Treatment technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA)

Fluorochemicals (FCs) are oxidatively recalcitrant, environmentally persistent, and resistant to most conventional treatment technologies. FCs have unique physiochemical properties derived from fluorine which is the most electronegative element. Perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA) have been detected globally in the hydrosphere, atmosphere and biosphere. Reducing treatment technologies such as reverses osmosis, nano-filtration and activated carbon can remove FCs from water. However, incineration of the concentrated waste is required for complete FC destruction. Recently, a number of alternative technologies for FC decomposition have been reported. The FC degradation technologies span a wide range of chemical processes including direct photolysis, photocatalytic oxidation, photochemical oxidation, photochemical reduction, thermally-induced reduction, and sonochemical pyrolysis. This paper reviews these FC degradation technologies in terms of kinetics, mechanism, energetic cost, and applicability. The optimal PFOS/PFOA treatment method is strongly dependent upon the FC concentration, background organic and metal concentration, and available degradation time.     

Trophic levels and trophic tangles: the prevalence of omnivory in real food webs

The concept of trophic levels is one of the oldest in ecology and informs our understanding of energy flow and top-down control within food webs, but it has been criticized for ignoring omnivory. We tested whether trophic levels were apparent in 58 real food webs in four habitat types by examining patterns of trophic position. A large proportion of taxa (64.4%) occupied integer trophic positions, suggesting that discrete trophic levels do exist. Importantly however, the majority of those trophic positions were aggregated around integer values of 0 and 1, representing plants and herbivores. For the majority of the real food webs considered here, secondary consumers were no more likely to occupy an integer trophic position than in randomized food webs. This means that, above the herbivore trophic level, food webs are better characterized as a tangled web of omnivores. Omnivory was most common in marine systems, rarest in streams, and intermediate in lakes and terrestrial food webs. Trophic-level-based concepts such as trophic cascades may apply to systems with short food chains, but they become less valid as food chains lengthen.     

The influence of spatial and size scale on phylogenetic relatedness in tropical forest communities

The relative importance of biotic, abiotic, and stochastic processes in structuring ecological communities continues to be a central focus in community ecology. In order to assess the role of phylogenetic relatedness on the nature of biodiversity we first quantified the degree of phylogenetic niche conservatism of several plant traits linked to plant form and function. Next we quantified the degree of phylogenetic relatedness across two fundamental scaling dimensions: plant size and neighborhood size. The results show that phylogenetic niche conservatism is likely widespread, indicating that closely related species are more functionally similar than distantly related species. Utilizing this information we show that three of five tropical forest dynamics plots (FDPs) exhibit similar scale-dependent patterns of phylogenetic structuring using only a spatial scaling axis. When spatial- and size-scaling axes were analyzed in concert, phylogenetic overdispersion of co-occurring species was most important at small spatial scales and in four of five FDPs for the largest size class. These results suggest that phylogenetic relatedness is increasingly important: (1) at small spatial scales, where phylogenetic overdispersion is more common, and (2) in large size classes, where phylogenetic overdispersion becomes more common throughout ontogeny. Collectively, our results highlight the critical spatial and size scales at which the degree of phylogenetic relatedness between constituent species influences the structuring of tropical forest diversity.     

Crab herbivory regulates plant facilitative and competitive processes in Argentinean marshes

Interactions among plants have been hypothesized to be context dependent, shifting between facilitative and competitive in response to variation in physical and biological stresses. This hypothesis has been supported by studies of the importance of positive and negative interactions along abiotic stress gradients (e.g., salinity, desiccation), but few studies have tested how variation in biotic stresses can mediate the nature and strength of plant interactions. We examined the hypothesis that herbivory regulates the strength of competitive and facilitative interactions during succession in Argentinean marshes dominated by Spartina densiflora and Sarcocornia perennis. Spartina densiflora is preferred by the dominant herbivore in the system, the crab Chasmagnathus granulatus. We experimentally manipulated crab herbivory, plant structure, and shade, and we found that, when herbivory was low in the spring and summer, competitive interactions between plants were dominant, but in the fall, when herbivory was highest, facilitative interactions dominated, and Spartina densiflora survival was completely dependent upon association with Sarcocornia perennis. Moreover, experimental removal of Sarcocornia perennis across recently disturbed tidal flats revealed that, while Sarcocornia perennis positively affected small Spartina densiflora patches by decreasing herbivory, as patch size increases and they can withstand the impact of herbivory, competitive interactions predominated and Spartina densiflora ultimately outcompeted Sarcocornia perennis. These results show that herbivory can mediate the balance between facilitative and competitive processes in vascular plant communities and that the strength of consumer regulation of interactions can vary seasonally and with patch size.     

