Accepted Manuscript

Uncertainties in tritium mass balance models for groundwater recharge estima-

tion

Zhi Li, Scott Jasechko, Bingcheng Si

PII: S0022-1694(19)30096-4
DOI: https://doi.org/10.1016/j.jhydrol.2019.01.030
Reference: HYDROL 23425

To appear in: Journal of Hydrology

Received Date: 5 September 2018

Revised Date: 29 December 2018
Accepted Date: 1 January 2019

Please cite this article as: Li, Z., Jasechko, S., Si, B., Uncertainties in tritium mass balance models for groundwater
recharge estimation, Journal of Hydrology (2019), doi: https://doi.org/10.1016/j.jhydrol.2019.01.030

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Uncertainties in tritium mass balance models for groundwater recharge estimation

Zhi Li1, Scott Jasechko2, Bingcheng Si3

1
College of Natural Resources and Environment, Northwest A&F University, Yangling, Shaanxi, China
2
Bren School of Environmental Science and Management, University of California, Santa Barbara, California,
United States of America
3
Department of Soil Science, University of Saskatchewan, Saskatoon SK, Canada
Correspondence to Zhi Li (lizhibox@nwafu.edu.cn)

Abstract: Understanding the time that water takes to traverse the vadose zone is important to
quantify groundwater recharge rates and to assess the vulnerability of aquifers to contamination.
Tritium mass balance models provide measurement-driven estimates of soil water velocities, yet
uncertainties embedded in these groundwater recharge estimates are rarely investigated. Here we
analyze six >15-m tritium profiles collected from thick unsaturated zones located on China’s
Loess Plateau and compare recharge rates obtained from various calculation approaches. Models
used to estimate recharge based on unsaturated zone data include the tritium peak method and
the tritium storage method; models used to estimate recharge using saturated zone data include
the ‘modern groundwater’ method and a method that assumes groundwater is well-mixed in the
aquifer. The tritium peak method presents reliable recharge; however, the recharge from the
tritium storage method is two times of that from the tritium peak method. The well-mixed
reservoir method overestimates groundwater renewal rates because the implicit assumption that
groundwater is well-mixed in aquifers is not realistic. For potential recharge, considerable
uncertainties arise from precipitation tritium reconstruction; while for actual recharge estimation,
uncertainties come from the mismatched recharge mechanism between the model assumption
and local characteristics. Selection of appropriate tritium mass balance models is of utmost
importance for recharge estimation.

Keywords: tritium-based recharge model; uncertainty analysis; precipitation tritium

reconstruction; modern water percentage; potential recharge

1 Introduction

Quantifying recharge is important for understanding groundwater sustainability and

pollution vulnerability (Böhlke and Denver, 1995; Johnston et al., 1998; Currell et al., 2010;
Pang et al., 2013; Han et al., 2015; Alikhani et al., 2016; Hagedorn et al., 2018). Tritium (3H)

1
levels in subsurface waters are measured widely to develop data-driven estimates of groundwater
recharge (Vogel et al., 1974; Allison and Hughes, 1978; Małoszewski and Zuber, 1982; Gaye
and Edmunds, 1996; Le Gal La Salle et al., 2001; Chen et al., 2006; Wang et al., 2008; Gleeson
et al., 2016). However, tritium-based recharge estimates are often highly-uncertain (Cartwright
and Morgenstern, 2012; Cartwright et al., 2017; Li and Si, 2018). It is therefore important to
evaluate uncertainties to improve interpretations of estimated recharge rates.
Tritium-based assessments of groundwater recharge can be classified into two broad groups
according to the employed subsurface waters (Scanlon et al., 2002). The first group estimates
potential recharge—deep drainage bypassing the shallow and often root-rich portion of the
vadose zone—using tritium measurements of waters within unsaturated zones (i.e. soil water).
This first group includes the ‘tritium peak method’ and ‘tritium storage method’ (Table 1). The
second group estimates actual recharge or aquifer renewal rates using tritium measurements from
saturated zones (i.e. groundwater). This second group includes ‘modern groundwater’
calculations and aquifer renewal rate calculations that assume aquifer systems are well-mixed
(the validity of this assumption is unclear; Table 1). The two groups focus on partially-
overlapping hydrological processes: the first—downward soil water movements; the second—
precipitation’s transformation into groundwater via recharge. Critically, each approach requires
assumptions and applications of imperfect input data that introduce uncertainties into resulting
tritium-based H2O flux estimates.

