Bestimmung von Atrazin,Terbutylazin und ihrer Desethyl- sowie Hydroxymetaboliten in Boden mittels SFE und HPLC/UV-DAD

Determination of Atrazine, Terbutylazine and their Deethyl- and Hydroxymetabolites in Soil by SFE and HPLC/UV-DAD The supercritical fluid extraction (SFE) (CO₂ and CH₃OH as modifier) of the herbicides atrazine and terbutylazine as well as their deethyl- and hydroxymetabolites from soil was investigated. The analytes were determined after extraction by HPLC/UV-DAD using a C18 column. The limits of detection of the chromatographic step were between 0.01 μg/mL and 0.07 μg/mL, the relative standard deviations between 0.8% and 1.4%. With the aid of a control chart, the stability of the chromatographic system was evaluated. For extraction, soil was spiked with 5 μg/g for each component. For SFE, CO₂ and methanol as modifier were used, and a pressure program was applied. Beside SFE, Soxhlet extraction with methanol and a solid-liquid extraction with acetone/water by shaking were carried out. For chlorine-containing triazines, the recovery rates were comparable for all extraction methods. The following recovery rates for SFE were obtained: deethylterbutylazine 77.4%, terbutylazine 80.2%, deethylatrazine 87.4%, atrazine 92.6%. However, the recovery rates for the hydroxymetabolites (4.1% for hydroxyatrazine, 21% for hydroxyterbutylazine) were not satisfying compared with the “classical” methods of extraction (above 50%). The limits of detection for the total process (SFE and HPLC/UV-DAD) estimated by the signal to noise ratio amounted 0.08 μg/g soil for chlorine-containing derivates, for hydroxyatrazine 2…3 μg/g, and for hydroxyterbutylazine 0.8 μ/g.     

A generalized garnet-forming reaction for metaigneous rocks in the Adirondacks

A generalized reaction is presented to account for garnet formation in a variety of Adirondack metaigneous rocks. This reaction, which is the sum of five partial reactions written in aluminum-fixed frames of reference, is given by: 4(y+1+w)Anorthite+4k(y+1+2w)Olivine +4(1–k)(y+1+2w)Fe-oxide+(8(y+1) –4k(y+1+2w))Orthopyroxene = 2(y+1)Garnet +2(y+1+2w)Clinopyroxene+4wSpinel where y is a function of plagioclase composition, k refers to the relative amounts of olivine and Fe-oxide participating in the reaction, and w is a measure of silicon mobility. When mass balanced for Mg and Fe, this reaction is found to be consistent with analyzed mineral compositions in a wide range of Adirondack metaigneous rocks. The reaction applies equally well whether the garnets were formed directly from the rectants given above or went through an intermadiate stage involving the formation of spinel, orthopyroxene, and clinopyroxene.The actual reactions which have produced garnet in both undersaturated and quartz-bearing rocks are special cases of the above general reaction. The most important special cases appear to be those in which the reactants include either olivine alone (k=1) or Fe-oxide alone (k=0). Silicon is relatively immobile (w =2) in olivine bearing, magnesium-rich rocks (k1), and this correlates with the increased intensity in spinel clouding of plagioclase in these rocks. Silicon mobility apparently increases in the more iron-rich rocks, which also tend to contain clear or lightly clouded plagioclase. In all the rocks studied the most common composition of metamorphic plagioclase is close to An₃₃ (i.e., y=1). Plagioclase of lower anorthite content may be too sodic to participate in garnet formation at the P-T conditions involved.Published by permission of the Director, New York State Museum and Science Service; Journal Series No. 282     

Comparisons of 210Pb and pollen methods for determining rates of estuarine sediment accumulation

Comparisons of sedimentation rates obtained by ²¹⁰Pb and pollen analyses of 1-m cores collected throughout the Potomac Estuary show good agreement in the majority of cores that can be analyzed by both methods. Most of the discrepancy between the methods can be explained by the analytical precision of the ²¹⁰Pb method and by the exactness with which time horizons can be identified and dated for the pollen method. X-radiographs of the cores and the distinctness of the pollen horizons preclude significant displacement by reworking and/or mixing of sediments. Differences between the methods are greatest where uncertainties exist in assigning a rate by one or both methods (i.e., ²¹⁰Pb trends and/or “possible” horizon assignments). Both methods show the same relative rates, with greater sediment accumulation more common in the upper and middle estuary and less toward the mouth. The results indicate that geochronologic studies of estuarine sediments should be preceded by careful observation of sedimentary structures, preferably by X-radiography, to evaluate the extent of mixing of the sediments. Time horizons, whether paleontologic or isotopic, are generally blurred where mixing has occurred, precluding precise identification. Whenever possible, two methods should be used for dating sediments because a rate, albeit erroneous, can be obtained isotopically in sediments that are mixed; accurate sedimentation rates are also difficult to determine where the time boundary is a zone rather than a horizon, where the historical record does not provide a precise date for the pollen horizon, or where scouring has removed some of the sediment above a dated pollen horizon.     

