Atomic Fluorescence Spectrometry (AFS) is an ideal detection technique for speciation studies concerning hydride forming elements (mainly As, Se and Sb) and Hg. The analytical features of AFS, such as detection limits below the µg L⁻¹ and the wide linear calibration range, up to the mg L⁻¹, allow its application to a great variety of environmental, biological and food samples. AFS represents a suitable alternative to other atomic spectrometers commonly employed in speciation studies such as Atomic Absorption Spectrometry (AAS) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The instrumentation used for AFS and the design of the vapour generation and optical layouts required to sustain the full benefits of the AFS approach are also described. The present review explains and comments on the instrumental couplings of chromatographic (HPLC and GC) and non-chromatographic separations (CE) with AFS detection, with online hydride generation for the speciation of inorganic and organic compounds of As, Se and Sb, and cold vapour for Hg. Other optional intermediate steps are online photo-oxidation (UV), pyrolysis or Microwave Assisted Digestion (MAD) for non-directly reducible compounds. Many different sample types (e.g. water, soils, air, biota, food) have been analysed using these instrumental couplings with AFS detection. These are summarised and discussed.

Arsenic is one of the regulated hazard materials in the environment and a persistent pollutant creating environmental, agricultural and health issues and posing a serious risk to humans. In the present review, sources and mobility of As in various compartments of the environment (air, water, soil and sediment) around the World are comprehensively investigated, along with measures of health hazards. Multiple atomic spectrometric approaches have been applied for total and speciation analysis of As chemical species. The LoD values are basically under 1 μg L⁻¹, which is sufficient for the analysis of As or its chemical species in environmental samples. Both natural and anthropogenic sources contributed to As in air, while fine particulate matter tends to have higher concentrations of arsenic and results in high concentrations of As up to a maximum of 1660 ng m⁻³ in urban areas. Sources for As in natural waters (as dissolved or in particulate form) can be attributed to natural deposits, agricultural and industrial effluents, for which the maximum concentration of 2000 μg L⁻¹ was found in groundwater. Sources for As in soil can be the initial contents, fossil fuel burning products, industrial effluents, pesticides, and so on, with a maximum reported concentration up to 4600 mg kg⁻¹. Sources for As in sediments can be attributed to their reservoirs, with a maximum reported concentration up to 2500 mg kg⁻¹. It is notable that some reported concentrations of As in the environment are several times higher than permissible limits. However, many aspects of arsenic environmental chemistry including contamination of the environment, quantification, mobility, removal and health hazards are still unclear.

A new and simple technique for the determination of total mercury in gas condensate was developed which eliminates the use of chemicals/additives and complicated digestion procedures. The determinations are carried out by vaporisation of the samples at 400 °C with adsorption of mercury species on a gold trap (Amasil) maintained at 200 °C. The trap is then heated at 900 °C to release metallic mercury, which is determined by atomic fluorescence spectrometry. The mercury recoveries from seven species, dimethylmercury (DMM), diethylmercury (DEM), diphenylmercury (DPM), methylmercury chloride (MMC), ethylmercury chloride (EMC), phenylmercury chloride (PMC) and mercury(II) chloride (MC) spiked individually into gas condensate were found to be in the range 80–100%. The mercury recoveries for mixtures of the seven species added in equal amounts to gas condensate were in the range 88–97%. For Conostan mercury standard added to the condensate, the recovery was 88%. The instrumental precision from 10 measurements of a toluene control was 4% RSD. For three mercury species. DEM, MC and EMC, added to condensate, the precision was between 2 and 5% RSD (n = 10). The limit of detection (3ς_n–1 criterion) for the procedure was calculated to be 180 pg Hg in toluene and 270 pg in condensate. For three mercury species added to a condensate sample, the absolute detection limits were 270 pg Hg for DEM, 450 pg Hg for MC and 630 pg Hg for EMC. Total mercury measurements in five real condensate samples from two sites at different stages of production covered the range 7–50 ng ml^–1 with uncertainties in the range 4–7% RSD. The total mercury concentration of two commercial heavy gas oil samples were found to be 22.2 ± 0.6 µg ml^–1 with RSD 3% (n = 4) and 2.3 ± 0.1 µg ml^–1 of mercury with RSD 3% (n = 7).