Science of the Total Environment 659 (2019) 884–894

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

A multi-method approach for the assessment of natural background

levels in groundwater
Daniele Parrone ⁎, Stefano Ghergo, Elisabetta Preziosi
IRSA-CNR, Water Research Institute - National Research Council, Via Salaria km 29.300, PB 10, 00015 Monterotondo, Rome, Italy

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Natural background levels are assessed

by using pre-selection and statistical
methods.
• The pre-selection of influenced samples
is based on locally derived NO3 thresh-
olds.
• Outliers detection allows to identify
data deviating from the background
population.
• The choice of the NBL depends on the
normality of the distribution of residual
data.
• The integration of different approaches
strengthens and improves the NBLs
evaluation.

a r t i c l e i n f o a b s t r a c t

Article history: The assessment of geochemical Natural Background Levels (NBLs) in groundwater, aims at distinguishing the
Received 2 October 2018 naturally high levels of geogenic compounds from anthropogenic pollution. This is a fundamental issue in
Received in revised form 26 November 2018 groundwater management, in particular when the concentration of inorganic compounds exceeds the threshold
Accepted 22 December 2018
values set for the evaluation of the groundwater chemical status, as requested by environmental regulations.
Available online 24 December 2018
In this paper, we describe a new procedure that integrates the pre-selection method and statistical techniques,
Editor: Damia Barcelo using the example of two case studies.
The pre-selection aims to identify suitable groundwater samples for the NBLs assessment. The nitrate concentra-
Keywords: tion threshold, for the removal of the groundwater samples affected by human activities, is established locally
Natural background level through different graphical and statistical approaches. Then, the statistical distribution of each compound is an-
Pre-selection alyzed and the outliers are identified. Normality tests on the datasets allow one to select the most appropriate
Nitrates value, e.g. one percentile, to be adopted as NBL within the data distribution.
Arsenic In the selected case studies, we have defined the NBLs for As, F, Mn, Fe and SO4. The two sites are part of a
Q-Q plot
volcanic-sedimentary aquifer in central Italy, where the geochemical background is frequently well above the
Outliers
standards for human consumption.
The results of the simple and easily reproducible pre-selection method are strengthened by integration with sta-
tistical techniques, notably in selecting the appropriate percentile. New criteria are suggested for the choice of the
nitrate threshold to be used for the pre-selection of uncontaminated samples.
© 2018 Elsevier B.V. All rights reserved.

⁎ Corresponding author.
E-mail addresses: parrone@irsa.cnr.it (D. Parrone), ghergo@irsa.cnr.it (S. Ghergo), preziosi@irsa.cnr.it (E. Preziosi).

