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Christopher L. Babiarz

Publications and source records attributed to Christopher L. Babiarz.

11 recordsLinked to original sources
USGS2021

The influence of legacy contamination on the transport and bioaccumulation of mercury within the Mobile River Basin

Past industrial use and subsequent release of mercury (Hg) into the environment have resulted in severe cases of legacy contamination that still influence contemporary Hg levels in biota. While the bioaccumulation of legacy Hg is commonly assessed via concentration measurements within fish tissue, this practice becomes difficult in regions of high productivity and methylmercury (MeHg) production, like the Mobile River Basin, Alabama in the southeastern United States. This study applied Hg stable isotope tracers to distinguish legacy Hg from regional deposition sources in sediments, waters, and fish within the Mobile River. Sediments and waters displayed differences in δ 202 Hg between industrial and background sites, which corresponded to drastic differences in Hg concentration. Sites that were affected by legacy Hg, as defined by δ 202 Hg, produced largemouth bass with lower MeHg content (59–70%) than those captured in the main rivers (>85%). Direct measurements of Hg isotopes and mathematical estimates of MeHg isotope pools in fish displayed similar distinctions between legacy and watershed sources as observed in other matrices. These results indicate that legacy Hg can accumulate directly into fish tissue as the inorganic species and may also be available for methylation within contaminated zones decades after the initial release.

Alabama↗
USGS2019

Isolation of methylmercury using distillation and anion-exchange chromatography for isotopic analyses in natural matrices

The development of mercury (Hg) stable isotope measurements has enhanced the study of Hg sources and transformations in the environment. As a result of the mixing of inorganic Hg (iHg) and methylmercury (MeHg) species within organisms of the aquatic food web, understanding species-specific Hg stable isotopic compositions is of significant importance. The lack of MeHg isotope measurements is due to the analytical difficulty in the separation of the MeHg from the total Hg pool, with only a few methods having been tested over the past decade with varying degrees of success, and only a handful of environmentally relevant measurements. Here, we present a novel anion-exchange resin separation method using AG 1-X4 that further isolates MeHg from the sample matrix, following a distillation pretreatment, in order to obtain ambient MeHg stable isotopic compositions. This method avoids the use of organic reagents, does not require complex instrumentation, and is applicable across matrices. Separation tests across sediment, water, and biotic matrices showed acceptable recoveries (98 ± 5%, n = 54) and reproducible δ 202 Hg isotope results (2 SDs ≤ 0.15‰) down to 5 ng of MeHg. The measured MeHg pools in natural matrices, such as plankton and sediments, showed large deviations from the non-speciated total Hg measurement, indicating that there is an important isotopic shift during methylation that is not recorded by typical measurements, but is vital in order to assess sources of Hg during bioaccumulation.

Analytical and Bioanalytical Chemistry↗
USGS2019

Mercury source changes and food web shifts alter contamination signatures of predatory fish from Lake Michigan

To understand the impact reduced mercury (Hg) loading and invasive species have had on methylmercury bioaccumulation in predator fish of Lake Michigan, we reconstructed bioaccumulation trends from a fish archive (1978 to 2012). By measuring fish Hg stable isotope ratios, we related temporal changes in Hg concentrations to varying Hg sources. Additionally, dietary tracers were necessary to identify food web influences. Through combined Hg, C, and N stable isotopic analyses, we were able to differentiate between a shift in Hg sources to fish and periods when energetic transitions (from dreissenid mussels) led to the assimilation of contrasting Hg pools (2000 to present). In the late 1980s, lake trout δ 202 Hg increased (0.4‰) from regulatory reductions in regional Hg emissions. After 2000, C and N isotopes ratios revealed altered food web pathways, resulting in a benthic energetic shift and changes to Hg bioaccumulation. Continued increases in δ 202 Hg indicate fish are responding to several United States mercury emission mitigation strategies that were initiated circa 1990 and continued through the 2011 promulgation of the Mercury and Air Toxics Standards rule. Unlike archives of sediments, this fish archive tracks Hg sources susceptible to bioaccumulation in Great Lakes fisheries. Analysis reveals that trends in fish Hg concentrations can be substantially affected by shifts in trophic structure and dietary preferences initiated by invasive species in the Great Lakes. This does not diminish the benefits of declining emissions over this period, as fish Hg concentrations would have been higher without these actions.

