Aerostat-lofted instrument and sampling method for determination of emissions from open area sources

An aerostat-borne instrument and sampling method was developed to characterize air samples from area sources, such as emissions from open burning. The 10 kg battery-powered instrument system, termed “the Flyer”, is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by means of one or two tethers. The Flyer can be configured variously for continuous CO₂ monitoring, batch sampling of semi-volatile organic compounds (SVOCs), volatile organic compounds (VOCs), black carbon, metals, and PM by size. The samplers are controlled by a trigger circuit to avoid unnecessary dilution from background sampling when not within the source plume. The aerostat/Flyer method was demonstrated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnance. A carbon balance approach was used to derive emission factors that showed excellent agreement with published values.     

Oxygenated volatile organic compounds (OVOCs) at an urban background site in Zürich (Europe): Seasonal variation and source allocation

Twenty-one oxygenated volatile organic compounds (OVOCs) were measured in four seasonal campaigns at an urban background site in Zürich (Switzerland) with a newly developed double adsorbent sampling unit coupled to a gas chromatograph–mass spectrometer (GC–MS). In addition, selected non-methane hydrocarbons (NMHCs) were measured, as well as formaldehyde in the summer and winter campaign. The most abundant compound measured in all seasons was ethanol, with peak values of more than 60 ppb. Its seasonal variation with a lower mean value in summer compared to that in winter implied mostly anthropogenic sources. In contrast, compounds with additional biogenic sources, or compounds known to be produced in the troposphere by oxidation processes, had seasonal maxima in summer (e.g. methanol, acetone, formaldehyde, methacrolein and 2-butenone (methyl vinyl ketone, MVK)).For the OVOCs it was estimated that local sources contributed 40% and 49% to the mixing ratios of the measured compounds in summer and in winter, respectively. Combustion was estimated to contribute 75% to these local sources independent of the season. About 50% of both the OVOC and NMHC levels in Zürich could be explained by the regional background, which included regional biogenic and anthropogenic sources in addition to secondary production. Industrial sources were identified for acetone, butanone (methyl ethyl ketone, MEK), n-propanol, iso-propanol, n-butanol, ethyl acetate and butyl acetate.     

Validation of regression models for nitrate concentrations in the upper groundwater in sandy soils

For Dutch sandy regions, linear regression models have been developed that predict nitrate concentrations in the upper groundwater on the basis of residual nitrate contents in the soil in autumn. The objective of our study was to validate these regression models for one particular sandy region dominated by dairy farming. No data from this area were used for calibrating the regression models. The model was validated by additional probability sampling. This sample was used to estimate errors in 1) the predicted areal fractions where the EU standard of 50 mg l⁻¹ is exceeded for farms with low N surpluses (ALT) and farms with higher N surpluses (REF); 2) predicted cumulative frequency distributions of nitrate concentration for both groups of farms.Both the errors in the predicted areal fractions as well as the errors in the predicted cumulative frequency distributions indicate that the regression models are invalid for the sandy soils of this study area.     

The effects of dissolved organic matter and pH on sampling rates for polar organic chemical integrative samplers (POCIS)