https://doi.org/10.1016/j.scitotenv.2018.12.350
0048-9697/© 2018 Elsevier B.V. All rights reserved.
 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894
1. Introduction
High levels of inorganic compounds in groundwater represent a sig-
nificant problem in many parts of the world, with important economic,
social and environmental drawbacks. They may derive from both an-
thropogenic contamination and natural processes affecting aquifers.It
is therefore important to determine the Natural Background Level
(NBL) of these substances, defined as the “relative measure to distin-
guish between natural and anthropogenically influenced concentra-
tions” (Matschullat et al., 2000). The European Community (2006)
requests the EU Member States to individuate appropriate threshold
values (TV) for various potentially harmful substances, taking into ac-
count NBLs when necessary, in order to evaluate the chemical status
of groundwater bodies.
Preziosi et al. (2014) review the most common approaches for NBLs
assessment, including many statistical techniques and the so-called Pre-
Selection methods (PS). The latters assume that groundwater samples,
showing no evidence of anthropogenic inputs, may represent pristine
groundwaters, hence be used to determine the NBL for that groundwa-
ter body. Many examples of PS method applications can be found in the
literature (Griffioen et al., 2008; Marandi and Karro, 2008; Wendland
et al., 2008; Coetsiers et al., 2009; European Commission, 2009;
Molinari et al., 2012; Rotiroti and Fumagalli, 2013; Preziosi et al.,
2014). Hinsby et al. (2008) have applied PS methods for the NBL deriva-
tion for Cl, SO4 and As in a number of groundwater bodies across Europe.
Preziosi et al. (2010) have assessed the NBL for arsenic, vanadium, fluo-
ride in groundwater bodies in central Italy. Gemitzi (2012) has
established the NBL for EC, Cl, SO4 in northern Greece aquifers. Ducci
et al. (2016) report examples for As, Mn and Fe in Portugal and Italy.
Most of these examples make use of nitrates to discard the impacted
samples. Infact, because they are the most widespread anthropogenic
pollutant (Goodchild, 1998; Liu et al., 2005; Almasri, 2007; Masetti
et al., 2008; Menciò et al., 2016) and easily detecteable, nitrates are
commonly used as markers of anthropogenic contamination, along
with other more specific pollutants, during the pre-selection of the pris-
tine groundwater samples. Indeed, samples not exceeding 10.0 mg/L
NO3 could be representative of the pristine groundwater (Muller et al.,
2006). Unfortunately, due to the extensive diffusion of nitrates in aqui-
fers, this limit may produce an excessive reduction of the dataset
(Preziosi et al., 2010). On the other hand, a less stringent limit could fa-
cilitate the inclusion of contaminated samples in the “uninfluenced”
dataset.
Differently from the PS methods, purely statistical approaches aim at
separating the background and a non-background population of geo-
chemical data applying statistical techniques. Some of these methods
point to eliminate the outliers, assuming that the remaining data belong
to the background. The “mean + 2σ” (Hawkes and Webb, 1962), the
Median Absolute Deviation (MAD, Tukey, 1977), the Box&Whisker plot
(Reimann et al., 2005) and other parametric or non-parametric tech-
niques, including graphical methods as probability plots or Quantile-
Quantile plots, have been largely used for this purpose (Tennant and
White, 1959; Sinclair, 1974; Edmunds et al., 2003; Wendland et al.,
2005; Panno et al., 2006; Edmunds and Shand, 2008; Walter, 2008;
Molinari et al., 2012; Preziosi et al., 2014).
The data distribution is not a secondary aspect and has been
long debated (Hawkes and Webb, 1962; Matschullat et al., 2000;
Buccianti et al., 2006; Edmunds et al., 2003; Edmunds and Shand,
2004; Reimann and Filzmoser, 2000; Reimann et al., 2005), but
still an agreement is missing. Wendland et al. (2005) suggested
that the natural and anthropogenic components could be described
by a Log-Normal and Normal distribution, respectively. Molinari
et al. (2012) also shared this interpetation. Preziosi et al. (2014)
addressed this point and found that, in some cases, the iterative
elimination of the outliers may lead to a normal population corre-
sponding to the background, a least for such elements as arsenic
and fluoride.
885
Recently, a national guideline for the NBLs assessment in groundwa-
ter bodies has been published in Italy (Ghergo et al., 2017). The proce-
dure is based on the pre-selection method and the percentile
calculation; it takes into account the groundwater body conceptual
model and different assessment paths are proposed according to the
sample size both in the spatial and time dimensions. Normality distribu-
tion test is also used to select the percentile for NBL assessment. Regard-
ing the pre-selection, the guideline suggests three options for choosing
the limits for nitrates/ammonia (according to the redox conditions of
the groundwater body):
- 10.0 mg/L for NO3 and 0.1 mg/L for NH4 (20% of their respective EC
drinking water standards), which are the levels set in the first pro-
posal of PS method (Muller et al., 2006);
- 37.5 mg/L for nitrates and 0.375 mg/L for ammonia, equivalent to
75% of their respective EU drinking water standards;
- locally defined limits, to be identified by appropriate statistical tech-
niques, that cannot anyway exceed the 75% of the EU drinking water
standards.
The choice of the most appropriate threshold for the separation of
influenced and non-influenced samples still remains uninvestigated. It
would be more correct to refer to an Ambient Background Level (ABL)
of nitrates, as the “unmeasurably perturbed and no longer pristine nat-
ural background” (Reimann and Garrett, 2005), as the pristine NBL is
objectively hard to identify in many densely populated areas of the
world.
The main objective of this study is to define and test a methodology
able to integrate the PS method with the statistical approaches com-
monly used today for the definition of NBLs, verifying its applicability
at the site/local scale. We identified the local ABL for nitrates using dif-
ferent statistical methods in two neighboring study areas where the
land use and the level of anthropogenic impact differ. Then, the deter-
mined ABLs were used for the pre-selection of the unimpacted ground-
water samples. Finally, applying the above-mentioned statistical
techniques, we have definined the NBLs for arsenic, fluoride, iron, man-
ganese and sulphate, and we have compared the values obtained sepa-
rately for the two study areas.
2. Data and methods
2.1. Case studies description
The study area is located in Latium (Fig. 1), in the eastern flank of the
Sabatini Volcanic apparatus, which was active between 0.6 Ma and
0.1 Ma. The middle Pleistocene volcanites, ranging from trachybasalts
to trachytes and phonolites, belong to the potassic and high potassic se-
ries (Peccerillo and Manetti, 1985; Sottili et al., 2010; Masotta et al.,
2010), overlap in angular unconformity the Plio-Pleistocene marine
and continental sedimentary deposits and a Meso-Cenozoic carbonatic
sequence, which outcrops at the Monte Soratte on the East. The Tiber
