Development of a portable electroanalytical method using nickel modified screen-printed carbon electrode for ethinylestradiol determination in organic fertilizers.

Urine and struvite are organic fertilizers that have all nutritional requirements for the growth of a plant. However, these fertilizers may contain some emerging organic contaminants, such as ethinylestradiol, which is one of the most common hormones found in aquatic environments and can cause several changes in living organisms. Thus, the present study developed a fast, sensitive, inexpensive, and portable method for determining ethinylestradiol in urine and struvite, using square wave voltammetry (SWV) and screen-printed carbon electrodes modified with electrodeposited nickel film (SPCE-Ni). The electrodeposition of the nickel film on the screen-printed electrode was performed by cyclic voltammetry and optimized using complete factorial design 23 and central composite design. The parameters optimized for SPCE-Ni were: number of cycles (1000); scan rate (5 V s-1) and Ni2+ concentration (9.4 mmol L-1). The operational parameters of the SWV for ethinylestradiol analysis were also optimized by experimental designs and obtained the following optimal values: step potential (10 mV), modulation amplitude (40 mV), and frequency (20 Hz). The method used 0.1 mol L-1 BR buffer (pH 8.0) as support electrolyte and presented a limit of detection of 0.052 µmol L-1 (R2 = 0.996). Ethinylestradiol recovery test in struvite, human urine, synthetic urine, and pharmaceutical tablets ranged from 93.9% to 107.5%, indicating that there is no matrix effect. Furthermore, an interference test was performed with several drugs did not show any significant changes in the ethinylestradiol analytical signal, guaranteeing a greater precision of the method. These results reinforce the possibility of applying the proposed method in loco with a practical and fast way, without the need to use significant amounts of sample.

Development of electroanalytical procedure for monitoring of metamizole in organic fertilizers (human urine and struvite) associated with portable equipment.

Urine and struvite are promising organic fertilizers that can replace conventional fertilizers. However, these fertilizers can have some emerging contaminants, such as dipyrone. This drug is one of the main painkillers consumed in the world and its continuous and indiscriminate intake can promote the camouflage of symptoms of other diseases, anaphylactic shock and even death. Thus, a fast, sensitive, inexpensive and portable method for metamizole (dipyrone) determination in several matrices, applied as organic fertilizers, has been successfully developed using portable equipment and bare carbon screen-printed electrodes in conjunction with square wave voltammetry (SWV). The main SWV operating parameters were optimized (equilibrium time (60 s), step potential (6 mV), modulation amplitude (50 mV) and frequency (10 Hz)) using univariate experiments. The proposed method presented a limit of detection of 0.097 ± 0.002 µmol L-1 (RSD = 2.72%, n = 3) for dipyrone in 0.1 mol L-1 HCl and R2 equal to 0.993. The determination in the struvite sample presented a concentration of 0.47 µmol L-1 of dipyrone. Urine sample used in the production of struvite and urine collected from an individual 10h after ingestion of 500 mg dipyrone tablet showed concentrations of 15.2 and 590 µmol L-1 of dipyrone, respectively. The recovery test in fortified struvite sample showed values between 91 and 102% (RSD = 3.1%, n = 3) and of 102% (SD = 3.7%, n = 3) in human urine, indicating that there is no matrix effect. These results reinforce the possibility of applying the proposed method on-site in a practical and fast way, without the need of significant amounts of sample promoting a more sustainable chemistry.