The effect of solution pH and levels of dissolved organic matter (DOM) on the sampling rates for model pharmaceuticals and personal care products (PPCPs) and endocrine disrupting substance (EDS) by polar organic chemical integrative samplers (POCIS) was investigated in laboratory experiments. A commercially available POCIS configuration containing neutral Oasis HLB (hydrophilic-lipophilic balance) resin (i.e. pharmaceutical POCIS) and two POCIS configurations prepared in-house containing MAX and MCX anion and cation exchange resins, respectively were tested for uptake of 21 model PPCPs and EDS, including acidic, phenolic, basic and neutral compounds. Laboratory experiments were conducted with dechlorinated tap water over a pH range of 3, 7 and 9. The effects of DOM were studied using natural water from an oligotrophic lake in Ontario, Canada (i.e. Plastic Lake) spiked with different amounts of DOM (the concentration of dissolved organic carbon ranged from 3 to 5 mg L⁻¹ in uptake experiments). In experiments with the commercial (HLB) POCIS, the MCX-POCIS and the MAX-POCIS, the sampling rates generally increased with pH for basic compounds and declined with pH for acidic compounds. However, the sampling rates were relatively constant across the pH range for phenols with high pKa values (i.e. bisphenol A, estrone, estradiol, triclosan) and for the neutral pharmaceutical, carbamazepine. Thus, uptake was greatest when the amount of the neutral species in solution was maximized relative to the ionized species. Although the solution pH affected the uptake of some model ionic compounds, the effect was by less than a factor of 3. There was no significant effect of DOM on sampling rates from Plastic Lake. However, uptake rates in different aqueous matrixes declined in the order of deionized water > Plastic Lake water > dechlorinated tap water, so other parameters must affect uptake into POCIS, although this influence will be minor. MAX-POCIS and MCX-POCIS showed little advantage over the commercial POCIS configuration for monitoring in natural waters.     

Risk Assessment of 26 Polycyclic Aromatic Hydrocarbon (PAH) Compounds in Parkıng Garages

The aim of this study was to determine the level of 26 polycyclic aromatic hydrocarbons (PAHs) at parking garages and to provide the necessary annual information based on occupational inhalation exposure and non-occupational inhalation exposure, which carry risks for the environment. For this purpose, 22 samples were collected continuously from both gas and particulates phase PAHs from two parking garages at Konya City Center, Turkey. The exposure-based risk of these samples was evaluated using concentrations of the carcinogenic PAH compounds. None of the 26 PAHs measured had values exceeding the recommended exposure limits (RELs) standard values for inhalation rate recommended by the World Health Organization (WHO). Exposure levels of gas and particulate PAHs for the occupational group and the public (children and adults who spend time in shopping centers) were found to be 0.07–28.24 μgm^?3 and 0.05–5.753 μgm^?3, respectively, representing levels two to four times higher than those at the control site. Maximum daily inhalation of B[a]Py was estimated at 1.33 ngd^?1 for exposure of the public and as 274 ngd^?1 for the occupational group. It is believed that traffic makes a substantial contribution to the PAH profile, which had relatively high concentrations of naphthalene (Napth) and coronene (Coro). Highly carcinogenic dibenzo(a,l)pyrene (B[al]Pyre) was found in the ambient air at two parking garages. Napth and phenanthrene (Phen) were the main compounds found in nearly all the tested samples. In this study, benzo[e]pyrene (B[e]Py) was used as a reference for PAHs because its concentration is stable and does not change seasonally. Considering the importance of these compounds in relation to human health, the aim of this work was to characterize and quantify the more toxic PAHs in parking garages. Conducting PAH sampling and their chemical analysis is very costly and labor intensive. This study produced data that can be a powerful tool for environmental forensics.     

A comparison of octanol-water partitioning between organic chemicals and their metabolites in mammals

Bioaccumulation models take various elimination and uptake processes into account, estimating rates from chemical lipophilicity, expressed as the octanol-water partition ratio (K_ow). Here, we focussed on metabolism, which transforms parent compounds into usually more polar metabolites, thus enhancing elimination. The aim of this study was to quantify the change in lipophilicity of relevant organic pollutants undergoing various biotransformation reactions in mammals. We considered oxidation reactions catalyzed by three enzyme groups: cytochrome P450 (CYP), alcohol dehydrogenase (ADH), and aldehyde dehydrogenase (ALDH). Estimated log K_ow values of a selected dataset of parent compounds were compared with the log K_ow of their first metabolites. The log K_ow decreased by a factor that varies between 0 and −2, depending on the metabolic pathway. For reactions mediated by CYP, the decrease in K_ow was one order of magnitude for hydroxylated and epoxidated compounds and two orders of magnitude for dihydroxylated and sulphoxidated xenobiotics. On the other hand, no significant change in lipophilicity was observed for compounds N-hydroxylated by CYP and for alcohols and aldehydes metabolized by ADH and ALDH. These trends could be anticipated by the calculus method of log K_ow. Yet, they were validated using experimental log K_ow values, when available. These relationships estimate the extent to which the elimination of pollutants is increased by biotransformation. Thus, the quantification of the K_ow reduction can be considered as a first necessary step in an alternative approach to anticipate biotransformation rates, which are hard to estimate with existing methods.     

