Electrochemical Sensing of PFAS Using Gold Nanoparticle Functionalized Electrodes

Abstract

A method of electrochemical sensing includes providing an electrochemical sensor comprising a glassy carbon substrate and gold nanoparticles located on a surface of the glassy carbon substrate; and sensing electrochemically a compound selected from the group consisting of polyfluoroalkyl compounds or perfluoroalkyl compounds using the electrochemical sensor. PFOA quantification was performed by Square Wave Adsorptive Cathodic Stripping Voltammetry (SW-AdCSV) in test solutions with a 100-5,000 ppt concentration. The concentration has a linear relationship with the stripping current within this range. Analysis of tap and groundwater samples performed by additions method demonstrated precision and accuracy above 95%. These electrodes show stability throughout 200 cycles, and reproducibility across similarly prepared but different electrodes above 97.5%. Providing the electrochemical sensor can include providing at least one member selected from the group consisting of perfluoro-1-octanethiol (PFTO), 2,2,2-trifluoroethanethiol (TFET) or perfluorodecanethiol (PFDT) on the surface of the glassy carbon substrate.

Claims

1. A method of electrochemical sensing, comprising: providing an electrochemical sensor comprising a glassy carbon substrate and gold nanoparticles located on a surface of the glassy carbon substrate; and sensing electrochemically a compound selected from the group consisting of polyfluoroalkyl compounds or perfluoroalkyl compounds using the electrochemical sensor.

2. The method of claim 1, wherein the compound comprises perfluorooctanoic acid (PFOA).

3. The method of claim 1, wherein sensing electrochemically comprises square wave cathodic stripping voltammetry.

4. The method of claim 1, wherein the electrochemical sensor has, for perfluorooctanoic acid in aqueous media, a relative standard deviation range of from approximately 2.36% to approximately 3.08%.

5. The method of claim 1, wherein the electrochemical sensor has, for perfluorooctanoic acid in aqueous media, a limit of detection of approximately 0.228 ppb and a limit of quantification of approximately 0.759 ppb.

6. The method of claim 1, wherein the compound is located in an aqueous media.

7. The method of claim 1, wherein the compound comprises at least one perfluorocarboxylic acid.

8. The method of claim 7, wherein the compound comprises at least one member selected from the group consisting of trifluoroacetic acid, TFA; perfluoropropanoic acid, PFPrA; perfluorobutanoic acid, PFBA; perfluoropentanoic acid, PFPA; perfluorohexanoic acid, PFHxA; perfluoroheptanoic acid, PFHpA; perfluorononanoic acid, PFNA; perfluorodecanoic acid, PFDA; perfluoroundecanoic acid, PFUnA; perfluorododecanoic acid, PFDoA; perfluorotridecanoic acid, PFTrDA; and perfluorotetradecanoic acid, PFTA.

9. The method of claim 1, wherein the compound comprises at least one sulfonated polyfluoroalkyl compound or at least one sulfonated perfluoroalkyl compound.

10. The method of claim 9, wherein the compound comprises at least one member selected from the group consisting of perfluorohexanosulfonic acid, PFHxS; perfluorobutanosulfonate, PFBS; perfluorooctanosulfonate, PFBS; N-methyl perfluorooctanesulfonamidoacetic acid, NMeFOSAA; N-ethyl perfluorooctanesulfonamidoacetic acid, NEtFOSAA; and fluorinated phenols such as pentafluorophenol, PFPh.

11. The method of claim 1, wherein providing the electrochemical sensor comprises providing at least one member selected from the group consisting of perfluoro-1-octanethiol (PFTO), 2,2,2-trifluoroethanethiol (TFET) or perfluorodecanethiol (PFDT) on the surface of the glassy carbon substrate.

12. An article of manufacture, comprising: an electrochemical sensor comprising a glassy carbon substrate having a surface and a plurality of gold nanoparticles coupled to the surface of the glassy carbon substrate.

13. The article of manufacture of claim 12, wherein the plurality of gold nanoparticles is coupled to the surface of the glassy carbon substrate at a density of approximately 17407 m.sup.2.

14. The article of manufacture of claim 12, wherein the plurality of gold nanoparticles have an average diameter of from approximately 1406 m to approximately 1607 m.

15. The article of manufacture of claim 12, wherein the electrochemical sensor has, for perfluorooctanoic acid in aqueous media, a relative standard deviation range of from approximately 2.36% to approximately 3.08%.

16. The article of manufacture of claim 12, wherein the electrochemical sensor has, for perfluorooctanoic acid in aqueous media, a limit of detection of approximately 0.228 ppb and a limit of quantification of approximately 0.759 ppb.

17. The article of manufacture of claim 12, further comprising at least one member selected from the group consisting of perfluoro-1-octanethiol (PFTO), 2,2,2-trifluoroethanethiol (TFET) or perfluorodecanethiol (PFDT) coupled to the surface of the glassy carbon substrate.

18. A method of making an electrochemical sensor, comprising: providing a glassy carbon substrate having a surface; and electrodepositing gold nanoparticles on the surface of the glassy carbon substrate.

19. The method of claim 18, further comprising drying the surface of the glassy carbon substrate under an N.sub.2 atmosphere before electrodepositing and activating the electrochemical sensory in a 0.5 M H.sub.2SO.sub.4 solution.

20. The method of claim 18, wherein electrodepositing gold nanoparticles on the surface of the glassy carbon substrate comprises using cyclic voltammetry.

