Partitioning and removal of perfluorooctanoate during rain events: the importance of physical-chemical properties

The potential for airborne emissions to undergo long-range transport or to be removed from the atmosphere is influenced by their physical-chemical properties. When perfluorooctanate (PFO) enters the environment, its physical-chemical properties can vary significantly, depending on whether it exists as an acid, a salt, or a dissociated ion. A summary of the physical-chemical properties of the three most likely environmental states: ammonium perfluorooctanoate (APFO), perfluorooctanoic acid (PFOA) and the dissociated perfluorooctanoate anion (PFO(-)) is presented to illustrate the distinct environmental properties of each. The most volatile species, PFOA, is shown to have a pH-dependent air-water partitioning coefficient (K(aw)). The variability of K(aw) with pH influences the potential for vapor formation from aqueous environments, including rain events. Using the pH-dependent K(aw) and measured rain and air concentrations, it is shown that vapor-phase PFOA is not likely to be present above measurable levels of 0.2 ng m(-3) (12 parts per quadrillion v/v) during a rain event. Because rain concentrations determined in this work are comparable to measurements in other parts of North America, it is unlikely that rain events are a significant source of vapor-phase PFOA for the general North American region. It is shown that PFOA exists primarily in the particle phase in ambient air near direct sources of emissions and is efficiently scavenged by rain droplets, making wet deposition an important removal mechanism for emissions originating as either PFOA or APFO. Washout ratios of particle-associated PFO were determined to range between 1 x 10(5) and 5 x 10(5), in the same range as other semi-volatile compounds for which wet deposition is an important mechanism for atmospheric removal and deposition onto soils and water bodies.     

Fecal source tracking by antibiotic resistance analysis on a watershed exhibiting low resistance

The ongoing development of microbial source tracking has made it possible to identify contamination sources with varying accuracy, depending on the method used. The purpose of this study was to test the efficiency of the antibiotic resistance analysis (ARA) method under low resistance by tracking the fecal sources at Turkey Creek, Oklahoma exhibiting this condition. The resistance patterns of 772 water-isolates, tested with nine antibiotics, were analyzed by discriminant analysis (DA) utilizing a five-source library containing 2250 isolates. The library passed various representativeness tests; however, two of the pulled-sample tests suggested insufficient sampling. The resubstitution test of the library individual sources showed significant isolate misclassification with an average rate of correct classification (ARCC) of 58%. These misclassifications were explained by low antibiotic resistance (Wilcoxon test P < 0.0001). Seasonal DA of stream E. coli isolates for the pooled sources human/livestock/deer indicated that in fall, the human source dominated (P < 0.0001) at a rate of 56%, and that human and livestock respective contributions in winter (35 and 39%), spring (43 and 40%), and summer (37 and 35%) were similar. Deer scored lower (17–28%) than human and livestock at every season. The DA was revised using results from a misclassification analysis to provide a perspective of the effect caused by low antibiotic resistance and a more realistic determination of the fecal source rates at Turkey Creek. The revision increased livestock rates by 13–14% (0.04 ≤ P ≤ 0.06), and decreased human and deer by 6–7%. Negative misclassification into livestock was significant (0.04 ≤ P ≤ 0.06). Low antibiotic resistance showed the greatest effect in this category.     

Water quality characteristics of discharge from reforested loose-dumped mine spoil in eastern Kentucky

Surface mining is a common method for extracting coal in the coal fields of eastern Kentucky. Using the Forestry Reclamation Approach (FRA), which emphasizes the use of minimally compacted or loose-dumped spoil as a growth medium for trees, reclamation practitioners are successfully reestablishing forests. Yet, questions remain regarding the effects FRA has on the quality of waters discharged to receiving streams. To examine the effect of FRA on water quality, this study compared waters that were discharged from three types of spoils: predominantly brown, weathered sandstone (BROWN); predominantly gray, unweathered sandstone (GRAY); and an equal mixture of both aforementioned sandstones and shale (MIXED). The water quality parameters pH, EC, Ca, K, Mg, Na, NO-N, NH-N, SO, Cl, TC, suspended sediment concentration (SSC), settleable solids (SS), and turbidity were monitored over a 2-yr period on six 0.4-ha plots (two replications per spoil type). Generally, levels of Cl, SO, Ca, NO-N, NH-N, SS, SSC, and turbidity decreased over time. The pH for all spoils increased from about 7.5 to 8.5. The EC remained relatively level in the BROWN spoil, whereas the GRAY and MIXED spoils had downward trajectories that were approaching 500 μS cm. The value of 500 μS cm has been reported as the apparent threshold at which certain taxa such as Ephemeroptera (e.g., Mayfly) recolonize disturbed headwater streams of eastern Kentucky and adjacent coal-producing Appalachian states.     

