In situ chemical oxidation: Lessons learned at multiple sites

This paper compiles a detailed set of in situ chemical oxidation (ISCO) lessons learned pertaining to design, execution, and safety based on global experiences over the last 20 years. While the benefits of a “correct” application are known (e.g., cost effectiveness, speed, permanence of treatment), history also provides examples of a variety of “incorrect” applications. These provide an opportunity to highlight recurring themes that resulted in failures. ISCO is, and will continue to provide, an important remedial tool for site remediation, particularly as a component of a multifaceted approach for addressing large and complex sites. Future success, however, requires an objective understanding of both the benefits and the limitations of the technology. The ability to learn from the mistakes of the past provides an opportunity to eliminate, or at least minimize, them in the future. Over the last 25 years of ISCO application, process understanding and knowledge have improved and evolved. This paper combines a thorough discussion of lessons learned through decades of ISCO implementation throughout all aspects of ISCO projects with an analysis of changes to the ISCO remediation market. By discussing the interplay of these two themes and providing recommendations from collective lessons learned, we hope to improve the future of safe, cost‐effective, and successful applications of ISCO.     

A comparison of mesh-adaptive LES with wind tunnel data for flow past buildings: Mean flows and velocity fluctuations

In this paper we address two important aspects of micro-scale urban airflow model evaluation: (a) the identification of key flow features as dictated by the physics of the problem and as captured by the simulations, and (b) the comparison of important model output parameters (mean flows and fluctuations) with experimental data. A series of mesh-adaptive large eddy simulations (LES) was carried out for the study of air flows within two intersecting street canyons with varying building configurations. The novelty of the approach lies in the combination of LES with mesh adaptivity, which allows a variable-filter length and the implementation of an anisotropic eddy-viscosity model. Both coarse and fine-mesh simulations were carried out, using single and parallel-processor systems respectively. The simulations showed clearly that the expected flow patterns such as the street canyon recirculation and the street-mouth vortices, as well as the exchange of air flow at the street intersections, can readily be captured by the mesh-adaptive LES.In addition, the detailed comparisons of mean flows and fluctuations of the resolved velocity field with the measured data showed that the simulation results agreed well with the patterns and trends of the wind tunnel measurements. In most cases the finer-mesh simulations improved considerably the accuracy of the mean flows, especially for the symmetrical configuration. The improvement in the predicted fluctuations was less obvious, with several detector locations underpredicting the measured values, although the overall comparison was also satisfactory. The typical errors for the mean flows for all three building configurations were less than 30%, whilst for the velocity fluctuations less that 40%. Both the simulated means flows and turbulence levels were generally more accurate in the streets parallel to the wind (streamwise direction) than in the streets normal to the wind.     

An Approach for Evaluating the Repeatability of Rapid Wetland Assessment Methods: The Effects of Training and Experience

We sampled 92 wetlands from four different basins in the United States to quantify observer repeatability in rapid wetland condition assessment using the Delaware Rapid Assessment Protocol (DERAP). In the Inland Bays basin of Delaware, 58 wetland sites were sampled by multiple observers with varying levels of experience (novice to expert) following a thorough training workshop. In the Nanticoke (Delaware/Maryland), Cuyahoga (Ohio), and John Day (Oregon) basins, 34 wetlands were sampled by two expert teams of observers with minimal protocol training. The variance in observer to observer scoring at each site was used to calculate pooled standard deviations (SD_pool), coefficients of variation, and signal-to-noise ratios for each survey. The results showed that the experience level of the observer had little impact on the repeatability of the final rapid assessment score. Training, however, had a large impact on observer to observer repeatability. The SD_pool in the Inland Bay survey with training (2.2 points out of a 0–30 score) was about half that observed in the other three basins where observers had minimal training (SD_pool = 4.2 points). Using the results from the survey with training, we would expect that two sites assessed by different, trained observers who obtain DERAP scores differing by more than 4 points are highly likely to differ in ecological condition, and that sites with scores that differ by 2 or fewer points are within variability that can be attributed to observer differences.     

Exploring the Crowding–Satisfaction Relationship in Recreational Boating

Along with the growing boating population and the number of boats in use on limited inland waterways, boater expectations of setting density, safety perceptions, and the associated impacts on their experience (e.g., satisfaction) are becoming increasingly important. The primary purpose of this article was to explore a recreational boating crowding–satisfaction model derived from previous work using safety and enjoyment as mediating variables. We also tested our crowding–satisfaction model among day and overnight users. Our analysis revealed no significant difference between day and overnight users for any of the relationships tested in our model. Our final model indicated as respondents’ expectations for seeing people increased along with their feelings of being crowded, they were more inclined to consider the conditions on the lake as being unsafe. They were also more inclined to indicate that the number of people they had seen on the lake detracted from their boating experience. Respondents’ satisfaction was tied to their perceptions of crowding. Mediating variables illustrated that the relationship was conditioned by perceptions of safety and enjoyment. Analysis of the indirect effect observed in our study illustrate that when the number of people seen on the lake exceed respondents’ expectations, their perceptions of safety and enjoyment both decline, resulting in lower satisfaction. These findings have implications for managing recreational boating use on inland lake systems. Given the role played by expectations in our model, efforts to communicate with boaters about conditions on these waterways is important for helping them plan their boating experience and avoid situations they consider unsafe or unsatisfactory.     

