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Hydrothermal vents and prebiotic chemistry: A review

December 2016
Boletín de la Sociedad Geológica Mexicana 68(3):599-620

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Authors:

María Colín-García

National Autonomous University of Mexico

Alejandro Heredia-Barbero

National Autonomous University of Mexico

Guadalupe Cordero

National Autonomous University of Mexico

Antoni Camprubí

National Autonomous University of Mexico

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A hydrothermal system is an environment where there is a flow of hot fluids beneath and up to the surface of the Earth. Hy - drothermal vents are systems whose heat source is the underlying magma or hot water generated by convection currents due to high thermal gradients. Hydro - thermal fossil deposits have also been re - cognized in impact craters. Besides Earth, the other place in the Solar System that shows evidence of past impact-induced hydrothermal systems is Mars. The circu - lation of hydrothermal solutions and in - teraction with country rocks leads to the precipitation of different mineral phases. In fact, hydrothermal vents, due to their characteristics (redox potential, abundan - ce of organic matter and the presence of certain minerals), have been proposed as places where chemical evolution could have occurred. In this article, a review of hydrothermal environments (submarine, subaerial and impact-induced) and their advantages and disadvantages as primi - tive environments is presented. Thus far, the synthesis of organic compounds in si - mulation experiments has been achieved, although the role of prebiotic processes in these environments is still ill-defined. The conditions accompanying white vents are perhaps the best suited for the synthesis of organic molecules; however, this syn - thesis could have also occurred around black vents, where favorable temperature gradients are present.

Structural section that combines evidence from active submarine magmatic-hydrothermal vents and from fossil volcanogenic massive sulfide (VMS) deposits, especially in Kuroko-type settings, including all typical styles of mineralization and hydrothermal assemblages. Based on Lydon (1988) and Hannington et al. (1995). Key: T = temperature.

…

Size of hydrothermal chimneys in the Lost City Hydrothermal Field, compared to those of a blue whale, an orca, a 17-story building, and a diver.

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Frequency histograms for the geographical distribution of submarine hydrothermal vents worldwide, regarding (A) latitude, (B) longitude, and (C) depth, constructed by using the

…

. Experiments of oligomerization and synthesis of organic molecules in physicochemical conditions that simulate those of hydrothermal vents.

…

Figures - uploaded by Antoni Camprubí

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Content uploaded by Antoni Camprubí

Content may be subject to copyright.

Hydrothermal vents and prebiotic chemistry

ABSTRACT

A hydrothermal system is an environment

where there is a ow of hot uids beneath

and up to the surface of the Earth. Hy-

drothermal vents are systems whose heat

source is the underlying magma or hot

water generated by convection currents

due to high thermal gradients. Hydro-

thermal fossil deposits have also been re-

cognized in impact craters. Besides Earth,

the other place in the Solar System that

shows evidence of past impact-induced

hydrothermal systems is Mars. The circu-

lation of hydrothermal solutions and in-

teraction with country rocks leads to the

precipitation of dierent mineral phases.

In fact, hydrothermal vents, due to their

characteristics (redox potential, abundan-

ce of organic matter and the presence of

certain minerals), have been proposed as

places where chemical evolution could

have occurred. In this article, a review of

hydrothermal environments (submarine,

subaerial and impact-induced) and their

advantages and disadvantages as primi-

tive environments is presented. Thus far,

the synthesis of organic compounds in si-

mulation experiments has been achieved,

although the role of prebiotic processes in

these environments is still ill-dened. The

conditions accompanying white vents are

perhaps the best suited for the synthesis

of organic molecules; however, this syn-

thesis could have also occurred around

black vents, where favorable temperature

gradients are present.

Keywords: Submarine

hydrothermal vents, subaerial

hydrothermal springs, impact

cratering, chemical evolution,

origin of life.

RESUMEN

Un sistema hidrotermal involucra la circulación

de uidos calientes a profundidades variables

en la corteza terrestre, y hasta la supercie. Las

fuentes hidrotermales son sistemas cuyas fuentes

de calor son magmas subyacentes o bien gradientes

térmicos de diverso origen, que generan corrientes

de convección en las que circula agua caliente. Los

depósitos hidrotermales fósiles también han sido

reconocidos en los cráteres de impacto. Además

de la Tierra, el otro lugar en el Sistema Solar

que presenta evidencias de actividad hidrotermal

inducida por impacto es Marte. El proceso de

circulación de las soluciones hidrotermales y su

interacción con las rocas encajonantes es capaz de

precipitar diferentes fases minerales. Las fuentes

hidrotermales se han reconocido por sus caracte-

rísticas (potencial redox, fuentes abundantes de

materia orgánica y presencia de minerales caracte-

rísticos) como lugares en los que la evolución quí-

mica pudiera haberse producido. En este artículo

se presenta una revisión de los ambientes hidroter-

males (submarinos, subaéreos y de impacto), sus

ventajas y desventajas como ambientes relevantes

para la química prebiótica. Hasta el momento

se ha logrado la síntesis de compuestos orgánicos

en experimentos de simulación, aunque el papel

de estos ambientes en procesos prebióticos aún es

parte de un fuerte debate. Las condiciones presen-

tes en los manantiales submarinos blancos son,

quizá, las más adecuadas para que se presentara

la síntesis de moléculas orgánicas; sin embargo,

también pudo darse esta síntesis en los alrededores

de los manantiales negros, donde se encuentran

gradientes de temperatura favorables.

Palabras clave: Manantiales hidro-

termales submarinos, manantiales

hidrotermales subaéreos, crateris-

mo de impacto, evolución química,

origen de la vida.

Hydrothermal vents and prebiotic chemistry: a review

María Colín-García

mcolin@geologia.unam.mx

Fernando Ortega-Gutiérrez

Instituto de Geología, Universidad Nacional

Autónoma de México, Ciudad Universitaria, 04510,

Ciudad de México, México.

SIOV, Seminario Interdisciplinario sobre el Origen

de la Vida, Universidad Nacional Autónoma de

México, 04510, Ciudad de México, México.

Alejandro Heredia

Alicia Negrón-Mendoza

Sergio Ramos-Bernal

Instituto de Ciencias Nucleares, Universidad

Nacional Autónoma de México, 04510, Ciudad de

México, México.

SIOV, Seminario Interdisciplinario sobre el Origen

de la Vida, Universidad Nacional Autónoma de

México, 04510, Ciudad de México, México.

Guadalupe Cordero

Instituto de Geofísica, Universidad Nacional

Autónoma de México, Ciudad Universitaria, 04510,

Ciudad de México, México.

SIOV, Seminario Interdisciplinario sobre el Origen

de la Vida, Universidad Nacional Autónoma de

México, 04510, Ciudad de México, México.

Antoni Camprubí

Instituto de Geología, Universidad Nacional

Autónoma de México, Ciudad Universitaria, 04510,

Ciudad de México, México.

Hugo Beraldi

SIOV, Seminario Interdisciplinario sobre el Origen

de la Vida, Universidad Nacional Autónoma de

México, 04510, Ciudad de México, México.

María Colín-García, Alejandro Heredia, Guadalupe Cordero, Antoni Camprubí,

Alicia Negrón-Mendoza, Fernando Ortega-Gutiérrez, Hugo Beraldi,

Sergio Ramos-Bernal

Boletín de la Sociedad Geológica Mexicana

/ 2016 /

599

BOL. SOC. GEOL. MEX. 2016

VOL. 68 NO. 3

P. 599‒620

Manuscript received: March 13, 2016

Corrected manuscript: July 18, 2016

Manuscript accepted: July 22, 2016

ABSTRACT

Hydrothermal vents and prebiotic chemistry

600

Boletín de la Sociedad Geológica Mexicana

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600

1. Introduction

Since its formation, the Earth has undergone

many changes, among which one of the most

remarkable has been the emergence of life. This

must have occurred before 3500 Ma, the age of

the rocks where the oldest known fossils have been

found (Schopf, 2006). The event was preceded by

a period called “chemical evolution”, which invol-

ved chemical reactions among components of the

ocean, the lithosphere and the early atmosphere.

Life possibly emerged as a result of chemical pro-

cessing in these media, with a continuous increase

in molecular complexity (Morowitz, 2002). Multi-

ple examples of water-based systems in which life

could have arisen include seas and oceans, lakes,

pools and ponds (plus other ephemeral water bo-

dies), and intertidal zones.

The quest to explain how life originated on Earth

is an old and unsolved topic. Several scientic

hypotheses try to explain how life emerged as a

result of the physicochemical interactions between

organic molecules and the physical environment.

The experimental evidence of chemical synthe-

sis under conditions that possibly existed on early

Earth provides support for the hypothesis of che-

mical evolution. The precise mechanism that led

to the transformation of organic compounds to

simple biological entities is still an open problem

nonetheless. Two theories attempt to explain how

life appeared: the “gene rst” theory and the “me-

tabolism rst” approach (e.g., Bada and Lazcano,

2003; Delaye and Lazcano, 2005). According to

the genetic approach, prebiotic soup produced or-

ganic compounds that gave rise to the rst genetic

systems; whereas the metabolic theory proposes

the existence of a rudimentary primary metabo-

lism (Orgel, 2000, Lazcano, 2010; Luisi, 2014).

Both theories have been supported by several ex-

perimental as well as theoretical results (Orgel,

1998). Such is the case of the synthesis of many

important organic compounds for present living

beings—including some amino acids, nitrogenous

bases, carboxylic acids and sugars. However, the

formation of biological polymers, and how the

relationship between proteins and nucleic acids

evolved is still a far too complex and unresolved

problem.

Either theory requires the synthesis of organic ma-

tter, which necessarily involves the participation of

an energy source. Although there are many plau-

sible energy sources for the generation of organic

compounds, one of the most conspicuous sources

on Earth is its internal heat, which is released in

many environments. Such is the case of anoma-

lously high thermal gradients around volcanoes

and volcanic hot springs (Lathe, 2004, 2005),

which can be subaerial and submarine—some

with temperatures that may range from 90° to >

400 °C (Russell and Hall, 1997; Kelley et al., 2001).

Processes driven by external sources for energy

include many other interfaces such as those be-

tween rocks, water, air, and snow-air (Muller and

Schulze-Makuch, 2006). From the point of view

of prebiotic chemistry, high temperature gradients

would have provided the necessary energy ux to

promote chemical reactions. But at the same time,

however, such gradients could have been harmful

to organic compounds, thus promoting the degra-

dation of the synthesized products (Muller and

Schulze-Makuch, 2006).

