Soil and Sediment Contamination: An International

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Field-Tests versus Laboratory Methods for

Determining Metal Pollutants in Soil Extracts

Michaela Zeiner, Raimund Pirkl & Iva Juranović Cindrić

To cite this article: Michaela Zeiner, Raimund Pirkl & Iva Juranović Cindrić (2020) Field-Tests
versus Laboratory Methods for Determining Metal Pollutants in Soil Extracts, Soil and Sediment
Contamination: An International Journal, 29:1, 53-68, DOI: 10.1080/15320383.2019.1670136

To link to this article: https://doi.org/10.1080/15320383.2019.1670136

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SOIL AND SEDIMENT CONTAMINATION
2020, VOL. 29, NO. 1, 53–68
https://doi.org/10.1080/15320383.2019.1670136

Field-Tests versus Laboratory Methods for Determining Metal

Pollutants in Soil Extracts
a,b
Michaela Zeiner , Raimund Pirklb, and Iva Juranović Cindrićc
a
Man-Technology-Environment Research Centre, School of Science and Technology, Örebro University,
Örebro, Sweden; bDivision of Analytical Chemistry, Department of Chemistry, BOKU – University of Natural
Resources and Life Sciences, Vienna, Austria; cDepartment of Chemistry, Faculty of Science, University of
Zagreb, Zagreb, Croatia

ABSTRACT KEYWORDS
Soil is one of the vehicles by which metals enter plants and ground- Field tests; metal analysis;
water. Compared to organic pollutants, metals do not biodegrade soil extract; spectrometry;
and are usually not mobile. In order to estimate the potential impact titrimetry
on groundwater, the amount of extractable metals from soil are thus
of concern. Soil matrices represent quite a complex matrix; thus, the
appropriate choice of sample preparation and analytical method is of
great importance and challenging to ensure reliable and fast data
while keeping labor and time need as low as possible. Soil extracts
using acetic acid were analyzed, on the one hand, using classical
analytical methods such as titrimetry (complexometry) and spectro-
photometry, and on the other hand, by instrumental methods,
including inductively coupled plasma optical emission spectrometry
(ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS)
and graphite furnace atomic absorption spectrometry (GF-AAS). The
classical methods are characterized by higher limits of detection
(LODs), nevertheless their application as screening method on-site
is promising. Applying specific reagents, precise measurements can
be obtained by photometry with LODs about 0.1 mg/L. Titrimetric
methods can be used for specific single element determination and
for determining the sum of certain metals at contaminated sites due
to LODs around 60 mg/L.

Introduction
Regarding metals in soil: terms like “contamination”, “pollution”, “heavy metal bur-
den” and “trace metal content” are widely used as synonyms for the same chemical
parameter but being defined with different meanings. A common definition of “heavy
metals” is based on their density, considering metals with ρ > 5 g/cm3 (at standard
conditions) as such, including up to 70 elements, e.g., Cd, Cr, Cu, Fe, Hg, Ni, Pb, Sn
and Zn (Karcher 2007). According to IUPAC, since there is no association between the
density and contamination as well as potential toxicity or ecotoxicity, this term should
be not be used to avoid misunderstandings (Duffus 2002). Even some of these heavy
metals are essential for humans: such as Fe, Mn and Zn. In this respect, their
recommended uptake dosage determines the correct term “trace elements” equal to

CONTACT Michaela Zeiner [email protected] Man-Technology-Environment Research Centre, School of

Science and Technology, Örebro University, Fakultetsgatan 1, Örebro 70182, Sweden
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/bssc.
© 2019 The Author(s). Published with license by Taylor & Francis Group, LLC.
This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial-NoDerivatives License
(http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium,
provided the original work is properly cited, and is not altered, transformed, or built upon in any way.
54 M. ZEINER ET AL.

