Optimization of River Water Quality Surveys by Multivariate Analysis of Physicochemical, Bacteriological and Ecotoxicological Data

This study aims to optimize the water quality monitoring of a polluted watercourse (Leça River, Portugal) through the principal component analysis (PCA) and cluster analysis (CA). These statistical methodologies were applied to physicochemical, bacteriological and ecotoxicological data (with the marine bacterium Vibrio fischeri and the green alga Chlorella vulgaris) obtained with the analysis of water samples monthly collected at seven monitoring sites and during five campaigns (February, May, June, August, and September 2006). The results of some variables were assigned to water quality classes according to national guidelines. Chemical and bacteriological quality data led to classify Leça River water quality as “bad” or “very bad”. PCA and CA identified monitoring sites with similar pollution pattern, giving to site 1 (located in the upstream stretch of the river) a distinct feature from all other sampling sites downstream. Ecotoxicity results corroborated this classification thus revealing differences in space and time. The present study includes not only physical, chemical and bacteriological but also ecotoxicological parameters, which broadens new perspectives in river water characterization. Moreover, the application of PCA and CA is very useful to optimize water quality monitoring networks, defining the minimum number of sites and their location. Thus, these tools can support appropriate management decisions.

Chemical composition of phytoplankton from the estuaries of Eastern Amazonia

Phytoplankton is important bioindicator of chemical and biological modifications of natural ecosystems. The objective of this study was to determine the total chemical composition of the phytoplankton of the Pará and Mocajuba estuaries on the eastern coast of the Amazon region in the Brazilian state of Pará. The chemical composition of the surface water, bottom sediments (total sample and bioavailable fraction), and the phytoplankton were determined by inductively coupled plasma optical emission spectrometry. Phytoplankton contained high concentrations of Ca, P, Mn, Fe, Zn, Al, Ba, and Pb. The phytoplankton of the Mocajuba estuary is rich in Fe (2,967-84,750 µg g-1), while those from the Pará is rich in Al (1,216-15,389 µgg-1), probably reflecting divergent anthropogenic inputs. Both samples indicated a high bioconcentration factor derived from both the water and the bioavailable fraction, reflecting the efficiency of these organisms in the concentration of metals.

Multiplex PCR-based detection of Leptospira in environmental water samples obtained from a slum settlement

The aim of this study was to apply a molecular protocol to detect leptospiral DNA in environmental water samples. The study was carried out in a peri-urban settlement in Petrópolis, state of Rio de Janeiro. A multiplex PCR method employing the primers LipL32 and 16SrRNA was used. Three out of 100 analysed samples were positive in the multiplex PCR, two were considered to have saprophytic leptospires and one had pathogenic leptospires. The results obtained supported the idea that multiplex PCR can be used to detect Leptospira spp in water samples. This method was also able to differentiate between saprophytic and pathogenic leptospires and was able to do so much more easily than conventional methodologies.

Tillage Manure Managemen and Water Quality, April 2005

Tillage and manure application practices significantly impact surface and ground water quality in Iowa and other Midwestern states. Tillage and manure application that incorporates residue and disturbs soil result in higher levels of soil erosion and surface runoff. Phosphorus and sediment loading are closely linked to the increase in soil erosion and surface water runoff. Manure application (i.e., injection or incorporation) reduces surface residue cover, which can worsen soil erosion regardless of the tillage management system being used. An integrated system approach to manure and tillage management is critical to ensure effi cient nutrient use and improvement of soil and water quality. This approach, however, requires changes in manure application technology and tillage system management to ensure the success of an integrated

Stable O and H isotopic composition of hydrous minerals as proxies for paleoclimate and -topography : application to the European Alps

