Biosensors and Nanotheranostics

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Bismuth-Based Electrodes in Electroanalysis: A Systematic Review and Meta-Analysis of Performance, Sensitivity, and Applications

Lamiah Hossain 1*, Sarenur Turan 2

+ Author Affiliations

Biosensors and Nanotheranostics 4 (1) 1-8 https://doi.org/10.25163/biosciences.4110521

Submitted: 16 May 2025 Revised: 10 July 2025  Published: 19 July 2025 


Abstract

Bismuth-based electrodes have emerged as important alternatives to traditional mercury electrodes, offering a safer, environmentally friendly platform for electrochemical detection across environmental, biological, and industrial samples. This systematic review and meta-analysis evaluated evidence from published studies investigating the analytical performance, sensitivity, and application range of bismuth-based electrodes, including bismuth film electrodes, bismuth-modified carbon electrodes, and bismuth-embedded screen-printed systems. Searches were performed across Google Scholar, PubMed, and Scopus, and studies reporting analytical limits, calibration performance, and application outcomes were included. Data were extracted using a standardized template, and meta-analytic comparisons were conducted on limit-of-detection (LOD) values and sensitivity across electrode types. Across the included studies, bismuth-based electrodes consistently demonstrated high sensitivity, simple fabrication, and strong compatibility with stripping voltammetric techniques. Meta-analysis showed that bismuth film electrodes provided significantly improved LODs compared to carbon-only electrodes, supporting their role as highly effective platforms for trace metal detection. Evidence also highlighted their broad applicability—from detecting heavy metals and pesticides to monitoring pharmaceutical compounds and hormones in environmental matrices. Overall, results confirm that bismuth-based electrodes represent a robust, versatile, and green analytical tool. Their performance characteristics make them promising candidates for future analytical development, particularly in portable sensors and low-resource environmental monitoring settings.

Keywords: Bismuth electrodes; electroanalysis; bismuth film electrode; stripping voltammetry; screen-printed electrodes; sensitivity; analytical performance.

1. Introduction

Electroanalysis has long played a central role in environmental monitoring, pharmaceutical control, food safety, and clinical diagnostics. For decades, mercury-based electrodes dominated stripping voltammetry due to their wide cathodic potential window, high hydrogen overpotential, and reproducible metal-film formation. However, environmental and health concerns associated with mercury toxicity accelerated the search for safer alternatives. A pivotal breakthrough occurred with the introduction of bismuth-coated carbon electrodes for anodic stripping voltammetry, which demonstrated analytical performance comparable to mercury while significantly reducing toxicological risk (Wang et al., 2000). This development initiated a transformative period in electroanalysis, establishing bismuth as a “green” metal with remarkable electrochemical compatibility.

The early mechanistic understanding of bismuth film formation and its electroanalytical advantages was further consolidated in comprehensive reviews documenting a decade of progress in the field (Švancara et al., 2010). These works highlighted how bismuth forms intermetallic alloys with target metal ions during the preconcentration step, thereby enhancing stripping signals while maintaining operational stability. Compared with mercury, bismuth films provide similar sensitivity for cadmium, lead, zinc, and thallium detection but without the associated environmental hazards. This combination of performance and safety positioned bismuth-based electrodes as a major advancement in sustainable electrochemical sensing.

A key factor influencing analytical response in bismuth systems is the plating regime and deposition conditions used to form the bismuth layer. Microscopic investigations demonstrated that film morphology, thickness, and uniformity depend strongly on deposition potential and time (Švancara et al., 2005). Subsequent studies systematically evaluated how Bi(III) concentration affects stripping voltammetric performance, confirming that optimized precursor concentrations yield improved peak definition and sensitivity (Baldrianová et al., 2006). More recently, refined control over the Bi(III)-to-metal ion concentration ratio has been shown to further enhance analytical response, particularly for trace-level metal detection using glassy carbon substrates (Guo et al., 2024). Collectively, these findings emphasize that analytical optimization of bismuth electrodes requires careful control of electrochemical deposition parameters.

Beyond in situ film formation, alternative fabrication strategies have broadened electrode design. Carbon paste electrodes modified with bismuth powder represent an early innovation that eliminated the need for continuous in situ plating, offering a simplified yet highly sensitive platform for stripping analysis (Hocevar et al., 2005). Such powder-modified systems demonstrated robust performance and improved operational convenience. Similarly, modified electrode architectures have been extensively reviewed in the context of environmental metal monitoring, highlighting the versatility of bismuth-coated and bismuth-modified substrates for field analysis (March et al., 2015).

The integration of bismuth with screen-printed electrodes (SPEs) marked another milestone in electroanalysis. Screen-printed platforms enable mass production, portability, and disposability, making them highly suitable for on-site applications. Studies optimizing screen-printed bismuth film electrodes (SP-BiFEs) demonstrated that chemical surface treatments and deposition strategies significantly improve reproducibility and signal intensity (Dossi et al., 2016). Advanced characterization techniques, such as laser-ablation ICP-MS, have provided deeper insight into the composition and distribution of salt-derived bismuth films on printed substrates (Dossi et al., 2020). These investigations confirm that structural uniformity and elemental distribution are critical determinants of analytical efficiency.

The environmental relevance of bismuth-modified SPEs has been underscored in comparative analyses of “green” metal films for stripping voltammetry (Economou, 2018). Bismuth films have consistently demonstrated competitive detection limits for toxic elements in water samples, often outperforming alternative non-toxic metals. Paper-based working electrodes coated with bismuth films further extend this portability, offering low-cost analytical tools suitable for decentralized testing (Sánchez-Calvo et al., 2020). These developments reflect a broader shift toward sustainable and accessible electroanalytical platforms.

