Elemental Proxies For Paleosalinity

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Elemental proxies for paleosalinity analysis of ancient shales and mudrocks
Article in Geochimica et Cosmochimica Acta · July 2019

DOI: 10.1016/j.gca.2019.06.034
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Geochimica et Cosmochimica Acta xxx (2019) xxx–xxx
www.elsevier.com/locate/gca
Elemental proxies for paleosalinity analysis of ancient shales

and mudrocks
Wei Wei a,b,⇑, Thomas J. Algeo b,c,d,⇑
a
Faculty of Earth Resources, China University of Geosciences (Wuhan), Wuhan 430074, China
b
Department of Geology, University of Cincinnati, Cincinnati, Ohio 45221-0013, USA
c
State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China
d
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074, China
Received 24 January 2019; accepted in revised form 20 June 2019; available online xxxx
Abstract
Salinity is a fundamental property of watermasses that is useful in paleoenvironmental and paleoecological studies, yet the
theory of application of geochemical proxies to paleosalinity reconstruction is underdeveloped. Here, we explore the use of
three elemental ratios for paleosalinity reconstruction: boron/gallium (B/Ga), strontium/barium (Sr/Ba), and sulfur/total
organic carbon (S/TOC) ratios. We compiled a large set of modern aqueous and sedimentary chemical data representing a
range of salinity facies (i.e., freshwater, brackish, marine) in order to test the relationships of these proxies to ambient water-
mass salinity and to determine their viability for paleosalinity analysis. Sediment data were limited to fine-grained siliciclastic
units (muds/shales/mudstones) without significant carbonate content, in which the elements of interest were mainly acquired
through adsorption of dissolved species, forging a connection between elemental proxy values and watermass chemistry. In
modern systems, watermass salinity is correlated with these proxies, yielding r of +0.99 and +0.76 for aqueous and sediment
B/Ga, +0.66 and +0.54 for aqueous and sediment Sr/Ba, and +0.98 for aqueous sulfate and +0.66 for sediment S/TOC (all
significant at p(a) < 0.01). These relationships establish the basis for use of these elemental ratios as paleosalinity proxies. Ele-
mental crossplots permitted estimation of approximate salinity thresholds for each proxy: (1) B/Ga is <3 in freshwater, 3–6 in
brackish, and >6 in marine facies; (2) Sr/Ba is <0.2 in freshwater, 0.2–0.5 in brackish, and >0.5 in marine facies; and (3) S/
TOC is <0.1 in freshwater and >0.1 in brackish and marine facies. S/TOC did not discriminate effectively between brackish
and marine facies, probably because microbial sulfate reduction (MSR) is generally Corg-limited rather than sulfate-limited in
both facies. The accuracies of these thresholds for prediction of the salinity facies of sediments are 88% for B/Ga, 66% for
Sr/Ba, and 91% for S/TOC. Although the Sr/Ba proxy is slightly less robust owing to difficulty in removing all carbonate Sr
influence and/or to greater mobility of Sr and Ba in the burial environment, we strongly advocate use of multiple proxies in
order to support paleosalinity interpretations. Finally, we illustrate the application of these proxies with case studies of (1) the
Ordos Basin in North China, which contains Ordovician marine shales and Triassic terrestrial mudstones, and (2) the mid-
Eocene Bohai Bay Basin in NE China, which accumulated brackish to marine mudstones.
Ó 2019 Elsevier Ltd. All rights reserved.
Keywords: Boron; B/Ga; Sr/Ba; Brackish; Freshwater; Seawater
1. INTRODUCTION
⇑ Address: Department of Geology, University of Cincinnati,
Cincinnati, Ohio 45221-0013, USA.
Salinity is an essential chemical feature of watermasses,
E-mail addresses: weiwei910911@163.com (W. Wei), thomas. and it is routinely reported for modern aqueous systems.
algeo@uc.edu (T.J. Algeo). For many ancient sedimentary formations, either fully
https://doi.org/10.1016/j.gca.2019.06.034
0016-7037/Ó 2019 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Wei W. and Algeo T. J. Elemental proxies for paleosalinity analysis of ancient shales and mudrocks.
Geochim. Cosmochim. Acta (2019), https://doi.org/10.1016/j.gca.2019.06.034
2 W. Wei, T.J. Algeo / Geochimica et Cosmochimica Acta xxx (2019) xxx–xxx
marine (e.g., Yan et al., 2018) or fully freshwater (e.g., Qiu narrower range of salinity variation in the open ocean pre-
et al., 2015) conditions can be inferred from general strati- sents different challenges from paleosalinity determinations
graphic and paleogeographic considerations with little to in freshwater-seawater mixing systems (as in the present
no uncertainty. However, for ancient sedimentary forma- study). Clumped isotopes allow concurrent paleosalinity-
tions deposited in marginal-marine or coastal terrestrial set- temperature determinations (Ghosh et al., 2006; Eiler,
tings, watermass salinity may have been influenced by both 2007), but their utility depends on the timing of carbonate
freshwater and marine inputs (e.g., Dávila et al., 2002; Wei stabilization, which is commonly diagenetic (Huntington
et al., 2018), and determination of secular variation or long- et al., 2011), and on the degree of post-depositional solid-
term mean paleosalinity conditions becomes important. state isotope exchange (Henkes et al., 2014). Biomarkers
For systems of this type, the availability of geochemical such as alkylated chromans and C20 isoprenoid thiophenes
proxies that can track changes in watermass salinity in are potential paleosalinity proxies (Barakat and Rullkötter,
space and time would be highly useful. 1997), although the controls on their abundance are not
Paleosalinity analysis has a long history, and many well understood. FeS2/FeS ratios may be salinity-
different types of data–both geochemical and non- dependent, with values >10 and <1 indicative of marine
geochemical–have been used for this purpose. Fossil and freshwater conditions, respectively (Berner et al.,
assemblages are particularly useful (LeGrande and 1979), although the speciation of sulfur depends on multi-
Schmidt, 2011) and various faunal and floral groups have ple factors in addition to sulfate availability. Strontium iso-
been pressed into service, including coccoliths (Bukry, topes in biogenic carbonates have been used as a
1974), chrysophyte cysts, fish scales, sponges, and diatoms paleosalinity proxy in marginal marine environments
(Cumming et al., 1993), ostracods (Anadón et al., 2002), because freshwater generally contains more radiogenic Sr
and dinoflagellates (Van der Meer et al., 2008). In addition than seawater (Holmden et al., 1997; Reinhardt et al.,
to abundance data, fossil morphology is also potentially 1998), although diagenetic overprinting of the 87Sr/86Sr sig-
related to watermass salinity, as in the case of coccolith pla- nal is a concern in such studies. Mg/Ca, Sr/Ca, and Na/Ca
coliths (Bollmann and Herrle, 2007). However, fossil-based ratios in ostracod shells have been for paleosalinity recon-
techniques are feasible only when fossils are deposited and struction (Dwyer and Cronin, 2001), although these ele-
preserved, and in many cases fossil assemblages are only mental ratios are subject to diagenetic modification.
crudely diagnostic of salinity levels. For example, modern To generalize somewhat, all of the techniques discussed
brackish watermasses down to 20 psu (practical salinity above require special conditions, e.g., the presence of speci-
units; https://salinometry.com/pss-78/) contain a euryha- fic lithologies, fossils, or biomarkers, limiting their wide-
line fauna similar to that in the open ocean, with only a spread application to ancient sedimentary formations.
slight reduction in diversity, as in the modern Baltic Sea The most useful type of paleosalinity proxy would be one
(Hallfors et al., 1981). Within modern river estuaries, spe- that is applicable to fine-grained siliciclastic sediments,
cies diversity is slowly reduced upchannel, but faunal diver- which comprise 80% of total Phanerozoic sediment mass
sity remains at least 50% of that of adjacent open-marine (Mackenzie and Garrels, 1971). Although bulk-sediment
habitats to salinities as low as 15 psu, and the transition geochemical proxies for paleosalinity have received a lim-
to a community containing diagnostic brackish-water taxa ited degree of attention to date (e.g., Potter et al., 1963;
generally occurs only at 10–15 psu (Friedrich, 1969; Nelson, 1967; Ye et al., 2016), their general applicability
Raffaelli, 1996). Salinity dynamics also play a role: water- to fine-grained siliciclastic sediments has not been suffi-
masses with low but stable salinities (e.g., many epiconti- ciently demonstrated to date. Here, we investigate the util-
nental seas) allow marine organisms to live closer to their ity of three elemental proxies for paleosalinity analysis, i.e.,
lower salinity tolerance limits than those with strong salin- boron/gallium (B/Ga), strontium/barium (Sr/Ba), and sul-
ity fluctuations (e.g., many estuaries; Wallentinus, 1991). fur/organic carbon (S/TOC) ratios. Although most dis-
Thus, faunas are generally useful but not highly accurate solved elements are present in higher concentrations in
paleosalinity proxies. seawater than in brackish or fresh waters, certain elements
Various sedimentological and geochemical proxies have show relatively higher concentrations in seawater (e.g., B
been used to constrain paleosalinity (Frederickson and and Sr) or freshwater (e.g., Ga and Ba) on a salinity-
Reynolds, 1960; Nelson, 1967; Couch, 1971; Holmden normalized basis. For such non-redox-sensitive elements,
et al., 1997; Ye et al., 2016). Primary evaporite minerals adsorption and desorption processes on (mainly) clay min-
such as gypsum and halite provide evidence of elevated erals result in fine-grained sediments acquiring an elemental
watermass salinity (Butler et al., 1999; Hay et al., 2006; inventory that is proportional to that of the overlying water
Tosca et al., 2008). Paleosalinities can be estimated using column. Thus, the bulk composition of fine-grained silici-
isotopic techniques such as d18O in carbonates (Ingram clastic sediments can reflect the chemistry of the watermass
et al., 1996) or phosphates (Joachimski and Lambert, in which they were deposited.
2015), which, however, generally requires an assumption Historically, the development of elemental paleosalinity
regarding watermass d18O. Several techniques have been proxies can be traced to Goldschmidt’s (1932) observations
developed to assess open-ocean salinity variation, e.g., alke- on the distributions of trace elements in different sedimen-
none d2H (Rohling, 2007; LeGrande and Schmidt, 2011; tary environments, which served as inspiration for a num-
Gould et al., 2019; Weiss et al., 2019) and carbonate ber of later studies (e.g., Degens et al., 1957; Potter et al.,
Na/Ca ratios (Bertlich et al., 2018), although the much 1963; Walker and Price, 1963). Among these elemental
W. Wei, T.J. Algeo / Geochimica et Cosmochimica Acta xxx (2019) xxx–xxx 3
proxies, boron has received the most attention to date: 2. SALINITY VARIATION IN MODERN
Walker (1968) created the ‘equivalent boron method’ based DEPOSITIONAL SYSTEMS
on clay-fraction data, and Couch (1971) developed a tech-
nique based on the boron contents of different clay miner- We adopt the following definitions of commonly used
als, which has received sporadic use (e.g., Spjeldnaes, salinity terms: freshwater (<1 psu), brackish (1–30 psu),
1979; Chen et al., 1997; Ye et al., 2016). Sr/Ba ratios were marine (30–38 psu). Freshwater systems include most rivers
initially applied to Cenozoic successions in China to distin- and lakes as well as many terrestrial wetlands. The elemen-
guish watermasses of different salinities (Wang et al., 1979; tal chemistry of freshwaters depends mainly on the types of
Qian and Shi, 1982), and their relationship to equivalent B geological materials undergoing weathering (Newton et al.,
concentrations was noted by Li and Xiao (1988). Sr/Ba 1987; Gaillardet et al., 2003), although basinal climate,
ratios were later investigated in modern marine, estuarine, local relief, atmospheric inputs, and evaporation-
and freshwater sediments in China (Deng and Qian, precipitation processes can be important (Czaya, 1983;
1993), with subsequent applications as a paleosalinity proxy Lerman et al., 1995; Bohacs et al., 2000; Wetzel, 2001).
(Chen et al., 1997; Ye et al., 2016; Zhang et al., 2017). How- Freshwater systems located in strongly leached (e.g., tropi-
ever, these studies mostly appeared in Chinese language cal) areas of low relief can have exceedingly low dissolved
journals and did not find an international audience. The salt content, in which case inputs from precipitation
basis for sulfur/carbon ratios (S/TOC, or sometimes become relatively more important, as shown for low-
TOC/S) as a paleosalinity proxy (e.g., Hieshima and salinity tropical rivers in Africa and South America
Pratt, 1991; Ge et al., 2003) is the large differences in aque- (Gibbs, 1970; Allan and Castillo, 2007). Evaporation pro-
ous sulfate concentrations between freshwater and marine cesses can change both the absolute and relative concentra-
systems (Berner and Raiswell, 1984). However, this proxy tions of dissolved salts as a function of precipitation of
is fundamentally different in character from the B/Ga and evaporative minerals in soils or sediments (Gibbs, 1970;
Sr/Ba proxies in that it (1) does not depend on adsorption Wetzel, 2001). In contrast to exorheic lakes (i.e., having a
of ions onto clay minerals, (2) requires a catalyst (i.e., positive water balance), endorheic lakes (i.e., having a neg-
organic matter) to drive sulfate reduction, generating ative water balance) exhibit a wide range of salinities, from
reduced sulfur species that can accumulate in the sediment, <10 to >400 psu (Wetzel, 2001), and solute chemistries
and (3) is limited in utility mainly to distinguishing freshwa- (Eugster and Hardie, 1978; Bennett et al., 2007). Owing
ter (low-sulfate) from brackish/marine (moderate- to high- to their highly evolved chemical compositions, hypersaline
sulfate) systems. With regard to the final point, brackish watermasses generally cannot be analyzed using the elemen-
waters often contain sufficient sulfate to allow extensive tal proxies discussed in this study.
oxidation of organic matter by microbial sulfate reduction Brackish waters are generated mainly through mixing of
(MSR), potentially leading to similar sediment S/TOC freshwater and seawater and are characteristic of estuaries,
ratios over a wide range of salinity conditions from brack- many marginal-marine basins, and some lagoons and coastal
ish to fully marine. lakes (Anadón et al., 2002). Such water bodies are prone to
Despite their occasional application to ancient sedimen- strong lateral and/or vertical salinity gradients, as in the mod-
tary formations, these elemental ratios (i.e., B/Ga, Sr/Ba, ern Baltic Sea (Boyer, 1982; Bohacs et al., 2000; Carroll and
and S/TOC) have not been systematically surveyed in mod- Bohacs, 2001; Ma et al., 2016). Short-term salinity changes in
ern fresh, brackish, and marine environments to establish coastal settings can be produced inter alia by variations in
