Study of the effects of particle-phase carbon on the gas/particle partitioning of semivolatile organic compounds in the atmosphere using controlled field experiments

A controlled field experiment (CFE) methodology with a filter/sorbent sampler was used to minimize artifact effects when measuring values of the gas/particle (G/P) partitioning constant (Kp, m3 microg(-1)) for semivolatile organic compounds (SOCs) in the atmosphere. CFE sampling was conducted at three different locations (Beaverton, OR; Denver, CO; and Hills, IA). Kp values were measured for a series of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs). To examine the possible effects on the G/P partitioning of the amounts of organic material (om) phase, organic carbon (OC), and elemental carbon (EC) in the sampled particulate material, the measured Kp values were normalized by the aerosol mass fractions f(om), f(OC), and f(EC) according to Kp/ f(om), Kp/f(OC), and Kp/f(EC). Using a log-log format, the resulting normalized values were all found to be more highly correlated with the subcooled liquid vapor pressure p(L)o than were the unnormalized Kp values. For the PAHs,the one-parameter model assuming Kp = Kp,OC f(OC) yielded only slightly less variability in the predicted Kp values than did the one-parameter model Kp = Kp,EC f(EC). The two-parameter model Kp = Kp,OC f(OC) + Kp,EC f(EC) was found to provide only small improvements over each of the one-parameter models. Overall, the data are more consistent with an absorptive mechanism of partitioning to the particulate material but do not rule out some role for adsorption to particle surfaces. The data suggest that small amounts of organic carbon (f(OC) approximately 0.02) can have significant effects on the G/P partitioning of SOCs.     

Herbicide sorption to fine particulate matter suspended downwind of agricultural operations: field and laboratory investigations

Tillage-induced erosion of herbicides bound to airborne soil particles has not been quantified as a mechanism for offsite herbicide transport. This study quantifies the release of two preemergent herbicides, metolachlor and pendimethalin, to the atmosphere as gas- and particle-phase species during soil incorporation operations. Fine particulate matter (PM2.5) and gas-phase samples were collected at three sampling heights during herbicide disking into the soil in Davis, CA, in May 2000 and May 2001 using filter/PUF sampling. Quartz fiber filters (QFFs) were used in May 2000, and Teflon membrane filters (TMFs) were used in May 2001. The field data were combined with laboratory filter/PUF partitioning experiments to account for adsorption to the filter surfaces and quantify the mass of PM2.5-bound herbicides in the field samples. Laboratory results indicate a significant adsorption of metolachlor, but not pendimethalin, to the quartz filter surfaces. Metolachlor partitioning to PM2.5 collected on TMF filters resulted in corrected PM2.5 field partition coefficient values, Kp,corr = Cp/Cg, of approximately 10(-3.5) m3/microg, indicating its preference for the gas phase. Pendimethalin exhibited more semivolatile behavior,with Kp,corr values that ranged from 10(-3) to 10(-1) m3/ microg and increased with sampling height and distance downwind of the operation. An increase in pendimethalin enrichment at a height of 5 m suggests winnowing of finer, more sorptive soil components with corresponding higher transport potential. Pendimethalin was enriched in the PM2.5 samples by up to a factor of 250 compared to the field soil, indicating thatfurther research on the processes controlling the generation of PM-bound herbicides during agricultural operations is warranted to enable prediction of off-site mass fluxes by this mechanism.     

Gas-particle partitioning of semivolatile organic compounds (SOCs) on mixtures of aerosols in a smog chamber

The partitioning behavior of a set of diverse SOCs on two and three component mixtures of aerosols from different sources was studied using smog chamber experimental data. A set of SOCs of different compound types was introduced into a system containing a mixture of aerosols from two or more sources. Gas and particle samples were taken using a filter-filter-denuder sampling system, and a partitioning coefficient Kp was estimated using Kp = Cp/(CgTSP). Particle size distributions were measured using a differential mobility analyzer and a light scattering detector. Gas and particle samples were analyzed using GCMS. The aerosol composition in the chamber was tracked chemically using a combination of signature compounds and the organic matter mass fraction (f(om)) of the individual aerosol sources. The physical nature of the aerosol mixture in the chamber was determined using particle size distributions, and an aggregate Kp was estimated from theoretically calculated Kp on the individual sources. Model fits for Kp showed that when the mixture involved primary sources of aerosol, the aggregate Kp of the mixture could be successfully modeled as an external mixture of the Kp on the individual aerosols. There were significant differences observed for some SOCs between modeling the system as an external and as an internal mixture. However, when one of the aerosol sources was secondary, the aggregate model Kp required incorporation of the secondary aerosol products on the preexisting aerosol for adequate model fits. Modeling such a system as an external mixture grossly overpredicted the Kp of alkanes in the mixture. Indirect evidence of heterogeneous, acid-catalyzed reactions in the particle phase was also seen, leading to a significant increase in the polarity of the resulting aerosol mix and a resulting decrease in the observed Kp of alkanes in the chamber. The model was partly consistent with this decrease but could not completely explain the reduction in Kp because of insufficient knowledge of the secondary organic aerosol composition.     

