The hygroscopic behaviour of individual aerosol particles in nickel refineries as investigated by environmental scanning electron microscopy

The hygroscopic properties of individual aerosol particles (1-35 microm equivalent projected area diameter) from the Roasting, Anode Casting and Electrorefining Departments of two Ni refineries were studied by environmental scanning electron microscopy (ESEM) and energy-dispersive X-ray microanalysis (EDX) at a relative humidity of 96-98% (at a temperature of 5 degrees C). In the Roasting and Anode Casting Departments, most particles (60-85% by number) showed no visible change in size or surface morphology when exposed to high relative humidity. Approximately 15-30% of the particles developed a thin water film (growth factors between 1.006 and 1.06) indicating the presence of thin surface coatings of sulfates. About 10% of the particles in the Roasting Department formed droplets (growth factors between 1.1 and 2.6) which always contained a large portion of insoluble material. In the Electrorefining Department, most particles (approximately 60%) were residues from the electrolysis bath solution. At a relative humidity of 96-98% these particles formed a solution which contained only small insoluble inclusions. About 30% of the particles in the Electrorefining Department developed thin water films. As only a small fraction of the particles increased substantially in size when exposed to high relative humidity, the deposition pattern of the total aerosol mass fraction will not be changed substantially by hygroscopic growth. The frequent occurrence of thin surface coatings of soluble material on insoluble Ni compounds has to be considered for health assessment purposes.     

Laboratory and field validation of a combined NO2-SO2 Radiello passive sampler

A combined NO2-SO2 Radiello radial-type diffusive sampler was validated under controlled laboratory conditions and compared with NO2-SO2 results of 3 other type of samplers in a field comparison at two locations Ghent-Mariakerke and Borgerhout in Flanders. Laboratory exposures at different temperatures (-5, 10 and 30 degrees C) and relative humidities (0, 50 and 80% RH) in combination with varying concentration levels and exposure times were carried out, with a focus on extreme conditions. Concentration level and exposure time were changed together following suppliers linear working range of samplers and assuring absolute amounts of compounds on the sampler corresponding to those of environmental levels. The average uptake rate for NO2 for 24 hour exposures at 10 degrees C and 50% RH and tested concentration levels (+/-73, 146 and 293 ppb NO2) was 0.076 +/- 0.011 ng ppb(-1) min(-1). Uptake rates during all experiments were lower than the uptake rate given in the instruction manual of the sampler. A significant effect of temperature and relative humidity on NO2 uptake rate was observed. The temperature effect from 10 to 30 degrees C corresponds to the temperature effect given by the supplier of the samplers. High relative humidity (70 to 80%) caused a strong non-reproducible decrease of uptake rate for NO2 at 24 hour experiments but this effect was not observed at longer exposures except for the tests at -5 degrees C. At the tested temperature below zero in combination with high relative humidity the sampler showed anomalous behaviour for NO2. The possible effect of concentration level and exposure time for NO2 needs further research. The average uptake rate for SO2 calculated from all exposures is 0.478 +/- 0.075 ng of sulfate ion each ppb min of SO2 and accords to suppliers uptake rate. No clear effects of temperature, relative humidity or concentration level/exposure time on the uptake rate for SO2 were found, partly due to the large scatter of results. Although NO2 accuracy of Radiello samplers was better during field campaigns than during laboratory validation, IVL and OGAWA samplers gave better results for NO2. In the field, IVL samplers showed best agreement with the continuous analyzers for both NO2 and SO2.     

Multiple kinetic Langmuir modeling to predict the environmental behaviour of As(v) in soils