Holocene geomagnetic secular variation recorded by volcanic deposits at Mount St. Helens,Washington

A compilation of paleomagnetic data from volcanic deposits of Mount St. Helens is presented in this report. The database is used to determine signature paleomagnetic directions of products from its Holocene eruptive events, to assign sampled units to their proper eruptive period, and to begin the assembly of a much larger database of paleomagnetic directions from Holocene volcanic rocks in western North America. The paleomagnetic results from Mount St. Helens are mostly of high quality, and generally agree with the division of its volcanic deposits into eruptive episodes based on previous geologic mapping and radiocarbon dates. The Muddy River andesite's paleomagnetic direction, however, indicates that it is more likely part of the Pine Creek eruptive period rather than the Castle Creek period. In addition, the Two-Fingers andesite flow is more likely part of the Middle Kalama eruptive period and not part of the Goat Rocks period. The paleomagnetic data from Mount St. Helens and Mount Hood document variation in the geomagnetic field's pole position over the last ~2,500 years. A distinct feature of the new paleosecular variation (PSV) record, similar to the Fish Lake record (Oregon), indicates a sudden change from rapid clockwise movement of the pole about the Earth's spin axis to relatively slow counterclockwise movement at ~800 to 900 years B.P.     

Evaluation of a Model for Predicting Simultaneous Contrast on Color Maps

Perceptions of colors of individual map symbols are affected by simultaneous contrast, or induction, from surrounding colors. In an experiment with human subjects, reaction times were significantly slower, with significantly more errors, for test maps on which an induction model predicted that colors would be misinterpreted. Reaction times and error rates improved significantly with map color adjustments that the model predicted would remove induced confusions. These results represent progress toward establishing objective guidance for the design of effective color schemes in computer-assisted mapping environments common in cartography, geographic information systems, and scientific visualization.     

Low-Flow Purging and Sampling of Ground Water Monitoring Wells with Dedicated Systems

A field study was conducted to assess purging requirements for dedicated sampling systems in conventional monitoring wells and for pumps encased in short screens and buried within a shallow sandy aquifer. Low-flow purging methods were used, and wells were purged until water quality indicator parameters (dissolved oxygen, specific conductance, turbidity) and contaminant concentrations (chromate, trichloroethylene, dichloroethylene) reached equilibrium. Eight wells, varying in depth from 4.6 to 15.2 m below ground surface, were studied. The data show that purge volumes were independent of well depth or casing volumes. Contaminant concentrations equilibrated with less than 7.5 I. of purge volume in all wells. Initial contaminant concentration values were generally within 20 percent of final values. Water quality parameters equilibrated in less than 10 L in all wells and were conservative measures for indicating the presence of adjacent formation water. Water quality parameters equilibrated faster in dedicated sampling systems than in portable systems and initial turbidity levels were lower.     

The Use of Industrial Hygiene Samplers for Soil-Gas Surveying

Soil-gas surveying by the use of a passive sampler which allows quantitative determination of concentrations of volatile organic compounds and remote analysis of samples is described. The results of a survey using the sampler above a chloroform ground water plume are compared to ground water analysis results and to results from a previous soil-gas study above the same plume. Chloroform concentrations measured with passive samplers correlate well (r = 0.79, n = 6; r = 0.93, n = 7) with the other two techniques. The short-range variability of the technique is characterized by a coefficiet of variation of 12 percent over a 27-foot distance for nine samplers, and compares favorably with grab-sample results at the same location.     

Implications of radiolarian assemblages for the late Quaternary Paleoceanography of the eastern equatorial Pacific

The distribution of radiolarian assemblages identified by Q-mode factor analysis of radiolarian microfossils in surface sediments from low latitudes in the Pacific Ocean reflects their associations with surface water masses. Downcore fluctuations of these radiolarian assemblages at two sites, RC10-65 and V19–29, indicate changes in circulation in the eastern equatorial Pacific during the past 500,000 yr. Surface-water radiolarian assemblages characteristic of zonal flow have dominated siliceous sedimentation in the eastern equatorial Pacific, except during times of intense upwelling which can occur along the coast of Peru and in the Equatorial Undercurrent. Fluctuations in the importance of this upwelling have not been consistent with glacial/interglacial changes in ice volume throughout the late Quaternary. Intensification of upwelling in the equatorial divergence, however, has consistently coincided with increases in ice volume in the past 500,000 yr. The times at which changes in the nature of the relationship between upwelling and ice volume occur (approximately 240,000 and 380,000 yr B.P.) roughly coincide with times of observed changes in other proxy indicators of oceanographic conditions in the Pacific and Indian oceans.     

Evidence for a postglacial low relative sea-level stand in the drowned delta of the Merrimack River, Western Gulf of Maine

A submerged delta of the Merrimack River, located offshore between Cape Ann, Massachusetts, and the New Hampshire border, indicates a postglacial low relative see-level stand of about −47 m. The low stand is inferred to date to 10,500 yr B.P., but a lack of age control makes this assignment uncertain. A curve based on a late Wisconsinan, high relative sea-level stand of +32m at 13,000 yr B.P., a low stand of −47m at 10,500 yr B.P., and younger radiocarbon dates related to sea-level rise indicates an early postglacial crustal rise of at least 5 m per century.