Apportionment of Ambient Primary and Secondary Pollutants during a 2001 Summer Study in Pittsburgh Using U.S. Environmental Protection Agency UNMIX

Abstract

Apportionment of primary and secondary pollutants during the summer 2001 Pittsburgh Air Quality Study (PAQS) is reported. Several sites were included in PAQS, with the main site (the supersite) adjacent to the Carnegie Mellon University campus in Schenley Park. One of the additional sampling sites was located at the National Energy Technology Laboratory, located ～18 km southeast of downtown Pittsburgh. Fine particulate matter (PM_2.5) mass, gas-phase volatile organic material (VOM), particulate semivolatile and nonvolatile organic material (NVOM), and ammonium sulfate were apportioned at the two sites into their primary and secondary contributions using the U.S. Environmental Protection Agency UNMIX 2.3 multivariate receptor modeling and analysis software. A portion of each of these species was identified as originating from gasoline and diesel primary mobile sources. Some of the organic material was formed from local secondary transformation processes, whereas the great majority of the secondary sulfate was associated with regional transformation contributions. The results indicated that the diurnal patterns of secondary gas-phase VOM and particulate semivolatile and NVOM were not correlated with secondary ammonium sulfate contributions but were associated with separate formation pathways. These findings are consistent with the bulk of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport and, thus, decoupled from local activity involving organic pollutants in the metropolitan area.     

Seawater Intrusion and Sustainable Yield of Basal Aquifers1

Liu, Clark C.K. and John J. Dai, 2012. Seawater Intrusion and Sustainable Yield of Basal Aquifers. Journal of the American Water Resources Association (JAWRA) 48(5): 861‐870. DOI: 10.1111/j.1752‐1688.2012.00659.x Abstract: Basal aquifers, in which freshwater floats on top of saltwater, are the major freshwater supply for the Hawaiian Islands, as well as many other coastal regions around the world. Under unexploited or natural conditions, freshwater and the underlying seawater are separated by a relatively sharp interface located below mean sea level at a depth of about 40 times the hydraulic head. With forced draft, the hydraulic head of a basal aquifer would decline and the sharp interface would move up. It is a serious problem of seawater intrusion as huge amounts of freshwater storage is replaced by saltwater. Also, with forced draft, the sharp interface is replaced by a transition zone in which the salinity increases downward from freshwater to saltwater. As pumping continues, the transition zone expands. The desirable source‐water salinity in Hawaii is about 2% of the seawater salinity. Therefore, the transition zone expansion is another serious problem of seawater intrusion. In this study, a robust analytical groundwater flow and salinity transport model (RAM2) was developed. RAM2 has a simple mathematical structure and its model parameters can be determined satisfactorily with the available field monitoring data. The usefulness of RAM2 as a viable management tool for coastal ground water management is demonstrated by applying it to determine the sustainable yield of the Pearl Harbor aquifer, a principal water supply source in Hawaii.     

Application of Rosgen’s BANCS Model for NE Kansas and the Development of Predictive Streambank Erosion Curves1

Sass, Christopher K. and Tim D. Keane, 2012. Application of Rosgen’s BANCS Model for NE Kansas and the Development of Predictive Streambank Erosion Curves. Journal of the American Water Resources Association (JAWRA) 48(4): 774‐787. DOI: 10.1111/j.1752‐1688.2012.00644.x Abstract: Sedimentation of waterways and reservoirs directly related to streambank erosion threatens freshwater supply. This study sought to provide a tool that accurately predicts annual streambank erosion rates in NE Kansas. Rosgen (2001, 2006) methods were employed and 18 study banks were measured and monitored from 2007 through 2010 (May‐June). Bank profiles were overlaid to calculate toe pin area change due to erosional processes. Streambanks experienced varied erosion rates from similar Bank Erosion Hazard Index (BEHI)‐Near Bank Stress (NBS) combinations producing R² values of 0.77 High‐Very High BEHI rating and 0.75 Moderate BEHI rating regarding predictive erosion curves for NE Kansas. Moderate ratings demonstrated higher erosion rates than High‐Very High ratings and BEHI trend lines intersected at lower NBS ratings, suggesting a discrepancy in the fit of the model to conditions in the NE Kansas region. BEHI model factors were evaluated and assessed for additional influences exerted in the region. Woody vegetation adjacent to the stream seemed to provide the most variation in erosion rates. This study’s findings allowed us to calibrate and modify the existing BEHI model according to woody vegetation occurrence levels along streambanks with high clay content. Modifications regarding vegetation occurrence of the BEHI model was completed and the results of these modifications generated new curves resulting in R² values of 0.84 High‐Very High BEHI and 0.88 Moderate BEHI ratings.     

Treelines will be understood once the functional difference between a tree and a shrub is

Trees are taller than shrubs, grasses, and herbs. What is the disadvantage of being tall so that trees are restricted to warmer regions than low stature life forms? This article offers a brief review of the current state of biological treeline theory, and then explores the significance of tallness from a carbon balance, freezing resistance, and microclimatological perspective. It will be argued that having of a woody stem is neither a burden to the carbon balance nor does it add to the risk of freezing damage. The physiological means of trees to thrive in cold climates are similar to small stature plants, but due to their size, and, thus, closer aerodynamic coupling to air circulation, trees experience critically low temperatures at lower elevation and latitude than smaller plants. Hence, trees reach a limit at treeline for physical reasons related to their stature.     

