Ionic liquids as lubricants or lubrication additives: An ecotoxicity and biodegradability assessment

This paper reports on the (eco)toxicity and biodegradability of ionic liquids considered for application as lubricants or lubrication additives. Ammonium- and pyrrolidinium-based cations combined with methylsulphate, methylsulphonate and/or (CF₃SO₂)₂N⁻ anions were investigated in tests to determine their aquatic toxicity using water fleas Daphnia magna, green algae Selenastrum capricornutum and marine bacteria (Vibrio fischeri). Additional test systems with an isolated enzyme (acetylcholinesterase) and isolated leukaemia cells from rats (IPC-81) were used to assess the biological activity of the ionic liquids. These compounds generally exhibit low acute toxicity and biological activity. Their biodegradability was screened according to OECD test procedures 301 B and 301 F. For choline and methoxy-choline ionic liquids ready biodegradability was observed within 5 or 10 d, respectively. Some of the compounds selected have a considerable potential to contribute to the development of more sustainable products and processes.     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.     

pH effect on the susceptibility to parasitoid infection in the marine diatom Coscinodiscus spp. (Bacillariophyceae)

The pH on the frustule of individual cells of the marine centric diatoms Coscinodiscus granii and Coscinodiscus wailesii (Bacillariophyceae) was measured with pH microsensors in culture media with increasing pH values of 8.04, 8.14, and 8.22, respectively. In 85–96% of the C. granii cells the pH on the frustule was up to 0.4 units higher than that of the medium, reaching a maximum pH 8.95. Only in 2–3% the surface pH exceeded that of the medium by up to 0.7 pH units. These results strongly suggest that diatoms in batch cultures differ, at least temporarily, in their individual photosynthetic activities. Infection experiments with the parasitoid nanoflagellate Pirsonia diadema (Stramenopile) showed that flagellates failed to infect when the culture pH was 8.8 and above. pH measurements on freshly infected C. granii showed that the prevalence of infection was higher in tendency on diatoms with low surface pH. Application of these results to parasitoid-diatom interactions in natural waters suggests that within phytoplankton populations a strong photosynthetic activity might prevent diatom cells temporarily from infection by pH-sensitive parasitoids.     

Inter-seasonal maintenance of individual nest site preferences in hawksbill sea turtles

Within a single population of hawksbill sea turtles (Eretmochelys imbricata), we found a behavioral polymorphism for maternal nest site choice with respect to beach microhabitat characteristics. Some females preferred to nest in littoral forest and in places with overstory vegetation cover, and others preferred to nest in more open, deforested areas. Nest site choice was consistent within and between nesting seasons two years apart. This was not a result of females simply returning to the same location along the shoreline; beach sections used by individual turtles varied between seasons. Nest site choice was not influenced by changes in beach environment (e.g., beach width and foliage cover) or by changes in females' reproductive output (e.g., clutch size), suggesting that fidelity to particular microhabitats is a major determinant of the observed nesting patterns. Because hawksbills exhibit temperature-dependent sex determination, if the behavioral polymorphism in nest site choice has a genetic basis, as is plausible, then this would have implications for sex ratio evolution and offspring survival. By taking an individual-based approach to the study of maternal behavior we reveal previously overlooked individual variation and hope to provide some impetus for more detailed studies of nest site choice.     

Evaluating the role of desorption in bioavailability of sediment-associated contaminants using oligochaetes, semipermeable membrane devices and Tenax extraction

The success of the rapidly desorbing fraction as an available fraction was challenged by using sediment ingesting and non-ingesting oligochaetes (Lumbriculus variegatus) together with passive samplers (semipermeable membrane devices, SPMDs) in accumulation and kinetic modelling exercises for carbon-14 labelled model compounds (pyrene, benzo[a]pyrene and 3,4,3',4'-tetrachlorobiphenyl). Passive samplers clearly produced lower uptake rate constants and steady state factors than either of the oligochaete treatments when residue concentrations were based on animal lipid or total SPMD weight. The rapidly desorbing chemical fractions in sediments did not show a significant relationship with the biota sediment accumulation factors or SPMD accumulation factors. A distinctly better relationship was observed between the accumulation factors and the desorption rate constants. The results support the assumption that desorption plays an important role in bioavailability, although animal behaviour and the diffusional limitations of hydrophobic contaminants in sediment together probably affect the actual available pool.     

