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.

     

Chemistry, mineralogy and radioactivity in posidonia oceanica meadows from North-Western Sicily

This paper presents measurements of major, minor, metal trace elements and radionuclides in sediments and in Posidonia oceanica samples from north-western Sicily (Italy). The mineralogical and chemical composition of sediments were determined by X-ray diffraction and X-ray fluorescence techniques, respectively. A flame atomic absorption spectrophotometry was used to measure concentrations of Cu, Zn, Cd and Pb in P. oceanica samples and in sediments. Specific activities of selected radionuclides have been determined by high-resolution gamma spectrometry. Standard statistical analysis was used to assess correlations between different elements and different sample types.     

Chemistry,mineralogy and radioactivity in posidonia oceanica meadows from North-Western Sicily

This paper presents measurements of major, minor, metal trace elements and radionuclides in sediments and in Posidonia oceanica samples from north-western Sicily (Italy). The mineralogical and chemical composition of sediments were determined by X-ray diffraction and X-ray fluorescence techniques, respectively. A flame atomic absorption spectrophotometry was used to measure concentrations of Cu, Zn, Cd and Pb in P. oceanica samples and in sediments. Specific activities of selected radionuclides have been determined by high-resolution gamma spectrometry. Standard statistical analysis was used to assess correlations between different elements and different sample types.     

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.     

Geochemical and mineralogical characteristics of elephant geophagic soils in Udawalawe National Park,Sri Lanka

Geophagy or deliberate ingestion of soils was observed among Asian elephants (Elephas maximus) in the Udawalwe National Park, Sri Lanka, for several years. The geochemical and mineralogical composition of the clayey soil layers which are purposefully selected and eaten by elephants in the park were studied, in order to identify the possible reasons for elephant geophagy. The concentrations of major and trace elements were determined by means of X-ray fluorescence spectrometry in 21 soil samples from eight geophagic sites and six soil samples collected from four non-geophagic sites. The mineralogical composition of selected soil samples was investigated using X-ray diffractometry (XRD). These geochemical analyses revealed that geophagic soils in the study areas are deeply weathered and that most of the elements are leached from the soil layers under extreme weathering conditions. The XRD data showed that the soils of the area consisted mainly quartz, feldspar, and the clay minerals kaolinite, Fe-rich illite, and smectite. Although no significant geochemical differences were identified between geophagic and non-geophagic soils, a clear difference was observed in their clay mineralogical content. Soils eaten by elephants are richer in kaolinite and illite than non-geophagic soils, which contain a higher amount of smectite. It is suggested that elephants in Udawalawe National Park ingest soils mainly not to supplement the mineral contents of their forage but to detoxify unpalatable compounds in their diet.     

Inorganic pollution in water—the analyst's viewpoint†

Inorganic pollution comprises both major and minor constituents, although only 12 chemical elements may be considered major components. Twenty‐eight elements constitute a group of common minor elements and an additional 13 elements comprise a group of less common minor constituents. Reliable quantitative data are required on the occurrence of these substances in a wide variety of water types, usually at extremely low concentrations. The analysis of standard reference water samples provides information on the overall reliability of water‐quality data. Although most major constituents may be determined with acceptable reliability, determinations of certain minor constituents lack comparable precision; for example, determinations of boron, nickel, and chromium. Few precision data are available on the determination of the less common trace elements. Several comparatively new analytical techniques, such as flameless atomic absorption spectrophotometry, voltammetry, and emission spectroscopy with plasma excitation, appear capable of providing improved sensitivity.     

Concentration effect of trace metals in Jordanian patients of urinary calculi

Due to the increase in the number of urinary calculi disease cases in Jordan, stone samples were collected from patients from various Jordanian hospitals (Princes Basma (PBH), King Abdullah University (KAUH), Al-Basheer (ABH) and Al-Mafraq (AMH)). This study concentrates on the effect of trace metals in patients of urinary calculi. Trace metals were detected in 110 urinary calculi samples using X-ray fluorescence (XRF) and atomic absorption spectroscopy (AAS) techniques. Of the calculi examined, 21 were pure calcium oxalate (CaOax), 29 were mixed calcium oxalate/uric acid, 23 were mixed calcium oxalate/phosphate (apatite), 25 were phosphate calculi (apatite/struvite), five were mixed calcium oxalate monohydrate/struvite, four were urate calculi (mixed ammonium acid urate/sodium acid urate) and three were pure cystine calculi. The concentration measurement of Ca and other trace metals levels has been found useful in understanding the mechanism of stone formation and in evaluating pathological factors. It has been found that Ca is the main constituent of the urinary calculi, especially those stones composed of calcium oxalate and calcium phosphate. The concentration of most of the trace metals that were analyzed was (Ca = 48.18, Na = 1.56, K = 0.9, Mg = 3.08, Fe = 1.17, Al = 0.49, Zn = 0.7, Cu = 0.19, Mn = 0.029, P = 10.35, S = 1.88, Sr = 0.306, Mo = 0.2, Cr = 0.146, Co = 0.05, Ni = 0.014)%. In conclusion, metals concentration in Jordanian patient’s urinary calculi samples was higher than its equivalents of other patients’. It has been noted that there is no concentration of toxic trace elements (like Li, V, Pb, Cd, and As). Some heavy metals, however, were detected Mo, Cr, Co and Ni as traces. P and S ions are present in few calculi stones as traces.     