valley on the South-East, is filled with Quaternary unconsolidated
sands, gravels and clays of alluvial origin.
Volcanic rocks have a medium permeability due to porosity and frac-
tures (Ventriglia, 1989; Capelli et al., 2005). They host a large uncon-
fined basal aquifers, with a piezometric surface roughly following the
topography. It is largely exploited for both human consumption, irriga-
tion and industry. The frequent vertical variation of relative permeabil-
ity allows for the existence of several discontinuous perched aquifers.
Pliocene marine clays and silts represent the bottom boundary of the
basal aquifer, whose morphology locally controls the gradient of the po-
tentiometric surface. The aquifer discharges directly into streams and
rivers and locally into springs. Groundwaters are mainly of the
alkaline-earth bicarbonate and alkaline bicarbonate type; due to
water–rock interaction, they are naturally enriched in arsenic and
886 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894
Fig. 1. Hydrogeological scheme of Latium volcanic domain (modified from Capelli et al., 2012).
fluoride with values often higher than the standards set for human con-
sumption by WHO (2011) and Directive 98/83/EC.
In the study area (Fig. 2), a “northern” and “southern” sector have
been distinguished and the NBLs have been calculated separately for
each sector.
2.2. Groundwater sampling and analysis
A total of 69 groundwater samples (Fig. 2) from the water table aqui-
fer were collected from wells (64) and springs (5) between March and
November 2012, 10 of which, only in the southern sector, have been
resampled twice more in November 2014 and October 2015 to analyze
the time variation of the groundwater chemistry.
All samples have been filtered with 0.45 μm membrane filters in N2
pressure in the field and stored in HNO3 1% treated polyethylene bottles.
One fraction was added with HNO3 to pH 2 for major cations and trace
metal determination. Electrical conductivity (EC), redox potential
(ORP), dissolved oxygen (DO), pH and water temperature were mea-
sured in situ with probes. Bicarbonates were determined in laboratory
by HCl titration on 50 mL of sample within 24 h from sampling, along
with the analysis of other anions. Field blanks with ultrapure water
were periodically collected in order to distinguish the ambient contam-
ination. The samples were analyzed for anions by ion chromatography
(IC, Dionex DX-120), for major cations by ICP-OES (Perkin Elmer
P400) and trace elements by inductively coupled plasma mass
spectrometry (ICP-MS, Agilent technologies 7500c); certified mate-
rials (NIST 1640a, trace elements in natural waters) were used to
check the quality of the laboratory results. The electro-neutrality
(EN%) evaluated as the percent difference for major cations and an-
ions, including F and NO 3, ranges between −3.96% and + 5.10%.
Values below detection limits were assumed to be equal to half of
the detection limit itself.
For a more detailed explanation of sampling methods and laboratory
analysis, see Preziosi et al. (2014).
2.3. Procedure for NBLs assessment
This procedure (Fig. 3) integrates the pre-selection and the statistical
methods for the definition of the geochemical background of the target
compounds (As, F, Mn, Fe and SO4). As a first step, the total validated
datasets for both study areas were separated in the oxidizing and reduc-
ing facies by using physical-chemical parameters such as ORP (bN
100 mV) and DO (bN 3 mg/L). Then, all the samples with nitrogen excess
were discarded (nitrate for the oxydizing facies, ammonia for the reduc-
ing facies). The nitrate ABL was defined on a case-by-case approach
using the following statistical techniques:
○ Q-Q plot analysis (QQ): the nitrate distribution is represented by Q-
Q plot and the most evident inflection point is individuated. Samples
beyond this limit are discarded.
 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894
Fig. 2. Study area detail and sampling point location. The sites in red have been sampled three times. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
○ Box plot analysis (BW): the data distribution is represented by
Box&Whisker plot; the identified outliers/extremes are discarded.
○ Box plot iterative method (BWI): the data distribution is repre-
sented by Box&Whisker plot; the identified outliers/extremes are
discarded and the residual distribution is then plotted again via
box plot, so possible new outliers are detected. The iterative process
continues until all outliers are excluded and the distribution can be
said to be approximately normal.
○ Mean + 2σ iterative method (MSD): mean and standard deviation
of data are calculated and the values over the mean + 2σ range
are excluded. The procedure is repeated until all the residual values
fall within the interval.
○ Outliers parametric test (OT): parametric tests for detection of data
outliers are applyed to the NO3− datasets, in particular Rosner's test
for data ≥25 (Rosner, 1983) and Dixon's test for data b25 (Dean
and Dixon, 1951). All values listed as outlier are eliminated.
○ Outliers non-parametric test (MAD): a non-parametric test for out-
liers detection is applyed to the nitrate values, such as the Huber's
test (Huber, 1981). On the available dataset the median absolute de-
viation (MAD) is calculated and all those values providing a result
greater than the critical value of 4.5 are considered outliers and con-
sequently discarded.
Each method was applied to the datasets. Then, the Shapiro-Wilk
test (Shapiro and Wilk, 1965) allowed determining if the remaining
dataset fits a normal distribution. If the remaining dataset consists of a
single normal population, its maximum value is chosen as NO3 ABL.
887
Else, the 95th percentile of the remaining dataset can be selected as
ABL. Once defined the local threshold for nitrogen, the samples beyond
are eliminated.
The last step is the calculation of the NBLs for the target chemical pa-
rameters. The choice of the value to be adopted as NBL is driven by the
statistical distribution of the geochemical dataset. If the dataset consists
of a normal population, the maximum value is chosen as possible NBL.
Otherwise, the statistical methods described above (e.g. box plot, Q-Q
plot Rosner's test, Dixon's test, Huber's test) and iterative approaches
(e.g. calculation of mean + 2std.dev) allow detecting the outliers.
Once the latter are discarded, the remaining dataset is tested for nor-
mality and, if verified, the maximum value is chosen as NBL. Else, the
95th percentile of the remaining data distribution is calculated and se-
lected as NBL.
3. Results
3.1. Geochemical and statistical characterization of groundwater
Groundwater table elevation decreases according to the main flow
direction NNW-SSE, towards the Tiber River (Fig. S1 in the supplemen-
tary material).
Sampled waters have been classified using a Piper Diagram. Ground-
waters show the dominance of a bicarbonate–earth–alkaline facies,
ranging from alkaline-HCO3 types to Ca-HCO3 type, while only 3 sam-
ples from the northern sector are classified as sulfate–chloride waters
888 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894

