Mercury Redox Chemistry in the Negro River Basin, Amazon: The Role of Organic Matter and Solar Light

Pristine water bodies in the Negro River basin, Brazilian Amazon, show relatively high concentrations of mercury. These waters are characterized by acidic pH, low concentrations of suspended solids, and high amounts of dissolved organic matter and are exposed to intense solar radiation throughout the year. This unique environment creates a very dynamic redox chemistry affecting the mobility of mercury due to the formation of the dissolved elemental species (Hg⁰). It has been shown that in this so-called black water, labile organic matter from flooded forest is the major scavenger of photogenerated H₂O₂. In the absence of hydrogen peroxide, these black waters lose their ability to oxidize Hg⁰ to Hg²⁺, thus increasing Hg⁰ evasion across the water/atmosphere interface, with average night time values of 3.80 pmol m^?2 h^?1. When the dry period starts, labile organic matter inputs gradually diminish, allowing the increasing concentration of H₂O₂ to re-establish oxidative water conditions, inhibiting the metal flux across the water/atmosphere interface and contributing to mercury accumulation in the water column.     

Nutrient uptake in a highly turbid estuary (the Humber, United Kingdom) and adjacent coastal waters

Surveys were conducted in April and June 1995 to quantify the uptake of dissolved nutrients in a highly turbid estuary (the Humber, United Kingdom) and to determine the factors controlling nutrient uptake rates. A combination of isotope labelling methods were used in conjunction with on-deck incubation techniques to estimate the uptake of dissolved nutrients (PO₄ ^3?, NH₄ ⁺, NO₃ ^?, and urea) in surface samples collected from coastal waters. Similarly, isotope labelling and laboratory incubgation techniques were employed to estimate dissolved nitrogen uptake (NH₄ ⁺, NO₃ ^?, and urea) in surface samples collected from the estuary mouth. Nutrient uptake rates were at the low end of ranges for coastal and estuarine environments reported in the literature. Concentrations of chlorophyll and the availability of photosynthetically active radiation were identified as potentially important factors controlling the uptake rates of nutrients. Uptake rates of dissolved nitrogen in the Humber mouth appeared to be related to the location of smapling sites. Depletion rates of dissolved nutrients in situ were estimated on the basis of integrated water column nutrient uptake rates and indicated assimilation of up to 16% of nutrients in the entire water column. Estimated depletion rates did not indicate preferential loss of any of the nutrient species investigated.     

Tsunami deposits: Present knowledge and future challenges

Tsunami deposits are the primary source of information on (past) large tsunami events and thereby are crucial for accurate hazard assessments. Tsunami deposits studies have developed over the last three decades, but this is still a young geoscience discipline. Following the 5^th International Tsunami Field Symposium in 2017 an opportunity arose to publish a Special Issue focusing on present knowledge and future research challenges. This paper aims to briefly review current state-of-the-art research, summarizing major findings and gathering relevant works that describe the progress achieved over the last three decades. In this paper the relevance of tsunami deposits, their peculiar sedimentary characteristics and their differentiation from other high energy events are presented. Especially over the last decade an incredibly high number of studies have been published on tsunami deposits, many of which are of a high quality and provide detailed literature reviews. Some of these studies represent the current progress discussed here. Challenges are also introduced, to spur a discussion on future scientific questions that can and should be addressed by tsunami geoscientists. Coupling onshore–offshore records is an area where tsunami geoscience faces some of its major challenges. Moreover, the application of non-destructive high-resolution techniques to study the internal structure and composition of tsunami deposits can also provide an opportunity to further examine deposits, and from this derive physical parameters of the forcing mechanism. Another topic is better understanding of the erosional signature of tsunami events and a continuation of the effort to better incorporate age-estimation methods by developing more accurate dating methodology. Finally, there is also the need for the improvement of empirical, forward and regressive numerical models to better contribute to the characterization of tsunami events.     