The isotopie composition of clay minerals can be used to gain information on paleoaltitude, -topography and -climate during the time of their formation, as they form in isotopie equilibrium with ambient water, which has an isotopie composition that is determined by previous rain-out. In this thesis, the usability of this approach is evaluated for sample material from both the North Alpine Foreland Basin and internal parts of the European Alps. The isotopie composition of precipitation is determined by the air temperature and the extent of previous rain-out, which in turn is affected by the distance to the point of origin of the water vapor and the condensation conditions. An orographic barrier leads to uplift and adiabatic cooling of air masses and thereby enhances rainfall with a characteristic depletion in heavy 0 and H isotopes. Processes such as evaporation and mixing of water with different origin affect the isotopie composition further on the surface. Clay minerals are hydrous phyllosilicates that can form during weathering or pedogenesis in isotopie equilibrium with the present water and inherit its isotopie composition with a characteristic fractionation. If their isotopie composition was preserved after formation and the necessary parameters are known, it is possible to calculate the isotopie composition of the ambient water and thereby reconstruct climatic and topographic conditions during their formation. Due to the hygroscopic behavior of the sample material, analytical procedures needed to be modified to allow an analysis of the oxygen and hydrogen isotopie composition of the hydroxyl water built into their crystal structure and not the one of recently adsorbed water. In order to determine typical 5lsO and 8D values of meteoric water and minerals in the weathering environment in high Alpine regions, samples of surface water and soils from the valley of Visp in the Swiss Alps were studied that were collected along a transect with varying altitudes and host rock lithologies. The actual aim to attempt the reconstruction of Alpine paleoelevations was addressed by the analysis of sediments deposited under marine and terrestrial conditions during the Miocene and Oligocene, which were sampled from different locations in Switzerland, Germany and Austria. Further bentonite and fault gouge clay samples were used as reference material from low and high elevations. Results show that the isotopie composition of clay minerals can be influenced by several factors, such as the mode and site of their formation, possible isotope exchange (which is evident for 8D values), the samples' mineral composition (such as the presence of detrital material) and the deposition environment. With a consideration of these parameters and limitation to certain sample material, conclusions are drawn on the isotopie composition of the water from which the clay minerals formed. Most of the obtained values lie in the same range as has been reported in literature for foreland precipitation. The reconstruction of paleoelevation might be possible for selected sites with a geographical setting close to the Alpine chain or for intramontane basins. - La composition isotopique des argiles, qui se forment typiquement en contact avec des eaux superficielles, peut être utilisée pour obtenir des informations sur la paléoaltitude, la paléotopographie et le paléoclimat pendant leur création. La composition en isotopes stable (oxygène et hydrogène) des eaux de pluie est déterminée par l'altitude, la température, la distance depuis le lieu d'évaporation et par le taux de précipitation. Certains processus comme l'évaporation, l'interaction avec des minéraux et le mélange d'eaux d'origines variées peuvent aussi changer la composition des eaux de surface. Les argiles sont des pliyllosilicates hydratés qui sont crées par l'altération des roches au contact de ces eaux de surface et ils acquièrent une composition isotopique qui est soumise à un certain fractionnement. L'objectif de cette thèse est d'évaluer si l'effet de l'altitude des Alpes, est détectable dans la composition isotopique des sédiments du bassin d'avant-pavs pendant le Miocène. Après avoir établi la procédure analytique, des compositions isotopiques typiques de régions de hautes altitudes ont été determine sur les eaux de surfaces (rivières) et sur des échantillons de sols, le long d'une coupe dans la valée de Visp, dans les Alpes Suisses. Une reconstruction des paléoaltitudes Miocènes Alpines a ensuite été mené par l'analyse de sédiments marins et terrestres en utilisant des échantillons d'âges variés et provenant de Suisse, d'Allemagne et d'Autriche. Les résultats montrent que la composition isotopique des échantillons est impactée par de multiples facteurs, tels que le mode de et le lieu de formation. un possible échange isotopique tardif (surtout pour 5D). leur composition minéralogique et l'environnement de leur sédimentation. Après un examen prudent de ces paramètres, et en se limitant à un certain assortiment d'échatillons, on peut tirer des conclusions sur la composition isotopique des eaux originelles pour en déduire l'effet du climat et de la topographie.

Fate of the herbicide glyphosate and its metabolite AMPA in soils and their transfer to surface waters: A multi-scale approach in the Lavaux vineyards, western Switzerland

