Analysis of phytochelatin complexes in the lead tolerant vetiver grass [Vetiveria zizanioides (L.)] using liquid chromatography and mass spectrometry

Ethylenediamene tetraacetic acid (EDTA) has been used to mobilize soil lead (Pb) and enhance plant uptake for phytoremediation. Chelant bound Pb is considered less toxic compared to free Pb ions and hence might induce less stress on plants. Characterization of possible Pb complexes with phytochelatins (PC_n, metal-binding peptides) and EDTA in plant tissues will enhance our understanding of Pb tolerance mechanisms. In a previous study, we showed that vetiver grass (Vetiveria zizanioides L.) can accumulate up to 19,800 and 3350 mg Pb kg⁻¹ dry weight in root and shoot tissues, respectively; in a hydroponics set-up. Following the basic incubation study, a greenhouse experiment was conducted to elucidate the efficiency of vetiver grass (with or without EDTA) in remediating Pb-contaminated soils from actual residential sites where Pb-based paints were used. The levels of total thiols, PC_n, and catalase (an antioxidant enzyme) were measured in vetiver root and shoot following chelant-assisted phytostabilization. In the presence of 15 mM kg ⁻¹ EDTA, vetiver accumulated 4460 and 480 mg Pb kg⁻¹ dry root and shoot tissue, respectively; that are 15- and 24-fold higher compared to those in untreated controls. Despite higher Pb concentrations in the plant tissues, the amount of total thiols and catalase activity in EDTA treated vetiver tissues was comparable to chelant unamended controls, indicating lowered Pb toxicity by chelation with EDTA. The identification of glutathione (referred as PC₁) (m/z 308.2), along with chelated complexes like Pb-EDTA (m/z 498.8) and PC₁-Pb-EDTA (m/z 805.3) in vetiver root tissue using electrospray tandem mass spectrometry (ES-MS) highlights the possible role of such species towards Pb tolerance in vetiver grass.     

Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg_d), DOC concentration and DOC composition, and UV₂₅₄ absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg_d to DOC (r² = 0.87), but progressively stronger correlations of THg_d with the hydrophobic acid fraction (HPOA) of DOC (r² = 0.91) and with UV₂₅₄ absorbance (r² = 0.92). The strength of the UV₂₅₄ absorbance-THg_d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg_d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg_d flux in drainage waters.     

Long-term evaluation of coal fly ash and mine tailings co-placement: A site-specific study

This study presents the results of a laboratory investigation conducted to evaluate the efficiency of coal fly ash to control the formation of acid mine drainage (AMD) from mine waste. Site-specific materials, coal fly ash from Atikokan Thermal Generating Station and mine tailings from Musselwhite mine, were mixed at different proportions for the investigation of the drainage chemistry and the optimal mix using static testing (acid–base accounting) and kinetic (column) testing. The acid–base accounting (ABA) results indicated that the fly ash possessed strong alkaline (neutralization) potential (NP) and could be used in the management of reactive mine tailings, thus ensuring prevention of AMD in the long-term. Column tests conducted in the laboratory to further investigate long-term performance of fly ash in the neutralization and prevention of acid mine drainage from tailings similarly showed that mixing fly ash with mine tailings reduces dissolution of many heavy metals from tailings by providing alkalinity to the system. It was found that a fly ash to tailings mass ratio equal to or greater than 15% can effectively prevent AMD generation from Musselwhite mine tailings in the co-placement approach.     

Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: Equilibrium, kinetics, and regeneration studies

In the present study, an adsorbent was prepared from tamarind seeds and used after activation for the removal of Cr(VI) from aqueous solutions. The tamarind seeds were activated by treating them with concentrated sulfuric acid (98% w/w) at a temperature of 150 °C. The adsorption of Cr(VI) was found to be maximum at low values of initial pH in the range of 1–3. The adsorption process of Cr(VI) was tested with Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan, Tempkin, Dubinin–Radushkevich and Generalized isotherm models. Application of the Langmuir isotherm to the system yielded a maximum adsorption capacity of 29.7 mg/g at an equilibrium pH value ranging from 1.12 to 1.46. The adsorption process followed second-order kinetics and the corresponding rate constants obtained were 2.605 × 10⁻³, 0.818 × 10⁻³, 0.557 × 10⁻³ and 0.811 × 10⁻³ g/mg min⁻¹ for 50, 200, 300 and 400 mg/L of initial Cr(VI) concentration, respectively. The regenerated activated tamarind seeds showed more than 95% Cr(VI) removal of that obtained using the fresh activated tamarind seeds. A feasible solution is proposed for the disposal of the contaminants (acid and base solutions) containing high concentrations of Cr(VI) obtained during the regeneration (desorption) process.     

Multi-criteria evaluation technique for SFI site identification of NORMS and oil industry waste disposal – Possibilities in Kuwait

Waste generation and accumulating quantities of oil field waste are a matter of environmental concern. This study proposes the Slurry Fracture Injection (SFI) technique as an alternative waste disposal method. The slurried solids injection waste disposal method is environmentally secure and permanent, leaving no future liabilities that must be risk-evaluated or priced. An entire waste stream comprising ground solids and waste water can be injected into deep and hydraulically secure target strata with no contamination of potable water-bearing formations or formations outside the target zone that may contain resources (gas and oil). The slurry injection method can be used to clean and reclaim landfills, oil pits and granular waste dumps. This article proposes a two-tier screening method for evaluating the feasibility of this technique and the identification of suitable target zones. A stringent environmental and process control monitoring program should complement the planning and operational period to ensure environmental protection, waste containment, and regulatory HSE compliance.     

