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J.M. Holloway

Publications and source records attributed to J.M. Holloway.

8 recordsLinked to original sources

Ammonium in thermal waters of Yellowstone National Park: Processes affecting speciation and isotope fractionation

Dissolved inorganic nitrogen, largely in reduced form (NH 4 (T)≈NH 4(aq) + +NH 3(aq) o ), has been documented in thermal waters throughout Yellowstone National Park, with concentrations ranging from a few micromolar along the Firehole River to millimolar concentrations at Washburn Hot Springs. Indirect evidence from rock nitrogen analyses and previous work on organic compounds associated with Washburn Hot Springs and the Mirror Plateau indicate multiple sources for thermal water NH 4 (T), including Mesozoic marine sedimentary rocks, Eocene lacustrine deposits, and glacial deposits. A positive correlation between NH 4 (T) concentration and δ 18 O of thermal water indicates that boiling is an important mechanism for increasing concentrations of NH 4 (T) and other solutes in some areas. The isotopic composition of dissolved NH 4 (T) is highly variable (δ 15 N = −6‰ to +30‰) and is positively correlated with pH values. In comparison to likely δ 15 N values of nitrogen source materials (+1‰ to +7‰), high δ 15 N values in hot springs with pH >5 are attributed to isotope fractionation associated with NH 3(aq) o loss by volatilization. NH 4 (T) in springs with low pH typically is relatively unfractionated, except for some acid springs with negative δ 15 N values that are attributed to NH 3(g) o condensation. NH 4 (T) concentration and isotopic variations were evident spatially (between springs) and temporally (in individual springs). These variations are likely to be reflected in biomass and sediments associated with the hot springs and outflows. Elevated NH 4 (T) concentrations can persist for 10s to 1000s of meters in surface waters draining hot spring areas before being completely assimilated or oxidized.

Yellowstone National Park

A regional soil and sediment geochemical study in northern California

Regional-scale variations in soil geochemistry were investigated in a 20,000-km 2 study area in northern California that includes the western slope of the Sierra Nevada, the southern Sacramento Valley and the northern Coast Ranges. Over 1300 archival soil samples collected from the late 1970s to 1980 in El Dorado, Placer, Sutter, Sacramento, Yolo and Solano counties were analyzed for 42 elements by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry following a near-total dissolution. These data were supplemented by analysis of more than 500 stream-sediment samples from higher elevations in the Sierra Nevada from the same study site. The relatively high-density data (1 sample per 15 km 2 for much of the study area) allows the delineation of regional geochemical patterns and the identification of processes that produced these patterns. The geochemical results segregate broadly into distinct element groupings whose distribution reflects the interplay of geologic, hydrologic, geomorphic and anthropogenic factors. One such group includes elements associated with mafic and ultramafic rocks including Cr, Ni, V, Co, Cu and Mg. Using Cr as an example, elevated concentrations occur in soils overlying ultramafic rocks in the foothills of the Sierra Nevada (median Cr = 160 mg/kg) as well as in the northern Coast Ranges. Low concentrations of these elements occur in soils located further upslope in the Sierra Nevada overlying Tertiary volcanic, metasedimentary and plutonic rocks (granodiorite and diorite). Eastern Sacramento Valley soil samples, defined as those located east of the Sacramento River, are lower in Cr (median Cr = 84 mg/kg), and are systematically lower in this suite compared to soils from the west side of the Sacramento Valley (median Cr = 130 mg/kg). A second group of elements showing a coherent pattern, including Ca, K, Sr and REE, is derived from relatively silicic rocks types. This group occurs at elevated concentrations in soils overlying volcanic and plutonic rocks at higher elevations in the Sierras (e.g. median La = 28 mg/kg) and the east side of the Sacramento Valley (median 20 mg/kg) compared to soils overlying ultramafic rocks in the Sierra Nevada foothills (median 15 mg/kg) and the western Sacramento Valley (median 14 mg/kg). The segregation of soil geochemistry into distinctive groupings across the Sacramento River arises from the former presence of a natural levee (now replaced by an artificial one) along the banks of the river. This levee has been a barrier to sediment transport. Sediment transport to the Valley by glacial outwash from higher elevations in the Sierra Nevada and, more recently, debris from placer Au mining has dominated sediment transport to the eastern Valley. High content of mafic elements (and low content of silicic elements) in surface soil in the west side of the valley is due to a combination of lack of silicic source rocks, transport of ultramafic rock material from the Coast Ranges, and input of sediment from the late Mesozoic Great Valley Group, which is itself enriched in mafic elements. A third group of elements (Zn, Cd, As and Cu) reflect the impact of mining activity. Soil with elevated content of these elements occurs along the Sacramento River in both levee and adjacent flood basin settings. It is interpreted that transport of sediment down the Sacramento River from massive sulfide mines in the Klamath Mountains to the north has caused this pattern. The Pb, and to some extent Zn, distribution patterns are strongly impacted by anthropogenic inputs. Elevated Pb content is localized in major cites and along major highways due to inputs from leaded gasoline. Zinc has a similar distribution pattern but the source is tire wear.

