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D. I. Siegel

Publications and source records attributed to D. I. Siegel.

15 recordsLinked to original sources

Isotopic evidence for glacial meltwater recharge to the Cambrian-Ordovician aquifer, north-central United States

The chemistry of water in the Cambrian-Ordovician aquifer in six midwestern states has been studied as part of the Northern Midwest Regional Aquifer-System Analysis of the U.S. Geological Survey. Dissolved-solids concentrations generally increase perpendicular to the direction of regional groundwater flow, from less than 400 mg/liter in southeast Minnesota, southwest Wisconsin, and northeast Iowa to more than 10,000 mg/liter in northwest Missouri. Isotopic ratios of hydrogen and oxygen are significantly depleted from north to south, with an areal distribution approximately parallel to the distribution of dissolved solids. For example, ??18O in southern Iowa and northern Missouri is about 6 parts per thousand lighter than ??18O of modern recharge water in Minnesota and Wisconsin. Covariance between ??18O and ??D of the groundwater, similar to that of modern precipitation, suggests that the differences in isotopic ratios between groundwater and modern recharge water reflect meteoric signatures of water during past recharge events rather than geochemical processes such as isotopic exchange with aquifer materials. The pronounced parallelism between the distribution of isotopes and dissolved solids over large areas probably reflects largescale recharge of Pleistocene glacial meltwater into the aquifer system, which probably had a paleoflow system with a gradient from northeast to southwest rather than from northwest to southeast. ?? 1984.

Quaternary Research↗

The effect of snowmelt on the water quality of Filson Creek and Omaday Lake, northeastern Minnesota

Sulfate concentration and p H were determined in surface water, groundwater, and precipitation samples collected in the Filson Creek watershed to evaluate the sources of sulfate in Filson Creek. During and immediately after snowmelt, sulfate concentrations in Filson Creek increased from about 2 to 14 mg/l. Concurrently, H + ion activity increased from an average of 10 −6.6 to 10 −5.5 . These changes suggest that sulfate acidity is concentrated in the snowpack at snowmelt, which is similar to changes reported in Scandinavia in areas subject to acid precipitation. Mass balance calculations indicate that the sulfate contribution from groundwater during snowmelt was minimal in comparison to that from snow. During base flow, sulfate did not appreciably increase from the headwaters of Filson Creek to the mouth, even though sulfate was as high as 58 mg/l in groundwater discharging to the creek from surficial materials overlying a sulfide-bearing mineralized zone in the lower third of the watershed. Approximately 10.6 kg of sulfate per hectare per year was retained in 1977.

Minnesota↗

Groundwater flow with energy transport and water-ice phase change: Numerical simulations, benchmarks, and application to freezing in peat bogs

In northern peatlands, subsurface ice formation is an important process that can control heat transport, groundwater flow, and biological activity. Temperature was measured over one and a half years in a vertical profile in the Red Lake Bog, Minnesota. To successfully simulate the transport of heat within the peat profile, the U.S. Geological Survey's SUTRA computer code was modified. The modified code simulates fully saturated, coupled porewater-energy transport, with freezing and melting porewater, and includes proportional heat capacity and thermal conductivity of water and ice, decreasing matrix permeability due to ice formation, and latent heat. The model is verified by correctly simulating the Lunardini analytical solution for ice formation in a porous medium with a mixed ice-water zone. The modified SUTRA model correctly simulates the temperature and ice distributions in the peat bog. Two possible benchmark problems for groundwater and energy transport with ice formation and melting are proposed that may be used by other researchers for code comparison.

Minnesota↗

Heat transport in the Red Lake Bog, Glacial Lake Agassiz Peatlands

We report the results of an investigation on the processes controlling heat transport in peat under a large bog in the Glacial Lake Agassiz Peatlands. For 2 years, starting in July 1998, we recorded temperature at 12 depth intervals from 0 to 400 cm within a vertical peat profile at the crest of the bog at sub‐daily intervals. We also recorded air temperature 1 m above the peat surface. We calculate a peat thermal conductivity of 0·5 W m −1 °C −1 and model vertical heat transport through the peat using the SUTRA model. The model was calibrated to the first year of data, and then evaluated against the second year of collected heat data. The model results suggest that advective pore‐water flow is not necessary to transport heat within the peat profile and most of the heat is transferred by thermal conduction alone in these waterlogged soils. In the spring season, a zero‐curtain effect controls the transport of heat through shallow depths of the peat. Changes in local climate and the resulting changes in thermal transport still may cause non‐linear feedbacks in methane emissions related to the generation of methane deeper within the peat profile as regional temperatures increase.

