Extraction of highly polar organophosphorus pesticides from water

Some of the pesticides listed in the European 76/464/EC Directive and in the Directive 2000/60/EC are very polar and require special analytical methodology with respect to their extraction from water. The extraction of the organophosphorus pesticides methamidophos, omethoate, oxydemeton‐methyl, mevinphos and trichlorfon with lg P_OW below 1 was investigated using 21 different solid‐phase materials. Each material was tested on spiked natural water at 4 different pH values, adjusted prior to extraction. The following range of materials were tested: octadecyl silica, polymers, modified silica, ion exchange and carbon. Extraction of the above compounds from water is possible. A relationship between the octanol‐water partition coefficient and recovery rates was obtained not only for octadecyl solid phases but also for some polymeric materials. General conclusions about the use of solid‐phase materials and specific conclusions about the extraction of particular compounds were made. An optimized extraction procedure was deduced and confirmed.     

Distribution of sedimentary organic matter in Anisian carbonate series of S Poland: evidence of third-order sea-level fluctuations

The stratigraphic distribution of sedimentary organic matter in Anisian carbonate series of southern Poland is studied with respect to relative sea-level fluctuations. Palynofacies patterns clearly reflect transgressive–regressive trends that are interpreted in terms of third-order cyclicity. Major flooding phases are detected by maximum abundance of marine plankton in the upper Bithynian and Pelsonian. Transgressive and highstand deposits are recognized by changes in the terrestrial input of organic particles and the relative percentages and diversity of the plankton group. The palynological data support the sequence stratigraphic interpretation based on sedimentological features and geochemical signatures. The corresponding eustatic signals of sedimentary and organic facies are discussed. The study highlights the potential of palynofacies analysis for sequence stratigraphical interpretation.     

The significance of phenocryst diversity in tephra from recent eruptions at Popocatepetl volcano (central Mexico)

Tephra lapilli from six explosive eruptions between April 1996 and February 1998 at Popocatepetl volcano (=Popo) in central Mexico have been studied to investigate the causes of magma diversification in thick-crusted volcanic arcs. The tephra particles are sparsely porphyritic (≈5 vol%) magnesian andesites (SiO₂=58–65 wt%; MgO=2.6–5.9 wt%) that contain phenocrysts of NiO-rich (up to 0.67 wt% NiO) magnesian olivine (Fo_89–91 cores) with inclusions of Cr-spinel (cr#=59–70), orthopyroxene (mg#=63–76), clinopyroxene (mg#=68–86), intermediate to sodic plagioclase (An_33–66), and traces of amphibole. Major and trace element systematics indicate magma mixing. The liquid mg#_melt ratios inferred from the ferromagnesian phenocrysts suggest the existence of a mafic (mg#_melt ≈ 72–76) and an evolved component magma (mg#_melt ≈ 35–40). These component magmas form a hybrid magnesian andesite with an intermediate range of mg#_melt=50–72. The mafic end member (mg#_melt ≈ 72–75) is saturated with olivine and spinel and crystallizes at temperatures ≈1170–1085 °C with oxygen fugacities close to the fayalite–magnetite–quartz buffer and elevated water contents of several wt% H₂O. A likely location of crystallization is at lower crustal levels, possibly at the Moho. Olivine is followed by high-mg# clinopyroxene which could start to crystallize during magma ascent. At depths of ≈4 to 13 km, the mafic magma mixes with an evolved composition containing low-mg# clino- and orthopyroxene and plagioclase at a temperature of ≈950 °C. The repetitive ascent of batches of mafic magmas spaced days to weeks apart implies multiple episodes of crystallization and magma mixing. The tephra is similar to the Popo magnesian andesites, suggesting similar generic processes for the common lavas of the volcano. The advantage of the tephra is that it can be used to reconstruct the composition of the mafic magma. Building on the elemental systematics of the tephra and a comparison to the near-primary basalts from the surrounding monogenetic fields, we infer that the Popo mafic end member is a magnesian andesite with variable, but high SiO₂ contents of ≈55–62 wt% and near-primary characteristics, such as high-mg#_melt of 72–75, FeO*/MgO ratios <1 (if extrapolated to an mg#_melt of 72–75), and high Ni contents (=200 ppm Ni). This model implies that the typical elemental signature of the Popo andesites, such as the low CaO, Al₂O₃, FeO*, high Na₂O contents, and the depletion in high-field strength elements (e.g., P, Zr, Ti), are mantle source phenomena. Thus, determining the elemental budget of the magnesian andesite, as it is prior to the modifications by crustal differentiation, is central to quantifying the subcrustal mass fluxes beneath Popo. Received: 13 December 1999 / Accepted: 11 August 2000     

