Improvements in the two-dimensional nuclear magnetic resonance spectroscopy of humic substances

Understanding pollutant sorption, bioremediation of these pollutants, and their interactions with humic substances requires knowledge of molecular-level processes. New developments with nuclear magnetic resonance (NMR) experiments and labeled compounds have improved the overall understanding of these mechanisms. The advancements made with two-dimensional NMR show great promise, as structural information and hydrogen-carbon bond connectivity can be discerned. This communication presents the application of improved two-dimensional NMR methods, the double quantum filtered (DQF) correlation spectroscopy (COSY) and echo/anti-echo heteronuclear single quantum coherence (HSQC) experiments, for use in structural studies of humic substances. Both experiments were found to produce significant improvements over the conventional COSY and heteronuclear multiple quantum coherence (HMQC) experiments that have been previously employed in similar studies. The more sensitive echo/anti-echo HSQC experiment produced more cross-peaks with higher resolution when compared with the HMQC spectra. The DQF-COSY significantly suppressed the diagonal signals and allowed numerous signals previously hidden in the standard COSY experiment to be observed. These improvements will aid current characterization strategies of humic substances from soils, sediments, and water and their subsequent reactions with pollutants and microorganisms.     

Heterozygosity‐Fitness Correlations and Inbreeding Depression in Two Critically Endangered Mammals

The relation among inbreeding, heterozygosity, and fitness has been studied primarily among outbred populations, and little is known about these phenomena in endangered populations. Most researchers conclude that the relation between coefficient of inbreeding estimated from pedigrees and fitness traits (inbreeding‐fitness correlations) better reflects inbreeding depression than the relation between marker heterozygosity and fitness traits (heterozygosity‐fitness correlations). However, it has been suggested recently that heterozygosity‐fitness correlations should only be expected when inbreeding generates extensive identity disequilibrium (correlations in heterozygosity and homozygosity across loci throughout the genome). We tested this hypothesis in Mohor gazelle (Gazella dama mhorr) and Iberian lynx (Lynx pardinus). For Mohor gazelle, we calculated the inbreeding coefficient and measured heterozygosity at 17 microsatellite loci. For Iberian lynx, we measured heterozygosity at 36 microsatellite loci. In both species we estimated semen quality, a phenotypic trait directly related to fitness that is controlled by many loci and is affected by inbreeding depression. Both species showed evidence of extensive identity disequilibrium, and in both species heterozygosity was associated with semen quality. In the Iberian lynx the low proportion of normal sperm associated with low levels of heterozygosity was so extreme that it is likely to limit the fertility of males. In Mohor gazelle, although heterozygosity was associated with semen quality, inbreeding coefficient was not. This result suggests that when coefficient of inbreeding is calculated on the basis of a genealogy that begins after a long history of inbreeding, the coefficient of inbreeding fails to capture previous demographic information because it is a poor estimator of accumulated individual inbreeding. We conclude that among highly endangered species with extensive identity disequilibrium, examination of heterozygosity‐fitness correlations may be an effective way to detect inbreeding depression, whereas inbreeding‐fitness correlations may be poor indicators of inbreeding depression if the pedigree does not accurately reflect the history of inbreeding. Correlaciones Heterocigosidad‐ Adaptabilidad y Depresión Endogámica en Dos Especies de Mamíferos Críticamente en Peligro     

New aspect in seagrass acclimation: leaf mechanical properties vary spatially and seasonally in the temperate species Cymodocea nodosa Ucria (Ascherson)

Seagrasses may acclimate to environmental heterogeneity through phenotypic plasticity. In contrast to leaf morphology, which has been a central point in seagrass acclimation studies, plasticity in leaf biomechanics and fibre content is poorly understood, despite being crucial in plant ecological performance, especially regarding physical forces. We hypothesised that mechanical traits (e.g. breaking force, strength, toughness, and stiffness) and fibre content of seagrass leaves vary as morphology does under differential environments. Cymodocea nodosa was seasonally monitored at three locations around Cádiz Bay (southern Spain) with hydrodynamic regime as the most noticeable difference between them. Leaves showed plasticity in both morphology and mechanical traits, with wave-exposed individuals presenting short but extensible and tough leaves. Leaf fibre content was invariant along the year and with little spatial variability. Cross-sectional area rather than material properties or fibre content differentiates leaf mechanical resistance. Seagrass capacity to thrive under a range of mechanical forces may be dictated by their plasticity in morpho-biomechanical traits, a key element for the hydrodynamical performance and, hence, for species colonisation and distribution.     

