Trace elements and ions in Italian bottled mineral waters: Identification of anomalous values and human health related effects

Microbiological studies have always had an important role in the evaluation of drinking water quality. However, since geological processes are the most important factors controlling the source and distribution of chemical elements in natural waters, the importance of geochemical data must not be underestimated. This study presents data on pH, conductivity and concentrations of 69 elements and ions (Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Pb, Pr, Rb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, Br⁻, HCO₃⁻, Cl⁻, F⁻, NH₄⁺, NO₂⁻, NO₃⁻, PO₄³⁻, SO₄²⁻, SiO₂) from 186 bottled mineral waters of 158 different Italian name brands. Analyses show a large range in concentrations for most of these elements, with variations up to four orders of magnitude. Our data demonstrate that some elements (such as Be), generally considered unlikely to occur, can instead reach surprisingly high levels in drinking water, and also how packaging can release some trace elements to the bottled water. Data analysis shows that the implementation of an international database of bottled water geochemistry and of potential toxicological effects is of paramount importance to provide a robust data set which would be useful to set international action levels and guidelines to secure bottled water quality, whose consumption has steadily increased in the recent years. A new formula to calculate nitrate and nitrite tolerable concentration levels in waters intended for human consumption is proposed, to take into account that about 5% of dietary nitrate in humans is converted to nitrite.     

Chemical composition of bottled mineral waters in Estonia

Five commercially available in Estonia brands of bottled water have been analysed for 59 chemical elements by ICP-QMS and ICP-AES techniques to assess the quality of domestic mineral waters in scope of the European Groundwater Geochemistry Project initiated by the Geochemistry Expert Group of EuroGeoSurveys. Contents of 9 cations and anions, pH and electrical conductivity (EC) were measured in the bottled mineral waters by IC, titration and photometric methods. The data showed a significant difference between natural undiluted mineral water (Värska Originaal) characterised by the highest values of pH, EC and majority of trace elements studied, and other domestic waters sold in Estonia.     

General ground water geochemistry of Hellas using bottled water samples

Sixty-one still bottled water samples, representing 41 locations, were collected from Hellas for the purpose of studying the geochemistry of ground water. Since, the dominating lithology comprises limestone, dolomitic limestone, marble, and mafic–ultramafic rocks (ophiolites), the dominant major ions in Hellenic bottled waters are Ca²⁺, Mg²⁺, CO₃²⁻ and HCO₃⁻, and are, thus, classified in the Ca²⁺–Mg²⁺–HCO₃⁻ hydrochemical facies. The source aquifers of Hellenic bottled water are apparently continuously replenished by fresh water. Comparison of values of Ca, Mg, K, Na, Cl⁻, HCO₃⁻, NO₃⁻, SO₄²⁻, pH and electrical conductivity, displayed on bottle labels with those of this study, has shown that there is a fairly good correlation between the two data sets, suggesting that the geochemistry of source aquifers is relatively stable over time, at least from 1998 to 2008.     

Major and trace elements in German bottled water,their regional distribution,and accordance with national and international standards

The market for mineral water has been growing steadily over the last few years. Germany is the country with the highest number of bottled mineral water brands (908 bottled water samples from 502 wells/brands were analyzed). The per capita consumption of mineral water in Germany in 2003 was 129 L. A wide range of values of one to seven orders of magnitude was determined for 71 elements in the bottled water samples analyzed by ICP-QMS, ICP-AES, IC, titration, photometric, conductometric and potentiometric methods. A comparison of the element concentrations and the legal limits for both bottled and tap water (EU, Germany, US EPA, WHO) shows that only 70% of the 908 mineral water samples fulfill the German and EU drinking water (i.e., tap water) regulations for all parameters (not including pH) for which action levels are defined. Nearly 5% of the bottled water samples not fulfill the German and EU regulations for mineral and table water. Comparison of our results with the current German and European action levels for mineral and table water shows that only 42 of the bottled water samples exceed the limits for one or more of the following elements: arsenic, nitrate, nitrite, manganese, nickel and barium concentrations. Ten of the bottled water samples contain uranium concentrations above the 10 μg/L recommended limit.     