While heavy metal determination remains the primary application area, bismuth electrodes have proven versatile for organic analytes as well. Modified carbon-based electrodes incorporating bismuth have been successfully applied to the voltammetric detection of neonicotinoid insecticides, compounds of significant agricultural and environmental concern (Guzsvány et al., 2011). Given the global regulatory attention surrounding neonicotinoids (Jeschke et al., 2011), the ability of bismuth electrodes to detect these substances with sensitivity highlights their relevance beyond inorganic analysis. Additional applications include pharmaceutical detection, such as sulfadiazine determination using cathodic stripping voltammetry at bismuth film electrodes (Campestrini et al., 2010).

Pharmaceutical and biologically relevant molecules have also been explored using bismuth-based systems. For example, the voltammetric behavior of dantrolene sodium has been compared across silver amalgam and bismuth film electrodes, demonstrating competitive analytical performance for bismuth substrates (Šelešovská et al., 2017). Nanostructured bismuth films have further enhanced adsorptive cathodic stripping voltammetry for hormone detection, including progesterone, by increasing active surface area and adsorption efficiency (Zidaric et al., 2018). These findings underscore the adaptability of bismuth films to structurally diverse organic compounds.

Microelectrode arrays and advanced gold-based substrates plated with bismuth films have recently pushed detection limits even lower, particularly for thallium(I) analysis (Królicka & Korolczuk, 2024). Such innovations combine microfabrication techniques with bismuth’s favorable alloying behavior, illustrating how electrode miniaturization and material engineering synergistically enhance analytical sensitivity. Similarly, quantum dot-based DNA biosensors incorporating screen-printed graphite surfaces with embedded bismuth precursors demonstrate the compatibility of bismuth platforms with bioelectrochemical sensing architectures (Kokkinos et al., 2015). These hybrid systems bridge the gap between classical stripping voltammetry and biosensor development.

The electrochemical determination of small biomolecules further illustrates the breadth of bismuth applications. Cathodic stripping voltammetric detection of cysteine at bismuth powder-modified carbon paste electrodes revealed stable and reproducible analytical signals (Baldrianová et al., 2008). Such work expands the analytical horizon of bismuth beyond environmental monitoring into biochemical and clinical contexts.

Taken together, the literature reveals several unifying themes. First, bismuth-based electrodes combine environmental safety with electrochemical performance comparable to mercury. Second, analytical sensitivity is strongly influenced by deposition conditions, precursor concentration, and film morphology. Third, innovations in substrate integration—including carbon paste, glassy carbon, screen-printed, paper-based, and microelectrode arrays—have broadened application contexts from centralized laboratories to portable and field-ready systems. Finally, the scope of detectable analytes now extends from trace metals to pesticides, pharmaceuticals, hormones, and biomolecules.

Despite substantial progress, critical questions remain regarding long-term stability, matrix tolerance in complex samples, and standardization of fabrication protocols. Variability in film thickness and morphology across studies complicates cross-comparison of detection limits. Moreover, while numerous experimental investigations report excellent sensitivity under optimized laboratory conditions, systematic meta-analytic evaluation is needed to quantify reproducibility and identify performance determinants across electrode architectures.

This systematic review and meta-analysis therefore aims to synthesize existing evidence on bismuth-based electrodes, focusing on performance metrics such as detection limit, sensitivity, linear range, and stability. By integrating findings across fabrication strategies and application domains, the present work seeks to clarify design–performance relationships and identify emerging research directions. As electroanalysis continues to prioritize sustainability, portability, and high sensitivity, bismuth-based electrodes stand at the forefront of next-generation green electrochemical sensing technologies.

2. Materials and Methods

2.1 Search Strategy

A systematic literature search was conducted to identify peer-reviewed studies evaluating the performance, analytical behavior, and applications of bismuth-based electrodes in electroanalysis. Searches were carried out between January and March 2025 in PubMed, Google Scholar, Scopus, and Web of Science. No publication year limits were applied to ensure complete coverage of developments from the early introduction of bismuth electrodes to recent advancements. Search terms included: “bismuth film electrode,” “bismuth-based electrode,” “bismuth-modified carbon,” “screen-printed bismuth electrode,” “stripping voltammetry,” “bismuth electroanalysis,” “heavy metal detection bismuth,” and “bismuth sensor performance.” Additional studies were identified by screening the reference lists of relevant articles. The review protocol and reporting structure were aligned with established systematic review guidelines to ensure transparency and reproducibility (Page et al., 2021; Higgins et al., 2022). The study selection process followed PRISMA 2020 guidelines and is presented in Figure 1

Figure 1. PRISMA 2020 Flow Diagram of Study Selection Process. This PRISMA 2020 flow diagram illustrates the systematic identification, screening, eligibility assessment, and final inclusion of studies evaluating bismuth-based electrodes in electroanalysis. From database searching to full-text review, nine studies met the predefined criteria and were included in the quantitative meta-analysis.

2.2 Eligibility Criteria

Studies were included if they met the following criteria:
• Investigated bismuth-based electrodes, including bismuth films, bismuth-modified carbon electrodes, embedded bismuth precursors, nanostructured bismuth systems, or screen-printed bismuth electrodes.
• Reported quantitative electroanalytical outcomes such as limit of detection (LOD), sensitivity, linear range, repeatability, or recovery.
• Employed voltammetric electrochemical techniques, including ASV, DPASV, or SWASV.
• Were original experimental research studies.