Ozonation of azo dye Acid Red 14 in a microporous tube-in-tube microchannel reactor: decolorization and mechanism

Despite the great success of time-weighted average passive sampling of hydrophobic contaminants, such as PCBs and PAHs, the sampling of polar organic compounds still presents a challenge because the equilibrium between water and most sampling phases is attained in a relatively short time. In this study, we proposed a new time-integrative sampler using in situ solvent extraction (TISIS) for polar organic chemicals. The sampler was composed of a 15 cm poly(dimethylsiloxane) (PDMS) tubing, with an internal diameter of 0.5 mm and wall thickness of 0.5 mm, through which an extraction solvent (acetonitrile) was passed. Four polar organic contaminants, caffeine, atrazine, diuron and 17α-ethynylestradiol, were chosen for the evaluation of the performance of the sampler. Without the use of in situ solvent extraction, the PDMS tubing when exposed to a constant aqueous concentration of the four model compounds was able to linearly accumulate those compounds for less than 12 h and equilibrium between the PDMS tubing and water was attained in 2 d under our laboratory conditions. However, TISIS when exposed to a constant aqueous concentration was able to linearly accumulate all the model compounds without any exposure time limitation. The measured sampling rates at three different extraction flow rates (0.2, 0.5, 1.5 mL min⁻¹) were similar, regardless of the chemicals, indicating that the overall mass transfer from aqueous solution to the extraction solvent was most likely dominated by partitioning to the PDMS tubing and the internal diffusion within PDMS. In addition, a pulsed exposure experiment confirmed that TISIS operated in a time-integrative mode when the environmental concentration was highly fluctuated.     

Comparisons of PCBs dechlorination occurrences in various contaminated sediments

A comparison was made of reductive dechlorination occurrences of polychlorinated biphenyls (PCBs) by microorganisms collected from contaminated sediments including Er-Jen River (Tainan, Taiwan), Hudson River (Ft. Edward, NY), Silver Lake (Pittsfield, MA) and Puget Sound (Washington State). Comparisons was made in terms of chromatographic data (referring to the biological activity, including microbial availability) and thermodynamic data (demonstrating the selectivity of anaerobic microorganisms in the dechlorination of chlorinated compounds). Chromatographic data was established in terms of difference in relative retention time (delta ln RRT) and thermodynamic data was estimated as heat of reaction (delta H(r)0). Both were calculated and correlated to occurrences of dechlorination reactions. Observed dechlorination reactions for individually introducing PCB congener had delta ln RRT levels measured as >0.47 (Er-Jen River), >0.29 (Hudson River), >0.36 (Silver Lake) and >0.45 (Puget Sound, for Aroclor 1254 dechlorination). Critical of delta H(r)0 and delta ln RRT values showed that Hudson River and Silver Lake microorganisms were capable of dechlorinating PCBs through reactions with larger H(r)0 value (lower levels of released energy) and smaller delta ln RRT value compared with those found in Er-Jen River and Puget Sound sediments. Differences in the critical delta ln RRT values of these sediments may be due to differences in their levels of PCB contamination.     

