Field-scale colloid migration experiments in a granite fracture

An understanding of particle migration in fractured rock, required to assess the potential for colloid-facilitated transport of radionuclides, can best be evaluated when the results of laboratory experiments are demonstrated in the field. Field-scale migration experiments with silica colloids were carried out at AECL's Underground Research Laboratory (URL), located in southern Manitoba, to develop the methodology for large-scale migration experiments and to determine whether colloid transport is possible over distances up to 17 m. In addition, these experiments were designed to evaluate the effects of flow rate and flow path geometry, and to determine whether colloid tracers could be used to provide additional information on subsurface transport to that provided by conservative tracers alone. The colloid migration studies were carried out as part of AECL's Transport Properties in Highly Fractured Rock Experiment, the objective of which was to develop and demonstrate methods for evaluating the solute transport characteristics of zones of highly fractured rock. The experiments were carried out within fracture zone 2 as two-well recirculating, two-well non-recirculating, and convergent flow tests, using injection rates of 5 and 10 1 min⁻¹. Silica colloids with a 20 nm size were used because they are potentially mobile due to their stability, small size and negative surface charge. The shapes of elution profiles for colloids and conservative tracers were similar, demonstrating that colloids can migrate over distances of 17 m. The local region of drawdown towards the URL shaft affected colloid migration and, to a lesser extent, conservative tracer migration within the flow field established by the two-well tracer tests. These results indicate that stable colloids, with sizes as small as 20 nm, have different migration properties from dissolved conservative tracers. - 1997 Atomic Energy of Canada.     

Mobilization of colloids in groundwater due to infiltration of water at a coal ash disposal site

We investigated groundwaters in the vicinity of a coal ash site near an electric generating station in the western U.S.A. The purpose of the study was to ascertain why fine particles or colloids appear in some subsurface water samples there. If such fine particles are merely introduced during bailing or pumping operations which suspend otherwise immobile soil colloids, we should exclude these particulate materials from the water samples before analysis intended to quantify what is moving through the aquifer. However, if the colloids were truly suspended and moving with the groundwater flow in situ, then we should includes their contribution to our assessment of the mobile loads.Application of very careful sampling techniques (slow pumping rates, no atmospheric exposure) did not cause the large quantities of colloids observed previously to disappear from well water in which they occured. Additionally, the same sampling procedures did not cause similar abundances of colloids to appear in waters collected from neighboring wells installed and developed in the same manner and in the same geologic strata. Thus we believe sampling artifacts do not explain the colloids' presence in the groundwater samples.On the other hand, the groundwater chemistry and the nature of the suspended colloids (size, composition) strongly suggest these fine particles were suspended and therefore moving with the groundwater flow. At wells exhibiting large amounts of suspended colloids (≈10–100 mg L⁻¹), the water was enriched in CO₂ and depleted in O₂ relative to nearby locations. The colloids were typically between 0.1 and 2 μm in size and were primarily silicates. These results suggest to us that, where infiltrating water is percolating through a site that has been mixed with coal ash, the secondary carbonate mineral in the soils are being dissolved; removal of this cementing carbonate phase may consequently release soil silicate colloids to be carried in the flowing water.Such processes may enhance contaminant transport in groundwater by augmenting the pollutant load moving in the groundwater, and increasing the permeability of the porous medium to pollutant infiltration with water water and/or rainwater.     

Polychlorinated biphenyls in the Kupa River, Croatia, Yugoslavia

The presence of polychlorinated biphenyls (PCBs) was investigated in samples of water, suspended particles, sediments and fish from the Kupa river, Croatia, Yugoslavia, along a river stretch extending up to 10 km upstream and 200 km downstream of the primary contaminated karst region. Contamination was due to improper disposal of industrial waste discharge. The PCB levels detected in the samples collected downstream ranged from 1 to 52 ng 1⁻¹ for water, from 50 to 190 μg kg⁻¹ for suspended particles and from 8 to 39 μg kg⁻¹ for the sediment. A wide range of PCB concentrations, from 0.1 to 42.3 μg g⁻¹, which were measured in edible portions of different fish confirmed a long-term contamination of the river with PCBs. As the Kupa may be classified among low to moderately contaminated waters, it is essential that the investigations of the presence and behaviour of PCBs in the river and its environment be continued.     

