Recent advances in mercury speciation analysis with focus on spectrometric methods and enriched stable isotope applications

This paper discusses some recent advances in spectrometric methods and approaches for mercury speciation analysis of environmental samples with focus on isotope dilution techniques for determination of mercury species' concentrations in gaseous samples and reaction rates in soils and sediments. Such analytical data is important inter alia in fundamental research on mercury biogeochemistry and for risk assessments of mercury-contaminated soils and sediments and for designing effective remedial actions. The paper describes how the use of enriched stable isotope tracers in mercury speciation analysis can improve the traceability and accuracy of results, facilitate rational method developments, and be useful for studying biogeochemical processes, i.e. rate of reactions and fluxes, of mercury species. In particular the possibilities to study and correct for unwanted species transformation reactions during sample treatment and to study "natural" transformations of species in environmental samples, or micro- and mesocosm ecosystems, during incubations are highlighted. Important considerations to generate relevant data in isotope tracer experiments as well as reliability and quality assurance of mercury speciation analysis in general are also discussed.     

Temporal Trends in Mercury Accumulation in Lake Sediments in Sweden

Lake sediment cores were analyzedto study the history of mercury (Hg) pollution andparticularly to determine whether recent sedimentconcentrations have declined in response todeclining atmospheric deposition of Hg. Sedimentcores from 6 forest lakes distributed fromsouthern to northern Sweden and 3 northernmountain lakes were analyzed for Hg using CVAAS. A400 cm sediment profile from Måkevatten insouthwest Sweden indicates that the onset of Hgpollution occurred in the 18th century. Anindisputable increase in Hg concentrationsoccurred concurrent with the appearance ofspheroidal carbonaceous flyash particles (SCP)derived from fossil-fuel combustion, in themid-19th century. There is a strong correlationbetween Hg and SCP concentrations in the sedimentcores (r=0.67 to 0.91), which suggests a strongrelationship between historical Hg pollution andfossil fuel burning. In contrast to sediment corestaken in 1979, maximum Hg concentrations are nowobserved below the sediment surface and declinetowards the sediment surface. This study confirmsthat reductions in atmospheric deposition of Hgover Sweden have resulted in a decreased transferof total Hg to aquatic environments as reflectedby lake sediments, and that lake sediment profilesof Hg concentrations reflect relative trends inthe atmospheric deposition of Hg rather thanpost-depositional diagenetic processes.     

Characterization and classification of complex PAH samples using GC-qMS and GC-TOFMS

The aim of this study was to compare the polycyclic aromatic hydrocarbon (PAH) contents in a number of complex samples, including soil samples from industrial sites, anti-skid sand, urban dust and ash samples from municipal solid waste incinerators. The samples were characterized by routine analysis of PAHs (gas chromatography–quadrupole mass spectrometry) and gas chromatography–time of flight mass spectrometry (GC–TOFMS). Classification of the samples by principal component analysis (PCA) according to their composition of PAHs revealed that samples associated with traffic and the municipal incinerator formed homogeneous clusters, while the PAH-contaminated soils clustered in separate groups. Using spectral data to resolve co-eluting chromatographic peaks, 962 peaks could be identified in the GC–TOFMS analysis of a pooled sample and 123–527 peaks in the individual samples. Many of the studied extracts included a unique set of chemicals, indicating that they had a much more diverse contamination profile than their PAH contents suggested. Compared to routine analysis, GC–TOFMS provided more detailed information about each sample and in this study a large number of alkylated PAHs were found to be associated with the corresponding unsubstituted PAHs. The possibility to filter peaks according to different criteria (e.g. to include only peaks that were detected in the analysis of another sample) was explored and used to identify unique as well as common compounds within samples. This procedure could prove to be valuable for obtaining relevant chemical data for use in conjunction with results from various biological test systems.