Minnesota↗

The hydrology of northern peatlands as affected by biogenic gas: Current developments and research needs

Recent research indicates that accumulation and release of biogenic gas from northern peatlands may substantially affect future climate. Sudden release of free-phase gas bubbles into the atmosphere may preclude the conversion of methane to carbon dioxide in the uppermost oxic layer of the peat, resulting in greater contribution of methane to the atmosphere than is currently estimated. The hydrology of these peatlands also affects and is affected by this process, especially when gas is released suddenly and episodically. Indirect hydrological evidence indicates that ebullitive gas releases are relatively frequent in some peatlands and time-averaged rates may be significantly greater than diffusive releases. Estimates of free-phase gas contained in peat have ranged from 0 to nearly 20% of the peat volume. Abrupt changes in the volume of gas may alter hydraulic gradients and movement of water and solutes in peat, which in turn could alter composition and fluxes of the gas. Peat surfaces also move vertically and horizontally in response to accumulation and release of free-phase gas. Future research should address the distribution, temporal variability, and relative significance of ebullition in peatlands and the consequent hydrological responses to these gas-emission events. Copyright ?? 2006 John Wiley & Sons, Ltd.

Hydrological Processes↗

Flow path oscillations in transient ground-water simulations of large peatland systems

Transient numerical simulations of the Glacial Lake Agassiz Peatland near the Red Lakes in Northern Minnesota were constructed to evaluate observed reversals in vertical ground-water flow. Seasonal weather changes were introduced to a ground-water flow model by varying evapotranspiration and recharge over time. Vertical hydraulic reversals, driven by changes in recharge and evapotranspiration were produced in the simulated peat layer. These simulations indicate that the high specific storage associated with the peat is an important control on hydraulic reversals. Seasonally driven vertical flow is on the order of centimeters in the deep peat, suggesting that seasonal vertical advective fluxes are not significant and that ground-water flow into the deep peat likely occurs on decadal or longer time scales. Particles tracked within the ground-water flow model oscillate over time, suggesting that seasonal flow reversals will enhance vertical mixing in the peat column. The amplitude of flow path oscillations increased with increasing peat storativity, with amplitudes of about 5 cm occurring when peat specific storativity was set to about 0.05 m-1. ?? 2005 Elsevier B.V. All rights reserved.

Journal of Hydrology↗

Surface deformations as indicators of deep ebullition fluxes in a large northern peatland

Peatlands deform elastically during precipitation cycles by small ( ±3 cm ) oscillations in surface elevation. In contrast, we used a Global Positioning System network to measure larger oscillations that exceeded 20 cm over periods of 4-12 hours during two seasonal droughts at a bog and fen site in northern Minnesota. The second summer drought also triggered 19 depressuring cycles in an overpressured stratum under the bog site. The synchronicity between the largest surface deformations and the depressuring cycles indicates that both phenomena are produced by the episodic release of large volumes of gas from deep semi-elastic compartments confined by dense wood layers. We calculate that the three largest surface deformations were associated with the release of 136 g CH4 m-2, which exceeds by an order of magnitude the annual average chamber fluxes measured at this site. Ebullition of gas from the deep peat may therefore be a large and previously unrecognized source of radiocarbon depleted methane emissions from northern peatlands.

Minnesota↗

Estimating methane production rates in bogs and landfills by deuterium enrichment of pore water

Raised bogs and municipal waste landfills harbor large populations of methanogens within their domed deposits of anoxic organic matter. Although the methane emissions from these sites have been estimated by various methods, limited data exist on the activity of the methanogens at depth. We therefore analyzed the stable isotopic signature of the pore waters in two raised bogs from northern Minnesota to identify depth intervals in the peat profile where methanogenic metabolism occurs. Methanogenesis enriched the deuterium (2H) content of the deep peat pore waters by as much as +11% (Vienna Standard Mean Sea Water), which compares to a much greater enrichment factor of +70% in leachate from New York City's Fresh Kills landfill. The bog pore waters were isotopically dated by tritium (3H) to be about 35 years old at 1.5 m depth, whereas the landfill leachate was estimated as ~ 17 years old from Darcy flow calculations. According to an isotopic mass balance the observed deuterium enrichment indicates that about 1.2 g of CH4m-3 d-1 were produced within the deeper peat, compared to about 2.8 g CH4 m-3 d-1 in the landfill. The values for methane production in the bog peat are substantially higher than the flux rates measured at the surface of the bogs or at the landfill, indicating that deeper methane production may be much higher than was previously assumed.