Exclusion criteria were review papers, conference abstracts, commentary articles, studies without extractable numerical data, and studies where bismuth was used as a catalyst or additive without electroanalytical measurement. All retrieved records were imported into a reference manager and screened for duplicates. Two reviewers independently screened titles and abstracts to assess relevance. Full texts were then evaluated against the eligibility criteria. Any disagreements were settled through discussion or by involving a third reviewer. The overall screening process followed PRISMA principles, including identification, screening, eligibility assessment, and final inclusion (Page et al., 2021).

2.3 Data Extraction

A structured extraction form was developed to ensure uniform data collection. Extracted information included electrode type, substrate material, deposition method, Bi(III) concentration, target analyte, electrochemical technique, LOD, sensitivity, linear range, repeatability, sample matrix, and key experimental conditions such as pH, electrolyte composition, deposition potential, and deposition time. Data extraction was performed independently by two reviewers, and discrepancies were resolved by checking original articles. The extraction framework was informed by methodological standards outlined in meta-analytic literature to ensure consistency and comparability across studies (Borenstein et al., 2009).

2.4 Quality Assessment

Methodological quality of the included studies was evaluated using a modified analytical method validation checklist. Quality criteria included clarity of electrode fabrication procedures, reproducibility of measurements, validation using real samples, completeness of calibration data, and statistical rigor. Studies that failed to meet minimum quality thresholds were excluded from the meta-analysis but included in the qualitative narrative if relevant. The assessment process followed recommendations for systematic review methodology and risk-of-bias evaluation (Higgins et al., 2022).

2.5 Meta-Analysis Procedures

Quantitative synthesis focused primarily on comparing LOD and sensitivity across various categories of bismuth-based electrodes. To standardize the data, LOD values were converted to consistent units (micrograms per liter or nanomolar) depending on reported measurements. A random-effects model was applied to account for methodological and experimental heterogeneity across studies, consistent with the DerSimonian and Laird approach (DerSimonian & Laird, 1986). Effect sizes were calculated as mean differences with 95 percent confidence intervals, following established statistical guidance for meta-analysis (Borenstein et al., 2009).

Heterogeneity was assessed using the I² statistic to quantify inconsistency among studies (Higgins et al., 2003). Potential sources of variability were explored through subgroup analyses based on electrode type, target analyte, deposition strategy (in situ, ex situ, or embedded precursor), and voltammetric method. Funnel plots and Egger’s regression test were used to evaluate publication bias and small-study effects (Egger et al., 1997). Statistical analyses were performed using RevMan and R (metafor package), in accordance with widely accepted meta-analytic best practices (Higgins et al., 2022).

3. Results

 3.1 Interpretation and Discussion of Forest Plot

The forest plot (Figure 2) summarizes the pooled effect sizes from the included studies evaluating the analytical performance of bismuth-based electrodes. Most individual studies show effect estimates that fall consistently on the positive side of the reference line, indicating that bismuth-based electrodes generally improve sensitivity, reduce detection limits, and enhance analytical reliability compared with conventional electrodes such as mercury, carbon paste, or glassy carbon. For example, bismuth-modified carbon electrodes have demonstrated enhanced voltammetric responses for neonicotinoid insecticides and related organic analytes (Guzsvány et al., 2011), while optimized screen-printed bismuth film electrodes (SP-BiFEs) have shown improved reproducibility and signal intensity due to controlled chemical surface treatment (Dossi et al., 2016). Although the magnitude of effect varies slightly across studies, the direction remains stable, demonstrating a consistent analytical advantage of bismuth-based platforms.

Figure 2: Forest Plot of Pooled Analytical Performance of Bismuth-Based Electrodes. This plot presents the individual and pooled effect sizes for detection performance across included studies. It visualizes confidence intervals, study weights, and overall summary effect, demonstrating consistency and robustness of analytical enhancement.

The confidence intervals of several studies are narrow, reflecting good internal precision and low measurement variability. Applications involving disposable nanostructured conductive carbon tape modified with bismuth in paper-based analytical devices have reported consistent stripping signals with acceptable repeatability (Feng et al., 2013). Similarly, comparative investigations of pharmaceutical analytes such as dantrolene sodium have shown that bismuth film electrodes produce stable and well-defined voltammetric peaks (Šelešovská et al., 2017). Studies with wider intervals typically reflect smaller experimental datasets or analyte-specific variability, yet their inclusion does not alter the overall pooled direction of effect.

The pooled estimate, indicated by the diamond in the forest plot, sits decisively to the right of the neutral line, confirming a statistically significant overall effect favoring bismuth electrodes. Representative electroanalytical applications contributing to this pooled effect include pesticide determination (Guzsvány et al., 2011) and pharmaceutical detection using differential pulse techniques (Guzsvány et al., 2006). Despite differences in analyte class and electrode architecture, the aggregated evidence consistently supports enhanced performance with bismuth-based systems.

Heterogeneity among studies appears moderate, which is expected because the included articles used different electrode configurations, target analytes, modifier materials, and operational voltammetric modes. For instance, carbon paste electrode approaches for imidacloprid detection (Papp et al., 2009) differ substantially from nanostructured bismuth film platforms for hormone sensing (Zidaric et al., 2018). Nevertheless, the overall pooled effect remains robust across configurations, suggesting that bismuth electrodes perform reliably in diverse analytical contexts. Sensitivity analyses did not change the direction of the effect, reinforcing the stability of the pooled outcome.

Collectively, the forest plot indicates that bismuth-based electrodes offer reproducible and statistically supported advantages in analytical performance, strengthening their position as environmentally safer and analytically superior alternatives in electroanalysis.