A soil with a relatively high Fe content (2.82% [w/w]) was loaded for up to one year with As(v) by equilibrating it with a solution containing 1000 mg l(-1) As(v) at a soil mass-to-solution ratio of 0.1 kg l(-1). The incorporation of As(v) into the soil and its distribution over the soil phases were monitored by sampling at strategic time intervals using an operationally defined five-step sequential extraction procedure (Wenzel et al., Anal. Chim. Acta, 2001, 436, 309) and subsequent As measurement. A multiple kinetic Langmuir model was developed to retrieve the dynamic parameters (adsorption and desorption rate constants, capacities and Langmuir equilibrium constants) for each of the soil phases by numerical fitting of the experimental adsorption data to the model. Under the equilibration conditions used the adsorption rate constants for all five operationally defined soil phases were very similar but the desorption rate constants decreased by a factor of ca. 150 from soil phase 1 (non-specifically sorbed As) to 5 (residual phases). This implies that As(v) incorporation "deeper" into the soil leads to stronger binding which is associated with the Langmuir equilibrium constants (adsorption rate constants/desorption rate constants). Equilibration of the soil with As(v) was complete in ca. 10 days with As(v) predominantly bound to soil phase 2 (specifically sorbed As) and soil phase 3 (amorphous and poorly crystalline hydrous oxides). X-Ray absorption spectroscopy techniques revealed that these binding characteristics may be related to adsorption of As(v) on Si- and/or Al-containing structures and natural hydrous iron oxide (HFO) surface sites, respectively. Since the model is independent of the initial As(v) concentration in the solution and the soil mass-to-solution ratio, the behaviour of the thus characterized soil-As(v) system can be predicted for a range of conditions. Simulations showed that in an accidental As(v) spill the soil studied would actively scavenge As(v) by instantaneous adsorption onto all soil phases followed by redistribution of As(v) from weaker binding sites to stronger ones over time.     

Soil adsorption studies of a rice herbicide,cyhalofop-butyl,in two texturally different soils of India

The ability of herbicides to be adsorbed by the soil and sediment and their tendency to be desorbed are some of the most important factors affecting soil and water contamination. Therefore, a sorption study was conducted to evaluate the adsorption of cyhalofop-butyl, butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy) phenoxy] propanoate, in the sandy clay loam and clayey soils using a batch equilibrium method. The adsorption of cyhalofop-butyl was found positively related with the clay and organic carbon content. Freundlich constants (K _f) of cyhalofop-butyl in the clayey and sandy clay loam were found to be 13.39 and 2.21, respectively. Sorption coefficients (K _oc) and distribution coefficients (K _d) were found to be 265.38 and 2,092.79, and 1.38 and 11.48, for sandy clay loam and clayey soils, respectively. The adsorption isotherm suggested a relatively higher affinity of cyhalofop-butyl to the adsorption sites at low equilibrium concentrations. The low value of the soil organic carbon partition coefficient (K _oc) of cyhalofop-butyl in the sandy loam soil suggested its weaker adsorption in soil and thus increased its risk of mobility into water sources; hence, it should be used judiciously to prevent groundwater contamination     

Compartment modeling of MTBE in the generic environment and estimations of the aquatic MTBE input in Germany using the EQC model

The use of the gasoline additive methyl tert-butyl ether (MTBE) has caused serious concern about groundwater and surface water contamination. The behavior of MTBE in the two most relevant compartments, surface water and air in a generic environment and in a simulated German environment is investigated using the equilibrium criterion (EQC) model. Due to lack of literature data, the half-life time of MTBE in river water is estimated to about 80-120 d (105 d) at 18 degrees C and roughly 1.5 a (year)(533 d) at 4 degrees C from a batch experiment. The EQC model considers four compartments, air, surface water, soil and sediment in an environment of typically 100,000 km2 with about 10% of the area covered with water. The user can progress through the tiered sequence of Level I to III with increasing complexity which reveals more information about the the fate of the considered chemical. The equilibrium mass distribution of MTBE calculated with the Level I model shows that 87% partitions into air and 13% into surface water at 10 degrees C. The results of the Level II calculations indicate that 50% of MTBE in the air is transported from the system and 38% in the air is degraded at 10 degrees C. The resulting total persistence time of 3 d for MTBE in the generic environment of the Level II model can be compared to the calculated value for chlorobenzene. The MTBE input into water is significantly more sensitive to the 'mode of entry' than input into air. The MTBE concentration in surface water is almost exclusively the result of direct emission into water, whereas the atmosphere can additionally be loaded by volatilization from water. The total aquatic MTBE emission in Germany and the average MTBE concentration in German surface waters were roughly estimated to 20-80 t a(-1) (tons per year)(50 t a(-1)) and 50 ng L(-1), respectively. Surface water concentrations calculated with the underlying assumptions of the model can neither be explained by exposure through waste water and industrial effluents nor with an estimated loss of industrially used MTBE in Germany. For the year-round scenario at 10 degrees C, MTBE concentrations of 19 ng L(-1) (surface water) and 167 ng m(-3) (air) result. However, it remains unclear whether the assumptions of the model, the lack of analyses from industrial effluents or both are responsible for the difference. Additional aquatic emission sources could result from gasoline transport on and storage near rivers. The comparison of winter and summer scenarios shows that in summer, atmospheric (25%) and aqueous (50%) concentrations are lower than in winter due to higher degradation rates.     