C2–C10 nonmethane hydrocarbons measured in Dallas,USA—Seasonal trends and diurnal characteristics

Nonmethane hydrocarbons (NMHCs) are important precursors of ozone and other photo oxidants. We presented continuous hourly average concentrations of 45 C₂–C₁₀ NMHCs measured in urban area of Dallas, USA from 1996 to 2004. Most of the selected compounds are good variables with less noise. The top 10 species with high ozone-generating potential were identified according to their concentrations and reactivities. The ambient concentrations of abundant anthropogenic emission hydrocarbons measured in Dallas were about 2–4 times of the background values measured in the remote areas with adjacent latitude. The time series for anthropogenic emission hydrocarbons showed an obvious seasonal cycle with relatively high concentration in winter and low concentration in summer. The sinusoidal function with a linearly decreasing factor could well fit the time series of NMHCs. The phase of seasonal cycle for the aromatic hydrocarbons of toluene, m/p xylene and o-xylene that might come from both vehicle emission and solvent utilities evaporation was about 1 month earlier than that for alkanes and alkenes that mainly came from vehicle emission. Ambient NMHCs in Dallas decreased with a stable rate during 1996–2004. For most of compounds with high ozone-generating potential, the rate of ambient concentration decrease was higher or much higher than the rate of volatile organic compounds (VOCs) source emission reduction estimated by EPA's National Emission Inventory. On weekdays, the morning hydrocarbon concentration peak was coincident with morning traffic rush time in Dallas. Another concentration peak was delayed to afternoon traffic rush time. The characteristics of VOCs sources, photochemical removal processes and atmospheric dilution could be interpreted by the diurnal variations of benzene/ethylbenzene (B/E), toluene/ethylbenzene (T/E) and xylene/ethylbenzene (X/E). The ratio of VOC/NO_x measured in Dallas was substantially smaller than that calculated for USA cities. Ozone formation in Dallas was VOC sensitive.     

Effects assessment: boron compounds in the aquatic environment

In previous studies, boron compounds were considered to be of comparatively low toxicity in the aquatic environment, with predicted no effect concentration (PNEC) values ranging around 1 mg B/L (expressed as boron equivalent). In the present study, we describe an evaluation of toxicity data for boron available for the aquatic environment by different methods.For substances with rich datasets, it is often possible to perform a species sensitivity distribution (SSD). The typical outcome of an SSD is the Hazardous Concentration 5% (HC₅), the concentration at which 95% of all species are protected with a probability of 95%. The data set currently available on the toxic effects of boron compounds to aquatic organisms is comprehensive, but a careful evaluation of these data revealed that chronic data for aquatic insects and plants are missing. In the present study both the standard assessment factor approach as well as the SSD approach were applied. The standard approach led to a PNEC of 0.18 mg B/L (equivalent to 1.03 mg boric acid/L), while the SSD approach resulted in a PNEC of 0.34 mg B/L (equivalent to 1.94 mg boric acid/L). These evaluations indicate that boron compounds could be hazardous to aquatic organisms at concentrations close to the natural environmental background in some European regions. This suggests a possible high sensitivity of some ecosystems for anthropogenic input of boron compounds. Another concern is that the anthropogenic input of boron could lead to toxic effects in organisms adapted to low boron concentration.     

What are the sources and conditions responsible for exceedences of the 24 h PM10 limit value (50 μg m−3) at a heavily trafficked London site?

