Anthropogenic influence on trace element geochemistry of healing mud (peloid) from Makirina Cove (Croatia)

Due to their balneotherapeutic features, the organic-rich sediments in Makirina Cove are an important source of healing mud. An environmental geochemistry approach using normalization techniques was applied to evaluate the anthropogenic contribution of trace metals to sediments used as healing mud. Sediment geochemistry was found to be associated with land-use change and storm events, as well as with proximity of a road with heavy traffic in the summer months. Local valley topography preferentially channels lithogenic and pollutant transport to the cove. Concentrations and distribution of trace metals indicate lithogenic (Ni, Cr, Co) and anthropogenic (Pb, Cu, Zn and Se) contributions to the sediments. The calculation of enrichment factors indicates a moderate (EFs between 2–3.5) input of anthropogenic Cu and Pb in surficial sediments to a depth of 10 cm. Patients using the Makirina Cove sediments as healing mud could be to some extent exposed to enhanced uptake of metals from anthropogenic sources via dermal contact.     

Stable sulfur isotopes in the water column of the Cariaco Basin

Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ³⁴S_SO4) and sulfide (δ³⁴S_H2S) were similar to trends observed in the Black Sea water column: δ³⁴S_H2S and δ³⁴S_SO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in ³⁴S relative to sulfate. Near the oxic-anoxic interface, however, the δ³⁴S_H2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ³⁴S_H2S and Δ³³S_H2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ³⁴S_SO4 values near the interface suggests ‘readdition’ of ³⁴S-depleted sulfate during sulfide oxidation. A slight increase in δ³⁴S_SO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of ³⁴S-depleted sulfur during sulfide production through SR. Our δ³⁴S_H2S and Δ³³S_H2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ³⁴S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.     

The Scale Matcher: a procedure for assessing scale compatibility of spatial data and models

It is becoming easier to combine environmental data and models to provide information for problem-solving by environmental policy analysts, decision-makers, and land managers. However, the scale dependencies of each of these (data, model, and problem) can mean that the resulting information is misleading or even invalid. This paper describes the development of a systematic framework (dubbed the ‘Scale Matcher’) for identifying and matching the scale requirements of a problem with the scale limitations of spatial data and models.

The Scale Matcher framework partitions the complex array of scale issues into more manageable components that can be individually quantified. First, the scale characteristics of data, model, and problem are separated into their scale components of extent, accuracy, and precision, and each is associated with suitable metrics. Second, a comprehensive set of pairwise matches between these components is defined. Third, a procedure is devised to lead the user through a process of systematically comparing or matching each scale component. In some cases, the matches are simple comparisons of the relevant metrics. Others require the combination of data variability and model sensitivity to be investigated by randomly simulating data and model imprecision and inaccuracy. Finally, a conclusion is drawn as to the scale compatibility of the Data–Model–Problem trio based on the overall procedure result. Listing the individual match results as a set of scale assumptions helps to draw attention to them, making users more aware of the limitations of spatial modelling.

Application of the Scale Matcher is briefly illustrated with a case study, in which the scale suitability of two sources of soil map data for identifying areas of vulnerability to groundwater pollution was tested. The Scale Matcher showed that one source of soil map data had unacceptable scale characteristics, and the other was marginal for addressing the problem of nitrate leaching vulnerability. The scale-matching framework successfully partitioned the scale issue into a series of more manageable comparisons and gave the user more confidence in the scale validity of the model output.     

Subduction-related mafic to felsic magmatism in the Malayer–Boroujerd plutonic complex,western Iran

The Malayer–Boroujerd plutonic complex (MBPC) in western Iran, consists of a portion of a magmatic arc built by the northeast verging subduction of the Neo-Tethys plate beneath the Central Iranian Microcontinent (CIMC). Middle Jurassic-aged felsic magmatic activity in MBPC is manifested by I-type and S-type granites. The mafic rocks include gabbroic intrusions and dykes and intermediate rocks are dioritic dykes and minor intrusions, as well as mafic microgranular enclaves (MMEs). MBPC Jurassic-aged rocks exhibit arc-like geochemical signatures, as they are LILE- and LREE-enriched and HFSE- and HREE-depleted and display negative Nb–Ta anomalies. The gabbro dykes and intrusions originated from metasomatically enriched garnet-spinel lherzolite [Degree of melting (f_mel) ~ 15%] and exhibit negative Nd and positive to slightly negative ε_Hf(T) (+ 3.0 to ? 1.6). The data reveal that evolution of Middle Jurassic magmatism occurred in two stages: (1) deep mantle-crust interplay zone and (2) the shallow level upper crustal magma chamber. The geochemical and isotopic data, as well as trace element modeling, indicate the parent magma for the MBPC S-type granites are products of upper crustal greywacke (f_mel: 0.2), while I-type granites formed by partial melting of amphibolitic lower crust (f_mel: 0.25) and mixing with upper crustal greywacke melt in a shallow level magma chamber [Degree of mixing (f_mix): 0.3]. Mixing between andesitic melt leaving behind a refractory dense cumulates during partial crystallization of mantle-derived magma and lower crustal partial melt most likely produced MMEs (f_mix: 0.2). However, enriched and moderately variable ε_Nd(T) (? 3.21 to ? 4.33) and high (⁸⁷Sr/⁸⁶Sr)_i (0.7085–0.7092) in dioritic intrusions indicate that these magmas are likely experienced assimilation of upper crustal materials. The interpretations of magmatic activity in the MBPC is consistent with the role considered for mantle-derived magma as heat and mass supplier for initiation and evolution of magmatism in continental arc setting, elsewhere.     

