Trace Metal Enrichment Research Articles

Controls on the Spatial Distribution of Trace Metal Concentrations along the Bedrock-Dominated South Fork New River, North Carolina

In marked contrast to alluvial rivers, few studies have examined the physical and geochemical controls on the spatial distribution of toxic trace metals along bedrock channels. This study examined the factors controlling the geographical pattern of selected trace metal (Cu, Cr, and Zn) concentrations along the bedrock-dominated channel of the South Fork New River (SFNR). The SFNR is located in the Blue Ridge Physiographic Province of North Carolina, and is representative of many rivers in mountainous terrains that are often subjected to the influx of toxic trace metals from historic and contemporary mining operations. The topography of the SFNR’s channel bed is highly variable and can be subdivided into pool and shallow bedrock reaches. The latter contained localized cascades characterized by topographically higher bedrock ribs that are separated by topographic lows, both of which are oriented oblique to flow. Accumulations of bed sediments are predominantly associated with the traverse bedrock ribs that generate high hydraulic roughness. Except for a few localized zones of enrichment, sediment-associated trace metal concentrations tended to vary within a narrow range of background values over the 36 km study reach. Elevated trace metal concentrations were closely linked to zones of high Fe and Mn concentrations, and were associated with pools located within or immediately downstream of bedrock cascades. The elevated concentrations of the metals appear to be derived from the erosion of lithologic units within the cascades that contain sulfidic layers or zones of mafic mineral enrichment, and which are known to occur in the underlying bedrock. Once eroded, these minerals and/or rock fragments were deposited within low-velocity zones created by the transverse ribs or within downstream pools. The enrichment of trace metals downstream of the cascades may also be due to the formation of Fe and Mn oxyhydroxides as turbulent flows aerate river waters as they traverse the cascades. Chemically reactive fine-grained (<63 µm) sediments had a relatively limited influence on the downstream variations in metal concentrations, presumably because the channel bed sediments are composed primarily of sand-sized and larger particles. Although a principal component analysis (PCA) suggested that reach-scale variations in channel and valley morphology may have partly influenced downstream variations in trace metal concentrations, the geographical patterns were primarily controlled by local geological and geomorphic factors associated with the bedrock cascades. The design of future sampling programs along such coarse-grained, bedrock rivers should consider the significance of these local controls on trace metal storage to effectively characterize and interpret downstream patterns in metal concentrations.

Distribution and contamination assessment of trace metals in surface sediments of the South China Sea, Vietnam

The distribution and enrichment of trace metals in sediments of the South China Sea along the entire coast of Vietnam were described. The concentrations of Cr, Ni, Zn, and Pb in the sediments showed a significant positive correlation with fine-sized fractions and TOC. In contrast, the concentration of As was not positively correlated with particle size and other metals. The relatively positive correlations of Cd with Fe, Al, Ti, Sc, TOC, P, Cr, Ni, Zn, and Pb indicated that it comes from different sources. Ecotoxicological indexes of all elements showed low values, except for Cd in the southwestern part of the South China Sea area, which is likely related to the influx of suspended matter from the Mekong River.

A multi-proxy approach to constrain reducing conditions in the Baltic Basin during the late Silurian Lau carbon isotope excursion

The Silurian was a dynamic time characterized by significant climatic and sea level changes, biotic crises, and carbon cycle volatility. The largest magnitude perturbation to the Silurian global carbon cycle was the mid-Ludfordian carbon isotope excursion, termed the Lau CIE, which was coincident with the Lau/Kozlowskii extinction (LKE). Much of the published research on the late Silurian has described changes in the biotic record and global marine redox conditions. Limited work has been done, however, to elucidate the variability in local paleo-redox conditions. Here, we use a suite of paleo-redox proxies to examine a shallow shelf carbonate succession from Gotland, Sweden, and a deep shelf clastic sequence from Latvia. Low iodine-to‑calcium ratios from the carbonate succession suggest an anoxic water column, or significant exchange with nearby reducing water masses. Iron speciation data and moderate trace metal enrichments suggest that the sediments of the deeper shelf were deposited in an oxygen minimum zone with a denitrifying water column before and during the LKE with sulfidic conditions limited to the sediment porewaters. After the extinction, a relative depletion in trace metal concentrations (V, Hg, U, Mo) suggest that water column conditions were locally less reducing. The depletion in trace metal concentrations is coeval with previously reported global increases in anoxia and euxinia after the LKE and, thus, potentially could have resulted from a global drawdown in trace metals overprinted upon the local record of paleo-redox change.

