Patrick R. Gorski

Factors affecting enhanced mercury bioaccumulation in inland lakes of Isle Royale National Park, USA

We investigated factors causing mercury (Hg) concentrations in northern pike to exceed the consumption advisory level (>500 ng/g) in some inland lakes of Isle Royale National Park. Using Hg-clean techniques, we collected water, zooplankton, macro invertebrates, and fishes in 1998 and 1999 from one advisory lake, Sargent Lake, for analysis of total mercury (Hg(T)) and methylmercury (MeHg). For comparison, samples were also collected from a non-advisory lake, Lake Richie. Concentrations of Hg(T) in northern pike were significantly higher in Sargent Lake (P<0.01). Counter to expectations, mean concentrations of both Hg(T) and MeHg in open water samples were slightly higher in Lake Richie. However, zooplankton in Sargent Lake contained higher average concentrations of Hg(T) and MeHg than in Lake Richie. Mercury concentrations in macro invertebrates were similar between lakes, but different between taxa. The two lakes exhibited similar Hg(T) concentrations in age-1 yellow perch and adult perch but concentrations in large adult perch (>160 mm) in Sargent Lake were twice the concentrations in Lake Richie. Analysis of stable isotopes (delta(13)C and delta(15)N) in biota showed that pike from the two lakes are positioned at the same trophic level (4.2 and 4.3), but that the food web is more pelagic-based in Sargent and benthic-based in Richie. Factors causing concentrations in large pike to be higher in Sargent Lake may include higher bioavailability of methylmercury and a food web that enhances bioaccumulation.

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga.

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5mg L(-1). These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.

Speciation of aqueous methylmercury influences uptake by a freshwater alga (Selenastrum capricornutum)

Uptake of methylmercury (MeHg) by the alga Selenastrum capricornutum was measured in freshwater batch culture bioassays. The concentration of MeHg in the alga increased rapidly (within 15 min), reached a maximum by 6 h, and then declined because of growth dilution. The algas rapid growth rate (doubling time, approximately 10 h) contributed to the importance of growth dilution. Conditional first-order rate constants were calculated for uptake (k1 = 6.95 x 10(-9) L/cell/h) and growth (kG = 0.07/h). A competitive synthetic ligand, disodium ethylenediaminetetra-acetate, formed strong complexes with MeHg and reduced MeHg uptake, consistent with the biotic ligand model. A conditional equilibrium formation constant (K) for the MeHg-algae complex was estimated to be approximately 10(16) and was used to model the influence of natural ligands on MeHg bioavailability. Model results suggested MeHg would be most bioavailable at concentrations of dissolved organic matter (DOM) less than 10 mg/L and increasingly unavailable at higher DOM concentrations for the specific humic acid modeled. Similarly, at molar concentrations of sulfide (and, possibly, metal-sulfide clusters) equal to approximately half the MeHg concentration, MeHg was predicted to be unavailable to algae because of the formation of strong 2:1 MeHg-sulfide complexes.

Mercury content and speciation in the plankton and benthos of Lake Superior.

As part of a study is to assess the importance of watersheds in controlling sources, transport, fate, and bioavailability of monomethyl mercury (MeHg) in Lake Superior, biotic samples were collected and analyzed to determine total mercury (HgT) and MeHg content, and to examine size, species, trophic and geographic trends. Plankton was collected in two ways: vertical tows of non-metallic, 153 microm mesh net (bulk zooplankton), and by passively filtering near-surface water through stacked Nitex sieves, generating size-fractionated seston (<35, 35-63, 63-112, and >112 microm). Benthos was sampled using a Ponar grab to collect sediment, and a non-metallic sieve to separate biota from substrate. Samples were processed to quantify dry weights, HgT and MeHg. Results for bulk zooplankton sampled offshore showed a range of approximately from 35 to 50 ng MeHg/gram dry weight (gdw) and from 80 to 130 ng HgT/gdw during April, and from 15 to 25 ng MeHg/gdw and from 20 to 70 ng HgT/gdw during August. Results from sieved, near-surface water from offshore sites in April showed a dominance by the <35 microm size fraction both in total mass and mass of MeHg compared to other size fractions. On a dry weight basis, however, we found little difference between the size fractions in April (MeHg ranges from 2 to 10 ng/gdw). During the summer cruise, we found similar concentrations in the <35 microm fraction, but higher in the 112-243 microm size fraction (MeHg 14-16 ng/gdw). The MeHg concentration in Mysis relicta ranged from 33 to 54 ng/gdw throughout the lake. Chironomid larvae were 8 ng MeHg/gdw and amphipods were 32 ng MeHg/gdw.

Characterization of the elemental composition of newborn blood spots using sector-field inductively coupled plasma-mass spectrometry

We developed extraction and analysis protocols for element detection in neonatal blood spots (NBSs) using sector-field inductively coupled plasma-mass spectrometry (SF-ICP-MS). A 5% (v/v) nitric acid element extraction protocol was optimized and used to simultaneously measure 28 elements in NBS card filter paper and 150 NBSs. NBS element concentrations were corrected for filter paper background contributions estimated from measurements in samples obtained from either unspotted or spotted NBS cards. A lower 95% uncertainty limit (UL) that accounted for ICP-MS method, filter paper element concentration, and element recovery uncertainties was calculated by standard methods for each individuals NBS element concentration. Filter paper median element levels were highly variable within and between lots for most elements. After accounting for measurement uncertainties, 11 elements (Ca, Cs, Cu, Fe, K, Mg, Na, P, Rb, S, and Zn) had lower 95% ULs>0 ng/spot with estimated concentrations ranging from 0.05 to >50,000 ng/spot in ≥50% of NBS samples in both correction methods. In a NBS sample minority, Li, Cd, Cs, Cr, Ni, Mo, and Pb had estimated concentrations ≥20-fold higher than the respective median level. Taking measurement uncertainties into account, this assay could be used for semiquantitative newborn blood element measurement and for the detection of individuals exposed to supraphysiologic levels of some trace elements. Adequate control of filter paper element contributions remains the primary obstacle to fully quantitative element measurement in newborn blood using NBSs.

Seasonal and Size-specific Distribution of Methylmercury in Seston and Zooplankton of Two Contrasting Great Lakes Embayments

Abstract The use of a large volume sieve system is described which allows quantification of mass, pigments, and methylmercury (MeHg) in five distinct size classes of suspended material: > 243 μm, 112–243 μm, 63–112 μm, 35–63 μm, and