For many years, a common feature in prebiotic

experiments was their lack of any geological con-

text. The discovery of hydrothermal vents in mid-

ocean ridges in the 1970s led many scientists to

propose that these systems would make plausible

geological sites for the origin of life (Holm and

Charlou, 2001; Holm and Andersson, 2005). Most

of these vents build up mineralized chimneys by

means of hot uids associated with Earth’s mant-

le magmas at temperatures above 300 °C. French

(1968, 1970) suggested that hydrothermal systems

might have allowed organic compounds to be syn-

thesized by non-biological processes through Fis-

cher-Tropsch-like reactions (FT). These reactions

involve gases at high pressures and temperatures,

as well as minerals like siderite and other carbona-

tes, sulfates, iron oxides, and some silicates. Those

processes could have taken place at some depth

within the Earth’s crust, where organic matter

INTRODUCTION

Hydrothermal vents and prebiotic chemistry

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601

could be produced, and then transferred to the

surface (Holm and Andersson, 2005). Furthermo-

re, Corliss et al. (1981) suggested that hydrothermal

vents along mid-ocean ridges were likely sites for

the origin and evolution of life. Also, Baross and

Homan (1985) suggested that submarine hydro-

thermal systems have retained some characteris-

tics, making them environments where reactions

and evolutionary processes can be examined.

Such ideas began to gain importance when Wä-

chtershäuser (1988 a, b) hypothesized that the rst

organisms on Earth could have been thermophilic

and chemoautotrophic beings. These organisms

could have had a primitive metabolism that took

place on the surface of solid particles, especially

suldes (most likely, iron suldes) that formed from

hydrothermal venting (Wächtershäuser 1988 a,

b). However, these ideas remain controversial and

there is no compelling evidence to support that the

rst organisms were thermophilic. Regardless of

how life originated, this process must be thermod-

ynamically favored or it would have been unlikely

(Martin and Russell, 2007). The chemical and

thermal dynamics in hydrothermal vents makes

such environments highly suitable thermodyna-

mically for chemical evolution processes to take

place. Therefore, thermal energy ux is a perma-

nent agent and contributed to the evolution of the

planet, including prebiotic chemistry.

2. Hydrothermal systems and prebiotic

synthesis

A hydrothermal system is an environment where

hot uids circulate below the Earth’s surface and

may (or not) reach the surface as hot springs or

vents. The two main components of a hydrother-

mal system are a heat source, and a uid phase. In

addition, uid circulation requires faults, fractures

and permeable lithologies (Pirajno, 2009).

Such systems can be classied according to their

tectonic setting, the characteristics of their empla-

cement, and the sources for uids, among other

geological variables. As for the matter of prebio-

tic synthesis, a variety of such environments have

been invoked as likely sites to harbor the plausible

chemical reactions thus involved. These are sub-

marine and subaerial hydrothermal systems, and

similar systems associated with impact cratering.

2.1. SUBAQUEOUS HYDROTHERMAL SYSTEMS

These hydrothermal systems (submarine or su-

blacustrine) can be divided into those linked to

magmatism as both source for heat and chemical

components, and those associated with venting of

basinal brines. Such environments correspond,

respectively, to volcanogenic massive sulde (VMS)

and sedimentary-exhalative (SEDEX) deposits

and their present-day analogues. Paleo-hydrother-

mal systems associated with metalliferous deposits

in black shales may be likely candidates as well. All

theoretical and experimental approaches to pre-

biotic reactions have been carried out considering

VMS-like hydrothermal systems, while neglecting

the others. SEDEX systems and those associated

with metalliferous black shales provide all geologi-

cal and physicochemical characteristics that would

have favored prebiotic reactions as eectively as

VMS systems, like the necessary temperature gra-

dients, euxinic environments, and a wide range of

depths of formation (see Table 1). The problem in

the involvement of SEDEX systems with prebiotic

reactions resides in the age of the oldest examples

of such systems, as no known deposits are older

than late Paleoproterozoic (ca. 1.8 Ga; Lydon,

1996). Metalliferous black shales can be signi-

cantly older (middle Paleoproterozoic, ca. 2.1 Ga

or older; Mossman et al., 2005) than SEDEX de-

posits. However, neither type has yet been found

to be old enough as to be coeval with prebiotic

processes or, least of all, be involved with them.

In contrast, Archean VMS deposits are numerous

(ca. 3.5 Ga; Barrie and Hannington, 1999). The

striking lack of Archean SEDEX deposits can be

associated with the limiting eect of high reduced iron

contents on the activity of reduced sulfur in anoxic oceans

(sic, Goodfellow, 1992) in which metals in hydrother-

mal uids […] were dispersed because a lack of reduced

sulfur to precipitate them (sic, Misra, 1999). Therefore,

INTRODUCTION / HYDROTHERMAL SYSTEMS AND

PREBIOTIC SYNTHESIS

Hydrothermal vents and prebiotic chemistry

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HYDROTHERMAL SYSTEMS AND PREBIOTIC

SYNTHESIS

Table 1. Comparison between shallow hydrothermal environments (both fossil ore deposits and present examples). Based loosely on Misra (1999), Jébrak and Marcoux

(2008) and Pirajno (2009).

Type of deposit and

metallic associations

Tectonic setting Association with

volcanism

Main types of

mineralizing fluids and

mechanisms of formation

Range of

temperatures Depth Sources for sulfur Age distribution Fossil examples Actualistic examples Further readings

Volcanogenic

massive sulfide

deposits (VMS)

Magmatic, fresh marine,

and modified marine

water (evolved within the

crust)

~100º to >500 ºC Mid-ocean ridges: Lucky

Strike, Lost City, East

Pacific Rise at 21ºN, Sonne

Field

Cu(-Pb-Zn-Ag-Au) Seafloor venting Important T

gradients occur

from central to

peripheral vents

Arcs, back-arcs and passive

margins: Manus basin, Lau

basin, Woodlark basin,

Mariana trough, Okinawa

trough, Guaymas basin

Sedimentary-

exhalative deposits

(SEDEX) and

subaqueous brine

ools

Sedimentary brines, fresh

marine, and modified

marine water

~50º to <300 ºC

Zn-Pb-Ba(-Cu), Fe-

Seafloor venting and

precipitation from

seawater combined

Important T

gradients possibly

occurred (stratiform

deposits are

frequently separated

from their

hydrothermal

feeders)

Metalliferous black

shales (and closely

associated

phosphorites)

Sedimentary brines, fresh

marine, and modified

marine water

~100º to >300 ºC

Zn-Cu-Pb(-Mo-Au-Ni

PGE), Cu-Co-Zn, Sb-

W-Hg, etc.

Seafloor venting?

Precipitation from

seawater? (Impact-

related?)

Epithermal deposits Magmatic, fresh

meteoric, and modified

meteoric water

~50º to ~400 ºC Campbell (Canada),

Emperor (Fiji), Kelian

(Indonesia), Hishikari

(Japan), Fresnillo,

Pachuca, Tayoltita

(México), Yanacocha

(Perú), Lepanto,

Baguio (Philippines),

Au-Ag, Ag-Pb-Zn-

Epigenetic structures and

subaerial precipitation

(sinters)

Important T

gradients occur

from central to

peripheral springs

Comstock Lode,

Summitville, Creede

(USA)

Willyama Supergroup

(Australia), Selwyn

Basin (Canada),

Niutitang Formation

(China), Bohemian

massif (Czech Rep.,

Germany, Poland),

Outokumpu, Talvivaara

(Finland), Franceville

Series (Gabon)

Black Sea, Caspian Sea,

Ontong Java Plateau

Pašava (1993), Coffin

and Edholm (1994),

Mossman et al . (2005),

Laznicka (2006)

Continental and

island arcs

Close time, space and

genetic association

between volcanism and

hydrothermal activity

Between >1500 m and

subaerial paleosurfaces

Magmatic, also

sedimentary or

metasedimen-tary

Vastly Cenozoic; known

Archean and

Paleoproterozoic

examples

Campi Flegrei (Italy), Los

Azufres, Cerro Prieto

(México), Taupo Volcanic

Zone, White Island (New

Zealand), Yellowstone,

Steamboat Springs, The

Geysers (USA)

Sillitoe and Hedenquist

(2003), Simmons et al .

(2005), Camprubí and

Albinson (2006, 2007)

Intracontinental rift-

related sedimentary

basins

Unclear, may be

correlated with mantle

plumes; may occur

without associated

magmatism or

associated with mafic

volcanism

Between a few

hundreds of m and

>1000 m below sea

level

Seawater sulfate Since the middle

Paleoproterozoic (ca .

2.1 Ga) or earlier,

peaking during the

Paleozoic, associated

with worldwide anoxic

events (?) after the

global oceanic

oxygenation

Magmatic, also from

seawater sulfate

Since the Archean (ca .

3.5 Ga); numerous

Paleozoic examples

Pilbara craton

(Australia), Noranda,

Abitibi, Windy Craggy

(Canada), Troodos

ophiolite (Cyprus),

Hokuroku and the

Green Tuff region

(Japan), Semail

ophiolite (Oman),

Iberian Pyrite Belt

(Spain, Portugal),

Almadén (Spain)

Franklin (1996), Barrie

and Hannington (1999),

Franklin et al . (2005),

Hannington et al .

(2005)

Advanced stages of

continental rifting,

failed rifts, and

passive continental

margins

None, but volcanic

rocks can be present in

the hosting sedimentary

series

Between a few

hundreds of m and

>1000 m below sea

level

Seawater sulfate Since the late

Paleoproterozoic (ca .

1.8 Ga); peaking during

the Mesoproterozoic and

Paleozoic

Broken Hill, Mount Isa,

McArthur River

(Australia), Sullivan

(Canada), Matahambre

(Cuba), Rammelsberg,

Meggen (Germany),

Rajpura-Dariba (India),

Molango (México),

Gamsberg-Aggeneys

(South Africa), Red

Dog, Anarraaq (USA)

Atlantis II Deep (Red Sea),

Salton Sea, lakes in the East

African Rift

Goodfellow et al .

(1993), Lydon (1996),

Hannington et al .

(2005), Leach et al .

(2005), Lyons et al .

(2006)

Arc to back-arc

settings (Kuroko and

Besshi types), and

mid-ocean ridges

(Cyprus type)

Close time, space and

genetic association

between volcanism and

hydrothermal activity

Generally ~2 km below

sea level; known

shallow examples

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HYDROTHERMAL SYSTEMS AND PREBIOTIC

SYNTHESIS

it is likely that SEDEX-type hydrothermal systems

did eectively exist during the Archean, despite

being unable to generate sulde deposits because

reduced sulfur in the oceans would have been pre-

viously “sequestered” by iron to precipitate iron

suldes directly from seawater. After the oxygena-

tion of Earth’s oceans SEDEX deposits formed,

during worldwide anoxic events of the Paleozoic,

as might also be the case for Proterozoic deposits

(Misra, 1999).

