NMR study of the humification process during sewage sludge treatment

Humic acids, extracted from sludge at the biologic-mechanical sewage treatment plant in Jastrzebie Zdroj, have been investigated by means of (1)H, (13)C and (31)P NMR spectroscopy. Sludge samples for studies were taken from the primary settling tank, the nitrification chamber, the digestion chamber and the sludge drying beds. The (1)H NMR analysis of humic acid extracted from sludge at various stages of sewage treatment confirmed the presence of the functional groups that are characteristic for humic substances, and the analysis showed changes in their relative intensities. The (13)C NMR indicated that the aromatisation of the humic acid increased during sewage treatment. Moreover, the analysis of the (31)P NMR spectra allowed us to observe the changes in the phosphorus groups of the studied humic acids.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Cadmium stress alters gene expression of DNA mismatch repair related genes in Arabidopsis seedlings

Cadmium (Cd) is a non essential element, and is a widespread environmental pollutant. Exposure to Cd can result in a variety of adverse health effects in plant and humans. In the current study, Arabidopsis seedlings were used as a bio-indicator of Cd pollution. Seedlings were grown on MS media containing 0-6.0 mg L(-1) Cd for 18 days, and the gene expression patterns were used to link increased Cd exposure with progressive biological effects. Reduction of total soluble protein content in shoots of the Arabidopsis seedlings occurred with increase in Cd concentrations. For the gene expression patterns, seven genes known to be involved in cell division and DNA mismatch repair (MMR) system were investigated by semi-quantitative RT-PCR, and normalized using 18S rRNA gene expression. Expression of the proliferating cell nuclear antigen 2 (atPCNA 2), MutS 3 homolog (atMSH 3) and MutL1 homolog (atMLH1) genes in shoots of Arabidopsis was strongly induced by exposure to 0.75 mg L(-1) Cd, but were repressed by other Cd concentrations whereas exposure to 0.75-6 mg L(-1) of Cd resulted in a decreased expression of atPCNA1, atMSH 2, 6 and 7 genes independently of any observable biological effects, including survival, fresh weight and chlorophyll level of shoots. This work demonstrated that specific gene expression changes could serve as useful molecular biomarkers indicative of Cd exposure and related biological effects.     

Comparison of surface emissions and subsurface distribution of cis- and trans-1,3-dichloropropene and chloropicrin in sandy field beds covered with four different plastic films

The purpose of this study was to conduct a field study at a Florida field site on surface emissions and subsurface distribution of cis-and trans-1,3-dichloropropene (1,3-D) and chloropicrin (CP) in raised beds injected with Telone C35 with four replications. A total of 16 beds were applied with Telone C35 by chisel injection and covered with four different plastic films, 4 beds for each film. Each bed was installed with five 20-cm long soil pore air probes and a surface air collection pan at arbitrarily locations along the length of each bed for sampling soil pore air and surface air, respectively, for analysis of the three biologically active compounds, cis- and trans-1,3-D and CP. We found that average concentrations of the three compounds at 20-cm depth among the beds covered with four different plastic films generally were not statistically different. Among the four beds covered with the same plastic film, average concentrations of the three compounds were statistically different only in the four metallic PE covered beds at 5 and 24 hours after injection. Volatilization rates of the three compounds among the beds covered with four different plastic films, with the exception of CP at 48 hours after injection, were not statistically different. It appeared that initial upward diffusion and volatilization flux were influenced by solar radiation. Initial subsurface concentrations of the three compounds and volatilization flux, especially cis-1,3-D, were greater in the beds on the east side of the field than that in the beds on the west side of the field. Whether or not difference in initial subsurface concentrations of the compounds between east side beds and west side beds may influence fumigant efficacy remains to be determined.     

An evaluation of global QSAR models for the prediction of the toxicity of phenols to Tetrahymena pyriformis

This study presents an analysis of the ability of a two-parameter response surface, a multiple linear regression and a neural network model to produce global quantitative structure-activity relationships (QSARs) to predict the toxic potency of phenols to Tetrahymena pyriformis. The phenolic toxicity data set analysed is characterised by multiple mechanisms of toxic action. The study aimed to evaluate the confidence that can be applied to the modelling of the differing mechanisms of action. Assessment of confidence was decided in terms of whether the statistics for the global models reflect the ability of the QSARs to model the individual mechanisms of toxic action present in the data set. The results showed that the global statistics only reflected the ability of models to predict the two non-covalent mechanisms (polar narcosis and respiratory uncoupling), with the metabolically transformed and electrophilic mechanism (pre-electrophiles and soft electrophiles) being modelled poorly by all three model building methods. The results confirm the difficulty in modelling electrophilic mechanisms of toxic action. The results also highlight the fact that this poor predictivity is often 'hidden' in good statistical fit of some global models. In particular these results emphasise that for practical predictive purposes the mechanistic applicability domain is required to give confidence to estimated toxicity values.     

