Characterization and optimization of long-term controlled release system for groundwater remediation: a generalized modeling approach

A well-based reactive barrier system using controlled-release KMnO4 has been recently developed as a long-term in situ treatment option for plumes of dense and non-aqueous phase liquids in groundwater. In order to take advantage of the merits of controlled release systems (CRS) in environmental remediation, the release behavior needs to be optimized for the hydrologic and environmental conditions of target treatment zone. Where release systems are expected to be operated over long times, like for the reactive barriers, it may only be practical to describe the long-term behavior numerically. We developed a numerical model capable of describing release characteristics associated with variable forms and structures of long-term CRS. Sensitivity analyses and illustrative simulations showed that the release kinetics and durations would be constrained by changes in agent solubility, bulk diffusion coefficients, or structures of the release devices. The generality of the numerical model was demonstrated through simulations for CRS with monolithic and double-layered matrices. The generalized model was then used for actual design and analyses of an encapsulated-matrix CRS, which can yield constant release kinetics for several years. A well-based reactive barrier system (4.05 x 10(3)m3) using the encapsulated-matrix CRS can release approximately 1.65 kg of active agent (here MnO4(-)) daily over the next 6.6 yr, creating prolonged reaction zone in the subsurface. The generalized model-based, target-specific approach using the long-term CRS could provide practical tool for improving the efficacy of advanced in situ remediation schemes such as in situ chemical oxidation, bioremediation, or in situ redox manipulation. Development of techniques for adjusting the bulk diffusion coefficients of the release matrices and facilitating the lateral spreading of the released agent is warranted.     

Polychlorinated biphenyl contamination trends in Lake Hartwell, South Carolina (USA): sediment recovery profiles spanning two decades

To assess the ca. 20-year polychlorinated biphenyl (PCB) contamination trends in Lake Hartwell, SC, sediment cores from the Twelve Mile Creek arm were collected in July 2004 at two sites (G30 and G33) first sampled in the mid-1980s. Congener-specific PCB data as a function of depth from the sediment-water interface for the 2004 sediment samples were compared to data obtained from 1987 and 1998 samples taken from the same locations. Despite modest decreases in total PCB levels near the G30 sediment-water interface, historical increases in average degrees of chlorination may elevate the overall toxic risk at this site. Unlike G30, the more rapid recovery in the near-surface sediment of G33 suggests that the effectiveness of the U.S. EPA natural attenuation record of decision is site-specific and is unlikely to result in uniform surface sediment recovery throughout the most contaminated regions of Lake Hartwell.     

Phosphorus supply influences heathland responses to atmospheric nitrogen deposition

On an upland moor dominated by pioneer Calluna vulgaris and with an understorey of mosses and lichens, experimental plots were treated with factorial combinations of nitrogen (N) at +0 and +20kg Nha(-1)yr(-1), and phosphorus (P) at +0 and +5kg Pha(-1)yr(-1). Over the 4-year duration of the experiment, the cover of the Calluna canopy increased in density over time as part of normal phenological development. Moss cover increased initially in response to N addition but then remained static; increases in cover in response to P addition became stronger over time, eventually causing reductions in the cover of the dominant Calluna canopy. Lichen cover virtually disappeared within 4 years in plots receiving +20kg Nha(-1)yr(-1) and also in separate plots receiving +10kg Nha(-1)yr(-1), but this effect was reversed by the addition of P.     

Source apportionment of fine particulate matter in the southeastern United States

Particulate matter (PM) less than 2.5 microm in size (PM2.5) source apportionment by chemical mass balance receptor modeling was performed to enhance regional characterization of source impacts in the southeastern United States. Secondary particles, such as NH4HSO4, (NH4)2SO4, NH4NO3, and secondary organic carbon (OC) (SOC), formed by atmospheric photochemical reactions, contribute the majority (>50%) of ambient PM2.5 with strong seasonality. Source apportionment results indicate that motor vehicle and biomass burning are the two main primary sources in the southeast, showing relatively more motor vehicle source impacts rather than biomass burning source impacts in populated urban areas and vice versa in less urbanized areas. Spatial distributions of primary source impacts show that each primary source has distinctively different spatial source impacts. Results also find impacts from shipping activities along the coast. Spatiotemporal correlations indicate that secondary particles are more regionally distributed, as are biomass burning and dust, whereas impacts of other primary sources are more local.     