Global Biogeochemical Cycles↗

Crude oil in a shallow sand and gravel aquifer-III. Biogeochemical reactions and mass balance modeling in anoxic groundwater

Crude oil floating on the water table in a sand and gravel aquifer provides a constant source of hydrocarbons to the groundwater at a site near Bemidji, Minnesota. The degradation of hydrocarbons affects the concentrations of oxidized and reduced aqueous species in the anoxic part of the contaminant plume that developed downgradient from the oil body. The concentrations of Fe 2+ , Mn 2+ and CH 4 , Eh measurements, and the δ 13 C ratios of the total inorganic C indicate that the plume became more reducing ver a 5-a period. However, the size of the contaminant plume remained stable during this time. Field data coupled with laboratory microcosm experiments indicate that benzene and the alkylbenzenes are degraded in an anoxic environment. In anaerobic microcosm experiments conducted under field conditions, almost complete degradation (98%) was observed for benzene in 125 d and for toluene in 45 d. Concentrations of aqueous Fe 2+ and Mn 2+ increased in these experiments, indicating that the primary reactions were hydrocarbon degradation coupled with Fe and Mn reduction. Mass transfer calculations on a 40-m flowpath in the anoxic zone, downgradient from the oil body, indicated that the primary reactions in the anoxic zone are oxidation of organic compounds, precipitation of siderite and a ferroan calcite, dissolution of iron oxide and outgassing of CH 4 and CO 2 . The major difference in the two models presented is the ratio of CO 2 and CH 4 that outgasses. Both models indicate quantitatively that large amounts of Fe are dissolved and reprecipitated as ferrous iron in the anoxic zone of the contaminant plume.

Minnesota↗

Hydrogeology of the Cambrian-Ordovician aquifer system in the northern Midwest, United States with a section on ground-water quality