Analysis of long- and short-term temporal variations of the diffuse CO2 emission from Timanfaya volcano,Lanzarote, Canary Islands

Reported herein are the results of eight soil CO₂ efflux surveys performed from 2006 to 2011 at Timanfaya Volcanic Field (TVF), Lanzarote Island with the aim of evaluating the long- and short-term temporal variations of the diffuse CO₂ emission. Soil CO₂ efflux values ranged from non-detectable up to 34.2 g m⁻² d⁻¹, with the highest values measured in September 2008. Conditional sequential Gaussian simulations (sGs) were applied to construct soil CO₂ efflux distribution maps and to estimate the total CO₂ output from the studied area at the TVF. Soil CO₂ efflux maps showed a high spatial and temporal variability. Total CO₂ emission rates ranged between 41 and 518 t d⁻¹, February 2011 (winter) being the season when maximum diffuse CO₂ emission rates were observed. To investigate the influence of external variables on the soil CO₂ efflux, a geochemical station (LZT01) was installed at TVF to measure continuously the soil CO₂ efflux between July 2010 and March 2012 Since external factors such as barometric pressure, rainfall, soil water content, soil and air temperatures, and wind speed influence strongly the observed soil CO₂ effluxes, multiple regression analysis was applied to the time series recorded by the automatic geochemical station LZT01 to remove the contribution of these external factors. The influence of meteorological variables on soil CO₂ efflux oscillations accounts for 13% of total variance, with barometric pressure, rainfall and/or soil water content having the most influence in the control of the soil CO₂ efflux. These observations along with the results from the eight soil gas surveys performed at TVF indicate that the short and long-term trends in the diffuse CO₂ degassing are mainly controlled by environmental factors.     

成岩作用与油气侵位对鄂尔多斯盆地延长组砂岩储层物性的影响

对鄂尔多斯盆地不同地区上三叠统延长组砂岩的岩石学、储层物性与成岩作用特征及其分布与变化规律的对比研究表明,盆地东部与盆地西部延长组来自不同物源区。压实作用是造成延长组砂岩孔隙丧失的主要原因,分别使长1—长3砂岩和长4 5—长10砂岩丧失的平均孔隙度占原始孔隙的59%和73.3%。胶结作用导致长1—长3和长4 5—长10砂岩丧失的平均孔隙度分别占原始孔隙的25.8%和27.5%,碳酸盐是造成砂岩物性降低的主要胶结物。晚成岩阶段盆地中发生的油气侵位和烃类物质在砂岩孔隙中的聚集抑制了自生石英和碳酸盐胶结物的沉淀。油气的富集对伊利石和绿泥石薄膜的形成没有明显的影响,后者可能对油气的聚集起了促进作用。晚成岩阶段水-岩反应产生的无机酸性流体和烃源岩中有机质向烃类转化过程中产生的有机酸性流体、以及表生成岩阶段的大气降水是导致砂岩储层物性改善的重要途径。     

Geochemical evolution of groundwater in the Maneadero coastal aquifer during a dry year in Baja California, Mexico

Water pumped from 25 shallow wells (<31 m) in the Maneadero unconfined coastal aquifer was studied geochemically in order to determine the short-term compositional variability of the aquifer due to seawater intrusion during a drier than normal year (Fall 2001 to Fall 2002). The groundwater was commonly found to be mixed with seawater, with TDS concentrations in November 2002 ranging from 0.99 to 9.46 g l^–1, having an intermediate Na⁺Cl^– to Ca²⁺Cl^– water-type. Rapid recharge events of short duration, after low and short rainfall events during the study period, are suggested from short-term fluctuations in water quality. Seawater intrusion is progressing faster in the central and southern coastal sections of the aquifer and has recently affected the quality of the sites pumping water to the nearby city of Ensenada. Only one of the wells used for the Ensenada water supply had a TDS concentration lower than the 1.0 g l^–1 official limit. Low flow rates and high residence times of water are inferred to be the cause for high alkalinity in the east-central section of the aquifer. High NO₃ in the east-central aquifer indicates that any NO₃ infiltration due to fertilizer use was only slightly dispersed. After a short rainfall season during winter 2001, a significant decrease was seen for the previously most enriched site. However, concentrations above the 10 mg l^–1 official limit persisted in 2002, affecting one well for urban supply (15.9 mg l^–1). The water from this well is nevertheless mixed with better-quality water from other wells before being distributed through the citys piping system.

