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.     

Geographic Profiling to Assess the Risk of Rare Plant Poaching in Natural Areas

We demonstrate the use of an expert-assisted spatial model to examine geographic factors influencing the poaching risk of a rare plant (American ginseng, Panax quinquefolius L.) in Shenandoah National Park, Virginia, USA. Following principles of the analytic hierarchy process (AHP), we identified a hierarchy of 11 geographic factors deemed important to poaching risk and requested law enforcement personnel of the National Park Service to rank those factors in a series of pair-wise comparisons. We used those comparisons to determine statistical weightings of each factor and combined them into a spatial model predicting poaching risk. We tested the model using 69 locations of previous poaching incidents recorded by law enforcement personnel. These locations occurred more frequently in areas predicted by the model to have a higher risk of poaching than random locations. The results of our study can be used to evaluate resource protection strategies and to target law enforcement activities.     

Distributions of heavy metals in the sediments of South Korean harbors

Mechanisms of natural attenuation of arsenic (As) by wetland plants may be classified by plant uptake and adsorption and/or co-precipitation by iron (oxy)hydroxide formed on the root surface of plants or in rhizosediment. A natural Cattail (Typha spp.) wetland impacted by tailings containing high levels of As from the Myungbong abandoned Au Mine, South Korea was selected, and the practical capability of this wetland to attenuate As was evaluated. The As concentrations in the plant tissues from the study wetland were several-fold higher than those from control wetland. SEM-EDX analyses demonstrated that iron plaques exist on the rhizome surface. Moreover, relatively high As contents bonded with hydrous iron oxides were found in the rhizosediments rather than in the bulk sediments. It was revealed through the leaching and sequential extraction analyses that As existed as more stable forms in the wetland sediment compared with adjacent paddy soil, which is also contaminated with As due to input of mine tailings. The As concentration ratios of extracted solution to sediment/soil represented that the wetland sediment showed significant lower values (10-fold) rather than the paddy soil with indicating high As stability. Also, As in the wetland sediment was predominantly bonded with residual phases on the basis of results from sequential extraction analysis. From these results, it is concluded that transformation of As contaminated agricultural field to wetland environment may be helpful for natural attenuation until active remediation action.     

A survey on the temporal and spatial distribution of perchlorate in the Potomac River

Samples of river water and treated drinking water were obtained from eight sites along the Potomac River between western Maryland and Washington DC. Samples were collected each month from October 2007 to September 2008 and analyzed for perchlorate by ion chromatography/mass spectrometry. Data on anions were also collected for seven of the twelve months. Data were analyzed to identify spatial and temporal patterns for the occurrence of perchlorate in the Potomac. Over the year of sampling, the largest monthly increase occurred from June to July, with levels then decreasing from July to September. Samples from the period between December and May had lower perchlorate concentrations, relative to the remainder of the study year. Spatially, higher levels of perchlorate were found at sites located in west-central Maryland, the eastern panhandle of West Virginia, and central northern Virginia, with levels decreasing slightly as the Potomac approaches Washington DC. Within the sampling boundaries, river (untreated) water perchlorate concentrations ranged from 0.03 μg L(-1) to 7.63 μg L(-1), averaged 0.67 ± 0.97 μg L(-1) over the year-long period and had a median value of 0.37 μg L(-1). There was no evidence that any of the existing drinking water treatment technologies at the sampling sites were effective in removing perchlorate. There were no correlations found between the presence of perchlorate and any of the anions or water quality parameters examined in the source water with the exception of a weak positive correlation with water temperature. Results from the summer (June-August) and fall (September-November) months sampled in this study were generally higher than from the winter and spring months (December-May). All but one of the locations had annual average perchlorate levels below 1 μg L(-1); however, 7 of the 8 sites sampled had river water perchlorate detections over 1 μg L(-1) and 5 of the 8 sites had treated water detections over this level.     

Glass recycling in cement production--an innovative approach

An innovative approach of using waste glass in cement production was proposed and tested in a laboratory and cement production plant. The laboratory characterization of 32 types of glass show that the chemical composition of glass does not vary significantly with its color or origin but depends on its application. The alkali content of glass, a major concern for cement production varies from 0 to 22%. For the glass bottles mainly found in Hong Kong waste glasses, the alkali content (Na2O) ranges from 10 to 19% with an average around 15%. There is no significant change of the SO2 content in the gas exhaust of the rotary kiln when about 1.8 t/h of glass bottles were loaded along with the 280-290 t/h raw materials. The content of NOx, mainly depends on the temperature of the kiln, does not show significant change either. The SO3 content of the clinker is comparable with that obtained without the loading of glass. The alkaline content shows a slight increase but still within three times the standard deviation obtained from the statistical data of the past year. The detailed analysis of the quality of the cement product shows that there is not any significant impact of glass for the feeding rate tested.