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org/est Article

Machine-Learning Predictions of High Arsenic and High Manganese

at Drinking Water Depths of the Glacial Aquifer System, Northern
Continental United States
Melinda L. Erickson,* Sarah M. Elliott, Craig J. Brown, Paul E. Stackelberg, Katherine M. Ransom,
James E. Reddy, and Charles A. Cravotta, III
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sı Supporting Information

ABSTRACT: Globally, over 200 million people are chronically exposed to arsenic
(As) and/or manganese (Mn) from drinking water. We used machine-learning (ML)
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boosted regression tree (BRT) models to predict high As (>10 μg/L) and Mn (>300
μg/L) in groundwater from the glacial aquifer system (GLAC), which spans 25 states
in the northern United States and provides drinking water to 30 million people. Our
BRT models’ predictor variables (PVs) included recently developed three-dimen-
sional estimates of a suite of groundwater age metrics, redox condition, and pH. We
also demonstrated a successful approach to significantly improve ML prediction
sensitivity for imbalanced data sets (small percentage of high values). We present predictions of the probability of high As and high
Mn concentrations in groundwater, and uncertainty, at two nonuniform depth surfaces that represent moving median depths of
GLAC domestic and public supply wells within the three-dimensional model domain. Predicted high likelihood of anoxic condition
(high iron or low dissolved oxygen), predicted pH, relative well depth, several modeled groundwater age metrics, and hydrologic
position were all PVs retained in both models; however, PV importance and influence differed between the models. High-As and
high-Mn groundwater was predicted with high likelihood over large portions of the central part of the GLAC.

■ INTRODUCTION
Geogenic arsenic (As) and/or manganese (Mn) contamination
of groundwater can limit drinking water availability in aquifers
around the world.1−10 Globally, over 200 million people are
chronically exposed to As and/or Mn.11−13 Inorganic As
exposure is linked to increased risk of cancer (skin, liver,
kidney, bladder)14−19 and to noncancer adverse health
outcomes (immune, nervous, pulmonary, reproductive, car-
diovascular).11,15,20−23 Manganese is an essential element, but
infants and children exposed to higher concentration Mn in
drinking water may suffer adverse survival, neurological, and
intellectual outcomes (infant mortality, intelligence, memory,
attention, motor function, hyperactivity).4,24−28 Groundwater-
quality models can provide important decision-making
information to drinking water managers and others. Con-
tinuous, single-domain deterministic models, however, are
often impractical for modeling expansive, hydrogeologically
complex aquifer systems that provide large populations with
drinking water.
Regulatory and nonregulatory standards or other bench-
marks provide human-health context with which to evaluate
groundwater As and Mn concentrations, but standards differ
among jurisdictions. For example, As standards range from 5
μg/L in Denmark29,30 to 50 μg/L in Bangladesh.31 The U.S.
Environmental Protection Agency (USEPA) and World Health
Organization (WHO) As standards lie within that range, at 10
μg/L.32,33 In the United States, New Jersey and New
Not subject to U.S. Copyright. Published
2021 by American Chemical Society
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Hampshire have standards of 5 μg/L As.34,35 Standards for
Mn typically reflect aesthetics or human-health risk. In the
United States, there is no primary Mn drinking water standard,
nor does WHO have a standard; however the USEPA lifetime
health advisory (HA), U.S. Geological Survey (USGS) health-
based screening level (HBSL), and the standard of the Indian
Bureau of Standards is 300 μg/L.36−38 WHO has a health-
based value of 400 μg/L,33 and Canada has a maximum
acceptable concentration of 120 μg/L Mn;24 the State of
Minnesota has a Health-Based Value of 100 μg/L for infants,
and recommends the USEPA HA of 300 μg/L for older
children and adults.39 Although exposure to lower concen-
trations may have risks, in this paper, we define high
concentrations as >10 μg/L for As (USEPA, WHO standard)
and >300 μg/L for Mn (USEPA HA, USGS HBSL).
High As concentrations in groundwater adversely affect
drinking water quality in geologically diverse aquifers in
Europe, Africa, and North and South America, and particularly
Southeast Asia.2,13,40−45 In unconsolidated aquifers, high As
Received: October 6, 2020
Revised: March 23, 2021
Accepted: March 24, 2021
Published: April 6, 2021
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Environmental Science & Technology
Figure 1. Hydrogeologic setting of the glaciated area of the conterminous United States. (a) hydrogeologic terranes (Table S1), (b) median depth
of domestic wells (presented in Figure A299), and (c) median depth of public supply wells (presented in Figure A299).
has primarily been attributed to release via dissolution of iron
(Fe) and Mn hydroxides under Fe- or Mn-reducing
conditions2,46−48 and desorption at alkaline pH.2,10,48−50
Dissolved oxyanions, such as arsenite (AsIIIO3−3) and arsenate
(AsVO4−3), tend to be weakly sorbed and partly immobilized
by sorption to hydrous FeIII and MnIII−IV oxides at the acidic
pH range (4.5−6.5) of natural groundwater. In the alkaline pH
range (7.5−9.5), sorption of As anions generally decreases with
increasing pH and is accompanied by corresponding increases
in dissolved As concentration. In the United States, As is
commonly found at high concentrations in many important
bedrocks and unconsolidated drinking water aquifers.51−53
High-As solid-phase source material is not necessary to cause
high-As groundwater. Rather, geochemical factors such as
redox condition or pH are often the important drivers of As
mobilization processes.54−61 Consistent with known As
mobilization processes, recent predictive models for As-
affected aquifers in Southeast Asia and elsewhere have found
factors or variables related to redox condition (e.g., ground-
water age, organic carbon, Fe, depth) and pH (e.g., soil
chemistry, precipitation, hydrologic position) to be influential
in predicting As occurrence or hazard.13,41,42,54,61−76
Around the world, important drinking water aquifers are also
adversely affected by high Mn concentrations.3,6,8,12,53,67,77−82
Similar to As, groundwater geochemical factors like redox
condition and pH can influence Mn mobilization.3,6,79,81,82
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High Mn has been attributed to acidic conditions and
reductive dissolution of Mn,6,48,83,84 river-derived dissolved
organic carbon (DOC),85,86 and the oxidation of ammonium
in agricultural areas,87,88 which can decrease pH and enhance
Mn mobility to a significant degree.6 In the United States, high
Mn concentrations are most commonly found in the drinking
water aquifers in the Northeast, upper Midwest, and
Mississippi River Valley.6 Models predicting Mn occurrence
in groundwater find that aquifer, rainfall, land use, hydrologic
properties, and soil type are influential in predicting high
Mn.7,89 Fewer Mn models are found in the literature, however,
compared with the number of As models.
