Field study of the migration of Sr, Nd and Ce in a weak loess aquifer

The migration of Sr, Nd and Ce in a weak loess aquifer was investigated with an Underground Research Facility. Quartz mixed with SrCl₂ ·6H₂O, NdCl₃ ·7H₂O, CeCl₃ ·7H₂O and NaBr was introduced into the aquifer with a stainless steel pipe. The local water flow field in the aquifer was monitored using a 3-dimensional sampling system. A block of the aquifer medium was obtained wholly with a special sampling method and cut into 3-dimensional small pieces (samples) and analyzed. Based on the experimental data, the diffusion coefficients of Sr, Nd and Ce in the aquifer were obtained. This revised version was published online in July 2006 with corrections to the Cover Date.     

Variations of mercury distribution in the water column during the course of a tidal cycle in the Yangtze Estuarine intertidal zone, China

Tidally induced resuspension processes play an important role in the release of mercury (Hg) into the water column, which increases the risk of Hg exposure to estuarine eco-systems. In order to further understand the geochemical activities of Hg in the intertidal area, the temporal variations of dissolved Hg (Hg D ) and particulate Hg (Hg P ) in the water column during the course of a tidal cycle and its geochemical processes were studied in the southern intertidal zone of the Yangtze Estuary, China. The concentrations of Hg D and Hg P varied between 37-612 ng/L and 51-638 ng/L respectively during the tidal cycle. The increase of Hg D was distinguished at the early flood tide and late ebb tide when the water flow rates were higher. The Hg D concentrations were negatively correlated with Hg P (r = 0.523, p < 0.05) and positively correlated with dissolved organic carbon (DOC) (r = 0.605, p < 0.05) in the bottom water, indicating that the Hg D released from the sediments into the overlying water was associated with the simultaneously released colloidal material in the bottom water. The main pathways for the translocation of Hg from the sediments to the overlying water include the processes of desorption from resuspended particles, advection or diffusion from sediments, and the oxidation of resuspended sulfide. The results of principal components analysis (PCA) and Pearson correlation analysis showed that the combined effects of the total suspended substrate (TSS), DOC, pH and dissolved oxygen (DO) influenced the geochemical activities of Hg in the water column during the course of a tidal cycle.     

Time trends of 1,1,1-trichloroethane, trichloroethylene, and perchloroethylene in confined and unconfined aquifers of a groundwater system in northern Italy

The concentrations of 1,1,1-trichloroethane, trichloroethylene, and perchloroethylene were recorded in a groundwater system of Northern Italy over the period 1985-1997. In the unconfined recharging aquifer these chemicals showed a remarkable overall decline which was accompanied by a five-fold reduction in their consumption (from approx. 250 to approx. 50 tons year-1) over the same period. The time trends for the confined aquifers indicated a steady decline for 1,1,1-trichloroethane which was accompanied by a constant concentration of trichloroethylene and an increasing presence of perchloroethylene. It is suggested that the confined aquifers are recording a contamination which took place in the unconfined recharging aquifer before monitoring period (1982) started. At present, in most of the study area 1,1,1-trichloroethane contamination is below the detection limit (0.1 microgram/L). For trichloroethylene and perchloroethylene, the average unconfined aquifer contamination accounts for approx. 1 +/- 1 and approx. 4 +/- 3 micrograms/L, respectively, while in the confined aquifers the average concentrations are approx. 8 +/- 3 and approx. 35 +/- 5 micrograms/L, respectively.     

Electrodecomposition in subcritical water using o-xylene as a model for benzene, toluene, ethylbenzene, and xylene pollutants

The possibility of the combination of electrolysis and subcritical water as a novel electrolyte was investigated. A stainless steel reactor was used as an undivided electrochemical cell containing platinum as the anode and a stainless steel reactor as the cathode. At first, the effect of temperature on the electrolysis current as the main parameter was studied in a cell containing only pure water and a supporting electrolyte. It was realized that the electrolysis current (and, consequently, the electrolysis efficiency) increased linearly with temperature because of the change in viscosity and other physicochemical properties of subcritical water. As a result, at 553 K the electrolysis efficiency was over 14-fold higher than that under ambient conditions. The possibility of the applicability of the above combined techniques for the decomposition of o-xylene was also followed as a model for benzene, toluene, ethylbenzene, and xylene (BTEX) compounds. The effect of experimental conditions such as the electrolysis duration, the electrolysis voltage, and the temperature of subcritical water was investigated. Several decomposed products were identified. o-Xylene was directly electro-oxidized to 2-methylbenzyl alcohol and consecutively to the other oxidation products. Also, hydroxide ions were oxidized to oxygen molecules, where hydrogen was generated on the cathodic surface. The final oxidation product of the electro-oxidation reaction was identified as carbon dioxide. The results indicate that more than 95% of o-xylene can be decomposed under optimum conditions.     

