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Phase and microstructural study of urinary stones
Microchemical Journal 152 (2020) 104429
Contents lists available at ScienceDirect
Microchemical Journal journal homepage: www.elsevier.com/locate/microc
Phase and microstructural study of urinary stones a,⁎
a
b
b
a
Miljana Mirković , Anja Dosen , Suzana Erić , Predrag Vulić , Branko Matović , Aleksandra Rosićb a b
T
University of Belgrade, Vinča Institute of Nuclear Sciences, Department of Material Science, P.O Box 522, Belgrade, Serbia University of Belgrade, Faculty of Mining and Geology, Department of Mineralogy, Crystallography, Petrology and Geochemistry, Djusina 7, Belgrade, Serbia
ARTICLE INFO
ABSTRACT
Keywords: Urinary stones Phase composition Statistics X – Ray powder diffraction Scanning electron microscopy
In this paper we present the phase and morphological characteristics of urinary stones from Serbian patients. The study included for the first time the determination of the phase composition and a statistical analysis of the presence of different types of urinary stones in both men and women in Serbia. The main goal of study was representation of collected data for the first time. For past three years, more than 600 samples were collected from Serbian patients. The phase composition of all samples of urinary stones was investigated using XRD analysis. Morphology and chemical composition of phases in some characteristic samples was determinate by the SEM-EDS analysis. Results indicate that there are several different types of urinary stones that vary in mineral composition, chemistry and morphology. It was found that 312 (52%) of the 600 stones were composed of calcium oxalate minerals (CaOx): 17.3% of which were pure calcium oxalate monohydrate COM, 4% were pure calcium oxalate dihydrate COD; 200 (33.3%) were a mixture of CaOx and Hydroxyapatite HA, 19 (3.1%) were uric acid (uricite) UA and uric acid dihydrate UAD, 17 (2.8%) were a combination of UA and CaOx minerals, 41 (6.8%) were combination of CaP minerals and CaOx, 11 (1.9%) were cystine (Cy) stones. The obtained data shows the diversity of types of urinary stones. Morphological, chemical and XRPD analysis give us statistical data which shows that the most common urinary stones from Serbian patients are from CaOx group and in most of cases are associated with CaP.
Introduction The occurrence of urinary stones in human body is very common and formation of urinary stones are caused by certain processes that are not yet fully understood. The analysis included in this paper is related to the morphological and phase composition of urinary stones and represents the possibility of understanding the occurrence and morphology of urinary stones from patients from Serbia. Due to the limitations in terms of the amounts of the materials, best suited method for determination of urinary stones composition was XRD. For confirmation and stone morphology of analyzed samples we used SEM and EDS analysis. These methods have a very wide application in the analysis of crystalline materials and can be helpful as in this case for urinary stones determination. Urinary stone disease is a very common medical problem in industrialized countries, and it is affecting an increasing number of people [1,2]. Risk factors can be: dietary, non – dietary, and urinary that may contribute to the formation of urinary stones [3]. Several reasons for the formation of urinary stones are: metabolic disorders,
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increased secretion of uroproteins, environmental influences, civilization factor and eating habits [4,5]. Urolithiasis is a common disorder in the western world that affects 1–5% of population, causing urinary tract disease [2,6–8]. The disorders such as: hypercalciuria, hypocitraturia and urinary tract infection have influenced active stone formation [9]. Calcium oxalate (CaOx) stones are most common in people from Western European countries, accounting for about 70% compared to other types of stones [10]. CaOx has three types of crystalline forms: calcium oxalate monohydrate – Whewellite (COM) which is the most frequent form, calcium oxalate dihydrate – Weddelite (COD) which is two times less frequent and calcium oxalate trihydrate – Caoxite which is fairly rare. Note that for whewellite stones, various morphological aspects corresponding to lithogenic factors exist and a classification of whewellite stones into five main types, namely Ia, Ib, Ic, Id and Ie has been proposed [11–15]. Some literature data have suggested that urinary proteins play a major role for the COM aggregation [10,15,16]. These studies explain the predominance of COM in urinary stones. Difference in pathological activity of COM and COD is related to the adhesive character of their crystal faces [12,16]. Kidney stones made of
Corresponding author. E-mail address: [email protected] (M. Mirković).
https://doi.org/10.1016/j.microc.2019.104429 Received 17 September 2019; Received in revised form 12 November 2019; Accepted 14 November 2019 Available online 15 November 2019 0026-265X/ © 2019 Elsevier B.V. All rights reserved.
