Hydrothermal components in marine sediments: an insight into sea floor mineralization process

Abstract

Hydrothermal process is an essential phenomenon for seafloor metallic enrichments and mineral accumulations. The seawater -oceanic crust circulations near all the submarine volcanic structures had led to the production of essential base metals, metallic sulfides and natural hydrogen. The non-renewable, slow growth and accumulation rate of the mineral deposits has made the search for more hydrothermal fields to be of utmost importance. Hydrothermal components in sediments are liable to act as geological records on the reconstruction of: history, intensity, location and environmental conditions of hydrothermal activities, with respect to their unique mineralogy and geochemistry. It further provides essential data for locating active and inactive hydrothermal systems. Here we highlight some of the integrated approach on the applications of isotopes, mineralogical and chemical investigations on hydrothermal influenced sediments from Mid Ocean Ridge System. These investigations on near ridge metalliferous sediments have been used to complement fluids and rock geochemistry, with respect to having an insight into the processes of sea-floor mineralization. This review has further suggested some important methodological approach to the understanding of the near vent marine sediments' fingerprints.

Full text

Hydrothermal components in marine sediments: an insight into sea floor mineralization
process
Popoola Samuel Olatunde1*, Unyimadu John Paul 1, Adegbie Adesina Thompson2, Akinnigbagbe Akintoye Edward2,
Ladigbolu Ismail Adejare1, Adekunbi Falilu Olaiwola 1, Ebohon Joy Osiuare 3
Department of Physical and Chemical Oceanography, Nigerian Institute for Oceanography and Marine Research, Lagos, P.M.B, 12729, Nigeria.
Department of Marine Geology and Geophysics, Nigerian Institute for Oceanography and Marine Research, Lagos, P.M.B, 12729, Nigeria.
Department of Biological Oceanography, Nigerian Institute for Oceanography and Marine Research, Lagos, P.M.B, 12729, Nigeria.
Corresponding author: popoolaos@niomr.gov.ng
Abstract
Hydrothermal process is an essential phenomenon for seafloor metallic enrichments and mineral
accumulations. The sea-water-oceanic crust circulations near all the submarine volcanic structures
had led to the production of essential base metals, metallic sulfides and natural hydrogen. The non-
renewable, slow growth and accumulation rate of the mineral deposits has made the search for
more hydrothermal fields to be of utmost importance. Hydrothermal components in sediments are
liable to act as geological records on the reconstruction of: history, intensity, location and
environmental conditions of hydrothermal activities, with respect to their unique mineralogy and
geochemistry. It further provides essential data for locating active and inactive hydrothermal
systems. Here we highlight some of the integrated approach on the applications of isotopes,
mineralogical and chemical investigations on hydrothermal influenced sediments from Mid Ocean
Ridge System. These investigations on near ridge metalliferous sediments have been used to
complement fluids and rock geochemistry, with respect to having an insight into the processes of
sea-floor mineralization. This review has further suggested some important methodological
approach to the understanding of the near vent marine sediments’ fingerprints.
Keywords: Hydrothermal process; seafloor metallic enrichments; geological records; Mid
Ocean Ridge System; sea-floor mineralization

1.0 Introduction
Marine sediments are generally pelagic and are made up of high constituents of calcareous, or
siliceous ooze, with minor contents of red clay [1]. Whereas, others may be precipitated from sea
water (e.g., authigenic sediments), or as a product of precipitations of hydrothermal fluids,
seawater-sediments interactions (commonly referred to as hydrothermal sediments [2].
Hydrothermal components in marine sediments are often enriched in metal contents termed
‘metalliferous’, with respects to the background pelagic sediments, and are related to the global
Mid Ocean Ridge System (MORS) [3-8]. They are generally adjudged to be derived from two
processes: (1) Mass wasting, slumping, erosion and transportation of sulfide debris from sulfide
mounds. (2) Hydrothermal plume fallouts from neutrally buoyant plume [6, 10-13]. The former
had been related to be deposited in close proximity to the hydrothermal vent [14], and constitutes
<10% of medium-coarse grained enriched hydrothermal particles. Whereas, the latter
constitutes >90% dispersed hydrothermal fluid precipitates deposited distal to the vent [15-18].
The drifting away of hydrothermal plume particles from the Mid Ocean Ridges has led to the
scavenging of Fe - Mn oxyhydroxides, trace elements and Rare Earth Elements as a sink into the
surrounding sediments [19]. The top core characteristics of the Al/ (AI+Fe+Mn) ratio had been
used to reveal Fe and Mn enriched sediments along the MORS, and to effectively delineate the
spreading centres [6, 13, 20]. The metalliferous sediments in the Red Sea were adjudged to
constitute the largest hydrothermal mineral deposit in the world’s oceans, and are liable to provide
a substrate on which the macro and micro fauna live [21].

