13 September 2016

Lecture # : CHEMICAL EXAMINATION OF URINE



1.      pH

One of the functions of the kidney is to help maintain acid–base balance in the body. To maintain a constant pH (hydrogen ion concentration) in the blood (about 7.40), the kidney must vary the pH of the urine to compensate for diet and products of metabolism. This regulation occurs in the distal portion of the nephron with the secretion of both hydrogen and ammonia ions into the filtrate, and the reabsorption of bicarbonate. If sufficient hydrogen ions (H+) are secreted into the tubule, all of the bicarbonate present will be reabsorbed, but if fewer H+ are secreted into the tubule, all of bicarbonate present will be reabsorbed, but if fewer H+ are secreted or if an excess of bicarbonate is present, some of the bicarbonate will be excreted in the urine. The continued secretion of H+ after all bicarbonate has been reabsorbed will drop the pH of the filtrate and result in acidic urine.

The secretion of H+ in the tubule is regulated by the amount present in the body. If there is an excess of acid in the body (acidosis), more H+ will be excreted and the urine will be acidic. When there is an excess base in the body (alkalosis), less H+ will be excreted and the urine will be alkaline. The hydrogen ions in the urine are excreted as either free H+, in association with a buffer such as phosphate, or bound to ammonia as ammonium ions. The pH of the urine is determined by the concentration of the free H+.

Because pH is the reciprocal of the hydrogen ion concentration, as the H+ concentration increases, the pH decreases or becomes more acidic. As the H+ concentration decreases, the pH increases or becomes more alkaline. The pH of the urine may range from 4.6 to 8.0 but averages around 6.0, it is usually slightly acidic. There is no abnormal range as such, since the urine can normally vary from acid to alkaline.

Method of determination

All brands of dipstick uses the same two indicators: methyl red and bromthymol blue, and measure a range of pH from 5.0 to 8.5.

Most manufacturers recommend that the pH be read immediately as this will prevent misreading due to “run–over” effect. This term is used to describe what happens when excess urine is left on the stick after dipping, and so the acid buffer from the reagent in the protein area runs onto the pH area. This type of contamination can cause a false lowering of the pH reading especially in the case of alkaline or neutral urine.

Recent advances have been made to prevent “run–over” by integrating a hydrophobic interpad surface which causes the urine to concentrate. Other brand of dipstick integrates nylon mesh on the test pad and underlying absorbent papers in place on the plastic strip. The mesh allows for even diffusion of the urine on the test pads, and the underlying paper absorbs excess urine to prevent “run over.”

2.      Protein

The presence of increased amounts of protein in the urine can be an important indicator of renal disease. It may be the first sign of a serious problem and may appear long before other clinical symptoms. There are, however, physiologic conditions such as exercise and fewer that can lead to increased protein excretion in the urine in the absence of renal disease. There are also some renal disorders in which proteinuria are absent.

In the normal kidney, only a small amount of low–molecular weight protein is filtered at the glomerulus. The structure of the glomerular membrane prevents the passage of high molecular weight proteins including albumin (MW = 69,000). After filtration, most of the protein is reabsorbed in the tubules with less than 150 mg/24 hour being excreted. In a child, the normal excretion is less than 100 mg/m2/24 hour. The protein that is normally excreted includes a mucoprotein called Tamm–Horsfall protein, which is not contained in the plasma but is secreted by the renal tubules.

Click here for discussion of Protein in Blood

Method of determination

a.      Screening Tests

This is based on the “protein error of indicators” principle or on the ability of protein to be precipitated by acid or heat. The dipsticks are more sensitive to albumin than to other proteins.

b.     Reagent Test Strips

This is also based on the concept of “protein error of indicators,” a phenomenon which means that the point of color change of some pH indicators is different in the presence of protein from that observed in the absence of protein, because protein act as hydrogen ion acceptors at a constant pH. Be guided also that reagent strips detect albumin primarily and are less sensitive to globulins.

Since the dipstick procedure is very sensitive to albumin, the protein that is primarily excreted as the result of glomerular damage or disease. Other urine proteins such as gamma globulins, glycoproteins, ribonuclease, lysozyme, hemoglobin, Tamm–Horsfall mucoprotein, and Bence–Jones protein are much less readily detected than albumin. Therefore, a negative urinary dipstick result does not necessarily rule out the presence of these proteins.

Tetrabromphenol blue, citric acid or sodium citrate is the active ingredient which is usually present on the dipstick for protein determination.

