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Organic contaminants, trace and major elements, and nutrients in water and sediment sampled in response to the Deepwater Horizon oil spill

Beach water and sediment samples were collected along the Gulf of Mexico coast to assess differences in contaminant concentrations before and after landfall of Macondo-1 well oil released into the Gulf of Mexico from the sinking of the British Petroleum Corporation's Deepwater Horizon drilling platform. Samples were collected at 70 coastal sites between May 7 and July 7, 2010, to document baseline, or "pre-landfall" conditions. A subset of 48 sites was resampled during October 4 to 14, 2010, after oil had made landfall on the Gulf of Mexico coast, called the "post-landfall" sampling period, to determine if actionable concentrations of oil were present along shorelines. Few organic contaminants were detected in water; their detection frequencies generally were low and similar in pre-landfall and post-landfall samples. Only one organic contaminant--toluene--had significantly higher concentrations in post-landfall than pre-landfall water samples. No water samples exceeded any human-health benchmarks, and only one post-landfall water sample exceeded an aquatic-life benchmark--the toxic-unit benchmark for polycyclic aromatic hydrocarbons (PAH) mixtures. In sediment, concentrations of 3 parent PAHs and 17 alkylated PAH groups were significantly higher in post-landfall samples than pre-landfall samples. One pre-landfall sample from Texas exceeded the sediment toxic-unit benchmark for PAH mixtures; this site was not sampled during the post-landfall period. Empirical upper screening-value benchmarks for PAHs in sediment were exceeded at 37 percent of post-landfall samples and 22 percent of pre-landfall samples, but there was no significant difference in the proportion of samples exceeding benchmarks between paired pre-landfall and post-landfall samples. Seven sites had the largest concentration differences between post-landfall and pre-landfall samples for 15 alkylated PAHs. Five of these seven sites, located in Louisiana, Mississippi, and Alabama, had diagnostic geochemical evidence of Macondo-1 oil in post-landfall sediments and tarballs. For trace and major elements in water, analytical reporting levels for several elements were high and variable. No human-health benchmarks were exceeded, although these were available for only two elements. Aquatic-life benchmarks for trace elements were exceeded in 47 percent of water samples overall. The elements responsible for the most exceedances in post-landfall samples were boron, copper, and manganese. Benchmark exceedances in water could be substantially underestimated because some samples had reporting levels higher than the applicable benchmarks (such as cobalt, copper, lead and zinc) and some elements (such as boron and vanadium) were analyzed in samples from only one sampling period. For trace elements in whole sediment, empirical upper screening-value benchmarks were exceeded in 57 percent of post-landfall samples and 40 percent of pre-landfall samples, but there was no significant difference in the proportion of samples exceeding benchmarks between paired pre-landfall and post-landfall samples. Benchmark exceedance frequencies could be conservatively high because they are based on measurements of total trace-element concentrations in sediment. In the less than 63-micrometer sediment fraction, one or more trace or major elements were anthropogenically enriched relative to national baseline values for U.S. streams for all sediment samples except one. Sixteen percent of sediment samples exceeded upper screening-value benchmarks for, and were enriched in, one or more of the following elements: barium, vanadium, aluminum, manganese, arsenic, chromium, and cobalt. These samples were evenly divided between the sampling periods. Aquatic-life benchmarks were frequently exceeded along the Gulf of Mexico coast by trace elements in both water and sediment and by PAHs in sediment. For the most part, however, significant differences between pre-landfall and post-landfall samples were limited to concentrations of PAHs in sediment. At five sites along the coast, the higher post-landfall concentrations of PAHs were associated with diagnostic geochemical evidence of Deepwater Horizon Macondo-1 oil.

Alabama, Arkansas, Florida, Georgia, Louisiana, Te

Concentrations of selected trace elements in fish tissue and streambed sediment in the Clark Fork-Pend Oreille and Spokane River basins, Washington, Idaho, and Montana, 1998

