Concentration Effect of Trace Metals in Jordanian Patients of Urinary Calculi
Concentration Effect of Trace Metals in Jordanian Patients of Urinary Calculi
DOI 10.1007/s10653-007-9103-3
ORIGINAL PAPER
Abstract Due to the increase in the number of               Zn = 0.7, Cu = 0.19, Mn = 0.029, P = 10.35, S = 1.88,
urinary calculi disease cases in Jordan, stone samples      Sr = 0.306, Mo = 0.2, Cr = 0.146, Co = 0.05,
were collected from patients from various Jordanian         Ni = 0.014)%. In conclusion, metals concentration in
hospitals (Princes Basma (PBH), King Abdullah               Jordanian patient’s urinary calculi samples was
University (KAUH), Al-Basheer (ABH) and Al-                 higher than its equivalents of other patients’. It has
Mafraq (AMH)). This study concentrates on the               been noted that there is no concentration of toxic
effect of trace metals in patients of urinary calculi.      trace elements (like Li, V, Pb, Cd, and As). Some
Trace metals were detected in 110 urinary calculi           heavy metals, however, were detected Mo, Cr, Co
samples using X-ray fluorescence (XRF) and atomic           and Ni as traces. P and S ions are present in few
absorption spectroscopy (AAS) techniques. Of the            calculi stones as traces.
calculi examined, 21 were pure calcium oxalate
(CaOax), 29 were mixed calcium oxalate/uric acid,           Keywords Urinary calculi  Urinary stones 
23 were mixed calcium oxalate/phosphate (apatite),          Renal stones  Kidney stones  Calcium oxalate 
25 were phosphate calculi (apatite/struvite), five were     Medical geochemistry  Medical geology 
mixed calcium oxalate monohydrate/struvite, four            X-ray fluorescence  Atomic absorption spectroscopy
were urate calculi (mixed ammonium acid urate/
sodium acid urate) and three were pure cystine
calculi. The concentration measurement of Ca and            Introduction
other trace metals levels has been found useful in
understanding the mechanism of stone formation and          Some metals are naturally present in the human body
in evaluating pathological factors. It has been found       and are essential to human health. Over 40 elements
that Ca is the main constituent of the urinary calculi,     in the periodic table have biological functions on the
especially those stones composed of calcium oxalate         human body and health if taken during eating,
and calcium phosphate. The concentration of most of         drinking, or breathing. Many of these elements occur
the trace metals that were analyzed was (Ca = 48.18,        at highly variable concentration ranging from very
Na = 1.56, K = 0.9, Mg = 3.08, Fe = 1.17, Al = 0.49,        low to high. This variance depends on the analytical
                                                            method used (Fell 1984). They normally occur at low
                                                            concentrations and are known as trace metals. In high
I. A. Abboud (&)
                                                            doses, they are toxic to the human body or produce
Institute of Earth and Environmental Sciences, Al al-Bayt
University, Al-Mafraq, Jordan                               deficiencies in the case of other trace metals (Pouls
e-mail: Abboud_Iyad@Yahoo.com                               and Payne 2006). In recent years, the interest in the
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role of trace elements analyses in all fields of           many of which are considered to be either inhibitors
chemical, biochemical, geochemical, biological and         or promoters of urinary stone formation. While the
environmental researches has been optimised. They          study of effects on solubility and crystallization, the
are currently considered to be either harmless             determination of the trace elements content of human
impurities or essential, depending on their concen-        concentrations has attracted increasing attention
tration and the influence they have on physiological       (Levinson et al. 1978).
phenomena (Feinendegen and Kasperek 1980; Wandt               Several techniques have been used in the analysis
and Underhill 1988). Heavy metals are considered as        of urinary stones and determination of elements: wet
traces with a density at least five times that of water    chemical tests (Al-Kinani et al. 1984; Jhaumeer-L
(Pouls and Payne 2006). As such, they are stable           and Subratty 1999), inductive coupled plasma
elements and cannot be metabolized by the human            (ICP-AES) (Wandt and Underhill 1988), flame pho-
body and bio-accumulative passed up the food chain         tometry, electron microprobe analysis, and neutron
to humans (Harte et al. 1991; Pouls and Payne 2006).       activation analysis (Al-Kinani et al. 1984). The
They are taken into the human body via inhalation,         following techniques were have been found to best
ingestion, and skin absorption, while liberated into       serve the purpose of the present study: X-ray
the environment through the air, drinking water, food,     fluorescence (XRF) spectroscopy and Atomic absorp-
or countless human-made chemicals and products             tion spectroscopy (AAS).
