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Systematic variation of rare earths in monazite

Ten monazites from widely scattered localities have been analyzed for La, Ce, Pr, Nd, Sm, Gd, Y and Th by means of a combined chemical and emission spectrographic method. The analytical results, calculated to atomic percent of total rare earths (thorium excluded), show a considerable variation in the proportions of every element except praseodymium, which is relatively constant. The general variation trends of the elements may be calculated by assuming that the monazites represent different stages in a fractional precipitation process, and by assuming that there is a gradational increase in the precipitability of rare earth elements with decreasing ionic radius. Fractional precipitation brings about an increase in lanthanum and cerium, little change in praseodymium, and a decrease in neodymium, samarium, gadolinium, and yttrium. Deviations from the calculated lines of variation consist of a simultaneous, abnormal increase or decrease in the proportions of cerium, praseodymium, and neodymium with antipathetic decrease or increase in the proportions of the other elements. These deviations are ascribed to abnormally high or low temperatures that affect the precipitability of the central trio of elements (Ce, Pr, Nd) relatively more than that of the other elements. The following semiquantitative rules have been found useful in describing the composition of rare earths from monazite: 1. The sum of lanthanum and neodymium is very nearly a constant at 42 ± 2 atomic percent. 2. Praseodymium is very nearly constant at 5 ± 1 atomic percent. 3. The sum of Ce, Sm, Gd, and Y is very nearly a constant at 53 ± 3 atomic percent. No correlation could be established between the content of Th and that of any of the rare earth elements.

Geochimica et Cosmochimica Acta↗

Characterizing coal beds in western Kentucky with the Al-La-Sc coherent triad

Cyclic sedimentation and lateral facies changes make coal bed correlations inconclusive and difficult. This uncertainty can be further complicated if a coal basin has been structurally deformed. Coal macerals can be studied to indicate the nature and degree of coalification. Their use in coal bed correlation, however, is limited. Most of the trace elements and their ratios that have been studied show significant within-bed lateral and stratigraphic variations, and thus are not effective in correlating coal beds regionally. Geochemically coherent groups of elements, such as rare earth elements (REE) and platinum group elements (PGE), appear to be highly differentiated in coal-forming environments. Geochemical coherent elemental triads appear to be useful for coal bed identification or fingerprinting. The best triad which was demonstrated to be effective in coal bed characterization in western Kentucky, is that of Al, La and Sc. These three elements are highly correlated with one another and they can be determined accurately and simultaneously with instrumental neutron activation analysis (INAA). The elemental triad Al-La-Sc is used to identify and fingerprint three key coal beds in western Kentucky: the Springfield (western Kentucky No. 9), the Davis (western Kentucky No. 6), and the Mining City and Dawson Springs are both considered to be the No. 4 coal bed in western Kentucky). Four distinct groupings can be recognized by use of the Al-La-Sc triad. The Dawson Springs coals have the highest Al/(La + Sc) ratios, followed by the Springfield, the Davis and the Mining City. The Mining City coal bed generally has the highest La/Sc ratio. However, the Dawson Springs is not correlated with the Mining City using the triad analysis, even though they have reportedly similar stratigraphic positions in the western Kentucky coal basin. The Al-La-Sc triad appears to be effective in discriminating between the Springfield and the Davis coal beds throughout the entire Illinois Basin. Furthermore, the range of concentration variation of the AL-La-Sc triad suggests individual groupings of the No. 4 coal in western Kentucky. In addition to characterizing these coal beds, the Al-La-Sc triad may be used to confirm stratigraphic correlations.

International Journal of Coal Geology↗

Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii

Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35??years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9??wt.%, with temperatures prior to quench ranging from 1140????C to ambient (110????C). Five eruption samples were also analyzed. Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006-1.40??ppb for Os and 0.0006-2.01??ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF6 in some of the most magnesian samples. Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values in both eruption and lava lake samples suggest the presence of unevenly distributed, unidentified Pt-rich trace phases in some Kilauea Iki materials. Estimated mineral (olivine + chromite)/melt D values for Os, Ir, Ru and Pt for equilibrium crystallization for samples from ~ 7 to 27??wt.% MgO are 26, 8.2, 19 and 0.55, respectively. These Os, Ir and Ru estimates are somewhat higher than previous estimates for similar systems. If fractional crystallization is instead assumed, D values are much more similar. Results confirm many prior observations in other mafic systems that olivine (together with included phases) has a major effect on absolute and relative abundances of Re and the PGE. The relatively linear correlations between these elements and MgO potentially permit accurate estimation of the concentrations of these elements in the primary melts of comparable systems, especially in instances where the MgO content of the primary melt is well constrained. ?? 2008 Elsevier B.V.

Chemical Geology↗

Geochemistry and radiogenic isotopes constrain the mantle source region of the Mountain Pass Intrusive Suite, California

The Mountain Pass carbonatite stock is the largest rare earth element (REE) deposit and only active REE mine in the United States. The carbonatite intrusion and spatially associated alkaline silicate intrusions constitute the Mountain Pass Intrusive Suite, which is located within the Mojave Province in California. Both the carbonatite and the alkaline silicate rocks are enriched in large ion lithophile elements and light REEs, and less enriched to depleted in high field strength elements, indicating the mantle source region was metasomatically enriched in incompatible trace elements. The cause of this metasomatic mantle enrichment and the genetic relationship between the carbonatite and the alkaline silicate stocks are poorly understood. In this study, major and trace element geochemical data and isotopic (Rb-Sr, Sm-Nd, and Lu-Hf) data are presented to constrain genesis of the Mountain Pass Intrusive Suite, from mantle source region to the intrusion of the stocks. Our geochemical data are consistent with derivation of the alkaline silicate and carbonatite melts through partial melting from a shared mantle source region rather than through liquid immiscibility or fractional crystallization and separation of a carbothermal fluid. Although the Rb-Sr isotopic system in the Mountain Pass Intrusive Suite is disturbed at the whole-rock scale, the isotopic systems for whole-rock Sm-Nd (εNd i = ‐2.2 ± 0.8) and zircon Lu-Hf (εHf i = 0.1 ± 1.1) are robust and support mantle derivation of the magmas. Geochemical modeling using experimentally derived partition coefficients was used to identify possible causes of enrichment in incompatible elements through metasomatism in the mantle source region. Modeling of metasomatism by melts derived by partial melting of deeply subducted carbonated sediments approximates observed Mountain Pass Intrusive Suite trace element chemistry. Scattered εHf i in inherited zircon (2.8 ± 2.6) is consistent with derivation from an arc-related environment with substantial crustal contamination. Paleotectonic studies in the Mojave Province indicate that regional subduction preceded emplacement of the Mountain Pass Intrusive Suite by ∼300 Ma. Melting of the Mountain Pass source region may have been caused by post-collisional thermal relaxation and extension.