Tritium-based approaches estimate recharge by comparing the tritium mass in soil water or
groundwater by meteoric tritium inputs via precipitation. The uncertainties in the estimated
recharge rates thus arise from two aspects: model input data and model assumptions (Scanlon,
2000; McGuire and McDonnell, 2006; Gallart et al., 2016). Model inputs include the tritium
contents in precipitation and in the sampled subsurface water (soil water or groundwater). In
general, tritium contents in soil water or groundwater are determined from sampling and
subsequent measurements, and these uncertainties derive from analytical uncertainties
(Morgenstern and Taylor, 2009), which can be reduced by enriching samples or using ultra-low
level liquid scintillation spectrometer. For precipitation inputs, time series of precipitation tritium
dating from the year ~1953 are needed. So far, the International Atomic Energy Agency’s
(IAEA’s) Global Network of Isotopes in Precipitation (GNIP) stations provide the longest
records of precipitation tritium. However, most of these records are discontinuous, short-in-

2
length, and cover the globe incompletely. At the majority of locations where tritium is used to
tracer soil- and ground-water movements, precipitation tritium time-series must be reconstructed.
Methods applied to reconstruct precipitation tritium include interpolation (Watson, 1971; Celle et
al., 2001) and reference curve methods (Weiss and Roether, 1980; Wu, 1986; Doney et al., 1992;
Zhang et al., 2011). Yet reconstructed precipitation tritium time series derived from either
approach can differ substantially, with interpolation-based methods possibly outperforming
reference curve methods in some areas (Zhai et al., 2013; Li and Si, 2018).

Table 1 Methods used for groundwater recharge estimation

No Method Equation Parameter Description Source
zp and zr are the depth of tritium peak
Estimate diffuse
and active rooting zone; Δt is the
Tritium recharge as percentage Si and
elapsed years since 1963; θ(z) and is
Eq.1 peak of mean annual de Jong
volumetric water content at depth z or
method precipitation based on (2007)
the average value for the profile of
soil water movement.
interest.
Ts is the total amount of tritium stored in
Estimate diffuse
the profile, Tp the decay corrected total
recharge as the ratio of
Tritium tritium inputs from precipitation; Pi the Allison
tritium stored in profile
Eq.2 storage annual precipitation amount; Tpi is the et al.
to accumulated tritium
method tritium content in the ith year (1994)
inputs from
precipitation amount; λ is the
precipitation.
radioactive constant.
Tsample, Told and Tmodern represent 3H for
groundwater in sample (Tsample), and the
Estimate of the
possible range of tritium activities for
percentage of
Modern precipitation that fell more than 50 years Gleeson
groundwater less than
Eq.3 water before the sample was analyzed (Told) or et al.
~50 years old expressed
percentage more recently (Tmodern; radioactive decay (2016)
as the ratio of modern
between the time the precipitation fell
groundwater to sample.
and the time the sample was measured is
accounted for)
Estimate renewal rate
Le Gal
Well- Tgw is groundwater tritium content; Rr is as the fraction of
La
mixed the annual renewal rate; To is the tritium aquifer volume.
Eq.4 Salle et
reservoir content of input water; i is the time by Assuming a complete
al.
model year. mixing of groundwater
(2001)
within the aquifer.

Model assumptions regarding recharge mechanisms introduce further uncertainty. For

tritium-based models of potential recharge, the tritium peak method assumes piston flow and
relies on the existence of an identifiable depth at which tritium activities reach a maximum (i.e.,
‘peak’ tritium in the vadose zone), while the tritium storage method estimates recharge
regardless of the recharge mode. As for the models for actual recharge, the well-mixed aquifer
model assumes the complete mixing of old and recently-recharged groundwater within the
aquifer. Groundwaters in aquifer systems are not well mixed; assuming so is an
oversimplification. Modern water calculations estimate the proportion of a groundwater sample

3
that is less than 50 years old, making no assumptions about the degree of mixing in the aquifer to,
instead, focus on groundwater samples themselves. A similar approach uses the calendar year
1953 as a threshold distinguishing young from old groundwater, and determines the proportion
of a groundwater sample derived from precipitation that fell more recently than the year 1953
(Jasechko, 2016). To understand uncertainties related to the application of these tritium-based
models, inter-model comparisons and evaluations are necessary, but have not been completed
yet.

The reason why a different tritium-based models have not been systematically compared
may be the lack of reliable ground truth data for each type of calculation—that is, the existence
of both a vadose-zone tritium profile and a dataset of tritium levels in underlying groundwaters.
For the methods based on unsaturated zones, complete tritium profiles and precipitation tritium
time series data are required. However, unsaturated zones are relatively thin in many regions
(Fan et al., 2013) and published records demonstrating clear tritium peaks at depth remain
uncommon. To develop clear records of the ‘bomb peak’ (i.e., spike of high tritium associated
with maximum precipitation tritium concentrations ~1963), one usually must focus their study
area to thick unsaturated zones with slow infiltration rates.

China’s Loess Plateau meets these criteria. The loess is up to ~350 m thick, infiltration rates
are expectedly slow, and water tables may be more than 100 m below the land surface. Within
the loess, complete tritium profiles still exist because of the thick unsaturated zone, arid climate
conditions and concomitant low infiltration rates (Lin and Wei, 2006; Zhang et al., 2017; Li et
al., 2018; Li and Si, 2018). China’s Loess Plateau is thus a suitable site to evaluate and juxtapose
tritium reconstruction methods and uncertainties in tritium-based water flux estimates.

