The Pliensbachian–Toarcian succession of North Yorkshire provides a global reference for the interval incorporating the Toarcian Oceanic Anoxic Event (T-OAE, ∼183 Ma). Major and trace element, carbon stable-isotope (δ13Corg) and total organic carbon (TOC) data for the Dove’s Nest core, drilled close to the classic outcrop sections of the Yorkshire coast, demonstrate geochemical, mineralogical and grain-size trends linked to sea level and climate change in the Cleveland Basin. High-resolution correlation between the core and outcrop enables the integration of data to generate a comprehensive chemostratigraphic record. Palaeoredox proxies (Mo, U, V, TOC/P, DOP and Fe speciation) show a progressive shift from oxic bottom waters in the late Pliensbachian through dysoxic–anoxic conditions in the earliest Toarcian to euxinia during the T-OAE. Anoxia–dysoxia persisted into the middle Toarcian. Elemental and isotope data (Re, Re/Mo, δ34SCAS, δ98Mo and ε205Tl) from the coastal sections evidence global expansion of anoxic and euxinic seafloor area driving drawdown of redox-sensitive metals and sulfate from seawater leading to severe depletion in early Toarcian ocean water. The record of anoxia–euxinia in the Cleveland Basin largely reflects global-scale changes in ocean oxygenation, although metal depletion was temporarily enhanced by periods of local basin restriction. Osmium and Sr isotopes demonstrate a pulse of accelerated weathering accompanying the early Toarcian hyperthermal, coincident with the T-OAE. The combined core and outcrop records evidence local and global environmental change accompanying one of the largest perturbations in the global carbon cycle during the last 200 Ma and a period of major biotic turnover.

The conditions under which an exchanger phase will behave as an ideal mixture are established from thermodynamic principles. It is shown that, if a stoichiometric cation-exchange reaction is reversible, the exchanger phase will exhibit ideal behavior if the Vanselow selectivity coefficient is independent of the exchanger composition. This criterion is applied to some recently published data for Na+-trace metal cation exchange on Camp Berteau montmorillonite. An analysis of the data suggests that, so long as the exchange process is reversible, Na+-trace metal cation exchange produces an exchanger phase that behaves as an ideal mixture.

Secondary Fe(III) oxyhydroxides play a key role in controlling the mobility and bioavailability of trace metals in acidic, sulfate-rich soils, such as mining and smelter sites. Schwertmannite, jarosite, goethite, and ferrihydrite are the most common mineral phases identified in such soils. A good understanding of the precipitation and transformation of these minerals in soils is very important for predicting the mobility and long-term stability of trace metals associated with them. In the present study, bulk powder X-ray diffraction (XRD), scanning electron microscopy (SEM), synchrotron based micro- X-ray diffraction (µ-XRD), and micro X-ray fluorescence (µ-SXRF) spectroscopy were used to investigate precipitates fromthe surface horizon of an organic soil (Histosol) at a site that once contained a lead smelter. Soil samples were collected from 0 to ≈10 cm depth during both wet and dry seasons. Goethite and akaganeite were identified as the major mineral phases in this soil. Schwertmannite and jarosite were also occasionally identified, particularly in the soil samples from dry periods. The peaks in the akaganeite XRD pattern were significantly broadened and the relative intensities of some major peaks were distinctly different compared with the diffraction pattern of synthetic akaganeite, possibly due to the effects of pH and the incorporation of sulfate. The SEM and µ-XRD data support the hypothesis that the goethite in the precipitates is not the product of direct precipitation froms olution but the transformation of previously precipitated schwertmannite or akaganeite.