Fig. 3. Flow chart representing the integrated procedure for NBLs assessment.

(Fig. S2). Main statistics for the field parameters and the analyzed com-
pounds are reported in Table 1.
The sampled groundwaters are very similar. However, in the north-
ern sector temperature, pH, electrical conductivity and dissolved oxy-
gen tend to be lower. The concentration of some typical parameters of
the volcanic environments (e.g. PO4, V), as well as aluminum, tends to
be higher in the northern zone, while the Na/K ratio is higher in the
south (median = 0.9) than in the north (median = 0.6). The enrich-
ment in alkalis, in particular K, represents a typical characteristic of
the waters circulating in the alkaline-potassic volcanites of central
Italy (Dinelli et al., 2012; Vivona et al., 2007).
As and F concentration shows an uneven distribution, with slightly
higher values in the southern zone and some isolated hot spots. In the
northern sector fluorine ranges from 0.3 to 3.5 mg/L, with a percentage
 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894 889

Table 1
Main statistics for physical-chemical parameters and the inorganic compounds.

Parameter Mean Median Min Max STD. Dev.

North South North South North South North South North South

ORP (mV) 253 207 279 227 −323 −177 546 294 156 82
T (°C) 15.9 17.2 15.7 17.3 14.6 13.1 18.0 20.4 0.9 1.6
pH 6.2 7.7 6.1 7.7 5.4 7.0 7.3 8.6 0.5 0.3
DO (mg/L) 5.2 6.3 4.9 7.1 0.1 0.1 9.2 9.7 2.9 2.6
El. Cond. (μS/cm) 618 613 557 605 245 449 2660 1025 440 119
F (mg/L) 1.31 1.76 1.12 1.44 0.30 0.67 3.52 4.00 0.70 0.90
Cl (mg/L) 19.5 33.1 18.7 32.3 10.6 16.4 35.3 67.6 4.9 10.6
NO3 (mg/L) 16.0 12.0 13.3 11.8 0.7 1.7 50.7 37.2 10.9 7.3
PO4 (mg/L) 1.06 0.10 1.09 0.03 0.03 0.03 2.63 0.84 0.44 0.16
SO4 (mg/L) 49.0 17.8 8.8 12.0 3.7 3.7 1018.6 122.6 178.1 21.0
HCO3 (mg/L) 258.0 274.1 224.5 263.5 36.6 176.9 966.2 434.3 205.7 61.3
Na (mg/L) 26.9 38.5 26.4 34.4 15.2 23.8 59.3 70.6 9.1 12.5
Mg (mg/L) 15.9 10.4 12.0 9.8 4.1 5.5 132.0 19.7 22.2 3.3
K (mg/L) 45.1 40.0 44.1 37.9 12.1 28.4 138.0 57.3 24.5 8.0
Ca (mg/L) 55.3 48.3 41.9 42.1 10.3 29.5 378.0 131.8 66.9 19.6
Li (μg/L) 27.4 26.0 22.3 21.6 5.4 9.6 121.0 73.3 26.5 14.1
B (μg/L) 88.4 93.5 78.5 83.7 37.3 47.8 212.0 256.0 41.9 43.7
Al (μg/L) 88.2 23.8 46.0 3.9 5.8 0.1 1006.0 471.0 175.7 77.6
V (μg/L) 42.6 27.7 40.9 27.1 1.1 0.4 99.4 66.2 18.8 14.1
Cr (μg/L) 0.9 1.0 0.9 1.1 0.2 0.4 1.9 2.1 0.5 0.4
Mn (μg/L) 102.9 12.8 4.1 0.7 0.2 0.1 1904.2 282.0 346.9 47.0
Fe (μg/L) 160.6 84.7 15.4 17.1 5.8 0.9 3953.0 887.2 696.6 194.4
Ni (μg/L) 1.1 0.4 0.7 0.2 0.2 0.1 5.3 2.2 1.4 0.5
Cu (μg/L) 1.9 0.8 0.8 0.4 0.2 0.1 13.5 4.5 2.6 1.0
Zn (μg/L) 26.4 16.5 7.2 9.6 1.1 0.5 256.0 88.1 55.0 19.9
As (μg/L) 18.8 23.0 15.4 20.8 0.2 4.7 50.6 50.2 11.0 12.2
Se (μg/L) 0.2 0.3 0.2 0.2 0.2 0.1 0.3 1.1 0.0 0.2
Ba (μg/L) 55.9 58.4 44.5 54.8 8.3 1.6 193.0 155.0 44.5 29.9
U (μg/L) 1.8 9.8 0.8 6.6 0.2 0.9 13.9 34.6 2.6 9.3