“micronutrients” or “ultra-trace elements” (Adriano 2001). Conversely, the geochem-

ical definition of a trace element refers to its percentage in soil composition, which
should not exceed 0.1% (Zovko and Romic 2011).
Also, regarding “soil contamination” various definitions are circulating. Knox et al.
(1999) focuses exclusively on a deviation in soil composition compared to its natural
composition profile. It does not include any statement regarding resulting consequences
on living organisms nor does it provide information about absolute (Kabata-Pendias
2011). A soil contaminant turns into a pollutant once it is derived by anthropogenic
influences and once it has an impact or a significant risk of impact on organisms due to
direct or indirect (toxic) effects or is restricted in its use (Knox et al. 1999). Usually, the
definition of a certain pollutant is linked to a threshold concentration given by European,
national or local legislations (EurLex 86/278/EEC; OÖ Klärschlammverordnung 2006;
ÖNORM L1075; 2017).
Regarding biochemical processes, the presence of heavy metals in soil only turns out to be
relevant once the elements are in a physical state available for organisms or may enter the
groundwater. In context of plant–soil interactions: bioavailability of heavy metals is reduced to
that amount of an element, which is present in ionic state, in aqueous solution of soil water
(chemical activity) and therefore directly available for plant structures and their cellular
membranes due to diffusion, sorption and partitioning (Reichernberg and Mayer 2006;
Semple et al. 2004). Those metals, precipitated or ligated to clay minerals and/or organic matter,
are temporarily immobilized but can be released into the aqueous soil solution at any time due
to a change in the surrounding milieu (e.g., pH) or of other physical state variables. Metals
trapped in soil mineral matrix, which represent a chemically inert condition, can nevertheless be
affected by long-term processes like weathering (Zovko and Romic 2011; Kabata-Pendias 2011).
Thus, even if the total metal content in soil influences its bioavailability (Schreck et al. 2011;
Wijayawardena et al. 2015; Yan et al. 2018), other parameters have to be taken into account.
These include, amongst others, the basic soil composition (mother rock, especially influenced by
cation-binding substances like humic acid or clays) alongside soil characteristics (pH-value,
cation exchange capacity – CEC) (Schreck et al. 2011; Wijayawardena et al. 2015; Zeiner et al.
2015a), age of contamination (Schreck et al. 2011; Wijayawardena et al. 2015), way of soil
treatment (Blaylock et al. 1997), and target organisms tested (Juranović Cindrić et al. 2019;
Schreck et al. 2011; Zeiner et al. 2015b).
Not only the influencing parameters vary widely, but also the analytical methods used in
soil analysis. An overview is presented in Figure 1. The choice of the most appropriate method
for the determination of certain metals present in soil extracts depends on several factors, such
as the costs and ease of analysis, the time required, the number of analytes, the expected
concentration range, the interest in qualitative, semi-quantitative or quantitative determina-
tion and the available amount of sample. The interest in field-tests as a fast screening method
for geochemical purposes has been already reported some decades ago (Bloom 1955). All
methods differ regarding the limits of detection, sensitivity and selectivity, as well as the
possible interferences caused by the sample matrix. There is no best method at all, it always
depends on the actual analytical test. Even if regulatory and standards-setting organizations
have revised their validation guidelines during the past few decades, the basic idea has
remained the same, namely that the chosen method meets the needs of the customer as well
as of the intended analytical task. In the course of this investigation, in order to optimize the
analytical expenditure, low budget titrimetric and photo-spectrometric screening methods for
 SOIL AND SEDIMENT CONTAMINATION 55

Figure 1. Soil fractions in context of heavy metal availability – sample preparation and applied
methods. Modified scheme from Pirkl (2016).

soil extracts were tested and compared with modern, but apparatus-intensive, standard
methods such as flame or graphite furnace atomic absorption spectrometry ((G)FAAS),
inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled
plasma mass spectrometry (ICP-MS). The titrimetric and photo-spectrometric analysis were
performed focusing only on the elements copper (Cu), nickel (Ni), and zinc (Zn), which are
well-documented anthropogenic contaminants.
In the present paper, the preparation of an acidic, aqueous soil extract was chosen to
determine only those heavy metal portions of soil which are soluble (exchangeable) under
acidic soil conditions. This choice was made in analogy to the first standardized fraction of
the “standard 3-step extraction procedure for the fractionation of heavy metals” proposed by
the European Commission, Community Bureau of Reference (BCR) considered as the
exchangeable fraction of (heavy) metals in soil matrices. This well-known procedure has
been modified and optimized several times by the international scientific community (Bacon,
Hewitt, and Cooper 2005; Sutherland and Tack 2001; Zeiner et al. 2013; Zemberyova,
Baretkova, and Hagarova 2006) and seems therefore to be an interesting and useful approach.

