Fractionation of Cu, Pb and Zn in certified reference soils SRM 2710 and SRM 2711 using the optimized BCR sequential extraction procedure

Sequential extraction of metals from solid media is a common analytical tool used in environmental and exploration geochemistry. A number of procedures exist, but without harmonization and standardization, meaningful comparisons are tenuous without baseline data. A newly developed, standardized sequential extraction procedure (optimized BCR) was applied to two contaminated certified reference soils from Montana, US (SRM 2710 and SRM 2711) for Cu, Pb and Zn. Four operationally defined fractions were isolated, acid extractable, reducible, oxidizable, and residual (by aqua regia). Fraction-specific concentrations, percentages and recoveries for Cu, Pb and Zn were used to explore differences between the optimized BCR procedure and three other sequential extraction schemes with published data for SRM 2710 and 2711 (i.e. Tessier scheme, Geological Survey of Canada scheme and the original BCR scheme). Results indicate significant differences between the four schemes, even for schemes that are closely associated (i.e. the original and optimized BCR schemes). Order-of-magnitude fraction-specific concentration differences were observed, especially for Pb in the reducible fraction. Differences between schemes are worrisome because trends varied between metals, between fractions and between reference soils. These data reinforce the need for increased adoption of standardized sequential extraction procedures and further examination of different solid media.     

Radiogenic Lead Isotopes and Time Stratigraphy in the Hudson River, New York

Radionuclide, radiogenic lead isotope and trace metal analyses on fine-grained sediment cores collected along 160 km of the upper and tidal Hudson River were used to examine temporal trends of contaminant loadings and to develop radiogenic lead isotopes both as a stratigraphic tool and as tracers for resolving decadal particle transport fluxes. Very large inputs of Cd, Sb, Pb, and Cr are evident in the sediment record, potentially from a single manufacturing facility. The total range in radiogenic lead isotope ratios observed in well-dated cores collected about 24 km downstream of the plant is large (e.g., maximum difference in ²⁰⁶Pb/²⁰⁷Pb is 10%), characterized by four major shifts occurring in the 1950s, 1960s, 1970s and 1980s. The upper Hudson signals in Cd and radiogenic lead isotopes were still evident in sediments collected 160 km downstream in the tidal Hudson. The large magnitude and abrupt shifts in radiogenic lead isotope ratios as a function of depth provide sensitive temporal constraints that complement information derived from radionuclide analyses to significantly improve the precision of dating assignments. Application of a simple dilution model to data from paired cores suggests much larger sediment inputs in one section of the river than previously reported, suggesting particle influxes to the Hudson have been underestimated.     

Metal contents of marine turtle eggs (Chelonia mydas; Lepidochelys olivacea) from the tropical eastern pacific and the implications for human health

Concentrations of eight elements were measured in Chelonia mydas and Lepidochelys olivacea eggs collected along the Pacific coast of Panama. Manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd), and mercury (Hg) concentrations were similar to previous reports of these species from around the world, while lead (Pb) was lower than previous reports. Cd posed the highest health risk to people who regularly eat the eggs, with average consumption rates leading to target hazard quotients (THQ) of up to 0.35 ± 0.15. Our conclusions indicate that current turtle egg consumption in isolated, coastal Pacific communities may pose a health concern for young children, and that youth and young adults should limit their consumption of turtle eggs to reduce their total intake of nonessential metals.     

Extraction of labile metals from solid media by dilute hydrochloric acid

Extraction of labile metals from solid media is environmentally more meaningful than a total digestion. A variety of reagents have been introduced in the literature, but dilute HCl has received the greatest attention. We compare metal concentrations liberated by a dilute HCl leach with the sum of the 3-step optimized (standardized) BCR sequential extraction procedure. This is the first study to compare these procedures over a range of grain sizes. Road-deposited sediments from 10 sites in Honolulu were fractionated into six grain size classes. Aliquots of individual fractions were digested with dilute HCl, the 3-step BCR procedure (‘labile’), and a 4-acid (total) procedure. Results indicated that the weighted labile concentrations of Al, Cu, Fe, Mn, Ni, Pb and Zn were statistically greater than those from the dilute HCl leach. However, regression analysis indicated strong statistically significant relationships between the two partial extraction procedures for all metals. On a whole-sample basis, the toxicity classifications for anthropogenic-enhanced metals (Cu, Pb and Zn) were similar between extractions. Taken together, results suggest that the application of dilute HCl to solid media provides a rapid, cost-effective, and environmentally meaningful approach for contaminant monitoring.     

Elemental concentrations and in vitro bioaccessibility in Canadian background soils

Elemental concentrations and bioaccessibility were determined in background soils collected in Canada as part of the North American Geochemical Landscapes Project. The concentrations of As, Cr, Cu, Co, Ni and Zn were higher in the C-horizon (parent material) compared to 0–5 cm (surface soil), and this observation along with the regional distribution suggested that most of the variability in concentrations of these elements were governed by the bedrock characteristics. Unlike the above-stated elements, Pb and Cd concentrations were higher in the surface layer reflecting the potential effects of anthropogenic deposition. Elemental bioaccessibility was variable decreasing in the order Cd > Pb > Cu > Zn > Ni > Co > As > Cr for the surface soils. With the exception of As, bioaccessibility was generally higher in the C-horizon soils compared to the 0–5 cm soils. The differences in metal bioaccessibility between the 0–5 cm and the C-horizon and among the provinces may reflect geological processes and speciation. The mean, median or 95th percentile bioaccessibility for As, Cr, Cu, Co, Ni and Pb were all below 100 %, suggesting that the use of site-specific bioaccessibility results for these elements will yield more accurate estimation of the risk associated with oral bioavailability for sites where soil ingestion is the major contributor of human health risk.     

