1,4‐Dioxane: Emerging technologies for an emerging contaminant

The synthetic chemical, 1,4‐dioxane, is classified by the U.S. Environmental Protection Agency (EPA) as a probable human carcinogen. Between 2013 and 2015, the EPA detected 1,4‐dioxane in public drinking water supplies in 45 states at concentrations up to 33 µg/L and in groundwater from releases at hazardous waste sites across the United States. Although a Federal maximum contaminant level drinking water standard has not yet been proposed, state‐specific standards and criteria are as low as 0.3 µg/L. 1,4‐Dioxane is a recalcitrant chemical in that applications of conventional treatment technologies have had limited success in reducing concentrations in water to meet current and proposed health‐protective levels. Although mainly used as a stabilizer for the solvent 1,1,1‐trichloroethane, it has been used in other industrial processes and has been detected in a variety of consumer products, such as foods, pharmaceuticals, cosmetics, and detergents. The high aqueous solubility of 1,4‐dioxane coupled with limited solubility of chlorinated solvents typically found in conjunction with 1,4‐dioxane contamination is the primary reason for its treatment challenges. In the last several years, an alternative, cost‐effective technology has been developed that has demonstrated treatment to levels significantly lower than the Federal and state‐specific goals. This article provides a Federal and state‐by‐state summary of 1,4‐dioxane‐specific drinking water and groundwater concentration criteria and qualitative comparison of the effectiveness of conventional treatment technologies compared to the effectiveness of an alternative treatment technology. A case study is also provided to present details regarding the application of an alternative treatment technology at an active groundwater remediation site in California.     

Ecosystem Consequences of Contrasting Flow Regimes in an Urban Effects Stream Mesocosm Study1

Abstract: A stream mesocosm experiment was conducted to study the ecosystem‐wide effects of two replicated flow hydrograph treatments programmed in an attempt to compare a simulated predevelopment condition to the theoretical changes that new development brings, while accounting for engineering design criteria for urban stormwater management. Accordingly, the treatments (three replicates each) differed in base flow between events and in the rise to, fall from, and duration of peak flow during simulated storm hydrographs, which were triggered by real rain events occurring outside over a 96‐day period from summer to fall, 2005. Incident irradiance, initial substrate quality, and water quality were similar between treatments. Sampling was designed to study the interactions among the treatment flow dynamics, sediment transport processes, streambed nutrients, and biotic structure and function. What appeared most important to the overall structure and function of the mesocosm ecosystems beyond those changes resulting from natural seasonality were (1) the initial mass of fines that infiltrated into the gravel bed, which had a persistent effect on nitrogen biogeochemistry and (2) the subsequent fine sediment accumulation rate, which was unexpectedly similar between treatments, and affected the structure of the macroinvertebrate community equally as the experiment progressed. Invertebrate taxa preferring soft beds dominated when the gravel was comprised of 5‐10% fines. The dominant invertebrate algal grazer had vacated the channels when fines exceeded 15%, but this effect could not be separated from what appeared to be a seasonal decline in insect densities over the course of the study. Neither hydrograph treatment allowed for scour or other potential for flushing of fines. This demonstrated the potential importance of interactions between hydrology and fine sediment loading dynamics on stream ecosystems in the absence of flows that would act to mobilize gravel beds.     

Anticipating public attitudes toward underground CO2 storage

Carbon capture and storage (CCS) may play a central role in managing carbon emissions from the power sector and industry, but public support for the technology is unclear. To address this knowledge gap, and to test the use of discrete choice analysis for determining public attitudes, two focus groups and a national survey were conducted in Canada to investigate the public's perceptions of the benefits and risks of CCS, the likely determinants of public opinion, and overall support for the use of CCS.The results showed slight support for CCS development in Canada, and a belief that CCS is less risky than normal oil and gas industry operations, nuclear power, or coal-burning power plants. A majority of respondents indicate that they would support the use of CCS as part of a greenhouse gas reduction strategy, although it would likely have to be used in combination with energy efficiency and alternative energy technologies in order to retain public support.     

