Coral Ba/Ca molar ratios as a proxy of precipitation in the northern Yucatan Peninsula,Mexico

The Yucatan Peninsula consists of a karstic terrain that allows the aquifer to directly recharge from rainfall. Due to the various dissolution/precipitation reactions occurring during groundwater flow, the groundwater discharge in the coastal zone becomes a source of trace elements including Ba. The aim of this study was to use the coralline Ba/Ca record as a proxy of precipitation under the consideration that rainfall rates vary at inter-annual time scales. Annual Ba/Ca ratios, both the total content (Ba/Ca_TC) and the Ca-substitutive fraction (Ba/Ca_CaF), were quantified in a 52-a old coral colony of Montastraea annularis from the Punta Nizuc Reef, Mexican Caribbean. Average Ba/Ca_TC (5.90 ± 0.56 μmol/mol) was ∼20% higher than Ba/Ca_CaF (4.85 ± 0.33 μmol/mol) indicating that Ba is also incorporated in other fractions. Correlation between annual precipitation and Ba/Ca_TC time-series is significant (r = 0.77, p < 0.05), allowing the use of the Ba/Ca_TC ratio as a proxy of precipitation, and hence, enabling the reconstruction of precipitation patterns through time. Likewise, the Ba/Ca_CaF ratio can be used for the reconstruction of dissolved Ba in coastal seawater.     

Magnetic record associated with tree ring density: Possible climate proxy

A magnetic signature of tree rings was tested as a potential paleo-climatic indicator. We examined wood from sequoia tree, located in Mountain Home State Forest, California, whose tree ring record spans over the period 600 – 1700 A.D. We measured low and high-field magnetic susceptibility, the natural remanent magnetization (NRM), saturation isothermal remanent magnetization (SIRM), and stability against thermal and alternating field (AF) demagnetization. Magnetic investigation of the 200 mm long sequoia material suggests that magnetic efficiency of natural remanence may be a sensitive paleoclimate indicator because it is substantially higher (in average >1%) during the Medieval Warm Epoch (700–1300 A.D.) than during the Little Ice Age (1300–1850 A.D.) where it is <1%. Diamagnetic behavior has been noted to be prevalent in regions with higher tree ring density. The mineralogical nature of the remanence carrier was not directly detected but maghemite is suggested due to low coercivity and absence of Verwey transition. Tree ring density, along with the wood's magnetic remanence efficiency, records the Little Ice Age (LIA) well documented in Europe. Such a record suggests that the European LIA was a global phenomenon. Magnetic analysis of the thermal stability reveals the blocking temperatures near 200 degree C. This phenomenon suggests that the remanent component in this tree may be thermal in origin and was controlled by local thermal condition.     

Landslides as a geomorphological proxy for climate change: A record from the Dolomites (northern Italy)

The periphery of the Qinghai-Tibet Plateau is renowned for its susceptibility to landslides. However, the northwestern margin of this region, characterised by limited human activities and challenging transportation, remains insufficiently explored concerning landslide occurrence and dispersion. With the planning and construction of the Xinjiang-Tibet Railway, a comprehensive investigation into disastrous landslides in this area is essential for effective disaster preparedness and mitigation strategies. By using the human-computer interaction interpretation approach, the authors established a landslide database encompassing 13003 landslides, collectively spanning an area of 3351.24 km² (36°N-40°N, 73°E-78°E). The database incorporates diverse topographical and environmental parameters, including regional elevation, slope angle, slope aspect, distance to faults, distance to roads, distance to rivers, annual precipitation, and stratum. The statistical characteristics of number and area of landslides, landslide number density (LND), and landslide area percentage (LAP) are analyzed. The authors found that a predominant concentration of landslide origins within high slope angle regions, with the highest incidence observed in intervals characterised by average slopes of 20° to 30°, maximum slope angle above 80°, along with orientations towards the north (N), northeast (NE), and southwest (SW). Additionally, elevations above 4.5 km, distance to rivers below 1 km, rainfall between 20‒30 mm and 30‒40 mm emerge as particularly susceptible to landslide development. The study area’s geological composition primarily comprises Mesozoic and Upper Paleozoic outcrops. Both fault and human engineering activities have different degrees of influence on landslide development. Furthermore, the significance of the landslide database, the relationship between landslide distribution and environmental factors, and the geometric and morphological characteristics of landslides are discussed. The landslide H/L ratios in the study area are mainly concentrated between 0.4 and 0.64. It means the landslides mobility in the region is relatively low, and the authors speculate that landslides in this region more possibly triggered by earthquakes or located in meizoseismal area.     