The glacial aquifer system (GLAC) is a collection of aquifers
composed of late Pleistocene/Holocene sediments90 that
underlies parts of 25 states across 1.87 million km2 of the
northern tier of the formerly glaciated area of the
conterminous United States (Figure 1a). The GLAC is the
single largest source of U.S. domestic and public drinking
water, supplying about 30 million people,91,92 but because of
its expanse and heterogeneity, the depth interval used for
drinking water supply wells significantly varies spatially (Figure
1b,c). Arsenic and Mn are the two contaminants most
commonly found at high concentration in groundwater of
the GLAC,58,92 and the GLAC hydrogeological and geo-
chemical setting shares some important characteristics to
deltaic and other unconsolidated, As and Mn-contaminated
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aquifers in different parts of the world: late Pleistocene/
Holocene age, complex layering of aquifers and aquitards, and
geochemical controls on contaminant occurrence or mobi-
lization. Redox condition and pH have been demonstrated to
influence the mobilization of As and Mn in unconsolidated and
bedrock aquifers around the globe3,6,79,93−95 and in the GLAC
specifically.58,92
Arsenic and Mn mobilization processes are related to
spatially distributed predictor variables that can be incorpo-
rated into machine-learning (ML) models, and models can
then be used to map areas likely to have high As and high Mn.
Groundwater age is a key factor relating mechanistic increased
water−rock interaction processes with desirable predictor
variables such as anoxic condition, pH, flowpath length: as
the distance from a recharge area increases, groundwater age,
pH, ionic strength, total dissolved solids, As, Mn, and Fe
generally increase while dissolved oxygen (DO) decreases.
In this study, we demonstrate the use of ML to estimate the
occurrence of As and Mn at concentrations of human-health
concern throughout the GLAC through the process of
statistical learning.96 Our models use a novel set of predictor
variables, which characterize multiple three-dimensional
aspects of the groundwater flow system,97 redox condition,98
and pH,99 to estimate the occurrence of high As and high Mn.
We also include typical measured or interpolated ML predictor
variables, such as aquifer texture and thickness (e.g., percent
coarse material), precipitation, and soil chemistry (e.g., C-
horizon As, Mn). The novel GLAC-specific predictor variables
provide new, three-dimensional, mechanism-related informa-
tion relevant to predicting As and Mn.97−99 Estimates of high
As and high Mn in three dimensions throughout the GLAC
were not previously available.
This study illustrates the utility of using ML to predict the
probability of high As and high Mn in an aquifer system whose
size and complexity precludes the use of single-domain,
process-based modeling approaches. We also demonstrate a
successful approach to significantly improve ML predictions
for imbalanced data sets; ML can result in models biased to the
majority class.100 Our As data were highly imbalanced with
only about 10% of samples having high As, and imbalance is
common for environmental data sets. Across the study area, we
present 1 km spatial resolution maps of predicted probabilities
of high-As and high-Mn groundwater and calculated
uncertainty at the depths of domestic and public supply
wells. Our results can be used to identify areas where elevated
concentrations of As and Mn are likely to occur but where little
data are available, so additional monitoring may be prioritized.
These findings can also inform water managers on the
availability of drinking water supplies, well drillers on improved
well siting (shallower or deeper), and plant operators on
treatment needs and strategies (co-occurrence of contami-
nants). Finally, our modeling methodology could be used in
other areas where high concentrations of As and/or Mn in
groundwater-derived drinking water supplies are known
human-health concerns.