Materials and methods

Chemicals and glassware
Chemicals of at least p.a. or even higher quality purchased from Merck (Darmstadt,
Germany) were used, their compositions/concentrations given in the following subchap-
ters for the respective experimental procedures.
56 M. ZEINER ET AL.

All glass- and plastic-ware were cleaned in a two-step process including repeated nitric
acid soaking and rinsing with ultra-pure water. In order to avoid recontamination, the
dried utensils were stored in clean PE bags prior to further use.

Samples and sample preparation

Sampling
The soil samples (n = 6), showing a general composition of quartz, illite, chlorite, chlorite-
smectite and plagioclase, were collected from A-horizon by a team of the University of Zagreb in
July 2012 inside a defined sampling area of the national park Northern Velebit, Croatia. This
area represents a typically mountain terrain in an altitude of approximately 1400 m above sea
level. After sampling, the soils were ground with a metal-free device, dried at 105°C for 24 h, and
subsequently stored in PE bags.

Basic soil characteristics

pH-value in H2O. The dried soil samples were suspended in ultra-pure water in a w/w ratio
1:5. These suspensions were then shaken for 1 h using an orbital shaker. The pH-values were
subsequently measured with a two-point calibrated pH glass electrode (single-rod measuring
cell; calibration buffers pH 4.0 and 7.0) under controlled temperature conditions.

pH-value in CaCl2-solution. These measurements were performed in the same way as

described above, replacing only the water with a CaCl2 solution (c(CaCl2) = 0.01 mol/L).

Cation exchange capacity (CEC). The CEC was determined applying a slightly modified
method by Bergaya and Vayer (2005, 1997). 200 mg of dried soil sample was mixed with 8 mL
Cu(EDA)22+-solution (copper ethylene diamine; c(Cu(EDA)22+) = 0.01 mol/L), brought to pH
7.0 with a tris buffer and filled up with ultra-pure water to 25 mL. After centrifugation for 30 min
and ensuring that the pH was 7.0, the remaining concentration of remaining Cu(EDA)22+ in the
supernatant was determined by photometric analysis at a wavelength of 548 nm.

Soil extracts
The soil extracts were prepared analogously to BCR step-1 method: Approximately 1 g of
each dried soil sample (weighed to the nearest 0.1 mg) were mixed with 40.0 mL acetic
acid (c(CH3COOH) = 0.11 mol/L) in an appropriate beaker. The suspension was shaken
for 16 h by using a magnetic stirring device, afterward centrifuged (3000 rpm for 20 min)
and decanted to obtain the liquid supernatant. In order to achieve a clear extract without
any disturbing cloudiness, the extracts were filtered through 1.0 µm syringe-filter units.
Prior to measurements, the extracts were stored in pre-cleaned PP-tubes.

Metal determinations
In the course of this investigation, different instrumental analytical techniques were tested
for their applicability alongside a classical method, namely titrimetry.
 SOIL AND SEDIMENT CONTAMINATION 57

Titrimetry
To test the feasibility of a titrimetric approach for quantifying selected metal ions in soil extracts:
three Titriplex® methods (Merck 1976) on selected heavy metals (Cu, Ni, Zn), respectively, on
a class of metals represented by these elements, were selected and their key data are presented in
Table 1. By using NaF as a masking reagent, the number of interfering cations could be reduced.
All applied titrimetric procedures are based on titration with ethylene diamine tetra acetic acid (c
(EDTA) = 0.10 mmol/L; 1.0 mmol/L; 10 mmol/L) with visual indication. A previous screening
of method’s LOD limitation in general was performed in order to estimate the practicability of
this approach on extracts of none-contaminated soil with foreseeable low heavy metal concen-
trations. Three standard solutions of each of the three selected metals were prepared in ultra-
pure water (using Ni(NO3)2 x 6 H2O, Cu(NO3)2 x 6 H2O and ZnSO4 x 7 H2O), having amount
concentrations of 0.10 mol/L, 1.0 mmol/L and 10 mmol/L. All titrations were performed in
triplicate.

Copper. 5.0 mL of the respective Cu2+ standard solution was mixed with five drops of
murexide indicator solution, brought to pH 8 with NH3 (25% w/w) and titrated with the
adequate EDTA volumetric solution until a color-change from orange to purple was
observed.

