Electrolytes

Chapter KEY TERMS

Anion
Anion Gap
Cation
Active transport
Diffusion
Electrolyte
Osmolality
Osmolality
Polydipsia
Tetany
ADH
Hypothalamus Gland
Renin - Angiotensin Aldosterone System

Hyper / Hypo natremia ,

kalemia, calcemia
Parathyroid Hormone ( PTH )
Acidosis / Alkalosis
Calcitonin
Ion Selective Electrode

Na
K
Cl
CO2
Ca
Mg
PO4

= Sodium
= Potassium
= Chloride
= Carbon Dioxide
= Calcium
= Magnesium
= Phosphate

Electrolytes
Electrolytes
Substances whose molecules dissociate into ions
when they are placed in water.
ANIONS (-)
CATIONS (+)
Medically significant / routinely ordered electrolytes
include:
sodium (Na)
potassium (K)
chloride (Cl)
and CO2 (in its ion form = HCO3- )

Electrolyte Functions

Volume and osmotic regulation

Myocardial rhythm and contractility
Cofactors in enzyme activation
Regulation of ATPase ion pumps
Acid-base balance
Blood coagulation
Neuromuscular excitability
Production of ATP from glucose

Electrolytes
General dietary requirements

Most need to be consumed only in small

amounts as utilized
Excessive intake leads to increased
excretion via kidneys
Excessive loss may result in need for
corrective therapy

loss due to vomiting / diarrhea; therapy

required - IV replacement, Pedialyte, etc.

Electrolytes
Water (the diluent for all
electrolytes) constitutes
40-70% of total body and
is distributed:
Intracellular inside cells
2/3 of body water
(ICW)
Extracellular outside cells

1/3 of body water

Intravascular plasma 93%
water
Intrastitial -surrounds the
cells in tissue (ISF)

Electrolytes

Electrolytes
Ions exist in all of these fluids, but the
concentration varies depending on individual
ion and compartment
The body uses active and passive transport
principles to keep water and ion concentration
in place

Electrolytes
Sodium has a pulling effect on water

Na affects extracellular fluids (plasma &

interstitial) equally.
However, because there is considerably more Na
outside cells than inside, the water is pulled out
of cells into the extracellular fluid.
Na determines osmotic pressure of extracellular
fluid.

Electrolytes
Proteins (especially albumin) inside the
capillaries strongly pulls/keeps water inside
the vascular system
Albumin provides oncotic pressure.
By keeping Na & albumin in their place, the
body is able to regulate its hydration.

When there is a disturbance in osmolality,

the body responds by regulating water intake,

not by changing electrolyte balance

10

Electrolytes
Laboratory assessment of body
hydration is often by determination
of osmolality and specific gravity of
urine

11

Electrolytes
Osmolality Physical property of a solution based
on solute concentration
Water concentration is regulated by
thirst and urine output
Thirst and urine production are
regulated by plasma osmolality

12

Electrolytes
Osmolality osmolality stimulates two responses that
regulate water
Hypothalamus stimulates the sensation of
thirst
Posterior pituitary secrets ADH
( ADH increases H2O re-absorption by renal
collection ducts )

In both cases, plasma water increases

13

Electrolytes
Osmolality

concentration of solute / kg
reported as mOsm / kg

another term:
Osmolarity - mOsm / L - not often
used

14

Electrolytes
Determination
2 methods or principles to determine
osmolality
Freezing point depression
(the preferred method)

Vapor pressure depression

Also called dewpoint

15

Specimen Collection
Serum
Urine
Plasma not recommended due to
osmotically active substances that can be
introduced into sample
Samples should be free of particulate
matter..no turbid samples, must centrifuge

16

Electrolytes
Calculated osmolality

uses glucose, BUN, & Na values

(Plasma Sodium accounts for 90 % of plasma osmolality)

Formula:

1.86 (Na) + glucose18 + BUN2.8 = calculated osmolality

Osmolal gap = difference between calculated and

determined osmolatity
Should be less than 10-15 units difference
(measured calculated = 10 to 15)

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Electrolytes
Increase in the difference between
measured and calculated

would indicate presence of osmo active

substances such as possibly alcohol - ethanol,
methanol, or ethylene glycol or other substance.

