Water Resources and Industry 30 (2023) 100216

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Water Resources and Industry

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

Raman spectroscopy and XRF identification: First step in industrial

wastewater management
Paweł Lochyński *, Magdalena Szymańska, Sylwia Charazińska, Emilia Poznańska,
Justyna Kubicz
Institute of Environmental Engineering, Wrocław University of Environmental and Life Sciences, pl. Grunwaldzki 24, 50-365, Wroclaw, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: Considering the environmental risk, industrial facilities should strive to maximise the effective­
XRF ness of on-site treatment processes. It is important to detect the types of pollutants in wastewater
Raman spectroscopy and their concentrations, which can be challenging in industrial conditions. In this study, in­
On-site identification
dustrial wastewater samples from pickling and electropolishing of stainless steel were analyzed
Industrial wastewater
through Raman spectroscopy and XRF techniques using portable instruments. A 3-step procedure
Pickling
Electropolishing for the rapid identification of type of wastewater was proposed. The identification and analysis of
Stainless steel peaks present in the Raman spectroscopy at 900, 990, 1050, 1380 cm− 1allows for the differen­
tiation of wastewater type and dilution. The final step is to employ XRF measurements to
determine the approximate content of the investigated elements. The use of portable analytical
instruments for the estimation of contamination levels is essential for the management of the
industrial wastewater neutralization process as well as during emergency operations in cases of
accidents.

1. Introduction

Industrial wastewater from electroplating, tanning, printing, metallurgical, pharmaceutical, woodworking industries etc. Or even
landfill leachate due to the presence of heavy metal ions can have adverse effects on the environment and human health [1]. Therefore,
the effective removal of harmful pollutants already at the stage of wastewater treatment at the industrial plant from which they
originate is extremely important [2–4]. Wastewater generated by the plating industry can contain heavy metal ions and other pol­
lutants that, in excessive concentrations, cause poisoning of the body and can ultimately lead to death [5,6]. Faced with this threat,
industrial plants are required to minimize the pollutants discharged by setting up appropriate systems for monitoring the composition
and neutralization of hazardous wastewater, which is often produced in very large quantities [7,8].
The manufacturing industry generates significant amounts of wastewater in the course of its operations with evidence that the
water used in manufacturing typically ends up almost entirely as wastewater, often with little or no treatment [9]. Research into
wastewater treatment has mainly focused on how to improve treatment levels in particular industries or on the preferred technology
[5,10,11]. However, this set of managerial decisions is influenced by a number of factors, such as discussions with authorities at
various levels [12], internal capacity and management awareness [13]. Despite ample literature on both technical issues related to
wastewater treatment including specific treatment technologies [14–18], the broader choice of a treatment system has been largely

* Corresponding author.
E-mail address: pawel.lochynski@upwr.edu.pl (P. Lochyński).

https://doi.org/10.1016/j.wri.2023.100216
Received 2 March 2023; Received in revised form 20 May 2023; Accepted 11 June 2023
Available online 12 June 2023
2212-3717/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
P. Lochyński et al. Water Resources and Industry 30 (2023) 100216