The Ediacaran ‘Miaohe Member’ of South China: new insights from palaeoredox proxies and stable isotope data

AbstractThroughout the Ediacaran Period, variable water-column redox conditions persisted along productive ocean margins due to a complex interplay between nutrient supply and oceanographic restriction. These changing conditions are considered to have influenced early faunal evolution, with marine anoxia potentially inhibiting the development of the ecological niches necessary for aerobic life forms. To understand this link between oxygenation and evolution, the combined geochemical and palaeontological study of marine sediments is preferable. Located in the Yangtze Gorges region of southern China, lagoonal black shales at Miaohe preserve alga and putative metazoans, including Eoandromeda, a candidate total-group ctenophore, thereby providing one example of where integrated study is possible. We present a multi-proxy investigation into water-column redox variability during deposition of these shales (c. 560–551 Ma). For this interval, reactive iron partitioning indicates persistent water-column anoxia, while trace metal enrichments and other geochemical data suggest temporal fluctuations between ferruginous, euxinic and rare suboxic conditions. Although trace metal and total organic carbon values imply extensive basin restriction, sustained trace metal enrichment and δ15Nsed data indicate periodic access to open-ocean inventories across a shallow-marine sill. Lastly, δ13Corg values of between −35‰ and −40‰ allow at least partial correlation of the shales at Miaohe with Member IV of the Doushantuo Formation. This study provides evidence for fluctuating redox conditions in the lagoonal area of the Yangtze platform during late Ediacaran time. If these low-oxygen environments were regionally characteristic, then the restriction of aerobic fauna to isolated environments can be inferred.

Iron Isotopes Reveal a Benthic Iron Shuttle in the Palaeoproterozoic Zaonega Formation: Basinal Restriction, Euxinia, and the Effect on Global Palaeoredox Proxies

The Zaonega Formation in northwest Russia (~2.0 billion years old) is amongst the most complete successions that record the middle of the Palaeoproterozoic era. As such, geochemical data from the formation have played a central role in framing the debate over redox dynamics in the aftermath of the Great Oxidation Event (GOE). However, uncertainty over local redox conditions and the degree of hydrographic restriction in the formation has led to contradictory interpretations regarding global oxygen (O2) fugacity. Here, we provide new iron (Fe) isotope data together with major and trace element concentrations to constrain the local physiochemical conditions. The Zaonega Formation sediments show authigenic Fe accumulation (Fe/Al ≫ 1 wt.%/wt.%) and δ56Fe ranging from −0.58‰ to +0.60‰. Many of the data fall on a negative Fe/Al versus δ56Fe trend, diagnostic of a benthic Fe shuttle, which implies that Zaonega Formation rocks formed in a redox-stratified and semi-restricted basin. However, basin restriction did not coincide with diminished trace metal enrichment, likely due to episodes of deep-water exchange with metal-rich oxygenated seawater, as evidenced by simultaneous authigenic Fe(III) precipitation. If so, the Onega Basin maintained a connection that allowed its sediments to record signals of global ocean chemistry despite significant basinal effects.

Enrichment of Trace Metals (V, Cu, Co, Ni, and Mo) in Arctic Sediments—From Siberian Arctic Shelves to the Basin

AbstractWith 50% of the Arctic Ocean is consisted of continental shelves, extensive shelf‐basin exchange processes exist here and plays a key role in regulating the biogeochemical recycling process of trace metals in the Arctic region. In this study, short sediment cores were collected along three transects from Siberian‐Chukchi shelves to adjacent slope/basin areas. An increasing trend was found for the bulk concentrations of several metals (V, Cu, Co, Ni, and Mo) from shelf to slope/basin cores with increasing water depth. Sequential extraction experiments indicated that the Fe/Mn oxide fractions increased significantly from shelf (9%–21%) to basin cores (24%–76%) for Cu, Co, Ni, and V, while the organic/sulfide phase remained significant (∼40%) for Mo. In addition, the observed dissolved metal concentrations in porewater indicated the remobilization of Fe, Mn, and Mo from shelf sediment, while V was always removed from water to the sediment, both on the shelf or in the slope/basin. Overall, in combination with the statistical analysis, we proposed that metals are transported from shelves to the central Arctic and are scavenged mainly by Mn oxides from the water column, which results in the enrichment of metals in slope/basin sediment. With the climate change, such transport and accumulation mechanism may be intensified over time, slowly leading the Arctic sediment to be a more and more important sink for those metals.