their viability as paleosalinity proxies. In the present study, atmospheric pressure systems, meteoric precipitation and run-
we undertake a detailed survey of these elemental proxies in off, and marine washover events into enclosed basins as a
modern aqueous environments, determining the concentra- result of storms (Hatton et al., 1983; Leatherman et al.,
tions and ratios of these proxies in both the watermass and 2000; Simas et al., 2001; Anthony et al., 2009). At annual
sediment as well as their relationship to watermass salinity timescales, salinity cycles are common due to seasonal precip-
(Section 2), and establishing optimal thresholds between itation and/or evaporation (Sumner and Belaineh, 2005;
salinity facies for each proxy (Section 3). The analysis of Trenberth, 2011). At longer timescales, watermass salinity is
the present study yields several semiquantitative salinity frequently influenced by water balance changes related to cli-
proxies that can distinguish between freshwater, brackish, matic changes in evaporation and precipitation (Paerl et al.,
and marine facies in ancient shales and mudrocks. We did 2006; Michener et al., 1997). Changes in the salinity of coastal
not consider hypersaline aqueous systems in this study watermasses can also occur in response to (e.g.) isostatic
owing to their highly variable ionic chemistry. Finally, we rebound, eustatic fluctuations, or changes in coastal morphol-
illustrate the application of these proxies to ancient sedi- ogy triggered by storms or fluvial avulsion events (Björck,
mentary formations with case studies of (1) Ordovician 1995; Emeis et al., 2003).
marine and Triassic lacustrine shales from the Ordos Basin The salinity of modern seawater varies only modestly,
of North China, and (2) brackish to marine oil shales in the with 1 psu variation (34.5–35.5 psu) in the subthermo-
Eocene Bohai Bay Basin of NE China (Section 4). We clinal region (>1000 m), mainly linked to higher salinities
intend for the present study to serve as a general guide to in the Atlantic Ocean relative to the Indo-Pacific Oceans
application of elemental paleosalinity proxies in analysis (Roemmich and Gilson, 2009). In contrast, surface waters
of fine-grained siliciclastic sediments of any age and envi- vary by at least 6 psu as a function of multiple influences,
ronment type. including regional net positive or negative water balances,
coastal influx of freshwater, and formation of sea ice mass spectrometry (ICP-MS) in younger studies. Precisions
(Johnson and Polyakov, 2001; Yu, 2011). In the Atlantic are usually reported as the coefficient of variation (CV) or
Ocean, net evaporation in the subtropics results in surface relative standard deviation (RSD), which are both defined
salinities 1 psu higher than in the tropics or high- as the ratio of the standard deviation (r) to the mean (l)
latitude regions (Weber et al., 2007), and similar effects of a dataset. The Curcumin colorimetry method, which is
are seen in the Pacific Ocean (Fu and Bell, 2003). Net atmo- specific to B, was widely used during the 1950s–1970s and
spheric water transport across the Central American Isth- had a precision of 2% (Liss and Pointon, 1973). AAS
mus results in 1–2 psu lower salinity in the tropical East measurements have a precision of 12% for Ga (Orians
Pacific relative to the central Atlantic/Caribbean region and Bruland, 1988) and 8% for Sr and Ba (Fabricand
(Gussone et al., 2004; Schmidt et al., 2004). Surface water et al., 1966). ICP-OES and ICP-AES analyses of water sam-
salinities around large river mouths or in river-fed large ples have precisions of 1.6% for B (Singh et al., 2014),
bays can result in significantly reduced salinities (e.g., as 5% for Ga (McAlister and Orians, 2012), and 1–4% for
low as 17 psu in some regions of the East China Sea; Sr and Ba (Bernat et al., 1972; Sultan, 2012). Water samples
Beardsley et al., 1985). Brine rejection during sea-ice forma- can also be diluted and tested using ICP-MS in solution
tion can lead to salinity increases (Markus et al., 1998; mode with a precision of 10% for Sr and Ba (Walther
Gordon et al., 2000). Long-term changes in seawater salin- and Nims, 2015). Instrumental neutron activation-analysis
ity can be caused by changes in (e.g.) sea-ice formation in (INAA) was also used for aqueous analyses, mainly in older
Arctic marginal seas (Polyakov et al., 2003), total continen- studies, with precisions of 5% for Sr and 10% for Ba
tal ice mass (Markus et al., 1998; Stott et al., 2004), reaction (Bowen, 1956). Sulfate concentrations in water samples
of seawater with oceanic crust (Bischoff and Rosenbauer, are measured gravimetrically from precipitated BaSO4 after
1989; Chester, 2009), and massive evaporite precipitation removal of sulfide and the addition of BaCl2, with a preci-
events (Hay et al., 2006). Such changes generally occur sion of 3% (Wilkin and Barnes, 1997).
slowly and have limited effects (<1 psu) on global seawater For sediment samples, emission spectrography and AAS
salinity, although massive evaporite precipitation events are were used in some older studies, and X-ray fluorescence
thought to be capable of shifting seawater salinity by up to (XRF) and ICP-AES/MS are in wide use today. Emission
5 psu at timescales of one to a few million years (Hay spectrography yielded precisions of 6.2% for B and 11.1%
et al., 2006). for Ga (Thompson, 1968). The precision of measurements
by AAS for all elements is 2–10%. The accuracy and pre-
3. SALINITY PROXIES IN MODERN DEPOSITIONAL cision of XRF for trace elements like Sr and Ba varies from
SYSTEMS 5% to 10% (Algeo and Maynard, 2004; Silva et al., 2014).
ICP-MS is capable of high precision in elemental analysis
3.1. Development and testing of the salinity proxy dataset (e.g., 0.4% for Ga, 1.0% for Ba, and 0.6% for Sr;
Thomas, 2013, his table 18.6), although precisions of 3–
The elemental datasets used in this study were compiled 5% are commonly reported in practice (Brunskill et al.,
from published literature. Our database includes B and Ga 2001; Wei et al., 2003). The total organic carbon (TOC)
concentrations from modern aqueous systems (Table S1) and total S contents of sediments are analyzed using titra-
and modern sediments (Table S2), Sr and Ba concentration techniques or Carlo Erba or Leco C-S elemental ana-
tions from modern aqueous systems (Table S3) and modern lyzers. TOC can be obtained by acidification of a sample
sediments (Table S4), SO24 concentrations from modern aliquot to remove carbonate carbon prior to instrumental
aqueous systems (Table S6) and TOC and sulfur concentra- analysis, or by determining carbonate carbon content in
tions from modern sediments (Table S7). The 54 datasets of the form of evolved CO2 and then calculating TOC from
modern sediments in our database include (1) 25 sets of sur- total carbon by difference (Lyons et al., 2003). Using a
face grab samples and 5 sets of hand samples (depth 0 m), Carlo Erba Elemental Analyzer, TOC can be measured
(2) 10 sets of piston core samples, 4 sets of gravity core sam- directly from decarbonated samples with a precision of
ples, and 2 sets of vibrocore samples (depth <5 m), and (3) 8 6% (Mason and Lawrence, 1999; Xiong et al., 2012).
sets of drillcore samples (depth <12.5 m). The age of the Using a Leco C-S elemental analyzer, precisions of 2.5%
source literature ranges from the 1950s to the present. for carbon and 5% for sulfur are possible (Xiong et al.,
The analytical methods used to measure each analyte have 2012). In some studies, pyrite sulfur content (rather than
evolved with time, trending toward greater accuracy in total sulfur) is determined using the chromium reduction
younger datasets. Thus, there is a degree of variability in method (Lyons et al., 2003). Significantly, the uncertainties
the quality of data in our compiled dataset that is unavoid- in measured values for all of these techniques are much
able given the varied nature of the sources. smaller than the salinity-related trends documented in our
Most studies of the elemental chemistry of water sam- study, so there is very little possibility that measurement
ples make use of pretreatments consisting of concentration errors invalidate our results.
and rinsing (e.g., McAlister and Orians, 2012; Sultan,
2012). The analytical methods used include Curcumin col- 3.2. The B/Ga proxy
orimetry, emission spectrography, and atomic adsorption
spectrometry (AAS) in older studies, switching to induc- 3.2.1. B and Ga chemistry
tively coupled plasma optical emission spectroscopy Boron (B) is a metalloid trace element belonging to
(ICP-OES), atomic emission spectroscopy (ICP-AES), and group 13 (IIIA; boron group) of the periodic table. It has
an atomic number (z) of 5, an atomic weight of correlated with dissolved oxygen (DO) concentrations and
10.81 g mol 1, and a single oxidation state (B3+) with an positively correlated with pH, and, thus, anoxic waters tend
ionic radius of 0.23 Å (Pais and Jones, 1997). Its chemical to have higher seawater B concentrations than oxic waters
properties are more similar to those of carbon (z = 6) and (Bennett, 2017; Kuliński et al., 2017).
silicon (z = 14) than to other group 13 elements Gallium is derived primarily from weathering of quart-
(DeFrancesco et al., 2016). Boron has two naturally occur- zose and feldspathic silicate rocks (Shiller and Frilot,
ring stable isotopes, 10B (19.9%) and 11B (80.1%), whose 1996; Foley et al., 2017). It is relatively immobile and can
ratio in biogenic carbonates has been widely used as a pH be concentrated through weathering processes (e.g., lateriti-
proxy (e.g., Lécuyer et al., 2002). Boron exists in seawater zation, greisenization, albitization), especially if pH values
mainly as B(OH)3 and B(OH)4 , the relative abundances are high (>7), to levels of >100 ppm associated with sec-
of which also depend on pH (Dickson, 1990; You et al., ondary minerals such as gibbsite and kaolinite (Couch,
1995). B has an average crustal concentration of 15 ppm 1971; Chen et al., 1997; Hieronymus et al., 2001;
(McLennan, 2001). Clay minerals have a strong affinity Salminen et al., 2005). Weathering generates Ga-
for B(OH)4 , resulting in strong adsorption of boron under hydroxide (Kopeykin, 1984), which is more soluble than
neutral to weakly alkaline pH conditions (as in seawater), Al-hydroxide for pH values from 3 to 7, leaching Ga into
but a weaker affinity for B(OH)3, leading to less boron soil water under moderately acidic conditions. In aqueous
adsorption under low-pH conditions (as in many freshwa- solutions it forms fluoride and hydroxide complexes
ter systems) (Vengosh et al., 1991). (Wood and Samson, 2006), although due to its low solubil-
Gallium (Ga) is a trace element that also belongs to ity it is transported mainly in particulate form (Shiller and
group 13 (IIIA; boron group). It has an atomic number Frilot, 1996; Foley et al., 2017). It is readily removed from
(z) of 31, an atomic weight of 69.72 g mol 1, and two oxi- freshwaters via adsorption onto clay minerals such as smec-
dation states: a trivalent form (Ga3+) with an ionic radius tite (Sirocko, 1995). The riverine flux is the major Ga source
of 0.62 Å and a rarer monovalent form (Ga+) with an ionic to seawater, where it has a relatively short residence time of
radius of 1.13 Å (Pais and Jones, 1997; De Vos and 100–750 years (Shiller, 1998; McAlister and Orians, 2015).
Tarvainen, 2006). Its geochemical behavior is similar to The oceanic distribution of dissolved Ga is controlled by
that of its group 13 neighbor Al (z = 13) (Orians and a complex set of factors: aeolian inputs of dissolved Ga
Bruland, 1988; Salminen et al., 2005). Ga has two naturally to the surface waters, a deepwater source (ocean crust),
occurring stable isotopes, 69Ga (60.1%) and 71Ga (39.9%) and removal by particle scavenging throughout the water
(Pais and Jones, 1997). It has an average crustal concentra- column (Orians and Bruland, 1988; Shiller, 1998;
tion of 16–17 ppm (McLennan, 2001; Moskalyk, 2003). McAlister and Orians, 2015). Ga scavenging is most intense
In the 3+ oxidation state, Ga can form many substances in areas of high productivity and organic sinking fluxes, and
such as bromides, chlorides, hydrides, iodides, nitrides, oxi- as a result of scavenging, dissolved Ga concentrations in
des, selenides, sulfides, and tellurides (Moskalyk, 2003; De seawater vary as a function of both water depth and geo-
Vos and Tarvainen, 2006). graphic location (Orians and Bruland, 1988; Shiller, 1998;
McAlister and Orians, 2015).
3.2.2. B and Ga cycling
The major reservoirs of boron are continental and ocea- 3.2.3. B and Ga concentrations and ratios in natural waters
nic crust (1018 kg), the oceans (1015 kg), and groundwa- Freshwaters are characterized by low concentrations of
ter (1011 kg) (Spivack et al., 1987; Argust, 1998; Ishikawa B and Ga, with average concentrations in groundwaters
and Nakamura, 1993; Tenthorey and Hermann, 2004). The and surface waters of 13 ppb and <5 ppb, respectively
natural sources of boron to soils and surface waters include (Choi and Chen, 1979; Shiller and Frilot, 1996; Vengosh
continental weathering, volcanic gases, geothermal- et al., 1999; Drever, 2005; Huheey et al., 2006; De Vos
hydrothermal waters, saline soils, and sea salts via atmo- and Tarvainen, 2006). Elevated concentrations of B in
spheric deposition (De Vos and Tarvainen, 2006; Singh freshwater systems are usually due to inputs from geother-
et al., 2014). In the crust, boron is present mainly as mal systems, connate waters from older marine formations,
borates, which are readily soluble and enter the hydrologi- or evaporate deposits (Choi and Chen, 1979; Bennett,
cal system as boric acid (Rose et al., 2000; Lemarchand 2017). Seawater contains higher and more uniform concen-
et al., 2002). Boron can be present in elevated concentra- trations: 4.5 ppm for B and 3 10 4 ppm for Ga
tions in volcanic springs, forming the toxic gas boron triflu- (Hemming and Hanson, 1992; Tenthorey and Hermann,
oride (BF3) (Mellor, 1980; Anovitz and Grew, 1996). The 2004; Huheey et al., 2006). B behaves conservatively in sea-
riverine flux is an important source of B to seawater, water, and its concentration can be estimated as a function
although the flux from oceanic crust, especially linked to of salinity, owing to a nearly constant boron-to-salinity
hydrothermal venting at convergent margins, may be larger ratio of 0.133 mg/kg ‰ 1 (Lee et al., 2010; Fig. 1a). Nearly
(Spivack and Edmond, 1987; Spivack et al., 1987; Rose identical boron-to-salinity relationships have been reported
et al., 2000; Lemarchand et al., 2002). Boron is the 10th from the Baltic Sea, North Pacific and North Atlantic
most abundant element in seawater, where it has a long res- oceans, although some estuaries show deviations owing to
idence time (20 Myr), and its concentration is thought to variable inputs of riverine B (Lee et al., 2010; Kuliński
have varied little over the past two to three billion years et al., 2017). Ga-bearing minerals are mostly insoluble
(Reynolds, 1965; Mellor, 1980; You et al., 1995; (Foley et al., 2017), and due to strong particulate scaveng-
Lemarchand et al., 2002). B is significantly negatively ing Ga concentrations in seawater are usually lower than in
a median of 5.3 10 3 ppb, and Ga in seawater ranges

