Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.     

Effects of industrial outfalls on tropical macrobenthic sediment communities in Reunion Island (Southwest Indian Ocean)

Temporal changes in the composition of soft bottom macrobenthic assemblages at Reunion Island (Southwest Indian Ocean) were studied in the context of a long-term environmental monitoring programme studying the impacts of effluents of industrial sugar cane refineries that are transferred to shallow and deep coastal environments by different pathways: surface discharge and deep underground injection. Seven stations (between 20 and 160 m depth) were surveyed between 1994 and 2003 on the industrial zone. One additional station was surveyed on a reference site. Spatio-temporal changes in the composition of macrobenthic communities were assessed using several diversity indices, ABC curves, MDS and associated ANOSIM tests and biotic indices. Among the 171 taxa recorded, polychaetes were dominant (89 species), followed by crustaceans and molluscs. The analysis of spatial changes in the composition of macrobenthos showed the existence of distinct benthic communities along the depth gradient. Temporal changes in macrobenthos composition were most prominent at the shallowest station. They mainly corresponded to the decline of several initially dominant taxa and the increase of the Eunicid polychaete Diopatra cuprea. This station further showed increasing macrofaunal abundance, biomass and sediment organic content over time, concomitant with decreasing sediment grain sizes. In deeper environments, temporal changes were much smaller. Macrofaunal abundance and species richness increased progressively, suggesting a moderate impact on benthic ecosystems resulting from slight enrichments due to effluents rich in organic matter. Our results highlight an original response to disturbance pattern involving opportunistic Eunicidae species (D. cuprea) not previously described. Moreover, they allow for the comparison of the impact on macrofauna caused by industrial effluents exported by two distinct and different pathways in a tropical coastal high-energy marine environment.     

Evidence of centennial-scale drought from southeastern Massachusetts during the Pleistocene/Holocene transition

A principal method for studying past hydroclimatic change is the reconstruction of paleo-lake levels. Here, we provide high-resolution lake-level records from New Long Pond and Rocky Pond in southeastern Massachusetts, which each contain evidence for multiple, sub-centennial-to-millennial scale low stands during the transition between the Late Pleistocene (15.0 ka) and Middle Holocene (ca 7.0 ka). Data from New Long Pond also demonstrate sedimentary evidence for a drop in water levels in the early to mid AD 20th century, when long-term trends in instrumental data show lower-than-average precipitation in the northeastern United States. Local data show the most precipitous declines in precipitation and groundwater levels are concurrent with the most severe drought in the AD 1960s, which occurred during a period of low sea-surface temperatures in the western North Atlantic. Ground penetrating radar and sediment core data indicate five intervals with numerous paleo-shoreline deposits between ca 15.0 and 7.0 ka, similar to the layer deposited in the AD 1960s. Many of the intervals of low lake levels coincide with proposed meltwater release events or abrupt climate oscillations in the circum North Atlantic. For example, we document at least three low stands during the Younger Dryas (12.9–11.6 ka) and in association with the “9.2” and “8.2” ka events. The combined evidence of (1) concurrent paleo-droughts in southeastern New England with documented North Atlantic abrupt cooling events and (2) recent drought with the modern association of low sea-surface temperatures indicates that freshening and cooling of the western North Atlantic is a viable mechanism for decreasing moisture within the region. Large-scale changes in seasonality and ice sheet extent also may have increased the susceptibility of the northeast to dry conditions triggered by changes in the North Atlantic.     

ROBUST: The ROle of BUffering capacities in STabilising coastal lagoon ecosystems