Laboratory testing of a continuous emissions monitor for hydrochloric acid

Continuous monitoring of exhaust flue gas has become a common practice in power plants in response to Federal Mercury and Air Toxics Standards (MATS) standards. Under the current rules, hydrochloric acid (HCl) is not continuously measured at most plants; however, MATS standards have been proposed for HCl, and tunable diode laser (TDL) absorption spectroscopy is one method that can be used to measure HCl continuously. The focus of this work is on the evaluation and verification of the operation performance of an HCL TDL over a range of real-world operating environments. The testing was conducted at the University of California at Riverside (UCR) spectroscopy evaluation laboratory. Laboratory tests were conducted at three separate temperatures, 25ºC, 100ºC, and 200ºC, and two distinct moisture levels for the enhanced temperatures, 0%, (2 tests) and 4%, over a concentration range from 0 ppmv to 25 ppmv-m at each of the elevated temperatures. The results showed good instrument accuracy as a function of changing temperature and moisture. Data analysis showed that the average percentage difference between the ammonia concentration and the calibration source was 3.33% for varying moisture from 0% to 4% and 2.69% for varying temperature from 25 to 100/200ºC. An HCl absorption line of 1.742 μm was selected for by the manufacturer for this instrument. The Hi Tran database indicated that CO₂ is probably the only major interferent, although the CO₂ absorption is very weak at that wavelength. Interference tests for NO, CO, SO₂, NH₃, and CO₂ for a range of concentrations typical of flue gasses in coal-fired power plants did not show any interference with TDL HCl measurements at 1.742 μm. For these interference tests, CO₂ was tested at a concentration of 11.9% concentration in N₂ for these tests. Average precision over the entire range for all 10 tests is 3.12%.

Implications: The focus of this study was an evaluation of the operation performance of a tunable diode laser (TDL) for the measurement of hydrochloric acid (HCl) over a range of real-world operating environments. The results showed good instrument accuracy as a function of changing temperature from 25ºC to 200ºC and moisture from 0% to 4%. Such as an instrument could be used for continuous monitoring of exhaust flue gas in power plants once the Federal Mercury and Air Toxics Standards (MATS) standards have been fully implemented.     

A Method for Setting the Size of Plant Conservation Target Areas

Abstract: Realistic time frames in which management decisions are made often preclude the completion of the detailed analyses necessary for conservation planning. Under these circumstances, efficient alternatives may assist in approximating the results of more thorough studies that require extensive resources and time. We outline a set of concepts and formulas that may be used in lieu of detailed population viability analyses and habitat modeling exercises to estimate the protected areas required to provide desirable conservation outcomes for a suite of threatened plant species. We used expert judgment of parameters and assessment of a population size that results in a specified quasiextinction risk based on simple dynamic models. The area required to support a population of this size is adjusted to take into account deterministic and stochastic human influences, including small-scale disturbance, deterministic trends such as habitat loss, and changes in population density through processes such as predation and competition. We set targets for different disturbance regimes and geographic regions. We applied our methods to Banksia cuneata, Boronia keysii, and Parsonsia dorrigoensis, resulting in target areas for conservation of 1102, 733, and 1084 ha, respectively. These results provide guidance on target areas and priorities for conservation strategies.     

Use of continuous monitoring to assess stream nitrate flux and transformation patterns

Delivery of nitrogen from farmed fields to the stream network is an ongoing water quality issue in central North America and other parts of the world. Although fertilization and other farming practices have been refined to produce environmental improvements, stemming loss of nitrogen, especially in the soluble nitrate form, is a problem that has seemingly defied solution. The Iowa Nutrient Reduction Strategy is a policy initiative designed to implement conservation and other farm management practices to produce reductions in nitrate loading. The strategy does not focus on how the streams themselves may or may not be processing nitrogen and reducing downstream loading. We used continuous high-frequency nitrate and discharge monitoring over 3 years at two sites separated by 18 km in a low-order, agricultural stream in eastern Iowa to estimate how nitrogen is processed, and whether or not these processes are reducing downstream loading. We conclude that the upstream to downstream nitrate concentration decline between the two sites was not driven by denitrification. These data also show that nitrate concentrations are closely coupled to discharge during periods of adequate moisture, but decoupling of concentration from discharge occurs during dry periods. This decoupling is a possible indicator of in-stream nitrate processing. Finally, nitrate concentrations are likely diluted by water sourced from non-row crop land covers in the lower reaches of the watershed.     

Modification of an Ambient Air Quality Model for Assessment of U. S. Naval Aviation Emittants

Previous studies have indicated that the EPA-HIWAY model significantly overestimates the pollutant concentrations for stable atmospheric conditions, especially under parallel wind-road orientation angles with low wind speed. This overestimation is due to the fact that the model's dispersion parameters do not properly account for the traffic-induced turbulence near roadways. In this paper, the Pasquill- Gifford dispersion curves used by the model are modified based on the recent studies that have quantified the nature of the trafficinduced turbulence and its influence on the pollutant dispersion in the near-field. The results show that the model performance is significantly improved when these new dispersion curves in conjunction with an aerodynamic drag factor, which in a rough way accounts for the change in the mean wind field due to the moving vehicles, are used in the HIWAY model.     

