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Chemistry of illite/smectite and end-member illite

Chemical data from three different series of diagenetic illite/smectites (I/S), analyzed statistically by two regresion techniques, indicate that the content of fixed-K per illite layer is not constant, but ranges from ∼0.55 per O 10 (OH) 2 for illite layers in randomly interstratified I/S (R=0; > 50% smectite layers) to ∼1.0 per O 10 (OH) 2 for illite layers formed in ordered I/S (R>0; <50% smectite layers). By extrapolation of the experimental data, the following chemical characteristics were obtained for end-member illite derived from the alteration of smectite in bentonite: average fixed-K per illite layer = 0.75 per O 10 (OH) 2 ; total charge = about −0.8; cation-exchange capacity = 15 meq/100 g; surface area (EGME) = 150 m 2 /g.

Clays and Clay Minerals

Vanadium chlorite from a sandstone-hosted vanadium-uranium deposit, Henry basin, Utah

An unusual vanadium chlorite precipitated during the formation of a vanadium-uranium ore deposit in the Henry Basin, southeastern Utah. The ore deposit formed by reduction and precipitation of U and V in the presence of organic matter at the interface between a stagnant brine and overlying, circulating meteoric water. Some samples of the vanadium chlorite (heated before analysis) contain > 10% V 2 O 5 . In fresh samples, most of the vanadium is in the trivalent oxidation state. X-ray powder diffraction data suggest that Fe and V are concentrated preferentially in the interlayer hydroxide sheets of the chlorite. A d(060) value of 1.52 Å indicates that the chlorite probably has a dioctahedral structure which is distended by the presence of octahedral Fe and V. The vanadium ore zone is flanked by peripheral zones containing perfectly ordered chlorite/smectite. This chlorite/smectite contains much less V than the pure chlorite. This chlorite may have formed by the progressive precipitation of vanadium-rich interlayer hydroxide sheets in the mixed-layer chlorite/smectite in the most reducing portion of the ore zone. The pure chlorite is a IIb polytype, which, for nonvanadiferous analogs, is ordinarily found in high-temperature environments; however, no evidence exists to show that these rocks have ever been exposed to elevated temperatures. In fact, the presence of unreacted smectite in a potassium-rich setting and the low vitrinite reflectance of coalified plant debris indicate a low-temperature history for these sediments.

Utah

Changes in particle morphology during illitization: An experimental study

Smectite was reacted at several temperatures between 200°C and 500°C to produce interstratified illite/smectite (I/S) with different proportions of expandable layers. Dispersed and sedimented products were examined using a transmission electron microscope. Particle size and aspect ratio showed no systematic change as a function of reaction extent during R0 illitization. However, particles exhibited rounded edges during the early stages of the reaction, suggesting some dissolution of primary smectite. Additionally, increasing particle contrast in the electron beam suggests thickening of particles with increasing reaction extent. The thickening of particles is thought to be produced by the nucleation and precipitation of secondary illite layers on primary smectite layers. In the most extensively reacted I/S, particles have become aggregated into clumps or quasicrystals by lateral growth of illite layers. Internal uniformity of crystallographic alignment of individual growing crystals within each aggregate was reflected in the increasing frequency of 60° and 120° interfacial angles within each aggregate. In highly illitic I/S, these aggregates took on an overall euhedral form and became crystallographically contiguous, producing single crystal electron diffraction patterns.

Clays and Clay Minerals

Studies of the Reactivity of the Ferrihydrite Surface by Iron Isotopic Exchange and Mössbauer Spectroscopy