Evidence of bias in air-water Henry's law constants for semivolatile organic compounds measured by inert gas stripping

Accurate knowledge of the air-water Henry's law constant (H) is crucial for understanding an organic compound's environmental behavior. The inert gas stripping (IGS) method, widely used to measure H of semivolatile organic compounds (SOCs), may yield erroneously high values for compounds with a high water surface adsorption coefficient, K(IA), because chemical adsorbed to the bubble surface may be transferred to the head space upon bursting at the top of the stripping column. Experiments with alkanols of variable chain length identified a K(IA) threshold of approximately 10(-3) m, above which IGS is susceptible to this artifact. Most SOCs are predicted to have K(IA) values well above that threshold. IGS-determined H-values for chemicals belonging to various groups of SOCs were evaluated by comparison with H-values either calculated from reliable vapor pressure and solubility data or derived from data compilations that achieve thermodynamic consistency through optimized adjustment of measured physical-chemical property data. The investigated deviations were found to be generally consistent with what would be expected from a surface adsorption artifact. Namely, the apparent bias in IGS-determined H-values, if it occurs, (1) is positive, (2) increases with increasing size of an SOC, and (3) increases with decreasing temperature. It generally is also of a magnitude predicted using estimated K(IA) values. However, different studies display different K(IA) threshold values, beyond which the artifact becomes notable, and some studies appear to succeed in avoiding the artifact altogether. Whereas the use of aerosol traps cannot explain the absence of a surface adsorption artifact, it may be related to higher flow rates used by some investigators. For large compounds or those with more than one functional group, the predicted deviation is too large when compared to observations, suggesting that the estimated K(IA) values for those compounds are too high. A full quantitative understanding of the artifact requires more accurate predictions of the adsorption of SOCs to the water surface.     

Effects of sampling artifacts on occupational samples of diesel particulate matter

Total carbon (TC) is sometimes used to measure or characterize diesel particulate matter (DPM) in occupational settings such as underground mines. DPM samples are collected on quartz fiber filters. When using quartz fiber filters, adsorption of gas phase organic carbon (OC) has been reported, causing a positive bias in the particulate TC results (adsorption artifact). Most of the data on the sampling artifacts and corrections applyto environmental air sampling, where samples are collected at a much higher filter face velocity and the OC concentrations are generally much lower relative to occupational sampling. In this study, we investigated the effects of adsorption artifact on samples from occupational settings. Samples were collected with and without denuders to determine the amount of gas phase OC collected and the accuracy of certain corrections. In underground stone mines, the adsorption artifact was found to positively bias the particulate TC by greater than 20% for filter loadings below 25 microg/cm2 TC (8-h time weighted average = 262 microg/m3). The tandem filter correction reduced the effect of the artifact, as high as 60% of the TC value, to less than 11% for laboratory data. It also significantly reduced the effect of the artifact obtained for field samples.     

Sampling atmospheric carbonaceous aerosols using an integrated organic gas and particle sampler

