Tris(1,3-dichloro-2-propyl) phosphate disrupts dorsoventral patterning in zebrafish embryos.

Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) is a high-production volume organophosphate flame retardant widely used within the United States. Within zebrafish, initiation of TDCIPP exposure at 0.75 h post-fertilization (hpf) results in genome-wide alterations in methylation during cleavage (2 hpf) as well as epiboly delay or arrest (at higher concentrations) during late-blastula and early-gastrula (4-6 hpf). To determine whether these TDCIPP-induced effects were associated with impacts on the transcriptome, embryos were exposed to vehicle (0.1% DMSO) or 2 µM TDCIPP from 0.75 hpf to 6 hpf, and total RNA was extracted from triplicate embryo pools per treatment and hybridized onto duplicate Affymetrix Zebrafish Gene 1.0 ST Arrays per RNA sample. Based on transcriptome-wide profiling, TDCIPP resulted in a significant impact on biological processes involved in dorsoventral patterning and bone morphogenetic protein (BMP) signaling. Consistent with these responses, TDCIPP exposure also resulted in strongly dorsalized embryos by 24 hpf-a phenotype that mimicked the effects of dorsomorphin, a potent and selective BMP inhibitor. Moreover, the majority of dorsalized embryos were preceded by epiboly arrest at 6 hpf. Our microarray data also revealed that the expression of sizzled (szl)-a gene encoding a secreted Frizzled-related protein that limits BMP signaling-was significantly decreased by nearly 4-fold at 6 hpf. Therefore, we used a splice-blocking morpholino to test the hypothesis that knockdown of szl phenocopies TDCIPP-induced delays in epiboly progression. Interestingly, contrary to our hypothesis, injection of szl MOs did not affect epiboly progression but, similar to chordin (chd) morphants, resulted in mildly ventralized embryos by 24 hpf. Overall, our findings suggest that TDCIPP-induced epiboly delay may not be driven by decreased szl expression, and that TDCIPP-induced dorsalization may-similar to dorsomorphin-be due to interference with BMP signaling during early zebrafish development

Impact of deep-sea mining on redox environment, biogeochemical processes and element fluxes within and from sediments of the Clarion-Clipperton Zone, Pacific Ocean

The economic interest in deep-sea mineral resources has grown in recent years. Minerals of interest include polymetallic nodules, which occur in extensive deposits at more than 4000 m water depth in the Clarion-Clipperton Zone (CCZ), NE Pacific Ocean. In light of recent technological advances in mining equipment, the CCZ represents a prospective area for commercial deep-sea mining. In the framework of this PhD thesis, sediments from four European contract areas for the exploration of polymetallic nodules in the CCZ and one of the protected Areas of Particular Environmental Interest (APEI) were investigated. Comprehensive pore-water and solid phase data were produced for undisturbed sediments and sediments from disturbance tracks of small-scale deep sea mining experiments. The presented studies provide new insights into the spatial and temporal variation of redox zonation, biogeochemical processes and element fluxes in the sediments and the impact of potential mining activities in the CCZ

Data report: solid-phase major and minor elements and iron and sulfur species in sediments of the Anholt Basin, Baltic Sea, collected during IODP Expedition 347

In this report, we present bulk solid-phase major and minor element contents and Fe and S species in sediments from Site M0060 in the Anholt Basin recovered during Integrated Ocean Drilling Program Expedition 347 to the Baltic Sea. Site M0060 is characterized by alternating sand- and clay-/silt-dominated sediment sequences that indicate deposition under brackish-marine and limnic conditions, respectively. We use Al-normalized elemental ratios and transition metal data to characterize the different sediment sequences and to study the impact of early diagenetic processes on the abundance and reactivity of Fe oxide and Fe sulfide mineral phases across lithologic boundaries. Ratios of Fe/Al and Mn/Al exceed the continental crustal average in the clay-/silt-dominated sequences, whereas low ratios are associated with the sandy units. About 10%–20% of the total bulk Fe content is associated with Fe oxides and Fe sulfides, whereas the major Fe fraction is bound in clay minerals. The transition metals (V, Ni, Cr, and Co) correlate with the depth profile of Fe/Al, which indicates that they are adsorbed onto Fe oxides and concomitantly deposited. Sequential leaching reveals that magnetite is the most abundant Fe oxide phase. Leached contents approach 1 wt% followed by crystalline and easily reducible Fe oxides. Pyrite is the dominant Fe sulfide phase and is enriched at several lithologic boundaries that can likely be associated with the formation of pyrite. Pyrite is formed through the reaction of Fe monosulfides with (1) polysulfides and/or S0 in zones dominated by organoclastic sulfate and Fe oxide reduction and (2) sulfide released during the anaerobic oxidation of methane

Active metal-cycling microbial communities of polymetallic nodules from the Eastern Pacific Ocean

