In order to characterize the mercury hazard in soil, a sequential extraction scheme has been developed to classify mercury species based on their environmental mobility and/or toxicity for either routine lab analysis or on-site screening purposes. The alkyl mercury species and soluble inorganic species that contribute to the major portion of potential mercury toxicity in the soil are extracted by an acidic ethanol solution (2% HCl+10% ethanol solution) from soil matrices as "mobile and toxic" species. A High-Performance Liquid Chromatography (HPLC) system coupled with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) detection has been developed to further resolve the species information into soluble inorganic species (Hg(2+)), methylmercury(II) (MeHg(+)) and ethylmercury(II) (EtHg(+)) species. Alternatively, these species can be separated into "soluble inorganic mercury" and "alkyl mercury" sub-categories by Solid-Phase Extraction (SPE). A custom Sulfydryl Cotton Fiber (SCF) material is used as the solid phase medium. Optimization of the SCF SPE technique is discussed. Combined with a direct mercury analyzer (DMA-80), the SCF SPE technique is a promising candidate for on-site screening purposes. Following the ethanol extraction, the inorganic mercury species remaining in soil are further divided into "semi-mobile" and "non-mobile" sub-categories by sequential acid extractions. The "semi-mobile" mercury species include mainly elemental mercury (Hg) and mercury-metal amalgams. The non-mobile mercury species mainly include mercuric sulfide (HgS) and mercurous chloride (Hg(2)Cl(2)).

Eight different analytical extraction procedures commonly used to extract mercury species from biological samples were evaluated by analyzing Tuna Fish Tissue Certified Reference Material (ERM-CE464) certified for the content of total mercury and methylmercury. Speciated isotope dilution mass spectrometry (SIDMS; US Environmental Protection Agency's method 6800) was utilized to evaluate and effectively compensate for potential errors during measurement and accurately quantify mercury species using all the extraction methods. SIDMS was used to accurately evaluate species transformations during sample pretreatment, preparation and analysis protocols. The extraction methods tested in this paper were based on alkaline extraction with KOH or tetramethylammonium hydroxide; acid leaching with HCl, HNO(3) or CH(3)COOH; extraction with L: -cysteine hydrochloride; and enzymatic digestion with protease XIV. Detection of total mercury and mercury species from all extraction methods was carried out by inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography-ICP-MS, respectively. Microwave-assisted extraction and ultrasound-assisted extraction were found to be the most efficient alkaline digestion protocols that caused the lowest levels of transformation of mercury species (6% or less). Extraction with 5 M HCl or enzymatic digestion with protease resulted in the second-highest extraction efficiency, with relatively lower transformation of methylmercury to inorganic mercury (3 and 1.4%, respectively). Despite frequent use of acid leaching for the extraction of mercury species from tuna fish samples, the lowest extraction efficiencies and the highest mercury species transformation were obtained when microwave-assisted extraction with 4 M HNO(3) or CH(3)COOH was used. Transformations as high as 30% were found using some literature protocols; however, all the extractions tested produced accurate quantitation when corrected in accordance with the SIDMS method standardized in the US Environmental Protection Agency's method 6800. [figure: see text]

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Extraction techniques commonly used to extract methylmercury or mercury species from various matrixes have been evaluated regarding their potential to transform inorganic mercury to methylmercury, or vice versa, during sample preparation steps by applying speciated isotope dilution mass spectrometry. Two of the five tested methods were highly prone to form inorganic mercury from methylmercury. Some published methods converted methylmercury to inorganic mercury approximately 100% (including the spiked CH(3)(201)Hg(+)). In other methods, as much as 45% of methylmercury was converted to inorganic mercury during extraction. The methods evaluated included cold acid extraction and sonication. Other methods, such as the proposed EPA RCRA Draft Method 3200, microwave-assisted extraction, and another sonication-based methods induced very little or no methylmercury transformation to inorganic mercury. Among these three methods, the proposed Draft EPA Method 3200 was found to be the most efficient.

In order to determine the health impact of chromium in dietary supplements, the Cr(III) and Cr(VI) must be independently measured and verified with mass balance (sum of both species equaling independent measurements of total chromium), as both may be present in finished products. Because Cr(III) is stable in acidic conditions and Cr(VI) in alkaline conditions, interconversions between species may occur in complex matrices and during analytical extraction, increasing the difficulty of quantification. A study was conducted to determine Cr(VI) and Cr(III) in dietary supplements. EPA Method 3060A extraction protocol was performed to extract Cr(VI), and EPA Method 3052 was performed on the extracted residue to digest the remaining Cr(III). Speciated isotope dilution mass spectrometry (SIDMS), as described in the EPA Method 6800 (update V), was implemented with ion-exchange chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS). Method 6800 uniquely enables tracking and correcting for the bidirectional chromium interspecies conversions that occur during extraction and sample handling prior to instrumental analysis. Mass balance results indicated that the off-the-shelf dietary supplements analyzed during this study contained hexavalent chromium ranging from