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Christopher T. Mills

Publications and source records attributed to Christopher T. Mills.

24 records · Page 2Linked to original sources

Carbon and nitrogen biogeochemistry of a Prairie Pothole Wetland, Stutsman County, North Dakota, USA

The concentration and form of dissolved organic C (DOC) and N species (NH 4 + and NO 3 - ) were investigated as part of a larger hydrogeochemical study of the Cottonwood Lake Study Area within the Prairie Potholes region. Groundwater, pore water and surface wetland water data were used to help characterize the relationships between surface and groundwater with respect to nutrient dynamics. Photosynthesis and subsequent decomposition of vegetation in these hydrologically dynamic wetlands generates a large amount of dissolved C and N, although the subsurface till, derived in part from organic matter rich Pierre Shale, is a likely secondary source of nutrients in deeper groundwater. While surface water DOC concentrations ranged from 2.2 to 4.6 mM, groundwater values were 0.15 mM to 3.7 mM. Greater specific UV absorbance (SUVA 254 ) in the wetland water column and in soil pore waters relative to groundwater indicate more reactive DOC in the surface to near-surface waters. Circumneutral wetlands had greater SUVA254, possibly because of variations in vegetation communities. The dominant inorganic nitrogen species was NH 4 + in both wetland water and most ground water samples. The exceptions were 3 wells with NO 3 - ranging from 38 to 115 μM. Shallow groundwater wells (Well 28 and Well 13S) with greater connection to wetland surface water had greater NH 4 + concentrations (1.1 mM and 120 μM) than other well samples (3–90 μM). Pore water nutrient chemistry was more similar to surface water than ground water. Nitrogen results suggest reducing conditions in both groundwater and surface water, possibly due to the microbial uptake of O 2 by decaying vegetation in the wetland water column, labile organic C available in shallow groundwater, or the oxidation of pyrite associated with the subsurface.

North Dakota↗

Using stable isotopes to understand hydrochemical processes in and around a Prairie Pothole wetland in the Northern Great Plains, USA

Millions of internally drained wetland systems in the Prairie Potholes region of the northern Great Plains (USA and Canada) provide indispensable habitat for waterfowl and a host of other ecosystem services. The hydrochemistry of these systems is complex and a crucial control on wetland function, flora and fauna. Wetland waters can have high concentrations of SO 2- 4 due to the oxidation of large amounts of pyrite in glacial till that is in part derived from the Pierre shale. Water chemistry including δ 18 O H2O , δ 2 H H2O , and δ 34 S SO4 values, was determined for groundwater, soil pore water, and wetland surface water in and around a discharge wetland in North Dakota. The isotopic data for the first time trace the interaction of processes that affect wetland chemistry, including open water evaporation, plant transpiration, and microbial SO 4 reduction.

Applied Geochemistry↗

Chromium(VI) generation in vadose zone soils and alluvial sediments of the southwestern Sacramento Valley, California: a potential source of geogenic Cr(VI) to groundwater

Concentrations of geogenic Cr(VI) in groundwater that exceed the World Health Organization’s maximum contaminant level for drinking water (50 μg L −1 ) occur in several locations globally. The major mechanism for mobilization of this Cr(VI) at these sites is the weathering of Cr(III) from ultramafic rocks and its subsequent oxidation on Mn oxides. This process may be occurring in the southern Sacramento Valley of California where Cr(VI) concentrations in groundwater can approach or exceed 50 μg L −1 . To characterize Cr geochemistry in the area, samples from several soil auger cores (approximately 4 m deep) and drill cores (approximately 25 m deep) were analyzed for total concentrations of 44 major, minor and trace elements, Cr associated with labile Mn and Fe oxides, and Cr(VI). Total concentrations of Cr in these samples ranged from 140 to 2220 mg per kg soil. Between 9 and 70 mg per kg soil was released by selective extractions that target Fe oxides, but essentially no Cr was associated with the abundant reactive Mn oxides (up to ~1000 mg hydroxylamine-reducible Mn per kg soil was present). Both borehole magnetic susceptibility surveys performed at some of the drill core sites and relative differences between Cr released in a 4-acid digestion versus total Cr (lithium metaborate fusion digestion) suggest that the majority of total Cr in the samples is present in refractory chromite minerals transported from ultramafic exposures in the Coast Range Mountains. Chromium(VI) in the samples studied ranged from 0 to 42 μg kg −1 , representing a minute fraction of total Cr. Chromium(VI) content was typically below detection in surface soils (top 10 cm) where soil organic matter was high, and increased with increasing depth in the soil auger cores as organic matter decreased. Maximum concentrations of Cr(VI) were up to 3 times greater in the deeper drill core samples than the shallow auger cores. Although Cr(VI) in these vadose zone soils and sediments was only a very small fraction of the total solid phase Cr, they are a potentially important source for Cr(VI) to groundwater. Enhanced groundwater recharge through the vadose zone due to irrigation could carry Cr(VI) from the vadose zone to the groundwater and may be the mechanism responsible for the correlation observed between elevated Cr(VI) and NO 3 - source concentrations in previously published data for valley groundwaters. Incubation of a valley subsoil showed a Cr(VI) production rate of 24 μg kg −1 a −1 suggesting that field Cr(VI) concentrations could be regenerated annually. Increased Cr(VI) production rates in H + -amended soil incubations indicate that soil acidification processes such as nitrification of ammonium in fertilizers could potentially increase the occurrence of geogenic Cr(VI) in groundwater. Thus, despite the natural origin of the Cr, Cr(VI) generation in the Sacramento Valley soils and sediments has the potential to be influenced by human activities.

