Orwik

Bioavailability of organochlorine compounds in aqueous suspensions of fullerene: evaluated with medaka (Oryzias latipes) and negligible depletion solid-phase microextraction.

The wide application of engineered nanomaterials, such as fullerene (C(60)), will inevitably lead to their release into the aqueous environment, which may alter the bioavailability of organic compounds to aquatic organisms. Negligible depletion solid... expand abstract-phase microextraction (nd-SPME) together with medaka (Oryzias latipes) bioaccumulation were used to study the effects of aqueous suspensions of fullerene (nC(60)) on the bioavailability of eight organochlorine compounds (OCCs) (logK(OW) 3.76-6.96). Freely dissolved concentrations of OCCs decreased by 11.5-88.4% at addition of 5mgL(-1)nC(60) as indicated by reduced equilibrium concentrations in the SPME fiber coating, the highest reduction being observed for the most hydrophobic OCCs. Medaka bioaccumulation study demonstrated that at the kinetic uptake regime, nC(60) significantly decreased the bioaccumulation of the high hydrophobic OCCs (logK(OW)>6), but slightly enhanced the bioaccumulation of the less hydrophobic OCCs (logK(OW)<6). The OCC concentrations in medaka (C(fish)) at the kinetic uptake regime linearly correlated with that in nd-SPME fiber (C(fiber)) without nC(60) (p=0.007-0.013, R(2)=0.666-0.723), but this correlation deteriorated with the presence of nC(60) (p=0.073-0.081, R(2)=0.423-0.440). These results suggest that in nC(60) the uptake mechanism of OCCs to medaka is different from that to nd-SPME fiber. While only the freely dissolved OCCs are available to nd-SPME fiber, both the freely dissolved and the nC(60) associated OCCs contributed to the accumulation of OCCs to medaka. collapse abstract

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Do complex matrices modify the sorptive properties of polydimethylsiloxane (PDMS) for non-polar organic chemicals?

The partitioning of non-polar analytes into the silicone polydimethylsiloxane (PDMS) is the basis for many analytical approaches such as solid phase microextraction (SPME), stir bar sorptive extraction (SBSE) and environmental passive sampling. Recen... expand abstracttly, the methods have been applied to increasingly complex sample matrices. The present work investigated the possible effect of complex matrices on the sorptive properties of PDMS. First, SPME fibers with a 30 microm PDMS coating were immersed in 15 different matrices, including sediment, suspensions of soil and humic substances, mayonnaise, meat, fish, olive oil and fish oil. Second, the surface of the fibers was wiped clean, and together with matrix-free control fibers, they were exposed via headspace to 7 non-polar halogenated organic chemicals in spiked olive oil. The fibers were then solvent-extracted, analyzed, and the ratios of the mean concentrations in the matrix-immersed fibers to the control fibers were determined for all matrices. These ratios ranged from 92% to 112% for the four analytes with the highest analytical precision (i.e. polychlorinated biphenyls (PCBs) 3, 28, 52 and brominated diphenyl ether (BDE) 3), and they ranged from 74% to 133% for the other three compounds (i.e. PCBs 101, 105 and gamma-hexachlorocyclohexane (HCH)). We conclude that, for non-polar, hydrophobic chemicals, the sorptive properties of the PDMS were not modified by the diverse investigated media and consequently that PDMS is suited for sampling of these analytes even in highly complex matrices. collapse abstract

Low accessibility and chemical activity of PAHs restrict bioremediation and risk of exposure in a manufactured gas plant soil.

Composting of manufactured gas plant soil by a commercial enterprise had removed most of its polycyclic aromatic hydrocarbons (PAHs), but concentrations remained above regulatory threshold levels. Several amendments and treatments were first tested t... expand abstracto restart the PAH degradation, albeit with little success. The working hypothesis was then that PAHs were "stuck" due to strong sorption to black carbon. Accessibility was measured with cyclodextrin extractions and on average only 4% of the PAHs were accessible. Chemical activity of the PAHs was measured by equilibrium sampling, which confirmed a low exposure level. These results are consistent with strong sorption to black carbon (BC), which constituted 59% of the total organic carbon. Composting failed to remove the PAHs, but it succeeded to minimize PAH accessibility and chemical activity. This adds to accumulating evidence that current regulatory thresholds based on bulk concentrations are questionable and alternative approaches probing actual risk should be considered. collapse abstract

Passive dosing to determine the speciation of hydrophobic organic chemicals in aqueous samples.