Submarine vents in association with magmas at

or near mid-ocean ridges are usually described as

the likeliest hydrothermal systems to be associated

with the emergence of life on Earth (i.e. Corliss et

al., 1981, Nisbet and Sleep, 2001). Besides their

possible role in the emergence and development

of life on Earth, hydrothermal vents could sus-

tain living organisms on Europa or Mars (Pope

et al., 2006; Chyba and Phillips, 2007). The most

common case for the formation of submarine hy-

drothermal vents occurs when seawater migrates

through fractures into the crust and reaches the

vicinity of a magmatic intrusion. While approa-

ching the magmas, water is heated up by the

anomalously high thermal gradient induced by

their emplacement. Additionally, magmas release

aqueous uids upon their cooling down. Therefo-

re, hydrothermal uids in magma-related systems

may come from either magmatic or marine sour-

ces. Similarly, sulfur, iron, copper, zinc and other

metals may come from magmas, ocean water or

host rock leachates. The dissolved minerals nou-

rish chemosynthetic bacteria that constitute the

base of the food chain for a variety of invertebra-

tes, including large tubeworms (Levin, 2009).

The importance of submarine hydrothermal

vents for studies related to the origin of life lies

in: (1) providing hot water from shallow to surcial

environments, (2) upwelling uids interact with

seawater, provide nutrients, are agents for chemi-

cal imbalance, thus potentially allowing the syn-

thesis of organic compounds, (3) they produce a

rapid crystallization of carbonates and silicates at

low temperatures, which increases the local poten-

tial to preserve microbial organisms as fossils and

their chemical signatures, despite later diagenetic

or low-grade metamorphic processes (Pope et al.,

2006), and (4) according to some authors, the ol-

dest forms of terrestrial life might have been auto-

trophic-thermophiles (Pope et al., 2006).

The so-called “black smokers” are the most cons-

picuous submarine hydrothermal manifestations

(Figure 1). These are hydrothermal fumaroles with

abundant suldes in suspension that upon preci-

pitation form mounds along favorable faults or

within submarine calderas. In association with di-

vergent margins, these are usually located close to

mid-ocean ridges. In these fumaroles, due to their

proximity to magmas, water may attain tempera-

tures above 400 °C and low pH (see Table 1). The

latter facilitates the leaching of iron and other me-

tals as the water seeps through the country rocks.

Such uids come in contact with cold seawater,

thus generating a rapid nucleation of suldes and

other minerals and resulting in a turbid suspension

resembling a cloud of black smoke.

Another type of hydrothermal vents is dubbed

“white smokers”, which are generally distant from

their heat source (Figure 1); therefore, their tem-

peratures are lower than those in black smokers.

Black and white smokers may coexist in the same

hydrothermal eld, but they generally represent

proximal and distal vents to the main upow zone,

respectively (Figure 1). However, white smokers

correspond mostly to waning stages of such hydro-

thermal elds, as magmatic heat sources become

progressively more distant from the source (due to

magma crystallization) and hydrothermal uids

become dominated by seawater instead of mag-

matic water (see references in Table 1 for VMS

systems). The temperature in white smokers can

be as low as 40° to 75 °C and are alkaline (pH be-

tween 9 and 9.8; Kelley et al., 2001). Mineralizing

uids from this type of vents are rich in calcium

and they form dominantly sulfate-rich (i.e., barite

and anhydrite) and carbonate deposits. These may

form giant chimneys, the largest of which stand al-

most 60 m above the bottom of the ocean (Figure

2) at the Lost City hydrothermal eld (Kelley et al.,

2001). Hydrothermal uids in this location con-

Hydrothermal vents and prebiotic chemistry

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HYDROTHERMAL SYSTEMS AND PREBIOTIC

SYNTHESIS

Figure 1 Structural section that combines evidence from active submarine magmatic-hydrothermal vents and from fossil volcanogenic

massive sulde (VMS) deposits, especially in Kuroko-type settings, including all typical styles of mineralization and hydrothermal

assemblages. Based on Lydon (1988) and Hannington et al. (1995). Key: T = temperature.

tain methane, ethane and propane, and organic

acids such as formate and acetate form in associa-

tion with this hydrothermal system (Proskurowski

et al., 2008).

The global frequency distribution of depths for

the occurrence of actualistic examples of VMS

deposits (magmatic-hydrothermal seaoor vents,

either black or white smokers) shows a dominant

range between 2000 and 3000 m (Figure 3; also,

Figures 2 and 3 in Hannington et al., 2005), which

is consistent with calculated depths of fossil exam-

ples (see Table 1 and references therein). In spite

of this, much shallower examples are known both

in present-day manifestations (Figure 3) as well as

in fossil VMS deposits (e. g., Camprubí et al., 2017).

Their global frequency distributions in latitude

and longitude, however, are not expected to be

clear because such spatial variables do not govern

any geological characteristics for the location of

venting. In fact, the present-day convergent or

divergent margins that are capable of sustaining

hydrothermal manifestations analogous to VMS

deposits (see Figure 1 in Hannington et al., 2005)

can be found in a wide variety of latitudes and

longitudes, including divergent margins within the

Arctic Circle and the convergent margin adjacent

to the Antarctic Peninsula. However, the latitudi-

nal distribution of those vents shows a bimodal

pattern between 40ºN and 40ºS (Figure 2), which

includes dierent types of both convergent and di-

vergent margins (see Figure 1 in Hannington et al.,

2005). The distribution is deemed to be an artifact

due to the diculties of carrying out oceanogra-

phic campaigns in extremely low latitudes, either

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dered as the modern analogues of low-suldation

and high-suldation epithermal deposits, respec-

tively (which, in both cases, may include interme-

diate-suldation deposits; Simmons et al., 2005;

Camprubí and Albinson, 2006, 2007; Sillitoe,

2015). The uppermost part of such systems has a

tendency to display wide variations in temperatu-

re, salinity, volatile content, pH and redox poten-

tial, hence the broad range in reactivity between

the associated hydrothermal uids and host rocks.

Such variables are largely controlled by the verti-

cal or lateral nearness of hydrothermal discharge

zones to their parental intrusions (see Figure 1 in

Sillitoe, 2015) and the geological and hydrological

characteristics in each area (White and Heden-

quist, 1990). Besides the broad temperature and

salinity gradients that may occur in the actual va-

north or south, in comparison with peri-equatorial

regions.

2.2. SUBAERIAL HYDROTHERMAL SYSTEMS

Hydrothermal manifestations are abundant in

subaerial settings, particularly in association with

convergent plate boundaries (that is, continental

and island volcanic arcs), but also in transform

boundaries. For instance, hydrothermal activity

is known to occur in the Salton Sea, in associa-

tion with the San Andreas fault system but, unlike

volcanic arcs, this case is normally placed among

modern equivalents to SEDEX deposits and su-

baqueous brine pools (see Table 1). The most re-

levant and numerous recent/active hydrothermal

elds are found in geothermal and magmatic-hy-

drothermal contexts, which are normally consi-

Figure 2 Size of hydrothermal chimneys in the Lost City Hydrothermal Field, compared to those of a blue whale, an orca, a 17-story

building, and a diver.

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Figure 3 Frequency histograms for the geographical distribution

of submarine hydrothermal vents worldwide, regarding (A)

latitude, (B) longitude, and (C) depth, constructed by using the

InterRidge Vents Database 3.3 (http://vents-data.interridge.org)

dated April 30th 2014.

riety of such environments, the occurrence of deep

hypogene low- to intermediate-suldation uids

(generally near-neutral and reduced; geothermal

context) or high- to intermediate-suldation uids

(acidic and oxidized; magmatic-hydrothermal

context) determines (1) the possible zonation of

alteration assemblages around the uid conduits,

and (2) the mineralogy of the mineral precipitates

(if any) that may occur on the surface. In addition

to the “original” physicochemical characteristics

of hydrothermal uids, their chemical characte-

ristics may vary depending on the occurrence of

(relatively) near-surface boiling, which may ge-

nerate H2SO4-rich uids locally in steam-heated

grounds (shallow hypogene acidic uids), indepen-

dently from the composition of pre-boiling uids

(e. g., Sillitoe, 2015). This means that hydrothermal

uids of any kind that undergo boiling may gene-

rate acidic uids upon condensation of boiled-o

steam, and the associated alteration assemblages

and surcial hydrothermal features.

Acidic uids from either deep or shallow hypoge-

ne sources generate alteration assemblages that

result from extremely reactive to relatively mild

reactions between uids and host rocks, from

proximal to distal areas to hydrothermal upow,

respectively. No surface sinter deposits, either car-

bonate- or silica-rich, can be expected from highly

reactive high-suldation type uids. In this envi-

ronment, silica is the only residue after extreme

acid leaching of every other mineral, or as a late

overprint. Common hydrothermal manifestations

of the high-suldation type are high-tempera-

ture solfataras and fumaroles centered on recent

volcanic edices, and hyper-acidic crater lakes.

Near-neutral low-suldation type uids, on the

contrary, may develop sinter deposits in hot spring

environments unless the hydrothermal discharge

occurs in high-relief terrains. Common hydro-

thermal manifestations of the low-suldation type

are hot springs and geysers. Common manifesta-

tions associated with steam-heated grounds are fu-

maroles, steaming grounds, and mud pots (or mud

“volcanoes”). The position of the groundwater

table is sensitive to seasonal variations in rainwater

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availability, climatic and tectonic changes, or seve-

ral other phenomena (e. g., Sillitoe, 2015).

2.3. IMPACT CRATERING AND HYDROTHERMAL

SYSTEMS

Impact cratering is a major geological process

that occurs on the Earth and all other solid bodies

of the Solar System. Impact cratering alludes to

a process in which an asteroid or comet at high

speed collides with a planetary surface, producing

a cavity known as an impact crater (Melosh et al.,

1990; Melosh, 2011). Temperatures and pressures

produced by the collision are typically > 10000 K

and a few hundred GPa, respectively. For compa-

rison, in the Earth’s core, the pressure is estimated

at ~350 GPa and temperature at ~5000 K. Under

these conditions, both the target and projectile

material melt or vaporize near the point of con-

tact (Collins et al., 2012).

Since Alvarez et al. (1980) proposed a possible ex-

traterrestrial impact to explain the mass extinction

at the K-T (Cretaceous-Cenozoic) boundary; ex-

tensive work has been carried out to try to unders-

tand the consequences of an impact due to objects

larger than one km in diameter. An object 10 km

across, similar to the one that formed the Chicxu-

lub crater in the Yucatán Peninsula, would throw

a huge amount of dust into the air, thus blocking

sunlight and inhibiting photosynthesis and cutting

o heterotrophs’ primary food source. Also, the

ejecta that failed to escape Earth’s gravitational

pull would reenter the atmosphere and raise the

atmospheric temperature enough to cause global

forest res (Melosh et al., 1990; Kring and Durda,

2002). Although, at rst glance, such impacts may

prevent life from developing instead of being favo-

rable for it, some positive eects can be expected.