Elasmobranchs in the Gulf of California have been found with malformations, probably originated during embryonic development or caused by environmental anomalies and pollution associated with intense mining activity in the region. Clasper malformations are reported for the first time in two specimens of Pseudobatos buthi, a species recently described from the Gulf of California. The function of the claspers was not affected by the size difference, because specimens presented the distinctive characteristics of an adult individual. The reproductive system did not show any malformation, with symmetrical testes. Histological analysis of the testes revealed a normal spermatogenic development. To elucidate the causes and to detect a possible effect of the morphological malformations due to high levels of heavy metals, trace concentration values (cadmium, copper, iron, manganese, silver, lead and zinc) were determined in muscle and liver. Cadmium and lead concentrations in the muscle of the two specimens were below the permissible limit for human consumption (<0.05 mg kg−1); however, iron and zinc presented high values (0.455, 4.024 mg kg−1 in muscle and 21.931, 3.694 mg kg−1 in liver respectively). Mining activity and heavy metal pollution in the sampling area may have caused the malformations, which might be attributed to the high values of iron and zinc discovered in the muscle and liver.

This paper highlights new research on the biomineralization of otoliths and uses a mineralogical approach to understand mechanisms of crystal growth and metal incorporation into otoliths. Petrographic observations of the nucleation of otolith growth in the core for several fish species reveals that sagittal otoliths appear to nucleate around a few or many nucleation sites (primordia) and that these sites vary in size (ranging in diameter from 1 to 20 μm), depending on the species. Spectroscopic data show a large Mn-enrichment in the primordia within the core but the reasons for this enrichment are still unclear (e.g. organic matter or possibly another material other than CaCO3). This study also provides the first multi trace-element data for endolymph fluid and the growing otolith; we found large enrichments (Ca and Sr) and depletions (Na, K, Zn and Rb) of elements in the otolith relative to the endolymph. The last part of this paper examines the effect of crystal structure on the microchemistry ofotoliths. Our investigation helps understand how the chemical characteristics of the metal ions (i.e. ionic radii) and the crystalline structure interact to cause differential trace-metal uptake between the CaCO3 polymorphs, aragonite and vaterite.

A temporal analysis of the benthic polychaete community and its relationship with environmental variables was conducted by comparing coastal sediment samples collected in three separate sampling events between 1998 and 2013 from the southern end of the Southern California Bight (SCB). Environmental variables indicated a spatio-temporal increase of the sand fraction in sediment composition. Station stratification by depth from shallow to deep, and a reduction of trace metal enrichment (Co, Cr, Cu, Mn, Ni, Pb and Zn) was also found. There was a notable change in polychaete family composition due to high abundances and frequency of Spionidae, Chaetopteridae and Phyllodocidae in 2013, especially close to the Binational wastewater treatment plant discharge. An increase in polychaete abundance, richness and diversity was indicative of a probable relationship with regional weather conditions (El Niño-Southern Oscillation and recent drought events during sampling) along with local anthropogenic discharges of wastewater treatment plants in the area.

New speleothem records from northeastern Iberian caves provide data to explore the climatic patterns during the Holocene. We present δ13C and Mg/Ca from three speleothems from two different caves located in the Iberian Range allowing replication of the climatic signal for several millennia. Through the integration of those stalagmites covering since the Holocene onset to 2 ka, the early Holocene (11.7–8.5 ka) appears as the wettest interval. A marked change towards aridity is observed during the middle Holocene (8.5–4.8 ka) and an increase of humidity afterwards (4.8–2 ka). This three-part pattern, contrasting with other Iberian sequences, seems to be associated with the different role that seasonality has played in the response of different proxies (or records) to changes in water availability. Interpreting our speleothem records as changes in winter-spring precipitation along the Holocene allows reconciling previous data on hydrological variability from the western Mediterranean borderlands.

Levels of pollution, including contamination by toxic metals, in the Thames estuary reduced over the last four decades of the 20th century. This 2014 study investigates whether the declines in the bioavailabilities of trace metals (Ag, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, Zn) have continued in the 21st century, using a suite of littoral biomonitors also employed in 2001 – the brown seaweed Fucus vesiculosus, the strandline, talitrid amphipod Orchestia gammarellus and the estuarine barnacle Amphibalanus improvisus. Bioaccumulated concentrations represent relative measures of the total bioavailabilities of each metal to the biomonitor over a previous time period, and can be compared over space and over time. Trace metal bioavailabilities varied along the estuary, and, in general, fell between 2001 and 2014, a reflection of the continuing remediation of the Thames estuary from its severely polluted state in the middle of the 20th century.

