Sea water contamination in underground waters of salento (Southern Italy)

In the present work, a study of a physico-chemical characterisation of underground waters, utilised for agriculture and human use in the Lecce district (Southern Italy) has been reported. The aim of the work has been to define the quality of underground waters in the different areas and to value salt contamination due to seawater intrusion. Statistical techniques, such as Principal Component Analysis (PCA) and Cluster Analysis (CA), have been utilised to examine the correlations among the different parameters and to define contamination areas. The results have shown a high salt contamination in artesian wells of the Ionian Sea coast.     

Determination of the chloride and fluoride contents in the ebrie lagoon and the underground waters in ivory Coast by means of X-ray fluorescence analysis and potentiometric method

This study is devoted to the determination of percentages of fluoride and chloride in Ebrié located in Abidjan and wells located in the central and southern areas of Ivory Coast. Nondispersive X-Ray Fluorescence method and potentometric method with ion sensitive electrodes have been used. For underground water, the concentrations obtained are, with the exception of some isolated cases, lower than the upper limits tolerated for drinking water. These waters are drinkable. In a lagunal environment, the results show that the elements drawn from the bottom of the sea, through the Vridi Canal, spread in the lagoon. The ratio of the concentration of elements and the corresponding salinity confirm the fact that chloride undergoes an essential dilution in the lagoon due to contact with continental waters. A semi-diurnal periodicity of the concentration of elements has been firmly established. This period is the same as the tidal one.     

Characteristics of the tritium distribution in the Danube basin region in Yugoslavia

The investigated water samples were collected from rivers, underground waters and precipitations at different locations near Belgrade during the period 1976–1979. By preconcentration and scintillation counting, the individually and monthly collected samples were analyzed for³H contents. It has been found that the³H-concentration in monthly river water samples (Danube, Sava, Tisa) varies from 39 to 196 TU with a maximum in summer, between 0–192 TU in the underground water depending on the sampling depth and distance from river Sava and Danube, while values of 26 to 153 TU have been detected in the monthly precipitation samples attaining a maximum during the break-through of arctic and polar continental air masses. The results were used to calculate the³H quantity deposited per m² (Bq/m²) of surface, due to precipitations and the flow per second (Bq/s) in the investigated locations in rivers. The interrelation between rivers, underground waters and precipitations is discussed. The³H-distributions obtained are correlated with the water level in rivers and with the precipitation quantities and are interpreted in light of the relevant meteorological parameters and other related phenomena.     

合并带异步注入-流动注射分光光度法快速测定地热水中高浓度硅酸盐

去除地热发电的废水回补管道中硅酸盐结垢是个难题。若能连续监测地热水中高浓度的硅酸盐含量、控制硅垢抑制剂的添加量,就可控制硅垢产生。本实验采用直接自动测定地热水中高浓度硅酸盐的合并带异步注入流动注射分光光度法,并优化了测定条件:2%(w/V)钼酸铵,0.1mol/L NaOH,1.0%草酸,预混合盘管长度350cm,反应盘管长度160cm,干扰掩蔽盘管长度300cm,载流流量2.0mL/min。本方法每次测定所需样品用量仅为25μL,显色剂用量仅为120μL,测定范围为25～800mg/L(SiO2),相对标准偏差小于1.96%,回收率为94.1%～110.5%,每小时可分析60个样品;本方法重现性好、分析速度快、测定成本极低,测定高浓度硅酸盐时无需预稀释处理。     

GC/MS analysis of pesticides in the Ferrara area (Italy) surface water: a chemometric study

The development of a network to monitor surface waters is a critical element in the assessment, restoration and protection of water quality. In this study, concentrations of 42 pesticides--determined by GC-MS on samples from 11 points along the Ferrara area rivers--have been analyzed by chemometric tools. The data were collected over a three-year period (2002-2004). Principal component analysis of the detected pesticides was carried out in order to define the best spatial locations for the sampling points. The results obtained have been interpreted in view of agricultural land use. Time series data regarding pesticide contents in surface waters has been analyzed using the Autocorrelation function. This chemometric tool allows for seasonal trends and makes it possible to optimize sampling frequency in order to detect the effective maximum pesticide content.     