Lake Michigan↗
USGS2019

Rapid pre-concentration of mercury in solids and water for isotopic analysis

The precise quantification of mercury (Hg) stable isotope compositions in low concentration or dilute samples poses analytical challenges due to Hg mass limitations. Common Hg pre-concentration procedures require extended processing times, making rapid Hg stable isotope measurements challenging. Here we present a modified pre-concentration method that combines commonly used Hg reduction and gold trap amalgamation followed by semi-rapid thermal desorption (less than 1 h) and chemical trapping. This custom designed system was demonstrated to perform adequately on multiple trapping matrices including a new bromine monochloride (BrCl) wet oxidant trap (40% 3HNO 3 :BrCl), capable of trapping consistently in 2 mL volume over a wide range of Hg masses (5–200 ng). The procedure was also shown to work effectively on natural matrices, waters and sediments, producing comparable isotope results to the direct digestion analyses. Here, we present a method that can effectively triple sample throughput in comparison to traditional procedures, and also access lower concentration matrices without compromising the accuracy or precision of Hg isotope measurements.

Analytica Chimica Acta↗
USGS2010

The role of groundwater transport in aquatic mercury cycling

Mercury, which is transported globally by atmospheric pathways to remote aquatic environments, is a ubiquitous contaminant at very low (nanograms Hg per liter) aqueous concentrations. Until recently, however, analytical and sampling techniques were not available for freshwater systems to quantify the actual levels of mercury concentrations without introducing significant contamination artifacts. Four different sampling strategies were used to evaluate ground water flow as a mercury source and transport mechanism within aquatic systems. The sampling strategies employ ultraclean techniques to determine mercury concentrations in groundwater and pore water near Pallette Lake, Wisconsin. Ambient groundwater concentrations are about 2–4 ng Hg L −1 , whereas pore waters near the sediment/water interface average about 12 ng Hg L −1 , emphasizing the importance of biogeochemical processes near the interface. Overall, the groundwater system removes about twice as much mercury (1.5 g yr −1 ) as it contributes (0.7 g yr −1 ) to Pallette Lake. About three fourths of the groundwater mercury load is recycled, thought to be derived from the water column.

Wisconsin↗
USGS2009

Cycling of mercury across the sediment-water interface in seepage lakes: Chapter 13, Advances in Chemistry

The magnitude and direction of Hg fluxes across the sediment—water interface were estimated by groundwater, dry bulk sediment, sediment pore water, sediment trap, and water-column analyses in two northern Wisconsin seepage lakes. Little Rock Lake (Treatment Basin) received no groundwater discharge during the study period (1988—1990), and Follette Lake received continuous groundwater discharge. In Little Rock Lake, settling of particulate matter accounted for the major Hg delivery mechanism to the sediment—water interface. Upward diffusion of Hg from sediment pore waters below 2—4-cm sediment depth was apparently a minor source during summer stratification. Time-series comparisons suggested that the observed buildup of Hg in the hypolimnion of Little Rock Lake was attributable to dissolution and diffusion of Hg from recently fallen particulate matter close to the sediment—water interface. Groundwater inflow represented an important source of new Hg, and groundwater outflow accounted for significant removal of Hg from Pallette Lake. Equilibrium speciation calculations revealed that association of Hg with organic matter may control solubility in well-oxygenated waters, whereas in anoxic environments sulfur (polysulfide and bisulfide) complexation governs dissolved total Hg levels.

Wisconsin↗
USGS2007

Whole-ecosystem study shows rapid fish-mercury response to changes in mercury deposition

Methylmercury contamination of fisheries from centuries of industrial atmospheric emissions negatively impacts humans and wild-life worldwide. The response of fish methylmercury concentrations to changes in mercury deposition has been difficult to establish because sediments/soils contain large pools of historical contamination, and many factors in addition to deposition affect fish mercury. To test directly the response of fish contamination to changing mercury deposition, we conducted a whole-ecosystem experiment, increasing the mercury load to a lake and its watershed by the addition of enriched stable mercury isotopes. The isotopes allowed us to distinguish between experimentally applied mercury and mercury already present in the ecosystem and to examine bioaccumulation of mercury deposited to different parts of the watershed. Fish methylmercury concentrations responded rapidly to changes in mercury deposition over the first 3 years of study. Essentially all of the increase in fish methylmercury concentrations came from mercury deposited directly to the lake surface. In contrast, <1% of the mercury isotope deposited to the watershed was exported to the lake. Steady state was not reached within 3 years. Lake mercury isotope concentrations were still rising in lake biota, and watershed mercury isotope exports to the lake were increasing slowly. Therefore, we predict that mercury emissions reductions will yield rapid (years) reductions in fish methylmercury concentrations and will yield concomitant reductions in risk. However, a full response will be delayed by the gradual export of mercury stored in watersheds. The rate of response will vary among lakes depending on the relative surface areas of water and watershed.