Measurement of particle-bound organic carbon (OC) may be complicated by sampling artifacts such as adsorption of gas-phase species onto particles or filters or evaporation of semivolatile compounds off the particles. A denuder-based integrated organic gas and particle sampler (IOGAPS), specifically designed to minimize sampling artifacts, has been developed to sample atmospheric carbonaceous aerosols. IOGAPS is designed to first remove gas-phase chemicals via sorption to the XAD-coated denuder, and subsequently particles are trapped on a quartz filter. A backup sorbent system consisting of sorbent- (XAD-4 resin) impregnated filters (SIFs) was used to capture the semivolatile OC that evaporates from the particles accumulated on the upstream quartz filter. A traditional filter pack (FP) air sampler, which uses a single quartz filter to collect the particles, was employed for comparison in this study. Elemental and organic carbon were determined from filter punches by a thermal optical transmittance aerosol carbon analyzer. Field measurements show that there was no significant difference between the elemental carbon concentrations determined by the FP and IOGAPS, indicating that particle loss during the transit through the denuder tube was negligible. Compared with the OC determined by FP (3.9-12.6 microg of C/m3), the lower OC observed on the quartz filter in the IOGAPS (2.2-6.0 microg of C/m3) was expected because of the removal of gas-phase organics by the denuder. Higher semivolatile organic carbon (SVOC) on the backup SIFs during the night (1.24-8.43 microg of C/m3) suggests that more SVOC, emitted from primary sources or formed as secondary organic compounds, partitions onto the particles during the night because of the decreased ambient temperature. These data illustrate the utility of an IOGAPS system to more accurately determine the particle-bound OC in comparison to FP-based systems.     

Development and evaluation of a personal particulate organic and mass sampler

Accurate measurement of personal exposure to particulate matter and its constituents requires samplers that are accurate, compact, lightweight, inexpensive, and convenient to use. The personal particulate organic and mass sampler (PPOMS) has been developed to meet these criteria. The PPOMS uses activated carbon-impregnated foam as a combined 2.5-microm size-selective inlet and denuder for assessment of fine particle mass and organic carbon. Proof of the PPOMS concept has been established by comparing mass and organic carbon in particles collected with collocated samplers in Seattle, at a central outdoor site, and in residences. Daily particulate mass concentrations averaged 10.0 +/- 5.2, 12.0 +/- 5.3, and 11.2 +/- 5.1 microg m(-3) for the Federal Reference Method, the Harvard Personal Exposure Monitor, and the PPOMS, respectively, for 10 24-h sampling periods. During a series of PM2.5 indoor organic carbon (OC) measurements from single quartz filters, the apparent indoor OC averaged 7.7 +/- 0.8 microg of C m(-3), which was close to the indoor PM2.5 mass from collocated Teflon filters (7.3 +/- 2.3 microg of C m(-3)), indicating the presence of a large positive OC artifact. In collocated measurements, the PPOMS eliminated this artifact just as well as the integrated gas and particle sampler that incorporated a macroreticular polystyrene-divinylbenzene (XAD-4) resin-coated denuder, yielding OC concentrations of 2.5 +/- 0.4 and 2.4 +/- 1.0 microg of C m(-3), respectively. Thermal analysis for OC indicated that the indoor positive artifact was due to adsorption of gas-phase semivolatile organic compounds (SVOC). This study shows that the PPOMS design provides a 2.5-microm size-selective inlet that also prevents the adsorption of gas-phase SVOC onto quartz filters, thus eliminating the filter positive artifact The PPOMS meets a significant current challenge for indoor and personal sampling of particulate organic carbon. The PPOMS design can also simplify accurate ambient sampling for PM2.5.     

Filter and electrostatic samplers for semivolatile aerosols: physical artifacts

Adsorptive and evaporative artifacts often bias measurements of semivolatile aerosols. Adsorption occurs when the sampling method disrupts the gas-particle partitioning equilibrium. Evaporation occurs because concentrations of semivolatiles are rarely constant over time. Filtration is subject to both adsorptive and evaporative artifacts. By comparison, electrostatic precipitation reduces these artifacts by minimizing the surface area of collected particles without substantially disrupting the gas-particle equilibrium. The extent of these artifacts was determined for filter samplers and electrostatic precipitator samplers for semivolatile alkane aerosols in the laboratory. Adsorption of gas-phase semivolatiles was lower in electrostatic precipitators by factors of 5-100 compared to the filter method. Particle evaporation from the electrostatic sampler was 2.3 times lower than that from TFE-coated glass-fiber filters. Use of a backup filter to correct for compound-specific adsorption artifacts can introduce positive or negative errors to the measured particle-phase concentration due to competition among the adsorbates for available adsorption sites. Adsorption of evaporated particles from the front filter onto the backup filter increased the measured evaporative artifact by a factor of 1.5-2.     

