The application of ICP-SMS, GF-AAS and HG-AFS to the analysis of water and sediment samples from a temperate stratified estuary

Three atomic spectrometry techniques, namely sector field inductively coupled plasma mass spectroscopy, graphite furnace atomic absorption spectrometry and hydride generation atomic fluorescence spectroscopy (ICP-SMS, GF-AAS and HG-AFS, respectively), housed at separate independent laboratories, were used to analyse water and sediment samples collected from the Huon River Estuary, SE Tasmania (Australia) in the Austral spring 1998. A dithiocarbamate-chelation/back-extraction technique was used to separate and preconcentrate Co, Ni, Cu, Zn, Cd and Pb from eight collected water samples prior to analysis by ICP-SMS and GF-AAS. A number of other elements in the waters were analysed directly (Mn, Fe and Zn by GF-AAS; As by HG-AFS), or following sample dilution (1 + 19: V, Mn, Fe, As, Mo, Ba and U by ICP-SMS). Where possible, previously corroborated GF-AAS and HG-AFS techniques were used to verify obtained ICP-SMS results. From the analysis of four reference waters (SLEW-1 and -2, SLRS-3 and NASS-5), good agreement, to within +/- 10-20%, was typically found between certified (or information only values) and measured results (irrespective of analytical technique). Exceptions included Zn (and sometimes Fe) that could not be quantified by ICP-SMS due to elevated blank signals, and As which was found to lie below ICP-SMS detection limits. For Huon Estuary water samples, inter-method agreement was within +/- 10-20% (for those elements amenable to analysis by more than one technique). Nitric acid extracts of two certified reference materials (Buffalo River Sediment and BCSS-1) and six Huon Estuary sediments were analysed by ICP-SMS (for Al, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd and Pb) and HG-AFS (for As). Results from the certified reference materials indicated extraction efficiencies of 60 70% (for most elements). A close correlation between ICP-SMS and HG-AFS was obtained for leachable As in the sediments. In terms of potential inorganic contaminants, the Huon Estuary was found to be a relatively 'clean' water system. The elemental concentrations measured in water and sediment samples from this region were found to lie within current Australian guidelines for estuaries. In general, no one analytical technique was able to accurately determine all elements in all samples from this relatively pristine estuarine environment. A combination of all three analytical techniques was necessary for the successful analysis of the elements considered in this study.     

Heavy metal concentrations in groundwaters and soils of Thane Region of Maharashtra, India

Thane district is one of the most industrialized districts in Maharashtra. The heavy industrialization and the increasing urbanization are responsible for the rapidly increasing stress on the water and soil environment of the area. Therefore, an attempt has been made through comprehensive study on the groundwater contamination and soil contamination due to heavy metals in Thane region of Maharashtra. The area undertaken for the study was Thane and its suburbans Kalwa, Divajunction, Dombivali, Kalyan, and Ulhasnagar. Industrialization and urbanization lead to generation of large volumes of wastewater from domestic, commercial, industrial, and other sources, which discharged in to natural water bodies like river and creek in this region. Groundwater samples and soil samples were collected from residential, commercial, agriculture, and industrial areas. Groundwater samples were analyzed for various water quality parameters. The analytical data shows very high concentration of total dissolved solids, total hardness, total alkalinity, chemical oxygen demand, chloride etc. Groundwater and soil samples were analyzed for ten heavy metals by inductively coupled plasma (ICPE-9000) atomic emission spectroscopy. The analytical data reveal that, very high concentration level of arsenic, cadmium, mercury, and nickel throughout the industrial area. The random dumping of hazardous waste in the industrial area could be the main cause of the groundwater and soil contamination spreading by rainwater and wind. In the residential areas the local dumping is expected to be the main source for heavy metals. A comparison of the results of groundwater with WHO guidelines show that most of the groundwater sampling station are heavily contaminated with organic matter and heavy metals. Groundwater samples are heavily contaminated by arsenic, cadmium, mercury, and nickel. Similarly, the results of heavy metals in soil compared with Swedish soil guideline values for polluted soil show that soil samples collected from residential, commercial and industrial areas are heavily contaminated by arsenic, cadmium, mercury, and nickel.     

