Mineralogy and chemistry of urinary stones: patients from North Jordan

Urinary stone diseases are increasing in the Middle East. The majority of urinary stone cases are found in the northern part of the country. Stone samples taken from patients living in the Irbid area were collected from Princess Basma Hospital. The present study concentrates on the mineralogical and chemical composition of the urinary stones and on the effective environmental factors that assist in developing the different types of urinary stones. Using X-ray diffraction techniques, the mineralogical composition of the urinary stones was found to be as follows: oxalate, cholesten, and uric acid, with cystine stones occuring more frequently than the others. Cholesten and calcium oxalate stones are the most dominant types of stones. Calcium oxalate is the most common type of oxalate stone. Calcium oxalate is represented in: whewellite, wheddellite, and calcium carbonate oxalate hydrate minerals, in addition to other minerals such as brushite, ammonium phosphate, vaterite, valleriite, and bobierrite from other types of stones. Bobierrite (phosphate group) is a new mineral reported in urinary stones, and this has not been determined in any previous study worldwide. Apatite (calcium phosphate) is deduced using scanning electron microscope (SEM) images. The SEM technique determined crystal forms and systems, shapes, morphological features, and the names of the minerals forming urine stones, while optical properties are studied by polarizing microscope. X-ray fluorescence technique determined the concentrations of major and some trace elements. It revealed that Ca is the main constituent of the urinary stones, especially those composed of calcium oxalate and calcium phosphate. The concentration of trace elements was Ba = 1.57, P = 3.61, Fe = 1.78, S = 2.08, Zr = 4.63, Mo = 3.92, Cu = 1.89, Co = 1.56, and F = 4.2% and was higher in the urinary stones of Jordanian patients than in foreigners in the country. Questionnaires completed by patients suggest that the most significant factors directly effecting the formation of stones are water, climate conditions, food rich in protein and rich in different chemicals. Moreover, some drugs and diseases might also help in developing other stones.     

Mineralogical studies of human urinary calculi from Natal

Knowledge of the composition of human urinary calculi within a geographical area can lead to an understanding of the epidemiology of renal stone disease. Studies in the Durban area, with its high incidence of kidney and bladder stones, indicate that calcium oxalate is the overwhelmingly dominant (circa 80%) component, followed by uric acid. An important feature is the low occurrence of phosphate stones, especially those containing struvite.     

Mineralogical,compositional and isotope characterization of human kidney stones (urolithiasis) in a Sri Lankan population

In order to understand the processes of stone formation, compositional, spectroscopic, mineralogical and crystallographic characteristics of human urinary stones collected from patients in Sri Lanka were investigated in detail. The data showed that the majority of urinary calculi were calcium oxalate, either whewellite or weddellite. Other solid phases of stones were composed of struvite, uricite and hydroxylapatite. However, mixed compositions were common except for whewellite stones which occur frequently in pure form. Scanning electron microscope observations and associated energy-dispersive X-ray analyses revealed that whewellite or weddellite was well crystalized compared to other stones types, while phosphate stones were mostly cryptocrystalline. The average δ¹³C and δ¹⁸O of stones were − 32.2‰ (− 37.3 to − 17.4‰) and − 24.2‰ (− 26.7‰ to − 8.9‰), respectively. The δ¹³C values were highly depleted compared to North American and European urinary stones. This may be due to food habits of Asians who consume rice as the staple food.

     

Urinary stones as a novel matrix for human biomonitoring of toxic and essential elements

Monitoring of body burden of toxic elements is usually based on analysis of concentration of particular elements in blood, urine and/or hair. Analysis of these matrices, however, predominantly reflects short- or medium-term exposure to trace elements or pollutants. In this work, urinary stones were investigated as a matrix for monitoring long-term exposure to toxic and essential elements. A total of 431 samples of urinary calculi were subjected to mineralogical and elemental analysis by infrared spectroscopy and inductively coupled plasma mass spectrometry. The effect of mineralogical composition of the stones and other parameters such as sex, age and geographical location on contents of trace and minor elements is presented. Our results demonstrate the applicability of such approach and confirm that the analysis of urinary calculi can be helpful in providing complementary information on human exposure to trace metals and their excretion. Analysis of whewellite stones (calcium oxalate monohydrate) with content of phosphorus <0.6 % has been proved to be a promising tool for biomonitoring of trace and minor elements.