The use of herbicides in agriculture may lead to environmental problems, such as surface water pollution, with a potential risk for aquatic organisms. The herbicide glyphosate is the most used active ingredient in the world and in Switzerland. In the Lavaux vineyards it is nearly the only molecule applied. This work aimed at studying its fate in soils and its transfer to surface waters, using a multi-scale approach: from molecular (10-9 m) and microscopic scales (10-6 m), to macroscopic (m) and landscape ones (103 m). First of all, an analytical method was developed for the trace level quantification of this widely used herbicide and its main by-product, aminomethylphosphonic acid (AMPA). Due to their polar nature, their derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) was done prior to their concentration and purification by solid phase extraction. They were then analyzed by ultra performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The method was tested in different aqueous matrices with spiking tests and validated for the matrix effect correction in relevant environmental samples. Calibration curves established between 10 and 1000ng/l showed r2 values above 0.989, mean recoveries varied between 86 and 133% and limits of detection and quantification of the method were as low as 5 and 10ng/l respectively. At the parcel scale, two parcels of the Lavaux vineyard area, located near the Lutrive River at 6km to the east of Lausanne, were monitored to assess to which extent glyphosate and AMPA were retained in the soil or exported to surface waters. They were equipped at their bottom with porous ceramic cups and runoff collectors, which allowed retrieving water samples for the growing seasons 2010 and 2011. Results revealed that the mobility of glyphosate and AMPA in the unsaturated zone was likely driven by the precipitation regime and the soil characteristics, such as slope, porosity structure and layer permeability discrepancy. Elevated glyphosate and AMPA concentrations were measured at 60 and 80 cm depth at parcel bottoms, suggesting their infiltration in the upper parts of the parcels and the presence of preferential flow in the studied parcels. Indeed, the succession of rainy days induced the gradual saturation of the soil porosity, leading to rapid infiltration through macropores, as well as surface runoff formation. Furthermore, the presence of more impervious weathered marls at 100 cm depth induced throughflows, the importance of which for the lateral transport of the herbicide molecules was determined by the slope steepness. Important rainfall events (>10 mm/day) were clearly exporting molecules from the soil top layer, as indicated by important concentrations in runoff samples. A mass balance showed that total loss (10-20%) mainly occurred through surface runoff (96%) and, to a minor extent, by throughflows in soils (4%), with subsequent exfiltration to surface waters. Observations made in the Lutrive River revealed interesting details of glyphosate and AMPA dynamics in urbanized landscapes, such as the Lavaux vineyards. Indeed, besides their physical and chemical properties, herbicide dynamics at the catchment level strongly depend on application rates, precipitation regime, land use and also on the presence of drains or constructed channels. Elevated concentrations, up to 4970 ng/l, observed just after the application, confirmed the diffuse export of these compounds from the vineyard area by surface runoff during main rain events. From April to September 2011, a total load of 7.1 kg was calculated, with 85% coming from vineyards and minor urban sources and 15% from arable crops. Small vineyard surfaces could generate high concentrations of herbicides and contribute considerably to the total load calculated at the outlet, due to their steep slopes (~10%). The extrapolated total amount transferred yearly from the Lavaux vineyards to the Lake of Geneva was of 190kg. At the molecular scale, the possible involvement of dissolved organic matter (DOM) in glyphosate and copper transport was studied using UV/Vis fluorescence spectroscopy. Combined with parallel factor (PARAFAC) analysis, this technique allowed characterizing DOM of soil and surface water samples from the studied vineyard area. Glyphosate concentrations were linked to the fulvic-like spectroscopic signature of DOM in soil water samples, as well as to copper, suggesting the formation of ternary complexes. In surface water samples, its concentrations were also correlated to copper ones, but not in a significant way to the fulvic-like signature. Quenching experiments with standards confirmed field tendencies in the laboratory, with a stronger decrease in fluorescence intensity for fulvic-like fluorophore than for more aromatic ones. Lastly, based on maximum concentrations measured in the river, an environmental risk for these compounds was assessed, using laboratory tests and ecotoxicity data from the literature. In our case and with the methodology applied, the risk towards aquatic species was found negligible (RF<1).

Practical Data Collection: Establishing Methods and Procedures for Measuring Water Clarity and Turbidity of Storm Water Run-Off from Active Major Highway Construction Sites, 2014

In anticipation of regulation involving numeric turbidity limit at highway construction sites, research was done into the most appropriate, affordable methods for surface water monitoring. Measuring sediment concentration in streams may be conducted a number of ways. As part of a project funded by the Iowa Department of Transportation, several testing methods were explored to determine the most affordable, appropriate methods for data collection both in the field and in the lab. The primary purpose of the research was to determine the exchangeability of the acrylic transparency tube for water clarity analysis as compared to the turbidimeter.