Fish tissue and bed sediment samples were collected from 16 stream sites in the Northern Rockies Intermontane Basins study area in 1998 as part of the U.S. Geological Survey National Water-Quality Assessment Program. Bed sediment samples were analyzed for 45 trace elements, and fish livers and sportfish fillets were analyzed for 22 elements to characterize the occurrence and distribution of these elements in relation to stream characteristics and land use activities. Nine trace elements of environmental concern&mdash;arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc&mdash;were detected in bed sediment, but not all of these elements were detected in fish tissue. Trace-element concentrations were highest in bed sediment samples collected at sites downstream from significant natural mineral deposits and (or) mining activities. Arsenic, cadmium, copper, lead, mercury, and zinc in bed sediment at some sites were elevated relative to national median concentrations, and some concentrations were at levels that can adversely affect aquatic biota. Although trace-element concentrations in bed sediment exceeded various guidelines, no concentrations in sportfish fillets exceeded U.S. Environmental Protection Agency screening values for the protection of human health. Correlations between most trace-element concentrations in bed sediment and fish tissue (liver and fillet) were not significant (r<&plusmn;0.50, p>0.05). Concentrations of arsenic, cadmium, copper, lead, mercury, nickel, selenium, and zinc in bed sediment were significantly correlated (r=0.53 to 0.88, p<0.05) with natural mineral deposits and mining activities, but concentrations in fish tissue generally were not correlated with these measures. Regression analysis between mine density and the sum of trace-element concentrations in bed sediment identified two statistically significant relations (r 2 =0.95 and 0.99, p<0.001) that corresponded to trace-element enrichment categories. These strong relations warrant further study using mine density as an explanatory variable to predict trace-element concentrations in bed sediment.

Idaho, Montana, Washington

Development and certification of the new SRM 695 trace elements in multi-nutrient fertilizer

During the past seven years, several states within the US have enacted regulations that limit the amounts of selected non-nutritive elements in fertilizers. Internationally, several countries, including Japan, China, and Australia, and the European Union also limit the amount of selected elements in fertilizers. The elements of interest include As, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, and Zn. Fertilizer manufacturers and state regulatory authorities, faced with meeting and verifying these limits, need to develop analytical methods for determination of the elements of concern and to validate results obtained using these methods. Until now, there were no certified reference materials available with certified mass fraction values for all elements of interest in a blended, multi-nutrient fertilizer matrix. A new standard reference material (SRM) 695 trace elements in multi-nutrient fertilizer, has been developed to help meet these needs. SRM 695 has recently been issued with certified mass fraction values for seventeen elements, reference values for an additional five elements, and information values for two elements. The certificate of analysis includes an addendum listing percentage recovery for eight of these elements, determined using an acid-extraction inductively-coupled plasma optical-emission spectrometry (ICP-OES) method recently developed and tested by members of the Association of American Plant Food Control Officials. ?? Springer-Verlag 2007.

Conference Paper

Process recognition in multi-element soil and stream-sediment geochemical data

Stream-sediment and soil geochemical data from the Upper and Lower Coastal Plains of South Carolina (USA) were studied to determine relationships between soils and stream sediments. From multi-element associations, characteristic compositions were determined for both media. Primary associations of elements reflect mineralogy, including heavy minerals, carbonates and clays, and the effects of groundwater. The effects of groundwater on element concentrations are more evident in soils than stream sediments. A "winnowing index" was created using ratios of Th to Al that revealed differing erosional and depositional environments. Both soils and stream sediments from the Upper and Lower Coastal Plains show derivation from similar materials and subsequent similar multi-element relationships, but have some distinct differences. In the Lower Coastal Plain, soils have high values of elements concentrated in heavy minerals (Ce, Y, Th) that grade into high values of elements concentrated into finer-grain-size, lower-density materials, primarily comprised of carbonates and feldspar minerals (Mg, Ca, Na, K, Al). These gradational trends in mineralogy and geochemistry are inferred to reflect reworking of materials during marine transgressions and regressions. Upper Coastal Plain stream-sediment geochemistry shows a higher winnowing index relative to soil geochemistry. A comparison of the 4 media (Upper Coastal Plain soils and stream sediments and Lower Coastal Plain soils and stream sediments) shows that Upper Coastal Plain stream sediments have a higher winnowing index and a higher concentration of elements contained within heavy minerals, whereas Lower Coastal Plain stream sediments show a strong correlation between elements typically contained within clays. It is not possible to calculate a functional relationship between stream sediment-soil compositions for all elements due to the complex history of weathering, deposition, reworking and re-deposition. However, depending on the spatial separation of the stream-sediment and soil samples, some elements are more highly correlated than others. Crown Copyright ?? 2009.