In this study, we analyze unusually-deep soil water tritium content datasets (>15 m below
surface) as well as some groundwater (i.e., well water) tritium data in China’s Loess Plateau to
test various approaches for groundwater recharge. With them, we address the following
questions: (i) what is the difference in the estimated recharge inferred from different tritium mass
balance (TMB) models (i.e. soil water tritium contents or groundwater tritium contents)? (ii) how
should we select appropriate TMB models to evaluate groundwater recharge? Overall, the
foremost objective of this study is to analyze world-class vadose-zone tritium profiles from
China to evaluate uncertainties in recharge arising from different TMB approaches.

4
2 Data and Methodology

2.1 Dataset development

Tritium activities of soil water and groundwater samples were measured in China’s Loess
Plateau. Annual volume-weighted precipitation tritium contents were extracted from IAEA
Global Network of Isotopes in Precipitation (GNIP) stations. The available precipitation data
span the 1980s through the 1990s. Because precipitation tritium time-series spanning the tritium-
peak in the year 1963 are critical to recharge estimation, reconstructing precipitation tritium prior
to the 1980s is important. Several sites from nearby regions with precipitation tritium records for
the 1960s−1970s were chosen to reconstruct precipitation tritium for years preceding the 1980s:
Pohang (Korea), Tokyo (Japan), Irkutsk (Russia), Hong Kong (China), and Ottawa (Canada)
(Table 2).

Table 2 Sites from IAEA used as reference sites for data reconstruction or method evaluation
Site WMO code Longitude Latitude Data period Years of record
Hongkong 4500400 114.17 22.32 1961-1982, 1985-2009 47
Irkutsk 3071000 104.35 52.27 1969-1976, 1980-1983 12
Ottawa 7162800 -75.67 45.32 1954-2011 58
Pohang 4713800 129.38 36.03 1961-1976 16
Tokyo 4766200 139.77 35.68 1961-1979 19
Batou 5452701 109.85 40.67 1986-1991 6
Lanzhou 5288900 103.88 36.05 1985-1987, 1996-1999 7
Xian 5703600 108.93 34.30 1985-1991 7
Yinchuan 5361400 106.22 38.48 1988-1992, 1999-2000 7
Zhengzhou 5708300 113.65 34.72 1985-1991 7
The former five sites are used for tritium reconstruction and the latter five sites located within the Loess Plateau were used for
method evaluation.

We sampled four 18 m soil profiles by a hollow-stem auger from Changwu County and
Qingjian County in Shaanxi Province during 2014−2015 (Figure 1 and Table 3). Soil samples
were collected at 20 cm intervals. Soil gravimetric water contents were determined by oven
drying (i.e. heating soil samples at 105 °C for 12 hours). Soil water was extracted using
cryogenic extraction method: heating soil samples at 95 °C for 3 hours to evaporate water and
freezing the vapor via a liquid nitrogen cold trap. As soil tritium contents were at high enough
concentrations, no electrolytic enrichment was carried out for soil water before tritium
measurements. Each water sample was mixed with a fluorescent solution (Hisafe 3) at a ratio of

5
8:12 in a 20‐ mL container, and its tritium content was measured by an ultra-low level liquid
scintillation spectrometer (Quantulus 1220, Perkin Elmer) with a detection limit of 10.5 tritium
units (TU) and precision of ±1 TU. The sampling and analyzing methods have been described in
detail in a previous study (Zhang et al., 2017). We also used data reported by Lin and Wei (2006)
that include two 15-m profiles from Pingding in Shanxi Province and Wudan in Inner Mongolia
in 1997−1998. The sampling sites have mean annual precipitation rates ranging from ~300−600
mm, spanning semiarid to sub-humid climates and thus encompassing a range of hydroclimate
conditions.

Figure 1 Locations of soil water and groundwater sampling sites and IAEA gauge for
precipitation tritium measurements

We collected groundwater tritium contents from our own sampling and literature (Figure 1,
Table 3). We sampled groundwater in one well with water level of 100 m below the land surface
in Changwu County in Shaanxi Province in 2016. The groundwater was pumped for half an hour
before collection to ensure the sample represented water stored in the aquifer. The pumped well
water samples mix waters within the aquifer system, especially where the well is perforated
across a long interval. Next, the water sample was electrolytically enriched from 500 mL to 8 ml
before tritium was measured with an ultra-low-level scintillation counter. In addition, we used
tritium contents in groundwater measured at Wudan and Pingding in 1997−1998 (Lin and Wei,
2006), and data from Longchuan measured in 2015 (Tan et al., 2016). One tritium value for one
well water at Wudan, Pingding and Longchuan was collected from literature (note: Longchuan
only has groundwater sample but no soil water tritium profile). The groundwater samples were
collected close to soil sampling sites, reducing the potential for impacts arising from spatial
variability in recharge rates and precipitation tritium time-series. Precipitation amounts were
measured at China Meteorology Administration meteorology stations, and soil water data were
measured directly from the soil profiles.