Nickel. Five drops of murexide indicator solution were added to 5.0 mL of the Ni2+ standard
solution, brought to pH 10 with NH3 (25% w/w) and titrated with EDTA volumetric solution
of the same amount concentration until a color change from yellow to purple/blue occurred.

Zinc. 1 mL of ammonia (25% w/w), 1 MERCK Eriochrome-black-t buffer tablet and 5.0 mL
of the Zn2+ standard solution were mixed and the mixture then titrated with EDTA volu-
metric solution until a color-change from red to green was visible.

Photometry
Methods for photo-spectrometric determination of Cu, Ni and Zn were selected, based on
previously reported ones by Fries and Getrost (1977) and already applied on wastewater matrices
by Zeiner, Rezić, and Šantek (2010), providing promising results regarding a fast and easy
detection method in context of low cost/low complexity frame conditions. Some modifications
concerning pH adjustment and buffer systems were implemented in order to respond to the
actual acidic properties of the soil extracts (see detailed description below). The key data are
summarized in Table 2. A previous calibration, covering a wide working range, was set up to

Table 1. Tested titrimetric methods – procedures analogous to Merck (1976).

Change of Included in
Analyte Indicator color Disturbing metals Masking measures determination
Cu Murexide Orange/ All bivalent metals, and Masking alkaline earth All metals apart of
(ammonium purpurate) yellow → especially Al, Fe metals and Fe with Fe, alkaline earth
purple NaF metals
Ni Murexide Yellow → Cd, Co, Zn, Hg, alkaline Masking alkaline earth Ni, Cd, Co, Zn, Hg,
(ammonium purpurate) blue/purple earth metals, noble metals with NaF noble earths
earths
Zn Merck Indicator buffer Red → All heavy metals, Masking alkaline earth All heavy metals
tablet (Eriochrome- green alkaline earth, metals and Fe with apart of Fe
black-T) magnesium NaF
58 M. ZEINER ET AL.

Table 2. Applied photo-spectrometric methods on soil extracts (Fries and Getrost 1977; Zeiner, Rezić,
and Šantek 2010).
Analyte Reagent Reaction/Product Wavelength Interfering metals
Cu Diethyldithiocarbamate At pH 4–11: brownish 440 nm Ag, Co, Cr, Fe, Hg, Mn, Ni, V and other ions
complex in high concentrations
Ni Dimethylglyoxime In alkaline milieu: red 450 nm Co, Cr(III), Cu(II), Mn(II), Fe, Zn if γ > 1 mg/L
colored complex
Zn Zincon monosodium At pH 8.5–9.5: blue 625 nm Al, Be, Bi, Cd, Co, Cr, Cu, Fe, Mo, Mn, Ni, Ti
salt colored complex

confirm the linearity of the method (Beer-Lambert law) and to determine the limit of detection.
For this purpose, solutions of Cu(NO3)2 x 6 H2O, Ni(NO3)2 x 6 H2O and ZnSO4 x 7 H2O were
prepared in ultra-pure water, additionally acidified with acetic acid to simulate the pH milieu of
a soil extract. The mass concentration ranges for the analytes were 0.0250 mg/L – 6.20 mg/L for
Cu, 0.0250 mg/L – 5.00 mg/L for Ni and 0.00500 mg/L – 6.50 mg/L for Zn. All three methods
were subsequently applied to determine the particular heavy metal concentrations in soil
extracts. The instrument used was an EASYSPEC UV/Vis-photometer.

Copper. 2.5 mL of citric acid/NH3 solution (75 g citric acid in 100 mL ultra-pure water +95 mL
NH3 25% w/w, filled up to 250 mL with ultra-pure water) was added to 10 mL of test solution
(blank, standard, soil extract) and mixed with 2.5 mL diethyldithiocarbamate reagent solution
(1 g/L). After homogenization, the absorbance was determined at 440 nm after 20-min reaction
time.

Nickel. To 40 mL test solution 1.0 mL citric acid (40% w/w), 1.0 mL of NH3 (25% w/w)
and finally 1.0 mL of dimethylglyoxime (10 g/L adjusted to pH 10 with NaOH) were
added. The resulting mixture was filled up to 50.0 mL with ultra-pure water, shaken and
the absorbance measured at 450 nm after a 30-min reaction period.

