Suitability of passive sampling for the monitoring of pharmaceuticals in Finnish surface waters

The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4–2.9 ng L^?1, 15–35 ng L^?1, 13–31 ng L^?1, 16–27 ng L^?1, and 3.3–32 ng L^?1, respectively. Similarly, the results in River Vantaa ranged between 1.2–40 ng L^?1, 15–65 ng L^?1, 13–33 ng L^?1, 16–31 ng L^?1, and 3.3–6.4 ng L^?1. The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.     

Electrospun and functionalized PVDF/PAN nanocatalyst-loaded composite for dechlorination and photodegradation of pesticides in contaminated water

A novel approach for the electrospinning and functionalization of nanocatalyst-loaded polyvinylidene fluoride/polyacrylonitrile (PVDF/PAN) composite grafted with acrylic acid (AA; which form polyacrylic acid (PAA) brush) and decorated with silver (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd) designed for the dechlorination and photodegradation of pesticides was carried out. PAN was used both as a nitrogen dopant as well as a co-polymer. Smooth nanofibers were obtained by electrospinning a solution of 12:2 wt.% PVDF/PAN blend using dimethylformamide (DMF) as solvent. The nanofibers were grafted with AA by free-radical polymerization using 2,2′azobis(2-methylpropionitrile) (AIBN) as initiator. Both bimetallic iron–palladium (Fe–Pd) and titania (TiO₂) nanoparticles (NP) were anchored on the grafted nanofibers via the carboxylate groups by in situ and ex situ synthesis. The Fe–Pd and nitrogen-doped TiO₂ nanoparticles were subsequently used for dechlorination and oxidation of target pollutants (dieldrin, chlorpyrifos, diuron, and fipronil) to benign products. Structural and chemical characterizations of the composites were done using various techniques. These include surface area and porosity analyzer (ASAP) using the technique by Brunner Emmett Teller (BET), Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM) analyses were done. After dechlorination, the transformation products (TPs) for dieldrin, chlorpyrifos, diuron, and fipronil were obtained and identified using two-dimensional gas chromatography (time-of-flight) with a mass spectrometer detector (GCxGC-TOFMS). Analysis of total organic carbon (TOC) was carried out and used to extrapolate percentage mineralization. Experimental results showed that dechlorination efficiencies of 96, 93, 96, and 90 % for 1, 2, 2, and 3 h treatment period were respectively achieved for 5 ppm solutions of dieldrin, chlorpyrifos, diuron, and fipronil. The dechlorination of dieldrin, diuron, and fipronil follows first-order kinetics while that of chlorpyrifos followed pseudo-first order. Mineralization performance of 34 to 45 % were recorded when Fe–Pd was used, however upon electrospinning, doping, and grafting (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd composite); it significantly increased to 99.9999 %. This composite reveals great potential for dechlorination and mineralization of pesticides in contaminated water.     

The in vitro effect of selected essential oils on the growth and mycotoxin production of Aspergillus species

The aim of the present study was to assess the antifungal and anti-toxinogenic activity of 15 essential oils (EOs) against three fungi of the genus Aspergillus (A. parasiticus KMi-227-LR, A. parasiticus KMi-220-LR and A. flavus KMi-202-LR). The minimum inhibitory doses (MIDs) of the tested essential oils and their antifungal activity were determined using the micro-atmosphere method. The original commercial essential oil samples of Jasminum officinale L., Thymus vulgaris L., Syzygium aromaticum (L.) Merrill &; Perry, Rosmarinus officinalis L., Ocimum basilicum L., Eucalyptus globulus Labill., Salvia officinalis L., Citrus limon (L.) Burm, Origanum vulgare L., Lavandula angustifolia Mill., Carum carvi L., Citrus sinensis (L.) Osbeck., Zingiber officinalis Rosc., Mentha piperita L. and Cinnamomum zeylanicum Nees. (C. verum J.S.Presl.) were produced in Slovakia (Calendula a.s., Nová ?ubovňa, Slovakia). All essential oils exhibited activity against all tested strains of fungi. After 14 days of incubation, A. flavus (KMi-202-LR) showed the highest susceptibility with a growth inhibition percentage (GIP) of 18.70% to C. limon and 5.92% to C. sinensis, while A. parasiticus (KMi-220-LR) exhibited a GIP of 20.56% to J. officinale. The minimum inhibitory doses (MIDs) of EOs with the most significant activity were recorded. The best antifungal activity, using the micro-atmosphere method was found in S. aromaticum with an MID of 62.5 μL L^?1 air, T. vulgaris (MID of 62.5 μL L^?1 air) and O. vulgare (MID of 31.5 μL L^?1 air) against all tested strains. Mycotoxin production of the tested strains was evaluated by the thin layer chromatography (TLC) method. Mycotoxin production of AFB₁ and AFG₁ was inhibited following all treatments with C. carvi, R. officinale and S. officinale, Eucalyptus globulus L. and O. basilicum L. Essential oils exhibited a potential inhibition activity against toxic fungi, although, these affected only the production of AFB₁.     