Table 3 Description of the soil water or groundwater data

Groundwater: Averaged soil water (cm3
Precipitation
Sites Latitude Longitude Tritium (TU) Vegetation cm-3) / Peak depth (m) / Sources
(mm)
/Year Peak tritium (TU) / Year
Farmland 0.31 / 6.0 / 49 / 2014
Changwu 35.24° N 107.69º E 581 2.5 /2016 Our experiment
18-year apple 0.27 / 7.2 / 46 / 2014
16-year grassland 0.15 / 9.8 / 72.2 / 2015
Qingjian 37.25° N 118.30° E 505 NA Our experiment
16-year jujube 0.18 / 12.6 / 57.3 / 2015
Pingding 37.68º N 113.68º E 550 43.4 / 1998 N.A. 0.23 / 10.5 / 235 / 1998 Lin and Wei

6
 (2006)
Lin and Wei
Wudan 42.87º N 118.93º E 360 34.4 / 1997 No vegetation 0.16 / 10.4 / 230 / 1997
(2006)
Longchuan 35.34º N 105.46º E 335 10.5 / 2015 N.A. NA Tan et al. (2016)
N.A., not available.

2.2 Reconstructing precipitation tritium contents

Several methods are available to reconstruct precipitation tritium time series. We applied
the ‘trend surface analysis’ method that assumes precipitation tritium contents are can be
estimated by coupling geospatial data and measurements of precipitation tritium; this method has
been successfully applied in past (Zhai et al., 2013; Li and Si, 2018).

where Ti(x, y) is the tth year tritium content at site (x, y), x and y refer to longitude and latitude, Ai,
Bi and Ci are regression parameter for the tth year.

The equation was fitted with volume-weighted tritium data of Pohang, Tokyo, Irkutsk and
Hong Kong over the period of 1969–1976 (Table 2). The fitted parameters in Table 4 confirm
that precipitation tritium contents are well correlated with the latitudes and longitudes of nearby
sites, suggesting that the established equation can satisfactorily reconstruct precipitation tritium
activities. Subsequently, the regression equation was used to interpolate the annual tritium
contents to the study region for the same period of 1969−1976. Then, linear equations were
developed between the interpolated precipitation tritium contents at the target site and those at
Ottawa for 1969−1976, and used to extrapolate annual precipitation tritium contents to construct
tritium time-series spanning the Ottawa precipitation tritium record: 1954−2011 (Figure 2a). The
above procedures were applied to each station in Table 3.

Table 4 Estimated parameters for trend surface analysis method for the period of 1969−1976
Year A B C R2 F statistic Error variance
1969 -5.84 11.72 446.6 0.99 40.55 1388
1970 -5.24 12.82 333.0 0.97 19.49 3062
1971 -6.64 14.28 456.0 0.98 31.01 2575
1972 -3.39 6.22 273.3 0.99 36.60 462
1973 -2.03 4.69 138.2 0.98 31.75 260
1974 -2.89 5.71 217.8 0.99 38.32 352
1975 -2.59 5.12 190.3 0.98 23.63 459
1976 -2.13 3.89 165.6 0.98 30.26 219

To further evaluate model reliability, we compared modelled precipitation tritium contents

against observations from short-term precipitation tritium records at sites in the vicinity of

7
China’s Loess Plateau: measurements in the 1980s and 1990s for Baotou, Lanzhou, Xian,
Yinchuan and Zhengzhou (Table 2). Overall, the reconstructed results are reproduced
satisfactory (Figure 2b), increasing our confidence in the reconstructed precipitation tritium time-
series. Although the model performance varied across sites, previous work suggests that trend
surface analyses may be the optimal option for precipitation tritium time-series reconstructions
(Zhai et al., 2013; Li and Si, 2018).

Figure 2 (a) Reconstructed time series of tritium contents in precipitation for 1954−2011. (b) Observed
versus reconstructed precipitation tritium contents at five IAEA sites including Baotou, Lanzhou, Xi’an,
Yinchuan and Zhengzhou

2.3 Estimating groundwater recharge

Both unsaturated-zone and saturated-zone TMB models were evaluated. The models for
unsaturated zones focus on soil water movement including tritium peak method and tritium
storage method (Allison et al., 1994; Si and de Jong, 2007). When applying data from saturated
zones, TMB models can be used to estimate the percentage of a groundwater sample comprised
of modern groundwater (i.e. groundwater less than ~50 years old; Gleeson et al., 2016) or
groundwater renewal rates (Equation 3−4 of Table 1) (Le Gal La Salle et al., 2001).

Some other models are also available for recharge estimates in either unsaturated or
saturated zones, such as the convection-dispersion equation for solute transport and lumped
parameter models for groundwater age distribution (Cartwright et al., 2017). However, with
hydraulic parameters related to soil properties or geology, these models may introduce additional
uncertainties that are greater than those arising from the reconstruction of precipitation tritium or
the assumption of a recharge mechanism(s). Instead, the models in Table 1 only include the
amount or tritium contents of precipitation, soil water and groundwater without additional
parameters, and highlight uncertainties from precipitation tritium reconstruction and recharge
mechanism assumptions.
For unsaturated zones, the tritium peak method calculates recharge by dividing the distance
from the bottom of active root zones to peak tritium by the elapsed years and by multiplying by
volumetric water contents (Equation 1 in Table 1). Depths at which soil water tritium reach a
peak were determined by fitting Gauss equations to the tritium-depth profiles. The tritium
storage method indirectly estimates recharge as the ratio of tritium stored in soil profiles to the

8
total atmospheric tritium inputs (Equation 2 in Table 1), and it may represent both piston and
preferential flows that remain within the sampled soil profile. The two methods consider
recharge rates as a percentage of mean annual precipitation.

