Kara E. Huff Hartz

Cloud condensation nuclei activation of monoterpene and sesquiterpene secondary organic aerosol

[1] The ability of biogenic secondary organic aerosol (SOA) to contribute to the concentration of cloud condensation nuclei (CCN) in the atmosphere is examined. Aerosol is generated by the ozonolysis reaction of monoterpenes (α-pinene, β-pinene, 3-carene, and limonene) and sesquiterpenes (β-caryophyllene, α-humulene, and o-cedrene) in a 10 m 3 temperature-controlled Teflon smog chamber. In some cases, a self-seeding technique is used, which enables high particle concentrations with the desired diameters without compromising particle composition and purity. The monoterpene SOA is excellent CCN material, and it activates similarly (average activation diameter equals 48 ± 8 nm at 1% supersaturation for the species used in this work) to highly water-soluble organic species. Its effective solubility in water was estimated to be in the range of 0.07- 0.40 g solute/g H 2 O. CCN measurements for sesquiterpene SOA (average activation diameter equals 120 ± 20 nm at 1% supersaturation for the species used in this work) show that it is less CCN active than monoterpene SOA. The initial terpene mixing ratio (between 3 and 100 ppb) does not affect the CCN activation for freshly generated SOA.

Effect of bark beetle infestation on secondary organic aerosol precursor emissions.

Bark beetles are a potentially destructive force in forest ecosystems; however, it is not known how insect attacks affect the atmosphere. The emissions of volatile organic compounds (VOCs) were sampled i.) from bark beetle infested and healthy lodgepole pine (Pinus contorta var. latifolia) trees and ii.) from sites with and without active mountain pine beetle infestation. The emissions from the trunk and the canopy were collected via sorbent traps. After collection, the sorbent traps were extracted with hexane, and the extracts were separated and detected using gas chromatography/mass spectroscopy. Canister samples were also collected and analyzed by a multicolumn gas chromatographic system. The samples from bark beetle infested lodgepole pine trees suggest a 5- to 20-fold enhancement in total VOCs emissions. Furthermore, increases in the β-phellandrene emissions correlated with bark beetle infestation. A shift in the type and the quantity of VOC emissions can be used to identify bark beetle infestation but, more importantly, can lead to increases in secondary organic aerosol from these forests as potent SOA precursors are produced.

Laboratory measurements of the oxidation kinetics of organic aerosol mixtures using a relative rate constants approach

[1] Organic aerosols in the atmosphere are exposed to oxidants, but the oxidation kinetics are largely unknown. We investigate the decay of organic species in laboratory-generated organic aerosols exposed to atmospherically relevant ozone concentrations in a smog chamber. The experiments were conducted using five different organic aerosols, varying in complexity from three to twelve components. These mixtures include alkenoic acids, alkanoic acids, alkanedioic acids, n-alkanes, and sterols and are designed to simulate meat cooking emissions. A relative rate constants approach was used to compare reaction rates of individual organic species and to compare the reaction rates of the aerosol species to gas phase tracers. Significant decay was observed for all species (except for the n-alkanes) in at least one of the experimental systems. By relating the decomposition of condensed phase alkenoic acids to gas phase alkenes, we show that the reaction rate constants of oleic acid and palmitoleic acid evolve as the aerosol is processed, decreasing by a factor of ∼10 over the course of a 4-hour experiment. The decay rate constants of cholesterol, oleic acid, and palmitic acid all depend strongly on aerosol composition, with more than an order of magnitude change in the effective rate constants depending on mixture composition. Effects of aerosol composition are likely to be even more significant in atmospheric aerosol, where particle compositions are highly variable. The data presented here indicate these mixture effects are complicated, making it difficult to extrapolate from simple laboratory systems to atmospherically relevant conditions.

Fate and risk of atrazine and sulfentrazone to nontarget species at an agriculture site

The present study evaluated the risk associated with the application and co-occurrence of 2 herbicides, atrazine and sulfentrazone, applied to a 32-ha corn and soybean rotational field. Field concentrations of the compounds were measured in soil, runoff water, and groundwater, with peak mean atrazine and sulfentrazone concentrations found in the soil (144 ng/g dry wt, and 318 ng/g dry wt, respectively). Individual and mixture laboratory bioassays were conducted to determine the effects of atrazine and sulfentrazone on the survival of Daphnia magna and Pimephales promelas, the germination of Lactuca sativa, and the growth of Pseudokirchneriella subcapita and Lemna minor. Pseudokirchneriella subcapita and L. minor were the most susceptible species tested, and the effects on growth of the herbicides in mixtures best fit an independent action model. Risk quotients and margin of safety of 10% (MOS10) values were used to estimate risk and were calculated using runoff water concentrations. The MOS10 values were more sensitive than risk quotients in estimating risk. The MOS10 value for sulfentrazone runoff water concentration effects on P. subcapita was 7.8, and for L. minor was 1.1, with MOS10 values < 1 indicating potential risk. Overall, the environmentally relevant concentrations fell below the effect concentrations; therefore, atrazine and sulfentrazone posed little to no risk to the nontarget species tested. Environ Toxicol Chem 2017;36:1301-1310.