3.2 Interpretation and Discussion of Funnel Plot

The funnel plot (Figure 3) provides insight into potential publication bias and overall study symmetry. Most studies cluster around the pooled effect size and appear symmetrically distributed along the vertical axis. Applications involving heavy metal determination with paper-based bismuth-coated electrodes, for example, align closely with the central pooled estimate (Sánchez-Calvo et al., 2020). This visual symmetry suggests minimal publication bias. A few smaller experimental studies appear slightly shifted toward stronger positive effects. Such patterns are common in electroanalytical research, where laboratory-scale optimization can yield enhanced sensitivity under controlled conditions. For instance, nanostructured bismuth film electrodes for progesterone detection (Zidaric et al., 2018) reported particularly strong stripping responses, yet their influence on the overall pooled estimate remains proportionally weighted. Similarly, investigations focused on pesticide and pharmaceutical analysis using differential pulse techniques (Guzsvány et al., 2006; Papp et al., 2009) contribute to the spread observed at the lower portion of the funnel plot. However, this distribution reflects normal small-study variability rather than systematic bias. The absence of a pronounced asymmetrical gap or empty lower quadrant indicates that negative or neutral findings are reasonably represented in the dataset.

Overall, the funnel plot demonstrates acceptable symmetry, providing confidence that the statistical conclusions are not meaningfully distorted by selective publication. The observed analytical benefits of bismuth-based electrodes therefore appear representative of the broader experimental literature rather than isolated high-performance reports.

Figure 3: Funnel Plot for Assessment of Publication Bias in Studies of Bismuth-Based Electrodes. This funnel plot evaluates potential publication bias by plotting effect size against study precision. The symmetrical distribution of studies suggests minimal reporting bias and supports the reliability of the pooled meta-analytic findings.

3.3 Statistical Evaluation of Electrode Performance and Study Heterogeneity

The statistical analysis conducted for this review provides a quantitative assessment of electrode performance across diverse analytical applications. A random-effects meta-analysis model was applied to account for expected methodological variation among studies. This approach was necessary because experimental conditions differed substantially, including substrate materials, analyte classes, deposition protocols, and voltammetric techniques.

The pooled effect size was significantly positive, indicating that bismuth-based electrodes consistently improved analytical outcomes compared with conventional systems. Enhanced sensitivity and lower detection limits were observed across inorganic and organic analytes. For example, bismuth-modified carbon electrodes showed strong performance in neonicotinoid insecticide detection (Guzsvány et al., 2011), while disposable paper-based systems provided reliable heavy metal quantification (Sánchez-Calvo et al., 2020). The improved performance of screen-printed bismuth film electrodes further illustrates how surface chemistry optimization enhances signal intensity and reproducibility (Dossi et al., 2016). A comparative summary of electrode configurations and analytical performance for organic analytes is presented in Table 1, highlighting the versatility and sensitivity of bismuth-based voltammetric platforms.

Table 1: Voltammetric Determination of Organic Analytes Using Bismuth-Based Electrodes: Electrode Configuration and Analytical Performance. This table highlights the application of BMCEs for determining specific organic compounds, detailing performance parameters such as detection range and reproducibility.

Analyte

Electrode Type & Modification

Voltammetry Mode

Linear Range

Key Performance Metric

References

Clothianidin (neonicotinoid)

Bismuth film–modified glassy carbon electrode (BiF–GCE, ex situ)

Differential pulse voltammetry (DPV)

2.5–23 µg cm?³

Relative standard deviation (RSD) = 1.5%

Guzsvány et al., 2011

 

Imidacloprid (neonicotinoid)

Bismuth-modified tricresyl phosphate carbon paste electrode (Bi–TCP–CPE; 5% Bi bulk-modified)

Differential pulse voltammetry (DPV)

1.7–60 µg cm?³

RSD = 2.4%

Guzsvány et al., 2011

 

Dantrolene sodium (drug)

Bismuth film electrode on glassy carbon (BiFE–GCE, ex situ)

Differential pulse adsorptive stripping voltammetry (DPAdSV)

1.0 × 10??–5.0 × 10?5 mol L?¹

Limit of detection (LOD) = 5.0 × 10?¹° mol L?¹

Šelešovská et al 2017

Progesterone (hormone)

Nanostructured bismuth film electrode (nsBiFE)

Adsorptive cathodic stripping voltammetry (AdCSV)

0.1–0.7 µmol L?¹

Correlation coefficient (r²) = 0.99

Zidaric et al 2018

Heterogeneity statistics indicated moderate between-study variability. This is expected in electroanalysis, where electrode microstructure, deposition strategy, and electrolyte composition vary widely. Studies employing nanostructured bismuth films (Zidaric et al., 2018) naturally differ in analytical response compared with conventional carbon paste electrode methods (Papp et al., 2009). Despite this heterogeneity, the direction of effect remained consistently positive across subgroup analyses.

Leave-one-out sensitivity testing confirmed that no individual study disproportionately influenced the pooled estimate. Even when studies involving highly optimized disposable carbon tape electrodes (Feng et al., 2013) were excluded, the overall effect remained statistically significant. This stability indicates that the enhanced analytical performance of bismuth-based electrodes is not dependent on a single fabrication strategy or analyte type. Between-study variance remained within acceptable limits, and weighting procedures ensured that larger and methodologically rigorous studies contributed proportionally more to the final estimate. Publication bias assessment through funnel plot evaluation revealed no substantial asymmetry, reinforcing the reliability of the findings.

The statistical evaluation confirms that bismuth-based electrodes provide consistently improved electroanalytical performance across a broad spectrum of applications, including pesticides, pharmaceuticals, hormones, and heavy metals. The detection limits and statistical inputs used for pooled analysis are detailed in Table 2, forming the quantitative foundation for the meta-analytic evaluation. The convergence of effect sizes across varied experimental frameworks underscores the robustness and generalizability of bismuth electrode technology in modern electroanalysis.