21. The method of claim 20, wherein using cyclic voltammetry includes using a work solution of 0.1 M NaNO.sub.3+0.25 mM HAuCl.sub.4.

22. The method of claim 18, wherein electrodepositing gold nanoparticles on the surface of the glassy carbon substrate comprises using chronoamperometry.

23. The method of claim 22, wherein using chronoamperometry includes using a work solution of 0.1 M NaNO.sub.3+0.25 mM HAuCl.sub.4.

24. The method of claim 18, further comprising depositing on the surface of the glassy carbon substrate at least one member selected from the group consisting of perfluoro-1-octanethiol (PFTO), 2,2,2-trifluoroethanethiol (TFET) or perfluorodecanethiol (PFDT).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The drawings accompanying and forming part of this specification are included to depict certain embodiments of the present disclosure. A clearer concept of the embodiments described in this application will be readily apparent by referring to the exemplary, and therefore nonlimiting, embodiments illustrated in the drawings (wherein identical reference numerals (if they occur in more than one view) designate the same elements). The described embodiments may be better understood by reference to one or more of these drawings in combination with the following description. It should be noted that the features illustrated in the drawings are not necessarily drawn to scale.

[0015] FIG. 1 illustrates a perfluorooctanoic acid (PFOA) structure appropriately labeled prior art.

[0016] FIG. 2A-2H illustrate SEM images of AuNPs/glassy carbon electrodes prepared in 0.1 M NaNO.sub.3+0.25 mM HAuCl.sub.4 using FIG. 2A) CA: t.sub.d=15 s FIG. 2B) CA: t.sub.d=3 s FIG. 2C) cyclic voltammetry: N=10 FIG. 2D) cyclic voltammetry: N=4. FIGS. 2E-2H are histograms displaying corresponding nanoparticle size distributions.

[0017] FIG. 3A-3B illustrate electrochemical characterization of the AuNPs/glassy carbon electrode. FIG. 3A (top) shows voltammogram recorded in a 0.5 M H.sub.2SO.sub.4 at v=100 mV s.sup.1 and FIG. 3B (bottom) shows anodic stripping of gold in 0.1 HCl by linear sweep voltammetry at v=50 mV s.sup.1. =3 mm.

[0018] FIG. 4 illustrates cyclic voltammetry of 1 mM PFOA+0.1 M ABS pH 5 for glassy carbon electrode bare (black line), Au (red line), and AuNPs/glassy carbon electrode (blue line) prepared by chronoamperometry using t.sub.d=15 s, E.sub.D=0.044 V vs. saturated calomel electrode v=100 mV s.sup.1, =3 mm.

[0019] FIGS. 5A-5B illustrate scan rate effect of 1 mM PFOA+0.1 M acetate buffer (pH 5) of AuNPs/glassy carbon electrode prepared by chronoamperometry using t.sub.d=15 s, E.sub.d=0.044 V vs. saturated calomel electrode FIG. 5A) voltammograms of 25 mV s.sup.1-1000 mV s.sup.1 FIG. 5B) ip vs v.sup.1/2 FIG. 5C) log v vs log ip FIG. 5D) Ep vs log v. =3 mm.

[0020] FIG. 6 illustrates SW-AdSV of 500 ppt PFOA+0.1 M acetate buffer (pH 5) for glassy carbon electrode bare (red line), Au (blue line), AuNPs/glassy carbon electrode (green line) prepared by chronoamperometry using t.sub.d=15 s, E.sub.d=0.044 V vs. saturated calomel electrode f=20 Hz, E.sub.step=25 mV, E.sub.sw=5 mV, t.sub.dep=45 s. =5 mm.

[0021] FIGS. 7A-7B illustrate SW-AdCSV of AuNPs/glassy carbon electrode FIG. 6A) effect of the concentration in the Ai FIG. 6B) calibration curve in a range of 100-5000 ppt. f=20 Hz, E.sub.step=25 mV, E.sub.sw=5 mV, t.sub.dep=45 s. =5 mm.

[0022] FIGS. 8A-8B illustrate SW-AdCSV response of 5000 ppt PFOA+0.1 M ABS pH 5 at of AuNPs/glassy carbon electrode prepared by chronoamperometry using t.sub.d=15 s and E.sub.d=0.044 V vs. saturated calomel electrode FIG. 8A) variation of i throughout 200 cycles of sensing FIG. 8B) responses of i with five different electrodes modified with the same procedure.

[0023] FIG. 9 illustrates the CV response of 1000 ppt PFOA+0.1 M KCl (pH 7.0) at bare, AuNPs, Au and PFDT/AuNPs glassy carbon electrodes. v=100 mV s.sup.1, =3 mm.

[0024] FIG. 10 illustrates SW-AdCSV of PFDT/AuNPs/GCE in 0.1 M KCl (pH 7.0), effect of the concentration in the i response in a range of 100-5000 ppt. f=20 Hz, E.sub.step=25 mV, E.sub.sw=5 mV, t.sub.dep=45 s. Inset: calibration curve from 100 to 5000 ppt (i=0.0852C.sub.ppt+16.705, R.sup.2=0.99671).

[0025] FIGS. 11A-11C illustrate SW-AdCSV response of 1000 ppt PFOA+in 0.1 M KCl (pH 7.0). (a) Variation of i throughout 200 cycles of sensing. (b) Responses of i with 5 different electrodes modified with the same procedure. (c) Effect of the interference species for the PFDT.