California↗

The geochemical and magnetic record of coal combustion products in West Virginia reservoir sediments and soils

Western West Virginia lies downwind from numerous coal-fired power plants along the Ohio River Valley. To test whether geochemical and mineralogical impacts from these power plants are detectable on the West Virginia landscape, we obtained reservoir cores, soils, and rocks from two separate sites in West Virginia, one in Harrison County (Hinkel and Deegan Reservoirs) and the other in Roane County (Miletree Run Reservoir). Both have small drainage basins that have the effect of maximizing atmospheric inputs relative to weathering inputs. Sediments from Hinkel Reservoir were dated using the 137 Cs method, and by knowledge of the age of the base of the sedimentary section. Major elements in Hinkel Reservoir sediments do not vary systematically over time, suggesting that the depositional history of these sediments has been relatively constant. In contrast, minor elements and sulfur do show dramatic shifts. Zn, Pb, As, S, Cd, Ge, and Hg all peak during the late 1960s and early 1970s. Polyaromatic hydrocarbons associated with combustion processes likewise show this same behavior. Coincident with these maxima is a peak in isothermal remnant magnetization (IRM), a parameter that is proportional to magnetite abundance. We separated the magnetic fraction of the sediments and examined this fraction petrographically. It is dominated by magnetite with a spherical morphology, which is characteristic of magnetite produced by combustion processes. Chemical analyses on local rocks showed that they were not the likely source for the trace element and magnetite enrichments. To compare soils and reservoir sediments, we normalized geochemical data to Ti; the underlying assumption is that Ti will track physical inputs of soil materials into the reservoir sediments. The normalized sediment data for the elements Zn, Pb, As, and S are all higher for sediments deposited during the late 1960s and early 1970s compared to normalized soil data, implying that soils are not the source for the element enrichments. We thus attribute the enrichment to atmospheric inputs. However, a coal-burning zinc smelter within 10 km of the reservoir site that operated until 1971 may have supplied some or all of the anomalous input: There are no nearby major atmospheric pollution sites near Miletree Run Reservoir. A core from this reservoir was dated based on knowledge of the time it was impounded. Like Hinkel Reservoir, there are no systematic shifts in major element contents over its depositional history. Like Hinkel Reservoir, there are also significant shifts in trace elements and IRM that cannot be explained by local soil sources. Magnetic separates from this reservoir are also dominated by spherical combustion-produced magnetite. Covariance over the period 1930-1980 between magnetite and sulfur with US SO 2 production (which comes dominantly from coal combustion) is strongly suggestive of a significant atmospheric input into Miletree Run Reservoir sediments. The nearest upwind power plants are between 50 and 75 km distant. Thus, relatively long distance transmission of particulate matter from the power plants of the Ohio River Valley is likely in this case.

West Virginia↗

Pillow basalts of the Angayucham terrane: Oceanic plateau and island crust accreted to the Brooks Range

The Angayucham Mountains (north margin of the Yukon-Koyukuk province) are made up of an imbricate stack of four to eight east-west trending, steeply dipping, fault slabs composed of Paleozoic (Devonian to Mississippean), Middle to Late Triassic, and Early Jurassic oceanic upper crustal rocks (pillow basalt, subordinate diabase, basaltic tuff, and radiolarian chert). Field relations and geochemical characteristics of the basaltic rocks suggest that the fault slabs were derived from an oceanic plateau or island setting and were emplaced onto the Brooks Range continental margin. The basalts are variably metamorphosed to prehnite-pumpellyite and low-greenschist facies. Major element analyses suggest that many are hypersthene-normative olivine tholeiites. Classification based on immobile trace elements confirms the tholeiitic character of most of the basalts but suggests that some had primary compositions transitional to alkali basalt. Although field and petrographic features of the basalts are similar, trace element characteristics allow definition of geographically distinct suites. A central outcrop belt along the crest of the mountains is made up of basalt with relatively flat rare earth element (REE) patterns. This belt is flanked to the north and south by LREE (light rare earth element)-enriched basalts. Radiolarian and conodont ages from interpillow and interlayered chert and limestone indicate that the central belt of basalts is Triassic in age, the southern belt is Jurassic in age, and the northern belt contains a mixture of Paleozoic and Mesozoic ages. Data for most of the basalts cluster in the “within-plate basalt” fields of trace element discriminant diagrams; none have trace-element characteristics of island arc basalt. The Triassic and Jurassic basalts are geochemically most akin to modern oceanic plateau and island basalts. Field evidence also favors an oceanic plateau or island setting. The great composite thickness of pillow basalt probably resulted from obduction faulting, but the lack of fault slabs of gabbro or peridotite suggests that obduction faults did not penetrate below oceanic layer 2, a likely occurrence if layer 2 were anomalously thick, as in the vicinity of an oceanic island. The presence of basaltic tuff interbeds indicates proximity to an explosive basaltic eruptive center. The juxtaposition of submarine basalts of differing chemical affinity and age, adjacent to higher-grade Paleozoic metamorphic rocks of the Brooks Range to the north, may be explained by obduction of internally complex (thickened) oceanic crust formed in an ocean plateau setting. Emplacement and rotation of thrust plates to steep attitudes occurred during accretion of the Brooks Range passive margin, probably beginning in the Late to Middle Jurassic.

Journal of Geophysical Research Solid Earth↗

Some thoughts on problems associated with various sampling media used for environmental monitoring

Modern analytical instrumentation is capable of measuring a variety of trace elements at concentrations down into the single or double digit parts-per-trillion (ng l-1) range. This holds for the three most common sample media currently used in environmental monitoring programs: filtered water, whole-water and separated suspended sediment. Unfortunately, current analytical capabilities have exceeded the current capacity to collect both uncontaminated and representative environmental samples. The success of any trace element monitoring program requires that this issue be both understood and addressed. The environmental monitoring of trace elements requires the collection of calendar- and event-based dissolved and suspended sediment samples. There are unique problems associated with the collection and chemical analyses of both types of sample media. Over the past 10 years, reported ambient dissolved trace element concentrations have declined. Generally, these decreases do not reflect better water quality, but rather improvements in the procedures used to collect, process, preserve and analyze these samples without contaminating them during these steps. Further, recent studies have shown that the currently accepted operational definition of dissolved constituents (material passing a 0.45 ??m membrane filter) is inadequat owing to sampling and processing artifacts. The existence of these artifacts raises questions about the generation of accurate, precise and comparable 'dissolved' trace element data. Suspended sediment and associated trace elements can display marked short- and long-term spatial and temporal variability. This implies that spatially representative samples only can be obtained by generating composites using depth- and width-integrated sampling techniques. Additionally, temporal variations have led to the view that the determination of annual trace element fluxes may require nearly constant (e.g., high-frequency) sampling and subsequent chemical analyses. Ultimately, sampling frequency for flux estimates becomes dependent on the time period of concern (daily, weekly, monthly, yearly) and the amount of acceptable error associated with these estimates.