■ HYDROGEOLOGIC SETTING
A brief description of the GLAC hydrogeologic setting is
provided here; detailed descriptions are provided in past
publications and references therein.90,92,101 The glaciated
United States includes Quaternary sediment of glacial
(Pleistocene), postglacial (Holocene), and nonglacial (resid-
uum) materials. Multiple glacial advances and retreats occurred
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in the study area during the Pleistocene (≈2.5 million to
≈12 000 years ago), and most aquifers are composed of
materials from the late Pleistocene (≈22 to ≈12 000 years
ago). Ice contact sediments and outwash are present in
extensive areas of the Midwest; those types of sediments are,
however, generally confined to valleys in the Northeast and
Northwest. At land surface, about 60% of glacial sediment is
till.101 Adjacent to the current Great Lakes and in former
glacial Lake Agassiz (northwestern Minnesota and eastern
Dakotas), lacustrine sediments were deposited in proglacial
lakes.90 Across the GLAC, regional median thicknesses of
sediment range from 6 to 45 m, but the maximum thickness is
more than 500 m in the Northwest. Quaternary sediments
generally contain <10% coarse material, and about 80% of
coarse material lies 25−40 m below land surface. Many (42%)
of the wells are confined by at least 7.5 m of overlying fine-
grained materials. The rest are confined by thinner layers of
fine-grained material or are unconfined. Most drinking water
well depths are 10−50 m.92
Given the nature of glaciofluvial processes and the numerous
glaciations, predicting subsurface geometry and lithology of
buried sediment is difficult in the GLAC. A “hydrogeologic
terrane” classification system (terrane; Figure 1a, Table S1,
Figure S1) has been previously defined on the basis of the
overall thickness of Quaternary sediment,101 the predominant
texture of the geologic materials at land surface,102 the
predominant modes of glacial deposition, and the age of
deposition.90 Two principal caveats apply: within a delineated
terrane, there is substantial hydrogeologic variation, and
terrane boundaries are highly generalized. The terrane
classification system gives context to water availability and
quality.90
Because of the heterogeneity of the GLAC, the typical
depths of drinking water wells vary across the study area by
well use (domestic or public) and by location (Figures 1b,c
and S1). Not surprisingly, median depths of water supply wells
are generally shallower in terranes with thin glacial sediment,
for example, in some eastern and western parts of the study
area, and in southwest Wisconsin (e.g., terranes 1A, 1F, 1G,
1D). Conversely, in the central and western coastal parts of the
study area, where the glacial sediment is thick, water well
depths tend to be deeper (e.g., 1G, 2E, 3B, 4B).
■ METHODS
As and Mn Concentrations in Glacial Aquifer Wells. A
total of 10 001 As and 14 565 Mn measurements and
associated well locations and depths were compiled from
three data sources: a collection of state and local groundwater
ambient monitoring programs (collectively grouped and given
the acronym “GWAM”), U.S. Geological Survey National
Water Information System (NWIS),103 and U.S. Environ-
mental Protection Agency Safe Drinking Water Information
System (SDWIS).104 The maximum and most common
detection levels were both 10 μg/L for As and were 100 and
10 μg/L, respectively, for Mn; therefore, all nondetect values
fell below model thresholds. The three data sources provided
data collected 1988−2018 across the study area (Supporting
Information Table S2, Figure S2). Most sites had one
measurement; if more than one measurement was available
for a site, the most recent value was included in analyses (more
detail in the Supporting Information). Final data sets used to
predict high As and Mn across the GLAC are available online
in a USGS Data Release.105 We predicted the probability of
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high As (>10 μg/L is an event100) and Mn (>300 μg/L is an
event) concentrations in groundwater using boosted regression
tree (BRT) with a Bernoulli distribution.100
A subset of 4486 groundwater sites in the GLAC106 were
used to compute Eh values for samples and plot them on Eh−
pH diagrams of the As, Fe, and Mn stability fields. PHREEQC
v.3.1 (WATEQ4F database)107,108 was used to compute
thermodynamic aqueous species distributions and saturation
with respect to selected minerals (mackinawite (FeS), pyrite
(FeS2), Fe(OH)3(a), pyrolusite, manganite, rhodochrosite, and
pyrochroite). Potential sulfide concentrations for reducing
samples were computed using measured aqueous iron
concentration (assumed Fe+2) in equilibrium with pyrite or
mackinawite.109 Eh and pe are equivalent electrochemical
descriptions of redox potential for a system in equilibrium.110
However, waters at low temperature rarely achieve redox
equilibrium,111 so no single value of Eh or pe can be used to
represent the redox state.108,110 Thus, to ascertain the possible
range of redox conditions of groundwater samples in this
investigation, Eh estimates were computed using the Nernst
equation with activity ratios for several redox pairs:108,110−112
water/oxygen (H2O/O2), methane/carbonate (CH4/CO3−2),
and sulfide/sulfate (H2S/SO4−2). The Eh for the H2O/O2
redox pair was computed using both the standard equilibrium
expression (2H2O = O2 + 4H+ + 4e−; log K −86.08) and the
relation of Sato113 (log K −45.54), which indicates a lower
equilibrium potential at a given pH than the standard log K
and is generally consistent with that for the reaction H2O2 =
O2 + 2H+ + 2e−.
Model Variables. Predictor variables considered for initial
model development were compiled from publicly available data
sets. From the variables that were initially considered, those
with ≥50% missing values, little variance, or high correlation
(r2 ≥ 0.90) to other predictor variables were removed prior to
model tuning. Considered predictor variables included aquifer
properties, soil geochemistry, hydrologic position on the
landscape, and estimates of groundwater age (Supporting
Information Table S3; example maps Supporting Information
Figure S3). Novel predictor variables included recent three-
dimensional models of groundwater age,97 redox condition98
(as indicated by low DO or high Fe), and pH.99 Values for
predictor variables were extracted for each well using ESRI
ArcGIS Desktop software114 depending on source format
because the source data for predictor variables included
discrete and continuous data in both vector and raster formats.
A point extraction method was used to assign variable
attributes directly to each well for all vector data and raster
data having a cell resolution greater than 1 km. A zonal analysis
method was used to assign variable attributes to each well for
raster data having a cell resolution of 1 km or less. A 500 m
radius zone around each well was used to evaluate the variable
raster. Percent categories were computed for discrete raster
data, and summary statistics were computed for continuous
raster data. In the case where the mapped predictor variable
was missing information around a well, no value was assigned.
Model Development. We developed BRT Bernoulli
distribution models to produce three-dimensional probabilities
of high As (>10 μg/L) and high Mn (>300 μg/L) across the
GLAC. A brief description is provided here; additional detail is
presented in the Supporting Information. Analysis was
completed using the gbm (v. 2.1.5115) and caret (v. 6.0−
86116) packages using R (v. 4.0.0117) in Rstudio (v. 1.2.5042).