[0026] FIG. 12A illustrates effect of the SAM structure in the selectivity with perfluoro-1-octanethiol (PFOT).

[0027] FIG. 12B illustrates effect of the SAM structure in the selectivity with 2,2,2-trifluoroethanethiol (TFET).

DETAILED DESCRIPTION

1. Materials and Methods

1.1. Materials and Apparatus

[0028] All chemical reagents were analytical grade. The dilutions for the electroanalytical analysis were prepared using ultra-pure water (18 M) and a stock solution of 100.3 g mL.sup.1 perfluorooctanoic acid (PFOA) in methanol from Sigma-Aldrich. The AuNPs electrodeposition was performed in a gold solution prepared with HAuCl.sub.4 1% (w/v) solution (Ricca USA) and NaNO.sub.3 (99.0%) from Sigma-Aldrich. The H.sub.2SO.sub.4 (98%) and HCl (37%) used for the activation and characterization were from Fisher Scientific. The effect of pH was performed with phosphate buffer solutions prepared with H.sub.3PO.sub.4 (98%), NaH.sub.2PO.sub.4.Math.H.sub.2O (98%), and Na.sub.2HPO.sub.4.Math.7H.sub.2O (99%), all from Fisher. The acetate buffers were prepared with CH.sub.3COOH (99%) and CH.sub.3COONa (99%), both reagents from Sigma-Aldrich.

[0029] All electrochemical experiments were carried out in an electrochemical cell at 20 C.2 C. with a three-electrodes arrangement in a CHI760D potentiostat, the working electrode was a glassy carbon disk (=5 mm), and a platinum wire was used as a counter electrode and a saturated calomel electrode (SCE) as a reference electrode. The PFOA solutions were deaerated using N.sub.2 gas for 2 minutes before each measurement.

1.2. Electrode Preparation and Modification

[0030] The glassy carbon electrodes were carefully polished on a cloth polishing pad for 2 min using 0.3 m and 0.05 m alumina slurry. Between each polishing step, the electrodes were washed in DI water for 1 min and in the last step, the electrode was ultrasonicated for 5 min in DI water, ethanol, and acetone. The electrode was dried under an N.sub.2 atmosphere for 1 min.

[0031] AuNPs were deposited onto the glassy carbon surface using cyclic voltammetry (CV) and chronoamperometry (CA) methods in a work solution of 0.1 M NaNO.sub.3+0.25 mM HAuCl.sub.4. The experimental conditions were chosen to optimize NP diameter and density.

[0032] Electrodeposition by chronoamperometry was made by applying a deposition potential (E.sub.d) of 0.044 V for a time deposition (t.sub.d) of 3 s and 15 s. The modification by cyclic voltammetry was performed with several cycles (N) of 4 and 10 in a window potential from 1V to 0.2 V vs saturated calomel electrode. Subsequently, the electrodes were subjected to ultrasound in DI water for 2 minutes to remove physisorbed AuNPs to form a strong stable nanoparticle layer. Thereby all glassy carbon modified electrodes were activated in a 0.5 M H.sub.2SO.sub.4 solution by running 10 scans between 0.6 V to 1.5 V vs. saturated calomel electrode (anodic direction) at v=100 mV s.sup.1.

1.3. AuNPs/Glassy Carbon Electrodes Characterization

[0033] The AuNP electrodeposits were characterized using glassy carbon disks (=5 mm) which were observed in a Hitachi S-4800 scanning electronic microscope (SEM) operated at 15 kV. The distribution and average size of the nanoparticles were calculated using ImageJ image processing toolbox software, counting the maximum number of AuNPs in every micrograph (depending on stripping charge). AuNPs density was determined by the proportion of the number of nanoparticles (N) over the electrode area (A) expressed in um.sup.2.

2. Results and Discussion

2.1.1. Surface Characterization by SEM

[0034] SEM analysis was performed to characterize the size and density of electrodeposits on the glassy carbon surface by cyclic voltammetry and CA. FIGS. 2A-2H show the formation and distribution of AuNPs under different conditions and Table 1 shows the summary and other characterization parameters.

[0035] FIG. 2A shows a first formation 210. FIG. 2B shows a second formation 220. FIG. 2C shows a first formation 230. FIG. 2D shows a first formation 240. FIG. 2E shows a first particle size distribution 250. FIG. 2F shows a second particle size distribution 260. FIG. 2G shows a third particle size distribution 270. FIG. 2H shows a first particle size distribution 280.

[0036] As shown in FIG. 2A, by chronoamperometry at t.sub.d=15 s, homogeneous electrodeposits with broad coverage, minimal agglomeration, and hemispherical shape were obtained. Nanoparticles were (d=16 nm07 nm), Moreover, the best AuNPs density (17407 m.sup.2) was obtained. At 3 s td (FIG. 2B), the smallest nanoparticles were obtained (d=14 nm06 nm), however, the NPs density is lower than in electrode A and multiple nucleation sites were observed on the surface possibly due to the short time of electrolysis.