ignored. In the scientific literature, few attempts to develop support tools for managers can be found [19–22].
Enhanced research methods make it possible to control and manage production processes at the point of demand. Portable testing
equipment is used directly at the site of contamination to test the content of metals and other elements. This makes it possible to make
quick decisions on, for example, field extraction [23,24] or material selection directly at the production line [25,26]. Determining the
chemical properties of waste is crucial to ensuring the most efficient disposal method. Near Infrared Spectroscopy,
Infrared-Transmission, Line Scan Cameras and X-ray Fluorescence are a few examples of advanced systems used in waste sorting and
quality control processes [27]. The methods described are also used in the management of municipal solid waste incineration [28]. The
use of portable devices, e.g. XRF, yields very good results in assessing the environmental impact and in planning remedial actions for
the impact of highly saline mine waters containing toxic elements [29].
In industrial settings, a variety of methods are used for wastewater composition monitoring, but not all of them are fast, relatively
inexpensive and uncomplicated. Currently, common methods for analyzing wastewater composition in industrial plants are: AAS [30],
ICP, UV–vis and Raman spectroscopy [31], and XRF [32]. Fourier transform infrared (FTIR) spectroscopy is an analytical technique
that is characterized by very high measurement capabilities, and is therefore often used for qualitative evaluation of various substances
and products. Its main advantages over other techniques are the high selectivity achieved by high-resolution measurements, the ability
to measure the content of multiple substances simultaneously, and its high sensitivity. New measurement possibilities have emerged
with the availability of portable FTIR spectrometers. Such instruments have made it possible to monitor a variety of substances in situ.
This makes it possible to perform analysis directly at the industrial process [33–35]. Of particular value is the high temporal resolution
of the measurement, which is unattainable with methods that require classical sampling for analysis in the laboratory. As a result, the
device can be used to monitor the effects of accidents and industrial accidents. X-ray fluorescence spectrometry (XRF) is used to
determine the content of elements, especially heavy and trace elements in qualitative and quantitative analyses of solids, liquids, and
powders [36]. Because it is non-destructive, relatively simple and fast, and can be performed directly at the sample site thanks to the
portable XRF spectrometers, the method has found wide application in many fields. The origins of the commercial application of this
technique date back to the 1950s, when XRF spectrometers were mainly used in the metallurgical industry, in work that required fast
and reliable detection of metal alloys. However, the equipment used in the past was very expensive and large, and required highly
specialized operators. Nowadays, thanks to portable spectroscopes, the XRF technique is used for the analysis of soils [37], minerals
and other geological samples [38,39], in archaeology for the chemical characterization of excavations [40,41], and for the analysis of
food: fruits, vegetables, grains or dairy products [42,43]. The method is also used for the rapid determination of heavy metal con­
centrations in contaminated water, which may in the future significantly support wastewater neutralization processes in industry [32].
As with XRF, for many decades Raman spectroscopy was not considered a useful analytical method due to the need to use con­
centrations greater than 0.01 M when recording conventional Raman spectra. Moreover, the Raman spectrometers used in the past
were expensive and large, and therefore not suitable for onsite analysis. Recent advances in Raman spectroscopy have made the
technique one of the most sensitive analytical tools, and the instruments themselves are inexpensive, can be battery-powered and thus
portable. A portable Raman camera connected to a small probe head via optical fiber is used for Raman signal collection, so analysis
can be conveniently carried out anywhere even with very large objects. The application potential of various Raman techniques with the
technical development of spectroscopes is constantly improving, and the technique is eagerly used for the analysis of various types of
samples. Raman spectroscopy finds application in the in-real-time study of industrial wastewater, biological materials, archaeological
discoveries or environmental samples [44–49]. Raman spectroscopy often goes through comparisons with other spectroscopic tech­
niques like FTIR, however, these techniques are better treated as complementing each other rather than as alternatives. In general, the
FTIR technique is based on changes in dipole moment, while Raman is based on changes in molecular polarizability. As a result, the
spectral profile of a given sample measured by the two techniques will be different. In the spectra obtained by these techniques,
characteristic spectral features will be present at specific wavenumber in the Raman spectrum, while not in the FTIR spectrum. From
the point of view of practical applications, these techniques have several differences. Raman spectroscopy is more sensitive technique
while FTIR is more robust. For liquid samples, Raman spectroscopy provides better results due to the fact that the presence of water in
the sample has a very strong influence and causes interference in the FTIR spectra. On the other hand, in the case of Raman spec­
troscopy, interference can be caused by cosmic rays and fluorescence, which can be a complication especially when analysing coloured
substances. Raman spectroscopy allows the measurement of both crystalline and amorphous substances, allows the analysis of even
single grains or particles. Raman spectroscopy can be performed under simple conditions that do not require vacuum production, or
control of relative humidity, heating, or cooling [50–52].
In this study, we dealt with the issue of industrial wastewater monitoring in a plant engaged in the chemical and electrochemical
processing of stainless steels. There are two wastewater streams, the first coming from pickling and the second from electropolishing of
chromium-nickel steels. Identifying the level of contaminants in the wastewater is crucial for deciding on a properly conducted
treatment and neutralization process. It is important to note that managing wastewater streams in a production company is chal­
lenging. In some cases, there is a need to make quick decisions due to the variability of pollutant concentrations in incoming
wastewater streams.
The purpose of this paper is to present the use of portable Raman and XRF spectrometers for preliminary identification of the type of
industrial wastewater. Measurement results of industrial wastewater samples of varying composition and dilution served as input data
for further analysis and the creation of a decision-making scheme. The development of a novel research and decision-making pro­
cedure is expected to be the first step in the management of wastewater stream in a stainless steel processing company, and in a further
stage to enable a more efficient neutralization of the resulting wastewater.