     

Biomineralogy of human urinary calculi (kidney stones) from some geographic regions of Sri Lanka

Kidney stones (urinary calculi) have become a global scourge since it has been recognized as one of the most painful medical problems. Primary causative factors for the formation of these stones are not clearly understood, though they are suspected to have a direct relationship to the composition of urine, which is mainly governed by diet and drinking water. Sixty nine urinary calculi samples which were collected from stone removal surgeries were analyzed chemically for their Na, K, Ca, Mg, Cu, Zn, Pb, Fe and phosphate contents. Structural and mineralogical properties of stones were studied by XRD and FT-IR methods. The mean contents of trace elements were 1348 mg kg⁻¹ (Na); 294 mg kg⁻¹ (K); 32% (Ca); 1426 mg kg⁻¹ (Mg); 8.39 mg kg⁻¹ (Mn); 258 mg kg⁻¹ (Fe); 67 mg kg⁻¹ (Cu); 675 mg kg⁻¹ (Zn); 69 mg kg⁻¹ (Pb); and 1.93% (PO₄³⁻). The major crystalline constituent in the calculi of Sri Lanka is calcium oxalate monohydrate. Principal component analysis was used to identify the multi element relationships in kidney stones. Three components were extracted and the first component represents positively correlated Na-K-Mg-PO₄³⁻ whereas the␣second components represent the larger positively weighted Fe–Cu–Pb. Ca–Zn correlated positively in the third component in which Mn–Cu correlated negatively. This study indicates that during the crystallization of human urinary stones, Ca shows more affinity towards oxalates whereas other alkali and alkaline earths precipitate with phosphates.Contribution from the Environmental Geology Research Group (EGRG), Department of Geology, University of Peradeniya, Sri Lanka.     

Association of minor and trace elements with mineralogical constituents of urinary stones: A hard nut to crack in existing studies of urolithiasis

The role of metals in urinary stone formation has already been studied in several publications. Moreover, urinary calculi can also be used for assessing exposure of humans to minor and trace elements in addition to other biological matrices, for example, blood, urine, or hair. However, using urinary calculi for biomonitoring of trace elements is limited by the association of elements with certain types of minerals. In this work, 614 samples of urinary calculi were subjected to mineralogical and elemental analysis. Inductively coupled plasma mass spectrometry and thermo-oxidation cold vapor atomic absorption spectrometry were used for the determination of major, minor, and trace elements. Infrared spectroscopy was used for mineralogical analysis, and additionally, it was also employed in the calculation of mineralogical composition, based on quantification of major elements and stoichiometry. Results demonstrate the applicability of such an approach in investigating associations of minor and trace elements with mineralogical constituents of stones, especially in low concentrations, where traditional methods of mineralogical analysis are not capable of quantifying mineral content reliably. The main result of this study is the confirmation of association of several elements with struvite (K, Rb) and with calcium phosphate minerals, here calculated as hydroxylapatite (Na, Zn, Sr, Ba, Pb). Phosphates were proved as the most important metal-bearing minerals in urinary calculi. Moreover, a significantly different content was also observed for Fe, Zr, Mo, Cu, Cd, Se, Sn, and Hg in investigated groups of minerals. Examination of such associations is essential, and critical analysis of mineral constituents should precede any comparison of element content among various groups of samples.     

