Predicting toxicity to Hyalella azteca in pyrogenic-impacted sediments-Do we need to analyze for all 34 PAHs?

Polycyclic aromatic hydrocarbons (PAHs) are major drivers of risk at many urban and/or industrialized sediment sites. The US Environmental Protection Agency (USEPA) currently recommends using measurements of 18 parent + 16 groups of alkylated PAHs (PAH-34) to assess the potential for sediment-bound PAHs to impact benthic organisms at these sites. ASTM Method D7363-13 was developed to directly measure low-level sediment porewater PAH concentrations. These concentrations are then compared to ambient water criteria (final chronic values [FCVs]) to assess the potential for impact to benthic organisms. The interlaboratory validation study that was used to finalize ASTM D7363-13 was developed using 24 of the 2-, 3-, and 4-ring PAHs (PAH-24) that are included in the USEPA PAH-34 analyte list. However, it is the responsibility of the user of ASTM Method D7363 to establish a test method to quantify the remaining 10 higher molecular weight PAHs that make up PAH-34. These higher molecular weight PAHs exhibit extremely low saturation solubilities that make their detection difficult in porewater, which has proven difficult to implement in a contract laboratory setting. As a result, commercial laboratories are hesitant to conduct the method on the entire PAH-34 analyte list. This article presents a statistical comparison of the ability of the PAH-24 and PAH-34 porewater results to predict survival of the freshwater amphipod Hyalella azteca, using the original 269 sediment samples used to gain ASTM D7363 Method approval. The statistical analysis shows that the PAH-24 are statistically indistinguishable from the PAH-34 for predicting toxicity. These results indicate that the analysis of freely dissolved porewater PAH-24 is sufficient for making risk-based decisions based on benthic invertebrate toxicity (survival and growth). This reduced target analyte list should result in a cost-saving for stakeholders and broader implementation of the method at PAH-impacted sediment sites. Integr Environ Assess Manag 2016;12:493-499. © 2015 SETAC.

Review of polyoxymethylene passive sampling methods for quantifying freely dissolved porewater concentrations of hydrophobic organic contaminants.

Meth ods involving polyoxymethylene (POM) as a passive sampler are increasing in popularity to assess contaminant freely dissolved porewater concentrations in soils and sediments. These methods require contaminant-specific POM-water partition coefficients, KPOM . Certain methods for determining KPOM perform reproducibly (within 0.2 log units). However, other methods can give highly varying KPOM values (up to 2 log units), especially for polycyclic aromatic hydrocarbons (PAHs). To account for this variation, the authors tested the influence of key methodological components in KPOM determinations, including POM thickness, extraction procedures, and environmental temperature and salinity, as well as uptake kinetics in mixed and static systems. All inconsistencies in the peer-reviewed literature can be accounted for by the likelihood that thick POM materials (500 µm or thicker) do not achieve equilibrium (causing negative biases up to 1 log unit), or that certain POM extraction procedures do not ensure quantitative extraction (causing negative biases up to 2 log units). Temperature can also influence KPOM , although all previous literature studies were carried out at room temperature. The present study found that KPOM values at room temperature are independent (within 0.2 log units) of POM manufacture method, of thickness between 17 µm and 80 µm, and of salinity between 0% and 10%. Regarding kinetics, monochloro- to hexachloro-polychlorinated biphenyls (PCBs) were within 0.2 log units of equilibrium after 28 d in the mixed system, but only dichloro-PCBs achieved near equilibrium after 126 d in the static system. Based on these insights, recommended methods and KPOM values to facilitate interlaboratory reproducibility are presented.

Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques.

Passive sampling methods for contaminated sediments: scientific rationale supporting use of freely dissolved concentrations.

Passive sampling methods (PSMs) allow the quantification of the freely dissolved concentration (Cfree ) of an organic contaminant even in complex matrices such as sediments. Cfree is directly related to a contaminant's chemical activity, which drives spontaneous processes including diffusive uptake into benthic organisms and exchange with the overlying water column. Consequently, Cfree provides a more relevant dose metric than total sediment concentration. Recent developments in PSMs have significantly improved our ability to reliably measure even very low levels of Cfree . Application of PSMs in sediments is preferably conducted in the equilibrium regime, where freely dissolved concentrations in the sediment are well-linked to the measured concentration in the sampler via analyte-specific partition ratios. The equilibrium condition can then be assured by measuring a time series or a single time point using passive samplers with different surface to volume ratios. Sampling in the kinetic regime is also possible and generally involves the application of performance reference compounds for the calibration. Based on previous research on hydrophobic organic contaminants, it is concluded that Cfree allows a direct assessment of 1) contaminant exchange and equilibrium status between sediment and overlying water, 2) benthic bioaccumulation, and 3) potential toxicity to benthic organisms. Thus, the use of PSMs to measure Cfree provides an improved basis for the mechanistic understanding of fate and transport processes in sediments and has the potential to significantly improve risk assessment and management of contaminated sediments.

Evaluation of PCB bioaccumulation by Lumbriculus variegatus in field-collected sediments.

