The vertical hydraulic conductivity of an aquitard at two spatial scales

Aquitards protect underlying aquifers from contaminants and limit recharge to those aquifers. Understanding the mechanisms and quantity of ground water flow across aquitards to underlying aquifers is essential for ground water planning and assessment. We present results of laboratory testing for shale hydraulic conductivities, a methodology for determining the vertical hydraulic conductivity (K(v)) of aquitards at regional scales and demonstrate the importance of discrete flow pathways across aquitards. A regional shale aquitard in southeastern Wisconsin, the Maquoketa Formation, was studied to define the role that an aquitard plays in a regional ground water flow system. Calibration of a regional ground water flow model for southeastern Wisconsin using both predevelopment steady-state and transient targets suggested that the regional K(v) of the Maquoketa Formation is 1.8 x 10(-11) m/s. The core-scale measurements of the K(v) of the Maquoketa Formation range from 1.8 x 10(-14) to 4.1 x 10(-12) m/s. Flow through some additional pathways in the shale, potential fractures or open boreholes, can explain the apparent increase of the regional-scale K(v). Based on well logs, erosional windows or high-conductivity zones seem unlikely pathways. Fractures cutting through the entire thickness of the shale spaced 5 km apart with an aperture of 50 microns could provide enough flow across the aquitard to match that provided by an equivalent bulk K(v) of 1.8 x 10(-11) m/s. In a similar fashion, only 50 wells of 0.1 m radius open to aquifers above and below the shale and evenly spaced 10 km apart across southeastern Wisconsin can match the model K(v).     

Correlating Bedrock Folds to Higher Rates of Arsenic Detection in Groundwater,Southeast Wisconsin,USA

Arsenic in private drinking water wells is a significant problem across much of eastern Wisconsin, USA. The release mechanism and stratigraphic distribution of sulfide and iron (hydr)oxide sources of arsenic in bedrock aquifers are well understood for northeastern Wisconsin. However, recent geologic mapping has identified numerous small bedrock folds to the south, and the impact of these geologic structures on local groundwater flow and well contamination has been little studied. This paper examines the hydrologic and structural effects of the Beaver Dam anticline, southeast Wisconsin, on arsenic in groundwater in the region. Multivariate logistic regression shows wells near the Beaver Dam anticline are statistically more likely to detect arsenic in groundwater compared to wells farther away. Structural and hydrologic changes related to folding are interpreted to be the cause. Core drilled near the fold axis is heavily fractured, and many fractures are filled with sulfides. Elevated hydraulic conductivity estimates are also recorded near the fold axis, which may reflect a higher concentration of vertical fractures. These structural and hydrologic changes may have led to systematic changes in the distribution and concentration of arsenic-bearing mineral hosts, resulting in the observed detection pattern. For areas with similar underlying geology, this approach may improve prediction of arsenic risk down to the local level.     

Sorption modelling on illite. Part II: Actinide sorption and linear free energy relationships

Sorption edge data for Ni(II), Co(II), Eu(III) and Sn(IV) [Bradbury M. H. and Baeyens B. (2009) Sorption modelling on illite. Part I: titration measurements and sorption of Ni(II), Co(II), Eu(III) and Sn(IV), Part I] on purified Na-Illite du Puy are available from some previous work, and some new measurements for Am(III), Th(IV), Pa(V) and U(VI) are presented here. All of these sorption edge measurements have been modelled with a 2 site protolysis non-electrostatic surface complexation and cation exchange (2SPNE SC/CE) sorption model for which the site types, site capacities and protolysis constants were fixed [Bradbury M. H. and Baeyens B. (2009), Part I]. In addition, two further data sets for the sorption of Am(III) and Np(V) on Illite du Puy, obtained from the literature, were also modelled in this work. Thus, surface complexation constants for the strong sites in the 2SPNE SC/CE sorption model for nine metals with valence states from II to VI have been obtained. A linear relationship between the logarithm of strong site metal binding constants, ^SK_x−1, and the logarithm of the corresponding aqueous hydrolysis stability constant, ^OHK_x, extending over nearly 35 orders of magnitude is established here for illite for these nine metals. Such correlations are often termed linear free energy relationships (LFER), and although they are quite common in aqueous phase chemistry, they are much less so in surface chemistry, especially over this large range. The LFER for illite could be described by the equation: where, “x” is an integer. A similar relationship has been previously obtained for montmorillonite, thus LFERs relating to the sorption on two of the most important clay minerals present in natural systems have been established. Such an LFER approach is an extremely useful tool for estimating surface complexation constants for metals in a chemically consistent manner. It provides a means of obtaining sorption values for radionuclides for which there are no measured values and thus allows gaps in missing sorption data to be filled. An ultimate goal of this approach is to develop a thermodynamic sorption database. This could then be used in radioactive waste management performance assessment studies to calculate sorption in natural systems, and thereby replace the current usage of single solid liquid distribution coefficients (K_d values) to describe radionuclide uptake. Finally, with the data now available, the 2SPNE SC/CE sorption model can be ported into reactive transport models allowing radionuclide migration to be calculated under spatially and temporally changing conditions.     