of exceedances of the drinking water limit (1.5 mg/L) equal to 28.1%. In
the southern sector this percentage rises to 48.6% (range 0.7–4.0 mg/L).
Arsenic ranges from 0.2 to 50.6 μg/L in the north and from 4.7 to 50.2
μg/L in the south, and both the datasets (90.6% and 91.9%) shows wide-
spread overruns of the standard for human consumption (10.0 μg/L).
Manganese and iron show highly variable concentrations, due to the ex-
istence of localized anoxic conditions in a few situations, causing the re-
ductive dissolution of oxy-hydroxides, with a consequent enrichment of
the concentrations up to four orders of magnitude. In both areas we
measured values up to some hundreds of μg/L for both elements, espe-
cially in the northern side.
The time variation observed from March 2012 to October 2015 in the
10 resampled points located in the southern sector show that, apart a
few exceptions, geochemistry of the groundwater is very stable in
time, even with different hydrological conditions (Fig. 4). The variation
of most chemicals is negligible, even with an increase of groundwater
levels up to 2.4 m.
3.2. Pre-selection and NBLs assessment
Nine samples in the northern sector and five in the southern were
attributed to the dataset of the reducing conditions facies. The limited
size of thiese datasets did not allow for any further statistical processing.
The resulting datasets (23, north, and 32, south,) of the oxidizing waters
have been the basis for the statistical analysis of nitrates and the defini-
tion of the limits to be used for the pre-selection of the unimpacted
samples.
The Pearson correlation coefficient, between NO3 and the com-
pounds for which we assess the NBL, was also analyzed (Tab. S1), both
for the total dataset and for the oxidizing facies, and it was found that
there is no correlation between nitrate and the target parameters.
In Fig. 5a–b the nitrate Q-Q plots for the two study areas are shown.
For the southern sector, all techniques (with the only exception of MSD
method) provided the same result, leading to the exclusion of one value.
The resulting population shows a normal distribution and the
maximum value (23.5 mg/L) was chosen as the nitrate ABL for the
pre-selection. For the northern area, the methods provided three differ-
ent results. Dixon's test is ineffective in this case, as the remaining pop-
ulation does not show a normal distribution. We therefore decided to
consider as NO3 limit the more conservative value of 32.0 mg/L, ob-
tained by the Huber's test. In this case, the remaining dataset shows a
normal distribution, so the maximum value was selected as ABL for
the pre-selection. Again, the MSD method gave a lower result, which
has not been taken into account.
For the NBLs assessment of As, F, Mn, Fe and SO4 in the two investi-
gated areas, the same statistical techniques adopted to identify the NO3
ABL to be used for the definition of the PS datasets (31, south and 21,
north) have been used, together with the calculation of the 95th percen-
tile. For the two study sectors, simple and iterative box plots, together
with the corresponding Q-Q plots, are shown in Fig. 6 for fluoride. The
plots for the other compounds can be found in the supplementary ma-
terial (Figs. S3–S6).
The distributions of arsenic and fluoride are fairly close to normality,
while Mn, Fe and SO4 show strong asymmetries and high variances,
which are greatly reduced by the application of the BWI method as ex-
pected. All the results obtained with the different methods are summa-
rized in Table 2, where the possible values to be selected as NBLs are
highlighted in bold.
4. Discussion
This approach relies on the hypothesis that, when the basal popula-
tion has a normal distribution, it represents one single phenomenon and
it might be representative of the geochemical background. The presence
of multiple populations might indicate the presence of overlapping pro-
cesses, which we aim at separating, which might be either natural (geo-
chemical anomaly) or anthropogenic (contamination). However, the
distinction of additional statistically significant populations is often
not possible. In many cases, the data distribution shows only the exis-
tence of few anomalous values. They could represent localized
890 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894
Fig. 4. Variations in time of some parameters for the 10 water points resampled between 2012 and 2015.
situations, either natural or anthropogenic, not connected to a wide-
spread natural background process. In this study, after the preselection
step, the background population was further defined through the elim-
ination of these outliers. Indeed, anomalous values could indicate a con-
tamination process that the marker used for the pre-selection (in this
case, nitrates) has not been able to identify. The use of this common in-
dicator of anthropic activities such as farming, livestock, urban sewage,
aims to eliminate the groundwater samples for which the human im-
pact is apparent, even if unrelated to other contamination processes.
The lack of correlation observed between NO3 and the target compunds,
suggests that in this study the use of such a marker in the preselection
will hardly affect the calculation of the natural background levels.
The NBLs calculated with different techniques show differences up
to one order of magnitude, notably for manganese. The statistical distri-
butions of As and F are close to normal, except for the presence of a few
anomalous values. We can reasonably consider these distributions as
the result of a single natural phenomenon, linked to the dissoluton pro-
cesses occurring in the water-rock interaction. On the other hand, Fe
and Mn are highly redox sensitive elements in groundwater and never
approach normal distributions. For these parameters, whose oxides
are practically insoluble in oxidizing conditions, the redox facies distinc-
tion is fundamental. However, the use of the field parameters DO and
ORP for this purpose is often not fully efficient. This translates into an
evident difficulty in studying the statistical populations of these
compounds and determine their natural background. For these param-
eters, the chemical speciation could support a more efficient separation
of the redox facies and, therefore, a better definition of their relative
datasets.
In the PS method, a value is chosen in the “pristine groundwater” as
representative of the natural background, tipically a percentile between
90th and 97.7th, depending on the degree of knowledge of the hydro-
geochemical system. Preziosi et al. (2014) pointed out that the choice
of the percentile in the PS method is critical.
For highly skewed distributions, or in presence of numerous outliers,
the NBL selected as a given percentile, might be very different from the
results of other methods, notably in the case of highly variable com-
pounds as observed for Fe and Mn.
The NBLs determined with the box plots (BW and BWI), are gener-
ally comparable to those obtained with the statistical tests OT and
MAD (Table 2). In half of the cases, the BWI identified the same outliers;
else, the BWI identified a higher number of outliers hence the resulting
NBLs are lower.
In 90% of the cases the iterative elimination of outliers has led to nor-
mal distributions (confidence coefficient = 99%); the percentage drops
to 50% when a confidence level of 95% is allowed; in any case, variance
and skewness are always strongly attenuated.
Positioning the thresholds in the Q-Q plot, has a certain degree of
subjectivity. Nevertheless, Q-Q plot results are not far from those
 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894 891

Fig. 5. Nitrate Q-Q plots for the southern (a) and northern (b) area. Dotted lines indicate limits identified by the different methods. QQ: Q-Q plot method; BW: Box&Whisker plot method;
BWI: Box&Whisker Iterative method; MSD: Mean + 2Std.Dev. method; OT: Outliers Test method; MAD: Median Absolute Deviation method (Huber's test).

