Comparison of Function of Created Wetlands of Two Age Classes in Central Pennsylvania

Hydrogeomorphic (HGM) functional assessment models were used to assess whether function in created wetlands of two ages (1 year old and >12 years old) was equivalent to that of natural (reference) mainstem floodplain wetlands. Reference wetlands scored higher than both created age classes for providing energy dissipation and short-term surface water storage. Reference wetlands scored higher in maintaining native plant community and structure than 1-year-old sites, and 12-year-old wetlands scored higher than reference sites for providing vertebrate habitat structure. Analysis of individual model variables showed that reference wetlands had greater vegetative biomass and higher soil organic matter content than both created wetland age classes. Created wetlands were farther from natural wetlands and had smaller mean forest patch sizes within a 1-km-radius circle around the site than did the reference sites, indicating less hydrologic connectivity. Created wetlands also had less microtopographic variation than reference wetlands. The 1-year-old created sites were placed in landscape settings with greater land use diversity and road density than reference sites. The 12-year-old sites had a higher gradient and a higher percentage of their surrounding area in urban land use. These results show that the created wetlands were significantly structurally different (if not functionally so) from reference wetlands even after 12 years. The most profound differences were in hydrology and the characteristics of the surrounding landscape. More attention needs to be focused on placing created wetlands in appropriate settings to encourage proper hydrodynamics, eliminate habitat fragmentation, and minimize the effects of stressors to the site.     

Exploring the Crowding–Satisfaction Relationship in Recreational Boating

Along with the growing boating population and the number of boats in use on limited inland waterways, boater expectations of setting density, safety perceptions, and the associated impacts on their experience (e.g., satisfaction) are becoming increasingly important. The primary purpose of this article was to explore a recreational boating crowding–satisfaction model derived from previous work using safety and enjoyment as mediating variables. We also tested our crowding–satisfaction model among day and overnight users. Our analysis revealed no significant difference between day and overnight users for any of the relationships tested in our model. Our final model indicated as respondents’ expectations for seeing people increased along with their feelings of being crowded, they were more inclined to consider the conditions on the lake as being unsafe. They were also more inclined to indicate that the number of people they had seen on the lake detracted from their boating experience. Respondents’ satisfaction was tied to their perceptions of crowding. Mediating variables illustrated that the relationship was conditioned by perceptions of safety and enjoyment. Analysis of the indirect effect observed in our study illustrate that when the number of people seen on the lake exceed respondents’ expectations, their perceptions of safety and enjoyment both decline, resulting in lower satisfaction. These findings have implications for managing recreational boating use on inland lake systems. Given the role played by expectations in our model, efforts to communicate with boaters about conditions on these waterways is important for helping them plan their boating experience and avoid situations they consider unsafe or unsatisfactory.     

Radionuclide transfer to animal products: revised recommended transfer coefficient values

A compilation has been undertaken of data which can be used to derive animal product transfer coefficients for radionuclides, including an extensive review of Russian language information. The resultant database has been used to provide recommended transfer coefficient values for a range of radionuclides to (i) cow, sheep and goat milk, (ii) meat (muscle) of cattle, sheep, goats, pigs and poultry and (iii) eggs. The values are used in a new IAEA handbook on transfer parameters which replaces that referred to as ‘TRS 364’. The paper outlines the approaches and procedures used to identify and collate data, and assumptions used. There are notable differences between the TRS 364 ‘expected’ values and the recommended values in the revised Handbook from the new database. Of the recommended values, three milk values are at least an order of magnitude higher than the TRS 364 values (Cr, Pu (cow) Pu (sheep)) and one milk value is lower (Ni (cow)). For meat, four values (Am, Cd, Sb (beef) I (pork)) are at least an order of magnitude higher than the TRS 364 values and eight values are at least an order of magnitude lower (Ru, Pu (beef), Ru, Sr, Zn (sheep), Ru, Sr (pork), Mn (poultry)). Many data gaps remain.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

The herbicide paraquat induces alterations in the elemental and biochemical composition of non-target microalgal species

Huge quantities of pesticides are dispersed in the environment, affecting non-target organisms. Since paraquat affects the photosynthetic process, the biochemical composition of affected species should be altered. The effect of paraquat on Chlamydomonas moewusii, a freshwater non-target species, was studied. After 48 h of herbicide exposure, growth rate, dry weight, and chlorophyll a and protein content were affected by paraquat concentrations above 0.05 μM. C/N ratio was also affected due to a decrease in nitrogen content in the dry biomass, while the carbon content remained constant for all paraquat concentrations assayed. Enzymes involved in nitrogen assimilation were affected by paraquat, being nitrate reductase activity more sensitive to paraquat than nitrite reductase. Based on the results obtained in the present study, paraquat exerts adverse effects upon a common freshwater green microalga, thus the application of this herbicide for weed control must be carried out very carefully, so that any disturbance affecting algae will have severe repercussions on higher trophic levels and on the elemental biogeochemical cycles.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

Sorption of alkylphenols on Ebro River sediments: comparing isotherms with field observations in river water and sediments

