PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.     

Overflow risk analysis for designing a nonpoint sources control detention

This paper presents a design method by which the overflow risk related to a detention for managing nonpoint pollutant sources in urban areas can be evaluated. The overall overflow risk of a nonpoint pollutant sources control detention can be estimated by inherent overflow risk and operational overflow risk. For the purpose of calculating overflow risk, the 3-parameter mixed exponential distribution is applied to describe the probability distribution of rainfall event depth. As a rainfall-runoff calculation procedure required for deriving a rainfall capture curve, the U.S. Natural Resources Conservation Service runoff curve number method is applied to consider the nonlinearity of the rainfall-runoff relation. Finally, the detention overflow risk is assessed with respect to the detention design capacity and drainage time. The proposed overflow risk assessment is expected to provide a baseline to determine quantitative parameters in designing a nonpoint sources control detention.     

Cadmium in blood of Tunisian men and risk of bladder cancer: interactions with arsenic exposure and smoking

Prior investigations identified an association between low-level blood arsenic (As) and bladder cancer risk among Tunisian men but questions remain regarding confounding by cadmium (Cd), a well-established bladder carcinogen. A case–control study of Tunisian men was re-examined to assess the levels of cadmium in blood and reparse the association between the simultaneous exposure to these metals and bladder cancer risk. Levels of blood Cd were significantly twice higher among cases than in controls (P?<?0.05) and were positively correlated with smoking and age. Additionally, analysis of metal levels among non-smokers according to the region of residence showed very high blood Cd and As levels for the coastal regions of Sfax and central Tunisia. After controlling for potential confounders, for low blood As levels (<0.67 μg/L), the OR for blood Cd was 4.10 (95 % CI 1.64–10.81), while for higher levels (>0.67 μg/L), it was reduced to 2.10 (CI, 1.06–4.17). Adjustment for Cd exposure did not alter the risk associated to As exposure. This study is the first to report the relationship between Cd exposure and risk of bladder cancer occurrence in interaction with smoking and As exposure. Smoking is shown to be the main exposure source to Cd in the Tunisian population but also environmental pollution seems to be responsible of Cd exposure among non-smokers. Exposure assessment studies encompassing a wider population are needed.     

Monitoring of Vegetation Impact Due to Trampling on Cadillac Mountain Summit Using High Spatial Resolution Remote Sensing Data Sets

Cadillac Mountain—the highest peak along the eastern seaboard of the United States—is a major tourist destination in Acadia National Park, Maine. Managing vegetation impact due to trampling on the Cadillac Mountain summit is extremely challenging because of the large number of visitors and the general open nature of landscape in this fragile subalpine environmental setting. Since 2000, more intensive management strategies—based on placing physical barriers and educational messages for visitors—have been employed to protect threatened vegetation, decrease vegetation impact, and enhance vegetation recovery in the vicinity of the summit loop trail. The primary purpose of this study was to evaluate the effect of the management strategies employed. For this purpose, vegetation cover changes between 2001 and 2007 were detected using multispectral high spatial resolution remote sensing data sets. A normalized difference vegetation index was employed to identify the rates of increase and decrease in the vegetation areas. Three buffering distances (30, 60, and 90?m) from the edges of the trail were used to define multiple spatial extents of the site, and the same spatial extents were employed at a nearby control site that had no visitors. No significant differences were detected between the mean rates of vegetation increase and decrease at the experimental site compared with a nearby control site in the case of a small spatial scale (≤30?m) comparison (in all cases P?>?0.05). However, in the medium (≤60?m) and large (≤90?m) spatial scales, the rates of increased vegetation were significantly greater and rates of decreased vegetation significantly lower at the experimental site compared with the control site (in all cases P?<?0.001). Research implications are explored that relate to the spatial extent of the radial patterns of impact of trampling on vegetation at the site level. Management implications are explored in terms of the spatial strategies used to decrease the impact of trampling on vegetation.     

Bioaccumulation and the soil factors affecting the uptake of arsenic in earthworm, Eisenia fetida

To better understand arsenic (As) bioaccumulation, a soil invertebrate species was exposed to 17 field soils contaminated with arsenic due to mining activity. Earthworms (Eisenia fetida) were kept in the soils for 70 days under laboratory conditions, as body burden increased and failed to reach equilibrium in all soils. After 70 days of exposure, XANES spectra determined that As was biotransformed to a highly reduced form. Uptake kinetics for As was calculated using one compartment model. Stepwise multiple regression suggested that sorbed As in soils are bioaccessible, and uptake is governed by soil properties (iron oxide, sulfate, and dissolved organic carbon) that control As mobility in soils. As in soil solution are highly related to uptake rate except four soils which had relatively high chloride or phosphate. The results imply that uptake of As is through As interaction with soil characteristics as well as direct from the soil solution. Internal validation showed that empirically derived regression equations can be used for predicting As uptake as a function of soil properties within the range of soil properties in the data set.     

Modeling water and sediment contamination of Lake Pontchartrain following pump-out of Hurricane Katrina floodwater

Levee failure and overtopping as a result of Hurricane Katrina caused major flooding of New Orleans, Louisiana. Floodwaters, which were contaminated with heavy metals, organic chemicals, and fecal coliform bacteria (FCB), were pumped into neighboring Lake Pontchartrain during dewatering. The impact of levee failure on water and benthic sediment concentrations in the lake was investigated by applying a numerical water quality model coupled to a three-dimensional, numerical hydrodynamic model. The model was used to compute water and benthic sediment concentrations throughout the lake for lead, arsenic, benzo(a)pyrene (BaP), and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE), and water concentrations for FCB. Computed concentrations resulting from actual pumped discharges with levee failure and overtopping were compared to computed concentrations resulting from pumped discharges without levee failure or overtopping, and concentrations from both sets of conditions were compared to ecological water and sediment quality screening guideline values. The model indicated that incremental increases above pre-Katrina benthic sediment concentrations are about a factor of 10 greater with dewatering of the floodwaters than with dewatering of storm water without flooding. However, these increases for the metals are small relative to pre-Katrina concentrations. The results showed that the ecological screening-level sediment quality guideline values were exceeded for BaP and DDE in areas near the south shoreline of the lake as a result of floodwater pump-out, whereas, this was not the case for storm water removal without flooding. The model showed that lake water column concentrations should be about the same during both dewatering conditions regardless of whether there is flooding or not.     