Mercury deposition/accumulation rates in the vicinity of a lead smelter as recorded by a peat deposit

Mercury (Hg) concentration profiles and historical accumulation rates were determined in three ²¹⁰Pb-dated cores from a peat deposit in the vicinity of a lead (Pb) smelter at Příbram, Czech Republic. The Hg concentrations in peat samples ranged from 66 to 701 μg kg⁻¹. Cumulative Hg inventories from each core (for the past 150 yr) varied by a factor of 1.4 (13.6–18.5 mg Hg m⁻²), indicating variations of net Hg accumulation rate within the peat deposit. Historical changes in vegetation cover (leading to variable interception by trees) are probably responsible for this variation in space and time. The uncorrected Hg accumulation rates peaked between the 1960s and 1980s (up to 226 μg m⁻² yr⁻¹). Recent findings show that Hg records from peat tend to overestimate historical levels of Hg deposition. Therefore we used the mass loss compensation factor (MLCF) to normalize Hg accumulation rates. These corrected Hg accumulation rates were significantly lower (maximum 129 μg m⁻² yr⁻¹) and better corresponded to changes in historical smelter emissions, which were highest in the 1960s. The agreement between the corrected Hg accumulation rates in the uppermost peat sections (2–38 μg m⁻² yr⁻¹) and biomonitoring of atmospheric deposition by mosses in several recent years (4.7–34.4 μg m⁻² yr⁻¹) shows the usefulness of MLCF application on Hg accumulation in peat archives. However, the MLCF correction was unsuitable for Pb. The recent Pb deposition rates obtained by an independent biomonitoring study using mosses (0.5–127 mg m⁻² yr⁻¹) were better correlated with net Pb accumulation rates recorded in peat (7–145 mg m⁻² yr⁻¹) than with corrected rates obtained by the MLCF approach (1–28 mg m⁻² yr⁻¹).     

The potential inhalation hazard posed by dioxin-contaminated soil

Conservative models were used to estimate the airborne concentrations of 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) vapor and particulates originating from soil containing 100 ppb TCDD. The upper-bound estimates were 3.25 pg/m³ of airborne TCDD vapor on-site and 0.51 pg/m³ for TCDD vapor 100 meters downwind. The TCDD air concentration on-site due to suspended particulate is estimated to be 1.4 pg/m³, based on a TSP level of 0.07 mg/m³. Assuming 70 years of continuous exposure to these concentrations, the upper-bound cancer risks determined from the Jury model were estimated to be 9.4 × 10⁻⁶ to 1.1 × 10⁻⁴ and 1.5 × 10⁻⁶ to 1.7 × 10⁻⁵ for inhalation of on- and off-site vapor, respectively, and 4.1 × 10⁻⁶ to 4.6 × 10⁻⁵ for dust inhalation. Since few sites have average soil concentrations as high as 100 ppb TCDD, this worst-case analysis indicates that inhalation will rarely, if ever, be a significant route of exposure to TCDD-contaminated soil. Experimental results support this claim and point to much lower risk estimates (8.4 × 10⁻⁹ to 9.9 × 10⁻⁸), suggesting that the parameters used in the Jury model are likely to overestimate the actual airborne levels of TCDD at contaminated sites.     