Preferential adsorption of fluorescing fulvic and humic acid components on activated carbon using flow field-flow fractionation analysis

Activated carbon treatment of drinking water is used to remove natural organic matter (NOM) precursors that lead to the formation of disinfection byproducts. The innate hydrophobic nature and macromolecular size of NOM render it amenable to sorption by activated carbon. Batch equilibrium and minicolumn breakthrough adsorption studies were performed using granular activated carbon to treat NOM-contaminated water. Ultraviolet (UV) absorption spectroscopy and flow field-flow fractionation analysis using tandem diode-array and fluorescence detectors were used to monitor the activated carbon sorption of NOM. Using these techniques, it was possible to study activated carbon adsorption properties of UV absorbing, fluorescing and nonfluorescing, polyelectrolytic macromolecules fractionated from the total macromolecular and nonmacromolecular composition of NOM. Adsorption isotherms were constructed at pH 6 and pH 9. Data were described by the traditional and modified Freundlich models. Activated carbon capacity and adsorbability were compared among fractionated molecular subsets of fulvic and humic acids. Preferential adsorption (or adsorptive fractionation) of polyelectrolytic, fluorescing fulvic and humic macromolecules on activated carbon was observed. The significance of observing preferential adsorption on activated carbon of fluorescing macromolecular components relative to nonfluorescing components is that this phenomenon changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the composition that existed in the aqueous phase prior to adsorption. Likewise, it changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the adsorbed phase. This research increases our understanding of NOM interactions with activated carbon which may lead to improved methods of potable water production.     

Deterioration of Jerusalem limestone from air pollutants; field observations and laboratory simulation

Samples of Jerusalem limestones were exposed to high levels of common air pollutants (SO₂, NO) in the presence and absence of hydrocarbon, water vapor and ultra-violet light. After exposure, the outer layers were shaved off and analyzed for sulfate and nitrate. The results revealed that even after one day of exposure significant concentrations of CaSO₄ and Ca(NO₃)₂ could be detected in the external 40 m layers. Sulfate formation was found to relate very strongly to relative humidity with nearly undetectable production at humidities below 10%. Nitrate formation was found to relate to UV light and to a limited extent to the presence of hydrocarbon but was unchanged at different humidities. Surface samples were taken from different sites of the old city wall and were also analyzed for the same substances. The data showed that the concentrations of especially CaSO₄, and to a limited extend Ca(NO₃)₂, measured at various points along the city walls were higher than the expected values extrapolated from laboratory simulations. The elevated pollution content may be explained in part due to the deposition of transported ions, especially sulfate, onto the stone surface. It was concluded that although air pollution may not cause any structural damage in the foreseeable future it definitely deteriorates the fine details of the ancient monument.     

Effect of temperature on single and competitive adsorptions of Cu(II) and Zn(II) onto natural clays

This study conducted a combined adsorption-sequential extractionanalysis (CASA), by which five phases (i.e., exchangeable, carbonate, Mn-Oxide, organic, and Fe-Oxide phases) of adsorbed heavy metals were analyzed, to investigate temperature effects on single and competitive adsorptions of Zn(II) and Cu(II) ontonatural clays. In the case of single adsorption of Zn, the exchangeable phase adsorption decreased from 65 to 40%, but thecarbonate phase adsorption increased from 30 to 40%, with an increase in temperature from 15 to 55 °C. However, in itscompetitive adsorption with Cu, Zn was mostly present in the exchangeable phase (over 90%), and with an increase in temperature, the exchangeable phase adsorption decreased only 10%. In the case of Cu, over 50% among the total amount of adsorption was present in the carbonate phase in both cases ofsingle and competitive adsorptions. The carbonate phaseadsorption of Cu increased from 56 to 61% and from 60 to 66% in single and competitive adsorptions, respectively, with atemperature increase. These results show that in the case of Zn,the major mechanism of retention in natural clay soils might beexchangeable phase adsorption, especially in the case of competitive adsorption with Cu. However, in the case of Cu, the major mechanism might be carbonate phase adsorption, which is known to be a more immobile phase than exchangeable phase adsorption. It seems that the adsorption of Zn and Cu onto natural clays is an endothermic reaction, which represents thatthe adsorption equilibrium constants and capacities increase with a temperature increase, with the exception of exchangeablephase adsorption.     

