Dissipation,half-lives,and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre^?1. Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T_1/2 = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T_1/2 = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

PM10 source apportionment in a Swiss Alpine valley impacted by highway traffic

Although trans-Alpine highway traffic exhaust is one of the major sources of air pollution along the highway valleys of the Alpine regions, little is known about its contribution to residential exposure and impact on respiratory health. In this paper, source-specific contributions to particulate matter with an aerodynamic diameter?<?10 μm (PM₁₀) and their spatio-temporal distribution were determined for later use in a pediatric asthma panel study in an Alpine village. PM₁₀ sources were identified by positive matrix factorization using chemical trace elements, elemental, and organic carbon from daily PM₁₀ filters collected between November 2007 and June 2009 at seven locations within the village. Of the nine sources identified, four were directly road traffic-related: traffic exhaust, road dust, tire and brake wear, and road salt contributing 16 %, 8 %, 1 %, and 2 % to annual PM₁₀ concentrations, respectively. They showed a clear dependence with distance to highway. Additional contributions were identified from secondary particles (27 %), biomass burning (18 %), railway (11 %), and mineral dust including a local construction site (13 %). Comparing these source contributions with known source-specific biomarkers (e.g., levoglucosan, nitro-polycyclic aromatic hydrocarbons) showed high agreement with biomass burning, moderate with secondary particles (in winter), and lowest agreement with traffic exhaust.     

Lessons learned from classroom training on natural attenuation of chlorinated solvents

Technology and information transfer are critical functions within the remediation industry. Researchers in the private sector, academia, and government all struggle to have their findings accepted and put to good use by the remediation industry at large but must work even harder to have their findings accepted and put into practice by state and federal regulators in the environmental agencies overseeing cleanups. Unfortunately, many technology and information transfer efforts fail to reach state and federal regulators, and even fewer achieve regulatory acceptance. A two‐year‐long campaign to deliver a training class on the natural attenuation of chlorinated solvents in groundwater is one prominent example of very effective technology and information transfer. Several of the elements and aspects of that successful training class are presented and discussed in order to provide others with a proven and workable template. © 2010 Wiley Periodicals, Inc.     

Improved VOC bioremediation using a fluidized bed peat bioreactor

A gas–solid fluidized bed bioreactor was successfully used to treat air contaminated with a volatile organic compound (VOC). A bioreactor containing both a fluidized and packed bed of moist peat granules removed ethanol, a representative VOC, from an air stream. The fluidized bed operation mode of the bioreactor outperformed the packed bed mode. The maximum elimination capacity (EC) of ethanol in the fluidized mode was 1520 g m⁻³ h⁻¹, with removal efficiencies ranging between 45 and 100%, at loadings up to 3400 g m⁻³ h⁻¹. Maximum EC was 530 g m⁻³ h⁻¹ in the packed bed mode. Removal efficiency in the fluidized bioreactor was best at the lowest velocity, where the bubbling bed fluidization regime predominated. As gas velocity increased, the size and amount of large bubbles (slugs) increased and removal efficiency decreased while elimination capacity increased.     

Evaluation of various chemical extraction methods to estimate plant-available arsenic in mine soils

Elevated levels of bioavailable As in mining soils, agricultural areas and human habitats may cause potential toxicity to human health, plants and microbe. Therefore, it is essential to determine proper soil chemical extraction method in order to estimate plant-available As in mining soils and protect agricultural and environmental ecosystems by evaluation of environmental risk and implementation of remediation measures. In this study, six single soil chemical extraction processes and four-step sequential chemical extraction protocol were used to determine the relative distribution of As in different chemical forms of soils and their correlations with total As in plants grown in mining areas and greenhouse experiments. The strongest relationship between As determined by single soil chemical extraction and As in plant biomass was found for sodium acetate and mixed acid extractant. The mean percent of total As extracted was: ammonium oxalate (41%)>hydroxylamine hydrochloride (32%)>mixed acid (16%)>phosphate (6%)>sodium acetate (1.2%)>water (0.13%). This trend suggests that most of the As in these soils is inside the soil mineral matrix and can only be released when iron oxides and other minerals are dissolved by the stronger chemical extractant. Single soil chemical extraction methods using sodium acetate and mixed acids, that extract As fractions complexed to soil particles or on the surface of mineral matrix of hydrous oxides of Fe, Mn and Al (exchangeable+sorbed forms) can be employed to estimate and predict the bioavailable As fraction for plant uptake in mining affected soils. In sequential chemical extraction methods, ammonium nitrate and hydroxylamine hydrochloride may be used to provide closer estimates of plant-available As in mining soils.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by FeII-bearing minerals

The long-lived radionuclide 79Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (SeVIO4(2-)) and selenite (SeIVO3(2-)). Previous investigations have demonstrated, however, that SeIV and SeVI are reduced by surface-associated FeII, thereby forming insoluble Se0 and Fe selenides. Here we show that the mixed FeII/III (hydr)oxides green rust and magnetite, and the FeII sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the FeII carbonate siderite produces elemental Se. In the case of mackinawite, both S(-II) and FeII surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these FeII systems is controlled by the concentration of HSe(-); Se0 forms only at lower HSe(-) concentrations related to slower HSeO3(-) reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe2+-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 x 10(-8) M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since FeII phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product 79Se may be much lower than previously assumed.     

Estimating Evapotranspiration and Seepage for a Sinkhole Wetland From Diurnal Surface‐Water Cycles1

Abstract: This study used measured diurnal surface‐water cycles to estimate daily evapotranspiration (ET) and seepage for a seasonally flooded sinkhole wetland. Diurnal surface‐water cycles were classified into five categories based on the relationship between the surface‐water body and the surrounding ground‐water system (i.e., recharge/discharge). Only one class of diurnal cycles was found to be suitable for application of this method. This subset of diurnal cycles was used to estimate ET and seepage and the relative importance of each transfer process to the overall water budget. The method has limited utility for wetlands with erratic hydrologic regimes (e.g., wetlands in urban environments). This is due to violation of the critical assumption that the inflow/outflow rate remains constant throughout the day. For application to surface‐water systems, the method is typically applied with an assumed specific yield of 1.0. This assumption was found to be invalid for application to surface‐water systems with a noncylindrical pond geometry. An overestimation of ET by as much as 60% was found to occur under conditions of low pond stage and high water loss. The results demonstrate the high ET rates that can occur in isolated wetlands due to contrasting roughness and moisture conditions (oasis and clothesline effects). Estimated ET rates ranged from 4.1 to 18.7 mm/day during the growing season. Despite these large ET rates, seepage (recharge) was found to be the dominant water loss mechanism for the wetland.