For example, in recent years scientists have retaken

the idea that prebiotic compounds, water, and

other gaseous components that are now present

on Earth were brought and deposited by asteroids

and comets that collided with the planet (Berns-

tein et al., 1999; Horneck, 2006).

The rst authors who propose that impact craters

may produce hydrothermal systems were AlDahan

(1990), Kring (1995), and McCarville and Crossey

(1996). This was sustained because pressures and

temperatures during the contact and compression

stage are capable of melting the country rocks

(Melosh et al., 1990). Such melts act as heat sour-

ces for hydrothermal systems in impact craters as

the associated high geothermal gradient is esta-

blished (Newsom, 2012). This proposal has been

supported by hydrothermal deposits that have

been recognized in the Chicxulub, Sudbury and

Haughton impact craters (Kring, 1995; Osinski et

al., 2005; Ames et al., 2006; Parnell et al., 2006). In

fact, there is evidence of impact-induced hydro-

thermal systems in 60 out of the 181 conrmed

terrestrial impact craters (Kirsimäe and Osinski,

2012).

The life span calculated for these systems is in the

order of 104 – 105 years if the crater is 100 km in

diameter, and up to 106 years for a 180 km crater

like Chicxulub (Daubar and Kring, 2001). Mag-

ma-related hydrothermal activity may normally

last in the order of 105 – 106 years, even several

million years, for epithermal and porphyry-re-

lated deposits, including similar subaerial active

geothermal systems (Cathles et al., 1997; Arehart

et al., 2002; Camprubí and Albinson, 2007; Baum-

gartner et al., 2009; Redmond and Einaudi, 2010;

Chiaradia et al., 2013). Single fossil VMS deposits

also exhibit similar age spans (e.g., Ross et al., 2014;

Belford et al., 2015), and thus the temporal likeli-

hood for all these types of hydrothermal systems

to have roles in prebiotic chemistry is essentially

the same.

Besides Earth, the other place in the inner Solar

System that presents evidence of impact-indu-

ced hydrothermal systems is Mars (Rathbun and

Squyres, 2002; Pirajno, 2009). As less energy is

necessary to produce an impact crater of any size

on Mars than on Earth, so would be the volume

of molten rock that could be produced in Mars.

Therefore, it is expected that for similar craters

on Mars and Earth, the hydrothermal activity on

Mars would be shorter in duration than on Earth

by about an order of magnitude (Pope et al., 2006).

Another interesting aspect about craters on Mars

HYDROTHERMAL SYSTEMS AND PREBIOTIC

SYNTHESIS

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is that they could have been occupied by paleo-

lakes. These could have existed over thousands of

years as crater lakes, much like as on Earth, co-

vered by an ice layer and heated from below by

impact melts (Kirsimäe and Osinski, 2012). Phy-

llosilicates have been detected in impact-induced

hydrothermal systems on Mars (Kirsimäe and

Osinski, 2012); these minerals have been proposed

as natural catalysts for prebiotic reactions.

It has been considered that the main sources for

uids in an impact-induced hydrothermal system

would be seawater and meteoric water. The che-

mical composition of these uids depends on the

composition of the ground that received the im-

pact (or target material). In this kind of systems,

Ca-Mg or K-rich minerals will dominate depen-

ding on the target material, the size of the impact

crater, the sources for uids and the evolution of

the hydrothermal system. Usually, Na-K minerals

dominate at the beginning of the lifetime of the

hydrothermal system, and evolve into Ca-Mg mi-

nerals at the last phase of the impact cooling. For

example, in the early stages of such hydrothermal

activity, magmatic feldspars (plagioclase, microcli-

ne) are replaced by hydrothermal alkali feldspars

(albite, “pericline”- and “adularia”-type potassium

feldspar). During waning stages of hydrothermal

systems, calcite and dolomite can precipitate de-

pending on the enrichment of Ca and Mg in the

uids (Kirsimäe and Osinski, 2012).

3. Minerals in hydrothermal vent

systems

Mineral parageneses are a key for the denition of

physicochemical parameters that characterize the

conditions for mineral precipitation, including ti-

ming. Mineralization in submarine magmatic-hy-

drothermal systems is a product of the chemical

and thermal exchange between the ocean, the

lithosphere, and the magmas emplaced within it.

Dierent mineral associations precipitate during

the typical stages of mineralization that characte-

rize the life span of such systems. For comprehen-

sive reviews of this subject see Franklin et al. (1981,

2005), Lydon (1988), Ohmoto (1996), Barrie and

Hannington (1999), Hannington et al. (2005). Mi-

nerals present in a hydrothermal system or a fossil

VMS deposit are deposited passively or reactively.

Mineral associations may vary (1) in dierent mi-

neralized structures, either syngenetic (namely,

passive precipitation in chimneys, mounds and

stratiform deposits) or epigenetic (structures that

correspond to feeder channels, and replacements

of host rocks or pre-existing massive sulde bo-

dies), or structural zonation, (2) from proximal to

distal associations with respect to venting areas

within the same stratigraphic horizon, or horizontal

zonation, (3) from deep to shallow associations

(i.e., stockworks to mounds), or vertical zonation, (4)

from early and climactic to late stages of mine-

ralization (dominated by suldes, and sulfates or

oxides, respectively), or temporal zonation, and (5) in

various volcano sedimentary contexts, depending

essentially on the composition of volcanic rocks

and, ultimately, on the tectonomagmatic context.

The most common minerals in ore-bearing asso-

ciations of VMS deposits (non-metamorphosed or

oxidized) and their modern analogues are pyrite,

pyrrhotite, chalcopyrite, covellite, sphalerite, ga-

lena, tetrahedrite-tennantite, marcasite, realgar,

orpiment, proustite-pyrargyrite, wurtzite, stannite

(suldes), Mn oxides, cassiterite, magnetite, hema-

tite (oxides), barite, anhydrite (sulfates), calcite, si-

derite (carbonates) quartz and native gold, and are

dierently distributed in the various associations

schematized above. The most common hydrother-

mal alteration assemblages are chloritic (including

Mg-rich ones) and phyllic (dominated by “serici-

te”, mostly illite), and also silicication, deep and

shallow talcose alteration, and ferruginous (inclu-

ding Fe oxides, carbonates and suldes) alteration.

Paleosurface features for the various types of su-

baerial/sublacustrine magmatic - hydrothermal

systems (that is, epithermal-like systems) and their

mineralogy were summarized in detail by Sillitoe

(2015) as (1) steam-heated grounds, with opal/

chalcedony, alunite, kaolinite and smectite, (2)

groundwater table silicication, with opal/chal-

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cedony, (3) lacustrine amorphous silica sediments,

with opal and cristobalite, (4) hydrothermal erup-

tion craters and breccias, with illite and smectite,

(5) hot spring sinter, with opal/chalcedony, (6)

hot spring travertine, with calcite and aragonite,

(7) hydrothermal chert, with opal/chalcedony,

and (8) silicied lacustrine sediments, with opal/

chalcedony. See their occurrence and nature sche-

matized in Figure 11 by Sillitoe (2015), as repla-

cements, open-space or on-surface (subaerial or

subaqueous) precipitation. Cases 6 to 8 (particu-

larly case 6) occur distally to their hydrothermal

upow zone, which implies that their temperatu-

res are lower than in proximal features, and their

chemical characteristics attenuated by interaction

with meteoric water. Such features and their par-

ticular mineral assemblages may be found topping

various hydrothermal alteration assemblages in

association with either acidic or near-neutral to

alkaline uids (high-suldation, and intermediate-

to low-suldation uids, respectively), but not ne-

cessarily. Alteration assemblages in the uppermost

part of these systems are characteristically zoned

as follows, from the central portion of hydrother-

mal upow outwards into non-altered host rocks

(see Storegen, 1987; Corbett and Leach, 1998;

Camprubí and Albinson, 2006, 2007):

1. high-suldation systems: residual quartz (with

opal, cristobalite and tridymite), advanced ar-

gillic (from silica + alunite, to alunite + kaoli-

nite outwards), argillic (from kaolinite + silica,

to kaolinite + silica + smectite outwards), illi-

te- or smectite-rich phyllic, montmorillonite-to

chlorite-rich propylitic alteration, including

zeolites and carbonates (calcite and dolomite)

in association with the most alkaline uids;

2. intermediate- to low-suldation systems: phy-

llic to propylitic alteration, with the same

mineral assemblages as those described for hi-

gh-suldation systems.

Additionally, all the features in the uppermost

portions of epithermal deposits and their modern

analogues may have anomalously high concentra-

tions of Mn, As, Sb, Hg, Tl, Se, Au, Ag, Ga and

W (Hedenquist et al., 2000; Sillitoe, 2015). These

anomalies occur in association with minerals like

pyrite, cinnabar, stibnite, orpiment, realgar, native

sulfur, livingstonite, corderoite, several amorphous

phases and, exceptionally, borates (Sillitoe, 2015,

and references therein).

4. Hydrothermal vents and chemical

evolution

In the eld of chemical evolution, the search for

a suitable location for chemical reactions to occur

constitutes a major issue. Hydrothermal vents are

environments that harbor very special physical,

chemical and geological conditions, which could

have been important for chemical evolution. On

the one hand, the exergonic reactions in such sys-

tems could have been a source of free energy that

promoted chemical reactions. This energy could

eventually lead to the synthesis of prebiotic or-

ganic molecules, primarily from carbon dioxide

reduction into hydrocarbons (Berndt et al., 1996),

but also via methane oxidation and phosphate

condensation (Russell et al., 2013).

On the other hand, probably one of the most im-

portant characteristics of hydrothermal vents is

their high mineralogical diversity. A broad array

of minerals could have acted as catalytic inorganic

surfaces that favored the formation of organic mo-

lecules. Such mineralogical complexity implies the

induction of important chemical gradients, thus

favoring the interaction between electron donors

(e. g., methane, hydrogen, formate) and electron ac-

ceptors (e.g., carbon dioxide, nitrate, nitrite, sulte,

native sulfur and ferric iron). As a consequence,

these reactions would yield complex organic mo-

lecules aided by pH and thermal gradients, and

perhaps also by mineral fracturing and uid ow

(Russell and Hall, 1997; Russell et al., 2013).

There are numerous experiments proposed to test

the role of hydrothermal vents in prebiotic syn-

thesis. A review of the literature (Tables 2, 3 and

4) indicates several types of experiments that can

be performed. The rst group is related to de-

composition experiments, sometimes referred as

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Table 2. Experiments of decomposition and stability of organic molecules in physicochemical conditions that simulate those of

hydrothermal vents.

Note: All amino acids are abbreviated according to the IUPAC indications.