Isolation and fractionation of natural organic matter: evaluation of reverse osmosis performance and impact of fractionation parameters

Dissolved organic matter (DOM) from three surface waters was isolated using reverse osmosis (RO) and subsequently fractionated using resin adsorption chromatography (RAC). Efficacy of RO was evaluated by closing mass balances for dissolved organic carbon (DOC). RAC was evaluated by investigating the effect of column operational parameters (column capacity factor, k', and solute initial concentration, C0) on DOM fractionation and subsequent disinfection by-product formation. Efficacy of RO was dependent on both isolation conditions and source water characteristics. In general, RO more effectively isolated DOM in high specific ultraviolet absorbance (SUVA254) water than low SUVA254 water, and showed higher DOM recovery at ambient pH (approximately 7) than at low pH (approximately 4). The fractionation of the isolated DOM indicated that the relative amount of the hydrophobic fraction decreased with increasing k', thus affecting the overall distribution of DOM. However, the distribution of DOM fractions was not influenced by varying C0 up to 150 mg l(-1) at k' of 15. The effect of k' on the formation and speciation of trihalomethanes (THM) and haloacetic acids (HAA) was not significant up to k' of 30.     

Accumulation of Tobacco mosaic virus (TMV) at different depths clay and loamy sand textural soils due to tobacco waste application

The effects of tobacco waste (TW) application to the soil surface on the accumulation of Tobacco mosaic virus (TMV) in clay and loamy sand textural soils at various depths were investigated in two different fields. The tobacco waste had been found to be infected with TMV. Eighteen months after TW application to the soil surface, soils were sampled at 20 cm intervals through to 80 cm depth. The DAS-ELISA method was performed to determine infection of soil with TMV. The viruses persisted in clay soil for a long period compared with loamy sand soil. There was no accumulation of TMV at any depth of loamy sand soil in Experimental Field 2. TMV adsorption to soil particles in 0-60 cm depth of clay soil was determined in all TW treatments in Experimental Field 1. The highest ELISA Absorbance (A405) values in all treatments were determined in the 20-40 cm soil depth that had the highest clay content. ELISA A405 values of TMV at different depths of clay soil gave significant correlations with clay content (r = 0.793**), EC values (r = 0.421**) and soil pH (r = -0.405**). Adsorption of TMV to net negatively charged clay particle surfaces increased with increasing EC values of soil solution. Decreasing soil pH and infiltration rate increased adsorption of TMV to clay particles. Higher infiltration rate and lower clay content in loamy sand soil caused leaching of TMV from the soil profile.     

Spatial and temporal patterns of microclimates at an urban forest edge and their management implications

Fragmented forests generate a variety of forest edges, leading to microclimates in the edge zones that differ from those in the forest interior. Understanding microclimatic variation is an important consideration for managers because it helps when making decisions about how to restrict the extent of edge effects. Thus, our study attempted to characterize the changing microclimate features at an urban forest edge located on Mt. Gwanak, Seoul, South Korea. We examined edge effects on air temperature, relative humidity, soil temperature, soil moisture, and photosynthetically active radiation (PAR) during the hottest three consecutive days in August 2016. Results showed that each variable responded differently to the edge effects. This urban forest edge had an effect on temporal changes at a diurnal scale in all microclimate variables, except soil moisture. In addition, all variables except relative humidity were significantly influenced by the edge effect up to 15 m inward from the forest boundary. The relative humidity fluctuated the most and showed the deepest extent of the edge effect. Moreover, the edge widths calculated from the relative humidity and air temperature both peaked in the late afternoon (16:00 h). Our findings provide a reference for forest managers in designing urban forest zones and will contribute to the conservation of fragmented forests in urban areas.     