Blowing policy bubbles: rethinking emissions targets and low-carbon energy policies in the U.K.

The issue of proportionality is central to climate policy debates about setting targets for the reduction of greenhouse gas emissions and the development of low-carbon energy. In effect, these debates centre on whether the perceived social costs outweigh the benefits of policies and, if not, whether this may lead to over-investment or ‘policy bubbles’. Political attention, agenda setting and policy image are all crucial drivers of ambitious policy formation, as seen in the case of the United Kingdom's (U.K.) Climate Change Act (2008). However, as political salience waned and economic depression dragged on, the cost of long-term climate targets has been reconsidered. Based on documentary analysis and 33 interviews with central political actors, this article presents a detailed account of how economic arguments have been used to reinterpret and challenge policies, using the heuristics of ‘over-investment’ and ‘policy bubbles’. Ultimately, arguments about proportionality hinge on which costs and benefits are considered. In the U.K., economic and technical framings are typically prioritised, but they do not explain contradictory and politically motivated policy decisions. We discuss these dynamics within the context of maturing renewable energy technologies, high energy prices and the U.K.’s cross-party consensus approach to climate politics.     

Comparative effect of thymol or its glucose conjugate,thymol-β-d-glucopyranoside,on Campylobacter in avian gut contents

Campylobacter jejuni is an important human food-borne pathogen that can contaminate meat and poultry during processing. Consequently, strategies are sought to reduce the carriage of C. jejuni in food animals before they arrive at the abattoir. Thymol is a natural product that reduces survivability of Campylobacter in vitro, but its rapid absorption from the proximal alimentary tract limits its bactericidal efficacy in vivo. Thymol-β-d-glucopyranoside is more resistant to absorption than free thymol, but its administration to chickens has not been reported. In the present studies, 1 mM thymol-β-d-glucopyranoside was shown to exhibit near equal anti-Campylobacter activity as 1 mM thymol when incubated anaerobically in avian crop or cecal contents in vitro, resulting in reductions of 1.10–2.32 log₁₀ colony forming units mL^?1 in C. jejuni concentrations after 24 h incubation. In a follow-up live animal study, oral administration of thymol-β-d-glucopyranoside, but not free thymol, significantly lowered (>10-fold) recovery of Campylobacter from the crop of market-aged broilers when compared to placebo-treated controls (n = 6 broilers/treatment). Neither thymol-β-d-glucopyranoside nor thymol affected recovery of Campylobacter from cecal contents of the treated broilers. These results indicate that rapid absorption or passage of free thymol from the crop precluded its anti-Campylobacter activity at this site and throughout the entire gastrointestinal tract. Conversely, lower recovery of Campylobacter from the crop of birds treated with thymol-β-d-glucopyranoside indicates this conjugate was retained and able to be hydrolyzed to biologically active free thymol at this site as intended, yet was not sufficiently protected to allow passage of efficacious amounts of the intact glycoside to the lower gut. Nevertheless, these results warrant further research to see if higher doses or encapsulation of thymol-β-d-glucopyranoside or similar glycosides may yield an efficacious additive to reduce carriage of Campylobacter as well as other pathogens throughout the avian gut.     

Exhaust Temperature Profiles for Application of Passive Diesel Particulate Filters to Solid Waste Collection Vehicles in California

Abstract

To reduce public exposure to diesel particulate matter (DPM), the California Air Resources Board has begun adoption of a series of rules to reduce these emissions from in-use heavy-duty vehicles. Passive diesel particulate filter (DPF) after-treatment technologies are a cost-effective method to reduce DPM emissions and have been used on a variety of vehicles worldwide. Two passive DPFs were interim-verified in California and approved federally for use in most 1994–2002 engine families for vehicles meeting min engine exhaust temperature requirements for successful filter regeneration. Some vehicles, however, may not be suited to passive DPFs because of lower engine exhaust temperatures. The purpose of this study was to determine the applicability of two types of passive DPFs to solid waste collection vehicles, the group of vehicles for which California recently mandated in-use DPM reductions. We selected 60 collection vehicles to represent the four main types of collection vehicle duty cycles—roll-offs, and front-end, rear, and side loaders—and collected second-by-second engine exhaust temperature readings for one week from each vehicle. As a group, the collection vehicles exhibited low engine exhaust temperatures, making the application of passive DPFs to these vehicles difficult. Only 35% of tested vehicles met the temperature requirements for one passive DPF, whereas 60% met the temperature requirements for the other. Engine exhaust temperatures varied by vehicle type. Side and front-end loaders met the engine exhaust temperature requirements in the greatest number of cases with ～50–90% achieving the required regeneration temperatures. Only 8–25% of the rear loader and roll-off collection vehicles met the engine exhaust temperature requirements. Solid waste collection vehicles represent a diverse fleet with a variety of duty cycles. Low engine exhaust temperatures will need to be addressed for successful use of passive DPFs in this application.