Noble Gases as Environmental Tracers in Sediment Porewaters … · 2015-05-12 · Noble Gases as...

Noble Gases as Environmental Tracersin Sediment Porewaters and StalagmiteFluid Inclusions

M. S. Brennwald, N. Vogel, Y. Scheidegger, Y. Tomonaga,D. M. Livingstone and R. Kipfer

Abstract

In well-studied aquatic systems such as surface waters and groundwater,noble gases are used extensively as natural tracers to reconstructpalaeoenvironmental conditions, to study transport and mixing, and toidentify the geochemical origin of geogenic fluids. It has been suggestedthat less well-studied aquatic systems such as the porewaters of lacustrineand oceanic sediments and the fluid inclusions present in stalagmitesmight also be suitable as noble gas archives for environmental studies,but until recently the lack of adequate experimental techniques hadhindered the development of noble gas geochemistry in these systems.This chapter reviews recent technical advances in this field and describesthe scientific applications that these advances have made possible. Theporewaters of lacustrine and oceanic sediments are now well establishedas noble gas archives in studies of temperature, salinity and mixingconditions that prevailed in the overlying water body in the past, as wellas in studies of the transport and origin of solutes and pore fluids in thesediment. The geochemistry of noble gases in stalagmite fluid inclusionsis still in the early stages of development. However, the results availableto date suggest that stalagmite fluid inclusions have great potential as anoble gas archive in reconstructing palaeoclimatic conditions near caveswith suitable stalagmites.

1 Introduction

Noble gases have been used extensively asenvironmental tracers in lakes, oceans andgroundwater since the 1960s. They have provedhighly useful in reconstructing palaeoenviron-mental conditions, studying transport andmixing in aqueous environments, and in con-straining the geochemical origin of geogenicfluids injected into natural water bodies

M. S. Brennwald (&) � N. Vogel � Y. Scheidegger �Y. Tomonaga � D. M. Livingstone � R. KipferDepartment of Water Resources and DrinkingWater, Eawag, Swiss Federal Institute of AquaticScience and Technology, CH-8600, Dübendorf,Switzerlande-mail: [email protected]

N. Vogel � R. KipferInstitute for Geochemistry and Petrology, SwissFederal Institute of Technology Zurich (ETH),CH-8092, Zurich, Switzerland

P. Burnard (ed.), The Noble Gases as Geochemical Tracers, Advances in Isotope Geochemistry,DOI: 10.1007/978-3-642-28836-4_6, � Springer-Verlag Berlin Heidelberg 2013

123

(for reviews see Ballentine and Burnard 2002;Ballentine et al. 2002; Kipfer et al. 2002; Sch-losser and Winckler 2002; Aeschbach-Hertigand Solomon 2012; Stanley and Jenkins 2012).

The concentrations of dissolved noble gasesin natural water bodies are determined by vari-ous processes involving different noble gas res-ervoirs (Sect. 2). On the one hand, thepartitioning of noble gases between air andwater is governed by the exchange of these gasesacross the air-water interface and by the solu-bility equilibrium as described by Henry’s Law.This allows the concentrations of dissolvedatmospheric noble gases (i.e., those derived fromthe atmosphere) in a water body to be used toreconstruct the temperature and salinity of thewater as well as the atmospheric pressure thatprevailed during gas exchange. On the otherhand, non-atmospheric noble gas isotopes mayaccumulate in the water either as a result of theirin-situ production by radioactive decay andother nuclear reactions or because of the addi-tion of geogenic fluids to the water. The con-centrations of such non-atmospheric noble gasescan be used to determine the water age (definedas the time that elapsed since the last occurrenceof gas exchange between the water and theatmosphere), to quantify the rates at which waterand solutes are transported, and to study theaccumulation and the geochemical origin ofgeogenic fluids. These concepts can, in princi-ple, be adapted to other, more unconventionalaquatic environments, such as the porewaters oflacustrine and oceanic sediments or waterinclusions in stalagmites.

Lakes generally react sensitively to changesin climatic forcing. More than three decades ago,the porewater of lacustrine and oceanic sedi-ments was therefore proposed as a potentialnoble gas archive for palaeoenvironmentalreconstruction (Barnes 1979). In addition, theabundance and relative composition of non-atmospheric noble gases accumulating in theporewater as a result of in-situ production or theinjection of geogenic fluids reflect the transportdynamics and the geochemical origin of the porefluids (Sect. 3.1).

In caves, microscopic water inclusionsembedded in the minerals of stalagmites containa mixture of noble gases that were trapped at thetime the inclusions were formed. It has beensuggested that the elemental composition ofthese noble gases may reflect the cave temper-ature prevailing at that time. Because theambient air temperature in caves remains rela-tively constant throughout the year at a valuewhich corresponds closely to the local annualmean soil temperature and to the annual meanair temperature outside the cave, it may bepossible to use the noble gases archived in sta-lagmite water inclusions to reconstruct air tem-peratures in the distant past (Sect. 4.1).

Until recently, however, a lack of suitableexperimental techniques has hindered the devel-opment of noble gas geochemistry in lacustrineand oceanic sediment porewater and in stalagmitefluid inclusions. Various research groups havetherefore begun to develop new methods of noblegas analysis for these more unconventionalaquatic systems (Sects. 3.2 and 4.2).

The resulting experimental advances havemeant that lacustrine and oceanic sedimentporewaters are now well established as a newtype of noble gas archive for environmentalstudies (Sect. 3.3). New experimental techniqueshave also allowed the scientific potential ofstalagmite fluid inclusions as noble gas archivesfor palaeoenvironmental research to be assessed(Sect. 4.3).

2 Noble Gases in AqueousSolution

2.1 Sources and Processes

The noble gas components found in naturalwaters are characterised in terms of the geo-chemical reservoirs from which they originateand in terms of the processes by which theyenter the water (see also Aeschbach-Hertig andSolomon 2012). Figure 1 illustrates the termi-nology used in this chapter for the differentnoble gas components.

124 M. S. Brennwald et al.

Noble gases from the atmosphere enter thewater by gas exchange across the air-waterinterface and, to a lesser extent, by the (partial)dissolution of air bubbles in the water. Theatmospheric noble gas component in the watertherefore comprises all noble gases (and theirisotopes) that are found in the atmosphere (He,Ne, Ar, Kr and Xe). The non-atmospheric noblegas isotopes originate mainly from the solidearth (terrigenic noble gases), including the rockmatrix within which the water is embedded, orfrom the radioactive decay of 3H in the water.Among the non-atmospheric noble gas isotopes,3He and 4He have been used most frequently forenvironmental field investigations so far. Rn, theheaviest naturally occurring noble gas, may alsobe used as an environmental tracer. However,due to the rapid radioactive decay of the differ-ent Rn isotopes (which have half-lives rangingfrom seconds to days), Rn is most useful as aproxy for rapid transport and mixing processesin surface waters and groundwater (e.g., Hoehnand von Gunten 1989; Bertin and Bourg 1994;Huxol et al. 2012) rather than for the muchslower processes dealt with in this chapter. Rnwill therefore not be considered further here.

2.1.1 Atmospheric Noble GasesIn meteoric water, the concentrations of dissolvednoble gases are dominated by the atmosphericcomponent. When using noble gases as

environmental proxies in meteoric water, the noblegas composition of the atmosphere (Table 1) isassumed to be constant in space and time. Thisassumption is justified because water renewal inthe aquatic environment occurs much more rapidlythan the evolution of the noble gas composition ofthe atmosphere (Kipfer et al. 2002).The abundanceof atmospheric noble gases dissolved in water istherefore determined solely by the processes gov-erning air-water gas partitioning and by the trans-port processes occurring within the water body.

Noble Gas Concentrations in Air-Saturated

Water

At the water surface, noble gases are partitionedbetween the atmosphere and the water by exchangeacross the air-water interface. Because gas exchangeusually occurs much faster than the mixing of thewater immediately below the air-water interfacewith the bulk water, solubility equilibrium is attainedat the water surface (e.g., Schwarzenbach et al.2003). The resulting equilibrium concentrations C�iin the air-saturated water (ASW) are given byHenry’s Law (see also Fig. 2 and Kipfer et al. 2002):

Pi ¼ HiðT ; SÞC�ii ¼ He, Ne, Ar, Kr, Xe

ð1Þ

where Pi is the partial pressure of the noble gas iin the gas phase; Hi is the Henry coefficient,which is a function of the water temperature Tand salinity S; and C�i is the equilibrium con-centration of noble gas i in the water.

The partial pressure is given by Pi ¼ ðPatm

�esðTÞÞvi, where Patm is the total atmosphericpressure, esðTÞ is the vapour pressure, and vi isthe volume fraction of gas i in dry air (Table 1).

Excess Air

Excess air is formed by the (partial) dissolution ofair bubbles in water. Excess air is of paramountimportance in groundwater, whereas it is usuallynegligible in surface waters (Sect. 3.1). Stalag-mites usually contain many air inclusions inaddition to water inclusions (Sect. 4.1). Althoughthe air in these inclusions is not dissolved in water,the mathematical treatment of this air componentin Sect. 2.1.3 is analogous to that of excess air.

Noble gasesin water

Atmosphericcomponent

(He, Ne, Ar, Kr, Xe)

Non-atmosphericcomponent

(3He, 4He, 21Ne, 40Ar)

Air-saturatedwater (ASW)

Excess air(EA)

Terrigeniccomponent

Radiogeniccomponent

Fig. 1 Terminology and classification of the differentnoble gas components found in natural waters. Termsassociated with geochemical reservoirs are indicated byrectangles and terms associated with the processesgoverning noble gas abundance by ellipses. Note thatradiogenic noble gases are often, but not always, ofterrigenic origin (e.g., 3He produced by the radioactivedecay of 3H in the atmosphere or the hydrosphere is notterrigenic)

Noble Gases in Sediments and Stalagmites 125

2.1.2 Non-atmospheric Noble GasesNoble gases that are not of atmospheric origincan also accumulate in the aquatic environment.Noble gas isotopes can be produced in situ byradioactive decay and other nuclear reactions,and they can also be released into the aquaticenvironment from the solid earth. The concen-trations of these radiogenic or terrigenic noblegas isotopes can provide information on waterresidence times and the dynamics of relevantfluid transport processes.