Applied Geochemistry

Multi-element fingerprinting of waters to evaluate connectivity among depressional wetlands

Establishing the connectivity among depressional wetlands is important for their proper management, conservation and restoration. In this study, the concentrations of 38 elements in surface water and porewater of depressional wetlands were investigated to determine chemical and hydrological connectivity of three hydrological types: recharge, flow-through, and discharge, in the Prairie Pothole Region of North America. Most element concentrations of porewater varied significantly by wetland hydrologic type ( p < 0.05), and increased along a recharge to discharge hydrologic gradient. Significant spatial variation of element concentrations in surface water was observed in discharge wetlands. Generally, higher element concentrations occurred in natural wetlands compared to wetlands with known disturbances (previous drainage and grazing). Electrical conductivity explained 42.3% and 30.5% of the variation of all element concentrations in porewater and surface water. Non-metric multidimensional scaling analysis showed that the similarity decreased from recharge to flow-through to discharge wetland in each sampling site. Cluster analysis confirmed that element compositions in porewater of interconnected wetlands were more similar to each other than to those of wetlands located farther away. Porewater and surface water in a restored wetland showed similar multi-element characteristics to natural wetlands. In contrast, depressional wetlands connected by seeps along a deactivated drain-tile path and a grazed wetland showed distinctly different multi-element characteristics compared to other wetlands sampled. Our findings confirm that the multi-element fingerprinting method can be useful for assessing hydro-chemical connectivity across the landscape, and indicate that element concentrations are not only affected by land use, but also by hydrological characteristics.

North Dakota

Trace elements have limited utility for studying migratory connectivity in shorebirds that winter in Argentina

Trace-element analysis has been suggested as a tool for the study of migratory connectivity because (1) trace-element abundance varies spatially in the environment, (2) trace elements are assimilated into animals' tissues through the diet, and (3) current technology permits the analysis of multiple trace elements in a small tissue sample, allowing the simultaneous exploration of several elements. We explored the potential of trace elements (B, Na, Mg, Al, Si, P, S, K, Ca, Ti, Cr, Mn, Ni, Cu, Zn, As, Sr, Cs, Hg, Tl, Pb, Bi, Th, and U) to clarify the migratory connectivity of shorebirds that breed in North America and winter in southern South America. We collected 66 recently replaced secondary feathers from Red Knots (Calidris canutus) at three sites in Patagonia and 76 from White-rumped Sandpipers (C. fuscicollis) at nine sites across Argentina. There were significant differences in trace-element abundance in shorebird feathers grown at different nonbreeding sites, and annual variability within a site was small compared to variability among sites. Across Argentina, there was no large-scale gradient in trace elements. The lack of such a gradient restricts the application of this technique to questions concerning the origin of shorebirds to a small number of discrete sites. Furthermore, our results including three additional species, the Pectoral Sandpiper (C. melanotos), Wilson's Phalarope (Phalaropus tricolor), and Collared Plover (Charadrius collaris), suggest that trace-element profiles change as feathers age. Temporal instability of trace-element values could undermine their application to the study of migratory connectivity in shorebirds. ?? The Cooper Ornithological Society 2010.

Condor

Trace-element contents of postorogenic granites of the eastern Arabian Shield, Kingdom of Saudi Arabia

Trace-element contents for 46 postorogenic granitoids vary by as much as two orders of magnitude; most samples are strongly enriched in incompatible elements (such as the heavy rare earths, yttrium, niobium, and uranium) and depleted in the compatible elements (such as barium, strontium, scandium, europium, and cobalt). These trace-element characteristics are typical of A-type granites found in other areas of the world. In spite of the wide range in trace-element contents, no samples contained economically significant concentrations of a single element. Samples range from peralkaline to strongly peraluminous; most are weakly peraluminous or metaluminous. All three subgroups (peralkaline, metaluminous, and peraluminous) are enriched in uranium and hafnium and are depleted in compatible elements. The peralkaline granites are generally enriched in yttrium and niobium - the strongly peraluminous granites in rubidium and tantalum; both groups are also somewhat enriched in the heavy-rare-earth elements. Several of the peraluminous granites are known to be tin-bearing and, like tin-bearing granites found elsewhere in the world, their chondrite-normalized, rare-earth-element patterns are flat and have large negative europium anomalies. Samples from several plutons have very anomalous ratios for geochemically similar elements such as yttrium and holmium, niobium and tantalum, and zirconium and hafnium. These ratios may reflect differential complexing with a halogen-rich aqueous phase that may be characteristic of plutons that have been subjected to an ore-forming process. A program to test these hypotheses, through study of known mineralized areas and laboratory experiments, should be implemented. The regional trends for the chemical data and geochemical correlations over the large area sampled, suggest that the postorogenic granites were derived from a single protolith that formed by the mixing of oceanic sediments from the west, continental sediments from the east.

