Trace elements in New Zealand ferromanganese nodules: implications for deep sea environments

<p>Ferromanganese nodules are authigenic marine sediments that form over millions of years from the precipitation of Fe oxyhydroxides and Mn oxides from seawater (hydrogenetic-type growth) and sediment pore-water (diagenetic-type growth). Fe-Mn (oxyhydr)oxides grow in layers about nuclei, effectively scavenging minor metals such as Ni, Cu and Co from the waters they grow in. The uptake of different elements into the ferromanganese nodules reflects their environment and mechanism of growth, and these deposits are of interest both as a potential source of metals of economic interest, and as records of changing ocean conditions. This study investigates the composition of 77 ferromanganese nodules from the seafloor around New Zealand. Samples analysed come from locations several thousand kilometres apart under the same water mass (Lower Circumpolar Deep Water – LCDW), but with varying depth, current velocity, and sediment type. The outermost 1 mm rim of each nodule, representing near-modern growth, was sampled to compare with modern environmental parameters including substrate sediment composition and chemical and physical oceanography. Major, minor, and trace element analysis of nodule rims were undertaken, and the authigenic and detrital components examined via leaching experiments to evaluate their relative influence on growth mechanisms. Overall, New Zealand ferromanganese nodules are hydrogenetic in origin. However, there are systematic variations in composition that reflect variable diagenetic influence. Hydrogenetic endmember compositions are defined by samples from two localities in the Southern Ocean that have no evidence for diagenetic influence. Diagenetic influence on nodule composition is exemplified by samples from the two locations in the Tasman Sea, but also include nodules from the Campbell nodule field. Nodules from the Campbell nodule field come from two transects perpendicular to the Campbell Plateau, and the Deep Western Boundary Current (DWBC). Both sediment composition and nodule rim chemistry vary systematically across both transects. Areas closest to the slope have sediment profiles indicating high energy, erosive environments, continental-sourced sand components, and are dominated by nodules with hydrogenetic chemical characteristics similar to those of the Southern Ocean. Further from the slope, the sediment profiles indicate silt dominated sediments of a more oceanic crustal provenance, lower energy environment, and increased influence of oxic diagenetic processes on the major, minor and trace element profiles of the nodules. No hydrothermal contribution was identified in the chemistry of any of the nodules analysed. The physical and chemical properties of the sediment, along with current velocities, were found to be the key influences in diagenetic enrichment in the nodules. The influence of seawater chemistry was difficult to determine due to the lack of direct analyses in the area. Ferromanganese nodule chemistry is a function of the nodule environment, including water body, sediment composition and depth. The authigenic components of nodules can therefore be used to investigate the deep-sea environment. The redox conditions of sediments and the productivity of the overlying water will affect the trace metal constituents of the pore-waters of a sediment (Kuhn et al., 2017). Sediments with a larger fraction of labile organic matter may result in trace element enrichment of the pore-water. Sediments below the CCD will be higher in trace elements than sediments below the CCD (U1413, U1406B, U1402, U1398, U1398, and U1378) due to carbonate matter acting as a dilutant that can limit the supply of trace elements mobilised in the pore-water during diagenesis (Glasby, 2006). Terrigenous clasts such as quartz (Chester, 1990), will also reduce trace element enrichment in the pore-water due to their low reactivity, e.g. for the sediment U1406B, which has a high lithic component (Table 3.2). Sediments with a higher biogenic silica component (such as U1373, U1374, and U1378) (Table 3.2, Table 3.4) are predicted to produce nodules with higher trace element contents (ISA, 2010). In contrast to both the CCZ and Indian Ocean nodules, the Campbell nodule field samples formed above the CCD, and hence in sediments that include a significant carbonate component. This minimises the trace element pore-water enrichment and can account for the lower Cu+Ni+Co contents observed in the Campbell nodule field nodules compared with those that formed below the CCD (CCZ and Indian Ocean).</p>

Trace elements in New Zealand ferromanganese nodules: implications for deep sea environments