Assessment of ground water quality in a fractured aquifer under continue wastewater injection

Experimental studies have been carried out in a fractured coastal aquifer of the Salento Region (Nardò (Le), Italy), subject since 1991 to injection of 12,000 m3/d of treated municipal wastewater in a natural sink. The analytical parameters of ground water sampled in monitoring wells, have been compared before and after the injection started. The mound of water table (1.5 m), the reduction of seawater extent of 2 km and the spreading of pollutants injected were evaluated by means of mathematical model results. After ten years operation, the volume of the available resource for agricultural and drinking use has been increased, without notable decrease of the preexistent ground water quality. Moreover for preserving such resource from pollution, the mathematical model allowed the standards of wastewater quality for recharge to be identified. Around the sink, a restricted area was also defined with prohibition of withdrawals, to avoid infection and other risks on human health.     

Degradation of aromatic compounds in ground-water, and methods of sample preservation

The degradation of acenaphthylene, acenaphthene, 2-methylnaphthalene, 2-methylindene, 3-methylindene and indene in water solutions was studied. These compounds at the 25-150 mug/l. level were almost totally degraded at ambient temperature within three days. The microbial population responsible for the degradation occurs naturally in ground-water taken from an aquifer in Ames, Iowa, which is contaminated with coal-tar products. These unidentified micro-organisms adapt readily to other waters when used as an inoculant for the degradation of aromatic compounds. The preservation of water to prevent such degradation was also investigated. Filtration through a 0.45-mum filter was found the most effective procedure for preserving the hydrocarbons in these waters.     

Determination of Organic Acids in Ground Water by Liquid Chromatography/Atmospheric Pressure Chemical Ionization/Mass Spectrometry

ABSTRACT

Current methods of determining organic acids in ground water are labor-intensive, time-consuming and require a large volume of sample (100 milliliter to 1.0 liter). This paper reports a new method developed to determine aliphatic, alicyclic, and aromatic acids in ground water using liquid chromatography/atmospheric pressure chemical ionization/mass spectrometry (LC/APCI/MS). This method was shown to be fast (less than 1 hour), effective, and reproducible, requiring only 1.0 mL of ground-water sample. Ground water was pH-adjusted, filtered through 0.45 μm filters and directly injected into the LC. A binary solvent system consisting of 40 mM of aqueous ammonium acetate and methanol and a C18 column were used for chromatographical separation. The APCI was operated under negative ionization mode. Selected ion monitoring (SIM) was used for detection and quantitation of the analytes. This method was applied to the analysis of organic acids in ground-water samples collected from an aquifer contaminated with JP-4 fuel hydrocarbons at Wurtsmith Air Force Base in Oscoda, Michigan. Aromatic acids identified in the contaminated ground water include o-, m-toluic acids (2- and 3-methylbenzoic acids), 2,6-dimethylbenzoic acid, 2,3,5- and 2,4,6-trimethylbenzoic acids and two additional trimethylbenzoic acids with unknown location of methylation. The detection of aromatic acids in groundwater from the KC-135 site provided evidence for in situ microbial degradation of hydrocarbons occurring in the aquifer.     

Molecular dynamics study of tryptophylglycine: a dipeptide nanotube with confined water

To investigate the mechanism of structural changes of a peptide nanotube and water confined inside the channel, the helical peptide tryptophylglycine monohydrate (WG.H2O) was studied by molecular dynamics (MD) simulations using the three-dimension parallel MD program ddgmq (software package) and a consistent force field. Simulations were performed on both the water-containing system and a model system without water molecules. The details of the structural behavior with temperature are investigated for the entire simulated temperature range. Phase transitions were obtained at 115, 245, 270, 310, and 385 K, due to the contributions of both the peptide and the confined water subsystems. The crystalline, amorphous, liquidlike, liquid, and superheated phases of water were observed in the temperature ranges 40-115, 115-245, 245-310, 310-385, and >385 K, respectively. At 300 K, the diffusion constant of the confined water is 0.46 x 10-5 cm2 s-1, a value comparable to that of other peptide nanotubes. The empty peptide system melts at 440 K. Mechanisms of the negative thermal expansion (NTE) along the tube axis were investigated for different temperature ranges. The contraction of the crystalline water (or amorphous water) draws also the tube walls in and leads to NTE below 245 K. The other NTEs appear to be connected to the collapse of the ice network or the solid peptide network between 245 K and room temperature or from 310 to 440 K, respectively.     