Concentrations of various elements and inorganic ions in rice straw and ash

Various elements and inorganic ions in rice straw and ash samples were analyzed by using inductively coupled plasma atomic emission spectrometry (ICP‐AES) and ion chromatography (IC). Five major elements: Mg, Mn, Al, Ca, and Fe and eight minor and trace elements: Cr, Cu, Ti, Zn, La, Sr, Ba, and Hg were detected in these samples, at more than ppm‐level. In ash samples the trace elements such as Y, As, V, Se, and Sc were also identified. The concentrations of SO₄, PO₄, Cl, Na, and K ions in these samples were higher than those of other ions measured. These elements and inorganic ion concentrations were approximately one order of magnitude higher in the ash than in the straw samples. Gas chromatography/mass spectrometry (GC/MS) and library search showed the presence of fatty‐, carboxylic‐ and nicotinic acids, and their derivatives in small quantities in the straw samples.     

Multidisciplinary work on barium contamination of the karstic upper Kupa River drainage basin (Croatia and Slovenia); calling for watershed management

The present work was designed as an extension of a previous study of a barium anomaly observed in stream sediments of the Kupa River. In its upper part the Kupa River drains a region underlain by a trans-boundary aquifer. The river is a significant water resource in a region of tourism, sport, and fishing in both Croatia and Slovenia. The contamination source is situated in Homer (Lokve), Croatia, where barite was mined until 10 years ago. The barium processing waste material (<3-mm fraction) was carelessly deposited in gardens, forests, and into a sinkhole, which has an underground link with the Kupica River, a tributary of the Kupa River. Barium waste and stream sediments were analyzed using comparative techniques: X-ray diffraction (XRD), X-ray fluorescence (XRF), Mössbauer spectroscopy, and grain size analysis. XRD of the waste material identified the major minerals quartz, barite, and dolomite and the Fe-containing minor minerals muscovite and goethite. Barite was identified as a minor or trace mineral in the Kupica River sediments. XRF analysis of the waste material has shown Ba and Fe to be the predominant elements, Ca and K to be minor elements, and Mn, Zn, Sr, Pb, Co, Cu, As, Zr, Rb, Y, and Mo to be trace elements. Mössbauer spectroscopy performed at room temperature (RT) was used to study iron minerals, particularly to obtain information on the valence status of Fe ions. Grain size analysis of the waste material (<63-μm fraction) has shown that it contains 23.5% clay-size material in comparison with 7–8% clay-size material in stream sediments. It is our aim to combine geochemical and medical methods to investigate the possible impact of waste disposal on human health in Lokve. At this stage of the work, concentrations of Ba and other toxic elements in the water compartment of the Kupica River (a source of drinking water) have not been monitored by Croatian Waters (name of the Croatian water authorities). The necessity of such measurements in future studies has been highlighted. A preliminary study of diseases diagnosed in Lokve shows that about 18% of the total inhabitants have serious medical problems. Diseases of the circulatory system, endocrine, nutritional, and metabolic diseases, neoplasms, and respiratory diseases predominate. This paper calls for further multidisciplinary research on the health effects of barium and trace elements, as well as for bioremediation of contaminated gardens and for watershed management of vulnerable karstic aquifers.     

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.     

Characterization of Santa Catarina (Brazil) coal with respect to human health and environmental concerns

The current paper presents the concentration, distribution, and modes of occurrence of trace elements of 13 coals from south Brazil. The samples were collected in the state of Santa Catarina. Chemical analyses and the high ash yields indicate that all studied coals are rich in mineral matter, with SiO₂ and Al₂O₃ dominating as determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Quartz is the main mineral species and is associated with minor levels of feldspars, kaolinite, hematite, and iron-rich carbonates. The contents of trace elements, including As, Pb, Cd, Ni, Cr, Mn, Be, V, U, Zn, Li, Cu, Tl, and Ni, in coals were determined. A comparison of ranges and means of elemental concentrations in Santa Catarina, Brazil, and world coals shows that the ranges of most elements in Santa Catarina coal are very close to the usual worldwide concentration ranges in coal.     