Gas-particle partitioning of polycyclic aromatic hydrocarbons in urban, adjacent coastal, and continental background sites of western Greece

Particle- and gas-phase polycyclic aromatic hydrocarbons (PAHs) were collected from an urban, an adjacent coastal, and a continental background site located in Eordea basin, western Greece, to investigate their gas/ particle distributions. Thirteen two- to six-ring PAHs, included in the U.S. EPA priority pollutant list, were determined in 24-h integrated glass fiber filters and polyurethane foam samples. At the prevailing ambient temperature levels, the three-ringed species (phenanthrene, anthracene) and the four-ringed fluoranthene and pyrene were primarily found in the gas phase. Conversely, the five- and six-ring PAHs were mainly associated with the particle phase. Gas/particle partitioning coefficients, Kp, were calculated, and their relationship with the subcooled liquid vapor pressure p degrees L of individual PAHs was investigated. Despite the large variability among samples, a good linear relationship between log Kp and log p degrees L was obtained for all sampling sites following the equation log Kp = m(r) log p degrees L + b(r). In the majority of sampling events, particularly in the adjacent coastal and the continental background sites, slopes (m(r)) were found to be shallower than the value of -1, which has been suggested as reflecting equilibrium partitioning. The deviations from predicted aerosol behavior observed in the present study may be attributed to several reasons, such as the presence of nonexchangeable PAH fraction, nonequilibrium as well as different particle characteristics.     

Organic/inorganic hybrid filters based on dendritic and cyclodextrin "nanosponges" for the removal of organic pollutants from water

Long-alkyl chain functionalized poly(propylene imine) dendrimer, poly(ethylene imine) hyperbranched polymer, and beta-cyclodextrin derivatives, which are completely insoluble in water, have the property of encapsulating organic pollutants from water. Ceramic porous filters can be impregnated with these compounds resulting in hybrid organic/ inorganic filter modules. These hybrid filter modules were tested for the effective purification of water, by continuous filtration experiments, employing a variety of water pollutants. It has been established that polycyclic aromatic hydrocarbons (PAHs) can be removed very efficiently (more than 95%), and final concentrations of several ppb (microg/ L) are easily obtained. Representatives of the pollutant group of trihalogen methanes (THMs), monoaromatic hydrocarbons (BTX), and pesticides (simazine) can also be removed (>80%), although the filters are saturated considerably faster in these cases.     

Trophic dilution of polycyclic aromatic hydrocarbons (PAHs) in a marine food web from Bohai Bay, north China

Trophic transfer of polycyclic aromatic hydrocarbons (PAHs) in aquatic ecosystems is an important criterion for assessing their ecological risk. This study analyzed 18 PAHs in phytoplankton/seston, zooplankton, five invertebrate species, five fish species, and one seabird species collected from Bohai Bay, and trophic transfer of the PAHs was determined in the food web, of which the length was approximately 4 on the basis of stable nitrogen isotope values. The concentrations of PAHs (2-64.5 ng/g wet weight) in the marine ecosystem were moderate compared with other marine organisms worldwide, and the PAH compositions exhibited species-specific profiles that were related to trophic levels in some organisms. Significant negative relationships were also found between trophic levels and lipid-normalized concentrations for 10 PAH compounds (acenaphthylene, anthracene, fluoranthene, pyrene, chrysene, benz[a]anthracene, benzo[b]fluoranthene + benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, and perylene), and their trophic magnification factors (TMFs) ranged from 0.11 for fluoranthene to 0.45 for acenaphthylene. These results confirm that PAHs undergo trophic dilution in the marine food web, which is likely to be the combined results of low assimilation efficiencies and efficient metabolic transformation at higher trophic levels.     

Comparison of lichen, conifer needles, passive air sampling devices, and snowpack as passive sampling media to measure semi-volatile organic compounds in remote atmospheres

