The formation of reactive oxygen species catalyzed by neutral, aqueous extracts of NIST ambient particulate matter and diesel engine particles

It is important to characterize the chemical properties of particulate matter in order to understand how low doses, inhaled by a susceptible population, might cause human health effects. The formation of reactive oxygen species catalyzed by neutral, aqueous extracts of two ambient particulate samples, National Institute of Standards & Technology (NIST) Standard Reference Materials (SRM) 1648 and 1649, and two diesel particulate samples, NIST SRM 1650 and SRM 2975, were measured. The formation of reactive oxygen species was estimated by measuring the formation of malondialdehyde from 2-deoxyribose in the presence of ascorbic acid; H2O2 was not added to this assay. SRM 1649, ambient particulate matter collected from Washington, DC, generated the most malondialdehyde, while SRM 2975, diesel particulate matter collected from a forklift, yielded the least amount. Desferrioxamine inhibited the formation of malondialdehyde from the particulate samples providing additional data to support the observation that transition metals were involved in the generation of reactive oxygen species. Six transition metal sulfates (iron sulfate, copper sulfate, vanadyl sulfate, cobalt sulfate, nickel sulfate, and zinc sulfate) were assayed for their ability to generate reactive oxygen species under the same conditions used for the particulate samples in order to facilitate comparisons between particles and these transition metals. The concentration of transition metals was measured in aqueous extracts of these particulate samples using ion-coupled plasma mass spectrometry (ICP-MS) analysis. There was qualitative agreement between the concentrations of Fe, Cu, and V and the amount of malondialdehyde produced from extracts of these particulate samples. These data suggest that transition metals can be dissolved from particles in neutral, aqueous solutions and that these metals are capable of catalyzing the formation of reactive oxygen species.     

Modelling sulphate-enhanced cadmium uptake by Zea mays from nutrient solution under conditions of constant free Cd2+ ion activity

A controlled hydroponic experiment was undertaken to investigate Cd uptake in relation to the activity of Cd species in solution other than the free ion (Cd²⁺) by maintaining a constant Cd²⁺ activity under variable SO₄₂⁻ and Cl⁻ concentrations exposed to maize (Zea mays var. Cameron) plants. The objectives of these experiments were: (1) to distinguish and quantify the different uptake rates of free and inorganic-complexed Cd from nutrient solution, and (2) to model the uptake of Cd by maize with a Biotic Ligand Model (BLM) in a system which facilitates the close examination of root characteristics. Results of the current experiments suggest that, in addition to the free ion, CdSO₄⁰ complexes are important factors in determining Cd uptake in nutrient solution by maize plants. Higher nominal SO₄²⁻ concentrations in solution generally resulted in a greater Cd accumulation by maize plants than predicted by the Cd²⁺ activity. A better integration of the complete dataset for the 3 harvest times (6, 9 and 11 days after treatment) was achieved by including consideration of both the duration of Cd exposure and especially the root surface area to express Cd uptake. Similarly, the fit of the BLM was also improved when taking into account exposure time and expressing uptake in terms of root morphological parameters.     

Collective fit perceptions: A multilevel investigation of person–group fit with individual‐level and team‐level outcomes

This study describes a multilevel examination of person–group (PG) fit perceptions in a sample of 1023 individuals working in 92 teams at a private sector R&D firm. Using confirmatory factor analysis and multilevel random coefficient modeling, we provide evidence that perceptions of team‐level collective fit are unique from aggregated individual‐level PG fit perceptions at the individual and team levels. We demonstrate that collective values‐based and abilities‐based fit perceptions showed unique and positive relationships with team cohesion, team efficacy, and team performance, after accounting for aggregated individual perceptions of PG fit. Results also demonstrate that cohesion partially mediates the relationship between collective fit and team performance. Cross‐level effects were also supported, indicating that collective fit explains additional variance in individual‐level outcomes, beyond individual‐level PG fit perceptions. The usefulness of employing a multilevel approach to studying PG fit is discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

The importance of solid-phase distribution on the oral bioaccessibility of Ni and Cr in soils overlying Palaeogene basalt lavas, Northern Ireland

Potentially toxic elements (PTEs) including nickel and chromium are often present in soils overlying basalt at concentrations above regulatory guidance values due to the presence of these elements in underlying geology. Oral bioaccessibility testing allows the risk posed by PTEs to human health to be assessed; however, bioaccessibility is controlled by factors including mineralogy, particle size, solid-phase speciation and encapsulation. X-ray diffraction was used to characterise the mineralogy of 12 soil samples overlying Palaeogene basalt lavas in Northern Ireland, and non-specific sequential extraction coupled with chemometric analysis was used to determine the distribution of elements amongst soil components in 3 of these samples. The data obtained were related to total concentration and oral bioaccessible concentration to determine whether a relationship exists between the overall concentrations of PTEs, their bioaccessibility and the soils mineralogy and geochemistry. Gastric phase bioaccessible fraction (BAF %) ranged from 0.4 to 5.4 % for chromium in soils overlying basalt and bioaccessible and total chromium concentrations are positively correlated. In contrast, the range of gastric phase BAF for nickel was greater (1.4–43.8 %), while no significant correlation was observed between bioaccessible and total nickel concentrations. However, nickel BAF was inversely correlated with total concentration. Solid-phase fractionation information showed that bioaccessible nickel was associated with calcium carbonate, aluminium oxide, iron oxide and clay-related components, while bioaccessible chromium was associated with clay-related components. This suggests that weathering significantly affects nickel bioaccessibility, but does not have the same effect on the bioaccessibility of chromium.     