[0037] Significant differences were observed in the cyclic voltammetry modified electrodes (FIGS. 2C and 2D) as both the sizes of AuNPs were larger and the coverage was lower. These differences in morphology and coverage depend on the Q.sub.Au(III) electrodeposition charge since for both CA-modified electrodes a charge of 30-75 C is recorded while by cyclic voltammetry a charge of 260-445 C was recorded. Both techniques electrodeposit NPs on the electrode surface in different ways, by chronoamperometry there is better control in the growth of the NPs due to the imposition of a deposition potential (E.sub.d), which favors monodispersion and avoids agglomeration because the cathodic reaction is continuous during the whole deposition time. In addition, the agitation of the solution contributes to mass transport so that a more uniform coating and a wider distribution of AuNPs are achieved. By cyclic voltammetry, a potential sweep is imposed in a certain window in which the electrodeposition happens when the cathodic peak potential (Epc) is reached, at this point the reduction of Au(III) to Au(0) is thermodynamically and kinetically favorable, so a large amount of Au.sup.3+ ions is reduced, this is why a higher charge was recorded. Consequently, a large amount of AuNPs is formed but in a short period, which possibly does not allow the formation of small NPs and favors nucleation. After the peak potential, a current drop is recorded in the voltammograms where there is a diffusional control regime, in this step, there is the overlapping of the diffusion layers which probably interferes with the monodispersion of AuNPs.

2.1.2. Electrochemical Characterization

[0038] The electrochemical characterization was made by cyclic voltammetry in a 0.5 M H.sub.2SO.sub.4 solution under anaerobic conditions. FIG. 3A shows the voltammogram by glassy carbon electrode bare 310 presenting no redox signals under these conditions, therefore no other reactions interfere in the characterization. The voltammogram by AuNPs/glassy carbon electrode 320 shows an anodic peak between 1.0 V and 1.2 V vs. saturated calomel electrode, corresponding to the formation of different types of crystalline gold oxides (mainly AuO) according to the following reactions.

Au.sub.(ads)+H.sub.2O.sub.(l).fwdarw.AuOH.sub.(ads)+H.sup.+.sub.(ac)+e.sup.(.sub.1)

AuOH.sub.(ads).fwdarw.AuO.sub.(ads)+H.sup.+.sub.(ac)+e.sup.(2)

[0039] In the reverse scan a cathodic peak was observed at 0.87 V vs. saturated calomel electrode, which were related to the reduction of gold oxides to produce Au(0).

[0040] FIG. 3B shows a voltammogram by glassy carbon electrode bare 330 and a voltammogram by AuNPs/GC 340. The number of electrodeposited nanoparticles (N) on the electrode surface was estimated by the anodic stripping charge (Q) of AuNPs in 0.1 M HCl solution by linear sweep voltammetry in FIG. 3B. In this system with high chloride ions concentration, the oxidized gold atoms form coordination complexes as products of the anodic reaction. According to the morphology observed in the SEM micrographs, a spherical shape was considered, therefore, N can be determined based on the charge (Q) and the average radius (r) of the nanoparticles according to the following equation.

[00001]$N=Q\frac{M_{Au}}{1.9e\frac{4}{3}{r}^3{}_{Au}{N}_A}$

where e is the elemental charge, .sub.Au is the density of gold (19.32 g cm.sup.3), M.sub.Au is the atomic weight of gold and N.sub.A is the Avogadro constant. Subsequently, with N it is possible to calculate the coverage of the electrode modified with AuNPs () with the following equation.

[00002]$=100\frac{r^{2}N}{A}$

[0041] Table 1 shows the results of the electrochemical and SEM characterization.TT

TABLE-US-00001 TABLE 1 Characterization of AuNPs modified glassy carbon electrodes with different methods. NPs QAu(III) Q density d i Electrode Method t.sub.d (C).sup.a (C).sup.b (m.sup.2).sup.c (nm).sup.c N (A).sup.d A CA 15 s 124.5 1059.1 175 08 16 07 (660) 3.43 10.sup.9 14.1% 0.7 489.1 7.82 B CA 3 s 53.1 613.8 151 07 14 06 (729) 2.97 10.sup.9 9.32% 0.5 421.4 8.01 Cycles C CV N = 10 771.9 554.6 100 01 33 14 (380) 2.05 10.sup.8 3.57% 0.1 409.5 9.41 D CV N = 4 436.6 827.1 23 01 62 23 (319) 4.61 10.sup.7 2.35% 0.1 401.7 4.05 .sup.aQ.sub.Au(III) is the charge consumed in the electrochemical reduction step in 0.1M NaNO.sub.3 + 0.25 mM HAuCl.sub.4. .sup.bQ is the anodic stripping charge of Au-NPs Q obtained by integrating the area under the curve of the LS voltammograms. .sup.cNPs density estimation. Values in parentheses indicate the number of nanoparticles measured for the calculation. .sup.di is the stripping peak of SW-AdCSV 5000 ppt PFOA + 0.1M acetate buffer solution pH 5.

2.2. Electrochemical Behavior of PFOA on AuNPs/Glassy Carbon Electrode

2.2.1. Cyclic Voltammetry Study

[0042] The redox behavior of PFOA in the cathodic direction was studied in the glassy carbon bare, Au, and AuNPs/glassy carbon electrodes. FIG. 4 shows data for GCE bare 410, data for Au 420, and data for AuNPs/GCE 430. PFOA shows an electrochemically irreversible cathodic reduction, such behavior is maintained in all electrodes. Significant differences in cathodic peak potential (Ep.sub.c) and cathodic peak current (ip.sub.c) were observed. The Ep.sub.c is 1.1 V for the gold electrode, while for the glassy carbon electrode bare is not observed a peak in the acetate buffer window potential, indicating that the redox reaction is thermodynamically and kinetically more favorable when is carried out on a gold surface. Subsequently, the response with gold nano-surface was evaluated. The AuNPs/glassy carbon electrode showed an Ep.sub.c of 1.26 V and the highest ip.sub.c which increased by a ratio close to two with respect to the Au electrode. The above evidenced the kinetic effect of AuNPs during electron transfer, whereby gold in nanometer form is better than gold macroelectrode in detecting lower concentrations of PFOA.