Concentrations of carbon monoxide and methane at two heights above a grass field and their deposition onto the field

To investigate whether wind is a significant driving force in the diffusion of CO and CH₄ from the atmosphere into soil, we measured the concentrations of these two gases at two heights above a temperate grass field in Japan and estimated their deposition velocities using micrometeorological techniques. The concentrations were inversely correlated with wind speed, indicating that the local concentrations were influenced by ground sources. The CO and CH₄ concentrations at 0.33 m were usually lower than those at 1.3 m. Although nocturnal data are suspected to be non-stationary, by selecting several periods when the changes of the concentrations were small but larger than analytical precision, we obtained a CO velocity of 2.9 and 3.9×10⁻² cms⁻¹, agreeing with a CO deposition velocity, 3.4×10⁻² cms⁻¹, obtained by applying a method using CO₂ as a tracer. The CH₄ influx obtained by the method using CO₂ as a tracer was 13 ngm⁻² s⁻¹. The ranges of the CO deposition velocity and CH₄ influx were similar to those obtained in previous studies in grassfields and in a nearby arable field using a closed-chamber technique. This shows that light winds do not greatly accelerate CO and CH₄ uptake by soil.     

Traffic generated non-exhaust particulate emissions from concrete pavement: A mass and particle size study for two-wheelers and small cars

This study aimed to understand the non-exhaust (NE) emission of particles from wear of summer tire and concrete pavement, especially for two wheelers and small cars. A fully enclosed laboratory-scale model was fabricated to simulate road tire interaction with a facility to collect particles in different sizes. A road was cast using the M-45 concrete mixture and the centrifugal casting method. It was observed that emission of large particle non exhaust emission (LPNE) as well as PM₁₀ and PM_2.5 increased with increasing load. The LPNE was 3.5 mg tire⁻¹ km⁻¹ for a two wheeler and 6.4 mg tire⁻¹ km⁻¹ for a small car. The LPNE can lead to water pollution through water run-off from the roads. The contribution of the PM₁₀ and PM_2.5 was smaller compared to the LPNE particles (less than 0.1%). About 32 percent of particle mass of PM₁₀ was present below 1 μm. The number as well as mass size distribution for PM₁₀ was observed to be bi-modal with peaks at 0.3 μm and 4–5 μm. The NE emissions did not show any significant trend with change in tire pressure.     

Particle emissions of a railway line determined by detailed single particle analysis

The goal of this study was to identify and quantify particles emitted from railway traffic. For that purpose PM10 samples were collected near a busy railway line using a wind direction and speed controlled sampling equipment consisting of five devices. Measurements taken perpendicular to the railway lines at 10, 36 and 120 m distance enable an identification and separation of particles caused by the railway traffic from background particles. Morphology and chemistry of more than 11,000 particles were analysed by computer controlled scanning electron microscopy (CCSEM). Based on chemical composition five particle classes are defined and assigned to their sources. The mass of the individual particles is determined by multiplying their volumes, calculated based on their morphology with a density assigned specifically to each particle class. The density of the particle classes is derived from their chemical composition. To estimate the PM10 contributions of the railway lines, the mass of PM10 at 120 m (background, not influenced by the railway lines) is subtracted from the mass of PM10 at 10 m. The emissions of the railway lines are dominated by ‘iron’ particles, which contribute 2.9 μg m⁻³ or 67% to the railway related PM10. In addition, ‘aluminium’ and ‘calcium’ particles contribute also to the railway related PM10 (1.0 μg m⁻³ or 23% for the ‘aluminium’ and 0.4 μg m⁻³ or 10% for the ‘calcium’ particles). These particles are assigned to abrasion of the gravel bed and re-suspension of mineral dust.Long-term gravimetric results of the contribution of iron to the mass of railway related PM10 from a study performed earlier at the same site are in good agreement with the data presented in this study.     

Particle size distribution of airborne Aspergillus fumigatus spores emitted from compost using membrane filtration

Information on the particle size distribution of bioaerosols emitted from open air composting operations is valuable in evaluating potential health impacts and is a requirement for improved dispersion simulation modelling. The membrane filter method was used to study the particle size distribution of Aspergillus fumigatus spores in air 50 m downwind of a green waste compost screening operation at a commercial facility. The highest concentrations (approximately 8 × 10⁴ CFU m⁻³) of culturable spores were found on filters with pore diameters in the range 1–2 μm which suggests that the majority of spores are emitted as single cells. The findings were compared to published data collected using an Andersen sampler. Results were significantly correlated (p < 0.01) indicating that the two methods are directly comparable across all particles sizes for Aspergillus spores.     