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Resumen Se estudió la geoquímica de aguas bombeadas por medio de 25 pozos no muy profundos (<31 m) en el acuifero costero no confinado de Maneadero con el objetivo de determinar la variación de la composición en el corto plazo en el acuifero por la intrusión de agua de mar durante un año más seco de lo normal (otoño 2001 a otoño 2002). Se observó que comúnmente las aguas subterráneas estaban mezcladas con agua de mar, con concentraciones de sólidos totales disveltos (STD) de entre 0.99--9.46 g l^–1 y un tipo de agua intermedia Na⁺Cl^– to Ca²⁺Cl^–. A partir de las fluctuaciones en la calidad del agua en el corto plazo se puede inferir que se dan eventos de recarga rápida de poca duración después de eventos de poca lluvia de poca duración y poco volumen durante el periodo de estudio. La intrusión de agua de mar está progresando más rápido en el centro y sur del acuifero costero y ha afectado recientemente la calidad de los sitios de bombeo de agua para la ciudad de Ensenada. Solamente uno de los pozos usados para el abastamiento de Ensenada tiene un STD por debajo del límite oficial de 1.0 g l^–1. Se presume que las razones lentas de flujo y los tiempos de residencia largos del agua son la causa de la alta alcalinidad en el centro-este del acuifero. Una concentración alta de NO₃ en el este-centro del acuifero indica que cualquier infiltración de NO₃ por aplicación de fertilizantes ha sido poco dispersad. Después de poca lluvia en el invierno de 2001, se observó una disminución importante en la zona previamente más enriquecida. Sin embargo, concentraciones sobre el límite oficial de 10 mg l^–1 continuaron en 2002, afectando a un pozo para suministro de agua urbana (15.9 mg l^–1). El agua extraída de este pozo es mezclada con agua de mejor calidad y se distribuye por el sistema urbano de suministro de agua.

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Résumé Leau de pompage de 25 puits peu profonds (<31 m) situés dans laquifère côtier non-confiné de Maneadero a été étudiée dans le but de déterminer la variation géochimique à court terme qui résulte de lintrusion deau de mer lors dune année plus sèche quà lhabitude (automne 2001 à automne 2002). Leau souterraine est souvent retrouvée mélangée avec de leau de mer, avec des concentrations en résidus solides dissous (RSD) qui sétalent entre 0.99 et 9.46 g l^–1 pour novembre 2002, avec un type intermédiaire en Na⁺Cl^– jusquà Ca²⁺Cl^–. Les processus suggérés pour les fluctuations rapides de la qualité de leau sont des événements de recharge de courte duré suite à de faibles et brèves périodes de précipitations. Lintrusion deau de mer progresse plus rapidement dans les parties centrales et sud de laquifère côtier où la qualité de leau pompée vers la ville de Ensenada a récemment été affectée. Un seul des puits utilisés par la ville de Ensenada pour lapprovisionnement en eau potable a une concentration en RSD sous la limite officielle permise de 1.0 g l^–1. Le temps de résidence élevé et le faible taux découlement de leau souterraine sont présumés être la cause de lalcalinité élevée dans la partie centrale-est de laquifère. La concentration élevée en NO₃ dans cette partie de laquifère indique que la totalité de linfiltration de NO₃ dû à lutilisation de fertilisants ne sest que très peu dispersée. Suite à une courte saison des pluies à lhiver 2001, une diminution substantielle a été notée au site qui était le plus enrichi avant la saison des pluies. Malgré tout, des concentrations dépassant la limite officielle permise de 10 mg l^–1 ont persisté, affectant un puits utilisé pour lapprovisionnement urbain (15.9 mg l^–1). Leau provenant de ce puits est toutefois mélangée avec de leau de meilleure qualité provenant dautres puits avant dêtre distribuée par laqueduc municipal.

     

Age and significance of the Quaternary cemented deposits of the Duje Valley (Picos de Europa,Northern Spain)

Cemented calcareous breccias appear in the Picos de Europa (Cantabrian Mountains, Spain) resting on glacially abraded surfaces and covered by moraines. U/Th dating of the calcite coating the clasts was successful in two samples, the oldest one indicating that the breccias accumulated during or prior to Marine Isotope Stage (MIS) 11, and the youngest indicating later cementation during MIS 8. The former introduces a limit for the age of the glaciation preceding the breccias, which cannot correspond to an event younger than MIS 12. This is the oldest absolute age so far obtained for intercalated glacial/interglacial deposits of the Iberian Peninsula.     