Cryo-electron microscopy of vitreous sections of native biological cells and tissues : methodology and applications

Résumé L'eau est souvent considérée comme une substance ordinaire puisque elle est très commune dans la nature. En fait elle est la plus remarquable de toutes les substances. Sans l'eau la vie sur la terre n'existerait pas. L'eau représente le composant majeur de la cellule vivante, formant typiquement 70 à 95% de la masse cellulaire et elle fournit un environnement à d'innombrables organismes puisque elle couvre 75% de la surface de terre. L'eau est une molécule simple faite de deux atomes d'hydrogène et un atome d'oxygène. Sa petite taille semble en contradiction avec la subtilité de ses propriétés physiques et chimiques. Parmi celles-là, le fait que, au point triple, l'eau liquide est plus dense que la glace est particulièrement remarquable. Malgré son importance particulière dans les sciences de la vie, l'eau est systématiquement éliminée des spécimens biologiques examinés par la microscopie électronique. La raison en est que le haut vide du microscope électronique exige que le spécimen biologique soit solide. Pendant 50 ans la science de la microscopie électronique a adressé ce problème résultant en ce moment en des nombreuses techniques de préparation dont l'usage est courrant. Typiquement ces techniques consistent à fixer l'échantillon (chimiquement ou par congélation), remplacer son contenu d'eau par un plastique doux qui est transformé à un bloc rigide par polymérisation. Le bloc du spécimen est coupé en sections minces (d’environ 50 nm) avec un ultramicrotome à température ambiante. En général, ces techniques introduisent plusieurs artefacts, principalement dû à l'enlèvement d'eau. Afin d'éviter ces artefacts, le spécimen peut être congelé, coupé et observé à basse température. Cependant, l'eau liquide cristallise lors de la congélation, résultant en une importante détérioration. Idéalement, l'eau liquide est solidifiée dans un état vitreux. La vitrification consiste à refroidir l'eau si rapidement que les cristaux de glace n'ont pas de temps de se former. Une percée a eu lieu quand la vitrification d'eau pure a été découverte expérimentalement. Cette découverte a ouvert la voie à la cryo-microscopie des suspensions biologiques en film mince vitrifié. Nous avons travaillé pour étendre la technique aux spécimens épais. Pour ce faire les échantillons biologiques doivent être vitrifiés, cryo-coupées en sections vitreuse et observées dans une cryo-microscope électronique. Cette technique, appelée la cryo- microscopie électronique des sections vitrifiées (CEMOVIS), est maintenant considérée comme étant la meilleure façon de conserver l'ultrastructure de tissus et cellules biologiques dans un état très proche de l'état natif. Récemment, cette technique est devenue une méthode pratique fournissant des résultats excellents. Elle a cependant, des limitations importantes, la plus importante d'entre elles est certainement dû aux artefacts de la coupe. Ces artefacts sont la conséquence de la nature du matériel vitreux et le fait que les sections vitreuses ne peuvent pas flotter sur un liquide comme c'est le cas pour les sections en plastique coupées à température ambiante. Le but de ce travail a été d'améliorer notre compréhension du processus de la coupe et des artefacts de la coupe. Nous avons ainsi trouvé des conditions optimales pour minimiser ou empêcher ces artefacts. Un modèle amélioré du processus de coupe et une redéfinitions des artefacts de coupe sont proposés. Les résultats obtenus sous ces conditions sont présentés et comparés aux résultats obtenus avec les méthodes conventionnelles. Abstract Water is often considered to be an ordinary substance since it is transparent, odourless, tasteless and it is very common in nature. As a matter of fact it can be argued that it is the most remarkable of all substances. Without water life on Earth would not exist. Water is the major component of cells, typically forming 70 to 95% of cellular mass and it provides an environment for innumerable organisms to live in, since it covers 75% of Earth surface. Water is a simple molecule made of two hydrogen atoms and one oxygen atom, H2O. The small size of the molecule stands in contrast with its unique physical and chemical properties. Among those the fact that, at the triple point, liquid water is denser than ice is especially remarkable. Despite its special importance in life science, water is systematically removed from biological specimens investigated by electron microscopy. This is because the high vacuum of the electron microscope requires that the biological specimen is observed in dry conditions. For 50 years the science of electron microscopy has addressed this problem resulting in numerous preparation techniques, presently in routine use. Typically these techniques consist in fixing the sample (chemically or by freezing), replacing its water by plastic which is transformed into rigid block by polymerisation. The block is then cut into thin sections (c. 50 nm) with an ultra-microtome at room temperature. Usually, these techniques introduce several artefacts, most of them due to water removal. In order to avoid these artefacts, the specimen can be frozen, cut and observed at low temperature. However, liquid water crystallizes into ice upon freezing, thus causing severe damage. Ideally, liquid water is solidified into a vitreous state. Vitrification consists in solidifying water so rapidly that ice crystals have no time to form. A breakthrough took place when vitrification of pure water was discovered. Since this discovery, the thin film vitrification method is used with success for the observation of biological suspensions of. small particles. Our work was to extend the method to bulk biological samples that have to be vitrified, cryosectioned into vitreous sections and observed in cryo-electron microscope. This technique is called cryo-electron microscopy of vitreous sections (CEMOVIS). It is now believed to be the best way to preserve the ultrastructure of biological tissues and cells very close to the native state for electron microscopic observation. Since recently, CEMOVIS has become a practical method achieving excellent results. It has, however, some sever limitations, the most important of them certainly being due to cutting artefacts. They are the consequence of the nature of vitreous material and the fact that vitreous sections cannot be floated on a liquid as is the case for plastic sections cut at room temperature. The aim of the present work has been to improve our understanding of the cutting process and of cutting artefacts, thus finding optimal conditions to minimise or prevent these artefacts. An improved model of the cutting process and redefinitions of cutting artefacts are proposed. Results obtained with CEMOVIS under these conditions are presented and compared with results obtained with conventional methods.