For the saturated zones, the modern groundwater calculation estimates the proportion of
modern groundwater within a given water sample taken from a certain depth (Equation 3 in
Table 1). The estimated value represents actual recharge from all pathways including piston and
preferential flows. These estimates may also potentially include imperfections in well-bore seals
that allow for fast movements of surface waters down to well intakes. The well-mixed reservoir
model (Le Gal La Salle et al., 2001) estimates the proportion of newly recharged water to the
aquifer, assuming complete mixing in the groundwater aquifer (Equation 4 in Table 1); such
thorough groundwater mixing is unlikely in the great majority of aquifer systems.

For the two models applied to saturated zones, the groundwater tritium activity, older than
50 years or before the earliest recharge events from bomb water, is usually assumed to have a
constant input activity of 10 TU (Le Gal La Salle et al., 2001; Gleeson et al., 2016).
Measurements of precipitation tritium during the early 1950s exist and suggest that most non-
polar precipitation had <10 TU (Craig et al., 1961; Begemann and Libby, 1957; Taylor, 1966;
compilation of pre-bomb precipitation tritium: Jasechko and Taylor, 2015). Here we apply 10
TU as an estimate of groundwater tritium activity before 1954.

2.4 Uncertainty analyses

We completed two levels of uncertainty analyses.

The first level is a presentation of uncertainties associated with each approach used to
estimate recharge (e.g., post-1953 water calculation; tritium peak method). As the two
unsaturated zone models employ mean values of soil water or precipitation, their uncertainties
were estimated by error propagation analyses through a first-order perturbation analysis to the
equations listed in Table 1 (Li et al., 2017). For the saturated zones, the two models mainly use
accumulated precipitation tritium inputs; we applied the methodology reported by Jasechko et al.
(2017) that uses the range of possible precipitation tritium activities for precipitation postdating
the year 1953. This approach also assumes that at least some hydrodynamic dispersion occurs in
the groundwater system by applying a 5-year running average before calculating maximum and

9
minimum Tpost-1953 values, effectively smoothing peaks in the precipitation tritium input curves to
a minor extent.
The second level is an inter-model comparison to discuss the uncertainties from model
inputs and recharge mechanism assumption. Specifically, for the models applied to unsaturated
zones, the tritium peak method provides a reliable baseline as this approach depends less on a
highly accurate precipitation tritium time-series relative to the tritium storage method. Similarly,
for the saturated zones, the post-1953 water percentage presents a baseline to evaluate the other
models since it requires minimal assumptions.

3 Results and Discussion

3.1 Potential recharge in unsaturated zones

Uncertainties in potential recharge were investigated at four sites with tritium profiles
(Changwu, Qingjian, Wudan and Pingding, Figure 3). Soil water contents vary vertically because
of rainfall infiltration and evapotranspiration in shallow layers (mostly in active layers), root
water uptake and soil texture in deep layers, and geologic heterogeneity (Wang et al., 2013). For
example, soil water contents beneath the farmland and apple orchard in Changwu (Figure 3a)
differ at depths of 5−12 m, likely because of greater potential for root water uptake by apple trees
at these depths (Zhang et al., 2017). In addition, temporal-variations in soil water levels at a
given depths is almost constant based on continuously monitoring of soil water profiles (Liu et
al., 2010; Wang et al., 2015a; Wang et al., 2015b).

Tritium profiles show clear peaks and generally reach near-constant low-levels at deeper
depths (Figure 3d-f). At a point scale, soil water movement and groundwater recharge may be
approximated as piston flow. Although preferential flow may contribute to groundwater recharge
in the study area, these paths may be more likely to occur in topographical depressions with
macropores and fissures or holes (Huang et al., 2013; Li et al., 2017; Tan et al., 2017; Huang et
al., 2018). As such, these results support the occurrence of piston flow and further the
applicability of the tritium peak method, though the co-existence of preferential flow paths
cannot be ruled out (Equation 1 in Table 1).

10
Figure 3 Soil moisture (a-c) and tritium profiles (d-f). (a) and (d): Changwu under long-term
farmland and 17-year-old apple trees; (b) and (e): Qingjian under 16-year-old grassland and
jujube; (c) and (f): Pingding and Wudan from Lin and Wei (2006). Vertical lines in d and e
represent the tritium detection limit.

