Simultaneous separation of arsenic and cadmium from interfering salt matrix of multivitamin/mineral supplements by sequential coprecipitation and determination by inductively coupled plasma mass spectrometry.

Multivitamin/mineral (MVM) supplements possess highly saline matrix which, unless eliminated, precludes accurate determination of trace amounts of toxic metal impurities by inductively coupled plasma mass spectrometry (ICP-MS). Multi-step separations (up to four-steps) are described in literature; often for single element determinations due to difficulties in removing the matrix components. In this study, we developed a three-step sequential coprecipitation procedure for simultaneous separation of As and Cd impurities from MVM supplements for determination by ICP-MS. The procedure provided effective elimination of salt matrix, including Ca, Mg and KCl along with the interfering molybdenum (Mo) and tin (Sn) from MVM solutions. KCl, Mo and Sn were removed by two-step Mg(OH)2 coprecipitation to about 34 µg mL-1 K (ca. 31 µg mL-1 Cl) and 0.4 µg mL-1 Mo. Levels of Sn and Na were not significant. A third coprecipitation of the resulting MVM solution with HF + NH4OH mixture precipitated virtually all Ca and Mg to as low as 1 and 10 µg mL-1, respectively. The recoveries for As and Cd in the spiked MVM solutions were about 96% and 95%, respectively. The accuracy of the method was validated with analysis of multivitamin/multielement tablets certified reference material (SRM 3280). Experimental values were 112 ± 37 ng g-1 for 75As, and 76 ± 5, 79 ± 5, and 78 ± 7 ng g-1 for 110Cd, 111Cd and 114Cd isotopes, respectively, that were not significantly different from the certified values of As (132 ± 44 ng g-1) and Cd (80.2 ± 0.9 ng g-1) at 95% confidence level. Several commercially available MVM supplements were analyzed with the procedure. Mean As levels measured in the tablets varied between 24 and 128 ng g-1 and that for Cd were between 28 and 125 ng g-1 indicating total amount of As or Cd ingested per serving size were below the safe daily exposure limits. In addition, the results obtained for As and Cd with the procedure were lower in comparison to the values reported in literature indicating that ICP-MS analysis of complex MVM supplements could be prone to higher risks of inaccuracy without removal of interfering matrix.

Relations between mercury fractions and microbial community components in seawater under the presence and absence of probable phosphorus limitation conditions.

Microbial transformations of toxic monomethylmercury (MMHg) and dissolved gaseous mercury (DGM) at the lower levels of the marine food web are not well understood, especially in oligotrophic and phosphorus-limited seas. To examine the effects of probable phosphorus limitation (PP-limitation) on relations between mercury (Hg) fractions and microorganisms, we determined the total mercury (THg), total methylated mercury (MeHg), DGM, and microbiological and chemical parameters in the Central Adriatic Sea. Using statistical analysis, we assessed the potential microbial effects on Hg transformations and bioaccumulation. Only in the absence of PP-limitation conditions (NO-PP-limitation) is MeHg significantly related to most chemical and microbial parameters, indicating metabolism-dependent Hg transformations. The heterotrophic activity of low nucleic acid bacteria (abundant in oligotrophic regions) seems responsible for most of Hg methylation under NO-PP-limitation. Under these conditions, DGM is strongly related to microbial fractions and chlorophyll a, indicating biological DGM production, which is probably not metabolically induced, as most of these relations are also observed under PP-limitation. MMHg biomagnification was observed through an increased bioaccumulation factor from microseston to mesozooplankton. Our results indicate that Hg transformations and uptake might be enhanced under NO-PP-limitation conditions, emphasizing their impact on the transfer of Hg to higher trophic levels.