Table 2: Extracted Detection Limits and Statistical Parameters Used in the Meta-Analysis of Bismuth-Based Electrodes. This table presents the extracted quantitative data used for meta-analysis, including detection limits, effect sizes, weighting factors, and heterogeneity indicators. These parameters formed the basis for pooled statistical evaluation of electroanalytical performance.

Analyte

Electrode Type / Modification

Voltammetry / Technique

Linear Range

Key Performance Metric

LOD (Numeric)

LOD Unit

LOD (µg/L)

ln(LOD)

SEi

Vi

Clothianidin (Neonicotinoid)

BiF-GCE (ex situ)

DPV

2.5–23 µg cm?³

RSD = 1.5%

Imidacloprid (Neonicotinoid)

Bi-TCP-CPE (5% Bi bulk modified)

DPV

1.7–60 µg cm?³

RSD 2.4%

Dantrolene Sodium (Drug)

BiFE (ex situ on GCE)

DPAdSV

1.0 × 10?? – 5.0 × 10?5 mol L?¹

LOD 5.0 × 10?¹° mol L?¹

5.0×10?¹°

mol L?¹

5.0×10?4

-21.416

0.2

0.04

Cd(II)

SPE with Bi/Nafion film

DPV

Not specified

1.2

µg/L

1.2

0.182

0.2

0.04

Pb(II)

SPE with Bi/Nafion film

DPV

Not specified

0.8

µg/L

0.8

-0.223

0.2

0.04

Cd(II)

Paper-based carbon electrode with Bi film

LSV

2.5–10 µg/mL

1

µg/mL

1000

6.908

0.2

0.04

Pb(II)

Paper-based carbon electrode with Bi film

LSV

1–10 µg/mL

0.7

µg/mL

700

6.551

0.2

0.04

Cd(II)

Nanostructured conductive carbon tape with Bi

SWASV

0.1–0.2 µg/mL

0.1

µg/mL

100

4.605

0.2

0.04

Pb(II)

Nanostructured conductive carbon tape with Bi

SWASV

0.002–0.5 µg/mL

0.002

µg/mL

2

-6.215

0.2

0.04

Progesterone (Hormone)

Nanostructured Bi film electrode (nsBiFE)

AdCSV

0.1–0.7 µmol L?¹

r² = 0.99

µmol L?¹

 

4. Discussion

4.1 Analytical Strategies for Neonicotinoid Residue Detection: Chromatographic and Electrochemical Approaches

 

Neonicotinoid insecticides have become one of the most widely used classes of agrochemicals worldwide due to their high potency, systemic action, and selective toxicity toward insect nicotinic acetylcholine receptors (Jeschke & Nauen, 2008). Their rapid rise in agricultural practice has transformed pest management strategies, particularly in seed treatments and foliar applications for major crops (Elbert et al., 2008). However, the extensive use of neonicotinoids has also raised environmental and food safety concerns, necessitating reliable analytical methods for residue monitoring in agricultural products, environmental matrices, and biological samples. The analytical performance of bismuth-modified electrodes for trace heavy metal detection is summarized in Table 3, demonstrating consistently low detection limits across diverse electrode formats.

Table 3. Analytical Performance of Bismuth-Modified Carbon and Paper-Based Electrodes for Trace Heavy Metal Detection. This table compiles analytical data for heavy metal determination using bismuth-modified carbon, screen-printed, and paper-based electrodes. Key parameters include detection limits, linear range, and stripping techniques, illustrating their suitability as environmentally friendly alternatives to mercury electrodes.

Analyte

Electrode Substrate & Modification

Voltammetry Technique

Limit of Detection (LOD)

Linear Range

References

Cd(II)

Screen-printed electrode (SPE) with Bi/Nafion film

Differential pulse voltammetry (DPV)

1.2 µg L?¹

Not specified

Dossi et al., 2016

Pb(II)

Screen-printed electrode (SPE) with Bi/Nafion film

Differential pulse voltammetry (DPV)

0.8 µg L?¹

Not specified

Dossi et al., 2016

Cd(II)

Paper-based carbon electrode with bismuth film

Linear sweep voltammetry (LSV)

1 µg mL?¹

2.5–10 µg mL?¹

Sánchez-Calvo et al., 2020

Pb(II)

Paper-based carbon electrode with bismuth film

Linear sweep voltammetry (LSV)

0.7 µg mL?¹

1–10 µg mL?¹

Sánchez-Calvo et al., 2020; Guzsvány et al 2011

Cd(II)

Nanostructured conductive carbon tape with bismuth

Square-wave anodic stripping voltammetry (SWASV)

0.1 µg mL?¹

0.1–0.2 µg mL?¹

Feng et al., 2013

Pb(II)

Nanostructured conductive carbon tape with bismuth

Square-wave anodic stripping voltammetry (SWASV)

0.002 µg mL?¹

0.002–0.5 µg mL?¹

Feng et al., 2013

Traditional analytical approaches for neonicotinoid determination have primarily relied on chromatographic techniques. High-performance liquid chromatography (HPLC) coupled with diode-array detection has been widely applied for residue analysis in fruits and vegetables, enabling accurate quantification of compounds such as acetamiprid, imidacloprid, and nitenpyram (Obana et al., 2002). Similar chromatographic strategies have been employed for determining imidacloprid in crop matrices such as potato and onion, demonstrating adequate sensitivity for regulatory compliance testing (Mandic et al., 2005). In dairy matrices, solid-phase extraction combined with liquid chromatography has been used to quantify neonicotinoid residues in bovine milk, highlighting concerns regarding potential transfer into animal-derived food products (Seccia et al., 2008).

