Prediction of contaminant transport in fractured carbonate aquifer types: a case study of the Permian Magnesian Limestone Group (NE England,UK)

Viruses and bacteria which are characterized by finite lives in the subsurface are rapidly transported via fractures and cavities in fractured and karst aquifers. Here, we demonstrate how the coupling of a robust outcrop characterization and hydrogeophysical borehole testing is essential for prediction of contaminant velocities and hence wellhead protection areas. To show this, we use the dolostones of the Permian Magnesian Limestone aquifer in NE England, where we incorporated such information in a groundwater flow and particle tracking model. Within this aquifer, flow in relatively narrow (mechanical aperture of ~?10^?1–1 mm) fractures is coupled with that in pipe cavities (~?0.20-m diameter) following normal faults. Karstic cavities and narrow fractures are hydraulically very different. Thus, the solutional features are represented within the model by a pipe network (which accounts for turbulence) embedded within an equivalent porous medium representing Darcian flowing fractures. Incorporation of fault conduits in a groundwater model shows that they strongly influence particle tracking results. Despite this, away from faulted areas, the effective flow porosity of the equivalent porous medium remains a crucial parameter. Here, we recommend as most appropriate a relatively low value of effective porosity (of 2.8?×?10^?4) based on borehole hydrogeophysical testing. This contrasts with earlier studies using particle tracking analyses on analogous carbonate aquifers, which used much higher values of effective porosity, typically ~?10² times higher than our value, resulting in highly non-conservative estimates of aquifer vulnerability. Low values of effective flow porosities yield modelled flow velocities ranging from ~?100 up to ~?500 m/day in un-faulted areas. However, the high fracturing density and presence of karstic cavities yield modelled flow velocities up to ~?9000 m/day in fault zones. The combination of such flow velocities along particle traces results in 400-day particle traces up to 8-km length, implying the need for large well protection areas and high aquifer vulnerability to slowly degrading contaminants.

     

Silica-quaternary ammonium “Fixed-Quat” nanofilm coated fiberglass mesh for water disinfection and harmful algal blooms control

Intensification of pollution loading worldwide has promoted an escalation of different types of disease-causing microorganisms, such as harmful algal blooms(HABs), instigating detrimental impacts on the quality of receiving surface waters. Formation of unwanted disinfection by-products(DBPs) resulting from conventional disinfection technologies reveals the need for the development of new sustainable alternatives. Quaternary Ammonium Compounds(QACs) are cationic surfactants widely known for their effective biocidal properties at the ppm level. In this study, a novel silica-based antimicrobial nanofilm was developed using a composite of silica-modified QAC(Fixed-Quat) and applied to a fiberglass mesh as an active surface via sol–gel technique. The synthesized Fixed-Quat nanocoating was found to be effective against E. coli with an inactivation rate of 1.3 × 10~(-3) log reduction/cm min. The Fixed-Quat coated fiberglass mesh also demonstrated successful control of Microcystis aeruginosa with more than 99% inactivation after 10 hr of exposure.The developed antimicrobial mesh was also evaluated with wild-type microalgal species collected in a water body experiencing HABs, obtaining a 97% removal efficiency. Overall,the silica-functionalized Fixed-Quat nanocoating showed promising antimicrobial properties for water disinfection and HABs control, while decreasing concerns related to DBPs formation and the possible release of toxic nanomaterials into the environment.     

Species' traits predict phenological responses to climate change in butterflies

How do species' traits help identify which species will respond most strongly to future climate change? We examine the relationship between species' traits and phenology in a well-established model system for climate change, the U.K. Butterfly Monitoring Scheme (UKBMS). Most resident U.K. butterfly species have significantly advanced their dates of first appearance during the past 30 years. We show that species with narrower larval diet breadth and more advanced overwintering stages have experienced relatively greater advances in their date of first appearance. In addition, species with smaller range sizes have experienced greater phenological advancement. Our results demonstrate that species' traits can be important predictors of responses to climate change, and they suggest that further investigation of the mechanisms by which these traits influence phenology may aid in understanding species' responses to current and future climate change.     

Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (<100 nm) that contained high molecular weight nitrogenated species (m/z 400–500), which can be due to accretion/acid–base reactions and formation of oligomers. In addition, nicotine was found to contribute significantly (with yields 4–9%) to the formation of secondary organic aerosol through reaction with ozone. The main constituents of the resulting SOA were tentatively identified and a reaction mechanism was proposed to elucidate their formation. These findings identify a new component of thirdhand smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.     

