ChemTexts (2022) 8:13

https://doi.org/10.1007/s40828-022-00164-3

LECTURE TEXT

Gas hydrates in nature and in the laboratory: necessary requirements

for formation and properties of the resulting hydrate phase
Judith M. Schicks1

Received: 29 October 2021 / Accepted: 15 March 2022 / Published online: 6 April 2022
© The Author(s) 2022

Abstract
Clathrate hydrates—also known as gas hydrates—are ice-like compounds consisting of gas and water molecules. They occur
wherever elevated pressures and low temperatures prevail; and where enough water and hydrate-forming gas molecules are
available. Therefore, natural gas hydrates occur at all active and passive continental margins, in permafrost regions, in some
deep lakes, and under unfavorable circumstances, also, in pipelines. This article provides an overview of the (thermodynamic)
requirements and various models for the nucleation and growth of gas hydrates and the different gas hydrate structures that
may occur and which have been detected in nature. Furthermore, this study also shows the influence of the properties of the
enclosed gas molecules such as size and shape on the structure and thermodynamic properties of the resulting hydrate phase.
Finally, the complexity of a natural environment with regard to the various influences of sediments, microbial activity, and
salinity of the pore fluid on hydrate formation is also discussed.

Keywords Gas hydrates · Nucleation and growth · Thermodynamic properties · Guest-to-cavity ratio · Occurrences

Introduction the history of gas hydrates in 1927 that there were a large
number of researchers performing experiments in which an
Clathrate hydrates, also known as gas hydrates, are ice-like, attempt was made to determine the structure and composi-
crystalline solids composed of water and gas molecules. tion of gas hydrates. The fact that gas hydrates are nonstoi-
Water molecules form defined cage (cavity)1 structures via chiometric compounds made these efforts even more diffi-
hydrogen bonds, which are connected into a three-dimen- cult and methods that are used today in many laboratories to
sional network. The cages are stabilized by the encasement analyze gas hydrates such as Raman spectroscopy were not
of a mostly nonpolar guest molecule; however, it should be available to researchers at the time. Therefore, at the end of
noted that gas hydrates are nonstoichiometric compounds. the nineteenth century, it was assumed that a direct analysis
From a chemical point of view, gas hydrates therefore belong of gas hydrates was not possible [3].
to the inclusion compounds (clathrates). They form under With the production of oil and gas at the beginning of
elevated pressures and low temperature conditions when suf- the twentieth century, gas hydrates were discovered in a
ficient amounts of gas and water are available. completely new context. Hammerschmidt realized that the
The English chemist Humphry Davy is considered to be ice-like solids that formed in pipelines were gas hydrates
the first scientist who formed gas hydrates in his laboratory [4]. The scientific studies of gas hydrates then concentrated
by dissolving chlorine gas into water at low temperatures, on the conditions under which gas hydrates form and how
which was reported to the Royal Society of Chemistry [1, their formation could be avoided to prevent blockage of
2]. In the following years, gas hydrates were examined in pipelines. It took further decades before Makogon realized
some laboratories, but for a long time they were considered in 1966 that the conditions for the formation of gas hydrates
as laboratory curiosities. Schroeder described in his work on are also present in nature [5]. In 1972, the recovery of a drill
core containing hydrates in Prudhoe Bay in Alaska provided
* Judith M. Schicks evidence that gas hydrates also occur in nature. Since then,
[email protected] several attempts have been made to detect and quantify natu-
ral gas hydrate deposits all over the world. It was possible to
1
Department Geochemistry, GFZ German Research Centre
1
for Geosciences, Telegrafenberg, 14473 Potsdam, Germany The terms “cavity “ and “cage “ are used synonymously.

