Modeling contaminant behavior in Lake Superior : a comparison of PCBs, PBDEs, and mercury

A mass‐balance model for Lake Superior was applied to polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and mercury to determine the major routes of entry and the major mechanisms of loss from this ecosystem as well as the time required for each contaminant class to approach steady state. A two‐box model (water column, surface sediments) incorporating seasonally adjusted environmental parameters was used. Both numerical (forward Euler) and analytical solutions were employed and compared. For validation, the model was compared with current and historical concentrations and fluxes in the lake and sediments. Results for PCBs were similar to prior work showing that air‐water exchange is the most rapid input and loss process. The model indicates that mercury behaves similarly to a moderately‐chlorinated PCB, with air‐water exchange being a relatively rapid input and loss process. Modeled accumulation fluxes of PBDEs in sediments agreed with measured values reported in the literature. Wet deposition rates were about three times greater than dry particulate deposition rates for PBDEs. Gas deposition was an important process for tri‐ and tetra‐BDEs (BDEs 28 and 47), but not for higher‐brominated BDEs. Sediment burial was the dominant loss mechanism for most of the PBDE congeners while volatilization was still significant for tri‐ and tetra‐BDEs. Because volatilization is a relatively rapid loss process for both mercury and the most abundant PCBs (tri‐ through penta‐), the model predicts that similar times (from 2 ‐ 10 yr) are required for the compounds to approach steady state in the lake. The model predicts that if inputs of Hg(II) to the lake decrease in the future then concentrations of mercury in the lake will decrease at a rate similar to the historical decline in PCB concentrations following the ban on production and most uses in the U.S. In contrast, PBDEs are likely to respond more slowly if atmospheric concentrations are reduced in the future because loss by volatilization is a much slower process for PBDEs, leading to lesser overall loss rates for PBDEs in comparison to PCBs and mercury. Uncertainties in the chemical degradation rates and partitioning constants of PBDEs are the largest source of uncertainty in the modeled times to steady‐state for this class of chemicals. The modeled organic PBT loading rates are sensitive to uncertainties in scavenging efficiencies by rain and snow, dry deposition velocity, watershed runoff concentrations, and uncertainties in air‐water exchange such as the effect of atmospheric stability.

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

Effects of elevated atmospheric CO2 and O3 on wood density, antomical proerties and decomposition of Northern Hardwoods

Anthropogenic activities continue to drive atmospheric CO2 and O3 concentrations to levels higher than during the pre-industrial era. Accumulating evidence indicates that both elevated CO2 and elevated O3 could modify the quantity and biochemistry of woody plant biomass. Anatomical properties of woody plants are largely influenced by the activity of the cambium and the growth characteristics of wood cells, which are in turn influenced by a range of environmental factors. Hence, alterations in the concentrations of atmospheric CO2 and / or O3 could also impact wood anatomical properties. Many fungi derive their metabolic resources for growth from plant litter, including woody tissue, and therefore modifications in the quantity, biochemistry and anatomical properties of woody plants in response to elevated CO2 and / or O3 could impact the community of wood-decaying fungi and rates of wood decomposition. Consequently carbon and nutrient cycling and productivity of terrestrial ecosystem could also be impacted. Alterations in wood structure and biochemistry of woody plants could also impact wood density and subsequently impact wood quality. This dissertation examined the long term effects of elevated CO2 and / or O3 on wood anatomical properties, wood density, wood-decaying fungi and wood decomposition of northern hardwood tree species at the Aspen Free-Air CO2 and O3 Enrichment (Aspen FACE) project, near Rhinelander, WI, USA. Anatomical properties of wood varied significantly with species and aspen genotypes and radial position within the stem. Elevated CO2 did not have significant effects on wood anatomical properties in trembling aspen, paper birch or sugar maple, except for marginally increasing (P < 0.1) the number of vessels per square millimeter. Elevated O3 marginally or significantly altered vessel lumen diameter, cell wall area and vessel lumen area proportions depending on species and radial position. In line with the modifications in the anatomical properties, elevated CO2 and O3, alone, significantly modified wood density but effects were species and / or genotype specific. However, the effects of elevated CO2 and O3, alone, on wood anatomical properties and density were ameliorated when in combination. Wood species had a much greater impact on the wood-decaying fungal community and initial wood decomposition rate than did growth or decomposition of wood in elevated CO2 and / or O3. Polyporales, Agaricales, and Russulales were the dominant orders of fungi isolated. Based on the current results, future higher levels of CO2 and O3 may have moderate effects on wood quality of northern hardwoods, but for utilization purposes these may not be considered significant. However, wood-decaying fungal community composition and decomposition of northern hardwoods may be altered via shifts in species and / or genotype composition under future higher levels of CO2 and O3.