Numerical Investigation of the Effects of Boundary-Layer Evolution on the Predictions of Ozone and the Efficacy of Emission Control Options in the Northeastern United States

This paper examines the effects of two different planetary boundary-layer (PBL) parameterization schemes – Blackadar and Gayno–Seaman – on the predicted ozone (O₃) concentration fields using the MM5 (Version 3.3) meteorological model and the MODELS-3 photochemical model. The meteorological fields obtained from the two boundary-layer schemes have been used to drive the photochemical model to simulate O₃ concentrations in the northeastern United States for a three-day O₃ episodic period. In addition to large differences in the predicted O₃ levels at individual grid cells, the simulated daily maximum 1-h O₃ concentrations appear at different regions of the modeling domain in these simulations, due to the differences in the vertical exchange formulations in these two PBL schemes. Using process analysis, we compared the differences between the different simulations in terms of the relative importance of chemical and physical processes to O₃ formation and destruction over the diurnal cycle. Finally, examination of the photochemical model's response to reductions in emissions reveals that the choice of equally valid boundary-layer parameterizations can significantly influence the efficacy of emission control strategies.     

Bench-scale testing of a novel soil PFAS treatment train for informed remedial planning and decision-making

Bench-scale batch tests were conducted to assess the potential applicability of a combined separation/concentration/destruction treatment train to address soils and sediments impacted by per- and polyfluoroalkyl substances (PFAS) contamination at Schriever Space Force Base with historic aqueous film-forming foam (AFFF). Specifically, a novel treatment train coupling soil washing (for treatment of impacted soil/sediment) with foam fractionation (for treatment of the wash water [WW] generated during soil washing) and electrochemical oxidation (ECO, for treatment of the foam fractionate generated during foam fractionation) was evaluated at the bench scale using site-specific materials. Results presented herein show that the AFFF-impacted sandy soils with low organic content were amenable to treatment via soil washing. However, the removal of hydrophobic PFAS, such as perfluorooctanesulfonic acid (PFOS), from the organic-rich sediments was challenging. Results from batch desorption experiments were within a factor of 2 of those generated by soil washing bench studies, suggesting that simple batch tests can potentially be used to reasonably predict the treatment efficacy of soil washing. Long-chained perfluoroalkyl acids (PFAAs) within the WW were removed more effectively in the foam fractionation studies as compared to short-chain PFAAs. Addition of a surfactant, such as cetrimonium bromide (CTAB), enhanced foaming but only marginally improved the treatment of short-chained PFAAs and in some cases inhibited PFOS removal. ECO reduced PFAS concentrations in the foam fractionate generated during foam fractionation by several orders of magnitude. However, generation of unwanted byproducts may warrant further treatment and/or disposal. Overall, results from this study provide a novel data set highlighting the site-dependent nature of these PFAS remedial technologies and how simple, low-cost bench tests can be reliably leveraged for informed decision-making during PFAS remedial planning.     

Photo-oxidation and Photo-toxicity of Crude and Refined Oils

The fate and effects of an oil spill are effected by solar radiation through the action of photo-oxidation and photo-toxicity. Photo-oxidation, an important process in the weathering of oil, produces a variety of oxidized compounds, including aliphatic and aromatic ketones, aldehydes, carboxylic acids, fatty acids, esters, epoxides, sulfoxides, sulfones, phenols, anhydrides, quinones and aliphatic and aromatic alcohols. Some of these compounds contribute to the marine biota toxicity observed after an oil spill. Photo-toxicity occurs when uptake of certain petroleum compounds, e.g. certain polycyclic aromatic hydrocarbons and benzothiophenes, is followed by solar exposure which results in much greater toxicity than after dark uptake. The mechanism of PAH photo-toxicity includes absorbance of solar radiation by the PAH which produces a free radical and this free radical in turn reacts with oxygen to produce reactive oxygen species that can damage DNA and other cellular macromolecules. While most studies on photo-toxicity have been carried out in the laboratory, there are studies showing that water from an oil spill is photo-toxic to bivalve embryos for at least a few days after the spill. Other studies have found that oil contaminated sediments are photo-toxic to several marine invertebrates. More studies are required to determine if marine fauna at an oil spill site are effected by the action of photo-toxicity and photo-oxidation.     

Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Relationships Between Macroinvertebrate Assemblages of Stony Littoral Habitats and Water Chemistry Variables Indicative of Acid-stress

Gradient analyses were used to correlatively determine the importance of acid-related variables for littoral macroinvertebrate assemblages. To better ascertain the effects of acidity on macroinvertebrate assemblages we removed sites judged to be affected by other stressors such as agriculture, urbanization and liming. PCA of land use and water chemistry confirmed the presence of an acidity gradient; several acidity variables (e.g. pH and buffering capacity) were strongly correlated with the first PC axis, which explained Ca 32% of the variance in the environmental data. Partial constrained ordination of littoral macroinvertebrate assemblages with water chemistry, after removing the effect of other confounding variables (e.g. land use/type), showed that acidity variables accounted for significant amounts of among-lake variability in assemblage structure. Regression of canonical scores (a metric of community composition) and diversity with pH and alkalinity was used to visually determine ecological breakpoints or threshold values. Five classes were established for pH: pH?<?5 (extremely acid), 5?<?pH?≤?5.6 (very acid), 5.6?<?pH?≤?6.2 (acid), 6.2?<?pH?≤?6.8 (weakly acid) and pH?>?6.8 (neutral-alkaline). Similarly, three classes were determined for alkalinity/acidity: <0.02, 0.02–0.1 and >0.1 meq/L.     

A Large-Eddy Simulation Study of the Convective Boundary Layer over Philadelphia during the 1999 Summer NE-OPS Campaign

This study presents a large-eddy simulation (LES) study of the convective boundary layer on August 1, 1999 over Philadelphia, PA during a summer ozone episode. The study is an evaluation of the Colorado State University's Regional Atmospheric Modeling System Version 4.3 (RAMS4.3) with the LES option using Northeast Oxidant and Particulate Study (NE-OPS) data. Simulations were performed with different imposed sensible heat fluxes at the ground surface. The model was initialized with the atmospheric sounding data collected at Philadelphia at 1230 UTC and model integrations continued till 2130 UTC. The resulting mean profiles of temperature and humidity obtained from the LES model were compared with atmospheric soundings, tethered balloon and aircraft data collected during the NE-OPS 1999 field campaign. Also the model-derived vertical profiles of virtual temperature were compared with NE-OPS Radio Acoustic Sounder System (RASS) data while the humidity profiles were compared with NE-OPS lidar data. The comparison of the radiosonde data with the LES model predictions suggests that the growth of the mixing layer is reasonably well simulated by the model. Overall, the agreement of temperature predictions of the LES model with the radiosonde observations is good. The model appears to underestimate humidity values for the case of higher imposed sensible heat flux. However, the humidity values in the mixing layer agree quite well with radiosonde observations for the case of lower imposed sensible heat flux. The model-predicted temperature and humidity profiles are in reasonable agreement with the tethered balloon data except for some small overestimation of temperature at lower layers and some underestimation of humidity values. However, the humidity profiles as simulated by the model agree quite well with the tethered balloon data for the case of lower imposed sensible heat flux. The model-predicted virtual temperature profile is also in better agreement with RASS data for the case of lower imposed sensible heat flux. The model-predicted temperature profile further agrees quite well with aircraft data for the case of lower imposed heat flux. However, the relative humidity values predicted by the model are lower compared with the aircraft data. The model-predicted humidity profiles are only in partial agreement with the lidar data. The results of this study suggest that the explicitly resolved energetic eddies seem to provide the correct forcing necessary to produce good agreement with observations for the case of an imposed sensible heat flux of 0.1 K m s^–1 at the surface.     

Environmental risk assessment of metals contaminated soils at silvermines abandoned mine site,Co Tipperary,Ireland

A centuries long history of mining and mineral processing has resulted in elevated Cd, Pb and Zn soil concentrations in the vicinity of the Silvermines abandoned mine site (AMS), Co. Tipperary, Ireland. A process for preliminary evaluation of environmental risk was developed and implemented. Potential pathways of metal compound transport and deposition were mapped and used to optimise the subsequent site investigation. Elevated soil metals are shown to be predominantly in areas where metal deposition in soil is associated with water related pathways (surface runoff, seasonal groundwater seepage and floodplains). Extensive areas of soil in the surrounding district are classified as contaminated on the basis of Cd, Pb and Zn concentrations, both total and potential bioavailable (EDTA-extractable). The most affected areas, with metal concentrations in soil comparable with that within the AMS, were floodplains located 2–3 km downstream from the site. Assessment of the sequential effects on grass and grazing animals indicates that Pb poses the greatest risk due to its high toxicity and high concentrations in soil (more than 10 000 mg kg^–1). Within floodplain areas grazing cattle may intake a lethal dose of Pb. On the basis of the investigation an approach to risk assessment was developed which allowed quantified assessment of the risks related to individual metals, areas of contamination and contamination targets.     