“In situ” radiation cleaning of underground water contaminated with cyanides - six years of experience

The locality of underground water, contaminated with cyanides, has been successfully cleaned by using the hydraulic barrier method (assembly of pumped wells) since 1986. The average cyanide concentrations in the outflow exceeded 35 m per litre. Contamination had to be eliminated before the discharge into the sewer system. The radiation approach “in situ” i.e. decomposition of cyanides by barrier, was applied and is still being used today. The cyanide concentration was lowered more than one order of magnitude. This process was approved by the Czechoslovak radiation security authorities and further applications of “in Situ” regeneration of underground water contamination is anticipated.     

Interferences in the determination of total nitrogen in natural waters by photo-oxidation to nitrate-nitrite mixture

The method proposed by Armstrong, Williams and Strickland for the photo-oxidation of total nitrogen in sea-water to nitrate and nitrite has been studied in some detail, to extend its use to fresh and brackish waters, applying a more accurate method for the determination of the reaction products. Variables influencing the yield of nitrate and nitrite are irradiation time, pH and type of buffer, kind of nitrogen compound and its concentration, and the concentrations of oxygen, carbon dioxide, organic matter and salts, especially bromides, even at the low concentrations found in brackish waters. All these variables interact in a rather complicated way. Interferences from halides, organic matter and carbon dioxide are considerably reduced by ensuring that the pH is kept at 8.5-9 during the irradiation. Because pure solutions of many substances give quantitative yields (> or = 98%) in the pH-range 7-9 usually recommended, whereas others require lower pH for maximal oxidation, a method has been developed involving photo-oxidation first at pH 2.1 and then at pH 8.5-9. In the absence of interfering concentrations of halides the relative increase in yield by an initial irradiation at low pH is especially large (10-36%) for proteins, organic nitrogen in fresh waters, uric acid and urea. A comparison is made between determination of total nitrogen in some natural waters by using photo-oxidation and by a Kjeldahl method modified to give total nitrogen. By making use of the optimal conditions presented in this paper, a negative error of less than 8% is expected in the determination of total nitrogen in fresh waters. For saline waters the error will probably be larger, at least at a high ratio of organic to inorganic nitrogen.     

Rheology Properties and Plugging Performance of Fluorescent Polyacrylamide Microspheres in Fractures

Polyacrylamide microspheres have recently drawn great attention in conformance control due to their advantages over traditional gel treatments. One important question that has been raised is whether the tiny particles can be produced from production wells. However, current products are difficult to use for detecting fluids generated by production wells. In this paper, the fluorescent polyacrylamide microspheres were successfully synthesized; they can emit blue fluorescence under ultraviolet irradiation. Their swelling property, fluorescence characteristics, rheology property, creep-recovery property, and plugging performance were evaluated in the laboratory. The results indicated that the microspheres could emit blue fluorescence under ultraviolet irradiation after passing through a fracture model. Their creep-recovery ability after deformation was very high, and their elastic recovery rate extended to 94.1%, which suggests that the microspheres almost recover to their original shape and size after deformation. The transparent fracture model plugging test shows that the microspheres can migrate and plug a fracture with a width of 0.3 mm, which is much smaller than the diameter of the microspheres.     

The use of charcoal from agriculture waste in the speciation of iodine from well and river waters

The concentrations of iodine in fresh waters are known to be within the range of 0.5 to 35 ng·ml⁻¹, much lower than in oceanic waters. The iodine concentrations, particularly that of¹²⁹I which is significant from the radiation safety aspect, in public drinking waters have to be specified in order to verify the required level before distribution for domestic use. A modified version of an established method was used in the adsorption of iodine, iodate, total inorganic iodine and charcoal-adsorbable iodine using activated carbon prepared from oil palm kernel wastes. A thorough investigation of the physical properties of the activated carbon was carried out to determine its viability as an adsorbent for volatile species such as iodine. The iodine species were preconcentrated from water samples collected from wells in villages and from water intake points along rivers. The quantitative analysis of the species adsorbed was done by irradiating the activated charcoal loaded with the respective species in a neutron flux of 5.1·10¹² n·cm⁻²·s⁻¹ from a TRIGA MkII, nuclear reactor. Recovery experiments using spiked samples was done to provide quality assurance controls.     

