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A new method for the detection of trace levels of organomercury species has been developed by combining the high enrichment capacity of purge and trap with aqueous phenytation derivatization. Phenylation products of monomethylmercury (MeHg) and monoethylmercury (EtHg) were first separated by capillary gas chromatography and then detected by atomic fluorescence spectrometry (AFS) or inductively coupled plasma mass spectrometry (ICPMS). This combination made it possible to simultaneously quantify trace or ultratrace level of MeHg and EtHg in environmental samples. Method detection limits were 0.03 ng/L for both MeHg and EtHg when AFS was used as the detector and 0.02 and 0.01 ng/L for MeHg and EtHg with ICPMS, respectively. Certified reference materials, IAEA-405 and DORM-2, were analyzed and the results were in accordance with certified values. Both MeHg and EtHg were detected in sediment samples collected from the Florida Everglades and a Canadian wetland. This new method has been validated for the direct detection of trace organomercury species in freshwater samples and has the additional benefits of being free from interference by [Cl.sup.-] and dissolved organic matter.

The role of macrophytes in mercury (Hg) cycling in the Florida Everglades ecosystem has not been fully understood. In this study, a stable isotope ((199)Hg(2+)) addition technique was used to trace the methylation, uptake, and translocation of Hg by sawgrass ( Cladium jamaicense ) and quantitatively evaluate the contribution of atmospheric and soil Hg to Hg in sawgrass leaves and below-ground biomass. The results showed that spiked (199)Hg(2+) could be rapidly methylated to monomethylmercury (Me(199)Hg) in the soil of the sawgrass pots. Only small portions of total Hg (THg) and monomethylmercury (MeHg) in the soil could be taken up by sawgrass, indicated by the ratios of T(199)Hg and Me(199)Hg (tracer) concentrations in the sawgrass below-ground biomass (BGBM) over that in the soil (6.50 ± 1.9% and 12.8 ± 3.6% for THg and MeHg, respectively). Concentrations of T(199)Hg (tracer) and Me(199)Hg (tracer) in sawgrass leaves only accounted for 5.50 ± 2.8% and 15.6 ± 4.0%, respectively, of that in the BGBM, implying that the fractions of mercury species transported upward by sawgrass were also small. Statistical analysis (t test) showed that sawgrass preferred MeHg over THg in both uptake and upward translocation. The majority (>90%) of THg in sawgrass leaves were estimated to be obtained from atmospheric Hg, rather than from soil, suggesting that assimilation of atmospheric Hg could increase the overall Hg stock in the Florida Everglades ecosystem. The finding about foliar uptake of Hg is especially important for a better understanding of mercury cycling in the Everglades, given the large amount of sawgrass biomass in this ecosystem.

Methylmercury (MeHg) is recognized as one of the major water quality concerns in the Florida Everglades. Degradation of MeHg in the water is thought to be one of the most important processes to the cycling of MeHg, but there is a lack of quantitative estimations of its effect on the distribution and cycling of MeHg in this ecosystem. Stable isotope (Me201Hg) addition method was implemented to investigate the degradation of MeHg in the Everglades. By combining these results with the field monitoring data, effects of photodegradation on MeHg distribution and its contribution to MeHg cycling were estimated. The results indicate that degradation of MeHg in Everglades water is mediated by sunlight and that UV-A and UV-B radiations are the principal driver. The spatial pattern of MeHg photodegradation potential (PPD) generally illustrated an increasing trend from north to south in the Everglades, which was opposite to the distribution of MeHg in water column. Correlation analysis shows that MeHg concentration in the water had a significant negative relation to PPD, suggesting that photodegradation could play an important role in controlling the distribution of MeHg in Everglades water. Furthermore, about 31.4% of MeHg input into the water body was removed by photodegradation, indicating its importance in the biogeochemical cycling of MeHg in the Everglades. This percent reduction is much lower than that reported for other ecosystems, which could be caused by the higher concentration of DOC in the Everglades. The relatively slower degradation of MeHg could be one of the main reasons for the high ratio of MeHg to total mercury (THg) in this ecosystem.

Spatial patterns in mercury cycling and bioaccumulation at the landscape level in the Everglades were investigated by collecting and analyzing multimedia samples for mercury species and biogeochemical characteristics from 228 randomly located stations. Higher total mercury (THg) in environmental compartments (surface water, soil, flocculent detrital material (floc), and periphyton) generally occurred in the northern and central Everglades, but higher THg in water and periphyton in the Everglades National Park was an exception. Multiple biogeochemical characteristics, such as surface water dissolved organic matter (DOC(sw)), pH, chloride, and compositional properties of solid compartments (soil and floc), were identified to be important factors controlling THg distribution. Methylmercury (MeHg) was also higher in the northern Everglades for water, soil, and floc, but not for periphyton. Higher mosquitofish THg and bioaccumulation factor were observed in the central and southern Everglades, partially in accordance with periphyton MeHg distribution, but not in the "hot spot" areas of water, soil, or floc MeHg. The discrepancy in mercury bioaccumulation and mercury distribution in environmental compartments suggests that in addition to MeHg production, biogeochemical controls that make MeHg available to aquatic organisms, such as DOC(sw) and compositional properties of soil and floc, are important in mercury bioaccumulation.