A new analytical approach to determine the speciation of hydrophobic organic analytes is presented. The freely dissolved concentration in a sample is controlled by passive dosing from silicone (poly(dimethylsiloxane)), and the total sample concentrat... expand abstraction at equilibrium is measured. The free fraction is determined as the ratio between measured concentrations in pure water and sample. (14)C-labeled fluoranthene served as model analyte, and total sample concentrations were easily measured by liquid scintillation counting. The method was applied to surface water, stormwater runoff, and wastewater. In the untreated wastewater, 61% of the fluoranthene was bound to suspended solids, 28% was associated to dissolved organic matter, and 11% was freely dissolved, while in treated wastewater, the speciation was 16% bound to suspended solids, 4% bound to dissolved organic matter, and 80% freely dissolved. The free fraction in roof runoff (85%) and surface water (91%) was markedly higher than in runoff from paved areas, which ranged from 27 to 36%. A log K(DOC) value of 5.26 was determined for Aldrich humic acid, which agrees well with reported values obtained by fluorescence quenching and solid phase microextraction (SPME). This analytical approach combines simplicity with high precision, and it does not require any phase separation steps. collapse abstract

Controlling and maintaining exposure of hydrophobic organic compounds in aquatic toxicity tests by passive dosing.

The risk assessment of hydrophobic organic compounds (HOCs) in aquatic toxicity or bioconcentration tests is a challenge due to their low aqueous solubilities, sorption and losses leading to poorly defined exposure and reduced test sensitivity. Passi... expand abstractve dosing overcomes these problems via the continual partitioning of HOCs from a dominating reservoir loaded in a biocompatible polymer such as silicone, providing defined and constant freely dissolved concentrations and eliminating spiking with co-solvents. This study characterised the performance of a passive dosing format for aquatic tests with small organism such as invertebrates and algae, consisting of PDMS silicone cast into the base of the glass test vessel. The PDMS silicone was loaded by partitioning from a methanol solution containing PAHs (logK(OW) 3.56-6.63) as model compounds, followed by removal of the methanol with water. This resulted in highly reproducible PDMS silicone HOC concentrations. When shaking, release of PAHs into aqueous solution was rapid and reproducible, and equilibrium partitioning was reached within 5h for all compounds. The buffering capacity was sufficient to maintain stable concentrations over more than 10 weeks. This format was applied in a 48h Daphnia magna immobilisation assay to test the toxicity of a range of PAHs at their aqueous solubility. D. magna immobilisation did not show a trend with aqueous solubility or hydophobicity (K(OW)) of the PAHs. However, the immobilisation data for all compounds could be fitted with one maximum chemical activity response curve. Those PAHs with the lowest maximum chemical activities resulted in no immobilisation. Naphthalene and phenanthrene showed full toxicity at aqueous solubility, and passive dosing was also used for the concentration-response testing of these compounds. The freely dissolved aqueous concentrations causing 50% immobilisation (EC-50) were 1.96 mg L(-1) for naphthalene and 0.48 mg L(-1) for phenanthrene. Therefore, passive dosing is a practical and economical means of improving the exposure of HOCs in aquatic toxicity or bioconcentration tests. collapse abstract

Passive dosing for producing defined and constant exposure of hydrophobic organic compounds during in vitro toxicity tests.

Toxicity testing of hydrophobic organic compounds (HOCs) in plastic cell culture plates is problematic due to compound losses through volatilization and sorption to the wells and culture medium constituents. This leads to poorly defined exposure and ... expand abstractreduced test sensitivity. Passive dosing can overcome these problems by the continual partitioning of HOCs from a dominating reservoir loaded in a biologically inert polymer such as silicone, providing defined and constant freely dissolved concentrations and also eliminating spiking with cosolvents. This study aimed to select a suitable passive dosing format for in vitro tests in multiwell plates and characterize its performance at 37 degrees C. Silicone O-rings were the most suitable format; they were both practical and demonstrated excellent passive dosing performance. (1) The rings were loaded by partitioning from a methanol solution containing polycyclic aromatic hydrocarbons (PAHs) (log K(OW), 3.33-6.43) that served as model compounds, followed by removal of the methanol with water. This resulted in highly reproducible HOC concentrations in the silicone O-rings. (2) The release of PAHs into aqueous solutions was rapid and reproducible, with equilibrium partitioning being reached within hours. (3) The buffering capacity of the O-rings was sufficient to maintain stable concentrations over more than 72 h. The O-rings were then applied to test a range of PAHs at their aqueous solubility in an array of established in vitro cell culture assays with human cells and cell lines. These included the formation of reactive oxygen species, induction of the IL-8 cytokine promoter, and secretion of MCP-1 by the cells. The biological responses depended on the melting point of the individual PAHs and their maximum chemical activities (a(max)). Only those PAHs with the highest a(max) stimulated the formation of reactive oxygen species and MCP-1 secretion, while they inhibited the induction of the IL-8 cytokine promoter. collapse abstract