obtained by iterative or statistical techniques. In 80% of the cases, this
value represents the upper limit of an approximately normal population
(60% of the cases with a 95% confidence coefficient).
The values obtained with the iterative MSD method are mostly very
conservative (i.e. the lowest) in 8 out of 10 cases.
The iterative elimination of outliers with the MSD method, is
more efficient than with the BWI and resulted in approximately nor-
mal distributions in all the datasets (confidence coefficient = 99%);
the assumption of normality is still verified for half of datasets with
a 95% confidence coefficient. However, the percentage of the
discarded samples might be very high (up to 40% for Mn). For its na-
ture strongly linked to Gaussian distributions, MSD is an appropriate
technique to identify basal populations; however, for distributions
showing high variances and asymmetries, this methodology is overly
conservative.
For numerous (n N 25) distributions close to normal, the parametric
Rosner's outliers test is more appropriate and more powerful than the
Huber's test; similarly, for n ≤ 25 the Dixon's test ensures the most reli-
able results. In 50% of the cases the remaining dataset is an approximately
normal population (confidence coefficient = 99%), a percentage that
drops to just 10% for confidence coefficients of 95%. In the case of high
variances, the Huber's test is a robust alternative to the two parametric
tests. However, when data do not follow a Gaussian distribution, the
method based on the MAD calculation is the only viable statistical test
892 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894
Fig. 6. Box&Whisker plots (BW = simple and BWI = iterative, normal scale) and Q-Q plots of F for the two study areas. NBLs are indicated by the upper whiskers for the box plots and by
the hatched lines for the Q-Q plots.
for outliers detection and provides rather conservative results. In 60% of
the examined cases, the assumption of normality has been verified on
the remaining dataset (30% for a 95% confidence coefficient).
All the methods are able to identify the boundary between two
existing populations when the outliers are numerous as the case of
manganese. In some cases, the different methods can also be used to de-
tect two different attention levels: the NBL and the upper limit of an-
other population, natural or contaminated.
The logarithmic transformation or, more generally, any normali-
zation of the data, appears a choice incompatible with the research
of outliers, since it tends to excessively flatten the distributions.
The outliers' detection should therefore be performed prior to trans-
formation. The normalization of data can be admitted for distribu-
tions of very variable elements (ratio N 100, like Mn and Fe), while
it is preferable not to transform data when the variability is more
limited (ratio b 100, like As and F), so as to keep evident the differ-
ences between diverse populations.
The obtained NBLs for the two case studies (Table 3) are broadly
comparable. The defined NBLs for As and F are above the Drinking
Water standards, while Mn, Fe and SO4 are largely below.
As regards the two elements that showed on average the most dif-
ferent concentrations between the two areas (Al and U, not shown in
the tables), the obtained background values have confirmed this differ-
ence. The NBLs for uranium are 2.3 μg/L for the southern area and 10.9
for the northern one, while the values for aluminum are 8.4 μg/L
(south) and 84.1 μg/L (north).
5. Conclusions
The proposed procedure combines the selection of unimpacted
samples among a larger dataset and a statistical analysis of the geo-
chemical data. This integration of methods allows for a reasoned
and more robust assessment of the natural background levels in
groundwater.
The suggested recipee for the definition of the NBLs include the fol-
lowing steps:
1. After the validation of the total dataset and the redox facies separation,
perform the pre-selection of uncontaminated samples by using the
appropriate marker (nitrate/ammonia), whose local threshold can be
defined through the previously described techniques.
2. For each compounds, if the PS dataset consists of a normal popula-
tion, choose the maximum value as NBL.
3. Else, data outliers can be detected using the parametric tests
(Rosner's test, Dixon's test) and eliminated.
4. On the remaining dataset, if the normality test is verified, the maxi-
mum value can be chosen as NBL. Else, go back to point 3 and
apply the non-parametric Huber's test to the PS dataset. The outliers
so identified should be eliminated.
5. If the remaining dataset shows a Gaussian distribution, choose the
maximum value as NBL. Else, calculate the 95th percentile.
The proposed procedure allows to maintain the advantages of the
pre-selection method (simplicity and reproducibility), and suggests
new criteria for the choice of the nitrate threshold for the pre-
selection of uncontaminated samples.
The definition of a locally tailored NO3 limit allows adopting a more
reasoned value for the pre-selection instead of using an a priori limit for
the separation of impacted and unimpacted samples.
The choice of the maximum value/percentile for the NBL is linked
to the statistical analsysis of the dataset. The statistical techniques
allow to identify and discard anomalous values for each target pa-
rameter, when they are significantly different from the background
population. The possibility to consider a lower “attention” threshold,
the NBL, and a higher “risk” threshold, has been explored. For this
purpose, the use of simple techniques (e.g. box plots) might be
very helpful. Samples falling between the two levels should be fur-
ther investigated in order to exclude any possible non-natural
origins.
This approach, also valid at the groundwater body scale, overcomes
the limitation of having few sampling points available, frequent at the
site-scale. Infact it allows to better exploiting a limited number of
data, distinguishing the basal population of natural origin from the
anomalous values, whether they are due to natural conditions rather
than to anthropogenic influences.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2018.12.350.
 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894 893

122.6
Max

76.9

23.5
14.1

14.1
14.1

25.7
25.7
21.8
25.7
25.7
25.7
8.4

8.4
Table 3
Defined NBLs for the two case studies.

95th

15.5
14.0

14.0
14.0

21.1
21.1
20.0
21.1
21.1
21.1
66.2

36.4
Parameter NBL Drinking water directive

8.3

8.3
North South
SO4 (mg/L)

Normality
As (μg/L) 27.2 38.0 10.0

Yes

Yes
No

No
No

No
No

No

No
No
No
No
No
No
F (mg/L) 2.38 2.76 1.50
Mn (μg/L) 8.6 1.3 50.0
Fe (μg/L) 31.9 42.9 200.0
SO4 (mg/L) 14.0 21.1 250.0
Remaining
samples

21

14
18
17
14
17
17

31

29
29
28
29
29
29
References
409.0

376.1
Max

17.6

17.6
22.8
36.1

42.5
36.1

44.1
67.3
31.4
44.1
44.1
67.3
Almasri, M.N., 2007. Nitrate contamination of groundwater: a conceptual management
framework. Environ. Impact Assess. Rev. 27, 220–242.
Buccianti, A., Mateu-Figueras, G., Pawlowsky-Glahn, V., 2006. Frequency distributions and
220.2 natural laws in geochemistry. Compositional data analysis in the geosciences: from
95th

31.9

36.7
31.9

39.8
42.9
31.3
39.8
39.8
42.9
71.6

16.8

16.8
18.9

theory to practice. Geol. Soc. Lond., Spec. Publ. 264, 175–189.