An assessment of the Sr/Ca ratio in shallow water hermatypic corals as a proxy for sea surface temperature

The high precision measurement of the Sr/Ca ratio in corals has the potential for measuring past sea surface temperatures at very high accuracy. However, the veracity of the technique has been questioned on the basis that there is both a spatial and temporal variation in the Sr/Ca ratio of seawater, and that kinetic effects, such as the calcification rate, can affect the Sr/Ca ratio of corals, and produce inaccuracies of the order of 2-4 °C. In the present study, a number of cores of the massive hermatypic scleractinian coral Porites, from the central Great Barrier Reef, have been analyzed for Sr/Ca at weekly to monthly resolution. Results from a 24 year record from Myrmidon Reef show an overall variation from 22.7 °C to 30.4 °C. The record shows a warming/cooling trend with maximum warming centred on the 1986-1987 summer. While some bleaching was reported to have occurred at Myrmidon Reef in 1982, the Sr/Ca record indicates that subsequent summer temperatures were much higher. The 4.5 year record from Stanley Reef shows a maximum SST of 30 °C during the 1997-1998 El Niño event. The calibrations from Myrmidon and Stanley Reefs are in excellent agreement with previously published calibrations from nearby reefs. While corals do not calcify in equilibrium with seawater due to physiological control on the uptake of Sr and Ca into the lattice of coralline aragonite, it can be argued that, provided only a single genus such as Porites sp. is used, and that the coral is sampled along a major vertical growth axis, then the Sr/Ca ratio should vary uniformly with temperature. Similarly, objections based on the spatial and temporal variability of the Sr/Ca activity ratio of seawater can be countered on the basis that in most areas where coral reefs grow there is a uniformity in the Sr/Ca activity ratio, and there does not appear to be a change in this ratio over the growth period of the coral. Evidence from several corals in this study suggest that stress can be a major cause of the breakdown in the Sr/Ca-SST relationship. Thermal stress, resulting from either extremely warm or cool temperatures, can produce anomalously low Sr/Ca derived SSTs as a result of the breakdown of the biological control on Sr/Ca fractionation. It is considered that other stresses, such as increased nutrients and changes in light intensity, can also lead to a breakdown in the Sr/Ca-SST relationship. Two of the main issues affecting the reliability of the Sr/Ca method are the calibration of the Sr/Ca ratio with measured SST and the estimation of tropical last glacial maximum (LGM) palaeotemperatures. Instead of producing a constant calibration, just about every one published so far is different from the others. What is obvious is that for most calibrations while the slope of the calibration equation is similar, the intercepts are not. While the cause for this variation is still unknown, it would appear that corals from different localities around the world are responding to their own particular environment or that certain types of environments exert a control on the corals’ physiology. Sr/Ca derived SST estimates for the LGM and deglaciation of 5 °C-6 °C cooler than present are at odds with estimates of 2 °C-3 °C cooling by other climate proxies. The apparent lack of reef growth during the LGM suggests that SSTs were too cold in many parts of the tropics for reefs to develop. This would lend support to the idea that tropical SSTs were much cooler than what the CLIMAP data suggests.     

Variations of the Ca/Ca ratio in seawater during the past 24 million years: evidence from δCa and δO values of Miocene phosphates