Behaviour of polycyclic aromatic hydrocarbons and triazine herbicides in water and aquifer material of a drinking water recharge plant

Summary In the fourth part of this series the solid phase in the water gathering ground is considered. Methods for the determination of PAHs in aquifer materials, sediments and suspended matter are described. A concentration profile for PAHs as a function of the depth is established in an aerobic aquifer. Sediment samples from the barrage lake of the water gathering plant and suspended matter from the area of the artificial infiltration were investigated; PAHs could be found in all materials.Parts I and II: (1993) Fresenius J Anal Chem 346:988–994, 346:995–999; Part III: (1993) Fresenius J Anal Chem 347:37–43     

Adsorption Capacities of Iron Hydroxide for Arsenate and Arsenite Removal from Water by Chemical Coagulation: Kinetics,Thermodynamics and Equilibrium Studies

Arsenic (As)-laden wastewater may pose a threat to biodiversity when released into soil and water bodies without treatment. The current study investigated the sorption properties of both As(III, V) oxyanions onto iron hydroxide (FHO) by chemical coagulation. The potential mechanisms were identified using the adsorption models, ζ-potential, X-ray diffraction (XRD) and Fourier Transform Infrared Spectrometry (FT-IR) analysis. The results indicate that the sorption kinetics of pentavalent and trivalent As species closely followed the pseudo-second-order model, and the adsorption rates of both toxicants were remarkably governed by pH as well as the quantity of FHO in suspension. Notably, the FHO formation was directly related to the amount of ferric chloride (FC) coagulant added in the solution. The sorption isotherm results show a better maximum sorption capacity for pentavalent As ions than trivalent species, with the same amount of FHO in the suspensions. The thermodynamic study suggests that the sorption process was spontaneously exothermic with increased randomness. The ζ-potential, FT-IR and XRD analyses confirm that a strong Fe-O bond with As(V) and the closeness of the surface potential of the bonded complex to the point of zero charge (pH_zpc) resulted in the higher adsorption affinity of pentavalent As species than trivalent ions in most aquatic conditions. Moreover, the presence of sulfates, phosphates, and humic and salicylic acid significantly affected the As(III, V) sorption performance by altering the surface properties of Fe precipitates. The combined effect of charge neutralization, complexation, oxidation and multilayer chemisorption was identified as a major removal mechanism. These findings may provide some understanding regarding the fate, transport and adsorption properties onto FHO of As oxyanions in a complex water environment.     

Double Bond Migration Mechanism in Allyl Systems Involving the Hydroxide Ion. 3. Supermolecular Approach

The mechanism of a proton transfer in an allyl system involving the hydroxide ion was investigated by the RHF/6-31+G* and MP2/6-31+G* methods with one, two, and four water molecules (water regarded as a solvent) included in the calculation; in the fourth model, the reactant system and two H₂O molecules were placed into continuum. A possible mechanism of intramolecular proton transfer involving easy exchange of water molecules between the first and second coordination spheres of the propenide ion is considered. The results are compared with those obtained with gas-phase and polarizable continuum models.     

An ab initio conformational study on 2,3-dihydrobilin-1,19(21H,24H)-dione, a model compound for open-chain tetrapyrroles

The molecule 2,3-dihydrobilin-1,19(21H,24H)-dione (DHB) was studied as a model of the fully conjugated linear open-chain tetrapyrroles phycocyanobilin (PCB), phycoerythrobilin (PEB) and phytochrome (PC) as well as biliverdin (BV) and bilirubin (BR). The rotations around the single bonds of the exocyclic methine bridges were investigated for all possible cis and trans, E and Z isomers of DHB. The geometries and energies of conformers were investigated with semiempirical and ab initio methods using AM1 and RHF/3-21G levels of theory. Results indicate that geometries with a central syn–cis configuration are preferred to other conformations around the central methine bridge. Four lowest energy conformations stabilized by hydrogen bonding and favorable geometric arrangements minimizing steric strain were predicted. This model elucidated the trends and identified variables associated with tetrapyrrole conformation and energy and thus may serve as a preliminary basis for studying other open-chain tetrapyrrole structures.     