Conference Paper↗

Analysis of trace metals in water by inductively coupled plasma emission spectrometry using sodium dibenzyldithiocarbamate for preconcentration

Since concentrations of trace elements in most natural waters seldom exceed the μg/L level, analysis of trace elements in natural waters by inductively coupled plasma emission spectrometry (ICP) requires a preconcentration procedure. The elements Ag, Bi, Cd, Co, Cu, Fe, Mo, Ni, Pb, Sn, V, W, and Zn were separated and concentrated from 500 mL of water by coprecipitating them with sodium dibenzyldithiocarbamate (NaDBDTC) using nickel or silver as a carrier. The precipitated trace elements were collected on a membrance filter, redissolved from the filter with hot nitric and hydrochloric acids, and analyzed using ICP. Recoveries for all the trace elements except tungsten exceeded 80%. Coprecipitation of trace elements with NaDBDTC eliminated the use of difficult-to-inject organic solvents, and NaDBDTC coprecipitated a wider array of trace elements than ammoniumpyrrolidinedithiocarbamate (APDC), another commonly used coprecipitate.

Analytical Letters↗

Geochemistry of oceanic igneous rocks - Ridges, islands, and arcs - With emphasis on manganese, scandium, and vanadium

A database on a number of elements in oceanic volcanic rocks is presented, including the principal major-element oxides-SiO 2 , TiO 2 , Al 2 O 3 , Fe 2 O 3 (T), MnO, MgO, CaO, Na 2 O, K 2 O, and P 2 O 5 (where T refers to total iron)–and the trace elements–Ba, Ce, Cr, Cu, Ni, Sc, Sr, V, Pb (mainly by isotope dilution), Yb, Zn, and Zr. Interpretations are given for transition metals, with emphasis on Mn, Sc, and V, in order to determine the concentration of the elements in primitive melts and assess their trends in magmatic differentiation. Transition metals are not enriched in plagioclase, so all are incompatible with pure plagioclase removal–that is, they become enriched in the melt. Both Cr and Ni are known to be highly compatible with olivine separation-i.e., they are depleted in the melt early in differentiation. Also, Sc is compatible with clinopyroxene (Cpx) removal from the melt and is depleted by separation of Cpx. Copper does not fit well in any of the principal silicates, but Cu, like Ni, is greatly enriched in sulfides that may remain in the source or separate from the magma. Decreasing Ni abundances and increasing Cu contents during differentiation are a sign of olivine separation. In the analysis presented herein, V–in the absence of Cpx separation–is found to behave remarkably like the moderately incompatible element Zn, and these two elements add to the list of element pairs of similar incompatibility whose ratios are insensitive to differentiation and to submarine weathering as well. Both are enhanced in titanomagnetite, so both would be compatible during titanomagnetite separation. When Cpx separates, however, V becomes compatible like Sc, but Zn remains incompatible. Thus, decreasing V (and Sc) contents and increasing Zn contents during differentiation are a sign of Cpx separation. Manganese often behaves much like Zn and therefore is moderately incompatible, but Mn is less compatible than Zn and V in titanomagnetite. Thus, decreasing Zn and V with increasing Mn is an indication of titanomagnetite removal. Dual compatible and incompatible trends with differentiation are found chiefly for Cu, Sc, and Sr. Distinguishing mid-ocean ridge basalts (MORB), oceanic-island volcanic rocks (OIV), and island-arc volcanic rocks (IAV) may be accomplished by plots of Ce/Yb versus Ba/Ce, where OIV plot to higher values of Ce/Yb than do MORB, and IAV data plot to higher values of Ba/Ce than do those of MORB. These ratios do not seem to be significantly affected by submarine weathering.

International Geology Review↗

Origin and geochemistry of Cretaceous deep-sea black shales and multicolored claystones, with emphasis on Deep Sea Drilling Project Site 530, southern Angola Basin

Deep-water sedimentary sequences of mid-Cretaceous age, rich in organic carbon, have been recovered at many DSDP sites in the Atlantic Ocean. Most of these sequences have a marked cyclicity in amount of organic carbon resulting in interbedded multicolored shale, marlstone, and (or) limestone that have cycle periods of 20,000 to 100,000 years and average 40,000 to 50,000 years. These cycles may be related to some climatic control on influx of terrigenous organic matter and sediment, rates of upwelling and sea-surface production of organic matter, and preservation of organic matter related to deeper-water dissolved oxygen concentration. These variations in supply of organic matter had pronounced effects on the potential of the sediment for subsequent diagenetic changes and geochemical partitioning in adjacent beds. Many trace elements are enriched in organic-carbon-rich lithologies relative to interbedded organic-carbon-poor lithologies. Elements that are most commonly enriched are Cr, Ni, V, Cu, Zn, and Mo. The association of high traceelement concentrations with organic matter may be the result of concentration of these elements by organisms or by chemical sorption and precipitation processes under anoxic conditions. Detailed trace-element profiles from organiccarbon-rich strata at Site 530 suggest that there may be differential mobility of trace elements, with diffusion of some elements over distances of at least tens of meters. The sequence of trace-element mobility, from highest to lowest, is approximately Ba, Mn, Pb, Ni, Co, Cr, Cu, Zn, V, Cd, and Mo. Slowly deposited, oxidized clays directly overlying some black shale sequences are enriched in some metals, particularly Fe, Mn, Zn, and Cu, relative to normal pelagic clays, and this enrichment may be the result of upward migration of metals in pore waters during compaction or diffusion from the underlying black shale. Most depositional models that have been used to explain the accumulation of the organic-carbon-rich strata imply that reducing conditions in the sediments (and therefore the increased degree of preservation of organic matter) were the result of anoxic or near-anoxic conditions in oceanic bottom waters, or in a midwater oxygen-minimum zone. Evidence from several DSDP sites in the Atlantic, however, indicate that some of these middle Cretaceous "black shale" beds may be the result of variations in rate of supply of organic matter that produced anoxia or near-anoxia within midwater oxygen-minimum zones and possibly, under extreme conditions, throughout much of the bottomwater mass. Although bottom-water anoxia may have occurred during periods of organic-carbon-rich strata, it was not necessarily the only cause for accumulation of these strata. The main reason for the accumulation of organic-carbonrich strata was an increase in the relative amount of organic debris being deposited. Some of this organic debris was derived from continental-margin areas of increased production, accumulation, and preservation of organic matter from marine, terrestrial, or mixed sources and transported to slope and basinal sites by turbidity currents.