The Ca isotope variation of 11 Miocene and Pleistocene, authigenic, marine phosphates is rather small compared to the corresponding variation in δ¹⁸O values. The δ⁴⁴Ca values are not correlated with the δ¹⁸O values and, therefore, they are not temperature controlled. It is likely that the δ⁴⁴Ca values of the phosphorites reflect the variation in the δ⁴⁴Ca values of paleo-seawater but, in contrast to Sr, not the isotopic composition of seawater itself. Furthermore, Ca and Sr isotopic compositions are decoupled with decreasing stratigraphic age of the phosphate peloids with Sr isotopic compositions changing to more radiogenic values while Ca isotopic compositions remain rather stable. All samples have δ⁴⁴Ca values below present-day seawater values, suggesting that phosphate formation discriminates against heavy Ca isotopes.Phosphorites and carbonaceous sediments have a similar Ca isotopic variation during the Miocene. A systematic and more or less constant shift between marine carbonates and phosphates is observed: the phosphate samples are slightly less enriched in ⁴⁰Ca compared to carbonates. This shift has been related to a mineral-dependent kinetic mass fractionation during precipitation from seawater. The rather stable δ⁴⁴Ca value for the 19 to 9 Ma old phosphorites points to a constant δ⁴⁴Ca fractionation of about 1.1 between seawater and phosphorites during the past and suggests steady-state conditions for the Mid-Miocene seawater (sedimentation flux equals erosion flux).     

Calcium isotope record of Phanerozoic oceans: Implications for chemical evolution of seawater and its causative mechanisms

A total of 280 brachiopods of Ordovician to Cretaceous age, complemented by published data from belemnites and planktonic foraminifera, are used to reconstruct the evolution of calcium isotope composition of seawater (δ^44/40Ca_SW) over the Phanerozoic. The compiled δ^44/40Ca_SW record shows a general increase from ∼1.3‰ (NIST SRM 915a) at the beginning of the Ordovician to ∼2‰ at present. Superimposed on this trend is a major long-term positive excursion from the Early Carboniferous to Early Permian as well as several short-term, mostly negative, oscillations.A numerical model of the global cycles of calcium, carbon, magnesium and strontium was used to estimate whether the recorded δ^44/40Ca_SW variations can be explained by varying magnitudes of input and output fluxes of calcium to the oceans. The model uses the record of marine ⁸⁷Sr/⁸⁶Sr ratios as proxy for seafloor spreading rates, a record of oceanic Mg/Ca ratios to estimate rates of dolomite formation, and reconstructed atmospheric CO₂, discharge and erosion rates to estimate continental weathering fluxes.The model results indicate that varying magnitudes of the calcium input and output fluxes cannot explain the observed δ^44/40Ca_SW trends, suggesting that the isotope signatures of these fluxes must also have changed. As a possible mechanism we suggest variable isotope fractionation in the sedimentary output flux controlled by the dominant mineralogy in marine carbonate deposits, i.e. the oscillating ‘calcite-aragonite seas’. The ultimate control of the calcium isotope budget of the Phanerozoic oceans appears to have been tectonic processes, specifically variable rates of oceanic crust production that modulated the hydrothermal calcium flux and the oceanic Mg/Ca ratio, which in turn controlled the dominant mineralogy of marine carbonates, hence the δ^44/40Ca_SW. As to the causes of the short-term oscillations recorded in the secular δ^44/40Ca_SW trend, we tentatively propose that these are related to variable rates of dolomite formation and/or to changing chemical composition of the riverine flux, in particular and ratios, induced by variable proportions of silicate vs. carbonate weathering rates on the continents.     

Benthic foraminiferal Mg/Ca-paleothermometry: a revised core-top calibration

Core-top samples from different ocean basins have been analyzed to refine our current understanding of the sensitivity of benthic foraminiferal calcite magnesium/calcium (Mg/Ca) to bottom water temperatures (BWT). Benthic foraminifera collected from Hawaii, Little Bahama Bank, Sea of Okhotsk, Gulf of California, NE Atlantic, Ceara Rise, Sierra Leone Rise, the Ontong Java Plateau, and the Southern Ocean covering a temperature range of 0.8 to 18°C were used to revise the Cibicidoides Mg/Ca-temperature calibration. The Mg/Ca-BWT relationship of three common Cibicidoides species is described by an exponential equation: Mg/Ca = 0.867 ± 0.049 exp (0.109 ± 0.007 × BWT) (stated errors are 95% CI). The temperature sensitivity is very similar to a previously published calibration. However, the revised calibration has a significantly different preexponential constant, resulting in different predicted absolute temperatures. We attribute this difference in the preexponential constant to an analytical issue of accuracy. Some genera, notably Uvigerina, show apparently lower temperature sensitivity than others, suggesting that the use of constant offsets to account for vital effects in Mg/Ca may not be appropriate. Downcore Mg/Ca reproducibility, as determined on replicate foraminiferal samples, is typically better than 0.1 mmol mol⁻¹ (2 S.E.). Thus, considering the errors associated with the Cibicidoides calibration and the downcore reproducibility, BWT may be estimated to within ±1°C. Application of the revised core-top Mg/Ca-BWT data to Cenozoic foraminiferal Mg/Ca suggests that seawater Mg/Ca was not more than 35% lower than today in the ice-free ocean at 50 Ma.     