Relative to the atmospheric noble gas con-centrations, non-atmospheric He usually showsthe highest concentrations of all terrigenic noblegas isotopes (Mamyrin and Tolstikhin 1984;

Ozima and Podosek 2002; Solomon 2000). Thisis mainly because of (i) the high rate of Heproduction by the radioactive decay of U and Thisotopes in the crust coupled with the low degreeof He retention in rock (radiogenic He, typical3He/4He ratio � 10�8), and (ii) the release ofprimordial and radiogenic He from the earth’smantle (typical 3He/4He ratio � 10�5). In addi-tion, the radioactive decay of 3H bound to watermolecules produces considerable amounts of3He (known as tritiogenic 3He; see, e.g., Solo-mon and Cook 2000). 3H is produced naturallyby spallation in the atmosphere. It is also a by-product of earlier nuclear weapons testing in theatmosphere. The latter resulted in a distinct 3H

Table 1 Characteristic properties of noble gases

Element vi di (Å) Isotope Ri (%)

He (5.24 � 0.05) � 10�6 2.55 3He 0.0001404He �100

Ne (1.818 � 0.004) � 10�5 2.82 20Ne 90.5021Ne 0.26822Ne 9.23

Ar (9.34 � 0.01) � 10�3 3.45 36Ar 0.336438Ar 0.063240Ar 99.60

Kr (1.14 � 0.01) � 10�6 3.65 78Kr 0.34780Kr 2.25782Kr 11.5283Kr 11.4884Kr 57.0086Kr 17.40

Xe (8.7 � 0.1) � 10�8 4.04 124Xe 0.0951126Xe 0.0887128Xe 1.919129Xe 26.44130Xe 4.070131Xe 21.22132Xe 26.89134Xe 10.430136Xe 8.857

Volume fraction in dry air, vi (Ozima and Podosek 2002); atomic diameter, di (Huber et al. 2006); relative atomicisotope abundance in air, Ri (Ozima and Podosek 2002).


maximum in the atmosphere in the 1960s, tem-porarily increasing the global inventory of ter-restrial 3H by several orders of magnitude. Onlocal spatial scales the use of 3H in technologicalapplications can also affect 3H concentrations inthe aquatic environment.

Apart from the isotopes of He, other isotopesof radiogenic origin found in the aquatic envi-ronment include 40Ar and, to a lesser extent,21Ne. However, in most cases their presence ismasked by higher concentrations of 40Ar and21Ne of atmospheric origin (for an extendeddiscussion see Kipfer et al. 2002).

2.1.3 Disentangling and Quantifyingthe Various Noble GasComponents

From the above discussion it follows that theoverall concentration of each of the noble gases inwater is given by the sum of the ASW concen-tration, the excess air component (‘‘EA’’), and theterrigenic He (‘‘terr’’) and tritiogenic 3He (‘‘trit’’)components (note that except for He, all non-atmospheric noble gas components are neglectedas to their abundance is extremely low):

3Hetot

4Hetot

Netot

Artot

Krtot

Xetot

¼¼¼¼¼¼

3HeASWðT ; S;PatmÞ4HeASWðT ; S;PatmÞNeASWðT ; S;PatmÞArASWðT ; S;PatmÞKrASWðT ; S;PatmÞXeASWðT ; S;PatmÞ

þþþþþþ

3HeEA

4HeEA

NeEA

ArEA

KrEA

XeEA|fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}

atmospheric

þþ

3Heterr

4Heterr

þ 3Hetrit

|fflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflffl}

non�atmospheric

ð2Þ

Experimental analysis yields only the overallconcentrations (the left-hand side of Eq. 2), butnot the individual components, which are nee-ded to interpret the noble gas data in terms ofT , S, Patm, excess air, and the accumulation ofterrigenic and radiogenic He isotopes.

Depending on the type of environment andarchive (surface-water body and sediments, orcave and stalagmites), the values of some of theseenvironmental parameters can be constrainedusing independent information. For instance, Patm

can be determined from the altitude of the watersurface of a lake or the altitude of the rechargearea of a groundwater system. The values of theremaining unknown parameters can then be esti-mated by regression from the measured data

0 10 20 30 40

HeNeArKrXe40%

60%

80%

100%

0 5 10 15 20 25 30

C i*

C

/ i0

T (°C) S (g/kg)

Fig. 2 Noble gas equilibrium concentrations in air-saturated water (C�i ) as a function of water temperature T(left) and salinity S (right, for a sea-salt solution). Theconcentrations are normalised to the ASW

concentrations C0i at T ¼ 0 �C and S ¼ 0 g/kg, respec-

tively. Concentrations were calculated using the solubil-ity data recommended by Kipfer et al. (2002)


analogously to the techniques used in surfacewaters and groundwater (Aeschbach-Hertiget al. 1999; Ballentine and Hall 1999). Thesetechniques have been used widely to infer thegroundwater temperature that prevailed duringthe last occurrence of gas exchange betweengroundwater and soil air. This temperature isknown as the ‘‘noble gas temperature’’ and theprocedures used to determine it are known as the‘‘noble gas thermometer’’ (Mazor 1972).

2.2 Experimental Methods

Water samples taken in the field need to betransported to a laboratory that is speciallyequipped for the extraction and analysis of noblegases (see also Aeschbach-Hertig and Solomon2012). In the laboratory, the concentrations ofdissolved noble gases are determined from theamounts of each noble gas in the water sampleand the mass of the water sample. Because noblegases are only slightly soluble in water, contactbetween the water samples and air (or any othergas reservoir) must be avoided during sampling,transport, storage and processing.

Conventional bulk water samples from sur-face waters or groundwater are allowed toexpand into a vacuum system to extract thedissolved noble gases from the water (e.g.,Bayer et al. 1989; Jean-Baptiste et al. 1992;Beyerle et al. 2000; Sültenfuss et al. 2009). Theanalysis of noble gases from sediment porewateror stalagmite water inclusions requires addi-tional experimental steps to separate the waterfrom its confining matrix prior to the vacuumextraction process. This critical step, which mustbe carried out in such a way that the watersample is not exposed to air or to any other gas,needs to be adapted to the type of sample(Sects. 3.2 and 4.2). After separation from thematrix, the dissolved gases are extracted fromthe water and transferred to a vacuum system topurify and separate out the different noble gases.The gas amounts and isotope ratios are thendetermined by static mass spectrometry usingpeak-height comparison (e.g., Beyerle et al.2000).

The minimum sample size required for noblegas analysis is determined by the sensitivity ofthe mass spectrometer, the degree of dilution ofthe sample during the extraction and purificationof the sample gas, and the detection limit of theanalytical system. Taking these factors together,the practical minimum sample size required fora typical analytical system is approximately0.1–1 mg of water.

3 Lacustrine and OceanicSediments

3.1 Noble Gases in SedimentPorewater

Because gas exchange across the air-waterinterface is rapid, noble gas concentrations at thesurface of lakes and the ocean correspond clo-sely to ASW concentrations as computed fromthe water temperature, salinity and atmosphericpressure (Sect. 2.1.1).

For the purpose of this chapter, concentra-tions of excess air are assumed to be negligiblein surface waters. Small amounts of excess airare observed only in large lakes and in theocean, where excess air can be produced by thedissolution of bubbles entrained by breakingwaves (Craig and Weiss 1971; Bieri 1971) or bythe addition of meltwater from air-rich ice(Hohmann et al. 2002; Loose et al. 2009). Theresulting noble gas excesses are usually � 5 %for Ne and even less for the heavier noble gases(Craig and Weiss 1971; Peeters et al. 2000).

The vertical distribution of heat and conser-vative solutes (e.g., noble gases and salts) in thewater column is dominated by vertical transportresulting from advection and macroscopic tur-bulence (‘‘eddy diffusion’’, Lerman et al. 1995).The atmospheric noble gas concentrationsobserved at a given water depth are thereforecoupled to the temperature and salinity of thewater at that depth. They therefore correspondclosely to the ASW concentrations calculatedfrom this water temperature and salinity, asconfirmed experimentally by, for instance,


Aeschbach-Hertig et al. (1999) and Peeters et al.(2000).

During sedimentation, part of the open waterjust above the sediment-water interface isincorporated into the sediment pore space. Thenoble gas concentrations in this porewatertherefore carry information about the tempera-ture and salinity of the bottom water in the past(see examples discussed in Sect. 3.3.1). Analo-gously, dissolved chloride concentrations andthe d18O signature in the sediment porewaterhave been used to reconstruct palaeoenviron-mental conditions in the ocean (Adkins et al.2002; Schrag et al. 1996, 2002). However,geochemical alteration of the chloride concen-trations in the porewater may mask the palae-osalinity information (e.g., Austin et al. 1986;Swart 2000). Also, the d18O signature in seawater depends not only on water temperatureand salinity, but also on the volumes of reser-voirs of freshwater (ice, groundwater), whichchange in response to different climate condi-tions. Further, d18O in the porewater may evenbe affected by the recrystallisation of dissolvedcarbonates (Swart 2000). By contrast, the con-centrations of dissolved atmospheric noble gasesare unaffected by such secondary processes andthus provide a direct measure of water temper-ature and salinity in the past.

While the noble gas signature in the bottomwater is recorded and buried in the sediment,molecular diffusion acts at the same time tosmooth out the noble gas profiles. This smoothingwill, in principle, result in a loss of informationwith regard to the past noble gas signature in thewater body, leading to a loss of information aboutthe corresponding past environmental conditions.To assess the relative importance of sedimentburial (advection) and diffusion for the archivednoble gas signature, the distances by which sol-utes are transported by sediment burial or diffu-sion need to be compared (see also Strassmannet al. 2005, and references therein):• Sediment burial: The sediment burial velocity

relative to the sediment surface is governedby the rates of sediment accumulation andcompaction. For simplicity, compaction isassumed to be so small, that the vertical

porewater offset relative to the sediment matrixis negligible. The porewater burial velocity istherefore approximately equal to the sedimentaccumulation rate (s). Within a given timeinterval Dt, the porewater is transported down-wards a distance Dzadv:

Dzadv � sDt ð3Þ

• Diffusion: In contrast to advection, the char-acteristic transport length (Dzdiff;i) of a diffu-sive process increases with the square root ofthe elapsed time according to the Einstein-Smoluchowski equation (e.g., Einstein 1905;Grathwohl 1998; Schwarzenbach et al. 2003):

Dzdiff;i �ffiffiffiffiffiffiffiffiffiffiffiffiffi

/DiDtp

ð4Þ

where / is the sediment porosity and Di is theeffective diffusivity of the noble gas i in thesediment, given by:

Di ¼ D0i =a ð5Þ

where D0i is the molecular diffusivity of gas i in

bulk water and a 1 is a scaling factordescribing the effect of diffusion retardation inthe sediment. This scaling factor takes intoaccount the tortuosity of the sediment matrix,but also accounts for any other effects that mayresult in the retardation of diffusion in theporewater (Sect. 3.3.3).