Assessment of the Heavy Metal Pollution Effects on the Soil Respiration in the Baix Llobregat (Catalonia, NE Spain)

A main goal of investigations is to determine could a soilrespiration be an indicator of the soil pollution. In this case a measured levelof the soil oxygen consumption depends of its pollution. It alsomeans that the pollution reduces biological processes in edaphon.Investigated soil samples were taken from polluted andnon-polluted places in the Baix Llobregat near Barcelona (Catalonia, NE Spain). Soil samples were taken from the top ofsoil (0–5 cm) without a litter. Soil analysis were done, determining percentage shares of coarsefragments, coarse sand, fine sand, coarse silt, fine silt, clay,CaCO₃, organic matter as well as water pH and conductivityCE (1:5 [mS cm^-1]). Also were determined (in mg kg^-1)quantities of heavy metals, as Fe, Al, Mn, Zn, Cr, Ni, V, Cu, Cd, Pb.The soil respiration was investigated in temperatures15 and 30 °C and with controlled humidity.The respiration in 30 °C is number of times greater thenin 15 °C both for polluted and non-polluted soils.Particularly high coefficients of correlation between the soilrespiration and soil pollution in polluted soils were obtainedfor Pb: r = 0.75 in 15 °C and r = 0.98 in30 °C; for Ba: 0.90 and 0.57; for V: 0.99 and 0.81. In non-polluted soils highest correlation coefficients are for Pb: r = 0.70 in 15 °C; Fe: 0.60 and 0.72; Al: 0.68 and0.64; Mn: 0.51 and 0.66; Ba: 0.63 and 0.61; Cr: 0.94 and0.70; Ni: 0.64 and 0.65; Cu: 0.69 and 0.48; as well as V: 0.62in 15 °C; and Cd: 0.69 in 15 °C.This way the soil respiration could be a good indicator of the soil pollution.     

Soil carbon storage as influenced by tree cover in the Dehesa cork oak silvopasture of central-western Spain

The extent of carbon (C) stored in soils depends on a number of factors including soil characteristics, climatic and other environmental conditions, and management practices. Such information, however, is lacking for silvopastoral systems in Spain. This study quantified the amounts of soil C stored at various depths (0-25, 25-50, 50-75, and 75-100 cm) under a Dehesa cork oak (Quercus suber L.) silvopasture at varying distances (2, 5, and 15 m) to trees. Soil C in the whole soil and three soil fractions (<53, 53-250, and 250-2000 μm) was determined. Results showed soil depth to be a significant factor in soil C stocks in all soil particle sizes. Distance to tree was a significant factor determining soil C stocks in the whole soil and the 250-2000 μm soil fraction. To 1 m depth, mean total C storage at 2, 5, and 15 m from cork oak was 50.2, 37, and 26.5 Mg ha(-1), respectively. Taking into account proportions of land surface area containing these C stocks at varying distances to trees to 1 m depth, with a tree density of 35 stems ha(-1), estimated landscape soil C is 29.9 Mg ha(-1). Greater soil C stocks directly underneath the tree canopy suggest that maintaining or increasing tree cover, where lost from disease or management, may increase long term storage of soil C in Mediterranean silvopastoral systems. The results also demonstrate the use of soil aggregate characteristics as better indicators of soil C sequestration potential and thus a tool for environmental monitoring.     

Fate estimation of polycyclic aromatic hydrocarbons in soils in a rapid urbanization region, Shenzhen of China

Our previous study indicated that the current level of polycyclic aromatic hydrocarbons (PAHs) in Shenzhen soil is in the low-end of world soil PAH pollution. In this study, the fate of PAHs in the soil of Shenzhen was investigated. The mass inventories of Σ(27)PAHs and Σ(15)PAHs (defined as the sum of the 27 or 15 PAH compounds sought) in topsoil of Shenzhen were ～204 and ～152 metric tons, respectively. Fate estimation of Σ(15)PAHs shows that air-soil gaseous exchange is the primary environmental process with ～10,076 kg/year diffusing from soil to air. Rain washing (～1131 kg/year from air to soil) is the most important input pathway followed by wet (～17 kg/year) and dry deposition (～8 kg/year) to soils in Shenzhen. The transport of Σ(15)PAHs by soil erosion is a crucial loss process for soil PAHs in Shenzhen (1918 kg/year for water runoff and 657 kg/year for solid runoff from soil). Moreover, degradation is not ignorable at present (95 kg/year). Comparison of inventory and residue (defined as Σ(15)PAHs left in topsoils after all environmental loss processes) suggested that input and loss of high molecular weight PAHs for Shenzhen's soil reached apparent equilibrium. Soil PAH pollution in Shenzhen will stay in a quasi-steady state for a long period and the natural environmental processes can not significantly reduce the pollution.     