Initial Reports of the D.S.D.P.↗

Chemistry and mineralogy of natural bitumens and heavy oils and their reservoir rocks from the United States, Canada, Trinidad and Tobago, and Venezuela

Twenty-one samples from natural bitumen and heavy oil deposits in seven States of the United States and six samples from outside the United States form the basis of this initial study. This Circular gives the mineral content of the reservoir rock, the trace-element distribution in the reservoir rock and hydrocarbons, and the composition of the heavy oil and natural bitumen. The reservoir rock and sediment residues from California contain more trace-element maximum amounts than any of the other rock samples. These relatively high concentrations of trace elements may be due, in part, to the low quartz content of the rock and to the presence of heulandite, cristobalite, siderite, and pyrite. The reservoir rock and sediment residues from Oklahoma contain more minimum amounts of trace elements than any of the other rock samples. This pattern probably results from the large amount of quartz in four of the samples and a large amount of calcite in the other sample. The maximum and minimum amounts of trace elements in the bitumen and heavy oil do not correlate with those in the reservoir rocks. The bitumen from Utah contains the greatest number of trace-element maxima, whereas there is no trend in the trace-element minima in the bitumen and heavy oil.

Circular↗

Mineralogy and instrumental neutron activation analysis of seven National Bureau of Standards and three Instituto de Pesquisas Tecnologicas clay reference samples

The concentrations of 3 oxides and 29 elements in 7 National Bureau of Standards (NBS) and 3 Instituto de Pesquisas Techno16gicas (IPT) reference clay samples were etermined by instrumental neutron activation analysis. The analytical work was designed to test the homogeneity of constituents in three new NBS reference clays, NBS-97b, NBS-98b, and NBS-679. The analyses of variance of 276 sets of data for these three standards show that the constituents are distributed homogeneously among bottles of samples for 94 percent of the sets of data. Three of the reference samples (NBS-97, NBS-97a, and NBS-97b) are flint clays; four of the samples (NBS-98, NBS-98a, NBS-98b, and IPT-32) are plastic clays, and three of the samples (NBS-679, IPT-28, and IPT-42) are miscellaneous clays (both sedimentary and residual). Seven clays are predominantly kaolinite; the other three clays contain illite and kaolinite in the approximate ratio 3:2. Seven clays contain quartz as the major nonclay mineral. The mineralogy of the flint and plastic clays from Missouri (NBS-97a and NBS-98a) differs markedly from that of the flint and plastic clays from Pennsylvania (NBS-97, NBS-97b, NBS-98, and NBS-98b). The flint clay NBS-97 has higher average chromium, hafnium, lithium, and zirconium contents than its replacement, reference sample NBS-97b. The differences between the plastic clay NBS-98 and its replacement, NBS-98b, are not as pronounced. The trace element contents of the flint and plastic clays from Missouri, NBS-97a and NBS-98a, differ significantly from those of the clays from Pennsylvania, especially the average rare earth element (REE) contents. The trace element contents of clay sample IPT-32 differ from those of the other plastic clays. IPT-28 and IPT-42 have some average trace element contents that differ not only between these two samples but also from all the other clays. IPT-28 has the highest summation of the average REE contents of the 10 samples. The uranium content of NBS-98a, 46 parts per million, is very much higher than that of the other clays. Plots of average REE contents of the flint and plastic clays, normalized to chondritic abundances, show that the clays from Missouri differ from the same types of clay from Pennsylvania. The plot of REE contents for the miscellaneous clays shows that the normalized means for the elements lanthanum through samarium for IPT-28 are much greater than those for the other miscellaneous clays. The means for the elements europium through lutetium are similar for all three miscellaneous clays.

Circular↗

Concentrations and loads of cadmium, lead, zinc, and nutrients measured during the 1999 water year within the Spokane River basin, Idaho and Washington

The Remedial Investigation/Feasibility Study conducted by the U.S. Environmental Protection Agency within the Spokane River Basin of northern Idaho and eastern Washington included extensive data-collection activities to determine the nature and extent of trace-element contaminationwithin the basin. The U.S. Geological Survey designed and operated a streamflow and water quality monitoring network in the basin during the 1999 water year (October 1, 1998, through September 30, 1999) in support of this Remedial Investigation/Feasibility Study. The objective for the network was to quantify the absolute and relative magnitude of hydrologic, trace-element, and nutrient loads transported by numerous stream reaches within the Spokane River Basin. Of the 29 water-quality stations in the network, 19 were in the Coeur d?Alene River Basin, 2 were in the St. Joe River Basin, and the remaining 8 were on the Spokane River downstream from Coeur d'Alene Lake. All stations were sampled for whole-water recoverable and dissolved concentrations of cadmium, lead, and zinc. Nitrogen and phosphorus concentrations were sampled at nine stations to determine loads of nutrients into and out of Coeur d'Alene Lake and transported down the Spokane River into the Columbia River. Mean daily discharge during the 1999 water year was about 120 percent of the long-term average. Trace-element loads to the Columbia River were calculated for the basin's terminal station, Spokane River at Long Lake. For whole-water recoverable cadmium, 2,110 pounds, 92 percent of which was dissolved, was delivered to the Columbia River. The Columbia River received 25,000 pounds of whole-water recoverable lead, 29 percent of which was dissolved, from the Spokane River Basin. The largest trace-element load delivered to the Columbia River by the Spokane River was 764,000 pounds of whole-water recoverable zinc, 76 percent of which was dissolved. The primary source of trace-element loads in the Spokane River Basin was the Coeur d'Alene River Basin. The South Fork Coeur d'Alene River was the largest source of dissolved and wholewater recoverable loads of cadmium and zinc. In contrast, the main stem of the Coeur d'Alene River was the largest source of dissolved and wholewater recoverable loads of lead. Within the South Fork, substantial increases in dissolved loads of cadmium, lead, and zinc were detected in excess of those measured by the monitoring network stations upstream from the terminal station, South Fork Coeur d'Alene River near Pinehurst. Much of the added load was attributed to inflow of traceelement-contaminated ground water. Similarly, increases in whole-water recoverable loads of cadmium, lead, and zinc were detected in the South Fork in excess of measured loads; these were attributed largely to erosion and transport of sediment-associated trace elements during increased stream discharge events. Coeur d'Alene Lake received nearly all its trace-element loads from the Coeur d'Alene River. The lake retained the majority of the dissolved and whole-water recoverable loads of lead input to it, but retained almost none of its dissolved and whole-water recoverable loads of zinc. About one-half of the dissolved and whole-water recoverable loads of cadmium was retained in the lake. Within the Spokane River Basin, the largest loads of total nitrogen, 13,000,000 pounds, and total phosphorus, 677,000 pounds, were measuredat Spokane River at Long Lake, the station closest to the Columbia River. At Coeur d'Alene Lake, total nitrogen loads input to the lake from the Coeur d'Alene and St. Joe Rivers totaled 1,890,000 pounds; the lake discharged 2,430,000 pounds. The lake received 253,000 pounds of total phosphorus and discharged 187,000 pounds; thus, 66,000 pounds was retained by the lake.

