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Unravelling structures of molecules contained in complex, chromatographically inseparable mixtures is a challenging task. Due to the number of overlapping resonances in NMR spectra of these mixtures, unambiguous chemical shift correlations attributable to individual molecules cannot be achieved and thus their structure determination is elusive by this technique. Placing a tag carrying an NMR active nucleus onto a subset of molecules enables (i) to eliminate signals from the non-tagged molecules, and (ii) to obtain a set of correlated chemical shifts and coupling constants belonging to a single molecular type. This approach provides an opportunity for structure determination without the need for compound separation. Focusing on the most abundant functional groups of natural organic matter molecules, the carboxyl and hydroxyl groups were converted into esters and ethers, respectively by introducing 13CH3O groups. A set of 13C-filtered nD NMR experiments was designed yielding structures/structural motives of tagged molecules. The relative sensitivity of these experiments was compared and a step-by-step guide how to use these experiments to analyse the structures of methylated phenolics is provided. The methods are illustrated using an operational fraction of soil organic matter, fulvic acid isolated from a Scottish peat bog. Analysis of 33 structures identified in this sample revealed a correlation between the position of the methoxy cross-peaks in the 1H, 13C HSQC spectra and the compound type. This information enables profiling of phenolic compounds in natural organic matter without the need to acquire a full set of experiments described here or access to high field cryoprobe NMR spectrometers. [ABSTRACT FROM AUTHOR]

Cores collected from ombrotrophic peat bogs in west central, east central, northeast and southwest Scotland were dated (14C, 210Pb) and analyzed (ICP-OES, ICP-MS) to derive and compare their historical records of atmospheric anthropogenic Pb deposition over the past 2500 years. On the basis of Pb isotopic composition (e.g., 206Pb/207Pb), clear indications of Pb contamination during the pre-Roman/Roman, post-Roman and medieval periods were attributed to the mining and smelting of Pb ores from Britain and elsewhere in Europe. Between the 17th and early 20th centuries, during the industrial period, the mining and smelting of indigenous Scottish Pb ores were the most important sources of anthropogenic Pb deposition at three of the sites. In contrast, at the most southerly site, influences from the use of both British Pb ores and imported Australian Pb ores (in more southern parts of Britain) since the late 19th century were evident. At each of the sites, Australian-Pb-influenced car exhaust emissions (from the 1930s to late 1990s), along with significant contributions from coal combustion (until the late 1960s and onset of the postindustrial period), were evident. Atmospheric anthropogenic Pb deposition across Scotland was greatest (~10 to 40 mg m-2 a-1) between the late 1880s and late 1960s, increasing southward, declining to 0.44 to 5.7 mg m-2 a-1 by the early 2000s. The records from four peat bogs extend knowledge of the chronology of atmospheric Pb deposition trends across the northern hemisphere, there being general agreement with other environmental archive records from not only Scotland but also other countries in western Europe and Greenland. Nevertheless, during all periods investigated here, the isotopic composition of atmospheric Pb deposition across western Europe and Greenland exhibited variations in the relative importance of different sources of anthropogenic Pb, as well as some differences in timings and magnitudes of anthropogenic Pb contamination, arising from variations in local and regional sources of Pb deposition and possibly climatic regimes. [ABSTRACT FROM AUTHOR]

Hydrological budgets and flow pathways have been quantified for a small upland catchment (1.76 km²) in the northeast of Scotland. Water balance calculations for four subcatchments identified spatial variability within the catchment, with an estimated runoff enhancement of up to 25% for the upper western area, compared with the rest of the catchment. Data from spatial hydrochemical sampling, over a range of flow conditions, were used to identify the principal hillslope runoff mechanisms within the catchment. A hydrochemical mixing analysis revealed that runoff emerging from springs in various locations of the hillslope accounted for a significant proportion of flow in the streams, even during storm events. A hydrological model of the catchment was calibrated using the calculated stream flows for four locations, together with results from the mixing analysis for different time points. The calibrated model was used to predict the temporal variability in contributions to stream flow from the hillslope springs and soil water flows. The overall split ranged from 57% : 43% spring water: soil water in the upper eastern subcatchment, to 76% 24% in the upper western subcatchment. [ABSTRACT FROM AUTHOR]

The article presents analytical characterisation of solid and solution-phase chromium species at chromite ore processing residue (COPR)-contaminated sites. The solid phases present in COPR from three of the sites investigated were identified and quantified using X-ray powder diffractometry and scanning electron microscopy combined with energy dispersive X-ray microanalysis. The valency of the constituent ions is not obtained directly from the electron microprobe analysis but is derived from the stoichiometry and the known mineral structures.