Zinc. 4.0 mL of the testing solutions were brought to pH 9 by adding 4–5 drops of NaOH-
solution (c(NaOH) = 4 mol/L) and mixed with 1.8 mL buffer (5 g K-hydrogen phthalate in
100 mL H2O, pH 9 adjusted with NaOH 4 mol/L). Afterward, 0.6 mL of reagent solution
(2-(α-(2-Hydroxy-5-sulfophenylazo)-benzylidene-hydrazino)-benzoic acid monosodium salt
100 mg dissolved in 100 mL NaOH-solution c(NaOH) = 0.02 mol/L) were added, as well as
ultrapure water to reach a final volume of 10.0 mL. The absorbance of each solution was
measured directly subsequent to sample preparation after homogenization at 625 nm.

GFAAS
The measurements were performed in triplicate using a PE 4100 ZL instrument, equipped
with an AS-70 autosampler. In the atomizing unit, transverse heated end capped graphite
tubes with L’vov platform were placed. Acidified standard solutions of Cu, Ni and Zn were
analyzed; the instrumental conditions are given in Table 3.

ICP-OES
Cu, Ni, Zn (besides Al, B, Ba, Ca, Cd, Co, Cr, Fe, K, Mg, Mn, Mo, Na, Pb and Sr) were
quantified in the soil extracts by a Prodigy HD ICP-AES instrument at 324.754, 231.604
and 213.856 nm, respectively. The sample uptake rate was 1.0 mL/min; the aerosol was
 SOIL AND SEDIMENT CONTAMINATION 59

Table 3. Instrumental conditions for GFAAS-measurements.

Sample
Wavelength Tpyrolysis Ramppyrolysis Holdpyrolysis Tatomization Rampatomization Holdatomization volume
Analyte (nm) (°C) (s) (s) (°C) (s) (s) (µL)
Cu 324.8 1200 10 20 2200 0 5 20
Ni 232.0 1000 10 20 2100 0 5 20
Zn 213.9 700 10 20 1800 0 5 5

produced in a pneumatic nebulizer and passed a glass cyclone spray-chamber prior to

entering the Ar-plasma (coolant gas flow 18 L/min; auxiliary gas flow 0.8 L/min).

ICP-MS
A Thermo Fischer Element 2 ICP – sector field MS was used for the determination of metals
present in expectable low concentrations, based on their common isotopes: 65Cu, 60Ni and 66Zn
along with 75As, 111Cd, 59Co, 52Cr, 56Fe, 208Pb, 88Sr and 115In as internal standard. The sample
solution was introduced through a self-aspirating PFA microflow nebulizer at a flow rate of 100
µL/min followed by a Peltier cooled cyclonic quartz chamber. The Ar flows applied were 16
L/min for the plasma gas flow, 1.06 L/min for the sample gas and 0.86 L/min for the auxiliary gas.

Calculations
All calculations were performed using Microsoft Excel 2013 with the data-analysis add-in.
The final elemental concentrations in the test solutions were blank corrected prior to
calculating the results as contents per dry weight considering dilution steps as well as mass
of dried material.

Quality control and method validation

Based on the goal of the paper on testing the methods’ applicability, no complete method
validation was performed in course of this study. The ICP-OES method applied has been
validated using soils and sediment-certified reference materials in a previous investigation, the
obtained results being satisfying (Zeiner et al. 2015a). The main criteria chosen were the LOD
(which was calculated for the instrumental methods based on 3 σ), the accuracy, the rugged-
ness as well as the selectivity. A different approach is needed for classical methods, like
titrimetry, where the endpoint indication was used to estimate the LOD. For checking the
accuracies of the individual methods, their results were compared with those obtained by the
previously validated ICP-OES method. Analysis of Variance (ANOVA) was used for this
statistical evaluation.
All measurements were performed with soil extracts and standard solution, to which
the LODs in mg/L refer. To compare these values with soil contents, the volume of
extraction medium (40 mL) and mass of sample (1 g) were used to convert the mass
concentration of the respective analyte in the extract solution to a content (mg/kg) in soil.
60 M. ZEINER ET AL.