Efficiency of perchlorate consumption in road flares, propellants and explosives

When an explosive detonates or a propellant or flare burns, consumption of the energetic filler should be complete but rarely is, especially in the presence of large amounts of non-combustible materials. Herein we examine three types of perchlorate-containing devices to estimate their potential as sources of contamination in their normal mode of functioning. Road flares, rocket propellants and ammonium nitrate (AN) emulsion explosives are potentially significant anthropogenic sources of perchlorate contamination. This laboratory evaluated perchlorate residue from burning of flares and propellants as well as detonations of ammonium nitrate emulsion explosives. Residual perchlorate in commercial products ranged from 0.094 mg perchlorate per gram material (flares) to 0.012 mg perchlorate per gram material (AN emulsion explosives). The rocket propellant formulations, prepared in this laboratory, generated 0.014 mg of perchlorate residue per gram of material.     

MODIS Biophysical States and NEXRAD Precipitation in a Statistical Evaluation of Antecedent Moisture Condition and Streamflow1

Abstract: The potential of remotely sensed time series of biophysical states of landscape to characterize soil moisture condition antecedent to radar estimates of precipitation is assessed in a statistical prediction model of streamflow in a 1,420 km² watershed in south‐central Texas, Moderate Resolution Imaging Spectroradiometer (MODIS) time series biophysical products offer significant opportunities to characterize and quantify hydrologic state variables such as land surface temperature (LST) and vegetation state and status. Together with Next Generation Weather Radar (NEXRAD) precipitation estimates for the period 2002 through 2005, 16 raw and deseasoned time series of LST (day and night), vegetation indices, infrared reflectances, and water stress indices were linearly regressed against observed watershed streamflow on an eight‐day aggregated time period. Time offsets of 0 (synchronous with streamflow event), 8, and 16 days (leading streamflow event) were assessed for each of the 16 parameters to evaluate antecedent effects. The model results indicated a reasonable correlation (r² = 0.67) when precipitation, daytime LST advanced 16 days, and a deseasoned moisture stress index were regressed against log‐transformed streamflow. The estimation model was applied to a validation period from January 2006 through March 2007, a period of 12 months of regional drought and base‐flow conditions followed by three months of above normal rainfall and a flood event. The model resulted in a Nash‐Sutcliffe estimation efficiency (E) of 0.45 for flow series (in log‐space) for the full 15‐month period, ?0.03 for the 2006 drought condition period, and 0.87 for the 2007 wet condition period. The overall model had a relative volume error of ?32%. The contribution of parameter uncertainties to model discrepancy was evaluated.     

Incorporating Uncertainty Into the Ranking of SPARROW Model Nutrient Yields From Mississippi/Atchafalaya River Basin Watersheds1

Abstract: Excessive loads of nutrients transported by tributary rivers have been linked to hypoxia in the Gulf of Mexico. Management efforts to reduce the hypoxic zone in the Gulf of Mexico and improve the water quality of rivers and streams could benefit from targeting nutrient reductions toward watersheds with the highest nutrient yields delivered to sensitive downstream waters. One challenge is that most conventional watershed modeling approaches (e.g., mechanistic models) used in these management decisions do not consider uncertainties in the predictions of nutrient yields and their downstream delivery. The increasing use of parameter estimation procedures to statistically estimate model coefficients, however, allows uncertainties in these predictions to be reliably estimated. Here, we use a robust bootstrapping procedure applied to the results of a previous application of the hybrid statistical/mechanistic watershed model SPARROW (Spatially Referenced Regression On Watershed attributes) to develop a statistically reliable method for identifying “high priority” areas for management, based on a probabilistic ranking of delivered nutrient yields from watersheds throughout a basin. The method is designed to be used by managers to prioritize watersheds where additional stream monitoring and evaluations of nutrient‐reduction strategies could be undertaken. Our ranking procedure incorporates information on the confidence intervals of model predictions and the corresponding watershed rankings of the delivered nutrient yields. From this quantified uncertainty, we estimate the probability that individual watersheds are among a collection of watersheds that have the highest delivered nutrient yields. We illustrate the application of the procedure to 818 eight‐digit Hydrologic Unit Code watersheds in the Mississippi/Atchafalaya River basin by identifying 150 watersheds having the highest delivered nutrient yields to the Gulf of Mexico. Highest delivered yields were from watersheds in the Central Mississippi, Ohio, and Lower Mississippi River basins. With 90% confidence, only a few watersheds can be reliably placed into the highest 150 category; however, many more watersheds can be removed from consideration as not belonging to the highest 150 category. Results from this ranking procedure provide robust information on watershed nutrient yields that can benefit management efforts to reduce nutrient loadings to downstream coastal waters, such as the Gulf of Mexico, or to local receiving streams and reservoirs.