Forensics

Forensics is a Division C chemistry event that involves identification of powders, polymers, fibers, and hair samples, blood serum and fingerprint analysis, and interpretation of chromatography. Given a scenario and some possible suspects, students will perform a series of tests. These tests, along with other evidence or test results, will be used to solve a crime.

The competition will involve using pre-brought materials to analyze data. The participants may also bring one Note Sheet. This event is closely associated with the Division B event, Crime Busters.

Topics Covered

 * Qualitative Analysis (powders)
 * Polymers
 * Chromatography/Spectroscopy
 * Fingerprint Analysis
 * DNA
 * Glass Analysis
 * Entomology
 * Spatters
 * Seeds and Pollen
 * Tracks and Soil
 * Blood
 * Bullet Striations

Qualitative Analysis
Qualitative Analysis is the section of the test that involves the identification of unknown powders. The number of powders given can be within the given ranges based upon the level of competition. 3-8 powders will be given at the regional level, 6-10 samples will be given at the state level, and 8-12 powders will be given at the national level competition.

It is helpful to include a flowchart to aid with powders identification on your cheat sheet.

There are fifteen different substances that may be given in a test. These are sodium acetate, sodium chloride, sodium hydrogen carbonate (sodium bicarbonate), sodium carbonate, lithium chloride, potassium chloride, calcium nitrate, calcium sulfate, calcium carbonate, cornstarch, glucose, sucrose, magnesium sulfate, boric acid, and ammonium chloride. Utilizing all availible means of identification will give the best results and help draw a more accurate conclusion.

Methods of Identification
Flame test: The flame test uses a Bunsen burner and a nichrome wire. To perform this test, dip a clean nichrome wire in distilled water, and then dip the loop of the wire into a small sample of the dry chemical. Hold the loop of the wire in the cone of the flame, and observe the color of the burning chemical. If desired, a piece of cobalt blue glass may be used for viewing. Chemical cations determine the color of the flame, and their characteristics may indicate the chemical identity. Note that sodium can easily contaminate some substances, and its presence can mask the other cation colors, giving off a yellow flame. The purpose of the cobalt blue glass is to block of the yellow color given off by sodium in case the sample may have been contaminated. In some cases, this yellow color can appear a little orangish.
 * Sodium: yellow flame, very distinct. Even a small amount of sodium will contaminate other compounds.
 * Lithium: carmine or red flame
 * Calcium: yellow-red flame
 * Boric Acid: bright green flame, very visable
 * Ammonium Chloride: faint green flame
 * Potassium: light purple, lavender flame

Tests with liquids: Liquids used for identification are iodine, sodium hydroxide, hydrochloric acid, Benedict's solution, and water. Not all liquids are applicable to all samples.
 * Iodine: When iodine is added to cornstarch, the sample will turn black. If cornstarch is not present, the iodine will remain brown.
 * Sodium Hydroxide: Sodium hydroxide is used simply to categorize your samples into two fields: NaOH reactive- and non-reactive. For this reason, it is extremely useful when using a flowchart.  To perform this test, a few drops of NaOH is added to a small sample of chemical dissolved in water.  If a milky-white precipitate forms, the sample is NaOH reactive.  If a precipitate does not form, the sample is NaOH non-reactive.
 * Hydrochloric Acid: Hydrochloric acid will react when added to samples contaning carbonates--therefore, it is useful in identifying calcium carbonate, sodium carbonate, and sodium hydrogen carbonate.
 * Benedict's solution: Benedict's solution is used to detect glucose. To perform this test, dissolve a small sample of chemical in water in a test tube.  Add two to three drops of Benedict's solution, then place the test tube in a hot water bath.  If the glucose is present, the sample will react and form an orange precipitate.  This test may take a few minutes; be patient.
 * Water: Water is used for determining the solubility of chemical samples, and is used for making solutions.

pH: The pH data for chemicals can be useful, especially for determining between two similar chemicals. Most samples have a pH of between 5 and 7, but two are distinct: sodium carbonate has a pH of 12, while sodium bicarbonate has a pH of around 10.

Conductivity: Certain chemical samples will dissociate and become conductive when dissolved in water. To perform this test, dissolve a small sample of dry chemical in water. Using a 9-volt conductivity tester will determine whether a sample is conductive or semi-conductive. This data is especially helpful when following a flowchart.