Perfluorosulfonates and perfluorocarboxylates in snow and rain in Dalian,China

Samples of precipitation events (snow and rain) in Dalian, a typical coastal town in China, were analyzed for perfluorosulfonates (PFSAs) and perfluorocarboxylates (PFCAs) to investigate atmospheric contamination by these compounds. In the snow event on December 16, 2006, samples were collected from 21 different sites and in another 6 precipitation events, samples were collected from a single location. Four PFSAs (C4, C6, C8, C10) and seven PFCAs (C6–12) were analyzed. Among the homologues, perfluorooctane sulfonate (PFOS) concentrations were the highest with a geometric mean (GM) of 145 ng/L (n = 21) during the snow event on December 16, 2006, followed by perfluorooctanoate (PFOA) with a GM of 24.7 ng/L (n = 21). Concentrations of perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS) and perfluoroheptanoate (PFHpA) were more than two orders of magnitude lower than that of PFOS. Other PFSAs and PFCAs were found to be below the limit of detection in all the samples. In other 6 precipitation events, PFSAs and PFCAs were detected approximately in the same order of magnitude in both snow and rain. The results indicate that wet deposition may be a potential transport mechanism of perfluorinated chemicals in the environment.     

Fast response measurements of the dispersion of nanoparticles in a vehicle wake and a street canyon

The distributions of nanoparticles (below 300 nm in diameter) change rapidly after emission from the tail pipe of a moving vehicle due to the influence of transformation processes. Information on this time scale is important for modelling of nanoparticle dispersion but is unknown because the sampling frequencies of available instruments are unable to capture these rapid processes. In this study, a fast response differential mobility spectrometer (Cambustion Instruments DMS500), originally designed to measure particle number distributions (PNDs) and concentrations in engine exhaust emissions, was deployed to measure particles in the 5–1000 nm size range at a sampling frequency of 10 Hz. This article presents results of two separate studies; one, measurements along the roadside in a Cambridge (UK) street canyon and, two, measurements at a fixed position (20 cm above road level), centrally, in the wake of a single moving diesel-engined car. The aims of the first measurements were to test the suitability and recommend optimum operating conditions of the DMS500 for ambient measurements. The aim of the second study was to investigate the time scale over which competing influences of dilution and transformation processes (nucleation, condensation and coagulation) affect the PNDs in the wake of a moving car. Results suggested that the effect of transformation processes was nearly complete within about 1 s after emission due to rapid dilution in the vehicle wake. Furthermore, roadside measurements in a street canyon showed that the time for traffic emissions to reach the roadside in calm wind conditions was about 45 ± 6 s. These observations suggest the hypothesis that the effects of transformation processes are generally complete by the time particles are observed at roadside and the total particle numbers can then be assumed as conserved. A corollary of this hypothesis is that complex transformation processes can be ignored when modelling the behaviour of nanoparticles in street canyons once the very near-exhaust processes are complete.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.     

The use of NTA and EDDS for enhanced phytoextraction of metals from a multiply contaminated soil by Brassica carinata

The potential of nine different species to grow in the presence of metals (As, Cd, Cu, Pb and Zn) and to accumulate them in the shoots was assessed for each metal separately by germination and root length tests, and successively by hydroponic experiments. Of the nine species tested, Brassica carinata was the species that accumulated the highest amounts of metals in shoots without suffering a significant biomass reduction. To further evaluate the potential of B. carinata for chelant-enhanced phytoextraction of a natural, multiply metal-polluted soil (As, Cd, Cu, Pb and Zn), both hydroponic and pot experiments were carried out with nitrilotriacetic acid (NTA) or (S,S)-ethylenediamine disuccinic acid (EDDS) as complexing agents. The hydroponic study with solutions containing the five metals together showed that accumulation of Cd, Cu, Pb and Zn in shoots was higher following EDDS addition compared to NTA. EDDS was more effective than NTA in desorbing Cu, Pb and Zn from the soil, whereas As and Cd were poorly extracted. B. carinata plants were grown for 4 weeks in the multiply metal-contaminated soil and then the soil was amended with 5 mmol kg(-1) NTA or EDDS. All plants were harvested 1 week after amendment. In comparison to NTA, EDDS was more effective in enhancing the concentrations of Cu, Pb and Zn in B. carinata shoots (2- to 4-fold increase compared to the control). One week after chelant addition, the DTPA-extractable metal concentrations in the polluted soil were lower in the EDDS treatment in comparison with the NTA amendment. Even though B. carinata showed a reduced growth and a relatively low metal uptake, it demonstrated the ability to survive and tolerate the presence of more metals simultaneously.     

Identification of methyl chloride-emitting plants and atmospheric measurements on a subtropical island

A survey of methyl chloride (CH3Cl)-emitting plants was performed at a subtropical island in Japan (Iriomote Island). Among the 187 species of tropical/subtropical plants investigated, 33 species from a variety of families were identified as CH3Cl-emitting plants. The strongest emitters were Osmunda banksiifolia, Cibotium balometz, Angiopteris palmiformis, Vitex rotundifolia, Vitex trifolia, and Excoecaria agalloch, each with CH3Cl emission rates exceeding 1microg (gdrywt)(-1)h(-1). The first three species are ferns, and the last three are halophilous plants. Based on our results, the character of CH3Cl emission is likely to be shared at the genus level but not always at the family level. The atmospheric CH3Cl distribution measured on Iriomote Island showed significant enhancement in forested sites (up to 2750 ppt) and a higher concentration on the downwind shore than on the upwind shore. As previously reported, our findings provide strong evidence for the high emission of CH3Cl from tropical/subtropical forests.