Key: ABA = aminobutyric acid, Ala = alanine, Arg = arginine, Asp = asparagine, Cys = cysteine, Gaba = gamma-aminobutyric acid, Glu

= glutamic acid, Gly = glycine, His = histidine, Hyp = hydroxyproline, Ile = isoleucine, Leu = leucine, Lys = lysine, Met = metionine,

Nva = norvaline, Orn = ornithine, PCA = pyroglutamic acid, Phe = phenylalanine, Pro = proline, Pyr = pyruvate, Ser = serine, Thr =

threonine, Tyr = tyrosine, Val = valine.

Type of Study Description of experiments Organic molecule used Mineral Main findings Reference

Interconversion of amino acids (i.e. methylamine from

glycine; ethylamine from alanine; glycine, alanine and

ethanolamine from serine, etc.).

There is an order of relative thermal stability at

temperatures between 216 and 280°C: (1) Asp, Thr, Ser,

Arg.HCl; (2) Lys-HCl, His-HCl, Met; (3) Tyr, Gly, Val,

Leu, Ile; (4) Ala, Pro, Hyp, Glu.

Decomposition Amino acid in water solutions. Glu, PCA. N.A. Kinetic parameters Povoledo and Vallentyne, (1964).

Decomposition Amino acid decomposition (6 h of

incubation at 250 °C and 260 bar).

Ala, Arg, Asp, Glu, Gly, His, Ile,

Leu, Lys, Met, Phe, Ser, Thr, Tyr,

Val.

N.A. Amino acids are drastically affected by high temperature

and pressure. Some amino acids are almost quantitatively

transformed or decomposed (Asp, Glu, Ser, Thr, Cys,

Trp); apolar amino acids as well as His, Lys, Arg and Phe

are partially degraded.

Bernhardt et al . (1984).

Dipeptide hydrolysis and amino acid decomposition have a

first order rate-law.

Magnetite accelerates the decomposition.

Decomposition Amino acids, at high temperatures (240 °C). Ala, Gly + Leu. Quartz-fayalite-magnetite mixture Amino acids are destroyed by heating at 240 °C. Bada et al . (1995).

Decomposition Amino acids at different temperatures,

controlling the oxidation state of the

environment.

Ala, Ala, ABA, Asp, Glu,

Gly, Leu, Ser, Val.

The decomposition rate is lower in high hydrogen fugacity

environments.

Kohara et al . (1997).

Gly, and Ala were formed, from Ser.

Decomposition rates of Leu, Ala and Asp lower in

experiments containing the PPM assemblage.

Formation of Di-Gly, Tri-Gly (traces), diketopiperazine

and a 433 Da product. P & T influence both dimerization

and decom

osition.

Maximum dimers formation at 350°-375 °C, 22.2 - 40

Mpa.

Degradation rates Asp> Ser>Phe>Leu>Ala.

Two main reaction paths:  deamination (Asp) to produce

ammonia and organic acids, and decarboxylation to

produce carbonic acid and amine.

Production of glycine and alanine from serine.

Reactor type

Non inert (Ti-6-4 / Au reactor).

Inert reactor (Au reactor).

Hydrothemal reaction kinetic.

A custom spectrophotometric reaction cell

was constructed. In situ observations.

Decomposition of the amino acids sub- and

supercritical water.

The effect of T (250° to 450 °C), and

residence time (2.5 to 35 s), P (34 and 24

MPa), and reactant concentration (1.0 and

2.0%, w:v).

Iron oxide and sulfide minerals. Nva decomposes by 1) decarboxylation followed by

oxidative deamination, and by 2) deamination directly to

valeric acid.

Mineral assemblage

hematite–magnetite–pyrite (HMP) and

pyrite–pyrrhotite–magnetite (PPM).

Minerals accelerated decomposition rates.

Decomposition is faster in presence HMP than PPM.

Stability Hydrothermal stability of alanine

oligopeptides.

(Ala)3, (Ala)4, (Ala)5Small excess of oligopeptides longer than the starting

ones. Elongation of (Ala)4 and (Ala)5 was possible in Ala

excess. Elongation is competitive with degradation.

Kawamura et al . (2005).

Carbonaceous ooze: The upper limit temperature for the stable presence was

150° and 200 °C.

Calcite, with minor amounts of quartz

and huntite and traces of illite, smectite

and chlorite.

AAs cannot be synthesized or survive at T > 250 °C,

A decrease in the overall stability in amino acids mixtures.

Most of the amino acids decompose at acidic and near-

natural pH, stable at basic pH.

Stability Evaluation of the thermal stability of amino

acids under alkaline hydrothermal conditions

(an aqueous solution of NaCl and Na2CO3)

at high temperatures (100° to 300 °C).

Ala, Arg, Asp, β-Ala, Gaba, Glu,

Gly, His, Ile, Leu, Lys, Met, Orn,

Phe, Pro, Ser, Thr, Tyr, Val.

Siliceous ooze Compared with decomposition at neutral conditions, the

decomposition rates are lower under alkaline conditions.

Yamaoka et al . (2007).

Siliceous ooze: silica minerals (mostly

quartz and minor opaline silica);

moderate amounts of calcite and minor

amounts of smectite and illite.

Amino acids protected from decomposition by amorphous

silica and silicate minerals via adsorption and/or binding.

Montmorillonite The optimal temperature for amino acids was below 150

°C.

Saponite (synthesized). Amino acids are more stable at higher temperatures when

associated with silicates.

Effects of temperature (25°, 150°, 200° and

250 °C), pH (6 and 10) and redox state (13

mM aqueous H2) of hydrothermal fluids.

Glutamic acid at high-temperatures cyclizes and forms

pyroglutamate.

Reaction periods between 3 and 36 min. The formed products (succinate, formate, CO2 and NH4)

depend on temperature, pH and redox state.

Decomposition Solutions of amino acids sealed in Pyrex

glass.

Ala, Arg.HCl, Asp, Cys, Glu,

Gly, His.HCl, Hyp Pro, Ile, Leu,

Lys.HCl, Met, Phe, Pro, Ser, Thr,

Tyr,Val

N.A. Vallentyne (1964).

Decomposition Amino acid and oligomer at high

temperatures, at both high and low pressure.

Gly, Di-Gly, L-Ala, L-Glu. Magnetite Qian et al . (1993).

Decomposition Stability of amino acids. At 200 °C and 50

bar in Teflon-coated autoclaves.

Ala, Asp, Leu, Ser. Pyrite-pyrrhotite-magnetite (PPM) to

constrain the oxygen fugacity. K-feldspar

muscovite-quartz (KMQ) to control the

hydrogen ion activity.

Andersson and Holm (2000).

Dimerization and

decomposition

Influence of P (22.2 and 40.0 MPa).and T

(250, 300, 350, 374, 400 °C) in the

processes.

Gly. N.A. Alargov et al. (2002).

Decomposition High-temperature (200° to 340 °C) and high-

pressure (20 MPa), in a continuous-flow

tubular reactor.

Ala, Asp, Leu, Phe, Ser. N.A. Sato et al . (2004)

Decomposition Hydrothermal reaction kinetics. A custom-

built spectrophotometric reaction cell was

used. In situ observations.

Asp. The reaction kinetics of Asp is complicated, and highly

dependent on experimental conditions (P, T, catalytic

surfaces).

Cox and Seward (2007a).

Decomposition α-Ala, β-Ala, Gly. N.A. Under certain hydrothermal conditions, -Ala, Gly,and

�Ala undergo dimerization and cyclization reaction

pathways.

Cox and Seward (2007b).

Decomposition Ala, Gly. N.A. Decarboxylation and amino acid deamination reactions

were proposed for both molecules.

Klingler et al . (2007).

Decomposition The effect of iron oxide and sulfide minerals

on decomposition reactions of an amino

acid.

Nva. McCollom (2013).

Stability To test the thermal stability of amino acids in

seafloor hydrothermal systems.

Ala, Asp, Gaba, Glu, Gly, Leu,

Met, Ser.

Ito et al . (2006).

Stability Reactions of amino acids under subcritical

water conditions (220° to 290 °C).

Ala, Arg, Asp, Cys, Glu, Gly,

His, Ile, Leu, Lys, Met, Phe, Pro,

Ser, Thr, Tyr, Val.

N.A. Abdelmoez et al. (2007).

Stability Effect of the mineralogical and chemical

properties of host sediments on the thermal

stability of amino acids.

Ala, Arg, Asp, β-Ala, Gaba, Glu,

Gly, His, Ile, Leu, Lys, Met, Phe,

Pro, Ser, Thr, Tyr, Val.

Ito et al . (2009).

Stability Glu N.A. Lee et al. (2014).

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HYDROTHERMAL VENT AND CHEMICAL EVOLUTION

Table 3. Experiments of oligomerization and synthesis of organic molecules in physicochemical conditions that simulate those of

hydrothermal vents.

Type of Study Description of experiments Organic molecule

used

Mineral Main findings Reference

Oligomerization Amino acids. Gly, Phe, Tyr (Ni, Fe)S surfaces. The formation of oligopeptides was pH

dependent. Dipeptide formation (L-Phe, L-Tyr,

D,L-Tyr and Gly.

Huber and Wächtershäuser

(1998).

Oligomerization Amino acid in a flow reactor. Gly N.A. Formation of di-Gly. The addition of divalent

cations, resulted in the formation of hexa-Gly.

Imai et al . (1999).

Oligomerization Amino acids. Gly+Ala CuCl2 Exponential growth of the products. At least six

different oligopeptides were detected; Ala-Gly,

Gly-Ala, Ala-Ala, Gly-Ala-Ala, Ala-Ala-Ala,

Ala-Ala-Ala-Ala.

Ogata et al . (2000).

Oligomerization Amino acid solution heating at

different temperatures.

Gly N.A. Oligomers, up to tetra-Gly, formed at 200-350

°C. No glycine oligopeptides were produced at

400 °C.

Islam et al . (2003).

Oligomerization Hydrothermal stability of alanine

oligopeptides.

(Ala)3, (Ala)4, (Ala)5N.A. Small excess of oligopeptides longer than the

starting ones. Elongation of (Ala)4 and (Ala)5

was possible in Ala excess. Elongation is

competitive with degradation.

Kawamura et al . (2005).

Peptide synthesis (di-Gly, tri-Gly) is favored in

hydrothermal fluids.

Rapid recycling of products from cool into near-

supercritical fluids will enhance peptide chain

elongation.

Iron-sulfide

synthesized

chimneys.

Nucleotide oligomerization—for both the

activated and unactivated nucleotide—can

occur in synthetic alkaline hydrothermal

chimneys.

Montmorillonite. Generation of oligomers (up to 4 units) with

imidazole-activated ribonucleotides.

Calcium carbide.

Calcium.

Synthesis Formation of lipids through

Fischer-Tropsch-type synthesis of

aqueous solutions.

