Degradation of picric acid and 2,6-DNT in marine sediments and waters: the role of microbial activity and ultra-violet exposure

Bio- and photo-transformation of two munitions and explosives of concern, 2,6-dinitrotoluene (2,6-DNT) and 2,4,6-trinitrophenol (picric acid) were assessed in spiked marine sediments and water. A sandy and a fine-grained sediment, with 0.25% and 1.1% total organic carbon, respectively, were used for biotransformation assessments at 10 and 20 degrees C. Sterilized sediments were used as controls for biotic vs. abiotic transformation. Transformation products were analyzed by HPLC, GC/MS and LC/MS. Biotransformation in sediments started soon after the initial contact of the chemicals with the sediments and proceeded for several months, with rates in the following sequence: fine-grain at 20 degrees C > fine-grain at 10 degrees C > sand at 20 degrees C > sand at 10 degrees C. The biotransformation paths seemed to be similar for all conditions. The major biotransformation product of 2,6-DNT was 2-amino-6-nitrotoluene (2-A-6-NT). 2-Nitrotoluene (2-NT) and other minor components, including N,N-dimethyl-3-nitroaniline, benzene nitrile, methylamino-2-nitrosophenol and diaminophenol, were also identified. After more prolonged incubation these chemicals were replaced by high molecular weight polymers. Several breakdown products of picric acid were identified by GC/MS, including 2,4-dinitrophenol, amino dinitrophenols, 3,4-diamino phenol, amino nitrophenol and nitro diaminophenol. Photo-transformation of 2,6-DNT and picric acid in seawater was assessed under simulated solar radiation (SSR). No significant photolysis of picric acid in seawater was observed for up to 47 days, but photo-transformation of 2,6-DNT began soon after the initial exposure to SSR, with 89% being photo-transformed in 24 h and none remaining after 72 h. High molecular weight chemicals were generated, with mass spectra ranging from molecular weight 200-500 compared to 182 for DNT, and the color of the stock solution changed from clear to orange. Complexity of the mass spectra and mass differences among fragments suggest that multiple polymers were produced and were co-eluting during the LC/MS analyses.     

Use of 15N-depleted artificial compost in bound residue studies

Association of bound residues to soil humic matter may be accomplished by different binding mechanisms such as sequestration in hydrophobic interiors of the organic material or covalent linkage to the organic matter. The structures and chemical environments of compounds can be observed by NMR spectroscopy. We applied 15N-NMR spectroscopy to study the soil-bound residues of 15N-labeled simazine. As the 15N-isotope has a low sensitivity and natural abundance 15N-NMR experiments require long measurement times and often result in low signal-to-noise (S/N) ratios. Therefore, in addition to the use of 15N-labeled simazine, 15N-depleted compost was used to reduce the amount of background signal and enhance the sensitivity. The compost was produced from maize and wheat plants grown on sand with 15N-depleted NH4NO3 as sole nitrogen source. The plants were freeze-dried, ground and mixed with sand for composting. After a composting period of 224 days analysis of the compost revealed a 15N-content of 267 ppm as opposed to a natural abundance of 3650 ppm. Characterization of this artificial compost produced parameter values similar to those of a natural compost. The 13C-NMR-spectra of the humic and fulvic acids during different stages of maturity showed that there was a shift from single-bond functional groups to more complex double-bond and aromatic structures. Experiments with this compost showed an increased signal intensity. The improved sensitivity made it possible to obtain interpretable NMR signals in contrast to experiments with 15N-simazine on native soil where no signals were detectable. The data indicated that the bound residues of simazine are composed of metabolites resulting from N-dealkylation and triazine ring destruction. Silylation of the bound residues showed a very strong binding of the residues to the matrix as only a small fraction could be solubilized.     