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prove their existence directly or indirectly at all active and Referring to the thermodynamic relation between chemi-
passive continental margins, in permafrost regions, and also cal potentials in reaction equilibria, the chemical potential
in deep lakes (e.g., [6, 7]). of the hydrate building unit in an aqueous solution can be
Since natural gas hydrates contain predominantly meth- defined as
ane and owing to their global occurrences, natural gas
𝜇hs = 𝜇gs + nw 𝜇w .
hydrates are seen as a potential energy source on the one
hand. On the other hand, methane is also a strong green- Kashchiev and Firoozabadi [8] postulated that the driving
house gas and therefore the response of gas hydrate deposits force for the new phase formation is the difference between
to global warming is also of great interest. In addition, the the chemical potentials of the old phase (aqueous solution)
influence of gas hydrates on the geomechanical properties and the new phase (hydrate crystal). They called the driving
of the host sediments in which the hydrates occur has not force Δ𝜇 supersaturation, given as
yet been fully clarified.
In the following sections of this study, the prerequisites
( )
Δ𝜇 = 𝜇gs + nw 𝜇w − 𝜇h = 𝜇hs − 𝜇h .
for hydrate formation will be discussed in detail before the
various structures of the resulting hydrate phase and their Only if the aqueous solution is supersaturated with
properties are described. The occurrences of gas hydrates in the hydrate-forming gas can the hydrate nucleate or grow
nature and the influence of gas hydrates on their environment (Δ𝜇 > 0). A phase equilibrium in terms of a coexistence of
will also be discussed. Finally, the differences between the dissolved and crystalline hydrate phases is reached if Δ𝜇 = 0;
mostly simplified formation of gas hydrates in the laboratory in this case the aqueous solution is saturated. When Δ𝜇 < 0
and the more complex formation of gas hydrates in natural the solution is undersaturated; thus, hydrate crystals cannot
systems are discussed. nucleate in the solution, and existing hydrates decompose.
Kashchiev and Firoozabadi [8] pointed out that their concept
can also be applied to the formation of hydrates from the
ice phase and the decomposition of hydrates to gas and ice,
Thermodynamic requirements respectively.
for the formation of gas hydrates Since Kashchiev and Firoozabadi [8] define the super-
saturation of the liquid solution as a prerequisite for the
Gas hydrates are formed at elevated pressures and low tem- formation of gas hydrates, they apparently assume that the
peratures, provided that sufficient gas and water are avail- gas molecule must first be dissolved in the aqueous phase
able. But what does that mean exactly? before it can be incorporated into the hydrate phase. With
According to Kashchiev and Firoozabadi [8], the forma- this assumption, they support the labile cluster nucleation
tion of gas hydrates under given pressure and temperature hypothesis [9], which is one model for the nucleation and
conditions can be described with the following reaction growth process of gas hydrates and which will be described
equation: in more detail in the following section.
G + nw H2 O ↔ G ⋅ nw H2 O.

It is assumed that one molecule of the dissolved gas G Models for nucleation and hydrate growth
and nw water molecules of the aqueous solution form one at the molecular level
unit of the hydrate crystal ( G ⋅ nw H2 O ). Kashchiev and
Firoozabadi [8] take the approach that the difference in the First of all, it should be noted that a distinction is made
chemical potentials between the following three coexisting between nucleation and growth of gas hydrates. In general,
phases is the driving force for the formation or decompo- however, it is assumed that the nucleation comprises only a
sition of hydrates: (a) a pure gas phase (the proportion of few gas-filled water cages and changes into hydrate growth
water molecules in the gas phase is neglected), (b) an aque- when a critical size of the nucleus is reached ([10, 11] and
ous solution, and (c) a hydrate phase. In their hypothesis, the literature cited therein). If the thermodynamic require-
they differentiate between the chemical potential of the gas ments, as described in the previous section, are met, hydrate
molecules in the gas phase (𝜇gg ) and the chemical potential nucleation can be described as a stochastic and heterogene-
of the gas molecules that are dissolved in the aqueous phase ous crystallization process for which the following mecha-
(𝜇gs). They also define the chemical potential of a potential nisms are suggested.
hydrate building unit (𝜇hs), consisting of a gas molecule and According to Christiansen and Sloan [9], who developed
nw water molecules in the aqueous solution and the chemical the labile cluster nucleation hypothesis, water molecules
potential of the hydrate phase (𝜇h ), consisting of a gas mol- form labile clusters around dissolved gas molecules once the
ecule and nw water molecules within the hydrate structure. pressure and temperature conditions are within the hydrate