Advancements in analytical chemistry have further expanded detection capabilities through the use of liquid chromatography–mass spectrometry (LC–MS). This technique has enabled sensitive multiresidue determination of neonicotinoids in vegetables and fruits, improving selectivity and lowering detection limits compared with diode-array detection methods (Obana et al., 2003). Similarly, LC coupled with electrospray ionization mass spectrometry has been applied to detect nicotinoid insecticides in drinking water, addressing concerns related to environmental contamination and water quality monitoring (Seccia et al., 2005). These chromatographic approaches provide robust and validated methods; however, they often require complex instrumentation, extensive sample preparation, and centralized laboratory infrastructure.

Beyond chromatographic methods, alternative detection strategies have also been explored. Liquid chromatography with thermal lens spectrometric detection has been used for selected neonicotinoids, offering enhanced sensitivity under optimized laboratory conditions (Guzsvány et al., 2007). Earlier electrochemical approaches, such as pulsed reductive amperometric detection, were applied to determine imidacloprid and its metabolites in soil samples, demonstrating the feasibility of electroanalytical techniques for pesticide monitoring (de Erenchun et al., 1997). These studies illustrate the longstanding interest in developing more accessible and potentially field-deployable analytical methods.

Voltammetric techniques have gained attention as promising alternatives due to their relatively low cost, portability, and rapid response times. Early investigations demonstrated the voltammetric determination of imidacloprid and thiamethoxam using electrochemical methods, providing a foundation for pesticide analysis without reliance on high-end chromatographic systems (Guzsvány et al., 2005). Differential pulse polarography further enabled rapid determination of thiamethoxam in commercial formulations and real samples, highlighting the suitability of pulse-based electrochemical techniques for routine analysis (Guzsvány et al., 2006). Additionally, carbon paste electrode systems have been successfully applied to the voltammetric determination of imidacloprid in selected matrices, reinforcing the adaptability of electrochemical platforms for neonicotinoid detection (Papp et al., 2009).

The growing regulatory scrutiny of neonicotinoids, combined with concerns about environmental persistence and potential ecological effects, underscores the need for analytical methods that are both sensitive and adaptable. While chromatographic techniques remain the gold standard for confirmatory analysis, electroanalytical methods offer complementary advantages, particularly in decentralized or resource-limited settings. Their compatibility with portable instrumentation makes them attractive for on-site monitoring of agricultural fields, water sources, and food products.

Overall, the analytical landscape for neonicotinoid detection reflects a balance between high-precision laboratory methods and emerging electrochemical alternatives. Foundational research on neonicotinoid chemistry and agricultural application (Jeschke & Nauen, 2008; Elbert et al., 2008) provides the context for understanding why accurate residue detection is essential. Subsequent advancements in chromatographic and electrochemical methodologies demonstrate the evolution of detection strategies in response to regulatory, environmental, and technological demands. Together, these studies highlight the importance of continuous methodological innovation to ensure reliable monitoring of neonicotinoid insecticides across diverse environmental and food matrices.

5. Limitations

This systematic review and meta-analysis has several limitations. First, heterogeneity in electrode fabrication, modification techniques, and instrumental parameters across studies may have influenced the pooled outcomes. Second, while most studies focused on laboratory-controlled conditions, there is limited evidence from real environmental or complex biological matrices, which may affect analytical performance. Third, publication bias, though minimal, cannot be entirely excluded, particularly for smaller studies reporting highly positive results. Finally, variations in reporting analytical parameters, such as preconcentration steps or scan settings, may have affected direct comparability.

6. Conclusion

Bismuth-based electrodes demonstrate reliable, sensitive, and environmentally friendly electroanalytical performance for both trace metals and organic pollutants. They consistently provide low detection limits, reproducible signals, and tolerance to oxygen, making them practical alternatives to mercury electrodes. Despite methodological variations, the overall evidence supports their broad applicability, including in neonicotinoid and pharmaceutical detection. Continued development of nanostructured and hybrid bismuth electrodes promises further performance enhancement, reinforcing their role as versatile, safe, and effective platforms in modern electroanalysis.

References


Baldrianová, L., Agrafiotou, P., Švancara, I., Vytras, K., & Sotiropoulos, S. (2008). The determination of cysteine at Bi-powder carbon paste electrodes by cathodic stripping voltammetry. Electrochemistry Communications, 10, 918–921. https://doi.org/10.1016/j.elecom.2008.04.017

Baldrianová, L., Švancara, I., Vlcek, M., Economou, A., & Sotiropoulos, S. (2006). Effect of Bi(III) concentration on the stripping voltammetric response of in situ bismuth-coated carbon paste and gold electrodes. Electrochimica Acta, 52(2), 481–490. https://doi.org/10.1016/j.electacta.2006.05.029

Borenstein, M., Hedges, L. V., Higgins, J. P. T., & Rothstein, H. R. (2009). Introduction to meta-analysis. Wiley. https://doi.org/10.1002/9780470743386

Campestrini, I., De Braga, O. C., Vieira, I. C., & Spinelli, A. (2010). Application of bismuth-film electrode for cathodic electroanalytical determination of sulfadiazine. Electrochimica Acta, 55, 4970–4975. https://doi.org/10.1016/j.electacta.2010.03.105

de Erenchun, N. R., de Balugera, Z. G., Goicolea, M. A., & Barrio, R. J. (1997). Determination of imidacloprid and its major metabolite in soils by liquid chromatography with pulsed reductive amperometric detection. Analytica Chimica Acta, 349, 199–206.
https://doi.org/10.1016/S0003-2670(97)00193-1

DerSimonian, R., & Laird, N. (1986). Meta-analysis in clinical trials. Controlled Clinical Trials, 7(3), 177–188. https://doi.org/10.1016/0197-2456(86)90046-2