Nitrifying and Denitrifying Microbiological Mud Encapsulated by the Sol–Gel Method

The aquatic underground mantle in the Peninsula of Yucatan (Mexico) represents the only source of water supply for domestic consumption. Nevertheless, this mantle is extremely vulnerable to infiltration of pollutants as nitrates due to the karstic layer. Nitrates are inorganic pollutants, whose mobility and stability make them highly dangerous in aerobic systems such as underground water. This contaminant has been found at up to 223 mg/L in artesian wells, whereas the maximum limit permitted by the World Health Organization is 45 mg/L. The development of innovative biomaterials, as nitrifying and denitrifying microbiological mud encapsulated in an inert matrix using the sol–gel technique, represents a possible alternative to eliminate nitrates in situ from the underground water of Merida in the state of Yucatan, Mexico. The sol–gel method has been extensively used for the preparation of such materials permitting a higher stability and viability of useful organisms. In this work the thermal properties of nitrifying and denitrifying mud encapsulated in silica gel derived from tetraethoxysilane are presented as a function of temperature. The photopyroelectric technique was used to study how different types of mud interchanges heat with the environment. The specific surface area of the nitrified mud was determined by analyzing the pore size distribution.     

Solvent impact on esterification and film formation ability of nanofibrillated cellulose

In this study we have manufactured nanofibrillar cellulose and modified the fibre surface with ester groups in order to hydrophobise the surface. Nanofibrillated cellulose was chosen to demonstrate the phenomena, since due to its high surface area the effects at issue are pronounced. The prepared NFC ester derivatives were butyrate, hexanoate, benzoate, naphtoate, diphenyl acetate, stearate and palmitate. X-ray photoelectron spectroscopy, solid state NMR and contact angle measurements were used to demonstrate the chemical changes taking place on the cellulose surface. NFC ester derivatives can be prepared after a careful solvent exchange to a water-free solvent medium has been carried out. Butyl and palmitoyl esters were chosen for film forming tests due to the difference in their carbon chain lengths, and their contact angles and water vapour and oxygen permeation rates were studied. The prepared nanocellulose esters show increased hydrophobicity even at very low levels of substitution and readily form films when the films are prepared from acetone dispersions. The permeation rates suggest a potential use as barrier materials.     

Factor analytical approaches for evaluating groundwater trace element chemistry data

The multivariate statistical techniques principal component analysis (PCA), Q-mode factor analysis (QFA), and correspondence analysis (CA) were applied to a dataset containing trace element concentrations in groundwater samples collected from a number of wells located downgradient from the potential nuclear waste repository at Yucca Mountain, Nevada. PCA results reflect the similarities in the concentrations of trace elements in the water samples resulting from different geochemical processes. QFA results reflect similarities in the trace element compositions, whereas CA reflects similarities in the trace elements that are dominant in the waters relative to all other groundwater samples included in the dataset. These differences are mainly due to the ways in which data are preprocessed by each of the three methods.

The highly concentrated, and thus possibly more mature (i.e. older), groundwaters are separated from the more dilute waters using principal component 1 (PC 1). PC 2, as well as dimension 1 of the CA results, describe differences in the trace element chemistry of the groundwaters resulting from the different aquifer materials through which they have flowed. Groundwaters thought to be representative of those flowing through an aquifer composed dominantly of volcanic rocks are characterized by elevated concentrations of Li, Be, Ge, Rb, Cs, and Ba, whereas those associated with an aquifer dominated by carbonate rocks exhibit greater concentrations of Ti, Ni, Sr, Rh, and Bi. PC 3, and to a lesser extent dimension 2 of the CA results, show a strong monotonic relationship with the percentage of As(III) in the groundwater suggesting that these multivariate statistical results reflect, in a qualitative sense, the oxidizing/reducing conditions within the groundwater. Groundwaters that are relatively more reducing exhibit greater concentrations of Mn, Cs, Co, Ba, Rb, and Be, and those that are more oxidizing are characterized by greater concentrations of V, Cr, Ga, As, W, and U.     