Solubility: All samples can be divided into two fields--soluble and non-soluble. Water is used to perform this test.
 * Soluble Samples: sodium acetate, sodium chloride, sodium hydrogen carbonate, sodium carbonate, lithium chloride, potassium chloride, calcium nitrate, glucose, sucrose, magnesium sulfate, boric acid, ammonium chloride
 * Non-soluble Samples: calcium sulfate, calcium carbonate, cornstarch

Polymers
Methods of Identification
 * Burn test--fibers and hair only
 * Density in liquids--oil, water, alcohol, etc.--plastics
 * Microscope--useful for distinguishing different hairs and fibers

Hints Burn tests for fibers, when permitted, will usually be done with a small candle (Bunsen burners are too hot). Burn tests on plastics will not be permitted at the event, but burn test results may be provided. If not, it is important to know densities and other identifying properties. Common liquids used to test plastic densities include water, vegetable oil, isopropyl alcohol, and NaCl solution (10%, 25%, and saturated).

Plastics
Just to clarify how LDPE differs from HDPE ...



(Lines represent the connected ethylene monomer units)

Fibers
There are three types of fibers: animal, vegetable, and synthetic/man-made. Each of these types of fibers behave differently in different tests, but generally fibers of the same type will react in a similar way.

Burn Test

 * Animal fibers shrivel, but don't melt
 * Synthetic fibers melt and shrivel, and loose ends fuse together
 * Vegetable fibers do not melt or shrivel, but they ignite easily and usually appear charred after being burned.

Other Useful Facts

 * Animal fibers dissolve in bleach, but the other types will not react at all (nice to know although the bleach test isn't available during competition)
 * Smoother fibers are more likely to be synthetic
 * Synthetic fibers are generally uniform in thickness whereas natural fibers vary.

Individual Fiber Information
Wool (Animal)
 * most commonly used animal fiber
 * burn test: shrivels, leaves brown-black residue, smells like burning hair
 * looks like cylinder with scales under the microscope

Silk (Animal)
 * SMOOTHER THAN WOOL
 * burn test: shrivels, leaves black residue, smells like burning hair
 * looks like a thin, long and smooth cylinder under the microscope

Cotton (Vegetable)
 * most widely used plant fiber
 * rather short fibers
 * burn test: burns with a steady flame, smells like burning paper, able to blow flame from thread like a match, leaves behind a charred, whitish ash
 * looks like an irregular twisted ribbon under the microscope

Linen (Vegetable)
 * fibers generally longer and smoother than cotton
 * burn test: burns at a constant rate, does not produce smoke, smells like burning grass, produces sparks
 * looks like bamboo under a microscope

Polyester (Synthetic)
 * fibers can be any length
 * burn test: melts, only ignites when brought into the flame, drips when it burns and bonds quickly to any surface it drips on, produces sweet odor and hard, colored ash (color according to the color of the fiber itself)
 * looks like a completely smooth cylinder under microscope

Nylon (Synthetic)
 * long fibers
 * burn test: curls, melts, produces black residue, smells like burning plastic (some sources say it smells like celery?), ignites only when brought into flame
 * looks kind of like bamboo under microscope

Spandex (Synthetic)
 * can stretch to eight times its original length
 * burn test: melts quickly

Chromatography
There are two types of chromatography, which are paper chromatography and TLC (thin layer chromatography). Paper chromatography is just paper, and TLC is a glass slide with a thin silicone layer, but they both do the same thing, and you can set both up using the same process. There are plenty of youtube videos out there that can show how to set it up.

There is also ink chromatography and juice chromatography. Likewise, both are set up the same way, but with juice chromatograms, the sample must be applied to the paper or TLC slide by another instrument.

Most competitions ask for Rf calculations. Rf is retention factor or rate of flow.

Formula: $$Rf=\frac{p}{s}$$, where p is the distance the pigment (the ink or juice) travels and s is the distance the solvent (usually water or alcohol) travels.

Mass Spectrometry
Mass spectrometry is an analytical method used to determine the mass to charge ratio of charged particles. (Sample mass spec graph of dodecane)

A few things to note about said graph: -The y-axis is a measure of the percent abundance -The x-axis is the m/z ratio (molar mass) -The lines are known as peaks

Reading graphs of mass spec (aka everyone's least favorite part of Forensics):

1) Search for a molecular ion peak first. It may not always be present, but commonly is the largest peak, except for isotopic peaks. The Nominal Molecular Weight (MW) is a rounded value assigned to the molecule representing the closest whole number to the molecular weight. This value is even if the compound being analyzed contains simply Carbon, Hydrogen, Oxygen, Sulfer, or Silicon. The value will be odd if any of these elements are combined with an odd number of Nitrogen.

2) Attempt to calculate the chemical formula, using isotopic peaks and using this order: Look for A+2 elements: O, Si, S, Cl, Br; Look for A+1 elements:  C, N; And then: "A" elements:  H, F, P, I. From looking at the isotopic peaks, it is possible to determine relative abundance of specific elements.