BRT model tuning consisted of 630 combinations of the
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model parameters: number of trees, interaction depth, and
shrinkage. For both As and Mn, data were divided into training
and testing data sets for model training and testing,
respectively. Testing data, used for evaluating model predictive
performance, consisted of a random subset of 20% of the
original data set. To avoid overfitting, which can result in poor
predictive performance, the As and Mn models were tuned
using the training data set and 10-fold cross validation.118
Cross validation was implemented to optimize sensitivity for
As and accuracy for Mn. From cross-validation (CV) results,
the model with the highest sensitivity for As (to reduce bias
toward nonevents for this imbalanced data set100) and
accuracy for Mn (balanced data set) was identified (CV
models). Simpler models (less complex tuning parameters)
within 1 standard error of the CV models were identified (1SE
models). Tuning parameters were considered less complex if
the number of trees, interaction depth, or shrinkage decreased.
Simpler 1SE models can sometimes generalize to new data
better than the CV model without sacrificing overall predictive
power.119 The 1SE model selected for As had a combination of
the highest sensitivity and predicted prevalence that most
closely matched the data. The 1SE model selected for Mn had
a combination of the highest accuracy and highest predicted
prevalence. We further simplified the 1SE model by selecting a
more parsimonious set of predictor variables using recursive
feature elimination (RFE) within the R caret package (v. 60−
86116). The RFE method performs backward feature selection
within a 10-fold cross validation and then ranks the predictor
variables in order of importance based on their average
predictive power within the model. For Mn, we selected the
RFE model resulting in a combination of the highest accuracy
and highest predicted prevalence. For As, we selected the RFE
model resulting in a combination of the highest sensitivity and
highest predicted prevalence.
BRT model performance was evaluated by comparing model
estimates of the probability of high As or high Mn to measured
concentrations. Performance measures were the confusion
matrix metrics of sensitivity, specificity, total accuracy, and
predicted prevalence of high concentration; kappa; and area
under the receiver operating characteristic curve (AUC).
Sensitivity is the percent of correctly classified events (true
positives). Specificity is the percent of correctly classified
nonevents (true negatives). Total accuracy is the total
percentage of correct classifications. Predicted prevalence of
high concentration compared to data set prevalence of high
concentration is an indication of model performance.120 The
Kappa statistic (κ) is a measure of model estimates that
accounts for randomness; κ can range from 0 (no agreement)
to 1 (perfect agreement).121 AUC is an indication of model
performance at all classification thresholds, and values of AUC
range from 0.5 (no predictive power) to 1 (perfect model).
Estimated probabilities greater than 0.5 were assigned to be
above the model concentration threshold for the Mn model.
The probability threshold selected for the As model was 0.2,
which was the threshold that maintained model specificity and
total model accuracy while also increasing model sensitivity
given that the As data set was imbalanced100 (additional detail
is provided in the Supporting Information).
We calculated confidence intervals to map prediction
uncertainty across the GLAC using bootstrapping methods.122
Briefly, the training data was resampled with replacement to
create 199 bootstrapped training data sets, and a model was fit
to each bootstrapped data set. Predictions were made with
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each new model, for a total of 199 sets of predictions.
Percentile prediction intervals were calculated using quantile
indices and a significance of 0.10. The difference between the
lower (5%) and upper (95%) percentile predictions was then
calculated to obtain the width of the confidence at each grid
cell across the GLAC.
Mapping Estimated High As and High Mn. Predicted
probabilities of high As (>10 μg/L) and Mn (>300 μg/L) were
mapped across the GLAC at a 1 km scale using the RFE
models. The model is three-dimensional because several
influential predictor variables are three-dimensional (age
metrics, predicted redox conditions, and predicted pH). For
predictor variable source rasters with a higher resolution than 1
km, we used the gdalwarp utility123 with a bilinear resampling
method to generate 1 km resolution versions of the source
rasters. We created and presented maps of predicted
probability grids at domestic and public supply well depths
(Figure 1b,c) as they vary across the study area.
evaluated several methods (described in the Supporting
Information) to improve model predictive performance.
Based on the evaluation, we chose to use estimated
probabilities greater than 0.2 to assign a prediction as being
above the model concentration threshold. This alternate
probability threshold improved model sensitivity by 13%
while decreasing total accuracy by only 1%, compared to using
0.5 as the probability threshold to assign an event. The selected
RFE model for As had 79 predictor variables, and this simpler
model had the same total accuracy (90%) and a 2% increase in
sensitivity (51%) compared to the CV model, an illustration of
a simpler model having better predictive performance. The
predicted prevalence of high As (10.7%) virtually matched the
observed prevalence in the data set (10.5%). The AUC was
0.85 and κ was 0.46, indicating moderate to good model
performance. Our model had similar sensitivity and better
overall accuracy, AUC, and κ than a regional-scale As BRT
model developed with a balanced data set (≈40% As > 10 μg/

■
L) in the central part of the study area.75
RESULTS AND DISCUSSION The selected RFE model for Mn had 55 predictor variables.
This simpler BRT model resulted in total accuracy of 83% and
Model Selection and Performance Metrics. The sensitivity of 70%, only a 1% decrease in accuracy compared to
following model selection and performance discussion will the CV model and no decrease in sensitivity. The AUC was 0.9
focus on the testing data set, which evaluates model predictive and κ was 0.62, both of which indicate good model
performance with new data. Model parameters and perform- performance. The predicted prevalence of high Mn was
ance metrics for the CV, 1SE, and RFE models are presented about 2.5% lower than the observed prevalence of high Mn in
in Supporting Information (Table S4). Performance metrics the data set, and all models underpredicted high Mn to the
for the RFE models are presented in Table 1. same degree. Compared to a BRT model of high Mn in the
Because of the imbalanced As data set and known predictive Central Valley of California,89 the sensitivity of our model was
performance challenges with imbalanced data sets, we higher, a result of our data set being more balanced. The
Central Valley model data set had <7% of samples with Mn >
Table 1. Final Recursive Feature Elimination (RFE) 300 μg/L, and typical BRT models have low sensitivity with
Boosted Regression Tree (BRT) Threshold Model data sets imbalanced with a high proportion of nonevents.