“Buffer capacities” has been defined in ecology as a holistic concept (e.g., Integration of Ecosystem Theories: A Pattern, second ed. Kluwer, Dordrecht, 1997, 388pp), but we show that it can also be worked out in mechanistic studies. Our mechanistic approach highlights that “buffering capacities” can be depleted progressively, and, therefore, we make a distinction between current and potential “buffering capacities”. We have applied this concept to understand the limited “local stability” in seagrass ecosystems and their vulnerability towards structural changes into macro-algal dominated communities. We explored the following processes and studied how they confer buffering capacities to the seagrass ecosystem: (i) net autotrophy is persistent in Zostera noltii meadows where plant assimilation acts as a sink for nutrients, this contrasted with the Ulva system that shifted back and forth between net autotrophy and net heterotrophy; (ii) the Z. noltii ecosystem possesses a certain albeit rather limited capacity to modify the balance between nitrogen fixation and denitrification, i.e., it was found that in situ nitrogen fixation always exceeded denitrification; (iii) the nitrogen demand of organoheterotrophic bacteria in the sediment results in nitrogen retention of N in the sediment and hence a buffer against release of nitrogen compounds from sediments, (iv) habitat diversification in seagrass meadows provides shelter for meiofauna and hence buffering against adverse conditions, (v) sedimentary iron provides a buffer against noxious sulfide (note: bacterial sulfide production is enhanced in anoxic sediment niches by increased organic matter loading). On the other hand, in the coastal system we studied, sedimentary iron appears less important as a redox-coupled buffer system against phosphate loading. This is because most inorganic phosphate is bound to calcium rather than to iron. In addition, our studies have highlighted the importance of plant–microbe interactions in the seagrass meadows.     

The development of surface steps during mining subsidence: “Not due to fault reactivation”

In spite of the voluminous literature which has been collated over the past ca. 150 years regarding the occurrence, prediction and control of the various phenomena associated with mining subsidence, the behaviour of geological faults during such subsidence is still poorly understood. It is generally appreciated that the reactivation of faults during mining events, and the consequent formation of a step in the surface topography, is complex and variable, and can result in extensive and spectacular structural damage. Within the past ca. two yearsevidence from the British and Ukrainian coalfields has been correlated which suggests that the surface steps formed and effected in the topography may be centred over contrasting lithological contacts such as bedding planes, joints, unconformities and the outcrop of fold axes.     

Sulphur isotope studies of the Mount Gunson copper deposits,Pernatty Lagoon,South Australia

The Mount Gunson copper deposits occur in essentially unmetamorphosed gently-folded Upper Proterozoic sediments, far from any known igneous intrusions. They consist of a number of small ore bodies which can be divided into two groups on the basis of differences in location, texture and mineralogy. The groups are here termed the off-lagoon deposits, which are extensively oxidized and occur in low hills to the west of Pernatty Lagoon, and the lagoon deposits, which are not significantly oxidized and occur in basins of permeable bedrock under the lagoon floor. The topography and drainage of this region appear to have altered little since the Tertiary. This paper presents the results of a sulphur isotope ratio study of sulphide minerals, groundwaters and gypsum samples from the mineralized areas. The isotope ratios recorded for the lagoon sulphides provide an example of the pattern predicted for metal sulphide precipitation due to bacterial reduction of sulphate in an environment with limited replenishment of sulphate. This finding is in accord with the suggestion that the copper sulphides were precipitated during recent geological times in groundwater traps in the permeable bedrock under the lagoon. However, sulphate from groundwater and gypsum in the lagoon is not enriched in the S³⁴ isotope, and hence it is concluded that no significant bacterial reduction of sulphate is occurring in the areas examined at the present time. The isotope ratios recorded for the off-lagoon sulphides, in contrast, fall in a narrower range. They can be interpreted to reflect metal sulphide precipitation by bacterial reduction of sulphate in a fairly open system, with considerable replenishment of sulphate, but they provide no information concerning the time of this precipitation. Mineralogical studies of the sulphide samples show that individual samples contain a mixture of sulphide minerals and that one mineral is usually dominant. It appears, for samples with co-existing chalcopyrite and djurleite, that S³⁴ is preferentially enriched in the chalcopyrite.

