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.     

Comparison of homologous and heterologous formats in nanocolloidal gold-based immunoassays for parathion residue determination

The effectiveness of homologous and heterologous formats in a nanocolloidal gold-based immunoassay for pesticide residue determination was investigated. Parathion, one of the most toxic organophosphorus pesticides, was used as the target analyte. One-step homologous and heterologous test strips based on a nanocolloidal gold-labeled monoclonal antibody were developed for the rapid detection of parathion residues. The results showed that the heterologous format was more effective than the homologous format, being more sensitive, more specific to parathion and more tolerant of matrix interferences. The best competitive hapten was found to have a moderate heterology and the opposite electronic distribution to the immunizing hapten. The detection limits for parathion using the preferred heterologous strip were 1 μg/L in water samples and 5 μg/kg in soil and food samples.     

Microwave enhanced advanced oxidation process for treating dairy manure at low pH

This study investigated the treatment of dairy manure using the microwave enhanced advanced oxidation process (MW-AOP) at pH 2. An experimental design was developed based on a statistical program using response surface methodology to explore the effects of temperature, hydrogen peroxide dosage and heating time on sugar production, nutrient release and solids destruction. Temperature, hydrogen peroxide dosage and acid concentration were key factors affecting reducing sugar production. The highest reducing sugar yield of 7.4% was obtained at 160°C, 0 mL, 15 min heating time, and no H(2)O(2) addition. Temperature was a dominant factor for an increase of soluble chemical oxygen demand (SCOD) in the treated dairy manure. The important factors for volatile fatty acids (VFA) production were microwave temperature and hydrogen peroxide dosage. Temperature was the most important parameter, and heating time, to a lesser extent affecting orthophosphate release. Heating time, hydrogen peroxide dosage and temperature were significant factors for ammonia release. There was a maximum of 96% and 196% increase in orthophosphate and ammonia concentration, respectively at 160°C, 0.5 mL H(2)O(2) and 15 min heating time. The MW-AOP is an effective method in dairy manure treatment for sugar production, nutrient solubilisation, and solids disintegration.     

Toxicity persistence in runoff and soil from experimental soybean plots following insecticide applications

Persistence of toxicity in runoff water and soil was investigated in experimental soybean plots subjected to successive runoff events following pesticide application. Runoff events were produced by irrigation using a sprinkler system. The pesticides applied were cypermethrin and endosulfan, which are widely used in soy production in Argentina. Toxicity tests were performed on two abundant components of the regional fauna, the amphipod Hyalella curvispina and the fish Cnesterodon decemmaculatus. Runoffs from two pesticide applications were assayed at different stages of the growing season: an early application when the soil was almost bare and a late one close to harvest, when the ground was covered by vegetation and just before soy leaves fell. Toxicity to H. curvispina in runoff ceased almost one month after the early application of the two pesticides, while it persisted for over three months after the late application. Soil toxicity to H. curvispina and runoff toxicity to C. decemmaculatus followed the same pattern. Higher temperatures and solar radiation are likely to have enhanced insecticide degradation after the early application. Lower temperatures and solar radiation in combination with increased organic matter from litter probably contributed to the longer persistence of toxicity recorded after the late application, as compared with the early application. Cypermethrin caused no mortality to C. decemmaculatus after the early application, while endosulfan toxicity persisted for almost four months after the late one.     

Climate change impacts on the leaching of a heavy metal contamination in a small lowland catchment

The Keersop catchment (43km(2)) in the south of The Netherlands has been contaminated by the emissions of four zinc ore smelters. The objective of this study was to assess the effects of future projected climate change on the hydrology and the leaching of heavy metals (i.e. Cd and Zn) in the catchment. The numerical, quasi-2D, unsaturated zone Soil Water Atmosphere Plant model was used with 100-year simulated daily time series of precipitation and potential evapotranspiration. The time series are representative of stationary climates for the periods 1961-1990 ("baseline") and 2071-2100 ("future"). The time series of future climate were obtained by downscaling the results of eight regional climate model (RCM) experiments, driven by the SRES A2 emissions scenario, using change factors for a series of climate statistics and applying them to stochastic weather generator models. The time series are characterized by increased precipitation in winter, less precipitation in summer, and higher air temperatures (between 2°C and 5°C) throughout the year. Future climate scenarios project higher evapotranspiration rates, more irrigation, less drainage, lower discharge rates and lower groundwater levels, due to increased evapotranspiration and a slowing down of the groundwater system. As a result, lower concentrations of Cd and Zn in surface water are projected. The reduced leaching of heavy metals, due to drying of the catchment, showed a positive impact on a limited aspect of surface water quality.     