Microchemical Journal 152 (2020) 104429
M. Mirković, et al.
Whewellite (COM) are induced by hyperoxaluria while the other crystalline form, i.e. Weddellite (COD) is induced by hypercalciuria [17]. Formation of COD crystals depends mostly on the presence of high Ca2+/oxalate ratios, ionic strength, ascorbic acid (citrate), and colloidal CaP, and pH ≥ 6 [6,12]. Besides these types, there are also other types of stones such as group of calcium phosphates (CaP): Hydroxyapatite – HA (Ca5(PO4)3(OH)), Struvite – St (MgNH4PO4•6H2O), Brushite – Br (Ca (HPO4)2•2H2O) and Whitlockite – Whl (Ca3(PO4)2). Stones which rarely occur are Cystine – Cy (C6H12N2O4S2), uric acid (uricite) – UA (C5H4N4O3) and uric acid dihydrate – UAD (C5H4N4O3•2H2O) [7,18–28]. Formation of investigated types of urinary stones is in good agreement with literature data [6,16,29]. Knowledge of stone composition is very important, for example, the presence of Struvite indicates an infection [30]. More precisely, different publications show clearly that stones resulting from urinary tract infection due to urea-splitting bacteria consist of calcium phosphate admixed with struvite and exhibit a high CO32− content, since UA, COM and Cy stones are hard and therefore less responsive to treatment with extracorporeal shock wave lithotripsy (ESWL) [31,32]. This method is the most common procedure used for the stone fragmentation [33]. The effectiveness of this method depends on the physicochemical composition of the stones [11,34–36]. Analyses of these characteristics of urinary stones are most commonly done with following methods: XRD, infrared spectroscopy, polarizing microscopy and SEM [5,11,28,37,38]. Main idea of this paper is to demonstrate the application of methods and approaches that are commonly used in various fields of materials science and geology on the matter that has biological origin and belongs to a field of bio crystallization and medicine. The present study reports findings of the composition and morphology of urinary stones in Serbian population for the first time. XRD and SEM analysis are very useful for detailed results of phase and morphological composition of urinary stones. This data correlated with XRD results can be helpful for complete and adequately medical treatment of patients. Experimental In this study we present the results of urinary tract stone samples collected from both genders, ages between 15 and 65. Analyzed samples were collected from hospitals across Serbia, collection took place from past three years, and during this period 600 samples were collected. Urinary stones vary from 1 mm to several millimeters in diameter. Samples were washed in alcohol and distilled water in order to remove organic matter and air-dried. X-ray powder diffraction data were collected at the Philips PW 1710, with CuKα. radiation. All samples were tested under the same experimental conditions: 40 KV/ 30 mA, 10–50° 2θ, step size 0.02°, count time 0.5 s. For phase identification we use JCPDS database and card standards. The following JCPDS file numbers with crystal system information were used for phase identification: COD (Wheddelite): 17-0541, Tetragonal; COM (Whewellite): 77-1160, Monoclinic; UA (Uricite): 28-2016, Monoclinic; HA (Hydroxyapatite): 89-6440, Hexagonal; Cy (Cystine): 37-1802, Hexagonal; Br (Brushite): 72-0713, Monoclinic; St (Struvite): 15-0762, Orthorhombic; Whl (Whitlockite): 9-0169, Rhombohedral. For SEM-EDS analyses were selected the samples with characteristic XRD patterns that differed in phase composition. SEM-EDS analysis was performed using a JEOL JSM-6610LV scanning electron microscope connected to an X-Max energy dispersive spectrometer to identify the morphologies and chemical compositions of the present phases. The samples were covered with gold using a BALTEC-SCD-005 sputter coating device, and the results were recorded under high vacuum conditions.
Fig. 1. Powder patterns of selected samples; a) COD and COM, b) UA and c) HA.
mineral composition and percentage of urinary stones in all samples from Serbian people. Number of females samples was 274 (45%), which is little less than males 326 (54%) samples. Kidney and urinary stones are biomaterials which contains mineral and organic phases as well as some trace elements [39,40]. Such complexity in chemical composition leads to the use of various characterization techniques [41,42]. The phase composition of urinary stones was determined by XRD as described previously. In half of all the samples COM and COD occur together, as single phases and in mixtures have almost 90% of occurrence. XRD analysis showed that the most common phases are from CaOx and CaP mineral group. These phases often occur together with other, infection stones such as UA, UAD and Cy [43,44]. The phases mentioned above exhibit a high degree of crystallinity in all samples. XRD results of most common phases were presented on Fig. 1. Well defined
Results and discussion All of collected samples are presented in Table (S1), which shows 2
Microchemical Journal 152 (2020) 104429
M. Mirković, et al.
Fig. 2. SEM images of COM; a) EDS spectrum of indicated tabular crystals of COM b) Sheet – like layers of COM crystals bonded together.