The diffusive smoothing of vertical noble gasprofiles can be considered negligible when thediffusive transport length (Dzdiff;i) is negligiblecompared to the advective transport length(Dzadv); i.e., when Dzdiff;i Dzadv. CombiningEqs. (3), (4) and (5), and assuming / � 1 yields:

D0i =a s2Dt � sL, Pe ¼ sL

D0i =a� 1 ð6Þ

where Pe is the Peclet number and L is thesediment-depth range considered. With L � sDt(still neglecting compaction), the importance ofdiffusion for smoothing the noble gas profilestherefore depends on the sediment accumulationrate and the time range considered. Strassmannet al. (2005) showed that in a ‘‘typical’’ sediment


a step-like Xe profile would be smoothed out bydiffusion over appoximately 2 m in 102 years,5 m in 103 years, and 20 m in 104 years. Ascaling factor a � 2 was assumed in these cal-culations to reflect the tortuosity of the sedimentmatrix. These results illustrate that even if dif-fusion does smooth out the noble gas profiles,the palaeoenvironmental information is retainedin the sediment over a large depth range L (i.e.,if Pe� 1).

Apart from the reconstruction of palaeoenvi-ronmental conditions, noble gases dissolved insediment porewater have been shown to besensitive tracers for the transport of solutes andpore fluids within the sediment column and forthe exchange of solutes and fluids between thesediment and the overlying water body (seeexamples discussed in Sect. 3.3.2). The transientbehaviour of radiogenic He isotopes accumu-lating in the porewater is especially suitable forstudying the dynamics of the transport of solutesand fluids in the sediment. In addition, the3He/4He ratio of the different He componentsreflects the geochemical origin and history of thepore fluids.


Peeper methods have been used to sample dis-solved He in sediment porewater (Stephenson et al.1994). A peeper is a dialysis sampler which isburied in the sediment. A gas-permeable mem-brane separates the sediment porewater from thesample cells, which are filled with gas or water.However, peepers need to be left at the samplingsite for several days or weeks to allow the He in thesample cells to equilibrate with the He in the sur-rounding porewater (Dyck and Da Silva 1981).Because of their lower diffusivity, the heaviernoble gases would require even longer equilibra-tion times. Also, gases are lost rapidly from thesample cells during peeper retrieval and sampleprocessing as a result of degassing caused by thedecrease in hydrostatic pressure. Finally, peepersmay not be suitable for sampling at great water

depths because the membranes of the peeper cellscollapse under the hydrostatic pressure exerted.

A wireline tool has been used for the in-situsampling of porewater in marine sediment drillholes to quantify He fluxes through the sedi-ment-water interface (Barnes 1973; Barnes andBieri 1976; Barnes 1979, 1988; Sano and Wakita1987). This non-standard sampler is complicatedto operate and gas leakage may occur from thesamples. Torres et al. (1995) and Winckler(1998) determined He, Ne, Ar, Kr and Xe con-centrations in samples obtained using this tool,but it was also noted that gas bubbles may formin the system during sampling. Hence, the noblegas concentrations in the sample can vary in anuncontrollable manner because of gas exchangebetween the sample and the gas bubbles. Also,contamination with the drilling fluid or the waterused to fill the in-situ sampler may occur(Winckler 1998).

To overcome the shortcomings of the meth-ods described above, Brennwald et al. (2003),Chaduteau et al. (2007) and Tomonaga et al.(2011a) developed new experimental methodsthat rely on simple, robust, and standard sedi-mentological equipment. In the following, thesestate-of-the art methods will be described indetail.

3.2.1 SamplingSediment cores are collected in plastic tubes(liners) using a gravity corer or a similar coringdevice. After recovering the sediment core,about 30 g of bulk sediment is sampled from thedesired sediment depths. Similar to noble gassampling in bulk water (e.g., Beyerle et al.2000), copper tubes are used as sample con-tainers. The copper tubes are connected to thesediment core via fittings that penetrate into thecore (Fig. 3a; Brennwald et al. 2003). Samplingports can be drilled and covered with adhesivetape before coring to minimise the risk of con-taminating the sediment with air.

Immediately after collecting the core, thesediment sample is transferred from the liner


into the copper tubes utilising the squeezer set-up shown in Fig. 3a. The copper tubes are flu-shed with sediment to remove residual air and toexpel the sediment fraction which may haveexchanged noble gases with the atmospherewhile the copper tubes were being mounted. Thesamples are closed and sealed by pinching offthe copper tubes at both ends using the samestandard clamps as those used with conventionalwater samples. This procedure allows the sam-pling of intact sediment cores and avoids aircontamination and gas loss during sampling. Byinspection of a layered sediment core aftersampling, the uncertainty in sampling depth hasbeen estimated to be less than 5 cm (Brennwaldet al. 2004).

An alternative sampling method was devel-oped by Chaduteau et al. (2007). Sediment issampled in copper tubes by pushing the tubes intothe sediment either parallel or perpendicular to theaxis of the sediment core (Fig. 3b). This methodhas the advantage of being less destructive to thesediment core, and of requiring less sedimentmaterial because the copper tubes are not flushedwith sediment. This ‘‘sub-coring’’ into the coppertubes causes hardly any interference with mostother classical sedimentological analyses of thecore. Also, the sampling depth within the sedi-ment core is well defined, as there is no offset dueto squeezing. This method works best with softsediments that will easily fill the copper tubes. Forother sediments, the squeezing method may bebetter suited. A disadvantage of the method ofChaduteau et al. (2007) is that it does not allow the

copper tubes to be flushed with sediment material,which would help to avoid contamination of thesample with air.

3.2.2 Extraction and Analysisof Dissolved Noble Gases

The methods used to extract dissolved noblegases from conventional water samples (Bayeret al. 1989; Beyerle et al. 2000) cannot beapplied directly to the porewater of unconsoli-dated sediments because the porewater isembedded and trapped in the sediment matrix.Brennwald et al. (2003), Chaduteau et al. (2007)and Tomonaga et al. (2011a) therefore devel-oped other methods of extracting the gases fromthe porewater.

The method of Brennwald et al. (2003) forextracting the dissolved noble gases from thesediment porewater involves heating and openingthe copper tube, which is attached to an evacuatedextraction vessel. Heating increases the pressurein the copper tube, causing the whole sedimentsample to be extruded explosively into theextraction vessel when the tube is opened. Thedissolved noble gases are then extracted into thevacuum of the extraction vessel. The sample gasesare transferred into a gas purification system,where the noble gases are cleansed of other gaseswhich would interfere with the subsequent massspectrometric analysis. This allows the noble gasconcentrations to be determined with a standarderror of \2 %. In some sediments, however,considerable amounts of radiogenic He can bereleased from the minerals when the sediment

Fitting

Clamps

Sediment core

Copper tube

Liner

Tube

Fitting

Copper tube (a) (b)

PistonCopper tubes

Plexiglass platewith hole

(1)

(2)

Liner

Sedimentcore

Fig. 3 a Sediment squeezer and sampling set-up (after Brennwald et al. 2003). b Sampling set-up for direct ‘sub-coring’ into copper tubes parallel (1) or perpendicular (2) to the axis of the sediment core (after Chaduteau et al. 2007)


sample is heated during analysis, resulting inlower accuracy.

To reduce the release of radiogenic He fromthe sediment minerals by excessive heating,Chaduteau et al. (2007) developed an alternativemethod for the analysis of dissolved He inporewater. The sediment is transferred from thecopper tube to an evacuated glass flask by firstbriefly flame-heating the copper tube and sub-sequently flushing it with degassed, hot water.The dissolved He is then extracted from thewater in the glass flask at approximately 40 �Cwith the help of a magnetic stirrer, and is thentransferred into the He analysis system.Although untested, this method would seem tobe suitable for analysing not only dissolved He,but all other dissolved noble gases also.

Tomonaga et al. (2011a) optimised theextraction process of Brennwald et al. (2003) bycentrifuging the sediment samples in the coppertubes to separate the porewater from the sedi-ment matrix. After centrifuging, the part of thecopper tube containing pure porewater is sepa-rated from the compacted sediment at the sedi-ment-water interface using a third clamp. Theporewater in the water-filled part of the coppertube is then analysed in the same way as astandard water sample (e.g., Beyerle et al. 2000).This method completely avoids heating thesediment and therefore guarantees reliableanalysis of the concentration and isotopic sig-nature of the He dissolved in the porewater.

Compared to the method of Chaduteau et al.(2007), the method of Tomonaga et al. (2011a)avoids the extra step of producing water free ofnoble gases, but requires that the sediment sam-ple be centrifuged before analysis. Note also thatone has to be careful to avoid gas fractionationwhen centrifuging gas-rich sediment samples. Ifgas bubbles form in the sample because of gassupersaturation at the temperature and pressureprevailing in the copper tube, the noble gasesoriginally dissolved in the porewater will par-tially escape into these bubbles. The gas bubblesare quantitatively removed from the sedimentmatrix during centrifuging, whereas only afraction of the porewater is separated from thesediment. Centrifuging gas-rich sediments may

therefore result in an undesirable fractionation ofnoble gases between the compacted sediment andthe porewater sample used for analysis, whichincludes the gas headspace.

3.3 Applications in EnvironmentalStudies

3.3.1 PalaeoenvironmentalConditions

Barnes (1979) was the first to suggest that archivedconcentrations of atmospheric noble gases dis-solved in sediment porewater might be useful aspalaeotemperature proxies. Implementation ofthis idea, however, was long hampered by the lackof suitable experimental methods. This obstaclewas removed by the recently developed methodsdescribed in Sect. 3.2.

These new methods were applied for the firsttime by Brennwald et al. (2004) to study thenoble gas record in the sediments of Lake Issyk-Kul (Kyrgyzstan, central Asia), one of theworlds largest high-altitude lakes. The lake hasno outflow and is therefore slightly saline(S ¼ 6 g/kg). Such closed lakes are known toexhibit large changes in lake level and salinity inresponse to changes in local climate (e.g., Fritz1996). Analyses of the lake basin morphologyand sedimentological proxies showed that dur-ing the mid-Holocene the salinity of the lakewater was highly variable and that the lake levellay several hundred metres below its presentlevel (e.g., De Batist et al. 2002; Giralt et al.2003; Ricketts et al. 2001; Romanovsky 2002).

Distinct minima in the concentrations of atmo-spheric noble gases in the sediment porewater wereobserved at approximately 90 cm sediment depth(Fig. 4). The effective diffusivities of the noblegases in the sediment porewater were found to be atleast two orders of magnitude lower than in thebulk water, implying that the noble gas profiles inthe sediment are virtually unaffected by verticaldiffusion in the porewater. The ratio of themolecular diffusivity of Ar in water to that of Xe is2.1. Assuming the diffusive pathways in the porespace to be the same for Ar and Xe, Eqs. (4) and

(5) yield Dzdiff;Ar=Dzdiff;Xe �ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

D0Ar=D0

Xe

p

� 1:5.


