Mark M. Dornblaser

Mercury export from the Yukon River Basin and potential response to a changing climate

We measured mercury (Hg) concentrations and calculated export and yield from the Yukon River Basin (YRB) to quantify Hg flux from a large, permafrost-dominated, high-latitude watershed. Exports of Hg averaged 4400 kg Hg yr(-1). The average annual yield for the YRB during the study period was 5.17 μg m(-2) yr(-1), which is 3-32 times more than Hg yields reported for 8 other major northern hemisphere river basins. The vast majority (90%) of Hg export is associated with particulates. Half of the annual export of Hg occurred during the spring with about 80% of 34 samples exceeding the U.S. EPA Hg standard for adverse chronic effects to biota. Dissolved and particulate organic carbon exports explained 81% and 50%, respectively, of the variance in Hg exports, and both were significantly (p < 0.001) correlated with water discharge. Recent measurements indicate that permafrost contains a substantial reservoir of Hg. Consequently, climate warming will likely accelerate the mobilization of Hg from thawing permafrost increasing the export of organic carbon associated Hg and thus potentially exacerbating the production of bioavailable methylmercury from permafrost-dominated northern river basins.

Mercury Loading and Methylmercury Production and Cycling in High-Altitude Lakes from the Western United States

Studies worldwide have shown that mercury (Hg) is a ubiquitouscontaminant, reaching even the most remote environments such ashigh-altitude lakes via atmospheric pathways. However, very fewstudies have been conducted to assess Hg contamination levels ofthese systems. We sampled 90 mid-latitude, high-altitude lakes from seven national parks in the western United States during afour-week period in September 1999. In addition to the synoptic survey, routine monitoring and experimental studies were conducted at one of the lakes (Mills Lake) to quantify MeHg fluxrates and important process rates such as photo-demethylation. Results show that overall, high-altitude lakes have low total mercury (HgT) and methylmercury (MeHg) levels (1.07 and 0.05 ng L-1, respectively), but a very good correlation of Hg to MeHg (r2= 0.82) suggests inorganic Hg(II) loading is a primary controlling factor of MeHg levels in dilute mountain lakes. Positive correlations were also observed for dissolved organic carbon (DOC) and both Hg and MeHg, although to a much lesser degree. Levels of MeHg were similar among the seven national parks, with the exception of Glacier National Park where lowerconcentrations were observed (0.02 ng L-1), and appear to berelated to naturally elevated pH values there. Measured rates ofMeHg photo-degradation at Mills Lake were quite fast, and thisprocess was of equal importance to sedimentation and stream flowfor removing MeHg. Enhanced rates of photo-demethylation are likely an important reason why high-altitude lakes, with typically high water clarity and sunlight exposure, are low in MeHg.

Using dissolved organic matter age and composition to detect permafrost thaw in boreal watersheds of interior Alaska

Recent warming at high latitudes has accelerated permafrost thaw, which can modify soil carbon dynamics and watershed hydrology. The flux and composition of dissolved organic matter (DOM) from soils to rivers are sensitive to permafrost configuration and its impact on subsurface hydrology and groundwater discharge. Here, we evaluate the utility of DOM composition and age as a tool for detecting permafrost thaw in three rivers (Beaver, Birch, and Hess Creeks) within the discontinuous permafrost zone of interior Alaska. We observed strong temporal controls on Δ14C content of hydrophobic acid isolates (Δ14C-HPOA) across all rivers, with the most enriched values occurring during spring snowmelt (75 ± 8‰) and most depleted during winter flow (−21 ± 8‰). Radiocarbon ages of winter flow samples ranged from 35 to 445 yr BP, closely tracking estimated median base flow travel times for this region (335 years). During spring snowmelt, young DOM was composed of highly aromatic, high molecular-weight compounds, whereas older DOM of winter flow had lower aromaticity and molecular weight. We observed a significant correlation between Δ14C-HPOA and UV absorbance coefficient at 254 nm (α254) across all study rivers. Using α254 as an optical indicator for Δ14C-HPOA, we also observed a long-term decline in α254 during maximum annual thaw depth over the last decade at the Hess Creek study site. These findings suggest a shift in watershed hydrology associated with increasing active layer thickness. Further development of DOM optical indicators may serve as a novel and inexpensive tool for detecting permafrost degradation in northern watersheds.

Basin scale controls on CO2 and CH4 emissions from the Upper Mississippi River

The Upper Mississippi River, engineered for river navigation in the 1930s, includes a series of low-head dams and navigation pools receiving elevated sediment and nutrient loads from the mostly agricultural basin. Using high-resolution, spatially resolved water quality sensor measurements along 1385 river kilometers, we show that primary productivity and organic matter accumulation affect river carbon dioxide and methane emissions to the atmosphere. Phytoplankton drive CO2 to near or below atmospheric equilibrium during the growing season, while anaerobic carbon oxidation supports a large proportion of the CO2 and CH4 production. Reductions of suspended sediment load, absent of dramatic reductions in nutrients, will likely further reduce net CO2 emissions from the river. Large river pools, like Lake Pepin, which removes the majority of upstream sediments, and large agricultural tributaries downstream that deliver significant quantities of sediments and nutrients, are likely to persist as major geographical drivers of greenhouse gas emissions.