Osmolality are concerns for

Infants
Unconscious patients
Elderly

18

Electrolytes
Decreased osmolality
Diabetes insipidus
ADH deficiency
Because they have little / no water reabsorption, produce 10 20 liters of urine
per day

19

Electrolytes
Osmolality normal values

Serum 275-295 mOsm/Kgm

24 hour urine 300-900 mOsm/Kgm
urine/serum ratio 1.0-3.0
Osmolal gap < 10-15 mOsm (depending on
author)

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Electrolytes
Classifications of ions -

by their charge

Cations have a positive charge - in an

electrical field, (move toward the cathode)
Na+ = most abundant extracellular cation
K+ = most abundant intracellular cation

21

Electrolytes
Anions have a negative charge - move
toward the anode

Cl (1st) most abundant extracellular anion

HCO3 (bicarbonate) second most
abundant extracellular anion

22

Electrolytes
Phosphate is sometimes discussed as
an electrolyte, sometimes as a
mineral.
HPO-24 / H2PO-4
when body pH is normal, HPO-24 is the
usual form (@ 80 % of time)

23

Electrolyte Summary
cations (+)

Na 142
K
5
Ca
5
Mg
2
154 mEq/L

anions (-)

Cl 105
HCO324
HPO4-2
2
SO4-2
1
organic acids 6
proteins
16

154 mEq/L

24

Routinely measured electrolytes

Sodium
the major cation of extracellular fluid outside
cells
Most abundant (90 %) extracellular cation
Functions - recall influence on regulation of
body water

Osmotic activity - sodium determines osmotic activity

(Main contributor to plasma osmolality)
Neuromuscular excitability - extremes in concentration
can result in neuromuscular symptoms

25

Routinely measured electrolytes

Diet - sodium is easily absorbed
Na-K

ATP-ase Pump

pumps Na out and K into cells

Without this active transport pump, the

cells would fill with Na and subsequent
osmotic pressure would rupture the cells

26

Regulation of Sodium
Concentration depends on:
intake of water in response to thirst
excretion of water due to blood volume or osmolality changes
Renal regulation of sodium
Kidneys can conserve or excrete Na+ depending on ECF and
blood volume
by aldosterone
and the renin-angiotensin system
this system will stimulate the adrenal cortex to
secrete aldosterone.

27

Sodium (Na)
Aldosterone
From the (adrenal cortex)
Functions

promote excretion of K
in exchange for reabsorption of Na

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Sodium (Na)
Sodium normal values
Serum 135-148 mEq/L
Urine (24 hour collection) 40-220
mEq/L

29

Sodium (Na)
Urine testing & calculation:

1st. Because levels are often increased, a

dilution of the urine specimen is usually
required.
Then the result from the instrument (mEq/L or
mmol/L) X # L in 24 hr.

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Clinical Features: Sodium

Hyponatremia: < 135 mmol/L
Increased Na+ loss
Aldosterone deficiency

Addisons disease (hypo-adrenalism, result in aldosterone)

Diabetes mellitus
In acidosis of diabetes, Na is excreted with
ketones
Potassium depletion
K normally excreted , if none, then Na
Loss of gastric contents

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Hyponatremia
Increased water retention
Dilution of serum/plasma Na+
excretion of > 20 mmol /mEq urine sodium)
Renal failure
Nephrotic syndrome
Water imbalance
Excess water intake
Chronic condition

32

Hypernatremia
Excess water loss resulting in dehydration
(relative increase)
Sweating
Diarrhea
Burns
Dehydration from inadequate water intake,
including thirst mechanism problems
Diabetes insipidus
(ADH deficiency H2O loss )

33

Hypernatremia
Excessive IV therapy
comatose diabetics following
treatment with insulin. Some Na in
the cells is kicked out as it is
replaced with potassium.
Cushing's syndrome - opposite of
Addisons

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Specimen Collection:
Sodium (Na)

serum (slight hemolysis is OK, but not gross)

heparinized plasma
timed urine
sweat
GI fluids

liquid feces (would be only time of

excessive loss)

35

Sodium (Na)
Note:
Increased lipids or proteins may
cause false decrease in results.
artifactual/pseudo-hyponatremia

36

Sodium (Na)
Sodium determination
Ion-selective (specific) electrode
Membrane composition = lithium aluminum silicate glass
Semi-permeable membrane allows sodium ions to cross
300X faster than potassium and is insensitive to hydrogen
ions.

direct measurement

where specimen is not diluted

gives the truest results
systems that dilute the sample give lower results
(called dilutional effect)
37

Sodium (Na)
Flame emission spectrophotometry (flame
photometer)
Na emits 589 nm (yellow)
Use internal standard of lithium or cesium
Possible for a dilutional error to occur in some
flame photometer systems, but literature does
not dwell on it.

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Routinely measured
electrolytes
Potassium

(K)

the major cation of intracellular fluid

Only 2 % of potassium is in the plasma
Potassium concentration inside cells is 20 X
greater than it is outside.
This is maintained by the Na pump,
(exchanges 3 Na for 1 K)
INSIDE
20

OUTSIDE
1

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Potassium

(K)

Function critically important to the

functions of neuromuscular cells
Critical for the control of heart muscle
contraction!
decreased potassium promotes muscular
excitability
Increased potassium decreases
excitability (paralysis and arrhythmias)

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Potassium

(K)

Regulation
Diet

easily consumed (bananas etc.)