The rising demand for minerals and metals is encouraging the great international interest for alternative sources in the deep sea. Deposits of deep-sea polymetallic nodules attracted the attention for a long time because they are rich in nickel, copper, cobalt, and rare earth elements. The environmental consequences of large-scale mining of polymetallic nodules are currently less known. In 2019 the Belgian and German licence area in the Clarion-Clipperton Zone (Eastern Pacific) were studied to obtain further baseline characteristics of the 4000 m deep polymetallic nodule fields. Here, we present: i) diversity and distribution of the present & active microbial communities of polymetallic nodules and ii) abundance and activity of relevant metal-cycling microorganisms by quantification of extracellular enzyme activity and 16S rRNA amplicon sequencing. Further we aim to enrich potential metal-cycling microorganisms and investigate microbial metabolisms by metagenomic/-transcriptomic from polymetallic nodules. Our results may provide a new set of tools for monitoring ecosystem impacts associated with deep-sea polymetallic nodule mining. New regulations are required to protect these areas from irreversible anthropogenic impacts

Alpha radiation from polymetallic nodules and potential health risks from deep-sea mining

In search for critical elements, polymetallic nodules at the deep abyssal seafloor are targeted for mining operations. Nodules efficiently scavenge and retain several naturally occurring uranium-series radioisotopes, which predominantly emit alpha radiation during decay. Here, we present new data on the activity concentrations of thorium-230, radium-226, and protactinium-231, as well as on the release of radon-222 in and from nodules from the NE Pacific Ocean. In line with abundantly published data from historic studies, we demonstrate that the activity concentrations for several alpha emitters are often higher than 5 Bq g−1 at the surface of the nodules. These observed values can exceed current exemption levels by up to a factor of 1000, and even entire nodules commonly exceed these limits. Exemption levels are in place for naturally occurring radioactive materials (NORM) such as ores and slags, to protect the public and to ensure occupational health and radiation safety. In this context, we discuss three ways of radiation exposure from nodules, including the inhalation or ingestion of nodule fines, the inhalation of radon gas in enclosed spaces and the potential concentration of some radioisotopes during nodule processing. Seen in this light, inappropriate handling of polymetallic nodules poses serious health risks

Natural variability of geochemical conditions, biogeochemical processes and element fluxes in sediments of the CCZ

During RV SONNE cruise SO239 in March/April 2015 five sites in the area of the Clarion-Clipperton Fracture Zone (CCZ) in the eastern equatorial Pacific were visited as part of the JPI Oceans pilot action Ecological Aspects of Deep-Sea Mining“. Here, we present a comparable study on (1) the redox zonation in the sediments induced by the input flux of organic matter, (2) biogeochemical reactions including the driver of organic matter degradation and (3) diagenetic manganese redistribution and implications for manganese nodule formation

Impact of small-scale disturbances on geochemical conditions, biogeochemical processes and element fluxes in surface sediments of the eastern Clarion-Clipperton Zone, Pacific Ocean

The thriving interest in harvesting deep-sea mineral resources, such as polymetallic nodules, calls for environmental impact studies, and ultimately, for regulations for environmental protection. Industrial-scale deep-sea mining of polymetallic nodules most likely has severe consequences for the natural environment. However, the effects of mining activities on deep-sea ecosystems, sediment geochemistry and element fluxes are still poorly conceived. Predicting the environmental impact is challenging due to the scarcity of environmental baseline studies as well as the lack of mining trials with industrial mining equipment in the deep sea. Thus, currently we have to rely on small-scale disturbances simulating deep-sea mining activities as a first-order approximation to study the expected impacts on the abyssal environment. Here, we investigate surface sediments in disturbance tracks of seven small-scale benthic impact experiments, which have been performed in four European contract areas for the exploration of polymetallic nodules in the Clarion-Clipperton Zone (CCZ). These small-scale disturbance experiments were performed 1 day to 37 years prior to our sampling program in the German, Polish, Belgian and French contract areas using different disturbance devices. We show that the depth distribution of solid-phase Mn in the upper 20 cm of the sediments in the CCZ provides a reliable tool for the determination of the disturbance depth, which has been proposed in a previous study (Paul et al., 2018). We found that the upper 5–15 cm of the sediments were removed during various small-scale disturbance experiments in the different exploration contract areas. Transient transport-reaction modelling for the Polish and German contract areas reveals that the removal of the surface sediments is associated with the loss of reactive labile organic carbon. As a result, oxygen consumption rates decrease significantly after the removal of the surface sediments, and consequently, oxygen penetrates up to tenfold deeper into the sediments inhibiting denitrification and Mn(IV) reduction. Our model results show that the post-disturbance geochemical re-equilibration is controlled by diffusion until the reactive labile TOC fraction in the surface sediments is partly re-established and the biogeochemical processes commence. While the re-establishment of bioturbation is essential, the geochemical re-equilibration of the sediments is ultimately controlled by the burial rates of organic matter. Hence, under current depositional conditions, the new geochemical equilibrium in the sediments of the CCZ is reached only on a millennia scale even for these small-scale disturbances simulating deep-sea mining activities