A study on emission of phthalate esters from plastic materials using a passive flux sampler

Phthalate esters are used as plasticizer in many plastics, and several studies have shown their toxicity. Phthalate esters are gradually emitted over time, and so it is conceivable that they pose a significant health risk. This study aims to investigate the temperature dependence of the emissions of various phthalate esters and to estimate the health risks of these emissions at various temperatures. A passive-type sampler was developed to measure the flux of phthalate esters from the surface of plastic materials. With this sampler, we examined three widely used plastic materials: synthetic leather, wallpaper and vinyl flooring. The observed maximum emissions of diethyl phthalate, dibutyl phthalate, and diethylhexyl phthalate (DEHP) from these materials at 20°C were 0.89, 0.77, and 14 μg m⁻² h⁻¹, respectively. Emissions at 80°C were 2.8, 4.5×10², and 1.5×10³ μg m⁻² h⁻¹, respectively. The results showed this temperature dependence is determined primarily by the type of phthalate ester and less so by the type of material. The estimation from the results of temperature dependence indicated the concentration of DEHP in a vehicle left out in the sunshine during the day can exceed the recommended levels of Japan Ministry of Health, Labour and Welfare.     

Analysis of colloid and tracer breakthrough curves

We consider the dispersion and elution of colloids and dissolved nonsorbing tracers within saturated heterogeneous porous media. Since flow path geometry in natural systems is often ill-characterized macroscopic (mean) flow rates and dispersion tensors are utilized in order to account for the sub-model scale microscopic fluctuations in media structure (and the consequent hydrodynamic profile). Even for tracer migration and dispersal this issue is far from settled.Here we consider how colloid and tracer migration phenomena can be treated consistently. Theoretical calculations for model flow geometries yield two quantitative predictions for the transport of free (not yet captured) colloids with reference to a non-sorbing dissolved tracer within the same medium: the average migration velocity of the free colloids is higher than that of the tracer; and that the ratio of the equivalent hydrodynamic dispersion rates of colloids and tracer is dependent only upon properties of the colloids and the porous medium, it is independent of pathlengths and fluid flux, once length scales are large enough.The first of these is well known, since even in simple flow paths free colloids must stay more centre stream. The second, if validated suggests how solute and colloid dispersion may be dealt with consistently in macroscopic migration models. This is crucial since dispersion is usually ill-characterized and unaddressed by the experimental literature. In this paper we present evidence based upon an existing Drigg field injection test for the validity of these predictions.We show that starting from experimental data the fitted dispersion rates of both colloids and non-sorbing tracers increase with the measured elution rates (obeying slightly different rules for tracers and colloids); and that the ratio of colloid and nonsorbing tracer elution rates, and the ratio of colloid and nonsorbing tracer dispersion rates may be dependent upon properties of the colloids and the medium (not the flow regime).It is important to realize that even for unretarded species, an earlier peak in the breakthrough curve does not necessarily correspond to a faster mean elution rate, or vice versa. But rather that a colloid may elute faster but disperse less than an equivalent tracer. Hence its peak may be retarded compared to that of the tracer, even assuming no retardation. Hence one must consider a combination of mean elution rate and mean dispersion rate, and not rely on “peak times” to corroborate chromatographic effects. The importance of this lies in the fact that these processes are not independent and yet upscale differently. Thus realistic estimates of effective colloid dispersion rates should be upscaled in a way consistent with that adopted for tracers within the same system.     

Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C₂H₄, C₂H₂, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m⁻³ (4000–50 000 μm² cm⁻³ surface area per volume) of NaCl, (NH₄)₂SO₄ or NH₄NO₃ aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: k_OH+CH3OH=(8.12±0.54)×10⁻¹³, k_OH+C2H5OH=(3.47±0.32)×10⁻¹² and k_OH+phenol=(3.27±0.31)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹.     

Colloid-facilitated transport of lead in natural discrete fractures

Colloid-facilitated transport of lead (Pb) was explored in a natural chalk fracture with an average equivalent hydraulic aperture of 139 μm. Tracer solution was prepared by adding montmorillonite (100 mg L^?1) and/or humic acid (HA) (10 mg L^?1) to modified artificial rainwater containing dissolved Pb (21.4 mg Pb L^?1), naturally precipitated PbCO₃ particles (16.4 mg Pb L^?1) and LiBr (39.0 mg L^?1). We found that Pb is only mobile when associated with colloids. PbCO₃ particles were not mobile in the fracture. The addition of HA to the montmorillonite suspension increased the suspension's mobility and therefore promoted the colloid-facilitated transport of Pb. The increases in pH and sodium absorption ratio induced by the chalk-tracer solution interactions appeared to increase the dispersion and mobilization of colloids entering the fracture. The dominant colloid-facilitated transport of Pb reported in this study has significant implications for risk assessment of Pb mobility in fractured rocks.     

Laboratory migration experiments with radionuclides and natural colloids in a granite fracture

Natural colloids in groundwater could facilitate radionuclide transport, provided the colloids are mobile, are present in sufficient concentrations and can adsorb radionuclides. This paper describes the results of a laboratory migration study carried out with combinations of radionuclides and natural colloids within a fracture in a large granite block to experimentally determine the impact of colloids on radionuclide transport. The 85Sr used in this study is an example of a moderately sorbing radionuclide, while the 241Am is typical of a strongly sorbed radionuclide with very low solubility. The natural colloids used in this study were isolated from granite groundwater from Atomic Energy of Canada (AECL) Underground Research Laboratory (URL), and consisted of mostly 1-10 nm organic colloids, along with lesser amounts of 10-450 nm colloids (organics and aluminosilicates). The measured coefficients for radionuclide sorption onto these colloids were between 3 x 10(2) and 1 x 10(3) ml/g for 85Sr, and between 7 x 10(4) and 7 x 10(5) mg/l for 241Am. The 85Sr sorption on the natural colloids appeared to be reversible. Migration experiments in the granite block were carried out by establishing a flow field between two boreholes (out of a total of nine) intersecting a main horizontal fracture. These experiments showed that dissolved 85Sr behaved as a moderately sorbing tracer, while dissolved 241Am was completely adsorbed by the fracture surfaces and showed no evidence of transport. However, when natural colloids were injected together with dissolved 241Am, a small amount of 241Am transport was observed, demonstrating the ability of natural colloids to facilitate the transport of radionuclides with low solubility. Natural colloids had only a minor effect on the transport of 85Sr. In a separate experiment to test the effect of higher colloid concentrations on 85Sr migration, synthetic colloids were produced from Avonlea bentonite. The introduction of a relatively high concentration of bentonite colloids actually reduced 85Sr transport because, compared to natural colloids, the bentonite colloids were less mobile and they sorbed 85Sr more strongly.     

Volcanic sulphate and arctic dust plumes over the North Atlantic Ocean

High time resolution aerosol mass spectrometry measurements were conducted during a field campaign at Mace Head Research Station, Ireland, in June 2007. Observations on one particular day of the campaign clearly indicated advection of aerosol from volcanoes and desert plains in Iceland which could be traced with NOAA Hysplit air mass back trajectories and satellite images. In conjunction with this event, elevated levels of sulphate and light absorbing particles were encountered at Mace Head. While sulphate concentration was continuously increasing, nitrate levels remained low indicating no significant contribution from anthropogenic pollutants. Sulphate concentration increased about 3.8 μg m⁻³ in comparison with the background conditions. Corresponding sulphur flux from volcanic emissions was estimated to about 0.3 TgS yr⁻¹, suggesting that a large amount of sulphur released from Icelandic volcanoes may be distributed over distances larger than 1000 km. Overall, our results corroborate that transport of volcanogenic sulphate and dust particles can significantly change the chemical composition, size distribution, and optical properties of aerosol over the North Atlantic Ocean and should be considered accordingly by regional climate models.     