The Cambrian-Ordovician aquifer system contains the most extensive and continuous aquifers in the northern Midwest of the United States. It is the source of water for many municipalities, industries, and rural water users. Since the beginning of ground-water development from the aquifer system in the late 1800's, hydraulic heads have declined hundreds of feet in the heavily pumped Chicago-Milwaukee area and somewhat less in other metropolitan areas. The U.S. Geological Survey has completed a regional assessment of this aquifer system within a 161,000-square-mile area encompassing northern Illinois, northwestern Indiana, Iowa, southeastern Minnesota, northern Missouri, and Wisconsin. Consolidated sedimentary rocks in the northern Midwest range in age from Precambrian to Cretaceous and crop out in generally concentric, arcuate patterns, dipping away from structural highs (arches) on the Precambrian basement in northern Minnesota and Wisconsin toward structural lows (basins) to the south and east. The sedimentary bedrock is generally overlain by a veneer of glacial drift. Thickness of the sedimentary sequence increases to about 5,000 feet in the Forest City basin of southwestern Iowa and to about 14,000 and more than 15,000 feet in the Illinois and Michigan basins, respectively. Cambrian and Ordovician age rocks, mainly marine sandstone and carbonate rocks, compose much of the sedimentary sequence and form the Cambrian-Ordovician aquifer system. The aquifer system lies on the Precambrian basement, regarded as a regional confining unit. Six hydrogeologic units are defined; they are arranged as alternating pairs of an aquifer and an overlying confining. unit. The units are named using the predominant geologic nomenclature of the upper Mississippi Valley, which includes most of the study area. In the southern quarter of the area, the hydrogeologic units consist of equivalent formations of the Ozark area (mostly carbonate rocks). The uppermost part of the aquifer system is the Maquoketa confining unit, which consists of the Maquoketa Shale and the underlying dolomite and shale of the Galena Dolomite and the Decorah, Platteville, and Glenwood Formations. The underlying St. Peter-Prairie du Chien-Jordan aquifer is an important source of ground water in the western part of the area in Iowa and Minnesota, where the uniform Jordan Sandstone is hydraulically connected to overlying fractured dolomite of the Prairie du Chien Group. The unit is less important in the eastern part of Wisconsin and Illinois because the Jordan Sandstone is absent and the Prairie du Chien Group is thin or absent due to pre-St. Peter Sandstone erosion. Equivalent rocks in northern Missouri-the Roubidoux Formation and the Gasconade and Eminence Dolomites-are mainly carbonate rocks that are somewhat permeable and contain some sandstone. The St. Lawrence and Franconia Formations underlying the St. Peter-Prairie du Chien-Jordan aquifer consist generally of silty and shaly, fine-grained, poorly sorted, and dolomitic sandstones that restrict vertical movement of ground water and form a regional confining unit. In the southern and eastern parts of the area, the Potosi and Derby-Doerun Dolomites and the upper part of the Davis Formation are the equivalent rocks (mainly carbonate rocks). In the east-central part of the area in Illinois and Wisconsin, the Ironton-Galesville aquifer forms the most important aquifer of the Cambrian-Ordovician aquifer system, contributing about one-third of the yield from wells in the aquifer system in the Chicago area. The aquifer terminates to the west, south, and east, where the sandstones grade into less permeable carbonate rocks in central Iowa, central Illinois, and northwestern Indiana, respectively. The underlying Eau Claire Formation and its partial equivalent to the southwest, the Bonneterre Formation, form an important confining unit above the Mount Simon aquifer throughout much of the study area. Siltstone and shale are fairly common in the upper part of the Eau Claire Formation but less so in its northernmost extent in Wisconsin. Dolomite content increases southward and westward, where a middle dolomite facies grades laterally into the Bonneterre in Missouri, southwestern Minnesota, extreme south-central Wisconsin, and possibly in western Iowa. The basal unit in the Cambrian-Ordovician aquifer system, the Mount Simon aquifer, is present throughout the study area, except where it is absent over local highs of the Precambrian basement. It consists primarily of the Mount Simon Sandstone in the north and its equivalent in northern Missouri, the Lamotte Sandstone. The underlying Hinckley Sandstone of Precambrian age is included in Minnesota, as is the overlying Elmhurst Sandstone Member of the Eau Claire Formation in northern Illinois. The aquifer increases greatly in thickness and the water is progressively more saline away from the northern structural highs toward the basins. Much of the movement and discharge of ground water in the northern Midwest occurs in local, unconfined, shallow flow systems within a few miles of points of recharge. The rest of the water is semiconfined or confined in intermediate or regional flow systems within the bedrock, where flow is deeper, slower, and traverses much longer distances from recharge areas to discharge areas. The major areas of recharge to regional confined flow are in northwestern Iowa, southeastern Minnesota, western, southern, and eastern Wisconsin, and northern Illinois. Although the rate of flow is small, significant