Two-line ferrihydrite is an important adsorbent of many toxics in natural and anthropogenic systems; however, the specific structural sites responsible for the high adsorption capacity are not well understood. A combination of chemical and spectroscopic techniques have been employed in this study to gain further insight into the structural nature of sites at the ferrihydrite surface. The kinetics of iron isotopic exchange demonstrated that there are at least two types of iron sites in ferrihydrite. One population of sites, referred to as labile sites, approached iron isotopic equilibrium within 24 hr in 59 Fe-NTA solutions, while the second population of sites, referred to as non-labile , exhibited a much slower rate of isotopic exchange. Adsorbed arsenate reduced the degree of exchange by labile sites, indicating that the anion blocked or greatly inhibited the rate of exchange of these sites. Mössbauer spectra were collected from a variety of samples including 56 Fe-ferrihydrite samples with 57 Fe in labile sites, samples containing 57 Fe throughout the structure, and samples with 57 Fe in non-labile sites. The spectra showed characteristic broad doublets signifying poor structural order. Refined fits of the spectra indicated that labile sites have larger quadrupole splitting, hence more local distortion, than non-labile sites. In all cases, the spectra demonstrated some degree of asymmetry, indicating a distribution of Fe environments in ferrihydrite. Overall spectral findings, combined with recent EXAFS results (Waychunas et al. , 1993), indicate that labile sites likely are more reactive (with respect to iron isotopic exchange) because they have fewer neighboring Fe octahedra and are therefore bound less strongly to the ferrihydrite structure. The labile population of sites probably is composed of end sites of the dioctahedral chain structure of 2-line ferrihydrite, which is a subset of the entire population of surface sites. Mössbauer spectra of samples containing adsorbed arsenate indicated that the anion may slightly decrease the distortion of labile sites and stabilized the structure as a whole by bidentate bonding.

Clays and Clay Minerals

Geologic control of severe expansive clay damage to a subdivision in the Pierre Shale, southwest Denver metropolitan area, Colorado

Shortly after construction of a subdivision in the southwest Denver metropolitan area in 1986, a portion of the subdivision built directly on steeply-dipping strata of the Pierre Shale began experiencing damaging differential movements, causing house foundations to fail and pavements to warp and crack. This formation is a Late Cretaceous marine clay-shale composed predominantly of fluvial mixed-layer illite/smectite and quartz. During deposition of the shale, periodic and explosive volcanism generated thin beds of bentonite, consisting initially of volcanic ash and subsequently altered to nearly pure smectite. Some of these bentonite beds were exposed in a trench adjacent to the subdivision and perpendicular to the strike of the steeply-dipping strata. The thickest bentonite beds correlated well with linear heave features that these beds parallel the bedrock strike throughout the subdivision were mapped via severely deformed pavements. Mineralogical data show the bentonite bed that correlates with the worst damage within the subdivision consists of about 62% smectite by weight with mixed-layer illite/smectite expandability of 92%. By comparison, a sample of the typical silty claystone, which is fluvial mixed-layer illite/smectite mixed with detrital quartz from the adjacent strata, had about 23% smectite by weight with 70% to 90% illite/smectite expandability. Geotechnical tests for swell potential show that samples of 2 bentonite beds swelled 39% to 43% compared to 2% to 8% for samples of the typical silty claystone. It is proposed that differential swell resulting from stratigraphically-controlled differences in clay mineralogy and grain-size is the primary factor controlling extreme damage for this geologic setting.

Clays and Clay Minerals

Effects of exchanged cation on the microporosity of montmorillonite

The micropore volumes of 2 montmorillonites (SAz-1 and SWy-1), each exchanged with Ca, Na, K, Cs and tetramethylammonium (TMA) ions, were calculated from the measured vapor adsorption data of N 2 and neo -hexane by use of t - and α s -plots. The corresponding surface areas of the exchanged clays were determined from Brunauer-Emmett-Teller (BET) plots of N 2 adsorption data. Micropore volumes and surface areas of the samples increased with the size of exchanged cation: TMA > Cs > K > Ca > Na. The SAz-1 exchanged clays showed generally greater micropore volumes and surface areas than the corresponding SWy-1 clays. The vapor adsorption data and d (001) measurements for dry clay samples were used together to evaluate the likely locations and accessibility of clay micropores, especially the relative accessibility of their interlayer spacing. For both source clays exchanged with Na, Ca and K ions, the interlayer spacing appeared to be too small to admit nonpolar gases and the accessible micropores appeared to have dimensions greater than 5.0 Å, the limiting molecular dimension of neo -hexane. In these systems, there was a good consistency of micropore volumes detected by N 2 and neo -hexane. When the clays were intercalated with relatively large cations (TMA and possibly Cs), the large layer expansion created additional microporosity, which was more readily accessible to small N 2 than to relatively large neo -hexane. Hence, the micropore volume as detected by N 2 was greater than that detected by neo -hexane. The micropore volumes with pore dimensions greater than 5 Å determined for clays exchanged with Na, Ca and K likely resulted from the pores on particle edges and void created by overlap regions of layers. The increase in micropore volumes with pore dimensions less than 5 Å determined for clays exchanged with TMA and possibly Cs could be caused by opening of the interlayer region by the intercalation of these large cations.