Formic acid or oxalic

acid

N.A. Heating at 175 °C for 2-3 days, lipid

compounds from C2 to >C35 (n-alkanols, n-

alkanoic acids, n-alkenes, n-alkanes and

alkanones).

McCollom andSeewald.

(2003).

Synthesis Conversion of CO2 into organic

compounds in hydrothermal

conditions (300 °C and 30 MPa).

CO2 and H2Cobalt-bearing

magnetite.

Formation of CH4, C2H6 and C3H8, but also n-

C4H10 and n-C5H12.

Ji et al . (2008).

Dinitrogen, nitrate

Nitrite solutions.

Amino acids synthesized (Gly, Ala, Asp, Glu,

Ser) from simple precursors under Submarine

Hydrothermal Systems conditions.

Degradation is privileged in such conditions.

Synthesis at lower temperatures.

FeCl2.4H2O Poi was synthesized.

Na2S.9H2O K2HPO4Iron-rich membranes with incorporated

phosphates were generated.

Sodium silicate

solution (Na2O/26.5%

SiO2).

Na-acetyl phosphate.

Pyrophosphate synthesis in

inorganic precipitates simulating

hydrothermal chimney structures

in thermal and/or ionic gradients.

Iron mineral films. Barge et al . (2014)Synthesis/

Precipitation

Synthesis Amino acids synthesis in function

of temperature, heating time,

starting material composition and

concentration.

NH4HCO2Aubrey et al . (2009).

Synthesis N-bearing molecules, to synthesize

ammonia, at different T (200°, 70°

and 22 °C).

Fe and Ni metal,

awaruite (Ni80Fe20)

and tetrataenite

(Ni50Fe50), alloys

bearing Fe Ni.

Nitrite and nitrate are converted to ammonium

rapidly. The reaction of dinitrogen is slower.

Reduction is strongly temperature-dependent.

Metals were more reactive than alloys.

Smirnov et al . (2008).

Synthesis Heating of NH4HCO3 solution

with C2H2, H2 and O2 (produced in

situ ).

Acetylene Amino acids (Gly, Ala, Asp, Glu, Pro, Ser, Leu,

Ile, Lys, Val, Thr) and amines formed at 200°-

275 °C, no formation at <150 °C.

Marshal (1994).

Lemke et al . (2009).

Oligomerization The effect of elemental

composition, pH, presence of clay,

doping with small organic

compounds, ribonucleotide

activation on RNA

oligomerization.

AMP, Imidazole-

activated AMP (ImpA)

Burcar et al . (2015).

Oligomerization Amino acid solution heating at

different T (160°, 220°, and 260

°C).

Gly Gold hydrothermal

reaction cells.

Note: All amino acids are abbreviated according to the IUPAC indications.

Key: ABA = aminobutyric acid, Ala = alanine, AMP = adenosine monophosphate, Arg = arginine, Asp = asparagine, Cys = cysteine, Gaba

= gamma-aminobutyric acid, Glu = glutamic acid, Gly = glycine, His = histidine, Hyp = hydroxyproline, Ile = isoleucine, Leu = leucine,

Lys = lysine, Met = metionine, Nva = norvaline, Orn = ornithine, PCA = pyroglutamic acid, Phe = phenylalanine, Pro = proline, Pyr =

pyruvate, Ser = serine, Thr = threonine, Tyr = tyrosine, Val = valine. PP i =Pyrophosphate.

Hydrothermal vents and prebiotic chemistry

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HYDROTHERMAL VENT AND CHEMICAL EVOLUTION

/ CONCLUDING REMARKS

stability experiments (Table 2), and comprises the

majority of available studies. In these experiments,

the decomposition rate of biomolecules, mainly

amino acids, is explored. The most surveyed one

is the simplest amino acid: glycine. It is noticeable

that the inclusion of mineral phases is considered

fundamental in breakdown experiments. In this

regard, the role of some iron-rich minerals has

been explored (e.g., magnetite, fayalite, pyrite, etc.);

however, other minerals (e.g. , quartz, feldspars,

muscovite, calcite) are also used. In this kind of

experiments the formation of other amino acids is

also pursued. An important nding is that there is

an order in the decomposition rates of the selec-

ted molecules (Vallentyne, 1964; see Table 2), and

that decomposition strongly depends on factors

(such as pH, pressure, ionic strength, etc.) other

than temperature. Another kind of information

that can be obtained by means of these studies is

the determination of kinetic parameters (Povoledo

and Vallentyne, 1964) in order to predict the beha-

vior of organic reactions.

A step forward in prebiotic chemistry is the forma-

tion of more complex molecules: oligomers. The

reason for this is that life is based in macromolecu-

les. In consequence, the formation of oligomers in

hydrothermal vents has also been explored (Table

3). Again, most experiments deal with glycine

(e. g., Huber and Wächtershäuser, 1998; Imai et al.,

1999), but the oligomerization of alanine has also

been addressed (Ogata et al., 2000; Kawamura et

al., 2005). Oligomerization in hydrothermal vents

is conrmed in some experiments (i.e. Islam et al.,

2003; Kawamura et al., 2005; see Table 3).

Models for the synthesis of organic compounds in-

clude those associated with a variety of mineral-ca-

talyzed reactions such as water-rock reactions (e.g.,

serpentinization), Fischer-Tropsch reactions, and

FeS-driven synthesis. Experiments listed on Table

3 show the synthesis of dierent types of amino

acids, as well as lipids and hydrocarbons.

Experiments related to (1) the adsorption of orga-

nic molecules onto minerals, those related to ex-

plore the possible role of mineral channels in the

concentration, and (2) the reactivity of some orga-

nics in hydrothermal vents are still scarce (Table

4).

Serpentinization has been proposed as a genera-

tor of drastic chemical, redox, pH, and thermal

gradients (Russell et al., 2013). In this way, the wea-

thering of mac and ultramac rocks constitutes

a sink for CO2 (Berndt et al., 1996), because mi-

nerals present in basalts (olivine, plagioclase and

augite) are highly reactive with CO2. It is likely

that hydrothermal systems of the early Earth were

largely hosted by olivine-rich ultramac rocks (e. g.,

komatiites) (Russell et al., 2010). The formation of

serpentine, brucite, and magnetite produces large

amounts of hydrogen and methane (Kelley, 1996).

The sustained production of hydrogen creates

strongly reducing environments yielding a favora-

ble environment for organic synthesis (Holm et al.,

2015). This process could have contributed to the

subsequent formation of organic compounds on

early Earth.

5. Concluding remarks

The origin of life remains one of the most fun-

damental issues in science, branching out into a

wide array of disciplines. Processes that might

have contributed to the inventory of organic com-

pounds, not only on early Earth but also on early

Mars, include mineral-catalyzed reactions; such

reactions may have occurred on submarine hydro-

thermal systems.

One of the principal reasons for the great deal

of attention paid to hydrothermal systems is that

their physical and chemical conditions could have

favored the synthesis of organic compounds out

of inorganic precursors. In these systems minerals

are quite abundant, and minerals may have aided

in the transition from geochemistry to biochemis-

try. Such environments are likely to have met the

requirements for the occurrence of chemical evo-

lution and the subsequent origin of life. The syn-

thesis/destruction of organic compounds lingers

as a controversial topic and many eorts are devo-

ted to testing the role of these systems in prebio-

Hydrothermal vents and prebiotic chemistry

613Boletín de la Sociedad Geológica Mexicana

/ 2016 /

613

CONCLUDING REMARKS / ACKNOWLEDGMENTS /

REFERENCES

Note: All amino acids are abbreviated according to the IUPAC indications.

Key: ABA = aminobutyric acid, Ala = alanine, AMP = adenosine monophosphate, Arg = arginine, Asp = asparagine, Cys = cysteine, Gaba

= gamma-aminobutyric acid, Glu = glutamic acid, Gly = glycine, His = histidine, Hyp = hydroxyproline, Ile = isoleucine, Leu = leucine,

Lys = lysine, Met = metionine, Nva = norvaline, Orn = ornithine, PCA = pyroglutamic acid, Phe = phenylalanine, Pro = proline, Pyr =

pyruvate, Ser = serine, Thr = threonine, Tyr = tyrosine, Val = valine.

Table 4. Compilation of various types of experiments in physicochemical conditions that simulate those of hydrothermal vents.

Type of Study Description of the experiment Organic molecule used Mineral Main findings References

Adsorption Adsorption–desorption experiments at

80°C for 10 days.

Lys Na-smectite (smectite (> 90 %), a

small amount of cristobalite (< 10

%) and traces of calcite and quartz.

Thermal treatment originates stronger

smectite–lysine binding, by H bonds between

NH3

+lysine groups and smectite basal O

atoms.

Cuadros et al . (2009).

Surface adsorption decreased at high Mg 2+

concentration.

At high Ca2+ concentration adsorption

augmented.

The increase in adsorption with Ca2+ due to

calcium adsorption.

Arrhenius parameters were determined.

The addition of KCl resulted in a reduction of

the decarboxylation rate.

Amino acids and fatty acids were formed.

Formation of lactate, propionate, and alanine,

among others.

Microcapillaries act as a thermal diffusion

column and concentrated the molecule.

Vesicle formation.

Formation of mackinawite and greigite iron

sulfide phases.

Mackinawite was probably the dominant

catalyst in ancient pre-biotic chemistry.

Mineral precipitation Raman spectroscopy to study ancient

hydrothermal iron sulfide formation

(growth temperatures from 40° to 80 

°C).

Aqueous alkaline solutions

containing bisulfide and

silicate injected into iron (II)

solutions.

N.A. White et al . (2015).

Concentration To test if channels within the mineral

could act as act as natural

Clusius−Dickel thermal diffusion

column and increase local amphiphile

concentrations.

Oleic acid Borosilicate microcapillaries. Budin et al . (2009)

Reactivity Pyruvate reactions in presence of

transition-metal sulfide minerals, at

moderate temperatures (25° to 110 °C)

Pyr Pyrrhotite, troilite, arsenopyrite,

pyrite, marcasite, sphalerite,

chalcopyrite

Novikov and Copley

(2013).

Estrada et al . (2015).

Reaction Decarboxylation of an amino acid

solution as a function of pH

α-Ala N.A. Li et al . (2002).

Adsorption Batch adsorption experiments and

surface-complexation modeling to

study the interaction of L-aspartate onto

brucite at different ionic strength (Ca2+

or Mg 2+).

L-aspartate Brucite.

tic chemistry. A better understanding of reaction

pathways that led to the synthesis of organic mo-

lecules in prebiotic hydrothermal vents requires

additional laboratory experiments under physical

and chemical conditions as close as possible to the

actual ones

6. Acknowledgments

The support of PAPIIT IA201114 and CONA-

CyT 168579/11 research grants is acknowledged.