Seasonal variations of monoterpene emissions from Pinus densiflora in East Asia

The emission rates and compositions of monoterpene from Pinus densiflora were investigated in the Gumsung (GM) and Worak (WM) mountains. The standard emission rates (ERs: ERs is the monoterpene emission rate at standard temperature, 30 degrees C) from P. densiflora ranged from 0.817 to 1.704 (mugC/gdw-h). The ERs and beta-values of total monoterpene were measured at the two study sites (GM and WM). In the spring and summer, the ERs were the highest, while relatively low values (<0.058mugC/gdw-h) were measured in the autumn and winter. In GM and WM sites the beta-value obtained for the different seasons ranged from 0.047 to 0.179, with an average of 0.09. The major monoterpene compounds from P. densiflora were alpha-pinene, myrcene, beta-phellandrene, d-limonene and alpha-terpinene. The fractional compositions of individual monoterpene compounds were significantly different between the two test sites in the summer and winter. The ERs of the older group (31-40 years) were higher than those in the younger group (21-30 years). However, the monoterpene compositions were similar between the two age groups.     

Comparison of Microscopic and Macroscopic Modeling Approaches for Subsurface Contaminant Transport

The practice of contaminant transport and remediation has shown significant progress in recent years. However, despite the significant progress made, remediation efforts are often delayed by extremely long breakthrough curve tails that render efforts to bring the level of contaminants below the regulatory standards inefficient. One hypothesis is that these long tails are due to the reservoir-like slow diffusive processes in soil micropore zones. This study compares the effects of micropores at macroscopic and microscopic levels and establishes a link between these approaches for validation and calibration purposes. The link between macroscopic and microscopic levels is established through comparisons and testing of the two models while incorporating appropriate scale and boundary effects. Despite the differences in conceptual approaches and simulation time, the two approaches rendered meaningful results. The link helps forecast the effects of micropore zone transport processes in the subsurface efficiently and thus allows development of numerical tools that could contribute towards more efficient remediation design.     

Abundance and sources of hydrophilic and hydrophobic water-soluble organic carbon at an urban site in Korea in summer

In this study, the characteristics of total water-soluble organic carbon (WSOC) and isolated WSOC fractions were examined to gain a better understanding of the pathway of organic aerosol production. 24 h PM(2.5) samples were collected during the summer (July 28-August 28, 2009) at an urban site in Korea. A glass column filled with XAD7HP resin was used to separate the filtered extracts into hydrophilic (WSOC(HPI)) and hydrophobic (WSOC(HPO)) fractions. The origins of air mass pathways arriving at the sampling site were mostly classified into three types, those originating over the East Sea of Korea that passed over the eastern inland urban and industrial regions (type I); those from the marine (western/southwestern/southern marine) and passed over the national industrial complex regions (type II); and those from northeastern China that passed through North Korea and metropolitan areas of South Korea (type III). Measurements showed an increase in the average WSOC fraction of total OC from the type II to III air mass (53 to 64%) periods. Also, higher SO(4)(2-)/SO(x) (=SO(2) + SO(4)(2-)) was observed in the type III air mass (0.70) than those in the types I (0.49) and II (0.43). According to the average values of WSOC/OC and SO(4)(2-)/SO(x), measurements suggest that the aerosols collected during the type III air mass period were more aged or photo-chemically processed than those during the types I and II air mass periods. The relationship between the SO(4)(2-)/SO(x) and WSOC/OC (R(2) = 0.64) suggests that a significant fraction of the observed WSOC at the site could be formed by an oxidation process similar to SO(4)(2-) aerosols, probably the oxidation process using OH radicals, or in-cloud processing. The photochemical production of WSOC(HPO) was also observed to significantly contribute to the total OC.     

Changes in thyroid peroxidase activity in response to various chemicals

Thyroperoxidase (TPO) is a large heme-containing glycoprotein that catalyzes the transfer of iodine to thyroglobulin during thyroid hormone (TH) synthesis. Previously, we established an in vitro assay for TPO activity based on human recombinant TPO (hrTPO) stably transfected into human follicular thyroid carcinoma (FTC-238) cells. It is important to determine whether environmental chemicals can disrupt TPO activity because it is an important factor in the TH axis. In this study, we used our assay to examine the changes in TPO activity in response to various chemicals, including benzophenones (BPs), polycyclic aromatic hydrocarbons (PAHs), and persistent organic pollutants (POPs). Overall, BPs, PAHs, and POPs slightly altered TPO activity at low doses, as compared with the positive controls methimazole (MMI), genistein, and 2,2',4,4'-tetrahydroxy BP. Benzophenone, benzhydrol, 3-methylchloranthracene, pyrene, benzo(k)fluoranthene, benzo(e)pyrene, perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and heptachlor decreased TPO activity, while 2,4-dihydroxy BP, 2,2'-dihydroxy-4-methoxy BP, and dibenzo(a,h)anthracene increased TPO activity. From these data, we can predict the disruption of TPO activity by various chemicals as a sensitive TH end point. TPO activity should be considered when enacting measures to regulate environmental exposure to thyroid-disrupting chemicals.