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2. Materials and methods

The materials used in the study were industrial wastewater from the pickling of stainless steels, further described as PWw (picking
wastewater), and electropolishing, further described as EPWw (electropolishing wastewater). PWw contains concentrated nitric acid
(V), hydrofluoric acid, and metal ions including iron, chromium, nickel, copper, among others. The other main stream is EPWw
wastewater containing phosphoric acid (V), sulfuric acid (VI) and metal ions of iron, chromium, nickel, and copper.
Samples of two types of wastewater (100%EPWw, 100%PWw) and mixtures of these wastewaters characterized by different
proportions (75%PWw+25%EPWw, 50%PWw+50%EPWw, 25%PWw+75%EPWw) with varying dilution factor (1–100) were tested.
In addition, acids were also examined. In order to best reflect the nature of industrial wastewater, the technical acids included in the
wastewater were examined: H3PO4, H2SO4 and HNO3. All samples with a dilution factor above 1 were diluted with tap water due to its
use in industrial conditions. The samples were subjected to the Raman spectrometry, XRF, and ICP-OES studies.
XRF measurements of liquid samples were carried out using a portable XRF Vanta C spectrometer from Olympus in the laboratory of
the Fire and Rescue Unit No. 3 in Wroclaw. Elements for analysis: iron, chromium, nickel, copper, phosphorus, sulfur, and calcium. The
results obtained showed the quantitative composition of elements included in the sample expressed in ppm and %. The contents of
other elements were also obtained. Each industrial wastewater sample was tested five times.
Raman spectroscopy measurements were conducted using the FirstDefender RM Chemical Identification System by Thermo
Scientific.
ICP-OES (inductively coupled plasma–optical emission spectroscopy) tests were conducted using the Thermo Scientific iCAP 7000
Series ICP-OES apparatus with an automated sample feeder and software manufactured by Qtegra Intelligent Scientific Data Solution.

3. Results

The first stage of the research conducted was Raman spectroscopy measurements of wastewater solutions from various techno­
logical processes: electropolishing and pickling, as well as solutions of pure technical acids that are contained in these wastewaters.
Analysis of the spectra obtained for the individual solutions has made it possible to identify the locations of characteristic peaks. A
comparison with the pure acid solutions has also made it possible to identify these peaks and determine which bonds they might
correspond to.
The interpretation of Raman spectroscopy spectra of all industrial wastewaters containing acids in their composition, with different
levels of dilution, is very complicated. The spectra of the studied wastewater (Figs. 1–5) show peaks within a range of 300–1900 cm− 1.
A broad peak D with a double maximum at about 1380 cm− 1 and 1630 cm− 1 is attributed to vibrations of hydroxyl groups originating
in water. This confirms the information that there is a lot of water in the initial wastewater. Observation of the spectrum for different
dilution levels of nitric acid (V) solution and PWw wastewater with nitric acid (V) in their composition indicates the presence of a
characteristic sharp peak C at 1050 cm− 1, which unambiguously corresponds to nitrate (V) ions (Figs. 1 and 2).
In the EPWw spectra (Fig. 3), three peaks A, B, C at respective wavenumbers of about 900 cm− 1, 990 cm− 1, and 1050 cm− 1 are
particularly noteworthy. For all EPWw dilutions studied, the magnitude of these three characteristic peaks maintains this order. The
highest intensity has a peak A at a wavenumbers of about 900 cm− 1, followed by a peak B at 990 cm− 1, and the lowest intensity is
characterized by a third peak C at about 1050 cm− 1. A closer analysis of the EPWw spectrum indicates the presence of three more
specific peaks with higher intensities. The first one at a wavenumbers of about 430 cm− 1, the second at about 600 cm− 1, and the third
spot worth mentioning is at a wavenumbers of about 500 cm− 1. In the case of the results obtained for wastewater samples from the
electropolishing process, overlapping peaks resulting from the presence of both sulfuric and phosphoric acid in this type of wastewater
simultaneously can be observed. In this case, the partial overlap of the peaks actually makes it impossible to determine the

Fig. 1. Raman spectroscopy spectra of pickling wastewater (PWw) at different levels of dilution.