narrow peaks imply well crystallized and well-ordered structure, which was observed for COM and COD samples presented on Fig. 1a. Degree of crystallinity both of COM and COD is about 68%. Pathological UA also shows sharp and narrow peaks, with degree of crystallinity about 65% based on powder diffractogram showed on Fig. 1b. In all other investigated samples phosphate phases like Br, Whl and St from has good structural order based on XRD results, which is in correlation with literature data [30]. Based on literature data CaP stones are more often represented in females, and reflect a wide diversity and etiology [45]. Brushite stones will be formed if its conversion to hydroxyapatite does not occur, where it is considered to be a precursor to the formation of hydroxyapatite [46]. Other phosphate such as HA is more frequently represented. XRD of HA shows low intensity broad peaks with degree of crystallinity about 16%, which is indicating low structural arrangement (Fig. 1c). XRD analyses showed that HA stones of female patients exhibit significantly lower crystallinity than in male samples. SEM results confirms high degree of crystallinity of pathological COM which is defined by well-developed tabular crystal forms, sizes between 10 μm and 60 μm (Fig. 2a). Crystals has tabular monoclinic prismatic morphology. Growth lines on mineral grains show the direction of crystal growth and stone formation. The striated layers on COM crystal surface show that it was formed by columnar juxtaposed sheet – like layers together (Fig. 2b). Based on SEM microphotographs it is identified classic crystal shape of COD which is the eight – face bipyramid (Fig. 3a). Pathological COD tetragonal bipyramid crystals have crystal forms that are flattened and elongated along Z –axis, sizes vary between 10 and 50 μm (Fig. 3b).
Tiselius et al. explained the process of developing CaOx and CaP stones [10]. The different conditions prevailing in the bodies of patients lead to the formation of crystals and aggregates of larger or smaller size and degree of order [45]. Crystal morphology of analyzed stones shows the differences in the pathologic behavior of COM and COD (Figs. 2 and 3) which is related to the adhesive character of their crystal faces. Pathological COD form is a thermodynamically unstable phase of CaOx, which transforms into to a stable monohydrate in contact with water. Based on SEM results it is evident that HA has low crystallinity i.e. it is amorphous (Fig. 4a and b). Spheres of HA pathological stones are characterized as cemented layers of amorphous material. Shape and morphology of analyzed samples depend on the physical – chemical conditions of formation of these minerals in the human body. High level of pathological COM and COD crystal form development indicates favorable crystal growth conditions in the human body. On the other hand, pathological HA have spherical occurrence. Spheres of HA are consisting of amorphous hydroxyapatite layers (Fig. 4b). Microscopically these layers seem amorphous. They are composed of small spheres, of amorphous material which is cemented together. This HA layers are most likely formed in urine as a basis for deposition and formation of CaOx. Porosity of the HA stones indicates they are easier to break up by ESWL method than CaOx stones (Figs. 2 and 3). In samples HA rarely occur alone and usually accompany other phases such as CaOx and St. Based on SEM analysis it is observed that UA as a pathological mineral formation has a very good structural arrangement and well developed and proper prismatic crystals sizes 30 μm (Fig. 5a and b).
Fig. 3. SEM images of COD; a) Eight – face bipyramid and EDS analysis of indicated COD crystal b) Tetragonal crystal forms that are flattened and elongated along Z –axis. 3
Microchemical Journal 152 (2020) 104429
M. Mirković, et al.
Fig. 4. SEM images of CaP; a) Spheres of CaP (HA) with EDS analysis of indicate sample b) Amorphous layers of HA.
Lines on monoclinic crystal plane indicate direction of crystal growth. UA crystals have developed different crystal forms of clinopinacoid (0 l 0), orthoprism (h k 0) and negative orthohemidome (h¯ k l) (Fig. 5b). High degree of crystal regularity indicates favorable crystallization conditions in human body. These types of stones are predominantly composed of uric acid (UAD), which crystallizes from an aqueous solution and transforms into the anhydrous salt. Factors which leads to this type of stone formation is in a first line: low urinary output, acidic urine and hyperuricuria [47]. Beside this phase, we identify UAD phase which is always in mixture with UA. We didn`t find pure UAD single stones. SEM results are confirmed structural arrangement of samples. EDS results are confirmed chemical composition of phases in selected and investigated samples. EDS analysis in all samples do not indicate existence of trace or toxic elements. The examination of the content of toxic elements was not the subject of this study. All the types of examined urinary stones from Serbian patients both female and male patients are presented as histograms S1 which presents stone composition as a function of distribution and stone representation in all samples. The most common types of urinary tract infection stones are COD and COM which occur more frequently in male patients 28.5% than in female patients 23.3%. Mixture of CaP and CaOx stones occurs more in males than in female's samples (male patients 112 (18.7%) and female patients 88 (14.7%)). Pure UA stones are identified mostly in male samples 2.6% while in female samples has occurrence of 0.5%. Mixture of UA, UAD and CaOx urinary stones occurs in 2.3% male and in 1% female samples. Group of CaP minerals as various types of mixtures (S1), occurs twice as often in females with abundance of 4.8%
