1. INTRODUCTION:

Fingerprint examination is recognized as one of the most significant parts of investigation processes. Fingerprints are the piece of evidence that inevitably left on the substances (weapon or other articles) present at the scene of crime and forms the basis for identification of the offender or criminal because everyone’s fingerprints are unique in nature.

Thus, Fingerprints have been accepted by the courts of law as forensic evidence¹. At the scene of the crime, the possible types of fingerprints left by suspects are:

I. Patent fingerprints:

Patent fingerprints result from transferring the coloring/visible substance from one surface to another through ridges of the finger.

II. Plastic fingerprints:

Plastic finger prints result from engraving the embossed part(ridges) of fingers on a malleable surface. Both patent and plastic are visible to the naked eye.

III. Latent fingerprints:

Latent or invisible fingerprints result from the deposits of perspiration from ridges of the finger to the surface and are not perceptible to the naked eye as sweat is colorless in nature. Thus, they need to be developed to make them visible. These prints are inevitably present on most of the pieces of evidence at the scene of a crime.²

1.1 Mindset of Criminals:

To escape from any criminal act, criminal offenders often try to hide their identity or presence at the scene of a crime. Some people have confidence or misconception that items collected from water have lost their fingerprint significance, thus they attempt to wipe the fingerprint evidence by discarding them into the water². Water washes away the constituents of latent fingerprints that are soluble in water, such as sodium/salt, amino acids, and proteins whereas the components that persist in the water are the insoluble ones viz. lipid³. Additionally, latent fingerprints on water immersed items are susceptible to various unknown physiochemical factors of the water (e.g., turbidity, pH, and BOD), which may hasten the deterioration of the latent fingerprints⁴. Thus, the visualization of latent print on substrate that has been soaked in water is a bit difficult and necessitates the establishment of good analytical methods.

1.2 Development of Wet Latent Fingerprints:

While there are several approaches for fingerprint detection on dry surfaces, the same method is not applicable or feasible for wet surfaces. The fingerprint development methods proposed for dry surfaces are the powder dusting method, ninhydrin method, silver nitrate method, cyanoacrylate fuming, iodine fuming method, etc. Presently, there are only a few well-established visualization methods reported for wet surfaces. SPR (Small Particle Reagent) and PD (Physical Developer) are a few of the well-established approaches for non-porous and porous surfaces, respectively⁴. SPR is a versatile development method that works well on a variety of surfaces, including cards, rocks, gravel, cement, polymer, compact disc, lumber, glassware, and fresh, corroded, or galvanized metal.⁵

1.3 Working Principle of SPR:

The key components of typical SPR composition are surfactant and suspending substance. The interaction between the fatty-acid residuals of latent fingerprint and the hydrophobic tails of the reagents underpins the SPR principle. These tails have a hydrophilic head that further reacts with a metal salt to yield a colorful deposition⁶. Surfactant is a synthetic detergent comprised of organic components that are detrimental to humans or the environment. Change in SPR’s pH may alter the efficiency of fingerprint development with favorable condition in pH range 3 to 4⁷.

2. Main Text:

This review paper dictates the estimation of efficiency of modified SPR on different surfaces, immersion medium, calculation of latent print immersion time, and for their stability as well. The SPR can be spread to the suspected surface via spraying or immersion, dependent on the size and shape of the object to be fingerprinted. The spray method is better for huge substances, whereas the immersing method is suitable for little substances. To remove extra powder particles from treated surfaces, gentle washing with distilled water is recommended⁸.

2.1 SPR Formulation:

The first small particle reagent was a detergent-based suspension of small molybdenum disulfide units that results in formation of a grey color fingerprint upon application to a water immersed latent fingerprint (Great Britain. Patent No. M. Patent 154, 147, 1979). Goode and Morris later described a full process and formulation⁹. However, because the color of molybdenum disulfide is grey, fingerprints generated on dark-colored substances are not as evident due to a dearth of distinction. Later, several certain modifications have been reported for a better contrast by replacing the molybdenum disulfide particles with other metal oxides and metal carbonate along with different dyes having color against of surface background color upon which fingerprint needs to be developed.