Efficacy of rapeseed residue and eggshell waste on enzyme activity and soil quality in rice paddy

Addition of plant residue into soils improves soil physiochemical properties and its fertility. Rapeseed residue is an emerging N source to paddy soils via rice-rape double-cropping practice. The objective of this study was to evaluate the effects of rapeseed residue and eggshell waste on chemical changes and enzyme activity in the rice paddy soil. The powdered eggshells at 0, 1, 3, and 5% were applied once to 7.0 kg paddy repacked soils in each pot treated with the rapeseed residue or the conventional N, P, and K fertilisers. Eight rice seedlings (Oriza sativa L. cv. Ilmibyeo) (40 days after sowing) were transplanted to the treated each pot. The contents of total C (TC) and N (TN), and organic matter (OM) were significantly increased in soils treated with the rapeseed residue compared to the N, P, and K fertilisers. With the addition of eggshell containing ～92% CaCO₃, a considerable increase of soil pH was observed in soils treated with the rapeseed residue and the N, P, and K fertilisers, compared to the untreated soil. Activities of β-glucosidase, urease, and arylsulfatase enzymes were higher in soils treated with the rapeseed residue than soils treated with the N, P, and K fertilisers. The eggshell additions at 1, 3, and 5% into soils treated with the rapeseed residue increased enzyme activity mainly resulting from N mineralisation, whereas no change in enzyme activity was observed in the soils treated with the NPK fertiliser. The combined use of the rapeseed residue and the eggshells can be beneficial to improve soil environment.     

Relationship between total concentration and dilute HCl extraction of heavy metals in sediments of harbors and coastal areas in Korea

Total concentrations of Cr, Ni, Cu, Zn, Cd and Pb in surface sediments were determined to investigate the regional trends of heavy metal contamination in 11 coastal areas in Korea. Enrichment factor (EF) of heavy metals was calculated by comparing the level of their regional background. The averages of EF values in study areas were 0.99 for Cr, 1.05 for Ni, 4.23 for Cu, 1.80 for Zn, 3.92 for Cd and 1.54 for Pb, respectively. Dilute HCl extractions were useful to deduce the anthropogenic sources of heavy metals and the 1 M HCl extractable fractions of each metal varied from 0.3 to 37.3% for Cr, 1.9 to 66.3% for Ni, 4.2 to 92.9% for Cu, 7.1 to 99.7% for Zn, 10.9 to 98.9% for Cd and 15.0 to 99.1% for Pb. Comparing 1 M HCl extractable fraction to total concentration, large portions of Cu, Zn, Cd and Pb were present as potentially bioavailable fractions from anthropogenic input and were significantly correlated with their EF values showing r > 0.68.     

Selective reduction of NO by photo-SCR with ammonia in an annular fixed-film photoreactor

Gaseous NO was photocatalytically reduced at room temperature by photo-assisted selective catalytic reduction (photo-SCR) with ammonia over TiO₂ in this study. NO reduction efficiency and N₂ selectivity were determined from gases composition at the outlet stream of photoreactor. Effect of operating conditions, e.g. light intensity and inlet concentrations of ammonia and oxygen, on the NO reduction efficiency and N₂ selectivity were discussed to determine the feasible operating condition for photocatalytic reduction of NO. Experimental results showed that selective catalytic reduction of NO with ammonia over TiO₂ in the presence of oxygen was a spontaneous reaction in dark. The photoirradiation on the TiO₂ surface caused remarkable photocatalytic reduction of NO to form N₂, NO₂, and N₂O under 254 nm UV illuminations, while almost 90% of N₂ selectivity was achieved in this study. The ammonia and oxygen molecules played the roles of reductant and oxidant for NO reduction and active sites regeneration, respectively. The reduction of NO was found to be increased with the increase of inlet ammonia and oxygen concentrations until specific concentrations because of the limited active sites on the surface of TiO₂. The kinetic model proposed in this study can be used to reasonably describe the reaction mechanism of photo-SCR.     

A spatial model approach for assessing windbreak growth and carbon stocks

Agroforestry, the deliberate integration of trees into agricultural operations, sequesters carbon (C) while providing valuable services on agricultural lands. However, methods to quantify present and projected C stocks in these open-grown woody systems are limited. As an initial step to address C accounting in agroforestry systems, a spatial Markov random field model for predicting the natural logarithm (log) of the mean aboveground volume of green ash ( Marsh.) within a shelterbelt, referred to as the log of aboveground volume, was developed using data from an earlier study and web-available soil and climate information. Windbreak characteristics, site, and climate variables were used to model the large-scale trend of the log of aboveground volume. The residuals from this initial model were correlated among sites up to 24 km from a point of interest. Therefore, a spatial dependence parameter was used to incorporate information from sites within 24 km into the prediction of the log of the aboveground volume. Age is an important windbreak characteristic in the model. Thus, the log of aboveground volume can be predicted for a given windbreak age and for values of other explanatory variables associated with a site of interest. Such predictions can be exponentiated to obtain predictions of aboveground volume for windbreaks without repeated inventory. With the capability of quantifying uncertainty, the model has the potential for large regional planning efforts and C stock assessments for many deciduous tree species used in windbreaks and riparian buffers once it is calibrated.