Chronology of Sediment Deposition in Upper Klamath Lake, Oregon

A combination of tephrochronology and ¹⁴C, ²¹⁰Pb, and ¹³⁷Cs measurements provides a robust chronology for sedimentation in Upper Klamath Lake during the last 45 000 years. Mixing of surficial sediments and possible mobility of the radio-isotopes limit the usefulness of the ¹³⁷Cs and ²¹⁰Pb data, but ²¹⁰Pb profiles provide reasonable average sediment accumulation rates for the last 100–150 years. Radiocarbon ages near the top of the core are somewhat erratic and are too old, probably as a result of detrital organic carbon, which may have become a more common component in recent times as surrounding marshes were drained. Below the tops of the cores, radiocarbon ages in the center of the basin appear to be about 400 years too old, while those on the margin appear to be accurate, based on comparisons with tephra layers of known age.Taken together, the data can be combined into reasonable age models for each site. Sediments have accumulated at site K1, near the center of the basin, about 2 times faster than at site CM2, on the margin of the lake. The rates are about 0.10 and 0.05 cm/yr, respectively. The chronological data also indicate that accumulation rates were slower during the early to middle Holocene than during the late Holocene, consistent with increasing wetness in the late Holocene.     

Site characterization in densely fractured dolomite: comparison of methods

One of the challenges in characterizing fractured-rock aquifers is determining whether the equivalent porous medium approximation is valid at the problem scale. Detailed hydrogeologic characterization completed at a small study site in a densely fractured dolomite has yielded an extensive data set that was used to evaluate the utility of the continuum and discrete-fracture approaches to aquifer characterization. There are two near-vertical sets of fractures at the site; near-horizontal bedding-plane partings constitute a third fracture set. Eighteen boreholes, including five coreholes, were drilled to a depth of approximately 10.6 m. Borehole geophysical logs revealed several laterally extensive horizontal fractures and dissolution zones. Flowmeter and short-interval packer testing identified which of these features were hydraulically important. A monitoring system, consisting of short-interval piezometers and multilevel samplers, was designed to monitor four horizontal fractures and two dissolution zones. The resulting network consisted of >70 sampling points and allowed detailed monitoring of head distributions in three dimensions. Comparison of distributions of hydraulic head and hydraulic conductivity determined by these two approaches suggests that even in a densely fractured-carbonate aquifer, a characterization approach using traditional long-interval monitoring wells is inadequate to characterize ground water movement for the purposes of regulatory monitoring or site remediation. In addition, traditional multiwell pumping tests yield an average or bulk hydraulic conductivity that is not adequate for predicting rapid ground water travel times through the fracture network, and the pumping test response does not appear to be an adequate tool for assessing whether the porous medium approximation is valid.     

Neoformation of Ni phyllosilicate upon Ni uptake on montmorillonite: A kinetics study by powder and polarized extended X-ray absorption fine structure spectroscopy

Wet chemistry kinetics and powder and polarized extended X-ray absorption fine structure (EXAFS and P-EXAFS) spectroscopy were combined to investigate the mechanism of Ni uptake on montmorillonite, at pH 8, high ionic strength (0.2 M Ca(NO₃)₂), initial Ni concentration of 660 μM, and solid concentration of 5.3 g/L. Approximately 20% of Ni sorbed within the first 24 h; thereafter, the Ni uptake rate slowed, and 12% of the initial Ni concentration remained in solution after 206 d of reaction time. Powder EXAFS spectra collected on wet pastes at 1, 14, 90, and 206 d showed the presence of Ni-Ni pairs at ∼3.08 Å in an amount that gradually increased with time. Results were interpreted by the nucleation of a Ni phase having either an α-Ni-hydroxide- or a Ni-phyllosilicate-like local structure. The latter possibility was confirmed by recording P-EXAFS spectra of a highly textured, self-supporting montmorillonite film prepared in the same conditions as the wet samples and equilibrated for 14 d. The orientation distribution of the c*-axes of individual clay particles off the film plane, as measured by quantitative texture analysis, was 32.8° full width at half maximum, and this value was used to correct from texture effect the effective numbers of Ni and Si nearest neighbors determined by P-EXAFS. Ni atoms were found to be surrounded by 2.6 ± 0.5 Ni atoms at 3.08 Å in the in-plane direction and by 4.2 ± 0.5 Si atoms at 3.26 Å in the out-of-plane direction. These structural parameters, but also the orientation and angular dependence of the Ni and Si shells, strongly support the formation of a Ni phyllosilicate having its layers parallel to the montmorillonite layers. The neoformation of a phyllosilicate on metal uptake on montmorillonite, documented herein for the first time, has important geochemical implications because this dioctahedral smectite is overwhelmingly present in the environment. The resulting sequestration of sorbed trace metals in sparingly soluble phyllosilicate structure may durably decrease their migration and bioavailability at the Earth’s surface and near surface.     