recharge to the Cambrian-Ordovician aquifer system also occurs as leakage through the Maquoketa confining unit, where the vertical hydraulic gradient is downward. Ground water in much of the confined aquifer system moves laterally from recharge areas toward the major river valleys and Lake Michigan or down dip toward the structural basins. The longest flow paths extend as much as 400 miles from northwestern Iowa southeast toward the Illinois basin or to the Mississippi River and Missouri River valleys near their confluence. Other major confined flow is from eastern Wisconsin toward the Michigan basin and southward flow from northeastern Illinois toward the Illinois basin. Regional ground-water discharge from the aquifer system is mainly diffuse upward leakage from confined aquifers along flow paths toward the structural basins. Very saline water around and brines within the basins restrict regional flow into the basins, forcing ground water to discharge upward. Water in intermediate flow systems discharges upward to the major river valleys. Original heads of more than 100 feet above land surface were recorded in the aquifer system near Lake Michigan in eastern Wisconsin and at Dubuque, Iowa, along the Mississippi River. The Cambrian-Ordovician aquifer system was developed rapidly in the late 1800's after the first deep well was drilled in Chicago in 1864. Many flowing wells were not controlled, which caused water levels in deep wells to decline, and many no longer flowed by the early 1900's. Heads in the aquifers have declined very little in most of the recharge or unconfined areas since ground-water withdrawal began, but major declines have occurred in confined areas. The largest declines in head are at Chicago, Illinois, Milwaukee and Green Bay, Wisconsin, and Mason City, Iowa, where the aquifer system is confined by the Maquoketa confining unit. The composite head in the aquifer system declined more than 900 feet in the deepest cones of depression in the Chicago area from 1864 to 1980 and about 375 feet in the cone at Milwaukee from 1880 to 1980. More than 200 feet of decline has occurred at Mason City. The head declined as much as 440 feet in Green Bay from 1886 to 1957, when the city discontinued use of its deep wells and began using water from Lake Michigan. The largest centers of pumping are in the Chicago and Twin Cities (Minneapolis-St. Paul, Minnesota) metropolitan areas about 180 million gallons per day each in 1980. Pumpage exceeded 10 million gallons per day in only a few other areas in 1980. Ground water in the Cambrian-Ordovician aquifer system in the northern Midwest is characterized by an extreme range of mineralization, but its quality in most of the area is good. The major cations are calcium, magnesium, and sodium, and the major anions are bicarbonate, sulfate, and chloride. Sodium, sulfate, and chloride distributions are closely related to the distribution pattern of dissolved solids but not in the same proportion. Dissolved-solids concentration is generally less than 1,000 milligrams per liter in the recharge areas of Wisconsin, southern Minnesota, northeastern Iowa, and north-central Illinois where the aquifer system crops out or subcrops beneath glacial drift. Ground water there is the Ca-Mg-HC03 type, derived from and identical to that in the overlying glacial drift. In northwestern Iowa and southwestern Minnesota, the water in both the glacial drift and the Cambrian-Ordovician aquifer system is a Ca-Na-S04HC03 type, derived from oxidation of pyrite in the overlying Cretaceous Dakota Formation. Transition to higher dissolved solids in the confined areas commonly is accompanied by increased sulfate concentration and· the occurrence of Ca-Na-S04-type water. Salinity of the ground water increases progressively toward the .basins, where dissolved solids exceed 200,000 milligrams per liter. Saline water is present in the Mount Simon aquifer near Lake Michigan in eastern Wisconsin and northeastern Illinois but occurs in successively younger rocks to the east and south as they dip toward the basins. Similarly, salinity increases down dip in Iowa to the southwest and south; however, regional ground-water flow in Iowa is from northwest to southeast. Much of the ground water in the confined aquifer system is isotopically depleted in 0180 and OD with respect to modern precipitation-an indication that the water originated as precipitation in a much colder climate than the present and probably was derived from recharge of glacial meltwater. On the basis of o34S values for sulfur in sulfate, it is believed that isostatic loading from glacial ice over the Michigan basin reversed the hydraulic gradient to trend westward, opposite from the present gradient, causing saline water in the Michigan basin to discharge westward through the present recharge areas. Natural water-quality problems in the Cambrian-Ordovician aquifer system are mainly the high dissolved-solids concentrations and associated high concentrations of sulfate and chloride, which limit the use of the water for municipal and domestic purposes in much of the confined aquifer system in central and southern Illinois, Indiana, southern and western Iowa, and northern Missouri. Another concern is that radium activity exceeds normal background concentrations of a few picocuries per liter in much of the confined aquifer system in eastern Wisconsin, northeastern Illinois, and central Iowa. Other common problems are high hardness and locally excessive concentrations of iron and hydrogen sulfide.