Temporary Phase Behavior of a System Containing Di(Hydrogenated Tallowalkyl) Dimethyl Ammonium Chloride-Water-Hexane

The phase behavior of a system containing di(hydrogenated tallowalkyl) dimethyl ammonium chloride (DHTDMAC)-water-hexane was investigated. In addition to water and the crystalline DHTDMAC, one isotropic liquid (a temporary W/O microemulsion) and two liquid crystals were found

The crystalline compound separated from the temporary microemulsion was identified as DHTDMAC based on the X-ray diffractograms. The effects of crystal hydrate of DHTDMAC on the phase behavior with time were studied by low angle X-ray diffraction and light scattering.     

Surfactant-free oil/water and bicontinuous microemulsion composed of benzene, ethanol and water

<正>Generally,a microemulsion consists of oil,water,surfactant and sometimes cosurfactant.Herein,we report a novel suffactant-free microemulsion(denoted as SFME) composed of benzene,water and ethanol without the amphiphilic molecular structure of traditional surfactant.The phase behavior of the ternary system was investigated,finding that there were a single-phase region and a two-phase region in ternary phase diagram.The electrical conductivity measurement was employed to investigate the microregion of the single-phase region,and a bicontinuous microregion and a benzene-in-water(O/W) microemulsion microregion were identified,which was confirmed by freeze-fracture transmission electron microscopy(FF-TEM) observations.The sizes of the microemulsion droplets are in the range of 20-50 nm.     

Characteristics of carbon nanoparticles synthesized by a submerged arc in alcohols, alkanes, and aromatics

Fullerene-related carbon nanostructures can be synthesized by an arc-in-liquid system as a cost-effective technique. In this work, we investigated the effects of additional carbon sources from liquid media that were alcohols (C(m)H(2m+1)OH, m = 1-8), alkanes (C(m)H(2m+2), m = 6-7), and aromatic compounds (C6H6-C(n)H(2n), n = 1-2) on the product structures and the yield of nanocarbon-rich deposits. It was found that carbon nanoparticles (CNPs) that included multi-walled carbon nanotubes (MW-CNTs) and multi-shelled carbon nanoparticles were produced at high concentrations in the hard deposit at the cathode tip formed by the arc in the alcohols and alkanes, similar to that in a water environment. Importantly, not only graphite electrodes but also these organic compounds played a role of a carbon source to produce CNPs that led to an approximately 8-100 times higher yield than the arc-in-water system. There was a tendency that the increase in alcohol concentration and carbon content in the organic molecules positively affected the yield and production rate of the CNPs. However, the selectivity of MW-CNTs was significantly reduced when aromatic compounds were used. Structural analyses by dynamic light scattering and Raman spectroscopy revealed the dependency of the hydrodynamic particle sizes of CNPs and their crystallinity on the liquid components. For a discussion on the reaction mechanism, optical emission spectra of the arc plasma were analyzed to estimate the arc temperature. In addition, liquid byproducts were analyzed by a UV-vis absorbance spectrometer.     

Monitoring and Evolution of the Pollution by Volatile Organic Compounds (Vocs) in the Groundwaters of The Najerilla River Basin (Spain)

VOCs were detected and identified in the water of several wells in the area of Nájera (La Rioja). The past uncontrolled spills from an important painting and varnishing industry and from other smaller ones devoted to the manufacture of furniture and varnishing activities were the sources of the VOCs plume detected in this aquifer. This article shows the results obtained in the monitoring and assessment of the pollution at 18 sampling points for more than a year. It has allowed us to study the evolution of the different pollutants and the influence of a remediation process applied by the company in the main pollution source. The analytical method is based on headspace-solid-phase microextraction (SPME) using a 75-μm carboxen-polydimethylsiloxane fibre. Quantification was carried out by gas chromatography with flame ionization detection. This method has allowed us to determine the 13 VOCs identified in the polluted underground samples providing good sensitivity (LOD between 0.1 and 6.0 ng/mL) and reproducibility (r.s.d. less than 10%).     

Screening, identification and quantification of glucosinolates in black radish (Raphanus sativus L. niger) based dietary supplements using liquid chromatography coupled with a photodiode array and liquid chromatography-mass spectrometry

The glucosinolate profile of black radish (Raphanus sativus L. niger) based dietary supplements has been investigated by HPLC-PDA, LC-ESI-MS/MS and LC-APCI-MS/MS systems. Optimization of the MS/MS parameters and LC conditions was performed using sinigrin reference standard and rapeseed certified reference material (BC190) respectively. An LC-ESI-MS/MS system was used to detect (screen) and identify the naturally occurring intact glucosinolates (GLs). The intact GLs identified were then desulfated and quantified on an HPLC-PDA system as desulfo-glucosinolates (DS-GLs). Prior to quantification, the DS-GLs were identified using an APCI-MS/MS. The HPLC-PDA method performance criteria were evaluated using glucotropaeolin potassium salt. The validated method was applied for the analysis of six dietary supplements. In total, six glucosinolates were identified and quantified in the dietary supplements; glucoraphasatin (0.2-0.48 mg/g), glucosisaustricin (0.37-0.91 mg/g), glucoraphenin (0.84-1.27 mg/g), glucoputrajivin (0.14-0.28 mg/g), glucosisymbrin (0.70-0.99 mg/g) and gluconasturtiin (0.06-0.12 mg/g). Glucoraphenin was the most abundant glucosinolate in all samples.     