Proceedings of the National Academy of Sciences of↗
USGS2003

Application of ultrafiltration and stable isotopic amendments to field studies of mercury partitioning to filterable carbon in lake water and overland runoff

Results from pilot studies on colloidal phase transport of newly deposited mercury in lake water and overland runoff demonstrate that the combination of ultrafiltration, and stable isotope amendment techniques is a viable tool for the study of mercury partitioning to filterable carbon. Ultrafiltration mass balance calculations were generally excellent, averaging 97.3, 96.1 and 99.8% for dissolved organic carbon (DOC), total mercury (Hg T ), and methylmercury (MeHg), respectively. Sub nanogram per liter quantities of isotope were measurable, and the observed phase distribution from replicate ultrafiltration separations on lake water agreed within 20%. We believe the data presented here are the first published colloidal phase mercury data on lake water and overland runoff from uncontaminated sites. Initial results from pilot-scale lake amendment experiments indicate that the choice of matrix used to dissolve the isotope did not affect the initial phase distribution of the added mercury in the lake. In addition there was anecdotal evidence that native MeHg was either recently produced in the system, or at a minimum, that this ‘old’ MeHg partitions to the same subset of DOC that binds the amended mercury. Initial results from pilot-scale overland runoff experiments indicate that less than 20% of newly deposited mercury was transported in the filterable fraction (<0.7 μm). There is some indication of colloidal phase enrichment of mercury in runoff compared to the phase distribution of organic carbon, but the mechanism of this enrichment is unclear. The phase distribution of newly deposited mercury can differ from that of organic carbon and native mercury, suggesting that the quality of the carbon (available ligands), not the quantity of carbon, regulates partitioning. Further characterization of DOC is needed to clarify the underlying mechanisms.

Science of the Total Environment↗
USGS1998

Methyl mercury dynamics in littoral sediments of a temperate seepage lake

The sites and rates of methyl mercury (MeHg) production and transport in littoral zone sediments were investigated at Pallette Lake in northern Wisconsin. In littoral areas where groundwater inflow occurs, sulfate supply from groundwater creates profiles of electron acceptors (sulfate) and donors (methane, sulfide) that are reversed from those found in sediments whose sulfate supply is delivered from overlying water. The highest MeHg concentrations in porewaters and the maximal advective MeHg flux rates (4.5-61.7 ng ·m -2 ·day -1 ) were observed in the spring, while highest bulk phase concentrations occur later in the summer. These estimated MeHg fluxes are greater than the mean areal production rates estimated previously for the water column and are similar to the atmospheric flux. Gross MeHg production was measured using the addition of 203 Hg as a tracer to sediments. The depth at which maximal 203 Hg methylation occurred coincided with the observed maximums in solid-phase and porewater MeHg concentrations. Because input, advection, and accumulation of MeHg in these sediments were measured directly, an independent estimate of MeHg production could be made and compared with 203 Hg-derived rates. This comparison suggests that that the 203 Hg tracer method provides reasonable estimates of gross methylation rates and that a substantial fraction of solid-phase Hg is available for methylation

Canadian Journal of Fisheries and Aquatic Sciences↗
USGS1995

Mercury cycling in the Allequash Creek watershed, northern Wisconsin

Although there have been recent significant gains in our understanding of mercury (Hg) cycling in aquatic environments, few studies have addressed Hg cycling on a watershed scale in particular, attention to Hg species transfer between watershed components (upland soils, groundwater, wetlands, streams, and lakes) has been lacking. This study describes spatial and temporal distributions of total Hg and MeHg among watershed components of the Allequash Creek watershed (northern Wisconsin, USA). Substantial increases in total Hg and MeHg were observed as groundwater discharged through peat to form springs that flow into the stream, or rivulets that drain across the surface of the wetland. This increase was concomitant with increases in DOC. During fall, when the Allequash Creek wetland released a substantial amount of DOC to the stream, a 23 fold increase in total Hg concentrations was observed along the entire length of the stream. Methylmercury, however, did not show a similar response. Substantial variability was observed in total Hg (0.9 to 6.3) and MeHg (<0.02 to 0.33) concentrations during synoptic surveys of the entire creek. For the Allequash Creek watershed, the contributing groundwater basin is about 50% larger than the topographic drainage basin. Total Hg concentrations in groundwater, the area of the groundwater basin, and annual stream flow data give a watershed-yield rate of 12 mg/km2/d, which equates to a retention rate of 96%. The calculated MeHg yield rate for the wetland area is 0.6 to 1.5 mg/km2/d, a value that is 3-6 fold greater than the atmospheric deposition rate.

Water, Air, & Soil Pollution↗