In situ silicone tube microextraction: a new method for undisturbed sampling of root-exuded thiophenes from marigold (Tagetes erecta L.) in soil.

The difficulties of monitoring allelochemical concentrations in soil and their dynamics over time have been a major barrier to testing hypotheses of allelopathic effects. Here, we evaluate three diffusive sampling strategies that employ polydimethyls... expand abstractiloxane (PDMS) sorbents to map the spatial distribution and temporal dynamics of root-exuded thiophenes from the African marigold, Tagetes erecta. Solid phase root zone extraction (SPRE) probes constructed by inserting stainless steel wire into PDMS tubing were used to monitor thiophene concentrations at various depths beneath marigolds growing in PVC pipes. PDMS sheets were used to map the distribution of thiophenes beneath marigolds grown in thin glass boxes. Concentrations of the two major marigold thiophenes measured by these two methods were extremely variable in both space and time. Dissection and analysis of roots indicated that distribution of thiophenes in marigold roots also was quite variable. A third approach used 1 m lengths of PDMS microtubing placed in marigold soil for repeated sampling of soil without disturbance of the roots. The two ends of the tubing remained out of the soil so that solvent could be washed through the tubing to collect samples for HPLC analysis. Unlike the other two methods, initial experiments with this approach show more uniformity of response, and suggest that soil concentrations of marigold thiophenes are affected greatly even by minimal disturbance of the soil. Silicone tube microextraction gave a linear response for alpha-terthienyl when maintained in soils spiked with 0-10 ppm of this thiophene. This method, which is experimentally simple and uses inexpensive materials, should be broadly applicable to the measurement of non-polar root exudates, and thus provides a means to test hypotheses about the role of root exudates in plant-plant and other interactions. collapse abstract

Possibilities and limitations of equilibrium sampling using polydimethylsiloxane in fish tissue.

Polydimethylsiloxane (PDMS) has been used for passive equilibrium sampling in numerous abiotic environmental matrices. Recently, this approach was extended to lipid-rich tissue. This work investigated the possibilities and limitations of using PDMS t... expand abstracthin-film extraction for in tissue equilibrium sampling in fish species of varying lipid content. Polychlorinated biphenyls (PCBs) were used as model lipophilic organic pollutants. PDMS thin-films were inserted in intact fish tissue for differing time periods (1h up to 1 week). The thin-films were then solvent-extracted and the extracts were analyzed using gas chromatography coupled to mass spectrometry. Whether equilibrium had been established was investigated either by using PDMS thin-films of multiple thicknesses (140-620 microm) or by assessing kinetics by means of time series. Equilibration was found to be rapid (i.e. in the range of hours) in lipid-rich fish whereas equilibrium was not achieved within one week in tissues with low or medium lipid content (i.e. up to 2% lipids). Regarding lipid-rich fish, the newly developed method was found to be sufficiently sensitive to determine equilibrium partitioning concentrations of PCBs in lipids of samples from the Baltic Sea, and it is a promising approach for any kind of fatty tissue. collapse abstract

Equilibrium sampling through membranes (ESTM) of acidic organic pollutants using hollow fibre modules in continuous steady-state mode.