Determination of diuron and the antifouling paint biocide irgarol 1051 in Dutch marinas and coastal waters

A sensitive LC–electrospray MS–MS method using off-line solid-phase extraction for the determination of diuron and Irgarol 1051 has been developed, enabling determination of both compounds at sub-ppt levels. Diuron and Irgarol 1051 are used as alternatives for tributyltin in antifouling paints that prevent growth on boats, and an increase in their application is anticipated because of the upcoming ban on tributyltin in 2003. In 2000, a survey was carried out to assess contamination with diuron and Irgarol 1051 of a number of Dutch marinas and coastal waters. Depending on the time of year, both compounds were encountered at levels higher than the maximum permissible concentrations of 430 and 24 ng/l for diuron and Irgarol 1051, respectively. Outside marinas at reference locations, concentrations were much lower, depending on the geographical situation and the nature of the water exchange with the environment related to tidal cycles. A seasonal influence was observed with highest levels in summer, corresponding to the yachting season for both compounds. For diuron, use in agriculture could have contributed to the high concentration encountered in surface waters.     

Determination of diethanolamine or <Emphasis Type="Italic">N</Emphasis>-methyldiethanolamine in high ammonium concentration matrices by capillary electrophoresis with indirect UV detection: application to the analysis of refinery process waters

Alkanolamines such as diethanolamine (DEA) and N-methyldiethanolamine (MDEA) are used in desulfurization processes in crude oil refineries. These compounds may be found in process waters following an accidental contamination. The analysis of alkanolamines in refinery process waters is very difficult due to the high ammonium concentration of the samples. This paper describes a method for the determination of DEA in high ammonium concentration refinery process waters by using capillary electrophoresis (CE) with indirect UV detection. The same method can be used for the determination of MDEA. Best results were achieved with a background electrolyte (BGE) comprising 10 mM histidine adjusted to pH 5.0 with acetic acid. The development of this electrolyte and the analytical performances are discussed. The quantification was performed by using internal standardization, by which triethanolamine (TEA) was used as internal standard. A matrix effect due to the high ammonium content has been highlighted and standard addition was therefore used. The developed method was characterized in terms of repeatability of migration times and corrected peak areas, linearity, and accuracy. Limits of detection (LODs) and quantification (LOQs) obtained were 0.2 and 0.7 ppm, respectively. The CE method was applied to the determination of DEA or MDEA in refinery process waters spiked with known amounts of analytes and it gave excellent results, since uncertainties obtained were 8 and 5%, respectively.     

Distribution of 99Tc and 129I in the vicinity of underground nuclear tests at the Nevada Test Site

⁹⁹Tc and ¹²⁹I are important contributors to risk assessment due to their long half-lives and high mobility as aqueous anionic species. We analyzed ⁹⁹Tc and ¹²⁹I in groundwater samples in and near 11 underground nuclear tests and in melt glass and rock samples retrieved from the Chancellor test cavity, Nevada Test Site. The ¹²⁹I/¹²⁷I ratio ranges from 10⁻³ to 10⁻⁶ in cavity water and 10⁻⁴ to 10⁻⁹ in satellite wells. The ⁹⁹Tc concentration ranges from 3 to 10⁻⁴ Bq/l in cavity waters and from 0.3 to 10⁻⁴ Bq/l in satellite wells. Downstream migration is apparent for both radionuclides. However, it is affected by both retardation and initial distribution. In-situ ⁹⁹Tc and ¹²⁹I K _d s calculated using rubble and water concentrations are 3 to 22 ml/g and 0 to 0.12 ml/g, respectively, and are suggestive of mildly reducing conditions. ¹²⁹I distribution in the melt glass, rubble and groundwater of the Chancellor test cavity is 28%, 24% and 48%, respectively, for ⁹⁹Tc, it is 65%, 35% and 0.3%, respectively. Our partitioning estimates differ from those of underground tests in French Polynesia, implying that fission product distribution may vary from test to test. Factors that may influence this distribution include geologic conditions (e.g., lithology, water and CO₂ content) and the cooling history of the test cavity.     

Fully automated determination of 74 pharmaceuticals in environmental and waste waters by online solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry

The present work describes the development of a fully automated method, based on on-line solid-phase extraction (SPE)-liquid chromatography-electrospray-tandem mass spectrometry (LC-MS-MS), for the determination of 74 pharmaceuticals in environmental waters (superficial water and groundwater) as well as sewage waters. On-line SPE is performed by passing 2.5 mL of the water sample through a HySphere Resin GP cartridge. For unequivocal identification and confirmation two selected reaction monitoring (SRM) transitions are monitored per compound, thus four identification points are achieved. Quantification is performed by the internal standard approach, indispensable to correct the losses during the solid phase extraction, as well as the matrix effects. The main advantages of the method developed are high sensitivity (limits of detection in the low ng L⁻¹ range), selectivity due the use of tandem mass spectrometry and reliability due the use of 51 surrogates and minimum sample manipulation. As a part of the validation procedure, the method developed has been applied to the analysis of various environmental and sewage samples from a Spanish river and a sewage treatment plant.     