Evaluation of the effect of data pre-treatment procedures on classical pattern recognition and principal components analysis: a case study for the geographical classification of tea

A simple transformation that uses the half-range and central value has been used as a data pre-treatment procedure for principal component analysis (PCA) and pattern recognition techniques. The results obtained have been compared with the results from classical normalisation of data (mean normalisation, maximum normalisation and range normalisation), autoscaling and the minimum-maximum transformation. Three data sets were used in the study. The first was formed by determining 17 elements in 53 tea samples (901 pieces of data). The second and third data sets arose from two long-term drift studies performed to examine instrumental stability at standard and robust conditions. The instruments used were an inductively coupled plasma atomic emission spectrometer and an inductively coupled plasma mass spectrometer. Each drift diagnosis experiment consisted of replicate determinations of a test solution containing 15 analytes at 10 mg l-1 over 8 h without recalibration. Twenty-nine emission lines were determined 99 times, thus, each data set was formed by 2881 pieces of data. Data pre-treatment was applied to the three data sets prior to the use of principal component analysis, cluster analysis, linear discrimination analysis and soft independent modelling of class analogy. The study revealed that the half-range and central value transformation resulted in a better classification of the tea samples than that achieved using the classical normalisation. The loadings in the PCA for the long-term stability study, under both standard and robust conditions, were found to be similar to the drift trends only when the minimum-maximum transformation and the mean or maximum normalizations were used as data pre-treatments.     

Homogeneity and stability study of the candidate reference material Adamussium colbecki for trace elements

The preparation of a new candidate certified reference material (CRM) for trace elements based on the antarctic bivalve Adamussium colbecki(IRMM 813) was carried out by the Istituto Superiore di Sanità(ISS, Rome, Italy) in cooperation with the Institute for Reference Materials and Measurements, Joint Research Centre of the European Commission (EC-JRC-IRMM), in the frame of the Italian National Programme of Research in Antarctica (Programma Nazionale di Ricerca in Antartide, PNRA). Samples were collected at Terra Nova Bay (Ross Sea) during the 2000-2001 expedition in Antarctica. The preparation of a material suitable for certification was performed by the EC-JRC-IRMM. Measurements for homogeneity and short-term stability tests were carried out by ISS. The elements selected for the certification project were As, Cd, Cu, Cr, Fe, Mn, Ni and Zn. For the above-mentioned tests, the determination of the elements of interest was performed on samples mineralised by microwave-assisted acid digestion. The analytical techniques employed to this end were inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry (ICP-DRC-Q-MS). The candidate material was shown to be fit for purpose with regard to homogeneity and short-term stability, thus allowing the following phases of the certification project to be undertaken, in the first place the selection of expert laboratories for the accomplishment of the certification campaign.     

Bromate analysis in groundwater and wastewater samples

Bromate (BrO(3)(-)) is a disinfection by-product formed during ozonation of potable water supplies containing bromide (Br(-)). Bromate has been classed by the World Health Organisation as a 'possible human carcinogen', leading to implementation of 10-25 microg L(-1)(as BrO(3)(-)) drinking water limits in legislative areas including the United States and European Union. Techniques have been developed for bromate analysis at and below regulatory limits, with Ion Chromatography (IC) coupled with conductivity detection (IC-CD), post-column reaction and ultra-violet (UV) detection (IC-PCR), or inductively coupled plasma-mass spectrometry detection (IC-ICPMS) in widespread use. The recent discovery of bromate groundwater contamination in a UK aquifer has led to a requirement for analysis of bromate in a groundwater matrix, for environmental monitoring and development of remediation strategies. The possibility of bromate-contaminated water discharge into sewage treatment processes, whether accidental or as a pump-and-treat strategy, also required bromate analysis of wastewater sources. This paper summarises techniques currently available for trace bromate analysis in potable water systems and details studies to identify a methodology for routine analysis of groundwater and wastewater samples. Strategies compared were high performance liquid chromatography (HPLC) with direct UV or PCR/UV detection, IC-CD, IC-PCR, and a simple spectrophotometric technique. IC-CD was the most cost-effective solution for simultaneous analysis of bromate and bromide within groundwater samples, having a 5 microg L(-1) detection limit of both anions with limited interference from closely-eluting species. Wastewater samples were successfully analysed for bromate only using HPLC with PCR/UV detection, with detection limits below 20 microg L(-1)(as BrO(3)(-)) and low interference. HPLC with direct UV detection was unsuitable for bromate analysis within the concentration range 50-5000 microg L(-1) which was required for this project, but column choice was shown to be a major factor in determining limits of detection. Spectrophotometry could not reproducibly determine bromate concentration, although the technique showed promise as a quick field method for high-level groundwater bromate analysis.     