from 6.0 10 4 to 2.3 10 3 ppb with a median of
1.6 10 3 ppb (Fig. 1b; Table S1). B/Ga ratios have a
median (range) in freshwater of 8.4 (2.4–655) and in seawa-
ter of 6.1 106 (5.9 106–6.2 106) (Fig. 1c; Table S1).
Thus, B concentrations are 110 greater
(i.e., 4634 ppb/41 ppb) and B/Ga ratios 730,000 higher
(i.e., 6.1 106/8.4) on average in seawater compared to
freshwater. B shows a strong linear relationship to salinity
(r = +0.99; p < 0.01; Fig. 1a) with a slope of 131 ppb/psu
(cf. Lee et al., 2010; Kuliński et al., 2017), and B/Ga shows
a strong exponential relationship to salinity (r = +0.91;
p < 0.01) (Fig. 1c). In contrast, Ga shows a moderate neg-
ative exponential relationship to salinity (r = 0.45;
p < 0.01; Fig. 1b). The negative exponential relationship
of Ga versus salinity is due to strong scavenging of aqueous
Ga by particulates within estuaries (Sirocko, 1995). The
positive exponential relationship of B/Ga versus salinity is
due to Ga being in the denominator of this ratio.
3.2.4. B and Ga concentrations and ratios in sediments