The systematics of chlorine, fluorine, and water in Izu arc front volcanic rocks: Implications for volatile recycling in subduction zones

We studied the systematics of Cl, F and H₂O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ∼400-4000 ppm and F ∼70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (∼6600-8600 ppm) and F (∼780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H₂O of basalt to andesite melt inclusions in plagioclase is estimated to range from ∼2 to ∼10 wt% H₂O. The Izu magmas should be undersaturated in H₂O and the halogens at their preferred levels of crystallization in the middle to lower crust (∼3 to ∼11 kbar, ∼820° to ∼1200°C). A substantial portion of the original H₂O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H₂O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H₂O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94 ± 0.25 wt%, F = 990 ± 270 ppm and H₂O = 25 ± 7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (∼77-129%). Conversely, H₂O (∼13-22% recycled at arc) and F (∼4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H₂O, the calculated percentage of Cl and H₂O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (∼37,000 km), the global arc outflux of fluid-recycled Cl and H₂O at subduction zones amounts to Cl ∼2.9-3.8 × 10¹² g/yr and H₂O ∼0.7-1.0 × 10¹⁴ g/yr, respectively—comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ∼0.3-0.4 × 10¹²g/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H₂O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H₂O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (∼9.5), slab melting will still produce components with low Cl/F ratios (∼0.9), similar to those characteristic of the upper continental crust (Cl/F ∼0.3-0.9).     

Characterization of Late Cretaceous to Miocene source rocks in the Eastern Mediterranean Sea: An integrated numerical approach of stratigraphic forward modelling and petroleum system modelling

Stratigraphic forward modelling was used to simulate the deposition of Upper Cretaceous, Eocene and Oligo‐Miocene source rocks in the Eastern Mediterranean Sea and, thus, obtain a process‐based 3D prediction of the quantity and quality distribution of organic matter (OM) in the respective intervals. Upper Cretaceous and Eocene models support the idea of an upwelling‐related source rock formation along the Levant Margin and the Eratosthenes Seamount (ESM). Along the margin, source rock facies form a narrow band of 50 km parallel to the palaeo shelf break, with high total organic carbon (TOC) contents of about 1% to 11%, and HI values of 300–500 mg HC/g TOC. On top of the ESM, TOC contents are mainly between 0.5% and 3% and HI values between 150 and 250 mg HC/g TOC. At both locations, TOC and HI values decrease rapidly towards the deeper parts of the basin. In the Oligo‐Miocene intervals, terrestrial OM makes up the highest contribution to the TOC content, as marine organic matter (OM) is diluted by high‐sedimentation rates. In general, TOC contents are low (<1%), but are distributed relatively homogenously throughout the whole basin, creating poor quality, but very thick source rock intervals of 1–2 km of cumulative thickness. The incorporation of these source rock models into a classic petroleum system model could identify several zones of thermal maturation in the respective source rock intervals. Upper Cretaceous source rocks started petroleum generation in the late Palaeocene/early Eocene with peak generation between 20 and 15 Ma ca. 50 km offshore northern Lebanon. Southeast of the ESM, generation started in the early Eocene with peak generation between 18 and 15 Ma. Eocene source rocks started HC generation ca. 25 Ma ago between 50 and 100 km southeast of the ESM and reached the oil to wet gas window at present day. However, until today they have converted less than 20% of their initial kerogen. Although the Miocene source rocks are mostly immature, Oligocene source rocks lie within the oil window in the southern Levant Basin and reached the onset of the wet gas window in the northern Levant Basin. However, only 10%–20% of their initial kerogen have been transformed to date.     