Further, SPR formulations based on CO₃O₄, TiO₂, Fe₃O₄, ZnO, PbO, and ZnCO₃has been proposed. The amalgamation of white SPR with fluorescent dye is a beneficial adjustment in the field, and the effectiveness of the resulting fingerprints in terms of immersion duration and reagent shelf life has also been highlighted ¹⁰. The most utilized white color powder suspensions are composed of zinc oxide, zinc carbonate, and titanium dioxide¹¹.

As illustrated in Table 1, the various components of SPR (Marked by tick ‘P’) utilized for the imaging of water immersed latent fingerprints on deteriorated articles. The labelling of double tick (PP) indicates that more than one composition has been prepared along with the combination of common base component (if present) marked by single tick ‘P’ within same row and tested for the development of water immersed fingerprint viz. Jasuja et.al (2007) who have studied 2 SPR formulations namely Zinc Carbonate and Black charcoal and, Rohatgi and Kapoor (2015) have also studied 2 SPR formulations namely Crystal violet-based Zinc Carbonate SPR and Basic Fuschin-based Zinc Carbonate SPR. The acronym ZC, TD, ZO, MD, IO, BC, CC, SP, CV, EY, BY, BB, BF, EB, RBD, ND, R6, RB, A0, CB, A, and SB of SPR composition (Top Horizontal Row) in table no.1 stands for Zinc Carbonate based SPR, Titanium Dioxide based SPR, Zinc Oxide based SPR, Molybdenum disulfide based SPR, Iron oxide based SPR, Black charcoal based SPR, Choline Chloride, SPR, Crystal violet, Eosin Y, Brilliant yellow 40, Brilliant blue R, Basic fuchsin, Eosin B, Rose Bengal dye, Natural dye, Rhodamine 6G, Rhodamine B, Acridine orange, Cyano blue, Anthracene, and Schiff's base respectively.

Table 1: Various SPR Compositions used for development of water immersed latent fingerprint

SPR Composition

RBD

Frank and Almog (1993) ¹²

Springer and Bergman (1995) ¹³

Wade DC,(2002)¹⁴

William and Elliott (2005)

Jasuja et al., (2007) ¹⁵

Jasuja et al., (2008) ¹⁰

Kabklang et al., (2009)¹⁶

Sodhi and Kaur (2010)¹⁷

Trapecar (2012a) and (2012b)^18,19

Sodhi and Kaur (2012)²⁰

Sodhi and Kaur, (2014) ¹⁷

Sanjiv et al., (2014)

Rohatgi et al., (2014)²¹

Kapoor et al., (2015)²²

Rohatgi and Kapoor (2015)⁶

Dhall and Kapoor (2016)¹¹

Doibut and Benchawattananon, (2017)²³

Downham, (2017)

Kaur et al., (2020)²⁴

Arora et al., (2021)¹

SPR of two other color variants other than black, i.e., white, and fluorescent has been suggested. Fluorescing compounds were advised for dark or multi-colored exteriors. Rhodamine 6G, has provided greater disparity of developed fingerprints in comparison with Brilliant Yellow 40 under illumination in the blue region of the electromagnetic spectrum¹³. An improved SPR formulation has been made by substituting the surface-active agent with a natural Saponin, an active chemical discovered in the fruit Sapindusmukorossi (also known as Ritha, Chinese soapberry, and soap-nut)¹⁵. It has been evaluated that basic yellow 40, anthracene, and zinc acridine orange based SPRs do not produce favorable fluorescence outcome whereas acridine orange did develop fresh fingerprints. Rhodamine B, Rhodamine 6G and cyano blue based SPRs shows positive results for developing latent fingerprints immersed in water. SPR based on cyano blue is preferred over Rhodamine B and Rhodamine 6G are designated as potential carcinogens which is not the case with cyano blue and thus safer to use¹⁰.