Results and discussion

Basic soil characteristics
The pH-values determined in water ranged from 4.78 to 7.90 with a mean of 6.52, whereby
those in CaCl2-solution were lower by 0.29 to 0.81 pH-units (average ΔpH −0.57), thus
covering the range from pH 4.14 to 7.13 (mean 5.75). This tendency is in accordance with
data reported in literature (Amman, Bergaya, and Lagaly 2005; Bergaya and Vayer 1997).
The CEC, defined as the maximum quantity of cations, which a soil is capable to hold at
a certain pH-level was determined to vary from 10.9 mEq/100 g to 28.2 mEq/100 g for the soils
studied. This parameter provides information on the potential capacity to bind or to release
cations as an interdependency between soil and its surrounding aqueous solution.
All obtained data on basic characteristics were within typical ranges for clay soils
(Bergaya and Vayer 1997; Pansu and Gautheyrou 2006; Mengel 1993; Sonon, Kissel, and
Saha 2014).

Metal determinations
Titrimetry
Not all tested titrimetric methods were capable of finding Cu, Ni or Zn at concentrations lower
than 1 mmol/L in simple matrices, since the indicator already showed the final color. Titrating
soil extracts showed side effects like flocculation or instability of color indication leading to
high variation in results of repeated measurements. Therefore, titrimetric methods are of
limited use for metal quantification in soil extracts. Due to the advantage of low time
consumption of these determinations, they should not be excluded at all, but they can be
applied to obtain a rough overview information on high single element contamination or for
determining sum-factors.
The above-mentioned amount concentration of 1 mmol/L is considered to be the limit of
detection (LOD) for all three metals based on the visibility of the endpoint using color-
indicators. Expressed in mass concentration, these values are 64 mg/L for Cu, 59 mg/L for Ni
and 65 mg/L for Zn. The common determination of LODs based on 3 σ of a blank measure-
ment cannot be applied for such a classical analytical method (Thompson, Ellison, and Wood
2002). Other approaches are based on the drop size not taking into account the endpoint
detection (Mahap 2017) or considering the smallest detectable signal change when an instru-
mental method is used for endpoint detection, e.g., fluorescence emission (Sahana et al. 2013).

Photometry
The determined limits of detection were 0.100 mg/L for Cu and Ni, alongside 0.0400 mg/L for
Zn. Compared to the above-mentioned titrimetric methods, the chosen photo-spectrometric
ones were capable of detecting small amounts of heavy metals in simple matrices. The working
range of Ni2+ is limited to a maximum mass concentration of 3.90 mg/L. In case of higher
concentrated solutions, flocculation and cloudiness was observed when mixed with buffer and
reagent solution. The linearity of the calibrations within the particular working ranges were
confirmed to be satisfying, the correlation coefficients of all calibration curves being >0.999.
The experiments highlighted the importance of working with clear and transparent soil
extracts, because any kind of cloudiness, color influence, or precipitation caused by matrix
 SOIL AND SEDIMENT CONTAMINATION 61

leads to measurement deviations and scattering of results. Remaining interferences needed

to be eliminated by filtration and/or centrifugation and collection of the supernatant.
Without this step, the photo-spectrometrically determined copper concentrations in soil
extracts were higher than the total copper contents in soil found by ICP-MS after sample
digestion. Regarding Ni, the extractable fractions found ranged from 27.1% to 95.6% of
the total amount in soil. All soil extracts had Zn levels below the LOD of the respective
photo-spectrometric method.
Concluding it can be stated that photo-spectrometric methods are an attractive low-
cost opportunity, especially for fast heavy metal screening in soil extracts. Whilst the
colored complex formation for Zn was fast, reaction times of 20 min and 30 min had to be
respected for Cu and Ni, resp. in order to ensure complete reaction.
The adopted methods were applied further on to soil extracts from six different soil samples
collected in the Croatian national park Northern Velebit. The total amounts of Cu, Ni and Zn
in these specimens were quantified after acidic microwave-assisted digestion using aqua regia
and hydrogen peroxide. The Cu contents range from 14.9 mg/kg to 34.8 mg/kg dry matter,
with an average of 24.5 mg/kg. Higher values were obtained for Ni ranging from 38.3 mg/kg
up to 89.0 mg/kg, the mean being 59.3 mg/kg. Zinc was found to be present in the sample with
a mean content of 106 mg/kg, whereby the minimum was 67.1 mg/kg and the maximum
138 mg/kg (Pirkl 2016).
For Cu and Ni, the concentrations in all extract solutions were above LOD, ranging from
0.249 mg/L to 2.93 mg/L and from 0.427 mg/L to 1.11 mg/L, respectively. The fact that for Cu
the extraction yield was found to exceed 100% for three soil samples indicates that the Copper
determination via photo-spectrometric analysis was interfered by the presence of other
cations or matrix compounds causing turbidity. The particular extractable fractions of the
total Nickel content ranged from 27.1% to 95.6%. These values are higher than that obtained
for the first step of a sequential BCR extraction study of urban soils (Zeiner et al. 2015a).
Since the obtained total soil metal contents are comparable with data reported in
literature (Massadeh et al. 2016a; Massadeh, El-Rjoob, and Al-Omari 2016b) and the
fact that Cu and Ni could be found in the extract solutions underlines the applicability
of the proposed analytical procedure.