Environmental and Geological Study of the Suggested Marine Port Site at Sahl Hasheesh area, Hurghada, Red Sea coast, Egypt (A case study).

This study deals with the geochemical nature of distribution, enrichment of total trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) in bulk sediments and its association with sediment texture, carbonates and organic carbon. Grain size and geochemical analyses have been carried out on 27 surface marine sediment samples collected from Sahl Hasheesh suggested marine port site on red sea coast. Grain size distribution and chemical characteristics of (27) sediments samples using some statistical methods reveal the dominance of muddy sediments in the dredging areas with an abundance of organic matter and trace elements reflect the negative impact on the biologic life and humans. Furthermore, the high concentration of Fe, Mn, Pb, Cd and Ni in these sediments were attributed to the contribution of terrigenous materials due to coastal development including landfilling to provide sites for resorts and recreation, and dredging of tidal flat to create marine ports and outlet of desalination. The study area is a very wide reef flat ranging from 160-350 m wide. Due to the nature of this reef flat and the extreme exposure during low tide, only a few living organisms exist, such as brown algae Lurancia sp., Cystoseira sp., and sometimes mixed with Padina sp. The reef morphology changes from a narrow reef flat (160 m) and gentle reef slope, with low relief (1 m) in the northern part, to a very wide reef flat (355 m) and steeper reef slope with higher relief (15 m). Reasonable recommendations have been outlined by this study to offer guidelines to mitigate the impact on the marine environment.

Mineralogy, Geochemistry, and Genesis of Kaolinitic Claystone Deposits in the Datong Coalfield, Northern China

AbstractGray-black kaolinitic claystones of industrial value are abundant in Upper Carboniferous–Lower Permian coal-bearing strata of the Datong Coalfield of northern China. The main types are tonsteins and cryptocrystalline kaolinitic claystones, distinguished by the thinness and greater crystallinity of kaolinite in the former and by the presence of detrital illite and authigenic pyrite in the latter. In order to determine the formation history of these two types of kaolinitic claystone, the petrological, mineralogical, and geochemical characteristics of borehole samples from the Upper Carboniferous Taiyuan Formation which comprises siliciclastics and coal seams deposited in a coastal environment, were analyzed. In addition to kaolinite, the claystones contain subordinate illite, quartz, pyrite, anatase, feldspar, siderite, and calcite. The tonsteins and cryptocrystalline kaolinitic claystones have different sources, as shown by petrographic data, elemental ratios, and chondrite-normalized rare earth element (REE) patterns. The volcanic origin of the tonsteins is revealed by an abundance of volcanic quartz and vitric fragments as well as Al2O3/TiO2, Zr/Hf, and Nb/Ta ratios consistent with a felsic igneous source. Their REE fraction was derived from feldspars or micas of the parent rocks, and the fraction decreased with alteration of these minerals to kaolinite. The sedimentary origin of the cryptocrystalline kaolinitic claystones is revealed by an abundance of detrital quartz and illite grains derived from either granite or sedimentary upper crust, and by the total REE contents (ΣREE) and (La/Yb)N values which are consistent with granitic material. Their depositional environment was in a transitional (coastal) setting (as shown by intermediate Sr/Ba ratios) hosting an open acidic hydrologic system (as shown by high chemical index of alteration (CIA) values indicative of intensive chemical weathering) that was suboxic to anoxic (as shown by high U/Th ratios and trace-metal enrichment factors). The present chemistry of these claystones was thus controlled by a combination of parent rock type and diagenetic alteration.

Exploration of the variations and relationships between trace metal enrichment in dust and ecological risks associated with rapid urban expansion