Review of data from several contaminated sediment sites suggested that biota-sediment accumulation factors (BSAFs) declined with increasing contaminant concentrations in the sediment. To evaluate the consistency and possible causes of this behavior, polychlorinated biphenyl (PCB)-contaminated sediment samples from the Hudson, Grasse, and Fox River Superfund sites were used in sediment bioaccumulation tests with the freshwater oligochaete, Lumbriculus variegatus, with PCB concentrations in interstitial water (IW) quantified using polyoxymethylene passive samplers. Measured BSAFs tended to decrease with increasing PCB concentration in sediment, especially for the more highly chlorinated congeners. Measures of partitioning between sediment, IW, and oligochaetes showed that measured sediment-IW partition coefficients (KTOC ) tended to increase slightly with increasing sediment contamination, whereas the ratio of tissue PCB to IW PCB tended to decrease with increasing concentration in IW. Variation in accumulation among sediments was clearly influenced by bioavailability, as reflected by IW measurements, although the specific cause of varying KTOC was not clear. Calculated partitioning between IW and organism lipid (Klipid ) indicated that accumulation was generally 5 to 10-fold higher than would be predicted if Klipid was approximately equal to the n-octanol-water partition coefficient (KOW ). While affirming previous observations of decreasing BSAFs with increasing PCB contamination, the relatively shallow slope of the observed relationship in the current data may suggest that this concentration dependence is not a major uncertainty in sediment risk assessment, particularly if measurements of PCBs in IW are incorporated.

Investigating differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans in soil and soil components using selective supercritical fluid extraction.

Supercritical fluid extraction (SFE) with pure carbon dioxide was performed at increasingly strong conditions to investigate differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in two impacted soils, in their sieved size fractions, and in small (a few mg) samples of industry-related waste products separated from impacted soil. The binding strengths of PCDD/Fs were shown to be different in the two soils, and in their different soil particle size fractions. As might be expected based on surface area considerations, one soil showed the strongest binding in the smallest (<5µm) sieved fraction. However, the other soil showed the strongest binding in the larger sized fractions, possibly indicating that process-related particles could be controlling PCDD/F binding. Selective SFE of various types of particles including black carbon and charcoal (separated from soil), and from a suspected process anode residue did show different PCDD/F binding behavior ranging from quite weak binding (charcoal) to very strong binding (anode particles). Shifts to the stronger SFE fractions in the soils after activated carbon treatment agreed well with the decreases previously found in the uptake of PCDD/Fs by earthworms, as well as decreases in their freely-dissolved aqueous concentrations in soil/water slurries. These results show that, as previously demonstrated for PAHs and PCBs, selective SFE can be a useful tool to investigate differences in PCDD/F binding behaviors in impacted soils and sediments and their component parts, as well as a rapid tool for estimating the effectiveness of activated carbon treatments on decreasing the bioavailability of PCDD/Fs in soils and sediments.

Improving predictability of sediment-porewater partitioning models using trends observed with PCB-contaminated field sediments.

More than 1900 sediment-water partitioning coefficients were measured for 58 polychlorinated biphenyl (PCB) congeners in 53 historically contaminated sediments collected from 10 urban and rural waterways in the United States and Canada. Freely dissolved porewater concentrations were determined using passive sampling with polyoxymethylene. Measured total organic carbon (TOC)/water partitioning coefficients, K(TOC), ranged from one to nearly three orders-of-magnitude higher than typical literature values based on spiking experiments and model predictions. Although total PCB concentrations ranged from 0.08 to 194 mg/kg, the more highly contaminated sediments showed only slightly lower K(TOC) values than less-contaminated sediments. No correlation was observed between log K(TOC) values and sediment TOC, black carbon (BC), or BC/TOC fractions (r(2) typically <0.1). Utilizing a two-carbon model incorporating anthropogenic BC did not improve predictions over a one-carbon TOC model. A comparison of models recently validated for field data showed that a coal-tar poly parameter linear-free energy relationship (PP-LFER) and a Raoult's Law model were successful at predicting average log K(TOC) values, without the need for any calibration or fitting (within a factor of 10 more than 90% of the time, and within a factor of 30 more than 99% of the time). Predictions were further improved by the introduction of a Weathering Factor (WF) that accounts for the relative depletion of lower molecular weight congeners due to weathering. Highly weathered sediments (with a WF near 1) tended to follow the coal-tar PP-LFER and Raoult's Law model the closest. Less-weathered sediments (with WF ≪ 1) sorbed less than predicted by these models. Noncalibrated WF inclusive coal-tar PP-LFER and Raoult's Law models performed as well or better than a quantitative-structure activity relationship (QSAR) model calibrated specifically to the data. These recommended partitioning models here can readily be used for all 209-PCB congeners.

Measuring picogram per liter concentrations of freely dissolved parent and alkyl PAHs (PAH-34), using passive sampling with polyoxymethylene.