3) Calculate the total number of rings plus double bonds: For the molecular formula: CxHyNzOn rings + double bonds = x - (1/2)y + (1/2)z + 1

4) Try to determine the molecular structure based upon abundance or isotopes and m/z of fragments.

Fingerprints
Fingerprints are formed by the arrangement of volmer (or volmar) pads. They are made mostly of sweat and water but can also contain various organic and nonorganic compounds.

Patterns
There are eight fingerprint patterns to know. They are:
 * Plain Whorl
 * Ulnar Loop
 * Radial Loop
 * Plain Arch
 * Tented Arch
 * Central Pocket Loop
 * Double Loop
 * Accidental Whorl



Whorls have two or more deltas. The presence of more than two deltas indicates an accidental whorl.

Loops have only one delta. The difference between an ulnar loop and a radial loop is that ulnar loops "enter and exit" on the side facing the pinky (the side of the wrist containing the ulna) while radial loops do so on the side facing the thumb (the side of the wrist containing the radius).

Arches have no deltas. Tented arches are easily distinguishable by the triangular core.

Types of Prints
Fingerprints can be in different forms when found.


 * Visible: As the name suggests, these ones can easily be seen because they were made with a substance like ink or blood. They can also easily be photographed without development.


 * Impression: Made in soft material such as clay. Less easy to detect than visible fingerprints, but can still be photographed without development.


 * Latent: Invisible fingerprints. These must be developed before photographed.

Methods of Development
Latent prints must be developed in order to be seen. The four methods of fingerprint development are:


 * Dusting: Powder applied to prints sticks to fatty acids and lipids.
 * Iodine Fuming: Self-explanatory by its name. It was one of the earliest methods of fingerprint development. The iodine reacts with body fats and oils in prints.
 * Ninhydrin: a chemical method useful for lifting latent prints on paper. It reacts with amino acids in prints.
 * Cyanoacrylate (Superglue) Fuming: Also self-explanatory by its name. It also reacts with moisture in the air as well as reacting with substances in the prints, forming sticky white material along ridges. Good for nonporous surfaces.

DNA
Although many competitions that have include DNA as evidence require matching of DNA fingerprints, questions about basic DNA physiology and principles come up along with them. PCR (Polymerase Chain Reaction), a method of synthetic DNA replication, also comes up sometimes.

Ground Facts You Should Know

 * DNA stands for deoxyribonucleic acid (yes, sometimes they ask this)
 * The four nucleotides that compose DNA are adenine, cytosine, thymine, and guanine.
 * With a DNA fingerprint, larger fragments of DNA are located on the right side while smaller ones are located on the left.
 * This is because of gel electrophoresis, which make the fingerprints. When the current runs through the gel during this process, because DNA is negatively charged, it will move towards the positive end of the box. Smaller fragments of DNA will obviously move farther through the gel filter than larger ones.

PCR
PCR, as already stated, stands for Polymerase Chain Reaction; it is a method of synthetic DNA replication developed in the late 20th century. PCR has been very crucial to molecular biology and forensics, then and now, so its development earned a Nobel Prize.



The Rule to Remember!
If the glass's refractive index is the same or close to that of a liquid, then the piece of glass will not be visible in that liquid (use exact same liquids that are used for plastics)

Other Facts about Cracks:

 * Cracks end at existing cracks
 * A small force forms circular cracks
 * Radial cracks and chonchoidal cracks make right angles, but face different ways
 * A force very close to the glass before impact will completely shatter the glass

Entomology
Stages of insects found on a dead body can tell how long the victim has been dead. The most common are the blowfly and the beetle. Blowflies appear first, within minutes of death. Beetles usually arrive after the blowflies. Certain amounts of time lapse between each life stage, which can tell this time. For example, if maggots were found on the dead body, that means the victim probably died less than twenty-four hours ago.



Blood Spatters
Blood Spatters are generally classified by velocity at which they form.

Angle of Impact: The angle at which a spatter hits a surface. The formula for it is:

θ=arcsin(W/L)

Where theta (θ) is the angle, W is the width of the spatter, and L is the length.

Note that arcsin is also known as inverse sine.

Bullet Striations
Bullet striations are pretty much just like tracks. Pretty much the only thing you have to do is try to match the one of the suspects' bullet striation to that of the one found at the scene.

Links

 * 2005 Qualitative Analysis Hints
 * Science Olympiad Official Resources for Forensics
 * Good site for paper chromatography
 * Mass Spectrometry