Hollow fibre (HF) membrane modules were applied in continuous mode for equilibrium sampling through membranes (ESTM) of polar organic pollutants. Phenolic compounds (chlorophenols, cresols and phenol) served as model substances and ESTM was tuned tow... expand abstractards the measurement of freely dissolved concentrations (C(free)). HF membrane modules were constructed using thin-walled membrane, 1-m module length and low packing density in order to optimise the uptake kinetics of the analytes into the acceptor solution. Such custom made devices were tested and compared to commercially available modules. The former modules performed best for continuous ESTM. The custom made modules provided steady-state equilibrium within 20-40 min and enrichment that was in general agreement with calculated distribution ratios between acceptor and sample. In experiments during which sample concentration was changed, acceptor response time to decreased sample concentration was around 30 min for custom built modules. In the presence of commercial humic acids, analytes showed lower steady-state enrichment, which is due to a decrease in C(free). Continuous ESTM may be automated and is suggested for use in online determination of C(free) of pollutants and studies on sorption of pollutants. Future studies should include optimisation of the membrane liquid and factors regarding the residence time of the acceptor solution in the fibre lumen. Qualitative aspects of DOM should also be included, as natural DOM can be fractionated. C(free) could be correlated to DOM properties that have previously been shown to influence sorption, such as aromaticity, carboxylic acid content and molecular size. collapse abstract

Development of a dynamic delivery method for in vitro bioassays.

Measuring the biological activity of hydrophobic chemicals using in vitro assays is challenging because their aqueous solubility is low and the high density of bio-suspensions strongly decreases the bioavailability of hydrophobic pollutants. Dynamic ... expand abstractdosing by partitioning from a stable polymer has a potential to overcome these limitations. Poly(dimethylsiloxane) (PDMS) was chosen due to its documented bio-compatibility and excellent partitioning properties. PDMS sheets were loaded with five polycyclic aromatic hydrocarbons (PAHs) and then immersed in model bio-suspensions composed of membrane vesicles ("chromatophores", composed of 30% lipids and 70% proteins) isolated from the photosynthetic bacterium Rhodobacter sphaeroides or phospholipid bilayer vesicles (liposomes) composed of palmitoyl-oleoyl phosphatidylcholine (POPC). Method development included the determination of partition coefficients between chromatophores or liposomes and water, desorption rate constants from PDMS to bio-suspensions, and diffusion resistances in both PDMS and bio-suspensions. The release of the PAHs from the PDMS into the bio-suspensions was measured and modeled as a combination of diffusion in pure water and diffusion in a completely mixed solvent composed of water and bio-suspensions. The mass transfer resistance for the release was lower in the PDMS than in the tested solutions, which demonstrates that PDMS can efficiently deliver PAHs even to dense biosuspensions. The contribution of aqueous diffusion to the mass transfer decreased with increasing hydrophobicity of the PAHs indicating that hydrophobic chemicals are efficiently transported with suspended biomaterial. The passive dosing system is versatile and offers a number of applications. Promising are tests with instantaneous response, where the time-dependent effect can be translated to concentration-effect curves but the system is also applicable for assuring constant dosing for longer-term testing. collapse abstract

Silicone membrane equilibrator: measuring chemical activity of nonpolar chemicals with poly(dimethylsiloxane) microtubes immersed directly in tissue and lipids.

The chemical activity of organic chemicals directs their diffusion and partitioning and is consequently crucial for their transport, distribution, and toxic effects. A silicone membrane equilibrator is introduced for measuring the chemical activity o... expand abstractf nonpolar organic chemicals in lipid-rich samples: (I) A 6 m poly(dimethylsiloxane) (PDMS) microtube (300 microm i.d., 640 microm o.d.) was placed in a sample, and a sample-PDMS equilibrium was reached within 10 min for 12 polycyclic aromatic hydrocarbons (PAHs) acting as model compounds. (II) A plug of 100 microL of methanol was pushed through the tube to equilibrate it with the PDMS and thus the sample. (III) This yielded an undiluted methanol extract that was injected into a high-performance liquid chromatograph (HPLC) with multiband fluorescence detection. Quantification limits expressed as unitless chemical activities ranged from 6 x 10(-9) to 5 x 10(-8), and relative standard deviations were from 6% to 19%. Chemical activities of PAHs in mussels from two polluted sites were measured between 10(-7) and 10(-5), and activity coefficients for PAHs in vegetable and fish oils hardly differed between oils. This method can be used for internal exposure measurements, for monitoring product safety/conformity, and process control. The method can also be applied to measure total analyte concentrations in lipid-rich samples and oils. collapse abstract

Measuring pyrethroids in sediment pore water using matrix-solid phase microextraction.