Robust cluster analysis for detecting physico-chemical typologies of freshwater from wells of the plain of Friuli (northeastern Italy)

An approach for the characterisation of the groundwater system of the southern plain of Friuli-Venezia Giulia Region (Italy) is proposed on the basis of its physico-chemical composition, in order to detect multivariate patterns for unpolluted waters typical of specific areas in the plain, as well as for eventual polluted zones. The analytical data are relative to 38 wells (depth ranging from 20 to 200 m) sampled in three different periods along a year. Ten physico-chemical parameters were determined: conductivity, temperature, dissolved oxygen, calcium, magnesium, chlorides, nitrates, sulphates, atrazine and desethylatrazine.

Cluster analysis (CA) provides the methodological bases for detecting the classes of freshwater being typical for the considered plain: partitioning around medoids (PAM) and fuzzy clustering are considered. The number of classes to be characterised and the clustering algorithm are selected by comparing the average silhouette index for models counting from 2 to 10 clusters; six classes obtained by PAM partition the data set at best.

Plotting the frequencies of cluster membership for each well on a map permits the association of the six classes of waters to five easily recognisable geographical areas and to one group of two wells that are highly polluted by nitrates and triazines.

Averages and ranges of values for physico-chemical parameters of each class can be provided according to this methodology, defining a set of values being characteristic for the composition of waters belonging to the classes of wells identified in the considered plain.     

Analyse du titane et de ses alliages par spectrométrie d'émission dans l'ultraviolet-vide

The large ultraviolet spectrograph for analysis in vacuum (VUV spectrograph) developed by ONERA and described in a previous article, has been used for multielements quantitative analysis: in pure titanium, concentrations of oxygen, nitrogen, hydrogen and carbon have been determined as well as silicon and iron impurities; in titanium-based alloys, addition metals at high concentration, Al, V, Mo, Zr, Si, have also been determined simultaneously with the gaseous elements and impurities. The analytical lines located between 200 and 2600 Å and corresponding to highly ionized atoms (II to VI) have been selected. The stability of the equipment has been tested and the repeatability of results has been investigated. This new analytical technique allows the study of various surface phenomena such as the variations in oxygen, nitrogen and carbon concentrations with a resolution in depth of a few microns. The method allows it to envisage the quantitative analysis of surface phenomena on metal films with a thickness below one micron.     

Photochemical performance of ZnO nanostructures in dye sensitized solar cells

In this work, the photoconversion efficiencies of ZnO having diverse microstructures and structural defects have been investigated. A conversion efficiency of 1.38% was achieved for the DSSCs fabricated with as prepared ZnO nanorods having minimum vacancy defects and a favourable one dimensional directional pathway for electron conduction. The DSSCs fabricated with ZnO nanoparticles exhibited relatively low conversion efficiency of 1.004% probably due to multiple trapping/detrapping phenomena within the grain boundaries and ZnO flowers though exhibited a high dye adsorption capability exhibited the lowest conversion efficiency of 0.59% due to a high concentration of structural defects. Based on the experimental evidences, we believe that the type of defects and their concentrations are more important than shape in controlling the overall performance of ZnO based DSSCs.     

The influence of the lithology and depth on water recharge of wells in two Moroccan Atlantic coastal regions by using solid state nuclear track detectors and radon as a natural tracer

Uranium and thorium contents as well as radon and thoron -activity concentrations were evaluated inside different underground water samples by using a method based on calculating the CR-39 and LR-115 type II solid state nuclear track detectors (SSNTDs) detection efficiencies for the emitted -particles and measuring the resulting track density rates. The validity of the SSNTD technique utilized was checked by analysing uranium nitrate standard solutions. A relationship between water radon concentration and recharge of wells dug in two Moroccan Atlantic coastal regions, for a given lithology, was found. The influence of the lithology and depth on radon concentration and salinity of well waters studied was investigated.