Biomonitoring of persistent organochlorine pesticides, PCDD/PCDFs and dioxin-like PCBs in blood of children from South West Germany (Baden-Wuerttemberg) from 1993 to 2003

In the context of a monitoring program, persistent organic pollutants (POPs) were quantified in the blood of 10 year old children at four different demographic regions in Baden-Wuerttemberg, a highly industrialised federal state in South West Germany. DDE, HCB, PCB 138, PCB 153 and PCB 180 were measured in 1996/1997, 1998/1999, 2000/2001 and 2002/2003 in individual samples of about 400 children per year. PCDD/PCDFs and some relevant coplanar PCBs were determined in pooled samples from children in seven cycles from 1993 to 2003. Blood concentrations of the investigated compounds decreased in that time period by a factor of 2-4 with the exception of most PCDFs. The concentrations of POPs in the blood of the children were distinctly lower than the concentrations reported for adults. Breast feeding was associated with about 30% higher median concentrations of DDE, HCB, PCBs and a 30% increase for mean PCDD/PCDF concentrations. Concerning demographic differences, significant lower concentrations of HCB, PCBs and PCDD/PCDFs could be seen in children from Mannheim compared to the region of Aulendorf. About 10-20% higher concentrations were found in boys compared to girls for HCB, indicator PCBs and PCDD/PCDFs. The pattern of non-ortho and mono-ortho PCBs in the blood of children was similar to the pattern reported for mother's milk, and PCB 126 and PCB 156 contributed about 70% to the toxicity of dioxin-like PCBs and about one-third to total TEQ including PCDD/PCDFs.     

Poliovirus and Other Enteroviruses from Environmental Surveillance in Italy, 2009–2015

Within the initiatives for poliomyelitis eradication by WHO, Italy activated an environmental surveillance (ES) in 2005. ES complements clinical Acute Flaccid Paralysis (AFP) surveillance for possible polio cases, detects poliovirus circulation in environmental sewage, and is used to monitor transmission in communities. In addition to polioviruses, the analyses comprised: (i) the monitoring of the presence of non-polio enteroviruses in sewage samples and (ii) the temporal and geographical distribution of the detected viruses. From 2009 to 2015, 2880 sewage samples were collected from eight cities participating in the surveillance. Overall, 1479 samples resulted positive for enteroviruses. No wild-type polioviruses were found, although four Sabin-like polioviruses were detected. The low degree of mutation found in the genomes of these four isolates suggests that these viruses have had a limited circulation in the population. All non-polio enteroviruses belonged to species B and the most frequent serotype was CV-B5, followed by CV-B4, E-11, E-6, E-7, CV-B3, and CV-B2. Variations in the frequency of different serotypes were also observed in different seasons and/or Italian areas. Environmental surveillance in Italy, as part of the ‘WHO global polio eradication program’, is a powerful tool to augment the polio surveillance and to investigate the silent circulation or the re-emergence of enteroviruses in the population.     

Large-Scale Survey of Human Enteroviruses in Wastewater Treatment Plants of a Metropolitan Area of Southern Italy

Human enteroviruses (HEVs) occur in high concentrations in wastewater and can contaminate receiving environmental waters, constituting a major cause of acute waterborne disease worldwide. In this study, we investigated the relative abundance, occurrence, and seasonal distribution of polio and other enteroviruses at three wastewater treatment plants (WWTPs) in Naples, Southern Italy, from January 2010 to December 2014. Influent and effluent samples from the three WWTPs were collected monthly. One hundred and sixty-one of the 731 wastewater samples collected (22.0%) before and after water treatment were CPE positive on RD cells; while no samples were positive on L20B cells from any WWTPs. Among the 140 non-polio enterovirus isolated from inlet sewage, 69.3% were Coxsackieviruses type B and 30.7% were Echoviruses. Among these, CVB3 and CVB5 were most prevalent, followed by CVB4 and Echo6. The twenty-one samples tested after treatment contained 6 CVB4, 5 CVB3, 3 Echo11, and 2 Echo6; while other serotypes were isolated less frequently. Data on viral detection in treated effluents of WWTPs confirmed the potential environmental contamination by HEVs and could be useful to establish standards for policies on wastewater management.     

Comparison of ordinary and lognormal kriging on skewed data of total cadmium in forest soils of Sweden