Open-File Report

Organochlorine compounds and trace elements in fish tissue and streambed sediment in the Mobile River Basin, Alabama, Mississippi, and Georgia, 1998

During the summer of 1998, as part of the National Water-Quality Assessment Program, a survey was conducted to determine which organochlorine compounds and trace elements occur in fish tissues and streambed sediments in the Mobile River Basin, which includes parts of Alabama, Mississippi, Georgia, and Tennessee. The data collected were compared to guidelines related to wildlife, land use, and to 1991 and 1994 National Water-Quality Assessment Program Study-Unit data.Twenty-one sites were sampled in subbasins of the Mobile River Basin. The subbasins ranged in size from about 9 to 22,000 square miles and were dominated by either a single land use or a combination of land uses. The major land-use categories were urban, agriculture, and forest.Organochlorine compounds were widespread spatially in the Mobile River Basin. At least one organochlorine compound was reported at the majority of sampling sites (84 percent) and in a majority of whole-fish (80 percent) and streambed-sediment (52 percent) samples. Multiple organochlorine compounds were reported at 75 percent of the sites where fish tissues were collected and were reported at many of the streambed-sediment sampling sites (45 percent). The majority of concentrations reported, however, were less than 5 micrograms per kilogram in fish-tissue samples and less than 1 microgram per kilogram in streambed-sediment samples.The majority of trace elements analyzed in fish-liver tissue (86 percent) and streambed-sediment (98 percent) samples were reported during this study. Multiple trace elements were reported in all samples and at all sites.Based on comparisons of concentrations of organochlorine compounds and trace elements in fish-tissue and streambed-sediment samples in relation to National Academy of Science and National Academy of Engineering and Canadian tissue guidelines, probable-effects concentrations, and mean probable-effects concentration quotients for streambed sediment, the potential exists for adverse effects to wildlife at 15 (72 percent) of the sites sampled. The potential for adverse effects at these sites is because of the presence of residues or breakdown products related to polychlorinated biphenyls (PCB?s), chlordane, dichlorodiphenyltrichloroethane (DDT), chromium, lead, and zinc.The majority of compounds reported (65 percent) were chlordane, DDT, and PCB?s, or their breakdown products. Concentrations of chlordane and heptachlor epoxide in whole-fish tissue were positively correlated to the amount of urban land use in a basin. Total DDT concentrations in whole-fish tissues were positively correlated to agriculture.The relation of trace elements to land use is not as clear as the relation of organochlorine compounds to land use. This lack of clarity may be due to the possibility of geologic sources of trace elements in the Mobile River Basin and to the ubiquitous nature of many of these trace elements. However, there may be a correlation between the amount of urban land use and concentrations of antimony, cadmium, lead, and zinc in streambed-sediment samples from the Mobile River Basin.Fewer organochlorine compounds and trace elements were reported in samples from the Mobile River Basin than in samples collected during the 1991 and 1994 National Water-Quality Assessment Program studies. Of the organochlorine compounds analyzed nationally, 57 percent were reported in whole-fish tissue samples collected locally and 41 percent were reported in streambed-sediment samples collected locally, whereas 96 percent and 86 percent, respectively, were reported nationally. Of trace elements analyzed nationally, 86 percent were reported in fish-liver tissue locally and 95 percent were reported in streambed-sediment samples locally, whereas 95 percent and 98 percent, respectively, were reported nationally.In general, concentrations of organochlorine compounds and trace elements and the frequency with which they were reported in the Mobile River Basin are similar to or less than t

Alabama, Georgia, Mississippi, Tennessee

Trace elements and organic compounds in sediment and fish tissue from the Great Salt Lake basins, Utah, Idaho, and Wyoming, 1998-99

