Tracing the anthropogenic lead sources in coastal sediments of SE-pacific (36 degrees Lat. S) using stable lead isotopes

This study evaluates the main sources of antropogenic Pb in one of the most industrialized centers of the southern Chilean coast (36 degrees S). Stable lead isotopes ((206)Pb/(207)Pb, (208)Pb/(207)Pb) were used to trace main Pb sources to coastal sediments, considering the suspended particulate matter (SPM) from marine (traps), continental (rivers) and industrial effluents, sediments and leaded gasoline samples. The atmospheric input was evaluated through natural collectors; i.e. Raqui-Tubul salt marsh. Results show that marine samples lie on a trend between industrial effluents ( approximately 1.16, 2.44) and natural sources (1.20, 2.50), not related to gasoline consumption. Salt marsh sediments show comparable isotopic composition to marine samples, suggesting the importance of the atmospheric input in the coastal sediments, not related to the leaded gasoline composition either. The continental input (1.18, 2.48) is highly influenced by precipitation, being difficult to separate both sources (atmosphere and continental runoff), showing also similar isotopic ratio to marine sediments. The signal of industrial emissions is masked with the introduction of Pb with higher isotopic ratios, compared to the values observed in the material collected from traps (SPM approximately 1.19, 2.48). The contribution of more radiogenic Pb by the upwelling is suggested.     

Isotope mixing models require individual isotopic tracer content for correct quantification of sediment source contributions

The use of isotopic tracers for sediment source apportionment is gaining interest with recent introduction of compound‐specific stable isotope tracers. The method relies on linear mixing of source isotopic tracers, and deconvolution of a sediment mixture initially quantifies the contribution of sources to the mixture's tracer signature. Therefore, a correction to obtain real sediment source proportions is subsequently required. As far as we are aware, all published studies to date have used total isotopic tracer content or a proxy (e.g., soil carbon content) for this post‐unmixing correction. However, as the relationship between the isotopic tracer mixture and the source mixture is different for each isotopic tracer, post‐unmixing corrections cannot be carried out with one single factor. This contribution presents an isotopic tracer model structure—the concentration‐dependent isotope mixing model (CD‐IMM)—to overcome this limitation. Herein, we aim to clarify why the “conventional” approach to converting isotopic tracer proportions to source proportions using a single factor is wrong. In an initial mathematical assessment, error incurred by not using CD‐IMM (NCD‐IMM) in unmixing two sources with two isotopic tracers showed a complex relation as a function of relative tracer contents. Next, three artificial mixtures with different proportions of three soil sources were prepared and deconvoluted using ¹³C of fatty acids using CD‐IMM and NCD‐IMM. Using NCD‐IMM affected both accuracy (mean average error increased up to a threefold compared with the CD‐IMM output) and precision (interquartile range was up to 2.5 times larger). Finally, as an illustrative example, the proportional source contribution reported in a published study was recalculated using CD‐IMM. This resulted in changes in estimated source proportions and associated uncertainties. Content of isotopic tracers is seldom reported in published work concerning use of isotopic tracers for sediment source partitioning. The magnitude of errors made by miscalculation in former studies is therefore difficult to assess. With this contribution, we hope the community will acknowledge the limitations of prior approaches and use a CD‐IMM in future studies.     

The fate of B, Cl and Li in the subducted oceanic mantle and in the antigorite breakdown fluids