Trace metals in street dust originate from many natural and anthropogenic sources and may directly or indirectly affect daily life and health. Here, the enrichment factor (EF), an efficient parameter to assess the contamination by trace metals, was evaluated and compared in four different zones of the urban area of Nanchang city during different seasons. Results showed that EFs of trace metals have regional seasonal variations. The EF range of Cr, Ni, Cu, Zn, As, Cd and Pb were found to be (0.76–16.38), (0.66–9.06), (1.09–169.58), (1.52–36.16), (0.44–7.17), (2.07–78.38), (0.95–20.94), respectively. These values indicate minimal to significant pollution. The EF values of Zn, Cd and Pb in street dust show very similar variations as their median and mean values of EF are higher in certain zones, and their seasonal variations are similar. The Ni and As results suggest that anthropogenic influences for these elements are not significant. The Ni may be influenced by land use type rather than point sources and As may be attributed to natural sources. The Principal Component Absolute Scores - Multivariate Linear Regression (PCAS-MLR) model was used to identify the types and contributions of trace metal sources. The main sources of trace metals in dust were found to be industrial discharges and traffic emissions. However, the percentages of their contributions have significant regional differences. The relationship between the EF of trace metals and the ecological risk index (ERI) was also investigated, and indicates that seriously polluted areas correspond to high ERI regions. The land use types and characteristics of the source jointly affects the relationship between EFs and ERI.

Novel watermass reconstruction in the Early Mississippian Appalachian Seaway based on integrated proxy records of redox and salinity

Redox state and salinity are fundamental properties of watermasses, and in modern environments, detailed analysis of spatial variability in redox and salinity is possible through direct measurement. Watermass reconstruction is difficult in deep-time systems, however, because the sedimentary record of ancient watermasses is often incomplete or difficult to access on spatial scales large enough to permit basin-scale reconstruction. During the Middle Devonian to Early Mississippian periods, the Appalachian Basin of eastern North America was characterized by a variably restricted watermass, leading to extensive deposition of organic-rich black shale associated with the regional development of bottom-water anoxia. Watermass reconstruction during deposition of these units has previously been attempted, but only on small spatial scales, with most studies focused on trace element proxies applied to individual study sections. Here, we focus instead on a broader geographic reconstruction of watermasses in the Lower Mississippian (Tournaisian) Sunbury Shale and present a new geochemical dataset that spans five drill cores across a basin transect from northeastern Ohio to southern Kentucky (USA). Iron speciation and trace metal abundances reveal a strong paleoredox gradient that can be related to water depth and basin hydrography. In the northeastern-most core of Ohio, iron speciation reveals largely ambiguous redox conditions; however, oxic conditions are potentially indicated by very low total organic carbon and trace metal contents. These oxygenated conditions were likely related to proximity to the Catskill deltaic wedge complex that fed freshwater into the basin and lowered the position of the regional pycnocline. In contrast, in central and southern Ohio, paleoredox indicators reveal the development of ferruginous conditions associated with rapid deepening to the south into the central axis of the Appalachian Basin. Further to the south in Kentucky, our data reveal dominantly euxinic conditions, which developed as environments shoaled towards the basin-bounding Cumberland Sill. We also investigated paleosalinity across the Appalachian Basin using strontium/barium (Sr/Ba) ratios. Our data reveal a subtle paleosalinity gradient from low-brackish (i.e., close to freshwater) conditions close to the Catskill Delta complex to increasingly brackish conditions to the southwest. This trend was disrupted by large paleosalinity variation across a shallow mixing zone in the southwestern-most core. Lastly, strong enrichments of redox-sensitive trace metals in both ferruginous and euxinic environments are parsimoniously attributed to the operation of an iron-manganese particulate shuttle that continuously supplied oxide-sensitive metals to the Appalachian Basin. Ultimately, this study is among the first to present detailed watermass reconstruction in an ancient epeiric sea using both redox and salinity proxies applied over a large lateral transect. We suggest that a similar approach may be useful in other deep-time systems of geobiological, paleoclimatic, and paleoceanographic significance.

Signals of combined chromium–cadmium isotopes in basin waters of the Early Cambrian – Results from the Maoshi and Zhijin sections, Yangtze Platform, South China