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stability field. Depending on the size of the gas molecule, cage by water molecules. As a result of the adsorption and
the number of water molecules that participate in these labile the incorporation of further gas molecules at the interface
clusters varies. These labile clusters combine and form unit between the aqueous phase and the gas phase, the nucleation
cells. This process is facilitated if the aqueous solution and further growth are directed into the gas phase.
already contains clusters with a suitable number of water If enough crystallization nuclei of critical size have
molecules that correspond to the cavity types in the result- formed, hydrate growth begins. So that hydrate growth can
ing hydrate structure. Once the agglomeration of these labile take place without restriction, sufficient transport of the mol-
clusters reaches a critical size, the hydrate crystal begins to ecules to the reaction site (mass transport) and the incorpo-
grow. ration of the guest molecule into the hydrate cage structure
Molecular dynamic simulations by Walsh et al. [12] show and the removal of the resulting heat of hydrate formation
a more complex process. Here, fragments of hydrate struc- from the reaction site (heat transport) must be ensured.
tures form around the dissolved gas (methane) molecules,
but some of these cavity fragments dissolve again whereas
others form first cage structures. Jacobson et al. [13, 14]
developed the “blob” hypothesis, which in a sense represents Gas hydrate structures
an extension of the labile cluster hypotheses. Here, dissolved
gas molecules with their hydration shells and additional As already mentioned, gas hydrates consist of gas and water
water molecules agglomerate and condense to form so-called molecules, whereby the latter form various cavity types
blobs. These change into an amorphous hydrate phase in (polyhedra) via hydrogen bonds. These polyhedra combine
which the first cage structures are already formed. Here, as to three-dimensional networks. A special nomenclature was
well as in the model published by Walsh et al. [12], unusual developed to describe the polyhedra: the various types of
cage types such as 5­ 1263 polyhedra form in this phase before cages are defined with nm. The variable m indicates the num-
the water and gas molecules change into an ordered, crystal- ber of faces and the variable n the number of edges of this
line hydrate structure. surface, e.g., a pentagonal dodecahedron (­ 512) consist of 12
The local structuring nucleation hypothesis is based on (m = 12) pentagonal (n = 5) faces.
molecular dynamic calculations by Radhakrishnan and Trout Depending on which gas molecules are encased, the type
[15] and describes the very special case of a homogeneous and size of the cavities and thus the structure of the resulting
nucleation mechanism at the liquid–liquid interface between gas hydrate vary. So far, a large number of different hydrates
water and liquid carbon dioxide. As a result of thermal fluc- have been described. The encased gas molecules vary in size
tuations, some of the carbon dioxide molecules are arranged from small molecules such as hydrogen or nitrogen to larger
in the aqueous phase similar to that in the hydrate struc- molecules such as n-butane or cyclohexane. In general, non-
ture. This arrangement of the guest molecules influences the polar, hydrophobic molecules such as methane are known
orientation of the water molecules. If such an arrangement as hydrate formers. In nature, the occurrence of three differ-
of the carbon dioxide molecules and correspondingly the ent hydrate structures has been reported, namely structure I
water molecules exceeds the critical size of a crystallization (sI), structure II (sII), and structure H (sH). A unit cell of
nucleus, hydrate formation occurs. Moon et al. [16] car- the cubic structure I is composed of 46 water molecules that
ried out similar simulations for the nucleation of methane form two pentagonal dodecahedra (­ 512) and six tetrakaideca-
hydrates at the interface between methane and water and hedra ­(51262). The pentagonal dodecahedra are connected
concluded that the formation of a methane hydrate nucleus to each other via shared edges [19]. A unit cell of the cubic
of critical size is the result of a locally denser arrangement of structure II consists of 16 pentagonal dodecahedra ­(512) and
methane molecules in the aqueous phase and the associated eight hexakaidecahedra (­ 51264) [19]. In structure II, layers
changes in the arrangement of the water molecules. of face-sharing pentagonal dodecahedra alternate with lay-
Both Long [17] and Kvamme [18] developed the hypoth- ers of hexakaidecahedra. The unit cell of structure II con-
esis of the nucleation at the interface. In this approach the tains 136 water molecules. For a unit cell of the hexago-
hydrate formation occurs directly at the interface between nal structure H, 34 water molecules form three pentagonal
the aqueous phase and the gas phase. While in the other dodecahedra ­(512), two irregular dodecahedra (­ 435663), and
hypotheses the hydrate-forming gas must first be dissolved one icosahedron ­(51268). The irregular dodecahedron is only
in the aqueous phase, in the hypothesis of the nucleation slightly larger than the pentagonal dodecahedron. However,
at the interface the gas molecule is incorporated into the the icosahedron can encase relatively large molecules such
hydrate phase directly from the gas phase. In this hypoth- as pentane or cyclohexane. In structure H, the pentagonal
esis, the gas molecule is adsorbed on the water surface and dodecahedra form two-dimensional layers over shared faces,
diffuses on the surface to a suitable point where it can be which are interconnected by layers with irregular dodecahe-
initially partially and then completely incased into a hydrate dra and icosahedra [20]. The aforementioned combinations

