Vertical concentration gradients of heavy metals in cultured mussels

Cultured mussels, Perna canaliculus (Gmelin), from two widely separated locations in New Zealand have been analysed for variation in heavy metal content with depth. The mussels, which are grown on vertically suspended ropes to a depth of 9 m, have been analysed for cadmium, lead, iron, and zinc at 1‐m intervals. At the first location (Kenepuru Sound), cadmium, lead, and iron increased with depth, while zinc decreased with depth. At the second location (Waiheke Island), concentrations of the four metals all remained essentially constant with depth. The differences in vertical concentration gradients between these two locations must result from differences in mixing of the water column. The differences in mixing may cause variations in the type of food organisms with depth, or variations in the ratio of particulate v. dissolved metal levels with depth. Either or both of these conditions could result in differences in the bioavailability of these metals with depth.     

Investigation of thallium fluxes from subaerial volcanism—Implications for the present and past mass balance of thallium in the oceans

A suite of 34 volcanic gas condensates and particulates from Kilauea (Hawaii), Mt. Etna and Vulcano (Italy), Mt. Merapi (Indonesia), White Island and Mt. Nguaruhoe (New Zealand) were analysed for both Tl isotope compositions and Tl/Pb ratios. When considered together with published Tl-Pb abundance data, the measurements provide globally representative best estimates of Tl/Pb = 0.46 ± 0.25 and ε²⁰⁵Tl = −1.7 ± 2.0 for the emissions of subaerial volcanism to the atmosphere and oceans (ε²⁰⁵Tl is the deviation of the ²⁰⁵Tl/²⁰³Tl isotope ratio from NIST SRM 997 isotope standard in parts per 10,000). Compared to igneous rocks of the crust and mantle, volcanic gases were found to have (i) Tl/Pb ratios that are typically about an order of magnitude higher, and (ii) significantly more variable Tl isotope compositions but a mean ε²⁰⁵Tl value that is indistinguishable from estimates for the Earth’s mantle and continental crust. The first observation can be explained by the more volatile nature of Tl compared to Pb during the production of volcanic gases, whilst the second reflects the contrasting and approximately balanced isotope fractionation effects that are generated by partial evaporation of Tl during magma degassing and partial Tl condensation as a result of the cooling and differentiation of volcanic gases.Mass balance calculations, based on results from this and other recent Tl isotope studies, were carried out to investigate whether temporal changes in the volcanic Tl fluxes could be responsible for the dramatic shift in the ε²⁰⁵Tl value of the oceans at ∼55 Ma, which has been inferred from Tl isotope time series data for ferromanganese crusts. The calculations demonstrate that even large changes in the marine Tl input fluxes from volcanism and other sources are unable to significantly alter the Tl isotope composition of the oceans. Based on modelling, it is shown that the large inferred change in the ε²⁰⁵Tl value of seawater is best explained if the oceans of the early Cenozoic featured significantly larger Tl output fluxes to oxic pelagic sediments, whilst the sink fluxes to altered ocean crust remained approximately constant.     

Anthrosols in Iron Age Shetland: Implications for arable and economic activity

The soils surrounding three Iron Age settlements on South Mainland, Shetland, were sampled and compared for indicators of soil amendment. Two of the sites (Old Scatness and Jarlshof) were on lower‐lying, better‐drained, sheltered land; the third (Clevigarth) was in an acid, exposed environment at a higher elevation. The hypothesis, based on previous regional assessments, soil thicknesses, and excavations at Old Scatness, was that the lowland sites would have heavily fertilized soils and that the thin upland soil would show little if any amendment. Our findings indicate that the Middle Iron Age soils at Old Scatness had extremely high phosphorus levels, while the soil at Jarlshof had lower levels of enhancement. At Clevigarth, where charcoal from the buried soil was 14C dated to the Neolithic and Bronze Age, there was no evidence of arable activity or soil amendment associated with the Iron Age phases of settlement. These observations indicate that not all sites put the same amount of effort into creating rich arable soils. The three sites had very different agricultural capacities, which suggests the emergence of local trade in agricultural commodities in Iron Age Shetland. © 2008 Wiley Periodicals, Inc.     

A preliminary prediction of seismic damage‐based degradation in RC structures

Estimation of structural damage from a known increase in the fundamental period of a structure after an earthquake or prediction of degradation of stiffness and strength for a known damage requires reliable correlations between these response functionals. This study proposes a modified Clough–Johnston single‐degree‐of‐freedom oscillator to establish these correlations in the case of a simple elasto‐plastic oscillator. It is assumed that the proposed oscillator closely models the response of a given multi‐degree‐of‐freedom system in its fundamental mode throughout the duration of the excitation. The proposed model considers the yield displacement level and ductility supply ratio‐related parameter as two input parameters which must be estimated over a narrow range of ductility supply ratio from a frequency degradation curve. This curve is to be identified from a set of recorded excitation and response time‐histories. Useful correlations of strength and stiffness degradation with damage have been obtained wherein a simple damage index based on maximum and yield displacements and ductility supply ratio has been considered. As an application, the proposed model has been used to demonstrate that ignoring the effects of aftershocks in the case of impulsive ground motions may lead to unsafe designs. Copyright © 2001 John Wiley & Sons, Ltd.     