Clays and Clay Minerals

Crystal structure refinement and Mössbauer spectroscopy of an ordered, triclinic clinochlore

The crystal structure of a natural, ordered IIb-4 triclinic clinochlore has been refined in space group C 1&macr; from 4282 unique X-ray intensity measurements of which 3833 are greater than 3 times the statistical counting error (3&sigma;). Unit cell parameters are a = 5.3262(6) Å; b = 9.226(1) Å; c = 14.334(3) Å; &alpha; = 90.56(2)&deg;; &beta; = 97.47(2)&deg;; and &gamma; = 89.979(9)&deg;, which represents the greatest deviation from monoclinic symmetry yet recorded for a triclinic chlorite. The final weighted R is 0.059 for reflections with I > 3&sigma; and 0.064 for all reflections. The chemical formula is (Mg 0.966 Fe 0.034 ) M1 (Mg 0.962 Fe 0.038 ) M2 2 (Si 2.96 Al 1.04 )O 10 (OH) 2 (Mg 0.996 Fe 0.004 ) M3 2 (Al 0.841 Fe III 0.102 Cr 0.004 Ti 0.004 ) M4 (OH) 6 , which is consistent with electron microprobe (EMP), wet chemical analyses, M&ouml;ssbauer spectroscopy and X-ray structure refinement. The high degree of ordering of the divalent versus trivalent octahedral cations in the interlayer is noteworthy, with Fe III and Al in M4 and virtually no Fe in M3. In the 2:1 layer, M1 and M2 each contain similar amounts of Fe. The 2 tetrahedral sites have nearly identical mean oxygen distances and volumes, and thus show no evidence of long-range cation ordering.

Clays and Clay Minerals

Effects of exchanged cation and layer charge on the sorption of water and EGME vapors on montmorillonite clays

The effects of exchanged cation and layer charge on the sorption of water and ethylene glycol monoethyl ether (EGME) vapors on montmorillonite have been studied on SAz-1 and SWy-1 source clays, each exchanged respectively with Ca, Na, K, Cs and tetramethylammonium (TMA) cations. The corresponding lattice expansions were also determined, and the corresponding N 2 adsorption data were provided for comparison. For clays exchanged with cations of low hydrating powers (such as K, Cs and TMA), water shows a notably lower uptake than does N 2 at low relative pressures ( P/P 0 ). By contrast, EGME shows higher uptakes than N 2 on all exchanged clays at all P/P 0 . The anomaly for water is attributed to its relatively low attraction for siloxane surfaces of montmorillonite because of its high cohesive energy density. In addition to solvating cations and expanding interlayers, water and EGME vapors condense into small clay pores and interlayer voids created by interlayer expansion. The initial (dry) interlayer separation varies more significantly with cation type than with layer charge; the water-saturated interlayer separation varies more with cation type than the EGME-saturated interlayer separation. Because of the differences in surface adsorption and interlayer expansion for water and EGME, no general correspondence is found between the isotherms of water and EGME on exchanged clays, nor is a simple relation observed between the overall uptake of either vapor and the cation solvating power. The excess interlayer capacities of water and of EGME that result from lattice expansion of the exchanged clays are estimated by correcting for amounts of vapor adsorption on planar clay surfaces and of vapor condensation into intrinsic clay pores. The resulting data follow more closely the relative solvating powers of the exchanged cations.

Clays and Clay Minerals

Measurement of fundamental illite particle thicknesses by X-ray diffraction using PVP-10 intercalation

The thicknesses of fundamental illite particles that compose mixed-layer illite-smectite (I-S) crystals can be measured by X-ray diffraction (XRD) peak broadening techniques (Bertaut-Warren-Averbach [BWA] method and integral peak-width method) if the effects of swelling and XRD background noise are eliminated from XRD patterns of the clays. Swelling is eliminated by intercalating Na-saturated I-S with polyvinylpyrrolidone having a molecular weight of 10,000 (PVP-10). Background is minimized by using polished metallic silicon wafers cut perpendicular to (100) as a substrate for XRD specimens, and by using a single-crystal monochromator. XRD measurements of PVP-intercalated diagenetic, hydrothermal and low-grade metamorphic I-S indicate that there are at least 2 types of crystallite thickness distribution shapes for illite fundamental particles, lognormal and asymptotic; that measurements of mean fundamental illite particle thicknesses made by various techniques (Bertant-Warren-Averbach, integral peak width, fixed cation content, and transmission electron microscopy [TEM]) give comparable results; and that strain (small differences in layer thicknesses) generally has a Gaussian distribution in the log-normal-type illites, but is often absent in the asymptotic-type illites.

