Multivariate analysis applied to X-ray fluorescence to assess soil contamination pathways: case studies of mass magnetic susceptibility in soils near abandoned coal and W/Sn mines.

Determining the origin and pathways of contaminants in the natural environment is key to informing any mitigation process. The mass magnetic susceptibility of soils allows a rapid method to measure the concentration of magnetic minerals, derived from anthropogenic activities such as mining or industrial processes, i.e., smelting metals (technogenic origin), or from the local bedrock (of geogenic origin). This is especially effective when combined with rapid geochemical analyses of soils. The use of multivariate analysis (MVA) elucidates complex multiple-component relationships between soil geochemistry and magnetic susceptibility. In the case of soil mining sites, X-ray fluorescence (XRF) spectroscopic data of soils contaminated by mine waste shows statistically significant relationships between magnetic susceptibility and some base metal species (e.g., Fe, Pb, Zn, etc.). Here, we show how qualitative and quantitative MVA methodologies can be used to assess soil contamination pathways using mass magnetic susceptibility and XRF spectra of soils near abandoned coal and W/Sn mines (NW Portugal). Principal component analysis (PCA) showed how the first two primary components (PC-1 + PC-2) explained 94% of the sample variability, grouped them according to their geochemistry and magnetic susceptibility in to geogenic and technogenic groups. Regression analyses showed a strong positive correlation (R2 > 0.95) between soil geochemistry and magnetic properties at the local scale. These parameters provided an insight into the multi-element variables that control magnetic susceptibility and indicated the possibility of efficient assessment of potentially contaminated sites through mass-specific soil magnetism.

Spatial patterns of microbial diversity in Fe-Mn deposits and associated sediments in the Atlantic and Pacific oceans.

Mining of deep-sea Fe-Mn deposits will remove crusts and nodules from the seafloor. The growth of these minerals takes millions of years, yet little is known about their microbiome. Besides being key elements of the biogeochemical cycles and essential links of food and energy to deep-sea, microbes have been identified to affect manganese oxide formation. In this study, we determined the composition and diversity of Bacteria and Archaea in deep-sea Fe-Mn crusts, nodules, and associated sediments from two areas in the Atlantic Ocean, the Tropic Seamount and the Rio Grande Rise. Samples were collected using ROV and dredge in 2016 and 2018 oceanographic campaigns, and the 16S rRNA gene was sequenced using Illumina platform. Additionally, we compared our results with microbiome data of Fe-Mn crusts, nodules, and sediments from Clarion-Clipperton Zone and Takuyo-Daigo Seamount in the Pacific Ocean. We found that Atlantic seamounts harbor an unusual and unknown Fe-Mn deposit microbiome with lower diversity and richness compared to Pacific areas. Crusts and nodules from Atlantic seamounts have unique taxa (Alteromonadales, Nitrospira, and Magnetospiraceae) and a higher abundance of potential metal-cycling bacteria, such as Betaproteobacteriales and Pseudomonadales. The microbial beta-diversity from Atlantic seamounts was clearly grouped into microhabitats according to sediments, crusts, nodules, and geochemistry. Despite the time scale of million years for these deposits to grow, a combination of environmental settings played a significant role in shaping the microbiome of crusts and nodules. Our results suggest that microbes of Fe-Mn deposits are key in biogeochemical reactions in deep-sea ecosystems. These findings demonstrate the importance of microbial community analysis in environmental baseline studies for areas within the potential of deep-sea mining.

Selective incorporation of rare earth elements by seaweeds from Cape Mondego, western Portuguese coast.