I/(Ca+Mg)作为指示碳酸盐沉积氧化还原条件的重要指标: 研究进展与问题评述*

海水氧化还原条件显著影响真核生物的起源与早期演化,但以往有关早期海水氧化还原条件研究的对象,主要依赖相对深水的细粒碎屑岩沉积(如黑色页岩),而对真核生物集中分布的浅水环境中的碳酸盐岩关注不够且手段缺乏。这显著制约了对真核生物起源与早期演化机理的认识。近年来,有学者提出碳酸盐岩的I/(Ca+Mg)值可作为反映海洋氧化还原条件的重要指标,并将其广泛应用于海相碳酸盐岩的古氧相研究中。该指标的提出主要基于对现代海洋碘组分的观测以及室内方解石合成实验结果: 观测结果表明,海水中的碘主要以氧化态(IO₃^-)和还原态(I^-)2种形式存在,随着氧含量的下降(如在氧极小带),氧化态的碘被逐步转换为还原态的碘,且海水中的IO₃^-浓度与海水氧含量大体呈正相关。实验研究证明,IO₃^-可按一定的分配系数进入到碳酸盐矿物晶格中,但I^-则不能。由于IO₃^-/I^-的还原势能与O₂/H₂O的还原势能接近,因此I/(Ca+Mg)值是最早响应海洋氧含量下降的指标之一,可用于表征深时(如前寒武纪)次氧化环境中表层海水的氧含量波动。此外,学者们也尝试建立I/(Ca+Mg)值与氧含量之间的半定量关系,如I/(Ca+Mg)值大于0和2.5μmol/mol这两个临界值所对应的海水氧含量。结合大量现代缺氧水体和氧极小带中碘组分与溶解氧浓度相关关系的研究,作者提出I/(Ca+Mg)=1.5μmol/mol为重要的临界值之一,可用于限定初级生产力在表层海水中所能产生的最大氧浓度值(~10 μM),并能进一步区分海水和大气的氧化。此外,对I/(Ca+Mg)值的应用进展及潜在问题进行评述,并对可能的发展方向进行展望。     

The Lateglacial and Holocene in Central Europe: a multi‐proxy environmental record from the Bohemian Forest,Czech Republic

The Hercynian mountain ranges were islands of mountain glaciation and alpine tundra in a Central European ice‐free corridor during the Late Pleistocene. Today they are notable areas of glacial landforms, alpine‐forest free areas, peatlands and woodlands. However, our knowledge of the Lateglacial and early Holocene environmental changes in this region is limited. We present a new multi‐proxy reconstruction of a mid‐altitude environment in the Bohemian Forest spanning this period. A core (5.2 m length) in the ?erné Lake cirque (1028 m a.s.l.) was subjected to lithological, geochemical, pollen and macrofossil analysis supplemented by two optically stimulated luminescence (OSL) and 10 AMS radiocarbon dates. We determined the impact of regional and supraregional climate changes on the environment. The two most significant changes in sedimentation during the Lateglacial (17.6 and 15.8–15.5 cal. ka BP) were synchronous with regional glacial chronostratigraphy. Unlike Central European mountain ranges, in the Bohemian Forest the Younger Dryas was not coincident with glacier re‐advance, but was a dry, cold episode with low lake levels, which prevailed until the early Preboreal. Plant macrofossils indicate local establishment of Betula nana and Betula pendula/pubescens at 15.4–13.4 cal. ka BP. Comparison with Holocene records from Central Europe shows a similar immigration history of vegetation at mid and higher altitudes. The tree line exceeded an altitude of ~1000 m a.s.l. around 10.5 cal. ka BP and coincided with rapid geochemical changes in the sediment. The 8.2 ka BP event did not have any response in the sedimentary record, but corresponded to stabilization of the Picea abies population and expansion of Fagus. Fagus colonized the Bohemian Forest earlier than other Hercynian mid‐mountains, but never predominated in the composition of the forest at higher elevations. Abies alba was the last tree species that immigrated to the study area.     