Idaho↗

Evolving magma storage conditions beneath Mount St. Helens inferred from chemical variations in melt inclusions from the 1980-1986 and current (2004-2006) eruptions

Major element, trace element, and volatile concentrations in 187 glassy melt inclusions and 25 groundmass glasses from the 1980-86 eruption of Mount St. Helens are presented, together with 103 analyses of touching FE-Ti oxide pairs from the same samples. These data are used to evaluate the temporal evolution of the magmatic plumbing system beneath the volcano during 1980-86 and so provide a framework in which to interpret analyses of melt inclusions from the current (2004-2006) eruption. Major and trace element concentrations of all melt inclusions lie at the high SiO 2 end of the data array defined by eruptive products of the late Quaternary age from Mount St. Helens. For several major and trace elements, the glasses define a trend that is oblique to the whole-rock trend, indicating that different mineral assemblages were responsible for the two trends. The whole-rock trend can be ascribed to differentiation of hydrous basaltic parents in a deep-seated magma reservoir, probably at depths great enough to stabilize garnet. In contrast, the glass trends were generated by closed-system crystallization of the phenocryst and microlite mineral assemblages at low pressures. The dissolved H 2 O content of the melt inclusions from 1980-86, as measured by the ion microprobe, ranges from 0 to 6.7 wt. percent, with the highest values obtained from the plinian phase of May 18, 1980. Water contents decrease with increasing SiO 2 , consistent with decompression-driven crystallization. Preliminary data for dissolved CO 2 in melt inclusions from the May 18 plinian phase from August 7, 1980, indicate that X H 2 O in a vapor phase was approximately constant at 0.80, irrespective of H 2 O content, suggestive of closed-system degassing with a high bubble fraction or gas streaming through the subvolcanic system. Temperature and f O 2 estimates for touching Fe-Ti oxides show evidence for heating during crystallization owing to release of latent heat. Consequently, magmas with the highest microlite crystallinities record the highest temperatures. Magmas also become progressively reduced during ascent and degassing, probably as a result of redox equilibria between exsolving S-bearing gases and magmas. The lowest temperature oxides have f O 2 ≈ NNO, similar to high-temperature fumarole gases from the volcano. The temperature and f O 2 of the magma tapped by the plinian phase of May 18, 1980, are 870-875°C and NNO+0.8, respectively. The dissolved volatile contents of the melt inclusions have been used to calculate sealing pressures; that is, the pressure at which chemical exchange between inclusion and matrix melt ceased. These are greatest for the May 18 plinian magma (120 to 320 MPa); lower pressures are recorded by samples of the preplinian cryptodome and by all post-May 18 magmas. Magma crystallinity, calculated from melt-inclusion Rb contents, is negatively correlated with sealing pressure, consistent with decompression crystallization. Elevated contents of Li in melt inclusions from the cryptodome and post-May 18 samples are consistent with transfer of Li in a magmatic vapor phase from deeper parts of the magma system to magma stored at shallower levels. The Li enrichment attains its maximum extent at ~150 MPa, which is ascribed to separation of a single vapor phase into H 2 O-rich gas and dense Li-rich brine at the top of the magma column. There are striking correlations between melt-inclusion chemistry and monitoring data for the 1980-86 eruption. Dissolved SO 2 contents of melt inclusions from any given event, multiplied by the mass of magma erupted during that event, correlate with the measured flux of SO 2 at the surface, suggesting that magma degassing and melt-inclusion sealing are closely related in time and space. Textural and chemical evidence indicates that melt inclusions became effectively sealed (physically or kinetically) shortly before eruption. Thus by converting pressure to depth using a density model and edifice-loading algorithm for the volcano, changing depths of magma extraction with time can be tracked and compared to the seismic record. The plinian eruption of May 18, 1980, involved magma stored 5-11 km below sea level; this is inferred to be the subvolcanic magma chamber. The preceding eruptions, including the May 18, 1980, blast, involved magma withdrawal from the cryptodome and conduit down to 5 km below sea level. Subsequent 1980 eruptions tapped magma down to depths of ≤10 km below sea level. Tapping of magma stored deeper than 2 km below sea level stopped abruptly at the end of 1980, coincident with the onset of extensive shallow seismicity and a change from explosive to effusive eruption style from 1981 to 1986. Overall, the 1980-86 eruption is consistent with the evisceration of a thin, vertically extensive body of magma extending from 5 to at least 11 km below sea level and connected to the surface by a thin conduit. In the absence of sustained high magma-supply rates from depth, decompression crystallization of magma ascending through the system leads eventually to plugging of the conduit. The current eruption of Mount St. Helens shares some similarities with the 1981-86 dome-building phase of the previous eruption, in that there is extensive shallow seismicity and extrusion of highly crystalline material in the form of a sequence of flows and spines. Melt inclusions from the current eruption have low H 2 O contents, consistent with magma extraction from shallow depths. Highly enriched Li in melt inclusions suggests that vapor transport of Li is a characteristic feature of Mount St. Helens. Melt inclusions from the current eruption have subtly different trace-element chemistry from all but one of the 1980-86 melt inclusions, with steeper rareearth-element (REE) patterns and low U, Th, and high-fieldstrength elements (HFSE), indicating addition of a new melt component to the magma system. It is anticipated that increasing involvement of the new melt component will be evident as the current eruption proceeds.