Organochlorine pesticides in soil under irrigated cotton farming systems in Vertisols of the Namoi Valley, north-western New South Wales, Australia

Organochlorine pesticides (OCPs) such as DDT and DDE have been detected in the surface 0.2 m of Vertisols in the lower Namoi Valley of north western New South Wales, Australia even though they have not been applied to crops since 1982. However, their presence in the deeper soil horizons has not been investigated. The objective of this study was to determine if OCPs were present to a depth of 1.2 m in Vertisols under irrigated cotton farming systems in the lower Namoi Valley of New South Wales. Soil was sampled from the 0-1.2 m depths in three sites, viz. the Australian Cotton Research Institute, ACRI, near Narrabri (149°36′E, 30°12′S), and two cotton farms near Wee Waa (149°27′E, 30°13′S) and Merah North (149°18′E, 30°12′S) in northern New South Wales, Australia. The OCPs detected and their metabolites were α-endosulfan, β-endosulfan, endosulfan sulphate, DDD, DDE, DDT and endrin. The metabolite DDE, a breakdown product of DDT, was the most persistent OCP in all depths analysed. Endosulfan sulphate was the second most persistent followed by endrin > α-endosulfan > β-endosulfan > DDT and DDD. DDT was sprayed extensively in the lower Namoi Valley up to the early 1980s and may explain the persistence of DDE in the majority of soil samples. Dicofol and Dieldrin, two OCPs previously undocumented in Vertisols were also detected. The movement of OCPs into the subsoil of Vertisols may occur when irrigation or rain transports soil colloids and organic matter via preferential flow systems into the deeper layers of a soil profile. Persistence of OCPs was closely correlated to soil organic carbon concentrations. The persistence in soil of OCP’s applied to cotton crops grown more than two decades ago suggests that they could enter the food chain. Their presence at depths of 1.2 m suggests that they could move into groundwater that may eventually be used for domestic and stock consumption.     

Detection of early effects of a single herbicide (diuron) and a mix of herbicides and pharmaceuticals (diuron, isoproturon, ibuprofen) on immunological parameters of Pacific oyster (Crassostrea gigas) spat

In the context of massive summer mortality events of the Pacific oyster Crassostrea gigas, the aim of this study was to investigate the early effects on genes, enzymes and haemocyte parameters implicated in immune defence mechanisms in C. gigas oysters exposed to a potentially hostile environment, i.e. to an herbicide alone or within a mixture. Following 2 h of exposure to the herbicide diuron at 1 μg L⁻¹, the repression of different genes implicated in immune defence mechanisms in the haemocytes and the inhibition of enzyme activities, such as laccase-type phenoloxidase (PO) in the plasma, were observed. The inhibition of superoxide dismutase (SOD) activity in the plasma was also observed after 6 and 24 h of exposure. In the mixture with the herbicides diuron and isoproturon, and the pharmaceutical ibuprofen, catecholase-type PO activity in the plasma and the percentage of phagocytosis in the haemocytes were reduced after 6 h of exposure. Our results showed that early effects on molecular, biochemical and cellular parameters can be detected in the presence of diuron alone or within a mixture, giving an insight of its potential effect in situations that can be found in natural environments, i.e. relatively high concentrations for short periods of time.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Characterization of silver release from commercially available functional (nano)textiles

Silver, both in the nano as well as in other forms, is used in many applications including antimicrobial textiles. Washing of such textiles has already been identified as an important process that results in the release of silver into wastewater. This study thus investigated the release of silver from eight different commercially available silver-textiles during a washing and rinsing cycle. The silver released was size-fractionated and characterized using electron microscopy. In addition, the antimicrobial functionality of the textiles was tested before and after washing. Three of the textiles contained nanosized silver (labeled or confirmed by manufacturers’ information), another used a metallic silver wire and four contained silver in undeclared form. The initial silver content of the textiles was between 1.5 and 2925 mg Ag/kg. Only four of the investigated textiles leached detectable amounts of silver, of which 34-80% was in the form of particles larger than 450 nm. Microscopic analysis of the particles released in the washing solutions identified Ti/Si-AgCl nanocomposites, AgCl nanoparticles, large AgCl particles, nanosilver sulfide and metallic nano-Ag, respectively. The nanoparticles were mainly found in highly agglomerated form. The identified nanotextiles showed the highest antimicrobial activity, whereas some of the other textiles, e.g. the one with a silver wire and the one with the lowest silver content, did not reduce the growth of bacteria at all. The results show that different silver textiles release different forms of silver during washing and that among the textiles investigated AgCl was the most frequently observed chemical form in the washwater.     

Influence of Suwannee River humic acid on particle properties and toxicity of silver nanoparticles

Adsorption of natural organic matter (NOM) on nanoparticles can have dramatic impacts on particle dispersion resulting in altered fate and transport as well as bioavailability and toxicity. In this study, the adsorption of Suwannee River humic acid (SRHA) on silver nanoparticles (nano-Ag) was determined and showed a Langmuir adsorption at pH 7 with an adsorption maximum of 28.6 mg g⁻¹ nano-Ag. It was also revealed that addition of <10 mg L⁻¹ total organic carbon (TOC) increased the total Ag content suspended in the aquatic system, likely due to increased dispersion. Total silver content decreased with concentrations of NOM greater than 10 mg TOC L⁻¹ indicating an increase in nanoparticle agglomeration and settling above this concentration. However, SRHA did not have any significant effect on the equilibrium concentration of ionic Ag dissolved in solution. Exposure of Daphnia to nano-Ag particles (50 μg L⁻¹ and pH 7) produced a linear decrease in toxicity with increasing NOM. These results clearly indicate the importance of water chemistry on the fate and toxicity of nanoparticulates.