Analogously, Dzdiff;Ar=Dzdiff;Kr � 1:3. However,this diffusive separation disagrees with the mea-sured noble gas data, because, within the verticalresolution of the measurements, the respectiveconcentration minima are all found at the samesediment depth. Brennwald et al. (2004) thereforeconcluded that diffusion is strongly limited and isinsufficient to decouple the Ar, Kr and Xe signals inthe porewater from the sediment matrix. The noblegas concentrations at a given sediment depth aretherefore essentially determined by the physicalconditions prevailing in the overlying water at thetime when the sediment was deposited.

The minima in the atmospheric noble gasconcentrations at 90 cm sediment depth indicatethat either the salinity of the water, its temper-ature, or both, were considerably higher duringthe mid-Holocene than they are now. A simplemodel linking the noble gas concentrations inthe deep water of Lake Issyk-Kul to the volumeof the lake, and hence to its water level, allowedBrennwald et al. (2004) to infer from the noblegas record of the porewater that the lake levelwas approximately 300 m lower in the mid-Holocene than it is today (Fig. 5).

In Soppensee, a small Swiss freshwater lakewith a maximum water depth of 27 m, noble gasconcentration profiles in the sediment porewater

90 100Ci / Ci,1

* (%)90 100

Ne Ar Kr Xe

90 100 90 1000 40 80

0

40

80

120

M (%)

Sed

imen

t dep

th (

cm) Cc

Mg-Cc

Cc-H2O

Fig. 4 Mineralogical sediment composition (M) andnoble gas concentrations in the porewater (Ci, norma-lised to present-day ASW noble gas concentrations C�i;1in the open water) as a function of sediment depth

(Brennwald et al. 2004). Cc: calcite. Mg-Cc: magnesiancalcite, which is precipitated in water of high salinity.Cc-H2O: monohydrocalcite

70 75 80 85 90 95 100260

280

300

291 m

307 m

320

ArKrXe

Present level h1: T1, S1, P1

Past level h2:T2, S2, P2

Lake bottom: Ci

T1 T2T

TP

Lake

leve

l h h

h (m

)

Ci / Ci,1 (%)

*

* *

Δ

Fig. 5 Quantification of the change in the water level ofLake Issyk-Kul (Brennwald et al. 2004) based on theconcentrations of dissolved Ar, Kr and Xe in theporewater. ASW concentrations in the water body (C�i )were calculated as a function of the change in lake levelDh. The C�i were normalised to present-day ASWconcentrations C�i;1 calculated from the present-day tem-perature (T1) and salinity (S1) of the overlying water andthe mean atmospheric pressure (P1) at the water surface.T2, S2 and P2 are the respective values of temperature,salinity and pressure during a period of lower lake level inthe past. The annual mean temperature profile in the lake(TP) was used to model C�i because the noble gasconcentrations in the porewater reflect the annual meantemperature of the deep water (Brennwald et al. 2003).The solid parts of the curves represent the analytical 2runcertainty range of the measured minimum concentra-tions in Fig. 4. In the range 291 m \ Dh \ 307 m(horizontal grey bar), all modelled concentrations simul-taneously match the measured minimum concentrationswithin the limits of analytical uncertainty


were used to study and reconstruct the formationof methane bubbles in the sediment and theirrelease into the overlying water body (Brenn-wald et al. 2005). The noble gas concentrationsin the porewater of Soppensee were found to bemuch lower than the ASW concentrations of theoverlying water (up to 75 % Ne depletion, andincreasingly less for Ar, Kr and Xe, which aremore soluble). This depletion is greatest justbelow the sediment surface and decreases stea-dily with sediment depth.

The decrease in noble gas depletion with thegas solubility is indicative of the loss of dissolvednoble gases into a gas phase which was initiallyfree of noble gases (Ballentine et al. 2002; Boschand Mazor 1988; Holzner et al. 2008; Winckleret al. 2000). Brennwald et al. (2005) attributed thisdepletion pattern to the stripping of dissolvednoble gases into gas bubbles forming in the sedi-ment as a result of supersaturation of the pore-water with biogenic CH4. The escape of these gasbubbles from the sediment results in the observednoble gas depletion of the porewater.

The 20Ne/22Ne and 40Ar/36Ar ratios in theSoppensee porewater agree with their respectiveatmospheric equilibrium ratios. Brennwald et al.(2005) assumed that the diffusion of noble gasesfrom the porewater into the gas bubbles wouldresult in their isotopic fractionation in theporewater, as expected from Graham’s Law

(Di=Dj ¼ffiffiffiffiffiffiffiffiffiffiffiffi

mj=mi

p

, where Di and Dj are thediffusion coefficients of two isotopes i and j ofthe same element and mi and mj are theirrespective masses). The lack of such an isotopicfractionation indicates that the observed noblegas depletion is not controlled by the kinetics ofgas partitioning between the porewater and thegas bubbles. In contrast, a secondary solubilityequilibrium between porewater and gas bubblesis attained. Brennwald et al. (2005) thereforeused a simple gas equilibration model to esti-mate the amount of exsolved CH4, which wasfound to correspond to about 25 % of the totalCH4 that can be stored in dissolved form in theSoppensee sediments.

Using an argument similar to that used forLake Issyk-Kul, Brennwald et al. (2005) showed

that the lack of isotope fractionation also indi-cates that the noble gas signature in the pore-water at a given sediment depth reflects theintensity of methane ebullition at the time whenthis sediment was deposited; i.e. that verticaldiffusion had virtually no effect on the noble gasprofiles in the porewater.

However, the molecular dynamics calcula-tions of Bourg and Sposito (2008) suggest thatisotopic fractionation owing to molecular diffu-sion in water might be much smaller thanexpected from Graham’s Law, which has beenvalidated experimentally only for the diffusioncoefficients of 3He and 4He (Jähne et al. 1987),but not for the diffusivities of the Ne or Arisotopes. The lack of experimental data on theextent to which the isotopic fractionation of Neand Ar is affected by diffusion in water does notallow the importance of diffusion for the noblegas profiles in the Soppensee porewater to beconclusively assessed.

3.3.2 Transport and GeochemicalOrigin of Pore Fluids

Dissolved noble gases make good tracers for thetransport of solutes within the sediment porewater.The transient behaviour of radiogenic He isotopesaccumulating in the porewater is particularly use-ful for studying the transport and geochemicalorigin of solutes and fluids in the sediment. In a fewearly studies (Barnes and Bieri 1976; Barnes 1987;Sano and Wakita 1987; Sayles and Jenkins 1982;Winckler 1998), the wireline tool discussed inSect. 3.2 was used to study the fluxes of He isotopesthrough oceanic sediments. Stephenson et al.(1994) used a modified peeper (Sect. 3.2) todetermine He concentrations when studying theinjection of groundwater through the sediment intotwo small lakes.

Noble gas signatures in the sediment porewaterand in the overlying water body of the Black Seahave been used to study the injection of geogenicfluids into the deep water, to determine theirgeochemical origin and to characterise CH4

emissions from high-intensity gas seeps in thevicinity of active mud volcanoes (Holzner et al.2008). Both the He concentrations and their


vertical gradients in the sediment porewater werefound to be much greater near the gas seeps than ata reference site located approximately 200 kmfrom the gas seeps that is unaffected by mudvolcanism. The terrigenic He component of thepore fluids and of the open water body (Fig. 6)shows a 3He/4He ratio of approximately 3.5 � 10�7

near the gas seeps, whereas the terrigenic He at thereference site is enriched in 3He (3He/4He�10�6). These differences in the abundance and inthe isotopic signature of the terrigenic He in thesediment porewater illustrate the variability inthe flux and the geochemical origin of the He (andthe associated pore fluids) released from the BlackSea sediments.

A similar approach was used to study the fluidsreleased from cold CH4 seeps off the coast of NewZealand (Tomonaga 2010). The He-Ne signaturesin the porewater at two sampling sites at OmakereRidge and one site at Rock Garden (near thePacific-Australian subduction zone) show a mix-ture of ASW and terrigenic He. The 3He/4He ratioof the terrigenic He at the two sites at OmakereRidge is approximately 6 � 10�7, which indicatesthat the terrigenic He is mainly of crustal origin. AtRock Garden, the pore fluids have a 3He/4He ratioof approximately 2.5� 10�6, which suggests that

these fluids are enriched with mantle-derived 3He.

At the Congo-Angola margin, the He dis-solved in the sediment pore fluids near cold fluidseeps was found to be a mixture of seawater-derived He and radiogenic He produced in thesediment column or in the underlying crust(Chaduteau et al. 2009). The vertical He con-centration profiles in the porewater and the pore-fluid temperature profiles were used to studypore-fluid circulation and to estimate pore-fluidadvection rates in the sediment. The porewaterHe concentration profiles were shown to bemore sensitive than the porewater temperatureprofiles to pore-fluid advection rates.

At the Mid-Okinawa Trough (Japan),3He/4He and 4He/20Ne ratios in sediment pore-water were used to study earth degassing atsubduction zones by estimating the fluxes ofterrigenic He isotopes through the sediment andinto the ocean (Lan et al. 2010). The 3He fluxesobserved at a hydrothermally active site amountto about 20 % of the 3He fluxes measured at theEast Pacific Rise. Lan et al. (2010) argued thatsubmarine hydrothermal systems in back-arcbasins may therefore contribute a significantamount of helium to the ocean.

0 20 40

0

50

100

150

He (10-8 cm3STP

/g)

Sed

imen

t dep

th (

cm)

0.5 1 1.53He/4He (10-6)

0 1 2 3 4

0.5

1

1.5

2

Ne/4He

3 He/

4 He

(10-6

)

1

0.35

Air-saturateddeep water

Top et al.(1990)

Mud volcano source

Reference profilesCTD108CTD109CTD110

Mean deep-water valueGC14

Sediment porewater (gravity cores) Open water (CTD profiles)

GC17GC41

(a) (b) (c)

Fig. 6 Noble gas signatures in the sediment porewater(squares) and the open water body (circles, triangle) ofthe Black Sea, measured near active gas seeps at theSorokin Trough (sediment cores GC17 and GC41, open-water profiles CTD109 and CTD110) and at a referencesite not affected by outgassing (GC14 and CTD108). a Heconcentrations in the sediment porewater. b 3He/4Heisotope ratios in the sediment porewater. c The 3He/4He

ratio as a function of the Ne/4He ratio for the sedimentporewater, the open water at the seep area and the meanopen-water reference profile (dashed line). Straight linesindicate mixing between ASW and a seafloor source witha 3He/4He ratio of 10�6 (dotted line) as determined byTop et al. (1990) for the southern Black Sea, and with amud-volcano source with an estimated 3He/4He ratio of3.5�10�7 (solid line). After Holzner et al. (2008)


In Lake Van (eastern Anatolia, Turkey), alarge, terminal, saline soda lake located in aregion of high tectonic and volcanic activity,Tomonaga et al. (2011b) studied the flux ofterrigenic He through the sediment. Analysis ofthe He profiles in 24 sediment cores taken atdifferent sites in the lake showed that the He fluxvaries strongly within the lake basin, from0.4� 108 atoms/m2/s to 42� 108 atoms/m2/s. Thelargest He fluxes were found at the steep bordersof the central, deep part of the lake basin (sta-tions S1, S2, and S3 in Fig. 7). The isotope ratiofor the terrigenic He is essentially the same inall sediment cores (3He/4He�(2.6–4.1)� 10�6),which suggests that this He is a mixture ofcrustal He and mantle He originating from asingle, sub-continental source. Tomonaga et al.(2011b) argued that the release of He from the

underlying lithosphere is fostered by faultstructures that are most likely related to theongoing subsidence of the circular main basin ofthe lake and to volcanic activity. This supportsthe hypothesis that the circular-shaped deepbasin was formed by the collapse of an ancientcaldera (Litt et al. 2009).