Washington↗

Altitude, age, and quality of groundwater, Papio-Missouri River Natural Resources District, eastern Nebraska, 1992 to 2009

The U.S. Geological Survey, in cooperation with the Papio-Missouri River Natural Resources District (PMRNRD), conducted this study to map the water-level altitude of 2009 within the Elkhorn River Valley, Missouri River Valley, and Platte River Valley alluvial aquifers; to present the predevelopment potentiometric-surface altitude within the Dakota aquifer; and to describe the age and quality of groundwater in the five principal aquifers of the PMRNRD in eastern Nebraska using data collected from 1992 to 2009. In addition, implications of alternatives to the current PMRNRD groundwater-quality monitoring approach are discussed. In the PMRNRD, groundwater altitude, relative to National Geodetic Vertical Datum of 1929, ranged from about 1,080 feet (ft) to 1,180 ft in the Elkhorn River Valley alluvial aquifer and from about 960 ft to 1,080 ft in the Missouri River Valley and Platte River Valley alluvial aquifers. In the PMRNRD, the estimated altitude of the potentiometric surface of the Dakota aquifer, predevelopment, ranged from about 1,100 ft to 1,200 ft. To assess groundwater age and quality, groundwater samples were collected from a total of 217 wells from 1992 to 2009 for analysis of various analytes. Groundwater samples collected in the PMRNRD from 1992 to 2009 and interpreted in this report were analyzed for age-dating analytes (chlorofluorocarbons), dissolved gases, major ions, trace elements, nutrients, stable isotope ratios, pesticides and pesticide degradates, volatile organic compounds, explosives, and 222radon. Apparent groundwater age was estimated from concentrations of chlorofluorocarbons measured in samples collected in 2000. Apparent groundwater-recharge dates ranged from older than 1940 in samples from wells screened in the Missouri River Valley alluvial aquifer to the early 1980s in samples from wells screened in the Dakota aquifer. Concentrations of major ions in the most recent sample per well collected from 1992 to 2009 indicate that the predominant water type was calcium bicarbonate. Samples from 4 wells exceeded the U.S. Environmental Protection Agency (USEPA) Secondary Drinking Water Regulation (SDWR) for sulfate [250 milligrams per liter (mg/L)], and samples from 4 wells exceeded the USEPA Drinking Water Advisory Table for sodium (30-60 mg/L). Eighteen of the 21 trace elements analyzed in samples from PMRNRD wells have USEPA drinking-water standards. Sixteen of the trace elements with USEPA standards were detected in the selected samples. In the samples selected for trace-element analysis, the only trace-element concentration that exceeded an enforceable USEPA drinking-water standard, the Maximum Contaminant Level (MCL), was for arsenic; arsenic concentration exceeded the USEPA MCL of 10 micrograms per liter (μg/L) in 4 percent of the samples. Trace-element concentrations that exceeded the USEPA SDWR or Lifetime Health Advisory level were iron (46 percent of the samples were greater than USEPA SDWR of 300 μg/L), manganese (70 percent of the samples were greater than USEPA SDWR of 50 μg/L), and strontium (4 percent of the samples were greater than USEPA Lifetime Health Advisory level of 4,000 μ/L). The concentration of nitrate plus nitrite as nitrogen (nitrate-N) in the most recent nutrient samples collected from the network wells and from one randomly selected well in the well nests from 1992 to 2009 for most wells (80 percent) ranged from less than 0.06 to 8.55 mg/L, with a median value of 0.12 mg/L. Concentrations of nitrate-N in 13 (7 percent) nutrient samples, 1992 to 2009, were greater than or equal to the USEPA MCL and Nebraska Title-118 standard of 10 mg/L, and concentrations of nitrate-N in 35 (18 percent) nutrient samples, 1992 to 2009, were greater than or equal to 5 mg/L, which is the PMRNRD action level for possible management implementation to reduce nitrate concentrations in groundwater. Of the 61 pesticides or pesticide degradates analyzed from 2007 to 2009, 21 were detected. Three of the 21 pesticides detected (alachlor, atrazine, and metolachlor) have established health-based criteria; all detections of these compounds were at concentrations less than their USEPA standards. From 2007 to 2009, 1 or more pesticide compounds were detected in 16 of the 82 network wells and in 18 of the 26 wells in well nests. From 2007 to 2009, the individual pesticide compounds that were detected most frequently were alachlor ethane sulfonic acid, a degradate of alachlor; deethylcyanazine acid, a degradate of cyanazine; and atrazine. Analytes with concentrations that exceeded 30 percent of the applicable Nebraska Title-118 standard were identified so that the PMRNRD can plan to monitor groundwater in the area and consider possible actions should the analyte concentrations continue to rise. The analytical results from the most recent samples collected in the network wells and all the wells in well nests from 1992 to 2009 indicate that, in at least 1 sample, there was a concentration that exceeded 30 percent of the Nebraska Title-118 standard for at least 1 of 3 major ions (chloride, fluoride, and sulfate), 1 nutrient (nitrate-N), 1 pesticide (atrazine), or 3 trace elements (arsenic, iron, and manganese). In addition, 30 percent of the USEPA MCL or Nebraska Title-118 standard for gross alpha activity likely was exceeded in samples from three wells screened in the Dakota aquifer. Study findings indicate that some alternatives to the current PMRNRD groundwater-sampling approach that could be considered are to collect fewer samples for nutrient analysis and to collect samples periodically for determining concentrations of additional analytes, particularly the analytes with concentrations that were at least 30 percent or more than the Nebraska Title-118 standard.

Nebraska↗

Water-quality trends for selected sampling sites in the upper Clark Fork Basin, Montana, water years 1996-2010