than in males 2.2% urinary stones. Struvite type of stone in combination with HA is more frequent in female samples 2%, in male samples has only 0.8% of occurrence. Cystine urinary stones have the lowest representation. Also it is important to note that formation of this type of kidney stone is related to genetic disease [43,44]. In all samples Cystine stones have almost three times as many are in female 1.3% than in male 0.5% urinary stones. This is the first study that shows the distribution and types of urinary stones and their morphological characteristics in Serbia in both male and female patients. Conclusion Morphological and crystallographic data, phase composition and distribution in the examined urinary stone samples collected from Serbia region are similar to the data distribution in the developed part of the world as Europe and United States. This study showed that there are several different types of urinary stones that vary in structure and composition in this region. XRD analyses confirmed both macroscopic and microscopic observations that COD, COM, St, Br, Cy and UA as well as well crystallized urinary stones occur in analyzed samples. Only HA type of pathological mineral form of CaP mineral group occurs in irregular shapes and as a phase with low crystallinity. The most common minerals in the CaOx group are COD and COM, where COM is found more frequently than COD. A phosphate mineral forms as well but to a lesser extent than CaOx. The most frequent minerals are from CaOx group, which occurs almost in every sample of urinary stone. HA is most commonly found of CaP minerals. The other phases such as UA,
Fig. 5. SEM images of UA; a) Proper prismatic crystals of UA and EDS analysis b) Lines on monoclinic crystal plane and crystal forms of UA. 4
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UAD and Cy which present group of organic compounds are rarely present. Cystine type of stone rarely occurs. This study reports the first data related to stone occurrence in Serba which can be helpful in area of medicine. Such approach can use for other pathological calcifications namely prostatic [48,49], or breast [50,51]. In the case of kidney stones, these techniques may bring valuable information on ectopic calcifications present in kidney tissues, for the clinician [52]. This work presents a good foundation for more detailed studies of urinary tract diseases. However, for the complete specification of the urinary stone profile in Serbia, medical studies with larger sample population should be carried out. Microscopic examination of urine samples, age of the patients, life habits, and medical treatments and history would contribute greatly to the knowledge of the urinary stone formation in this region.
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CRediT authorship contribution statement Miljana Mirković: Formal analysis, Methodology, Data curation. Anja Dosen: Formal analysis, Methodology, Data curation. Suzana Erić: Formal analysis, Methodology, Data curation. Predrag Vulić: Formal analysis, Methodology, Data curation. Branko Matović: Formal analysis, Methodology, Data curation. Aleksandra Rosić: Formal analysis, Methodology, Data curation. Declaration of Competing Interest None Acknowledgments This project was financially supported by the Ministry of Education and Science of the Republic of Serbia. Project numbers: III 45012 and OI 176016. Supplementary materials Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.microc.2019.104429. References [1] M. Cirillo, D. Stellato, P. Panarelli, M. Laurenzi, N.G. De Santo, G. Gubbio Study Research, Cross-sectional and prospective data on urinary calcium and urinary stone disease, Kidney Int. 63 (2003) 2200–2206. [2] A.E. Krambeck, J.C. Lieske, X. Li, E.J. Bergstralh, L.J. Melton, A.D. Rule, Effect of age on the clinical presentation of incident symptomatic urolithiasis in the general population, J. Urol. 189 (2013) 158–164. [3] N.P. Rao, G.M. Preminger, J.P. Kavanagh, Urinary Tract Stone Disease, first ed., Springer-Verlag, London, 2011. [4] D. Krausová, Using X-ray diffraction in medical practice, Acta Univ. Palackianae Olomucensis Facultas Rerum Nat. 37 (1998) 25–48. [5] V.S. Joshi, S.R. Vasant, J.G. Bhatt, M.J. Joshi, Some critical aspects of FT-IR, TGA, powder XRD, EDAX and SEM studies of calcium oxalate urinary calculi, Indian J. Biochem. Biophys. 51 (2014) 237–243. [6] P.K. Grover, D.-S. Kim, R.L. Ryall, The effect of seed crystals of hydroxyapatite and brushite on the crystallization of calcium oxalate in undiluted human urine in vitro: implications for urinary stone pathogenesis, Mol. Med. 8 (2002) 200–209. [7] M.A. Childs, L.A. Mynderse, L.J. Rangel, T.M. Wilson, J.E. Lingeman, A.E. Krambeck, Pathogenesis of bladder calculi in the presence of urinary stasis, J. Urol. 189 (2013) 1347–1351. [8] J. Talati, H.-G. Tiselius, D.M. Albala, Z. YE, Urolithiasis, Basic Science and Clinical Practice, Springer-Verlag, London, UK, 2012. [9] J.C. Netelenbos, P.J.G. Zwijnenburg, P.M. ter Wee, Risk factors determining active urinary stone formation in patients with urolithiasis, Clin. Nephrol. 63 (2005) 188–192. [10] H.G. Tiselius, Epidemiology and medical management of stone disease, BJU Int. 91 (2003) 758–767. [11] M. Daudon, D. Bazin, G. Andre, P. Jungers, A. Cousson, P. Chevallier, E. Veron, G. Matzen, Examination of whewellite kidney stones by scanning electron microscopy and powder neutron diffraction techniques, J. Appl. Crystallogr. 42 (2009) 109–115. [12] X. Sheng, M.D. Ward, J.A. Wesson, Crystal surface adhesion explains the pathological activity of calcium oxalate hydrates in kidney stone formation, J. Am. Soc.