<p>Ferromanganese nodules are authigenic marine sediments that form over millions of years from the precipitation of Fe oxyhydroxides and Mn oxides from seawater (hydrogenetic-type growth) and sediment pore-water (diagenetic-type growth). Fe-Mn (oxyhydr)oxides grow in layers about nuclei, effectively scavenging minor metals such as Ni, Cu and Co from the waters they grow in. The uptake of different elements into the ferromanganese nodules reflects their environment and mechanism of growth, and these deposits are of interest both as a potential source of metals of economic interest, and as records of changing ocean conditions. This study investigates the composition of 77 ferromanganese nodules from the seafloor around New Zealand. Samples analysed come from locations several thousand kilometres apart under the same water mass (Lower Circumpolar Deep Water – LCDW), but with varying depth, current velocity, and sediment type. The outermost 1 mm rim of each nodule, representing near-modern growth, was sampled to compare with modern environmental parameters including substrate sediment composition and chemical and physical oceanography. Major, minor, and trace element analysis of nodule rims were undertaken, and the authigenic and detrital components examined via leaching experiments to evaluate their relative influence on growth mechanisms. Overall, New Zealand ferromanganese nodules are hydrogenetic in origin. However, there are systematic variations in composition that reflect variable diagenetic influence. Hydrogenetic endmember compositions are defined by samples from two localities in the Southern Ocean that have no evidence for diagenetic influence. Diagenetic influence on nodule composition is exemplified by samples from the two locations in the Tasman Sea, but also include nodules from the Campbell nodule field. Nodules from the Campbell nodule field come from two transects perpendicular to the Campbell Plateau, and the Deep Western Boundary Current (DWBC). Both sediment composition and nodule rim chemistry vary systematically across both transects. Areas closest to the slope have sediment profiles indicating high energy, erosive environments, continental-sourced sand components, and are dominated by nodules with hydrogenetic chemical characteristics similar to those of the Southern Ocean. Further from the slope, the sediment profiles indicate silt dominated sediments of a more oceanic crustal provenance, lower energy environment, and increased influence of oxic diagenetic processes on the major, minor and trace element profiles of the nodules. No hydrothermal contribution was identified in the chemistry of any of the nodules analysed. The physical and chemical properties of the sediment, along with current velocities, were found to be the key influences in diagenetic enrichment in the nodules. The influence of seawater chemistry was difficult to determine due to the lack of direct analyses in the area. Ferromanganese nodule chemistry is a function of the nodule environment, including water body, sediment composition and depth. The authigenic components of nodules can therefore be used to investigate the deep-sea environment. The redox conditions of sediments and the productivity of the overlying water will affect the trace metal constituents of the pore-waters of a sediment (Kuhn et al., 2017). Sediments with a larger fraction of labile organic matter may result in trace element enrichment of the pore-water. Sediments below the CCD will be higher in trace elements than sediments below the CCD (U1413, U1406B, U1402, U1398, U1398, and U1378) due to carbonate matter acting as a dilutant that can limit the supply of trace elements mobilised in the pore-water during diagenesis (Glasby, 2006). Terrigenous clasts such as quartz (Chester, 1990), will also reduce trace element enrichment in the pore-water due to their low reactivity, e.g. for the sediment U1406B, which has a high lithic component (Table 3.2). Sediments with a higher biogenic silica component (such as U1373, U1374, and U1378) (Table 3.2, Table 3.4) are predicted to produce nodules with higher trace element contents (ISA, 2010). In contrast to both the CCZ and Indian Ocean nodules, the Campbell nodule field samples formed above the CCD, and hence in sediments that include a significant carbonate component. This minimises the trace element pore-water enrichment and can account for the lower Cu+Ni+Co contents observed in the Campbell nodule field nodules compared with those that formed below the CCD (CCZ and Indian Ocean).</p>

Landscape Setting Drives the Microbial Eukaryotic Community Structure in Four Swedish Mountain Lakes over the Holocene

On the annual and interannual scales, lake microbial communities are known to be heavily influenced by environmental conditions both in the lake and in its terrestrial surroundings. However, the influence of landscape setting and environmental change on shaping these communities over a longer (millennial) timescale is rarely studied. Here, we applied an 18S metabarcoding approach to DNA preserved in Holocene sediment records from two pairs of co-located Swedish mountain lakes. Our data revealed that the microbial eukaryotic communities were strongly influenced by catchment characteristics rather than location. More precisely, the microbial communities from the two bedrock lakes were largely dominated by unclassified Alveolata, while the peatland lakes showed a more diverse microbial community, with Ciliophora, Chlorophyta and Chytrids among the more predominant groups. Furthermore, for the two bedrock-dominated lakes—where the oldest DNA samples are dated to only a few hundred years after the lake formation—certain Alveolata, Chlorophytes, Stramenopiles and Rhizaria taxa were found prevalent throughout all the sediment profiles. Our work highlights the importance of species sorting due to landscape setting and the persistence of microbial eukaryotic diversity over millennial timescales in shaping modern lake microbial communities.