Otimização e validação de métodos analíticos para determinação de BTEX em água utilizando extração por headspace e microextração em fase sólida

Three analytical methods for the determination of BTEX in water were optimized and validated. With the best method the analytes were extracted of 10 mL of sample with 2.50 g of NaCl in headspace vial of 20 mL by HS and SPME to 40 ºC for 30 min for adsorption and to 250 ºC for 4 min for desorption and were analyzed by GC-MS. The recovery was between 97.9% and 104.3%, and the limit of detection was 2.4 ng L-1 for o-xylene. This method was using to analyze BTEX in water supply and surface water in Ouro Preto city. No sample had concentrations of BTEX above the legislation.

Occurrence of agrochemicals in surface waters of shallow soils and steep slopes cropped to tobacco

Tobacco cultivation in shallow soils and steep landscape under intense use of agrochemicals contributes to environment degradation. In this study, we assessed the concentration of agrochemicals in draw wells used for human consumption and a creek in a small catchment predominantly cropped to tobacco. Chlorpyrifos, flumetralin, and iprodione were determined by gas chromatography with electron capture detection, while imidalcloprid, atrazine, simazine, and clomazone were quantified by high-performance liquid chromatography with UV detection. Considering all sampling sites, all agrochemicals were detected at least once, except for flumetralin. The occurrence of agrochemicals in tobacco crops is a consequence of their fast transfer to surface water.

Impact of the substitution of reference annual streamflow by monthly streamflow on the potential use of water resources

The consideration of the streamflow seasonality has a high potential to improve the water use. In order to give subsidies to the optimization of water use, it was evaluated the impact of the change of reference annual streamflow by the monthly streamflows in the potential water use throughout the hydrography of Paracatu sub-Basin. It was evaluated the impact on Q7,10 (lowest average streamflow during a 7-day period with an average recurrence of 10 years) and on Q95 (permanent flow present 95% of the time). The use of monthly streamflow to substitute the annual streamflow had a high potential of improvement of water resources use in the sub-Basin studied. The use of monthly Q 7,10 in substitution of annual Q 7,10 increases the potential water use that vary from about 10% in the months of lower water availability to values exceeding 200% in the months with higher availability of surface water resources. The use of monthly Q95 in substitution of the annual Q95 implies in changes oscillating from reduction of 37% in months of higher water restriction to values exceeding 100% in the months of higher availability, so the use of monthly Q95 instead of the annual Q95 enables the more rational and safe use of water resources.