Chemistry and aerosols in the marine boundary layer: 1-D modelling of the three ACE-2 Lagrangian experiments

Three Lagrangian experiments were conducted during IGAC's second aerosol characterization experiment (ACE-2) in the area between Portugal, Tenerife and Madeira in June/July 1997. During each Lagrangian experiment, a boundary layer air mass was followed for about 30 h, and the temporal evolution of its chemical and aerosol composition was documented by a series of vertical profiles and horizontal box pattern flown by the Meteorological Research Flight research aircraft Hercules C130. The wealth of observational data that has been collected during these three Lagrangian experiments is the basis for the development and testing of a one-dimensional Lagrangian boundary layer model with coupled gas, aqueous, and aerosol phase chemistry. The focus of this paper is on current model limitations and strengths. We show that the model is able to represent the dynamical and chemical evolution of the marine boundary layer, in some cases requiring adjustments of the subsidence velocity and of the surface heat fluxes. Entrainment of a layer rich in ozone and carbon monoxide from a residual continental boundary layer into the marine boundary layer as well as in-cloud oxidation of sulphur dioxide by hydrogen peroxide are simulated, and coherent results are obtained, concerning the evolution of the small, presumably sulphate–ammonia aerosol mode.     

Functional models for colloid retention in porous media at the triple line

Spectral confocal microscope visualizations of microsphere movement in unsaturated porous media showed that attachment at the Air Water Solid (AWS) interface was an important retention mechanism. These visualizations can aid in resolving the functional form of retention rates of colloids at the AWS interface. In this study, soil adsorption isotherm equations were adapted by replacing the chemical concentration in the water as independent variable by the cumulative colloids passing by. In order of increasing number of fitted parameters, the functions tested were the Langmuir adsorption isotherm, the Logistic distribution, and the Weibull distribution. The functions were fitted against colloid concentrations obtained from time series of images acquired with a spectral confocal microscope for three experiments performed where either plain or carboxylated polystyrene latex microspheres were pulsed in a small flow chamber filled with cleaned quartz sand. Both moving and retained colloids were quantified over time. In fitting the models to the data, the agreement improved with increasing number of model parameters. The Weibull distribution gave overall the best fit. The logistic distribution did not fit the initial retention of microspheres well but otherwise the fit was good. The Langmuir isotherm only fitted the longest time series well. The results can be explained that initially when colloids are first introduced the rate of retention is low. Once colloids are at the AWS interface they act as anchor point for other colloids to attach and thereby increasing the retention rate as clusters form. Once the available attachment sites diminish, the retention rate decreases.     

Nanoremediation and International Environmental Restoration Markets

Nanoscale zero‐valent iron (nZVI) is the most commonly used nanoremediation material. While there has been a reasonable level of application of nZVI technologies for in situ remediation in the United States, its utilization across Europe has been much more limited. There has been significant uncertainty about the balance between deployment risks and benefits for nanoparticles (NPs), which has affected the regulatory position in several countries. Some member states of the European Union (EU) take a strong precautionary view of the risks from the deployment of NPs into the subsurface, preventing the adoption of the technology. This article provides a risk–benefit assessment for nZVI based on published information and describes the steps that will be taken by a major European research project (NanoRem), as part of its work to provide a basis for better informed decision making in European environmental restoration markets. A key part of this process is dialogue between practitioners and researchers. NanoRem therefore has an active process of communication with different stakeholder networks (regulators, service providers, and site owners). NanoRem hopes to stimulate a consensus on appropriate use of nanoremediation and thereby stimulate effective technology transfer to the European remediation market. ©2015 The Authors