A large-scale trend analysis was done on specific conductance, selected trace elements (arsenic, cadmium, copper, iron, lead, manganese, and zinc), and suspended-sediment data for 22 sites in the upper Clark Fork Basin for water years 1996–2010. Trend analysis was conducted by using two parametric methods: a time-series model (TSM) and multiple linear regression on time, streamflow, and season (MLR). Trend results for 1996–2010 indicate moderate to large decreases in flow-adjusted concentrations (FACs) and loads of copper (and other metallic elements) and suspended sediment in Silver Bow Creek upstream from Warm Springs. Deposition of metallic elements and suspended sediment within Warm Springs Ponds substantially reduces the downstream transport of those constituents. However, mobilization of copper and suspended sediment from floodplain tailings and stream banks in the Clark Fork reach from Galen to Deer Lodge is a large source of metallic elements and suspended sediment, which also affects downstream transport of those constituents. Copper and suspended-sediment loads mobilized from within this reach accounted for about 40 and 20 percent, respectively, of the loads for Clark Fork at Turah Bridge (site 20); whereas, streamflow contributed from within this reach only accounted for about 8 percent of the streamflow at Turah Bridge. Minor changes in FACs and loads of copper and suspended sediment are indicated for this reach during 1996–2010. Clark Fork reaches downstream from Deer Lodge are relatively smaller sources of metallic elements than the reach from Galen to Deer Lodge. In general, small decreases in loads and FACs of copper and suspended sediment are indicated for Clark Fork sites downstream from Deer Lodge during 1996–2010. Thus, although large decreases in FACs and loads of copper and suspended sediment are indicated for Silver Bow Creek upstream from Warm Springs, those large decreases are not translated to the more downstream reaches largely because of temporal stationarity in constituent transport relations in the Clark Fork reach from Galen to Deer Lodge. Unlike metallic elements, arsenic (a metalloid element) in streams in the upper Clark Fork Basin typically is mostly in dissolved phase, has less variability in concentrations, and has weaker direct relations with suspended-sediment concentrations and streamflow. Arsenic trend results for 1996–2010 indicate generally moderate decreases in FACs and loads in Silver Bow Creek upstream from Opportunity. In general, small temporal changes in loads and FACs of arsenic are indicated for Silver Bow Creek and Clark Fork reaches downstream from Opportunity during 1996–2010. Contribution of arsenic (from Warm Springs Ponds, the Mill-Willow bypass, and groundwater sources) in the Silver Bow Creek reach from Opportunity to Warm Springs is a relatively large source of arsenic. Arsenic loads originating from within this reach accounted for about 11 percent of the load for Clark Fork at Turah Bridge; whereas, streamflow contributed from within this reach only accounted for about 2 percent of the streamflow at Turah Bridge.

Montana↗

Surface-water quality and suspended-sediment quantity and quality within the Big River Basin, southeastern Missouri, 2011-13

Missouri was the leading producer of lead in the United States—as well as the world—for more than a century. One of the lead sources is known as the Old Lead Belt, located in southeast Missouri. The primary ore mineral in the region is galena, which can be found both in surface deposits and underground as deep as 200 feet. More than 8.5 million tons of lead were produced from the Old Lead Belt before operations ceased in 1972. Although active lead mining has ended, the effects of mining activities still remain in the form of large mine waste piles on the landscape typically near tributaries and the main stem of the Big River, which drains the Old Lead Belt. Six large mine waste piles encompassing more than 2,800 acres, exist within the Big River Basin. These six mine waste piles have been an available source of trace element-rich suspended sediments transported by natural erosional processes downstream into the Big River. A study was performed by the U.S. Geological Survey in cooperation with U.S. Environmental Protection Agency, Region 7, to calculate and characterize suspended-sediment quantity and quality within the Big River basin after reclamation of the mine waste piles ended in 2012. Streamflow and suspended sediments were quantified and sampled at two locations along a 68-mile reach of the Big River between Bonne Terre and Byrnes Mill, Missouri. The results will help regulatory agencies, such as the U.S. Environmental Protection Agency and U.S. Fish and Wildlife Service, determine impaired reaches and ecosystems for remedial and restoration efforts. Continuous stream stage, water temperature, and turbidity, and discrete suspended-sediment concentration data were collected at the two sites between October 2011 and September 2013. Suspended-sediment samples were collected during various hydrologic conditions to develop a regression model between discrete suspended-sediment concentration and continuous turbidity. Suspended sediments collected during stormflow events were analyzed for concentrations of trace elements such as barium, cadmium, lead, and zinc within two sediment size fractions. Event loads and annual loads of suspended sediment and select trace elements in suspended sediments also were calculated. Suspended-sediment loads computed by the regression model increased downstream from about 201,000 tons at the upstream site to about 355,000 tons at the downstream site during the study period. Stormflow-event-based (hereinafter referred to as “event-based”) suspended-sediment loads ranged from 180 to 32,000 tons at the upstream sampling site and 390 to 53,000 tons at the downstream site along the Big River. Although only seven stormflow events at the upstream site and six at the downstream site were sampled, the event-based suspended-sediment loads accounted for nearly 30 percent of the total suspended-sediment loads computed at both sites, indicating most of the suspended sediment transported through the Big River occurs during higher streamflows. Sediment quality guidelines, known as the threshold effect concentration and the probable effect concentration, used to assess toxicity of trace-element concentrations in sediments were compared to the cadmium, lead, and zinc concentrations in suspended sediment samples collected during stormflow events. All concentrations of cadmium, lead, and zinc in event-based suspended sediment samples exceeded the threshold and probable effect concentrations. Lead and zinc concentrations in the sediment size fraction less than 0.063 millimeters also exceeded the toxic effect threshold, above which sediment is considered to be heavily polluted causing adverse effects on sediment-dwelling organisms. Concentrations of cadmium and zinc in event-based suspended sediment samples were notably higher in samples from the upstream site than samples from the downstream site, indicating the sources of sediments enriched in these trace elements decrease in the downstream area of the watershed. The reduction in concentration of cadmium and zinc could be from dissolution of the constituents during transport or possibly a decrease in downstream source material. The lead concentration exceedance of the probable effects concentration as well as the threshold effects concentration indicates that lead-rich suspended sediments in the fraction less than 0.063 millimeters are readily available within the Big River Basin for transport. These sediments remain in the system from historical mining, and as the reclamation of mine waste piles in the upstream area of the watershed reduce additional sediment loadings, these fine sediments may be continually released as the river scours the streambed and erodes stream banks causing the lead-rich suspended sediment to remain in a state of equilibrium. Barium concentrations in suspended-sediments were nearly twice as high in stormflow event samples collected at the downstream site as compared to samples from the upstream site. The source of barium in the Big River could be from Mineral Fork and Mill Creek, which flow through the historical barite (barium sulfate, also known as tiff) mining district in Washington County, and discharge into the Big River between the two study sites. Total trace-element loads and yields in suspended sediments were computed from the sampled events for each year in the study. The total barium loads in suspended sediments were higher for sampled events collected at the downstream site than the upstream site during both study years. Cadmium and zinc loads in suspended sediments were lower at the downstream site than the upstream site, although the decrease in total load was not substantial during the study period. Lead loads in suspended sediments were lower at the downstream site during the first study year, with a slightly higher load downstream in the second year though the increase from upstream to downstream was small. Event-based yields were higher at the upstream site, indicating that readily available sediment sources are closer to the upstream site where more mining affected areas are located. The estimates determined during large precipitation events indicate that large sources of suspended sediments with large concentrations of trace elements are still available for transport within the Big River.