Spatial character of polychlorinated biphenyls from soil and respirable particulate matter in Taiyuan, China

As one of China’s great metropolises, Taiyuan is affected by heavy chemical industry and manufacture of chemical products, and faces pollution from polychlorinated biphenyls (PCBs). Therefore, this study was conducted to determine the PCB concentrations in various environmental media in Taiyuan. We collected 15 soil samples, 34 respirable particulate matter (PM) samples (17 of PM_2.5 and 17 of PM₁₀) from urban areas of Taiyuan, and measured a total of 144 PCB congeners (including some coeluting PCB congeners). The total PCB concentrations were 51–4.7 × 10³ pg g⁻¹ in soil, 27–1.4 × 10² pg m⁻³ in PM_2.5 and 16–1.9 × 10² pg m⁻³ in PM₁₀. Of the PCB homologues, the dominant PCBs detected in the various media were all tri-CBs. Soil was relatively the most polluted media. Furthermore, principal-component analysis revealed that the major PCB source in Taiyuan may be associated with the main commercial PCB through long-range transmission. Toxic equivalency (TEQ) concentrations (based on ten dioxin-like PCBs) ranged from N.D. to 5.9 × 10⁻³ pg-WHO TEQ g⁻¹ in soil, 2.0 × 10⁻⁴–3.4 × 10⁻³ pg-WHO TEQ m⁻³ and 1.0 × 10⁻⁴–1.2 × 10⁻³ pg-WHO TEQ m⁻³ in PM_2.5 and PM₁₀, respectively. In previous studies, PCBs were not a severe component of contaminant in Taiyuan; however, this study suggested there is a potential threat of human exposure to PCBs for residents of Taiyuan.     

Effective diffusivity of the uranyl ion in a granite from Inada, Ibaraki, Japan

The effective diffusivity of uranium(VI) in Inada granite has been determined by through-diffusion. Experiments were performed at room temperature (20–25°C) in a 0.1 mol 1⁻¹ KCl solution where uranium is present predominantly as the poorly sorbing UO₂²⁺. An effective diffusivity (D_e) of (3.6 ± 1.6) × 10⁻¹⁴ m² s⁻¹ was obtained, close to that for uranine (nonsorbing organic tracer), but one order of magnitude lower than those obtained for Sr²⁺ and NpO₂⁺, and two orders of magnitude lower than that obtained for I⁻. According to well established theory, a proportional relationship exists between D_e and the diffusivity in the bulk of the solution (D_v). The effective diffusivity obtained in granite was not proportional to D_v. This agrees with results obtained for effective diffusivity in a Swedish granite. The ratio D_e/D_v was found to be not constant but increased with D_e or D_v. This result suggests a limit to the application of the theory.     

Assessment of the influence of climatic factors on concentration levels of volatile organic compounds (VOCs) in canadian homes

A nationwide study of indoor air concentrations of 26 VOCs was conducted in Canada in 1991. The study design was based upon random selection of private residences from 1986 Census data and incorporated a temporal stratification feature that allowed sampling of residences in each of four regions of the country at different times of the year with equal probability. Average 24 h concentrations of 26 VOCs in 754 residences were obtained by a passive monitoring method. Initially, climatic parameters were found to have the second highest relative weight among 14 factors identified by factor analysis. Further analysis by linear regression showed that individual VOC concentrations and average outdoor temperature or relative humidity were poorly correlated (r > 0.13). Detailed analysis of the data from four regions of Canada also gave poor correlations between household VOC concentrations and temperature or relative humidity. Concentrations of all 26 VOCs averaged 7.8 μg m⁻³ in winter, 10.3 μg m⁻³ in spring, 4.4 μg m⁻³ in summer and 10.8μ m⁻³ in fall. The highest concentrations of individual compounds averaged 84μm⁻³ for toluene in the spring and 42 μg m⁻³ in the fall, and 44 μg m⁻³ for decane in the spring and 48 μg m⁻³ in the fall. Segregation of the results into outdoor temperature ranges of 0°C, 0–15 and > 15°C gave mean indoor VOC concentrations of 10.3, 9.8 and 50μgm⁻³, respectively. Further examination of the results revealed that the likely presence of sources within homes had a far greater influence on indoor concentrations than ventilation which is partly influenced by climate.     