煤中痕量元素分布的多变量分析及实验研究

本文用多变量分析法研究了煤中痕量元素的分布，并用实验研究了有机溶剂提取前后青山烟煤中痕量元素的变化。多变量分析结果表明：Ａｓ，Ｃｒ，Ｃｏ，Ｎｉ，Ｃｕ，Ｃｄ，Ｖ，Ｐｂ等元素与Ｂｅ，Ｇｅ在煤中具有不同的分布特征，对青山烟煤的实验研究结果则表明：Ｃｒ，Ｃｏ，Ｎｉ，Ｃｕ，Ｃｄ，Ｐｂ等元素趋向于与煤中的矿物质相结合，而Ｂｅ，Ｇｅ两元素有较强的有机亲和性。实验研究结果与多变量分析结果相符。     

Evaluation of geochemical characteristics and health effects of some geophagic clays southern Nigeria

The geochemical characteristics of geophagic clays from Calabar and Okon-Eket, southern Nigeria were evaluated to determine their quality and the possible health effects of their consumption. The study involved the measurement of the pH, electrical conductivity (EC) and total dissolved solids (TDS) of the slurried clay samples soaked in distilled water for 48 h using digital multi-parameters probe as well as the elemental and mineralogical analyses of twenty geophagic clay samples for elemental and mineralogical constituents using both the ICP-MS and XRD, respectively. Medical data were also mined from medical facilities within the area in addition to the administering of questionnaire to adults involved in the geophagic practices in order to determine their justification for the practice as well as their and clay preferences. Results of physicochemical measurement revealed that the pH range of the samples ranges from 3.9 to 6.9 and 6.5 to 7.0; EC 0.3–377.7 and 0.12–82.38 µS/cm; TDS 1.98–2,432.65 and 0.08–52.95 mg/L for consumed and non-consumed clay, respectively. The elemental analyses revealed that the concentration of some potential harmful elements, PHEs, exceeded the recommended dietary intake by humans. This is especially true for Cu (9.1–23 ppm), Pb (16.7–55.6 ppm), Zn (13–148 ppm), Ni (11.1–46.4 ppm), Co (1.8–21.7 ppm), Mn (16–338 ppm), As (BDL-15 ppm) and Cd (BDL-0.2 ppm). The predominant phases established in the clay samples are quartz and kaolinite, while the minor minerals were montmorillonite and muscovite in all the clay samples. Respondents revealed that capacity for relief from gastrointestinal problems believes in the curative power to cure skin infections and cultural reasons as main justification for the geophagic practices. This is, however, not in conformity with information gleaned from the medical records which still indicated that the prevalent diseases in the area still include gastrointestinal problems in addition to malaria, hypertension and cardiac failure with minor cases of respiratory tract infections. The high concentrations of the PHEs may be responsible for or contribute in part to the prevalence of hypertension, cardiac failures and gastrointestinal problems within the study areas. Though the kaolinite present in the geophagic clays makes them suitable for use as traditional antacids; however, the toxic trace element concentrations and significant quartz content will most likely mask the beneficial effects of such kaolinite.     

Research review trends of food analysis in Latvia: major and trace element content

The current paper involves overview of several studies concerning quantitative major and trace element analysis of different food samples, such as products of plant origin, e.g., locally grown vegetables (carrots, onions, potatoes) and products of animal origin derived with or without processing (cottage cheese, eggs, honey). Food samples were collected over the territory of Latvia in the time period 2009–2012. Sample pre-treatment was chosen according to the product specifics but mostly wet mineralization with concentrated nitric acid was applied. Analysis of major elements (e.g., Ca, Fe, K, Mg, Na) and trace elements (e.g., As, Cd, Co, Cr, Cu, Ni, Pb, Se, Zn) was performed by appropriate quantitative analytical technique: atomic absorption spectrometry, inductively coupled plasma mass spectrometry or total reflection X-ray fluorescence spectrometry. Not only the influence of environmental factors (e.g., geographical or seasonal impact) was detected in element dissemination in food, also botanical origin (if applicable) and applied agricultural praxis, product processing and storage specifics were found to be important. Possible food contamination by potentially toxic elements can be associated mostly with the consequences of anthropogenic activities. The studies revealed the significance of food research in the context of environmental science.     