Hydrogeochemical analysis on Italian bottled mineral waters: Effects of geology

The use of bottled mineral waters use is increasingly becoming popular and the need for better knowledge of their chemical composition is a key issue for defining their quality, particularly for those elements that are not monitored on a regular basis. The link between geology and water chemistry is well known and can lead to extreme differences in element distribution and is an issue that needs to be addressed. Such an opportunity has been provided by a project of the EuroGeoSurvey Geochemistry Expert Group aimed at the characterization of groundwater geochemistry using bottled mineral waters purchased in supermarkets all over Europe. On these waters pH, conductivity and concentrations of 69 elements and ions were measured at the BGR geochemical laboratories. On a total of 1785 “samples”, 158 represent waters bottled in Italy in 126 different sites scattered throughout the country. Most of the purchased mineral water is packaged in PET bottles. In this paper, the dataset concerning Italy has been used to provide an overview on the relationship between natural concentration of the determined chemical elements in groundwater and geo-lithological features. These relationships have been investigated mostly taking into account the surface geology and other information available on water sources. Application of R-Mode factor analysis to the data set allowed the determination of the possible relationship between the distribution of individual elements and lithology or other surface enrichment phenomena. In particular waters draining through volcanic rocks are enriched in elements such as As, B, Br⁻, Cl⁻, Cs, I, K, Li, Na, NO₃⁻, PO₄³⁻, Rb, Sc, SiO₂, Sr, Te, Ti, and V up to 3 orders of magnitude higher than waters draining through other lithologies. REE and Y show significant difference in median concentration due to interaction of waters with plutonic rocks. Many elements have a large spread of concentrations, which reflects natural variations and interaction with particular lithologies. One of the five R-mode factor analysis associations, recognized as being representative of elements analysed shows high nitrate and V loadings along with As, PO₄³⁻ and Se. The latter association probably reflects a sign of anthropogenic contribution in some aquifers in volcano-sedimentary or silico-clastic deposits and in intensively cultivated areas.     

Geochemical assessment of groundwater contamination with special emphasis on fluoride concentration, North Jordan

The concentrations of fluorine in groundwater of North Jordan range from 0.009 to 0.055 mg/l. Other chemical parameters, e.g. pH, EC, TDS, Cl, TH, HCO₃, PO₄, SO₄, NO₃, NH₄, K, Ca, Mg, and NO₃ have been studied and showed higher concentrations in HCO₃⁻ and NO₃⁻ of 307 and 51 mg/l, respectively. Thermodynamic considerations show that almost all the analyzed samples are undersaturated with respect to calcite and fluorite. This undersaturation is probably due to their low availability in the locations. Fluoride concentration shows a positive relation to pH and HCO₃, whereas Cl, Mg, Ca, and Na initially increase and then decrease with increasing fluoride in the water. Saturation indexes of fluorite and calcite are estimated. The chemistry of the groundwater is controlled by the fluorite and calcite solubility. The topography of the area has exerted control on the aerial extent of fluoride concentration.     

Hydrogeochemical characteristics of spring water in the Harz Mountains,Germany

Spring water samples of the Harz Mountains were taken in several seasons of 2010, 2011, and 2012. The samples have been analysed for main components (Na⁺, K⁺, Ca²⁺, Mg²⁺, SO₄²⁻, Cl⁻, HCO₃⁻ and NO₃⁻), trace elements (Fe, Cu, Pb, Zn, Y and REE), DOC, δ¹⁸O and δ²H of water. Meteoric water is indicated as the main source of the springs sampled. High precipitation rates lead to a dilution of the measured elemental concentrations. Furthermore, regional differences of rock and water interactions were found. REE concentrations and patterns of the spring waters vary between the distinct geological units and reflect the geochemical characteristics of the surrounding rocks. The actual data compared to measured data from the seventies and nineties of the last century indicate a decrease of the sulphate concentrations in the spring waters which is typical of many European mountain catchments.     

Modeling of subsurface calcite dissolution, including the respiration and reoxidation processes of marine sediments in the region of equatorial upwelling off Gabon