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Fig. 1  Various hydrate structures are formed by combining different types of polyhedra (modified after Ismail [21] and Pan [22])

of the various polyhedra and the resulting hydrate structures and thus optimal stabilization of the cage structures. Nev-
are shown in Fig. 1. ertheless, hydrate structures may also occur where the
The cubic structures I and II can be stabilized with the guest-to-cavity ratio is less than 0.75 or greater than 1.0.
cages partially filled. For example, a propane hydrate with In particular, during hydrate formation and hydrate growth
structure II can be formed with only the hexakaidecahedra processes, metastable hydrate structures can be formed in
filled and the pentagonal dodecahedra empty. For the hex- which the ratio of the encased gas molecules to the hydrate
agonal structure H, however, it is necessary that, in addition cage does not correspond to this ideal ratio. For example,
to the large gas molecules that are encased into the icosahe- it has been shown experimentally that during the forma-
dron, smaller gas molecules (a so-called help gas) have to tion of both methane hydrates and carbon dioxide hydrates,
occupy the dodecahedra of the structure. crystals with structure II as a coexisting metastable phase
Which hydrate structure is formed depends, among oth- were formed besides the thermodynamically stable struc-
ers, on the hydrate-forming gas molecule. While the attrac- ture I hydrate crystals [25, 26]. According to Sloan and
tive forces of the water molecules in the cage structures lead Fleyfel, the formation of the pentagonal dodecahedra (­ 512)
to a force directed into the center of the cage, the encased is favored. During the induction phase the hydrate structure
gas molecules exert a stabilizing effect on the hydrate cages oscillates between structure I and structure II before struc-
through repulsive forces. For a stable hydrate, the gas mol- ture I achieves the critical size for a stable nucleus [27].
ecule should on the one hand be large enough to adequately Such a preferred formation of pentagonal dodecahedra can
shield the attractive forces of the water molecules in the also induce the formation of structure II hydrates, even if
cages. On the other hand, it should be small enough to fill this structure is not thermodynamically preferred, since in
the cage without deforming it. The guest-to-cavity ratio a unit cell of structure II the number of pentagonal dodeca-
provides a good estimate of how well a gas molecule can hedra is twice as large as the number of hexkaidecahedra.
stabilize a cage. This ratio is determined by dividing the This could be observed in experiments on the nucleation
diameter of the guest molecule by the diameter of the cavity and growth of simple and mixed hydrates [28, 29]. In other
type [23]. It should be noted that the van der Waals radius laboratory studies, however, the formation of a structure I
of the water molecules (0.14 nm) should be subtracted from methane hydrate besides a structure II mixed hydrate could
the average cage radius in advance. be observed, although the offered feed gas mixture contained
According to Lederhos et al. [24] a guest-to-cavity ratio higher hydrocarbons such as propane and thus a structure II
between 0.75 and 1.0 results in a minimization of energy mixed hydrate is the thermodynamically stable phase [30].

