Editorial Feature

Screening for Painkiller-Related Water Pollutants with Screen Printed Sensors

Increased outflow and presence of pharmaceuticals in wastewater from households and hospitals are associated with increased production and consumption of over-the-counter drugs such as painkillers like diclofenac, naproxen, ibuprofen, ketoprofen, or acetaminophen.

Image Credit: FotoMirta/Shutterstock.com

Certain pharmaceutical residues and sewage end up in wastewater treatment plants (WWTPs), which are ultimately not designed to break down those extremely specialized molecules. However, treated wastewater has been the largest source of pharmaceuticals in the environment. Pharmaceuticals are not removed by conventional WWTPs, hence cleanup rates vary.

Acidic medicines with high water solubility, like acetylsalicylic acid, ibuprofen, ketoprofen, naproxen, and diclofenac (pKa 4.2–4.9), are neither sorbed nor stay in the water. It was discovered that the presence of pharmaceuticals in the water generated severe oxidative stress in Cyprinus Carpio tissues, as well as disturbing microalgal development.

The presence of such compounds in surface waters is harmful to fish and other aquatic species, and it has been linked to an increase in the occurrence of certain diseases, such as cancer (female sex hormones). In research, including 98 pharmaceuticals discovered in various water matrices (treated wastewater, groundwater, and surface water), 11 out of 49 medicines were determined to pose a human health risk when consumed through India’s polluted surface water.

Voltammetric methods are distinguished by their cheap cost, ease of analytic procedure, and ability to collect analytics on the working electrode surface before the suitable electrode process, obviating the need for further concentrating approaches (e.g., the extraction to solid phase).

Screen-printed electrodes (SPEs) were the focus of a slew of studies aiming at determining their practical utility. These electrodes are an appealing analytical instrument because of their inexpensive manufacturing costs, adequate repetition levels, and electrochemical characteristics

Like other electrochemical sensors, the screen-printed electrodes have a small size that allows them to be used in portable/field devices. The use of screen-printed electrodes in in-situ measurements allows for the minimization or even elimination of errors and a reduction in test time and, as a result, expenses associated with the collection, transport, and storage of representative samples.

In recent research published in the MDPI journal sensors, researchers set out to provide a summary of advancements in the area of screen-printed voltammetric sensors used in painkiller environmental water monitoring. 


Although pharmaceutical concentrations in environmental matrices are typically low—less than 1 μg L−1—authorities are concerned about the long-term effect on animals and people because of their widespread use and abundance in the environment (Table 1).

Table 1. The concentrations and removal rates of painkillers in the environmental matrices. Source: Tyszczuk-Rotko, et al., 2022

Drug Excretion and Metabolites WWTP Removal Rate
Surface Water
diclofenac 5–10% unchanged, metabolites: glucuronide, sulfate conjugates [49] 9–60 [50]
57.9 [47]
up to 302 [50]
191,000 [47]
1300–3300 [51]
Up to 5450 [50]
10,000 [52]
80,000 [47]
up to 490 [50]
1200 [48]
1410 [53]
ibuprofen 1% unchanged
Metabolites: (+)-2-40-(2-Hydroxy-2-methylpropyl)-phenylpropionic acid (25%) and (+)-2-40-(2- carboxypropyl)-phenylpropionic acid (37%), conjugated ibuprofen (14%) [49]
78–100 [50]
94.8 [47]
5533 [50]
344,000 [47]
711 [50]
18,000 [47]
400 [50]
126 [53]
naproxen <1 unchanged, metabolites: 6-o-Desmethyl naproxen (o1%), conjugates (66–92%) [49] 50–98 [50] 611,000 [50] 33,900 [50]
10,000 [52]
297 [53]
390 [48]
400 [50]
ketoprofen Metabolites: Glucuronide conjugates [49] 15–100 [50] 5700 [50]
1000–10,000 [54]
1620 [50] 120 [48]
329 [50]
paracetamol 80% as conjugates, metabolites: Sulphate conjugate (30%), paracetamol cysteinate, mercapturate (5%) [49] 91–99 [50] 292,000 [50]
1000–10,000 [54]
1480 [50]
100,000 [52]
10,000 [48]
66 [50]
acetylsalicylic acid Metabolites: Salicylic acid (10%), salicyluric acid (75%), salicylic phenolic (10%) and acyl (5%) glucuronides, gentisic acid (o1%) [49] 0 [50] 1000–10,000 [54] 1510 [50] <50 [50]


On the same substrate surface, the whole electrode system (reference, counter, and working electrodes) is imprinted (Figure 1).