Mineralization of organic matter and the subsequent dissolution of calcite were simulated for surface sediments of the upper continental slope off Gabon by using microsensors to measure O₂, pH, pCO₂ and Ca²⁺ (in situ), pore-water concentration profiles of NO₃⁻, NH₄⁺, Fe²⁺, and Mn²⁺ and SO₄²⁻ (ex situ), as well as sulfate reduction rates derived from incubation experiments. The transport and reaction model CoTReM was used to simulate the degradation of organic matter by O₂, NO₃⁻, Fe(OH)₃ and SO₄²⁻, reoxidation reactions involving Fe²⁺ and Mn²⁺, and precipitation of FeS. Model application revealed an overall rate of organic matter mineralization amounting to 50 μmol C cm⁻² yr⁻¹, of which 77% were due to O₂, 17% to NO₃⁻ and 3% to Fe(OH)₃ and 3% to SO₄²⁻. The best fit for the pH profile was achieved by adapting three different dissolution rate constants of calcite ranging between 0.01 and 0.5% d⁻¹ and accounting for different calcite phases in the sediment. A reaction order of 4.5 was assumed in the kinetic rate law. A CaCO₃ flux to the sediment was estimated to occur at a rate of 42 g m⁻² yr⁻¹ in the area of equatorial upwelling. The model predicts a redissolution flux of calcite amounting to 36 g m⁻² yr⁻¹, thus indicating that ∼90% of the calcite flux to the sediment is redissolved.     

Benthic nitrogen cycling traversing the Peruvian oxygen minimum zone

Benthic nitrogen (N) cycling was investigated at six stations along a transect traversing the Peruvian oxygen minimum zone (OMZ) at 11°S. An extensive dataset including porewater concentration profiles and in situ benthic fluxes of nitrate (NO₃⁻), nitrite (NO₂⁻) and ammonium (NH₄⁺) was used to constrain a 1-D reaction-transport model designed to simulate and interpret the measured data at each station. Simulated rates of nitrification, denitrification, anammox and dissimilatory nitrate reduction to ammonium (DNRA) by filamentous large sulfur bacteria (e.g. Beggiatoa and Thioploca) were highly variable throughout the OMZ yet clear trends were discernible. On the shelf and upper slope (80-260 m water depth) where extensive areas of bacterial mats were present, DNRA dominated total N turnover (?2.9 mmol N m⁻² d⁻¹) and accounted for ?65% of NO₃⁻ + NO₂⁻ uptake by the sediments from the bottom water. Nonetheless, these sediments did not represent a major sink for dissolved inorganic nitrogen (DIN = NO₃⁻ + NO₂⁻ + NH₄⁺) since DNRA reduces NO₃⁻ and, potentially NO₂⁻, to NH₄⁺. Consequently, the shelf and upper slope sediments were recycling sites for DIN due to relatively low rates of denitrification and high rates of ammonium release from DNRA and ammonification of organic matter. This finding contrasts with the current opinion that sediments underlying OMZs are a strong sink for DIN. Only at greater water depths (300-1000 m) did the sediments become a net sink for DIN. Here, denitrification was the major process (?2 mmol N m⁻² d⁻¹) and removed 55-73% of NO₃⁻ and NO₂⁻ taken up by the sediments, with DNRA and anammox accounting for the remaining fraction. Anammox was of minor importance on the shelf and upper slope yet contributed up to 62% to total N₂ production at the 1000 m station. The results indicate that the partitioning of oxidized N (NO₃⁻, NO₂⁻) into DNRA or denitrification is a key factor determining the role of marine sediments as DIN sinks or recycling sites. Consequently, high measured benthic uptake rates of oxidized N within OMZs do not necessarily indicate a loss of fixed N from the marine environment.     

Geochemical survey of Slovenian bottled waters

The geochemistry of the major components and trace elements in Slovenian bottled water available on the market in 2004 and 2008 was studied. The waters were predominantly from the Radenska and Rogaška Slatina mineral water source region. In this paper, a comparison of two data sets from two time periods was performed based on the Kolmogorov–Smirnov independent two-sample test. The bottled waters in the data sets were in agreement with drinking water and mineral water standards. Discrepancies were only present for B and Ni in highly mineralised waters. Analyses of the labels on the bottle packaging showed that the analytical results were in general agreement with the values reported on the labels. At the same time, the values reported on the labels by the producers showed that the chemical compositions of products available on the market for longer time periods vary. Slovenian bottled waters are predominantly controlled by a CaCO₃–CO₂–H₂O system where Na, Cl⁻ and SO₄²⁻ are present as the major components, in different combinations.     