Total 11 SPR based on MoS₂, Fe₃O₄, TiO₂, ZnO and ZnCO₃in choline chloride were investigated. The best results were evident with the SPR formulation comprised of molybdenum disulfide in choline chloride and tergitol NP-7 at pH 3.1. Result on dark surface were prominently evident by ZnCO₃based SPR. All SPR compositions incorporating white particles yielded poor results²⁵. The effectiveness of the crystal violet dye-based ZnCO₃.2Zn(OH)₂.H₂O commonly known as basic zinc carbonate based SPR (Novel SPR) has also been explored as against molybdenum (IV) sulfide formulation (conventional SPR) on lamination sheet wherein conventional SPR develop inferior fingerprint as compared to fingerprints developed by novel SPR ²⁰. Sirchie's SPR-100 {a solution of small molybdenum disulfide (MoS₂) particles, detergent, and water} has also been used¹⁸^,¹⁹. The efficiency of SPR based on basic zinc carbonate has been explored as well. This mixture also contains eosin B dye and a surfactant¹⁷. In a similar attempt, a fluorescent rhodamine B dye formulation SPR based on basic zinc carbonate has been developed. The mixture also contains titanium dioxide, lycopodium, detergent, water, and gum rosin.²²whereas in another study, SPR based on basic zinc carbonate with crystal violet dye and a surfactant has been developed²¹.

A unique SPR formulation based on basic fuchsin dye and zinc carbonate has been developed for the water-soaked latent fingerprints development ⁶. Similarly, 3 novel fluorescent white SPR comprising zinc oxide, zinc carbonate, and titanium dioxide-based on fluorescent dye as rose bengal (tetraiodo composed of xanthene dye) has been formulated. The Lambda maximum of dye is 558 nm. TiO₂reagent is found to be more efficient than ZnCO₃ reagent which is more efficient than ZnO reagent ¹¹. The effective use of SPR based on basic zinc carbonate with natural colors such as curcumin and anthocyanin has been reported for analyzing latent fingerprints ²³. Apart from the dyes, SPR formulation utilizing activated charcoal ²⁴ and UV fluorescent Schiff's base, 2- (4-methylphenylimino) methylphenol (I) has been reported to develop fingerprints on water immersed surfaces. It is also concluded that schiff's base SPR is advantageous over dye based SPR due to its cost effectiveness and absence of heavy metals ¹.

2.2 Different Immersion Mediums used to assess the efficiency of SPR:

Table 2 illustrates immersion mediums selected by different researchers to soak the latent fingerprint for further development by SPR reagent. Researchers have used various conditions including clean, or dirty water, Normal and freezing water, Sea and lake water, water with various pH.

Table 2: Various immersion medium used to test the efficiency of SPR Reagent:

Authors	Immersion medium
Polimeni et al., (2004) ²⁶	Deionized water
McDonald et al., (2008) ²⁷	Acidic condition-Hydrogen chloride
Kabklang et al., (2009) ¹⁶	Tap water, Sodium hyroxide pH 8.0, Acetic acid pH 5.5, and Sodium chloride solutions at 10, 30, 50 and 70% (w/v)
Trapecar (2012a)¹⁸	Stagnant Cold water
Trapecar (2012b)¹⁹	Stagnant and cold drinking water
Castelló et al., (2013) ²⁸	Tap water
Sanjiv et al., (2014)	Clean and dirty water
Rohatgi et al., (2014) ²¹	Clean (tap water) and dirty water (stagnant water from pond)
Rohatgi and Kapoor (2015) ⁶	Clean water
Kapoor et al., (2015) ²²	Normal and freezing water
Dhall and Kapoor (2016) ¹¹	Drainage water
Madkour et al., (2017) ²⁹	Sea and lake water
Doibut and Benchawattananon, (2017)²³	Clean and Dirty water
Kaur et al., (2020) ²⁴	Basic, Acid and, Salty water

2.3 Comparison of SPR with other techniques for immersed latent prints:

Numbering in each row Table 3 indicates the comparison of the efficiency of the method wherein number 1 indicates the most efficient method found to develop water immersed fingerprints followed by number 2 and 3 assessed by respective researcher.

Marking cross (O) indicates the negative result.

2.4 Shelf life of SPR reagent:

Table 4 summarizes the composition of SPR, shelf life and maximum immersion time on water immersed surfaces by different researchers. The maximum immersion time for which the latent fingerprint can be developed as compared to other compositions studied is found to be 45 days⁶. Likewise, the maximum shelf life for which SPR Reagent remains vital to develop water immersed latent fingerprint as compared to other compositions is found to be 6 months²². Shelf life represents the maximum period for which the respective composition remains efficient to develop water-soaked latent fingerprints whereas immersion time indicates the maximum time for which the surfaces bearing latent fingerprints remain soaked in water and can be developed by the respective SPR composition.

Marking ‘-’ in Table 4 indicates that it is not determined by the respective researcher.