Analysis of waste management issues arising from a field study evaluating decontamination of a biological agent from a building

The Bio-response Operational Testing and Evaluation (BOTE) Project was a cross-government effort designed to operationally test and evaluate a response to a biological incident (release of Bacillus anthracis [Ba] spores, the causative agent for anthrax) from initial public health and law enforcement response through environmental remediation. The BOTE Project was designed to address site remediation after the release of a Ba simulant, Bacillus atrophaeus spp. globigii (Bg), within a facility, drawing upon recent advances in the biological sampling and decontamination areas. A key component of response to a biological contamination incident is the proper management of wastes and residues, which is woven throughout all response activities. Waste is generated throughout the response and includes items like sampling media packaging materials, discarded personal protective equipment, items removed from the facility either prior to or following decontamination, aqueous waste streams, and materials generated through the application of decontamination technologies. The amount of residual contaminating agent will impact the available disposal pathways and waste management costs. Waste management is an integral part of the decontamination process and should be included through “Pre-Incident” response planning. Overall, the pH-adjusted bleach decontamination process generated the most waste from the decontamination efforts, and fumigation with chlorine dioxide generated the least waste. A majority of the solid waste generated during pH-adjusted bleach decontamination was the nonporous surfaces that were removed, bagged, decontaminated ex situ, and treated as waste. The waste during the two fumigation rounds of the BOTE Project was associated mainly with sampling activities. Waste management activities may represent a significant contribution to the overall cost of the response/recovery operation. This paper addresses the waste management activities for the BOTE field test.Implications: Management of waste is a critical element of activities dealing with remediation of buildings and outdoor areas following a biological contamination incident. Waste management must be integrated into the overall remediation process, along with sampling, decontamination, resource management, and other important response elements, rather than being a stand-alone activity. The results presented in this paper will provide decision makers and emergency planners at the federal/state/tribal/local level information that can be used to integrate waste management into an overall systems approach to planning and response activities.     

Adsorption/desorption of arsenite and arsenate on chitosan and nanochitosan

Equilibrium sorption studies of anionic species of arsenite, As(III) ions and arsenate As(V) ions onto two biosorbents, namely, chitosan and nanochitosan, have been investigated and compared. The results and trends in the sorption behavior are novel, and we have observed during the sorption process of the As(III) and As(V) on chitosan, a slow process of desorption occurred after an initial maximum adsorption capacity was achieved, before reaching a final but lower equilibrium adsorption capacity. The same desorption trend, however, is not observed on nanochitosan. The gradual desorption of As(III) and As(V) in the equilibrium sorption on chitosan is attributed to the different fractions of the dissociated forms of arsenic on the adsorbent surface and in solution and the extent of protonation of chitosan with the changing of solution pH during sorption. The change of solution pH during the sorption of arsenite ions on chitosan was also influenced by the interaction between the buffering effect of the arsenite species in the aqueous medium and the physical properties of chitosan. The final equilibrium adsorption capacity of chitosan for As(III) and As(V) was found to be around 500 and 8000 μg/g, respectively, whereas the capacities on nanochitosan are 6100 and 13,000 μg/g, respectively.

     

Comprehensive Environmental Investigation at Former Industrial/Petroleum Underground Storage Tank Sites in Long Beach,CA: A Forensic Perspective

Two industrial sites were investigated based on years of available hydrogeologic information and monitoring data for soil and groundwater. Collected data were forensically evaluated using age-dating and fingerprinting methods. The previous business uses of the project sites were as a gas station, laundry/dry-cleaning service, and car wash with petroleum underground storage tanks (USTs). As a result, these sites were exposed to a number of toxic contaminants at relatively high concentrations. Source control was necessary for successful remediation and the ultimate removal of the remaining compounds from these industrial sites. Although contaminated soil around the source was excavated during the remedial action and the high concentrations of contaminants were reduced, typical groundwater contaminants such as petroleum hydrocarbons as gasoline (TPH-G), benzene, toluene, ethylbenzene, xylenes (BTEX), and oxygenates including methyl tert-butyl ether (MTBE), diisopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and tert-butyl alcohol (TBA) were persistently found at the studied sites around the source points. The plume and concentration of contaminants had changed their shapes and strength for all monitoring periods. Thus, additional source control seems to be a requirement for the complete removal of source contamination, which must be ascertained with groundwater and soil monitoring on a regular time base. For the study sites, monitored natural attenuation was relatively feasible for the long-term plan; however, it did not offer a perfect remediation solution for an ultimate goal because of residual toxic compounds that might have affected the surrounding residential areas at higher concentrations than their health limits. Therefore, as a remediation strategy, the combination of clean-up technology and natural attenuation with monitoring activities are more highly recommended than either clean-up or natural attenuation used separately.     

