ASH

The students will be able to: Define ash and examples of ash. State various methods for ash determinations Describe the principles for ash determinations. Analyse and evaluate the compositions of food products. To calculate the ash content in food

Definition
ASH

Inorganic residue remaining after ignition or complete oxidation of organic matter in a foodstuff.

Three major types of ashing:

Dry ashing majority samples Wet ashing/oxidation high fat samples; preparation step for elemental analysis. Plasma ashing preparation for volatile elemental analysis

Importance of Ash Analysis

Indicator of nutritional value for some food/feeds especially for exporting goods. Eg: Mineral content for bran 20 times than in endosperm, indicates thoroughness separation of bran and germ from wheat kernel. Indicator for adulteration of some juices and beverages. Eg: Able to distinguishes fruit vinegar from synthetic vinegar.

Index of fruit content for jellies and fruit preserves. Eg: In fruit jellies and marmalades, ash content used to estimate fruit content in product.

Ash content represents total mineral in foods. Part of proximate analysis for nutritional evaluation. Ashing is the first step in sample preparation for specific elemental analysis.

Minerals composed ash are: i) Calcium- high concentration in most dairy and dairy containing products, cereals, nut, egg, fish and certain vegetables. ii) Phosphorus- dairy products, grains, nut, meat, fish, poultry, eggs and legumes. iii) Iron- grains and grain products, eggs, legumes, seafood, poultry.

iv) Sodium- poultry, meat, fruits, cereals, fish, egg and others.

v) magnesium- nut, cereal and legumes.

vi) sulfur- in protein rich foods and vegetables. Others are potassium, zinc, copper, cobalt.

Ash Contents in Foods

Food
Milk and dairy products Meat, poultry and fish Fruits and vegetables Cereals Fats and oils

% Ash
0.5 5.1 0.8 3.0 0.3 2.3 0.4 1.7 0.0 4.0

Nuts

0.8 3.4

Sample Preparation
i) Most dry samples (eg. whole grain, cereals, dried vegetables) does not require preparation. ii) Fresh vegetables need to be dried prior to ashing. Plant materials pre-dried first then ground. If moisture <15% prior drying is not required. Fresh stem and leaf tissue should be dried in 2 stages : at low T of 55oC then at higher T to prevent artifact lignin.

continue
iii)High fat products, syrups and spices require treatments prior to ashing, where samples need to be dried on a steam bath and fat extracted before ashing. This is because high fat and moisture may cause spattering, swelling or foaming that may result in sample loss. Therefore cause underestimation of ash content.

iv) Solid foods must be finely ground but may add mineral contents from the grinders steel construction. Not suitable in analysis of specific mineral analysis.

Crucible Selection

Quartz : resistant to acids and halogens but not alkali at high temperatures. Vycor brand glass : stable up to 900oC, resistant to most chemicals and acid except bases. Porcelain : resemble quartz properties. Usual choice, withstand 1200oC, easy to clean, cheap, susceptible to alkali, but will crack with rapid T changes. Relatively inexpensive. Steel : resistant to both acids and alkali, inexpensive, but possible sources of contamination (composed of chromium and nickel). Platinum : very inert, the best crucibles but very expensive for routine use. Recommended procedures of AOAC, for cereal, dairy, meat and fish products.

DRY ASHING

Principle Incineration at high temperatures (500oC or higher) water and volatile materials are vaporized and organic substances burned in presence of O2 in air, producing CO2, H2O and N2. Most minerals converted to oxides, sulfates, phosphate, chloride and silicates. Crucibles are pre-dried and weighed before ashing and cooled to room temperature after ashing before weighing. % Ash (wet basis) = M ash x 100 M wet

Advantages

Safe method. Most common procedure to determine total mineral content of foods. Requires no reagents. Resultant ash can be used for other analyses e.g. water-soluble, water-insoluble, and acid-insoluble ash. Applicable also in determination of most common metals. Requires little attention and simple. Large numbers of samples can be handled at once. No blank subtraction required.

Disadvantages

Time consuming (12-18hrs or overnight). Loss of volatile minerals at high temperatures (e.g. Cu, Fe, Pb, Hg, Ni, Zn, As, Cd, Cr). Interaction between mineral components and crucibles.