Pyrethroids are hydrophobic insecticides commonly used in both agricultural and urban environments. Their high toxicity to aquatic organisms, including benthic invertebrates, and detection in the sediment at many locations in California, U.S.A., have... expand abstract spawned interest in understanding their bioavailability in bed sediments. A recent study showed good correlation between uptake of 14C-permethrin in Chironomus tentans and solid-phase microextraction (SPME) fibers in sediments. The present study was directed at the development of an SPME technique applicable to trace levels of nonlabeled pyrethroids in sediment. Disposable polydimethylsiloxane fibers were used to detect freely dissolved pore-water concentrations of bifenthrin, fenpropathrin, cis-permethrin, trans-permethrin, cyfluthrin, cypermethrin, and esfenvalerate under agitated and static conditions. Partition equilibrium between fiber and sediment was reached in <5 d when the samples were agitated on a shaker at low speed, while much longer times (>23 d) were needed without agitation. Polydimethylsiloxane to water partition ratios (K(PDMS)) of the seven pyrethroids were measured separately and ranged from 2.83 x 10(5) to 1.89 x 10(6). When applied to field-contaminated sediments, agitated matrix-SPME was able to detect pore-water concentrations as low as 0.1 ng/L. The method developed in the present study may be coupled with bioassays to gain mechanistic understanding of factors affecting pyrethroid toxicities, and applied to field samples to better predict sediment toxicities from pyrethroid contamination. collapse abstract

Matrix solid-phase microextraction for measuring freely dissolved concentrations and chemical activities of PAHs in sediment cores from the western Baltic Sea.

Sediment-pore water partitioning of polycyclic aromatic hydrocarbons (PAHs) was studied in sediment cores of a dumping area in the western Baltic Sea and compared to a reference site. Freely dissolved concentrations (C(free)) of nine PAHs were measur... expand abstracted in sediment samples using solid-phase microextraction (SPME), a cost and time-efficient method with detection limits in the lower ng L(-1) range. Elevated levels of C(free) were measured at the dumping site, where concentration peaks in the core correlated with the presence of the dumped material, which was conspicuous in its color and consistency. Sediment concentrations of PAHs were three orders of magnitude higher at the dumping site than at the reference site, whereas C(free) was only one order of magnitude greater. Chemical activities of the PAHs in the sediment cores were calculated from C(free) to predict the baseline toxic potential of the contaminant mixture. Finally, gradients in C(free) and chemical activity were used to determine the direction of diffusion within the sediment and to obtain a spatial characterization of the PAH exposure. C(free) and chemical activity are important exposure parameters for the prediction of bioconcentration and toxicity in sediment organisms, and their measurement should be included in risk-assessment and pollution-management strategies. collapse abstract

Combined chemical (fluoranthene) and drought effects on Lumbricus rubellus demonstrate the applicability of the independent action model for multiple stressor assessment.

The combined effect of a chemical (fluoranthene) and a nonchemical stress (reduced soil moisture content) to the widely distributed earthworm Lumbricus rubellus were investigated in a laboratory study. Neither fluoranthene (up to 500 microg/g) nor lo... expand abstractw soil moisture (15% below optimal) had a significant effect on the survival of the exposed worms, but a significant effect on reproduction (cocoon production rate) was found for both stressors (p < 0.001 in both cases). The response of cocoon production to each stressor could be well described by a logistic model; this suggested that the joint effects may be applicable to description using the independent action (IA) model that is widely used in pharmacology and chemical mixture risk assessment. Fitting of the IA model provided a good description of the combined stressor data (accounting for 53.7% of total variation) and was the most parsimonious model describing joint effect (i.e., the description of the data was not improved by addition of further parameters accounting for synergism or antagonism). Thus, the independent action of the two responses was further supported by measurement of internal fluoranthene exposure. The chemical activity of fluoranthene in worm tissue was correlated only with soil fluoranthene concentration and not with soil moisture content. Taken together these results suggest that the IA model can help interpret the joint effects of chemical and nonchemical stressors. Such analyses should, however, be done with caution since the literature data set suggests that there may be cases where interactions between stressors result in joint effects that differ significantly from IA predictions. collapse abstract

Equilibrium sampling: partitioning of organochlorine compounds from lipids into polydimethylsiloxane.