[0043] The effect of the scan rate (v) for the cathodic reduction of 1 mM PFOA+0.1 M ABS with the AuNPs/glassy carbon electrode was studied in a range from 25 mV s.sup.1 to 1000 mV s.sup.1. FIG. 5A shows 25 mV s.sup.1 510, 50 mV s.sup.1 520, 100 mV s.sup.1 530, 200 mV s.sup.1 540, 500 mV s.sup.1 550, and 1000 mV s.sup.1 560. The ip.sub.c increased as the v increased furthermore, a shift of Ep.sub.c towards more negative potentials was observed which confirmed the irreversibility of the cathodic process. The ip.sub.c was directly proportional to v.sup.1/2 (FIG. 5B) according to the Randles-Sevcik equation for an electrochemically irreversible system, therefore it was determined that the mass transport mechanism is diffusion-controlled. The foregoing was confirmed by the plot of log ip vs log v (FIG. 5C) since the slope of the equation of the line had a value close to 0.5, for a diffusional control. The variation of Ep.sub.c with respect to log v was directly proportional (FIG. 5D).

[0044] The above data indicated the possibility that there are coupled chemical reactions involved within the cathodic reduction mechanism, thus possibly an E-C mechanism with multiple chemicals (C) and charge transfer (E) reactions. Therefore, the number of electrons involved in the cathodic process was determined based on the Laviron theory.

[00003]$E_p=E+\frac{2.303RT}{nF}\log \left(\frac{RT{k}_S}{nF}\right)+\left(\frac{2.303RT}{nF}\right)\log v$

where E.sup.O is the formal potential, is the transfer coefficient, k.sub.s the electronic transfer constant (s.sup.1) and n the number of electrons. From the slope value, n=0.7416 was determined. To calculate with the equation.

[00004]$.Math.E_p-E_{p/2}.Math.=\frac{1.15RT}{F}$

[0045] From the voltammograms obtained at different scan rates, the value of half-peak potential (E.sub.p/2) was determined, with which it was possible to determine the following data shown in Table 2, as well as a comparison of the data obtained for Au electrode performed using the same method described previously.

TABLE-US-00002 TABLE 2 Voltammetric data for cathodic reduction of 1 mM PFOA in 0.1M Acetate buffer (pH 5). Electrode E n.sub.app k.sub.s Au 1.158 V 0.2849 4 4132.26 s.sup.1 AuNPs/GCE 1.335 V 0.2874 4 6970.03 s.sup.1

[0046] The difference between the electronic transfer constants showed the clear catalytic effect of the AuNPs in the cathodic reduction of PFOA, on the other hand, the reduction of E.sup.O evidenced the synergistic effect in the thermodynamics of the reaction, which was revealed by a smaller a value characterizing the symmetry of the energy barrier of the redox reaction.

2.2.2. Square Wave Adsorptive Cathodic Stripping Voltammetry

[0047] An evaluation of AuNPs/glassy carbon electrode in a 500 ppt PFOA solution in 0.1 M ABS (pH 5) was performed to study the voltammetric response in ppt levels. FIG. 6 shows cyclic voltammetry data for blank 610, data for GCE bare 620, data for Au 630, and data for AuNPs/GCE 640. As seen in FIG. 6, with the bare glassy carbon electrode no peaks were observed, as obtained by cyclic voltammetry. The gold electrode recorded a peak at a potential of 1 V, which was defined with a i=58 A. However, the AuNPs/glassy carbon electrode showed a peak with a higher current (i=161 A) at a potential of 1.15 V. Therefore, it is possible to detect lower concentrations of PFOA with the nanostructured electrode. This is due to the increased surface area, which favors the adsorption of PFOA during the preconcentration step.

2.3. Calibration Curve

[0048] A calibration curve was performed to evaluate the relation between the stripping current (i) and the PFOA concentration in a range of 100-5000 ppb by SW-AdCSV in 0.1 M ABS pH 5. FIG. 7A shows data for 0 ppt 710, 100 ppt 720, 250 ppt 730, 500 ppt 740, 1000 ppt 750, 2000 ppt 760, and 5000 ppt 770. Good linearity was obtained by the R.sup.2=0.99547, the equation of the linear regression as shown in FIG. 5B. The limits of detection (LOD) and quantification (LOQ) were calculated according to the following equations.

[00005]$LOD=\frac{3}{m};LOQ=\frac{10}{m}$

where is the standard deviation of the electrolyte support (without PFOA) and m is the slope of the equation of the line. The LOD and LOQ were 42.3 ppt and 141.2 ppt respectively, these results show a competitive advantage in comparison with other analytical techniques such as liquid chromatography-tandem mass spectrometry (LC-MS/MS) and high-performance liquid chromatography (HPLC-MS/MS), of which LODs in a range of 25-100 ppt have been reported.