Applied Geochemistry

Geomorphic controls on mercury accumulation in soils from a historically mined watershed, Central California Coast Range, USA

Historic Hg mining in the Cache Creek watershed in the Central California Coast Range has contributed to the downstream transport of Hg to the San Francisco Bay-Delta. Different aspects of Hg mobilization in soils, including pedogenesis, fluvial redistribution of sediment, volatilization and eolian transport were considered. The greatest soil concentrations (>30 mg Hg kg -1 ) in Cache Creek are associated with mineralized serpentinite, the host rock for Hg deposits. Upland soils with non-mineralized serpentine and sedimentary parent material also had elevated concentrations (0.9-3.7 mg Hg kg -1 ) relative to the average concentration in the region and throughout the conterminous United States (0.06 mg kg -1 ). Erosion of soil and destabilized rock and mobilization of tailings and calcines into surrounding streams have contributed to Hg-rich alluvial soil forming in wetlands and floodplains. The concentration of Hg in floodplain sediment shows sediment dispersion from low-order catchments (5.6-9.6 mg Hg kg -1 in Sulphur Creek; 0.5-61 mg Hg kg -1 in Davis Creek) to Cache Creek (0.1-0.4 mg Hg kg -1 ). These sediments, deposited onto the floodplain during high-flow storm events, yield elevated Hg concentrations (0.2-55 mg Hg kg -1 ) in alluvial soils in upland watersheds. Alluvial soils within the Cache Creek watershed accumulate Hg from upstream mining areas, with concentrations between 0.06 and 0.22 mg Hg kg -1 measured in soils ~90 km downstream from Hg mining areas. Alluvial soils have accumulated Hg released through historic mining activities, remobilizing this Hg to streams as the soils erode.

Applied Geochemistry

A regional-scale study of chromium and nickel in soils of northern California, USA

A soil geochemical survey was conducted in a 27,000-km 2 study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700-10,000 mg/kg Cr and 1300-3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80-1420 mg/kg Cr and 65-224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30-370 mg/kg Cr and 16-110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada. Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO 3 , HCl, HF, HClO 4 ), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO 3 ) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 ??g L -1 and averaging 16.4 ??g L -1 . This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.

Applied Geochemistry

Spatial and seasonal variations in mercury methylation and microbial community structure in a historic mercury mining area, Yolo County, California

The relationships between soil parent lithology, nutrient concentrations, microbial biomass and community structure were evaluated in soils from a small watershed impacted by historic Hg mining. Upland and wetland soils, stream sediments and tailings were collected and analyzed for nutrients (DOC, SO 4 = , NO 3 - ), Hg, MeHg, and phospholipid fatty acids (PLFA). Stream sediment was derived from serpentinite, siltstone, volcanic rocks and mineralized serpentine with cinnabar, metacinnabar and other Hg phases. Soils from different parent materials had distinct PLFA biomass and community structures that are related to nutrient concentrations and toxicity effects of trace metals including Hg. The formation of MeHg appears to be most strongly linked to soil moisture, which in turn has a correlative relationship with PLFA biomass in wetland soils. The greatest concentrations of MeHg (> 0.5??ng g - 1 MeHg) were measured in wetland soils and soil with a volcanic parent (9.5-37????g g - 1 Hg). Mercury methylation was associated with sulfate-reducing bacteria, including Desulfobacter sp. and Desulfovibrio sp., although these organisms are not exclusively responsible for Hg methylation. Statistical models of the data demonstrated that soil microbial communities varied more with soil type than with season.