Vacuum promotes metabolic shifts and increases biogenic hydrogen production in dark fermentation systems

The successful operation of any type of hydrogen-producing bioreactor depends on the performance of the microorganisms present in the system. Both substrate and partial gas pressures are crucial factors affecting dark fermentation metabolic pathways. The main objective of this study was to evaluate the impact of both factors on hydrogen production using anaerobic granular sludge as inoculum and, secondly, to study the metabolic shifts of an anaerobic community subjected to low partial gas pressures. With this goal in mind, seven different wastewater (four synthetic media, two industrial wastewater, and one domestic effluent) and the effect of applying vacuum on the systems were analyzed. The application of vacuum promoted an increase in the diversity of hydrogenproducing bacteria, such as Clostridium, and promoted the dominance of acetoclastic- over hydrogenotrophic methanogens. The application of different media promoted a wide variety of metabolic pathways. Nevertheless, reduction of the hydrogen partial pressure by application of vacuum lead to further oxidation of reaction intermediates irrespective of the medium used, which resulted in higher hydrogen and methane production, and improved the COD removal. Interestingly, vacuum greatly promoted biogenic hydrogen production from a real wastewater, which opens possibilities for future application of dark fermentation systems to enhance biohydrogen yields.     

Transport of simazine in unsaturated sandy soil and predictions of its leaching under hypothetical field conditions

The potential contamination of groundwater by herbicides is often controlled by processes in the vadose zone, through which herbicides travel before entering groundwater. In the vadose zone, both physical and chemical processes affect the fate and transport of herbicides, therefore it is important to represent these processes by mathematical models to predict contaminant movement. To simulate the movement of simazine, a herbicide commonly used in Chilean vineyards, batch and miscible displacement column experiments were performed on a disturbed sandy soil to quantify the primary parameters and processes of simazine transport. Chloride (Cl(-)) was used as a non-reactive tracer, and simazine as the reactive tracer. The Hydrus-1D model was used to estimate the parameters by inversion from the breakthrough curves of the columns and to evaluate the potential groundwater contamination in a sandy soil from the Casablanca Valley, Chile. The two-site, chemical non-equilibrium model was observed to best represent the experimental results of the miscible displacement experiments in laboratory soil columns. Predictions of transport under hypothetical field conditions using the same soil from the column experiments were made for 40 years by applying herbicide during the first 20 years, and then halting the application and considering different rates of groundwater recharge. For recharge rates smaller than 84 mm year(-1), the predicted concentration of simazine at a depth of 1 m is below the U.S. EPA's maximum contaminant levels (4 microg L(-1)). After eight years of application at a groundwater recharge rate of 180 mm year(-1) (approximately 50% of the annual rainfall), simazine was found to reach the groundwater (located at 1 m depth) at a higher concentration (more than 40 microg L(-1)) than the existing guidelines in the USA and Europe.     

Photocatalytic degradation of five sulfonylurea herbicides in aqueous semiconductor suspensions under natural sunlight

In the present study, the photocatalytic degradation of five sulfonylurea herbicides (chlorsulfuron, flazasulfuron, nicosulfuron, sulfosulfuron and triasulfuron) has been investigated in aqueous suspensions of zinc oxide (ZnO), tungsten (VI) oxide (WO₃), tin (IV) oxide (SnO₂) and zinc sulfide (ZnS) at pilot plant scale under natural sunlight. Photocatalytic experiments, especially those involving ZnO photocatalysis, showed that the addition of semiconductors in tandem with the oxidant (Na₂S₂O₈) strongly enhances the degradation rate of the herbicides in comparisons carried out with photolytic tests. The degradation of the herbicides follows a first order kinetics according to the Langmuir-Hinshelwood model. In our conditions, the amount of time required for 50% of the initial pesticide concentration to dissipate (t_½) ranged from 8 to 27 min (t_30W = 0.3-1.2 min) for sulfosulfuron and chlorsulfuron, respectively in the ZnO/Na₂S₂O₈ system. None of the studied herbicides was found after 120 min of illumination (except chlorsulfuron, 0.2 μg L⁻¹).     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