[0049] In addition, the AuNPs/glassy carbon electrode showed better sensitivity than a photoluminescence (PL) sensor or electrochemiluminescence (ECL) sensor. This showed the competitiveness of the SWCSV using the AuNPs/glassy carbon electrode in comparison with other analytical techniques to perform the PFOA sensing.

2.4. Validation of the Analytical Method

[0050] The AuNPs/GC electrode was evaluated to determine its applicability in several samples of tap water by the addition method. The samples analyzed only add them 0.1 M ABS (pH 5) therefore no pre-concentration treatment was applied (Table 3). In all of these cases, the PFAS concentration was below the LOD. The additions of 500 and 1000 ppt on tap water were very close to real concentration according to the recovery percentages and all values were inside of 1005% and the relative standard deviation (RSD) was less than 5%. These results demonstrated the precision and accuracy of this method, for this reason, the AuNPs/glassy carbon electrode is viable for sensing PFOA in real water samples.

TABLE-US-00003 TABLE 3 Recovery data for PFOA addition in tap water samples using AuNPs/glassy carbon electrode. Sample Original Added Found Recovery RSD (PFOA) (ppb) (ppt) (ppb) (%) (%) Tap water 1 ND 1000 985.3 98.53 2.67 Tap water 2 ND 500 516.9 103.38 2.12 Tap water 3 ND 1000 993.4 99.34 3.54 Tap water 4 ND 500 489.7 97.94 3.49 ND: not detected.

2.5. Reproducibility and Stability of Modified Electrode

[0051] The reproducibility and stability of the stripping current were evaluated under several conditions. As shown in FIG. 7A, the performance on the same solution and the stripping current ratio (% i) is 96.85% after 200 consecutive cycles which suggests good stability through frequent use. FIG. 7B shows the repeatability of 5 equally fabricated but different glassy carbon electrodes modified which show an RSD reproducibility variance of 2.44%.

3.0 Other PFAS to which this Method is Applicable:

[0052] All perfluorocarboxylic acids, PFCAs such as trifluoroacetic acid, TFA; perfluoropropanoic acid, PFPrA; perfluorobutanoic acid, PFBA; perfluoropentanoic acid, PFPA; perfluorohexanoic acid, PFHxA; perfluoroheptanoic acid, PFHpA; perfluorononanoic acid, PFNA; perfluorodecanoic acid, PFDA; perfluoroundecanoic acid, PFUnA; perfluorododecanoic acid, PFDoA; perfluorotridecanoic acid, PFTrDA; and perfluorotetradecanoic acid, PFTA; sulfonated PFAS (poly- and perfluoroalkyl compounds) such as perfluorohexanosulfonic acid, PFHxS; perfluorobutanosulfonate, PFBS; perfluorooctanosulfonate, PFBS; N-methyl perfluorooctanesulfonamidoacetic acid, NMeFOSAA; N-ethyl perfluorooctanesulfonamidoacetic acid, NEtFOSAA; and fluorinated phenols such as pentafluorophenol, PFPh.

[0053] FIGS. 8A-8B show SW-AdCSV response of 5000 ppt PFOA+0.1 M ABS pH 5 at of AuNPs/glassy carbon electrode prepared by chronoamperometry using t.sub.d=15 s and E.sub.d=0.044 V vs. saturated calomel electrode. FIG. 8A shows the variation of i throughout 200 cycles of sensing. FIG. 8B shows responses of i with five different electrodes modified with the same procedure.

[0054] The term glassy carbon, also called vitreous carbon, is intended to mean a non-graphitized carbon which combines glassy and ceramic properties with those of graphite. It takes its name from its shiny, conchoidal fracture surface, i.e. it looks like glass. Its most important properties are high temperature resistance, extreme resistance to chemical attack, and impermeability to gases and liquids. Glassy carbon is widely used as an electrode material in electrochemistry, as well as for high temperature crucibles. The term approximately is intended to mean within %5 of a value.

EXAMPLES

[0055] Specific exemplary embodiments will now be further described by the following, nonlimiting examples which will serve to illustrate in some detail various features. The following examples are included to facilitate an understanding of ways in which embodiments of the present disclosure may be practiced. However, it should be appreciated that many changes can be made in the exemplary embodiments which are disclosed while still obtaining like or similar result without departing from the scope of embodiments of the present disclosure. Accordingly, the examples should not be construed as limiting the scope of the present disclosure.

[0056] Examples include combining the AuNPs with at least one of a) perfluoro-1-octanethiol (PFTO), b) 2,2,2-trifluoroethanethiol (TFET) and/or c) perfluorodecanethiol (PFDT). An example includes electrochemical and surface characterization of PFTO/AuNPs/GCE. The electrochemical characterization of the AuNPs electrodeposited in the glassy carbon electrode (GCE) was performed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). According to the morphology observed in SEM micrographs, a spherical shape was considered, resulting in a surface coverage () of 39.11%1.95%, was calculated. The obtained is similar to other GCE modified via chronoamperometry (CA), in a range of 35-42% at similar experimental deposition conditions. SEM-EDX analyses were used to characterize the microscopic structure of the electrodeposited AuNPs and the AuNPs/GCE decorated with the SAM of perfluorodecanethiol (PFDT). Homogeneous coverage and high distribution of AuNPs is observed in the surface of the GCE indicating that AuNPs are highly dispersed with minimal agglomeration. The calculated average size of AuNPs of 16 nm7 nm and a density of 38624 nanoparticles per m.sup.2 was obtained using the observed hemispherical AuNPs shape. The EDX spectra exhibits signals for carbon, gold, and fluorine evidencing the presence of the PFDT on the electrode. Elemental mapping reveals a uniform dispersion of fluorine throughout the surface.