Parameters and Evaluation Metrics Model Variables. The 20 most influential predictor
BRT threshold model variables and their relative importance are shown in Figure
2. All predictor variables retained in the final models are
group description As > 10 μg/La Mn > 300 μg/La
b
described in Table S3, and the relative importance of each
model number of trees 4500 2500 retained model variable is provided in Table S5. Several of the
parameters tcb 10 10 most influential variables are common between the As and Mn
lrb 0.014 0.01 models, including two variables related to the predicted
training data ROCc 0.99 0.96 likelihood of anoxic condition (ProbHighFe100, ProbLow-
set kappa (κ)d 0.94 0.78 DOpt5) and predicted pH (Pred_pH), relative well depth
sensitivity (%)e 99 82 within the saturated thickness of the aquifer (RelativeDepth),
specificity (%)f 99 95
and distance to an eigth-order stream divide (DSD8).
total accuracy (%)g 99 90
Average available water capacity (AWC), average available
predicted prevalence 12.2 (11h) 31 (33.1h)
(%) water storage in the 0−25 cm soil horizon (AWC25), and soil
testing data set ROC 0.85 0.9 bulk density (SoilBulkDens) were three of the four most
kappa (κ) 0.46 0.62 influential variables for predicting the occurrence of high As.
sensitivity (%) 51 70 Estimated recharge (EstRecharge), baseflow index (BFI), and
specificity (%) 94 90 precipitation (PRISM_ppt) were three of the four most
total accuracy (%) 90 83 influential predictor variables for predicting the occurrence of
predicted prevalence 10.7 (10.7) 30 (32.6) high Mn. Differences in these top influential predictor variables
(%) are related to differences in As and Mn mobilization
mechanisms, such as weathering rates, which can be affected
a
As event threshold is 0.2 and tuned to optimize sensitivity; Mn event by redox chemistry and pH and can be further explored using
threshold is 0.5 and tuned to optimized accuracy. btc, number of partial dependence plots (PDPs).
interactions; lr, shrinkage parameter. cReceiver operator characteristic Partial dependence plots (PDPs) help qualitatively evaluate
curve, the ratio of the true positive rate to the false positive rate,
the relations of predictor variables to the model estimates.
integrated over a range of probability thresholds. dKappa statistic, an
indication of the agreement between observed and expected PDPs represent the partial dependence of the model estimate
accuracies. eSensitivity, percent of correctly predicted non-events. on the predictor variable of interest, after accounting for the
f
Specificity, percent of correctly predicted events. gPercentage of average effect of all other model variables.124 In parts of the
samples that are correctly classified. hActual prevalence of high predictor variable space with sparse data, however, the
concentration in dataset. relations depicted by PDPs may not be accurately
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Figure 2. Normalized relative influence of the 20 most influential model predictor variables for the final As and Mn recursive feature elimination
(RFE) Boosted Regression Tree models (see Table S3 for variable descriptions and references). AWC, average available water capacity; AWS25,
average available water storage in the 0−25 cm soil horizon; DSDN (N = stream order), distance from the Nth-order stream divide; LPN (N =
stream order), lateral position to the Nth-order stream; BFI, baseflow index; PRISM_ppt, mean annual precipitation; and TWI, topographic
wetness index. Normalized relative influence for all predictor variables (Table S5).

represented.125 PDPs can also illustrate the variable influence
on the predicted probability of high Mn or high As that is more
complex than linear increase or decrease relations.
Predicted anoxic condition, predicted pH, and other
predictor variables are common to both models (Figures 3
and S4−S7), but their prediction responses differ as illustrated
in the PDPs: mechanistic differences are noticeable from
model results. For example, as the probability of anoxic
condition increases, the likelihood of high Mn and high As
both increase. The response of increased probability of high
Mn, however, starts with 0.2 predicted probability of high Fe,
and with any predicted probability of low DO. In contrast, the
increased probability of high As begins at 0.5 predicted
probability of high Fe and 0.2 predicted probability of high DO
(Figure 3). These differing responses of the As and Mn model
predictions to predicted anoxic conditions are consistent with
Mn mobilization occurring earlier in the progression from oxic
to anoxic conditions compared to Fe, if As is primarily
mobilized with Fe from oxyhydroxides, as in the case in the
GLAC.3,92 Likewise, the probability of high Mn decreases with
increasing values of predicted pH from about 6.5 to 8, possibly
due to precipitation of MnCO3 or adsorption by Fe oxides;
however, the probability of high As increases with pH from 7
to about 8, consistent with desorption of the oxyanion species
at alkaline pH.126
Soil and aquifer characteristics related to water retention
capacity influence the probability of high As. A soil bulk
density (SoilBulkDens) increases from about 1.5 to 1.7 g/cm2
or estimated vertical hydrologic conductivity (GD_TexVer-
tHydCond) increases from 0.05 to 0.5 m/day each decreases
the likelihood of high As, and an increase in the available water
capacity (AWC) from about 0.1 to 0.2 volume fraction
5796
increases the likelihood. These factors are related to slowing
the rate of recharge and flow, increasing water−rock
interaction and groundwater age, all of which contribute to
conditions that promote As mobilization. Several variables
describing groundwater age or proximity to streams of various
sizes were also influential (e.g., DSD2, FrctnYngWtr,
StrmDensity), which is consistent with findings by others
studying As-contaminated aquifers in Southeast Asia and
elsewhere.63,75,127−129 Increasing soil As concentration is also
related to increased probability of high As in groundwater, but
increasing predicted nitrate concentration in groundwater is
related to a decreased probability of high As in groundwater
(Figure S5).