The European Union has set limit values for PM₁₀ to be met in 2005. At Marylebone Road, London, where the traffic is heavy, the daily limit value of 50 μg m⁻³ is exceeded more than 35 times a year. A total of 185 days with daily PM₁₀ concentrations exceeding the limit value of 50 μg m⁻³ measured between January 2002 and December 2004 (data capture of 89.5%) are discussed in this paper. These exceedences were more frequent in early spring and in autumn. Concentrations have been disaggregated into regional, urban (background) and local (street) contributions. Most of the episodes of gravimetric PM₁₀ above the limit value were associated with a high regional background and very often the regional contribution dominated the PM₁₀ mass. The secondary aerosol (especially the particulate nitrate) made a major contribution to the PM₁₀ load. These situations were frequently observed when air masses came from the European mainland (showing that both emissions from the UK and other EU countries contributed to the exceedences), and less frequently with maritime air masses that have stagnated over the UK (showing that emissions from the UK alone less frequently contributed to the high regional background). However, the higher frequency of episodes breaching the limit value at the roadside site than at the rural site and the higher frequency of PM₁₀ concentrations above the limit value on weekdays show that the high regional contributions are additional to local and urban emissions. Local emissions mainly due to traffic were the second important contributor to the exceedences, while the contribution of the urban background of London was less important than the local emissions and the regional background. Applying the pragmatic mass closure model of Harrison et al. [2003. A pragmatic mass closure model for airborne particulate matter at urban background and roadside sites. Atmospheric Environment 37, 4927–4933], revealed that the regional aerosol is comprised very largely of ammonium nitrate and sulphate and secondary organic aerosol. Findings suggest that international abatement of secondary aerosol precursors may be the most effective measure to fulfil the requirements of the European Directive 1999/30/CE by lowering the regional background.     

The diffusion and sorption of volatile organic compounds through kaolinitic clayey soils

Laboratory experiments to estimate the effective molecular diffusion coefficient (D(e)) and sorption coefficient (K(d)) for volatile organic compounds through natural clayey soils were conducted using diffusion testing apparatus. The compounds tested were methyl ethyl ketone (MEK), toluene and trichloroethylene (TCE). The D(e) and K(d) values were determined by a curve fitting procedure. The compound losses, and the effects of porous disks used in the apparatus were significant. The transport of MEK was faster than that of TCE and toluene because of the lower sorption to the soils. The D(e) values of all the compounds were of the order of 10(-10) m(2)/s and smaller than the diffusion coefficient in pure aqueous solution at infinite dilution (D(0)), due to the tortuosity of the samples. The effects of the sample thickness on the parameter determination were not significant. Comparison to the K(d) values estimated from batch sorption tests and from organic carbon content (f(oc))-based predictions showed that the diffusion test results were intermediate between those from the other two methods. The diffusion tests use compacted soil samples and should be more relevant to in situ conditions, but the reliability of the tests is affected by large compound losses that cause uncertainties in their interpretation. It is recommended that more than one method be used to assess K(d) values.     

Impact of proposed changes in IESTI equations for short-term dietary exposure to pesticides from Australian and Codex perspective

ABSTRACT

In 2015 a scientific workshop was held in Geneva, where updating the four equations for estimating the short-term dietary exposure (International Estimated Short Term Intake, IESTI) to pesticides was suggested. The impact of these proposed changes on the exposure was studied by using residue data and large portion consumption data from Codex and Australia. For the Codex data, the exposure increased by a median factor of 2.5 per commodity when changing to the proposed IESTI equations. The increase in exposure was highest for bulked and blended food commodities (case 3 equations), followed by medium-sized food commodities (case 2a equations) and small- and large-sized food commodities (case 1 and case 2b equations). For the Australian data, out of 184 maximum residue limit (MRL) large portion combinations showing acute exposures below the acute reference dose (ARfD) with the current IESTI equations, 23 exceeded the ARfD with the proposed IESTI equations (12%). The percentage exceeding the ARfD was higher for the Australian MRL large portion combinations (12% of 184) than for those of Codex (1.3% of 8,366). However, the percentage MRL loss in the Australian dataset may not be representative of all pesticide MRLs since it concerns six pesticides only, specifically selected to elucidate the potential effects of the use of the proposed IESTI equations. For the Codex data, the increase in exposure using the proposed equations resulted in a small increased loss of 2.6% of the 1,110 MRLs estimated by the Joint FAO/WHO Meeting on Pesticide Residues (JMPR): 1.4% of the MRLs were already not acceptable with the current equations, 4.0% of the MRLs were not acceptable with the newly proposed equations. Our study revealed that case 3 commodities may be impacted more by the proposed changes than other commodities. This substantiates one of the conclusions of the Geneva workshop to gather information on bulking and blending practices in order to refine MRL setting and dietary risk assessment for case 3 commodities where possible.     