Kidneys

Kidneys - responsible for regulation. Potassium

is readily excreted, but gets reabsorbed in the
proximal tubule - under the control of
ALDOSTERONE

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Potassium

(K)

Potassium normal values

Serum (adults) 3.5 - 5.3 mEq/L
Newborns slightly higher 3.7 - 5.9
mEq/L
Urine (24 hour collection) 25 - 125
mEq/L

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Hypokalemia
Decrease in K concentration

Effects

neuromuscular weakness & cardiac

arrhythmia

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Causes of hypokalemia
Excessive fluid loss ( diarrhea, vomiting,
diuretics )
Aldosterone promote Na reabsorption
K is excreted in its place (Cushings
syndrome = hyper aldosterone)
Insulin IVs promote rapid cellular potassium
uptake

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Causes of hypokalemia
Increased plasma pH ( decreased Hydrogen ion )

RBC
H+
K+
K+ moves into RBCs to preserve electrical balance,
causing plasma potassium to decrease.
( Sodium also shows a slight decrease )
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Hyperkalemia
Increased K concentration
Causes
IVS or other increased intake
Renal disease impaired excretion
Acidosis (Diabetes mellitus )
H+ competes with K+ to get into cells & to be
excreted by kidneys
Decreased insulin promotes cellular K loss
Hyperosomolar plasma (from glucose) pulls
H2O and potassium into the plasma

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Hyperkalemia
Causes
Tissue breakdown ( RBC hemolysis )
Addisons - hypo- adrenal; hypoaldosterone

Specimen Collection:Potassium
Non-hemolyzed serum
heparinized plasma
24 hr urine.
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Potassium

(K)

Determination
Ion-selective electrode (valinomycin
membrane)
insensitive to H+, & prefers K+ 1000 X
over Na+

Flame photometry
- K 766 nm

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Chloride ( Cl

Chloride - the major anion of extracellular fluid

Chloride moves passively with Na + or against HCO3to maintain neutral electrical charge
Chloride usually follows Na (if one is abnormal, so
is the other)
Function - not completely known
body hydration
osmotic pressure
electrical neutrality & other functions

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CO2 + H2O H2CO3 H+ + HCO3

Chloride shift

HCO3- accumulates inside RBCs as they pick

up carbon dioxide
Some diffuses out into plasma
To balance the loss of negative ions,
chloride (Cl-) moves into RBCs from plasma
Reverse happens in lungs Cl- moves out as
moves back into RBCs

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51

Chloride ( Cl

Regulation via diet and kidneys

In the kidney, Cl is reabsorbed in the
renal proximal tubules, along with
sodium.
Deficiencies of either one limits the
reabsorption of the other.

52

Chloride ( Cl

Normal values
Serum 100 -110 mEq/L
24 hour urine 110-250 mEq/L
varies with intake

CSF 120-132 mEq/L

53

Hypochloremia
Decreased serum Cl

loss of gastric HCl

salt loosing renal diseases
metabolic alkalosis;
increased HCO3- & decreased Cl-

54

Hyperchloremia
Increased serum Cl

dehydration (relative increase)

excessive intake (IV)
congestive heart failure
renal tubular disease
metabolic acidosis

decreased HCO3- & increased Cl-

55

Specimen Collection: Chloride

Serum
heparinized plasma
24 hr urine
sweat

56

Chloride ( Cl

Determination

Amperometric/Coulometric titration
involves titration with silver ions.

Digital Cotlove Chloridometer use this

principle

57

Chloride ( Cl

Mercurimetric titration of Schales and Schales

Precipitate protein out (tungstic acid PFF) - 1st step
Titrate using solution of mercury (mercuric nitrate)
Hg +2 + 2 Cl- = HgCl2

When all chloride is removed, next drop of mercury will complex

with diphenylcarbazone indicator to produce violet color =
endpoint

a calculation required to determine amt of Cl present

by the amt of Hg used

58

59

Chloride ( Cl

Colorimetric
Procedure suitable for automation
Chloride complexes with mercuric
thiocyanate
forms a reddish color proportional to
amt of Cl in the specimen.

60

Chloride ( Cl

Sweat chloride

Remember, need fresh sweat to accurately measure true

Cl concentration.
Testing purpose - to ID cystic fibrosis patients by the
increased salt concentration in their sweat.
Pilocarpine iontophoresis

Pilocarpine = the chemical used to stimulate the sweat

production
Iontophoresis = mild electrical current that stimulates
sweat production

61

Chloride ( Cl

CSF chloride
NV = 120 - 132 mEq/L (higher than
serum)
Often CSF Cl is decreased when CSF
protein is increased, as often occurs
in bacterial meningitis.