The probability of high Mn increases as the distances to
large stream divides increase (DSD8, Figure S6), indicating
that Mn concentrations increase approaching large rivers.
Similar relations to increased Mn and proximity to rivers and
streams have been noted in the United States, South America,
and Southeast Asia.6,85,94,130 Precipitation had a nonmonotonic
relation to the probability of high Mn, with precipitation about
500 mm per year coinciding with the highest predicted
probability of high Mn, and no relation above about 600 mm
per year (Figure S6). Recharge less than approximately 100
mm per year was associated with the highest predicted
probability of high Mn, steeply decreasing to no relation above
about 200 mm per year (Figure S6). These relations may relate
to the balance between lower pH rainwater (tending to
mobilize Mn) with oxidized rainwater (tending to precipitate
Mn) entering and interacting with shallow aquifer sediments
and shallow groundwater. Increasing concentrations of soil Mn
are also related to an increased probability of high Mn.
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Figure 3. Partial dependence plots (PDP) for three influential model predictor variables for the final As and Mn recursive feature elimination
(RFE) Boosted Regression Tree models. (a, b) Anoxic condition as indicated by the probability of high Fe, (c, d) anoxic condition as indicated by
the probability of low dissolved oxygen, and (e, f) predicted pH. Data deciles are denoted with tick marks. PDPs display the average model
prediction as the variable of interest is varied over a range of values. The relations depicted by PDPs may not be accurately represented where data
are sparse. Additional PDP plots are provided in Figures S4−S7. Units are provided in Table S3. Predicted anoxic redox conditions and predicted
pH are among the most influential predictor variables for both As and Mn. The character of the influence, as indicated by the PDP plots, however,
differs between the prediction of the probability of high As (a, c, e) and the prediction of the probability of high Mn (b, d, f).

Mapping Estimated High As and High Mn. BRT
models for high As (Figure 4) and high Mn (Figure 5) were
used to make predictions to 1 km2 grids at drinking water
depths estimated by depth surfaces of public supply well
depths across the GLAC (depth surfaces for domestic wells
shown in Figure S8). In some areas, the depth of drinking
water supply is similar for public supply and domestic wells
(Figures 1b,c and S1), but there are areas where the depth of
public supply wells is deeper than domestic wells. Well depths
tend to be deeper in central portions of the study area, where
glacial sediment is thick (Figure 1b,c). The influence of well
depth on the predicted likelihood of high As or high Mn is
reflected in the maps in part because the influential variables,
predicted redox condition, pH, and groundwater age,97−99 are
5797
themselves depth-dependent. Predicted high As is more
common at public supply well depths than at domestic well
depths; predicted high Mn is more common at domestic well
depths than at public supply well depths. These observations
are consistent with the differences in known As and Mn
mobilization mechanisms.3,6 High Mn is commonly predicted
in the central part of the GLAC and in proximity to streams
and rivers (Figures 5 and S8). High As is also commonly
predicted in the central part of the GLAC, but over a smaller
proportion of the area compared to high Mn. These findings
are consistent with past studies,3,52,53,58,92,131 but mapped
results also call attention to areas in which there are currently
few groundwater-quality sample results availablebut which
may have physical and geochemical conditions conducive to
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Environmental Science & Technology pubs.acs.org/est Article

Figure 4. Modeled probability of high As indicated by As > 10 μg/L, (a) predicted probability at public supply depth surface (Figure 1, Table S1),
and (b) prediction uncertainty category (Table S6) for public supply well depth. Maps for domestic supply well depths (Figure S8).

Figure 5. Modeled probability of high Mn indicated by Mn > 300 μg/L, (a) predicted probability at public supply well depth surface (Figure 1,
Table S1), and (b) prediction uncertainty category (Table S6) for public supply well depth. Maps for domestic supply well depths (Figure S8).

groundwater-quality problems from As or high Mn (e.g.,
terrane 1E). Our models and maps represent water quality in
the GLAC only, so known areas of high-As groundwater in
bedrock wells are not reflected (e.g., northeastern portions of
terrane 1A, with notable high As in bedrock aquifers132,133).
Quantification of Model Uncertainty and Model
Limitations. Although BRT and other ML techniques are
becoming more common in modeling water resources-related
variables, quantitative assessment of uncertainty is rarely
seen.134,135 In each 1 km2 map grid, we calculated 90%
confidence prediction intervals (lower, 5%; upper, 95%) as
measures of model uncertainty, and we add context and
relevance to prediction intervals using uncertainty categories
(Table S6). Comparisons between predicted probabilities and
associated prediction intervals were used to categorize the
likelihood of exceeding the threshold (0.2 for As; 0.5 for Mn)
for each cell (Figures 4b, 5b, S8b, and S8d). The areas with
predictions of high As and high Mn (terranes 2E, 3B) have
varying levels of confidence. Model predictions have higher
uncertainty in areas where the likelihood of high concentration
is predicted to be high, but the data density is low.
These models and maps were developed using predictor
variable data sets available at the large, subcontinental scale, so
5798
we caution against using results on a small, local scale. Regional
predictions of likely high As and Mn concentration conditions
can indicate a general likelihood of some contaminant
concentrations in groundwater, but predictions at any scale
are not a substitute for sampling water quality at individual
wells.