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Fig. 2  Examples for the 8

equilibrium curves (p, T) of
methane hydrate and mixed gas
7
hydrates that contain ethane
­(C2H6) and propane ­(C3H8) in
addition to methane (­ CH4). The 6 Hydrate stable
hydrate phase is stable in the
areas above the respective p–T
5
equilibrium curve (Data taken

Pressure [MPa]
from Schicks and Luzi-Helbing
[29] and Schicks [33]) 4

Feed gas composition:

2
100% CH4
98% CH4 - 2% C3H8
1 96% CH4 - 3% C2H6 - 1% C3H8
90% CH4 - 5% C2H6 - 5% C3H8
0
274 278 282 286 290

Temperature [K]

In these cases, the short-term formation of a metastable known exactly, this was given in mol%. However, even if the
structure I methane hydrate phase can be attributed to its composition given in Fig. 2 relates to the coexisting feed gas
faster formation kinetics [29]. It should also be noted that the phase, it can be assumed that with increasing partial pres-
correlation between the molecular size of the encased gas sure of a component in the gas phase, this component is also
molecule on the one hand and the resulting hydrate struc- increasingly incorporated into the hydrate phase.
ture on the other hand is not always straightforward. This is The stabilizing effect that occurs through the incorpora-
especially true for mixed hydrates. For example, methane, tion of larger guest molecules than methane, however, varies
ethane, and carbon dioxide alone form structure I hydrates. depending on the properties of the guest molecules. In gen-
Gas mixtures containing methane and carbon dioxide also eral, a connection can be observed between the ratio of the
form structure I hydrates. In contrast, it depends on the com- guest molecule diameter to each host cavity diameter (guest-
position of a methane–ethane gas mixture whether a struc- to-cavity ratio) of the different gas molecules and the shift in
ture I or a structure II hydrate is formed [31, 32]. the equilibrium curve of the respective hydrate. If the guest-
The enclosed gas molecules not only have an influence on to-cavity ratio approaches the value 1.0, this usually leads to
the structure formed. They also have a very strong influence an increase in the stability field of the resulting gas hydrate
on the thermodynamic properties of the resulting hydrate phase in the sense of a shift in the equilibrium curve to
phase, as will be shown in the following section. higher temperatures and lower pressures, respectively. With
increasing proportion of those cavities filled with larger
molecules and thus approaching a higher guest-to-cavity
Influence of the guest molecule properties ratio, the stability field of the hydrate phase also increases.
on the thermodynamic properties The examples shown in Fig. 2 show this trend very well.
of the resulting hydrate phase The guest-to-cavity ratio for ethane in the hexakaidecahe-
dra ­(51264) of structure II is 0.8, while it is 0.99 for propane
The properties of the gas molecules and their proportion [33]. Thus, with increasing proportion of propane in the gas
in the hydrate structure have a decisive influence on the phase and subsequently also in the hydrate phase, the stabil-
stability conditions of the resulting gas hydrate phase. For ity field of the resulting hydrate phase increases significantly.
example, the equilibrium curve of mixed gas hydrates, which If the guest-to-cavity ratio exceeds the value 1, then the mol-
contain higher hydrocarbons or carbon dioxide in addition to ecule is too large for the cavity and distortions or defects
methane, shifts to higher temperatures and lower pressures, in the cavity structure occur when it is encased. However,
respectively. This is demonstrated in Fig. 2, which shows such molecules are also encased into hydrate structures. An
the pressure and temperature conditions above the freezing example is n-butane, which, together with methane, forms
point of water in which a few selected mixed hydrates are a mixed hydrate of structure II. In its gauche conformation,
stable. Since only the composition of the feed gas phase is n-butane occupies the hexakaidecahedra ­(51264) [34]. Since

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the guest-to-cavity ratio of n-butane encased into the hex-

akaidecahedra of structure II is 1.12, the cage is distorted.
According to von Stackelberg and Jahns [35], with the
enclathration of a “too large” molecule into a hydrate cage,
its normal volume v0 has to be expanded to a volume v and
the energy E required for this is calculated according to
(with 𝜒 = compressibility)
( )2
v − v0
E= .
2𝜒v0