Polydimethylsiloxane (PDMS) can be used for equilibrium sampling of environmental pollutants in a large variety of matrices including biota. For comparison with lipid-normalized concentrations e.g. from biota monitoring programmes, reliable lipid to ... expand abstractPDMS partition ratios (K(Lipid,PDMS)) are required. Additionally, K(Lipid,PDMS) facilitate comparison of equilibrium sampling data obtained in various environmental media and can be helpful to convert equilibrium sampling data into a more informative form. This work investigated the equilibrium partitioning of polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs) between lipids from biota of different trophic levels and PDMS. One vegetable oil, a fish oil and seal oil were investigated. The lipid to PDMS partition ratios were compound-specific and ranged from 14.5 to 62.9 g/g with correction for lipid uptake into the PDMS and from 13.0 to 54.8 g/g without correction. Additionally, PDMS served as a reference partitioning phase for the accurate determination of lipid to lipid partition ratios, which for all analytes were close to unity. Evaluating the results in a bioaccumulation context, they indicate that the equilibrium partitioning of neutral lipophilic environmental contaminants into the lipids of the three investigated species will be very similar, although they represent three distinct trophic levels. collapse abstract

Passive dosing of soil invertebrates with polycyclic aromatic hydrocarbons: limited chemical activity explains toxicity cutoff.

The partitioning of organic soil pollutants into soil organisms is driven by their chemical activity, which normally does not exceed that of the pure pollutant. Passive dosing with the silicone poly(dimethylsiloxane) (PDMS) was used to initiate and m... expand abstractaintain the maximum chemical activity of 10 polycyclic aromatic hydrocarbons (PAHs) in toxicity tests with the springtail Folsomia candida. The test animals could move freely on the PDMS saturated with PAHs, resulting in direct contact and exposure to saturated air. After 7 days, springtail lethality correlated neither with the octanol-water partition coefficients of the PAHs nor with their molecular size, but with their melting point All low-melting PAHs (T(M) < or = 110 degrees C) caused 100% lethality, whereas all high-melting PAHs (TM > or = 180 degrees C) caused no significant lethality. The lethality was successfully fitted to one chemical activity response curve for all PAHs tested, with effective chemical activity causing 50% lethality (Ea-50) of 0.058. It was also fitted to the PAH concentration in the PDMS, resulting in an EC(PDMS)-50 of 8.7 mM. Finally, the combined exposure to anthracene and pyrene was described by the sum of chemical activities causing lethality, in good agreement with the chemical activity-response curve obtained. collapse abstract

Impacts of some environmentally relevant parameters on the sorption of polycyclic aromatic hydrocarbons to aqueous suspensions of fullerene.

The wide application of engineered carbon nanomaterials (CNMs), such as fullerene (C60), inevitably will result in their introduction into the aqueous environment. It is likely CNMs will associate with abundant natural organic matter (NOM) and engine... expand abstractered surfactants to form stable aqueous suspensions through various environmental processes. The present study reveals that sorption of polycyclic aromatic hydrocarbons (PAHs) to fullerene resulted in a remarkable decline of freely dissolved PAH concentrations. For the three PAHs studied (phenanthrene, fluoranthene, and chrysene) with log K(ow) in the range of 4.56 to 5.81, the measured sorption coefficients to aqueous suspensions of fullerene (log K(C60) = 4.71-5.48) were close to that of dissolved organic carbon (DOC) from Aldrich humic acid (log K(DOC) = 4.48-5.91). Aqueous suspensions of fullerene were stable for a wide range of pH (3.0-11.0) and salinity conditions (0-25 mM NaCl), and the pH and salinity had minor effects on the sorption of PAHs to aqueous suspensions of fullerene. The addition of humic acids (5 mg/L DOC) to the fullerene (5 mg/L) suspensions resulted in an additional reduction of freely dissolved PAH concentrations. The high PAH sorption coefficients to suspended fullerene suggest that the release of fullerene to the aquatic environment might affect PAH fate and exposures. collapse abstract

Isomer-specific biodegradation of methylphenanthrenes by soil bacteria.