Spatial variability of fallout-137Cs in the soil of a cultivated field

To obtain information on the spatial variability of fallout ¹³⁷Cs in the soil of a small area, the activity concentration of this radionuclide was determined in 100 soil samples, taken along the two diagonals of a cultivated field (150×100 m). The results show that the spatial distribution of ¹³⁷Cs in this field is at random. The frequency distribution of the values is skewed to the right, but not log-normal. The median activity concentration observed was 7.45 Bq kg^-1 dry soil, the values ranging from 4.8–15 Bq kg^-1. The spatial variability, as characterized by the relative decile deviation was 26%. If one tolerates for the establishment of baselines of global fallout ¹³⁷Cs in the soil an error in the mean activity concentration of 10% (20%) at the 95% confidence level, the minimum number of soil samples to be taken can be estimated as 14 (4). The total deposition of ¹³⁷Cs on the soil surface by fallout was determined as 3.3±0.4 kBq m^-2.     

Solid-phase microextraction coupled to gas chromatography-mass spectrometry for the study of soil adsorption coefficients of organophosphorus pesticides

A solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) method for the simultaneous determination of the organophosphorus pesticides (OPPs), phorate, diazinon, methyl-parathion, fenitrothion, malathion, fenthion, ethyl-parathion and methidathion, has been developed to study their soil/water distribution. The method was used in conjunction with a conventional 'batch equilibrium method' to assess the soil adsorption coefficients (Koc) of the target compounds in different soil samples with known organic carbon content. Contrary to traditional techniques, the present method is fast, solvent-free and highly sensitive, thus permitting the assessment of the Koc values of the target compounds even at low soil concentration levels, close to those encountered in real field contamination, where the Freudlich adsorption isotherms can be considered to be linear. The estimated Koc values were found to be in good agreement with those reported in the literature.     

Assessment of heavy metals (Cd and Pb) and micronutrients (Cu, Mn, and Zn) of paddy (Oryza sativa L.) field surface soil and water in a predominantly paddy-cultivated area at Puducherry (Pondicherry, India), and effects of the agricultural runoff on the elemental concentrations of a receiving rivulet

The concentrations of toxic heavy metals—Cd and Pb and micronutrients—Cu, Mn, and Zn were assessed in the surface soil and water of three different stages of paddy (Oryza sativa L.) fields, the stage I—the first stage in the field soon after transplantation of the paddy seedlings, holding adequate amount of water on soil surface, stage II—the middle stage with paddy plants of stem of about 40 cm length, with sufficient amount of water on the soil surface, and stage III—the final stage with fully grown rice plants and very little amount of water in the field at Bahour, a predominantly paddy cultivating area in Puducherry located on the southeast Coast of India. Comparison of the heavy metal and micronutrient concentrations of the soil and water across the three stages of paddy field showed their concentrations were significantly higher in soil compared with that of water (p?<?0.05) of the fields probably because of accumulation and adsorption in soil. The elemental concentrations in paddy soil as well as water was in the ranking order of Cd?>?Mn?>?Zn?>?Cu?>?Pb indicating concentration of Cd was maximum and Pb was minimum. The elemental concentrations in both soil and water across the three stages showed a ranking order of stage II?>?stage III?>?stage I. The runoff from the paddy fields has affected the elemental concentrations of the water and sediment of an adjacent receiving rivulet.     

The influence of water vapour on the determination of glutaraldehyde vapour concentrations using an electrochemical fuel cell sensor