(Pouls and Payne 2006).
   The human body is like a machine. It consumes
energy from the breakdown of food products to carry        Methodology
out function of life, and in so doing produces waste
products that must be removed. If the waste products       One hundred and ten urinary stones of different types,
are not eliminated, the machine becomes clogged up         including renal and gall bladder stones, were col-
and function ceases. The kidney, ureters, urinary          lected from patients aging between 21 and 62 years
bladder and urethra make up the urinary system of the      (73 males, 37 females). The stones were collected
body. Its function is to eliminate soluble waste           following medical surgeries that the aforementioned
materials from metabolism of food and water con-           patients undergone at the following hospitals: Princes
sumed (Fullerton 2003). Urinary stones may be              Basma (PBH), King Abdullah University (KAUH),
regarded as an example of biomineralization that           Al-Basheer (ABH), and Al-Mafraq (ABH) during the
involves the formation of inorganic minerals by living     period extending from April/1st/2004 to April/30th/
organisms (Lieske et al. 1995). However, kidney stone      2006 (Table 1). Stone analysis was carried out at the
is a pathological manifestation of the phenomenon,         laboratories of Al al-Bayt University, Al-Mafraq,
exhibiting features typical of uncontrolled biominer-      Jordan using XRF and atomic absorption techniques.
alization (Karlsen et al. 1995). Accurate stone analysis   All stones removed from patients were placed in
is therefore essential for the investigation and           polyethylene dry bottles (bearing the name, sex, age,
management of the stone forming patient (Vergauwe          weight, date and marital status of the patient) and
et al. 1994). Urinary stones may contain various           transferred to Al al-Bayt University labs.
combinations of chemicals. The most common types              All samples were washed several times with de-
of stones are comprised of calcium in combination          ionized water until they became free from urine,
with either oxalate (Dajani et al. 1988; Mhelan 1992;      blood debris and remnants of organic matter. Each
Yagisawa et al. 1999) or phosphate. Struvite (STR)         sample was washed with distilled water and then was
stone is a less common type of stones that is formed by    dried at 1008C overnight. After that, samples were
infection in the urinary tract. Uric acid stone is less    crushed and ground in agate mortar. The resulting
common than STR stone. Cystine stone is rare.              powder was homogenized chemically and then a
   Hammarsten (1929)—in Wandt and Underhill                pellet stups were made by exposing them to 200 Kn
1988—discovered the antagonistic influence of              pressure before analyzing them using XRF (model
urolithiasis, which Co, Mg and Ni have upon calcium        Philips Magix PW2424). Major and some trace
by increasing the solubility of calcium oxalate. Meyer     elements were measured as oxide in weight percent-
and Angino (1977) added various ions to the list,          age (wt%) (Tables 1, 2).
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Environ Geochem Health
                                                                                                                 123
      Table 2 Comparison of trace metal concentrations in urinary calculi from different studies (wt%)
      Element         Concentration (%)
123
                      Present study*    Al-Fawaaz 2006a     Jhaumeer-L & Subratty      Al-Maliki 1998c   Wandt et al.      Joost & Tessadri   Levinson et al.   Ohta 1957g
                      (n = 110)**       (n = 35)            1999b (n = 12)             (n = 19)          1988d (n = 102)   1985e (n = 24)     1978f (n = 69)    (n = 10)
Ohta 1957g
                                                                                                             Present study**: (21) Calcium oxalate calculi (CaOax), (29) Mixed calcium oxalate/uric acid calculi, (23) Mixed calcium oxalate/phosphate (APT & STR) calculi, (25) Phosphate
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                            The samples were studied after a standard diges-
                                        (n = 10)
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         tion process. Thirty milligrams of the homogenized
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         powder stones were dissolved in 1 ml of concentrated
                                                                 –
                                                                         –
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         boiling nitric acid (98%, Analar, BDH chemicals
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         Ltd., Poole, England) at 250 8C for at least 1 h.