Manganese accumulation by the antennule of the Norway lobster Nephrops norvegicus (L.) as a biomarker of hypoxic events

In laboratory tests, manganese accumulation by the appendages of the sediment burrowing Norway lobster. Nephrops norvegicus (L.) (including the lateral antennules) was approximately three times greater [600 microg Mn g(-1) (dry weight) after 5 days in 20 mg Mn l(-1)] than that by the carapace. The accumulation was linearly dose-dependent (10-40 mg Mn l(-1)) and duration-dependent (2-30 days). and showed no decrease after 3 weeks in undosed seawater. A high manganese uptakc to the lateral antennules during hypoxia in the field was verified from the SE Kattegat, Sweden. These results indicate that accumulation of Mn on the mobile appendages of the Norway lobster fulfils most of the criteria for a biomarker of exposure to hypoxia. Using these measurements in conjunction with Mn concentrations in the internal tissues, it may be possible to resolve both the timing and the extent of the Mn exposure and the underlying hypoxic event.     

Detrital spinels from alpinotype source rocks in middle Devonian sediments of the Rhenish Massif

Middle Devonian sandy siltstones of the Gummersbach area (Rhenish Massif) show increased Cr contents (up to 675 ppm). The chromium is mainly associated with detrital Cr-Al spinels. The spinels are characterized by a wide spectrum of chemical composition.In more than 50% of 134 analyzed spinel grains the Cr₂O₃ content exceeds 50 wt %. The A1₂O₃ content which is negatively correlated to Cr₂O₃ reaches 40 wt %. The MgO contents are, with few exceptions, lower than the FeO contents; both elements are negatively correlated. The Fe₂O₃ contents which were calculated from a quarter of the grains rarely exceed 5 wt %. Besides Cr, Al, Fe, Mg TiO₂ contents were determined.The chemical composition of the detrital spinels indicates provenance from peridotites of an ophiolite suite.Provenance analysis shows that the source area of the Middle Devonian clastic sediments was situated in the north.

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Zusammenfassung In sandigen Siltsteinen des Mitteldevons des Bergischen Landes (Rheinisches Schiefergebirge) wurden erhöhte Cr-Gehalte von maximal 675 ppm festgestellt. Das Chrom ist überwiegend an detritische Spinelle gebunden. Mikrosondenuntersuchungen erbrachten eine große Variationsbreite im Chemismus dieser Spinelle. Über die Hälfte der 134 analysierten Körner weist mehr als 50 Gew % Cr₂O₃ auf. Der Al₂O₃-Gehalt, umgekehrt proportional zum Cr₂O₃-Gehalt, erreicht 40 Gew %. Die MgO-Gehalte sind bis auf wenige Ausnahmen kleiner als die FeO-Gehalte; beide Elemente sind negativ korreliert. Die Fe₂O₃-Gehalte, die von einem Viertel der Körner berechnet wurden, liegen meist unter 5 Gew %. Neben Cr, Al, Fe, Mg treten in einigen Spinellen meßbare TiO₂-Gehalte auf. Von ihrem Chemismus her lassen sich die detritischen Cr-Al-Spinelle von Peridotiten alpinotyper Ophiolite ableiten. Sedimentologische Befunde zeigen an, daß das Liefergebiet der klastischen mitteldevonischen Sedimente im Norden des Rheinischen Schiefergebirges gelegen hat.

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Résumé Les siltites sableuses du Dévonien moyen de la région de Gummersbach (Massif Schisteux Rhénan) montrent des teneurs en Cr élevées, jusqu'à un maximum de 675 ppm. Le chrome est lié principalement à des spinelles détritiques. La microsonde révèle une grande variation du chimisme de ces spinelles.Plus de la moitié des 134 grains analysés contiennent plus de 50% en poids de Cr₂O₃. La teneur en Al₂O₃ est enversement proportionnelle à celle en Cr₂O₃ et atteint 40 % en poids. Les teneurs en MgO sont à quelques exceptions près plus petites que celles en FeO; les deux éléments ont une corrélation négative. Les teneurs en Fe₂O₃, déterminées dans un quart des grains, ne dépassent généralement pas 5 % en poids. En plus de Cr, Al, Fe, Mg, on rencontre, dans quelques spinelles, des teneurs mesurables en TiO₂.La composition chimique des spinelles détritiques permet de leur assigner comme origine des péridotites appartenant à une série ophiolitique de type alpin.Les études sédimentologiques montrent que la région d'origine des sédiments clastiques du Dévonien moyen se trouve au nord du Massif Schisteux Rhénan.

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/ / , 675 . . . . . 134 50 -% r₂₃. l₂₃ 40 .-%. MgO, , , FeO. . F₂₃, , 5 -%. , , iO. — , . , .