Determination of chlorophenols from water by solid phase microextraction - ion mobility spectrometry (SPME-IMS)

Chlorophenols have been classified as possible carcinogens for humans. Chlorophenols have been used as pesticides and wood preservatives. In Finland, during 1930 – 1980s, saw mills used KY-5 wood preservative that contained 2,4,6-TCP, 2,3,4,6-TeCP and PCP. Especially in Finland chlorophenols have entered the environment by leaking from contaminated grounds of old saw mills. Although chlorophenol concentrations found in environment do not cause acute concern, long term exposure can increase the risk of cancer. SPME is relatively cheap and simple sampling method, in which the sample extraction and concentration are performed in a single step. Solvents are not required in SPME. IMS is based on the detection of sample ion drift times. Based on the drift times, reduced mobilities are calculated, which are comparable despite the measurement conditions. SPME-IMS coupling has not been used earlier in the determination of chlorophenols from water samples. The scope of this work was to study, if SPME-IMS system is suitable for detecting chloro-phenols from water samples. The aim was to determine the most optimal extraction condi-tions, which were then applied to real water samples. Following detection limits were deter-mined: 2,4,6-TCP: 0.33 mg/l; 2,3,4,6-TeCP: 0.63 mg/l and PCP: 1.63 mg/l. Detection limits were high compared to the highest possible chlorophenol concentration that is allowed in Finnish drinking water, 10 μg/l. Detected concentrations from water sample differed from verified concentrations in the case of 2,3,4,6-TeCP by 4.6 % and in the case of 2,4,6-TCP by 48.4 %. Based on the results it can be said that SPME-IMS setup is suitable for preliminary analysis of mg/l chlorophenol concentrations from water samples.

Geochemistry and water quality of Lake Qarun, Egypt

Water geochemistry is a very important tool for studying the water quality in a given area. Geology and climate are the major natural factors controlling the chemistry of most natural waters. Anthropogenic impacts are the secondary sources of contamination in natural waters. This study presents the first integrative approach to the geochemistry and water quality of surface waters and Lake Qarun in the Fayoum catchment, Egypt. Moreover, geochemical modeling of Lake Qarun was firstly presented. The Nile River is the main source of water to the Fayoum watershed. To investigate the quality and geochemistry of this water, water samples from irrigation canals, drains and Lake Qarun were collected during the period 2010‒2013 from the whole Fayoum drainage basin to address the major processes and factors governing the evolution of water chemistry in the investigation area. About 34 physicochemical quality parameters, including major ions, oxygen isotopes, trace elements, nutrients and microbiological parameters were investigated in the water samples. Multivariable statistical analysis was used to interpret the interrelationship between the different studied parameters. Geochemical modeling of Lake Qarun was carried out using Hardie and Eugster’s evolutionary model and a model simulated by PHREEQC software. The crystallization sequence during evaporation of Lake Qarun brine was also studied using a Jänecke phase diagram involving the system Na‒K‒Mg‒ Cl‒SO4‒H2O. The results show that the chemistry of surface water in the Fayoum catchment evolves from Ca- Mg-HCO3 at the head waters to Ca‒Mg‒Cl‒SO4 and eventually to Na‒Cl downstream and at Lake Qarun. The main processes behind the high levels of Na, SO4 and Cl in downstream waters and in Lake Qarun are dissolution of evaporites from Fayoum soils followed by evapoconcentration. This was confirmed by binary plots between the different ions, Piper plot, Gibb’s plot and δ18O results. The modeled data proved that Lake Qarun brine evolves from drainage waters via an evaporation‒crystallization process. Through the precipitation of calcite and gypsum, the solution should reach the final composition "Na–Mg–SO4–Cl". As simulated by PHREEQC, further evaporation of lake brine can drive halite to precipitate in the final stages of evaporation. Significantly, the crystallization sequence during evaporation of the lake brine at the concentration ponds of the Egyptian Salts and Minerals Company (EMISAL) reflected the findings from both Hardie and Eugster’s evolutionary model and the PHREEQC simulated model. After crystallization of halite at the EMISAL ponds, the crystallization sequence during evaporation of the residual brine (bittern) was investigated using a Jänecke phase diagram at 35 °C. This diagram was more useful than PHREEQC for predicting the evaporation path especially in the case of this highly concentrated brine (bittern). The predicted crystallization path using a Jänecke phase diagram at 35 °C showed that halite, hexahydrite, kainite and kieserite should appear during bittern evaporation. Yet the actual crystallized mineral salts were only halite and hexahydrite. The absence of kainite was due to its metastability while the absence of kieserite was due to opposed relative humidity. The presence of a specific MgSO4.nH2O phase in ancient evaporite deposits can be used as a paleoclimatic indicator. Evaluation of surface water quality for agricultural purposes shows that some irrigation waters and all drainage waters have high salinities and therefore cannot be used for irrigation. Waters from irrigation canals used as a drinking water supply show higher concentrations of Al and suffer from high levels of total coliform (TC), fecal coliform (FC) and fecal streptococcus (FS). These waters cannot be used for drinking or agricultural purposes without treatment, because of their high health risk. Therefore it is crucial that environmental protection agencies and the media increase public awareness of this issue, especially in rural areas.