Dietary exposure of rainbow trout to 8:2 and 10:2 fluorotelomer alcohols and perfluorooctanesulfonamide: Uptake, transformation and elimination

The bioaccumulation of perfluorooctanesulfonamide (PFOSA) and two fluorotelomer alcohols (8:2 FTOH, 10:2 FTOH) by rainbow trout (Oncorhynchus mykiss) through dietary exposure, including depuration rates and metabolism was investigated. Concentrations in the spiked feed ranged from 10.9 μg g⁻¹ wet weight (wet wt) for PFOSA and 6.7 μg g⁻¹ wet wt for 8:2 FTOH to 5.0 μg g⁻¹ wet wt for 10:2 FTOH. Trout was fed at 1.5% body weight per day for 30 d and depuration was followed for up to 30 d following previously published dietary exposure protocols. Perfluorooctanesulfonate (PFOS) was the major perfluoroalkylsulfonate (PFSA) detected in fish following dietary exposure to PFOSA. Half-lives of PFOS and PFOSA were 16.9 ± 2.5 and 6.0 ± 0.4 d, respectively. A biomagnification factor (BMF) of 0.023 was calculated for PFOSA which indicates that dietary exposure to PFOSA does not result in biomagnification in the rainbow trout. PFOS had a BMF of 0.08. The fluorotelomer saturated acids (8:2 FTCA, 10:2 FTCA) and fluorotelomer unsaturated acids (8:2 FTUCA, 10:2 FTUCA) were the major products detected in rainbow trout following dietary exposure to 8:2 FTOH and 10:2 FTOH, respectively. Half-lives were 3.7 ± 0.4, 2.1 ± 0.5, 3.3, and 1.3 d for 10:2 FTCA, 10:2 FTUCA, 8:2 FTCA, and 8:2 FTUCA, respectively. Small amounts of perfluorooctanoate (PFOA) and perfluorodecanoate (PFDA) were also detected in the FTOH exposed fish.     

Ammonia emissions from field-simulated cattle defecation and urination

Atmospheric ammonia (NH(3)) is a concern because of its environmental impact. The greatest contribution to atmospheric NH(3) comes from agricultural sources. This study quantified NH(3) volatilization from cattle defecation and urination on pasture under field conditions in Auburn, Alabama. Treatments consisted of beef feces, dairy feces, dairy urine, and a control. The experiment was conducted during four seasons from June 2003 to April 2004. Fresh feces or urine was applied onto grass swards, and NH(3) volatilization was measured up to 14 d after application using an inverted chamber method. Dairy urine was the only significant source of NH(3). Ammonia nitrogen (N) loss differed among seasons, ranging from 1.8% in winter to 20.9% during the warmer summer months. Cumulative volatilization was best described in this experiment by the equation % NH(3)-N loss = N(max) (1 - e(-ct))(i). The highest rate of NH(3) volatilization generally occurred within 24 h. This study suggests that NH(3) volatilization from cattle urine on pasture is significant and varies with season, whereas NH(3) volatilization from cattle feces is negligible.     

Predicting organic contaminant concentrations in sediment porewater using solid-phase microextraction

Because of its cost and time saving features, solid-phase microextraction (SPME) is a leading candidate as a biomimic technique in assessing the bioavailable fraction of hydrophobic organic contaminants (HOCs) in sediment porewater. However, no predictive modeling framework in which to systematically address the effect of key parameters on SPME performance for this application exists. In this study, we derived two governing equations to predict (1) the minimum sediment volume (V(s)min) required to achieve non-depletive conditions, and (2) dissolved phase HOC porewater concentrations (C(pw)) as functions of HOC- and sediment specific characteristics in a conceptual three compartment system. The resulting model predicted that V(s)min was independent of HOC concentrations both in sediment and porewater, but did vary with hydrophobicity (characterized by logK(ow)), the fraction of sediment porewater (f(pw)), and the volume (V(f)) of the SPME sorbent phase. Moreover, the effects of these parameters were minimized (i.e., V(s)min reached plateaus) as logK(ow) approached 4-5. Model predictions of C(pw), a surrogate for SPME-based detection limits in porewater, decreased with increasing sediment volume (V(s)) at low V(s) values, but rapidly leveled off as V(s) increased. A third result suggested that the sediment HOC concentration required for SPME is completely independent of K(ow). These results suggest that relatively small sediment volumes participate in exchange equilibria among sediment, porewater and the SPME fiber, and that large sediment HOC reservoirs are not needed to improve the detection sensitivity of SPME-based porewater samplers. The ultimate utility of this modeling framework will be to assist future experimental designs and help predict in situ bioavailability of sediment-associated HOCs.