In the estuary of the St. Lawrence River(Québec, Canada), Pitre and Pinti (2010) studiedthe use of dissolved atmospheric noble gases insediment porewater as proxies for the dynamicsof dissolved or gaseous N2 produced by nitratereduction in the sediment. In contrast to previouswork, large excesses of atmospheric noble gaseswith respect to ASW were observed in theporewater samples of these estuarine sediments.The excess increased with increasing atomicmass, which led Pitre and Pinti (2010) to the

50

5050

50

50

50

50

50

100

100 100

100

100

100100

150

150

150

150

150

150

200

200200

200

200200

250

250250

250

300

300

300300

350

350350

400

400

400

Longitude (°E)

Latit

ude

(°N

)

Van

Erciş

Ahlat

Tatvan

Nemrut H3

D2

L6

L1

H4

L3

H7

L5H2

H1

H6

L12

S2 L9

L11

S3

H5

L7

L8 D1

L2

L4

S1

L10

Istanbul

Ankara

Izmir

Bursa

Adana Batman

Turkey

42.4

38.3

38.4

38.5

38.6

38.7

38.8

38.9

39.0

42.6 42.8 43.0 43.2 43.4

S1-3

H1-7

L1-12

D1-2

Volcanicrocks

Bitlismassif

Faults

Fig. 7 Geological map of Lake Van, showing thebathymetry of the lake basin and the sediment samplingsites (after Tomonaga et al. 2011b). (L) low He fluxes.

(H) high He fluxes. (S) ‘‘hot spots’’ with highest He fluxes.(D) noble gas concentrations showing degassing artefacts,possibly caused by bubble formation during sampling


hypothesis that the sediments were enrichedwith noble gases as a result of their sorption onto clay minerals or organic matter in thesediment.

3.3.3 Diffusion and TrappingMechanisms

Some of the data discussed in Sect. 3.3.1 showthat diffusion does not smooth out the noble gasprofiles in the sediment enough to cause theinformation on the environmental history of theoverlying water body to be lost, even over sed-iment depth ranges smaller than the diffusionlengths calculated by Strassmann et al. (2005)(Sect. 3.1). This can only be explained if thecorresponding scaling factors a are severalorders of magnitudes greater than would beexpected from conventional tortuosity models ofunconsolidated sediments.

Although a similar suppression of diffusionhas been observed for He and H2 in the pore-water of compacted clays (Horseman et al.1996), this phenomenon is not commonlyreported for other gases dissolved in the pore-water of slightly compacted lacustrine and oce-anic sediments. While little is known about themechanisms responsible for the suppression ofthe diffusion of noble gases in sediment pore-water, the following conceptual hypotheses canbe put forward as possible explanations:1. Because of the formation of new minerals or

because of a geometric realignment of thesediment grains during sedimentation, com-paction and early diagenesis, the diameter ofthe sediment pores or of the channels con-necting them can be as small as a few lm orless (e.g., Horseman et al. 1996). In this casethe Renkin effect (i.e., the increased viscosityof the water in the vicinity of the pore walls)will result in a reduction of molecular diffusionby several orders of magnitude (Renkin 1954;Grathwohl 1998; Schwarzenbach et al. 2003;Brennwald et al. 2004), as seems to be the casein firn (Beyerle et al. 2003; Huber et al. 2006).

2. A considerable fraction of the pore spacemight consist of ‘‘dead’’ pores; i.e., pores thatare not connected to the main pore spacethrough which diffusive transport occurs on

macroscopic scales. Solutes trapped in thedead pores cannot undergo macroscopictransport through the fully connected porespace. Note that conventional transportmodels axiomatically exclude the possibilityof the occurrence of dead pores (e.g., Berner1975; Imboden 1975; Strassmann et al.2005), although the retention of solutes indead pores results in a strong reduction inoverall diffusivity within the sediment (e.g.,Grathwohl 1998). To our knowledge, how-ever, this axiomatic exclusion of dead poresappears not to be based on solid experimentalevidence and may therefore represent aninappropriate model simplification.

3. Microscopic gas bubbles might act as gasreservoirs. In the presence of such gas bub-bles in the sediment, a large fraction of thenoble gases initially dissolved in the pore-water would escape into these bubbles,because noble gases are only slightly solublein water. This fraction of the noble gas con-tent of the sediment would be excluded frommacroscopic diffusion through the porewater(see also the discussion by Tomonaga 2010).As in the case of the postulated dead-poremechanism, this would result in the effectivediffusion of noble gases, and possibly of othervolatile gases, being strongly suppressed on amacroscopic scale.

4. Noble gases might be adsorbed on to the sed-iment matrix; e.g., on to organic matter (Pitreand Pinti 2010). To our knowledge, the quan-titative sorption of noble gases on to uncon-solidated sediments has not yet been observed.However, if noble gases are indeed adsorbedquantitatively on to the sediment matrix, onlythe fraction of the noble gases that remaindissolved in the porewater would be subject todiffusion, as the adsorbed fraction would beretained by the sediment matrix. This wouldresult in strong retardation of diffusive noblegas transport in the porewater.Up until now, however, a systematic and

conclusive assessment of these hypotheses hasnot been possible because of a lack of experi-mental evidence. Additional studies focusing onthe mechanisms described above would be


required to improve our understanding of howand why macroscopic noble gas diffusion insediment porewater can be attenuated muchmore strongly than would be expected fromconventional tortuosity models.

4 Stalagmites

4.1 Noble Gases in Stalagmite FluidInclusions

Stalagmites are formed in caves by the precipi-tation of calcite from drip water. The activelygrowing stalagmite surface is covered by a thinlayer of drip water on the order of 0.1 mm thick(Dreybrodt 1980). Gas concentrations in this layerattain solubility equilibrium with the cave airwithin seconds to minutes. This rapid gasexchange allows the outgassing of excess CO2,resulting in the precipitation of calcite in the waterlayer and promoting the growth of the stalagmite.Noble gas concentrations in the water layer,however, can be assumed to correspond closely toASW concentrations (Sect. 2.1.1).

During stalagmite growth, minute quantities ofdrip water and cave air are trapped in the bulkcalcite as fluid inclusions, which may contain

water, cave air, or both. The abundance of theinclusions, and the volumetric ratio of air to watercontained within them, vary strongly from stalag-mite to stalagmite, and also differ considerablywithin individual stalagmites (e.g., Kluge et al.2008). Microscopic investigations have shown thatwater and air inclusions differ in size and spatialarrangement within individual stalagmites (Sche-idegger et al. 2010). Water inclusions are foundmainly within the stalagmite calcite crystals, butonly rarely at crystal boundaries (Fig. 8). The waterinclusions usually do not exceed 50 lm in length.The water abundance per unit mass of calcitetypically lies between 0.1 and 1 mg/g (Kendall andBroughton 1978; Schwarcz et al. 1976; Kluge et al.2008). While air inclusions do occur within calcitecrystals (intra-crystalline inclusions), they occurpredominantly along grain boundaries between thecalcite crystals (inter-crystalline inclusions). Intra-crystalline air inclusions are similar in size andshape to water inclusions (Fig. 8), whereas inter-crystalline air inclusions are larger (20–80 lmlong) and more angular (Scheidegger et al. 2010).Air inclusions can account for up to 3 % of a sta-lagmite’s volume (Badertscher et al. 2007; Sche-idegger et al. 2010).

Once a fluid inclusion has been formed, it is nolonger in contact with the cave air. Using the Heand Ar diffusion data of Musset (1969) andCopeland et al. (2007), Kluge (2008) estimatednoble gas diffusivities in calcite at room temper-ature to be about 10�25 m2/s. The diffusion ofnoble gases through the calcite surrounding a fluidinclusion therefore has a negligible effect on thenoble gas concentrations in the inclusions even ontime-scales of several 100 ka. The concentrationsof dissolved noble gases in a given water inclusioncan thus be assumed to reflect the temperature andsalinity of the drip water at the time the inclusionwas formed. The salinity of the drip water enter-ing the cave is usually so low that it has no effecton noble gas solubilities. The concentrations ofnoble gases in water inclusions can thereforeexpected to be related directly and quantitativelyto cave palaeotemperatures.

In most caves, temperatures remain constantthroughout the year at a value corresponding

50 µm

A1

A2W

Crystal boundary

W (with gas bubble)

Fig. 8 Photomicrograph of a thin section from astalagmite (after Scheidegger et al. 2008, 2010). Waterinclusions (W) are located within the calcite crystals.Large air inclusions (A1) are observed at the crystalboundaries, whereas smaller air inclusions (A2) alsooccur within the calcite crystals


approximately to the annual mean air tempera-ture outside the cave (e.g., McDermott et al.2005; Poulson and White 1969; Smithson 1991).Noble gas records in stalagmite water inclusionsare thus expected to allow regional palaeotem-peratures to be reconstructed over long periodsof time. Stalagmites are especially valuable as asource of such information because of theirglobal distribution. This is in contrast to icecores, which can supply similar information, butonly for polar or high-altitude regions.

Stalagmites have therefore become a majorfocus for palaeoclimate studies over the past fewdecades. Stalagmite calcite contains precise, high-resolution d13C, d2H and d18O records coveringtime-scales of up to 105 years (e.g., Badertscheret al. 2011; Cheng et al. 2009; Fleitmann et al.2009; Henderson 2006; Wang et al. 2008). Also,the signatures of d2H and d18O in water inclusionshave been used to study palaeoclimate conditions(Fleitmann et al. 2003; Griffiths et al. 2010; vanBreukelen et al. 2008; Wainer et al. 2011). Thesestable-isotope records are controlled by differentenvironmental variables and processes such astemperature-dependent isotope fractionation dur-ing calcite formation, the local precipitationregime, the hydrological cycle, and amounts ofprecipitation. The complex interplay of thesevariables and processes makes it difficult to inter-pret stalagmite isotope records clearly andunequivocally (e.g., Lachniet 2009). Use of thenoble gas thermometer to provide an independentestimate of the temperature at which stalagmitewater inclusions were formed would therefore notonly provide valuable palaeoclimate informationin its own right; it would also help to overcomesome of the limitations involved in interpretingstalagmite stable-isotope records, thereby con-tributing to exploiting their full potential.