A primary limitation of our study is data availability and data
quality, as is true with any model. The As and Mn data used as
response variables to develop the models were collected for
other purposes. Arsenic and Mn concentrations were not
monitored equally across the study area; therefore, the data
density of constituents is not equal across the study area. We
performed a practical degree of quality assurance during data
compilation; exhaustive quality assurance was outside of the
scope of the study. Because the factors that control high As and
high Mn conditions differ between aquifer systems, models
developed for the GLAC are not directly transferable to
another region because model training and application
environments must be similar enough for successful model
transferability.136 The BRT modeling method we use, however,
is transferable to any type of aquifer setting with available
spatially distributed predictor variable and response variable
data. Although accurate predictions may be produced with
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Environmental Science & Technology pubs.acs.org/est Article

Figure 6. Eh−pH diagrams for (a) Fe and (b) Mn, showing aqueous speciation for As in the background. Assumed activities are ∑Fe = 10−6.0,
∑Mn = 10−5.26, ∑S = 10−4, ∑C = 10−3, and ∑As = 10−6.854, with speciation varied as a function of pH and redox. Dashed polygon delineates zone
of likely Eh−pH conditions for groundwater samples from the glacial aquifers in the United States. Point symbols are measured pH and computed
Eh. Black circles indicate Eh computed for the water/oxygen (H2O)/(O2) redox pair (2H2O = O2 + 4H+ + 4e−; log K −86.08); orange dots
indicate Eh computed for the water/oxygen (H2O)/(O2) redox pair using logK −45.54;113 green symbols indicate Eh for methane/carbonate
(CH4)/(CO3−2) redox pair (CO3−2 + 10H+ + 8e− = CH4 + 3H2O; log K 41.071); and red crosses indicate Eh for sulfide/sulfate (H2S)/(SO4−2)
redox pair (SO4−2 + 10H+ + 8e− = H2S + 4H2O; log K 40.644) assuming sulfide at equilibrium with mackinawite. Eh computed using
PHREEQC;107 diagram created using Geochemist’s Workbench (GWB12).147 Both programs used WATEQ4F database.108

predictor variable data sets that are complete, many predictor
variable data sets exhibit gaps in coverage. Lack of data (for
example, lack of detailed three-dimensional geologic mapping)
also restricts the pool of potentially useful predictor variables.
Uncertainties inherent in the individual predictor variables and
spatial variation in predictor variable importance were not
assessed but are quantified in the calculated prediction
intervals. Finally, there is growing evidence that season,
climate, and other factors can cause temporal geochemical
changes in groundwater quality,133,137−141 evident in our
models as the dominant predictors (EstRecharge, BFI, and
PRISM_ppt) for the Mn model; however, temporal changes
are not considered in this study, and our estimates represent
past climate averages.
Relating Model Predictor Variables to As and Mn
Geochemistry. Understanding how variables in regional
groundwater-quality prediction models might relate to the
aquifer geochemistry is important to help elucidate mobi-
lization/attenuation processes and may also provide insight to
improved well siting (shallower or deeper) or possible
treatment needs and strategies (co-occurrence of contami-
nants). Concentrations of As and Mn in the GLAC are related
to groundwater pH and redox among other predictor variables,
including natural sources (e.g., As and Mn in C-horizon soils,
which are indicators of geologic parent material142), soil
properties and recharge rates, aquifer properties, and the
various saturated thickness, water−rock interaction, and
groundwater age variables (Figures 2 and S4−7, Tables S3
and S5).
Both predicted redox condition and predicted pH of
groundwater are influential predictor variables in our models
(Pred_pH, ProbHighFe100, ProbLowDOpt5). These variables
indicate geochemical conditions that can affect the attenuation
or mobilization of aqueous As and Mn, mainly by adsorption
and desorption or precipitation and dissolution processes, as
illustrated by the complex relation of As species with Fe and
Mn aqueous and solid phases (Figure 6). These variables can
5799
also help provide more holistic geochemical information for
water treatment.
The GLAC groundwater has a wide range of pH and
estimated redox characteristics, from oxic conditions where
arsenate (H2AsO4− or HAsO42−) predominates to anoxic
conditions where arsenite (H3AsO30) predominates, with
associated variations in stabilities of Fe and Mn species and
solids (Figure 6). Hydrous FeIII and MnIII−IV oxides, in
particular, can act as sources and sinks for As and Mn. In
oxidizing systems, the hydrous FeIII oxides play an important
role in AsIII−V adsorption, while hydrous MnIII−IV oxides can
contribute to AsIII adsorption and oxidation.143,144 Under
moderately oxidizing conditions (Figure 6a, orange dots),
sorption processes can limit the mobility of arsenate and
arsenite, particularly at low pH; however, sorption efficiency
generally decreases with increasing pH with potential for
substantial release of sorbed As at pH > 7.5.2,10,48−50 Likewise,
under suboxic to reducing conditions (Figure 6, red and green
symbols), the reduction of FeIII and MnIII−IV hydroxides can
mobilize sorbed As with corresponding increases in dissolved
Fe and Mn concentrations. Concentrations of dissolved
phosphate, sulfate, carbonate, and silica can affect aqueous−
solid equilibrium boundaries and the distribution of aqueous
and surface species of As, Mn, and Fe.