It is assumed that bacteria generally degrade 2-methylphenanthrene (2MPhe) in preference to 1-methylphenanthrene (1MPhe), and that environmental biodegradation of methylated PAHs therefore can be described qualitatively by changes in relative concent... expand abstractrations of these isomers. Our objective was to investigate whether microbial phenanthrene degraders (Sphingomonas and Mycobacterium) show such isomer-specific PAH degradation. Eleven out of twenty-nine phenanthrene degraders could grow on methylphenanthrene. The mycobacteria grew only on 2MPhe, the sphingomonads grew mostly on 1MPhe, and one sphingomonad could utilize both substrates. Seven strains were tested in a two-phase system where 1MPhe and 2MPhe were supplied in heptamethylnonane. For these strains, a consistent description of biodegradation based on the 2MPhe/1MPhe diagnostic ratio would not be possible because three Mycobacterium and one Sphingomonas degraded 2MPhe faster than 1MPhe, another Sphingomonas degraded 1MPhe and 2MPhe at almost equal rates, and two Sphingomonas degraded 1MPhe faster than 2MPhe. Thus, environmental biodegradation of phenanthrenes may theoretically proceed with only minor changes in 2MPhe/1MPhe ratios if individual members of the degrader community have different isomer preferences. However, two soil microcosms polluted with bunker oil confirmed the general decline in 2MPhe/1MPhe ratio during oil biodegradation. collapse abstract

Determining the chemical activity of hydrophobic organic compounds in soil using polymer coated vials.

BACKGROUND: In soils contaminated by hydrophobic organic compounds, the concentrations are less indicative of potential exposure and distribution than are the associated chemical activities, fugacities and freely dissolved concentrations. The latter ... expand abstractcan be measured by diffusive sampling into thin layers of polymer, as in, for example, solid phase micro-extraction. Such measurements require equilibrium partitioning of analytes into the polymer while ensuring that the sample is not depleted. We introduce the validation of these requirements based on parallel sampling into polymer layers of different thicknesses. RESULTS: Equilibrium sampling devices were made by coating glass vials internally with 3-12 microm thick layers of polydimethylsiloxane (PDMS). These were filled with slurries of a polluted soil and gently agitated for 5 days. The concentrations of 7 polycyclic aromatic hydrocarbons (PAHs) in the PDMS were measured. Validation confirmed fulfilment of the equilibrium sampling requirements and high measurement precision. Finally, chemical activities of the PAHs in the soil were determined from their concentrations and activity coefficients in the PDMS. CONCLUSION: PAHs' thermodynamic activities in a soil test material were determined via a method of uptake into PDMS. This can be used to assess chemical exposure and predict diffusion and partitioning processes. collapse abstract

Field testing of equilibrium passive samplers to determine freely dissolved native polycyclic aromatic hydrocarbon concentrations.

Equilibrium passive samplers are promising tools to determine freely dissolved aqueous concentrations (C(W,free)) of hydrophobic organic compounds. Their use in the field, however, remains a challenge. In the present study on native polycyclic aromat... expand abstractic hydrocarbons (PAHs) in Oslo Harbor, Norway, two different passive sampler materials, polyoxymethylene (POM; thickness, 55 microm [POM-55] and 500 microm [POM-500]) and polydimethylsiloxane (PDMS; thickness, 200 microm), were used to determine in the laboratory C(W,free) in sediment pore water (C(PW,free)), and the suitability of five passive samplers for determination of C(W,free) in overlying surface water was tested under field conditions. For laboratory determinations of C(PW,free), both POM-55 and PDMS turned out to be suitable. In the field, the shortest equilibrium times (approximately one month) were observed for POM-55 and PDMS (thickness, 28 microm) coatings on solid-phase microextraction fibers, with PDMS tubing as a good alternative. Low-density polyethylene (thickness, 100 microm) and POM-500 did not reach equilibrium within 119 d in the field. Realistic values were obtained for dissolved organic carbon-water partition coefficients in the field (approximately one log unit under log K(OW)), which strengthened the conclusion that equilibrium was established in field-exposed passive samplers. At all four stations, chemical activity ratios between pore water and overlying water were greater than one for all PAHs, indicating that the sediment was a PAH diffusion source and that sediment remediation may be an appropriate treatment for PAH contamination in Oslo Harbor. collapse abstract

Immersed solid phase microextraction to measure chemical activity of lipophilic organic contaminants in fatty tissue samples.