Mineralogical Investigation of an Enterolith from a Grant's Zebra

An enterolith surgically removed from a Grant's zebra was investigated by standard mineralogical techniques including X-ray diffraction, scanning electron microscopy and electron microprobe analysis. It was predominantly composed of a suite of phosphate minerals which have precipitated on and between aggregates of undigested plant material. It was apparently cored by a small nidus of granitic rock which served as a site for heterogeneous nucleation for the larger phosphatic overgrowth. Phosphate was deposited by at least two distinct mechanisms. In the enterolith's core, phosphate minerals replaced or rimmed silicate grains (e.g. feldspars and quartz) which are relics of the disaggregated granitic nidus. As the enterolith subsequently accreted outwards from the nidus, struvite was precipitated directly onto fibres of plant material, or within the pore spaces between them. The generally fine grain size of struvite in enteroliths, relative to that in urinary calculi, may be due to the ubiquitous presence of the undigested plant fibres. Struvite, close to (NH₃)_0.9K_0.1MgPO₄ · 6H₂O in composition, is the only phosphate mineral in the outer portions of the enterolith. Within the enterolith's interior, struvite occurs subequally with Mg-vivianite, close to Mg_2.9Fe_0.1(PO₄)₂ · 8H₂O in composition. Textural relations suggest that the mineralogical transformation of struvite to Mg-vivianite is a consequence of diagenesis, presumably related to a decrease in pH and/or (NH₄)⁺ activity, within the core of the enterolith. If enterolith growth is mediated by the accumulation of a particular form of undigested plant fibre (e.g. lucerne hay), the identification and dietary removal of this material may prevent or at least impede the development of enteroliths.     

May a comprehensive mineralogical study of a jackstone calculus and some other human bladder stones unveil health and environmental implications?

This paper represents the first result of an active collaboration between the University of Sannio and the San Pio Hospital (Benevento, Italy), started in the 2018, that aims to a detailed mineralogical investigation of urinary stones of patients from Campania region. Herein, selected human bladder stones have been deeply characterized for clinical purposes and environmental biomonitoring, focusing on the importance to evaluate the concentration and distribution of undesired trace elements by means of microscopic techniques in the place of conventional wet chemical analyses. A rare bladder stone with a sea-urchin appearance, known as jackstone calculus, were also investigated (along with bladder stones made of uric acid and brushite) by means a comprehensive analytical approach, including Synchrotron X-ray Diffraction and Simultaneous Thermal Analyses. Main clinical assumptions were inferred according to the morpho-constitutional classification of bladder stones and information about patient’s medical history and lifestyle. In most of the analyzed uroliths, undesired trace elements such as copper, cadmium, lead, chromium, mercury and arsenic have been detected and generally attributable to environmental pollution or contaminated food. Simultaneous occurrence of selenium and mercury should denote a methylmercury detoxification process, probably leading to the formation of a very rare HgSe compound known as tiemannite.

     

TAR柱前络合、毛细管电泳分析痕量金属离子

1　IntroductionTransitionmetalswereamongthemostconcernelementsinenvironmentalanalysisduetotheirpotentialrolestoplantandanimals[1 ].Theserolesoftransitionmetalsinenvironmentdependedontheirconcentrationinthesoil,waterandlivingthings.Currently ,themostutiliz…     

Groundwater vulnerability to selenium in semi-arid environments: Amman Zarqa Basin,Jordan

An evaluation of ~250 samples of groundwater in the Amman Zarqa Basin for selenium along with other major and trace elements showed that concentrations of Se ranged between 0.09 and 742 μg/L, with an average value of about 24 μg/L. Selenium concentrations exceeded the recommended threshold for drinking water of the World Health Organization (WHO; 10 μ/L of Se) in 114 samples, with greater than 50 μg/L (quantity equivalent to the Jordanian standard of the allowed concentration of the element in water) of Se in nine cases. The average concentrations of Se in the lower, middle, and upper aquifers of the basin were 3.41, 32.99, and 9.19 μg/L, respectively. Based on the correlation with geologic formations and the statistical analysis of major/minor constituents and Piper tri-linear diagrams, we suggest that carbonate/phosphate dissolution, oxidation–reduction processes, and fertilizers/irrigation return flow are, together, the primary factors affecting the chemistry of the groundwater. Factor analysis helped to define the relative role of limestone-dolomitic dissolution in the aquifers (calcium, magnesium, and bicarbonate), agricultural activities (sulfate, nitrates, phosphorus, and potassium), oxidation–reduction factor (Eh, Fe, Mn, Cu, Zn, and Se), and anthropogenic (industrial) factor (EC, Fe, Cr, Co, Zn, and As). The high variability in Se concentrations might be related to the possibility of a multi-source origin of Se in the area.     