In contrast with As oxyanion species, dissolved manganese
predominates as a cation (Mn+2) (Figure 6b) that tends to be
poorly adsorbed and relatively mobile at acidic pH, whereas at
alkaline pH, aqueous Mn can form MnHCO3+ species and be
attenuated by precipitation of MnCO3 or by adsorption onto
hydrous FeIII and MnIII−IV oxide surfaces.6,48,84 Under highly
oxidizing conditions, the precipitation of MnIIIOOH (man-
ganite) and MnIVO2 (pyrolusite) could limit aqueous Mn
concentrations (Figure 6b). In suboxic to anoxic groundwater
settings, the reduction of MnIII−IV oxides coupled with
oxidation of dissolved organic carbon (DOC), Fe+2, AsIII,
and NH4+ liberates Mn+2.110,112,145
The importance of pH as a predictor variable for elevated As
and Mn concentrations (Figures 2 and 3e,f) is apparent for
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Environmental Science & Technology
aquifers lacking calcareous minerals that can buffer pH. The
low pH values could result from oxidation of naturally
occurring organic carbon, sulfide minerals, or ammonium (in
agricultural areas).88,146 McMahon et al.6 surmised that
ammonium oxidation can decrease pH and enhance Mn
mobility. In our setting, Mn concentrations in poorly buffered
terranes (1A, 1G & 4A) are significantly higher (Wilcoxon
rank sum test, p = 0.004) in samples with pH < 6 as compared
to those with pH ≥ 6, and in these areas, nitrate concentrations
are inversely related to pH (Spearman’s rank ρ = −0.45; p <
0.001). These findings are consistent with past studies6,58,92
and indicate that poorly buffered areas of the GLAC with pH <
6 may be susceptible to elevated Mn concentrations regardless
of redox condition.
Implications for Complex Unconsolidated Drinking
Water Aquifers. The GLAC hydrogeologic setting shares
some important characteristics to deltaic and other high-As
and high-Mn unconsolidated drinking water aquifers: late
Pleistocene/Holocene age, complex layering of aquifers and
confining units, low-As sediment concentrations, and geo-
chemical controls on As and Mn mobilization. Some of the
variables that were found to be most influential in our models
represented characteristics describing properties of the geo-
chemical evolution of groundwater, aquifer materials, and soil
geochemistry. Few groundwater Mn models exist, but recent
models for As-affected aquifers in Southeast Asia have
elucidated similar influential factors and variables (ground-
water age, organic carbon, aquifer, depth, etc.) related to
modeled As hazard in aquifers.13,41,42,54,63,67,69−74,76 Similar,
related geochemical mobilization mechanisms pertain to high
Mn. In many cases, known influential water-quality parameters
such as pH, Fe, and DO are not mapped across a study area, so
these important water-quality parameters cannot be considered
as model predictor variables. Instead, proxy variables (e.g.,
depth, thickness, and textural components of glacial materials
and soil chemistry) substitute for measurable physical or
geochemical causes of high As (or high Mn) because the
predictor variable proxies were mapped across a study area.
Predicted anoxic conditions and predicted pH were among the
most influential predictor variables in our model, demonstrat-
ing that spatially distributed (mapped) estimates of these
important geochemical drivers can simplify, benefit, and
strengthen predictive contaminant models. Translating geo-
chemical understanding of As and Mn mobility to quantifiable
variables for modeling could continue to improve predictions
and potentially help identify safer groundwater supply options
in the United States, Southeast Asia, and elsewhere.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.est.0c06740.
Additional method details; well construction box plots,
domestic and public wells by terrane (Figure S1);
response variable data distribution (Figure S2); example
maps of selected predictor variables (Figure S3); partial
dependence plots for As > 10 μg/L model, predictor
variables with relative influence 1−12 (Figure S4);
partial dependence plots for As > 10 μg/L model,
predictor variables with relative influence 13−24 (Figure
S5); partial dependence plots for Mn > 300 μg/L model,
predictor variables with relative influence 1−12 (Figure
5800
pubs.acs.org/est Article
S6); partial dependence plots for Mn > 300 μg/L model,
predictor variables with relative influence 13−24 (Figure
S7); modeled probability of high As indicated by As >10
μg/L (Figure S8) (PDF)
Generalized characteristics of Quaternary sediments
(Table S1); summary of data used to predict the
probabilities of high arsenic and high manganese (Table
S2); predictor variables included in boosted regression
tree (BRT) model development (Table S3); perform-
ance metrics (Table S4); relative influence of predictor
variables (Table S5); uncertainty category based on
predicted probability (Table S6) (XLSX)
■
AUTHOR INFORMATION
Corresponding Author
Melinda L. Erickson − U.S. Geological Survey, Mounds View,
Minnesota 55112, United States; orcid.org/0000-0002-
1117-2866; Phone: 763-783-3231; Email: merickso@
usgs.gov
Authors
Sarah M. Elliott − U.S. Geological Survey, Mounds View,
Minnesota 55112, United States
Craig J. Brown − U.S. Geological Survey, East Hartford,
Connecticut 06108, United States
Paul E. Stackelberg − U.S. Geological Survey, Troy, New York
12180, United States
Katherine M. Ransom − U.S. Geological Survey, Sacramento,
California 95819, United States
James E. Reddy − U.S. Geological Survey, Ithaca, New York
14850, United States
Charles A. Cravotta, III − U.S. Geological Survey, New
Cumberland, Pennsylvania 17070, United States;
orcid.org/0000-0003-3116-4684
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.est.0c06740
Funding
This work was funded by the U.S. Geological Survey National
Water-Quality Assessment Project (NAWQA), a component
of the National Water Quality Program.
Notes
The authors declare no competing financial interest.
Data may be obtained from the USGS ScienceBase data
release;105 summary of data used to predict the probabilities of
high arsenic and high manganese across the U.S. glacial aquifer
system.
■ ACKNOWLEDGMENTS
Reviews by Melissa Lombard, Joe Ayotte, and Jim Tesoriero
(USGS) and four anonymous reviewers (Environmental
Science & Technology) greatly improved the final manuscript.
Any use of trade, firm, or product names is for descriptive
purposes only and does not imply endorsement by the U.S.
Government.
■
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