Pleasure in using adaptive cruise control: A questionnaire study in The Netherlands

Objective: Adaptive cruise control (ACC), a technology that allows for automated car following, is becoming increasingly prevalent. Previous surveys have shown that drivers generally regard ACC as pleasant but that they have to intervene when the ACC reaches its operational limits. The former research has been mostly concerned with specific car brands and does not fully reflect the diversity of ACC types in traffic today. The objective of the present research was to establish the determinants of pleasure in using ACC.

Methods: A 55-item online questionnaire was completed by Dutch users of diverse ACC systems.

Results: Respondents (N = 182) rated their ACC highly, with a mean score of 8.0 on a scale from 1 (extraordinarily negative) to 10 (extraordinarily positive) and were most pleased with ACC on high-speed roads and in low-density traffic. Moreover, the findings point to specific operational limits such as associated with cut-in situations. Pleasure was greater for the types of ACC that are able to decelerate to a full stop, according to 48% of our sample. An analysis of the free-response items indicated that respondents who were displeased with ACC mentioned its occasional clumsiness and the dangerous situations it may evoke, whereas those who were pleased with ACC valued the complementarity of human and machine and emphasized the roles of responsibility and experience in using ACC.

Conclusion: Pleasure in using ACC is a function of both technological advances and human factors.     

Critique of “Precipitation in Light Extinction Reconstruction” by P.A. Ryan

Abstract

The goal of the Regional Haze Rule (RHR) is to return visibility in class I areas (CIAs) to natural levels, excluding weather-related events, by 2064. Whereas visibility, the seeing of scenic vistas, is a near instantaneous and sight-path-dependent phenomenon, reasonable progress toward the RHR goal is assessed by tracking the incremental changes in 5-yr average visibility. Visibility is assessed using a haze metric estimated from 24-hr average aerosol measurements that are made at one location representative of the CIA. It is assumed that, over the 5-yr average, the aerosol loadings and relative humidity along all of the site paths are the same and can be estimated from the 24-hr measurements. It is further assumed that any time a site path may be obscured by weather (e.g., clouds and precipitation), there are other site paths within the CIA that are not. Therefore, when calculating the haze metric, sampling days are not filtered for weather conditions. This assumption was tested by examining precipitation data from multiple monitors for four CIAs. It is shown that, in general, precipitation did not concurrently occur at all monitors for a CIA, and precipitation typically occurred 3-8 hr or less in a day. In a recent paper in this journal, Ryan asserts that the haze metric should include contributions from precipitation and conducted a quantitative assessment incorrectly based on the assumption that the Optec NGN-2 nephelometer measurements include the effects of precipitation. However, these instruments are programmed to shut down during rain events, and any data logged are in error. He further assumes that precipitation occurs as often on the haziest days as the clearest days and that precipitation light scattering (bprecip) is independent of geographic location and applied an average bprecip derived for Great Smoky Mountains to diverse locations including the Grand Canyon. Both of these assumptions are shown to be in error.     

Aerosol species concentrations and source apportionment of ammonia at Rocky Mountain National Park

Changes in ecosystem function at Rocky Mountain National Park (RMNP) are occurring because of emissions of nitrogen and sulfate species along the Front Range of the Colorado Rocky Mountains, as well as sources farther east and west. The nitrogen compounds include both oxidized and reduced nitrogen. A year-long monitoring program of various oxidized and reduced nitrogen species was initiated to better understand their origins as well as the complex chemistry occurring during transport from source to receptor. Specifically, the goals of the study were to characterize the atmospheric concentrations of nitrogen species in gaseous, particulate, and aqueous phases (precipitation and clouds) along the east and west sides of the Continental Divide; identify the relative contributions to atmospheric nitrogen species in RMNP from within and outside of the state of Colorado; identify the relative contributions to atmospheric nitrogen species in RMNP from emission sources along the Colorado Front Range versus other areas within Colorado; and identify the relative contributions to atmospheric nitrogen species from mobile sources, agricultural activities, and large and small point sources within the state of Colorado. Measured ammonia concentrations are combined with modeled releases of conservative tracers from ammonia source regions around the United States to apportion ammonia to its respective sources, using receptor modeling tools.

Implications: Increased deposition of nitrogen in RMNP has been demonstrated to contribute to a number of important ecosystem changes. The rate of deposition of nitrogen compounds in RMNP has crossed a crucial threshold called the “critical load.” This means that changes are occurring to park ecosystems and that these changes may soon reach a point where they are difficult or impossible to reverse. Several key issues need attention to develop an effective strategy for protecting park resources from adverse impacts of elevated nitrogen deposition. These include determining the importance of previously unquantified nitrogen inputs within the park and identification of important nitrogen sources and transport pathways.