Fate and transport of furrow-applied granular tefluthrin and seed-coated clothianidin insecticides: Comparison of field-scale observations and model estimates

The transport of agricultural insecticides to water bodies may create risk of exposure to non-target organisms. Similarly, widespread use of furrow-applied and seed-coated insecticides may increase risk of exposure, yet accessible exposure models are not easily adapted for furrow application, and only a few examples of model validation of furrow-applied insecticides exist using actual field data. The goal of the current project was to apply an exposure model, the Pesticide in Water Calculator (PWC), to estimate the concentrations of two in-furrow insecticides applied to maize: the granular pyrethroid, tefluthrin, and the seed-coated neonicotinoid, clothianidin. The concentrations of tefluthrin and clothianidin in surface runoff water, sampled from a field in central Illinois (USA), were compared to the PWC modeled pesticide concentrations in surface runoff. The tefluthrin concentrations were used to optimize the application method in the PWC, and the addition of particulate matter and guttation droplets improved the models prediction of clothianidin concentrations. Next, the tefluthrin and clothianidin concentrations were calculated for a standard farm pond using both the optimized application method and the application methods provided in PWC. Estimated concentrations in a standard farm pond varied by a factor of 100 for tefluthrin and 50 for clothianidin depending on the application method used. The addition of guttation droplets and particulate matter to the model increased the annual clothianidin concentration in a standard farm pond by a factor of 1.5, which suggested that these transport routes should also be considered when assessing neonicotinoid exposure.

Effects of type and quantity of organic carbon on the bioaccessibility of polychlorinated biphenyls in contaminated sediments

Organic carbon principally controls sorption and desorption of hydrophobic organic compounds in sediments. We investigated the effects of organic carbon type and quantity on compound bioaccessibility. The desorption of 21 polychlorinated biphenyl (PCB) congeners was determined in spiked sediments amended with black carbon, humic acid, and sawdust at either 3 or 6% organic carbon. Desorption parameters were determined using Tenax sequential extractions and then modeled as operationally defined rapid, slow, and very slow fractions and rate constants. The effects of the amendments on PCB bioaccumulation were also evaluated using Lumbriculus variegatus. The lowest and highest PCB bioaccessibilities were observed in the black carbon and sawdust amendments, respectively. The total amount of PCBs desorbed ranged from 3 to 27% for the black carbon amendments, 12 to 55% for humic acid amendments, 16 to 80% for sawdust amendments, and 35 to 89% for controls. The results also showed that desorption of PCBs was slower in 6% amendments than 3% amendments, and this finding was most evident in humic acid and black carbon amendments. Overall, the trend in PCB bioaccumulation was similar to what was found for compound desorption in that the highest PCB bioaccumulation was observed in controls and sawdust amendments, whereas humic acid and black carbon amendments showed lower bioaccumulation. Finally, the 24-h single-point Tenax and bioaccumulation data were fit to a Tenax regression model. The PCB bioaccumulation was effectively predicted by the model, with 80% of the data falling within the 95% confidence intervals. Environ Toxicol Chem 2018;37:1280-1290.

Effect of sample holding time on bioaccessibility and sediment ecotoxicological assessments

The ecotoxicological effects of hydrophobic organic compound (HOC) contamination in sediment are often assessed using laboratory exposures of cultured invertebrates to field-collected sediment. The use of a sediment holding time (storage at 4 °C) between field sampling and the beginning of the bioassay is common practice, yet the effect of holding time on the reliability of bioassay results is largely unknown, especially for current-use HOCs, such as pyrethroid insecticides. Single-point Tenax extraction can be used to estimate HOC concentrations in the rapidly desorbing phase of the organic carbon fraction of sediment (i.e., bioaccessible concentrations), which relate to sediment toxicity and bioaccumulation in invertebrates. In this study, repeated measurements of bioaccessible concentrations (via Tenax), were made as a function of sediment holding time using pyrethroid-contaminated field sediment, and Hyalella azteca 10-d survival and growth was measured concurrently for comparison. Similarly, bioaccessible concentrations and 14-d bioaccumulation were measured in Lumbriculus variegatus as a comparison using the legacy HOCs, polychlorinated biphenyls (PCBs). While the bioaccessible and bioaccumulated PCB concentrations did not change significantly through 244 d of holding time, the bioaccessible pyrethroid concentrations were more varied. Depending on when pyrethroid-contaminated sediments were sampled, the bioaccessible pyrethroid concentrations showed first-order loss with half-lives ranging from 3 to 45 d of holding, or slower, linear decreases in concentrations up to 14% decrease over 180 d. These findings suggest that at least for some contaminants in sediments, holding the sediments prior to bioassays can bias toxicity estimates.

The Value of Using Multiple Metrics to Evaluate PCB Exposure

Current methods for evaluating exposure in ecosystems contaminated with hydrophobic organic contaminants typically focus on sediment exposure. However, a comprehensive environmental assessment requires a more holistic approach that not only estimates sediment concentrations, but also accounts for exposure by quantifying other pathways, such as bioavailability, bioaccumulation, trophic transfer potential, and transport of hydrophobic organic contaminants within and outside of the aquatic system. The current study evaluated the ability of multiple metrics to estimate exposure in an aquatic ecosystem. This study utilized a small lake contaminated with polychlorinated biphenyls (PCBs) to evaluate exposure to multiple trophic levels as well as the transport of these contaminants within and outside of the lake. The PCBs were localized to sediments in one area of the lake, yet this area served as the source of PCBs to aquatic invertebrates, emerging insects, and fish and terrestrial spiders in the riparian ecosystem. The Tenax extractable and biota PCB concentrations indicated tissue concentrations were localized to benthic invertebrates and riparian spiders in a specific cove. Fish data, however, demonstrated that fish throughout the lake had PCB tissue concentrations, leading to wider exposure risk. The inclusion of PCB exposure measures at several trophic levels provided multiple lines of evidence to the scope of exposure through the aquatic and riparian food web, which aids in assessing risk and developing potential future remediation strategies.