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Microchemical Journal journal homepage: www.elsevier.com/locate/microc
Phase and microstructural study of urinary stones a,⁎
a
b
b
a
Miljana Mirković , Anja Dosen , Suzana Erić , Predrag Vulić , Branko Matović , Aleksandra Rosićb a b
T
University of Belgrade, Vinča Institute of Nuclear Sciences, Department of Material Science, P.O Box 522, Belgrade, Serbia University of Belgrade, Faculty of Mining and Geology, Department of Mineralogy, Crystallography, Petrology and Geochemistry, Djusina 7, Belgrade, Serbia
ARTICLE INFO
ABSTRACT
Keywords: Urinary stones Phase composition Statistics X – Ray powder diffraction Scanning electron microscopy
In this paper we present the phase and morphological characteristics of urinary stones from Serbian patients. The study included for the first time the determination of the phase composition and a statistical analysis of the presence of different types of urinary stones in both men and women in Serbia. The main goal of study was representation of collected data for the first time. For past three years, more than 600 samples were collected from Serbian patients. The phase composition of all samples of urinary stones was investigated using XRD analysis. Morphology and chemical composition of phases in some characteristic samples was determinate by the SEM-EDS analysis. Results indicate that there are several different types of urinary stones that vary in mineral composition, chemistry and morphology. It was found that 312 (52%) of the 600 stones were composed of calcium oxalate minerals (CaOx): 17.3% of which were pure calcium oxalate monohydrate COM, 4% were pure calcium oxalate dihydrate COD; 200 (33.3%) were a mixture of CaOx and Hydroxyapatite HA, 19 (3.1%) were uric acid (uricite) UA and uric acid dihydrate UAD, 17 (2.8%) were a combination of UA and CaOx minerals, 41 (6.8%) were combination of CaP minerals and CaOx, 11 (1.9%) were cystine (Cy) stones. The obtained data shows the diversity of types of urinary stones. Morphological, chemical and XRPD analysis give us statistical data which shows that the most common urinary stones from Serbian patients are from CaOx group and in most of cases are associated with CaP.
Introduction The occurrence of urinary stones in human body is very common and formation of urinary stones are caused by certain processes that are not yet fully understood. The analysis included in this paper is related to the morphological and phase composition of urinary stones and represents the possibility of understanding the occurrence and morphology of urinary stones from patients from Serbia. Due to the limitations in terms of the amounts of the materials, best suited method for determination of urinary stones composition was XRD. For confirmation and stone morphology of analyzed samples we used SEM and EDS analysis. These methods have a very wide application in the analysis of crystalline materials and can be helpful as in this case for urinary stones determination. Urinary stone disease is a very common medical problem in industrialized countries, and it is affecting an increasing number of people [1,2]. Risk factors can be: dietary, non – dietary, and urinary that may contribute to the formation of urinary stones [3]. Several reasons for the formation of urinary stones are: metabolic disorders,
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increased secretion of uroproteins, environmental influences, civilization factor and eating habits [4,5]. Urolithiasis is a common disorder in the western world that affects 1–5% of population, causing urinary tract disease [2,6–8]. The disorders such as: hypercalciuria, hypocitraturia and urinary tract infection have influenced active stone formation [9]. Calcium oxalate (CaOx) stones are most common in people from Western European countries, accounting for about 70% compared to other types of stones [10]. CaOx has three types of crystalline forms: calcium oxalate monohydrate – Whewellite (COM) which is the most frequent form, calcium oxalate dihydrate – Weddelite (COD) which is two times less frequent and calcium oxalate trihydrate – Caoxite which is fairly rare. Note that for whewellite stones, various morphological aspects corresponding to lithogenic factors exist and a classification of whewellite stones into five main types, namely Ia, Ib, Ic, Id and Ie has been proposed [11–15]. Some literature data have suggested that urinary proteins play a major role for the COM aggregation [10,15,16]. These studies explain the predominance of COM in urinary stones. Difference in pathological activity of COM and COD is related to the adhesive character of their crystal faces [12,16]. Kidney stones made of
Corresponding author. E-mail address: [email protected] (M. Mirković).
https://doi.org/10.1016/j.microc.2019.104429 Received 17 September 2019; Received in revised form 12 November 2019; Accepted 14 November 2019 Available online 15 November 2019 0026-265X/ © 2019 Elsevier B.V. All rights reserved.