The transfer of an aqueous B/Ga signal to the sediment
depends on the processes controlling B and Ga uptake and
their relative uptake kinetics. Sedimentary B and Ga uptake
is a function of adsorption and chemical complexation pro-
cesses (Potter et al., 1963; Liss and Pointon, 1973; Harder,
1970; Shirodkar and Dalal, 1988; Park and Schlesinger,
2002; Georgievskii et al., 2013), whose rates are influenced
by the aqueous chemical environment (e.g., pH, redox, tem-
perature, and ligand and oxyanion types and concentra-
tions) (Goldberg, 2002; Violante and Pigna, 2002;
Mitchell and Soga, 2005; Leybourne and Johannesson,
2008). B is adsorbed onto clay minerals by displacement
of H2O and OH from surface sites on a-Al2O3 (Keren
and Mezuman, 1981), and higher pH and lower tempera-
ture usually lead to a stronger adsorption affinity for clay
minerals (Palmer et al., 1987; Spivack et al., 1987). B may
also be adsorbed by other phases such as Fe and Mn-
oxyhydroxides, the importance of which has been inferred
Fig. 1. Aqueous concentrations of (a) B, (b) Ga and (c) B/Ga
from strong B-Fe correlations in sediments (Donahoe and
versus watermass salinity. Panel (c) contains fewer data points than
(a) or (b) because it was limited to samples for which both B and Liu, 1998). Although adsorption patterns are well-studied
Ga concentrations were available. The exponential relationships in for some elements (e.g., V; Chester and Hughes, 1967), no
(c) are both based on the Ga equation of McAlister and Orians published study has determined the specific pattern of B
(2012), with the dotted line making use of Ga data in that study adsorption by clay minerals versus Fe and Mn
(open symbols) and the dashed line making use of Ga data from oxyhydroxides.
other studies (solid symbols). Samples are color-coded by salinity The dominant hydroxide of Ga (i.e., Ga(OH)3) has a
facies: fresh (<1 psu; green), brackish (1–30 psu; blue), and marine low solubility, so most dissolved Ga tends to be precipitated
(30–38 psu; red). Data sources in Table S1. (For interpretation of as hydroxides in soils or sediments before transport to the
the references to colour in this figure legend, the reader is referred
ocean (Shiller and Frilot, 1996; De Vos and Tarvainen,
to the web version of this article.)
2006). Ga also adsorbs onto clay minerals in the sediment,
although it is comparatively less reactive than B (Shiller and
freshwater systems (Degens et al., 1957; Orians and Frilot, 1996; Foley et al., 2017). The pH of the aqueous
Bruland, 1988; McAlister and Orians, 2015). environment is an important control on Ga uptake by the
In our compiled dataset, B in freshwaters ranges from sediment, with stronger uptake under neutral to alkaline
6.3 to 203 ppb with a median value of 41 ppb, and B in sea- conditions (pH 7) (Kopeykin, 1984; De Vos and
water ranges from 4427 to 4798 ppb with a median of Tarvainen, 2006).
4634 ppb (Fig. 1a; Table S1). [Note: all ‘‘ranges” in this In our dataset, modern freshwater sediments have medi-
study represent the 16th-to-84th percentile values of the dis- ans (ranges) of B and Ga concentrations of 4.8 ppm (1.4–
tribution, in order to eliminate the effects of outliers.] Ga in 16.3 ppm) and 3.8 ppm (2.5–6.4 ppm), respectively, yielding
freshwaters ranges from 1.9 10 3 to 2.5 10 2 ppb with B/Ga ratios of 1.29 (0.35–3.44) (Table S2). Modern marine
sediments have medians (ranges) of B and Ga concentra- ships with watermass salinity. The slope of the B-versus-
tions of 300 ppm (155–351 ppm) and 19 ppm salinity regression for sediments (5.74 ppm/psu, or
(14–22 ppm), respectively, yielding B/Ga ratios of 15.3 5740 ppb/psu) is greater than that for waters (131 ppb/
(10.5–19.7). Thus, B concentrations are 62 higher psu; Fig. 1a), but the slope of the B/Ga-versus-salinity
(i.e., 300 ppm/4.8 ppm) and B/Ga ratios 12 higher regression for sediments (0.39 psu 1) is less than that for
(i.e., 15.3/1.29) on average in marine sediments compared waters (4300 psu 1; Fig. 1b). Sediment Ga shows little rela-
to freshwater sediments. Sediment B concentrations tionship to salinity, yielding a slope of 0.02 ppm/psu
(r = +0.66; p < 0.01; Fig. 2a) and B/Ga ratios (r = +0.76; (r = +0.02; p > 0.10; data not shown). A crossplot of B ver-
p < 0.01; Fig. 2b) both show pronounced positive relation- sus Ga shows clear separation of samples into freshwater,
brackish, and marine fields (Fig. 2c).
These patterns provide several insights into B and Ga
uptake dynamics that can inform the use of B/Ga as a pale-
osalinity proxy. First, B is strongly taken up by the sedi-
ment under all salinity conditions (hence, B
concentrations greater than average UCC; Fig. 2a),
although this effect is stronger for marine facies, as reflected
by a higher B-versus-salinity regression for sediments
(5740 ppb/psu; Fig. 2a) than for waters (131 ppb/psu;
Fig. 1a). We infer that enhanced B uptake in marine facies
relative to freshwater facies is due to the more alkaline
chemistry of the former (Palmer et al., 1987; Spivack
et al., 1987). Although effects related to differing adsorption
substrates (e.g., Donahoe and Liu, 1998) cannot be
excluded, the systematic enrichment of marine facies favors
an explanation related to watermass chemistry (i.e., pH)
rather than to sediment composition. Second, the generally
low Ga concentrations in all salinity facies, with values
close to or less than UCC (Fig. 2c), and the lack of a rela-
tionship to salinity (see above) are consistent with little to
no Ga uptake in most sediments. In this case, changes in
B/Ga ratios as a function of salinity (Fig. 2b) are due to
a combination of aqueous B concentration differences
(Fig. 1a) and the kinetics of B uptake in different salinity
facies (see above). Elevated B/Ga ratios in marine facies rel-
ative to freshwater facies are thus due in first order to the
higher B concentrations of seawater and in second order
to more rapid B uptake by sediments under alkaline pore-
water conditions.
3.2.5. Diagenetic remobilization of B and Ga in sediments

For any elemental proxy, one issue of importance is its
tendency toward post-depositional remobilization, which
can potentially alter the primary proxy signal. Boron that
is present in interlayer sites of clay minerals such as illite,
smectite, and mixed-layer illite/smectite (I/S) can undergo
adsorption-desorption processes in the burial environment
(You et al., 1995). It is readily remobilized within sediments
in response to changes in aqueous pH or ionic concentra-
tions (Leeman and Sisson, 1996; Ravenscroft and
McArthur, 2004; Zhou et al., 2016), with lower pH promot-
Fig. 2. Boron-gallium in modern sediments: (a) B and (b) B/Ga ing the release of borate from particulate (mainly clay-
versus watermass salinity, and (c) B versus Ga. In (a) and (b), red mineral) surfaces (Zeebe and Wolf-Gladrow, 2001;
arrows on y-axis show average B concentration and B/Ga ratio of Wallmann et al., 2008). Porewater B can substitute for
upper continental crust (UCC; McLennan, 2001). In (c), inferred
tetrahedral silicon during diagenetic reactions involving
thresholds between salinity facies are shown as diagonal lines, and
clay minerals, such as smectite-to-illite conversion (Perry,
black star indicates composition of average UCC. Samples are
color-coded by salinity facies: fresh (<1 psu; green), brackish (1– 1972; Spivack et al., 1987; Williams et al., 2001b). Metased-
30 psu; blue), and marine (30–38 psu; red). Data sources in imentary graphite contains negligible amounts of B
Table S2. (For interpretation of the references to colour in this (Douthitt, 1985), indicating that B tends to be released from
figure legend, the reader is referred to the web version of this organic matter during thermal maturation (Williams et al.,
article.) 2001c). Many oilfield brines are B-enriched owing to its
mobility and tendency to remain in the aqueous phase rock-forming minerals including K-feldspar, gypsum, pla-
rather than being taken up by diagenetic minerals gioclase, calcite, and dolomite, as well as in the Sr-
(Levinson, 1980; Williams et al., 2001a). minerals celestine (SrSO4) and strontianite (SrCO3)
Gallium in sediments occurs mainly in Al-bearing min- (Salminen et al., 2005). Its greatest abundance is in sedi-
erals such as clay minerals, and its mobility and precipita- mentary carbonates, in which Sr substitutes readily for
tion is controlled mainly by the chemistry of aluminum, Ca2+ through filling of lattice positions or occupation of
owing to substitution of Ga3+ into structural sites normally lattice defects in the mineral structure (Brand and Veizer,
occupied by Al3+ (Hawkins and Roy, 1963; Wang et al., 1980; Vahrenkamp and Swart, 1990; Roden et al., 2002).
2011; Breiter et al., 2013). During diagenesis, Ga is a rela- In terrestrial weathering environments, Sr is liberated more
tively immobile element owing to its presence mainly in rapidly than Ba (Ding et al., 2001; Yang et al., 2004a,
the structure of resistant minerals (Panahi et al., 2000). 2004b, 2006). Once released by weathering, Sr2+ is mobile
Ga adsorbed to clay minerals tends to remain immobile under most environmental conditions despite the relatively
under alkaline porewater conditions. However, Ga can be low solubility of Sr-carbonates and Sr-sulfates (Brookins,
remobilized under low-pH conditions, as in tropical soils 1988). The largest source of Sr to the oceans is riverine
with advanced argillic alteration (Rytuba et al., 2003; inputs, although hydrothermal Sr from mid-ocean ridges
Salminen et al., 2005). and alteration/dissolution of seafloor carbonates are impor-
tant secondary sources (Godderis and Veizer, 2000;
3.3. The Sr/Ba proxy Krabbenhöft et al., 2010). Sr exhibits relatively conservative
behavior in seawater, with a residence time (2.4 Myr) that is
3.3.1. Sr and Ba chemistry long compared to the mixing time of the oceans (1.5 kyr)
Strontium (Sr) is a trace metallic element in Group 2 (Goldberg, 1965; Krabbenhöft et al., 2010). The main sink
(IIA; alkaline earths) of the periodic table. It has an atomic of Sr in the ocean is substitution of Sr2+ for Ca2+ in carbon-
number (z) of 38, atomic weight of 87.62 g mol 1, elec- ate minerals, although some Sr can be removed through
tronegativity of 0.9, and an ionic radius for Sr2+ of reaction with oceanic crust (Roden et al., 2002;
1.27 Å (Pais and Jones, 1997). As an alkaline-earth metal, Krabbenhöft et al., 2010).
its chemical properties are intermediate between those of Barium has an average crustal concentration of 0.05%,
calcium (z = 20) and barium (z = 56). Sr has four naturally with the most common naturally occurring minerals being
occurring isotopes (84Sr, 86Sr, 87Sr, and 88Sr), of which the barite (BaSO4) and witherite (BaCO3) (Greenwood and
most abundant is 88Sr (82.6%) (Lide, 2012; De Vos and Earnshaw, 1997; Ropp, 2012). Ba contained in feldspar
Tarvainen, 2006). Sr can exist in two oxidation states and other granitoid silicates is not easily dissolved, so the
(0 and +2), but under normal environmental conditions weathering flux of Ba tends to be dominated by carbonate
only Sr2+ is stable enough to be of practical importance source rocks (Dalai et al., 2002; Salminen et al., 2005; Das
(Hibbins, 2013). Sr2+ forms a range of compounds includ- and Krishnaswami, 2006). In surface waters, weathered Ba
ing SrO, SrSO4, SrCO3, SrCl2, and Sr(NO3)2. is readily adsorbed by clay minerals, and it is transported in
Barium (Ba) is a trace metallic element also belonging to both sorbed and dissolved forms to the oceans (Von Allmen
Group 2 (IIA; alkaline earths). It has an atomic number (z) et al., 2010). In estuarine systems, aqueous Ba concentra-
of 56, an atomic weight of 137.32 g mol 1, an electronega- tions can increase at intermediate salinities (5–15 psu)
tivity of 0.9, and a single oxidation state (Ba2+) with an owing to desorption of Ba from suspended particulate mat-
ionic radius of 1.43 Å (Pais and Jones, 1997). It is most sim- ter, via ion exchange with major ions supplied by seawater.
ilar chemically to other alkaline earth elements Ca (z = 20) Thus, the behavior of Ba in estuarine systems is commonly
and Sr (z = 38) (De Vos and Tarvainen, 2006). It has seven non-conservative, although conservative mixing is typical at
naturally occurring isotopes, of which the most abundant is salinities >15 psu (Coffey et al., 1997; Vetter et al., 2017).
138
Ba (71.7%) (Pais and Jones, 1997). Barium atoms con- These processes can result in a Ba peak at intermediate
tain two electrons in the fifth (outermost) electron shell that salinities along river-to-ocean transects (Vetter et al.,
are easily lost (Greenwood and Earnshaw, 1997). The Ba2+ 2017; Fig. 3b). Seawater Ba is sourced mainly from riverine
ion is large and has a high charge ratio (radius/charge) fluxes, especially via desorption from suspended matter in
resulting in its concentration in more felsic components of estuaries (Coffey et al., 1997; Guay and Falkner, 1998;
magmas in the later stages of crystallization. Because of Vetter et al., 2017), and to a lesser degree from hydrother-
its high chemical reactivity, barium is never found in nature mal vents, which can produce local hydrothermal Ba depos-
as a free element. It is most commonly found combined its (Edmond et al., 1979; Von Allmen et al., 2010; Pyle
with sulfate and carbonate but can also form compounds et al., 2017). As a non-conservative element, Ba has a rela-
with hydroxide, chloride, nitrate, chlorate, and other tively short residence time in seawater (11 kyr) (Von Allmen
anions. et al., 2010). In the open ocean, the main processes affecting
Ba behavior are biological cycling and interaction with the
3.3.2. Sr and Ba cycling iron and manganese cycles (McGrath et al., 1989). Barium
Sr is present in the Earth’s crust at an average concen- is found in trace concentrations (30–160 nM) in the ocean
tration of 0.04% (Chegrouche et al., 2009) (note: ‘‘%” is and shows a nutrient-type concentration profile (i.e.,
weight percent throughout this study). Owing to an ionic depleted in surface waters) despite not being a nutrient ele-
radius (118 pm) similar to those of Ca2+ (100 pm) and K+ ment (Wolgemuth and Broecker, 1970). Ba depletion in
(138 pm), Sr substitutes into a variety of common ocean-surface waters is due to formation of BaSO4 on the
Broecker, 1970; Sigg et al., 1987; Lea and Spero, 1994;

