated to be 18.0, 7.7, 6.3 days at 1 mg/kg, 19.9, 11.0, 2.9 days at 10 mg/kg, and 23.2, 18.0, 10.8 days at 100 mg/kg, respectively. The experimental results show that the degradation of butachlor can be enhanced greatly in wheat rhizosphere, and especially in the rhizosphere inoculated with the bacterial community designated HD which is capable of degrading butachlor. It could be concluded that rhizosphere soil inoculated with microorganisms-degrading target herbicides is a useful pathway to achieve rapid degradation of the herbicides in soil.     

Modeling coupled interactions of carbon,water, and ozone exchange between terrestrial ecosystems and the atmosphere. I: model description

A new biophysical model (FORFLUX) is presented to study the simultaneous exchange of ozone, carbon dioxide, and water vapor between terrestrial ecosystems and the atmosphere. The model mechanistically couples all major processes controlling ecosystem flows trace gases and water implementing recent concepts in plant eco-physiology, micrometeorology, and soil hydrology. FORFLUX consists of four interconnected modules-a leaf photosynthesis model, a canopy flux model, a soil heat-, water- and CO2- transport model, and a snow pack model. Photosynthesis, water-vapor flux and ozone uptake at the leaf level are computed by the LEAFC3 sub-model. The canopy module scales leaf responses to a stand level by numerical integration of the LEAFC3model over canopy leaf area index (LAI). The integration takes into account (1) radiative transfer inside the canopy, (2) variation of foliage photosynthetic capacity with canopy depth, (3) wind speed attenuation throughout the canopy, and (4) rainfall interception by foliage elements. The soil module uses principles of the diffusion theory to predict temperature and moisture dynamics within the soil column, evaporation, and CO2 efflux from soil. The effect of soil heterogeneity on field-scale fluxes is simulated employing the Bresler-Dagan stochastic concept. The accumulation and melt of snow on the ground is predicted using an explicit energy balance approach. Ozone deposition is modeled as a sum of three fluxes- ozone uptake via plant stomata, deposition to non-transpiring plant surfaces, and ozone flux into the ground. All biophysical interactions are computed hourly while model projections are made at either hourly or daily time step. FORFLUX represents a comprehensive approach to studying ozone deposition and its link to carbon and water cycles in terrestrial ecosystems.     

The influence of untreated wastewater to aquatic communities in the Balatuin River,The Philippines

A risk assessment of chemical constituents in rivers that receive untreated wastewater should take into account the adverse effects of increased biological oxygen demand (BOD), ammonia and reduced dissolved oxygen (DO). This concept was tested via a field study in the Balatuin River, The Philippines, where the influence of physical and chemical factors, including the consumer product chemical linear alkylbenezene sulfonate (LAS), to aquatic communities (algae, invertebrates, fish) was determined. Periphytic algae were found to be insensitive to high BOD (>10 mg/l) and ammonia (>0.01 mg unionized NH(3)/l), concentrations from organically enriched untreated wastewater discharges. However, taxa richness and abundance of macroinvertebrates were influenced greatly by the discharges. Where BOD and ammonia concentrations were elevated, the dominant taxa were oligochaete worms and chironominds. Fish and crustaceans (freshwater crabs and prawns) were found only in sites with the least BOD concentrations (furthest upstream and downstream). The maximum concentration of LAS (0.122 mg/l) was less than that expected to affect 5% of taxa (0.245 mg/l), whereas exceedences of DO and ammonia criteria were observed in several sites. The lack of recovery observed was attributed to influences of low DO, high ammonia and poor colonization from upstream and downstream reaches due to organically-enriched discharges     

Monitoring the impact of sulphur with the Austrian Bioindicator Grid

In Austria, the impact of sulphur has been assessed since 1985 with the help of the Austrian Bioindicator Grid on 760 sample plots with Picea abies as the main tree species (90%). The annual sampling allows a precise evaluation of the temporal and regional development of the impact of sulphur on the basis of legal standards. Despite the reduction of SO2 emissions in Austria, the legal standard is still exceeded on 8% of the plots. These plots are mainly located near large Austrian emittors, but also in areas affected by transboundary sulphur emissions from neighbouring countries. The present paper describes how the Bioindicator Grid can be applied for the control of legal requirements to enact effective clean air measures in Austria and take supportive measures that reduce the impact of sulphur from emittors in neighbouring countries.     