Bat guano minerals and mineralization processes in Chameau Cave, Eastern Morocco

The decay of bat guano deposits in caves produces mineral accumulations, mainly phosphates and secondary sulfates. Chameau Cave, Eastern Morocco, is located in the semi-arid Bni Snassen Mountains. It is composed of semi-active and dry passages, and is featured by strong condensation-corrosion on the walls, presence of fluvial sediments, and old corroded flowstones. Due to forced and convective airflow, the cave is generally very dry, with some damp sites related to condensation. Samples collected on the surface of different passages and along two sediment profiles yielded minerals related to bat guano decay. On recent or fresh guano, precursor minerals correspond to sulfate (gypsum), phosphate-sulfate (ardealite) and phosphate (brushite). Phosphates (hydroxylapatite, fluorapatite) occur at the interface with host rock or carbonate speleothems. At the contact of phyllosilicates contained in allogenic fluvial deposits or shale partings, or with pyrite-rich sediments, various phosphates occur (Al-rich strengite, Fe-rich variscite, phosphosiderite, leucophosphite, spheniscidite, crandallite, minyulite, variscite, and strengite), the latter two minerals being the stable end-members. Black seams of oxyhydroxides (goethite, hematite, birnessite) line the contact between carbonate host rock and weathered fluvial deposits. After “digestion” by acidic guano leachates, fluvial deposits only display the most resistant minerals (quartz, muscovite, K-feldspars and Na-plagioclases) and weathering byproducts (kaolinite). We discuss the origin of a pure gypsum particle cone, possibly related to evaporation at the edge of a wet cupola and subsequent detachment of sulfate particles. Among environmental conditions, humidity is required for decay. In this dry cave, most of the damp originates from either permanent or seasonal condensation. Dust particle advection seems to be essential in providing compounds that are not present on fresh guano (quartz, clay minerals). Bat guano phosphatization has probably occurred since >100 ka. The Chameau Cave appears as an outstanding site for bat guano-related minerals (n = 12), including rare phosphates (spheniscidite and minyulite).

Sedimentological, Mineralogical and Geochemical Features of Late Quaternary Sediment Profiles from the Southern Tuscany Hg Mercury District (Italy): Evidence for the Presence of Pre-Industrial Mercury and Arsenic Concentrations

Southern Tuscany (Italy) is an important metallogenic district that hosts relevant S-polymetallic deposits that have intensely been exploited for centuries. Consequently, potential toxic elements, such as Hg and As, are widely distributed in the surrounding environment. In this paper, an extensive sedimentological, mineralogical and geochemical study of two Late Quaternary sediment profiles, partially outcropping along the coast of southern Tuscany (Ansedonia area), was carried out to evaluate the contents and mobility of Hg and As with the aims to contribute to the definition of the geochemical baseline of southern Tuscany before the human intervention and evaluate the potential dispersion of these harmful elements. The sedimentological, mineralogical and geochemical (major elements) features revealed that the studied profiles are mostly related to the local geological characteristics and the Quaternary geological history of the area. The concentrations and the normalized patterns of trace and rare earth elements highlighted the absence of any anthropogenic activity. This implies that the studied samples are to be regarded as good proxies for evaluating the geochemical baseline of southern Tuscany before the intense mining activity. The enrichment factors (EF) of most trace elements were indeed lower or close to 2, indicating a variability close to the average concentration of the Upper Continental Crust (UCC), while other elements slightly enriched, such as Pb, were in agreement with the natural baseline reported for southern Tuscany. Mercury and As displayed EF values >40 when compared to the average contents of UCC, although they decrease down to 4 when compared to the suggested baseline for southern Tuscany. The higher Hg and As contents detected in this study, inferred to natural sources, evidenced (i) the great natural variability occurring in largely mineralized areas and (ii) the importance of estimating reference environmental parameters in order to avoid misleading interpretations of the detected anomalies. Moreover, the results of leaching test on sediment samples denoted a relatively low mobility of Hg and As, suggesting that these elements are preferentially mobilized by transport of clastic sediments and such anomalies may be preserved for relatively long times in Quaternary sediments. However, leachable Hg (0.6–9.7 μg/L) and As (2.1–42.2 μg/L) concentrations are significantly high when compared to those of the Italian limit for groundwater (1 µg/L for Hg and 10 µg/L for As). Quaternary sediments from southern Tuscany could then be a potential, though natural, source of Hg and As to groundwater systems.

Impact of sedimentation history for As distribution in Late Pleistocene-Holocene sediments in the Hetao Basin, China

Purpose To understand the impact of geochemical sedimentation history for arsenic (As) distribution in the sediment profiles of the Hetao Basin, we (1) evaluated sediments provenance and variations of weathering intensities, (2) attempted to reconstruct the depositional environments, and (3) explored the As and Fe speciation in the sediments. Combining the information above, different sedimentation facies were distinguished in the vertical profiles. Methods Two sediments cores were drilled up to 80 m depth. Major and trace element compositions, including rare earth elements (REE), were analyzed. Carbon isotope ratios (δ13Corg) of embedded organic matter in the sediments were analyzed by isotope ratio mass spectrometry (IR-MS). Arsenic and Fe speciation of the sediments were determined by sequential extractions. Results and discussion The similar REE geochemistry of rocks from the Lang Mountains and sediments in the Hetao Basin indicated that the sediments originated from the Lang Mountains. The C/N ratio (~ 4 to ~ 10) in combination with δ13Corg (− 27‰ to −2 4‰) suggested that sediments were mainly deposited in aquatic environments. The unconfined aquifer equaled the lacustrine deposit with less intensive weathering during last glacial maximum (LGM). Here, the As content (average, 5.4 mg kg−1) was higher than in the aquifer sediments below (average, 3.6 mg kg−1). Conclusion Higher content of releasable As in combination with paleolake-derived organic matter aquifer sediments probably contributes to higher groundwater As concentration in the unconfined aquifer. This study provides the first insight into the impact of sedimentation history on As distributions in sediment profiles in the Hetao Basin.