Determination of the concentrations of noblegases dissolved in the water of stalagmite fluidinclusions was until recently not feasible, mainlybecause of the lack of adequate extractionmethods that would allow water and air inclu-sions to be separated. As noble gases are muchmore abundant in air inclusions than in waterinclusions, their concentrations in water

inclusions are often masked by the compara-tively large amounts of noble gases releasedfrom air inclusions during the extraction process.The noble gas excess from the air inclusions ismathematically analogous to the excess-aircomponent in groundwater Eq. (2). Noble gastemperatures in groundwater may be determinedeven in the presence of moderate amounts ofexcess air (e.g., Aeschbach-Hertig et al. 1999).However, if the excess-air component is large(i.e., if NeEA/ NeASWJ 10 in Eq. (2)), it willmask the ASW component to such a degree thatthe noble gas thermometer becomes unreliable.For the successful determination of noble gastemperatures from stalagmite water, it is ofparamount importance to minimise the propor-tion of noble gases in the final sample that arederived from air inclusions.


Different approaches have been used to extractnoble gases from stalagmite fluid inclusions(Sects. 4.2.2 and 4.2.3). Ayliffe et al. (1993) andKluge et al. (2008) crushed stalagmites in vacuoto release noble gases from fluid inclusions. Klugeet al. (2008) applied this technique successfully toa stalagmite from Bunker Cave (Germany) thathad an exceptionally low air-water volume ratio.However, the authors could not derive meaningfulnoble gas temperatures by applying their crushingmethod to more typical stalagmites with higherair-water volume ratios, because the noble gasesreleased from the air inclusions masked the noblegas concentrations in the water inclusions.

Scheidegger et al. (2010, 2011) thereforeexplored alternative approaches that wouldreduce the contribution of noble gases derivedfrom air inclusions to the final result. Theseapproaches were all based on the authors’observation that most of the air inclusions instalagmites occur along grain boundaries and canbe opened preferentially by gently crushing asample to yield grains approximately the samesize as that of its intrinsic crystals, whereasthe intra-crystalline water inclusions remain


mostly intact. The noble gases extracted from thecalcite in a second extraction step are thus derivedprimarily from water inclusions. The resultingnoble gas signatures indeed revealed a muchlower contribution of noble gases from air

inclusions, making feasible a mathematical cor-rection of the remaining air-related noblegas component (Scheidegger et al. 2010).Unfortunately, however, the procedures used toreduce the amount of noble gases released from

Sof

ular

Dim

arsh

imV

allo

rbe

Pit

200 µm 2 mm 100 µm

I II III

W

A

AW

W

A

W

W

A

Fig. 9 Petrographic information on stalagmites fromDimarshim Cave and Pit Cave (both Socotra Island,Yemen), Sofular Cave (Turkey), and Vallorbe Cave(Switzerland) (after Scheidegger 2011). I SEM imagesshowing the calcite texture of freshly crushed fractions.

II Photographs of thick sections taken using an opticalmicroscope at low magnification in cross-polarised light.III Photographs of thick sections taken using an opticalmicroscope showing typical water (W) and air (A)inclusions


the air inclusions introduce other complexitiesinto the noble gas signatures, thus still oftenpreventing the straightforward calculation ofmeaningful noble gas temperatures (Sect. 4.3).

A seemingly obvious way of avoiding theproblems associated with the release of noblegases from air inclusions would be to spot-drillindividual water inclusions in vacuo with a laser.However, because of the small amount of watercontained in a single inclusion and the low con-centrations of noble gases in this water, the noblegas content of each inclusion is very small. Toobtain amounts large enough for all stable noblegases to be analysed reliably, 104–105 waterinclusions would have to be opened up (assumingtypical detection limits for the mass-spectrometricnoble gas analysis system), thus rendering thisapproach impracticable.

4.2.1 Sample SelectionAs mentioned above, not all stalagmite samplesare equally suited for the determination of noblegas temperatures. To be suitable, samples shouldhave a water content of about 0.1 mg/g or higher(e.g. Kluge et al. 2008) and, equally importantly,the air-water volume ratio should not exceed acertain limit to avoid the ASW component fromthe water inclusions being masked by the noblegases released from the air inclusions. Klugeet al. (2008) give as an upper limit an air-watervolume ratio of 0.5.

Microscopic investigation of the samples to beanalysed for noble gases is therefore highly rec-ommended. Scheidegger et al. (2011) used scan-ning electron microscopy and optical microscopyto study samples of different stalagmites. Aselection of the images obtained is illustrated inFig. 9. In addition to yielding information on thesize and spatial distribution of air and waterinclusions, these images also provide informationon the size of individual calcite crystals. Thisinformation is essential for determining the grainsize to which a given stalagmite sample needs tobe pre-crushed in order to separate air and waterinclusions most effectively (Sect. 4.2.2). The sizeof water inclusions in comparison to the crystalsize and texture of the host calcite can also provide

information about the temperature required toassure quantitative gas extraction during heating(Sect. 4.2.3).

4.2.2 Crushing

Crushing in Vacuo

Several different devices for crushing a stalag-mite sample in vacuo have been described in theliterature. Kluge et al. (2008) used a cylindricalcell containing a steel ball, controlled by anexternal magnet, as a crusher. Badertscher et al.(2007) and Kluge et al. (2008) reported experi-ments in which a sample is placed in a coppertube which is evacuated and then squeezed witha vice to crush the sample. Scheidegger et al.(2010) used a pestle-operated vacuum crusher(Fig. 10) in which the pestle and the cylinderholding the sample are connected via a flexiblebellows. The sample is crushed by striking the

Flexible bellows

Connection to vacuum system

Knife-edge aluminium gasket

(closed with chain clamps)

Pestle

Stalagmite sample

30 c

m

Stainless steel tube

Fig. 10 Stainless steel vacuum crusher used to extractgases from fluid inclusions (after Scheidegger 2011). Thepestle is connected to the main chamber via a flexiblebellows. The sample is crushed by striking the top of thepestle with a hammer


top of the pestle with a hammer. Following thecrushing, the gases released from the sampleare allowed to expand into a gas purification lineleading to the noble gas mass spectrometer.

In an attempt to separate the gases releasedfrom the air inclusions from those released fromthe water inclusions, Scheidegger et al. (2010)applied several consecutive crushing steps toeach sample, often followed by a final heatingstep (Sect. 4.2.3).

Crushing in a Gas Atmosphere

For stalagmites with typical air-water volumeratios, simple stepwise crushing in vacuo oftendoes not allow the noble gases contained in waterinclusions to be separated sufficiently well fromthe noble gases contained in air inclusions.Scheidegger et al. (2010, 2011) thereforeexplored the possibility of crushing stalagmitesamples to a predefined grain size in different gasatmospheres. The appropriate grain size (e.g.,350–700 lm, Scheidegger et al. 2011), whichshould be close to the natural crystal size of thesample, is determined by microscopic inspectionprior to crushing (Sect. 4.2.1). The sample iscrushed using a stainless-steel mortar and pestle.After each gentle hammer stroke on the pestle, thesample is sieved to separate crystals of the desiredsize from larger crystal aggregates, and the largecrystal aggregates are then crushed again. Thecrushing and sieving process is repeated until thewhole sample consists of grains no larger than thepredefined grain size. The air content of theresulting grains is 102–103 lower than that of abulk stalagmite sample, because the air inclusionslocated at the grain boundaries are indeed pref-erentially opened during the crushing process(Scheidegger et al. 2011).

After crushing and sieving stalagmite samplesin air and in a glove box flushed with N2 (of purity6.0), Scheidegger et al. (2010) found that in bothcases residual atmospheric heavy noble gaseswere adsorbed on to the freshly produced grainsurfaces. During the subsequent extraction of

noble gases from these grains by heating (Sect.4.2.3), the adsorbed noble gases were releasedtogether with the noble gases extracted from thefluid inclusions (Sect. 4.3.2). This increased theresulting concentrations of heavy noble gasesconsiderably, so that in most cases, no meaningfulnoble gas temperature could be derived from theresulting data. Flushing the glove box with He (ofpurity 6.0) and further reducing the concentra-tions of residual heavy noble gases in the Heatmosphere with a sorption pump installed in theglove box reduced the Kr and Xe residuals tonegligible levels (Scheidegger et al. 2011). Toprevent a crushed sample being exposed to airwhen transferring it to the noble gas purificationline, it was first loaded into a stainless steel con-tainer sealed with a valve before removing it fromthe glove box.

4.2.3 HeatingKluge et al. (2008) heated their vacuum-crushedsamples to 50 �C to quantitatively transfer theextracted water into the analytical system (Sect.4.2.4). In contrast, Scheidegger et al. (2010)heated their crushed samples up to 600 �C to openthe intra-crystalline inclusions, which wereassumed to be filled predominantly with water.Scheidegger et al. (2010) emphasised that theapplied temperature must not exceed the thresh-old at which excessive amounts of gases such asCO2 or H2 are formed, as these prevent reliabledetermination of the amount of water released(Sect. 4.2.4). CO2 is produced during thedecomposition of calcite to CaO and CO2 attemperatures J600 �C (Faust 1950). H2 is pro-duced during the interaction of water releasedfrom the sample with the hot metal surfaces of thevacuum sample container. Scheidegger et al.(2010) found that at temperatures J400 �C, thepartial pressure of H2 and the corresponding (non-stoichiometric) loss of H2O exceed the limitsbelow which the amount of water released fromthe sample can be reliably determined (Sect.4.2.4). Best results were achieved by heating the


sample for 1 h to temperatures between 300 �Cand 400 �C (Scheidegger et al. 2011).

4.2.4 Quantification of the WaterMass

Due to the low water content of stalagmites, typ-ical stalagmite samples of 1–5 g yield no morethan few milligrammes of water upon crushing orheating. Accurate determination of such a smallmass of water is challenging and cannot easily beaccomplished merely by weighing a samplebefore and after the water is extracted. Instead, themass of water released is determined manomet-rically (Ayliffe et al. 1993; Kluge et al. 2008;Scheidegger et al. 2010). This requires theextracted water to be transferred quantitatively toa tempered expansion vessel large enough toprevent the water vapour from condensing. Apressure gauge is then used to determine thevapour pressure inside this vessel. Using theideal-gas law, the water mass is then calculatedfrom the vapour pressure, the temperature, and thevolume of the expansion vessel.