Late Cenozoic lacustrine and climatic environments at Tule Lake,northern Great Basin,USA

Cores of lake sediment to a depth of 334 m in the town of Tulelake, Siskiyou County, northern California, document the late Cenozoic paleolimnologic and paleoclimatic history of the northwestern edge of the Great Basin. The cores have been dated by radiometric, tephrochronologic and paleomagnetic analyses. Lacustrine diatoms are abundant throughout the record and document a nearly continuous paleolimnologic history of the Tule Lake basin for the last 3 Myr. During most of this time, this basin (Tule Lake) was a relatively deep, extensive lake. Except for a drier (and cooler?) interval recorded by Fragilaria species about 2.4 Ma, the Pliocene is characterized by a dominance of planktonic Aulacoseira solida implying a warm monomictic lake under a climatic regime of low seasonality. Much of the Pleistocene is dominated by Stephanodiscus and Fragilaria species suggesting a cooler, often drier, and highly variable climate. Benthic diatoms typical of alkaline-enriched saline waters commonly appear after 1.0 Ma, and tephrochronology indicates slow deposition and possible hiatuses between about 0.6 and 0.2 Ma. The chronology of even-numbered oxygen isotope stages approximately matches fluctuations in the abundance of Fragilaria since 800 ka indicating that glacial periods were expressed as drier environments at Tule Lake. Glacial and interglacial environments since 150 ka were distinct from, and more variable than, those occurring earlier. The last full glacial period was very dry, but shortly thereafter Tule Lake became a deep, cool lacustrine system indicating a substantial increase in precipitation. Aulacoseira ambigua characterized the latest glacial and Holocene record of Tule Lake. Its distribution indicates that warmer and wetter climates began about 15 ka in this part of the Great Basin. Diatom concentration fluctuates at 41 000 year intervals between 3.0 and 2.5 Ma and at approximately 100 000 year intervals after 1.0 Ma. In the late Pliocene and early Pleistocene, Aulacoseira solida percentages wax and wane in an approximately 400 000 year cycle. The possible response of Tule Lake diatom communities to orbitally-induced insolation cycles underscores the importance of this record for the study of late Cenozoic paleoclimate change.     

Paleolimnology of two lakes in the Klutlan Glacier region,Yukon Territory,Canada

Lakes developed on progressively younger end moraines of the Klutlan Glacier were initially assumed to have originated shortly after moraine emplacement and to have persisted to the present. Limnological differences between lakes on old vs young moraines were thought to result from limnological maturation within the lakes and ponds themselves and in response to the development of soils and vegetation on moraine surfaces. This study represents a paleolimnological test of this hypothesis. If true, the first-formed sediments of lakes on old moraines should be comparable to sediments presently forming in lakes on young moraines. Geochemical and paleontological studies of surface sediment to a series of lakes on progressively older moraines provide baseline information for comparing successive levels of lake sediment cores from older moraines. Results indicate that the time of lake initiation seldom reflects moraine age. Even on the oldest moraine (Harris Creek), lake basins are presently forming. Their sediment character more closely relates to the rapidity of basin formation due to melting of buried ice than to age of the lake itself or of the moraine on which it is situated. Vegetation and soil development play an important but secondary role in determining the character of lake sediments; rapid subsidence can convert humic-water lakes surrounded by second-generation spruce forests into turbid-water lakes with unstable, slumping margins. A detailed paleolimnological study of two lakes, one on the unglaciated upland and another in an outwash channel penetrating the oldest moraine, revealed progressive limnologic changes through time, suggesting that their basins were stable for 1200 and 400 yr, respectively. The changes in diatom stratigraphy of these lakes appear to relate to natural limnological changes associated with lake maturation and accumulation of nutrients as well as to changes in the surrounding vegetation and soils.