The combination of authigenic chromium and cadmium stable isotopes in marine sedimentary archives enables reconstruction of the redox conditions and levels of primary productivity in past oceans and basins. The Ediacaran to Cambrian Nanhua Basin (Yangtze Platform, South China) and its sedimentary sequences have been studied intensively in the past with respect to investigating the effects of post-Snowball Earth glaciations on the oxygenation of Earth's atmosphere, and intimately related, on the consequences of climate changes on the evolution of the ocean environment and of life during the Precambrian-Cambrian transition. Following recent propositions of using cadmium isotopes as a novel proxy for reconstructing the extent of primary productivity in paleooceans, we here present results from a combined cadmium (Cd)‑chromium (Cr) isotope study on metalliferous black shale, black shale and phosphorite sediments deposited during the Early Cambrian Niutitang Formation at the Maoshi and Zhijin sections. Results point toward strongly oxidized and highly productive surface water layers in the Nanhua Basin during this period. The samples have strongly positively fractionated δ114Cd and δ53Cr values up to +0.6‰ and + 1.4‰, respectively, similar to such values from carbonaceous sediments in modern oceans. The association of Cd with sulfides in the sediments, together with high Cd/TOC ratios particularly in the metalliferous black shales, implies a sulfide-controlled enrichment of Cd under restricted euxinic conditions. The lower Cd/TOC values in phosphorites and barren black shales and negatively fractionated δ114Cd values down to −0.33‰ point to less effective precipitation of Cd under more suboxic conditions as likely prevailing in an open shallow shelf. The Cr content in the sediments is mostly close to average shale, and the δ53Cr values are little fractionated in the 0–0.2‰ range, corroborated by flat shale-like rare earth element + yttrium (REE + Y) patterns. However, some metal-rich shale samples have clearly authigenic Cr isotope signatures with up to +1.4‰ δ53Cr, and the authigenic Cr component in the phosphorite samples is around 1‰ δ53Cr, indicating oxic surface waters. The latter sediments also depict seawater-like, middle REE enriched REE + Y patterns with distinct negative Ce and positive Y anomalies indicative of an oxygenated surface water layer, and with positive Eu anomalies which they likely received during phosphatogenesis in the euxinic bottom water environment. In accord with previous studies reporting on extreme trace metal enrichments (Mo, Ni, V, Hg, etc.) in these Early Cambrian sediments, our Cd and Cr isotope signatures favor a scenario of a strongly stratified basin in which high primary productivity thrived in an oxidized surface water layer, potentially as a result of increased nutrient supply from a strongly weathering continental hinterland in the aftermath of the last Snowball Earth glaciations in the Ediacaran.

Enrichment of trace metals from acid sulfate soils in sediments of the Kvarken Archipelago, eastern Gulf of Bothnia, Baltic Sea

Abstract. Rivers draining the acid sulfate soils of western Finland are known to deliver large amounts of trace metals with detrimental environmental consequences to the recipient estuaries in the eastern Gulf of Bothnia, northern Baltic Sea. However, the distribution of these metals in the coastal sea area and the relevant metal transport mechanisms have been less studied. This study investigates the spatial and temporal distribution of metals in sediments at nine sites in the Kvarken Archipelago, which is the recipient system of Laihianjoki and Sulvanjoki rivers that are impacted by acid sulfate soils. The contents of Cd, Co, Cu, La, Mn, Ni, and Zn increased in the cores during the 1960s and 1970s as a consequence of intensive artificial drainage of the acid sulfate soil landscape. Metal deposition has remained at high levels since the 1980s. The metal enrichment in sea floor sediments is currently visible at least 25 km seaward from the river mouths. Comparison with sediment quality guidelines shows that the metal contents are very likely to cause detrimental effects on marine biota more than 12 km out from the river mouths. The dynamic sedimentary environment of the shallow archipelago makes these sediments potential future sources of metals to the ecosystem. Finally, the strong association of metals and nutrients in the same sediment grain size class of 2–6 µm suggests that the transformation of dissolved organic matter and metals to metal–organic aggregates at the river mouths is the key mechanism of seaward trace metal transport, in addition to co-precipitation with Mn oxyhydroxides identified in previous studies. The large share of terrestrial organic carbon in the total organic C in these sediments (interquartile range – 39 %–48 %) highlights the importance of riverine organic matter supply. These findings are important for the estimation of environmental risks and the management of biologically sensitive coastal sea ecosystems.

Geochemical characteristics of trace elements in size-resolved coastal urban aerosols associated with distinct air masses over tropical peninsular India: Size distributions and source apportionment