It is known that solid phase microextraction (SPME) fibers can be equilibrated directly within environmental matrices such as water, sediment and soil slurries. Here it is shown that this method can also be applied to biological tissue. SPME extracti... expand abstracton of biological matrices reportedly causes lipophilic fouling of the fiber. However, we found no significant measurement bias when combining equilibrium sampling with fiber surface cleaning. The uptake of lipophilic organic pollutants from the tissue and into the SPME fiber coating was characterized by fast equilibrium partitioning without sample depletion and without impacting the sorptive properties of the fiber. The precision of the method when applied to hexachlorobenzene and several PCB congeners in harbor porpoise blubber was 15%, which includes the variation between SPME samplings, manual injections and the instrumental analysis. A good correlation (r(2)=0.95) was obtained between SPME measurements of PCB 153 in blubber and concentrations obtained via a traditional analytical approach. These results indicate that SPME is a promising technique for measuring chemical activity in biological tissue, which would make it a useful tool for studying chemical distribution in organisms as well as biodilution and biomagnification phenomena. collapse abstract

Effects of dilution on the exposure in sediment toxicity tests- buffering of freely dissolved concentrations and changes in mixture composition.

Some sediment toxicity tests, such as the Microtox test, are conducted by diluting either contaminated sediment or an aqueous phase with clean water. The present study aims to clarify how the dilution procedure affects the exposure of organisms. It i... expand abstracts shown that freely dissolved concentrations of hydrophobic compounds are buffered by desorption from the sediment matrix when sediment is diluted with water. The buffering depends on the properties of the sediment matrix and contaminant. Consequently, the composition of a contaminant mixture changes with dilution, and the exposure in a sediment dilution toxicity test is poorly defined. This questions the application and subsequent assessments of such tests. Additionally, the often-observed higher toxicity in sediment dilution tests relative to elutriate dilution tests is not sufficient to claim direct contact exposure, because the enhanced sensitivity in sediment dilution tests also can be explained by buffering from the sediment matrix. In applying these tests, one should be aware of the fundamental differences between the sediment dilution strategy and the dilution of an aqueous phase and of the consequences it has for the outcome of the test. collapse abstract

Degradation of PCB congeners by bacterial strains.

Biological in situ methods are options for the remediation of contaminated sites. An approach to quantify biodegradation by soil bacteria was developed, combining experiment with mathematical modelling. We performed in vitro assays to investigate the... expand abstract potential and kinetics of the wild-type degrader, Burkholderia sp. strain LB400 (expressing bph) and the genetically modified Pseudomonas fluorescens strains F113pcb and F113L::1180 (expressing bph under different promoters) to metabolise individual congeners of polychlorinated biphenyls (PCBs). Kinetics of metabolism was analysed using the Monod model. Results revealed similar patterns of degradable PCB congeners for LB400 and F113L::1180. The degree of PCB degradation was comparable for LB400 and F113L::1180 but was much lower for F113rifpcb. In additional mesocosm experiments with PCB-contaminated soil, the F113 derivatives demonstrated a good survival ability in willow (Salix sp.) rhizosphere. Strain F113L::1180 in combination with willow plants is expected to degrade a large spectrum of PCB congeners in soil. The data from the experiments were used to calculate the time scale of the degradation process in a PCB-contaminated soil. The uncertainty of the model predictions due to the uncertainties of experimental removal velocities and bacterial cell density in soil was quantified. collapse abstract

Enhanced diffusion of polycyclic aromatic hydrocarbons in artificial and natural aqueous solutions.

Uptake of hydrophobic organic compounds into organisms is often limited by the diffusive transport through a thin boundary layer. Therefore, a microscale diffusion technique was applied to determine the diffusive mass transfer of 12 polycyclic aromat... expand abstractic hydrocarbons through water, air, surfactant solutions, humic acid solutions, aqueous soil and horse manure extracts, digestive fluid of a deposit-feeding worm, and root exudates from willow plants. In most cases the diffusive mass transfer of PAHs was much higher through the tested media than through water, and the enhancement factors increased with increasing hydrophobicity of the PAHs. The diffusive flux of benzo[a]pyrene was for instance enhanced 74 times through gut fluid of a deposit-feeding worm when compared to water. These findings demonstrate that a wide variety of dissolved organic carbon (DOC) at environmental levels can enhance diffusive mass transfer in various transport scenarios. The diffusive uptake of PAHs into sediment dwelling organisms is particularly efficient within the gut and at direct contract with the sediment matrix. Bioremediation might be enhanced bythe addition of auxiliary agents that enhance diffusive mass transfer. Enhanced diffusion needs also to be considered in dynamic transport models and for the operation and calibration of passive sampling techniques. collapse abstract