[0057] ATR FT-IR spectra of the AuNPs/GCE surface decorated with PFDT is shown in FIG. 1d. The GCE bare and AuNPs/GCE show no signal in the IR windows, the PFDT/AuNPs/GCE shows peaks in vibrations comparable to PFOA, due to its similar structure. The band at approximately 1245 cm.sup.1 is associated to CF bond vibration, the bands at 1229 cm.sup.1 and 1145 cm.sup.1 were assigned to stretching vibrations of CF.sub.2 and CF.sub.3 groups, respectively..sup.29 The surface coverage (*) of the PFDT self-assembled monolayer attached to AuNPs/GCE was determinate by CV. In FIG. 1e, the PFDT onto the AuNPs/GCE surface presents a broad cathodic peak at 1.19 V vs. SCE (FIG. 1e, blue trace), with high capacitive current suggesting the presence of chemisorbed PFDT species. A second cycle shows the absence of the same cathodic peak which confirms the stripping of PFDT from the AuNPs/GCE surface (FIG. 1e, green trace). For comparison, PFDT deposited onto an Au macroelectrode shows a small cathodic peak at 1.4 V vs. SCE (FIG. 1e, red trace). The integration of this peak results in a charge of 1.86 C equivalent to 2.7210.sup.10 mol cm.sup.2. On the other hand, the integration of the PFDT/AuNPs/GCE yields a charge of 2.36 C, which corresponds to 3.4610.sup.10 mol cm.sup.2 of surface coverage. The higher * for the PFDT/AuNPs/GCE suggests that the PFDT adsorption is more favorable into the gold nanoparticles. The optimization of SAM coverage is shown in Figure S2, with a top coverage of 6.7110.sup.10 mol cm.sup.2.

TABLE-US-00004 TABLE 4 Recovery data for PFOA standard addition in tap and brackish water samples using PFDT/AuNPs/GCE Sample Original Added Found Recovery RSD (PFOA) (ppt) (ppt) (ppt) (%) (% A ND 2000 1930 96.5 2.36 B ND 500 523 104.6 2.96 C ND 100 96.4 96.4 3.42 D ND 2000 1976 98.8 3.85 E ND 500 486 97.2 3.06 F ND 100 105 105 3.89 Samples A, B and C: Tap water Samples D, E and F: Brackish water ND: Not detected, n = 10.

[0058] Electrochemical methods are often not selective since they measure i at specific potentials and can easily interfere with quantification if their reduction potentials are close to those of the target analyte. To avoid this, we added a self-assembled monolayer (SAM) of a perfluorinated thiol to the surface of our AuNPs, namely PFDT/AuNPs/GCE to enhance the molecular recognition of PFOA. To measure this molecular recognition, in the presence of interfering species, we performed a series of analytical PFOA quantification measurements with a variety of different perfluorocarboxylic acids (PFCAs). FIG. 4c shows the analytical interference results of quantification of PFOA in the presence of 10-fold concentrations of the interfering species. The PFDT/AuNPs/GCE shows a recovery percentage (i.sub.0i.sub.int)/i.sub.0) within 1005% of the expected PFOA i.sub.0 response for all interfering matrices. The selectivity of PFDT/AuNPs/GCE toward PFOA was also tested in a mixture of all nine tested PFCAs, and the results show a recovery (i.sub.0i.sub.int)/i.sub.0) within 10010% of the expected PFOA current response. These results show that the presence of interfering PFCAs (and PFOS) do not significantly affect the statistical recovery data and confirm that PFDT/AuNPs/GCE is a selective electrode for PFOA sensing. Different SAM modifications to the AuNPs with other perfluorinated thiols such as perfluorooctanethiol (PFOT) and 2,2,2-trifluoroethanethiol (TFET), were tested, and their recovery percentage (Figure S6) are within 10020% and 10030%, respectively. The low capacity of these PFOT and TFET modified electrodes for selectively detecting PFOA shows the important role of chemical structure in PFDT for the molecular recognition of PFOA.

[0059] Electrode Surface Modification

[0060] The glassy carbon electrodes were carefully polished on a cloth-polishing pad for 2 min using 0.3 m and 0.05 m alumina slurry. Between each polishing step the electrodes were washed in DI water for 2 min and in the last step, the electrode was ultrasonicated for 5 min in DI water, then ethanol, and finally acetone. The electrode was dried under N2 atmosphere for 30 seconds. AuNPs were deposited onto GC surface using chronoamperometry (CA) in a work solution of 0.1 M NaNO.sub.3+0.25 mM HAuCl.sub.4. Electrodeposition by CA was performed applying a deposition potential (E.sub.d) of 0.044 V vs. SCE for a time deposition (t.sub.d) of 15 s. Subsequently, the electrode was subjected to ultrasound in DI water for 2 minutes to remove physiosorbed AuNPs in order to form a strongly stable nanoparticle layer. Thereby the AuNPs/GCE was activated in a 0.5 M H.sub.2SO.sub.4 solution by running 20 scans between 0.6 V to 1.6 V vs. SCE (anodic direction) at v=100 mV s.sup.1. The SAM was fabricated by the static immersion of the AuNPs/GCE into a 50 mM of the organosulfur compounds (PFDT, PFOT and TFET) in anhydrous ethanol for 12 h at 20 C. Upon removal from solution, the electrodes were thoroughly rinsed with ethanol and acetone to remove the species not chemisorbed.

