Heavy Metals and Para-Phenylenediamine in Hair Dye


 Background: The use of cosmetics is widespread around the world, particularly in Arabian countries. Some cosmetics as hair dyes are used since very young ages. Hair dye has been one of the pollution resources of heavy metals. Aim: The present study aimed to determine the percentage of para-phenylenediamine (PPD) and heavy metals in various hair dyes sold in Aswan, Egypt. Methods: The study was done on four (n = 4) types of hair dyes commonly used in Aswan. Two analytical methods were used as (GC/MS and EDX). PPD was detected using gas chromatography/mass spectrometry (GC/MS), and the metal components of these dyes were determined using energy dispersive x-ray (E.D.X.). Results: The concentration of PPD was very high in SHD (99.706%) and tancho HD (99.80%) followed by bigen cream HD (5.563%) and finally bigen powder HD (0.492% ). The heavy metals content was arranged in decreasing order as follow: Al > Ca > Zn > Cu > Cl > Pb> Fe > Sc> Cr > Mn in SHD, Si > Mg> Cu > Zn > Cl > Ca in tancho HD, Pb> Cu > Zn >Si >K > Al > Ca > Cr in bigen powder HD and Al > Cu > Cl > Si > Zn > Ca > Pb> Cr in bigen cream HD. Conclusion: Poisoning with (PPD)-containing hair dye is emerging as a method of deliberate self-harm in various developing countries including the Middle-East, and it is accompanied with high human death rate specially among females. They were also polluted with heavy metals, therefore doctors and consumers should be aware of their potential toxicity as well as the symptoms of systemic poisoning. Even if it isn't stated on the label, many hair dyes contain PPD and heavy metals.

Toxicity with paraphenylenediamine (PPD)-containing hair dye is becoming a new form of suicide across Asia, Africa, and the Middle East, and it's linked to a signi cant risk of human death since it damages several organs, including the heart, liver, kidneys, and muscles. ( Many cosmetics, including hair dyes, contain heavy metals as components or contaminants (Alam et al., 2019).
Heavy metals (HMs) are a collection of elements with similar chemical properties. Some of them, such as copper, iron, zinc, play a crucial role in human organism and are referred to as essential metals, while others are not recognized to be bene cial to our health, or, to put it another way, they are toxic (Sommar et al., 2013).
Energy Dispersive X-ray (EDX) microanalysis is a type of elemental analysis that use specialized X-rays to detect the presence of elements in specimens. It is used in collaboration with electron microscopy, it is a useful technique for detecting nanoparticles of heavy metal components in these dyes (Sandonà et al., 2020) Gas chromatography/mass spectrometry technique (GC/MS) in spitless mode, as well as energy dispersive x-ray (E.D.X.) microanalysis, were key components of this study.

2-Aim Of The Study:
The purpose of this research is to determine the chemical and microelemental features of PPD-containing commercial hair dyes currently used in Egypt, nd adequate detection methods, and measure the components that ay pose a health risk if consumed.

Chemicals:
Commercially accessible and widely used hair colors in Aswan as Black hair dye, also known as "Stone Hair Dye" (SHD), Tancho dye powder and Bigen dye powder were obtained from hair supplies markets in Aswan while Bigen hair dye cream was obtained from pharmacy.

Instruments:
a-Gas chromatography/ mass spectrometry (GC/MS) analysis was carried out in Analytical Chemistry Unit (ACAL) -Faculty of Science-Assuit University using a GC/MS system (7890A-5975B) made in USA, equipped with capillary Column DB 5ms (30m*0.250mm*0.250 µl). b-Energy dispersive x-ray (E.D.X.) microanalysis was done in Electron Microscope Unit-Assuit University for analysis of elemental components of different hair dyes using Scanning Electron Microscope (JSM-5400LV), made in England.

Extraction procedure for dye in GC/MS:
Half gm of sample was added to 2 ml of ethyl acetate then sonicated for 15 minutes and centrifuged at 8000 rpm / 40°C for 15 minutes.
The GC/MS analysis was performed in a spitless mode using helium as the carrier gas at a ow rate of 0.5 ml/min for 10.9 minutes, then 1 ml/min per minute for 30 minutes. The injection port was set to 250°C, and the oven was preheated to 60°C for 2 minutes before being programmed at 14°C/min (11°C/min for trimethylsilyl derivatives) to a nal temperature of 280°C for 20 minutes. b-Quantitative analysis:
In our results, it was found that 99.706% of SHD and 99.80% of Tancho HD was PPD, and this means that SHD and tacho HD mainly PPD. This agreed with previous results done by Coligan et al., (1996) who reported that the conentration of PPD in SHD was 99.85%. Also, the result of our study was in accordance with the result of Ahmed et al., (2013) who reported that 99.66% of SHD was PPD.
The concentration of PPD of other commercial HDs in our results was shown in Table 1 as follow: 0.492% in bigen HD powder and 5.563% in bigen HD cream.
Heavy metals (HMs) are metals with a speci c density of more than 5 g/cm3 that harm the environment and living beings (Monisha et al., 2014).Some of them may be harmful to human health even at extremely low concentration since they have prolonged biological half-lives and are non-biodegradable, allowing them to persist in the body for long time ( There are currently no global limits for pollutants such as heavy metals in cosmetics, with the exception of 20 g/g for lead and 5 g/g for cadmium (Al-Dayel et al., 2011). While the regularity limits for certain metals in cosmetics in Canada are 10 g/g for Pb, 3 g/g for As, Cd, and Hg, and 5 g/g for Sb (Ullah et al., 2017).
The elemental composition of the sample is determined using Energy dispersive X-ray spectroscopy (E.D.X) (Mujeeb and Zafar., 2017).
In our study, we found that the amount of Aluminum (Al) in the hair dye samples studied varied greatly. Bigen cream HD had the greatest Al level (29.63%), followed by SHD (29.215%), and nally Bigen HD powder (3%), while absent in tancho H and this agreed with previous study done by Ahmed et al., (2013) who reported that Aluminum represented the highest component of stone hair dye (55.12 %). This could be due to a discrepancy in the dye's origin or a difference in the sensitivity of the devices.

Conclusions:
Based upon the results, we determined that hair dye samples purchased from salons and pharmacies contained high levels of para phenylenediamine, which raises the risk of sensitization among those who use them, even though the color's label did not state so.
Furthermore, continued use of these hair dyes may result in an increase in heavy metal levels (aluminium, chromium, copper, zinc, iron, lead, and nickel) through dermal contact, oral ingestion, or other forms of human exposure, causing harmful effects to consumers over time.
The two methods described in this study (GC/MS and EDX) have been shown to be suitable with satisfactory accuracy and good reproducibility for the determination of PPD in hair dye samples and for detection of heavy metals elements present on them.
EDX microanalysis could represent a powerful tool in different biomedical elds and forensic science.