Authors also want to thank GD Homero Heredia

for the design of Figure 2 in this paper.

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Sistemas hidrotermales: secretos del océano profundo

Article

Full-text available

Jan 2025

María Carolina Rodríguez Uribe

Los sistemas hidrotermales submarinos son manifestaciones del calor interno de la Tierra que ocurren principalmente en límites divergentes, convergentes y fallas transformantes. Se caracterizan por chimeneas de variadas formas y composiciones, que expulsan fluidos a temperaturas superiores a los 400°C. Estos entornos extremos permiten explorar procesos clave como el origen de la vida, la acidificación oceánica y dinámicas geológicas y químicas únicas. Además, albergan especies exclusivas, adaptadas a estas condiciones. Este artículo introduce los principales aspectos de los sistemas hidrotermales submarinos, resaltando su importancia científica y ecológica.

Strategies of chemolithoautotrophs adapting to high temperature and extremely acidic conditions in a shallow hydrothermal ecosystem

Article

Full-text available

Dec 2023

Background Active hydrothermal vents create extreme conditions characterized by high temperatures, low pH levels, and elevated concentrations of heavy metals and other trace elements. These conditions support unique ecosystems where chemolithoautotrophs serve as primary producers. The steep temperature and pH gradients from the vent mouth to its periphery provide a wide range of microhabitats for these specialized microorganisms. However, their metabolic functions, adaptations in response to these gradients, and coping mechanisms under extreme conditions remain areas of limited knowledge. In this study, we conducted temperature gradient incubations of hydrothermal fluids from moderate (pH = 5.6) and extremely (pH = 2.2) acidic vents. Combining the DNA-stable isotope probing technique and subsequent metagenomics, we identified active chemolithoautotrophs under different temperature and pH conditions and analyzed their specific metabolic mechanisms. Results We found that the carbon fixation activities of Nautiliales in vent fluids were significantly increased from 45 to 65 °C under moderately acidic condition, while their heat tolerance was reduced under extremely acidic conditions. In contrast, Campylobacterales actively fixed carbon under both moderately and extremely acidic conditions under 30 − 45 °C. Compared to Campylobacterales, Nautiliales were found to lack the Sox sulfur oxidation system and instead use NAD(H)-linked glutamate dehydrogenase to boost the reverse tricarboxylic acid (rTCA) cycle. Additionally, they exhibit a high genetic potential for high activity of cytochrome bd ubiquinol oxidase in oxygen respiration and hydrogen oxidation at high temperatures. In terms of high-temperature adaption, the rgy gene plays a critical role in Nautiliales by maintaining DNA stability at high temperature. Genes encoding proteins involved in proton export, including the membrane arm subunits of proton-pumping NADH: ubiquinone oxidoreductase, K⁺ accumulation, selective transport of charged molecules, permease regulation, and formation of the permeability barrier of bacterial outer membranes, play essential roles in enabling Campylobacterales to adapt to extremely acidic conditions. Conclusions Our study provides in-depth insights into how high temperature and low pH impact the metabolic processes of energy and main elements in chemolithoautotrophs living in hydrothermal ecosystems, as well as the mechanisms they use to adapt to the extreme hydrothermal conditions. 4ap83QbxwyKb6GHBwDJLyuVideo Abstract

Astrobiology: resolution of the statistical Drake equation by Maccone's lognormal method in 50 steps

Article

Full-text available

Jun 2023

The authors use the mathematical tool of Maccone's lognormal distribution to further factor the Drake equation, which calculates the number of advanced civilizations in the galaxy, from the seven original levels of the Drake equation to 49 levels of overall analysis. The Maccone approach, in fact, supported by the central limit theorem, becomes more reliable the more levels are introduced. The resulting study necessarily draws upon an array of disciplines ranging from astronomy, chemistry and geology to biology, palaeontology and futurology. The final result calculates the number of planetary systems suitable for life in its various stages of development: those which have probably hosted life in the past and those which still host it at its various evolutionary levels. The final evolutionary level is the so-called galactic civilization (often called ETC, or extraterrestrial civilizations). The number of resulting galactic civilizations is divided between static civilizations, which do not move around the galaxy and whose Kardašëv rating is still low (<1.4), of which we find three examples (we ourselves plus, perhaps, two others), and potentially dynamic civilizations, which move around the galaxy and have a sufficiently high Kardašëv rating (≥1.4), of which we find 2000.

Ribonucleoside stability and prebiotic synthesis

Thesis

Nov 2022

Gustavo Pinho Maia

Exogenous delivery of organic molecules could have played a significant role in prebiotic synthesis, based on the detection of RNA nucleobases and ribose in meteorites. However, ribonucleosides were never detected. Meteoroid atmospheric entry conditions are severe and could lead to chemical modifications, via mechanochemical reactions. Moreover, oxidation reactions are also plausible, producing reactive species, such as carbonate (CO32-). In this way, the mechanochemical treatment of ribonucleosides with carbonate and metal (Ni, Al, Na, and K, which are present within meteoroid) salts were explored, leading to the formation of guanine, adenine, and uracil, as degradation products. Ethanol formation was observed for metal samples (Ni2+ and Al3+), indicating ribose decomposition. Additionally, degradation mechanisms using theoretical studies were performed with carbonate and ribonucleosides as reagents, suggesting that water-assisted ring opening was the preferred mechanism. Considering the aforementioned results, this work proposes that ribonucleoside degradation using mechanochemical reactions, intensified by carbonate and metal ions, is a novel model that justifies the presence of nucleobases in meteorite extracts.

Metalloporphyrine als potentiell präbiotische Moleküle und chemische Biosignaturen

Thesis

Jan 2022

Hannes Lukas Pleyer

Diese Doktorarbeit befasst sich mit zwei wichtigen astrobiologischen Aspekten von Metalloporphyrinen. Erstens mit der möglichen abiotischen Entstehung von Metalloporphyrinen unter präbiotisch plausiblen Bedingungen und zweitens mit Metalloporphyrinen als mögliche molekulare Biosignaturen im Zusammenhang mit der Suche nach außerirdischem Leben. Diese zweigleisige Herangehensweise ermöglichte es, einen umfassenderen Überblick über Metalloporphyrine im astrobiologischen Kontext zu gewinnen. In den heute bekannten lebenden Organismen kommen Metallkomplexe von Porphyrinen und Porphyrinoiden ubiquitär vor; freie Porphyrinbasen spielen dagegen kaum eine Rolle. Zu den bekanntesten Beispielen zählen die Chlorophylle (Mg-Komplexe), die entscheidend an der Photosynthese beteiligt sind, und die Häm-Gruppe, z. B. als Cofaktor der Cytochrome, welche eine bedeutende Rolle bei der Zellatmung spielen. Evolutiv scheinen Porphyrinoid-Cofaktoren sehr alt zu sein, und tatsächlich wurden 1,1 Milliarden Jahre alte Geoporphyrine in Sedimentgestein gefunden. Vorfahren der heute bekannten Porphyrinoid-Cofaktoren, einfache Metalloporphyrine, könnten schon in den ersten Lebewesen oder noch früher in abiotischen Protometabolismen vorgekommen sein. Zudem legt die weite Verbreitung von Porphyrinoid-Cofaktoren in den bekannten Organismen sowie ihre Beteiligung an grundlegenden biologischen Funktionen nahe, dass auch in möglichen Lebensformen außerhalb der Erde Metalloporphyrinoide vorkommen könnten. Somit könnten Metalloporphyrinoide als chemische Biosignaturen für die Suche nach Leben auf Mars, Europa, Enceladus und darüber hinaus geeignet sein. Das erste Ziel dieser Arbeit war es, zu untersuchen, ob eine Komplexbildung mit ausgewählten Metallen (Fe, Mg, Co, Ni und Cu) unter präbiotisch plausiblen Bedingungen möglich ist. Ausgehend von einer zuvor von unserer Arbeitsgruppe beschriebenen präbiotischen Synthese von Octaalkylporphyrinen an simulierten urzeitlichen Vulkanküsten sollte der Einfluss von Nass-Trocken-Zyklen (NTZ) auf Octaethylporphyrin (OEP) und ausgewählte Metallquellen untersucht werden. Hierzu musste zunächst eine neuartige, automatisierte Apparatur entwickelt werden, die die Simulation der Bedingungen auf der frühen Erde, speziell an urzeitlichen Vulkanküsten, ermöglichte. Insbesondere musste diese Apparatur einen strikten Ausschluss von Luftsauerstoff sicherstellen und fluktuierende Wechsel zwischen Nass- und Trockenphasen ermöglichen. Zunächst wurden Experimente durchgeführt, um die neue Apparatur zu testen. Dabei konnte gezeigt werden, dass die Apparatur über einen längeren Zeitraum vollständig automatisch und zuverlässig arbeitete. In weiteren Versuchen wurde geprüft, ob oxidationsempfindliche Sub-stanzen in der Apparatur gehandhabt werden können. Hierbei konnte gezeigt werden, dass in der Tat ein strikter Ausschluss von Sauerstoff möglich ist. Damit erwies sich die Apparatur als geeignet für die Untersuchung der Bildung von Metall¬komplexen aus OEP und diversen Metallquellen unter dem Einfluss von wechselnden NTZ. Als Metallquellen wurden unter anderem Metall(II)-chloride, Metallsulfide, Basalt und Eisenmeteorite eingesetzt. Hierbei lag der Fokus auf Eisenquellen. Tatsächlich konnte gezeigt werden, dass sich mit den ent¬sprechenden Metallquellen Eisen-, Magnesium-, Cobalt , Nickel- und Kupfer-Komplexe in einer ungewöhnlichen Reaktion bildeten (vollständig wasserunlösliches OEP reagierte mit teilweise ebenfalls unlöslichen Metallquellen), wobei sich NTZ als essenziell erwiesen. In Süßwasser konnten Ausbeuten zwischen 20 und 78 % (bezogen auf das Porphyrin) erhalten werden. Außerdem wurde der Einfluss von künstlichem Meerwasser und niedrigen pH-Werten auf die Komplexbildung untersucht. Im zweiten Teil der Arbeit wurde der Frage nach der Stabilität von Metalloporphyrinen modellhaft anhand der Verbindung Chlorido(octaethylporphyrinato)eisen(III), [FeCl(oep)], nachgegangen. Für die durchgeführten Experimente wurden potentiell destruktive Bedingungen ausgewählt, die für Metalloporphyrine als mögliche chemische Biosignaturen relevant sind, aber auch Bedingungen, wie sie vermutlich an urzeitlichen Vulkanküsten herrschten. In umfangreichen Versuchsreihen konnte unter anderem gezeigt werden, dass (a) der Eisen-OEP-Kern über einen pH-Bereich von 0,0 bis 13,5 stabil ist, (b) [FeCl(oep)] bis ca. 250 °C in inerter Atmosphäre stabil ist, (c) eine Salzmatrix [FeCl(oep)] vor Röntgenstrahlung schützt, aber nicht vor Eisen-Partikelstrahlung, und (d) Hypochlorit, Wasserstoffperoxid, Chlorat und Salpetersäure [FeCl(oep)] oxidativ zersetzen (Oxidationswirkung in absteigender Reihenfolge). Perchlorat, das häufig im Zusammenhang mit seinem Vorkommen im Mars-Regolith genannt wird, zeigte dagegen keine Oxidationswirkung. Schließlich wird in der vorgelegten Arbeit die Bedeutung der Metalloporphyrine als potentielle Biosignaturen diskutiert, speziell vor dem Hintergrund ihrer Stabilität und möglicher abiotischer Synthesewege für diese Verbindungen.