A geochemical approach to distinguishing competing tectono-magmatic processes preserved in small eruptive centres

Small eruptive centres (SECs) representing short-lived, isolated eruptions are effective samples of mantle heterogeneity over a given area, as they are generally of basaltic composition and show evidence of little magmatic processing. This is particularly powerful in volcanic arcs where the original melting process generating stratovolcanoes is often obscured by additions from the down-going slab (fluids and sediments) and the overlying crust. The Pucón area of southern Chile contains active and dormant stratovolcanoes, Holocene, basaltic SECs and an arc-scale strike-slip fault (the Liquiñe Ofqui Fault System: LOFS). The SECs show unexpected compositional heterogeneity considering their spatial proximity. We present a detailed study of these SECs combining whole rock major and trace element concentrations, U-Th isotopes and olivine-hosted melt inclusion major element and volatile contents to highlight the complex inter-relations in this small but active area. We show that heterogeneity preserved at individual SECs relates to different processes: some start in the melting region with the input of slab-derived fluids, whilst others occur later in a centre’s magmatic history with the influence of crustal contamination prior to olivine crystallisation. These signals are deduced through the combination of the different geochemical tools used in this study. We show that there is no correlation between composition and distance from the arc front, whilst the local tectonic regime has an effect on melt composition: SECs aligned along the LOFS have either equilibrium U-Th ratios or small Th-excesses instead of the large—fluid influenced—U-excesses displayed by SECs situated away from this feature. One of the SECs is modelled as being generated from fluid-enriched depleted mantle, a source which it may share with the stratovolcano Villarrica, whilst another SEC with abundant evidence of crustal contamination may share its plumbing system with its neighbouring stratovolcano Quetrupillán, showing that polygenetic–monogenetic connections are unpredictable. Such marked preservation of individual magmatic histories highlights the isolation of individual melting events even in complex and highly volcanically active areas.     

Environmental and biological controls on elemental (Mg/Ca, Sr/Ca and Mn/Ca) ratios in shells of the king scallop Pecten maximus

The relationship between potential elemental proxies (Mg/Ca, Sr/Ca and Mn/Ca ratios) and environmental factors was investigated for the bivalve Pecten maximus in a detailed field study undertaken in the Menai Strait, Wales, U.K. An age model constructed for each shell by comparison of measured and predicted oxygen-isotope ratios allowed comparison on a calendar time scale of shell elemental data with environmental variables, as well as estimation of shell growth rates. The seasonal variation of shell Mn/Ca ratios followed a similar pattern to one previously described for dissolved Mn²⁺ in the Menai Strait, although further calibration work is needed to validate such a relationship. Shell Sr/Ca ratios unexpectedly were found to co-vary most significantly with calcification temperature, whilst shell Mg/Ca ratios were the next most significant control. The temporal variation in the factors that control shell Sr/Ca ratios strongly suggest the former observation most likely to be the result of a secondary influence on shell Sr/Ca ratios by kinetic effects, the latter driven by seasonal variation in shell growth rate that is in turn influenced in part by seawater temperature. P. maximus shell Mg/Ca ratio to calcification temperature relationships exhibit an inverse correlation during autumn to early spring (October to March-April) and a positive correlation from late spring through summer (May-June to September). No clear explanation is evident for the former trend, but the similarity of the records from the three shells analysed indicate that it is a real signal and not a spurious observation. These observations confirm that application of the Mg/Ca proxy in P. maximus shells remains problematic, even for seasonal or absolute temperature reconstructions. For the range of calcification temperatures of 5-19 °C, our shell Mg/Ca ratios in P. maximus are approximately one-fourth those in inorganic calcite, half those in the bivalve Pinna nobilis, twice those in the bivalve Mytilus trossulus, and four to five times higher than Mg/Ca ratios in planktonic and benthonic foraminifera. Our findings further support observations that Mg/Ca ratios in bivalve shell calcite are an unreliable temperature proxy, as well as substantial taxon- and species-specific variation in Mg incorporation into bivalves and other calcifying organisms, with profound implications for the application of this geochemical proxy to the bivalve fossil record.