Post-depositional manganese mobilization during the last glacial period in sediments of the eastern Pacific Ocean

Studies have provided compelling evidence that the Pacific Ocean has experienced substantial glacial/interglacial changes in bottom-water oxygenation. While the deep Pacific Ocean is currently well oxygenated, bottom-water oxygen concentrations (O2bw) were most likely lower during the last glacial period (LGP), which must have caused a much more compressed redox zonation in the sediments than at present. We have sequentially leached mobilizable MnO2 and various Fe (oxyhydr)oxides and used transport-reaction modelling in order to reconstruct past redox changes in sediments of the NE Pacific. We have investigated six sites situated in various contract areas for the exploration of polymetallic nodules within the Clarion-Clipperton Zone (CCZ) and one site located in a protected area (APEI3) north of the CCZ. We found bulk sediment Mn maxima of up to 1 wt% in the upper 10 cm of the sediments at all sites except for the APEI3 site. Mobilizable Mn(IV) was the dominant Mn phase representing more than 70% of bulk Mn. As oxygen penetration depths of more than 0.5 m currently do not allow for the formation of authigenic Mn(IV) in the surface sediments of the CCZ, we postulate that lower O2bw during the LGP caused a compressed redox zonation where authigenic Mn(IV) precipitated at a shallow oxic-suboxic redox boundary. Transport-reaction modelling reveals that at O2bw of 35 µM, which were suggested to have prevailed during the LGP, the oxic-suboxic redox boundary is located in the upper 5 cm of the sediments. A distinct mobilizable Mn(IV) maximum was not found in the surface sediments of the APEI3 site indicating that the redox zonation was not as condensed during the LGP at this site due to two- to threefold lower organic carbon burial rates. Our results suggest that oxygen-deprived bottom water conditions prevailed on a basin-wide scale during the LGP and were associated with significantly different rates of biogeochemical processes and element fluxes in sediments of the NE Pacific than today

Post-depositional manganese mobilization during the last glacial period in sediments of the eastern Clarion-Clipperton Zone, Pacific Ocean

Numerous studies have provided compelling evidence that the Pacific Ocean has experienced substantial glacial/interglacial changes in bottom-water oxygenation associated with enhanced carbon dioxide storage in the glacial deep ocean. Under postulated low glacial bottom-water oxygen concentrations (O), redox zonation, biogeochemical processes and element fluxes in the sediments must have been distinctively different during the last glacial period (LGP) compared to current well-oxygenated conditions. In this study, we have investigated six sites situated in various European contract areas for the exploration of polymetallic nodules within the Clarion-Clipperton Zone (CCZ) in the NE Pacific and one site located in a protected Area of Particular Environmental Interest (APEI3) north of the CCZ. We found bulk sediment Mn maxima of up to 1 wt% in the upper oxic 10 cm of the sediments at all sites except for the APEI3 site. The application of a combined leaching protocol for the extraction of sedimentary Mn and Fe minerals revealed that mobilizable Mn(IV) represents the dominant Mn(oxyhydr)oxide phase with more than 70% of bulk solid-phase Mn. Steady state transport-reaction modeling showed that at postulated glacial O of 35 μM, the oxic zone in the sediments was much more compressed than today where upward diffusing pore-water Mn2+ was oxidized and precipitated as authigenic Mn(IV) at the oxic-suboxic redox boundary in the upper 5 cm of the sediments. Transient transport-reaction modeling demonstrated that with increasing O during the last glacial termination to current levels of ∼ 150 μM, (1) the oxic-suboxic redox boundary migrated deeper into the sediments and (2) the authigenic Mn(IV) peak was continuously mixed into subsequently deposited sediments by bioturbation causing the observed mobilizable Mn(IV) enrichment in the surface sediments. Such a distinct mobilizable Mn(IV) maximum was not found in the surface sediments of the APEI3 site, which indicates that the oxic zone was not as condensed during the LGP at this site due to two- to threefold lower organic carbon burial rates. Leaching data for sedimentary Fe minerals suggest that Fe(III) has not been diagenetically redistributed during the LGP at any of the investigated sites. Our results demonstrate that the basin-wide deoxygenation in the NE Pacific during the LGP was associated with (1) a much more compressed oxic zone at sites with carbon burial fluxes higher than 1.5 mg Corg m−2 d−1, (2) the authigenic formation of a sub-surface mobilizable Mn(IV) maximum in the upper 5 cm of the sediments and (3) a possibly intensified suboxic-diagenetic growth of polymetallic nodules. As our study provides evidence that authigenic Mn(IV) precipitated in the surface sediments under postulated low glacial O, it contributes to resolving a long-standing controversy concerning the origin of widely observed Mn-rich layers in glacial/deglacial deep-sea sediments