Low intervention soil remediation approaches

Traditional bioremediation approaches have been used to treat petroleum source contamination in readily accessible soils and sludges. Contamination under existing structures is a greater challenge. Options to deal with this problem have usually been in the extreme (i.e., to dismantle the facility and excavate to an acceptable regulated residual, or to pump and treat for an inordinately long period of time). The excavated material must be further remediated and cleanfill must be added to close the excavation. If site assessments were too conservative or incomplete, new contamination adulterating fill soils may result in additional excavation at some later date. Innovative, cost-efficient technologies must be developed to remove preexisting wastes under structures and to reduce future remediation episodes. An innovative soil bioremediation treatment method was developed and evaluated in petroleum hydrocarbon contaminated (PHC) soils at compressor stations of a natural gas pipeline running through Louisiana. The in-situ protocol was developed for remediating significant acreage subjected to contamination by petroleum-based lubricants and other PHC products resulting from a chronic leakage of lubricating oil used to maintain the pipeline itself. Initial total petroleum hydrocarbon (TPH) measurements revealed values of up to 12,000 mg/kg soil dry weight. The aim of the remediation project was to reduce TPH concentration in the contaminated soils to a level of <200 mg/kg soil dry weight, a level negotiated to be acceptable to state and federal regulators. After monitoring the system for 122 days, all sites showed greater than 99-percent reduction in TPH concentration.     

Destocking as a drought-mitigation strategy: clarifying rationales and answering critiques

The idea of externally assisted emergency destocking of pastoralists has gained currency in recent years: increasing the incentives for pastoralists to sell animals, or removing the constraints to selling animals in the early stages of drought. We identify two separate rationales put forward by proponents of destocking: environmental benefits and purchasing power/welfare benefits. We consider whether specific recent critiques of 'new range ecology' and specifically of 'tracking policies' do in fact provide arguments against emergency destocking in pastoralist areas. We illustrate some of these themes with a case study of a successful destocking exercise in northern Kenya where a very specific form of support was requested and received by pastoralists themselves. The sorts of destocking that work are likely to have significant effects on pastoralist purchasing power at key points of the drought cycle, but minimal effects on the environment. Clarifying these points will make it easier to promote destocking as a drought-mitigation policy.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Using GIS to Delineate Headwater Stream Origins in the Appalachian Coalfields of Kentucky

Headwater streams have a significant nexus or physical, chemical, and/or biological connection to downstream reaches. Generally, defined as 1st‐3rd order with ephemeral, intermittent, or perennial flow regimes, these streams account for a substantial portion of the total stream network particularly in mountainous terrain. Due to their often remote locations, small size, and large numbers, conducting field inventories of headwater streams is challenging. A means of estimating headwater stream location and extent according to flow regime type using publicly available spatial data is needed to simplify this complex process. Using field‐collected headwater point of origin data from three control watersheds, streams were characterized according to a set of spatial parameters related to topography, geology, and soils. These parameters were (1) compared to field‐collected point of origin data listed in three nearby Jurisdictional Determinations, (2) used to develop a geographic information system (GIS)‐based stream network for identifying ephemeral, intermittent, and perennial streams, and (3) applied to a larger watershed and compared to values obtained using the high‐resolution National Hydrography Dataset (NHD). The parameters drainage area and local valley slope were the most reliable predictors of flow regime type. Results showed the high‐resolution NHD identified no ephemeral streams and 9 and 65% fewer intermittent and perennial streams, respectively, than the GIS model.     

Recycling of an industrial sludge and marine clay as light-weight aggregates

The geographical limitations of Singapore, its restricted natural resources and voluminous municipal and industrial waste streams, make environmental management a major challenge for the island state. In an attempt to find ways to reduce importation of raw materials and the waste sent to landfill, light weight aggregates were produced from marine clay and a CaF(2)-rich semiconductor industry sludge. Aggregates were produced in a bench-scale rotary kiln with three clay/sludge loadings (90/10, 70/30 and 50/50%). All three mixtures showed good bloating behavior during firing and the ceramic pellets (1-1.5cm diameter) had densities well below that required for light-weight aggregates. In the initial tests, the pore sizes of the aggregates were in general too large resulting in high water absorption. Comparisons between the composition of the two waste products and the aggregates showed a significant loss of fluorine (40-60%) during processing; a problem which may require flue gas treatment. Leach testing showed that the formed aggregates would not pose a human or environmental hazard in terms of fluorine mobilization.     

Characterizing perfluorooctanoate in ambient air near the fence line of a manufacturing facility: comparing modeled and monitored values

In order to improve our understanding of the nature, measurement and prediction of salts of perfluorooctanoic acid (PFOA) in air, two studies were performed along the fence line of a fluoropolymer manufacturing facility. First, a six-event, 24-hr monitoring series was performed around the fence line using the OSHA versatile sampler (OVS) system. Perfluorooctanoate concentrations were determined as perfluorooctanoic acid (PFOA) via liquid chromatography and mass spectrometry. Those data indicated that the majority of the PFOA was present as a particulate. No vapor-phase PFOA was detected above a detection limit of approximately 0.07 microg/m3. A follow-up study using a high-volume cascade impactor verified the range of concentrations observed in the OVS data. Both studies aligned with the major transport direction and range of concentrations predicted by an air dispersion model, demonstrating that model predictions agreed with monitoring results. Results from both monitoring methods and predictions from air dispersion modeling showed the primary direction of transport for PFOA was in the prevailing wind direction. The PFOA concentration measured at the site fence over the 10-week sampling period ranged from 0.12 to 0.9 microg/m3. Modeled predictions for the same time period ranged from 0.12 to 3.84 microg/m3. Less than 6% of the particles were larger than 4 microm in size, while almost 60% of the particles were below 0.3 microm. These studies are believed to be the first published ambient air data for PFOA in the environment surrounding a manufacturing facility.