False positive result

(1)   Highly buffered alkaline urine. The alkaline pH can overcome the acid buffer in the reagent and the area may change color in the absence of protein.

(2)   If the dipstick is left in the urine for too long, the buffer will be washed out of the reagent, the pH will increase, and the strip will turn blue or green even if protein is not present.

(3)   Quaternary ammonium compounds used in cleaning urine containers will alter the pH and will result in false positive reaction.

(4)   Treatment with phenazopyridine and after infusion of polyvinylpyrrolidone as a plasma expander.

(5)   Chlorhexidine gluconate, found in skin cleansers

Common causes of proteinuria

(1)   Transient proteinuria is a temporary change in glomerular hemodynamics that causes increase in protein such in the case of congestive heart failure, dehydration, emotional stress, exercise or fever. Orthostatic (postural) proteinuria is a benign condition that can result from prolonged standing; it is confirmed by obtaining a negative urinalysis result after eight hours of recumbency.

(2)   Persistent proteinuria is divided into three categories:

(a)   In glomerular proteinuria, albumin is the primary urinary protein as in the case of Focal segmental glomerulonephritis, IgA nephropathy (Berger’s disease), IgM nephropathy, Membranoproliferative glomerulonephritis, and Membranous nepropathy.

(b)   Tubular proteinuria results when malfunctioning tubule cells no longer metabolize or reabsorb normally filtered protein. In this condition, low–molecular–weight proteins predominate over albumin and rarely exceed 2 grams per day as in the case of Alport’s syndrome, Amyloidosis, Collagen vascular disease, Diabetes Mellitus, Fabry’s disease, Sarcoidosis, and Sickle Cell Disease.

(c)    In overflow proteinuria, low–molecular–weight proteins overwhelm the ability of the tubules to reabsorb filtered proteins as in the case of Hemoglobinuria, Multiple myeloma or myoglobinuria.

3.      Glucose

The presence of significant amounts of glucose in the urine is called glycosuria (or glucosuria). The quantity of glucose that appears in the urine is dependent upon the blood glucose level, the rate of glomerular filtration, and the degree of tubular reabsorption. Usually, glucose will not be present in the urine until the blood level exceeds 160 – 180 mg/dL, which is the normal renal threshold for glucose. When the blood glucose exceeds the renal threshold, the tubules cannot reabsorb all of the filtered glucose, and so glycosuria occurs. Normally, this level is not exceeded even after the ingestion of a large quantity of carbohydrate. A small amount of glucose may be present in normal urine, but the fasting level in an adult is only about 2 – 20 mg of glucose per 100 mL of urine.

Method of determination

There are two basic types of test that used to screen or monitor glycosuria. The procedures that use the enzyme glucose oxidase are specific for glucose, while the copper reduction test will detect any reducing substances. The most important correlation that must be made with urine glucose is the blood glucose level.

Click here for full discussion on Blood glucose

False negative result:

a.      Reactivity for glucose can vary with temperature because of the effect of temperature on enzymatic reactions.

b.      An elevated specific gravity may decrease the sensitivity of glucose oxidase.

c.       Alkaline pH may decrease sensitivity to glucose.

d.     The combination of high specific gravity and alkaline pH may result in false negatives at low concentrations of glucose.

e.      High urinary concentrations of ascorbate can inhibit the enzymatic reaction which will result in a reduced or false negative reading. The ascorbic acid will be oxidized by the hydrogen peroxide in the second part of the enzyme reaction, and will, therefore, compete with the oxidation of the chromogen, resulting in the inhibition of the color formation.

Screening for reducing substances

Reducing substances are sugars other than glucose that can be found in urine as well such as galactose, lactose, fructose and maltose. Other reducing substances include dextrin, homogentisic acid and glucuronates.

A test for reducing substances is of particular importance for routine urinalysis of all pediatric patients. This will provide for the early detection of those metabolic defects which are characterized by the excretion of reducing sugars such as galactose, which is present in the urine of patients with galactosemia

a.      Benedict’s Test

This test is based on the fact that in strong alkaline solution and in the presence of heat, reducing sugars will reduce cupric ions to cuprous oxide. The reaction produces a color change of blue through green to orange depending upon the amount of reducing substances present in the urine.

Interfering factors for this procedure includes the presence of Nalidixic Acid, cephalosporins and probenecid.