A study to determine the occurrence and distribution of trace elements, organochlorine pesticides, polychlorinated biphenyls (PCBs), and semivolatile organic compounds in sediment and in fish tissue was conducted in the Great Salt Lake Basins study unit of the National Water-Quality Assessment (NAWQA) program during 1998-99. Streambed-sediment and fish-tissue samples were collected concurrently at 11 sites and analyzed for trace-element concentration. An additional four sites were sampled for streambed sediment only and one site for fish tissue only. Organic compounds were analyzed from streambed-sediment and fish-tissue samples at 15 sites concurrently. Bed-sediment cores from lakes, reservoirs, and Farmington Bay collected by the NAWQA program in 1998 and by other researchers in 1982 were used to examine historical trends in trace-element concentration and to determine anthropogenic sources of contaminants. Cores collected in 1982 from Mirror Lake, a high-mountain reference location, showed an enrichment of arsenic, cadmium, copper, lead, tin, and zinc in the surface sediments relative to the deeper sediments, indicating that enrichment likely began after about 1900. This enrichment was attributed to atmospheric deposition during the period of metal-ore mining and smelting. A core from Echo Reservoir, in the Weber River Basin, however, showed a different pattern of trace-element concentration that was attributed to a local source. This site is located downstream from the Park City mining district, which is the most likely historical source of trace elements. Cores collected in 1998 from Farmington Bay show that the concentration of lead began to increase after 1842 and peaked during the mid-1980s and has been in decline since. Recent sediments deposited during 1996-98 indicate a 41- to 62-percent reduction since the peak in the mid-1980s. The concentration of trace elements in streambed sediment was greatest at sites that have been affected by historic mining, including sites on Little Cottonwood Creek in the Jordan River basin, Silver Creek in the Weber River basin, and the Weber River below the confluence with Silver Creek. There was significant correlation of lead concentrations in streambed sediment and fish tissue, but other trace elements did not correlate well. Streambed sediment and fish tissue collected from sites in the Bear River basin, which is predominantly rangeland and agriculture, generally had low concentrations of most elements. Sediment-quality guidelines were used to assess the relative toxicity of streambed-sediment sites to aquatic communities. Sites affected by mining exceeded the Probable Effect Concentration (PEC), the concentration at which it is likely there will be a negative effect on the aquatic community, for arsenic, cadmium, copper, lead, silver, mercury, and zinc. Sites that were not affected by mining did not exceed these criteria. Concentrations of trace elements in samples collected from the Great Salt Lake Basins study unit (GRSL) are high compared to those of samples collected nationally with the NAWQA program. Nine of 15 streambed-sediment samples and 11 of 14 fish-tissue samples had concentrations of at least one trace element greater than the concentration of 90 percent of the samples collected nationally during 1993-2000. Organic compounds that were examined in streambed sediment and fish-tissue samples also were examined in bed-sediment cores. A bed-sediment core from Farmington Bay of Great Salt Lake showed an increase in total polycyclic aromatic hydrocarbon (PAH) concentrations coincident with the increase in population in Salt Lake Valley, which drains into this bay. Analysis of streambed-sediment samples showed that the highest concentrations of PAHs were detected at urban sites, including two sites in the lower Jordan River (the Jordan River flows into Farmington Bay), the Weber River at Ogden Bay, and the Provo River near Provo. Other organic compounds detected in streambed sediment in the lower Jordan River were PCBs, DDT compounds, and chlordane compounds. Organic compounds were detected more frequently in fish tissue than in streambed sediment. Chlordane compounds and PCBs were detected more frequently at urban sites. DDT compounds were detected at 13 of 15 sites including urban and agricultural sites. Concentrations of total DDT in fish tissue exceeded the guideline for protection of fish-eating wildlife at two urban sites. The concentration of organic compounds in the GRSL study unit is low compared with that of samples collected nationally.