Table 4: Immersion time and shelf life of various SPR reagents

Authors	Composition	Immersion time	shelf life
*Polimeni et al.,* (2004)** ²⁶	SPR(Sirchie)	30 days	-
*Jasuja et al.,* (2007)** ¹⁵	Black charcoal/Zn carbonate basic, saponin	-	15 days
Jasuja et al., (2008) ¹⁰	SPR (Zinc carbonate, labolene) based on rhodamine 6G, rhodamine B, Cyano blue	96 hours	12 days
Kabklang et al., (2009) ²⁵	11 different SPR Formula that includes MoS2, Fe3O4, TiO2, ZnO and ZnCO3	30 minutes	-
Sodhi and Kaur (2010)	Basic zinc carbonate, eosin Y dye	36 hours	-
Trapecar (2012a)¹⁸	White and black SPR-100(MoS₂)	168 hours	-
Trapecar (2012b)¹⁹	White and black SPR-100(MoS₂)	1 week	-
Sodhi and Kaur (2012) ²⁰	basic zinc carbonate and crystal violet	36 hours	6 weeks
Castelló et al., (2013) ²⁸	Sirchie SPR DARK 1001	15 days	-
Sodhi and Kaur, (2014) ¹⁷	Basic zinc carbonate, eosin B dye	28hrs-aluminium foil/ 21hrs-lamination sheet	50 days
Sanjiv et al., (2014)	Basic Zn Carbonate, brilliant blur R dye, titanium dioxide, lycopodium gum rasin, Zn stearate	20 days-metal/ 15days- adhesive	7 weeks
Rohatgi et al., (2014)²¹	basic zinc carbonate, crystal violet dye	25days-clean water/ 10Days-Dirty water	50 days
Kapoor et al., (2015) ²²	Basic Zn Carbonate, fluorescent Rhodamine B dye, titanium dioxide, lycopodium, and gum rosin	96 hours	6 months
Rohatgi and Kapoor (2015) ⁶	Zn carbonate, Basic fuschin dye/crystal violet	45 days	50 days
Dhall and Kapoor (2016) ¹¹	Rose Bengal dye + titanium dioxide/ ZnO/ Zn carbonate	120 hrs	-
*Madkour et al.,* (2017)** ²⁹	SPR	10 days	-
Doibut and Benchawattananon, (2017)²³	Zinc carbonate mixed with natural dyes (curcumin and anthocyanin) and commercial liquid detergent	30 days to 10 days based upon dye and surface	5weeks
*Kaur et al., (2020)* ²⁴	SPR formulation using Activated Charcoal	12days-glass /11days-aluminium substrate	52 days
*Arora et al., (2021)* ¹	Schiff's base, 2- (4-methylphenylimino) methylphenol(I)	2 days	-

Table 5: Different surfaces used as a base for development of water immersed latent fingerprint

Surface	Glass	Glossy paper	Metal	Polythene	Tape	Plastic	Ceramic
Springer and Bergman (1995) ¹³	P	P	P	P
Wade DC, (2002)¹⁴					P
*Polimeni et al.,* (2004)** ²⁶	P		P			P
William and Elliott (2005)					P
*Jasuja et al.,* (2007)** ¹⁵	P	P	P	P		P
*Jasuja et al.,* (2008)** ¹⁰	P		P	P		P	P
Kabklanget al., (2009) ²⁵	P		P			P	P
Wood and James (2009) ³¹						P
Trapecar (2012a)¹⁸	P		P
Trapecar (2012b)¹⁹			P
Sodhi and Kaur (2012)²⁰	P		P	P		P	P
*Castellóet al.,* (2013)**²⁸	P					P
Sodhi and Kaur, (2014) ¹⁷			P P			P
Sanjiv et al., (2014)			P P		P
*Rohatgi et al.,* (2014)**²¹	P		P				P
*Kapoor et al.,* (2015)**²²	P		P		P	P	P
Joshi and Kesharwani (2015)³²	P		P			P
Rohatgi and Kapoor (2015)⁶	P		P
Dhall and Kapoor (2016)¹¹	P		P				P
*Madkour et al.,* (2017)**²⁹	P		P			P
Doibut and Benchawattananon, (2017)²³	P		P			P
*Kaur et al., (2020)*²⁴	P P		P
*Arora et al., (2021)*¹	P		P			P

2.6 Need for Green synthesis:

The utilization of SPR Reagents to develop water-soaked latent fingerprints has been extensively documented in the studies. At the same time, these reported composition of SPR reagents can lead to toxicities caused by long-term exposure to such hazardous chemicals. Such toxicity has been linked to a variety of detrimental impacts on humans⁴,^33,34.