Optical microscopic image of screen-printed carbon electrode (SPCE, Metrohm DropSens, Oviedo, Spain).

Figure 1. Optical microscopic image of screen-printed carbon electrode (SPCE, Metrohm DropSens, Oviedo, Spain). Image Credit: Tyszczuk-Rotko, et al., 2022

Non-steroidal anti-inflammatory medicines (NSAIDs) are a large pharmacological class since they are commonly used to treat muscular pain and inflammatory rheumatic disorders. Due to increased consumption along with inappropriate disposal and inefficient wastewater treatment, these drugs are commonly found. NSAIDs (Figure 2A–E) include diclofenac (DF), acetylsalicylic acid (AS), ibuprofen (IB), naproxen (NP), and ketoprofen (KP).

Paracetamol (N-acetyl-p-aminophenol, Figure 2F), often known as acetaminophen or Tylenol, is a pain reliever and fever reducer that is widely used across the world. Tramadol is a drug that is used to treat pain (1R, 2R) -2-[(dimethylamino)methyl] -1-(3-methoxyphenyl)cyclohexanol TR, (Figure 2G) is a l-opioid recipient agonist that works centrally on analgesics and is used to treat mild to moderate pain.

The structural formulas of diclofenac (A), ibuprofen (B), acetylsalicylic acid (C), naproxen (D), ketoprofen (E), paracetamol (F) and tramadol (G).

Figure 2. The structural formulas of diclofenac (A), ibuprofen (B), acetylsalicylic acid (C), naproxen (D), ketoprofen (E), paracetamol (F) and tramadol (G). Image Credit: Tyszczuk-Rotko, et al., 2022

Carbon black (CB), carbon nanofibres (CNDs), graphene-related materials, single-, double-, and multiwalled carbon nanotubes (SWCNTs, DWCNTs, and MWCNTs), carbon nanohorns (CNHs), and carbon nano-onions are among the carbon nanomaterials utilized as SPEs modifiers (CNOs).

Few studies in the literature mention the use of screen-printed sensors customized with carbon materials to monitor painkiller residues in water samples. Table 2 presents a comparison of different test techniques.

Table 2. Summary of voltammetric procedures to determine painkillers residues at the screen-printed electrodes modified with carbon materials in environmental water samples. Source: Tyszczuk-Rotko, et al., 2022

Electrode Analyte Method Linear Range
Application Ref.
SPCE/CNFs PA DPAdSV 0.002–0.05
0.00054 river water,
sea water
SPCE/MWCNTs-COOH DF DPAdSV 0.0001–0.01 0.000028 river water [102]
river water
SPCE PA DPV 13.20–377.0 7.17 tap water,
hospital wastewater
SPCNTE 2.64–33.70 0.66
SPCNFE 1.98–33.70 0.66
SPGPHE 3.31–23.20 0.66
SPCE IB 18.40–489.60 5.33
SPCNTE 9.21–155.10 2.91
SPCNFE 19.40–114.40 5.82
SPGPHE 30.50–86.30 9.21
SPCE CF 24.70–480.0 7.21
SPCNTE 20.60–480.0 6.18
SPCNFE 61.80–330.0 2.06
SPGPHE 15.50–44.80 4.63
SWV 0.80–30.0
river water [101]

PA–paracetamol; DF–diclofenac; IB–ibuprofen; CF–caffeine; LVF–levofloxacin; DPAdSV–differential-pulse adsorptive stripping voltammetry; PPA–pulsed potential accumulation; DPV–differential-pulse voltammetry; SWV–square-wave voltammetry; SPCE–screen-printed carbon electrode; SPCE/MWCNTs-COOH–carboxyl functionalized multiwalled carbon nanotubes modified screen-printed carbon electrode; SPCNTE–screen-printed carbon electrode modified with carbon nanotubes; SPCE/CNFs (SPCNFE)–screen-printed carbon electrode modified with carbon nanofibers; SPGPHE–screen-printed graphene electrode; CB/SPCE–screen-printed carbon electrode modified with carbon black.

Researchers identified a DPAdSV voltammetric technique for the trace measurement of diclofenac (DF) using an available commercially screen-printed carbon sensor altered with carboxyl functionalized multiwalled carbon nanotubes (SPCE/MWCNTs-COOH) (Figure 3).

SEM images and DPAdSV curves recorded at the SPCE and SPCE/MWCNTs-COOH. DPAdSV curves recorded at the surface of the SPCE/MWCNTs-COOH in solution containing increasing concentrations of DF: 0.1, 0.2, 0.5, 1.0, 2.0, 5.0 and 10.0 nmol L-1, and calibration graph of DF.