Trace elements in atmospheric particulate matter play a significant role in air quality, health and biogeochemical cycles. The present study reports on geochemical characteristics of size-resolved trace elements in PM10 aerosols collected under different air masses over a coastal urban location in peninsular India. A contrast in elemental distribution was observed for the particle size above 7.0 μm and below 1.1 μm under the influence of northeasterly air masses as characterized by Al > Fe > Zn and Fe > Al > Zn, respectively. The concentrations of the crustal elements (Al, Fe, Ti, P, Ba, Co) were high and illustrated by a unimodal size distribution with a peak in coarse mode (>2.0 μm) during northwesterly air masses. On the other hand, combustion-derived metals (Cu, Zn, Cd, Sb, and Pb) were maximized under northeasterly air masses, characterized by unimodal size distribution with a peak in fine mode (<2.0 μm). The enrichment factor (EF) analysis reveals the contribution of anthropogenic emissions to Cd, Sb, Pb, Zn, Cu, Cr, Ni, As, and Sn metals, particularly to the high enrichment of trace metals in fine mode. These results suggest that crustal emissions are major sources of trace metals in coarse mode aerosols; whereas combustion derived anthropogenic emissions contribute to the fine mode aerosols. The positive matrix factorization (PMF) analysis revealed that crustal sources (52–90%) were most abundant for particles >7.0 μm, whereas combustion related emissions such as vehicular and traffic sources are predominant for particles <1.1 μm. The present study demonstrates that trace metals in coastal urban aerosols are affected by changes in emission sources/strengths and regional transport of air masses originated from the northeasterly and northwesterly parts of the tropical Indian subcontinent.

Fe(II)-induced transformation of iron minerals in soil ferromanganese nodules

Recrystallization of iron (hydr)oxides by ferrous iron [Fe(II)] is an important part of the biogeochemical cycling of iron in earth surface environments. Ferromanganese nodules are complex assemblages of natural Fe and Mn minerals, which are widely found in soils and marine environments, and critically impact the geochemical behavior of trace metals and nutrients. However, little is known regarding the Fe(II)-induced recrystallization of ferromanganese nodules, in comparison to pure iron (hydr)oxides. Accordingly, the objective of this study was to elucidate the reaction processes of aqueous Fe(II) with ferromanganese nodules, and to use complementary spectroscopic techniques to characterize the products. Goethite in the nodule that underwent phase transformation to magnetite or Fe(II) oxidation to form magnetite has not been reported in previous studies with respect to pure goethite. 57Fe-enriched isotope tracer experiments confirmed Fe atom exchange between aqueous Fe(II) and structural Fe(III) of the nodule and was enhanced at higher pH conditions. The coexistence of Mn oxides and other minerals possibly make the goethite in the nodule more reactive for phase transformation to magnetite than pure synthetic goethite. In addition, Fe(III) precipitates were formed due to Fe(II) oxidation by Mn(III) of the nodule, and magnetite was likely consequently produced through further Fe(II)-induced reaction. Considering the enrichment of trace metals and nutrients in ferromanganese nodules, the observed Fe(II)-induced recrystallization of nodules in the study is expected to exert important effects on the geochemical behavior of the elements, especially in nodule-enriched soils.

Anthropogenic and climate signals in late-Holocene peat layers of an ombrotrophic bog in the Styrian Enns valley (Austrian Alps)

Abstract. Using peat bogs as palaeoenvironmental archives is a well-established practice for reconstructing changing climate and anthropogenic activity in the past. In this paper, we present multi-proxy analyses (element geochemistry, pollen, non-pollen palynomorphs, stable Pb isotopes, humification, ash content) of a 500 cm long, 14C-dated peat core covering the past ∼5000 years from the ombrotrophic Pürgschachen Moor in the Styrian Enns valley (Austrian Alps). Early indications of low settlement and agricultural activity date to ∼2900 cal BCE. An early enrichment of Cu was found in peat layers corresponding to the late Copper Age (∼2500 cal BCE). These enrichments are attributed to Cu mining activities in the Eisenerz Alps. More pronounced increases in cultural indicators (cultivated plants, shrubs, herbs, charcoal) in the pollen record and enrichments of trace metals suggest significant human impact in the vicinity of Pürgschachen Moor in the middle Bronze Age (∼1450–1250 cal BCE), in the late Bronze Age (∼1050–800 cal BCE) and in the period of the late La Tène culture (∼300 cal BCE–1 cal CE). The greater part of the Iron Age and the Roman imperial period are each characterized by a general decline in anthropogenic indicators compared to previous periods. Distinct enrichments of Pb and Sb in the sample that corresponds to ∼900 cal CE are attributed to medieval siderite mining activity in the immediate vicinity of Pürgschachen Moor. The results of this interdisciplinary study provide evidence that strong, climate-controlled interrelations exist between the pollen record, the humification degree and the ash content in an ombrotrophic environment. Human activity, in contrast, is mainly reflected in the pollen record and by enrichments of heavy metals. The study indicates a dry period in the region of the bog around ∼1950 cal BCE.