Capelli, G., Mazza, R., Gazzetti, C., 2005. Strumenti e strategie per la tutela e l'uso
Fe (μg/L)

compatibile della risorsa idrica nel Lazio. Gli acquiferi vulcanici. 88-371-
Normality

1450-8.
Yes

Yes
Yes
No

No

No
No

No

No
No
No
No
No
No
Capelli G., Mastrorillo L., Mazza R., Petitta M., 2012. Carta delle Unità Idrogeologiche della
Regione Lazio, scala 1:250.000. Ed. REGIONE LAZIO. Firenze: S.EL.CA.eurpen.
Coetsiers, M., Blaser, P., Martens, K., Walraevens, K., 2009. Natural background levels and
threshold values for groundwater in fluvial Pleistocene and tertiary marine aquifers
Remaining
samples

in Flanders, Belgium. Environ. Geol. 57, 1155–1168.

21

15
18
15
16
19
18

31

28
29
25
28
28
29

Dean, R.B., Dixon, W.J., 1951. Simplified statistics for small numbers of observations. Anal.
Chem. 1951.
Dinelli, E., Lima, A., Albanese, S., Birke, M., Cicchella, D., Giaccio, L., Valera, P., De Vivo, B.,
2012. Major and trace elements in tap water from Italy. J. Geochem. Explor. 112,
228.4
Max

17.4
17.4

95.6
12.7

36.5

54–75.
4.4
7.2

1.3
1.3
0.6
1.3
1.3
1.3

Ducci, D., Condesso de Melo, M.T., Preziosi, E., Sellerino, M., Parrone, D., Ribeiro, L., 2016.
Combining natural background levels (NBLs) assessment with indicator kriging anal-
95th

13.7
13.7

94.0
95.6

ysis to improve groundwater quality data interpretation and management. Sci. Total
4.0
5.9

8.6

1.3
1.3
0.5
1.3
1.3
1.3
9.8

Environ. 569-570, 569–584. https://doi.org/10.1016/j.scitotenv.2016.06.184.

Edmunds, W.M., Shand, P., 2004. Geochemical baseline as basis for the European Ground-
Mn (μg/L)

Normality

water Directive. Proc.WRI-11, Wanty and Seal. vol. II. Taylor & Francis Group,
London, pp. 393–397.
No

No
No
No
No
No
No

No

No
No
No
No
No
No
North

South

Edmunds, W.M., Shand, P., 2008. Natural Groundwater Quality. Wiley-Blackwell (978-
14051-5675-2 (488 pp.)).
Edmunds, W.M., Shand, P., Hart, P., Ward, R.S., 2003. The natural (baseline) quality of
Remaining

groundwater: a UK pilot study. Sci. Total Environ. 310, 25–35.

samples

European Commission, 2009. Guidance on groundwater status and trend assessment,

21

17
17
13
15
20
16

31

24
24
18
24
24
24

guidance document no 18. Technical Report 2009. European Communities,

Luxembourg. ISBN: 978-92-79-11374-1.
European Community, 2006. Groundwater directive 2006/118/CE. Directive of the
European Parliament and of the Council on the Protection of Groundwater Against
Max

1.74
2.38
1.74
1.74
2.38
2.38

2.28
2.76
2.06
2.28

2.76
3.52

3.82

3.23

Pollution and Deterioration, OJ L372, 27/12/2006, pp. 19–31.

Gemitzi, A., 2012. Evaluating the anthropogenic impacts on groundwaters; a methodol-
ogy based on the determination of natural background levels and threshold values.
95th

2.55
2.38

1.67
2.17
1.67
1.67
2.17
2.17

2.99

2.13
2.23
2.01
2.13

2.23

Environ. Earth Sci. 67, 2223–2237.

Ghergo, S., Guerra, M., Marcaccio, M., Menichetti, S., Parrone, D., Preziosi, E., 2017. Linee
Normality

guida recanti la procedura da seguire per il calcolo dei valori di fondo per i corpi idrici
F (mg/L)

sotterranei (DM 6 luglio 2016). Manuali e Linee Guida dell'Istituto Superiore per la
Yes
Yes
Yes
Yes
Yes
Yes

Yes

Yes
Yes
Yes
Yes

Yes
No

No

Protezione e la Ricerca Ambientale 155, 2017. 978-88-448-0830-3.

Goodchild, R.G., 1998. EU policies for the reduction of nitrogen in water: the example of
the Nitrates Directive. Environ. Pollut. 102, 737–740.
Griffioen, J., Passier, H.F., Klein, J., 2008. Comparison of selection methods to deduce nat-
Remaining
samples

ural background levels for groundwater units. Environ. Sci. Technol. 42, 4863–4869.
Results of the NBLs assessment with the different statistical methods.

21

18
20
18
18
20
20

31

28
29
26
28
30
29

Hawkes, H.E., Webb, J.S., 1962. Geochemistry in Mineral Exploration. Harper, New York.
Hinsby, K., Condesso de Melo, M.T., Dahl, M., 2008. European case studies supporting the
derivation of natural background levels and groundwater threshold values for the
protection of dependent ecosystems and human health. Sci. Total Environ. 401, 1–20.
Max

19.8
27.2
27.2
27.2

27.2

31.5

25.3
50.6

35.6

50.2

48.8

39.7
50.2
39.7

Huber, P.J., 1981. Robust Statistics. John Wiley, New York.

Liu, A., Ming, J., Ankumah, R.O., 2005. Nitrate contamination in private wells in rural Ala-
bama, United States. Sci. Total. Environ. 346, 112–120.
95th

27.6

39.4

38.0
44.3
38.0
35.6

19.1
27.0
27.0
27.0

27.0

44.3

30.1

23.8

Marandi, A., Karro, E., 2008. Natural background levels and threshold values of monitored
parameters in the Cambrian–Vendian groundwater body, Estonia. Environ. Geol. 54,
1217–1225.
As (μg/L)

Normality

Masetti, M., Poli, S., Sterlacchini, S., Beretta, G.P., Facchi, A., 2008. Spatial and statistical as-
Yes
Yes
Yes
Yes

Yes

Yes

Yes
No

No

No

No

No
No
No

sessment of factors influencing nitrate contamination in groundwater. J. Environ.