Regarding the tritium peak method, recharge rates, in terms of percentage of mean annual
precipitation, are estimated to be 4.3±1.2% and 3.6±0.9% in Changwu, 5.9±1.6% and 7.2±2.3%
in Qingjian, 10.3±3.1% and 10.8±3.0% in Pingding and Wudan (Table 5). Since these estimates
are independent of reconstructed precipitation tritium (Equation 1 in Table 1), they can be used
as observations to explore the impact factors of recharge and to evaluate the other methods. At
the same site, the recharge rates are similar with small variations under different land use types.
Overall the recharge rate estimates are similar among the study sites, possibly because they were
all farmlands in 1963 and because more recent land use changes may not have impacted the
depths that tritium levels peak. Small inter-site recharge rate variations may be influenced by
variable soil water contents arising from the different land use types and hydroclimatic
conditions among the sites.
In contrast, the tritium storage method results in recharge rates that are consistently greater
than the tritium peak method, exceeding the latter by a factor of ~two at most sites. Specifically,
the recharge rates are 7.4±1.2% and 7.3±1.0% in Changwu, 12.4±1.7% and 15.1±3.3% in
Qingjian, 23.2±3.7% and 12.3±1.8% in Pingding and Wudan (Table 5). If one assumes the
tritium peak method is a baseline, we conclude that the tritium storage method overestimates
recharge rates. As the tritium storage method estimates recharge through dividing the tritium
mass in soil by the atmospheric flux (Equation 2 in Table 1), the overestimated values may be
attributed to a larger soil water tritium mass or a smaller atmospheric tritium flux.
Table 5 Estimated diffuse recharge from data related to precipitation and soil water
Tritium peak method (%) Tritium storage method (%)
Site Vegetation
Average Error Average Error
Changwu 18-year apple 4.3 1.2 7.4 1.2
Changwu Farmland 3.6 0.9 7.3 1.0
Qingjian 16-year Jujube 5.9 1.6 12.4 1.7
Qingjian 16-year grassland 7.2 2.3 15.1 3.3
Pingding N.A. 10.3 3.1 23.2 3.7
Wudan No vegetation 10.8 3.0 12.3 1.8
Recharge rate is expressed as the percentage of mean annual precipitation.

11
 For the tritium storage method, the most likely reason for larger soil water tritium mass is
the high tritium detection limit, since tritium activities below 10.5 TU are approximated as 10.5
TU. The lower atmospheric tritium flux is likely to be caused by an underestimation arising from
the precipitation tritium reconstruction method. To evaluate the impacts on recharge estimates,
we carried out a sensitivity analysis of recharge rates to changing tritium detection limit from 0
to 10.5 TU or to increase in atmospheric tritium flux by 0 to 70% (Figure 4). Replacing soil
water tritium contents smaller than 10.5 TU with values from 0 to 10.5 TU, the recharge rates
change little for Qingjian and increase slightly (by ~9%) for Changwu, implying that the tritium
detection limit has little impact on recharge rate estimates. However, increasing the atmospheric
tritium flux up to 70% can decrease recharge rates by ~41%. As such, the larger infiltration rates
from tritium storage method are more likely to arise from underestimates in atmospheric tritium
fluxes.

Figure 4 Sensitivity of groundwater recharge rates, in terms of percentage of annual mean

precipitation, to changing tritium detection limit (a) and perturbed atmospheric tritium flux (b).

3.2 Actual renewal within saturated zones

The modern groundwater percentage—the proportion of groundwater less than ~50 years in
its age—was calculated for four sites using the groundwater tritium in Table 3 and reconstructed
precipitation tritium contents as inputs of Equation 3 in Table 1. The modern groundwater
percentage is 13% (ranging 4−44%), 56% (ranging 11−100%), 83% (ranging 19−100%) and
58% (ranging 12−100%) for samples collected at Changwu, Longchuan, Pingding and Wudan,
respectively (Table 6).

Table 6 Estimated recharge from data related to precipitation and groundwater

Modern groundwater
Groundwater: Tritium (TU) Mean annual renewal
Sites percentage (%)
/Year rate (%)
Mean Range
Changwu 2.5 /2016 13 4−44 0.23
Longchuan 10.5 / 2015 56 11−100 1.35
Pingding 43.4 / 1998 83 19−100 −
Wudan 34.4 / 1997 58 12−100 2.72
−, no results because the groundwater tritium contents exceed the ranges of groundwater tritium content versus
renewal rate curve

12
 With the well-mixed reservoir model, the relationships of groundwater renewal rate and
tritium activity can be analyzed according to Equation 4 in Table 1. For a series of given renewal
rates, a series of groundwater tritium activities were calculated to develop a renewal rate-tritium
activity curve (Figure 5). These curves can be used to identify the renewal rate of different
groundwater tritium contents. The mean annual renewal rates differ for the three sites: 0.23%,
1.35% and 2.72% for Changwu, Longchuan and Wudan (Table 6). The renewal rate in Pingding
(groundwater sample with 43.4 TU) cannot be estimated since the measured groundwater tritium
activity exceeds the highest groundwater tritium content in the renewal rate–tritium content
curve.

Figure 5 Curves of groundwater renewal rate versus tritium activity. P+X% represents curves
perturbed by increasing precipitation tritium contents by 0%, 10%, 30%, 50%, 70% and 100%.

