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.     

Application of biomarkers to assess the condition of European Marine Sites

A series of European Marine Sites has been designated as Special Areas of Conservation (SAC) in England. The aim of this study was to develop a practical methodology to assess the condition of SACs by applying a suite of biomarkers. Biomarkers were applied to the blue mussel Mytilus edulis and the shore crab Carcinus maenas from the Fal and Helford SAC (Cornwall). Individual biomarkers provided useful diagnostic information on the activity of certain classes of contaminants and an integrated Biomarker Response Index (BRI) was used to achieve a more holistic understanding of the condition of the SAC. The BRI indicated that the general health of both organisms was impacted in the upper part of the SAC (Fal Estuary) which correlated well with known chemical hotspots and sources of contamination. The BRI allows a pragmatic way to prioritise SAC sites that may require further investigative studies.     

Identifying natural and anthropogenic sources of metals in urban and rural soils using GIS-based data,PCA, and spatial interpolation

Determining sources of neurotoxic metals in rural and urban soils is important for mitigating human exposure. Surface soil from four areas with significant clusters of mental retardation and developmental delay (MR/DD) in children, and one control site were analyzed for nine metals and characterized by soil type, climate, ecological region, land use and industrial facilities using readily available GIS-based data. Kriging, principal component analysis (PCA) and cluster analysis (CA) were used to identify commonalities of metal distribution. Three MR/DD areas (one rural and two urban) had similar soil types and significantly higher soil metal concentrations. PCA and CA results suggested that Ba, Be and Mn were consistently from natural sources; Pb and Hg from anthropogenic sources; and As, Cr, Cu, and Ni from both sources. Arsenic had low commonality estimates, was highly associated with a third PCA factor, and had a complex distribution, complicating mitigation strategies to minimize concentrations and exposures.     

Ultrafine particle fluxes above four major European cities

Little information is known about the behaviour of ultrafine particles (UFP) on a citywide scale. Total particle number flux, dominated by UFP, and other meteorological parameters were collected from tower sites in Manchester, London, Edinburgh and Gothenburg between 1999 and 2006 using the eddy covariance technique. Averaged diurnal cycles were produced for particle number flux, concentration, sensible heat flux, emission velocity, friction velocity, wind speed and temperature. UFP flux cycles showed clear diurnal trends which were linked to traffic activity and local sources. Wind sector analysis showed contributions to flux from local heavily urbanised areas. A simple parameterised model linking UFP flux to traffic activity, sensible heat and friction velocity above the city was produced.     

Surface ozone background in the United States: Canadian and Mexican pollution influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.     

A validated 2-D diffusion–advection model for prediction of drift from ground boom sprayers

Correct field drift prediction is a key element in environmental risk assessment of spraying applications. A reduced order drift prediction model based on the diffusion–advection equation is presented. It allows fast assessment of the drift potential of specific ground boom applications under specific environmental wind conditions that obey the logarithmic wind profile. The model was calibrated based on simulations with a validated Computational Fluid Dynamics (CFD) model. Validation of both models against 38 carefully conducted field experiments is successfully performed for distances up to 20 m from the field edge, for spraying on flat pasture land. The reduced order model succeeded in correct drift predictions for different nozzle types, wind velocities, boom heights and spray pressures. It used 4 parameters representing the physical aspects of the drift cloud; the height of the cloud at the field edge, the mass flux crossing the field edge, the settling velocity of the droplets and the turbulence. For the parameter set and range considered, it is demonstrated for the first time that the effect of the droplet diameter distribution of the different nozzle types on the amount of deposition spray drift can be evaluated by a single parameter, i.e., the volume fraction of droplets with a diameter smaller than 191 μm. The reduced order model can be solved more than 4 orders of magnitude faster than the comprehensive CFD model.     

Evaluation and application of biomagnetic monitoring of traffic-derived particulate pollution

Inhalation of particulate pollutants below 10 μm in size (PM₁₀) is associated with adverse health effects. Here we use magnetic remanence measurements of roadside tree leaves to examine levels of vehicle-derived PM around Lancaster, UK. Leaf saturation remanence (SIRM) values exhibit strong correlation with both the SIRM and particulate mass of co-located, pumped-air samples, indicating that these leaf magnetic values are an effective proxy for ambient PM₁₀ concentrations. Biomagnetic monitoring using tree leaves can thus provide high spatial resolution data sets for assessment of particulate pollution levels at pedestrian-relevant heights. Leaf SIRM values not only increase with proximity to roads with higher traffic volumes, but are also ～100% higher at 0.3 m than at ～1.5–2 m height. Magnetic and SEM data indicate that the particle populations are dominated by spherical, iron-rich particles ～0.1–1 μm in diameter, with fewer larger, more angular, silica-rich particles. Comparison of the roadside leaf-calculated PM₁₀ concentrations with PM₁₀ concentrations predicted by a widely-used atmospheric dispersion model indicates some agreement between them. However, the model under-predicts PM₁₀ concentrations at ‘urban hotspots’ such as major–minor road junctions and traffic lights. Conversely, the model over-predicts PM₁₀ concentrations with distance from the road wherever one tree is screened by another, indicating the filtering/protective effect of roadside trees in leaf.     

Effect of diurnal changes in VOC source strengths on performances of receptor models

Introduction

The effect of diurnal changes in strengths of volatile organic compound (VOC) sources on the performances of positive matrix factorization (PMF) and principal component analysis (PCA) was investigated using ambient measurement results that were taken during daytime and nighttime hours between March 24 and May 14, 2011, within Davutpasa Campus of Yildiz Technical University (Istanbul, Turkey).

Methods

Forty-five VOC species, ranging from C₅ to C₁₁ in volatility, were measured in the samples, 40 of which are included in the analyses. Ambient samples were grouped as daytime, nighttime, and all day datasets, and both PMF and PCA were applied to each dataset. A total of six source groups were extracted from each dataset: solvent use, general industrial paint use, gasoline and diesel vehicle exhausts, and biogenic as well as evaporative emissions. Estimated source contributions showed great diurnal variations.

Results

The results suggested that extraction of possible sources by PCA depends greatly on the number of samples and the strength of the sources, while PMF produced stable results regardless of number of samples and source strengths.

Conclusion

Although PMF was unable to resolve gasoline vehicle and evaporative emissions, it was found to be successful in explaining diurnal fluctuations in source strengths, while the performance of PCA depends on the strength of emission source.     

Short-run allocation of emissions allowances and long-term goals for climate policy

We use economic analysis to evaluate grandfathering, auctioning, and benchmarking approaches for allocation of emissions allowances and then discuss practical experience from European and American schemes. In principle, auctions are superior from the viewpoints of efficiency, fairness, transparency, and simplicity. In practice, auctions have been opposed by important sectors of industry, which argue that carbon pricing without compensation would harm international competitiveness. In the European Union's Emissions Trading System, this concern led to grandfathering that is updated at various intervals. Unfortunately, updating gives industry an incentive to change behavior to influence future allocation. Furthermore, the wealth transferred to incumbent firms can be significantly larger than the extra costs incurred, leading to windfall profits. Meanwhile, potential auction revenues are not available to reduce other taxes. By circumscribing free allocation, benchmarking can target competitiveness concerns, incur less wealth transfer, and provide a strategy consistent with transitioning to auctions in the long run.