Idaho, Utah, Wyoming

U.S. Geological Survey Trace Elements and related reports through 1954

This report supersedes TEI-400, "U.S. Geological Survey Trace Elements and related reports through 1953." Part I is a numerical list of U.S. Geological Survey Trace Elements Investigations and Memorandum reports. This part lists not only reports (followed by a date) that have been transmitted to the U.S> Atomic Energy Commission, but also reports in preparation (followed by an asterisk) for which tentative titles were available on December 31, 1954. If a report, or portion of a report, has been published, the fact is indicated by the abbreviation of the medium of publication. (See also Part II.) Part II is a reference guide to Trace Elements and related reports that are available to the public (this part supersedes Part I of Bulletin 1019-B). These reports are grouped according to the type of publication or release. If a report, or portion of the report, has been published in more than one form, appropriate cross-references are given to indicate the other forms of publication. Abstracts published in Nuclear Science Abstracts are not included in Part II; however, if the abstract of a Trace Elements report has been published in NSA, the fact is indicated in Part I. Publications in process on December 31, 1954, are designated by an asterisk. Part III is a finding list of states, areas, and subjects and supersedes Part II of Bulletin 1019-B. It is based on information derived mostly from the titles of reports and, where titles are of general nature, from a cursory review of the reports. This list is not a complete index of the information given in Trace Elements and related reports, but is designed to find subjects of major interest, Because of the numerous entries for Colorado and Utah, information has been listed by counties and, where possible, by subject under these states. Other states have county listings only if a county is included in the title of a report; otherwise, area may be listed separately under the state. Major subjects are listed separately in the index and also, where appropriate under states. Analytical methods and subjects related to analytical research are listed under Analytical Methods and Research, but not separately throughout the index. Most mineralogic studies are included under the heading Mineralogy, but are not necessarily listed according to location. Part IV is an author index. The words “with” and “and” are used to indicate seniority of authorship. For example, a listing of Smith and Brown indicated that Smith is the senior author. A listing of Smith with Brown indicates that Brown is the senior author. In both parts III and IV all Trace Elements reports are listed, as well as other related reports that have not been issued as Trace Elements reports. The following abbreviations have been used: TEI, Trace Elements Investigations report; TEM, Trace Elements Memorandum report; OF, open file; TIS, Technical Information Service release; C, Circular; B, Bulletin; P, Professional Paper; MC, Maps and Charts; J, Journal; and NSA, Nuclear Science Abstracts.

Trace Elements Investigations

The occurrence and distribution of selected trace elements in the upper Rio Grande and tributaries in Colorado and Northern New Mexico

Two sampling trips were undertaken in 1994 to determine the distribution of trace elements in the Upper Rio Grande and several of its tributaries. Water discharges decreased in the main stem of the Rio Grande from June to September, whereas dissolved concentrations of trace elements generally increased. This is attributed to dilution of base flow from snowmelt runoff in the June samples. Of the three major mining districts (Creede, Summitville, and Red River) in the Upper Rio Grande drainage basin, only the Creede District appears to impact the Rio Grande in a significant manner, with both waters and sediments having elevated concentrations of some trace elements considerably downriver. For example, dissolved zinc concentrations upriver of Willow Creek, which primarily drains the Creede District, were about 2-3 μg/L; immediately downstream of the Willow Creek confluence, concentrations were above 20 μg/L; and elevated concentrations occurred in the Rio Grande for the next 100 km. The Red River District does not significantly impact the Upper Rio Grande for most trace elements. Because of current water management practices, it is difficult to assess the impact of the Summitville District on the Upper Rio Grande. There are, however, large increases in many dissolved trace element concentrations as the Rio Grande passes through the San Luis Valley, coincident with elevated concentrations of those same trace elements in tributaries. Among these elements are As, B, Cr, Li, Mn, Mo, Ni, Sr, U, and V. None of the trace elements exceeded U.S. EPA primary drinking water standards in either survey, with the exception of cadmium in Willow Creek. Secondary drinking water standards were frequently violated, especially in tributaries draining areas where mining has occurred. Dissolved zinc (in Willow Creek in both June and September) was the only element that exceeded the EPA Water Quality Criteria for aquatic life of 120 μg/L.

Archives of Environmental Contamination and Toxico

Biogeochemistry of the rare-earth elements with particular reference to hickory trees

Hickory trees concentrate the rare-earth elements in their leaves to a phenomenal degree and may contain as much as 2300 p.p.m. of total rare earths based on the dry weight of the leaves. The average proportions of the individual elements (atomic percent of the total rare-earth elements) in the leaves are: Y 36, La 16, Ce 14, Pr 2, Nd 20, Sm 1, Eu 0.7, Gd 3, Tb 0.6, Dy 3, Ho 0.7, Er 2, Tm 0.2, Yb 1, and Lu 0.2. The similarity in the proportions of the rare-earth elements in the leaves and in the exchange complex of the soil on which the hickory trees grow indicates that the trees do not fractionate the rare earths appreciably. The variation of the rare-earth elements in the leaves and soils can be explained generally in terms of the relative abundance of the cerium group and the yttrium group, except for the element cerium. The large fluctuations in the proportion of cerium [Ce/(La + Nd) atomic ratios of 0.16 to 0.86] correlate with oxidation-reduction conditions in the soil profile. The substitution of dilute H 2 SO 3 for dilute HC1 in the determination of available rare-earth elements brings about a large increase in the proportion of cerium that is extracted from an oxygenated subsoil. These relationships strongly suggest that quadrivalent cerium is present in oxygenated subsoil and is less available to plants than the other rare-earth elements that do not undergo such a change in valence. A few parts per billion of rare-earth elements have been detected in two samples of ground water.