To compare the results from the two methods, we convert mean annual renewal rates to
modern groundwater percentages through multiplying the mean annual renewal rates by the
period from 1954 to the sampling year (data are presented in Table 6). Consequently, the
indirectly estimated modern water percentages are 14% for Changwu, 83% for Longchuan, and
117% for Wudan. The results are much larger than those from the modern percentage method
(Equation 3 in Table 1). Although the two methods – i.e., the modern percentage method
(Gleeson et al., 2016) and the renewal rate method (Le Gal Le Salle et al., 2001) – use the same
datasets, they present different results because of the assumptions associated with each approach.

For assumed recharge mechanism, the modern percentage method represents all recharge
sources since the results are for specific groundwater samples, not for the whole aquifer. Modern
water percentages tend to decrease with increasing depth of groundwater, demonstrating that
complete mixing in aquifer systems is unlikely (Gleeson et al., 2016). The well-mixed reservoir
method largely presents groundwater renewal rates for the whole aquifer based on the
assumption of complete mixing (Le Gal La Salle et al., 2001); as such, it is probably most
relevant in thin aquifers with shallow water tables as these conditions that increase the likelihood
that groundwater tritium levels are consistent throughout the aquifer.

Tritium is measurable in groundwater, despite the fact that tritium peaks in soil profiles
have not reached water table (Figure 3). Our finding is consistent with the interpretation that
preferential flows bypass longer-term soil storage without mixing completely with pre-existing

13
soil water (Brooks et al. (2010)). The multiple modes of recharge thus violate the assumption of
well-mixed reservoir model, indicating assumptions linked to this method are inappropriate.

As for the effects of reconstructed precipitation tritium contents, the two models estimating
actual recharge both use decay-corrected 3H of groundwater recharged from pre- and post-bomb
water. The pre-bomb water tritium before decay-corrections was assumed to be 10 TU, and
subsequently the decay-corrected tritium value was near zero. As such, the recharge rates from
the two models are dominated by post-bomb water. As evaluated by the data from unsaturated
zones, the precipitation tritium contents were likely underestimated; as such, these approaches
overestimate modern groundwater percentages and renewal rates according to Equation 3 and 4
in Table 1. The incalculable renewal rate in Pingding with high groundwater tritium content is
probably caused by the groundwater tritium contents – renewal rates biased by the
underestimated precipitation tritium contents, along with potentially inappropriate assumptions
embedded in the renewal rate methodology (i.e., the assumption that the aquifer systems is well-
mixed; Le Gal La Salle et al., 2001).

To further address the effects of reconstructed precipitation tritium contents on recharge

rates, we carried out a sensitivity analysis through increasing the precipitation tritium input
estimates by a factor of 1.1 to 2 (i.e., by 10-100% for each time; Figure 5). By increasing
precipitation tritium contents up to 100%, annual mean renewal rates decrease from 0.23% to
0.11% for Changwu, 1.35% to 0.49% for Longchuan, from 2.72% to 0.81% in Wudan. We note
that the renewal rate in Pingding has values of 2.5% to 1.1% when the precipitation tritium
contents increase by 30% to 100%. The effects of reconstructed precipitation tritium contents on
modern water percentage are similar as those on renewal rates.

4 Summary

Although tritium mass balance-based recharge estimates are currently questioned for their
applicability because of decay of the 1963-tritium peak and dispersion in subsurface water, they
are not yet obsolete. In the northern hemisphere, TMB models will remain valuable for mapping
the pre-bomb groundwater volumes for some regions in future (Eastoe et al., 2012; Cartwright et
al., 2017). For example, measured rainfall tritium contents in June 1963 in Ottawa (5817 TU)
will remain above 10 TU through 2075, suggesting potential use of TMB methods for at least
another decade(s). Further, TMB methods remain applicable to regions with thick unsaturated

14
zones, since some soil water tritium profiles can still capture tritium peaks (Smith et al., 1970;
Edmunds and Walton, 1978; Cook et al., 1992; Bertolo et al., 2006; Lin and Wei, 2006; Li et al.,
2018; Li and Si, 2018). In the southern hemisphere, atmospheric tritium inputs from nuclear
bomb testing were relatively low, and these bomb-peaks may have decayed to negligible levels
in places.

However, without reliable recharge rates, the uncertainties in TMB models cannot be truly
tested. We used >15-m soil water tritium profiles and groundwater tritium measurements to
explore uncertainties in TMB models that are frequently applied to unsaturated or saturated zone
datasets. For the models applied to unsaturated zones, the tritium peak method may present
reliable infiltration rates because its accuracy does not depend as strongly on accurately
reconstructing precipitation tritium time-series. However, poor characterization of precipitation
tritium time series may be problematic for the tritium storage method, as underestimated
precipitation tritium fluxes can arise even when applying best available precipitation tritium
reconstruction data and methods. Our results highlight the importance of using accurate
precipitation tritium contents as model inputs for TMB models. However, despite the availability
of various interpolation methods (Watson, 1971; Celle et al., 2001), reference curve methods
(Weiss and Roether, 1980; Wu, 1986; Doney et al., 1992; Zhang et al., 2011) and isotope-
enabled general circulation models (Weiss and Roether, 1980; Koster et al., 1989; Ba and Xu,
2010; Cauquoin et al., 2015), it remains difficult to reconstruct atmospheric tritium time-series.