Pyle et al., 2017; Vetter et al., 2017). Because the biological
pump is responsible for transferring Ba from surface waters
into the deep ocean, sediment Ba concentrations are poten-
tially useful as a proxy for marine productivity (Dymond
et al., 1992; Pyle et al., 2017). In marine sediments, barium
is present mainly in the form of barite, often associated with
organic-rich deposits, and secondarily as a minor con-
stituent of detrital and authigenic feldspars (Schenau
et al., 2001; Tribovillard et al., 2006).
3.3.3. Sr and Ba concentrations and ratios in natural waters

Freshwaters exhibit highly variable Sr concentrations
globally, ranging from a few ng/L to nearly 100 mg/L with
a mean of 60 mg/L (Gaillardet et al., 2003; He and Xu,
2015; De Vos and Tarvainen, 2006). Freshwater Ba concen-
trations are similarly variable, ranging from 10 to 100 mg/L
with a mean of 23 mg/L. Variations in both elements are
due to strong spatial heterogeneity in bedrock lithology and
climate conditions (Coffey et al., 1997). Sr has a relatively
high concentration in seawater (7.85 ppm) with small varia-
tions (ca. ± 3%) as a function of depth and salinity
(Nagaya et al., 1971; De Villiers, 1999; Chegrouche et al.,
2009). Ba is present in only trace amounts in seawater (30–
160 nM) owing to the low aqueous solubilities of barium car-
bonate, sulfate, and phosphate minerals (Neff, 2002; Pyle
et al., 2017). Barium sulfate (=barite, BaSO4) has a solubility
product of 1.05 10 10, which, in combination with the
high sulfate content of the modern ocean, leads to pro-
nounced aqueous Ba drawdown through barite formation.
In our compiled dataset, Sr in freshwaters ranges from
12 to 231 ppb with a median value of 71 ppb, and Sr in sea-
water ranges from 7430 to 8006 ppb with a median value of
7719 ppb (Fig. 3a; Table S3). Ba in freshwater ranges from
13 to 62 ppb with a median of 26 ppb, and Ba in seawater
ranges from 0.008 to 7.7 ppb with median of 2.6 ppb
(Fig. 3b; Table S3). Sr/Ba ratios have a median (range) in
freshwater of 1.4 (0.6–3.8) and in seawater of 804 (369-
2111) (Fig. 3c; Table S3). Thus, Sr concentrations are
105 greater (i.e., 7430 ppb/71 ppb) and Sr/Ba ratios
575 higher (i.e., 804/1.4) on average in seawater compared
Fig. 3. Aqueous concentrations of (a) Sr, (b) Ba and (c) Sr/Ba ratio to freshwater. Both Sr concentrations (r = +0.98; p < 0.01)
versus watermass salinity. Although modeled with a linear regres- and Sr/Ba ratios (and r = +0.66; p < 0.01) show strong pos-
sion in (b), note that Ba concentrations actually peak under low- itive linear relationships with salinity (Fig. 3a, c), whereas
brackish conditions (1–15 psu), with lower values in freshwater and Ba shows a negative relationship to salinity (r = -0.48;
high-brackish to marine conditions. Some of the scatter in Ba p < 0.01) although with substantial variation (Fig. 3b).
concentrations is due to the inhomogeneous distribution of Ba in
The slope of the Sr-versus-salinity (214 ppb/psu) is rela-
seawater, which exhibits a nutrient-type vertical profile (i.e.,
depleted in the ocean-surface layer). Panel (c) contains fewer data
tively invariant, although the slope of the Sr/Ba-versus-
points than (a) or (b) because it was limited to samples for which salinity is not as well-defined, being 34.5 psu 1 based on
both Sr and Ba concentrations were available. In (c), the solid line paired Sr-Ba concentration data (Fig. 3c) or 14.0 psu 1
represents the ratio of the regressions in (a) and (b), and the dashed based on the paired regressions of Sr and Ba versus salinity
line is the regression based on data shown in (c). Samples are color- (Fig. 3a, b). The negative slope of the Ba-versus-salinity
coded by salinity facies: fresh (<1 psu; green), brackish (1–30 psu; relationship is due primarily to conservative mixing of
blue), and marine (30–38 psu; red). Data sources in Table S3. (For Ba-rich estuarine waters with comparatively Ba-poor mar-
interpretation of the references to colour in this figure legend, the ine waters (Coffey et al., 1997; Vetter et al., 2017); note that
reader is referred to the web version of this article.) Ba concentrations are lower for freshwater than for weakly
surfaces of sinking organic particles, as H2S generated via brackish systems (1–15 psu; Fig. 3b), which is due to strong
MSR is oxidized to sulfate, a process that operates vigor- Ba desorption from suspended particles in the latter, a pro-
ously throughout the ocean owing to the near-saturation cess triggered by ion exchange with major ions supplied by
of seawater with respect to barite (Wolgemuth and seawater (Von Allmen et al., 2010).
3.3.4. Sr and Ba concentrations and ratios in sediments

In fine-grained siliciclastic sediments, Sr2+ is mostly
adsorbed by clay minerals or fixed in the organic fraction
(Bors et al., 1997; Salminen et al., 2005), yielding Sr concen-
trations ranging from 50 to 1000 ppm (mean 250 ppm)
depending on parent rocks and climate (Taylor, 1964;
Hellstrom and McCulloch, 2000; Kabata-Pendias, 2001).
However, Sr concentrations can be much higher in sedi-
ments containing a carbonate fraction, which must be cor-
rected for in order to estimate clay-fraction Sr/Ba ratios
from bulk-sediment data (see Section 3.3.6). Ba2+ can sub-
stitute for K+ in K-feldspar (Kabata-Pendias, 2001),
although commonly most Ba in fine-grained sediments is
adsorbed on clay minerals or hydrous Fe and Mn oxides
(Manceau et al., 1992; De Vos and Tarvainen, 2006;
Plewa et al., 2006). Ba concentrations range from 270 to
800 ppm with a median of 375–600 ppm in shales
(Mielke, 1979; De Vos and Tarvainen, 2006; Chermak
and Schreiber, 2014). In marine sediments, the concentra-
tion of Ba can be related to primary productivity
(McManus et al., 1998; Plewa et al., 2006; see Section 3.3.2),
an issue that should be considered in using Sr/Ba ratios as
paleosalinity proxies (see Section 3.3.7).
In our dataset, modern freshwater sediments exhibit
median (range) of Sr and Ba concentrations of 79 ppm
(54–127 ppm) and 427 ppm (269–592 ppm), respectively,
yielding Sr/Ba ratios of 0.20 (0.14–0.28) (Table S4). Mod-
ern brackish sediments exhibit median (range) of Sr and
Ba concentrations of 182 ppm (89–309 ppm) and 404 ppm
(267–484 ppm), respectively, yielding Sr/Ba ratios of 0.44
(0.27–0.66). Modern marine sediments exhibit median
(range) of Sr and Ba concentrations of 160 ppm (112–
314 ppm) and 391 ppm (249–558 ppm), respectively, yield-
ing Sr/Ba ratios of 0.43 (0.24–0.82). Thus, Sr concentra-
tions are 2 greater (i.e., 160 ppm/79 ppm) and Sr/Ba
ratios 2 higher (i.e., 0.43/0.20) on average in marine sed-
iments compared to freshwater sediments. Sediment Sr con-
centrations (r = +0.48; p < 0.01; Fig. 4a) and Sr/Ba ratios (r
= +0.54; p < 0.01; Fig. 4b) both show pronounced positive
relationships with watermass salinity. The slope of the Sr-
versus-salinity regression for sediments (4.23 ppm/psu, or Fig. 4. Strontium-barium in modern sediments: (a) Sr and (b)
Sr/Ba versus watermass salinity, and (c) Sr versus Ba. Red arrows
4230 ppb/psu) is greater than that for waters (212 ppb/
on y-axis show average Sr concentration and Sr/Ba ratio of upper
psu; Fig. 3a), but the slope of the Sr/Ba-versus-salinity
continental crust (UCC; McLennan, 2001). In (c), inferred thresh-
regression for sediments (0.0084 psu 1) is less than that olds between salinity facies are shown as diagonal lines, and black
for waters (15–35 psu 1; Fig. 3b). Sediment Ba shows lit- star indicates composition of average UCC. Samples are color-
tle relationship to salinity, yielding a slope of 8.4 ppb/psu coded by salinity facies: fresh (<1 psu; green), brackish (1–30 psu;
(r = 0.00; p > 0.10; data not shown). A crossplot of Sr ver- blue), and marine (30–38 psu; red). All samples were evaluated for
sus Ba shows a modest degree of separation of samples into carbonate Sr content on a formation-specific basis, with applica-
freshwater, brackish, and marine fields (Fig. 4c). tion of CaCO3 cutoffs ranging from 2% to 10% (most commonly
These patterns provide a number of insights into Sr and 5%). Data sources in Table S4. (For interpretation of the references
Ba uptake by the sediment that can inform the use of Sr/Ba to colour in this figure legend, the reader is referred to the web
version of this article.)
as a paleosalinity proxy. The similar increases in sediment
[Sr] and Sr/Ba from freshwater to marine facies (2 for
both; Fig. 4) and the lack of significant variation of sedi- Sr/Ba in freshwater sediments (Ding et al., 2001; Yang
ment [Ba] with salinity (above) indicate dominant control et al., 2004a, 2004b, 2006). The more limited increase in
by Sr dynamics. Unlike for the B-Ga system, in which [B] Sr from freshwater to marine sediments (by a factor of
and B/Ga values are higher than UCC, sediment Sr concen- 2) relative to the increase in B (by a factor of 62; Sec-
trations and Sr/Ba ratios are mostly lower than UCC tion 3.2.4) is a reflection of the more rapid uptake kinetics
(Fig. 4). This relationship reflects leaching of Sr during sub- of B relative to Sr. The observation that aqueous [Sr] and
aerial weathering, generating comparatively low [Sr] and Sr/Ba increase much more rapidly than sediment [Sr] and
Sr/Ba as a function of salinity (Figs. 3, 4) may reflect the The most direct test for carbonate-hosted Sr is a cross-
role of carbonate sequestration of seawater Sr, limiting plot of Sr/Ba versus total inorganic carbon (TIC) content,
the amount that is ultimately available for uptake by the with a significant positive relationship indicative of the
clay-mineral fraction of the sediment. presence of carbonate-hosted Sr. Lacking TIC data for
many of the study formations, we used CaO as a proxy
3.3.5. Diagenetic remobilization of Sr and Ba in shales for carbonate content. Shales contain on average 3%
Sedimentary Sr can be remobilized during burial diage- CaO, so significantly larger amounts are a good indicator
nesis. Sr may be released through diagenetic reaction of Sr- of the presence of carbonate in a sample. We found empir-
bearing minerals, such as dissolution and albitization of ically that positive Sr/Ba-versus-CaO relationships were
plagioclase and K-feldspar, illitization of smectite, and present in most study units above CaO thresholds ranging
dehydration of clay minerals, or by degradation of organic from 2% to 10% with a mode around 5% (see example in
host phases (Sullivan et al., 1990; Feldman et al., 1993; Fig. 5). We therefore applied a formation-specific CaO
Salminen et al., 2005; Yang et al., 2004a, 2004b, 2006). Sr threshold to each study unit to eliminate samples that prob-
release is generally facilitated by higher temperatures, more ably contained carbonate-hosted Sr. This procedure permit-
acidic or reducing porewaters, and kerogen oxidation ted shale-fraction Sr/Ba ratios to be determined from the
(Sullivan et al., 1990; Land et al., 1997; De Vos and most carbonate-lean samples of each dataset, allowing us
Tarvainen, 2006). However, formation of authigenic albite
or Ca-bearing phases such as laumonitite and carbonate
can lead to incorporation of porewater Sr into secondary
phases. Mostly, these types of reactions occur during later
diagenetic stages, limiting loss of porewater Sr through dif-
fusion out of the sediment (Feldman et al., 1993).
Ba is also easily remobilized during burial diagenesis
(van Os et al., 1991; Kabata-Pendias, 2001; De Vos and
Tarvainen, 2006). Organic-rich sediments commonly con-
tain large amounts of barite, which is subject to reductive
dissolution in anoxic bottom waters or porewaters, a pro-
cess that can occur during early diagenesis when the pore-
water system is relatively open (Dymond et al., 1992;
Salminen et al., 2005; Holland and Turekian, 2010). The
remobilization of Ba frequently makes the relationship
between Ba concentrations and organic productivity tenu-
ous (e.g., Schoepfer et al., 2015), and care must be taken
in using Ba as a paleoproductivity indicator (van Os
et al., 1991; Tribovillard et al., 2006). In clay-rich sedi-
ments, dehydration and diagenetic transformation of clay
minerals can lead to release of Ba adsorbed to clays as well
as from structural sites of silicate minerals (Holland and
Turekian, 2010). These processes tend to occur during a
later diagenetic stage under less open porewater conditions,
limiting loss of Ba from the sediment through diffusion.
3.3.6. Influence of carbonate Sr on bulk-sediment Sr/Ba