The expansion work has the consequence that the equi-

librium curve of these hydrates shifts towards lower tem-
peratures at a given pressure and thus the stability field is
reduced (compared to a hydrate, in which the incorporation Fig. 3  Sources and processes for the formation and migration of
of the guest molecules does not require any expansion work). gases as a prerequisite for hydrate formation in the gas hydrate stabil-
The aforementioned relationship between the guest-to- ity zone (GHSZ) (based on Schicks [33]). The GHSZ is limited by
the equilibrium curve of the gas hydrate (here methane hydrate, black
cavity ratios of the gas molecules enclosed in the hydrate
curve) and the geothermal gradient (3 °C/100 m, dashed line). Hydro-
and the stability of the hydrate phase is also evident in the gen sulfide (­H2S) may be formed near the surface through anaerobic
enthalpies of formation and decomposition of the hydrates. oxidation of methane (­CH4) (AOM). The production of methane by
This applies to simple hydrates, which were formed with microbial processes can take place up to a depth of several hundred
meters. Hydrate-bound methane can be released through the decom-
only one hydrate former and water, as well as to mixed
position of hydrates if the hydrate reaches deeper layers through
hydrates and can be shown on the basis of calorimetric sedimentation processes and thus outside the stability field (red dot-
measurements. Handa [36] used calorimetry to determine ted area). Thermogenic processes in deeper layers can release meth-
the enthalpy of decomposition of simple hydrates that con- ane and other hydrocarbons ­(C2+)
tained either methane, ethane, propane, or iso-butane. His
results show a clear increase in the enthalpy of decompo- the hydrate-forming gas molecules. Of course, these gen-
sition with increasing guest-to-cavity ratio. The better sta- eral conditions also apply to hydrate formation in nature
bilization of the hydrate cages through the incorporation and we find them fulfilled on all active and passive conti-
of a spherical molecule (such as iso-butane) instead of a nental slopes, in permafrost areas, and in some deep lakes.
linear molecule of the same size (such as propane) leads Compared to the formation of gas hydrates in the laboratory
to a slightly higher enthalpy of decomposition for the iso- under controllable conditions, however, the formation of gas
butane hydrate (133 kJ/mol) compared to propane hydrate hydrates in a natural environment is much more complex.
(129 kJ/mol). For mixed hydrates, which were synthesized In addition to previously mentioned pressure, temperature,
from methane–carbon dioxide gas mixtures and from meth- water, and hydrate-forming gas concentrations, other param-
ane–ethane–propane gas mixtures, it could also be dem- eters play a role here. These include, e.g., the salinity of the
onstrated that not only the qualitative composition of the pore water, the sediment and the associated properties such
hydrate phase but also its quantitative composition has an as porosity and permeability, the origin and thus the compo-
influence on the enthalpies of decomposition [37, 38]. As a sition of the hydrate-forming gas, the presence or absence of
general trend, it can be seen that with increasing absolute a free gas phase, as well as the presence of microorganisms.
cage occupancy and with increasing cage occupancy with Figure 3 shows the equilibrium conditions of methane
molecules with a guest-to-cavity ratio that approaches the hydrate as a black curve. From a depth of at least 300 m,
value 1, the enthalpy of decomposition increases. methane hydrates may form at a water temperature of 0 °C.
At temperatures above this curve, methane hydrates are not
stable because the temperature is too high at the given pres-
Gas hydrate formation and occurrences sure. While the water temperature at the sea floor can be
in nature assumed to be relatively constant locally, it increases with
increasing depth into the sediment, as the dashed line in
In the previous sections we learned that high pressures and Fig. 3 shows. This temperature increase is referred to as a
low temperatures are necessary for the formation of gas geothermal gradient and can vary from region to region,
hydrate formation. In addition, sufficient amounts of water with an average temperature increase of 3 °C/100 m. As a
and a hydrate-forming gas must be present, which means result of this increasing temperature in the sediment profile,
that the aqueous solution should be supersaturated with the temperature at given pressure at a certain depth may be