The well-mixed reservoir approach—designed to calculate recharge rates from groundwater

samples—seems to be more uncertain than approaches designed for unsaturated zone tritium
profiles. The well-mixed reservoir approach is subject to uncertainties arising from both the
precipitation tritium reconstruction process and from inherent assumptions associated with
mixing (cf. Cartwright et al., 2017). Underestimates in precipitation tritium inputs serve to
increase estimates of modern water percentages and renewal rates. Further, results from these
two methods are not comparable because of recharge mechanism assumptions. As groundwaters
stored within different portions of an aquifer system are not well mixed, differences in sampling
infrastructure (e.g., deeper versus shallow wells; wells with short versus long screens) can yield
different tritium measurements because of vertical groundwater age stratification and
heterogeneous flow (e.g., Scott and Richard, 2015). Even in areas with similar recharge
mechanisms, TMB models present variable results because of differences in the extensiveness of

15
the spatial scales each sampling approach characterizes. For example, unsaturated-zone data
provide recharge estimation on point-scale, while groundwater data collected from many wells at
varying depths may provide regional-scale information (Scanlon et al., 2002). Choosing an
appropriate tritium-based model is thus important when applying tracer data to estimate critical-
zone water fluxes (Allison et al., 1994; Scanlon et al., 2002). Our results emphasize that model
selection for saturated zones should take into account precipitation tritium reconstruction
approaches, recharge mechanism assumptions and local hydrogeology.

Although precipitation tritium reconstructions and recharge mechanism assumptions both

introduce uncertainties, comparisons of recharge rate estimates derived from different methods
and sensitivity analyses show that precipitation tritium reconstructions and recharge mechanism
assumptions each contribute considerable uncertainties. It is thus important to improve
precipitation tritium reconstruction methods for long-term recharge estimations. This study
explored uncertainties in tritium-based recharge estimations; however, similar problems exist in
some other tracers. Therefore, our results may be helpful more broadly to tracer-based studies of
groundwater recharge.

Acknowledgments

We appreciate the Data Sharing Infrastructure of Loess Plateau for providing precipitation
data. This study is jointly funded by the National Natural Science Foundation of China
(51179161 & 41761144060) and Natural Science Foundation of Shaanxi Province
(2018JZ4001).

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Figure 1 Locations of soil water and groundwater sampling sites and IAEA gauge for
precipitation tritium measurements

Reconstructed precipitation tritium contents (TU)

(a) (b)
100
4000
Longchuan
Wudan 80
3500 Qingjian
Tritium contents (TU)

Pingding
Changwu 60
3000
Ottawa

40
Baotou
Lanzhou
500 20 Xian
Yinchuan
Zhengzhou
0 1:1 Line
0
1960 1970 1980 1990 2000 2010 0 20 40 60 80 100
Year Observed precipitation tritium contents (TU)
Figure 2 (a) Reconstructed time series of tritium contents in precipitation for 1954−2011. (b)
Observed versus reconstructed precipitation tritium contents at five IAEA sites including Baotou,
Lanzhou, Xi’an, Yinchuan and Zhengzhou

Figure 3 Soil moisture (a-c) and tritium profiles (d-f). (a) and (d): Changwu under long-term
farmland and 17-year-old apple trees; (b) and (e): Qingjian under 16-year-old grassland and
jujube; (c) and (f): Pingding and Wudan from Lin and Wei (2006). Vertical lines in d and e are
tritium detection limit.

20
 7.5 (a) (b) Apple 17yr
25 Farm
Wudan
Pingding
Recharge rate (%) 7.0
Jujube 16yr
20
Grass 16yr

6.5 15
Apple 17yr
6.0 Farmland 10

5
5.5
0.0 2.0 4.0 6.0 8.0 0 10 20 30 40 50 60 70 80
Detection limit (TU) Pertubed atmospheric tritium flux (%)

Figure 4 Sensitivity of groundwater recharge rates, in terms of percentage of annual mean

precipitation, to changing tritium detection limit (a) and perturbed atmospheric tritium flux (b).

30 (a) Changwu 30 (b) Longchuan

Groundwater tritium (TU)

20 20

10 10

0 0

0 2 4 6 8 10 0 2 4 6 8 10
80 (c) Pingding 80 (d) Wudan
Groundwater tritium (TU)

60 60

40 40

20 20

0 0

0 2 4 6 8 10 0 2 4 6 8 10
Renewal rate (%) Renewal rate (%)

P P+10% P+30% P+50% P+70% P+100%

Figure 5 Curves of groundwater renewal rate versus tritium activity. P+X% represents curves
perturbed by increasing precipitation tritium contents by 0%, 10%, 30%, 50%, 70% and 100%.

21
 Highlights

 Six >15-m tritium profiles present a unique record of bomb tritium storage

 Thick tritium profiles were used to evaluate tritium-based recharge estimation

 Recharge rates related to reconstructed precipitation tritium were overestimated

 Recharge mechanism between model assumption and local conditions should match

22