ratios
One important issue in using sediment Sr/Ba ratios as a
paleosalinity proxy is potential alteration of the clay-
fraction signal by carbonate-hosted Sr. Pure carbonate sed-
iments generally contain larger amounts of Sr (1000–
3000 ppm for calcite, 8000–10,000 ppm for aragonite of
primary marine origin, Bathurst, 1972; Salminen et al.,
2005; but lower for deep-sea carbonates and diagenetically Fig. 5. Example of threshold determination to screen out carbon-
altered carbonates; Turekian, 1964; Brand and Veizer, ate-hosted Sr based on the Upper Pennsylvanian Heebner Shale,
Kansas, USA. (a) Sr versus CaO, and (b) Sr/Ba versus CaO; inset
1980; Banner and Hanson, 1990) than pure fine-grained sili-
shows an expanded view of the 0–5% CaO interval. Note the strong
ciclastic sediments (400–700 ppm). Thus, the presence in a positive correlations for CaO > 5%, and the lack of correlations for
sample of more than small amounts of carbonate has the CaO < 5%. The graphs show baseline values (i.e., at CaO < 5%) of
potential to increase bulk Sr/Ba ratios relative to those of 120–150 ppm for Sr and 0.3–0.4 for Sr/Ba ratios. Data sources
the clay fraction. For this reason, it is essential to screen in Table S5. Application of a CaO cutoff of 5% thus permits robust
for the influence of carbonate-hosted Sr and to establish a estimation of the clay-fraction Sr/Ba ratio from the relatively
maximum carbonate threshold for each formation. carbonate-lean subset of samples from this formation.
to make use of sediment datasets in which some samples 32.06 g mol 1, and five oxidation states ( 2, 0, +2, +4
contained carbonate-hosted Sr and others did not for the and +6). Sulfide (S2 ) exhibits chalcophilic tendencies,
purpose of paleosalinity analysis. leading to the formation of many sulfide and sulfosalt ore
minerals such as chalcosite (Cu2S), pyrite (FeS2), sphalerite
3.3.7. Influence of biogenic Ba on bulk-sediment Sr/Ba ratios (ZnS), and galena (PbS) (De Vos and Tarvainen, 2006).
In marine sediments, the concentration of Ba can be Oxidized sulfur (S6+) as sulfate (SO24 ) forms (an)hydrous
related to primary productivity (McManus et al., 1998; evaporite minerals such as barite (BaSO4), anhydrite and
Plewa et al., 2006; Schoepfer et al., 2015). If excess (biogenic) gypsum (CaSO4), and epsomite (MgSO4). S is also present
Ba is present, it can potentially shift bulk-sediment Sr/Ba to in significant amounts (20–500 mg/kg) in common rock-
lower values than present in the clay fraction, leading to erro- forming silicate minerals, including feldspar, mica, and
neous paleosalinity assessments. However, this is unlikely to pyroxene (De Vos and Tarvainen, 2006; Vaughan, 2018).
be a frequently occurring issue for several reasons. Biogenic S has four naturally occurring isotopes (32S, 33S, 34S and
36
Ba is accumulated during sinking of organic matter through S), of which the most abundant is 32S (95%) (De Vos
the water column (François et al., 1995; Gonneea and and Tarvainen, 2006; Knossow et al., 2015).
Paytan, 2006), and deep-ocean deposits are therefore prone
to accumulating much more biogenic Ba than shallow-shelf 3.4.2. Aqueous sulfate concentrations in modern depositional
and marginal-marine deposits (Pirrung et al., 2008). The fully systems
marine character of deep-ocean sediments is almost never in Aqueous sulfate concentrations vary greatly among
doubt, obviating the need for paleosalinity analysis, and the watermasses of different salinities. In continental settings,
generally limited accumulation of biogenic Ba in marginal- weathering of sulfur in any form generally leads to its oxi-
marine deposits limits its influence on measured bulk- dation to highly soluble sulfate (SO24 ). Freshwater lakes
sediment Sr/Ba ratios in such settings. Biogenic Ba concentra- and rivers tend to have low sulfate concentrations (2–
tions can usually be estimated through correlation of total Ba 200 ppm; mean 27 ppm) (Berner and Raiswell, 1983),
to Al concentrations (e.g., Shen et al., 2012, their Fig. 6A; which is 0.1–10% of the sulfate concentration of modern
Shen et al., 2015, their Fig. 4) or, occasionally, to other seawater (28 mM, or 2900 ppm; Yao and Millero, 1996).
productivity-related proxies such as P and d13C (Shen et al., However, exceedingly high sulfate concentrations (to
2013). In the present study, we crossplotted total Ba versus >50,000 ppm) are encountered in some enclosed alkaline
Al for all sedimentary units for which these data were avail- lake basins, in which sulfate accumulates until removed
able and found no examples with obvious biogenic Ba influ- through precipitation of evaporitic sulfate minerals. Sulfate
ence. We recommend screening for biogenic Ba in all has an exceptionally long residence time in seawater
paleosalinity studies making use of Sr/Ba ratios but anticipate (20 Myr; Claypool et al., 1980), and high sulfate concen-
that it will not commonly be a problem. trations in seawater (>2 mM) are thought to have existed
since at least the Great Oxygenation Event II of the late
3.4. The S/TOC proxy Neoproterozoic (Halverson and Hurtgen, 2007; Algeo
et al., 2015).
3.4.1. Sulfur chemistry Except in evaporitic settings, sulfur is transferred from
Sulfur (S) belongs to group 16 of the periodic table. It the water column to the sediment mainly in a reduced form.
has an atomic number (z) of 16, an atomic weight of The most important reduced species are pyrite S and
organic S, in which S is present mainly in the 2 and 0 oxi-
dation states, and which account for 80–90% and 10–20%
of total sedimentary sulfur, respectively (Berner et al., 1985;
Krouse et al., 1988; Lin and Morse, 1991; Zaback and
Pratt, 1992; Cross et al., 2004). Two modes of sulfate reduc-
tion have been recognized: (1) microbial sulfate reduction
(MSR), in which microbes use sulfate (SO24 ) as an electron
acceptor and simple organic compounds or hydrogen as
electron donors (Sim et al., 2011); and (2) thermochemical
sulfate reduction (TSR), in which sulfate is reduced abioti-
cally at temperatures >100 °C by reaction with ferrous iron
or organic matter (Trudinger et al., 1985). Most sedimen-
tary pyrite precipitates from MSR-generated H2S that
reacts with Fe2+ in the sediment (Berner and Raiswell,
1983, 1984). Although a small amount of organic S is of
bioassimilatory origin, the bulk of organic S also represents
MSR-generated H2S that is taken up by sedimentary
Fig. 6. Aqueous SO24 concentration versus watermass salinity. organic matter through the process of vulcanization
Samples are color-coded by salinity facies: fresh (<1 psu; green), (Eglinton et al., 1994). TSR is regarded as the source of
brackish (1–30 psu; blue), and marine (30–38 psu; red). Data sources high H2S concentrations within deeply buried petroleum
in Table S5. (For interpretation of the references to colour in this
reservoirs (e.g., Heydari, 1997; Krouse et al., 1988; Cross
figure legend, the reader is referred to the web version of this article.)
et al., 2004). Other, minor S fractions in non-evaporitic
sediments include detrital sulfur-bearing phases, carbonate-

associated sulfate (CAS), and adsorbed volcanic aerosols
(Mackenzie and Garrels, 1971; Strauss, 1997; Ivanov and
Freney, 1983).
In our dataset, the median (range) of sulfate concentra-
tions is 12.3 ppm (3–52 ppm) in freshwater, 480 ppm (45–
1718 ppm) in brackish water, and 2950 ppm (2682–
3122 ppm) in seawater. Aqueous sulfate concentrations
show a strong positive linear relationship with watermass
salinity (r = +0.98; p < 0.01; Fig. 6).
3.4.3. Sedimentary sulfur concentrations in modern