Geochimica et Cosmochimica Acta

Composition of the earth's upper mantle-I. Siderophile trace elements in ultramafic nodules

Seven siderophile elements (Au, Ge, Ir, Ni, Pd, Os, Re) were determined by radiochemical neutron activation analysis in 19 ultramafic rocks, which are spinel lherzollites-xenoliths from North and Central America, Hawaii and Australia, and garnet Iherzolitexenoliths from Lesotho. Abundances of the platinum metals are very uniform in spinel lherzolites averaging 3.4 ± 1.2 ppb Os, 3.7 ± 1.1 ppb Ir, and 4.6 ± 2.0 ppb Pd. Sheared garnet lherzolite PHN 1611 has similar abundances of these elements, but in 4 granulated garnet lherzolites, abundances are more variable. In all samples, the Pt metals retain cosmic ( Cl-chondrite) ratios. Abundances of Au and Re vary more than those of Pt metals, but the Au/Re ratio remains close to the cosmic value. The fact that higher values of Au and Re approach cosmic proportions with respect to the Pt metals, suggests that Au and Re have been depleted in some ultramafic rocks from an initially chondrite-like pattern equivalent to about 0.01 of Cl chondrite abundances. The relative enrichment of Au and Re in crustal rocks is apparently the result of crust—mantle fractionation and does not require a special circumstance of core—mantle partitioning. Abundances of moderately volatile elements Ni, Co and Ge are very uniform in all rocks, and are much higher than those of the highly siderophile elements Au, Ir, Pd, Os and Re. When normalized to Cl chondrites, abundances of Ni and Co are nearly identical, averaging 0.20 ± 0.02 and 0.22 ± 0.02, respectively; but Ge is only 0.027 ± 0.004. The low abundance of Ge relative to Ni and Co is apparently a reflection of the general depletion of volatile elements in the Earth. The moderately siderophile elements cannot be derived from the same source as the highly siderophile elements because of the marked difference in Cl chondrite-normalized abundances and patterns. We suggest that most of the Ni, Co and Ge were enriched in the silicate by the partial oxidation of pre-existing volatile-poor Fe-Ni, whereas the corresponding highly siderophile elements remained sequestered by the surviving metal. The highly siderophile elements may have been introduced by a population of ~10 3 large (~10 22 g) planetisimals, similar to those forming the lunar mare basins.

Tectonophysics

A summary of the effects of mining and related activities on the sediment-trace element geochemistry of Lake Coeur d'Alene, Idaho, USA

During 1989 and 1990 a series of 12 gravity cores, and 150 surface grab samples were collected in Lake Coeur d'Alene, Idaho to determine trace element concentrations, partitioning and surface and subsurface distribution patterns in the bed sediments of the lake. In addition, selected subsamples from one core were analyzed for 117 Cs activity to begin to establish a trace element geochemical history for the lake. The intent was to try and relate the trace element concentrations and distributions in the sediment column to past and present mining and mining related activities in the area. Substantial portions of the surface and near-surface sediments in Lake Coeur d'Alene are markedly enriched in Ag, As, Cd, Hg, Pb, Sb and Zn, and somewhat enriched in Cu, Fe and Mn. Surface distribution patterns, as well as variations in the thickness of the trace element-rich subsurface sediments, indicate that the source of much of this enriched material is the Coeur d'Alene River. The similarity between the trace element-rich surface and subsurface sediments with respect to: their location, their bulk chemistry, and their trace element partitioning indicate that the sources and/or concentrating mechanisms causing the trace element enrichment in the lake sediments probably have been the same throughout their depositional history. An estimated 75 million metric tons of trace element-rich sediments have been deposited on or in the lakebed. Based on a Mt. St. Helens' ash layer from the 1980 eruption, ages estimated from 137 Cs activity, and the presence of 80 discernible and presumably annual layers in a core collected near the Coeur d'Alene River delta, indicate that the deposition of trace element-rich sediments began, at least in the Coeur d'Alene River delta, some time between 1895 and 1910, dates consistent with the onset of mining and ore-processing activities that began in the area in the 1880's.