贵州省原煤中微量元素的组成特征

研究了贵州省各主要煤田中主要采煤层的Ａｓ,Ｂ,Ｂａ,Ｂｅ,Ｃｄ,Ｃｏ,Ｃｒ,Ｃ,Ｈｇ,Ｌｉ,Ｎｉ,Ｐｂ,Ｓｂ,Ｓｅ,Ｓｒ,Ｔｌ,Ｖ,Ｚｎ等微量元素的组成特征,贵州省原煤中微量元素的含量总体上的世界范围内的一致,但Ｓｂ,Ａｓ,Ｈｇ等有害元素则明显富集,由于煤炭成因上的特殊性,其微量元素的组成除受煤植物的影响外,后期在煤作用对其有决定性的影响。     

Inorganic chemicals in domestic water of the United Arab Emirates

The concentration of selected inorganic chemicals was determined for 396 samples of bottled water, desalinated water, and groundwater used for drinking and domestic purposes in the United Arab Emirates (UAE). The objective of this study was to compare the concentrations of inorganic chemicals in different domestic water types used in the UAE with the World Health Organization (WHO) limits for drinking water. Results of the present study revealed a wide variation in the concentrations of major, minor, and trace inorganic chemicals in domestic water of the UAE. For example, the bottled water sold for drinking is depleted in major ions and the total dissolved solids (TDS) in some brands do not exceed 100 mg/l. On the other hand, some of the domestic water used may contain as much as 3,000 mg/l TDS, which is above the WHO recommended limit for drinking water (500–1,500 mg/l TDS). Similarly, while bottled water is almost free of trace ions and minor constituents, some natural groundwater may have concentrations higher than the WHO recommended limits for drinking water. The cause of this variation is related to the different water sources and the large number of companies producing and distributing drinking and domestic water. Moreover, it is clear that the current controls on domestic water quality in some areas, namely conformance of pH and electrical conductivity measurements with prescribed ranges of values, are currently inadequate. These two parameters are not enough to judge if water is suitable for drinking or not and some consumers may receive domestic water of uncertain quality.     

Trace elements distributions at Datoko-Shega artisanal mining site,northern Ghana

Environmental geochemistry classifies elements into essential, non-essential and toxic elements in relationship to human health. To assess the environmental impact of mining at Datoko-Shega area, the distributions and concentrations of trace elements in stream sediments and soil samples were carried out. X-ray fluorescence analytical technique was used to measure the major and trace element concentrations in sediments and modified fire assay absorption spectrometry in soils. The results showed general depletion of major elements except titanium oxide (TiO₂) compared to the average crustal concentrations. The retention of TiO₂ at the near surface environment probably was due to the intense tropical weathering accompanied by the removal of fine sediments and soil fractions during the harmattan season by the dry north-east trade winds and sheet wash deposits formed after flash floods. The results also showed extreme contamination of selenium (Se), cadmium (Cd) and mercury (Hg), plus strong contaminations of arsenic (As) and chromium (Cr) in addition to moderate contamination of lead (Pb) in the trace element samples relative to crustal averages in the upper continental crust. However Hg, Pb and Cd concentrations tend to be high around the artisanal workings. It was recognised from the analysis of the results that the artisanal mining activity harnessed and introduces some potentially toxic elements such as Hg, Cd and Pb mostly in the artisan mine sites. But the interpretation of the trace element data thus invalidates the elevation of As concentrations to be from the mine operations. It consequently noticed As values in the mine-impacted areas to be similar or sometimes lower than As values in areas outside the mine sites from the stream sediment results.

     

Trace element biomonitoring by leaves of Populus nigra L. from Western Anatolia, Turkey

The West Anatolian Region is one of the most important areas for industrialization, population density and traffic in Turkey. Therefore, the leaves of Populus nigra L. (Salicaceae), which are used as biomonitor to investigate the levels of the trace elements Cd, Pb, Fe, Zn and Cu, were sampled at 30 locations having different pollution levels in the region. The concentrations of elements were determined by atomic absorption spectrometry. The samples were collected at both reference and contaminated locations where iron was found as the priority element. The strong association between a gradient of contamination and concentration in all samples tested indicates that they are reflecting well the environmental changes, and that they appear as appropriate biological indicators of heavy metal contamination.     

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.     

Geochemical forms of trace metals in mangrove sediments—Red Sea (Egypt)

Seven sediment samples from mangrove sediments of the Red Sea were taken in order to evaluate the possible contamination of the sediments by trace metals (iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), lead (Pb) and cadmium (Cd)). Sequential extraction techniques were performed to study the different geochemical forms of these metals. X-ray diffraction analysis has been performed to correlate the mineralogical composition with the geochemical forms of the studied elements. The results of Fe and Mn contents indicate that they are in large part from lithogenous origin. The elevated concentrations are associated with the residual form ranged from 70 to 93% for Fe and 46 to 70% for Mn. The percentage of Zn, Cu, Cd and Pb in the non-residual form was much greater than that of the residual fractions. This reflects the high mobility and bioavailability of these metals in mangrove sediments of the Red Sea. X-ray diffraction analysis revealed the presence of silicate components including quartz, feldspars and clay minerals in some locality. Non-silicate components recorded in the study area as calcite as well as, Mg-calcite. Quantitatively both components i.e. silicate and carbonate varied according to their source material.