depositional systems
Pyrite is the main host of sulfur in most depositional sys-
tems. The formation of pyrite in aqueous systems is con-
trolled by the availability of metabolizable organic
matter, dissolved porewater sulfate, and reactive Fe
(Calvert and Karlin, 1991). The amount of H2S generated
through MSR depends on aqueous sulfate concentrations
in sulfate-limited systems (usually freshwater) versus the
types and amounts of reactive organic matter in C-limited
systems (usually marine) (Berner and Raiswell, 1984;
Calvert and Karlin, 1991; Pallud and Van Cappellen,
2006). Sedimentary S concentrations are generally low in
freshwater systems owing to the limited availability of
aqueous sulfate (Langmuir, 1997) and much higher in mar-
ine systems, in which seawater sulfate (28 mM) is the main
source (Millero, 2011).
In our dataset, freshwater sediments exhibit medians
(ranges) of 0.06% (0.03–0.16%) for sulfur, 2.2% (0.97–
5.2%) for organic carbon, and 0.02 (0.01–0.06) for S/TOC
ratios (Table S7). Brackish-water sediments exhibit medians
(ranges) of 0.69% (0.28–1.53%) for sulfur, 4.4% (2.8–5.7%)
for organic carbon, and 0.18 (0.07–0.35) for S/TOC. Mar-
ine sediments exhibit medians (ranges) of 1.18% (0.48–
1.69%) for sulfur, 4.1% (1.7–6.7%) for organic carbon,
and 0.26 (0.17–0.47) for S/TOC. Thus, S concentrations
are 20 greater (i.e., 1.18%/0.06%) and S/TOC ratios
13 higher (i.e., 0.26/0.02) on average in marine sedi-
ments compared to freshwater sediments. Both S (r = Fig. 7. Sulfur-TOC in modern sediments: (a) S and (b) S/TOC
+0.73; p < 0.01; Fig. 7a) and S/TOC (r = +0.66; p < 0.01; versus watermass salinity, and (c) S versus TOC. In (c), a S/TOC
Fig. 7b) show pronounced positive relationships with threshold of 0.1 is highly effective at differentiating freshwater
watermass salinity. The data for the salinity interval of 3– versus brackish/marine facies; the latter facies exhibit substantial
overlap is the range of 0.1–0.5, although nearly all samples with
13 psu were drawn from Chesapeake Bay (Mason and
S/TOC > 0.5 are marine. Samples are color-coded by salinity
Lawrence, 1999), and this water body shows an unusually facies: freshwater (<1 psu; green), brackish (1–30 psu; blue), and
rapid increase in [S] and S/TOC with rising salinity marine (30–38 psu; red). For reference, the normal-marine trend
(Fig. 7a, b), probably owing to localized enrichment of pyr- (0.36) of Berner and Raiswell (1983) is shown as a solid line. Data
ite in the deeper anoxic layer of the water column. A sulfur sources in Table S7. (For interpretation of the references to colour
versus TOC crossplot (Fig. 7c) shows considerable overlap in this figure legend, the reader is referred to the web version of this
for marine and brackish samples (the significance of which article.)
will be discussed in Section 3.5) but a largely separate field
for freshwater samples. The S-TOC data for our marine matter is thermodynamically unstable in all diagenetic envi-
sediments bracket the ‘‘normal marine trend” of Berner ronments (Machel, 2001), but here we consider early diage-
and Raiswell (1984), validating it. netic MSR to be part of the processes that ‘set’ the initial
S/TOC ratio of a sediment prior to burial. With deep bur-
3.4.4. Post-depositional alteration of sedimentary S/TOC ial, increasing temperatures can lead to abiotic thermo-
ratios chemical sulfate reduction (TSR), generating large
S/TOC ratios in ancient sediments potentially can be quantities of hydrogen sulfide that represent a loss of
affected by loss of sulfur, carbon, or both during burial dia- solid-phase sulfur from the sediment (Machel, 1987, 2001;
genesis. The association of dissolved sulfate and organic Watanabe et al., 2009). Some loss of H2S takes place from
the maturation of organic sulfur compounds as well, erals (Sim et al., 2011). It should also be noted that S/TOC
although organic sulfur usually constitutes a small fraction can become arbitrarily variable at low TOC and S concen-
(<20%) of total sulfur in sediments (Raiswell and Berner, trations, leading to erroneous salinity evaluations. We rec-
1987). During burial of sediments, increases in temperature ommend limiting S/TOC analysis to samples containing at
and pressure result in degradation of organic matter, least 1.0% TOC, a level below which determinations cannot
mostly through TSR, although the effects are complex be effectively made.
and depend strongly on the specific organic phases present The relative efficacies of the three paleosalinity proxies
(Tissot et al., 1974; Tyson, 2012). Type I and II kerogen, are largely a function of their discriminatory power, which
being more reactive, tend to be lost in larger proportions can be represented by the multiple of elemental concentra-
(up to 60%) than type III kerogen (up to 30%) tions and ratios between marine and freshwater sediments.
(Raiswell and Berner, 1987). With late-stage weathering in For the B-Ga proxy, marine sediments on average contain
the near-surface environment, oxic groundwaters may per- 62 as much B (i.e., 300 ppb/4.8 ppb) and have B/Ga ratios
colate downward and cause loss of S and/or TOC, obscur- 12 higher (i.e., 15.3/1.29) than freshwater sediments. For
ing original depositional S/TOC ratios (Bottrell et al., 1998; the Sr-Ba proxy, marine sediments on average contain only
Petsch et al., 2000; Tyson, 2012). 2 as much Sr (i.e., 160 ppm/79 ppm) and have Sr/Ba
ratios only 2 higher (i.e., 0.43/0.20) than freshwater sedi-
3.5. Salinity facies thresholds and relative efficacies of ments. For the S/TOC proxy, marine sediments on average
paleosalinity proxies contain 20 as much S (i.e., 1.18%/0.06%) and have S/TOC
ratios 13 higher (i.e., 0.26/0.02) than freshwater sedi-
Based on the relationships of modern sediment compo- ments. These differences in discriminatory power are
sitions to watermass salinity, we determined salinity facies reflected in the relative efficacies of the three proxies, as
thresholds for the three elemental proxies considered above. given above: 88% for B/Ga, 66% for Sr/Ba, and
For each proxy, we tested several thresholds over a limited 91% for S/TOC.
range of likely values and selected the ones that most effec- In summary, B/Ga and S/TOC are generally more accu-
tively separated sediments into their known salinity facies. rate predictors of paleosalinity than Sr/Ba. S/TOC is most
For B/Ga, freshwater and brackish sediments are most effective at distinguishing freshwater from brackish-marine
effectively separated by a ratio of 3, and brackish and mar- sediments, although the marine character of sediments can
ine sediments by a ratio of 6 (Fig. 2C). Using these thresh- sometimes be recognized based on very high S/TOC ratios
olds, 180 out of 204 sediment samples are assigned to their (i.e., >0.5). However, all three proxies are valid for pale-
correct salinity facies (i.e., 40 out of 49 freshwater samples, osalinity analysis, and we have found examples (i.e., specific
56 out of 68 brackish samples, and 84 out of 87 marine sam- formations) in which Sr/Ba appears to be more effective
ples), for an overall reliability of 88%. For Sr/Ba, fresh- than B/Ga. Thus, the general patterns summarized here
water and brackish sediments are most effectively do not necessarily pertain to all ancient formations. We
separated by a ratio of 0.2, and brackish and marine sedi- highly recommend the use of multiple paleosalinity proxies
ments by a ratio of 0.5 (Fig. 4C). Using these thresholds, in all studies in order to identify potential problems with
327 out of 493 sediment samples are assigned to their cor- any single proxy that might arise and to ensure accurate
rect salinity facies (i.e., 169 out of 221 freshwater samples, paleosalinity determinations.
88 out of 128 brackish samples, and 70 out of 144 marine
samples), for an overall reliability of 66%. For S/TOC, 4. CASE STUDIES OF PALEOSALINITY ANALYSIS
freshwater sediments are most effectively separated from
brackish and marine sediments by a ratio of 0.1 (Fig. 7C). 4.1. Ordovician marine and Triassic lacustrine facies of
Using this threshold, 968 out of 1064 sediment samples Ordos Basin, North China
are assigned to their correct salinity facies (i.e., 758 out of
824 freshwater samples, 64 out of 89 brackish samples, The Ordos Basin, with an area of 320,000 km2 in the
and 146 out of 151 marine samples), for an overall reliabil- western part of the North China Craton (Fig. 8a), accumu-
ity of 91%. lated mostly marine sediments during the Cambrian to
S/TOC ratios are less effective at separating brackish Ordovician (Yang et al., 2005) but evolved into an inland
and marine sediments, although a threshold of 0.5 distin- basin accumulating terrestrial sediments during the Triassic
guishes a range (i.e., 0.1–0.5) characterized by mixed sam- (Yang et al., 2005; Li et al., 2018). By the Middle-Late Tri-
ples (65 brackish, 123 marine) from a range (i.e., > 0.5) assic, the basin contained a large, deep freshwater lake that
occupied almost exclusively by marine samples (1 brackish, accumulated large amounts of oil-prone organic matter
21 marine). Thus, samples with S/TOC ratios of 0.1–0.5 (Luo et al., 2014).
should be regarded as potentially either brackish or marine, The Pingliang Formation accumulated during the Mid-
whereas those with S/TOC > 0.5 are likely to be marine. dle Ordovician on the western and southern margins of
The reason for the relatively poor discrimination of brack- the Ordos Basin (Ni et al., 2011; Li et al., 2018). It contains
ish versus marine sediments is that the S/TOC proxy a mixture of shallow platform/shelf facies and semi-deep
depends not only on sulfate concentrations (i.e., as an elec- slope facies, all of which are fully marine (Fig. 8b). A total
tron acceptor) but also on the availability of labile organic of 6 mudstone samples from 3 different outcrops of this for-
substrates to drive microbial sulfate reduction (MSR) and mation was analyzed (Ni et al., 2011; Table S8). The medi-
thus generate a precursor (H2S) to sedimentary sulfide min- ans (ranges) of B concentrations are 79 ppm (54–110 ppm),
Fig. 8. (a) Geologic map of the Ordos Basin, showing locales of Ordovician Pingliang Formation (red) and Triassic Yanchang Formation
(green). (b) Stratigraphic column of Middle Ordovician Pingliang Formation in study area (modified from Ni et al., 2011). (c) Stratigraphic
column of Upper Triassic Yanchang Formation in study area (modified from Li et al., 2018).
Ga concentrations are 13.8 ppm (11.3–18.1 ppm), and Triassic Chang 7 Member, which consists of oil shale, mud-
B/Ga ratios are 5.5 (4.7–6.3) (Fig. 9a). The medians stone, and silty mudstone (Fig. 8c), from locales on the
(ranges) of Sr concentrations are 199 ppm (102–645 ppm), Weibei Uplift of the southern Ordos Basin. A total of 16
Ba concentrations are 392 ppm (278–486 ppm), and Sr/Ba samples from three sections were analyzed (Li et al., 2017,
ratios are 0.73 (0.25–1.54) (Fig. 9b). TOC ranges from 2018; Table S8). The medians (ranges) of B concentrations
0.05 to 1.0% (median 0.39%; Fig. 9c), and most values (9 are 15.3 ppm (20.4–31.0 ppm), Ga concentrations are
out of 14) are below the threshold (0.5%) for reliable salin- 18.1 ppm (20.8–22.6 ppm), and B/Ga ratios are 0.83
ity interpretations based on S/TOC ratios; in any case, S (0.99–1.47) (Fig. 9a). The medians (ranges) of Sr concentra-
concentration data are not available for this formation. tions are 184 ppm (143–409 ppm), Ba concentrations are
Although some B/Ga ratios plot at the high end of the 587 ppm (463–785 ppm), and Sr/Ba ratios are 0.32 (0.29–
brackish field (i.e., 4.7–6.0), other B/Ga ratios and nearly 0.50) (Fig. 9b). After screening out samples that contain
all Sr/Ba ratios indicate fully marine salinity. Given field TOC < 0.5% (n = 1 out of 14), the medians (ranges) of S
and petrographic evidence of exclusively marine facies in concentrations are 0.48% (0.17–0.77%), TOC concentra-
the Pingliang Formation (Ni et al., 2011), we infer that tions are 12.1% (3.5–21.4%), and S/TOC ratios are 0.05
the B/Ga and Sr/Ba proxies are consistent with an interpre- (0.03–0.09) (Fig. 9c). The B/Ga and S/TOC ratios are
tation of fully marine salinity conditions. indicative of fully freshwater salinities, whereas the Sr/Ba
The Middle to Upper Triassic Yanchang Formation is a ratios plot entirely within the brackish field. Given the
1000–1300-m-thick succession of lacustrine strata (Yao known lacustrine character of these units, we infer that
et al., 2013). It has been subdivided into 10 members the B/Ga and S/TOC ratios are correctly identifying fresh-
(Chang 1–10) on the basis of sedimentary cycles and water conditions, and that the Sr/Ba ratios are somewhat
lithologies (Li et al., 2018). Here, we examine the Upper higher than typical for freshwater systems, owing to (e.g.)
(Yuan et al., 2007; Wu and Zhang, 2015). However, the