Identification and interpretation of representative ozone distributions in association with the sea breeze from different synoptic winds over the coastal urban area in Korea

To aid the studies of long-term impact assessment of cumulative ozone (O3) exposures, the representative 8-hr O3 pollution patterns have been identified over the Greater Seoul Area (GSA) in Korea. Principal component analysis and two-stage clustering techniques were used to identify the representative O3 patterns, and numerical and observational analyses were also used to interpret the identified horizontal distribution patterns. The results yielded three major O3 distribution patterns, and each of the three patterns was found to have strong correlations with local and synoptic meteorological conditions over the GSA. For example, pattern 1, accounting for 46% of O3 concentration distributions, mostly occurred under relatively weak westerly synoptic winds. The predominant features of this pattern were infrequent high O3 levels but a distinct gradient of O3 concentration from the western coastal area to the eastern inland area that was mainly induced by the local sea breeze. Pattern 2, accounting for 31% of O3 concentration distributions, was found with higher O3 levels in the western coastal area but lower in the eastern inland area. This is due to the modified sea breeze under the relatively stronger easterly opposing synoptic wind, affecting the high O3 occurrence in the western coastal area only. However, pattern 3, accounting for 21% of O3 concentration distributions, showed significantly higher O3 concentrations over the whole GSA mainly due to the retarded and slow-moving sea-breeze front under the weak opposing synoptic flow. Modeling study also indicated that local and synoptic meteorological processes play a major role in determining the high O3 concentration distribution patterns over the GSA.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Geochemical and microbial effects on the mobilization of arsenic in mine tailing soils

Arsenic (As) contamination has become a serious environmental problem in many countries. We have performed batch-type leaching experiments on mine tailing soils collected from three abandoned mine areas in South Korea with the objective of evaluating the effect of indigenous bacterial activity on As mobilization. The analysis of physicochemical properties and mineralogical compositions of the samples indicated that the secondary minerals or phases formed as a result of the oxidation or alteration of primary minerals were associated with the labile and bioleachable fractions of As. Compared to simulated abiotic processes using sterilization, the indigenous bacteria activated using a carbon source were able to enhance the dissolution of As under both aerobic and anaerobic conditions. The bacterial dissolution of iron (Fe) and manganese (Mn) was found to occur simultaneously with the dissolution of As, suggesting that the main bacterial mechanism was via the dissimilatory reduction of Fe(III), Mn(IV), and As(V). An anaerobic environment was more favorable for the prominent dissolution of As in the tailing soils. These results indicate that the mobilization of As can be enhanced in the oxygen-depleted part of the tailing dump, particularly with the infiltration of organic substrates. The difference in the degree of As lixiviation between the three tailing soils was found to be related to the bioavailability of As as well as the original biomass in the tailing soils.     

Phylogeography of the seaweed Ishige okamurae (Phaeophyceae): evidence for glacial refugia in the northwest Pacific region

Although benthic marine algae are essential components of marine coastal systems that have been influenced profoundly by past and present climate change, our knowledge of seaweed phylogeography is limited. The brown alga Ishige okamurae Yendo occurs in the northwest Pacific, where it occupies a characteristic belt in the exposed intertidal zone. To understand the patterns of genetic diversity and the evolutionary history of this species, we analyzed mitochondrial cox3 from 14 populations (221 individuals) throughout its range. The 17 haplotypes found in this study formed five distinct clades, indicating significant genetic structure. The high differentiation and number of unique (private) haplotypes may result from the recolonization of the species from glacial refugia. Three putative refugia, each with high genetic diversity, were identified: southern Korea (including Jeju Island), northern Taiwan, and central Pacific Japan. Recolonization of I. okamurae was probably determined by ocean currents and changes in sea level during the last glacial period.