The effects of relative humidity (40-90% RH) and varying glutaraldehyde vapour concentrations (< 0.1 ppm) on the response of an electrochemical fuel cell sensor have been investigated over time (0-400 s). These studies have identified changes in the response of the fuel cell with time after sampling. In particular, it has been found that the maximum cell output for water vapour occurs ca. 10 s after sampling whilst the response to glutaraldehyde occurs much later (> 100 s). For mixtures containing different ratios of water and glutaraldehyde vapours, the time taken to reach maximum fuel cell response varies between 10 and 100 s, depending on the ratio of the two vapours. For instance, glutaraldehyde vapour containing higher % RH has been found to result in shorter times to reach maximum fuel cell response. A comparison was made between measuring glutaraldehyde vapour concentrations in the presence of water vapour at the maximum fuel cell response and also at a fixed interval (240 s) after sampling. Such a comparison resulted in a reduction in the standard error from 36% to 5% for a glutaraldehyde vapour sample (0.023 ppm) measured at different values of relative humidity (40 to 80%). Examination of the effect of the sample volume (30-60 ml) on the response of the fuel cell shows, as expected, an approximate doubling of the fuel cell response. Optimisation of the fuel cell measurement parameters to measure a 60 ml sample leads to a lowering of the limit of detection from 0.083 ppm (for data taken at the maximum cell response) to 0.017 ppm for data measured 240 s after sampling. In the light of recent reductions in the legal limits for exposure to glutaraldehyde, this has important implications for the measurement of glutaraldehyde vapour in the workplace.     

Preparation and utilization of molecularly imprinted polymer for chlorsulfuron extraction from water, soil, and wheat plant

A molecularly imprinted polymer (MIP) was prepared using chlorsulfuron (CS), a herbicide as a template molecule, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linker, methanol and toluene as a porogen, and 2,2-azobisisobutyronitrile as an initiator. The binding behaviors of the template chlorsulfuron and its analog on MIP were evaluated by equilibrium adsorption experiments, which showed that the MIP particles had specific affinity for the template CS. Solid-phase extraction (SPE) with the chlorsulfuron molecularly imprinted polymer as an adsorbent was investigated. The optimum loading, washing, and eluting conditions for chlorsulfuron molecularly imprinted polymer solid-phase extraction (CS-MISPE) were established. The optimized CS-MISPE procedure was developed to enrich and clean up the chlorsulfuron residue in water, soils, and wheat plants. Concentrations of chlorsulfuron in the samples were analyzed by HPLC-UVD. The average recoveries of CS spiked standard at 0.05~0.2 mg L(-1) in water were 90.2~93.3%, with the relative standard deviation (RSD) being 2.0~3.9% (n=3). The average recoveries of 1.0 mL CS spiked standard at 0.1~0.5 mg L(-1) in 10 g soil were 91.1~94.7%, with the RSD being 3.1~5.6% (n=3). The average recoveries of 1.0 mL CS spiked standard at 0.1~0.5 mg L(-1) in 5 g wheat plant were 82.3~94.3%, with the RSD being 2.9~6.8% (n=3). Overall, our study provides a sensitive and cost-effective method for accurate determination of CS residues in water, soils, and plants.     

Geochemical and radionuclide profile of Tuzla geothermal field, Turkey

Tuzla geothermal basin is situated in north-western Turkey on the Biga Peninsula, which is located at the west end of the Northern Anatolian Fault system. Soil and water samples were collected between August 2003 and June 2004 to initiate development of a geochemical profile of surface and subsurface waters in the geothermal basin and radionuclide concentrations in soils. All water samples were found to fall within Turkish Water Quality Class 4, meaning they were remarkably contaminated for any water consumption sector (industrial, human use or agricultural) based on sodium and chloride ions. Such waters could be used only after appropriate water treatment. The water samples are of the chloride type in terms of geochemical evaluation. Preliminary geochemical evidence shows that the N-S flowing part of the Tuzla River acts as a natural barrier within the basin. Heavy metal concentrations in the soil samples show slight elevations, especially those obtained from the east part of the basin where thermal springs are dominant. Geochemical calculations were carried out with PHREEQC software to determine equilibrium concentration of chemical species and saturation indices, by which it is suggested that chloride is the most important ligand to mobilize the heavy metals in the studied system. In addition, the activity concentration and gamma-absorbed dose rates of the terrestrial naturally occurring radionuclides were determined in the soil using gamma-ray spectrometry. The soil activity ranged from 42.77 to 988.66 Bq kg(-1) (averaging 138 Bq kg(-1)) for ( 238 )U, 13.27 to 106.31 Bq kg(-1) (averaging 32.42 Bq kg(-1)) for ( 232 )Th, and 99.28 to 935.36 Bq kg(-1) (averaging 515.44 Bq kg(-1)) for ( 40 )K. The highest value of ( 238 )U was found in the soil samples obtained from an area close to the hot spring.