Chemical Geology

Nitrogen in rock: Occurrences and biogeochemical implications

There is a growing interest in the role of bedrock in global nitrogen cycling and potential for increased ecosystem sensitivity to human impacts in terrains with elevated background nitrogen concentrations. Nitrogen-bearing rocks are globally distributed and comprise a potentially large pool of nitrogen in nutrient cycling that is frequently neglected because of a lack of routine analytical methods for quantification. Nitrogen in rock originates as organically bound nitrogen associated with sediment, or in thermal waters representing a mixture of sedimentary, mantle, and meteoric sources of nitrogen. Rock nitrogen concentrations range from trace levels ( <200 mg N kg −1 ) in granites to ecologically significant concentrations exceeding 1000 mg N kg -1 in some sedimentary and metasedimentary rocks. Nitrate deposits accumulated in arid and semi-arid regions are also a large potential pool. Nitrogen in rock has a potentially significant impact on localized nitrogen cycles. Elevated nitrogen concentrations in water and soil have been attributed to weathering of bedrock nitrogen. In some environments, nitrogen released from bedrock may contribute to nitrogen saturation of terrestrial ecosystems (more nitrogen available than required by biota). Nitrogen saturation results in leaching of nitrate to surface and groundwaters, and, where soils are formed from ammonium-rich bedrock, the oxidation of ammonium to nitrate may result in soil acidification, inhibiting revegetation in certain ecosystems. Collectively, studies presented in this article reveal that geologic nitrogen may be a large and reactive pool with potential for amplification of human impacts on nitrogen cycling in terrestrial and aquatic ecosystems.

Global Biogeochemical Cycles

Nitrogen release from rock and soil under simulated field conditions

A laboratory study was performed to simulate field weathering and nitrogen release from bedrock in a setting where geologic nitrogen has been suspected to be a large local source of nitrate. Two rock types containing nitrogen, slate (1370 mg N kg-1) and greenstone (480 mg N kg-1), were used along with saprolite and BC horizon sand from soils derived from these rock types. The fresh rock and weathered material were used in batch reactors that were leached every 30 days over 6 months to simulate a single wet season. Nitrogen was released from rock and soil materials at rates between 10-20 and 10-19 mo1 N cm-2 s-1. Results from the laboratory dissolution experiments were compared to in situ soil solutions and available mineral nitrogen pools from the BC horizon of both soils. Concentrations of mineral nitrogen (NO3- + NH4+) in soil solutions reached the highest levels at the beginning of the rainy season and progressively decreased with increased leaching. This seasonal pattern was repeated for the available mineral nitrogen pool that was extracted using a KCl solution. Estimates based on these laboratory release rates bracket stream water NO3-N fluxes and changes in the available mineral nitrogen pool over the active leaching period. These results confirm that geologic nitrogen, when present, may be a large and reactive pool that may contribute as a non-point source of nitrate contamination to surface and ground waters. ?? 2001 Elsevier Science B.V. All rights reserved.

Chemical Geology

Seasonal and event-scale variations in solute chemistry for four Sierra Nevada catchments

Hydrobiogeochemical processes controlling stream water chemistry were examined in four small (<5 km2) catchments having contrasting bedrock lithologies in the western Sierra Nevada foothills of California. The Mediterranean climate with its cool/wet and hot/dry cycle produces strong seasonal patterns in hydrological, biological and geochemical processes. Stream water solutes fall into three general groups according to seasonal fluctuation in concentration: Strong, rainy season minimum-dry season maximum (Cl-, SO42-, base cations); weak, rainy season minimum-dry season maximum (Si); and rainy season maximum-dry season minimum (NO3- and K+). Solute dynamics in soil solutions and stream water suggest that mixing of drainage waters from bedrock and soil sources regulate stream water solute concentrations. Patterns are further altered by the leaching of solutes accumulated in the soil over the summer period of desiccation and the temporal discoupling of nutrient cycles that occurs due to differences in the timing between vegetation growth (late spring) and leaching (early winter). Solute concentrations are remarkably similar between watersheds with varying bedrock types, with the exception of nitrate, sulfate and bicarbonate. Three watersheds have nitrogen-bearing metasedimentary bedrock that contributes to elevated nitrate concentrations in stream waters. Watersheds whose bedrock includes mineralized veins of sulfide and carbonate minerals similarly have greater sulfate and bicarbonate concentrations in stream water. Hydrobiogeochemical processes are highly dynamic at the seasonal and storm-event temporal scales and spatially complex at the watershed scale making management of stream water chemical composition, such as nitrate concentrations, very challenging. ?? 2001 Elsevier Science B.V.

Journal of Hydrology