This study reports sorption isotherms of the endocrine disruptors nonylphenol (NP) and octylphenol (OP) in three sediment samples from the Ebro River basin (NE Spain), with organic carbon fractions (f_OC) ranging from 0.0035 to 0.082 g_OC g⁻¹. All isotherms were fitted to the Freundlich model with slightly nonlinear exponents ranging from 0.80 to 0.94. The solubility of the compounds as well as the organic carbon (OC) content had the strongest influences on the sorption behavior of these compounds. Comparison of the laboratory-spiked samples with the native contamination of NP of 45 water and concurrent sediment samples resulted in reasonable matches between both data sets, even though the lowest concentrations in the field were not completely reached in laboratory tests. This good agreement indicates that sorption laboratory data can be extrapolated to environmental levels and therefore the distribution of nonylphenol between sediments and water can be predicted with a precision of one order of magnitude. Furthermore, laboratory experiments with simultaneous loading of NP and OP revealed negligible competition for sorption sites at low concentrations.     

Study of lead phytoavailability for atmospheric industrial micronic and sub-micronic particles in relation with lead speciation

Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650 ± 20 mg Pb kg⁻¹) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO₄, PbSO₄·PbO, α-PbO and Pb⁰. Morphology investigations revealed that PM_2.5 (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 μm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01 M CaCl₂ extraction.     

C60 fullerene: a powerful antioxidant or a damaging agent? The importance of an in-depth material characterization prior to toxicity assays

Since the discovery of fullerenes in 1985, these carbon nanospheres have attracted attention regarding their physico/chemical properties. Despite little knowledge about their impact on the environment and human health, the production of fullerenes has already reached an industrial scale. However, the toxicity of C₆₀ is still controversially discussed.The aim of this study was to clarify the biological effects of tetrahydrofuran (THF) suspended C₆₀ fullerene in comparison to water stirred C₆₀ fullerene suspensions. Beyond that, we analyzed the effects on the Crustacea Daphnia magna an indicator for ecotoxicological effects and the human lung epithelial cell line A549 as a simplified model for the respiratory tract.We could demonstrate that water-soluble side products which were formed in THF nC₆₀ suspension were responsible for the observed acute toxic effects, whereas fullerenes themselves had no negative effect regardless of the preparative route on either A549 cell in vitro or D. magna in vivo.     

DOC removal paradigms in highly humic aquatic ecosystems

Background, aim, and scope  Dissolved humic substances (HS) usually comprise 50–80% of the dissolved organic carbon (DOC) in aquatic ecosystems. From a trophic and biogeochemical perspective, HS has been considered to be highly refractory and is supposed to accumulate in the water. The upsurge of the microbial loop paradigm and the studies on HS photo-degradation into labile DOC gave rise to the belief that microbial processing of DOC should sustain aquatic food webs in humic waters. However, this has not been extensively supported by the literature, since most HS and their photo-products are often oxidized by microbes through respiration in most nutrient-poor humic waters. Here, we review basic concepts, classical studies, and recent data on bacterial and photo-degradation of DOC, comparing the rates of these processes in highly humic ecosystems and other aquatic ecosystems. Materials and methods  We based our review on classical and recent findings from the fields of biogeochemistry and microbial ecology, highlighting some odd results from highly humic Brazilian tropical lagoons, which can reach up to 160 mg C L⁻¹. Results and discussion  Highly humic tropical lagoons showed proportionally lower bacterial production rates and higher bacterial respiration rates (i.e., lower bacterial growth efficiency) than other lakes. Zooplankton showed similar δ¹³C to microalgae but not to humic DOC in these highly humic lagoons. Thus, the data reviewed here do not support the microbial loop as an efficient matter transfer pathway in highly humic ecosystems, where it is supposed to play its major role. In addition, we found that some tropical humic ecosystems presented the highest potential DOC photo-chemical mineralization (PM) rates reported in the literature, exceeding up to threefold the rates reported for temperate humic ecosystems. We propose that these atypically high PM rates are the result of a joint effect of the seasonal dynamics of allochthonous humic DOC input to these ecosystems and the high sunlight incidence throughout the year. The sunlight action on DOC is positive to microbial consumption in these highly humic lagoons, but little support is given to the enhancement of bacterial growth efficiency, since the labile photo-chemical products are mostly respired by microbes in the nutrient-poor humic waters. Conclusions  HS may be an important source of energy for aquatic bacteria in humic waters, but it is probably not as important as a substrate to bacterial growth and to aquatic food webs, since HS consumption is mostly channeled through microbial respiration. This especially seems to be the case of humic-rich, nutrient-poor ecosystems, where the microbial loop was supposed to play its major role. Highly humic ecosystems also present the highest PM rates reported in the literature. Finally, light and bacteria can cooperate in order to enhance total carbon degradation in highly humic aquatic ecosystems but with limited effects on aquatic food webs. Recommendations and perspectives  More detailed studies using C- and N-stable isotope techniques and modeling approaches are needed to better understand the actual importance of HS to carbon cycling in highly humic waters.