[0061] Selectivity Testing

[0062] The selectivity tests were made in 10-fold excess to a standard solution of 1000 ppt PFOA in 0.1 M KCl (pH 7.0), the PFCAs: perfluoropropanoic acid (PFPrA), perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHA), perfluorononanoic acid (PFNA) and Perfluorooctanesulfonic acid (PFOS) were used. All reagents from Sigma-Aldrich. The effect of the interferences was expressed in percentage (i.sub.0i.sub.int)/i.sub.0) through normalizing the stripping currents of the PFOA in absence (i.sub.0) and presence (i.sub.int) of the interfering PFCAs.

[0063] Table 5 shows an exemplary brackish water composition.

TABLE-US-00005 TABLE 5 Recovery data for brackish water composition based on standards by NSF/ANSI 61-2016. General parameters Specification Water source De-ionized water (Conductivity <1 S cm.sup.1) pH adjusted with HCl 8.0 0.25 Temperature 20 2.5 C. Concentration Concentration Constituents (mg L.sup.1) (mM) Bicarbonate (HCO.sub.3.sup., initial) 244 4.0 Calcium (Ca.sup.2+) 120 3.0 Chloride (Cl.sup.) 1203 33.9 Magnesium (Mg.sup.2+) 49 2.0 Silica (SiO.sub.2) 20 as SiO.sub.2 0.33 Sodium (Na.sup.+) 750 32.6 Sulfate (SO.sub.4.sup.2) 194 2.0 Total Dissolved Solid (TDS) 2586 Ionic strength 49

[0064] The concentrations are achieved by adding the following to deionized water: [0065] 1690 mg L.sup.1 NaCl (99.0%, Sigma-Aldrich) [0066] 487 mg L.sup.1 MgSO.sub.4.Math.7H.sub.2O (98%, Fisher) [0067] 440 mg L.sup.1 CaCl.sub.2.Math.2H.sub.2O (99%, Fisher) [0068] 336 mg L.sup.1 NaHCO.sub.3 (99%, Sigma-Aldrich) [0069] 95 mg L.sup.1 Na.sub.2SiO.sub.3.Math.9H.sub.2O (98%, Fisher) Table 6 shows an exemplary drinking water (tap water) composition.

TABLE-US-00006 TABLE 6 Recovery data for drinking water composition based on standards by NSF/ANSI 61-2016. General parameters Specification Water source De-ionized water (Conductivity <1 S cm.sup.1) pH adjusted with HCl 7.25 0.25 Temperature 20 2.5 C. Concentration Concentration Constituents (mg L.sup.1) (mM) Bicarbonate (HCO.sub.3.sup., initial) 183 3.0 Calcium (Ca.sup.2+) 40 1.0 Chloride (Cl.sup.) 71 2.0 Fluoride (F.sup.) 1 0.053 Magnesium (Mg.sup.2+) 12 0.50 Nitrate (NO.sub.3.sup.) 8.9 (2.0 as N) 0.14 Phosphate (PO.sub.4.sup.3) 0.12 (0.04 as P) 0.0013 Silica (SiO.sub.2) 20 as SiO.sub.2 0.33 Sodium (Na.sup.+) 89 3.86 Sulfate (SO.sub.4.sup.2) 48 0.50 Total Diss, Solid (TDS) 478 Ionic strength 8.5

[0070] The concentrations are achieved by adding the following to deionized water: [0071] 252 mg L.sup.1 NaHCO.sub.3 (99%, Sigma-Aldrich) [0072] 147 mg L.sup.1 CaCl.sub.2.Math.2H.sub.2O (99%, Fisher) [0073] 124 mg L.sup.1 MgSO.sub.4.Math.7H.sub.2O (98%, Fisher) [0074] 95 mg L.sup.1 Na.sub.2SiO.sub.3.Math.9H.sub.2O (98%, Fisher) [0075] 12 mg L.sup.1 NaNO.sub.3 (99%, Sigma-Aldrich) [0076] 2.2 mg L.sup.1 NaF (99%, Sigma-Aldrich) [0077] 0.18 mg L.sup.1 NaH.sub.2PO.sub.4.Math.H.sub.2O (98%, Fisher)

[0078] The description of the different illustrative embodiments has been presented for purposes of illustration and description and is not intended to be exhaustive or limited to the embodiments in the form disclosed. The different illustrative examples describe components that perform actions or operations. In an illustrative embodiment, a component can be configured to perform the action or operation described. For example, the component can have a configuration or design for a structure that provides the component an ability to perform the action or operation that is described in the illustrative examples as being performed by the component. Further, To the extent that terms includes, including, has, contains, and variants thereof are used herein, such terms are intended to be inclusive in a manner similar to the term comprises as an open transition word without precluding any additional or other elements.

[0079] Many modifications and variations will be apparent to those of ordinary skill in the art. Further, different illustrative embodiments may provide different features as compared to other illustrative embodiments. The embodiment or embodiments selected are chosen and described in order to best explain the principles of the embodiments, and the practical applications, and to enable others of ordinary skill in the art to understand the disclosure for various embodiments with various modifications as are suited to the particular use contemplated.