Partitioning of organochlorine pesticides from water to polyethylene passive samplers

The mass transfer rates and equilibrium partitioning behaviour of 14 diverse organochlorine pesticides (OCP) between water and polyethylene (PE) passive samplers, cut from custom made PE sheets and commercial polyethylene plastic bags, were quantified. Overall mass transfer coefficients, k_O, estimated PE membrane diffusion coefficients, D_PE, and PE-water partitioning coefficients, K_PE-water, are reported. In addition, the partitioning of three polycyclic aromatic hydrocarbons (PAHs) from water to PE is quantified and compared with literature values. K_PE-water values agreed mostly within a factor of two for both passive samplers and also with literature values for the reference PAHs. As PE is expected to exhibit similar sorption behaviour to long-chain alkanes, PE-water partitioning coefficients were compared to hexadecane-water partitioning coefficients estimated with the SPARC online calculator, COSMOtherm and a polyparameter linear free energy relationship based on the Abraham approach. The best correlation for all compounds tested was with COSMOtherm estimated hexadecane-water partitioning coefficients.     

Size distribution of polycyclic aromatic hydrocarbons in a roadway tunnel in Lisbon, Portugal

Atmospheric aerosols of four aerodynamic size ranges were collected using high volume cascade impactors in an extremely busy roadway tunnel in Lisbon (Portugal). Dust deposited on the tunnel walls and guardrails was also collected. Average particle mass concentrations in the tunnel atmosphere were more than 30 times higher than in the outside urban background air, revealing its origins almost exclusively from fresh vehicle emissions. Most of the aerosol mass was concentrated in submicrometer fractions (65%), and polycyclic aromatic hydrocarbons (PAH) were even more concentrated in the finer particles with an average of 84% of total PAH present in sizes smaller than 0.49 μm. The most abundant PAH were methylated phenanthrenes, fluoranthene and pyrene. About 46% of the total PAH mass was attributed to lower molecular weight compounds (two and three rings), suggesting a strong influence of diesel vehicle emissions on the production of local particulate PAH. The application of diagnostic ratios confirmed the relevance of this source of PAH in the tunnel ambient air. Deposited dust presented PAH profiles similar to the coarser aerosol size range, in agreement with the predominant origin of coarser aerosol particles from soil dust resuspension and vehicle wear products.     

Residences with anomalous soil concentrations of dioxin-like compounds in two communities in Michigan, USA: a case study

Most contamination of residential property soil with dioxin-like compounds occurs as a result of proximity to industrial activity that produces such compounds and, outside the industrially impacted zone, the soil concentrations are at background levels. However, as part of the University of Michigan Dioxin Exposure Study, residential properties in the lower peninsula of Michigan, USA, were identified that were located far enough from known sources of these compounds that the soil concentrations should have been at background levels and yet the toxic equivalent (TEQ) of some properties' soil was greater than 2.5 standard deviations above the mean background level. In the three cases presented here from Midland/Saginaw Counties, the anomalously high-TEQ values were primarily due to the presence of polychlorinated dibenzofurans. Based on interviews with the residents and a comparison of soil congener profiles, it was deduced that these values resulted from anthropogenic soil movement from historically contaminated areas. In the cases from Jackson/Calhoun Counties, the unusually high-TEQ values were primarily due to polychlorinated biphenyls. In the case profiled here, it appears that the soil became contaminated through sandblasting to remove paint from the swimming pool. This study identified two mechanisms for soil contamination outside zones of industrial impact; thus, an assumption of background levels of soil contamination outside industrial zones may not be valid.     