California↗

Shoreline surveys of oil-impacted marsh in southern Louisiana, July to August 2010

This report describes shoreline surveys conducted in the marshes of Louisiana in areas impacted by oil spilled from the Deepwater Horizon offshore oil drilling platform in the Gulf of Mexico. Three field expeditions were conducted on July 7-10, August 12-14, and August 24-26, 2010, in central Barataria Bay and the Bird's Foot area at the terminus of the Mississippi River delta. This preliminary report includes locations of survey points, a photographic record of each site, field observations of vegetation cover and descriptions of oil coverage in the water and on plants, including measurements of the distance of oil penetration from the shoreline. Oiling in Barataria Bay marshes ranged from lightly oiled sections of stems of the predominant species Spartina alterniflora and Juncus roemerianus to wide zones of oil-damaged canopies and broken stems penetrating as far as 19 m into the marsh. For the 34 survey points in Barataria Bay where dimensions of oil damaged zones were measured, the depth of the oil-damaged zone extended, on average, 6.7 m into the marsh, with a standard deviation of 4.5 m. The median depth of penetration was 5.5 m. The extent to which the oil-damaged zone stretched along the shore varied with location but often extended more than 100 m parallel to the shoreline. Oil was observed on the marsh sediment at some sites in Barataria Bay. This oiled sediment was observed both above and a few centimeters below the water surface depending on the level of the tide. Phragmites australis was the dominant vegetation in oil-impacted zones in the Bird's Foot area of the Mississippi River delta. Oiling of the leaves and portions of the thick stems of P. australis was observed during field surveys. In contrast to the marshes of Barataria Bay, fewer areas of oil-damaged canopy were documented in the Bird's Foot area. In both areas, oil was observed to be persistent on the marsh plants from the earliest (July 7) to the latest (August 24) surveys. At sites repeatedly visited in Barataria Bay over this time period, oiled plant stems and leaves, laid over by the weight of the oil, broke and were removed from the vegetation canopy, likely due to tidal action. In these areas, a zone of 2-5 cm high plant stubble remained at the edge of the marsh. Signs of both further degradation and recovery were observed and varied with site. Oil damage to the marsh at some sites resulted in complete reduction of live vegetation cover and erosion of exposed sediments, while other damaged zones had signs of regrowth of vegetation in up to 10 percent of the areal coverage.

Open-File Report↗

Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δ13C and Δ14C values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ 13 C and Δ 14 C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7 c , cy 17:0, and 18:1ω7 c . A PLFA biomarker for type II methanotrophs, 18:1ω8 c , comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH 4 as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8 c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ 14 C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ 14 C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH 4 produced by the reduction of DIC. In contrast, δ 13 C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ 13 C CH 4 "> δ13CCH4 values (∼−95‰) for each water. The δ 13 C PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ 14 C PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ 14 C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ 13 C PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H 2 . Results of sample storage experiments showed substantial shifts in microbial community composition and δ 13 C PLFA values (as much as 5‰) during 2–4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ 13 C PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.

Tono Uranium Mine↗

The δ 15 N and δ 18 O values of N 2 O produced during the co-oxidation of ammonia by methanotrophic bacteria

In order to determine if the δ 15 N and δ 18 O values of N 2 O produced during co-oxidation of NH 4 + by methanotrophic (methane oxidizing) bacteria can be isotopically distinguished from N 2 O produced either by autotrophic nitrifying or denitrifying bacteria, we conducted laboratory incubation experiments with pure cultures of methanotrophic bacteria that were provided NH 4 Cl as an oxidation substrate. The N 2 O produced during NH 4 + oxidation by methanotrophic bacteria showed nitrogen isotope fractionation between NH 4 + and N 2 O ( ε N 2 O–NH 4 + ) of − 48 and − 55‰ for Methylomonas methanica and Methylosinus trichosporium , OB3b respectively. These large fractionations are similar to those previously measured for autotrophic nitrifying bacteria and consistent with N 2 O formation by multiple rate limiting steps that include NH 4 + oxidation by the methane monooxygenase enzyme and reduction of NO 2 − to N 2 O. Consequently, N 2 O formed by NH 4 + oxidation via methanotrophic or autotrophic nitrifying bacteria might generally be characterized by lower δ 15 N N 2 O values than that formed by denitrificaiton, although this also depends on the variability of δ 15 N of available nitrogen sources (e.g., NH 4 + , NO 3 − , NO 2 − ). Additional incubations with M. trichosporium OB3b at high and low CH 4 conditions in waters of different δ 18 O values revealed that 19–27% of the oxygen in N 2 O was derived from O 2 with the remainder from water. The biochemical mechanisms that could explain this amount of O 2 incorporation are discussed. The δ 18 O of N 2 O formed under high CH 4 conditions was ~ + 15‰ more positive than that formed under lower CH 4 conditions. This enrichment resulted in part from the incorporation of O 2 into N 2 O that was enriched in 18 O due to an isotope fractionation effect of − 16.1 ± 2.0‰ and − 17.5 ± 5.4‰ associated with O 2 consumption during the high and low methane concentration incubations, respectively. Therefore, N 2 O formed by NH 4 + oxidation via methanotrophic or autotrophic nitrifying bacteria can have very positive δ 18 O N 2 O values if the O 2 incorporated is previously enriched in 18 O from high rates of respiration. Nitrous oxide was collected from various depths in soils overlying a coal-bed methane seep where methanotrophic bacteria are naturally enriched. In one sampling when soil methane concentrations were very high, the δ 18 O VSMOW values of the N 2 O were highly enriched (+ 50‰), consistent with our laboratory experiments. Thus, soils overlying methane seeps could provide an 18 O-enriched source of atmospheric N 2 O.

Chemical Geology↗