Field studies of ethoprop movement and degradation in two Florida soils

Unsaturated- and saturated-zone field studies were conducted under two different agricultural conditions in Florida, U.S.A., to measure the movement and degradation of ethoprop.When ethoprop was applied to a sand soil in an orange grove located on the Florida central ridge, soil residues declined with a half-life of 13 days to near the limit of detection (0.01 μg g⁻¹ within 2 months. Ethoprop residues were generally contained in the upper 2 m of soil. Although low levels of ethoprop were found in four groundwater samples within the first 3 months after application, the cause of these isolated and transient residues could not be determined. The data show that there was no widespread plume of ethoprop residues beneath or downgradient from the treated area.On a flatwood soil on the west coast of Florida, ethoprop was incorporated into raised beds and protected by a plastic mulch in which tomatoes were grown. When the plastic mulch was present, ethoprop soil residues declined with a half-life of 40 days and were confined to the upper 0.3 m of soil. After the mulch was removed at crop harvest, the remaining ethoprop dissipated with a half-life of 12 days. Groundwater residues in excess of 1 μg L⁻¹ were confined to a single sample collected after the well had been damaged during a rototilling operation. Resides of < 1 μg L⁻¹ were present in three later samples from this well. At the sampling interval where the highest residues were detected in the damaged well, ethoprop residues of < 1 μg L⁻¹ were also found in three other wells but no residues were detected in these wells in later samples.     

Concentrations and elemental composition of particulate matter in the Buenos Aires underground system

Total suspended particulate (TSP) samples have been collected at six stations in the C and B lines of the Buenos Aires underground system and, almost simultaneously, at six ground level sites outside and nearby the corresponding underground stations, in the Oct 2005/Oct 2006 period. All these samples were analyzed for mass and elemental Fe, Cu, and Zn concentrations by using the Particle Induced X-ray Emission (PIXE) technique. Mostly, TSP concentrations were found to be between 152 μg m⁻³ (25% percentile) and 270 μg m⁻³ (75% percentile) in the platform of the stations, while those in outside ambient air oscillated from 55 μg m⁻³ (25% percentile) to 137 μg m⁻³ (75% percentile). Moreover, experimental results indicate that TSP levels are comparable to those measured for other underground systems worldwide. Statistical results demonstrate that subway TSP levels are about 3 times larger on average than those for urban ambient air. The TSP levels inside stations and outdoors are poorly correlated, indicating that TSP levels in the metro system are mainly influenced by internal sources.Regarding metal concentrations, the most enriched element in TSP samples was Fe, the levels of which ranged from 36 (25% percentile) to 86 μg m⁻³ (75% percentile) in Line C stations, while in Line B ones they varied between 8 μg m⁻³ (25% percentile) and 46 μg m⁻³ (75% percentile). As a comparison, Fe concentrations in ambient air oscillated between 0.7 μg m⁻³ (25% percentile) and 1.2 μg m⁻³ (75% percentile). Other enriched elements include Cu and Zn. With regard to their sources, Fe and Cu have been related to processes taking place inside the subway system, while Zn has been associated with outdoor vehicular traffic. Additionally, concerns about possible health implications based on comparisons to various indoor air quality limits and available toxicological information are discussed.