Determination of metal-humic complexes, free metal ions and total concentrations in natural waters

A comparison of two systems for the quantitation of metal-humic complexes and free metal ions, consisting of the separation by coupled ion exchange columns followed by detection by inductively coupled plasma mass spectrometry or cold vapour atomic fluorescence spectrometry, is presented. The systems evaluated comprised the serially coupled anion and cation exchangers, Sephadex A-25/Chelex 100 and Dowex 1X8/Chelamine Metalfix. Separation and preconcentration of the species studied were accomplished with both systems, elution being carried out using 2 M HNO3. Total concentrations, metal-humic complex fractions and free metal ion fractions of Al, Ba, Cd, Co, Cu, Fe, Hg, Mn, Pb, Sr, U and Zn in nine natural waters were determined. Statistical evaluation of the data from the two cation exchange materials, including results for additional elements, showed better precision (for Al, Ba, Cr, Cu and Mo) and higher recoveries (Al, Ba, Cd, Fe, Sr and Zn) for Chelex 100 than Chelamine Metalfix for free metal ions. On the other hand, Chelamine Metalfix recovered a significantly greater amount of Ni. The amounts of metal-humic complexes were compared with modelled distributions of these species, and one advantage of the preferred Sephadex A-25/Chelex 100 system is that the elements studied are all correctly classified with respect to their binding strengths to humic substances, which is not the case with the Dowex 1X8/Chelamine Metalfix pair. With the preferred system, metal-humic complexes can be reliably determined, as indicated by the results of equilibrium speciation modelling. However, comparison with the total concentrations showed statistically significant, non-quantitative recoveries of Al, Cu, Hg, Mn, U and Zn from some samples. Thus a combination of speciation and total concentration measurements is required to obtain a complete representation of the distribution of trace elements in natural waters.     

Determination of toxic inorganic elements pollution in ground waters of Kahuta Industrial Triangle Islamabad, Pakistan using inductively coupled plasma mass spectrometry

The present study deals with the ground water quality assessment in Kahuta Industrial Triangle Islamabad, Pakistan. The objective of the study was to assess ground water quality against the drinking water standards for various toxic inorganic elements. Representative groundwater samples were collected and analyzed in the Water Quality Laboratory of Pakistan Council of Research in Water Resources (PCRWR) at Islamabad, Pakistan. The samples were run on ICP-MS (Inductively coupled plasma mass spectrometry), which has the capability to separate and quantify 70 elements at a time. One of the finding of study is that ICP-MS is a very good tool to analyze broad range of toxic inorganic elements to the level of parts per billion (ppb). World Health Organization drinking water standards shows that these toxic inorganic elements such as heavy metals even at this concentration level (ppb) are injurious to human health. This analysis indicated pollution of various toxic elements including Selenium. Vertical leachate through industrial waste septic tanks is identified as major cause of groundwater pollution in the Industrial Triangle. Monitoring of the septic tanks and groundwater quality in study area is suggested along with remedial measures.     

Analysis of elemental concentration using ICP-AES and pathogen indicator in drinking water of Qasim Abad, District Rawalpindi, Pakistan