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Fig. 2. Raman spectroscopy spectra of nitric acid (V) at different levels of dilution.

Fig. 3. Raman spectroscopy spectra of electropolishing wastewater (EPWw) at different levels of dilution.

concentrations, but it makes it possible to determine whether this acids are present in the sample. Such information in the first stage of
identification is sufficient to determine type of wastewater (pickling or electropolishing). In the case of wastewater from the pickling
process, there is a clearly different characteristic which makes it possible to distinguish between the two types of wastewater.
Given that the composition of EPWw stainless steel electropolishing process wastewater includes sulfuric acid (VI) and ortho­
phosphoric acid, it was decided to compare the spectra of EPWw with the spectra of solutions of these acids (Figs. 4 and 5). Both
concentrated and diluted solutions with corresponding dilutions (diluted 2, 10, 25 and 100 times) were used for the analysis. The
convergence of the spectra for wastewater solutions and solutions of acids alone was observed. Peaks A, B, C at 990 cm− 1, 1050 cm− 1,

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Fig. 4. Raman spectroscopy spectra of sulfuric acid (VI) at different levels of dilution.

Fig. 5. Raman spectroscopy spectra of orthophosphoric acid at different levels of dilution.

and 900 cm− 1 in EPWw solutions (Fig. 3) are also present at the same wavenumbers in sulfuric acid solutions (Fig. 4). Sulfuric acid (VI)
also generates two smaller peaks at wavenumbers of 430 cm− 1 and 600 cm− 1. Analysis of peaks characteristic of phosphoric acid
(Fig. 5) indicates the presence of phosphate ions (V) in EPWw solution at wavenumbers of about 900 cm− 1 and 500 cm− 1 (Fig. 3). The
high intensity at a wavenumbers of about 900 cm− 1 in the EPWw solution is due to the co-occurrence in the wastewater of sulfuric (VI)
and orthophosphoric acid, for which a peak A at 900 cm− 1 is also observed. In the concentrated wastewater, sulfuric and ortho­
phosphoric acids are present at a volume ratio of 6:4. In the case of the spectra obtained for sulfuric acid (Fig. 4), differences in
characteristic points can be seen depending on the concentration of the acid. It should be mentioned at this point that wastewater in

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such a concentrated form never goes directly to the neutralization process, and the spectrum obtained is shown only for comparison.
The results obtained for the concentrated sample, due to the very high concentrations, should be treated only as indicative. It can be
noted that two characteristic peaks (A, C) are present for the concentrated sample, while three (A, B, C) are present for the diluted
samples. Very similar results were obtained by Myhre et al. in their publication, in which they presented spectra for different con­
centrations of sulfuric acid [53].
In a further stage of the study, mixtures of EPWw and PWw wastewater were used, due to the fact that in real conditions the
wastewater generated at the industrial site is also a mixture of wastewater from two technological processes. Raman spectroscopy
measurements were performed for mixtures of 75% PWw and 25% EPWw, 50% PWw and 50% EPWw, 25%PWw and 75% EPWw with

Fig. 6. Raman spectroscopy spectra of electropolishing and pickling wastewater mixed in proportions: (a) PWw 75% + EPWw 25%, (b) PWw 50%
+ EPWw 50%, (c) PWw 25% + EPWw 75%, at different levels of dilution.