Environmental Assessment of Trace Metals in San Simon Bay Sediments (NW Iberian Peninsula)

A gravity core (220 cm depth) was collected to investigate the geochemistry, enrichment, and pollution of trace metals in anoxic sediments from San Simon Bay, an ecosystem of high biological productivity in the northwest of Spain. A five-step sequential extraction procedure was used. The Cu, Pb, and Zn contents decreased with depth, with maximum values in the top layers. Ni and Zn were bound to pyrite fractions, while Cd and Pb were associated with the most mobile fractions. The analyzed metals were associated with the fractions bound to organic matter, mainly with the strongly bound to organic matter fraction. High Cd and Cu values were observed. The fractionation showed a high mobility for Cd (28.3–100%) and Pb (54.0–70.2%). Moreover, the pollution factor and the geoaccumulation index reflected a high contamination for Pb and a moderate contamination for Cu and Zn in the superficial layers, pointing to a possible ecotoxicological risk to organisms in San Simon Bay.

Reconstructing oxygen deficiency in the glacial Gulf of Alaska: Combining biomarkers and trace metals as paleo-redox proxies

Marine anaerobic oxidation of ammonium (anammox) plays a central role in the nitrogen cycle of modern Oxygen Deficient Zones (ODZs). The newly developed bacteriohopanetetrol stereoisomer (BHT-x) biomarker for anammox, which is largely unaffected by early diagenesis, allows for the reconstruction of the presence and dynamics of past ODZs from the sedimentary record of continental margins. In this study, we investigate the development and dynamics of the ODZ in the Gulf of Alaska (GOA) between 60 and 15 cal ka BP using records of redox sensitive trace metals (TM) and the BHT-x anammox biomarker from IODP Site U1419 (~700 m water depth). The biomarker record indicates that the ODZ in the GOA was in concert with global climate fluctuations in the late Pleistocene. Anammox was more pronounced during warmer periods and diminished during cooler periods, as indicated by correlation with the δ18O signal obtained by the North Greenland Ice core Project (NGRIP). Trace metal enrichments, however, do not match the trend in BHT-x. Systematic metal enrichments in intervals where biomarkers point to more intense water column deoxygenation are not observed. We suggest that this proxy discrepancy was caused by environmental factors, other than water column redox conditions, with opposing effects on the TM and biomarker records. Two of the most widely used redox indicators, Mo and U, are not significantly enriched throughout the sediment record at Site U1419. Site U1419 experienced some of the highest sedimentation rates (100–1000 cm ka−1) ever reported for late Pleistocene continental margin sediments, leading to a continuous and rapid upward migration of the sediment-water interface. We suggest that despite water column and seafloor oxygen depletion, significant sedimentary enrichments of these redox sensitive trace metals were prevented by a limited time for their diffusion across the sediment-water interface and subsequent enrichment as authigenic phases. Thus, depositional conditions were ideal for biomarker preservation but prevented significant authigenic trace metal accumulations. Similar discrepancies between organic and inorganic redox proxies could exist in other high sedimentation rate environments, potentially putting constraints on paleo-redox interpretations in such settings if they are based on trace metal enrichments alone.

Impact of different management systems on soil quality of farms in a semi-arid tropical setting

ABSTRACT In recent times, non-conventional farming practices have emerged as a viable alternative to check soil degradation due to the indiscriminate application of agrochemicals. However, limited studies have been conducted on soils under different management systems in farmer-managed settings. The present study aims to understand whether the documented advantages of going non-conventional are reflected in such a setting, provided its susceptibility to variations in nutrient input availability and environmental factors. The study was conducted on two different farm management systems, i.e. conventional and non-conventional, in close geographical proximity in a semi-arid tropical region of India. The soils were analysed for their physical and chemical properties, major and micronutrients and trace metals during the post-monsoonal season. The studied soils are sandy loam in texture, neutral to moderately alkaline and non-saline. These are deficient in organic carbon and total N, with very low to medium available P and low to high available K. Although adequate availability of Fe, Mn and Cu is observed, Zn deficiency is present in 16% of the soils. The soils are predominantly composed of SiO2, followed by Al2O3 and minor quantities of FeO, K2O and CaO, with generally low concentrations of trace metals (Cr, Zn, Ni, Cu, Pb, Co and Cd). Though no distinct differences are observed in major nutrient abundances and micronutrient availability, yet a significant difference is noticed in the trace metal concentration in soils from the two management systems. In light of similar parentage and absence of any significant difference in other soil properties, the relative trace metal enrichment observed in soils from the conventional farm might indicate an impact of differences in the management practices adopted.