Potential environmental impact of dissolution of raw phosphate in sea water of the Gulf of Aqaba

Dissolution of raw phosphate (apatite) in sea water of the Gulf of Aqaba was investigated through lab incubation experiments. Three types from three different sources (Al-Hasa, Al-Abyad and Esh-Shydiya) have been used for these experiments. Impact of quantity, grain size, and source (type) of raw phosphate on dissolution rate were studied. Statistical analysis shows significant differences between the results obtained from comparing each two weights; as weight of apatite increased, dissolved inorganic phosphate-phosphorus (DIP) and fluoride in sea water solution increased. The differences between the dissolution rates of raw phosphate from the three sites were not significant while the differences between the different grain size fractions were significant. Dissolution rates were inversely related to particle size. Using a worst-case scenario, a conservative estimate of the maximum increase in DIP in seawater of the Gulf of Aqaba due to the apatite particles lost to the sea during ship loading resulted in DIP concentrations of 0.03 μM per year. As the residence time of the water in the Gulf of Aqaba is about one year, the DIP concentration will not increase by more than 0.03 μM under the estimated annual quantity of exported phosphate. Fluoride will not increase by more than 0.03 mg/l under the same conditions.     

Potential environmental impact of dissolution of raw phosphate in sea water of the Gulf of Aqaba

Dissolution of raw phosphate (apatite) in sea water of the Gulf of Aqaba was investigated through lab incubation experiments. Three types from three different sources (Al-Hasa, Al-Abyad and Esh-Shydiya) have been used for these experiments. Impact of quantity, grain size, and source (type) of raw phosphate on dissolution rate were studied. Statistical analysis shows significant differences between the results obtained from comparing each two weights; as weight of apatite increased, dissolved inorganic phosphate-phosphorus (DIP) and fluoride in sea water solution increased. The differences between the dissolution rates of raw phosphate from the three sites were not significant while the differences between the different grain size fractions were significant. Dissolution rates were inversely related to particle size. Using a worst-case scenario, a conservative estimate of the maximum increase in DIP in seawater of the Gulf of Aqaba due to the apatite particles lost to the sea during ship loading resulted in DIP concentrations of 0.03 μM per year. As the residence time of the water in the Gulf of Aqaba is about one year, the DIP concentration will not increase by more than 0.03 μM under the estimated annual quantity of exported phosphate. Fluoride will not increase by more than 0.03 mg/l under the same conditions.     

Reduction of availability of trace metals in urban soils using inorganic amendments

Urban soils in medium- and large-sized cities generally have shown elevated contents of environmentally important trace metals (e.g. lead, copper, zinc). Such high concentrations in soils of green areas, mainly recreational areas, can be a source of potentially toxic elements and pose a risk for human health. Thus the availability of these contaminants is an essential control parameter, as it indicates potential plant uptake and their transfer to humans via inhalation of suspended dust, or direct ingestion (i.e. hand to mouth pathway), or consumption of contaminated foodstuff. Young children are the most sensitive segment of the population. Addition of amendments to the soil is a feasible technique to reduce the availability of trace metals. Accordingly, four urban soils of green areas of Seville (Spain), with relatively high lead contents and moderate copper and zinc contents, were amended in the laboratory with four inorganic materials [acid zeolite (AZ), sodium zeolite (SZ), Slovakite (SL), apatite (AP)], at two rates (1%, 5% w/w) and incubated for 1 year. Significant decreases in EDTA-extractable metal contents were observed in some of the treatments after adding the amendments even before the incubation begun, mainly for SL treatments. The amendment that produced the longest lasting immobilisation effect, compared to control treatments, was AZ at the higher rate. The effects of SZ and SL tended to decrease with time, while the AP effect was almost negligible after 3 months of ageing. This study confirms the feasibility of using certain inexpensive soil amendments to at least temporarily immobilise metals in urban soils for the purpose of protecting human health, especially that of young children.     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.     