A wide range of semivolatile organic compounds (SOCs), including pesticides and polycyclic aromatic hydrocarbons (PAHs), were measured in lichen, conifer needles, snowpack and XAD-based passive air sampling devices (PASDs) collected from 19 different U.S. national parks in order to compare the magnitude and mechanism of SOC accumulation in the different passive sampling media. Lichen accumulated the highest SOC concentrations, in part because of its long (and unknown) exposure period, whereas PASDs accumulated the lowest concentrations. However, only the PASD SOC concentrations can be used to calculate an average atmospheric gas-phase SOC concentration because the sampling rates are known and the media is uniform. Only the lichen and snowpack SOC accumulation profiles were statistically significantly correlated (r = 0.552, p-value <0.0001) because they both accumulate SOCs present in the atmospheric particle-phase. This suggests that needles and PASDs represent a different composition of the atmosphere than lichen and snowpack and that the interpretation of atmospheric SOC composition is dependent on the type of passive sampling media used. All four passive sampling media preferentially accumulated SOCs with relatively low air-water partition coefficients, while snowpack accumulated SOCs with higher log K(OA) values compared to the other media. Lichen accumulated more SOCs with log K(OA) > 10 relative to needles and showed a greater accumulation of particle-phase PAHs.     

Modeling the formation of secondary organic aerosol (SOA). 2. The predicted effects of relative humidity on aerosol formation in the alpha-pinene-, beta-pinene-, sabinene-, delta 3-carene-, and cyclohexene-ozone systems

Atmospheric oxidation of volatile organic compounds can lead to the formation of secondary organic aerosol (SOA) through the gas/particle (G/P) partitioning of the oxidation products. Since water is ubiquitous in the atmosphere, the extent of the partitioning for any individual organic product depends not only on the amounts and properties of the partitioning organic compounds, but also on the amount of water present. Predicting the effects of water on the atmospheric G/P distributions of organic compounds is, therefore, central to understanding SOA formation. The goals of the current work are to gain understanding of how increases in RH affect (1) overall SOA yields, (2) water uptake by SOA, (3) the behaviors of individual oxidation products, and (4) the fundamental physical properties of the SOA phase that govern the G/P distribution of each of the oxidation products. Part 1 of this series considered SOA formation from five parent hydrocarbons in the absence of water. This paper predicts how adding RH to those systems uniformly increases both the amount of condensed organic mass and the amount of liquid water in the SOA phase. The presence of inorganic components is not considered. The effect of increasing RH is predicted to be stronger for SOA produced from cyclohexene as compared to SOA produced from four monoterpenes. This is likely a result of the greater general degree of oxidation (and hydrophilicity) of the cyclohexene products. Good agreement was obtained between predicted SOA yields and laboratory SOA yield data actually obtained in the presence of water. As RH increases, the compounds that play the largest roles in changing both the organic and water masses in the SOA phase are those with vapor pressures that are intermediate between those of essentially nonvolatile and highly volatile species. RH-driven changes in the compound-dependent G/P partitioning coefficient Kp result from changes in both the average molecular weight MWom of the absorbing organic/water phase, and the compound-dependent activity coefficient zeta values. Adding water to the SOA phase by increasing the RH drives down MWom and thereby uniformly favors SOA condensation. The effect of RH on zeta values is compound specific and depends on the hydrophilicity of the specific compound of interest; the more hydrophilic a compound, the more increasing RH will favor its condensation into the SOA phase. The results also indicate that it may be a useful first approximation to assume that zeta = 1 for many compounds making up SOA mixtures.     

Trace analysis of semivolatile organic compounds in large volume samples of snow, lake water, and groundwater

An analytical method was developed for the trace analysis of a wide range of semivolatile organic compounds (SOCs) in 50-L high-elevation snow and lake water samples. The method was validated for 75 SOCs from seven different chemical classes (polycyclic aromatic hydrocarbons, organochlorine pesticides, amides, triazines, polychlorinated biphenyls, thiocarbamates, and phosphorothioates) that covered a wide range of physical-chemical properties including 7 orders of magnitude of octanol-water partition coefficient (log K(ow) = 1.4-8.3). The SOCs were extracted using a hydrophobically and hydrophilically modified divinylbenzene solid-phase extraction device (modified Speedisk). The average analyte recovery from 50 L of reverse osmosis water, using the modified Speedisk, was 99% with an average relative standard deviation of 4.8%. Snow samples were collected from the field, melted, and extracted using the modified Speedisk and a poly(tetrafluoroethylene) remote sample adapter in the laboratory. Lake water was sampled, filtered, and extracted in situ using an Infiltrex 100 fitted with a 1-microm glass fiber filter to trap particulate matter and the modified Speedisk to trap dissolved SOCs. The extracts were analyzed by gas chromatographic mass spectrometry with electron impact ionization and electron capture negative ionization using isotope dilution and selective ion monitoring. Estimated method detection limits for snow and lake water ranged from 0.2 to 125 pg/L and 0.5-400 pg/L, respectively. U.S. historic and current-use pesticides were identified and quantified in snow and lake water samples collected from Rocky Mountain National Park, CO. The application of the analytical method to the analysis of SOCs in large-volume groundwater samples is also shown.     