The present study was conducted to investigate drinking water quality (groundwater) from water samples taken from Qasim Abad, a locality of approximately 5,000 population, situated between twin cities Rawalpindi and Islamabad in Pakistan. The main sources of drinking water in this area are water bores which are dug upto the depth of 250–280 ft in almost every house. The study consists of the determination of physico-chemical properties, trace metals, heavy metals, rare earth elements and microbiological quality of drinking water. The data showed the variation of the investigated parameters in samples as follows: pH 6.75 to 8.70, electrical conductivity 540 to 855 μS/cm, total dissolved solids 325.46 to 515.23 ppm and dissolved oxygen 1.50 to 5.64 mg/L which are within the WHO guidelines for drinking water quality. The water samples were analysed for 30 elements (aluminium, iron, magnesium, manganese, silicon, zinc, molybdenum, titanium, chromium, nickel, tungsten, silver, arsenic, boron, barium, beryllium, cadmium, cobalt, copper, gallium, mercury, lanthanum, niobium, neodymium, lead, selenium, samarium, tin, vanadium and zirconium) by using inductively coupled plasma atomic emission spectroscopy. The organic contamination was detected in terms of most probable number (MPN) of faecal coliforms. Overall, elemental levels were lower than the recommended values but three water bores (B-1, B-6, B-7) had higher values of iron (1.6, 2.206, 0.65 ppm), two water bores (B-1, B-6) had higher values of aluminium (0.95, 1.92 ppm), respectively, and molybdenum was higher by 0.01 ppm only in one water bore (B-11). The total number of coliforms present in water samples was found to be within the prescribed limit of the WHO except for 5 out of 11 bore water samples (B-2, B-3, B-4, B-8, B-11), which were found in the range 5–35 MPN/100 mL, a consequence of infiltration of contaminated water (sewage) through cross connection, leakage points and back siphoning.     

Trace element concentration in groundwater of Pesarlanka Island, Krishna Delta, India

There is a growing concern over the potential accumulation of trace element concentration in groundwater of coastal aquifer owing seawater encroachment in the last several decades. A total of 29 groundwater samples collected from Pesarlanka Island, Krishna delta, Andhra Pradesh, India were analyzed for 13 trace elements (B, V, Mn, Fe, Ni, Co, Cu, Zn, As, Sr, Cd, Ba, and Pb) using inductively coupled plasma mass spectrometry. The results reveal that B, Fe, Ni, As, Sr, and Pb vary from 11.22 to 710.2, 1.25 to 684.6, 0.02 to 37.33, 27.8 to 282.3, 164.1 to 7,009, and 1.97 to 164.4 μg/l, respectively. Ba, Cd, Co, Cu, Ni, V, and Zn are almost within permissible limits for drinking water, but As, Fe, Mn, Pb, B, and Sr are above the permissible limit. The toxic element Pb is 1.64 times more than the maximum permissible limits of drinking water. The minimum value of As is also 2.78 times more, whereas the maximum is 28.2 times the permissible limit. The spatial distributions of alkaline earths (Sr, Ba), transition metals (V, Co, Ni, Fe), metallic elements (Cu, Pb), and (As) were found in considerable variation in the entire Island. Good cross-correlations were found between As, B, Co, and Sr with total dissolved solids and among other trace elements such as B, As, Co, and Sr. The variability observed within the groundwater samples is closely connected to the sea spray input; hence, it is primarily a consequence of geographical and meteorological factors, such as distance from the ocean and time of year. The trace element levels, in particular those of heavy metals, are very low, suggesting an origin from natural sources rather than from anthropogenic contamination. A few trace elements (Sr and B) are found as sensitive parameters responding to changes in fresh to saline groundwater environment. The highly elevated trace elements in this area which may be attributed to marine sediments or death and decay of plants are presented in this paper.     

环境水样中硫化物的分析方法研究进展

硫化物是水质检测的一个重要参数,因其对水生生物和人体具有很高的毒性而备受关注.综述了近5 a来环境水样中硫化物的分析方法研究进展,包括光谱法(分光光度法、荧光法、电致化学发光法、电感耦合等离子体-原子发射光谱、原子吸收法、流动注射法),色谱法,以及电化学法(阴极溶出伏安法、阳极溶出伏安法、电催化氧化法、生物传感器法),...     