                                         Levinson et al.
                                         1978f (n = 69)
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         (Ca, Mg) and trace metal (Fe, Al, Zn, Cu, Mn, P, S,
                                         1985e (n = 24)
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         Sr, Li, Mo, Cr, Co, Ni, V, Pb, Cd, As) elements were
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         found out. Zn, Cu, Mn, Co, Cr, Ni and V were being
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         indispensable with for life activity of an organism,
                                                                 –
                                                                         –
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         Batanjac 2000).
                                        (n = 19)
0.03
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         Results
                                         Jhaumeer-L & Subratty
                                                                                                                                                                                                                                                                                                                        3
                                                                                                                                                                                                                                                                                                                        in percent for all ions except phosphor as PO4
0.008–0.03
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         g
                                                                                                                                                                                                                                                                                             a
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                     123
                                                                                            Environ Geochem Health
calcium oxalate monohydrate (COM) mineral/stru-            (ranging between 0.002% and 1.05%, with an aver-
vite (STR) mineral calculi group. Four calculi             age value of 0.19%) (Table 1). Green foods, flour,
containing urates group (ammonium acid urate               milk products and meats are responsible for these
(AAU) and sodium acid urate (SAU) minerals) and            concentrations. Manganese ion is present in eleven
3 cystine mineral stones group (CYS) were contained        samples of different types of urinary calculi ranging
in the selection.                                          between 0.005% and 0.06% with an average value of
   The presence of different trace metals in the stones    0.029% (Table 1). The main source of Mn is beans,
was also been studied (Table 1). Table 1 shows the         tea, and green foods (Mena et al. 1969). It has been
results of the trace metals and their mean and average     noted that there is no concentrations of toxic trace
concentrations for all mineral groups of the calculi       elements like Li, V, Pb, Cd, and As. Furthermore,
type, respectively. It was been found that these           some heavy metals such as Mo, Cr, Co and Ni have
urinary calculi contain mostly calcium as cation,          been traces (Table 1). P and S ions are present in few
ranged between 6.80% and 38.25% with an average            calculi stones as traces (Table 1).
value of 20.33% (Table 1), and was considered as the          In Table 2, elemental concentrations obtained in
main constituent of stones of all different types. It is   the present study are compared with values obtained
obvious that Ca content is affected by the type of         by others (Ohta 1957; Levinson et al. 1978; Joost and
food and drinks patients take, including diary and         Tessadri 1987; Wandt et al. 1984; Al-Maliki 1998;
milk products, eggs, tea, and hard water (Robertson        Al-Fawaaz 2006). It is noteworthy mentioning that
et al. 1980; Abboud 2006; Sobhi 2006). By compar-          the sequence of the average trace metal concentration
ing the Ca content in urinary calculi with that within     values for the calculi in this study is similar to that
water in Jordan, it has been noted that there is a         found by other researchers (Table 2).
strong relationship between both. This indicates that
the main source of Ca comes from the water that
people drink (Abboud 2006). Percentage mass of             Discussion
magnesium ion in the stones was been found to be <
3% (Table 1), (ranging from 0.009% to 6.95% with           Studies confirm that heavy metals can directly
an average value of 3.08%). Presence of Magnesium          influence behavior by impairing mental and
in urinary stones is usually an indicator of an increase   neurological function, influencing neurotransmitter
in their concentration in human body (Deeming and          production, utilization, and altering numerous met-
Webu 1977). Drinks, food, drugs and vitamins are           abolic body processes. Systems in which toxic
also responsible for Mg content (Sobhi 2006).              metal elements can induce impairment and dys-
   Alkaline metals (Na, K) are present in low              function include the blood and cardiovascular,
concentrations ranging from 0.043% to 7.35% and            detoxification pathways (colon, liver, kidneys, skin),
0.002% to 1.57%, respectively, with an average value       endocrine, energy production pathways, enzymatic,
of 1.56% and 0.90%, respectively (Table 1). The            gastrointestinal, immune, nervous, reproductive, and
main contributor for magnesium, sodium and potas-          urinary (Kellas and Dworkin 1996; Pouls and Payne
sium in the urinary calculi is their presence in           2006).