Pesticide adsorption by granular activated carbon adsorbers. 1. Effect of natural organic matter preloading on removal rates and model simplification

The adsorptive removal of periodic spikes of the trace synthetic organic chemicals (SOCs) simazine and asulam from water containing natural organic matter (NOM) was studied in pilot-scale granular activated carbon (GAC) adsorbers over a period of nearly 3 years. The SOC removal percentage obtained at any preloading time and bed depth was independent of the liquid-phase SOC concentration, and equations derived from the ideal adsorbed solution theory and a pore surface diffusion model validated this observation. The pseudo-steady-state SOC removal rate, (dC/dz), at each preloading time and bed depth was therefore first order with respectto the liquid-phase SOC concentration, C. Furthermore, the removal modulus, k, in the resulting SOC removal rate expression was a reflection of the solid-phase concentration of the NOM fraction that interfered with the adsorption of SOCs. Analysis of the removal modulus values indicated that the mass transfer zone of the NOM fraction competing with asulamtraveled more rapidlythrough the GAC adsorber than that competing with simazine. Given the similar molecular sizes of the targeted SOCs, this result was primarily explained by differences in SOC adsorbabilities, where the more weakly adsorbing asulam was less capable of displacing preloaded NOM. Consequently, the NOM fraction competing with asulam constituted a larger percentage of the total NOM than that competing with simazine.     

Reduction of polycyclic aromatic hydrocarbons in common carp meat smoked in traditional conditions

Common carp meat was smoked in traditional conditions without filter and with zeolite, granular activated carbon, and gravel filters. The aim of this study was to determine the influence of using different filters in traditional smoking conditions on 16 polycyclic aromatic hydrocarbons from the Environmental Protection Agency list (16 US-EPA PAHs). Determination and quantification of PAHs were performed by gas chromatography–mass spectrometry (GC-MS). According to the obtained results, all examined samples of common carp meat smoked in traditional conditions were safe for consumers regarding to the European Commission Regulation on PAH content. After statistical analysis, the zeolite filter appeared to be the best one based on food safety of traditional production of smoked common carp meat. Application of any of these filters to produce smoked common carp meat in traditional conditions resulted in a safer product, as lower levels of PAHs were obtained.     

Occurrence of some organic UV filters in wastewater, in surface waters, and in fish from Swiss Lakes

Organic UV filters are used in personal care products such as sunscreen products, and in cosmetics, beauty creams, skin lotions, lipsticks, hair sprays, hair dyes, shampoos, and so forth. The compounds enter the aquatic environmentfrom showering, wash-off, washing (laundering), and so forth via wastewater treatment plants (WWTPs) ("indirect inputs") and from recreational activities such as swimming and bathing in lakes and rivers ("direct inputs"). In this study, we investigated the occurrence of four important organic UV filter compounds (benzophenone-3, BP-3; 4-methylbenzylidene camphor, 4-MBC; ethylhexyl methoxy cinnamate, EHMC; octocrylene, OC) in wastewater, and in water and fish from various Swiss lakes, using gas chromatographic/mass spectrometric analyses. All four UV filters were present in untreated wastewater (WWTP influent) with a maximum concentration of 19 microg L(-1) for EHMC. The data indicate a seasonal variation with influent loads higher in the warmer season (June 2002) than in the colder one (April 2002). The influent loads were in the order EHMC > 4-MBC approximately BP-3 > OC. The concentrations in treated wastewater (WWTP effluent) were considerably lower, indicating substantial elimination in the plants. 4-MBC was usually the most prevalent compound (maximum concentration, 2.7 microg L(-1)), followed by BP-3, EHMC, and OC. UV filters were also detected in Swiss midland lakes and a river (Limmat) receiving inputs from WWTPs and recreational activities. However, all concentrations were low (<2-35 ng L(-1)); no UV filters (<2 ng L(-1)) were detected in a remote mountain lake. Data from passive sampling using semipermeable membrane devices (SPMDs) supported the presence of these UV filters in the lakes and the river and suggested some potential for accumulation of these compounds in biota. SPMD-derived water concentrations increased in the order Greifensee < Zürichsee < Hüttnersee. This order is reversed from that observed for methyl triclosan, used as a chemical marker for WWTP-derived lipophilic contaminants in the lakes. This indicated inputs of UV filters from sources other than WWTPs to the lakes during summer,for example,inputs from recreational activities. Fish (white fish, Coregonus sp.; roach, Rutilus rutilus; perch, Perca fluviatilis) from these lakes contained low but detectable concentrations of UV filters, in particular, 4-MBC (up to 166 ng g(-1) on a lipid basis). 4-MBC concentrations relative to methyl triclosan were lower in fish than in SPMDs exposed in the same lakes, suggesting that 4-MBC is less bioaccumulated than expected or metabolized in fish. The lipid-based bioconcentration factor (BCF(L)) estimated from the fish (roach) data and SPMD-derived water concentrations was about 1-2.3 x 10(4) and thus approximately 1 order of magnitude lower than expected from its Kow value.     