The Late Pleistocene clastic deposits in the Romito Cave,southern Italy: a proxy record of environmental changes and human presence

Clastic sediments deposited in caves and rock shelters bear peculiar sedimentological characteristics and have seldom been considered as a high‐resolution proxy record of climatic or environmental changes. The Romito Cave has its entrance at 275 m above sea level, about 25 km from the Tyrrhenian coast of Calabria, southern Italy. New archaeological excavation performed since 2000 has revealed a sedimentary succession spanning the record of Gravettian to Late Epigravettian cultures (Late Pleistocene). The present study focuses on the lower part (2.5 m thick) of the succession, where three main unconformity‐bounded stratigraphic units have been recognised (labelled RM1–3). Each unit consists of water‐lain deposits indicating high‐ to low‐competence flow, capped with anthropogenic deposits. The gradual deactivation and reactivation of the water drainage between 23 475 ± 190 and 16 250 ± 500 cal. a BP is correlated with regional precipitation changes due to the onset of dry climatic conditions of the Last Glacial Maximum. However, the deactivation of cave drainage after the deposition of unit RM3, around 15 400 ± 500 cal. a BP, deviates from the regional hydrological trend of progressively increasing water discharges and is attributed to the drainage cut‐off by probable cave wall collapses. Copyright © 2008 John Wiley & Sons, Ltd.     

Chemical evolution of seawater during the Phanerozoic: Implications from the record of marine evaporites

The chemical evolution of seawater during the Phanerozoic is still a matter of debate. We have assembled and critically analyzed the available data for the composition of fluid inclusions in marine halite and for the mineralogy of marine evaporites. The composition of fluid inclusions in primary marine halite reveals two major long-term cycles in the chemistry of seawater during the past 600 myr. The concentration of Mg²⁺, Ca²⁺, and SO₄²⁻ has varied quite dramatically. The Mg²⁺ concentration in seawater during most of the early Paleozoic and Jurassic to Cretaceous was as low as 30 to 40 mmol/kg H₂O; it reached maximum values ≥50 mmol/kg H₂O during the Late Neoproterozoic and Permian. The Ca²⁺ concentration in seawater during the Phanerozoic has reached maximum values two to three times greater than the concentration in seawater today (10.6 mmol/kg H₂O), whereas SO₄²⁻ concentrations may have been as low as 5 to 10 mmol/kg H₂O (a third to a fifth of the modern value) during the Jurassic and Early Paleozoic. The Mg²⁺/Ca²⁺ ratio in seawater ranged from 1 to 1.5 during the early to middle Paleozoic and Jurassic-Cretaceous to a near-modern value of 5.2 during the Late Neoproterozoic and Permian. This change in seawater Mg²⁺/Ca²⁺ ratio is consistent with the notion of alternating “calcite-aragonite seas” recorded in oölites and marine carbonate cements.Several models have been proposed to explain the chemical evolution of seawater. These have invoked significant changes in one or more of the major geochemical processes that control the composition of seawater. The pattern and magnitude of the variations in the composition of seawater proposed in this study are similar to those proposed elsewhere that suggest that seawater fluxes through midocean ridges have played a major role in the evolution of seawater during the past 600 myr. Two Phanerozoic supercycles of the Earth’s exogenic processes were recognized in the literature that are caused by mantle convection and plate activity. The composition of seawater has apparently undergone dramatic secular changes in phase with these supercycles and as a consequence of biological evolution. Analyses of fluid inclusions containing unevaporated seawater and a better understanding of the processes that affect the composition of seawater are needed to refine our understanding of the history of Phanerozoic seawater.     