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different concentrations (Fig. 6 (a), (b), (c)). It is noted that each mixture is characterized by slightly different spectral lines. In all the
graphs, a water characteristic peak is clearly visible, which provides information about the degree of dilution of the wastewater. On the
basis of the height of the peaks characteristic of the various acids examined earlier, and with a high degree of certainty, it is possible to
determine their presence in the sample under study, and thus tentatively identify the type of wastewater. In the first solution of 75%
PWw and 25% EPWw, the peak C at a wavenumbers of 1050 cm− 1 indicating the presence of nitric acid stands out (Fig. 6A). The peaks
A and B at about 900 cm− 1 and 990 cm− 1 indicating the presence of sulfuric acid and phosphoric acid are much less visible in this case.
This is related to the large amount of PWw which contains nitric acid, and the smaller amount of EPWw containing sulfuric and
phosphoric acid. In the second mixture of 50% PWw and 50% EPWw, the same peaks are observed, but the value of their intensity for
characteristic wavenumbers (900 cm− 1, 990 cm− 1, 1050 cm− 1) changes. The spectrum of the third solution consisting of 25% PWw
and 75% EPWw differs from the previous ones. The most prominent peak A is the one present at about 900 cm− 1, indicating a high
content of phosphoric acid. The other two peaks B and C associated with the presence of sulfuric acid (λ = 990 cm− 1 and 1050 cm− 1)
tend to equalize their heights.
The results of measuring the concentrations of elements found in the studied wastewater (phosphorus, sulfur, iron, chromium,
nickel, copper) shown in Table 1 indicate that XRF spectrometry methods are not as accurate as the results of measurements using ICP-
OES emission spectrometry. However, due to the ease and speed of the analysis and the possibility of applying it on site, it can still find
application in situations where it is not necessary to know the concentrations with high accuracy but only an estimate. The values
closest to the correct one (the result of the ICP spectrometer measurement was considered as such) relate to sulfur, phosphorus, and
copper content. In the case of iron, nickel, and chromium, the values of XRF measurements show a low level of correlation, which
means a low level of accuracy in the analysis. In the case of the examination of samples of wastewater from EPWw electropolishing
processes, high concentrations of sulfur and phosphorus were correctly shown in XRF studies compared to samples in which EWw
stainless steel pickling wastewater was by far the predominant one. This analysis confirms that the XRF spectrometer measurement
allows for the possibility to determine the origin and differentiate the galvanic wastewater.
After analyzing the results of the XRF measurements for the previously mentioned elements, one notices a generalized relationship
in which a decrease in the concentration of a contamination causes an increase in the relative error between XRF and ICP measure­
ments. The initial concentration largely influences the accuracy of the XRF spectrometer measurement results obtained. For low
concentrations of contaminants, it is very common to assume that the result of an XRF measurement should be taken as the highest
possible concentration of a given element. In reality, this concentration is much lower. Overestimation of the results may affect the
evaluation of the concentration, which is an imperfection of this method for this type of sample. Studies indicate that at high dilutions
of wastewater, the results of XRF measurements are not accurate; however, they allow for an approximate order of magnitude
determination of the concentration value of the element under study. Such information is very helpful in quickly estimating the level of
pollution generated by a production company where the composition of wastewater is variable. Under conditions of quick sample
analysis prior to the neutralization process, the information itself on the concentration of metal ions presented not as an exact con­
centration but as a value of the estimated range is also important. Changes in the composition of wastewater are associated not so much

Table 1
Comparison of XRF and ICP-OES results for wastewater with varying ratios of pickling and electropolishing wastewater, including different dilution
levels.
Wastewater Dilution P [g/L] S [g/L] Fe [g/L] Cr [g/L] Ni [g/L] Cu [g/L]
composition factor
ICP- XRF ICP- XRF ICP- XRF ICP- XRF ICP- XRF ICP- XRF
OES OES OES OES OES OES

