The presence of vanadium in groundwater of southeastern extreme the pampean region Argentina Relationship with other chemical elements

Changes in the quality of groundwater resources are related to the presence and concentration of contaminants, especially trace elements such as arsenic, boron, fluoride and vanadium. Vanadium is a rare element naturally abundant, generally found in combination with other elements. Vanadium pentoxide is known to have aneugenic effects. Thus, a study was carried out to assess the presence of vanadium in the groundwater of the southeastern pampean region of Argentina, which constitutes the main water supply for the local population. Statistical and correlational analyses were applied to identify possible interrelationships between vanadium and another chemical elements. Vanadium was found in all groundwater samples. The minimum and maximum vanadium concentrations found were 0.05 mg/l and 2.47 mg/l, respectively. Vanadium is significantly correlated with other trace elements such as arsenic, fluoride and boron. The interrelationship between vanadium and the presence of volcanic glass in sediments is not significant as expected.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

Size and composition distributions of particulate matter emissions: part 1--light-duty gasoline vehicles

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965-2003; odometer readings 1264-207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-microm aerodynamic diameter) and fine PM1.8 (< or =1.8-microm aerodynamic diameter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emissions of 51 microg/km and 371 microg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1- and 0.18-microm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 microm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Fugitive emissions opacity determination using the digital opacity compliance system (DOCS)

Maintenance of Department of Defense (DoD) weapon systems, conducting battlefield training exercises as well as meeting military construction and/or demolition schedules, invariably generate fugitive air emissions, many of which are visible. Although there is no codified federal method for quantifying fugitive emissions opacity, many state and local air regulatory agencies have instituted enforceable fugitive emission opacity standards at DoD facilities. The current study focused on comparing the performance of the digital opacity compliance system (DOCS) with U.S. Environment Protection Agency Method 9 (Method 9) certified human observers in quantifying the visible opacity associated with fugitive emissions produced using a commercial fog generator. By systematically repositioning both DOCS cameras and Method 9-certified observers during field testing, differences in method performance as a function of observational locations were documented. At both the 30- and 300-ft off-set distances, opacity levels reported by the DOCS technology and Method 9-certified smoke readers were found to be statistically different at the 99% confidence level. Alternatively, at the 90- and 150-ft off-set distances, results suggested that there was an insignificant difference at the 99% confidence level between the two methods. Comparing the magnitude of the each method's standard deviation suggested that, at the 30-ft off-set distance, the DOCS technology was consistently more precise than Method 9-certified readers regardless of the observer's downwind distance. However, at the 90, 150, and 300-ft off-set distances, method precision seemed to vary as a function of both off-set and downwind distance. The primary factor affecting the consistency in opacity measurements appeared to be the impact of ground-level air turbulence on fog plume dispersion and transport. Field observations demonstrated that localized wind shear played a critical and decisive role in how and to what extent fugitive emissions opacity could be determined, regardless of the method selected.     

Real-time measurement of outdoor tobacco smoke particles

The current lack of empirical data on outdoor tobacco smoke (OTS) levels impedes OTS exposure and risk assessments. We sought to measure peak and time-averaged OTS concentrations in common outdoor settings near smokers and to explore the determinants of time-varying OTS levels, including the effects of source proximity and wind. Using five types of real-time airborne particle monitoring devices, we obtained more than 8000 min worth of continuous monitoring data, during which there were measurable OTS levels. Measurement intervals ranged from 2 sec to 1 min for the different instruments. We monitored OTS levels during 15 on-site visits to 10 outdoor public places where active cigar and cigarette smokers were present, including parks, sidewalk cafés, and restaurant and pub patios. For three of the visits and during 4 additional days of monitoring outdoors and indoors at a private residence, we controlled smoking activity at precise distances from monitored positions. The overall average OTS respirable particle concentration for the surveys of public places during smoking was approximately 30 microg m(-3). OTS exhibited sharp spikes in particle mass concentration during smoking that sometimes exceeded 1000 microg m(-3) at distances within 0.5 m of the source. Some average concentrations over the duration of a cigarette and within 0.5 m exceeded 200 microg m(-3), with some average downwind levels exceeding 500 microg m(-3). OTS levels in a constant upwind direction from an active cigarette source were nearly zero. OTS levels also approached zero at distances greater than approximately 2 m from a single cigarette. During periods of active smoking, peak and average OTS levels near smokers rivaled indoor tobacco smoke concentrations. However, OTS levels dropped almost instantly after smoking activity ceased. Based on our results, it is possible for OTS to present a nuisance or hazard under certain conditions of wind and smoker proximity.     

Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Reusing fly ash in glass fibre reinforced cement: a new generation of high-quality GRC composites

New composite materials based on an alkali-resistant glass-fibre reinforced cement (AR-GRC) system are being developed by using fly ash (FA) produced at coal thermoelectric power plants, and fluid catalytic cracking catalyst residue (FC3R) from the petrol industry as cement replacement materials. These wastes are reactive from the pozzolanic viewpoint, and modify the nature and the microstructure of the cement matrix when a part of the Portland cement is replaced in the formulation of GRC. Several microstructural and mechanical aspects are being studied for AR-GRC systems. The behaviour of composites exposed to ageing shows that the pozzolanic activity of the ground FA added in high amounts and its mixture with the FC3R increase the flexural strength and no evidences of strength decay are observed. Additionally, the fibres due to the high alkalinity of the cementing matrix can be deteriorated. Fibres in the control (only Portland cement) and FC3R containing composites were attacked, whereas composites with FA and their mixture with FC3R show that the fibres have not been attacked, due to the pozzolanic activity of replacing materials that reduce the calcium hydroxide content in the cementing matrix.     

Determination of selenium by GFAAS in slurries of fish feces to estimate the bioavailability of this micronutrient in feed used in pisciculture

This paper presents a simple, fast and sensitive method to determine selenium in samples of feces and of fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer's graphite tube. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of selenium) were 0.31 microg l(-1) and 1.03 microg l(-1), respectively, for the standard feces slurries and 0.35 microg l(-1) and 1.16 microg l(-1), respectively, for the standard feed slurries. The proposed method was applied in studies of bioavailability of selenium in different fish feeds and the results proved consistent with that obtained from samples mineralized by acid digestion using the microwave oven.     

Heterogeneous photocatalytic degradation of prometryn in aqueous solutions under UV-Vis irradiation

In this study, the heterogeneous photocatalytic degradation of prometryn using TiO(2) as photocatalyst was investigated. The main objectives of the study were: (I) to evaluate the kinetics of the pesticide disappearance, (II) to compare the photocatalytic efficiency of two different types of TiO(2), (III) to examine the influence of various parameters such as initial concentration of pesticide or catalyst and presence of oxidants (H(2)O(2) and K(2)S(2)O(8)), (IV) to evaluate the degree of mineralization and (V) to assess the detoxification efficiency of the studied processes. The experiments were carried out in a 500 ml pyrex UV reactor equipped with a 125 W high-pressure mercury lamp surrounded by a pyrex filter blocking wavelengths below 290 nm. Prometryn concentration was determined using HPLC. It was found that the degradation of the pesticide follows the first order kinetics according to the Langmuir-Hinshelwood model. Parameters like the type and concentration of the catalyst affect the degradation rate. A synergistic effect was observed when an oxidant was added in the TiO(2) suspensions increasing the reaction rate of photodegradation. In order to examine the extent of pesticide mineralization, DOC measurements were carried out. After 6h of illumination, mineralization was achieved up to almost 70%. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fisheri, in order to compare the acute toxicity of prometryn and its photoproducts. The detoxification efficiency was found to be dependent on the studied system and it did not follow the rate of pesticide disappearance.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.