Form, size and volumetric expansion of Adzuki beans (Vigna angularis) during soaking

This study analyzed the variation in shape and size of Adzuki beans during soaking at different temperatures. In addition, different mathematical models were fitted to the experimental values of volumetric expansion, selecting the best one. Grains of Adzuki beans (Vigna angularis) with moisture content of approximately 0.25 (decimal d.b.) were manually harvested; they were, then, dried to 0.128 (decimal d.b.). The beans were subjected to soaking in distilled water at the temperatures 18 ± 1, 27 ± 1, 36 ± 1, and 45 ± 1 °C, in five repetitions. Recipients containing 80 mL of distilled water and 20 g of beans for each sample were used. The samples were periodically weighed in order to determine the water absorption. After that, the samples were removed from the recipients and placed on filter papers for two minutes to drain the surface water. Water absorption continued until the beans reached the saturation moisture content. It was concluded that, the form of the Adzuki beans was altered regularly, the orthogonal axes expanded differentially in the radial and axial directions, and that the linear model appropriately described the volumetric expansion of the Adzuki beans, among the series of models analyzed for the temperatures 18, 27, 36 and 45 °C.

Investigations into the extraction and the determination of polycyclic aromatic hydrocarbons (PAHs) from water by solid-phase extraction and capillary gas chromatography/ mass spectrometry

Factors affecting the detennination of PAHs by capillary GC/MS were studied. The effect of the initial column temperature and the injection solvent on the peak areas and heights of sixteen PAHs, considered as priority pollutants, USillg crosslinked methyl silicone (DB!) and 5% diphenyl, 94% dimethyl, 1% vinyl polysiloxane (DBS) columns was examined. The possibility of using high boiling point alcohols especially butanol, pentanol, cyclopentanol, and hexanol as injection solvents was investigated. Studies were carried out to optimize the initial column temperature for each of the alcohols. It was found that the optimum initial column temperature is dependent on the solvent employed. The peak areas and heights of the PAHs are enhanced when the initial column temperature is 10-20 c above the boiling point of the solvent using DB5 column, and the same or 10 C above the boiling point of the solvent using DB1 column. Comparing the peak signals of the PAHs using the alcohols, p-xylene, n-octane, and nonane as injection solvents, hexanol gave the greatest peak areas and heights of the PAHs particularly the late-eluted peaks. The detection limits were at low pg levels, ranging from 6.0 pg for fluorene t9 83.6 pg for benzo(a)pyrene. The effect of the initial column temperature on the peak shape and the separation efficiency of the PARs was also studied using DB1 and DB5 columns. Fronting or splitting of the peaks was obseIVed at very low initial column temperature. When high initial column temperature was used, tailing of the peaks appeared. Great difference between DB! and.DB5 columns in the range of the initial column temperature in which symmetrical.peaks of PAHs can be obtained is observed. Wider ranges were shown using DB5 column. Resolution of the closely-eluted PAHs was also affected by the initial column temperature depending on the stationary phase employed. In the case of DB5, only the earlyeluted PAHs were affected; whereas, with DB1, all PAHs were affected. An analytical procedure utilizing solid phase extraction with bonded phase silica (C8) cartridges combined with GC/MS was developed to analyze PAHs in water as an alternative method to those based on the extraction with organic solvent. This simple procedure involved passing a 50 ml of spiked water sample through C8 bonded phase silica cartridges at 10 ml/min, dried by passing a gentle flow of nitrogen at 20 ml/min for 30 sec, and eluting the trapped PAHs with 500 Jll of p-xylene at 0.3 ml/min. The recoveries of PAHs were greater than 80%, with less than 10% relative standard deviations of nine determinations. No major contaminants were present that could interfere with the recognition of PAHs. It was also found that these bonded phase silica cartridges can be re-used for the extraction of PAHs from water.