Pressurized liquid extraction of six tetracyclines from agricultural soils

Veterinary antibiotics used in agriculture can be introduced into the environment through land application of animal manure, accumulating in soils and groundwaters and posing a significant risk to human health and animal well-being. As the analysis of tetracyclines in soil is challenging due to their strong interaction with soil minerals and organic carbon, the objective of this study was to develop a reliable and reproducible method for quantitative analysis of chlortetracycline and oxytetracycline, and their respective metabolites in soils. A method based on pressurized liquid extraction (PLE) with in-cell clean-up was developed for the extraction of chlortetracycline and oxytetracycline and four likely metabolites from a set of four soils. Optimized conditions included a cell size of 22?mL, soil loading of 5?g, pH of 8.0, methanol:water ratio of 3:1, 50?°C, and two cycles. Soil extracts were analysed by high-performance liquid chromatography (HPLC) coupled with ion trap mass spectrometry (MS). Recoveries of seven tetracyclines from soil ranged from 41% to 110%. The limits of detection for tetracyclines were 0.08–0.3 µg g^?1 soil, and intra- and inter-day variation ranged from 0.12–0.34%. The proposed PLE method is suitable for quantification of tetracyclines in agricultural soils at typical concentrations expected in contaminated environments.     

Trace elements and microbiological parameters in farmed Nile tilapia with emphasis on muscle,water, sediment and feed

Fish may bioaccumulate contaminants from the aquatic environment and extend them to the food chain provoking risks to human health. This study evaluated the microbiological parameters of the pond´s water and trace elements concentrations in samples of water, sediment, feed and muscle of farmed Nile tilapia used for human consumption in southern Brazil. A total of 240 fish were collected from 12 tilapia farms. Sediment, tank water and dry ration used in the animals' diet were collected for analysis. Analysis were performed by Energy Dispersion X-ray Fluorescence (EDXRF), Inductively Coupled Plasma Mass Spectrometer (ICP-MS), Induced Coupled Plasma Optical Emission Spectrometer (ICP-OES), and Atomic Absorption Spectrometer (AAS-VGA). In addition, the microbiological analysis of the water was carried out. The concentrations of Se, I, Fe, Cu and Zn in fish muscle were higher than the recommended by the Brazilian legislation, considering the advised daily intake for adults. The arsenic element had concentrations above the limit stipulated by the present Brazilian legislation, observed in all samples of muscle, sediment and tank water highlighting a possible environmental and fish contamination by the toxic element. Moreover, the arsenic concentration in the water presented a positive correlation (ρ?=?0.33) with arsenic in the muscle, suggesting that tilapia is a good environmental bioindicator, once they properly reflect the levels of arsenic in the water. It is suggested to perform an arsenic speciation for quantification of the inorganic form and accurate assessment of the degree of toxicity in the muscle samples and risks it can bring to human health. Regarding the other potentially toxic elements (Hg, Pb and Cd), and microbiological analysis of water it was verified that the consumption of the fish in question does not raise risks, since the values are within a quality benchmark established by law. The concentration of total and fecal coliforms in pond´s water in the facilities was in agreement with the microbiological indexes required by the legislation of CONAMA class II. Western region presented the lowest concentrations of fecal coliforms when compared to the other regions. There was no significant difference in the microbiological counts of total heterotrophic bacteria, Vibrio spp. and Pseudomonas spp. among the regions.     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.