Clays and Clay Minerals

Ordovician and Pennsylvanian berthierine-bearing flint clays

We report here the first occurrence of berthierine-bearing flint clays, one Ordovician and one Pennsylvanian in age. They are characterized by a berthierine-kaolinite-boehmite (bkb) assemblage. The Pennsylvanian flint clay from northeastern Kentucky is more typical in that it occurs in association with coal measures. The Ordovician occurrence from northwestern Illinois is the oldest flint clay of which we are aware. Because it is Ordovician, it formed before the evolution of terrestrial vascular plants. All previous reports of flint clays point to a genetic connection between flint-clay formation and the growth and decay of plants (Bohor and Triplehorn, 1993). Except for the high berthierine content and greenish color, the physical properties of this flint clay are similar to those of other kaolinitic flint clays. Some samples of the Ordovician flint clay are nearly pure berthierine.

Clays and Clay Minerals

Characterization of microbially Fe(III)-reduced nontronite: Environmental cell-transmission electron microscopy study

Microstructural changes induced by the microbial reduction of Fe(III) in nontronite by Shewanella oneidensis were studied using environmental cell (EC)-transmission electron microscopy (TEM), conventional TEM, and X-ray powder diffraction (XRD). Direct observations of clays by EC-TEM in their hydrated state allowed for the first time an accurate and unambiguous TEM measurement of basal layer spacings and the contraction of layer spacing caused by microbial effects, most likely those of Fe(III) reduction. Non-reduced and Fe(III)-reduced nontronite, observed by EC-TEM, exhibited fringes with mean d 001 spacings of 1.50 nm (standard deviation, σ = 0.08 nm) and 1.26 nm (σ = 0.10 nm), respectively. In comparison, the same samples embedded with Nanoplast resin, sectioned by microtome, and observed using conventional TEM, displayed layer spacings of 1.0–1.1 nm (non-reduced) and 1.0 nm (reduced). The results from Nanoplast-embedded samples are typical of conventional TEM studies, which have measured nearly identical layer spacings regardless of Fe oxidation state. Following Fe(III) reduction, both EC- and conventional TEM showed an increase in the order of nontronite selected area electron diffraction patterns while the images exhibited fewer wavy fringes and fewer layer terminations. An increase in stacking order in reduced nontronite was also suggested by XRD measurements. In particular, the ratio of the valley to peak intensity ( v/p ) of the 1.7 nm basal 001 peak of ethylene glycolated nontronite was measured at 0.65 (non-reduced) and 0.85 (microbially reduced).

Clays and Clay Minerals

Thickness distributions and evolution of growth mechanisms of NH4-illite from the fossil hydrothermal system of Harghita Bai, Eastern Carpathians, Romania

The crystal growth of NH 4 -illite (NH 4 -I) from the hydrothermal system of Harghita Bãi (Eastern Carpathians) was deduced from the shapes of crystal thickness distributions (CTDs). The 4-illite-smectite (I-S) interstratified structures (R1, R2, and R3-type ordering) with a variable smectite-layer content. The NH 4 -I-S (40–5% S) structures were identified underground in a hydrothermal breccia structure, whereas the K-I/NH 4 -I mixtures were found at the deepest level sampled (−110 m). The percentage of smectite interlayers generally decreases with increasing depth in the deposit. This decrease in smectite content is related to the increase in degree of fracturing in the breccia structure and corresponds to a general increase in mean illite crystal thickness. In order to determine the thickness distributions of NH 4 -I crystals (fundamental illite particles) which make up the NH 4 -I-S interstratified structures and the NH 4, -I/K-I mixtures, 27 samples were saturated with Li + and aqueous solutions of PVP-10 to remove swelling and then were analyzed by X-ray diffraction. The profiles for the mean crystallite thickness (T mean ) and crystallite thickness distribution (CTD) of NH 4 -I crystallites were determined by the Bertaut-Warren-Averbach method using the MudMaster computer code. The T mean of NH 4 -I from NH 4 -I-S samples ranges from 3.4 to 7.8 nm. The T mean measured for the NH 4 -I/K-I mixture phase ranges from 7.8 nm to 11.7 nm (NH 4 -I) and from 12.1 to 24.7 nm (K-I). The CTD shapes of NH 4 -I fundamental particles are asymptotic and lognormal, whereas illites from NH 4 -I/K-I mixtures have bimodal shapes related to the presence of two lognormal-like CTDs corresponding to NH 4 -I and K-I. The crystal-growth mechanism for NH 4 -I samples was simulated using the Galoper code. Reaction pathways for NH 4 -I crystal nucleation and growth could be determined for each sample by plotting their CTD parameters on an α–β 2 diagram constructed using Galoper . This analysis shows that NH 4 -I crystals underwent simultaneous nucleation and growth, followed by surface-controlled growth without simultaneous nucleation.