With the advent of high temperature active black smokers in 1979, at East Paific Ridge (EPR),
near 21°N [22-24]. Concerted efforts and concentrations had been directed to the studies on
hydrothermal fluids, sulfide mounds and chimney structures. Thereby limiting several interests
and research on distal metalliferous sediments [20]. Metalliferous sediments across the ocean
possess a genetic affinity to minerals precipitated in close proximity to the hydrothermal upflow
zones (Gurvich, 2006). They are liable to act as geological records on the reconstruction of: history,
intensity, location and environmental conditions of hydrothermal activities, with respect to their
unique mineralogy and geochemistry [26-27]. It further provides essential data for locating active
and inactive hydrothermal systems [26-27].
This paper, aim to review the previous studies on the use of distinct signatures of sediment
mineralogy and geochemistry to complement fluids, rocks and seawater; as an insight into sea
floor mineralization along the Mid Ocean Ridges. It also focuses on the needed area of research
and directions.

Fig1: Map of confirmed (red symbol) and inferred (yellow symbol) vent sites in the ocean adapted
from [28] and the reference therein.
2.0 Methodology and approach of isolating hydrothermal mineral grains from bulk
sediments
The process begins with the removal of carbonate in the samples either by dilute HCl or acetic
acid. The solution may be centrifuged and repeatedly washed in de-ionized water for the acid
neutralization, then wet-sieve analysis will follow to separate the sand size from the silt and clay
size. The investigation of isolated mineral grain will be focused on the sand size fractions, hence,
concentration will be shifted on this fraction (>63µm). Binocular microscope in conjunction with
Standard Electron Microscope (SEM), attached with Energy Dispersive Spectrometer (EDS) wil
further be utilized for qualitative spot investigations. Additionally. Sulfide aliquots with respect to
specific gravity, termed ethanol elutriation can also be used separate the denser minerals (e.g.,
sulfides) from the less dense non sulfide grains (e.g., amorphous silica, and others), [26-27]. Then
the hydrothermal mineral grains of interest such as sulfides (e.g., pyrite, chalcopyrite, bornite,
covellite), sulfate (barite, gypsum, anhydrite), and Fe-oxyhydroxides will be handpicked under the
binocular microscope (Fig.2 and 3). The selected mineral-grains will further be impregnated with
epoxy resin, after the elimination of bubbles, grounded and polished ready for Electron Probe
Micro Analysis (EPMA) and Laser Ablation Inductively Coupled Plasma Mass Spectrometer (LA-
ICPMS) investigation. The EPMA investigation can give detailed major and minor elements with
minimum detection limit of > 0.01 wt. %, whereas, the LA-ICPMS have the ability to probe further
into the trace elements to ppm level.

Fig. 2. Typical hydrothermal mineral-grains separated from bulk sediments (A) secondary Cu-sulfide
minerals (B) Reddish-brown Fe-oxy-hydroxide minerals (C) pyrite minerals (D) anhydrite minerals,
Source [29].

Fig. 3. Standard Electron Microscope (SEM) image of separated hydrothermal components from
marine sediments in Indian Ocean Ridge Systems, Source [26-27, 29].
3.0 Application of isotopes and REEs signature on hydrothermal sediments
Variability in mineral chemistry, degree of mixing of hydrothermal fluid and sea water,
physicochemical parameters (e.g., pH, Eh, chloride ions), and sea-floor rock interactions has been
highlighted as the triggering factor of different Rare Earth Element (REE) patterns in hydrothermal
vent environments [13, 30-32]. Previous studies have suggested that metalliferous sediments with