Bioaccessibility of trace elements as affected by soil parameters in smelter-contaminated agricultural soils: a statistical modeling approach

An investigation was undertaken to identify the most significant soil parameters that can be used to predict Cd, Pb, and Zn bioaccessibility in smelter-contaminated agricultural soils. A robust model was established from an extended database of soils by using: (i) a training set of 280 samples to select the main soil parameters, to define the best population to be taken into account for the model elaboration, and to construct multivariate regression models, and (ii) a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P(2)O(5), free Fe-Mn oxide, and pseudototal Al and trace element (TE) contents appeared as the main variables governing TE bioaccessibility. The statistical modeling approach was reasonably successful, indicating that the main soil factors influencing the bioaccessibility of TEs were taken into account and the predictions could be applicable for further risk evaluation in the studied area.     

Investigating phosphorus limitation in a fixed bed filter with phosphorus and nitrogen profile measurements

In 2000, the European Union adopted the European Water Framework Directive (WFD) (European Commission, 2000). The WFD focuses on increasingly stringent nutrient standards including ultra low nitrogen (< 2.2 mg N-total/L) and phosphorus concentrations (< 0.15 mg total phosphorus/L) in receiving surface waters and in relevant point sources like wastewater treatment plant (WWTP) effluent. Expansion of WWTPs with advanced post-treatment processes, like effluent filtration, is widely proposed to meet possible future effluent discharge standards. When combining biological nitrate-nitrogen and chemical phosphorus removal in one filter, phosphorus limitation in the denitrifying process may occur. This study investigated where in the filter bed and under which conditions phosphorus limitation occurs. Profile measurements for nitrate, nitrite, and orthophosphorus (PO4-P) combined with chemical oxygen demand (COD) and 02 were conducted. Results showed that the required PO4-P/NOx-N ratio is approximately 0.006 mg/mg after phosphorous precipitation and flocculation. Profile measurements have proven to be an applicable and useful tool. It showed how nitrate and orthophosphorus are removed through the filter bed based on the PO4-P/NOx-N ratio. When orthophosphorus is removed more rapidly and efficiently compared to nitrate, the PO4-P/NOx-N ratio decreases. When PO4-P/NOx-N ratio thresholds are approximately 0.006 mg/mg for a certain period of time and water temperatures varied significantly, orthophosphorus limitation may occur. Changing the filter-bed configuration or decreasing the coagulant dosage can prevent limitation of the denitrifying process because of a phosphorous shortage.     

Efficacy of recent state implementation plans for 8-hour ozone

The development of state implementation plans (SIPs) for attainment of criteria pollutant standards is an integral component of air quality management in the United States. However, the content and efficacy of SIPs have rarely been examined systematically. Here, 20 SIPs developed in response to the 1997 8-hr ozone standard are reviewed as case studies of attainment efforts at the state level. Comparison of observed and model predicted ozone concentrations shows the US Environmental Protection Agency (EPA) recommended modeled attainment test to be a somewhat conservative predictor of attainment. Among 12 SIPs for regions that sought attainment by 2009, the test correctly predicted attainment and nonattainment in four and five regions, respectively; in the other three regions, attainment was observed despite predictions of nonattainment. However weight-of-evidence determinations and deviations from the recommended modeled attainment test methodology led five of these SIPs to predict attainment that was not in fact observed by 2009; three of those regions achieved attainment in 2010. Ozone and NO2 concentrations declined across much of the United States during the period covered by the SIPs, with rates of improvement strongly correlated with the initial pollution levels and hence greatest in nonattainment regions. However at monitors with mid-range levels of ozone initially, rates of reduction were largely independent of the initial attainment status of the region. This is consistent with thefact that apart from California, the majority of ozone precursor reductions documented by SIPs resulted from federal measures rather than from state or local controls specific to the nonattainment regions.     