Temporal variations in the concentration and isotopic signature of ammonium- and nitrate–nitrogen in soils under a breeding colony of Black-tailed Gulls (Larus crassirostris) on Kabushima Island,northeastern Japan

Temporal variations in the concentration and N isotopic ratios of inorganic N (NH₄– and NO₃–N) as affected by the soil temperature regime together with the input of bird excreta were analyzed in a sedentary soil under a dense colony (1.6 nests/m²) of breeding Black-tailed Gulls (Laruscrassirostris: a ground-nesting seabird). Surface soil samples were taken monthly from mid-March to late July 2005 from Kabushima Island, Hachinohe, northeastern Japan. The spatial concentration of inorganic N in the soils varied considerably on all sampling dates. There may be a statistically significant trend, showing increased NH₄–N content from settlement up to early June when the input of fecal N attains its maximum, and then decreases towards the end of breeding activity (early August). Abundant NO₃–N was observed in all soils, particularly in the later stage of breeding (up to 3800 mg-N/kg dry soil), refuting earlier claims that nitrification is unimportant in the soils. δ¹⁵N values of NH₄ in the soils showed unusually high values up to +51‰, reflecting N isotope fractionation due to volatilization of NH₃ during the mineralization. Mean δ¹⁵N values of the monthly collected totals of NH₄ and NO₃ were not significantly different at the 5% level based on ANOVA and significant differences were observed only among the three means of NO₃–N collected in mid-March (settlement of colony: δ¹⁵N = −0.2 ± 3.5‰) and late July (later stages of breeding: δ¹⁵N = +22.1 ± 7.0‰, +23.3 ± 7.8‰) at the 1% and 5% levels by t-test, respectively. Such an observation of significantly increased δ¹⁵N values for NO₃–N in soils from the fledgling stage indicates the integration of denitrification coupled with nitrification under a limited supply of fecal N.     

Variations and net transport of dissolved inorganic nutrients in the South Passage of the Changjiang （Yangtze River） Estuary

Dissolved inorganic nutrient elements were analyzed from the samples collected in the South Passage of the Changjiang (Yangtze River) Estuary in March 2003, including NH4 , NO3-, NO2- and PO43-. The water samples were collected with a Niskin sampler hourly at the near-surface, middle and near-bottom depths at the three stations -A1, A2 and A3-during two complete tidal cycles of neap tide and spring tide. Results showed that 1) the concentrations of NH4 , NO3- and NO2- were a little higher respectively during the neap tide than those during the spring tide, while PO43- showed an opposite trend, and each was higher in the ebb tide than in the flood tide, either for the neap tidal cycle or the spring tidal cycle; 2) higher stratification of the nutrients existed obviously in this area, with the concentrations of which increased from the bottom to the surface, especially for NH4 and NO3-; 3) the coefficient of variation (C.V.) values of all dissolved inorganic nutrients varied from 4.06% to 36.8% beyond different influences of the tidal current and Changjiang runoff; 4) with increasing suspended matter in the water column, the concentrations of PO43- became lower in the filtered water; and 5) the total transport of each tidal cycle was much more in the spring tide than in the neap tide, and the positive values indicated that the nutrients had been exported to the East China Sea. Studies on the variations and net transport of dissolved inorganic nutrients in the South Passage of the Changjiang Estuary will provide the scientific basis for the study of the mechanism of red tide in the East China Sea.     

Monitoring of atmospheric deposition in European forests and an overview on its implication on forest condition

Forest conditions in Europe have been monitored over 20 years jointly by the International Cooperative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP Forests) and the European Union (EU). Maps for mean bulk SO₄, NO₃ and NH₄ deposition at around 400 intensive monitoring plots in the years 1999–2001, as well as time trends for the period 1996–2001, are presented. Mean bulk SO₄ deposition at 169 plots mostly located in central Europe decreased from 7.4 to 5.8 kgS ha⁻¹ a⁻¹. Mean NH₄ bulk deposition decreased from 6.2 to 5.3 kgN ha⁻¹ a⁻¹. Nitrate bulk deposition fluctuated around 5 kgN ha⁻¹ a⁻¹. On average, throughfall deposition was considerably higher than bulk deposition. Time trends for mean tree crown defoliation as an overall indicator for forest condition show a peak in the mid 1990s for most of the monitored main tree species and a recent increase for the years 2003 and 2004. Multivariate linear regression analyses show some significant relations between deposition and defoliation. These relations depend on the tree species and site characteristics. Effects of deposition are moderated by the influence of biotic stress factors such as insects and fungi and by abiotic stress factors, such as weather.     