timing and extent of these marine incursions remain poorly
known, and their significance for source rock formation has
not been unequivocally demonstrated. Here, we examine
changes in watermass salinity during deposition of the
mid-Eocene Es3L submember of the Shahejie Formation
from the central Dongying Depression (Fig. 10b). Elemen-
tal data (B, Ga, Sr, Ba, TOC and S) were generated for
samples collected from a 129-m-thick interval (2911.00–
3140.75 m) in drillcore Luo-69 (Fig. 10c; Wei et al., 2018).
The medians (ranges) of B concentrations are 32 ppm
(14–70 ppm), Ga concentrations are 5.0 ppm (2.2–
8.5 ppm), and B/Ga ratios are 6.5 (3.2–12.7) (Fig. 11a).
The medians (ranges) of Sr concentrations are 1203 ppm
(127–11000 ppm), Ba concentrations are 460 ppm (100–
2110 ppm), and Sr/Ba ratios are 2.1 (1.0–15.8) (Fig. 11b).
The medians (ranges) of S concentrations are 0.9% (0.7–
2.2%), TOC concentrations are 2.4% (1.4–5.5%), and
S/TOC ratios are 1.2 (0.6–2.2) (Fig. 11c) (note: all samples
contained TOC > 0.5%; n = 21). These values are broadly
consistent with brackish to marine conditions. All three
proxies exhibit pronounced trends toward lower values
from the base to the top of the study section, with B/Ga
declining by 40% from Zone A (9.1) to Zone C (5.4)
(Fig. 10c), Sr/Ba declining by 41% from Zone A (2.6) to
Zone C (1.7), and S/TOC declining by 65% from Zone
A (0.75) to Zone C (0.26; note: all values are means; Wei
et al., 2018). We note that the Sr/Ba ratios of the study
units are higher than those for modern aqueous systems,
the reason for which is almost certainly the presence of
incompletely corrected carbonate Sr (we screened for car-
bonate Sr, but these units are rather carbonate-rich making
full corrections impossible). We also note that Zone A is
exceptionally S-enriched, so the ratio of Zone C mean S/
TOC (0.26) to normal-marine S/TOC (0.36; Berner and
Fig. 9. Salinity proxies for marine mudstones of the Middle Raiswell, 1983) may provide a better estimate of the salinity
Ordovician Pingliang Formation (red) and lacustrine oil shales of decline during Es3L deposition (30%) than the Zone C/A
the Upper Triassic Yanchang Formation (green). (a) B versus Ga; ratio (65%). The proxy values at the base of the study sec-
(b) Sr versus Ba; and (c) S versus TOC. Data from Ni et al. (2011); tion are consistent with fully marine conditions, and, if
Li et al. (2017, 2018). Note: no S data available for the Pingliang taken as marine baseline values (i.e., 35 psu), then upsection
Formation in (c). (For interpretation of the references to colour in declines of 30–40% are indicative of a corresponding
this figure legend, the reader is referred to the web version of this
decline in watermass salinity (i.e., to 21–25 psu).
article.)
In summary, all three proxies are consistent with a grad-
ual decline of 30–40% in watermass salinity during deposi-
tion of the middle Eocene Es3L submember of the Shahejie
unusual lakewater chemistry, uncorrected carbonate Sr Formation in the Dongying Depression of the BBB. It
contamination, or post-depositional addition of Sr. should be noted that structural partitioning of the BBB into
multiple depressions was a product of Neogene tectonism,
4.2. Paleogene brackish to marine facies of Bohai Bay Basin, and that the BBB was a single large lacustrine basin in
northeastern China the Eocene. For this reason, the salinity interpretations
above are probably representative of the entire BBB region
The Bohai Bay Basin (BBB) is a major hydrocarbon during deposition of the Shahejie Formation, although
province in northeastern China containing thick accumula- paleosalinity analysis of drillcores from other parts of the
tions of fluvial and lacustrine source rocks during the Pale- BBB will be needed to verify this inference. Furthermore,
ogene (Wang et al., 2008; Fig. 10a). At that time, it formed Wei et al. (2018) showed that larger amounts of well-
a huge (2 105 km2) lake separated from the Pacific Ocean preserved, high-quality organic matter were associated with
by tectonic uplifts along the East Asian margin, but episo- the more brackish conditions of Unit C compared to the
dic breaches of these uplifts are thought to have led to mar- marine conditions of Unit A, indicating that seawater
ine incursions into the BBB, as evidenced by glauconite, incursions may have been generally detrimental to source-
calcareous nanofossil, macrofossil, and geochemical data rock accumulation.
Fig. 10. (a) Geologic map of the Bohai Bay Basin and location of drillcore Luo-69. (b) Stratigraphic column of middle Eocene Es3L
submember of Shahejie Formation. Modified from Wei et al. (2018) with original data from Liu et al. (2016), Wang et al. (2015), Feng et al.
(2016), and Ma et al. (2017), and astronomical age model from Liu et al. (2018). (c) Chemostratigraphy of study interval, with subdivision into
three zones based on lithofacies, geochemistry, and fossil content (see Wei et al., 2018, for full discussion).
5. GENERAL CONSIDERATIONS likely to have homogenized the proxy record of salinity

variations at length scales ranging from a few millimeters
Other factors such as sedimentation rates and localized, to a few centimeters in undisturbed (i.e., laminated) sedi-
non-riverine point sources of solutes have the potential to ments. Where physical and biological mixing of sediments
influence the paleosalinity proxies considered here. Many have occurred, the length scales of proxy homogenization
aqueous depositional systems exhibit salinity variations at are potentially much larger (Larsen and Chilingar, 1983;
geologically short timescales, ranging from subannual Revil et al., 2002).
(Ridd and Stieglitz, 2002) to annual (Boyer et al., 2005) Non-river point sources of particulates or solutes may
and longer variation (Pahnke et al., 2003). Given typical locally influence the contents of B, Ga, Sr, Ba and S in
sedimentation rates of 1–10 cm/kyr for ancient (>1 Ma) the sediment independently of watermass salinity
marine and lacustrine depositional systems (Sadler, 1981), (Jørgensen et al., 1992; Dai et al., 2008; Pyle et al., 2017).
samples of from one to a few centimeters thickness typically For example, volcanic activity can lead to local enrichments
represent at least several hundred to several thousand years of B and S in sediments (Jørgensen et al., 1992; Dai et al.,
of sediment accumulation. Thus, salinity analysis of most 2008; Zhou et al., 2016), and hydrothermal vent systems
stratigraphic sections will be subject to an inherent represent a point source of Ba to seawater (Edmond
medium-scale filter rendering recognition of short-term et al., 1979; Von Allmen et al., 2010; Pyle et al., 2017). At
salinity variations impossible, although higher temporal longer timescales, the Sr content of seawater may vary
resolution may be possible in sections that are stratigraph- owing to changes in Sr fluxes from mid-ocean ridge volcan-
ically expanded (e.g., Osete et al., 2007). However, it is ism (Raymo et al., 1988). Furthermore, it is well-established
doubtful whether higher temporal resolution in paleosalin- that seawater sulfate concentrations were much lower in
ity proxy records can be achieved through application of Neoproterozoic oceans than in the modern (Kah et al.,
high-density analytical techniques (e.g., laser ablation). 2004; Algeo et al., 2015), which is likely to result in system-
This is because vertical diffusion of porewater solutes is atically lower S/TOC ratios in sedimentary rocks of that
study establishes a solid basis for the use of boron/gallium

(B/Ga), strontium/barium (Sr/Ba), and sulfur/total organic
carbon (S/TOC) ratios as salinity proxies in fine-grained
siliciclastic units (muds/shales/mudstones) lacking signifi-
cant carbonate content. Aqueous B and Sr, which are pre-
sent in much higher concentrations in seawater than in
fresh water, are readily adsorbed onto clay minerals and,
to a lesser degree, organic matter and Fe-oxyhydroxides,
resulting in substantially higher B/Ga and Sr/Ba ratios in
marine sediments relative to freshwater sediments. Calibra-
tion of these proxies as a function of salinity in modern
watermasses allows identification of optimal salinity facies
thresholds. For B/Ga, sedimentary ratios of <3, 3–6, and
>6 are indicative of freshwater, brackish, and marine facies,
respectively. For Sr/Ba, sedimentary ratios of <0.2, 0.2–0.5,
and >0.5 are indicative of freshwater, brackish, and marine
facies, respectively. For S/TOC, sedimentary ratios of <0.1,
0.1–0.5, and >0.5 are indicative of freshwater, brackish or
marine, and marine facies, respectively. S/TOC does not
discriminate effectively between brackish and marine facies,
because microbial sulfate reduction (MSR) can be
Corg-limited rather than sulfate-limited in both facies. The
accuracies of these thresholds for prediction of salinity
facies are 88% for B/Ga, 66% for Sr/Ba, and 91%
for S/TOC based on modern sediments. The Sr/Ba proxy
is slightly less robust than B/Ga and S/TOC owing to the
common influence of carbonate Sr and/or to greater mobil-
ity of Sr and Ba in the burial environment. However, we
strongly advocate the systematic use of multiple proxies
in order to support paleosalinity interpretations.
ACKNOWLEDGMENTS
We thank Hui Jian for assistance with drafting figures. This

research was funded National Science and Technology Major
Project (2016ZX05027001-005, 2017ZX05049004), National
Natural Science Foundation of China (41690134, 41802175), and
China Scholarship Council (CSC). The project was supported by
the Fundamental Research Funds for National Universities, China
University of Geosciences (Wuhan).
Fig. 11. Crossplots of (a) B vs Ga, (b) Sr vs Ba, and (c) S vs TOC.
Data plotted by sample location in Zones A (green), B (red), or C
(blue) of Luo-69 drillcore. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version APPENDIX A. SUPPLEMENTARY MATERIAL
of this article.)
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.gca.2019.06.034.
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Elemental proxies for paleosalinity analysis of ancient shales and mudrocks

Article in Geochimica et Cosmochimica Acta · July 2019

Wei Wei Thomas Algeo

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Elemental proxies for paleosalinity analysis of ancient shales

Keywords: Boron; B/Ga; Sr/Ba; Brackish; Freshwater; Seawater

a median of 5.3 10 3 ppb, and Ga in seawater ranges

3.2.4. B and Ga concentrations and ratios in sediments

3.2.5. Diagenetic remobilization of B and Ga in sediments

Broecker, 1970; Sigg et al., 1987; Lea and Spero, 1994;

3.3.3. Sr and Ba concentrations and ratios in natural waters

3.3.4. Sr and Ba concentrations and ratios in sediments

3.3.6. Inﬂuence of carbonate Sr on bulk-sediment Sr/Ba

sediments include detrital sulfur-bearing phases, carbonate-

3.4.3. Sedimentary sulfur concentrations in modern

(Yuan et al., 2007; Wu and Zhang, 2015). However, the

5. GENERAL CONSIDERATIONS likely to have homogenized the proxy record of salinity

study establishes a solid basis for the use of boron/gallium

We thank Hui Jian for assistance with drafting ﬁgures. This

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