Virus removal in ceramic depth filters based on diatomaceous earth

Ceramic filter candles, based on the natural material diatomaceous earth, are widely used to purify water at the point-of-use. Although such depth filters are known to improve drinking water quality by removing human pathogenic protozoa and bacteria, their removal regarding viruses has rarely been investigated. These filters have relatively large pore diameters compared to the physical dimension of viruses. However, viruses may be retained by adsorption mechanisms due to intermolecular and surface forces. Here, we use three types of bacteriophages to investigate their removal during filtration and batch experiments conducted at different pH values and ionic strengths. Theoretical models based on DLVO-theory are applied in order to verify experimental results and assess surface forces involved in the adsorptive process. This was done by calculation of interaction energies between the filter surface and the viruses. For two small spherically shaped viruses (MS2 and PhiX174), these filters showed no significant removal. In the case of phage PhiX174, where attractive interactions were expected, due to electrostatic attraction of oppositely charged surfaces, only little adsorption was reported in the presence of divalent ions. Thus, we postulate the existence of an additional repulsive force between PhiX174 and the filter surface. It is hypothesized that such an additional energy barrier originates from either the phage's specific knobs that protrude from the viral capsid, enabling steric interactions, or hydration forces between the two hydrophilic interfaces of virus and filter. However, a larger-sized, tailed bacteriophage of the family Siphoviridae was removed by log 2 to 3, which is explained by postulating hydrophobic interactions.     

Secondary effects of catalytic diesel particulate filters: reduced aryl hydrocarbon receptor-mediated activity of the exhaust

Diesel exhaust contains numerous toxic substances that show different modes of action such as triggering aryl hydrocarbon receptor (AhR)-mediated pathways. We investigated AhR-mediated activity of exhaust generated by a heavy-duty diesel engine operated with or without iron- or copper/iron-catalyzed diesel particulate filters (DPFs). AhR agonists were quantified using the DR-CALUX reporter gene assay (exposure of cells for 24 h). We found 54-60 ng 2,3,7,8-tetrachlorodibenzo-p-dioxin CALUX equivalents (TCDD-CEQs) per m3 of exhaust in unfiltered samples and 6-16 ng TCDD-CEQ m3 in DPF-treated samples. DPF applications decreased TCDD-CEQ concentrations by almost 90%. Concentrations of known AhR agonists were determined with GC/HRMS and converted to TCDD-CEQ concentrations using compound-specific relative potency values. The analyzed nine polycyclic aromatic hydrocarbons (PAHs) and the 172,3,7,8-chlorinated dibenzodioxins/furans (23,7,8-PCDD/Fs) contributed only marginally (0.6-1.6%) to the total agonist concentration. However, both DPFs also decreased concentrations of individual PAHs by 7(0-80%. Variation of the assay exposure time (8, 24, 48,72, and 96 h) revealed that AhR-mediated activity decreased over time and reached a plateau after 72 h, which was most likely due to biotransformation of AhR agonists by the exposed H4IIE cells. At the plateau, we measured 1-2 ng TCDD-CEQ m(-3) in both an unfiltered and a filtered exhaust sample. Our findings show that DPFs are a promising technology to detoxify diesel exhaust regarding compounds with AhR-mediated activity.