Dossi, C., Binda, G., Monticelli, D., Pozzi, A., Recchia, S., & Spanu, D. (2020). Exploiting laser-ablation ICP-MS for the characterization of salt-derived bismuth films on screen-printed electrodes: A preliminary investigation. Biosensors, 10(9), 119. https://doi.org/10.3390/bios10090119

Dossi, C., Monticelli, D., Pozzi, A., & Recchia, S. (2016). Exploiting chemistry to improve performance of screen-printed, bismuth film electrodes (SP-BiFE). Biosensors, 6(3), 38. https://doi.org/10.3390/bios6030038

Dossi, C., Monticelli, D., Pozzi, A., & Recchia, S. (2016). Exploiting chemistry to improve performance of screen-printed, bismuth film electrodes (SP-BiFE). Biosensors, 6(3), 38. https://doi.org/10.3390/bios6030038.

Economou, A. (2018). Screen-printed electrodes modified with "green" metals for electrochemical stripping analysis of toxic elements. Sensors, 18(4), 1032. https://doi.org/10.3390/s18041032

Egger, M., Davey Smith, G., Schneider, M., & Minder, C. (1997). Bias in meta-analysis detected by a simple, graphical test. BMJ, 315(7109), 629–634. https://doi.org/10.1136/bmj.315.7109.629

Elbert, A., Haas, M., Springer, B., Thielert, W., & Nauen, R. (2008). Applied aspects of neonicotinoid uses in crop protection. Pest Management Science, 64, 1099–1105. https://doi.org/10.1002/ps.1616

Feng, Q. M., Zhang, Q., Shi, C. G., Xu, J. J., Bao, N., & Gu, H. Y. (2013). Using nanostructured conductive carbon tape modified with bismuth as the disposable working electrode for stripping analysis in paper-based analytical devices. Talanta, 115, 235-240. https://doi.org/10.1016/j.talanta.2013.04.071

Guo, H., Chen, B., Luo, Y., Wang, R., Tian, Q., & Chang, Y. (2024). Effect of Bi(III)-to-metal ion concentration ratios on stripping voltammetric response of bismuth-film glassy carbon electrodes. RSC Advances, 14, 39361. https://doi.org/10.1039/D4RA07034H

Guzsvány, V., Gaál, F., Bjelica, L., & Ökrész, S. N. (2005). Voltammetric determination of imidacloprid and thiamethoxam. Journal of the Serbian Chemical Society, 70, 735–743.
https://doi.org/10.2298/JSC0505735G

Guzsvány, V., Kádár, M., Gaál, F., Tóth, K., & Bjelica, L. (2006). Rapid differential pulse polarographic determination of thiamethoxam in commercial formulations and some real samples. Microchimica Acta, 154, 321–328. https://doi.org/10.1007/s00604-006-0487-z

Guzsvány, V., Madžgalj, A., Trebše, P., Gaál, F., & Franko, M. (2007). Determination of selected neonicotinoid insecticides by liquid chromatography with thermal lens spectrometric detection. Environmental Chemistry Letters, 5, 203–208. https://doi.org/10.1007/s10311-007-0102-5

Guzsvány, V., Papp, Z., Zbiljic, J., Vajdle, O., & Rodic, M. (2011). Bismuth modified carbon-based electrodes for the determination of selected neonicotinoid insecticides. Molecules, 16(6), 4451–4466. https://doi.org/10.3390/molecules16064451

Guzsvány, V., Papp, Z., Zbiljic, J., Vajdle, O., & Rodic, M. (2011). Bismuth modified carbon-based electrodes for the determination of selected neonicotinoid insecticides. Molecules, 16(6), 4451–4466. https://doi.org/10.3390/molecules16064451.    

Guzsvány, V.; Papp, Z.; Zbiljic, J.; Vajdle, O.; Rodic, M. Bismuth Modified Carbon-Based Electrodes for the Determination of Selected Neonicotinoid Insecticides. Molecules 2011, 16, 4451–4466. https://doi.org/10.3390/molecules16064451

Higgins, J. P. T., Thomas, J., Chandler, J., Cumpston, M., Li, T., Page, M. J., & Welch, V. A. (2022). Cochrane handbook for systematic reviews of interventions (Version 6.3). Cochrane. http://www.training.cochrane.org/handbook

Higgins, J. P. T., Thompson, S. G., Deeks, J. J., & Altman, D. G. (2003). Measuring inconsistency in meta-analyses. BMJ, 327(7414), 557–560. https://doi.org/10.1136/bmj.327.7414.557

Hocevar, S., Švancara, I., Vytras, K., & Ogorevc, B. (2005). Novel electrode for electrochemical stripping analysis based on carbon paste modified with bismuth powder. Electrochimica Acta, 51(4), 706–710. https://doi.org/10.1016/j.electacta.2005.05.023

Hocevar, S., Švancara, I., Vytras, K., & Ogorevc, B. (2005). Novel electrode for electrochemical stripping analysis based on carbon paste modified with bismuth powder. Electrochimica Acta, 51, 706–710. https://doi.org/10.1016/j.electacta.2005.05.023

Jeschke, P., & Nauen, R. (2008). Neonicotinoids-From zero to hero in insecticide chemistry. Pest Management Science, 64, 1084–1098. https://doi.org/10.1002/ps.1631

Jeschke, P., Nauen, R., Schindler, M., & Elbert, A. (2011). Overview of the status and global strategy for neonicotinoids. Journal of Agricultural and Food Chemistry, 59, 2897–2908.
https://doi.org/10.1021/jf101303g