100% PWw 1 0.00 1.40 0.17 0.40 16.04 5.60 4.34 2.00 1.84 3.40 0.08 0.10
2 0.00 1.70 0.09 0.30 8.12 18.80 2.19 2.20 0.93 2.60 0.04 0.30
5 0.00 1.70 0.06 0.20 3.40 8.90 0.91 2.20 0.39 1.20 0.02 0.20
10 0.00 1.90 0.05 0.30 1.81 4.80 0.47 2.40 0.20 0.60 0.01 0.20
25 0.00 1.80 0.02 0.20 0.87 2.00 0.22 2.40 0.09 0.30 0.00 0.20
50 0.00 1.90 0.01 0.20 0.50 1.00 0.13 2.50 0.05 0.10 0.00 0.10
100 0.00 2.10 0.00 0.30 0.31 0.60 0.08 2.60 0.03 0.00 0.00 0.20
25% PWw + 75% 2 77.64 71.60 47.71 60.30 23.35 33.00 6.67 2.80 0.77 0.70 0.62 0.90
EPWw 25 8.24 12.20 5.15 9.70 2.51 5.40 0.69 2.20 0.07 0.00 0.15 0.30
100 2.06 25.70 1.28 21.70 0.63 13.40 0.17 2.50 0.02 0.10 0.04 0.50
50% PWw + 50% 2 54.9 66.30 39.78 56.90 20.30 34.80 5.76 3.00 0.58 1.00 0.51 1.00
EPWw 25 5.57 10.90 4.04 8.20 2.11 5.80 0.58 2.40 0.06 0.10 0.05 0.30
100 1.39 16.20 1.01 13.10 0.53 10.00 0.15 2.20 0.02 0.30 0.01 0.30
75% PWw + 25% 2 30.03 35.90 21.66 30.60 13.97 28.20 3.79 3.00 0.49 1.80 0.26 0.70
EPWw 25 2.54 5.30 1.82 3.40 1.12 3.20 0.30 2.20 0.13 0.10 0.02 0.10
100 0.64 9.80 0.45 7.50 0.28 7.30 0.08 2.20 0.03 0.40 0.00 0.30
100% EPWw 1 206.15 144.50 119.88 126.50 54.82 63.50 16.36 4.50 0.72 0.90 1.64 1.90
2 103.05 97.30 59.91 84.00 27.83 47.00 8.26 3.60 0.36 0.70 0.81 1.30
5 48.54 60.30 28.79 53.10 12.80 29.30 3.88 3.10 0.17 0.50 0.39 1.10
10 26.39 36.60 15.99 31.40 7.11 17.90 2.14 2.90 0.09 0.30 0.21 0.70
25 10.56 20.00 6.40 16.10 3.69 10.20 1.09 3.10 0.05 0.00 0.12 0.50
50 5.28 11.30 3.20 8.90 1.48 5.36 0.64 3.00 0.03 0.00 0.07 0.40
100 2.65 6.20 1.60 3.80 0.69 2.40 0.36 2.70 0.01 0.00 0.03 0.25

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with changes in the production technology itself, but with variability in the produced elements. It was observed that as a result of the
pickling and electropolishing processes of products with a higher number of parts, wastewater with an increased concentration of
pollutants flows out through the technological orifices. Proportionally, more iron and chromium than other elements were observed in
the studied wastewater, which is directly related to the composition of chromium-nickel steel [3,54].

4. Industrial wastewater management procedure

With quick initial measurements using portable spectrometers plus knowledge of the wastewater composition, it should be possible
to select a specific path for handling wastewater. This will also help select the most efficient way of neutralizing them and reducing the
decision-making time on how to carry out this process.
On the basis of XRF and Raman spectroscopy studies along with comparison of the results with ICP-OES studies, and after an in-
depth analysis of the spectra for different mixtures of wastewater, a method for identifying the type of wastewater was proposed. It is
based on determining the occurrence and height of characteristic peaks in a wastewater sample when compared to pure acid solutions.
The developed graph (Fig. 7), consisting of 3 main stages, makes it possible to identify and estimate the composition of industrial
wastewater, as well as its dilution level. Proper identification is the first step in wastewater management, as it can facilitate further
planning of the treatment and neutralization process. Results obtained by Raman spectroscopy do not show a positive correlation
between concentration and peak area. The water contained in the samples has a very strong influence on the height of the peaks in the
regions 850 - 1100 cm− 1. The results do not allow to present an unambiguous relationship between concentration and peak area,
nevertheless, on the basis of the information obtained, it is possible to determine the type of wastewater under study according to the
proposed procedure.
With the presented decision-making procedure, we show how it is possible to quickly, with the use of portable measuring devices,
make a preliminary identification of the types of industrial wastewater generated within a single production plant. This is particularly
important in the case of wastewater from processes of pickling and electropolishing of stainless steel, where the precise setting of
parameters for treatment and neutralization processes is closely dependent on the concentrations of contaminants and water content in
the wastewater. A simple "I know what I have, I know what to do with it” assumption can thus be made. The result of the conducted
research amounts to the proposal of a 3-stage wastewater identification scheme (Fig. 7). The first step towards identifying the type of
wastewater is to evaluate the presence of sulfuric, orthophosphoric and nitric acids based on the Raman spectrum plot. If three peaks
are clearly visible on the spectrum plot at wavenumbers A - λ about 900 cm− 1, B - λ about 990 cm− 1, C - λ about 1050 cm− 1
respectively, we may conclude that the wastewater contains these elements. Based on this, we can thus determine whether the
analyzed wastewater sample is PWw or EPWw or a mixture of both. The size of the observed peaks and the ratio of their heights to each
other allow for further and more accurate characterization. When the height of the peaks is arranged according to the relationship A >
B > C, we are dealing with EPWw wastewater; when A ≥ C > B it is a mixture of 75%PWw and 25%EPWw; and when the relationship is
arranged C > A ≥ B it is a mixture of 25%EPWw and 75%EPWw or 50%EPWw and 50%PWw. On the spectra of the wastewater from
the pickling process of stainless steel PWw alone, only the C peak is present at a wavenumbers of about 1050 cm− 1. As mentioned
earlier, this is a peak that indicates the presence of nitric acid.
The second stage of the analysis makes it possible to determine the approximate water content of the wastewater. To do this, the
heights of peak C (at λ of about 1050 cm− 1) and peak D (at λ of about 1380 cm− 1 originating from water) are compared. If on the
spectrum peak D is greater than C, it means that the dilution factor is equal to or greater than 25. When peaks C and D have a similar
intensity or we observe the relationship D ~ 0.5C, we find a 10-fold dilution of the solution. When the D peak does not stand out clearly
on the spectrum graph, it indicates a most concentrated solution with a dilution factor of 2 or less.
The final step in the identification of wastewater is to check the concentration of sulfur, potassium, iron, chromium, nickel and
copper by XRF spectrometry. It should be noted that the methods presented are still being tested. Special attention is being paid to
wastewater with lower concentrations of pollutants, i.e. those with dilutions of more than 25 times. It is very important to develop
further testing techniques for diluted wastewater and mixtures. However, in managing the neutralization process while considering the
environmental aspects, it is concentrated wastewater that poses the greatest challenge.