The capacity to bioaccumulate trace metals present in San Jorge Bay, Antofagasta, Chile,was determined in northern scallop, Argopecten purpuratus, to examine thevalue of this important commercially species as a bioindicator of heavy metal pollution inareas where it is cultured. Scallops were sampled in summer 2009 in four sites: threenatural populations (Coloso, Historic District and La Rinconada, marine reserve), and acommercial hatchery (Colorado). The concentrations of three heavy metals (copper, cadmiumand lead) were then determined through stripping chronopotentiometric methods, and thelevels of four biomarkers: three genes implicated in the stress and oxidative metabolism,i.e., glutathione peroxidase (GPx), glutathione s-transferase (GST) and heat shock protein70 (HSP70), and a protein marker in the digestive gland and gill, a metallothionein (MT).The Historic District, located in the downtown area of the city, showed the highest metalconcentration of all the sampled sites, as well as the highest levels of the fourbiomarkers. This can be largely attributed to the nearby international port area of thetown and high sea traffic flow, exacerbated by the prevailing winds.

Cadmium, chromium, copper, nickel, lead and zinc concentrations in the bivalve mollusc Macoma balthica and the polychaete annelids Hediste diversicolor and Arenicola marina were measured, during winter and summer, at sites throughout the Severn Estuary and Bristol Channel. The mean concentration of each metal in A. marina was greater in the lower Severn Estuary than in the far less contaminated outer Bristol Channel and the concentration of a given metal, e.g. Cr, in a species occasionally peaked at a site, reflecting local metal contamination. The concentrations of each metal in each of these biomonitor species almost invariably differed significantly among sites and often seasons and there were sometimes interactions between site and season. This indicates that the various factors that determine the concentration of a metal in a species operate in a complex manner and that their individual effects can vary among sites and/or seasons. The rank order of each metal concentration in each species at a site within the estuary frequently did not match the sequence for the concentration of that metal measured in the sediment at that site at the same time. This lack of correspondence is likely to be due, at least in part, to one or both of the following: (1) variations in the bioavailability of certain metals among sites due to differences in such features as the metal-binding properties of the sediments; (2) the effects of the constant transport and redistribution of the sediments and thus also of their associated trace metals by the very strong tidal action that characterizes the Severn Estuary. This would mean that single time measurements do not accurately reflect the overall trace metal environment to which the biomonitor organism had been exposed in the weeks/months prior to sampling. Marked differences in the concentrations of certain metals, e.g. Cu and Zn, in co-occurring biomarker species could frequently be related to differences between the ability of these species to regulate certain metals. Non-metric multi-dimensional scaling ordination and associated tests emphasize that the relationships between the concentrations of the various metals differed markedly among species and between sites and seasons in individual species and elucidated which metals contributed most to those differences. If the proposed scheme for harnessing tidal power in the Severn Estuary proceeds, the data in this paper provide a baseline for assessing the impact of such major changes on the bioavailability of trace metals in this estuary. This information will also be invaluable for predicting the changes likely to occur in other estuaries that become subjected to major structural changes.

This work represents a concerted effort aimed at understanding the microbiological and chemical evolution of a small boreal lake during the diurnal cycle of photosynthesis. We studied diurnal variation of ∼40 dissolved macro- and trace elements, organic carbon and bacterial population dynamics in the surface and bottom water layer of the shallow Vilno Lake in the White Sea basin. Four-days continuous measurements with 6 h sampling steps both at the surface (0.5 m) and on the bottom (4.0 m depth) during no-bloom periods revealed constant concentrations (within ±20–30%) of all major elements (Na, Mg, Si, K, Ca), organic and inorganic carbon and most trace elements (B, V, Cr, Fe, Cu, Ga, As, Rb, Sr, Y, Zr, Sb, Cs, Ba, all REEs, Hf, Pb, Th, U). At the same time, the concentration of some biologically important trace metals (Mo, Mn, Co, Cd) was subjected to variations partially reflecting the change of bacterioplankton concentration. This work enables two types of element behavior to be distinguished during photosynthesis in the water column – constant concentration and sinusoidal variations – depending on their speciation in solution and their affinity to aquatic microorganisms.