Mitigating the effects of climate change on the nests of sea turtles with artificial irrigation

For sea turtles, like many oviparous species, increasing temperatures during development threaten to increase embryonic mortality, alter offspring quality, and potentially create suboptimal primary sex ratios. Various methods are being implemented to mitigate the effects of climate change on reproductive success, but these methods, such as breeding programs, translocations, and shading, are often invasive and expensive. Irrigation is an alternative strategy for cooling nests that, depending on location, can be implemented relatively quickly and cheaply. However, multiple factors, including ambient conditions, nest substrate, and species characteristics, can influence irrigation success. Additionally, irrigation can vary in duration, frequency, and the volume of water applied to nests, which influences the cooling achieved and embryonic survival. Thus, it is critical to understand how to maximize cooling and manage risks before implementing irrigation as a nest-cooling strategy. We reviewed the literature on nest irrigation to examine whether artificial irrigation is feasible as a population management tool. Key factors that affected cooling were the volume of water applied and the frequency of applications. Embryonic responses varied with species, ambient conditions, and the timing of irrigation during development. Nest inundation was the key risk to a successful irrigation regime. Future irrigation regimes must identify clear targets, either primary or adult sex ratios, that maximize population viability. Monitoring population responses and adjusting the irrigation regime in response to population characteristics will be critical. Most studies reported on the manipulation of only one or two variables, further research is required to understand how altering multiple factors in an irrigation regime influences the cooling achieved and embryonic responses.     

Release of nitrogen and trace metal species from field stacked biosolids

Concerns over elevated nitrate (NO3-) levels found in groundwater near former biosolid stockpiling locations resulted in the Maine Department of Environmental Protection (MDEP) imposing stricter regulations governing the stockpiling of biosolids in October 2002. The goals of this study were to measure the amount and speciation of nitrogen (N) and trace metals leaving stockpiled biosolids and travelling through the soil column. The biosolids were placed on plastic-lined cells to collect all leachate. Ammonium (NH4+), ranging from 2000 to 4900 mg L(-1), was the dominant N species (90% of total N) in the leachate from the Class B lime-stabilized biosolids in the lined cell experiment. Nitrate (NO3-) and nitrite (NO2-) concentrations were negligible, remaining below 0.25 and 0.1 mg L(-1), respectively. Dissolved organic carbon (DOC) concentrations as high as 8900 mg L(-1) and chemical oxygen demand (COD) as high as 37 000 mg L(-1) were measured in the leachate leaving the lined cell. Fifteen zero-tension pan lysimeters (ZTP-lysimeter) were installed in a 90 m2 plot at depth intervals of 30, 60, and 100 cm. Leachate passing through the soil column underlying the biosolids stockpile was collected in the ZTP-lysimeters. The average ZTP-lysimeter NH4+ concentrations ranged from 1400 mg L(-1) at 60 cm depth to 145 mg L(-1) at 90 cm depth. The average ZTP-lysimeter DOC concentrations ranged from 2000 mg L(-1) at 60 cm to 525 mg L(-1) at 90 cm. Trace metal determinations of the leachate collected from the lined cell and ZTP-lysimeters showed arsenic loading rates exceeded the state limits of 0.5 kg ha(-1) year(-1) by an order of magnitude. Arsenic concentrations were in excess of several thousand milligrams per litre in the lined-cell leachate and several hundred milligrams per litre in the ZTP-lysimeters as deep as 90 cm under the biosolid stockpile. Phosphorus, iron and manganese in excess of several thousand milligrams per litre were observed in both the lined-cell leachate and ZTP-lysimeters. Significant concentrations of other trace metals were found at depth in the zero-tension ZTP-lysimeter plot. Trace metals were largely mobilized by the DOC from the biosolids and due to the presence of anaerobic environment, especially in the underlying soil.