hydrothermal components are unlikely to possess positive Cerium (Ce+) anomaly [33-34].
Moreover, the equivalent values of Pb, Nd and Sr isotopes in sediments to the non-radiogenic local
Mid Ocean Ridge Basalt (MORB) or vent-fluid values have been related to the presence of
hydrothermal components [10-11]. Several studies have been conducted on REEs and isotopes,
which few are highlighted in this review.
Ref [35] used sulfur (32S) and oxygen (18O/16O) isotope compositions to suggest a low temperature
depositional conditions of seawater-interaction with basaltic crust from the Central North Pacific
Ocean. Ref [11] used the similarity in the non-radiogenic compositions of Pb isotopes in layered
components of core sediments with local basalts and vent fluid to confirm the proximal
hydrothermal origin of the Trans Adventure Geotraverse (TAG) sediments (Mid Atlantic Ridge),
and its close proximity to the hydrothermal upflow zones. They further used the similarity of the
REE patterns of the layered sediments with vent-fluid patterns to infer a hydrothermal vent fluid-
minimal seawater interactions in the deposition of the TAG metalliferous sediments. Moreover,
[36] used the similarities in the isotopic compositions of Pb with local MORB to suggest a
hydrothermal sourced Pb element in the OBS sediments, 21ºN, in the East Pacific Ridge (EPR).
They further utilized light Rare Earth Element (LREE) enrichment, low ∑REE concentrations,
pronounced Eu/Eu* (2.6-13.3) and negative Ce anomaly (Ce/Ce*) (0.63-0.83) to suggest vent fluid
characteristics. Whereas, the down core enrichment of the REE content was used to infer oxidation
and seawater contributions. Ref [32-33] conducted a sequential analysis on bulk sediments to
discriminate between leached and residual phase components from Rainbow hydrothermal vent
sites. The leached components which consist of biogenic carbonates (e.g., foraminifera and
cocolithopores) and Fe-oxyhydroxides are Heavy Rare Earth Elements (HREE) enriched with
negative Ce/Ce*, which are referred to as seawater related fingerprints. The counterparts in the

residual phase, which are made up of detrital materials (e.g., sulfide and sulfate fractions) exhibit
positive Europium anomaly (Eu/Eu*) and negative Ce/Ce* related to the mixing of hydrothermal
fluid and seawater components, with fragments of MORB and aeolian inputs. Ref [10] integrated
the Pb and Nd isotopic compositions of near vent sediment core of the Logatchev hydrothermal
site, with data from hydrothermal fluids and basalt. The spatial variations in the REE and
neodymium (Nd) concentrations were further used to understand the degree of seawater, vent fluid
and detrital influence on the precipitation of sulfide minerals in the Logatchev hydrothermal site.
[37 used the HREE enrichments in the Pacific sediments to reflect basaltic input into the sediments.
Finally, Ref [38] used seawater REE patterns of negative Ce/Ce* (0.61), negative Eu/Eu* (0.73)
to characterize a low temperature depositional conditions in the Saldanha Hydrothermal Field.
These aforementioned approaches have shown the effectiveness of REEs and isotopic signatures
as tracers in the understanding of the source and environmental conditions of hydrothermal
processes in Mid Ocean Ridges and environments.
4.0. Signatures from mineralogical assemblages and chemical compositions
Different sediment fingerprints are specific to various depositional conditions of precipitations in
Mid Ocean Ridge environments [39], (Table 1). Several studies have been conducted on the
sediments mineralogical and chemical compositions, with a view to the understanding of the
hydrothermal components and depositional conditions in the near vent environments. Few are
highlighted in this review. Ref [35] used the mineral assemblages (e.g., goethite, Fe-
montmorillonite, Mn-oxides/hydroxides) to infer a low temperature depositional conditions of the
sediments from the Central North Pacific Ocean. Ref [36] utilized the distinct enrichments of Fe
(up to 25wt. %); Cu (up to 22wt. %); Zn (up to 13 wt. %); S (up to 30 wt.%) and low Mn (<300ppm)