Iowa, Illinois, Indiana, Michigan, Minnesota, Miss↗

Oxidation of aromatic contaminants coupled to microbial iron reduction

THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically.

Nature↗

Geochemistry of the Cambrian-Ordovician aquifer system in the northern Midwest, United States: D in Regional aquifer-system analysis

Distributions of solutes in aquifers of Cambrian and Ordovician age were studied in Minnesota, Wisconsin, Iowa, Illinois, northwestern Indiana, and northern Missouri to determine the sources of solutes and the probable chemical mechanisms that control regional variations in water quality. This work is part of the Northern Midwest Regional Aquifer-System Analysis project, whose objective is to describe and model the regional hydrogeology of the Cambrian- Ordovician aquifer system in the study region. The data base used included more than 3,000 ground-water-quality analyses from all major aquifers, but especially from the St. Peter, Jordan, and Mount Simon Sandstones and their equivalents. Regional variations in the water chemistry of glacial drift and other sedimentary units that overlie the Cambrian-Ordovician aquifer system in recharge areas in Minnesota, Iowa, Wisconsin, and Illinois were also studied, but to a lesser degree. The most important chemical variation in the aquifer is the change in water type from calcium-sodium-sulfate-bicarbonate water to sodium-calcium-sulfate-bicarbonate and sodium-chloride waters along the longest regional flow path from northwestern Iowa to the Illinois basin. Sodium predominance downgradient from the recharge area is probably related to mechanisms of ion exchange and shalemembrane filtration near the Illinois and Forest City basins. The most striking aspect of the distribution of dissolved solids and carbon isotopic content of bicarbonate is the increase in concentration and isotopic enrichment from southwestern Wisconsin, southern Minnesota, and northwestern Illinois south toward Missouri. This trend is perpendicular to the present hydraulic gradient that trends from northwestern Iowa southeastward to the Illinois basin. The distribution of dissolved solids defines a "plume" of dilute water having a dissolved-solids concentration of about 500 milligrams per liter, compared with surrounding concentrations more than twice as large. Distribution of the isotopic content of oxygen (<518O) and hydrogen (5D) in water closely parallels that of dissolved solids and shows covariance similar to modern meteoric water. The isotopic contents are more depleted (lighter) toward the south, perpendicular to the direction of current hydraulic gradients. The degree of depletion, compared with the isotopic content of modern recharge water, indicates that the plume and a significant fraction of the ground water in Iowa, northern Missouri, and possibly central Illinois may have originated as recharge during Pleistocene time. Distributions of dissolved trace constituents in the aquifers probably are related to the proximity to mineralogic sources as well as chemical and hydraulic mechanisms. For example, concentrations of some constituents, such as cadmium and arsenic, are largest in the vicinity of the Dakota Formation in northwestern Iowa. Other constituents, such as beryllium and vanadium, have larger concentrations near the edge of the Forest City basin in southwestern Iowa and northwestern Missouri. Strontium and fluoride concentrations generally increase from north to south, which suggests the input of these trace constituents during the recharge events. However, concentrations of bromide, radium-226, and lithium show distribution patterns similar to the "plume" defined by dissolved solids and isotopes of water, suggesting dilution of concentrations of trace constituents by Pleistocene recharge. Concentrations of other constituents are partly controlled by aquifer temperature, such as silica in south-central Iowa, and solubility controls, such as barium in northeastern Illinois. Additional information on the chemical and mineralogical composition of the aquifer matrix and the isotopically lightest ground water is needed to evaluate the hypothesis of Pleistocene mixing before more quantitative studies can be done to evaluate the different proposed mechanisms that have controlled and modified the water chemistry over time. This study, however, indicates that the ground water in the region is thousands of years old. The study also indicates that the major chemical trends in the aquifers probably are related as much to paleohydrogeologic flow systems during Pleistocene time as to the present flow system, which may postdate the retreat of the last ice sheet about 12,000 years ago.

Iowa, Indiana, Illinois, Michigan, Minnesota, Miss↗

The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

Geochimica et Cosmochimica Acta↗

Increased solubility of quartz in water due to complexing by organic compounds

Quartz is the most stable natural solid phase of silica. It weathers extremely slowly at the Earth's surface 1 , and often resists weathering even after all other silicate minerals have been degraded. However, there is ample evidence from both ancient and modern environments indicating enhanced dissolution and mobility of silica under conditions that cannot easily be explained by the inorganic controls of quartz solubility 2 . Increased solubility of quartz has been observed particularly in soils rich in organic material; however, no direct link between dissolved organic carbon and dissolved silica has been identified 3 . Here we present evidence for an increase in the solubility of quartz in a natural water brought about by dissolved organic compounds. These compounds were produced by the biodegradation of petroleum, and consist largely of a complex mixture of organic acids. We propose that silica is being complexed and mobilized by these organic acids in waters having close to neutral p H.

Nature↗

Physiography and surficial geology of the copper-nickel study region, northeastern Minnesota

The Copper-Nickel study region lies in the Superior Upland physiographic province and is located approximately 60 miles north of Duluth and 100 miles southeast of International Falls, Minnesota. It straddles the Laurentian Divide, which separates Hudson Bay and Lake Superior drainage. The topography exhibits a southwesterly trending lineation that parallels the strike of southeastward-dipping bedrock units and the southwestward direction of ice movement during Pleistocene glaciation. For this study, the region has been divided into seven physiographic areas based on geomorphic features related to the bedrock surface, glacial deposits, and hydrogeologic significance. The surficial geology is largely a result of two southwestward advances of the Rainy Lobe of the Laurentian ice sheet. The Toimi Drumlin Field, the oldest glacial deposit, covers much of the southern part of the region. It is bounded on the north by the Vermilion Moraine Complex, an east-west trending series of terminal and recessional moraines that mark the southerly extent of the second advance of the Rainy Lobe. Thin ground moraine and small outwash deposits occur both within and north of the Vermilion Moraine Complex except in the Embarrass and Dunka River basins where outwash deposits up to 200 feet in thickness fill a deep bedrock valley.

Minnesota↗