Zur Genese des elementaren Schwefels im Gips von Weenzen (Hils)

Zusammenfassung In der Hilsmulde tritt bei Weenzen ein Salzstock durch Kreide- und Tertiärsedimente zutage. Dieser Gips führt an einigen Stellen elementaren Schwefel. Durch Isotopenanalysen wurde festgestellt, daß der elementare Schwefel gegenüber dem Ausgangssulfat an³⁴S verarmt und der Schwefelm Restsulfat entsprechend angereichert wurde. Schwefelfreie Bereiche des Gipses zeigen den für Zechsteinevaporite üblichen ³⁴S-Wert. Der Isotopenunterschied von durch-schnittlich 26% deutet auf bakteriellen Ursprung des Schwefels, weil eine anorganische Reduktion des Sulfates unter den vorauszusetzenden Temperaturen nicht möglich ist. Es wird angenommen, daß während des Aufstieges des Salzstockes ein geringfügiger Zutritt von Erdöl Lebensbedingungen für anaerobe Bakterien schuf, was zur Reduktion des Sulfats zu H₂S führte. Der dabei freiwerdende Schwefelwasserstoff wurde durch Reaktion mit SO ₄ ^2– in elementaren Schwefel umgewandelt. Da sich die Reduktion in den einzelnen Bereichen des Gipses sicher in Abhängigkeit von der Intensität der Bakterientätigkeit vollzog, hat sie primär wohl nicht zu homogener Verteilung der Schwefelisotope im Schwefelwasserstoff bzw. im Restsulfat geführt. Während für den elementaren Schwefel die nachträgliche Homogenisierung wegen der Beweglichkeit des Schwefelwasserstoffes verständlich ist, kann sie im Restsulfat so erklärt werden, daß dieses während der Neokomtransgression von oben her stärker der Lösung ausgesetzt war und umkristallisierte, wodurch sich die anfangs wahrscheinlich stärkeren Unterschiede in der Isotopenzusammensetzung des Gipses verwischten.

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Native sulphur is encountered occasionally within the gypsiferous cap-rock of a Permian salt dome in the Hils syncline, in the environs of Weenzen (see map, Fig. 1). A number of sulphur isotope analysis demonstrated that the native sulphur originated out of the primary sulphates, had been depleted in³⁴S, causing a relative enrichment of the remaining sulphate in³⁴S. Those parts of gypsum which are entirely devoid of native sulphur, exhibit a³⁴S value typical of Zechstein (upper Permian). The average enrichment of³²S in native sulphur of about 26% suggests its bacteriological origin, since under the temperatures usually prevailing during the origin of a salt dome, a sulphate cannot be reduced by petroleum. During the rise of the salt dome, the sulphates became contaminated with a small amount of petroleum as a result of which a congenial ecological condition for the development of the sulphate reducing bacterias was produced. The³⁴S depleted H₂S, produced by these bacterial, reacted with the sulphate, thus giving rise to native sulphur (Feely andKulp, 1957).The activity of the sulphate-reducing bacterial leads to different stages of fractionation in the different biochemical environments owing to the varying intensity of the bacterial growth, as well as to the variable ratios of reduced sulphate to primary sulphate. The highly mobile H₂S was homogenized already before the precipitation of native sulphur, whereas the homogenisation of the sulphate is viewed in the solution and recrystallisation processes taking place just below the Neocomian transgression horizon.

     

Carboxylic Acids: Seasonal Variation and Relation to Chemical and Meteorological Parameters

Formic and acetic acid measured as daily averages in 1993–1994show equal and highly correlated concentrations up to 3 ppb in the summer(May–August). In the winter (October–March) the formicacid/acetic acid ratio was 0.6 and the formic acid concentrations wereusually below 1 ppb. In winter the carboxylic acids correlate withO_x, NO_y, SO₂ and particulatesulphur. The main sources are suggested to be ozonolysis of anthropogenicalkenes and reactions between peroxyacetyl radicals and RO₂radicals. In spring–summer the carboxylic acids correlate withO₃, O_x, HNO₃, PAN,NO_y, SO₂, particulate sulphur and temperature.In addition to the sources of the winter a contribution from ozonolysis ofbiogenic alkenes is likely. Quite similar formic acid/acetic acid ratios forall wind directions suggest that the source(s) are atmospheric oxidationprocesses distributed over large areas. The highest concentrations occurringfor winds from east to south and the correlation with e.g., particulatesulphur indicate chemical production in polluted air masses during longrange transport.     

Evidence for rapid avian-mediated foraminiferal colonization of Lake Winnipegosis, Manitoba, during the Holocene Hypsithermal

A Holocene ecological succession was documented using palynological, foraminiferal, and molluscan faunas sampled from an excavated trench on the margin of Bell River Bay, Lake Winnipegosis, Manitoba. The palynological data record the known gradually isostatically-induced shift from aquatic to terrestrial conditions at the site, and clearly delineates the Holocene Hypsithermal maximal warm interval (commencing here about 5500 years BP). Concurrent with this warming the site became occupied by the extinct salt tolerant gastropod Marstonia gelida and the marine foraminifer Cribroelphidium gunteri by at least 5430 years BP. Water fowl-assisted colonization of non-marine habitats by foraminifera has previously been suggested as a dispersal mechanism for other non-marine foraminiferal occurrences. However, as this relatively warm-water foraminifer (presently found as far north as Cape Cod, MA on the Atlantic USA coast, and Vancouver, BC on the Canadian Pacific coast but also found in Canadian Maritime provinces during the Hypsithermal) did not inhabit the area either prior to or following the Hypsithermal warm interval, this occurrence indicates the efficiency with which foraminifera can utilize non-selective avian transport to colonize new non-marine and marine habitats. It may be that only a few years were required for colonization of the site to occur (2000–3000 km distant from native populations); this suggests that avian transport is a much more important foraminiferal dispersal mechanism than previously realized. The appearance of foraminifera at this site may also constrain models designed to determine the time required for hydraulically injected glacial freshwater to be flushed from normally brine producing aquifers in the region.