In general, SPR reagent is prepared by adding base material to the diluted solution of surfactant with the addition of dyes. The base material of most of the SPR formulations is a heavy metal that is toxic in nature. However, due to the toxicity of its components, MoS₂ and TiO₂, proactive measures are required when handling SPR. Zinc carbonate is antibacterial and astringent. It does irritate the eyes. Such problem emerges only when the dry powder is utilized. It is exceedingly unlikely that it would form basis of eye damage when immersed in a non-volatile liquid such as water²³. Hence the use of Safety glasses is a mandate to prevent the chances of eye injury.^35–39

Likewise, various synthetic dyes have been added to provide contrast which is also toxic in nature (Table- 6). Crystal violet shows clastogenic activity that is too toxic for chromosomal breakage enumeration⁴⁰. Chromatid exchanges and chromosome type damage is found to be common with hazardous compounds, such as crystal violet, acridine orange, bright crystal blue, neutral red, and gentian violet. Also, rhodamine 6 G was found to be carcinogenic. The different dyes demonstrated a considerable increase in induced chromosomal damage .^41–43.

Table 6: Illustration of dye component of SPR reagent and their toxic effect on the human body

Dye	Toxic Effect
Crystal violet	Toxic, Clastogenic
Rhodamine B	Carcinogenic
Rose Bengal	Induced physiologic changes
Acridine orange	Carcinogen, mutagenic

Exploring green biotechnological research may be a viable trial in fingerprint assessment to prevent such damaging consumption while recognizing the requirement to visualize latent fingerprints. As a result, it is becoming increasingly important to investigate biotechnology pathways for greener and safer alternatives to create visualizing/developing reagents ⁴.

3. CONCLUSION:

Small Particle Reagent (SPR) is a versatile and effective method for enhancing latent fingerprints in different mediums that are present on various non-porous surfaces. Upon comparison with other fingerprint enhancement techniques, SPR has demonstrated comparable or superior results. Modification of SPR composition by adding suitable dyes elevated its applicability by developing fingerprints on multi-coloured surfaces.

Different water conditions/mediums like stagnant water, fresh, dirty, tap water, Different pH, humidity level, chlorine water, sea, lake, and other types have been taken into consideration for immersing the latent fingerprint that were taken on various non-porous surfaces (ceramic, glass, plastic, metal, tape, polyethylene, glossy paper, etc.) which was further assessed by developing through SPR method. The immersion time required for SPR can vary, and the shelf life depends on the specific formulation and storage conditions. The maximum immersion time after which fingerprints can be developed has been reported till date is of 45 days. The maximum Shelf life of SPR reagent is 6 months having the composition of fluorescent rhodamine B dye (SPR) formulation based on zinc carbonate hydroxide monohydrate. The mixture also comprises lycopodium, titanium dioxide, detergent, water, and gum rosin. Overall, SPR has been considered as the best technique to develop water-soaked later fingerprints except for a study wherein cyanoacrylate was concluded to be the best one to develop a latent fingerprint on metal and glass surface immersed in stagnant cold water as well as in saline water. More research is required to make this method environmentally friendly as the base material used for SPR formulation is based on heavy metals that show toxicity in nature^.43.

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Received on 17.10.2023 Modified on 15.01.2024

Research J. Pharm. and Tech 2024; 17(8):4110-4116.

DOI: 10.52711/0974-360X.2024.00637

Comparison of Techniques and dyes	SPR	Cyanoacrylate ester fuming	Black powder	Ninhydrin	Silver Special powder	Fluorescent powder	Sudan Black
Onstwedder and Gamboe (1989) ³⁰	1	2	3
*McDonald et al.,* (2008)** ²⁷	1
Trapecar (2012a)¹⁸	2	1			3
Trapecar (2012b)¹⁹	1	2	2
Castelló et al., (2013)²⁸	1		2		2		1
*Madkour et al.,* (2017)**²⁹	2	1