A 20 million year record of planktic foraminiferal B/Ca ratios: Systematics and uncertainties in pCO2 reconstructions

We use new and published data representing a 20 million long record to discuss the systematics of interpreting planktic foraminiferal B/Ca ratios. B/Ca-based reconstructions of seawater carbonate chemistry and atmospheric pCO₂ assume that the incorporation of boron into foraminiferal tests can be empirically described by an apparent partition coefficient, (Hemming and Hanson, 1992). It has also been proposed that there is a species-specific relationship between K_D and temperature (Yu et al., 2007). As we discuss, although these relationships may be robust, there remain significant uncertainties over the controls on boron incorporation into foraminifera. It is difficult to be certain that the empirically defined correlation between temperature and K_D is not simply a result of covariance of temperature and other hydrographic variables in the ocean, including carbonate system parameters. There is also some evidence that K_D may be affected by solution ratios (i.e., pH), or by . In addition, the theoretical basis for the definition of K_D and for a temperature control on K_D is of debate. We also discuss the sensitivity of pCO₂ reconstructions to different K_D-temperature calibrations and seawater B/Ca. If a K_D-temperature calibration is estimated using ice core pCO₂ values between 0 and 200 ka, B/Ca ratios can be used to reasonably approximate atmospheric pCO₂ between 200 and 800 ka; however, the absolute values of pCO₂ calculated are sensitive to the choice of K_D-temperature relationship. For older time periods, the absolute values of pCO₂ are also dependent on the evolution of seawater B concentrations. However, we find that over the last 20 Ma, reconstructed changes in declining pCO₂ across the Mid-Pleistocene Transition, Pliocene glacial intensification, and the Middle Miocene Climate Transition are supported by the B/Ca record even if a constant coretop K_D is used, or different K_D-temperature calibrations and models of seawater B evolution are applied to the data. The inferred influence of temperature on K_D from coretop data therefore cannot itself explain the structure of a published pCO₂ reconstruction (Tripati et al., 2009). We conclude the raw B/Ca data supports a coupling between pCO₂ and climate over the past 20 Ma. Finally, we explore possible implications of B/Ca-based pCO₂ estimates for the interpretation of other marine pCO₂ proxies.     

A high‐resolution multi‐proxy stalagmite record from Mechara,Southeastern Ethiopia: palaeohydrological implications for speleothem palaeoclimate reconstruction

An annually laminated stalagmite from Southeastern Ethiopia grew for 443±8 yr starting at 5023 yr BP (±160 yr) as determined by lamina‐tuned U‐Th dating. The speleothem shows three growth phases: (1) an initial phase where the stalagmite has a candlestick shape, deposited by relatively slow rate drip water; (2) a middle growth phase where laminae grow on the flanks, suggesting faster drip rates; and (3) a final growth phase where the speleothem becomes narrower owing to a decrease in drip water supply towards the end of deposition. Morphometry, annual growth rate, fluorescence index, and ²³⁴U/²³⁸U isotope ratio show marked differences between the growth phases, while δ¹³C and δ¹⁸O do not show significant variation, except within the third phase towards the top of the stalagmite, where they have higher values. The study indicates that the multiproxy approach is crucial as the different proxies respond to single climate forcing in different manners. Our results can be widely applied to speleothem studies distinguishing the relative importance of the various proxies in recording cave ‘external’ (climate, hydrology) and cave ‘internal’ (e.g. evaporation) processes. Copyright © 2006 John Wiley & Sons, Ltd.     

CPI values of terrestrial higher plant-derived long-chain n-alkanes: a potential paleoclimatic proxy

Carbon Preference Index (CPI values) of higher plant-derived long-chain n-alkanes extracted from 62 surface soil samples in eastern China exhibited a specific pattern of variations, namely gradual increase with the increasing latitudes. Such regular variations existed in both forest soil and grassland soil. Our data implied that CPI values of higher plant-derived long-chain n-alkanes had a certain connection with climatic conditions, and such a connection was not influenced by vegetation types. Together with previous data from marine sediments, loess/paleosol sequences, tertiary red clay and modern plants, our observation made us conclude that CPI values of higher plant-derived long-chain n-alkanes may be used as an excellent proxy for paleoclimatic studies.     