Groundwater dynamics of a saline impacted coastal aquifer of western Maharashtra,India: insights from a radiotracer study

This paper presents application of a radiotracer technique in coastal groundwater for assessing the aquifer dynamics, which is very crucial for understanding flow conditions of an aquifer and its vulnerability to salinity and other contamination. Groundwater dynamics in shallow and deep zones of Palghar Taluk located in west coast of Thane district were studied using point dilution method. ⁸²Br in the form of NH₄Br solution was used as the radiotracer and loggings were carried out by NaI (Tl) scintillation detector. From the analysis of the radiotracer activity loggings, it is found that shallow groundwater is relatively dynamic as compared to deeper groundwater at the two studied sites. The groundwater velocity is about 40–50 cm/day in the shallow zone while it is in the range of 4–40 cm/day in the deep zone. High salinity in deeper parts could be due to seawater intrusion through fractured basalt, which is diluted/flushed in the shallow zone by rain and river water. These findings are helpful in assessing groundwater dynamics in shallow and deep zones of this region and also on the impact of pumping activity on groundwater dynamics.     

Structure of the molybdenum site in YedY, a sulfite oxidase homologue from Escherichia coli

YedY from Escherichia coli is a new member of the sulfite oxidase family of molybdenum cofactor (Moco)-containing oxidoreductases. We investigated the atomic structure of the molybdenum site in YedY by X-ray absorption spectroscopy, in comparison to human sulfite oxidase (hSO) and to a Mo(IV) model complex. The K-edge energy was indicative of Mo(V) in YedY, in agreement with X- and Q-band electron paramagnetic resonance results, whereas the hSO protein contained Mo(VI). In YedY and hSO, molybdenum is coordinated by two sulfur ligands from the molybdopterin ligand of the Moco, one thiolate sulfur of a cysteine (average Mo-S bond length of ～2.4 ?), and one (axial) oxo ligand (Mo═O, ～1.7 ?). hSO contained a second oxo group at Mo as expected, but in YedY, two species in about a 1:1 ratio were found at the active site, corresponding to an equatorial Mo-OH bond (～2.1 ?) or possibly to a shorter Mo-O(-) bond. Yet another oxygen (or nitrogen) at a ～2.6 ? distance to Mo in YedY was identified, which could originate from a water molecule in the substrate binding cavity or from an amino acid residue close to the molybdenum site, i.e., Glu104, that is replaced by a glycine in hSO, or Asn45. The addition of the poor substrate dimethyl sulfoxide to YedY left the molybdenum coordination unchanged at high pH. In contrast, we found indications that the better substrate trimethylamine N-oxide and the substrate analogue acetone were bound at a ～2.6 ? distance to the molybdenum, presumably replacing the equatorial oxygen ligand. These findings were used to interpret the recent crystal structure of YedY and bear implications for its catalytic mechanism.     

Steady state and dynamic simulation of a hybrid reactive separation process

Modelling and simulation of hybrid reactive separation system in steady state and in dynamic regime was carried out. The investigated hybrid process consisted of a reactive distillation column and a pervaporation membrane located in the distillate stream to remove water from the process. Heterogeneously catalysed esterification of propionic acid with propan-1-ol to propyl propionate and water was chosen as the model chemical reaction. Esterification reactions are a typical example of equilibrium-limited reactions producing water as a by-product. Using just a pervaporation membrane brings the biggest benefit in increasing the yield of one of the reactants due to the removal of water. To study reactive separation processes, a model of the hybrid system in steady state and in dynamic regime was developed. Steady state behaviour of the model was studied for different hybrid system configurations. The effect of catalyst amount doubling was also investigated. Dynamic behaviour of the system during the step changes of propionic acid feed flow rate and during the membrane module failure was investigated. For this reason, the conversion of propionic acid, purity of the product stream, mole fraction of water, and the temperature in three different parts of the reactive distillation column were monitored.