Catalytic ozonation of 2,4-dichlorophenoxyacetic acid using alumina in the presence of a radical scavenger

Using a laboratory-scale mixed reactor, the performance of alumina in degrading 2,4-Dichlorophenoxyacetic acid with ozone in the presence of tert-butyl alcohol radical scavenger was studied. The operating variables investigated were the dose of alumina catalyst and solution pH. Results showed that using ozone and alumina leads to a significant increase in 2,4-D removal in comparison to non-catalytic ozonation and adsorption processes. The observed reaction rate constants (k(obs)) for 2,4-D during ozonation were found to increase linearly with increasing catalyst dose. At pH 5, the k(obs) value increased from 19.3 to 26 M(-1) s(-1) and 67 M(-1) s(-1) when varying the alumina dose from 1 to 2 and 4 g L(-1), respectively. As pH was increased, higher reaction rates were observed for both non-catalytic ozonation and catalytic ozonation processes. Thus, at pH 3 and using a catalyst dose of 8 g L(-1), the k(obs) values for non-catalytic ozonation and catalytic ozonation processes were 3.4 and 58.9 M(-1) s(-1), respectively, whereas at pH 5 reaction rate constants of 6.5 and 128.5 M(-1) s(-1) were observed, respectively. Analysis of total organic carbon suggested that catalytic ozonation with alumina achieved a considerable level of mineralization of 2,4-D. Adsorption of 2,4-D on alumina was found to play an important role in the catalytic ozonation process.     

Aquivalence revisited--new model formulation and application to assess environmental fate of ionic pharmaceuticals in Hamilton Harbour, Lake Ontario

A model formulation based on "aquivalence", as defined in terms of activity is presented to estimate the multimedia fate of ionizing chemicals. The aquivalence approach is analogous to fugacity but aquivalence is applicable to neutral and ionizing compounds, and has been applied previously to speciating chemicals, notably metals. The new aquivalence-based mass-balance model treats ionizing organic compounds that exist as interconverting neutral and ionic species which are subject to fate processes at differing rates. The model is illustrated by application to four ionizing pharmaceuticals in Hamilton Harbour, Lake Ontario. At the system pH of 7.9-8.5, ibuprofen, gemfibrozil, and naproxen are expected to be almost entirely ionic and triclosan split between ionic and neutral forms. Measured seasonal surface water concentrations, which were 2-10 times lower in the late summer and fall than during spring, were used to solve for unknown values of chemical half-life in the water column due to degradation (photo- and bio-) of the ionizing and neutral forms and secondarily, ionic sorption coefficients of the ionizing forms. Model estimates of half-lives in the habour's water ranged from 11 to 77, 11 to 147 and 10 to 37 for ionic ibuprofen, gemfibrozil, and naproxen, respectively; and 4-22 days and 2-9 days for ionic and neutral triclosan, respectively, with the shortest half-lives in spring and the longest in summer.     

Political conservatism,religion, and environmental consumption in the United States

The role of political conservatism and religion in shaping attitudes toward environmental consumption in the US is examined. Previous research suggests that while there is a mixed relationship between religiosity (measured in various ways) and environmentalism, political conservatives are unlikely to support pro-environment measures. Using nationally representative survey data, mixed results are found regarding the relationship of religiosity and environmental consumption: religious attendance and religious identity are positively related to environmental consumption, while belief in an involved God and biblical literalism are negatively related. Increased levels of religiosity, however, mute the otherwise strong negative effect of political conservatism. This suggests, surprisingly, that Green marketers and activists are likely to face less conservative resistance to environmental consumption among religious Americans.     

Evolution rates and PCB content of surface films that develop on impervious urban surfaces

Surface films on impervious surfaces mediate the fate of organic contaminants in urban areas. Using sheltered 3-mm diameter glass beads as a surrogate impervious urban surface, studies in downtown Toronto showed that surface films developed at a consistent rate of 1.6–2.6 nm day⁻¹. Linear film growth was observed up to and including the last day of three studies of 89-, 273-, and 84-day duration. Total PCB content (sum of 15 PCB congeners) also increased linearly, at a similar rate as the surface film. A complementary study using unsheltered beads showed that up to 80% of film mass and PCB content were removed by film wash-off during rain events. The film growth rate on beads exposed at a rural site, 200 km northeast of Toronto, was 12–20 times lower with PCB burdens that were 7–22 times lower compared to Toronto. Based on these findings, it is estimated that approximately 56–226 g of PCBs are captured by a 70 nm thick film covering just the horizontal surface area of Toronto. This is a substantial quantity of PCB that is available for rapid surface–air exchange and wash-off.     

Use of Constructed Wetlands for Urban Stream Restoration: A Critical Analysis

/ Investigation of a delta marsh restoration project proposed forthe Don River in Toronto, Ontario, underlines several concerns aboutconstructed wetland projects designed for water quality improvement andaquatic habitat enhancement. The Don is a highly urbanized river that hasundergone significant physiographic modifications and continually receives acomplex mixture of conventional, metallic, and organic contaminants frommultiple point and nonpoint sources. Rather than providing permanent removalof urban contaminants, wetland processes offer a limited capacity fortemporary storage of contaminant inputs, and potential reactions may actuallyproduce more toxic and/or bioavailable forms of some chemicals. Theseprocesses tend to result in the concentration of watershed contaminants inwetland vegetation and sediments. As the restored marsh would be availablefor spawning and feeding by aquatic fauna, the potential exists for chemicalbioconcentration and biomagnification through the aquatic community.Accordingly, wetland systems are not suited to the dual purposes of waterquality improvement and aquatic habitat enhancement. Upstream controls,including source reduction of contaminant inputs, are recommended asessential components of all constructed wetland projects.KEY WORDS: Constructed wetlands; Water quality; Ecological restoration;Don River