We present an inventory of B, Cl and Li concentrations in (a) key minerals from a set of ultramafic samples featuring the main evolutionary stages encountered by the subducted oceanic mantle, and in (b) fluid inclusions produced during high-pressure breakdown of antigorite serpentinite. Samples correspond to (i) nonsubducted serpentinites (Northern Apennine and Alpine ophiolites), (ii) high-pressure olivine-bearing antigorite serpentinites (Western Alps and Betic Cordillera), (iii) high-pressure olivine-orthopyroxene rocks recording the subduction breakdown of antigorite serpentinites (Betic Cordillera). Two main dehydration episodes are recorded by the sample suite: partial serpentinite dewatering during formation of metamorphic olivine, followed by full breakdown of antigorite serpentine to olivine+orthopyroxene+fluid. Ion probe and laser ablation ICP-MS (LA ICP-MS) analyses of Cl, B and Li in the rock-forming minerals indicate that the hydrous mantle is an important carrier of light elements. The estimated bulk-rock B and Cl concentrations progressively decrease from oceanic serpentinites (46.7 ppm B and 729 ppm Cl) to antigorite serpentinites (20 ppm B and 221 ppm Cl) to olivine-orthopyroxene rocks (9.4 ppm B and 45 ppm Cl). This suggests release of oceanic Cl and B in subduction fluids, apparently without inputs from external sources. Lithium is less abundant in oceanic serpentinites (1.3 ppm) and the initial concentrations are still preserved in high-pressure antigorite serpentinites. Higher Li contents in olivine, Ti-clinohumite of the olivine-orthopyroxene rocks (4.9 ppm bulk rock Li), as well as in the coexisting fluid inclusions, suggest that their budget may not be uniquely related to recycling of oceanic Li, but may require input from external sources.Laser ablation ICP-MS analyses of fluid inclusions in the olivine-orthopyroxene rocks enabled an estimate of the Li and B concentrations in the antigorite breakdown fluid. The inclusion compositions were quantified using a range of salinity values (0.4-2 wt.% NaCl_equiv) as internal standards, yielding maximum average ^fluid/rockD_B∼5 and ^fluid/rockD_Li∼3.5. We also performed model calculations to estimate the B and Cl loss during the two dehydration episodes of serpentinite subduction. The first event is characterized by high fluid/rock partition coefficients for Cl (∼100) and B (∼60) and by formation of a fluid with salinity of 4-8 wt.% NaCl_equiv. The antigorite breakdown produces less saline fluids (0.4-2 wt.% NaCl_equiv) and is characterized by lower partition coefficients for Cl (25-60) and B (12-30). Our calculations indicate that the salinity of the subduction fluids decreases with increasing depths. ^fluid/rockD_B/^fluid/rockD_Cl<1 (∼0.5) indicates that Cl preferentially partitions into the evolved fluids relative to B and that the B/Cl of fluids progressively increases with increasing depths and temperatures.Despite light element release in fluids, appreciable B, Cl and Li are still retained in chlorite, olivine and Ti-clinohumite beyond the antigorite stability field. This permits a bulk storage of about 10 ppm B, 45 ppm Cl and 5 ppm Li, i.e., concentrations much higher than in mantle reservoirs. Chlorite is the Cl repository and its stability controls the Cl and H₂O budget beyond the antigorite stability; B and Li are bound in olivine and clinohumite. The subducted oceanic mantle thus retains light elements beyond the depths of arc magma sources, potentially introducing anomalies in the upper mantle.     

Allozyme genotypes and tolerance to copper stress in Hediste diversicolor (Polychaeta: Nereididae)

This study analysed the occurrence of genotypic shifts in laboratory populations of Hediste diversicolor (Polychaeta: Nereididae) exposed to copper stress. Specimens of H. diversicolor were collected at three sites, up to 10 km apart, in the estuarine area of the Pialassa lagoons (North Adriatic Sea, Italy) and were used in acute toxicity tests. Specimens were assigned to copper exposure (0.34 mg/l Cu2+) or control conditions. Each combination of Treatment and Site was replicated in two tanks containing 35 specimens of H. diversicolor. The genotypic structure of both dead and survived specimens was analysed by allozyme electrophoresis at six loci (ALD, FH, HBDH LDH, PGI, SDH). Under copper exposure, specimens with the genotypes ALD100/100 and PGI102/102 had significantly lower mortalities than other genotypes Results were consistent across the three sites, suggesting that, under laboratory conditions, effects of copper stress on H. diversicolor is related to individual genotypes at ALD and PGI loci.     

A database of the structural behavior of masonry in shear

This paper reports the results of several on-site investigations carried out by the authors in the last 20 years in central Italy (Umbria, Marche, Emilia and Abruzzo regions) on masonry wall panels. The use of stone and brickwork masonry has been common for centuries not only for rural residences but also for public and religious buildings. In many areas, where the stone was abundant, stone became the material of choice for all constructions. However from rubble stone to perfectly squared stones, the mechanical properties may highly differ. Test results are reported with an accurate survey and analysis of the masonry typology and mechanical characterization was performed according to ASTM standards and consisted of measurements of shear properties. The paper also reports the experimental results of full-scale tests conducted on brickwork walls using different bonding patterns, mortar types and brick dimensions. These data were recorded in terms of shear strength, elastic properties and deformation capacity and are of critical importance for design, reinforcement or retrofit purposes in earthquake-prone areas. All tests were conducted on site from pre-existing undamaged wall panels. Finally, test results are compared with existing standards and indicate that masonry shear strength is sometimes overestimated by the Italian Building Code.     