Journal of Geochemical Exploration

The relation of stream sediment surface area, grain size and composition to trace element chemistry

Intensive studies of 17 geographically and hydrologically diverse stream bed sediments provide information on the relation between grain size, surface area, and operationally defined geochemical phases (e.g. Mn oxides, amorphous Fe oxides) to trace element concentrations. Of the size fractions investigated (<2, <16, <63and<125 μm), the strongest correlation with trace elements occurs with the percent <63 μm or<125 μm fractions. As the proportion of these size fractions increases in the samples, so do the trace element concentrations. When surface area (as defined by nitrogen adsorption and the BET equations) increases, trace element levels also increase. Correlations between bulk sediment chemistry and surface area are as strong as those between sediment chemistry and the proportion of the <63or<125 μm fractions. Surface area appears to serve as a proxy for grain size. The strongest correlations between grain size and surface area are the same as for trace elements and grain size (with the <63or<125 μm fractions). Surface area also is affected by geochemical phase, as are the trace elements associated with sediments. Of the phases considered (carbonates, Mn oxides, reactive Fe, amorphous Fe, organic matter), amorphous Fe oxides appear to exert the greatest control over both surface area and trace element levels. The concentrations of various geochemical phases affect surface area, grain size, and trace element chemistry. However, the effect of phase is grain-size dependent. For material with mean grain sizes in the fine sand range and coarser (> 125 μm), each of the various phases contribute to overall sample surface area. For material having mean grain sizes in the very fine sand range and finer (<125 μm), the same phases act as surface-area inhibitors by cementing fine grains together to form aggregates. This increases the mean grain size of the sample and reduces the surface area. The presence of these aggregates may explain why the <63 μm or<125 μm size fractions are more important to sediment-trace element levels and surface area than other finer fractions.

Applied Geochemistry

Size and elemental distributions of nano- to micro-particulates in the geochemically-stratified Great Salt Lake

The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9-7.5 nm size range relative to the 10-250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter. ?? 2009 Elsevier Ltd.

Applied Geochemistry

Using lead isotopes and trace element records from two contrasting Lake Tanganyika sediment cores to assess watershed – Lake exchange

Lead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815&ndash;1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements &ndash; likely caused by changes in land use &ndash; over that period. For example, the flux of Pb increased by &sim;300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r = 0.77&ndash;0.99, p < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r = 0.82&ndash;0.98, p < 0.01, n = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake&rsquo;s watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions of sediment at the sites differed spatially, indicating that the Pb (and other trace elements by association) originated from different natural sources at the two locations.

Lake Tanganyika

Trace element emissions from spontaneous combustion of gob piles in coal mines, Shanxi, China

The emissions of potentially hazardous trace elements from spontaneous combustion of gob piles from coal mining in Shanxi Province, China, have been studied. More than ninety samples of solid waste from gob piles in Shanxi were collected and the contents of twenty potentially hazardous trace elements (Be, F, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Sn, Sb, Hg, Tl, Pb, Th, and U) in these samples were determined. Trace element contents in solid waste samples showed wide ranges. As compared with the upper continental crust, the solid waste samples are significantly enriched in Se (20x) and Tl (12x) and are moderately enriched in F, As, Mo, Sn, Sb, Hg, Th, and U (2-5x). The solid waste samples are depleted in V, Cr, Mn, Co, Ni, Cu, and Zn. The solid waste samples are enriched in F, V, Mn, Cr, Co, Ni, Cu, Zn, Sb, Th, and U as compared with the Shanxi coals. Most trace elements are higher in the clinker than in the unburnt solid waste except F, Sn, and Hg. Trace element abundances are related to the ash content and composition of the samples. The content of F is negatively correlated with the ash content, while Pb is positively correlated with the ash. The concentrations of As, Mn, Zn, and Cd are highly positively correlated with Fe2O3 in the solid waste. The As content increases with increasing sulfur content in the solid waste. The trace element emissions are calculated for mass balance. The emission factors of trace elements during the spontaneous combustion of the gobs are determined and the trace element concentrations in the flue gas from the spontaneous combustion of solid waste are calculated. More than a half of F, Se, Hg and Pb are released to the atmosphere during spontaneous combustion. Some trace element concentrations in flue gas are higher than the national emission standards. Thus, gob piles from coal mining pose a serious environmental problem. ?? 2007 Elsevier B.V. All rights reserved.

International Journal of Coal Geology