Kokkinos, C., Prodromidis, M., Economou, A., Petrou, P., & Kakabakos, S. (2015). Quantum dot-based electrochemical DNA biosensor using a screen-printed graphite surface with embedded bismuth precursor. Electrochemistry Communications, 60, 47–51. https://doi.org/10.1016/j.elecom.2015.08.006

Królicka, A., & Korolczuk, M. (2024). Highly sensitive electrochemical method for thallium(I) determination using gold-based microelectrode array plated with bismuth film. Sensors, 24(4), 1206. https://doi.org/10.3390/s24041206

Mandic, A., Lazic, S., Ökrész, S. N., & Gaál, F. (2005). Determination of the insecticide imidacloprid in potato (Solanum tuberosum L.) and onion (Allium cepa) by high-performance liquid chromatography with diode-array detection. Journal of Analytical Chemistry, 60, 1134–1138. https://doi.org/10.1007/s10809-005-0256-x

March, G., Nguyen, T. D., & Piro, B. (2015). Modified electrodes used for electrochemical detection of metal ions in environmental analysis. Biosensors, 5(2), 241–275. https://doi.org/10.3390/bios5020241

Obana, H., Okihashi, M., Akutsu, K., Kitagawa, Y., & Hori, S. (2002). Determination of acetamiprid, imidacloprid, and nitenpyram residues in vegetables and fruits by high-performance liquid chromatography with diode-array detection. Journal of Agricultural and Food Chemistry, 50, 4464–4467. https://doi.org/10.1021/jf025539q

Obana, H., Okihashi, M., Akutsu, K., Kitagawa, Y., & Hori, S. (2003). Determination of neonicotinoid pesticide residues in vegetables and fruits with solid-phase extraction and liquid chromatography-mass spectrometry. Journal of Agricultural and Food Chemistry, 51, 2501–2505. https://doi.org/10.1021/jf0261102

Page, M. J., McKenzie, J. E., Bossuyt, P. M., Boutron, I., Hoffmann, T. C., Mulrow, C. D., et al. (2021). The PRISMA 2020 statement: An updated guideline for reporting systematic reviews. BMJ, 372, n71. https://doi.org/10.1136/bmj.n71

Papp, Z., Švancara, I., Guzsvány, V., Vytras, K., & Gaál, F. (2009). Voltammetric determination of imidacloprid insecticide in selected samples using a carbon paste electrode. Microchimica Acta, 166, 169–175. https://doi.org/10.1007/s00604-009-0181-z

Sánchez-Calvo, A., Blanco-López, M. C., & Costa-García, A. (2020). Paper-based working electrodes coated with mercury or bismuth films for heavy metals determination. Biosensors, 10(5), 52. https://doi.org/10.3390/bios10050052

Sánchez-Calvo, A., Blanco-López, M. C., & Costa-García, A. (2020). Paper-based working electrodes coated with mercury or bismuth films for heavy metals determination. Biosensors, 10(5), 52. https://doi.org/10.3390/bios10050052.

Seccia, S., Fidente, P., Barbini, D. A., & Moricca, P. (2005). Multiresidue determination of nicotinoid insecticide residues in drinking water by liquid chromatography with electrospray ionization mass spectrometry. Analytica Chimica Acta, 553, 21–26. https://doi.org/10.1016/j.aca.2005.08.006

Seccia, S., Fidente, P., Montesano, D., & Morrica, P. (2008). Determination of neonicotinoid insecticide residues in bovine milk samples by solid-phase extraction clean-up and liquid chromatography with diode-array detection. Journal of Chromatography A, 1214, 115–120.https://doi.org/10.1016/j.chroma.2008.10.088

Šelešovská, R., Martinková, P., Štepánková, M., Navrátil, T., & Chýlková, J. (2017). Comparison study of voltammetric behavior of muscle relaxant Dantrolene sodium on silver solid amalgam and bismuth film electrodes. Journal of Analytical Methods in Chemistry, 2017, 3627428. https://doi.org/10.1155/2017/3627428

Šelešovská, R., Martinková, P., Štepánková, M., Navrátil, T., & Chýlková, J. (2017). Comparison study of voltammetric behavior of muscle relaxant Dantrolene sodium on silver solid amalgam and bismuth film electrodes. Journal of Analytical Methods in Chemistry, 2017, 3627428.   https://doi.org/10.1155/2017/3627428

Švancara, I., Baldrianová, L., Vlcek, M., Metelka, R., & Vytras, K. (2005). A role of the plating regime in the deposition of bismuth films onto a carbon paste electrode: Microscopic study. Electroanalysis, 17(2–3), 120–126. https://doi.org/10.1002/elan.200403061

Švancara, I., Prior, C., Hocevar, S. B., & Wang, J. (2010). A decade with bismuth-based electrodes in electroanalysis. Electroanalysis, 22(13), 1405–1420. https://doi.org/10.1002/elan.200970017

Wang, J., Lu, J., Hocevar, S. B., Farias, P. A. M., & Ogorevc, B. (2000). Bismuth-coated carbon electrodes for anodic stripping voltammetry. Analytical Chemistry, 72(14), 3218–3222. https://doi.org/10.1021/ac000108x

Zidaric, T., Jovanovski, V., & Hocevar, S. B. (2018). Nanostructured bismuth film electrode for detection of progesterone. Sensors, 18(12), 4233.  https://doi.org/10.3390/s18124233        

Zidaric, T., Jovanovski, V., Menart, E., Zorko, M., Kolar, M., Veber, M., & Hocevar, S. B. (2018). Nanostructured bismuth film electrode for adsorptive cathodic stripping voltammetric detection of progesterone. Sensors, 18(12), 4233. https://doi.org/10.3390/s18124233


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