GFAAS
GFAAS is a single-element method; thus, a high time consumption has to be taken into
account when being interested in many contaminants. Even if the instrument itself is
expensive, the operational costs are in the medium range. Measurements can only be
performed in a laboratory by trained personnel, but not directly on-site. Due to the high
matrix tolerance, no significant interferences are to be expected by the soil extracts in
comparison to acidified test solutions. The LODs obtained for the three analytes are
0.00140 mg/L, 0.00150 mg/L and 0.00130 mg/L for Cu, Ni and Zn, respectively. In contrast
to other instrumental methods, such as ICP-OES and ICP-MS, a reduction of LODs by the
factor 2, 3 and so on can be achieved by repetitive pipetting of the sample into the graphite
tube. This leads to longer analysis time, since the drying step has to done after each sample
introduction. Conversely, no complicated concentrations steps during the sample preparation
are needed, resulting in a shorter and simpler pretreatment time.
62 M. ZEINER ET AL.

ICP-OES
This fast and multi-element analytical method is recommended for time saving analyses when
many analytes are of interest. The instrument is expensive and the operational costs are high
due to high Ar need for the plasma. Precise and true results are to be expected, but the
measurements are limited to an equipped analytical laboratory with trained personnel. On-
site screening analysis is not possible. The LODs calculated for this method in the extract
solutions are 0.00215 mg/L for Cu, 0.00222 mg/L for Ni and 0.00242 mg/L for Zn.

ICP-MS
The extract solution had to be diluted 1:20 using 2% w/w nitric acid prior to measurement.
Even considering this dilution factor, the obtained LODs for the elements of interest are
very low, explicitly 0.000925 mg/L for Cu and 0.00180 mg/L for Ni. A higher LOD was
only determined for Zn with 0.0470 mg/L. Except for Zn, the values are in the same range
as those calculated for the ICP-OES and the GFAAS measurements.
As ICP-OES, also ICP-MS is a fast multi-element technique, requiring a clean room along
with skilled personnel. The additional dilution steps increases the sample preparation time
along with the need of consumables such as pipette tips and plastic ware, as well as of
chemicals. In context of generating data on soil heavy metal fingerprints, ICP-MS additionally
provides information on present isotopes which can be valuable regarding authenticity
analysis or as a basis of comparison for the determination of geographical origin.

Comparison of methods
Figures of merit
A classical approach to compare different analytical methods is based on the respective LODs.
The LOQ (limit of quantification) is three times LOD; thus, it was not calculated additionally,
since the ratio between all methods does remains the same. All obtained limits of detection are
summarized in Table 4, given in mg/L for the extract itself together with the value as extracted
from soil in mg/kg. As expected, the LOD for the titrimetry is much higher than the data for
the other methods tested and even beyond the stated soil threshold levels. Thus, even if
characterized by ease of performance, this method cannot be applied for uncontaminated soils
and is of limited use for contaminated ones. In the latter case, this can be a high contamination
of one pollutant or a sum-parameter since EDTA offers the possibility to determine the sum of
different metal ions in a solution (see also Table 1 for possible interferences). Accurate, i.e.,
precise and true, results are obtained by GFAAS, ICP-OES and ICP-MS; the results not
showing statistically significant differences based on ANOVA (p < .05). Conversely, the photo-
spectrometry suffers from interferences caused by other bivalent cations as well as from
cloudiness of the extract, especially regarding the quantification of Cu. A summary of the
applicability of the tested methods for soil extracts is shown in Figure 2.