Characteristics of animal-related motor vehicle crashes in select National Park Service units—United States, 1990–2013

Objectives: Nationally, animal–motor vehicle crashes (AVCs) account for 4.4% of all types of motor vehicle crashes (MVCs). AVCs are a safety risk for drivers and animals and many National Park Service (NPS) units (e.g., national park, national monument, or national parkway) have known AVC risk factors, including rural locations and substantial animal densities. We sought to describe conditions and circumstances involving AVCs to guide traffic and wildlife management for prevention of AVCs in select NPS units.

Methods: We conducted an analysis using NPS law enforcement MVC data. An MVC is a collision involving an in-transit motor vehicle that occurred or began on a public roadway. An AVC is characterized as a collision between a motor vehicle and an animal. A non-AVC is a crash between a motor vehicle and any object other than an animal or noncollision event (e.g., rollover crash). The final data for analysis included 54,068 records from 51 NPS units during 1990–2013. Counts and proportions were calculated for categorical variables and medians and ranges were calculated for continuous variables. We used Pearson’s chi-square to compare circumstances of AVCs and non-AVCs. Data were compiled at the park regional level; NPS parks are assigned to 1 of 7 regions based on the park’s location.

Results: AVCs accounted for 10.4% (5,643 of 54,068) of all MVCs from 51 NPS units. The Northeast (2,021 of 5,643; 35.8%) and Intermountain (1,180 of 5,643; 20.9%) regions had the largest percentage of the total AVC burden. November was the peak month for AVCs across all regions (881 of 5,643; 15.6%); however, seasonality varied by park geographic regions. The highest counts of AVCs were reported during fall for the National Capital, Northeast/Southeast, and Northeast regions; winter for the Southeast region; and summer for Intermountain and Pacific West regions.

Conclusions: AVCs represent a public health and wildlife safety concern for NPS units. AVCs in select NPS units were approximately 2-fold higher than the national percentage for AVCs. The peak season for AVCs varied by NPS region. Knowledge of region-specific seasonality patterns for AVCs can help NPS staff develop mitigation strategies for use primarily during peak AVC months. Improving AVC data collection might provide NPS with a more complete understanding of risk factors and seasonal trends for specific NPS units. By collecting information concerning the animal species hit, park managers can better understand the impacts of AVC to wildlife population health.     

The need for spatially explicit quantification of benefits in invasive‐species management

Worldwide, invasive species are a leading driver of environmental change across terrestrial, marine, and freshwater environments and cost billions of dollars annually in ecological damages and economic losses. Resources limit invasive‐species control, and planning processes are needed to identify cost‐effective solutions. Thus, studies are increasingly considering spatially variable natural and socioeconomic assets (e.g., species persistence, recreational fishing) when planning the allocation of actions for invasive‐species management. There is a need to improve understanding of how such assets are considered in invasive‐species management. We reviewed over 1600 studies focused on management of invasive species, including flora and fauna. Eighty‐four of these studies were included in our final analysis because they focused on the prioritization of actions for invasive species management. Forty‐five percent (n = 38) of these studies were based on spatial optimization methods, and 35% (n = 13) accounted for spatially variable assets. Across all 84 optimization studies considered, 27% (n = 23) explicitly accounted for spatially variable assets. Based on our findings, we further explored the potential costs and benefits to invasive species management when spatially variable assets are explicitly considered or not. To include spatially variable assets in decision‐making processes that guide invasive‐species management there is a need to quantify environmental responses to invasive species and to enhance understanding of potential impacts of invasive species on different natural or socioeconomic assets. We suggest these gaps could be filled by systematic reviews, quantifying invasive species impacts on native species at different periods, and broadening sources and enhancing sharing of knowledge.     

Residential indoor,outdoor, and workplace concentrations of carbonyl compounds: relationships with personal exposure concentrations and correlation with sources

Personal 48-hr exposures of 15 randomly selected participants as well as microenvironment concentrations in each participant's residence and workplace were measured for 16 carbonyl compounds during summer-fall 1997 as a part of the Air Pollution Exposure Distributions within Adult Urban Populations in Europe (EXPOLIS) study in Helsinki, Finland. When formaldehyde and acetaldehyde were excluded, geometric mean ambient air concentrations outside each participant's residence were less than 1 ppb for all target compounds. Geometric mean residential indoor concentrations of carbonyls were systematically higher than geometric mean personal exposures and indoor workplace concentrations. Additionally, residential indoor/outdoor ratios indicated substantial indoor sources for most target compounds. Carbonyls in residential indoor air correlated significantly, suggesting similar mechanisms of entry into indoor environments. Overall, this study demonstrated the important role of non-traffic-related emissions in the personal exposures of participants in Helsinki and that comprehensive apportionment of population risk to air toxics should include exposure concentrations derived from product emissions and chemical formation in indoor air.