Flexural uplift of a lithospheric slab near the Vema transform (Central Atlantic): Timing and mechanisms

The Vema Transverse Ridge (VTR) is a prominent, long and narrow topographic anomaly that runs for over 300 km along a sea floor spreading flow line south of the Vema transform at 11° N in the Atlantic. It rises abruptly about 140 km from the axis of the Mid-Atlantic Ridge (MAR) in 10 Myr old crust and runs continuously up to 25 Myr old crust. It reaches over 3 km above the predicted lithospheric thermal contraction level. It is absent in crust younger than 10 Myr; thus, the uplift of the VTR must have ended roughly 10 Ma. The VTR is interpreted as the exposed edge of a flexured and uplifted slab of oceanic lithosphere that was generated at an 80 km long MAR segment. Based on satellite gravimetry imagery this MAR segment was born roughly 50 Ma and increased its length at an average rate of 1.6 mm/yr. Multibeam data show that the MAR-parallel sea floor fabric south of the VTR shifts its orientation by 5° to 10° clockwise in 11–12 Myr old crust, indicating a change at that time of the orientation of the MAR axis and of the position of the Euler rotation pole. This change caused extension normal to the transform, followed between 12 and 10 Ma by flexure of the edge of the lithospheric slab, uplift of the VTR at a rate of 2 to 4 mm/yr, and exposure of a lithospheric section (Vema Lithospheric Section or VLS) at the northern edge of the slab, parallel to the Vema transform. Ages of pelagic carbonates encrusting ultramafic rocks sampled at the base of the VLS at different distances from the MAR axis suggest that the entire VTR rose vertically as a single block within the active transform offset. A 50 km long portion of the crest of the VTR rose above sea level, subsided, was truncated at sea level and covered by a carbonate platform. Subaerial and submarine erosion has gradually removed material from the top of the VTR and has modified its slopes. Spreading half rate of the crust south of the transform decreased from 17.2 mm/yr between 26 and 19 Ma to 16.9 mm/yr between 19 and 10 Ma, to 13.6 mm/yr from 10 Ma to present. The slowing down of spreading occurred close in time to the change in ridge/transform geometry, suggesting that the two events are related. A numerical model relates lithospheric flexure to extension normal to the transform, suggesting that the extent of the uplift depends on the thickness of the brittle layer, consistent with the observed greater uplift of the older lithosphere along the VTR.     

Deformation and stress regimes in the Hellenic subduction zone from focal Mechanisms

Fault plane solutions for earthquakes in the central Hellenic arc are analysed to determine the deformation and stress regimes in the Hellenic subduction zone in the vicinity of Crete. Fault mechanisms for earthquakes recorded by various networks or contained in global catalogues are collected. In addition, 34 fault plane solutions are determined for events recorded by our own local temporary network on central Crete in 2000–2001. The entire data set of 264 source mechanisms is examined for types of faulting and spatial clustering of mechanisms. Eight regions with significantly varying characteristic types of faulting are identified of which the upper (Aegean) plate includes four. Three regions contain interplate seismicity along the Hellenic arc from west to east and all events below are identified to occur within the subducting African lithosphere. We perform stress tensor inversion to each of the subsets in order to determine the stress field. Results indicate a uniform N-NNE direction of relative plate motion between the Ionian Sea and Rhodes resulting in orthogonal convergence in the western forearc and oblique (40–50^∘) subduction in the eastern forearc. There, the plate boundary migrates towards the SE resulting in left-lateral strike-slip faulting that extends to onshore Eastern Crete. N110^∘E trending normal faulting in the Aegean plate at this part is in accordance with this model. Along-arc extension is observed on Western Crete. Fault plane solutions for earthquakes within the dipping African lithosphere indicate that slab pull is the dominant force within the subduction process and responsible for the roll-back of the Hellenic subduction zone.