This study examined the mechanism of incorporation of the rare earth elements (REEs), La, Ce, Nd, Eu, Gd, Tb, Yb, into green (Codium tomentosum, Ulva rigida), red (Gracilaria gracilis, Osmundea pinnatifida, Porphyra sp), and brown seaweeds (Saccorhiza polyschides, Undaria pinnatifida) collected from a single site near the coastline of the Cape Mondego, western Portugal. The concentrations of REEs, Mg, Ca, Al, Fe, Zn, and Cu in the biomasses were determined by inductively-coupled plasma mass spectrometry (ICP-MS). The species showed differences in their incorporation and fractionation of REEs from the same environment: the sum of REEs was higher in U. rigida, C. tomentosum, G. gracilis, and O. pinnatifida (0.7-1.7 µg g-1) than in Porphyra sp., S. polyschides, and U. pinnatifida (0.1-0.2 µg g-1). Ratios of Ce/Yb ranged from 13 (in S. polyschides) to 103 (in U. rigida), indicating different proportions of light and heavy REEs among species. Good correlations were found between Al and Fe (R2 = 0.98), and between these elements and La, Ce, Nd, Gd (R2 = 0.88-0.97) and Yb (R2 = 0.66-0.71) for all species except C. tomentosum and G. gracilis. Profiles of REE values normalised to average upper-continental crust composition indicated positive anomalies of Eu and Tb that reinforced the singularity of these elements in the REE group. Correlations between the REEs and Al or Fe suggest that detrital terrigenous particles, adhered to seaweed walls, may be an important mechanism for the incorporation of REEs by seaweeds. Different patterns for C. tomentosum and G. gracilis may also be indicative of the higher influence of cell wall composition on REE incorporation.

Microbial Diversity of Deep-Sea Ferromanganese Crust Field in the Rio Grande Rise, Southwestern Atlantic Ocean.

Seamounts are often covered with Fe and Mn oxides, known as ferromanganese (Fe-Mn) crusts. Future mining of these crusts is predicted to have significant effects on biodiversity in mined areas. Although microorganisms have been reported on Fe-Mn crusts, little is known about the role of crusts in shaping microbial communities. Here, we investigated microbial communities based on 16S rRNA gene sequences retrieved from Fe-Mn crusts, coral skeleton, calcarenite, and biofilm at crusts of the Rio Grande Rise (RGR). RGR is a prominent topographic feature in the deep southwestern Atlantic Ocean with Fe-Mn crusts. Our results revealed that crust field of the RGR harbors a usual deep-sea microbiome. No differences were observed on microbial community diversity among Fe-Mn substrates. Bacterial and archaeal groups related to oxidation of nitrogen compounds, such as Nitrospirae, Nitrospinae phyla, Candidatus Nitrosopumilus within Thaumarchaeota group, were present on those substrates. Additionally, we detected abundant assemblages belonging to methane oxidation, i.e., Methylomirabilales (NC10) and SAR324 (Deltaproteobacteria). The chemolithoautotrophs associated with ammonia-oxidizing archaea and nitrite-oxidizing bacteria potentially play an important role as primary producers in the Fe-Mn substrates from RGR. These results provide the first insights into the microbial diversity and potential ecological processes in Fe-Mn substrates from the Atlantic Ocean. This may also support draft regulations for deep-sea mining in the region.

Bacterioplankton reveal years-long retention of Atlantic deep-ocean water by the Tropic Seamount.

Seamounts, often rising hundreds of metres above surrounding seafloor, obstruct the flow of deep-ocean water. While the retention of deep-water by seamounts is predicted from ocean circulation models, its empirical validation has been hampered by large scale and slow rate of the interaction. To overcome these limitations we use the growth of planktonic bacteria to assess the retention time of deep-ocean water by a seamount. The selected Tropic Seamount in the North-Eastern Atlantic is representative for the majority of isolated seamounts, which do not affect the surface ocean waters. We prove deep-water is retained by the seamount by measuring 2.4× higher bacterial concentrations in the seamount-associated or 'sheath'-water than in deep-ocean water unaffected by seamounts. Genomic analyses of flow-sorted, dominant sheath-water bacteria confirm their planktonic origin, whilst proteomic analyses of the sheath-water bacteria, isotopically labelled in situ, indicate their slow growth. According to our radiotracer experiments, it takes the sheath-water bacterioplankton 1.5 years to double their concentration. Therefore, the seamount should retain the deep-ocean water for 1.8 years for the deep-ocean bacterioplankton to grow to the 2.4× higher concentration in the sheath-water. We propose that turbulent mixing of the seamount sheath-water stimulates bacterioplankton growth by increasing cell encounter rate with ambient dissolved organic molecules.