to distinguish hydrothermal sediments from its pelagic counterparts in the OBS (21°N) vent Field
in the EPR. Ref [38] used nontronite, smectite, amorphous Mn-Mg oxyhydroxides and
manganobrucites mineral assemblages to infer a lower temperature of precipitation in the Mount
Saldanha Hydrothermal Field. Additionally, previous researchers had utilized the Fe/Ti versus
Al/Al+Fe+Mn ratio of < 0.3-0.4 and > 0.4 to indicate the presence of hydrothermal and detrital
components in marine sediments [20, 26-27]. Ref [40] utilized Zn, Cu, Pb enrichments and K, Rb
depletion to identify the hydrothermal components in axial sediments along the Carlsberg Ridge.
They further utilized the U/Fe enrichment, low (Nd/Yb) N and Mn depletion to infer the
characteristics of post-depositional oxidation and the limited fluid dilution into the sediments. Ref
[27] further used isolated mineral grain chemistry (e.g., SEM-EDS and EPMA) to reconstruct the
relative position, temperature and intensity of hydrothermal process in Wocan-1 and Wocan-2
hydrothermal sites, Carlsberg Ridge, Indian Ocean.
Table 1: Mineral assemblages and precipitating conditions
Mineralogical
assemblages
Inference
Goelthite, Fe-rich montmorillonitre and Mn
hydoxide
Evidence of low temperature environment of
precipitation
High Fe, Cu, Zn
and S
The presence of sulfidic
input in sediments
Sulfides, nontronite, smectite, Mn-oxyhydroxides, Mg-
oxyhydroxides, Manganobrucite
Extensive mixing of hydrothermal fluid with
seawater
Enriched Cu, Zn, Fe and low Mn in
sediments
Proximal location of the sampling point to
hydrothermal vent environments

Finally, the sediments-background ratio of Mn, Fe, Ni, Cu, Zn and Al and Ti, have been used in
several studies to indicate the enrichment of hydrothermal and detrital fractions in the near Ridge
sediments and hydrothermal vent environments [38-39, 41].
5.0 Conclusion and recommendations
Most of the aforementioned studies had focused on bulk sediments geochemical compositions.
There is a need to look in the direction of selective analysis of a specific group of metalliferous
mineral assemblages, hydrothermal components and the imprints of hydrothermal particulates in
marine sediment [26-27]. This can be achieved through wet-sieve analysis, with respect to the
separation and isolated mineral grains and phases of interest. SEM technique in conjunction with
Energy Dispersive Spectrometer (e.g., SEM-EDX) is an important tool at which variations in
shape, colour, and internal structures such as; zoning, fractures, streaks within a mineral phase can
be carried out to constrain their different mineral abundance and percentages [26-27, 42-44].
There is a need to give more attention to research on the morphological variations and chemical
signatures of near vent marine sediments using single grain geochemical techniques via high
resolution approach such as: Electron Microprobe Analysis (EMPA) and Laser ablation
Inductively Coupled Plasma Mass Spectrometer (LA-ICPMS) analysis. These suggested
approach, coupled with single grain radiogenic and stable isotopic tracers such as, Nd, Sr, Pb and
sulfur isotopes will further aid in the hydrothermal altered sediment fingerprints and thermo-
tectonic origin [44-45]. It is also liable to aid in the determination of the variations in the chemical
compositions among isolated mineral grains and mineral phases such as Cu, Zn and Pb
precipitations in the near vent sediments. These precipitations can be viewed via optical
microscopes in the form of sulfide mineral phases (e.g., chalcopyrite, pyrite, bornite, marcasite,
chalcocite and covellite). The combined approach is liable to offer more opportunity to supplement

and widen the earlier information on hydrothermal mineral assemblages, and create new findings
on the mode of precipitation and environmental conditions of marine sediments and hydrothermal
processes in Mid Ocean Ridges and its environments [46].
This review has highlighted the previous studies on mineralogy, elemental geochemistry, and
isotope applications on hydrothermal components in marine sediments located in close proximity
to the Mid Ocean Ridge environments. It has further suggested an important methodological
approach to the understanding of the near hydrothermal vent sediments’ fingerprint.
Acknowledgement
The authors acknowledge Professor Han Xiqiu, of the second institute of oceanography for the
opportunity to work on hydrothermal sediments in Carlsberg Ridge, Indian Ocean, and Professor
Ying Ye for his joint supervision on the studies. The staffs and managements of Zhejiang
University, Hangzhou, China and Second institute of oceanography, Hangzhou, China
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