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too high for the formation of gas hydrates. This depth is faster in the presence of surfactin compared to samples
defined by the intersection of the dashed straight line (geo- without biosurfactants and that the hydrate growth rate was
thermal gradient) and the black curve (equilibrium curve) increased significantly (by 288%).
in Fig. 3 and is referred to as the basis of the gas hydrate How well the hydrate-forming gas can migrate through
stability zone (BGHSZ). In the blue-yellow patterned area the sediments and get into the GHSZ or be distributed also
between the sea floor and the BGHSZ in Fig. 3, the pressure depends on the type of sediment. In coarse sediments with
and temperature conditions are within the stability field of high permeability and porosity such as sand or gravel, a
the methane hydrates. If enough gas and water molecules are methane-rich pore fluid or free methane gas can easily
present, gas hydrates may occur. This area is known as the migrate into the GHZS and form gas hydrates in the pore
gas hydrate stability zone (GHSZ). space between the sediment grains or as nodules. In sedi-
The gas required for hydrate formation can be formed ments with low permeability, such as clay, methane-rich flu-
locally in very different processes as shown in Fig. 3. Ther- ids or free methane gas preferentially moves through existing
mogenic conversion processes in deeper sediment layers, pathways such as fractures, in which the gas hydrates form
which are often coupled with oil deposits, are, e.g., a pos- as soon as the GHSZ is reached and thus gas hydrate veins
sible source not only for methane but also for other hydro- may occur. In the case that gas bubbles rise in the sediment,
carbons on the one hand. On the other hand, microbial deg- very porous, sponge-like hydrate structures can also form,
radation of organic material in the sediments of the ocean which can contain a great portion of free gas and therefore
floors or the microbial reduction of carbon dioxide produces have a relatively low density [45, 46].
methane, which is the predominant component in natural It should be noted that sediment grains may also serve
gas hydrates [39]. At the continental margins there are as crystallization nuclei in the heterogeneous crystalliza-
relatively high amounts of organic material. However, only tion process of hydrate formation. The presence of sediment
about 10% of this organic material reaches deeper sediment grains can thus enable hydrate formation immediately after
layers (> 10 cm) and is converted into methane by microbial the equilibrium curve has been exceeded without supercool-
processes. This proportion is much lower on the deep-sea ing, which could also be observed in experiments for sand
floor, so that in general no gas hydrates are expected at the and bentonite [47, 48].
sea floor of the free ocean waters [40]. Another source of While sediments or the products of microbial activity
hydrate-forming gases such as methane are decomposing gas can promote the formation of gas hydrates, the presence of
hydrates, which moved into a deeper and thus warmer sedi- salts can hinder or reduce the formation of hydrates. Mekala
ment layer because of a continuous sedimentation process et al. [49] observed a significant delay in hydrate formation
and thus outside the stability field. The gas released dur- at a salinity of 3 wt%. The hydrate formation was not only
ing the decomposition can migrate upwards and be encased delayed; the amount of hydrate formed was also significantly
into hydrates again [40]. Methane that has been formed or lower compared to hydrate formation experiments using
released deep down may migrate into shallower sediment pure water. With an increasing concentration of NaCl, the
layers and be oxidized there via anaerobic oxidation of equilibrium curve of methane hydrate also shifts to lower
methane (AOM) by a consortium of bacteria and archaea temperatures and higher pressures, and thus the stability
using sulfate. As a result, hydrogen sulfide can be formed field decreases. This relationship is observed until the satu-
locally in the sea floor [41, 42]. Hydrogen sulfide is also a ration concentration of NaCl is reached. Even at higher con-
good hydrate former and is therefore preferably encased into centration of NaCl in the aqueous phase no further changes
the hydrate structures even at low concentrations. In this with respect to the stability condition for methane hydrate
context, it should be pointed out that the microbial activity were observed [50].
not only leads to the availability of hydrate-forming gases. The complexity of hydrate formation in a natural environ-
Microbial activity, however, also produces plenty of other ment is also demonstrated by the fact that in recent years
organic materials, including biosurfactants which can act as there have been increasing reports of coexisting hydrate
nucleation seed during gas hydrate formation. Kalogerakis phases with different compositions and/or structures. In
et al. [43] were able to show in experiments with synthetic 2007, a complex hydrate sample with coexisting structure II
surfactants such as sodium dodecyl sulfate that the rate of and structure H hydrate phases containing n-pentane and
gas hydrate growth can be increased by several orders of n-hexane in addition to methane and lighter hydrocarbons
magnitude by adding surfactants. In nature, bacteria have was identified from Barkley Canyon on the northern Cas-
been found in hydrate-bearing sediments, which produces cadian margin [51]. A few years later in 2010, Klapp et al.
biosurfactants such as surfactin which could be found in nat- [11] reported the occurrence of sI and sII gas hydrates as
ural sediment cores. Rogers et al. [44] studied the influence coexisting phases from the Chapopote Knoll in the south-
of surfactin on the formation and growth of gas hydrates and ern Gulf of Mexico. Similar results were observed from
observed that the first hydrate crystals formed significantly the South China Sea by Wei et al. [52], who analyzed gas