Source limitation of carbon gas emissions in high‐elevation mountain streams and lakes

Inland waters are an important component of the global carbon cycle through transport, storage, and direct emissions of CO2 and CH4 to the atmosphere. Despite predictions of high physical gas exchange rates due to turbulent flows and ubiquitous supersaturation of CO2—and perhaps also CH4—patterns of gas emissions are essentially undocumented for high mountain ecosystems. Much like other headwater networks around the globe, we found that high-elevation streams in Rocky Mountain National Park, USA, were supersaturated with CO2 during the growing season and were net sources to the atmosphere. CO2 concentrations in lakes, on the other hand, tended to be less than atmospheric equilibrium during the open water season. CO2 and CH4 emissions from the aquatic conduit were relatively small compared to many parts of the globe. Irrespective of the physical template for high gas exchange (high k), we found evidence of CO2 source limitation to mountain streams during the growing season, which limits overall CO2 emissions. Our results suggest a reduced importance of aquatic ecosystems for carbon cycling in high-elevation landscapes having limited soil development and high CO2 consumption via mineral weathering.

Switching predominance of organic versus inorganic carbon exports from an intermediate‐size subarctic watershed

Hydrologic exports of dissolved inorganic and organic carbon (DIC and DOC) reflect permafrost conditions in arctic and subarctic river basins. DIC yields, in particular, increase with decreased permafrost extent. We investigated the influence of permafrost extent on DIC and DOC yield in a tributary of the Yukon River, where the upper watershed has continuous permafrost and the lower watershed has discontinuous permafrost. Our results indicate that DIC versus DOC predominance switches with interannual changes in water availability and flow routing in intermediate-size watersheds having mixed permafrost coverage. Large water yield and small concentrations from mountainous headwaters and small water yield and high concentrations from lowlands produced similar upstream and downstream carbon yields. However, DOC export exceeded DIC export during high flow 2011, whereas DIC predominated during low flow 2010. The majority of exported carbon was derived from near-surface organic sources when landscapes were wet or frozen and from mineralized subsurface sources when infiltration increased.

CO2 time series patterns in contrasting headwater streams of North America

We explored the underlying patterns of temporal stream CO2 partial pressure (pCO2) variability using high-frequency sensors in seven disparate headwater streams distributed across the northern hemisphere. We also compared this dataset of >40,000 pCO2 records with other published records from lotic systems. Individual stream sites exhibited relatively distinct pCO2 patterns over time with few consistent traits across sites. Some sites showed strong diel variability, some exhibited increasing pCO2 with increasing discharge, whereas other streams had reduced pCO2 with increasing discharge or no clear response to changes in flow. The only “universal” signature observed in headwater streams was a late summer pCO2 maxima that was likely driven by greatest rates of organic matter respiration due to highest annual temperatures. However, we did not observe this seasonal pattern in a southern hardwood forest site, likely because the region was transitioning from a severe drought. This work clearly illustrates the heterogeneous nature of headwater streams, and highlights the idiosyncratic nature of a non-conservative solute that is jointly influenced by physics, hydrology, and biology. We suggest that future researchers carefully select sensor locations (within and among streams) and provide additional contextual information when attempting to explain pCO2 patterns.

Methane in groundwater from a leaking gas well, Piceance Basin, Colorado, USA

Site-specific and regional analysis of time-series hydrologic and geochemical data collected from 15 monitoring wells in the Piceance Basin indicated that a leaking gas well contaminated shallow groundwater with thermogenic methane. The gas well was drilled in 1956 and plugged and abandoned in 1990. Chemical and isotopic data showed the thermogenic methane was not from mixing of gas-rich formation water with shallow groundwater or natural migration of a free-gas phase. Water-level and methane-isotopic data, and video logs from a deep monitoring well, indicated that a shale confining layer ~125m below the zone of contamination was an effective barrier to upward migration of water and gas. The gas well, located 27m from the contaminated monitoring well, had ~1000m of uncemented annular space behind production casing that was the likely pathway through which deep gas migrated into the shallow aquifer. Measurements of soil gas near the gas well showed no evidence of methane emissions from the soil to the atmosphere even though methane concentrations in shallow groundwater (16 to 20mg/L) were above air-saturation levels. Methane degassing from the water table was likely oxidized in the relatively thick unsaturated zone (~18m), thus rendering the leak undetectable at land surface. Drilling and plugging records for oil and gas wells in Colorado and proxies for depth to groundwater indicated thousands of oil and gas wells were drilled and plugged in the same timeframe as the implicated gas well, and the majority of those wells were in areas with relatively large depths to groundwater. This study represents one of the few detailed subsurface investigations of methane leakage from a plugged and abandoned gas well. As such, it could provide a useful template for prioritizing and assessing potentially leaking wells, particularly in cases where the leakage does not manifest itself at land surface.