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Whewellite (COM) are induced by hyperoxaluria while the other crystalline form, i.e. Weddellite (COD) is induced by hypercalciuria [17]. Formation of COD crystals depends mostly on the presence of high Ca2+/oxalate ratios, ionic strength, ascorbic acid (citrate), and colloidal CaP, and pH ≥ 6 [6,12]. Besides these types, there are also other types of stones such as group of calcium phosphates (CaP): Hydroxyapatite – HA (Ca5(PO4)3(OH)), Struvite – St (MgNH4PO4•6H2O), Brushite – Br (Ca (HPO4)2•2H2O) and Whitlockite – Whl (Ca3(PO4)2). Stones which rarely occur are Cystine – Cy (C6H12N2O4S2), uric acid (uricite) – UA (C5H4N4O3) and uric acid dihydrate – UAD (C5H4N4O3•2H2O) [7,18–28]. Formation of investigated types of urinary stones is in good agreement with literature data [6,16,29]. Knowledge of stone composition is very important, for example, the presence of Struvite indicates an infection [30]. More precisely, different publications show clearly that stones resulting from urinary tract infection due to urea-splitting bacteria consist of calcium phosphate admixed with struvite and exhibit a high CO32− content, since UA, COM and Cy stones are hard and therefore less responsive to treatment with extracorporeal shock wave lithotripsy (ESWL) [31,32]. This method is the most common procedure used for the stone fragmentation [33]. The effectiveness of this method depends on the physicochemical composition of the stones [11,34–36]. Analyses of these characteristics of urinary stones are most commonly done with following methods: XRD, infrared spectroscopy, polarizing microscopy and SEM [5,11,28,37,38]. Main idea of this paper is to demonstrate the application of methods and approaches that are commonly used in various fields of materials science and geology on the matter that has biological origin and belongs to a field of bio crystallization and medicine. The present study reports findings of the composition and morphology of urinary stones in Serbian population for the first time. XRD and SEM analysis are very useful for detailed results of phase and morphological composition of urinary stones. This data correlated with XRD results can be helpful for complete and adequately medical treatment of patients. Experimental In this study we present the results of urinary tract stone samples collected from both genders, ages between 15 and 65. Analyzed samples were collected from hospitals across Serbia, collection took place from past three years, and during this period 600 samples were collected. Urinary stones vary from 1 mm to several millimeters in diameter. Samples were washed in alcohol and distilled water in order to remove organic matter and air-dried. X-ray powder diffraction data were collected at the Philips PW 1710, with CuKα. radiation. All samples were tested under the same experimental conditions: 40 KV/ 30 mA, 10–50° 2θ, step size 0.02°, count time 0.5 s. For phase identification we use JCPDS database and card standards. The following JCPDS file numbers with crystal system information were used for phase identification: COD (Wheddelite): 17-0541, Tetragonal; COM (Whewellite): 77-1160, Monoclinic; UA (Uricite): 28-2016, Monoclinic; HA (Hydroxyapatite): 89-6440, Hexagonal; Cy (Cystine): 37-1802, Hexagonal; Br (Brushite): 72-0713, Monoclinic; St (Struvite): 15-0762, Orthorhombic; Whl (Whitlockite): 9-0169, Rhombohedral. For SEM-EDS analyses were selected the samples with characteristic XRD patterns that differed in phase composition. SEM-EDS analysis was performed using a JEOL JSM-6610LV scanning electron microscope connected to an X-Max energy dispersive spectrometer to identify the morphologies and chemical compositions of the present phases. The samples were covered with gold using a BALTEC-SCD-005 sputter coating device, and the results were recorded under high vacuum conditions.
Fig. 1. Powder patterns of selected samples; a) COD and COM, b) UA and c) HA.
mineral composition and percentage of urinary stones in all samples from Serbian people. Number of females samples was 274 (45%), which is little less than males 326 (54%) samples. Kidney and urinary stones are biomaterials which contains mineral and organic phases as well as some trace elements [39,40]. Such complexity in chemical composition leads to the use of various characterization techniques [41,42]. The phase composition of urinary stones was determined by XRD as described previously. In half of all the samples COM and COD occur together, as single phases and in mixtures have almost 90% of occurrence. XRD analysis showed that the most common phases are from CaOx and CaP mineral group. These phases often occur together with other, infection stones such as UA, UAD and Cy [43,44]. The phases mentioned above exhibit a high degree of crystallinity in all samples. XRD results of most common phases were presented on Fig. 1. Well defined
Results and discussion All of collected samples are presented in Table (S1), which shows 2
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Fig. 2. SEM images of COM; a) EDS spectrum of indicated tabular crystals of COM b) Sheet – like layers of COM crystals bonded together.