II. Wet Ashing / Oxidation

Use for samples with high fat content (meats and meat products), for determining trace elements and metallic poisons. Procedure involves oxidizing organic substances using acids and oxidizing agents (eg nitric acid with either perchloric and/or sulfuric acids) and heated to about 350oC. Minerals are solubilized without volatilization. Rapid decomposition of many organic compounds that difficult to oxidize. Adding salt (e.g. potassium sulfate) raises the boiling point of the acid and accelerates decomposition.

Principle
Oxidation of organic substances by strong acid, nitric acid (HNO3) and oxidizing agents perchloric acid (HCIO4). Heat slowly up to 350oC until organic matter completely digested and HNO3 evaporated. Boiling continues until sample becomes colourless or light in colour. Cool, add HCl then dilute with distilled deionized water. Pre-dry sample then incinerate at 525oC for 1-2hrs.

Advantages
Use low temperature therefore little or no loss from volatilization. Short oxidation time.

Disadvantages

Very hazardous. Requires a hood, hot plate, long tongs, and safety equipment. Require large amounts of corrosive reagents and correction for reagents. Small numbers of samples can be handled at one time. Need constant operator's attention. Single acid does not give complete and rapid oxidation of organic compounds. Nitric acid with sulfuric or perchloric acids and potassium chlorate or sulfate are used in varying combination. Special perchloric acid hood required (with wash-down capabilities to protect from explosion).

III. Plasma Ashing

Use for preparation of samples when volatile elemental analyses are determined. Plasma process is accomplished through the use of low pressure and radio frequency to induced gaseous discharge.

Principle

A sample is placed into a glass chamber which is evacuated using a vacuum pump A small amount of oxygen is pumped into the chamber and broken down to nascent oxygen by application of an electromagnetic radio frequency field The organic matter in the sample is rapidly oxidized by the nascent oxygen and the moisture is evaporated because of the elevated temperatures

Advantages & Disadvantages

Minimal chances of trace elements volatilization compared to classical dry ashing Equipment of choice for volatile salts analysis. Low temperatures used (<150oC) allows microscopic and crystalline structures to remain unaltered. No toxic chemicals employed.

Small sample capacity. High expense of the equipment

IV. Soluble & Insoluble Ash in Water

These measurements are an index of the fruit content of preserves and jellies. A lower ash in the water-soluble fraction is an indication that extra fruit is added to fruit and sugar products.

Procedure
Weigh total ash obtained and add the water Heat near to boiling, filter on ashless filter paper Rinse with hot water several times. Dry and re-ash filter paper for 30mins.

Weigh and calculate as % H2O-insoluble ash.

Calculate soluble ash by subtracting insoluble ash from total ash or dry the filtrate, re-ash and weigh

V. Ash Insoluble in Acid

Measure surface contamination of fruits and vegetables, wheat and rice coatings such as dirt or sand. E.g. surface contamination of fruits and vegetables, wheat washing prior to milling and rice coatings. These contaminants are silicates that remain insoluble in acid.

Procedure:

Add HCl 10% to total ash or H2O-insoluble ash. Boil for 5mins then filter on ashless filter paper and wash several times with hot water Re-ash filter paper and residue for 30mins. Weigh and calculate as a percentage (%).

Alkalinity of Ash

Useful measurement to determine the acidbase balance of foods and quality index of fruits and fruit juices.

Ash from fruits and vegetables is alkaline (Ca, Mg, K, Na). Ash from meat and some cereals is acid (P, S, Cl).

Procedures:

Place ash (total or H2O-insoluble ash) in platinum dish.

Add 0.1N HCl and warm on a steam bath.

Cool and transfer to Erlenmeyer flask. Titrate the excess HCl with 0.1N NaOH using methyl orange as indicator.

Summary

Ashing conducted by any one of 3 methodologies - dry ashing, wet ashing/oxidation and plasma ashing. Dry ashing based on incineration at high temperature in muffle furnace. Wet ashing uses corrosive reagents that require constants operator's attention. Dry ashing result in lost of volatile elements. Wet ashing and plasma ashing cause minimal volatilization. Wet ashing and low temperature plasma ashing are expensive; require operator time and limited to small number of samples. 3 post-ashing procedures (soluble and insoluble ash in water, ash insoluble in acid and ash alkalinity) are special measurements for certain foods.