To avoid bias in the determination of the massof water, the gas pressure in the expansion vesselmust be generated essentially by the water vapouronly. Formation of excessive amounts of othergases (e.g., CO2 or H2) must therefore be avoidedduring the extraction process (Sect. 4.2.3). If thisrequirement is met, the manometric methodallows the mass of a few milligrammes of water tobe determined with a standard error of about 1 %(Scheidegger et al. 2010).

4.3 First Applications of the NobleGas Thermometer

The occurrence of both air and water inclusionsin stalagmites suggests that the noble gas sig-natures in stalagmite samples should reflect asimple binary mixture of air and ASW. Noblegas data from Bunker Cave stalagmite sampleswith exceptionally low air-water volume ratiosare indeed consistent with this expectation (Sect.4.3.1). However, results from other stalagmite

samples with more typical air-water volumeratios indicate a more complex picture involvingadditional gas components, such as fractionatedair or lattice-trapped noble gases (Sect. 4.3.2).

4.3.1 Stalagmites from Bunker Cave(Germany)

Kluge et al. (2008) studied two stalagmites fromBunker Cave (Germany) with air-water volumeratios of 0.03–0.08, which is exceptionally low.It was therefore not necessary to reduce the aircontent of these samples by pre-crushing, andprecise noble gas temperatures could be derivedfrom the measured Ne, Ar, Kr and Xe con-centrations as described in Sect. 2.1.3.

From six samples of one Bunker Cave stalagmitecovering the time frame from 10.8–11.7 ka BP, amean noble gas temperature of 2.9 �C with a stan-dard deviation of 0.7 �C was determined. The noblegas temperatures derived from the different samplesagreed with each other within their error limits. Onesample from a second stalagmite with a U/Th age of1.3 � 0.3 ka yielded a noble gas temperature of7.1 � 0.8 �C. The temperature difference of about4 �C agrees with the results of other palaeotem-perature reconstructions (e.g., Davis et al. 2003),which imply similar temperature changes in centraland western Europe. However, while the absolutenoble gas temperatures obtained are not unreason-able for central Europe, Kluge et al. (2008) couldnot exclude a possible bias, because their valuesseem to be slightly lower than would be expectedfrom other palaeotemperature reconstructions in theBunker Cave region. Kluge et al. (2008) thereforeemphasised that the accuracy of noble gas temper-atures derived from stalagmite fluid inclusionsneeds to be tested on modern stalagmites, for whicha direct comparison with instrumental cave tem-perature records would be possible.

4.3.2 Stalagmites from CentralEurope and the Middle East

To test different noble gas extraction methods,Scheidegger et al. (2010, 2011) determinednoble gas concentrations in more than 50


stalagmite samples from Switzerland (Blättler-loch, Beatus Cave, Feés Cave, Vallorbe Cave),Germany (Bunker Cave), Turkey (SofularCave), Oman (Qunf Cave), and Yemen (Di-marshim Cave) covering a variety of climaticregions and time ranges (0–100 ka BP). Theanalytical errors of the noble gas concentrationsranged between 2 and 5 %.

Pre-crushing did indeed substantially reduce thenoble gas contributions from air inclusions relativeto those from water inclusions. However, it wasstill not possible to derive statistically acceptablenoble gas temperatures by regression from the Ne,Ar, Kr, and Xe concentrations as described in Sect.2.1.3. This was attributed to the fact that Eq. (2)assumes a binary mixture of ASW and air, whereasthe results also showed contributions from addi-tional noble gas components, such as adsorbed air(Sect. 4.2.2) or He and Ne trapped in the calcitelattice (see below). The elemental compositionsof these additional components are poorly con-strained and therefore cannot be included quanti-tatively in Eq. (2), thus precluding the robustdetermination of noble gas temperatures.

He and Ne Trapped in the Calcite Lattice?

In addition to the ASW and air components,excesses of He and Ne have been observed in var-ious stalagmites (Ayliffe et al. 1993; Kluge 2008;Scheidegger et al. 2010) regardless of the extraction

method employed (i.e., crushing in vacuo, crushingin a gas atmosphere, or heating; see Fig. 11). The Heand Ne excesses therefore seem to be present nat-urally in the stalagmite samples.

Ayliffe et al. (1993) and Scheidegger et al.(2010) hypothesised that the excesses of He andNe might be due to the trapping of He and Neatoms in crystallographic voids within the cal-cite structure during crystal growth. The maxi-mum diameter of a sphere that would fit into

-1

-0.5

0

0.5

1

1.5

He Ne Ar

Crushing Heating

Kr Xe He Ne Ar Kr Xe

log(

r ) i

(a) (b)

Fig. 11 Normalised elemental ratios ri observed(a) after crushing stalagmite samples in vacuo (Sect.4.2.2), and (b) after subsequently heating the samesamples (Sect. 4.2.3), where ri ¼ ði=ArÞsample=ði=ArÞair

with i ¼ He, Ne, Ar, Kr, Xe (after Scheidegger et al.2010). The noble gas compositions of ASW (watertemperatures 0–30 �C, grey areas) and of air (dashedlines) are shown for comparison

4

0.6

1.2

1.8

Xe / Kr0.20.1

pre-crushed in N 2

pre-crushed in He

pre-crushed in air

vacuum-crushed

Air

ASW (27ºC) Adsorbed Air

Ar

adso

rptio

n

Air adsorption

Ar/

Kr

( 1

0 )

Fig. 12 Relationship between the Ar/Kr and Xe/Krratios in the gas extracted from Dimarshim stalagmitesamples using different pre-crushing methods (pre-crush-ing in air, in N2, in extra-pure He, or in vacuo). The greyarea indicates the Ar-Kr-Xe composition of air adsorbedon to calcite grains (data on adsorbed air extends tohigher Xe/Kr ratios lying outside the range of the plot;see Scherer et al. 1994; Ozima and Podosek 2002)


these voids is approximately 3 Å (Scheideggeret al. 2010). Such voids would be large enoughto accommodate an atom of He or Ne, but not ofAr, Kr or Xe, which have diameters [3 Å(Table 1). This hypothesis is supported by evi-dence from the Martian meteorite GaG 476, inwhich substantial Ne excesses (‘‘extra Ne’’)were found (Mohapatra et al. 2009). This extraNe is likely to be of terrestrial atmospheric ori-gin: during the process of recrystallisation thataccompanied terrestrial weathering, atmosphericNe was probably trapped in newly formed cal-cite crystals (Ulrich Ott, 2009, Max PlanckInstitute for Chemistry, Mainz, Germany, per-sonal communication).

Scheidegger et al. (2010) observed that theHe/Ne ratio of the excess He and Ne resultingfrom gas extraction by heating was higher thanthat resulting from extraction by crushing (Fig.11). They attributed this to He enrichmentresulting from temperature-enhanced diffusionfrom the calcite, as the diffusivity of He is higherthan that of Ne.

Ar-Kr-Xe Signatures in Fluid Inclusions

Figure 12 shows a typical example of the Ar-Kr-Xe signatures, based on samples from a Di-marshim Cave stalagmite, to which Scheideggeret al. (2010, 2011) had applied the whole suite ofextraction methods discussed in Sects. 4.2.2 and4.2.3. The Ar-Kr-Xe data from most samples arelocated within the mixing triangle of air, ASW,and adsorbed air (the latter with a broad range ofelemental compositions). Samples pre-crushedin air clearly show the effect of the adsorption ofthe heavy noble gases on to the freshly producedgrain surfaces (Scheidegger et al. 2010). Sam-ples pre-crushed in N2 suffer from Ar excessesresulting from excessive residual Ar in the N2

protective gas. The Ar-Kr-Xe composition in thevacuum-crushed samples is similar to that of airbecause the air released from the air inclusionsmasks the ASW component from the waterinclusions. The Ar-Kr-Xe composition of thesamples pre-crushed in extra-pure He is closestto that of ASW, and many of these samplesshow Xe/Kr ratios indistinguishable from that ofASW. This led Scheidegger et al. (2010, 2011)

to conclude that pre-crushing in extra-pure Hesubstantially reduces the contribution of noblegases derived from air inclusions and alsoreduces the adsorption of Kr and Xe to negligi-ble levels. They therefore considered thismethod to be the most suitable for reliable noblegas temperature determination, although arte-facts cannot always be ruled out. Such artefactscan result, for instance, from the adsorption ofresidual heavy noble gases from the protectiveHe atmosphere (Sofular Cave samples werecrushed without using a sorption pump in theglove box), or from Kr and Xe deficits associ-ated with the incomplete extraction of noblegases from the fluid inclusions (possibly becauseof insufficient heating). Nevertheless, 12 out of30 noble gas temperatures calculated from theKr and Xe concentrations in an extended Di-marshim Cave data set (Scheidegger 2011) agreeto within analytical error with the modern cavetemperature of 27 �C. This cave temperature hasremained approximately constant since the mid-Holocene (e.g., Wanner et al. 2008). Likewise, 3out of 9 noble gas temperatures derived from Krand Xe concentrations in stalagmite samplesfrom Sofular Cave are identical to the moderncave temperature of 12 �C. Also, Kr and Xeconcentrations in 4 out of 7 samples from Val-lorbe Cave are conceptually consistent with abinary mixture of air and ASW.

5 Summary, Outlook and FutureResearch

The recent methodological advances in theextraction of noble gases from the porewater ofunconsolidated sediments (Sect. 3.2) representan essential step forward in overcoming theexperimental limitations that have hampered thedevelopment of terrestrial noble gas geochem-istry in sediment porewater for decades. Theexperimental methods described in Sect. 3.2 canbe employed by any noble gas laboratoryequipped for the analysis of terrestrial watersamples, thus allowing the laboratory to expandits activities to include the analysis of theporewater of unconsolidated sediments.


From a conceptual point of view, the keyconclusion of recent sediment porewater studiesis that in some sediments the noble gases diffu-sivities in the sediment porewater are similar totheir corresponding molecular diffusivities inbulk water. In other sediments, however, thenoble gases are quantitatively trapped in thesediment and diffusion is therefore stronglysuppressed (Sects. 3.3.1 and 3.3.3). This trap-ping results in a stratigraphical control of thenoble gas record in the sediment, which allows atime-scale to be associated with it. However, themechanisms responsible for trapping the noblegases have yet to be identified. A mechanisticunderstanding of the suppression of diffusionwould be required to fully establish the con-ceptual basis required for noble gases to beutilised as proxies for environmental conditionsor as tracers of pore-fluid transport.