62

bicarbonate ion (HCO3- )

Carbon dioxide/bicarbonate
* the major component of the buffering system
in the blood 2nd most important anion (2nd to Cl)

Note: 2nd most abundant extra-cellular

anion
2nd most abundant extra-cellular anion

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bicarbonate ion (HCO3- )

Total plasma CO2 =
HCO3- + H2CO3- + CO2
HCO3- (carbonate ion) accounts for
90% of total plasma CO2
H2CO3- carbonic acid (bicarbonate)
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bicarbonate ion (HCO3- )

Regulation:
Bicarbonate is regulated by
secretion / reabsorption of the
renal tubules
renal excretion
Acidosis :
renal excretion
Alkalosis :
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bicarbonate ion (HCO3- )

Kidney regulation requires the enzyme

carbonic anhydrase - which is present in
renal tubular cells & RBCs
carbonic anhydrase

carbonic anhydrase

Reaction: CO2 + H2O H2CO3 H+ + HCO3

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bicarbonate ion (HCO3- )

CO2 Transport forms
8% dissolved in plasma
dissolved CO2

27% carbamino compounds

C02 bound to hemoglobin

65% bicarbonate ion

HCO3-

- carbonate ion

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bicarbonate ion (HCO3- )

Normal values
Total Carbon dioxide (venous) @ 2230 mmol/L
includes bicarb, dissolved & undissociated
H2CO3 - carbonic acid (bicarbonate)

Bicarbonate ion (HCO3) 22-26 mEq/L

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bicarbonate ion (HCO3- )

Function

CO2 is a waste product

continuously produced as a result of cell metabolism,
the ability of the bicarbonate ion to accept a
hydrogen ion makes it an efficient and effective
means of buffering body pH
dominant buffering system of plasma
makes up @ 95% of the buffering capacity of
plasma
69

bicarbonate ion (HCO3- )

Significance
The bicarbonate ion (HCO3) is the body's
major base substance
Determining its concentration provides
information concerning metabolic acid/base

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bicarbonate ion (HCO3- )

CO2 /bicarb Determination
Specimen can be heparinized plasma, arterial
whole blood or fresh serum. Anaerobic
collection preferred.

methods

Ion selective electrodes

Colorimetric
Calculated from pH and PCO2 values
Measurement of liberated gas

71

Electrolyte balance
Anion gap an estimate of the unmeasured
anion concentrations such as sulfate,
phosphate, and various organic acids.

72

Electrolyte balance
Calculations
1. Na - (Cl + CO2 or HCO3-) =
NV 8-12 mEq/L

Or
2. (Na + K) - (Cl + CO2 or HCO3-)
14 mEq/L

NV 7-

which one to use may depend on whether K value is

available. Some authors feel that K value is so small and
usually varies little, that it is not worth including into the
formula.

73

Electrolyte balance

Causes in normal patients

what causes the anion gap?

2/3 plasma proteins & 1/3 phosphate& sulfate ions, along with organic acids

Increased AG
uncontrolled diabetes (due to lactic & keto acids)
severe renal disorders

Decreased AG a decrease AG is rare, more often it occurs when one test/instrument error

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Normal Ranges
SODIUM
135 145
mEq/L
POTASSIUM
3.5 5.0
mEq/L
CHLORIDE
100 110
mEq/L
CO2
20 30
mEq/L

ANION GAP

10 - 20

PLASMA OSMOLALITY
CALCIUM
8.5 10.0
IONIZED Ca
4.5
MAGNESIUM
PHOSPHATE
2.5
LACTATE
0.5 17.0

meq / L
275 - 295 mOsmol / kg
mg/dL
5.5
mg/dL
1.2 2.1
mEq/L
4.5
mg/dL
mgl/dl
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ELECTROLYTE TOP 10
Osmolality is detected by the Hypothalamus Gland
Thirst sensation
and secretion of ADH by Posterior Pituitary Gland. ADH increases renal
reabsorption of water
Blood Volume stimulates Renin - Angiotensin - Aldosterone system.
Aldosterone secretion by the Adrenal Cortex stimulates increased renal
absorption of sodium

Sodium is the main extracellular cation and contributor to plasma osmolality

Potassium is the main intracellular cation
Plasma CO2 = Dissolved CO2 + H2 CO3 + HCO3Chloride is usually a passive follower of Sodium to maintain electrical charge
Sodium and Potassium usually move opposite each other

Parathyroid Hormone ( PTH ) secretion increases plasma calcium ,

increases plasma magnesium and decreases phosphate

Acidosis is associated with Potassium ( Alkalosis with Potassium )

Most electrolytes are measured by Ion Selective Electrodes ( ISE )

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