Harghita Bai

Stable isotope and chemical relations during mineralization in the Bodie mining district, Mono County, California

Stable isotope and chemical relations have been determined in a typical epithermal Au-Ag deposit located in the Bodie mining district of California. Analyses were made of altered host rocks, vein minerals, alteration clays, fluid inclusions, modern spring waters, and unaltered rocks of the area.The results indicate that a hydrothermal convection system was set up by the interaction of a cooling shallow intrusion and local meteoric water. The water traveled to depth where it picked up ore constituents and SiO 2 , K, and Rb, without significant shifts in the stable isotope ratios of the water. The altered rocks have equilibrated to various degrees with an ore fluid of constant K/Rb, O 18 /O 16 and D/H ratios. Deposition of ore took place over the approximate temperature range 215 degrees -245 degrees . From C 13 /C 12 ratios of minor calcite, a volcanic source of CO 2 is postulated. The chemical and isotope composition of the ore fluid is strikingly similar to that of modern spring waters in the area.All ore deposition at Bodie took place from essentially isotopically unaltered ground water with delta O 18 = -13ppm and delta D = -98ppm.

California

Insight into the geology of the East Antarctic hinterland: a study of sediment inclusions from ice cores of the Lake Vostok borehole

The borehole at the southern part of subglacial Lake Vostok has been drilled into an ice layer that has been refrozen from the lake water. This ice layer contains random sediment inclusions, eight of which have been studied using state-of the-art analytical techniques. Six inclusions comprise soft aggregates consisting mainly of clay-mica minerals and micron-sized quartz grains while two others are solid clasts of fine-grained cemented rocks. The largest rock clast consists of poorly-rounded quartz and minor amounts of accessory minerals and is classified as quartzose siltstone. More than twenty grains of zircon and monazite have been identified in this siltstone and dated by SIMS SHRIMP-II. Two age clusters have been recognized for these detrital grains, in the ranges 0.8−1.2 Ga and 1.6−1.8 Ga. The compositions of the rock clasts suggest that the bedrock situated to the west of Lake Vostok is sedimentary. The age data on the detrital accessory minerals suggest that the provenance of these sedimentary rocks − the Gamburtsev Mountains and Vostok Subglacial Highlands, is mainly represented by Paleoproterozoic and MesoproterozoicNeoproterozoic crustal provinces