Rare earth element geochemistry of Late Devonian reefal carbonates, Canning Basin, Western Australia: confirmation of a seawater REE proxy in ancient limestones

Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements (n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average Nd_SN/Yb_SN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement (n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (Nd_SN/Yb_SN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of Devonian seawater REE concentrations from out data are unknown, hypothetical Devonian Canning Basin seawater REE patterns were obtained with coefficients derived from modern natural proxies and experimental values. Resulting Devonian seawater patterns are slightly enriched in LREE compared to most modern seawaters and suggest higher overall REE concentrations, but are very similar to seawaters from regions with high terrigenous inputs. Our results suggest that most limestones should record important aspects of the REE geochemistry of the waters in which they precipitated, provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high, non-seawater-like REE contents. Hence, we expect that many other ancient limestones will serve as seawater REE proxies, and thereby provide information on paleoceanography, paleogeography and geochemical evolution of the oceans.     

Social license to operate: Not a proxy for accountability in water governance

With the emergence of more collaborative, watershed governance arrangements and the engagement of various actors in decision-making processes, new questions emerge about the potential roles for these organizations and agencies in both upholding accountability, and in being held accountable. Therefore, this study explores the intersection between alternative collaborative watershed governance approaches, and the simultaneous emergence of the concept of social license as an accountability instrument in relation to water governance. Based on an empirical analysis of a case study in southeast British Columbia, where water quality contamination is primarily the result of coal mining, this study seeks to: (1) examine how social license is understood by a range of watershed actors; (2) better understand whether social license may be useful as a watershed-based or community accountability instrument as new collaborative modes of watershed governance emerge; and, (3) explore how social license may be enforced or enabled. Findings show how industry efforts to earn social license have created benefits, such as enabling community-based water monitoring, thereby building capacity for deeper community engagement in governance processes and a greater ability for the community to uphold accountability. However, we confirm that social license is not a proxy or silver bullet for enhancing accountability in collaborative watershed governance. Our findings reveal four specific limitations regarding the use of social license as a principle for accountability in collaborative watershed governance.     

Grain-scale iron isotopic distribution of pyrite from Precambrian shallow marine carbonate revealed by a femtosecond laser ablation multicollector ICP-MS technique: Possible proxy for the redox state of ancient seawater

The redox state of Precambrian shallow seas has been linked with material cycle and evolution of the photosynthesis-based ecosystem. Iron is a redox-sensitive element and exists as a soluble Fe(II) species or insoluble Fe(III) species on Earth’s surface. Previous studies have shown that the iron isotopic ratio of marine sedimentary minerals is useful for understanding the ocean redox state, although the redox state of the Archean shallow sea is poorly known. This is partly because the conventional bulk isotope analytical technique has often been used, wherein the iron isotopic record may be dampened by the presence of isotopically different iron-bearing minerals within the same sample. Here we report a microscale iron isotopic ratio of individual pyrite grains in shallow marine stromatolitic carbonates over geological time using a newly developed, near-infrared femtosecond laser ablation multicollector ICP-MS technique (NIR-fs-LA-MC-ICP-MS).We have determined that the grain-scale iron isotopic distribution of pyrite from coeval samples shows a bimodal (2.7 and 2.3 Ga) or unimodal pattern (2.9, 2.6, and 0.7 Ga). In particular, pyrite from the 2.7 Ga Fortescue Group shows a unique bimodal distribution with highly positive (+1.0‰ defined as Type 1) and negative δ⁵⁶Fe values (−1.8‰ defined as Type 2). Type 1 and 2 pyrites occasionally occur within different siliceous layers in the same rock specimen. Layer-scale iron isotopic heterogeneity indicates that the iron isotopic ratios of the two types of pyrite are not homogenized by diagenesis after deposition. Some cubic pyrites have a core with a positive δ⁵⁶Fe value (1‰) and a rim with a crustal δ⁵⁶Fe value (0‰). The observed isotopic zoning suggests that the positive δ⁵⁶Fe value is a primary signature at the time of stromatolite formation, while secondary pyrite precipitated during diagenesis.The positive δ⁵⁶Fe value of Type 1 and the large iron isotopic difference between Type 1 and 2 (2.8‰.) suggest partial Fe(II) oxidation in the 2.7-Ga shallow sea, i.e., pyritization of ⁵⁶Fe-enriched ferric oxyhydroxide (Type 1) and ⁵⁶Fe depleted Fe²⁺aq in seawater (Type 2). Type 2 pyrite was probably not produced by microbial iron redox cycling during diagenesis because this scenario requires a higher abundance of pyrite with δ⁵⁶Fe of 0‰ than of −1.8‰. Consequently, the degree of Fe(II) oxidation in the 2.7-Ga shallow sea can be estimated by a Fe²⁺aq steady-state model. The model calculation shows that half the Fe²⁺aq influx was oxidized in the seawater. This implies that O₂ produced by photosynthesis would have been completely consumed by oxidation of the Fe²⁺aq influx. Grain-scale iron isotopic distribution of pyrite could be a useful index for reconstructing the redox state of the Archean shallow sea.     