The chemistry of epiphytic lichens was determined in two Venezuelan cloud forests adjacent to the Caracas Valley at Altos de Pipe and El Avila National Park. This is the second component of a two-part study examining the chemistry of fogs and their effects on sensitive biota in these forests. The widespread lichen Parmotrema madagascariaceum was chosen as an indicator of trace metal input. Background lichen collections and transplant experiments were carried out to evaluate spatial trends in atmospheric depositon of trace metals at different altitudes and exposures of the two montane locations. Elevated concentratons of metals including Pb and Zn were seen in lichen tissue and associated bark. Lead levels in lichens reached 190 μg g-1 dry wt. Lichens transplanted from relatively ‘clean’ to more polluted sites showed significant increases of metals, particularly Pb. Increases of up to 6.3 μg Pb g-1 mo-1 after 6 and 10 months were recorded relative to background and in situ lichen material. In contrast, when lichsens were reciprocally transplanted in nylon net bags from less to more exposed sites there was a significant decrease in Pb and Zn concentrations after 6 and 10 months. With long-term exposure to elevated concentrations of these trace metals epiphytic lichens, as well as other sensitive cloud forest biota, may be at risk of decline.

This study aims to evaluate the health status of Bizerta lagoon using a sentinel species, the Neogastropod Murex trunculus. Trace metal concentrations (Cd, Cu and Zn) in the foot and digestive gland, and biomarkers such as acetylcholinesterase (AChE), catalase (CAT) and glutathione transferase (GST) activities in the digestive gland, were determined in samples collected at four sites at different periods of the year. One site, in the North of the lagoon, is influenced by urban and industrial waste waters. Another, to the south, is located at the outfall of Ichkeul Lake. A third site is one that may be impacted by eutrophication processes, and the last, in the center of lagoon, is considered as less polluted. Temperature and salinity were simultaneously measured during the mollusc samplings. They varied greatly, from 13.5 °C and 30 psu in February to much higher values in summer-autumn: 30.7 °C and 37 psu. Metal concentrations were always higher in the digestive gland than in the foot. In the digestive gland, the lowest Cd and Cu concentrations were found in the center of the lagoon (mean ± standard deviation: 9.35 ± 0.78 µg Cd g−1 and 84.5 ± 15.3 µg Cu g−1) and no significant Zn variations were noted (682± 38 µg g−1) between sites. Metal concentrations in both types of tissue were higher in winter than in summer. AChE varied significantly among sites with high activities for individuals in the center of lagoon (15.4 ± 0.3 nmol min−1 mg-1 protein), whereas GST were low (12.2 ± 0.8 nmol min−1 mg−1 protein); CAT activities were low in this site 8.7 ± 0.5 µmol min-1 mg-1 protein. Season also had an influence on biomarkers, with low AChE in winter and rather low CAT and GST in summer. Principal component analysis showed that the center of lagoon can be considered as a reference site, whereas high chemical and biochemical responses were found in M. trunculus from other sites; particularly at the site which may be subject to eutrophication.

The concentrations of the Al, Co, Cr, Cu, Pb, Sn, Ni, and Zn trace metals were monitored in Lake Ipê (Brazil) during twohydrological sub-periods : June - December 1999 (low water period, LW), and January - April 2000 (high water period, HW).A detailed study of the physical and chemical state of the metals was performed through the MINTEQA2 computer programusing 15 abiotic parameters. An increase in concentration of many trace metals in July 1999 was due to the sudden entry ofallochthonous matter. The seasonal study showed that the metal concentrations in the lake were governed by the hydrologicalregime of the Paran· River (HW), and by the occurrence of occasional flood pulses and rainfall (LW).