Open-File Report

Summary of the Oahu, Hawaii, regional aquifer-system analysis

Oahu, the third largest of the Hawaiian islands, is formed by the eroded remnants of two elongated shield volcanoes with broad, low profiles. Weathering and erosion have modified the original domed surfaces of the volcanoes, leaving a landscape of deep valleys and steep interfluvial ridges in the interior highlands. The Koolau Range in eastern Oahu and the Waianae Range in western Oahu are the eroded remnants of the Koolau and Waianae Volcanoes. The origin, mode of emplacement, texture, and composition of the rocks of Oahu affect their ability to store and transmit water. The volcanic rocks are divided into four groups: (1) lava flows, (2) dikes, (3) pyroclastic deposits, and (4) saprolite and weathered basalt. Stratified sequences of thin-bedded lava flows form the most productive aquifers in Hawaii. Dikes are near-vertical sheets of massive intrusive rock that typically contain only fracture permeability. Pyroclastic deposits include ash, cinder, and spatter; they are essentially granular, with porosity and permeability similar to those of granular sediments. Weathering of basaltic rocks in the humid, subtropical climate of Oahu alters igneous minerals to clays and oxides, reducing the permeability of the parent rock. Saprolite is weathered material that has retained textural features of the parent rock. Estimates of hydraulic conductivity along the plane of dike-free lava flows tend to fall within about one order of magnitude, from about 500 to about 5,000 feet per day. Estimates of specific yield range from about 1 to 20 percent; most of the values lie within a narrow range of about 5 to 10 percent. The occurrence of ground water on Oahu is determined by the type and character of the rocks and by the presence of geohydrologic barriers. The primary modes of freshwater occurrence on Oahu are as a basal lens of fresh ground water floating on saltwater, as dike-impounded ground water, and as perched ground water. Saltwater occurs at depth throughout much of the island. A regional aquifer system composed of the Waianae aquifer in the Waianae Volcanics and the Koolau aquifer in the Koolau Basalt is subdivided into well-defined areas by geohydrologic barriers. The aquifers are separated by the Waianae confining unit formed by weathering along the Waianae-Koolau unconformity. In some coastal areas, a caprock of sedimentary deposits overlies and confines the aquifers. The island of Oahu has been divided into seven major ground-water areas delineated by deep-seated structural geohydrologic barriers; these areas are further subdivided by shallower internal barriers to ground-water flow. The Koolau rift zone along the eastern (windward) side of the island and the Waianae rift zone to the west (Waianae area) constitute two of the major ground-water areas. North-central Oahu is divided into three smaller ground-water areas, Mokuleia, Waialua, and Kawailoa. The Schofield ground-water area encompasses much of the Schofield Plateau of central Oahu. Southern Oahu is divided into six areas, Ewa, Pearl Harbor, Moanalua, Kalihi, Beretania, and Kaimuki. Southeastern Oahu is divided into the Waialae and Wailupe-Hawaii Kai areas. Along the northeast coast of windward Oahu is the Kahuku ground-water area. The aquifers of Oahu contain shallow freshwater and deeper saltwater flow systems. There are five fresh ground-water flow systems: meteoric freshwater flow diverges from ground-water divides that lie somewhere within the Waianae and Koolau rift zones, forming an interior flow system in central Oahu (which is divided into the northern and southern Oahu flow systems) and exterior flow systems in western (Waianae area) Oahu, eastern (windward) Oahu, and southeastern Oahu. Development of the ground-water resources on Oahu began when the first well was drilled near Honouliuli in the summer of 1879. By 1890, 86 wells had been drilled on the island. From about 1891 to about 1910, development increased rapidly with the drilling of a

Hawaii

Evaluation of salinity and nutrient conditions in the Heart River Basin, North Dakota, 1970–2020