全氟辛酸对大鼠海马细胞内钙离子浓度的影响

采用连续灌胃染毒的方法,探讨了全氟辛酸(Perfluorooctanoic acid,PFOA)经口急性染毒对大鼠海马细胞内钙离子浓度的影响.选择雄性Wistar大鼠40只,实验组PFOA染毒剂量分别为2、8、30mg·kg-1(bw).连续灌胃染毒7天后,制备海马单细胞悬液,采用Fura-2/AM荧光探针法测定海马细胞内游离钙离子浓度([Ca2+]i),使用固相萃取-高效液相色谱/质谱联机法(HPLC/MS-MIS)检测血清与脑组织中PFOA浓度.结果表明,染毒组大鼠血清与脑中PFOA浓度均显著高于对照组水平(p<0.01),血清与脑中PFOA浓度之间存在显著的正相关关系(r2=0.611,p<0.01).PFOA染毒8、30mg·kg-1(bw)实验组海马细胞[Ca2+]i分别为(207.89±22.84)nmol·L-1和(284.19±14.75)nmol·L-1,显著高于对照组((141.68±11.47)nmol·L-1)和PFOA染毒2mg·kg-1(bw)实验组((147.38±19.23)nmol·L-1)(p<0.01).大鼠脑、血清中PFOA浓度分别与海马[Ca2+]i存在正相关关系(r2=0.552,p<0.01;r2=0.756,p<0.01).研究结果显示,PFOA暴露可使血清和脑组织中PFOA浓度增加,引起大鼠海马神经元细胞[Ca2+]i升高.     

不同阳离子影响下小麦根吸收镉的动力学过程

生物配体模型(BLM)是基于稳定态假设的一个平衡模型,能够较准确地运用于预测重金属的毒性及其生物有效性.根据BLM模型的假设条件模拟土壤溶液,研究了Ca2+、Mg2+、Cu2+和Ni2+对小麦根吸收Cd2+动力学的影响,阐述了BLM在应用中存在的局限性.结果表明:在8h内的短期动力学吸收实验中,小麦根对Cd的吸收及吸附量呈线性增加,但未达到稳定值,这说明Cd2+在根-液界面未达到稳定平衡;并且小麦根对Cd的吸收是受溶液中Cd2+扩散速率影响的.小麦根对Cd的吸收通量与Cd2+浓度[Cd2+]和Cd与小麦根表上的配体结合浓度{Cd-Rcel}l都具有较好的线性关系,但随着Cd2+浓度的增加稳定常数KM-Rcell、渗透常数p和同化速率常数kint均呈降低趋势.Ca2+、Mg2+和Cu2+降低了小麦根对Cd2+的吸收通量,而Ni2+对Cd2+的竞争作用不显著.由于Cd与Ca、Ni有共同的吸收通道,Ca通道吸收达到饱和后可降低小麦根对Cd的吸收,但是Ca2+、Mg2+和Cu2+通过降低内化速率常数也可使小麦根对Cd的内化通量减少,因此不能完全用竞争效应解释其结果.另外,阳离子的存在会改变小麦根表的性质,Ca2+、Mg2+的存在会增加亨利系数KCd,即生物配体浓度{Rcel}l和(或)离子与生物配体结合稳定常数KCd-Rcell会增加,同时这些离子的存在还会降低渗透常数p和kint;Cu2+、Ni2+的存在会降低KCd;且p和k在低浓度Cd(0.01～0.05μM)条件下增加,在高浓度Cd条件下降低.     