5. Conclusions

The research conducted allowed the creation of a graph to help identify and estimate the composition of industrial wastewater, as
well as the degree of dilution.

1. The use of portable Raman spectroscopy and XRF spectrometers makes it possible to proffer a preliminary estimate of the
composition of wastewater from the pickling and electropolishing of stainless steels
2. The analysis of Raman spectroscopy spectra and identification of characteristic peaks for sulfuric (VI), nitric (V) and orthophos­
phoric acids present in wastewater forms the basis for the development of a novel procedure for the identification of wastewater
type and what process the wastewater originates from.
3. The developed identification graph comprises 3 stages: identification of the type of wastewater (EPWw, PWw or mix), determi­
nation of the ratio of each type of wastewater, and determination of the dilution factor of wastewater.
4. Rapid identification of pollutants at the site of their formation can contribute to efficient management of the process of neutral­
ization and treatment of industrial wastewater by any production company.

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Fig. 7. Rapid wastewater identification procedure.

5. The authors of this paper see further prospects for research towards enhancing the precision of the proposed solution especially in
the analysis of wastewater characterized by a high dilution. However, it should be borne in mind that when conducting the
neutralization process under industrial conditions, wastewater with high concentrations poses the greatest challenge.

Credit author statement

Paweł Lochyński: Conceptualization, Methodology, Data/Results interpretation, Formal analysis, Writing- Reviewing and Editing;
Magdalena Szymańska: Investigation- Raman spectroscopy, Writing- Reviewing and Editing; Sylwia Charazińska: Investigation- ICP-
OES, Data visualization, Writing- Original draft preparation; Emilia Poznańska: Investigation- XRF; Justyna Kubicz: Data/Results
interpretation, Formal analysis, Writing- Original draft preparation.
All authors read and approved the final version of the manuscript.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Data availability

The authors confirm that the data supporting the findings of this study are available within the article.

Acknowledgments

We would like to thank the staff of the Rescue and Fire Fighting Unit No. 3 in Wrocław, specializing in chemical and environmental
rescue, st. kpt. mgr. inż. poż. Piotr Ciesielski (Senior Captain Master Engineer of firefighting Piotr Ciesielski) and mł. asp Piotr Furman
(Junior Fire Officer Piotr Furman) for providing access to research equipment and assistance in carrying out XRF and Raman spec­
troscopy measurements.
The APC is financed by Wrocław University of Environmental and Life Sciences.
Magdalena Szymańska is PhD student in the 6th edition of the implementation doctorate programme - Ministry of Education and
Science.

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