Monitoring of the three organophosphate esters TBP,TCEP and TBEP in river water and ground water (Oder,Germany)

The behaviour of the three organophosphate esters tributyl phosphate (TBP), tris(2-chloroethyl)phosphate (TCEP) and tris(2-butoxyethyl)phosphate (TBEP) during infiltration of river water to ground water has been investigated. The monitoring site is the Oder River and the adjacent Oderbruch aquifer. From March 2000 to July 2001, 76 ground water samples from monitoring wells located close to the Oder River and nine river water samples were collected. Additionally, influent and effluent samples from local waste water treatment plants, one sample of rain water and samples of roof runoff were collected. All samples were analysed by solid-phase-extraction followed by gas chromatography/mass spectrometry. TBP, TCEP and TBEP were detected at mean values of 622 ng l(-1), 352 ng l(-1), and 2955 ng l(-1), respectively in municipal waste water effluents. This points to a major input of these compounds into the Oder River by municipal waste water discharge. The concentrations of TBP and TBEP decreased downstream the Oder River possibly due to aerobic degradation. TBP, TCEP and TBEP were detected in ground water influenced predominantly by bank-filtered water. This demonstrates a transport of organic compounds by river water infiltration to ground water. TBP, TCEP and TBEP were also detected in rain water precipitation, roof runoff and ground water predominantly influenced by rain water infiltration. This hints to an input of these compounds to ground water by dry and wet deposition after atmospheric transport. Organophosphate esters were also detected in parts of the aquifer at 21 m depth. This demonstrates low anaerobic degradation rates of TBP, TCEP and TBEP.     

Quality assurance in measuring the elemental composition of the alga Fucus vesiculosus

Algae are increasingly used for the purpose of environmental biomonitoring, for instance in the long-term program of the Federal Environmental Specimen Bank of Germany. Therefore, for the studies presented here, freeze-dried samples of Fucus vesiculosus collected from the North Sea shores were analyzed for a broad range of elements by instrumental neutron activation analysis (INAA), while inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) were carried out on digests. The entire analytical procedures, including field sampling, cleaning of material, sample handling, determination of blanks and instrumental parameters, are described. Certified reference materials analyzed in parallel with real samples and intermethod comparisons were used for assuring the accuracy of the analytical data. Reproducibility of INAA measurements was between 4 and 6% depending on the element considered. Possible sources of uncertainty and variation of the contaminant origins are discussed. Boundary conditions for the performance of algae sampling within environmental monitoring programs and the application of this marine bioindicator for the purpose of controlling time-dependent and local differences in element patterns are presented.     

Integrating geospatial and ground geophysical information as guidelines for groundwater potential zones in hard rock terrains of south India

The increasing demand of water has brought tremendous pressure on groundwater resources in the regions were groundwater is prime source of water. The objective of this study was to explore groundwater potential zones in Maheshwaram watershed of Andhra Pradesh, India with semi-arid climatic condition and hard rock granitic terrain. GIS-based modelling was used to integrate remote sensing and geophysical data to delineate groundwater potential zones. In the present study, Indian Remote Sensing RESOURCESAT-1, Linear Imaging Self-Scanner (LISS-4) digital data, ASTER digital elevation model and vertical electrical sounding data along with other data sets were analysed to generate various thematic maps, viz., geomorphology, land use/land cover, geology, lineament density, soil, drainage density, slope, aquifer resistivity and aquifer thickness. Based on this integrated approach, the groundwater availability in the watershed was classified into four categories, viz. very good, good, moderate and poor. The results reveal that the modelling assessment method proposed in this study is an effective tool for deciphering groundwater potential zones for proper planning and management of groundwater resources in diverse hydrogeological terrains.     

The biological behaviour and bioavailability of aluminium in man, with special reference to studies employing aluminium-26 as a tracer: review and study update

Until 1990 biokinetic studies of aluminium metabolism and biokinetics in man and other animals had been substantially inhibited by analytical and practical difficulties. Of these, the most important are the difficulties in differentiating between administered aluminium and endogenous aluminium-especially in body fluids and excreta and the problems associated with the contamination of samples with environmental aluminium. As a consequence of these it was not possible to detect small, residual body burdens of the metal following experimental administrations. Consequently, many believed aluminium to be quantitatively excreted within a short time of uptake in all, but renal-failure patients. Nevertheless, residual aluminium deposits in a number of different organs and tissues had been detected in normal subjects using a variety of techniques, including histochemical staining methods. In order to understand the origins and kinetics of such residual aluminium deposits new approaches were required. One approach taken was to employ the radioisotope (67)Ga as a surrogate, but this approach has been shown to be flawed-a consequence of the different biological behaviours of aluminium and gallium. A second arose from the availability, in about 1990, of both (26)Al-a rare and expensive isotope of aluminium-and accelerator mass spectrometry for the ultra-trace detection of this isotope. Using these techniques the basic features of aluminium biokinetics and bioavailability have been unravelled. It is now clear that some aluminium is retained in the body-most probably within the skeleton, and that some deposits in the brain. However, most aluminium that enters the blood is excreted in urine within a few days or weeks and the gastrointestinal tract provides an effective barrier to aluminium uptake. Aspects of the biokinetics and bioavailability of aluminium are described below.     