            Obsolete method for test for glucose:

a.      Trommer’s Test – employs 10% NaOH and drops of CuSO4
b.      Fehling’s Test – employs a mixture of Rochelle salt and CuSO4
c.       Almen–Nylander Test – employs a mixture of Rochelle salt dissolved in NaOH and saturated with bismuth subnitrate. Black precipitate of metallic bismuth is a positive result.
d.     Neuman Test – employs 50% acetic acid saturated with sodium acetate and drops of phenylhydrazin. This will create crystals of phenylglucosazon and dissolved in 60% alcohol and allowed to recrystallize and melting point for glucose is determined at 205oC.

4.      Ketones

Ketone or ketone bodies are formed during catabolism of fatty acids. One of the intermediate products of fatty acid breakdown is acetyl CoA. Acetyl CoA enters the citric acid cycle (Krebs cycle) in the body if fat and carbohydrates degradation is appropriately balanced.

The ketone bodies are acetoacetic acid (diacetic acid), β– hydroxybutyric acid and acetone.

The odor of acetone may be detected in the breath of an individual who has high level of ketones in the blood because acetone is eliminated via the lungs.

Acetone is lost in the air if a sample is left standing at room temperature. Therefore, urines should be tested immediately or refrigerated in a closed container until testing.

Method of determination

Most reagent strips are embedded with sodium nitroprusside that reacts with acetoacetic acid to form glycine which forms a violet purple color in an alkaline pH.

Obsolete methods:

a.      Acetone

(1)   Legal’s Test – drops of concentrated sodium nitroprusside with potassium hydroxide is added to a urine sample.  

(2)   Gunning’s Test – Lugol’s iodine is added in urine sediment and observe microscopically for presence of six sided tablets or stars.

(3)   Lieben’s Test – drops of potassium hydroxide and Lugol’s iodine is added to urine sediment then warmed then observe for iodoform crystals.

(4)   Huppert–Messinger method

b.     Acetoactic acid

(1)   Gerhardt’s Test – urine is acidified with H2SO4 with ether and Fe2Cl6 is then added and there is formation of violet red color.

c.       β–hydroxybutyric acid

(1)   Black’s Qualitative Test – based on the oxidation of β–hydroxybutyric acid in the presence of ferric chloride.

(2)   Bergell method – urine is made weakly alkaline by addition of sodium carbonate until condensed. Phosphoric acid and copper sulfate is later added.

(3)   Bockelman and Bouma method – sodium hydroxide and benzoylchloride is added on the urine then polarized.

5.      Blood

The term “occult” means “hidden” and the methods used to test for blood in the urine are capable of detecting even minute amounts not visualized macroscopically. Another reason for this title is that these procedures actually detect the free hemoglobin from lysed red blood cells (RBCs).

The chemical method used in routine urinalysis for detecting blood (hematuria) will also detect free hemoglobin (hemoglobinuria) and myoglobin (myoglobinuria). The urine is normally free of all these substances; therefore, a positive test for occult blood should be followed by determination of the exact cause and origin of this abnormal finding.

a.      Hematuria is the presence of blood or intact RBCs in the urine. A urine that is highly alkaline or has a very low specific gravity (<1.007) can cause the red cells to lyse, thus releasing hemoglobin into the urine. The presence of this type of hemoglobin is still considered to be hematuria as far as the origin is concerned, but it is very difficult to distinguish from true hemoglobinuria. When lysing occurs, the microscopic examination may show the empty red cell membranes which are often referred to as “ghost” cells. In microhematuria, there is such a small amount of blood in the urine that the color of the specimen is unaffected and the hematuria can only be detected chemically or microscopically. On the other hand, gross hematuria alters the color of the urine and is easily visible macroscopically.

b.      Hemoglobinuria is the presence of free hemoglobin in the urine as a result of intravascular hemolysis. The hemolysis that occurs in the urine while in the urinary tract or after voiding because of a low specific gravity or highly alkaline pH may be considered to be hemoglobinuria, but it does not bear the same significance as true hemoglobinuria. Hemoglobinuria without hematuria occurs as a result of hemoglobinemia and, therefore, it has primarily nothing to do with kidneys even though it may secondarily result in kidney damage.

Click here for full discussion on Paroxysmal Cold Hemoglobinuria

c.       Myoglobin is the heme protein of striated muscle. It serves as a reserve supply of oxygen and also facilitates the movement of oxygen within muscle. Injury to cardiac or skeletal muscle results in the release of myoglobin into the circulation. Even just subtle injury to the muscle cells can bring about the release of myoglobin. Myoglobin has a molecular weight of approximately 17,000 and it is easily filtered through the glomerulus and excreted in the urine. Because myoglobin is cleared so rapidly from the circulation, the plasma is left uncolored even though the urine may be red to brown to black depending on the degree of myoglobinuria.