The Heart River Basin is predominantly an agricultural basin in western North Dakota and is approximately 3,350 square miles. The U.S. Geological Survey, in cooperation with the U.S. Department of Agriculture Natural Resources Conservation Service and the Grant County Soil Conservation District, completed a study to assess spatial and temporal patterns of water quality in the Heart River Basin. The purpose of this report is to describe the methods and results of a study to evaluate salinity and nutrients in the Heart River Basin in western North Dakota. Water-quality and streamflow data used in the study were compiled from 1970 to 2020 using the National Water Quality Monitoring Council Water Quality Portal and National Water Information System. Changes in streamflow characteristics were investigated at three sites from 1970 to 2020, and changes in water quality were investigated at four sites from 1974 to 2019. Streamflow analysis indicated decreasing streamflow from 1970 until the late 1990s followed by increasing streamflow through 2020, with the largest increase in the 7-day minimum streamflow or base flow. For the historical water-quality trend period (1974–2019), total dissolved solids, sulfate, sodium, chloride, and sodium adsorption ratio concentrations have increased since the mid-1970s through 2019. Potassium concentrations during the historical period remained mostly constant with some small fluctuations. Calcium and magnesium concentrations increased since the mid-1970s at all sites, except for a decrease at one site between 1974 and 1999. During the recent trend period (1999–2019), increasing concentrations in total dissolved solids, sulfate, sodium, chloride, calcium, magnesium, and sodium adsorption ratios were observed across the Heart River Basin. The magnitude of the increases was smaller at tributary sites compared to main-stem sites. During the recent period, potassium was mostly constant, although small (−0.9 milligram per liter or less) decreases on tributaries and minor (1.3 milligrams per liter) increases on the main-stem sites were detected. Unlike dissolved ion concentrations, significant increases in nutrient concentrations were not detected from 1999 to 2019, but nitrate plus nitrite concentrations most likely decreased upstream from Lake Tschida. Inverse modeling for period 1 (1974–99) in model zone 1 (Heart River reach from site 5 to site 6) had eight reasonable models that indicated the clay mineral-water interactions and dissolution of evaporites control the geochemistry. Results of the inverse modeling for period 2 (1999–2019) in model zone 1 also had eight reasonable models that indicated that the dissolution of evaporites was the major geochemical control. Results of the geochemical modeling for period 1 (1974–99) in model zone 2 (Heart River and Sweetbriar Creek reach from sites 20 and 21 to site 22) produced seven reasonable models, and the geochemical control of the system was the dissolution of sulfate evaporite minerals. Geochemical modeling results for period 2 (1999–2019) in model zone 2 produced 11 reasonable models and was also controlled by the dissolution of sulfate evaporite minerals. Differences between the two model zones indicated that geology controls some of the water-quality changes in the Heart River Basin. Loads were estimated for total dissolved solids, sulfate, sodium, and chloride and total phosphorus. Annual loads estimated for the Heart River from 2013 through 2020 at the Heart River site upstream from Lake Tschida (site 5) and near Mandan (site 22) were generally greatest in 2014 and least in 2016 for total dissolved solids, sulfate, sodium, and chloride. Most of the annual loads of total dissolved solids, sulfate, sodium, and chloride are delivered in March through July in the Heart River at these sites and are likely from snowmelt and spring and summer rains. The mean annual yields of total dissolved solids and sodium from 2013 to 2020 generally were largest in Big Muddy Creek (site 18), whereas yields of sulfate and chloride were largest at Sweetbriar Creek (site 21) compared to the other selected sites in the Heart River Basin. Larger yields of total dissolved solids, sulfate, sodium, and chloride at sites located on Big Muddy Creek and Sweet Briar Creek in the lower Heart River Basin were likely a result of differences in geology and soils upstream from the selected sites. A mass balance of total dissolved solids, sulfate, sodium, and chloride was estimated for the lower Heart River Basin, specifically the reach below Lake Tschida to Mandan (site 7 to site 22). Intervening flow was the largest contributor to the dissolved ion loads in the lower Heart River Basin and is an important part of understanding the transport of dissolved ions in the basin. The intervening load can include groundwater discharge, irrigation return flow, local runoff, and input from smaller ephemeral tributaries. Tributaries in the lower Heart River Basin contributed portions of the total dissolved solids, sulfate, sodium, and chloride loads at the Heart River near Mandan (site 22) that generally were proportional to the streamflow contributions. Annual loads for total phosphorus between 2013 and 2020 at the Heart River site upstream from Lake Tschida (site 5) and near Mandan (site 22) generally were largest in 2019 and smallest in 2016. Most of the total phosphorus loads for main-stem sites 5 and 22 were transported in March, April, and June, likely from snowmelt and early summer rains. The mean annual yields of total phosphorus for 2013–20 were largest on the main-stem site upstream from Lake Tschida (site 5) and Sweetbriar Creek (site 21), whereas the smallest yields were in Big Muddy Creek (site 18). Much of the phosphorus that enters Lake Tschida from the upper basin does not get transported downstream to the lower basin, and much of the phosphorus in the lower basin was attributed to intervening flow.

North Dakota

Mineral-produced high-pressure striae and clay polish: Key evidence for nonballistic transport of ejecta from Ries crater

Recently discovered mineral-produced, deeply incised striae and mirror-like polish on broken surfaces of limestone fragments from the sedimentary ejecta of the Ries impact crater of southern Germany are described. The striae and polish were produced under high confining pressures during high-velocity nonballistic transport of the ejecta mass within the time span of the cratering event (measured in terms of seconds). The striae on these fragments were produced by scouring by small mineral grains embedded in the surrounding clay matrix, and the polish was formed under the same condition, by movements of relatively fragment-free clay against the fragment surfaces. The occurrence of these striae and polish is key evidence for estimating the distribution and determining the relative importance of nonballistic and ballistic transport of ejecta from the shallow Ries stony meteorite impact crater.

southern Germany