The physical mechanisms responsible for thetrapping of noble gases in the porewater ofunconsolidated sediments are not yet fullyunderstood. However, the experimental toolsnecessary to study the noble noble gas isotopesdissolved in sediment porewater are now avail-able. Specifically, it is now possible to assess thefeasibility of using the concentrations of atmo-spheric noble gases in the porewater to recon-struct the geochemical evolution of the porefluids, and to reconstruct past environmentalconditions (such as the palaeosalinity of theocean). Recently, during a scientific drillingprogramme in Lake Van (Litt et al. 2009, 2011),sediment samples for noble gas analysis wereretrieved at depths of more than 200 m belowthe sediment surface. The highly compactedbulk sediments were squeezed into copper tubesusing a hydraulic press. Such a hydraulicsqueezer can, in principle, be used during anyscientific drilling campaign in which lacustrineor oceanic sediments are recovered (e.g., theIntegrated Ocean Drilling Program, IODP, or theInternational Continental Scientific DrillingProgram, ICDP). Of particular interest are oce-anic sediments from marginal seas, whose geo-chemical and physical conditions are expected toreact very sensitively to climate change andtectonic activity. Preliminary results from the

Sea of Japan (East Sea) suggest that the con-centrations of atmospheric noble gases in thesediment porewater might reflect changes infreshwater input and in the mixing conditions ofthe water body during the last glaciation, asdiscussed by Lee and Nam (2003).

The sampling techniques developed for theanalysis of noble gases in lacustrine and oceanicsediments might also be useful in groundwaterstudies. Up until now, groundwater dating usingtransient tracers (e.g., 3H/3He, terrigenic He,CFCs, SF6, etc.), and the reconstruction of envi-ronmental conditions from atmospheric noble gasconcentrations, have been restricted to watersamples taken from groundwater wells tappingflowing groundwater. However, availablegroundwater wells are often not located at theoptimum position to address a specific scientificproblem. Also, the groundwater flowing into thewells usually originates from a large and oftenpoorly defined domain around the well. A betterspatial resolution of the information on ground-water flow paths, water residence time and theenvironmental conditions pertaining throughoutthe aquifer is therefore desirable in manygroundwater studies. For instance, studies ongroundwater contaminants and their rates of nat-ural attenuation and removal from the ground-water (e.g., Aeppli et al. 2010; Amaral et al. 2010;Klump et al. 2006) would greatly benefit from theavailability of spatially accurate and highlyresolved information on water residence time.One way forward in improving the spatial reso-lution would be to obtain drill cores from aquifers,or even adjacent aquicludes, at locations that aredetermined by the specific scientific problem to beaddressed (see also Mazurek et al. 2011 for areview of similar porewater tracer analyses in drillcores from ‘tight’ rock formations). Porewatersamples for the analysis of dissolved gases at highspatial resolution could then be taken from thesedrill cores at the exact depths required by adaptingthe sampling techniques developed for noble gasanalysis in lacustrine and oceanic sediments; e.g.,using a hydraulic porewater squeezer.

Stalagmite fluid inclusions, viewed as a noblegas archive, have great potential in palaeoenvi-ronmental research. The recent experimental


advances described in Sect. 4.2 now make pos-sible the precise and accurate determination ofthe concentrations of noble gases dissolved inthe minute amounts of water contained in theseinclusions. It has become clear that the concen-trations of dissolved noble gases in stalagmitewater inclusions do indeed contain useful pal-aeotemperature information. This has beendemonstrated convincingly for samples withvery low air-water volume ratios and also forsome samples with more typical air-water vol-ume ratios (Sect. 4.3).

However, despite recent experimental pro-gress it is not yet possible to use stalagmites withtypical air-water volume ratios for the routinedetermination of noble gas temperatures that areof immediate relevance to state-of-the-art palae-otemperature reconstruction. This is because allextraction procedures that have been suggested sofar either release too much air from the fluidinclusions or introduce artefacts that affect thedetermination of the noble gas concentrations inthe water inclusions. In the case of Kr and Xe,contamination by adsorption on to the samplegrains is effectively reduced by pre-crushing thestalagmite samples in extra-pure He. However,this is not true for Ar. Extracting the noble gasesby crushing bulk stalagmite samples in vacuowould prevent such adsorption effects altogether.However, the large amounts of noble gasesreleased from the air inclusions that are opened bycrushing in vacuo usually mask the relativelysmall amounts of noble gases extracted from thewater inclusions. This is because existing vacuumcrushers do not allow the noble gases derivedfrom air inclusions to be removed beforeextracting the noble gases from water inclusions.An obvious step towards routine noble gas anal-ysis for the robust determination of noble gastemperatures would therefore be to pre-crush andthen sieve out stalagmite grains of appropriatesizes in vacuo. Carrying out both pre-crushingand sieving in vacuo would allow uncontami-nated calcite crystals of a suitable grain size to beprepared so that the noble gases can then beextracted from the intra-crystalline water inclu-sions (Vogel et al. 2012). Combining the crush-ing, sieving and subsequent heating steps in

vacuo is likely to be technically challenging.However, in light of the great potential that sta-lagmite water inclusions have as a noble gasarchive for palaeotemperature reconstruction, anattempt at implementing such an all-vacuumprocedure would seem to be justified.

It is clear that the concentrations of dissolvednoble gases in stalagmite water inclusions canprovide valuable information on palaeotempera-tures. However, preliminary studies have shownthat the gases contained in stalagmite air inclusionsshould perhaps not be viewed merely as ‘‘contam-ination’’ that complicates the determination ofnoble gas concentrations in the water inclusions, butthat they may possibly also contain additionalinformation that can aid in interpreting the noble gasconcentrations in the water inclusions. By applyingthe experimental techniques of trace-gas analysis inice cores to stalagmite samples, Badertscher et al.(2007) and Scheidegger (2011) found the airinclusions to be enriched with CO2 and CH4 relativeto atmospheric air. Gas inclusions in stalagmitesfrom poorly ventilated caves showed volumetricCO2 concentrations of up to � 10 % (Badertscher2007). An increased CO2 partial pressure at thestalagmite surface would reduce the partial pres-sures of the noble gases during gas-water parti-tioning before separation of the water inclusionsfrom the cave air. The increased CO2 partial pres-sure would therefore result in lower noble gasconcentrations, which would need to be taken intoaccount when calculating noble gas temperatures.

In addition, the trace gases in air inclusionsmight contain useful information about theevolution of cave climates. Badertscher et al.(2007) and Scheidegger (2011) observed that theconcentrations and isotopic compositions ofCO2 and CH4 changed with the age of the sta-lagmite samples. The gas inclusions thus seemto record the CO2 and CH4 composition of thecave air, which is, for instance, related to theprocesses and rates of biogeochemical turnoverin the soil overlying the cave.

It would seem obvious that the new experi-mental methods described here should also beapplied to determine noble gas concentrations inminute amounts of water in other materials con-taining fluid inclusions. Papp et al. (2010) and


Scheidegger (2011) applied these methods toanalyse noble gases in fluid inclusions in molluscshells and corals. However, Scheidegger (2011)found that such biogenic carbonates seem to havevery low noble gas concentrations. Shells areknown to contain organically bound water, whichis formed by biochemical processes and has neverbeen in contact with the surrounding water body.This organically bound water is thereforeexpected to exhibit lower noble gas concentra-tions than the surrounding water body. In order toexploit the noble gas concentrations in biologicalshells as proxies for environmental conditions,new methods would need to be developed toisolate those parts of the organism which containwater that is unaffected by biological processesfrom the parts of the organism which containwater that is affected by such processes.

The newly developed methods have also beenapplied to the porewater of consolidated claysthat have been targeted as possible host rocks fornuclear waste deposits (Scheidegger 2011). Thisporewater was shown to be strongly enriched inradiogenic 4He and 40Ar, indicating a long res-idence time of the porewater within the clays.However, the atmospheric noble gas concentra-tions determined exceeded the expected atmo-spheric equilibrium concentrations. Scheidegger(2011) speculated that the clay samples losewater preferentially as a result of surface dryingduring storage and during evacuation of the gasextraction system, whereas the (heavy) noblegases are retained in the sample (see also, e.g.,Osenbrück et al. 1998; Rübel et al. 2002; Ma-zurek et al. 2011). Although it is too early todraw final conclusions from these preliminaryresults, the data do seem to imply that the con-centrations of noble gases dissolved in theporewater of consolidated sediments reflect thehydrogeochemical origin of the porewater andmight allow the characteristic residence time ofpore fluids in formations with very low perme-ability to be estimated. Such analyses mighttherefore provide assistance in studying thetemporal evolution of sedimentary basins.

The new techniques for analysing noble gasesin the porewater of unconsolidated sedimentsmake possible a new experimental approach to the

study of gas/liquid partitioning in other uncon-ventional ‘‘aquatic’’ environments, such as bloodor other body fluids. We sampled human blood incopper tubes, where the blood coagulated. Theblood plasma was separated from the coagulatedblood (erythrocytes) for noble gas analysis usingthe centrifuging method of Tomonaga et al.(2011a). For comparison, we also analysed thenoble gas concentrations in the remaining eryth-rocyte fraction using the extrusion method ofBrennwald et al. (2003). The concentrations of Krand Xe in the plasma exceeded their respectiveASW concentrations in fresh water, whereas Heand Ne concentrations in the plasma were slightlylower than ASW concentrations (Fig. 13). Inaddition, the erythrocyte fraction showed anenrichment of all atmospheric noble gases relativeto the plasma. These results indicate clearly thepotential that noble gases possess as tracers tostudy gas partitioning in body liquids and livingtissues; for instance, in analysing gas-exchangeprocesses in the lung.

These examples show that the new experi-mental methods are powerful tools for studyinggas/liquid partitioning in new and sometimesunusual systems and environments. These newmethods open up entirely new fields and appli-cations in which terrestrial noble gas geochem-istry can play an important role in tracingphysical processes—we just have to free ourminds and go and find them.

He Ne Ar Kr Xe

2.0

1.5

1.0

Plasma

0.5

0

C i

C i*

/

Erythrocytes

Fig. 13 Noble gas concentrations in human bloodplasma and in the erythrocyte fraction remaining aftercentrifuging (Ci, see text), normalised to the relevantASW concentrations in fresh water (C�i ) computed usingT ¼ 36:5 �C and Patm ¼ 0:973 atm (the atmosphericpressure at the altitude where the blood samples weretaken)


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http://dx.doi.org/10.1016/0022-1694(94)90212-7


http://dx.doi.org/10.1080/10256010902871929






http://dx.doi.org/10.1038/nature06692

http://dx.doi.org/10.1016/S0016-7037(99)00441-X

Noble Gases as Environmental Tracers in Sediment Porewaters … · 2015-05-12 · Noble Gases as...

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