Effects of cations and anions on iron and manganese sorption and desorption capacity in calcareous soils from Iran

This study investigated the effect of cations and anions on the sorption and desorption of iron (Fe) and manganese (Mn) in six surface calcareous soil samples from Western Iran. Six 10 mM electrolyte background solutions were used in the study, i.e., KCl, KNO₃, KH₂PO₄, Ca(NO₃)₂, NaNO₃, and NH₄NO₃. NH₄NO₃ and NaNO₃ increased the soil retention of Fe and Mn, whereas Ca(NO₃)₂ decreased the soil retention of Fe and Mn. Iron and Mn sorption was decreased by NO₃ ^? compared with H₂PO₄ ^? or Cl^?. The Freundlich equation adequately described Fe and Mn adsorption, with all background electrolytes. The Freundlich distribution coefficient (K _F) decreased in the order H₂PO₄ ^? > Cl^? > NO₃ ^? for Mn and H₂PO₄ ^? > NO₃ ^? > Cl^? for Fe. The highest sorption reversibility was for Fe and Mn in competition with a Ca²⁺ background, indicating the high mobility of these two cations. A MINTEQ speciation solubility model showed that Fe and Mn speciation was considerably affected by the electrolyte background used. Saturation indices indicated that all ion background solutions were saturated with respect to siderite and vivianite at low and high Fe concentrations. All ion background solutions were saturated with respect to MnCO_3(am), MnHPO₄, and rhodochrosite at low and high Mn concentrations. The hysteresis indices (HI) obtained for the different ion backgrounds were regressed on soil properties indicating that silt, clay, sand, and electrical conductivity (EC) were the most important soil properties influencing Fe adsorption, while cation exchange capacity (CEC), organic matter (OM), and Mn-DTPA affected Mn adsorption in these soils.     

Water soluble components of PM10 Chongqing, China

The concentrations of water soluble ions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, NO₃ ^-, Cl^-, and SO ₄ ^2- ) in PM₁₀ samples collected on cellulose filters by a medium-volume cascade impactor were determined, which were obtained from three kinds of areas in Chongqing: industrial area (Jiulongpo district), commercial and residential area (Jiangbei district) and background area (Jinyun Mountain in the Beibei district). The results showed that except for the background site, the annual average values of PM₁₀ are 23% – 61% higher than the national air quality standard (GradeII) (0.1 mg/m³), even that the value of the control site is still 20% higher than American standard (0.05 mg/m³). This implied that serious pollution of fine particles occurred in Chongqing. Nine kinds of soluble ions in water of PM₁₀ were analyzed by ion chromatography (IC) and the annual average concentrations follow the order of [SO ₄ ^2- ] > [NO³ _-] > [Cl^-] > [F^-], and [Ca²⁺] > [NH₄ ⁺] > [K⁺] > [Na⁺] > [Mg²⁺]. Their values were different in these areas: the industrial area > the commercial and living area > the control area. As for NH_{4 +}, K⁺, Ca²⁺, NO₃ ^- and SO ₄ ^2- , their seasonal average concentrations show a similar variation trend: the values in spring and fall were higher than those in summer and winter. The seasonal average concentrations of [Cl^-], [F^-], [Na⁺] and [Mg²⁺] are much lower than those of other ions. However, the concentrations of [Na⁺] changed more greatly in different seasons than those of the other three ions. Correlation coefficients showed that the three areas have been polluted by coal smoke and dust to different extents, while some local resources of pollution should be taken into consideration as well.     

Interstitial water and hydrochemistry of a mangrove forest and adjoining water system, south west coast of India

 Eh, pH, salinity, total alkalinity, dissolved O₂, NO₂ ^–, PO₄ ^–3, SiO₂ and NH₄ ⁺ of waters from a mangrove forest, an estuary and a creek connecting the mangrove forest and the estuary have been measured. Further, the chemistry of interstitial waters of surficial and core sediments from the mangrove forest have been analyzed for the above parameters, except dissolved oxygen. To understand the flux of nutrients from the mangrove forest to the adjoining estuary, creek waters were monitored during tidal phases. PO₄ ^–3, SiO₂ and NH₄ ⁺ were found to be at elevated levels in mangrove waters whereas NO₂ ^– shows no variation compared to the estuary. Dissolved O₂ is low in mangrove waters. PO₄ ^–3, NH₄ ⁺ and SiO₂ are several times higher in interstitial waters than in overlying waters. Several fold enrichment of PO₄ ^–3, NH₄ ⁺ and, to some extent, SiO₂ were measured in creek waters during ebbing relative to flooding, indicating that mangroves act as a perennial source for the above nutrients. Received: 26 May 1998 · Accepted: 21 July 1998     