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hydrate samples and confirmed the coexistence of sI and sII understanding is sufficient for many applications in the
gas hydrates. Also, Jin et al. [53] detected the coexistence field of chemical engineering [59]. However, there are still
of two sI hydrates with different textures and compositions unanswered questions in these areas, such as the coexisting
in natural gas hydrate samples recovered from the Umitaka hydrate phases mentioned in the last section. The kinetics
Spur in the Joetsu Basin, Japan. Even hydrate samples from of hydrate formation and decomposition especially in natu-
Lake Baikal showed the coexisting hydrate phases with dif- ral systems are not yet adequately described. However, this
ferent structures and compositions [54, 55]. knowledge is crucial when it comes to the understanding of
It seems surprising that hydrate phases with different the response of natural gas hydrates to global warming and
compositions and structures form in nature and coexist over the question of how fast natural gas hydrate deposits will
a longer period of time. The reasons for the coexistence of decomposed and how fast and how much gas will be released
hydrate phases with different structures and composition into the atmosphere. Since gas hydrates can also influence
or strong heterogeneities in compositions within a hydrate the geomechanical properties of the host sediments, the
crystal formed in a natural environment can be diverse. question also arises as to what extent decomposition of the
Depending on the local conditions, a possible explanation gas hydrates could lead to destabilization of the subsurface
may be fluctuations of the composition of the feed gas flux and may induce slope failures.
from deeper sources or a fractionation of the gas in shal- A completely different interesting aspect of the research
lower sediments as a result of methane consumption and/or on gas hydrates and a future perspective is the utilization
the production of hydrogen sulfide as a result of biological of gas hydrates in industrial applications. This may include
processes such as the anaerobic oxidation of methane [11, the storage and transport of gases, gas separation, sea water
56]. Depending on the local sediment types and other cir- desalination, or waste water treatments as well as cooling
cumstances the migration of the feed gas may be limited and issues as reported elsewhere [60].
the local conditions can be described as a “closed system”.
Another possible approach to explain these observations is
to consider different hydrate formation kinetics: The forma- Author contributions Judith M. Schicks wrote the manuscript.
tion of methane hydrate seems to be kinetically preferred
Funding Open Access funding enabled and organized by Projekt
compared to the formation of mixed hydrates. Another DEAL. Not applicable.
explanation could be the formation of an initial hydrate
phase with a structure corresponding to the present feed gas Availability of data and material Not applicable.
composition and the formation of a second, additional and
coexisting hydrate phase in a second step because the com- Code availability Not applicable.
position of the migrating feed gas changes rapidly. The feed
gas composition may also change, because some gases are Declarations
preferentially incased into the hydrate structure compared
to methane [57]. Therefore, the hydrate formation process Conflicts of interest/Competing interests No conflict of interest.
may induce a fractionation of the feed gas and may result in
Open Access This article is licensed under a Creative Commons Attri-
the formation of coexisting hydrate phases with changing bution 4.0 International License, which permits use, sharing, adapta-
compositions in accordance with the changing feed gas com- tion, distribution and reproduction in any medium or format, as long
position. A recently published study, however, has shown as you give appropriate credit to the original author(s) and the source,
that the latter explanation does not lead to the formation provide a link to the Creative Commons licence, and indicate if changes
were made. The images or other third party material in this article are
of coexistent hydrate phases at least in the laboratory [58]. included in the article's Creative Commons licence, unless indicated
Even if one possible explanatory approach can be ruled out, otherwise in a credit line to the material. If material is not included in
the reasons for the coexistence of gas hydrate phases with the article's Creative Commons licence and your intended use is not
different compositions and/or structures have not yet been permitted by statutory regulation or exceeds the permitted use, you will
need to obtain permission directly from the copyright holder. To view a
clarified. copy of this licence, visit http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/.

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