Organic compounds in surface and groundwaters in the surrounding of a Mexican geothermal reservoir; case study Los Humeros, Puebla

Article

Sep 2022
APPL GEOCHEM

In this paper we evaluated if the Organic compounds (OC's) produced in the Los Humeros Geothermal Field (LHGF) could migrate to the surface and groundwaters in the surrounding areas; we report for the first time, the OC's of 2 maars, 24 springs, and 24 groundwater from sites surrounding the LHGF, in addition ten water/vapor condensates from the field were taken (all sampled in winter 2018). Using SPE-GC-MS, 141 OC's and 21 families were identified like alkanes, polyaromatics, sulphur-bearing, oxygen-bearing and halogen-bearing. Based on literature data, we assume that monoaromatics, alkanes and halogen-bearing could be some of the native families of the LHFG that migrate to the surrounding water bodies, without discarding an anthropogenic influence. In groundwater, 93 OC's and 19 families were identified. In the springs, 66 OC's grouped into 18 families were identified. In the case of the maars, 22 OC's and 10 families were identified. The most toxic polyaromatics identified in LHGF fluids are the heavy compounds pyrene and perylene which are naturally produced in the reservoir by combustion processes and carried to the surface by hydrothermal fluids at high temperatures. The results of this study do not prove a strong influence between the organic composition of condensates in the LHGF and the surrounding waters. How ever we provide new information to understand the dynamics of the LHGF. Furthermore, out of the scope of this study we could identify a strong antropogenic influence on the sampling zone waters that can cause an environmental impact.

The Transformation by Catalysis of Prebiotic Chemical Systems to Useful Biochemicals: A Perspective Based on IR Spectroscopy of the Primary Chemicals: I. The Synthesis of Peptides by the Condensation of Amino Acids

Article

Jan 2021

Submarine hydrothermal vent systems: The relevance of dynamic systems in chemical evolution and prebiotic chemistry experiments

Article

Nov 2021

Since their discovery, submarine hydrothermal vent systems have been pointed out as important places where chemical evolution on Earth could have occurred; and their role in the process has been highlighted. Similarly, some hypotheses have considered these systems in origin of life scenarios. In this way, many experiments have been developed, and the knowledge about these systems has increased. Due to their complexity, many experimental simulations have only included a few of the geochemical variables present in these environments, pressure and temperature. Other main variables have hardly been included, such as mineralogy, thermal and pH gradients, dissolved ions and/or redox reactions. As it has been understood, the dynamism and heterogeneity of these environments are huge, and it comprises different scales, from single vents to full hydrothermal fields. However, the vast majority of experiments focus on a specific part of these systems and do not include salinity, mineralogy and pH gradients. For this reason, in this paper, we pointed out some considerations about how this dynamism can be interpreted, and included in some models, as well their importance in prebiotic chemistry experiments and their extrapolations regarding the hypothesis about the origins of life.

Sedimentary Thickness and Upper Crustal Structure of the North Cambay Rift, India Deduced from Gravity Data: New Evidence of Pre-trappean Sediments

Article

Jun 2023
J GEOL SOC INDIA

A gravity survey was carried out to estimate the sedimentary thickness and to map upper crustal geometry over the northern part of the Cambay rift. Structural lineaments delineated using the total horizontal gradient of the Bouguer anomaly indicate a major lineament trend in the NW-SE direction. Results of the density modelling using residual Bouguer anomaly reveal the average thickness of the Quaternary and Tertiary sediments to be between 0.5 and 6 km, while the Deccan trap thickness varies between 0.5 and 3 km. It is seen that the Mesozoic sediment (maximum thickness ~0.6 km) is sandwiched between the Deccan trap and granitic basement, which indicates the possible existence of a rift in the late Jurassic-early Cretaceous. Based on the residual Bouguer and density modelling results, the spatial locations of the NE-SW trending Unhawa ridge and the N-S trending Mehsana uplift are provided, which are believed to be the remnant rock of the Proterozoic age. A high-density body, interpreted as a magmatic underplating layer, is also found in the lower part of the middle crust along the central part of the rift, which continues in the lower crust. The magmatic underplating layer is formed during the Reunion hotspot and lithospheric interaction in the Cretaceous period.

Prebiotic experiments simulating hydrothermal vents: Influence of olivine in the decomposition of simple carboxylic acids

Article

Full-text available

Dec 2021

Hydrothermal systems have been proposed as keen environments on the early Earth where chemical evolution processes could have occurred. The presence of minerals and a continuous energy flux stand out among the most remarkable conditions in such environments. In this research the decomposition of two organic acids was studied. Ionizing radiation and thermal energy were the sources selected for decomposition tests, as both are naturally present on hydrothermal systems and probably, they were present on early Earth. Radiation could come from unstable elements in minerals, and heat is the most abundant energy source in hydrothermal systems. As minerals play a key role in prebiotic chemistry experiments and are an essential component on hydrothermal environments, the role of olivine in decomposition was tested. Results indicate that both organic acids highly decomposed when irradiated or heated. Radiation is more efficient than heating in decomposing the carboxylic acids and forming other carboxylic acids. Interestingly, the occurrence of olivine affects decomposition on both heated and irradiated samples, as both the rate of decomposition, and the amount and type of products vary compared with experiments without the mineral. The formation of other carboxylic acids was followed in all samples. Succinic, tricarballilic, citric and carboxisuccinic acids were detected in radiolysis experiments of acetic acid. The radiolysis of formic acid produced oxalic and tartronic. The heating of acetic acid solutions formed succinic, tricarballilic, citric and carboxisuccinic acids. However, the heating of formic acids only generated oxalic acid. The presence of olivine affected the amount and type of carboxylic acids formed in radiation and heating experiments. Natural hydrothermal systems are complex environments and many variables are present in them. Our results reinforce the idea that a combination of variables is necessary to better simulate these environments in prebiotic chemistry experiments. All variables could have affected the prebiotic chemical reactions; and hence, the role of hydrothermal systems in prebiotic chemistry could be much more complex that thought.

Introduction: Classification of VMS deposits based on host rock composition

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Full-text available

Jan 1999

An hypothesis concerning the relationship between submarine hot springs and the origin of life on Earth

Article

Full-text available

Jan 1981
Oceanol Acta

The Emergence of Everything: How the World Became Complex

Book

Oct 2023

Harold J Morowitz

When the whole is greater than the sum of the parts--indeed, so great that the sum far transcends the parts and represents something utterly new and different--we call that phenomenon emergence. When the chemicals diffusing in the primordial waters came together to form the first living cell, that was emergence. When the activities of the neurons in the brain result in mind, that too is emergence. In The Emergence of Everything, one of the leading scientists involved in the study of complexity, Harold J. Morowitz, takes us on a sweeping tour of the universe, a tour with 28 stops, each one highlighting a particularly important moment of emergence. For instance, Morowitz illuminates the emergence of the stars, the birth of the elements and of the periodic table, and the appearance of solar systems and planets. We look at the emergence of living cells, animals, vertebrates, reptiles, and mammals, leading to the great apes and the appearance of humanity. He also examines tool making, the evolution of language, the invention of agriculture and technology, and the birth of cities. And as he offers these insights into the evolutionary unfolding of our universe, our solar system, and life itself, Morowitz also seeks out the nature of God in the emergent universe, the God posited by Spinoza, Bruno, and Einstein, a God Morowitz argues we can know through a study of the laws of nature. Written by one of our wisest scientists, The Emergence of Everything offers a fascinating new way to look at the universe and the natural world, and it makes an important contribution to the dialogue between science and religion.

Planetary Surface Processes

Book

Jun 2012

H. Jay Melosh

Planetary Surface Processes is the first advanced textbook to cover the full range of geologic processes that shape the surfaces of planetary-scale bodies. Using a modern, quantitative approach, this book reconsiders geologic processes outside the traditional terrestrial context. It highlights processes that are contingent upon Earth's unique circumstances and processes that are universal. For example, it shows explicitly that equations predicting the velocity of a river are dependent on gravity: traditional geomorphology textbooks fail to take this into account. This textbook is a one-stop source of information on planetary surface processes, providing readers with the necessary background to interpret new data from NASA, ESA and other space missions. Based on a course taught by the author at the University of Arizona for 25 years, it is aimed at advanced students, and is also an invaluable resource for researchers, professional planetary scientists and space-mission engineers.

Understanding Mineral Deposits

Book

Jan 2000

Kula C. Misra

Preface. 1. Introduction. 2. Formation of Mineral Deposits. 3. Interpretation of Mineral Deposits - I. 4. Interpretation of Mineral Deposits - II. 5. Chromite Deposits. 6. Nickel (-Copper) Sulfide Deposits. 7. Platinum-Group Element (PGE) Deposits. 8. Porphyry Deposits. 9. Skarn Deposits. 10. Volcanic-Associated Massive Sulfide (VMS) Deposits. 11. Sediment-Hosted Massive Zinc-Lead Sulfide (SMS) Deposits. 12. Sediment-Hosted Stratiform Copper (SSC) Deposits. 13. Mississippi Valley-Type (MVT) Zinc-Lead Deposits. 14. Uranium Deposits. 15. Precambrian Iron-Formations. 16. Gold Deposits. References. Index.

Géologie des ressources minérales

Article

Jan 2009

Southwest Pacific rim gold–copper systems: structure, alteration, and mineralization

Article

Jan 1998

Sub-surface processes.

Article

Jan 1979

Covers processes concerned with water in soil as a liquid and as ground ice. Darcy's law is explained. Water can cause piping, but the most important sub-surface effects are chemical. Ground ice processes include frost heaving, sorting, thermal contraction, and thermokarst phenomena. -Keith Clayton

Controls on hydrothermal alteration and mineralization; southwest pacific rim gold-copper systems structure, alteration, and mineralization

Article

Jan 1998

Volcanic-associated massive sulphide base metals

Article

Jan 1996

J.M. Franklin

Hydrothermal vents and prebiotic chemistry: A review

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