Trace element incorporation into quartz: A combined study by ICP-MS, electron spin resonance, cathodoluminescence, capillary ion analysis, and gas chromatography

Pegmatite quartz from different occurrences in Norway and Namibia was investigated by a combination of ICP-MS, Electron Spin Resonance (ESR), Capillary Ion Analysis (CIA) and Gas Chromatography (GC) to quantify trace elements in very low concentrations and to determine their position in the quartz structure.The studied quartz samples show similar geochemical characteristics with low contents of most trace elements. Remarkable are the elevated concentrations of Al (36-636 ppm), Ti (1.6-25.2 ppm), Ge (1.0-7.1 ppm), Na (5.2 to >50 ppm), K (1.6 to >100 ppm) and Li (2.1-165.6 ppm). These elements are preferentially incorporated into the quartz lattice on substitutional (Al, Ti, Ge) and interstitial (Li, Na, K) positions. Li⁺ was found to be the main charge compensating ion for Al, Ge and Ti, whereas some ppm of Na and K may also be hosted by fluid inclusions. Ti may be incorporated as substitutional ion for Si or bound on mineral microinclusions (rutile). The results of the ESR measurements show that there may be a redistribution of alkali ions during irradiation. The diamagnetic [AlO₄/M⁺]⁰ center transforms into the paramagnetic [AlO₄]⁰ center, whilst the compensating ions diffuse away and may be captured by the diamagnetic precursor centers of [GeO₄]⁰ and [TiO₄]⁰ to form paramagnetic centers ([TiO₄/Li⁺]⁰, [GeO₄/Li⁺]⁰).In general, fluid inclusions in pegmatite quartz can be classified as H₂O-CO₂-NaCl type inclusions with water as the predominant volatile. Among the main elements hosted by fluid inclusions in quartz are Na, K, NH₄, Ca, Mg and the anionic complexes Cl⁻, NO₃⁻, HCO₃⁻ and SO₄²⁻. Gas analysis of trapped fluids shows volatile components in the following order of abundance: H₂O > CO₂ > N₂(+) ≥ CH₄ > COS > C₂ and C₃ hydrocarbons. Additionally, traces of Co, Ni, Zn, Pb, and Cu were detected by CIA in fluid inclusions of some samples. There are indications that the REE and Rb are also bound in fluid inclusions, however, the concentrations of these elements are too low to be measured by CIA. Assuming that the REE preferentially occur in fluid inclusions, the typical chondrite normalized REE distribution patterns with tetrad effects and a distinct negative Eu anomaly would reflect the composition of the mineralizing fluid.For a number of elements, especially those with extremely low concentrations, the “type” of incorporation in quartz could not directly be determined. We conclude that these ions either are too large to substitute for the small Si⁴⁺ ion or they are not soluble in the mineralizing fluids to be hosted by fluid inclusions. Some of these elements, which are concentrated in the specific mineralization of certain pegmatites, are not present in elevated concentrations in the paragenetic pegmatite quartz itself. This was observed, for instance, for Be, Cs and Rb in the Li (Be-Cs-Rb) pegmatites of Rubicon or for Nb and Ta for Nb-Ta bearing pegmatites from Norway. It may be concluded that the concentrations of these trace elements in quartz do not reflect the mineralization and that these elements thus, cannot be used as petrogenetic indicator.     