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Zusammenfassung Die Mount Gunson-Kupferlagerstätten finden sich in im wesentlichen nicht metamorphisierten, schwach gefalteten ober-proterozoischen Sedimenten, weit entfernt von irgendwelchen bekannten Intrusiven. Sie bestehen aus einer Reihe kleiner Erzkörper, die sich auf Grund ihrer Unterschiede in bezug auf ihren Fundort, ihr Gefüge und ihre Mineralogie in zwei Gruppen unterteilen lassen. Diese beiden Gruppen werden hier als Off-Lagoon-Lagerstätten, die weitgehend oxidiert sind und in niedrigen Hügeln westlich von der Pernatty Lagoon vorkommen, beziehungsweise als Lagoon-Lagerstätten, die nicht significant oxidiert sind und in Becken permeablen Gesteins unter dem Lagunenboden gefunden werden, bezeichnet. Die Topographie und die Abflußverhältnisse scheinen sich in dieser Region seit dem Tertiär nur wenig verändert zu haben. Diese Arbeit zeigt die Ergebnisse einer Analyse der Schwefelisotopen-Verhältnisse von Sulfiden, Grundwasser- und Gips-Proben aus den mineralisierten Bereichen. Die für die Lagunen-Sulfide registrierten Isotopenverhältnisse sind ein Beispiel der für die Metallsulfid-Ausfällung auf Grund von bakterieller Sulfatzufuhr zu erwartenden Verteilung. Dieser Befund stimmt mit der Vorstellung, daß die Kupfersulfide während rezenter geologischer Zeiten in Grundwasserspeichern innerhalb des permeablen Gesteins unter der Lagune ausgefällt worden sind, überein. Die Sulfate aus dem Grundwasser und Gips der Lagune sind jedoch nicht mit dem Isotop S³⁴ angereichert, woraus der Schluß gezogen wird, daß in den untersuchten Gebieten gegenwärtig keine wesentliche bakterielle Reduktion von Sulfaten stattfindet. Im Gegensatz dazu fallen die für die Off-Lagoon-Lagerstätten-Sulfide registrierten Isotopen-Verhältnisse in einen engeren Streuungsbereich. Sie können als Darstellung von Metall-Sulfid-Ausfällung durch bakterielle Reduktion von Sulfaten in einem ziemlich offenen System mit erheblichem Sulfat-Nachschub gedeutet werden, geben aber keine Auskunft über den Zeitpunkt dieser Präzipitation. Mineralogische Untersuchungen der Sulfid-Proben zeigen, daß die einzelnen Proben eine Mischung von Sulfid-Mineralien enthalten und daß gewöhnlich ein Mineral überwiegt. In Proben, die sowohl Kupferkies als auch Djurleit enthalten, scheint S³⁴ vorzugsweise im Kupferkies angereichert zu sein.

     

Gravity and Inertia-Gravity Internal Waves: Breaking Processes and Induced Mixing

Internal gravity waves, whether influenced or not by the Earths rotation, are ubiquitous dynamical features in the stratosphere and in the interior of the ocean. We review the mechanisms by which such waves may break when propagating in an infinite (possibly moving) fluid with uniform stratification. The methods and models used to quantify mixing in a stably-stratified fluid are next recalled. The mixing properties induced by the breaking waves as obtained from several field, experimental and numerical experiments reported in the literature are presented.     

High-resolution coral records of rare earth elements in coastal seawater: biogeochemical cycling and a new environmental proxy

In this study we have used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to produce a high resolution coral record of rare earth elements (REE), Mn and Ba from coastal Porites corals from the Great Barrier Reef of Australia. Validation of the LA-ICP-MS technique indicated that the method provides accurate and reproducible (RSD = 13-18%) analysis of low concentration REE in corals (∼1 to 100 ppb). The REE composition in coral samples was found to closely reflect that of the surrounding seawater and distribution coefficients of ∼1-2 indicated minimal fractionation of the series during incorporation into coral carbonate. To explore the idea that coral records of REE can be used to investigate dissolved seawater composition, we analyzed two coastal corals representing a total of ∼30 yr of growth, including a 10-yr overlapping period. Comparable results were obtained from the two samples, particularly in terms of elemental ratios (Nd/Yb) and the Ce anomaly. Based on this evidence and results from the determination of distribution coefficients, we suggest that useful records of seawater REE composition can be obtained from coral carbonates. When compared to the REE composition of a mid shelf coral, coastal corals showed a significant terrestrial influence, characterized by higher REE concentrations (greater than 10 times) and light REE enrichment. The REE composition of coastal seawater inferred from the coral record was dependent on seasonal factors and the influence of flood waters. REE fractionation displayed a strong seasonal cycle that correlated closely with Mn concentration. We suggest that higher Nd/Yb ratios and higher Mn concentrations in summer result from scavenging of heavy REE by particulate organic ligands and Mn reductive dissolution respectively, both processes displaying higher rates during periods of high primary productivity. The Ce anomaly also displayed a strong seasonal cycle showing an enhanced anomaly during summer and during flood events. This is consistent with the Ce anomaly being primarily controlled by the abundance of Ce oxidizing bacteria. Based on these arguments, we suggest that the coral record of dissolved REE and Mn may be regarded as a useful proxy for biological activity in coastal seawater.