Method of determination

a.      The dipstick procedure is based on the peroxidase–like activity of hemoglobin and myoglobin which catalyzes the oxidation of a chromogen by organic peroxide.

b.      The usual chromogen and oxidant used are: diisoproplbenzene, dihydroperoxide, tetramethylbenzidine and cumene hydroperoxide.

6.      Bilirubin and Urobilinogen

Urine normally does not contain detectable amounts of bilirubin. Unconjugated bilirubin is water insoluble and cannot pass through the glomerulus; conjugated bilirubin is water soluble and indicated further evaluation for liver dysfunction and biliary obstruction when it is detected in the urine.

Normal urine contains only small amounts of urobilinogen, the end product of unconjugated bilirubin after it passed through the bile ducts and been metabolized in the intestine. Urobilinogen is reabsorbed into the portal circulation, and a small amount eventually is filtered by the glomerulus. Hemolysis and hepatocellular disease can elevate urobilinogen levels, and antibiotic use and bile duct obstruction can decrease urobilinogen levels.  

Click here for full discussion on Bilirubin

Method of determination

a.      The active ingredient in majority of dipstick that is being used in laboratory is the dichloroanaline diazonium salt for bilirubin and p– diethylaminobenzaldehyde  or 4–methloxybenzene–diazonium– tetrafluoroborate for urobilinogen.

b.      Ictotest is a tablet test that is based on the same diazo reaction as the dipsticks. However, Ictotest is much more sensitive than the dipsticks, being able to detect as little as 0.05 mg/dL. Because of this sensitivity, Ictotest is the recommended procedure when a test for just bilirubin is ordered. It also serves as a good confirmatory test for a positive dipstick.

The tablet contains 2,6–dicholorobenzene–diazonium–tetrafluroborate, sulfosalicylic acid and sodium bicarbonate. The mats that are used in the procedure are made of an asbestos–cellulose mixture. When the urine is placed on the mat, the absorbent qualities of the mat cause the bilirubin to remain on the outer surface. The sulfosalicylic acid provides the acid environment for the reaction. It also acts with the sodium bicarbonate to provide an effervescence which helps partially dissolve the tablet. The diazonium salt then couples with the bilirubin on the mat, giving a blue or purple reaction product.

Urine from patients receiving large doses of chlorpromazine may give false– positive reactions. If the urine is suspected of containing a large amount of chlorpromazine, the washthrough technique can be used where duplicate mats are prepared with 5 drops of urine each.

c.       Foam Test

If the urine is a yellowish–brown or greenish–yellow color and bilirubin is suspected, shake the urine. If yellow or greenish–yellow foam develops, then bilirubin is most likely present. Bilirubin alters the surface tension of urine and will develop after shaking. The yellow color is from the bilirubin pigment. A false–positive foam test occurs when the urine contains phenazopyridine.

7.      Nitrite

Nitrites normally are not found in urine but result when bacteria reduce urinary nitrates to nitrites. Many gram negative and some gram positive organisms are capable of this conversion, and a positive dipstick nitrite test indicates that these organisms are present in significant numbers (i.e., more than 10,000 per mL). This test is specific but not highly sensitive. Thus, a positive result is helpful, but a negative result does not rule out UTI. The nitrite dipstick reagent is sensitive to air exposure, so containers should be closed immediately after removing a strip. After one week exposure, one third of strips give false–positive results. Non– nitrate–reducing organisms also may cause false–negative results and patients who consume a low–nitrate diet may have false–negative results.

Method of determination

Reagent strips for the detection of nitrite in the urine commonly used p–arsanilic acid a quinolone compound. Nitrite reacts with p–arsanilic acid to form a diazonium compound. This compound then couples with the quinoloine compound to produce a pink color.

8.      Leukocyte esterase

White blood cells can be present in any body fluid depending on a cause for their presence. The most common white blood cell seen in a urine sample is the neutrophil, which is normally present in low numbers. Increased numbers of neutrophils usually indicate the presence of a urinary tract infection; and their presence is indicated by a positive leukocyte esterase test.

Method of determination

Neutrophils contain enzymes known as esterases. These esterases can be detected by reagent strips that contain an appropriate substrate such as indoxycarbonic acid ester.






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