地下水中高锰酸盐指数和硝酸根铵根稳定性研究

高锰酸盐指数(CODMn)、硝酸根(NO-3)、铵根(NH+4)是判断水体是否受到三氮污染的重要指标。对于测定这三个指标的水样保存方式和时间,地质行业标准和国内外主要国家标准间存在明显差异。地质行业标准规定地下水样品原水室温保存,CODMn和NH+4在3天内测定;NO-3在20天内测定;国家标准和美国标准推荐样品硫酸酸化,避光或冷藏保存,在2~7天内完成CODMn和NO-3和1~7天内完成NH+4测试。为了分析各类标准在样品保存要求上的差异对检测结果的影响,确保检测数据能真实地反映水体污染状况,找寻简便的保存方式,本文在广州地区采集地下水,按照地质行业标准与国家标准进行处理和保存,并在不同时间段对三个指标进行测试。分析验证结果表明:地质行业标准与国家和美国标准关于水样的保存方法均非常可靠。地质行业标准主要针对静态地下水,保存方法相对宽松;国家标准和美国标准适用范围除了地下水,还包括动态的地表水和废水,采样对象成分更为复杂,更不稳定,更容易受外界影响发生变化,故保存条件高于地质标准。在广州地区,采用原水室温避光保存水样,CODMn、NH+4保存时间可为5天,NO-3保存时间可为30天;采用酸化水室温保存水样,CODMn、NO-3和NH+4保存时间可长达30天。这两种方式均比地质行业标准和国家标准推荐的有效时间长,且原水和酸化水室温保存方式相对于冷藏保存方式更为方便。本文提出,如果采集的水样能方便、快速送达实验室,可采用原水保存;如果不能在短时间内送达实验室检测,可采用硫酸酸化保存。     

Effects of Torul dam on water quality in the stream Harşit,NE Turkey

This paper evaluates the effects of Torul dam on the stream Harşit water quality in terms of 13 physico-chemical parameters in the Gümüşhane Province, Eastern Black Sea Basin, Turkey. For this purpose, a study was fortnightly conducted during the four seasons between March 2009 and February 2010. In two monitoring stations selected in the upstream and downstream of the Torul dam, T, pH, DO and EC were determined in situ, and collected water samples were analyzed for TH, COD, NH₄ ⁺-N, NO₂ ⁻-N, NO₃ ⁻-N, TN, TKN, PO₄ ³⁻-P and MBAS. According to the Turkish Water Pollution Control Regulation (TWPCR), the stream Harşit was classified, and the obtained results were evaluated for the values proposed by Turkish Standard (TS) 266 and World Health Organization (WHO) guidelines. The results showed that the stream Harşit has high-quality water in terms of, T, pH, DO, COD, NH₄ ⁺-N and NO₃ ⁻-N, but slightly polluted water in terms of NO₂ ⁻-N, TKN and PO₄ ³⁻-P, and polluted for MBAS. It was concluded that Torul dam has a positive effect on the stream water quality in terms of decrease in the annual average concentration values. The percent decreases for TH, COD, NH₄ ⁺-N, NO₂ ⁻-N, NO₃ ⁻-N, TN, TKN, PO₄ ³⁻-P and MBAS were 17.1, 20.3, 56.2, 62.6, 11.7, 11.9, 11.4, 17.8 and 71.4, respectively. The reason for these decreases is probably due to the Torul dam reservoir where the water has a hydraulic residence time and the exposure to chemicals by aquatic organisms or populations that ingest the water. Also, statistical analysis shows that there are significant correlations among the studied parameters.     

Tracing the sources of nitrate in karstic groundwater in Zunyi,Southwest China: a combined nitrogen isotope and water chemistry approach

Nitrate (NO₃ ⁻) is major pollutant in groundwater worldwide. Karst aquifers are particularly vulnerable to nitrate contamination from anthropogenic sources due to the rapid movement of water in their conduit networks. In this study, the isotopic compositions (δ¹⁵N–NO₃ ⁻, δ¹⁵N–NH₄ ⁺) and chemical compositions(e.g., NO₃ ⁻, NH₄ ⁺, NO₂ ⁻, K⁺) were measured in groundwater in the Zunyi area of Southwest China during summer and winter to identify the primary sources of contamination and characterize the processes affecting nitrate in the groundwater. It was found that nitrate was the dominant species of nitrogen in most of the water samples. In addition, the δ¹⁵N–NO₃ ⁻ values of water samples collected in summer were lower than those collected in winter, suggesting that the groundwater received a significant contribution of NO₃ ⁻ from agricultural fertilizer during the summer. Furthermore, the spatial variation in the concentration of nitrate and the δ¹⁵N–NO₃ ⁻ value indicated that some of the urban groundwater was contaminated with pollution from point sources. In addition, the distribution of δ¹⁵N–NO₃ ⁻ values and the relationship between ions in the groundwater indicated that synthetic and organic fertilizers (cattle manure) were the two primary sources of nitrate in the study area, except in a few cases where the water had been contaminated by urban anthropogenic inputs. Finally, the temporal and spatial variation of the water chemistry and isotopic data indicated that denitrification has no significant effect on the nitrogen isotopic values in Zunyi groundwater.