drinking water (Abboud 2006). Food is another                 The human body’s organ systems, like the endo-
source of these elements (Robertson et al. 1980;           crine system, and immune system, are infected with
Sobhi 2006).                                               environmental toxicity through chemical pollutants
   Concentration of transition metal ions such as iron,    and chemicals added to our food, water and air.
manganese, copper and zinc have been very low to be        Fullerton (2003), has found heavy metals as one of
detected. The presence of Fe ions ranges between           the most common chemical causes of pathology,
0.09% and3.85% with an average value of 1.17%              especially aluminum and mercury (Pouls and Payne
(Table 1). Food and water are responsible for the          2006).
presence of Fe. Meats and beans are considered the            There are many possibilities, offered by different
main source of Fe (Meranger and Smith 1972). Most          technologies, to determine the chemical composition
samples of urinary calculi have no concentrations of       of urinary calculi. As can be seen in Table 1, all trace
Cu. Seventeen samples have had low presence of Cu          metal concentrations have been identified precisely
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Environ Geochem Health
by analysis with XRF and AAS. A high percentage of        not appear to play a significant role in urolithiasis
the urinary calculi investigated in this study has been   (Wandt and Underhill 1988).
found to consist mainly of either a calcium oxalate or       The insufficient detection of phosphate minerals in
a calcium phosphate salt (Al-Kinani et al. 1984;          uric acid (uricite) stones can lead to important clinical
Samuell and Kasidas 1995; Al-Maliki 1998; Jhau-           consequences. Alkalization therapy should be
meer-L and Subratty 1999; Abboud 2006; Al-Fawaaz          avoided even if there is only a small amount of
2006). It has long been hoped that knowledge of the       phosphate minerals in uric acid. This is due to the fact
relative concentrations of the different components       that the highest precipitation rate of phosphate is
present in calculi would lead to an understanding of      reached in the alkaline pH range. An exact urinary pH
the mechanisms of stone nucleation and growth.            control is important if oxalate stones have low
Trace elements determinations are currently being         phosphate minerals content and acidification below
investigated by many researchers (Meyer and Angino        pH 6.2 might be necessary for metaphylaxis (Joost
1977; Levinson et al. 1978; Meyer and Thomas 1982;        and Tessadri 1987). Phosphate stones may belong to
Wandt et al. 1984; Durak et al. 1988; Wandt and           the non-infection urinary stones (Abdel-Halim et al.
Underhill 1988; Abu-Farsakh 1997; Al-Maliki 1998;         1993; Sobhi 2006).
Saw et al. 2000; Torzewska et al. 2003; Chutipong-           The average calcium and magnesium contents
tanate et al. 2005; Reynolds 2005; Al-Fawaaz 2006;        (48.18, 3.08%, respectively) have been higher than
Abboud 2006). Some concentrations of Ca, P, S, F,         that of stone analysis in other correlation studies,
Cl, Al, Mn, Cu, Mg and Na in urinary stones have          except for the fact that Ca presence in Al-Fawaaz
been found to be much higher than normal and it has       study (2006) (Table 2). The high concentration of the
been suggested that elements with high concentra-         Ca2+ and Mg2+ cations present in calculi samples
tions might play a significant part in stone formation    with cholesterol could promote the formation of large
either in association with the structure of the           numbers of cholesten. This may increase the rate of
conglomerate crystals or in combination with organic      development of gall stones (Neithercut 1989). In
molecules (Al-Kinani et al. 1984; Durak et al. 1988).     addition, Ca phosphate and Ca carbonate have been
   In the present study, high concentrations of some      found in cholesterol (cholesten) gall stones (Malet
elements (Ca, P, S) have been recognized (Table 1).       et al. 1986). Scott et al. (1982) suggested that high
Table 2 gives a comparison of all results obtained        calcium levels are a risk factor in the development of
with the findings of other researches. The results        stone disease.
show that average zinc and strontium contents (0.7,          The average potassium and sodium contents (0.9,
0.306% respectively), have been higher when com-          1.56% respectively) have been higher than that of
pared to others (Table 2). It has been indicated that     stones analysis in other correlation studies, except for
Zn is positively correlated with Sr (Wandt and            Al-Fawaaz study (2006) (Table 2). K and Na
Underhill 1988) and predominantly associated with         elements can substitute Ca in apatite (Simpson
apatite, which is substantiated by correlations estab-    1968) as with Sr and Zn. Generally, these elements
lished between the Zn and P content of the stones.        are mainly limited to the crystal surface (Wandt and
This supports previous findings by Sutor (1969),          Underhill 1988).