narrow peaks imply well crystallized and well-ordered structure, which was observed for COM and COD samples presented on Fig. 1a. Degree of crystallinity both of COM and COD is about 68%. Pathological UA also shows sharp and narrow peaks, with degree of crystallinity about 65% based on powder diffractogram showed on Fig. 1b. In all other investigated samples phosphate phases like Br, Whl and St from has good structural order based on XRD results, which is in correlation with literature data [30]. Based on literature data CaP stones are more often represented in females, and reflect a wide diversity and etiology [45]. Brushite stones will be formed if its conversion to hydroxyapatite does not occur, where it is considered to be a precursor to the formation of hydroxyapatite [46]. Other phosphate such as HA is more frequently represented. XRD of HA shows low intensity broad peaks with degree of crystallinity about 16%, which is indicating low structural arrangement (Fig. 1c). XRD analyses showed that HA stones of female patients exhibit significantly lower crystallinity than in male samples. SEM results confirms high degree of crystallinity of pathological COM which is defined by well-developed tabular crystal forms, sizes between 10 μm and 60 μm (Fig. 2a). Crystals has tabular monoclinic prismatic morphology. Growth lines on mineral grains show the direction of crystal growth and stone formation. The striated layers on COM crystal surface show that it was formed by columnar juxtaposed sheet – like layers together (Fig. 2b). Based on SEM microphotographs it is identified classic crystal shape of COD which is the eight – face bipyramid (Fig. 3a). Pathological COD tetragonal bipyramid crystals have crystal forms that are flattened and elongated along Z –axis, sizes vary between 10 and 50 μm (Fig. 3b).
Tiselius et al. explained the process of developing CaOx and CaP stones [10]. The different conditions prevailing in the bodies of patients lead to the formation of crystals and aggregates of larger or smaller size and degree of order [45]. Crystal morphology of analyzed stones shows the differences in the pathologic behavior of COM and COD (Figs. 2 and 3) which is related to the adhesive character of their crystal faces. Pathological COD form is a thermodynamically unstable phase of CaOx, which transforms into to a stable monohydrate in contact with water. Based on SEM results it is evident that HA has low crystallinity i.e. it is amorphous (Fig. 4a and b). Spheres of HA pathological stones are characterized as cemented layers of amorphous material. Shape and morphology of analyzed samples depend on the physical – chemical conditions of formation of these minerals in the human body. High level of pathological COM and COD crystal form development indicates favorable crystal growth conditions in the human body. On the other hand, pathological HA have spherical occurrence. Spheres of HA are consisting of amorphous hydroxyapatite layers (Fig. 4b). Microscopically these layers seem amorphous. They are composed of small spheres, of amorphous material which is cemented together. This HA layers are most likely formed in urine as a basis for deposition and formation of CaOx. Porosity of the HA stones indicates they are easier to break up by ESWL method than CaOx stones (Figs. 2 and 3). In samples HA rarely occur alone and usually accompany other phases such as CaOx and St. Based on SEM analysis it is observed that UA as a pathological mineral formation has a very good structural arrangement and well developed and proper prismatic crystals sizes 30 μm (Fig. 5a and b).
Fig. 3. SEM images of COD; a) Eight – face bipyramid and EDS analysis of indicated COD crystal b) Tetragonal crystal forms that are flattened and elongated along Z –axis. 3
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Fig. 4. SEM images of CaP; a) Spheres of CaP (HA) with EDS analysis of indicate sample b) Amorphous layers of HA.
Lines on monoclinic crystal plane indicate direction of crystal growth. UA crystals have developed different crystal forms of clinopinacoid (0 l 0), orthoprism (h k 0) and negative orthohemidome (h¯ k l) (Fig. 5b). High degree of crystal regularity indicates favorable crystallization conditions in human body. These types of stones are predominantly composed of uric acid (UAD), which crystallizes from an aqueous solution and transforms into the anhydrous salt. Factors which leads to this type of stone formation is in a first line: low urinary output, acidic urine and hyperuricuria [47]. Beside this phase, we identify UAD phase which is always in mixture with UA. We didn`t find pure UAD single stones. SEM results are confirmed structural arrangement of samples. EDS results are confirmed chemical composition of phases in selected and investigated samples. EDS analysis in all samples do not indicate existence of trace or toxic elements. The examination of the content of toxic elements was not the subject of this study. All the types of examined urinary stones from Serbian patients both female and male patients are presented as histograms S1 which presents stone composition as a function of distribution and stone representation in all samples. The most common types of urinary tract infection stones are COD and COM which occur more frequently in male patients 28.5% than in female patients 23.3%. Mixture of CaP and CaOx stones occurs more in males than in female's samples (male patients 112 (18.7%) and female patients 88 (14.7%)). Pure UA stones are identified mostly in male samples 2.6% while in female samples has occurrence of 0.5%. Mixture of UA, UAD and CaOx urinary stones occurs in 2.3% male and in 1% female samples. Group of CaP minerals as various types of mixtures (S1), occurs twice as often in females with abundance of 4.8%