Characterization of soil contamination by lead around a former battery factory by applying an analytical hybrid method

Former battery factories have created environmental and health problems for years and the exposure to lead in surface soils has been underestimated. Nonetheless, the identification of lead contamination and its spatial distribution is crucial. The determination of heavy metals in soils can be performed using inductively coupled plasma mass spectrometry (ICP-MS). However, alternative techniques such as X-ray fluorescence (XRF) have been used lately in environmental studies since measurements can be taken in the field in a prompt manner, despite its lower accuracy. In this study, a former battery factory site in Monterrey, Mexico, has been studied in order to detect lead contamination. Soil samples were assessed for contamination by using an analytical hybrid method that comprises both analytical techniques, namely, ICP-MS and XRF. Samples were taken in 215 locations and, after a simple homogenization process, they were analyzed by using a portable XRF device. Within those 215 sampling points, 25 samples were analyzed concurrently by using ICP-MS according to international sampling guidelines. Results obtained were adjusted in order to define an analytical hybrid method, which encompasses the advantages of each technique. An improved characterization was achieved by using the proposed analytical hybrid method since maps of lead distribution and calculated areas of concern showed better predictability. The combination of spectroscopic techniques is of great applicability for environmental agencies and decision makers.     

Occupational exposure to beryllium in primary aluminium production

Alumina used in the production of primary aluminium contains Be which partly vaporises from the cryolite bath into the workroom atmosphere. Since Be may be toxic at lower exposure levels than previously thought, the personal exposure to Be among workers in 7 Norwegian primary smelters has been assessed. In total, 480 personal Respicon? virtual impactor full shift air samples have been collected during 2 sampling campaigns and analysed for water soluble Be, Al and Na using inductively coupled plasma optical emission spectrometry. In addition, water soluble F(-) has been measured by ion chromatography. The Be air concentrations in the inhalable, thoracic and respirable aerosol fractions have been calculated. The Be concentrations in the inhalable aerosol fraction vary between the different smelters. The highest GM concentration of Be in the inhalable fraction (122 ng m(-3), n = 30) was measured in the prebake pot room of a smelter using predominantly Jamaican alumina where also the highest individual air concentration of 270 ng m(-3) of Be was identified. The relative distribution of Be in the different aerosol fractions was fairly constant with the mean Be amount for the two sampling campaigns between 44-49% in the thoracic fraction expressed as % of the inhalable amount. Linear regression analysis shows a high correlation between water soluble Be, Al, F and Na describing an average measured chemical bulk composition of the water soluble thoracic fraction as Na(5.7)Al(3.1)F(18). Be is likely to be present as traces in this particulate matter by replacing Al atoms in the condensed fluorides and/or as a major element in a nanoparticle sized fluoride. Thus, the major amount of Be present in the work room atmosphere of Al smelter pot rooms will predominantly be present in combination with substantial amounts of water soluble Al, F and Na.     

Major and trace element contents in apples from a cultivated area of central Greece

Forty-two soil and apple samples from central Greece were collected and analyzed with regards to the content in major (Ca, Fe, K, Mg, Na, P, and S) and trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Sc, Se, Sr, Ti, and Zn). Soil samples were analyzed by inductively coupled plasma atomic emission spectrometry, while for the apples inductively coupled plasma mass spectrometry was implemented. Several elements such as As, B, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Se, Ti, and Zn, represent high concentrations in apples from the study area. These relatively high concentrations may be a consequence of the local geology, along with the excessive application of agricultural products such as fertilizers and agrochemicals.     