Field application
The three instrumental methods GFAAS, ICP-OES and ICP-MS cannot be used for fast on-
site screenings due to the required laboratory environment. Conversely, titrations can be
easily performed in PP-beakers and using plastic Pasteur pipettes with scale as burettes.
Adjusting the pH value and addition of the indicator solution are the only steps to have the
extract ready for analysis, but only high contaminations can be detected with this approach.
Table 4. Summary of LODs of the methods investigated in the extract solutions (1 – in mg/L) and as extracted from soil (2 – in mg/kg) alongside soil threshold
levels.
LOD Titration LOD Photometry LOD GFAAS LOD ICP-OES LOD ICP-MS
Threshold level in soil (mg/kg)
Analyte (EurLex 86/278/EEC) 1 2 1 2 1 2 1 2 1 2
Cu 50–140 64 2.5*104 0.100 4.00 0.00140 0.0560 0.00215 0.0860 0.000925 0.0370
Ni 30–75 59 2.3*104 0.100 4.00 0.00150 0.0600 0.00222 0.0890 0.00180 0.0720
Zn 150–300 65 2.6*104 0.0400 1.60 0.00130 0.0520 0.00242 0.0970 0.0470 1.88
SOIL AND SEDIMENT CONTAMINATION
63
64 M. ZEINER ET AL.

Figure 2. Overview on applicability of the tested methods for analyzing soil extracts.

Figure 3. Sample preparation for photo-spectrometric analysis (Pirkl 2016).

The second possible on-site technique is the photo-spectrometry. Buffer as well reagent
solution can already be filled in pre-cleaned PP-tubes of appropriate size (15 mL or 50 mL see
Figure 3) in the laboratory prior to the sampling. On-site, only the required amount of
extract-solution is added and the color intensity registered. This can be done by simple
comparison with previously prepared standard solutions as picture on the mobile phone.
 SOIL AND SEDIMENT CONTAMINATION 65

This leads to a fast semi-quantitative result. Individual differences in color recognition can be
avoided using smartphone apps measuring the R, G and B value of the colored test solutions
(Peng et al. 2019) or of commercially available field test kits for selected soil contaminants
like As (Haque et al. 2016). Furthermore, there is no problem with the disposal of the
chemicals, since everything is kept in the closed tubes. In contrast to the sum-determination
by titrimetry, specific coloring agents are needed to form the complexes to be measured.
Thus, the kind of contamination should be known prior to perform the field tests.
Furthermore, it has to be taken into account that the extract preparation on-site is based
on just sampled, i.e., wet soil, and does not offer the time frame of 16 h. To gather
preliminary data, usually, the soil to extracting medium ratio is higher (between 1:5 and
1:10 instead of 1:40) and the extraction time shorter (30–60 min instead of 16 h). Also, the
centrifugation step has to be replaced: after sedimentation the needed volume of supernatant
is filtered using a syringe filter directly into the prepared PP-tube containing buffer and
complexing agent. All these factors show that the concentrations obtained on-site can only be
estimations and have to be accurately quantified later on by a second method, but give a fast
screening result to decide further steps for soil treatment and risk assessments.

Conclusions
The choice of the most appropriate method for a given analytical task, in this case, the
(quantitative) determination of selected metals in soil extracts prepared with diluted acetic
acid, depends on several factors. Titrimetry and photo-spectrometry show the advantages of low
costs and ease of analysis, besides suffering from interferences and especially the former from
high limits of detection. The best results for sample analyses are usually achieved by combining
different analytical methods and applying a simple and fast screening method before ICP-OES,
ICP-MS, or GFAAS measurements. Thus, the aim of the first step is to determine the elements
qualitatively and estimate their concentration ranges. Depending on the expected concentration
range and available instrument, the following method for the exact quantification is chosen.
Performing a fast and simple sample preparation followed by a semi-quantitative
spectro-photometrical analysis using prepared PP-tubes containing all needed reagents,
promising in-field tests can be carried out.

Acknowledgments
The authors are very grateful to all colleagues who helped us during sampling, sample preparation,
measurements as well as for general advices.

Conflicts of interest
The authors declare no conflict of interest.

Funding
This work was supported by the Österreichischer Austauschdienst [HR-23-2012].
66 M. ZEINER ET AL.

ORCID
Michaela Zeiner http://orcid.org/0000-0002-1215-7705

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