The Canary Islands swell: a coherence analysis of bathymetry and gravity

The Canary Archipelago is an intraplate volcanic chain, located near the West African continental margin, emplaced on old oceanic lithosphere of Jurassic age, with an extended volcanic activity since Middle Miocene. The adjacent seafloor does not show the broad oceanic swell usually observed in hotspot-generated oceanic islands. However, the observation of a noticeable depth anomaly in the basement west of the Canaries might indicate that the swell is masked by a thick sedimentary cover and the influence of the Canarian volcanism. We use a spectral approach, based on coherence analysis, to determine the swell and its compensation mechanism. The coherence between gravity and topography indicates that the swell is caused by a subsurface load correlated with the surface volcanic load. The residual gravity/geoid anomaly indicates that the subsurface load extends 600 km SSW and 800 km N and NNE of the islands. We used computed depth anomalies from available deep seismic profiles to constrain the extent and amplitude of the basement uplift caused by a relatively low-density anomaly within the lithospheric mantle, and coherence analysis to constrain the elastic thickness of the lithosphere ( T_e ) and the compensation depth of the swell. Depth anomalies and coherence are well simulated with T_e =28–36 km, compensation depth of 40–65 km, and a negative density contrast within the lithosphere of ∼33 kg m⁻³. The density contrast corresponds to a temperature increment of ∼325°C, which we interpret to be partially maintained by a low-viscosity convective layer in the lowermost lithosphere, and which probably involves the shallower parts of the asthenosphere. This interpretation does not require a significant rejuvenation of the mechanical properties of the lithosphere.     

Trace metal concentrations in sediments of the Eastern Mississippi Bight

Sediments collected from 3 onshore-offshore transects (12 stations total) in the Eastern Mississippi Bight at 5 different times during 1987–1988 have been analyzed for total Ag, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Se, Sn, Th and Zn. The data show considerable variation both spatially and temporally, largely as a result of natural variability in grain size and mineralogy. Clay-rich samples from deep water were always more metal-rich than sandy samples from shallow areas. Many samples from near the Mississippi River Delta appeared to be enriched in Ba by about a factor of two, probably as a result of contamination from oil well drilling mud, but there were few other indications of pollution influences. Many samples from throughout the area gave Mn/Fe and Cd/Fe ratios a factor of two or more lower than their Mississippi River source material. This shows that biochemical activity in the sediment is capable of solubilizing reducible and adsorbed metals.     

Authigenic carbonates from the eastern Black Sea as an archive for shallow gas hydrate dynamics – Results from the combination of CT imaging with mineralogical and stable isotope analyses

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area (“Batumi seep area”) located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups.     

Relations between free copper and salinity, dissolved and particulate organic carbon in the Oosterschelde and Westerschelde, Netherlands

In a previous investigation, relatively simple relations were found to estimate free Cu, and hence a good approximation of bio-available Cu, at two sites in estuarine waters of the Dutch Oosterschelde and Westerschelde. In the present study, these relations are validated for the remainder of the two sea arms. In the Westerschelde the relation between the concentration of a dissolved organic ligand (K=10¹³), DOC (dissolved organic carbon) and salinity is valid in a range of salinities at least from 10 up to 25 to 30. This ligand group is primarily riverine and partly estuarine. It is, as far as we know, the strongest ligand for Cu, and its concentration dominantly affects the free Cu ion concentrations, which are around 50 fM. At high salinities, dilution and mineralisation diminish the riverine member of the ligand group too much and the relation with salinity and DOC is no longer valid. In the Oosterschelde the relations between POC (particulate organic carbon) and particulate Cu and between POC and the ratio of particulate and dissolved Cu are valid for the western, central and eastern compartments. Since equilibrium was assumed to exist between dissolved and particulate Cu, free Cu can be calculated from POC and particulate Cu concentrations. Due to the large adsorption capacity of POC, the Oosterschelde is with respect to Cu a very well-buffered system with [Cu²⁺] of 20 fM.     

Relationship between the daytime critical frequencies of the <Emphasis Type="Italic">F</Emphasis><Subscript>2</Subscript> layer and thermospheric characteristics

The relationship between the critical frequency of the F ₂ layer and the atmospheric characteristics has been obtained in a general form. It has been shown that this relation makes it possible to sufficiently accurately describe the daytime values of foF2 while comparing them with the observed monthly median values. Such comparisons were performed, first, for the data of measurements in Irkutsk using the DPS-4 digital ionosonde in 2003–2006 and, second, based on the annual variations in the noon foF2 values at 24 stations of the Northern Hemisphere in 1984. The calculations were performed using the MSIS-86 thermospheric model [Hedin, 1987].