Monitoring of dust emission on gravel roads: Development of a mobile methodology and examination of horizontal diffusion

Traffic-generated fugitive dust on gravel roads impairs visibility and deposits on the adjacent environment. Particulate matter smaller than 10 μm in diameter (PM₁₀) is also associated with human health problems. Dust emission strength depends on the composition of granular material, road moisture, relative humidity, local climate (precipitation, wind velocity, etc.), and vehicle characteristics.The objectives of this study were to develop a reliable and rapid mobile methodology to measure dust concentrations on gravel roads, evaluate the precision and repeatability of the methodology and correspondence with the currently used visual assessment technique. Downwind horizontal diffusion was studied to evaluate the risk of exceeding the maximum allowed particulate matter concentration in ambient air near gravel roads according to European Council Directive [European Council Directive 1999/30/EC of 22 April 1999 relating to limit values for sulphur dioxide, nitrogen dioxide and oxides of nitrogen, particulate matter and lead in ambient air. Official Journal of the European Communities. L163/41.].A TSI DustTrak Aerosol Monitor was mounted on an estate car travelling along test sections treated with various dust suppressants. Measured PM₁₀ concentrations were compared to visual assessments performed at the same time. Airborne particles were collected in filters mounted behind the vehicle to compare the whole dust fraction with the PM₁₀ concentration. For measuring the horizontal diffusion, DustTraks were placed at various distances downwind of a dusty road section.The mobile methodology was vehicle and speed dependent but not driver dependent with pre-specified driving behaviours. A high linear correlation between PM₁₀ of different vehicles makes relative measurements of dust concentrations possible. The methodology gives continuous data series, mobility, and easy handling and provides fast, reliable and inexpensive measurements for estimating road conditions to make road maintenance more efficient.Good correlations between measured PM₁₀-values, visually assessed dust generation and dust collected in filters were obtained. PM₁₀ seems to be correlated to the whole dust fraction that impairs visibility on gravel roads.A decay in PM₁₀ concentration as a function of distance from the road was observed. Measured particles principally did not travel further than 45 m from the road. The risk of exceeding the PM₁₀ concentration stated in the EC-directive seems small.     

Influence of dispersants on bioconcentration factors of seven organic compounds with different lipophilicities and structures

Seven compounds with different lipophilicities and structures—1,3,5-trichlorobenzene, pentachlorobenzene, acenaphthylene, 1,4-dimethyl-2-(1-methylphenyl)benzene, 4-ethylbiphenyl, 4,4′-dibromobiphenyl, and 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane—were subjected to bioconcentration tests in carp at concentrations below the water solubilities of the compounds in the presence or absence of a dispersant (either an organic solvent or a surfactant). The bioconcentration factors (BCFs) of the compounds were on the order of 10²–10⁴. The BCF values remained in the range of 15–49% for all the compounds, whether or not a dispersant was present, i.e., the BCF values in the presence of an organic solvent or a surfactant at a concentration below the critical micelle concentration were not significantly smaller than the BCF values in the absence of the solvent or surfactant. This result indicates that the dispersants had no influence on the evaluation of the bioconcentration potential of these test substances.     

Particle-size distribution and gas/particle partitioning of atmospheric polybrominated diphenyl ethers in urban areas of Greece

Ambient concentrations, gas/particle partitioning and particle-size distribution of polybrominated diphenyl ethers (PBDEs) were investigated in two urban areas (Athens and Heraklion) of Greece. Atmospheric (gas + particle) concentrations of ∑PBDE varied from 21 to 30 pg m⁻³ in the center of Athens and from 4 to 44 pg m⁻³ in the suburbs of Heraklion. A predominance of particulate PBDEs was observed in Athens (71-76% in particles), whereas the opposite was evident in Heraklion (69-92% in gas phase). In both urban areas, PBDE particle-size distribution featured a distinct enrichment in smaller particles. A similar trend was also observed in aerosols of a background marine site. For all sampling sites, more than 46% of ∑PBDE was associated with particles of <0.57 μm in diameter. Our results imply that particulate PBDEs may have long atmospheric residence time and they may be capable of reaching the deeper parts of the human respiratory system.     

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30 degrees dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.