Polymer biodegradation: mechanisms and estimation techniques

Within the frame of the sustainable development, new materials are being conceived in order to increase their biodegradability properties. Biodegradation is considered to take place throughout three stages: biodeterioration, biofragmentation and assimilation, without neglect the participation of abiotic factors. However, most of the techniques used by researchers in this area are inadequate to provide evidence of the final stage: assimilation. In this review, we describe the different stages of biodegradation and we state several techniques used by some authors working in this domain. Validate assimilation (including mineralisation) is an important aspect to guarantee the real biodegradability of items of consumption (in particular friendly environmental new materials). The aim of this review is to emphasise the importance of measure as well as possible, the last stage of the biodegradation, in order to certify the integration of new materials into the biogeochemical cycles. Finally, we give a perspective to use the natural labelling of stable isotopes in the environment, by means of a new methodology based on the isotopic fractionation to validate assimilation by microorganisms.     

Ecological literacy and beyond: Problem-based learning for future professionals

Ecological science contributes to solving a broad range of environmental problems. However, lack of ecological literacy in practice often limits application of this knowledge. In this paper, we highlight a critical but often overlooked demand on ecological literacy: to enable professionals of various careers to apply scientific knowledge when faced with environmental problems. Current university courses on ecology often fail to persuade students that ecological science provides important tools for environmental problem solving. We propose problem-based learning to improve the understanding of ecological science and its usefulness for real-world environmental issues that professionals in careers as diverse as engineering, public health, architecture, social sciences, or management will address. Courses should set clear learning objectives for cognitive skills they expect students to acquire. Thus, professionals in different fields will be enabled to improve environmental decision-making processes and to participate effectively in multidisciplinary work groups charged with tackling environmental issues.     

In situ assays with tropical cladocerans to evaluate edge-of-field pesticide runoff toxicity

Tropical regions’ economy is usually based on agriculture, which involves an intensive use, and even frequent overuse, of pesticides. Nevertheless, not much research has been done on the impact of pesticides on tropical aquatic ecosystems, which are often contaminated by runoff-related pesticide inputs due to unpredictable and torrential rainfalls. This study aimed to: (i) adapt and evaluate a short-term sublethal in situ assay using post-exposure feeding as an endpoint, to the tropical cladoceran species Diaphanosoma brachyurum (collected at the Pedra do Cavalo dam in the Paraguaçu River basin, Bahia, Brazil), and, (ii) assess the role of the standard species Daphnia magna as an adequate laboratory surrogate. Lethal and sublethal (post-exposure feeding) responses were assessed for the two species. To evaluate these responses under environmentally realistic exposure conditions, a runoff event was simulated in an agricultural area previously contaminated with different deltamethrin concentrations. The resultant runoff water was used to set up microcosms with different dilutions, simulating the entrance of runoff water in an adjacent lentic system. An in situ assay with D. brachyurum was performed inside the microcosms, allowing to discriminate the effects due to deltamethrin from those due to other potential stressors associated with the experimental design (e.g. organism handling, load of suspended particles, microcosm design). Water samples were collected from microcosms to conduct a laboratory assay with D. magna. The in situ methodologies revealed to be suitable to conduct assays with D. brachyurum under tropical conditions, since all exposed organisms were successfully retrieved from the chambers. Furthermore, none of the potential stressors associated with the experimental design influenced the daphnids’ performance. The tropical cladoceran species, exposed under more realistic conditions, revealed to be more sensitive than the laboratory standard species: lethal effects were only observed for D. brachyurum and sublethal effects were noticed at a lower deltamethrin concentration for this species than for D. magna.