Environmental magnetic studies on surface sediments: a proxy for metal and hydrocarbon contamination

Visakhapatnam is one of the major port cities, and it is developed into a hub of many large- and medium-scale industries. Due to growing industrialization and urbanization, coast is vulnerable to both organic and inorganic micro-pollutants. Twenty-five surface sediments were collected along the Visakhapatnam coast for the measurement of texture size, petroleum hydrocarbons, trace metals and environmental magnetic parameters. The percentage of coarser particles was more in the northern region, whereas the percentage of fine particles was increased toward south. Elevated levels of petroleum hydrocarbons and trace metals were attributed due to marine and land-based sources, in particular, those were due to shipping activities, treated and partially treated sewage and industrial wastes. The concentrations of trace metals, petroleum hydrocarbons and magnetic minerals were decreased from nearshore to seaward. Our results revealed that the magnetic mineralogy is dominated by magnetite with a small proportion of hematite, and the grain size of magnetic minerals was in the range of pseudo-single domain to multidomain nature with detrital origin. From the principal component analysis, the magnetic concentration and mineralogy-dependent parameters co-vary with the heavy metal and PHC concentrations, suggesting that the inputs of magnetic minerals, petroleum hydrocarbons and heavy metals in the Visakhapatnam shelf sediments were derived from the same anthropogenic sources. Thus, the large magnetic dataset can be used to reduce the number of chemical analysis; hence, environmental magnetic parameters were used as a proxy for both organic and inorganic micro-pollutants.     

Biological record of added manganese in seawater: a new efficient tool to mark in vivo growth lines in the oyster species Crassostrea gigas

The biological response of increased manganese in seawater was tested experimentally with the oyster species Crassostrea gigas by adding, once per day, a fixed quantity of MnCl₂ to the container where the oysters were living. Uptake of Mn²⁺ in the shell was traced with cathodoluminescence and quantified with a high spatial resolution proton microprobe. The daily addition of MnCl₂ resulted in the visualization of distinct growth increments seen simultaneously in both the calcitic shell and the aragonitic ligament. A relation was observed between the addition of Mn²⁺ to the seawater and incorporation of Mn in the mineral part of the shell. Thus, addition of MnCl₂ to seawater is an efficient tool to mark in vivo growth increments in bio-mineralised carbonates.     

Unsaturated zones as archives of past climates: toward a new proxy for continental regions

Natural chemical and isotopic tracers contained in unsaturated-zone moisture profiles are being developed as potential new archives for reconstructing recharge history, as well as palaeoclimatic or palaeobotanical conditions over time scales ranging from 20–120,000 years. Results worldwide to date are reviewed, and examples from northern Africa and the western USA are discussed in detail. Encouraging results are obtained from relatively homogeneous deposits such as Quaternary dune sands, where Cl profiles are compared both with the instrumental record, such as rainfall and river-gauging records, and ³H profiles. Model studies have helped to define the persistence time of unsaturated-zone signals, where evidence of a 20-year event such as the Sahel drought may persist for 1,000 years. Significant questions remain regarding the assumptions used in interpreting profiles, particularly the extent to which preferential flow may occur, transient flow phenomena, and stability of tracer-input function. Unsaturated zones that exhibit strong preferential flow are probably unsuitable as archives. Questions remain also on the assumption that flow remains downward, especially in deep unsaturated zones where non-isothermal vapour transport may occur. Estimation of depositional flux for Cl and other parameters is probably the greatest source of uncertainty, both at the spatial scale and also in the long term. Advances are being made in all areas, however, and the use of multiple tracers (chemical, especially Cl and NO₃) and isotopic signals (δ¹⁸O, δ²H, ³⁶Cl), together with soil hydraulic properties, is promising for palaeohydrological reconstruction. Electronic Publication