Geochemical insights into the relationship of rock varnish and adjacent mineral dust fractions

Rock varnishes are μm-thin, dark, manganese(Mn)-rich crusts that accrete in the order of few μm/ka on weathering-resistant lithologies. Although these crusts can form in all climates, they are best known in arid to semi-arid settings. Aeolian dust is understood as a major contributor to the distinct trace metal and REE enrichments in rock varnish. However, the exact proportions of abiotic and biotic formation mechanisms that may explain the oxidation-reactions of Mn2+ to Mn4+, present as Mn oxyhydroxides in the varnish, are still a matter of ongoing debate.We present here the first systematic study of trace element enrichment processes between the uppermost layer of the varnish sequence and their adjacent <50 μm and >50 μm dust fractions across a selection of 41 major and trace elements. This approach is used to investigate samples from three fully arid deserts: the An Nafud in Saudi Arabia, the Negev in Israel, and the Mojave in the USA, which are compared to the significantly different environment of the semi-arid Knersvlakte in South Africa. A new in situ trace element analysis protocol was developed to perform femto- and nanosecond sector-field LA-ICP-MS microanalyses at high-spatial resolution, which allows us to measure the most recent varnish layers for their comparison with recent dust. In agreement with previous studies, all varnishes are enriched in Mn, Pb, Ce, Co, Ba, Zn, Ni, and the Rare-Earth Elements (REE). Here we demonstrate that fine (<50 μm) dust is characterized by similar trace element trends as the varnishes, at overall lower mass fractions. Dust >50 μm has low trace element mass fractions, and enrichment patterns plotting distinctly away from varnish and fine dust. Based on these geochemical patterns, our results indicate a general enrichment mechanism from fine dust to varnish. Previous studies suggested dust to play an integral role in providing the trace elements that are incorporated into the varnish by pH-Eh fluctuations in short-term rain and fog events. We amalgamate and refine previous growth models by providing direct evidence that leaching of about 10% of the Mn and other trace elements from clay minerals in rain or fog droplets at pH ~5 and subsequent scavenging on varnish surfaces at pH ~8 leads integrated over time to the distinct enrichment patterns of the varnish, while initial Mn oxyhydroxide formation is suggested to follow pathways of metal oxide mediated photo-catalysis.For the semi-arid occurrence in the Knersvlakte we present a distinct growth model as both environment, varnish, and dust composition differ significantly from the arid settings. Here, thick, metallic-looking varnish occurs mainly on the rim of quartz pebbles, lacks microlamination, and likely has upscaled growth processes. Among other aspects, we suggest a more complex interplay between photo-catalysis, nocturnal condensation events on quartz pebbles with subsequent water trapping at the rock-soil-atmosphere interface, due to a salic top-soil layer, to mainly account for these differences.

Sources, Enrichment, and Geochemical Fractions of Soil Trace Metals in Ulaanbaatar, Mongolia.

Mongolia is a rapidly developing country that has experienced growing industrialization and urbanization in recent decades. This study was conducted to evaluate the enrichment and labile fractions of metals in urban soils of Mongolia and to identify major sources of soil metal pollution. The concentrations and geochemical fractions of Al, Fe, Mn, Cr, Cu, Cd, Co, Zn, V, Mo, As, Sb, and Pb in soils of the city Ulaanbaatar were investigated. The results demonstrate that only Fe, Mn, Co, Mo, and V occur at natural levels with enrichment factors close to unity. The majority of investigated toxic metals, including Cu, Zn, Cr, Sb, As, Cd, and Pb, are serious pollutants in urban soils, with enrichment factors of up to 2.8, 5.1, 2.1, 16, 13, 15, and 11, respectively. Studies of the chemical fractions of metals demonstrate that Zn is mainly found in its labile form and is considered a high risk to humans and biota. Industrial release, household ash, coal combustion, and tire abrasion were identified as key sources of toxic metals entering into the soil of Ulaanbaatar City, which should be controlled effectively to prevent the population as well as pollution distribution over a wider area by long-range atmospheric transport.