Figure 3. SEM images and DPAdSV curves recorded at the SPCE and SPCE/MWCNTs-COOH. DPAdSV curves recorded at the surface of the SPCE/MWCNTs-COOH in solution containing increasing concentrations of DF: 0.1, 0.2, 0.5, 1.0, 2.0, 5.0 and 10.0 nmol L−1, and calibration graph of DF. Image Credit: Tyszczuk-Rotko, et al., 2022

Figure 4 shows the flowchart of the individual steps of the improved voltammetric technique.

Scheme of voltammetric measurements of PA and DF at the SPCE/MWCNTs-COOH

Figure 4. Scheme of voltammetric measurements of PA and DF at the SPCE/MWCNTs-COOH. Image Credit: Tyszczuk-Rotko, et al., 2022

Table 3 lists the voltammetric techniques used to determine painkiller residues on electrochemically prepared screen-printed electrodes.

Table 3. Summary of voltammetric procedures for painkillers residues determination at the electrochemically pretreated screen-printed electrodes or modified with polymer film in environmental water samples. Source: Tyszczuk-Rotko, et al., 2022

Electrode Analyte Method Linear Range
Application Ref.
DPAdSV 0.001–0.2
river water [82]
electrochemically pretreated SPCE PA
DPV 0.5–10.0
tap water [100]
electrochemically pretreated SPGE IB SWV 0.80–30.0 6.30 river water,
MIP/SPCE DF DPV 0.1–10 0.07 river water,
tap water

PA–paracetamol; DF–diclofenac; HQ–hydroquinone; E2–estradiol; IB–ibuprofen; DPAdSV–differential-pulse adsorptive stripping voltammetry; DPV–differential-pulse voltammetry; SWV–square-wave voltammetry; aSPCE/SDS–activated screen-printed carbon electrode modified with sodium dodecyl sulfate; electrochemically pretreated SPCE–electrochemically pretreated screen-printed carbon electrode; electrochemically pretreated SPGE–electrochemically pretreated screen-printed graphite electrode; MIP/SPCE–screen-printed carbon electrode modified with molecularly imprinted polymer.

Polymers are commonly utilized as electrode and SPE modifiers. Conductive polymers, which combine traditional polymer characteristics with the electrical properties of metals and/or semiconductors, are the most often utilized polymers for this purpose. Polyacetylene, polyaniline, polypyrrole, and polythiophene are the most common materials employed.


Monitoring the water environment for pharmaceutical residues, especially painkiller residues, is a key challenge for modern analytical chemistry. This article shows how screen-printed sensors may be used to detect drug-related environmental water contaminants in a sensitive manner. The devised simple, sensitive, and selective voltammetric processes using screen-printed sensors might be useful instruments for this aim, as shown in several cases in this review paper.

Electroconductivity, catalytic activity, and surface area were all improved when screen-printed electrodes were treated with carbon nanomaterials, polymer film, or electrochemically activated. Furthermore, the screen-printed sensors might be used for in-field analysis as well as laboratory tests.

Screen-printed sensors can be used in environmental water monitoring because of their electrochemical characteristics, simplicity, disposability, rapid reaction time, and compactness.

With new application areas, the screen-printed sensor industry is likely to expand. Future research will concentrate on increasing the analytical characteristics of screen-printed sensors so that they may be adjusted to the relative quantities of analyses in ambient water samples, as well as creating processes and sensors for new analgesic compounds (AS, NP, KP).

Expected interfering species should be given more consideration, as well as known or potential ways for minimizing their impacts and enhancing selectivity. In addition, future research should focus on sensor miniaturization, lowering analysis time, reducing the number of examined samples, and using reagents.

Continue reading: The Applications of Nanoparticles as Synthetic Catalysts.

Journal Reference

Tyszczuk-Rotko, K., Kozak, J. and Czech, B. (2022) Screen-Printed Voltammetric Sensors—Tools for Environmental Water Monitoring of Painkillers. Sensors, 22(7), p.2437. Available Online: https://www.mdpi.com/1424-8220/22/7/2437/htm.

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Megan Craig

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Megan graduated from The University of Manchester with a B.Sc. in Genetics, and decided to pursue an M.Sc. in Science and Health Communication due to her passion for learning about and sharing scientific innovations. During her time at AZoNetwork, Megan has interviewed key Thought Leaders across several scientific, medical and engineering sectors and attended prominent exhibitions worldwide.


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