Missouri↗

Arsenic, chromium, uranium, and vanadium in rock, alluvium, and groundwater, Mojave River and Morongo Areas, western Mojave Desert, southern California

Trace elements within groundwater that originate from aquifer materials and pose potential public-health hazards if consumed are known as geogenic contaminants. The geogenic contaminants arsenic, chromium, and vanadium can form negatively charged ions with oxygen known as oxyanions. Uranium complexes with bicarbonate and carbonate to form negatively charged ions having aqueous chemistry similar to oxyanions. The concentrations of arsenic, chromium, uranium, and vanadium in groundwater result from the combined effects of (1) geologic abundance within aquifer materials; (2) the fraction of these elements that have weathered from and sorbed to the surfaces of mineral grains and are potentially available to groundwater; and (3) the aqueous chemistry of dissolved oxyanions in groundwater during different redox conditions and pH, both of which are affected by hydrogeology, including the length of time groundwater has been in contact with aquifer materials. Concentrations of arsenic, chromium, uranium, and vanadium were measured in samples of (1) rock, surficial alluvium, and drill cuttings using portable (handheld) X-ray fluorescence (pXRF); (2) operationally defined fractions extractable from these materials; and (3) water from wells sampled between 2000 and 2018 within the 3,500 square mile Mojave River area and Morongo area of the western Mojave Desert, southern California. Regionally, rock and surficial alluvium in the Mojave River and Morongo areas are high in arsenic, low in chromium and uranium, and near the average bulk continental crust concentration for vanadium. Locally, high chromium concentrations are present in mafic rock within the San Gabriel Mountains; high uranium concentrations are present in felsic rock within the San Bernardino Mountains; and high arsenic, uranium, and vanadium concentrations are present in extrusive (volcanic) felsic rock within uplands surrounding groundwater basins along the Mojave River downstream from Barstow, California. Elemental assemblages identified using principal component analyses (PCA) of pXRF data were used to characterize felsic, mafic, and felsic volcanic source terranes in rock, surficial alluvium, and in geologic material penetrated by selected monitoring wells drilled between 1994 and 2018. Highly felsic alluvium associated with recent deposition from the Mojave River was identified along the 90-mile length of the floodplain aquifer along the river. The thickness of these highly felsic alluvial deposits ranged from 200 feet (ft) near Victorville and near Barstow to a thin veneer about 30 ft thick downstream from Victorville and downstream portions of the floodplain aquifer within the Mojave Valley. Groundwater in the Mojave River and Morongo areas was generally oxic and alkaline (pH≥7.5). Maximum concentrations of arsenic, hexavalent chromium [Cr(VI)], uranium, and vanadium in water from as many as 498 wells sampled between 2000 and 2018 were 360, 140, 1,470, and 690 micrograms per liter (μg/L), respectively. Water from 22 percent of sampled wells exceeded the U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) for arsenic of 10 μg/L, with arsenic concentrations commonly exceeding the MCL in water from wells east of Barstow, deep wells in the Victorville fan, and in suboxic or reduced groundwater within the floodplain aquifer. Water from about 1 percent of sampled wells had Cr(VI) concentrations greater than the California MCL for total chromium of 50 μg/L, whereas 13 percent of sampled wells had Cr(VI) concentrations greater than the former California MCL of 10 μg/L. Hexavalent chromium concentrations were highest in water from wells in the Sheep Creek alluvial fan, eroded from mafic rock in the San Gabriel Mountains, although Cr(VI) concentrations greater than the former California MCL also were present elsewhere in the study area where mafic materials or older groundwater were present. Water from about 9 percent of sampled wells exceeded the EPA MCL for uranium of 30 μg/L, with concentrations exceeding the MCL commonly associated with irrigation return from agricultural land overlying the floodplain aquifer. Water from about 7 percent of sampled wells had vanadium concentrations greater than the California notification level of 50 μg/L; most of these wells were in the Victorville fan within the Mojave River area. In general, arsenic concentrations were higher in suboxic or reduced water; chromium concentrations were higher in oxic, alkaline (pH≥7.5) water; uranium concentrations were higher in circumneutral to slightly alkaline water (pH≤7.4); and vanadium concentrations were higher in highly alkaline (pH≥8.0) water, independent of redox status. Concentrations within geologic source terranes are not the sole factor controlling the concentrations of geogenic elements in groundwater. Differences in mineral weathering, pH-dependent sorption to surface-exchange sites on mineral grains, and aqueous geochemistry (especially redox status and pH) affect geogenic element concentrations in groundwater. Consequently, the relative abundances of arsenic, Cr(VI), uranium, and vanadium in groundwater differ from their relative abundances in the average bulk continental crust and their regional abundances in rock and surficial alluvium within groundwater basins of the western Mojave Desert. Processes that control the concentrations of arsenic, chromium, uranium, and vanadium in groundwater operate at the mineral-grain and aquifer scale. At the mineral-grain scale, sequential chemical extraction data show arsenic and uranium are more available to groundwater (under specific geochemical conditions) than chromium or vanadium, which largely are unavailable within unweathered mineral grains. Additionally, chromium and vanadium form few aqueous complexes and bind tightly with iron minerals within surface coatings on mineral grains making them less available to groundwater, whereas complexation with other dissolved ions enhances the solubility of uranium and, to a lesser extent, arsenic. Complexation also increases the valence (less negative charge) and increases the size of dissolved oxyanions and uranium complexes with bicarbonate and carbonate making them less readily sorbed to aquifer materials. At the aquifer scale, hydrogeology (including isolation of water in aquifers from surface sources of recharge, older groundwater age, and long contact times between groundwater and aquifer materials) combined with geochemical processes (such as silicate weathering) to produce alkaline groundwater. Desorption from sorption sites on the surfaces of mineral grains with increasing pH increases arsenic, chromium, and vanadium concentrations in water from wells and increases Cr(VI) concentrations as long as water remains oxic. Aqueous geochemistry and concentrations of geogenic contaminants also are affected by anthropogenic activities including (1) discharge of treated municipal wastewater, which may change the redox status of groundwater; (2) return from irrigated agriculture, which may alter the chemistry of groundwater and increase the solubility of trace elements such as uranium; and (3) groundwater pumping and subsequent water-level declines, which may change the source of water yielded by wells. The quality of water imported from northern California and infiltrated from ponds for groundwater recharge may be altered by naturally present trace elements, especially uranium in areas of agricultural land use or chromium within mafic alluvium.

California↗