     

Die Datierung geologischer Eriignisse im Altkristallin der Gleinalpe (Steiermark) mit der Rb/Sr-Methode

Zusammenfassung Die Datierung von Gneislagen einer Amphibolit-Gneis-Serie aus dem Kern der Gleinalpe, die dem Altkristallin angehört, ergibt ein Isochronenalter von 500±45 Mio. Jahre mit einem initialen Sr-Verhältnis von 0,7044±0,0012. Das geologische Erscheinungsbild weist auf vulkanische Entstehung des Ausgangsmaterials der Serie an der Wende Kambrium/ Ordoviz hin. Andere Gneistypen granitischer Zusammensetzung ergeben variszische Alter, deren Bedeutung (Bildungsalter der Granite oder Sr Homogenisierung während der variszischen Metamorphose) noch offen ist. Glimmer aus diesen Granittypen ergeben Alter von 81±9 bzw. 76±3 Mio Jahre für Muskovit bzw. Biotit und unterstreichen den starken thermischen Einfluß während der alpidischen Metamorphose in dem untersuchten Gebiet.

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Rb/Sr dating of geological events in the Altkristallin of the Gleinalpe (Steiermark)

Summary Plagioclase-quartz-gneisses from a series consisting of amphibolite and gneiss layers from the core of the Gleinalpe, which forms part of the Altkristallin, yielded a Rb-Sr isochron age of 500±45 m years, the initial Sr isotope ratio being 0.7044±0.0012. The geological state points to a volcanic origin of the series at the Cambrian/Ordovician boundary.Granitic gneisses indicate a Variscan age which might represent the time of rock formation or Sr homogenisation during metamorphism. Biotite from these granites gives an age of 76±3 and muscovite 81±9 m years. Both ages stress the strong thermal influence of the Alpine metamorphism in the area under investigation.

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Mit 3 Abbildungen     

Macrophyte trophic indicator values from a European perspective

Ecological optima and ranges of submerged macrophytes are, amongst other factors, assumed to be influenced by ecoregion and flow velocity. In order to test the influence of ecoregion within Europe, species indicator values of three European macrophyte river trophic indices were compared to each other. Species indicator values of the United Kingdom (UK), French and German bioindication methods are significantly correlated with each other. The most obvious difference between the three indicator systems is the number of included indicator taxa. Two species exhibit major differences in indicator values: Callitriche hamulata has a broader ecological amplitude in Germany and France than in the UK, where it is restricted to oligotrophic rivers, while Ranunculus fluitans has a broad ecological amplitude in the UK, whereas the species is restricted to eutrophic rivers in Germany and France.

In order to test if current velocity has an influence on macrophyte trophic indicator qualities, species indicator values of a river (Trophic Index of Macrophytes, TIM) and a lake macrophyte trophic index (Macrophyte Index, MI), both of them applicable in Bavaria, Germany, were compared to each other. Species indicator values are significantly correlated. The most important difference is that different species are included in lake and river indicator lists. Only approximately 60% of the total species are used in both TIM and MI. Three species exhibit a major difference in ecological optima between rivers and lakes: Ranunculus circinatus has a broader ecological amplitude in rivers whereas the species is restricted to eutrophic lakes, Myriophyllum spicatum and Nuphar lutea show the opposite reaction.     

Does groundwater influence the sediment fauna beneath a small, sandy stream?

Gradients in the sediment fauna comprising groundwater (GW) and hyporheic taxa were investigated in the sand/silt-bottomed Marbling Brook in Western Australia. The structure of sediment invertebrate assemblages from Marbling Brook sediments and the adjacent GW were studied at five sites over 1 year and hydrological interactions were characterized using a suite of abiotic factors. Although all five stream sites were upwelling, the sites differed in the degree of hydrological interactions between GW and surface water. Sediment fauna taxa abundances were not correlated with any of the abiotic factors investigated and did not change gradually with depth. Faunal assemblages in the stream sediments were distinct from faunal assemblages in alluvial GW. While water exchanged between alluvial GW and sediment water, as shown by abiotic factors, the distinct differences in faunal assemblages indicated an unpredicted complexity in the catchment with fundamentally different hydrogeological situations on the decimetre scale. Sampling in sandy sediments needs to take this small-scale variability into account.