Schneider et al. (1970), King (1971), and Wandt and          The average iron content (1.17%) has been slightly
Underhill (1988).                                         higher than that of stones analysis in other correlation
   Strontium competes with Ca for the apatite lattice     studies (Table 2). Urinary iron is thought to arise
(Sobel et al. 1949 in Wandt and Underhill 1988). It is    from microhaematuria and epithelial cells in the renal
so similar to Ca in its metabolism that it is generally   tubules. Iron ion presence in calculi is further
known to be a companion to the latter in salts, where     explained by the adsorption of Fe2+ and Fe3+ ions
Sr can exchange isomorphically with Ca in the lattice     on CaOx and Ca-phosphate (Wandt and Underhill
(Neuman and Neuman 1953 in Wandt and Underhill            1988).
1988). This can be concluded due to the fact that            The average aluminum content (0.49%) has been
there is a positive correlation between the amount of     slightly higher than that of stones analysis in other
apatite and Sr in the phosphate stones and with P and     correlation studies, except for Al-Fawaaz study
Sr in the calcium oxalate/phosphate stones. Sr does       (2006) (Table 2). Aluminum can make a very well
                                                                                                        123
                                                                                               Environ Geochem Health
correlation with phosphorous in phosphate calculi            The concentration of K, Mg, Fe, Mn, S and Sr in
(apatite, struvite). This result confirms that of Wandt   Jordanian patients of urinary calculi has been com-
and Underhill’s (1988) study. Sutor (1969) found that     patible with that of other patients in the many studies
very small concentrations of Al3+ removed oxalate         around the world (Table 2). While Ca, Na and P
ions and thus prevented the crystallization of CaOx.      presence in the Jordanian patients urinary calculi has
This association might result from its incorporation      slightly higher concentration than that of other
into the apatite lattice, where it probably substitutes   patients around the world, these concentrations may
for P (Levinson et al. 1978).                             be dependent on to the quality and quantity of
   The average copper and molybdenum contents             drinking water and food intakes. Water intake for
(0.19, 0.2% respectively), have been slightly higher      Jordanian patients is highly concentrated with Ca2+
than that of stones analysis in other correlation         ions because water is drawn carbonate reserve. Food
studies, except for Al-Fawaaz study (2006) (Table 2).     intake is also rich in Ca (like eggs, milk and green
Cu2+ ion can compete with Ca2+ in calcification           leaf of vegetables). Concentration of Na+ ions in
(Sobel et al. 1949 in Wandt and Underhill 1988).          urinary calculi of Jordanian patients may be due to
Neithercut (1989) and Abu-Farsakh (1997) clearly          the concentration of this ion during the depletion of
show that Cu2+ and Zn2+ have been present in gall         water through irrigation processes. Concentration of
stones in micromolar concentrations and there have        P ions in urinary calculi of Jordanian patients is
been no significant difference in Cu2+ and Zn2+           closely related to food intake like eggs, milk and
concentration in gall stones. The presence of Cu2+        green vegetable leafs.
and Zn2+ in calculi could be explained as simple
co-precipitation with cholesterol (cholesten)             Acknowledgements This research has been sponsored by Al
                                                          al-Bayt University. The researcher would like to express his
(Abu-Farsakh 1997). Molybdenum can make a good            appreciation for the help of Prof. Dr. Nadher Al Ansari, Dr. Ali
correlation with magnesium (Wandt and Underhill           Ahmed Bani Nasser, and Mr. Musa Al-Zghoul for their
1988). All other trace and heavy metals in this study     invaluable comments during the different stages of carrying out
have played only a minor role in the chemical effects     of this research.
of mineral formation. This is because of the very low
concentrations at which these metals have been
present.
   The average sulfur content (1.88% with range           References
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