than in males 2.2% urinary stones. Struvite type of stone in combination with HA is more frequent in female samples 2%, in male samples has only 0.8% of occurrence. Cystine urinary stones have the lowest representation. Also it is important to note that formation of this type of kidney stone is related to genetic disease [43,44]. In all samples Cystine stones have almost three times as many are in female 1.3% than in male 0.5% urinary stones. This is the first study that shows the distribution and types of urinary stones and their morphological characteristics in Serbia in both male and female patients. Conclusion Morphological and crystallographic data, phase composition and distribution in the examined urinary stone samples collected from Serbia region are similar to the data distribution in the developed part of the world as Europe and United States. This study showed that there are several different types of urinary stones that vary in structure and composition in this region. XRD analyses confirmed both macroscopic and microscopic observations that COD, COM, St, Br, Cy and UA as well as well crystallized urinary stones occur in analyzed samples. Only HA type of pathological mineral form of CaP mineral group occurs in irregular shapes and as a phase with low crystallinity. The most common minerals in the CaOx group are COD and COM, where COM is found more frequently than COD. A phosphate mineral forms as well but to a lesser extent than CaOx. The most frequent minerals are from CaOx group, which occurs almost in every sample of urinary stone. HA is most commonly found of CaP minerals. The other phases such as UA,
Fig. 5. SEM images of UA; a) Proper prismatic crystals of UA and EDS analysis b) Lines on monoclinic crystal plane and crystal forms of UA. 4
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UAD and Cy which present group of organic compounds are rarely present. Cystine type of stone rarely occurs. This study reports the first data related to stone occurrence in Serba which can be helpful in area of medicine. Such approach can use for other pathological calcifications namely prostatic [48,49], or breast [50,51]. In the case of kidney stones, these techniques may bring valuable information on ectopic calcifications present in kidney tissues, for the clinician [52]. This work presents a good foundation for more detailed studies of urinary tract diseases. However, for the complete specification of the urinary stone profile in Serbia, medical studies with larger sample population should be carried out. Microscopic examination of urine samples, age of the patients, life habits, and medical treatments and history would contribute greatly to the knowledge of the urinary stone formation in this region.
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CRediT authorship contribution statement Miljana Mirković: Formal analysis, Methodology, Data curation. Anja Dosen: Formal analysis, Methodology, Data curation. Suzana Erić: Formal analysis, Methodology, Data curation. Predrag Vulić: Formal analysis, Methodology, Data curation. Branko Matović: Formal analysis, Methodology, Data curation. Aleksandra Rosić: Formal analysis, Methodology, Data curation. Declaration of Competing Interest None Acknowledgments This project was financially supported by the Ministry of Education and Science of the Republic of Serbia. Project numbers: III 45012 and OI 176016. Supplementary materials Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.microc.2019.104429. References [1] M. Cirillo, D. Stellato, P. Panarelli, M. Laurenzi, N.G. De Santo, G. Gubbio Study Research, Cross-sectional and prospective data on urinary calcium and urinary stone disease, Kidney Int. 63 (2003) 2200–2206. [2] A.E. Krambeck, J.C. Lieske, X. Li, E.J. Bergstralh, L.J. Melton, A.D. Rule, Effect of age on the clinical presentation of incident symptomatic urolithiasis in the general population, J. Urol. 189 (2013) 158–164. [3] N.P. Rao, G.M. Preminger, J.P. Kavanagh, Urinary Tract Stone Disease, first ed., Springer-Verlag, London, 2011. [4] D. Krausová, Using X-ray diffraction in medical practice, Acta Univ. Palackianae Olomucensis Facultas Rerum Nat. 37 (1998) 25–48. [5] V.S. Joshi, S.R. Vasant, J.G. Bhatt, M.J. Joshi, Some critical aspects of FT-IR, TGA, powder XRD, EDAX and SEM studies of calcium oxalate urinary calculi, Indian J. Biochem. Biophys. 51 (2014) 237–243. [6] P.K. Grover, D.-S. Kim, R.L. Ryall, The effect of seed crystals of hydroxyapatite and brushite on the crystallization of calcium oxalate in undiluted human urine in vitro: implications for urinary stone pathogenesis, Mol. Med. 8 (2002) 200–209. [7] M.A. Childs, L.A. Mynderse, L.J. Rangel, T.M. Wilson, J.E. Lingeman, A.E. Krambeck, Pathogenesis of bladder calculi in the presence of urinary stasis, J. Urol. 189 (2013) 1347–1351. [8] J. Talati, H.-G. Tiselius, D.M. Albala, Z. YE, Urolithiasis, Basic Science and Clinical Practice, Springer-Verlag, London, UK, 2012. [9] J.C. Netelenbos, P.J.G. Zwijnenburg, P.M. ter Wee, Risk factors determining active urinary stone formation in patients with urolithiasis, Clin. Nephrol. 63 (2005) 188–192. [10] H.G. Tiselius, Epidemiology and medical management of stone disease, BJU Int. 91 (2003) 758–767. [11] M. Daudon, D. Bazin, G. Andre, P. Jungers, A. Cousson, P. Chevallier, E. Veron, G. Matzen, Examination of whewellite kidney stones by scanning electron microscopy and powder neutron diffraction techniques, J. Appl. Crystallogr. 42 (2009) 109–115. [12] X. Sheng, M.D. Ward, J.A. Wesson, Crystal surface adhesion explains the pathological activity of calcium oxalate hydrates in kidney stone formation, J. Am. Soc.
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