Blood serum concentrations of perfluorinated compounds in men from Greenlandic Inuit and European populations

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are used in large quantities. They are persistent and found in measurable levels in human serum around the world. They have been associated with developmental, hepatic, and carcinogenic effects in animal studies. The aim of the present study was to describe levels of PFCs in serum among Inuits from Greenland and inhabitants from Warsaw, Poland and Kharkiv, Ukraine. Furthermore, the aim was to define social- and lifestyle related determinants of exposure for these compounds. Serum levels of seven PFCs were analyzed by liquid chromatography/tandem mass spectrometry (LC/MS/MS). The concentrations of PFOS and PFOA were the highest of all PFCs in all three populations with a total amount of almost 90% of the PFCs. The mean levels of PFOS and PFOA were in the Greenlandic Inuits 52 and 4.8 ng mL(-1), in Poland 19 and 5.2 ng mL(-1), and in Ukraine 8.1 and 1.9 ng mL(-1), respectively. Thus, levels of PFCs in the serum of Inuits on Greenland were among the highest described in a general population whereas the levels in Poland were similar to other industrialized countries. The exposure in Ukraine was rather low. In the Greenlandic Inuit population, intake of seafood, tea, age and area of living were significant determinants of PFOS concentrations and explained about 22% of the variation. For the other populations no strong determinants were found.     

Analysis and comparison of inertinite-derived adsorbent with conventional adsorbents

To increase U.S. petroleum energy-independence, the University of Texas at Arlington (UT Arlington) has developed a coal liquefaction process that uses a hydrogenated solvent and a proprietary catalyst to convert lignite coal to crude oil. This paper reports on part of the environmental evaluation of the liquefaction process: the evaluation of the solid residual from liquefying the coal, called inertinite, as a potential adsorbent for air and water purification. Inertinite samples derived from Arkansas and Texas lignite coals were used as test samples. In the activated carbon creation process, inertinite samples were heated in a tube furnace (Lindberg, Type 55035, Arlington, UT) at temperatures ranging between 300 and 850 degrees C for time spans of 60, 90, and 120 min, using steam and carbon dioxide as oxidizing gases. Activated inertinite samples were then characterized by ultra-high-purity nitrogen adsorption isotherms at 77 K using a high-speed surface area and pore size analyzer (Quantachrome, Nova 2200e, Kingsville, TX). Surface area and total pore volume were determined using the Brunauer Emmet, and Teller method, for the inertinite samples, as well as for four commercially available activated carbons (gas-phase adsorbents Calgon Fluepac-B and BPL 4 x 6; liquid-phase adsorbents Filtrasorb 200 and Carbsorb 30). In addition, adsorption isotherms were developed for inertinite and the two commercially available gas-phase carbons, using methyl ethyl ketone (MEK) as an example compound. Adsorption capacity was measured gravimetrically with a symmetric vapor sorption analyzer (VTI, Inc., Model SGA-100, Kingsville, TX). Also, liquid-phase adsorption experiments were conducted using methyl orange as an example organic compound. The study showed that using inertinite from coal can be beneficially reused as an adsorbent for air or water pollution control, although its surface area and adsorption capacity are not as high as those for commercially available activated carbons. Implications: The United States currently imports two-thirds of its crude oil, leaving its transportation system especially vulnerable to disruptions in international crude supplies. UT Arlington has developed a liquefaction process that converts coal, abundant in the United States, to crude oil. This work demonstrated that the undissolvable solid coal residual from the liquefaction process, called inertinite, can be converted to an activated carbon adsorbent. Although its surface area and adsorption capacity are not as high as those for commercially available carbons, the inertinite source material would be available at no cost, and its beneficial reuse would avoid the need for disposal.