Manag. 86, 272–281.
Masotta, M., Gaeta, M., Gozzi, F., Marra, F., Palladino, D.M., Sottili, G., 2010. H2O and
temperature-zoning in magma chambers: the example of the Tufo Giallo della Via
Remaining
samples

Tiberina eruptions (Sabatini volcanic district, central Italy). Lithos 118, 119–130.
21

16
19
19
19
20
19

31

26
30
23
29
31
29

Matschullat, J., Ottenstein, R., Reimann, C., 2000. Geochemical background – can we calcu-
late it? Environ. Geol. 39, 990–1000.
Menciò, A., Mas-Pla, J., Otero, N., Regàs, O., Boy-Roura, M., Puig, R., Bach, J., Domènech, C.,
Zamorano, M., Brusi, D., Folch, A., 2016. Nitrate pollution of groundwater; all right…,
dataset

dataset
Method

but nothing else? Sci. Total Environ. 539, 241–251.

MAD

MAD
MSD

MSD
BWI

BWI
BW

BW
QQ

QQ
OT

OT
PS

PS
Table 2

Molinari, A., Guadagnini, L., Marcaccio, M., Guadagnini, A., 2012. Natural background
levels and threshold values of chemical species in three large-scale groundwater bod-
ies in northern Italy. Sci. Total Environ. 425, 9–19.
894 D. Parrone et al. / Science of the Total Environment 659 (2019) 884–894
Muller, D., Blum, A., Hart, A., Hookey, J., Kunkel, R., Scheidleder, A., Tomlin, C., Wendland,
F., 2006. Final proposal for a methodology to set up groundwater threshold values in
Europe. Report to the EU project “BRIDGE” 2006, Deliverable D18.
Panno, S.V., Kelly, W.R., Martinsek, A.T., Hackley, K.C., 2006. Estimating background and
threshold nitrate concentrations using probability graphs. Ground Water 44 (5),
697–709.
Peccerillo, A., Manetti, P., 1985. The potassium alkaline volcanism of central-southern
Italy: a review of the data relevant to petrogenesis and geodynamic significance.
Trans. Geol. Soc. S. Afr. 88, 379–394.
Preziosi, E., Giuliano, G., Vivona, R., 2010. Natural background levels and threshold values
derivation for naturally As, V and F rich groundwater bodies: a methodological case
study in Central Italy. Environ. Earth Sci. 61, 885–897.
Preziosi, E., Parrone, D., Del Bon, A., Ghergo, S., 2014. Natural background level assessment
in groundwaters: probability plot versus pre-selection method. J. Geochem. Explor.
143, 43–53.
Reimann, C., Filzmoser, P., 2000. Normal and lognormal data distribution in geochemistry:
death of a myth. Consequences for the statistical treatment of geochemical and envi-
ronmental data. Environ. Geol. 39 (9), 1001–1014.
Reimann, C., Garrett, R.G., 2005. Geochemical background—concept and reality. Sci. Total
Environ. 350, 12–27.
Reimann, C., Filzmoser, P., Garrett, G., 2005. Background and threshold: critical compari-
son of methods of determination. Sci. Total Environ. 346, 1–16.
Rosner, B., 1983. Percentage points for a generalized ESD many-outlier procedure.
Technometrics 25, 165–172.
Rotiroti, M., Fumagalli, L., 2013. Derivation of preliminary natural background levels for
naturally Mn, Fe, As and NH4 rich groundwater: the case study of Cremona area
(northern Italy). Rend. Online Soc. Geol. Ital. 24, 284–286.
Shapiro, S.S., Wilk, M.B., 1965. An analysis of variance test for normality (complete sam-
ples). Biometrika 52, 591.
Sinclair, A.J., 1974. Selection of threshold values in geochemical data using probability
graphs. J. Geochem. Explor. 3, 129–149.
Sottili, G., Palladino, D.M., Marra, F., Jicha, B., Karner, D.B., Renne, P., 2010. Geochronology
of the most recent activity in the Sabatini volcanic district, roman province, Central
Italy. J. Volcanol. Geotherm. Res. 196, 20–30.
Tennant, C.B., White, M.L., 1959. Study of the distribution of some geochemical data. Econ.
Geol. 54, 1281–1290.
Tukey, J.W., 1977. Exploratory Data Analysis. Addison-Wesley Publishing Company (688
pp.).
Ventriglia, U., 1989. Idrogeologia della Provincia di Roma, II volume: Regione Vulcanica
Sabatina (Amm. Prov. Roma. Ass. LL.PP).
Vivona, R., Preziosim, E., Made´, B., Giuliano, G., 2007. Arsenic of natural origin in a volca-
nic sedimentary aquifer: a case study in central Italy. Hydrogeol. J. 15, 1183–1196.
Walter, T., 2008. Determining natural background values with probability plots. EU
Groundwater Policy Developments Conference. UNESCO, Paris, France (13–15/11/
2008).
Wendland, F., Hannappel, S., Kunkel, R., Schenk, R., Voigt, H.J., Wolter, R., 2005. A proce-
dure to define natural groundwater conditions of groundwater bodies in Germany.
Water Sci. Technol. 51 (3–4), 249–257.
Wendland, F., Berthold, G., Blum, A., Elsass, P., Fritsche, J.G., Kunkel, R., Wolter, R., 2008.
Derivation of natural background levels and threshold values for groundwater in
the Upper Rhine Valley (France, Switzerland and Germany). Desalination 226,
160–168.
WHO, 2011. Guidelines for Drinking-water Quality. 4th edition. World Health Organiza-
tion 978 92 4 154815 1 (564 pp.).