Assessment and management of urbanization-induced ecological risks

The urban ecological risk incurred during the processes of urbanization has been constantly accumulating, creating a severe challenge for China to achieve sustainable urban development. At present, research on systematic evaluation of urban ecological risks is still inadequate, especially at an urban ecosystem level. In this special issue, we use Xiamen City as an example to identify the sources and receptors of urban ecological risks, to develop a methodology system of urban ecological risk assessment, and to propose a method for the management of urban ecological risks. This special issue contains 11 research articles resulting from a comprehensive research project funded by China’s National Natural Science Foundation. The innovations reported in this special issue include a framework of urban ecological risk assessment and a standardized procedure for carrying out urban ecological risk assessment using multiple stressors and endpoints.     

Planning and implementing sustainability in higher education institutions: an overview of the difficulties and potentials

Planning in sustainable development is believed to be an important element in allowing higher education institutions to set their goals and to commit themselves towards undertaking concrete actions and measures at all levels in order to implement sustainability. Yet, there is a paucity of research that has looked at the extent to which planning can support institutions of higher education to assess their performances and to determine whether the set aims have been met. This research gap needs to be met to allow a better understanding of how planning can help to promote the integration of the three components of sustainable development – economic development, social development and environmental protection in higher education. This paper explores the challenges for planning the sustainable development in higher education, also outlining the potentials lessons learned that could assist in improving Education for Sustainable Development efforts in Higher Education Institutions. Among its main results are the fact that many universities wish to pursue sustainable development, but their efforts are hindered by lack of institutional support and planning and limited emphasis on approaches, such as problem-based learning. The universities that are engaged in the field have to face many problems, varying from limited resources to lack of trained staff. As a result, integrated approaches to sustainability become difficult to implement. Finally, the paper has identified the fact that many opportunities offered mainstream developments, such as the UN Declaration ‘The World we Want’ or the UN Sustainable Development Goals are not being put to full use.     

Minimizing opportunity costs to aquatic connectivity restoration while controlling an invasive species

Controlling invasive species is critical for conservation but can have unintended consequences for native species and divert resources away from other efforts. This dilemma occurs on a grand scale in the North American Great Lakes, where dams and culverts block tributary access to habitat of desirable fish species and are a lynchpin of long‐standing efforts to limit ecological damage inflicted by the invasive, parasitic sea lamprey (Petromyzon marinus). Habitat restoration and sea‐lamprey control create conflicting goals for managing aging infrastructure. We used optimization to minimize opportunity costs of habitat gains for 37 desirable migratory fishes that arose from restricting sea lamprey access (0–25% increase) when selecting barriers for removal under a limited budget (US$1–105 million). Imposing limits on sea lamprey habitat reduced gains in tributary access for desirable species by 15–50% relative to an unconstrained scenario. Additional investment to offset the effect of limiting sea‐lamprey access resulted in high opportunity costs for 30 of 37 species (e.g., an additional US$20–80 million for lake sturgeon [Acipenser fulvescens]) and often required ≥5% increase in sea‐lamprey access to identify barrier‐removal solutions adhering to the budget and limiting access. Narrowly distributed species exhibited the highest opportunity costs but benefited more at less cost when small increases in sea‐lamprey access were allowed. Our results illustrate the value of optimization in limiting opportunity costs when balancing invasion control against restoration benefits for diverse desirable species. Such trade‐off analyses are essential to the restoration of connectivity within fragmented rivers without unleashing invaders.     

A high resolution measurement of the morning ABL transition using distributed temperature sensing and an unmanned aircraft system

We used an unmanned aircraft system (UAS) to lift and suspend distributed temperature sensing (DTS) technologies to observe the onset of an early morning transition from stable to unstably stratified atmospheric conditions. DTS employs a fiber optic cable interrogated by laser light, and uses the temperature dependent Raman scattering phenomenon and the speed of light to obtain a discrete spatial measurement of the temperature along the cable. The UAS/DTS combination yielded observations of temperature in the lower atmosphere with high resolution (1 s and 0.1 m) and extent (85 m) that revealed the detailed processes that occurred over a single morning transition. The experimental site was selected on the basis of previous experiments and long term data records; which indicate that diurnal boundary layer development and wind sectors are predictable and consistent. The data showed a complex interplay of motions that occur during the morning transition that resulted in propagation and growth of unstable wave modes. We observed a rapid cooling of the air aloft (layer above the strong vertical temperature gradient) layer directly after sunrise due to vertical mixing followed by an erosion of the strong gradient at the stable layer top. Midway through the transition, unstable wave modes were observed that are consistent with Kelvin–Helmholtz motions. These motions became amplified through the later stages of the transition.