X-ray diffraction and SEM study of kidney stones in Israel: quantitative analysis, crystallite size determination, and statistical characterization

Urinary calculi have been recognized as one of the most painful medical disorders. Tenable knowledge of the phase composition of the stones is very important to elucidate an underlying etiology of the stone disease. We report here the results of quantitative X-ray diffraction phase analysis performed on 278 kidney stones from the 275 patients treated at the Department of Urology of Hadassah Hebrew University Hospital (Jerusalem, Israel). Quantification of biominerals in multicomponent samples was performed using the normalized reference intensity ratio method. According to the observed phase compositions, all the tested stones were classified into five chemical groups: oxalates (43.2%), phosphates (7.7%), urates (10.3%), cystines (2.9%), and stones composed of a mixture of different minerals (35.9%). A detailed analysis of each allocated chemical group is presented along with the crystallite size calculations for all the observed crystalline phases. The obtained results have been compared with the published data originated from different geographical regions. Morphology and spatial distribution of the phases identified in the kidney stones were studied with scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). This type of detailed study of phase composition and structural characteristics of the kidney stones was performed in Israel for the first time.     

厌氧污泥释放磷的规律及鸟粪石法回收磷的应用研究

城市污水处理厂进行脱氮除磷工艺时,大量的磷从水体转入活性污泥中,如不能回收这部分磷,将造成磷的大量流失,这与磷矿稀缺的现状形成矛盾。通过建立污泥停留时间5 d和10 d的两个厌氧反应系统,对污泥中磷的释放规律进行研究,并采用鸟粪石法对上清液中的磷进行回收。研究结果表明,厌氧污泥上清液中的磷含量高达150 mg.L-1,SRT为5 d和10 d的系统,分别在4 d和2 d后磷的质量浓度由14 mg.L-1上升到100 mg.L-1,且基本上都以正磷酸盐的形式存在。将pH从8.3上升到9.0,磷的回收率可以从60%提升到90%,当pH达到8.8时,磷的回收率即可超过80%,表现出了较好的磷回收效果。研究还发现镁离子和磷酸根的摩尔比对磷的回收率的影响较小,在pH=8.8时,将镁磷比从1.43提升到1.83,磷的回收率仅从79.2%提升到85.5%;在pH=9.0时提高镁磷比对磷的回收基本没有影响。     

Optimization of anaerobic processes by speciation and bioavailability of trace metals

The deficiency trials of some trace metals (copper, nickel, zinc) were made in laboratory Upflow Anaerobic Sludge Blanket (UASB) reactors containing the inoculum of an industrial anaerobic sludge, a basal medium with the rest of nutrients and vitamins in comparison with a control reactor with the optimal doses of trace elements. From the main control parameters (alkalinity, acidity, DQO), no inactivation by deficit of essential elements was detected, but the control reactor showed greater mineralization and solid content, being necessary to make purge to avoid bulking. The inoculum has high metallic element contents, so the additional contribution produces high bacterial growth, also purge being necessary to avoid bulking. The purge, made after 120 days in continuous operation, eliminates a great quantity of solids and increases the volatile solids (VS)/total solids (TS) ratio. The comparison of the initial content of metallic elements in the solid and liquid phases with the contents after 120 days showed a progressive depletion of metals in all reactors without a clear appreciation of the lack of the studied metals. Finally, in 210 days, the reactors without addition of a metallic element accumulated greater quantity of major (Ca, Fe, Mg) and trace (Co, Ni, Cu) elements in the solid phase with respect to the control.     

Correlation between lead and iron in children's blood in Jordan

A total of 200 Jordanian children were classified into two groups: 100 Fe replete and 100 Fe deficient with ages ranging between 3.0 and 12.0 years (6.9 ± 2.7 years). All participants were chosen according to proper selection criteria followed by the sample collection: the samples were analyzed for hemoglobin and red blood cells; ferritin, an immunoassays-based instrument; and levels of Pb, Cu, and Zn. There were no significant differences between genders regarding Fe-deficiency (p = 0.57 and χ2 = 0.33), with a significant association of younger individuals (3.0–9.1 years) with Fe-deficiency (p < 0.05 and χ2 = 22.7).

In addition, there is a significant positive correlation between Fe-deficiency with blood levels of Pb, Cu, and Zn (p < 0.05), (r = 0.43, 0.35, and 0.42, respectively) as compared to control group, this findings supported, by comparing the levels of the examined metals in both groups, in individuals whom close to heavy metals source (highway traffic or oil gas station), and found that the mean of the heavy metals level in close Fe-deficient group higher than in close Fe-replete group.