A novel high-frequency groundwater quality monitoring system

High-frequency, long-term monitoring of water quality has revolutionized the study of surface waters in recent years. However, application of these techniques to groundwater has been limited by the ability to remotely pump and analyze groundwater. This paper describes a novel autonomous groundwater quality monitoring system which samples multiple wells to evaluate temporal changes and identify trends in groundwater chemistry. The system, deployed near Fresno, California, USA, collects and transmits high-frequency data, including water temperature, specific conductance, pH, dissolved oxygen, and nitrate, from supply and monitoring wells, in real-time. The system consists of a water quality sonde and optical nitrate sensor, manifold, submersible three-phase pump, variable frequency drive, data collection platform, solar panels, and rechargeable battery bank. The manifold directs water from three wells to a single set of sensors, thereby reducing setup and operation costs associated with multi-sensor networks. Sampling multiple wells at high frequency for several years provided a means of monitoring the vertical distribution and transport of solutes in the aquifer. Initial results show short period variability of nitrate, specific conductivity, and dissolved oxygen in the shallow aquifer, while the deeper portion of the aquifer remains unchanged—observations that may be missed with traditional discrete sampling approaches. In this aquifer system, nitrate and specific conductance are increasing in the shallow aquifer, while invariant changes in deep groundwater chemistry likely reflect relatively slow groundwater flow. In contrast, systems with high groundwater velocity, such as karst aquifers, have been shown to exhibit higher-frequency groundwater chemistry changes. The stability of the deeper aquifer over the monitoring period was leveraged to develop estimates of measurement system uncertainty, which were typically lower than the manufacturer’s stated specifications, enabling the identification of subtle variability in water chemistry that may have otherwise been missed.     

A study on chemical properties of groundwater and soil in ophiolitic rocks in Firuzabad, east of Shahrood, Iran: with emphasis to heavy metal contamination

In order to assess the chemical properties of groundwater and soil in ophiolitic zone of Firuzabad, in east of Shahrood, Iran, 10 soil samples with regard to sensitive points (vicinity to mine, ophiolitic rocks, and villages) and 10 groundwater samples including nine samples from springs, and also one sample from a well in a village of the study area were taken. These samples were analyzed in laboratories using inductively coupled plasma method. The soil samples were also evaluated for grain size. The obtained results show that most of heavy and major elements were exceeding the permissible levels in soil and water samples in the study area. On the subject of soil quality, concentrations of elements Cr, Mn, Fe, Ca, Mg, Ca, Ni, and Zn are above permissible levels. Enrichment factor and index of geoaccumulation have been calculated for heavy and major elements of all soil samples. According to the obtained results, it may be argued that soil samples are contaminated in relation to the above-mentioned indices. Comparing the concentrations of elements with results of grain size analysis illustrates that the concentrations of Cr, Ni, Fe, Mg, and Co are positively correlated with sand fraction and the concentrations of Al, P, Mn, and Pb are directly proportional with clay fraction in soil samples. The study on water contamination suggests that concentrations of elements Cr, Ni, and Mg in groundwater samples of the study area are above the permissible levels. Some indices like metal index and heavy metal pollution index show that most of the water samples include heavy metal contamination.     

Groundwater levels time series sensitivity to pluviometry and air temperature: a geostatistical approach to Sfax region,Tunisia

In this paper, the pattern of groundwater level fluctuations is investigated by statistical techniques for 24 monitoring wells located in an unconfined coastal aquifer in Sfax (Tunisia) for a time period from 1997 to 2006. Firstly, a geostatistical study is performed to characterize the temporal behaviors of data sets in terms of variograms and to make predictions about the value of the groundwater level at unsampled times. Secondly, multivariate statistical methods, i.e., principal component analysis (PCA) and cluster analysis (CA) of time series of groundwater levels are used to classify groundwater hydrographs regard to identical fluctuation pattern. Three groundwater groups (A, B, and C) were identified. In group “A,” water level decreases continuously throughout the study periods with rapid annual cyclic variation, whereas in group “B,” the water level contains much less high-frequency variation. The wells of group “C” represents a steady and gradual increase of groundwater levels caused by the aquifer artificial recharge. Furthermore, a cross-correlation analysis is used to investigate the aquifer response to local rainfall and temperature records. The result revealed that the temperature is more affecting the variation of the groundwater level of group A wells than the rainfall. However, the second and the third groups are less affected by rainfall or temperature.