Spatial statistical analysis of georeferenced data of total cadmium (TCd) in forest soils of Sweden was assumed to providemore advantageous maps than traditional interpolated maps. However, 264 measurements of TCd in O-horizon of forest soils displayed skewed frequency distribution. Since atypicalobservations affect badly the variogram, outliers wereidentified, different data transformations were tested andordinary (OK) and lognormal kriging (LK) scenarios werecompared based on cross-validation. Results were comparedusing overall measures of predictors, e.g. traditionalmean squared prediction error (MSPE), mean of krigingvariances, variance ratio, median of internallystandardised residuals, and assessments of classificationaccuracy, such as percentage of correctly predictedsamples and within-class MSPE.One outlier was identified based on the absolute value of skewness of value differences less or equal to one in data pairs separated at certain lag classes. Mapping categories characterised by percentage of correct classification and within-class MSPE were found to be essential in comparison of kriging results additionally to the overall measures. In comparison of kriging methods, OK predicted high values moreaccurately and LK was more effective to predict low and mediumvalues. Thus, OK was suggested for mapping high concentration of TCd and other pollutants. Percentage of correctly predictedsamples and within-class MSPE were found to be dependent on kriging method, as well as on the number and limits of categories.     

Biotic landfill cover treatments for mitigating methane emissions

Landfill methane (CH₄) emissions have been cited as one ofthe anthropogenic gas releases that can and should be controlledto reduce global climate change. This article reviews recent research that identifies ways to enhance microbial consumptionof the gas in the aerobic portion of a landfill cover. Use of these methods can augment CH₄ emission reductions achievedby gas collection or provide a sole means to consume CH₄ atsmall landfills that do not have active gas collection systems.Field studies indicate that high levels of CH₄ removal can be achieved by optimizing natural soil microbial processes. Further, during biotic conversion, not all of the CH₄ carbonis converted to carbon dioxide (CO₂) gas and released to theatmosphere; some of it will be sequestered in microbial biomass.Because biotic covers can employ residuals from other municipalprocesses, financial benefits can also accrue from avoided costsfor residuals disposal.     

Evaluation of biodegradability of poly(ε-caprolactone)/poly(ethylene terephthalate) blends

The results of an investigation aimed at evaluation of the biodegradability of blends of poly(-caprolactone) (PCL) with poly(ethylene terephthalate) (PET) as the major component are reported. Specimens of the blends, as melt extruded films and/or powders, were submitted to degradation tests under different environmental conditions including full-scale composting, soil burial, bench-scale accelerated aerobic degradation, and exposure to axenic cultures and esterolytic enzymes. Indications have been gained that blending in the melt gives rise to insertion of PCL segments in the PET chain. Copolymers thus attained acted as macromolecular compatibilizers, allowing for a complete miscibility of PCL and PET. The biodegradation detected on the blend samples was, however, well below the values expected from chemical composition and behavior of individual homopolymers under the same environmental conditions. The presence of PET as the major component in PET/PCL blends apparently reduces the propensity of PCL to be degraded, at least in the investigated composition range. The degradation data collected under different environmental conditions indicate that the full-scale composting system is the most efficient among the tested degradation procedures.     

ESTIMATED IMPACTS OF CLIMATE WARMING ON CALIFORNIA WATER AVAILABILITY UNDER TWELVE FUTURE CLIMATE SCENARIOS1

Spatially disaggregated estimates of over 131 stream‐flow, ground water, and reservoir evaporation monthly time series in California have been created for 12 different climate warming scenarios for a 72‐year period. Such disaggregated hydrologic estimates of multiple hydrologic cycle components are important for impact and adaptation studies of California's water system. A statewide trend of increased winter and spring runoff and decreased summer runoff is identified. Without operations modeling, approximate changes in water availability are estimated for each scenario. Even most scenarios with increased precipitation result in less available water because of the current storage systems' inability to catch increased winter streamflow in compensation for reduced summer runoff. The water availability changes are then compared with estimated changes in urban and agricultural water uses in California between now and 2100. The methods used in this study are relatively simple, but the results are qualitatively consistent with other studies focusing on the hydrologies of single basins or surface water alone.     

Inspiring England's urban fringes: multi-functionality and planning

The urban fringe has been described as 'planning's last frontier'; a zone of transition and interface between town and country where a broad variety of land uses and activities come together, and where development pressure is often intense.

In this paper, we argue that the urban fringe possesses special characteristics, making it more than simply a transitional landscape. These characteristics centre on patterns of land use, biodiversity and leisure/development opportunity which are unique to the urban edge and to land extending away from built-up areas. The uniqueness, diversity and particular dynamics of the urban fringe demands a special brand of planning and management response. Therefore we suggest that the principle of 'multi-functionality' provides a framework for action, showing how diversity can be managed and supported. Through brief case studies, we demonstrate how functional interactions at the urban fringe might be promoted in the future.