Impact of ferromanganese ore pollution on phytoplankton CO2 fixation in the surface ocean.

Because ferromanganese polymetallic crusts can become a global resource of valuable elements the ecological impact of seafloor crust mining requires evaluation. Whilst the detrimental impact on deep-ocean benthos is established, experimental evidence about the mining hazard to surface-ocean is sparse. When retrieved, mined crusts can leach elements potentially harmfull to the core oceanic CO2-fixers - phytoplankton. To directly assess the magnitude of this potential hazard at ocean-basin scale, we examine the impact of ore slurry on phytoplankton CO2 fixation along a meridional transect through the South Atlantic Ocean. Within 12 h crust slurry additions caused a 25% decrease of CO2 fixation in the subtropical region and 15% in the temperate-polar region. Such moderate susceptibility of phytoplankton indicates limited release of harmful elements from tested polymetallic powder. Although this implies that environmentally sustainable seafloor mining could be feasible, longer-term complex studies of the mining impact on the surface ocean are required.

Detachment tectonics at Mid-Atlantic Ridge 26°N.

Spreading processes associated with slow-spreading ridges are a complex interplay of volcanic accretion and tectonic dismemberment of the oceanic crust, resulting in an irregular seafloor morphology made up of blocks created by episodes of intense volcanic activity or tectonic deformation. These blocks undergo highly variable evolution, such as tilts or dissection by renewed tectonic extension, depending on their positions with respect to the spreading axis, core complexes, detachment or transform faults. Here, we use near-seafloor magnetic and bathymetric data and seismic profiles collected over the TAG Segment of the Mid-Atlantic Ridge to constrain the tectonic evolution of these blocks. Our study reveals that the presence and evolution of oceanic core complexes play a key role in triggering block movements. The deep subvertical detachment fault roots on the plate boundary, marked by a thermal anomaly and transient magma bodies. Thermal and magmatic variations control the structure and morphology of the seafloor above the subhorizontal detachment surface, occasionally leading to relocating the detachment.

Talc-dominated seafloor deposits reveal a new class of hydrothermal system.

The Von Damm Vent Field (VDVF) is located on the flanks of the Mid-Cayman Spreading Centre, 13 km west of the axial rift, within a gabbro and peridotite basement. Unlike any other active vent field, hydrothermal precipitates at the VDVF comprise 85-90% by volume of the magnesium silicate mineral, talc. Hydrothermal fluids vent from a 3-m high, 1-m diameter chimney and other orifices at up to 215 °C with low metal concentrations, intermediate pH (5.8) and high concentrations (667 mmol kg(-1)) of chloride relative to seawater. Here we show that the VDVF vent fluid is generated by interaction of seawater with a mafic and ultramafic basement which precipitates talc on mixing with seawater. The heat flux at the VDVF is measured at 487±101 MW, comparable to the most powerful magma-driven hydrothermal systems known, and may represent a significant mode of off-axis oceanic crustal cooling not previously recognized or accounted for in global models.

Hydrothermal vent fields and chemosynthetic biota on the world's deepest seafloor spreading centre.

The Mid-Cayman spreading centre is an ultraslow-spreading ridge in the Caribbean Sea. Its extreme depth and geographic isolation from other mid-ocean ridges offer insights into the effects of pressure on hydrothermal venting, and the biogeography of vent fauna. Here we report the discovery of two hydrothermal vent fields on the Mid-Cayman spreading centre. The Von Damm Vent Field is located on the upper slopes of an oceanic core complex at a depth of 2,300 m. High-temperature venting in this off-axis setting suggests that the global incidence of vent fields may be underestimated. At a depth of 4,960 m on the Mid-Cayman spreading centre axis, the Beebe Vent Field emits copper-enriched fluids and a buoyant plume that rises 1,100 m, consistent with >400 °C venting from the world's deepest known hydrothermal system. At both sites, a new morphospecies of alvinocaridid shrimp dominates faunal assemblages, which exhibit similarities to those of Mid-Atlantic vents.