Passive sampling with nondepletive sorbents is receiving increasing interest because of its potential to measure freely dissolved concentrations of hydrophobic organic compounds (HOCs) at very low concentrations, as well as its potential for both laboratory use and field deployment. However, consistent approaches have yet to be developed for the majority of HOCs of environmental and regulatory interest. In the present study, a passive sampling method was developed which allows the freely dissolved concentrations of 18 parent and 16 groups of alkyl polycyclic aromatic hydrocarbons (PAHs) on the U.S. Environmental Protection Agency (USEPA)'s "PAH-34" target compound list to be measured. Commercially available 76-µm-thick polyoxymethylene (POM) was placed in sediment/water slurries and exposed for up to 126 days, with 28 days found to be sufficient to obtain equilibrium among the sediment, water, and POM phases for the target 2- to 6-ring PAHs. The POM/water partition coefficients (K(POM)) necessary to calculate freely dissolved concentrations for parent PAHs were determined in two separate laboratories (one using pure standards, and the other using coal tar/petroleum-contaminated sediments) and agreed very well. Since the so-called "16" alkyl PAHs on the PAH-34 list actually include several hundreds of isomers for which no standards exist, sediments impacted by coal tar, or spiked with a coal tar/petroleum nonaqueous phase liquid (NAPL) were also used to measure K(POM) values for each alkyl PAH cluster. The log K(POM) values ranged from ca. 3.0 to 6.2 for 2- to 6-ring parent PAHs, and correlated well with SPARC octanol/water coefficients (K(OW)) (correlation coefficient of r(2) = 0.986). However, log K(POM) values for alkyl PAHs deviated increasingly from SPARC log K(OW) values with increasing degree of alkylation. A simple empirical model that incorporates the number of carbon atoms in a PAH gave a better fit to the experimental log K(POM) values, and was used to estimate log K(POM) for alkyl PAHs that could not be directly measured. Detection limits (as freely dissolved concentrations) ranged from ca. 1 part per trillion (ng/L) for the 2-ring PAH naphthalene, down to <1 pg/L (part per quadrillion) for the 5- and 6-ring PAHs. Sorption isotherms were linear (r(2) > 0.99) over at least 4 orders of magnitude.

Predicting pore water EPA-34 PAH concentrations and toxicity in pyrogenic-impacted sediments using pyrene content.

Sediment and freely dissolved pore water concentrations of the U.S. Environmental Protection Agency's list of 34 alkyl and parent PAHs (EPA-34) were measured in 335 sediment samples from 19 different sites impacted by manufactured gas plants, aluminum smelters and other pyrogenic sources. The total EPA-34 freely dissolved pore water concentration, C(pw,EPA-34), expressed as toxic units (TU) is currently considered one of the most accurate measures to assess risk at such sites; however, it is very seldom measured. With this data set, we address how accurately C(pw,EPA-34) can be estimated using limited 16 parent PAH data (EPA-16) commonly available for such sites. An exhaustive statistical analysis of the obtained data validated earlier observations that PAHs with more than 3 rings are present in similar relative abundances and their partitioning behavior typically follows Raoult's law and models developed for coal tar. As a result, sediment and freely dissolved pore water concentrations of pyrene and other 3- and 4-ring PAHs exhibit good log-log correlations (r² > 0.8) to most individual EPA-34 PAHs and also to C(pw,EPA-34). Correlations improve further by including the ratio of high to low molecular weight PAHs, as 2-ring PAHs exhibit the most variability in terms of their relative abundance. The most practical result of the current work is that log C(pw,EPA-34) estimated by the recommended pyrene-based estimation techniques was similarly well correlated to % survival of the benthic amphipods Hyalella azteca and Leptocheirus plumulosus as directly measured log C(pw,EPA-34) values (n = 211). Incorporation of the presented C(pw,EPA-34) estimation techniques could substantially improve risk assessments and guidelines for sediments impacted by pyrogenic residues, especially when limited data are available, without requiring any extra data or measurement costs.

Comparison of polymeric samplers for accurately assessing PCBs in pore waters.

Assessing the hazard posed by sediments contaminated with hydrophobic organic compounds is difficult, because measuring the freely dissolved porewater concentrations of such low-solubility chemicals can be challenging, and estimating their sediment-water partition coefficients remains quite uncertain. We suggest that more accurate site assessments can be achieved by employing sampling devices in which polymers, with known polymer-water partition coefficients, are used to absorb the contaminants from the sediment. To demonstrate the current accuracy and limitations of this approach, we compared use of three polymers, polydimethylsiloxane, polyoxymethylene, and polyethylene, exposed to a single sediment in two modes, one in which they were exhaustively mixed (tumbled) with the sediment and the other in which they were simply inserted into a static bed (passive). Comparing porewater concentrations of specific polychlorinated biphenyl (PCB) congeners with results obtained using air bridges, we found the results for tumbled polymers agreed within 20%, and the passive sampling agreed within a factor of 2. In contrast, porewater estimates based on sediment concentrations normalized to f(OC)K(OC), the weight fraction of organic carbon times the organic-carbon normalized partition coefficient, averaged a factor of 7 too high. We also found good correlations of each polymer's uptake of the PCBs with bioaccumulation by the polychaete, Neanthes arenaceodentata. Future improvements of the passive sampling mode will require devices that equilibrate faster and/or have some means such as performance reference compounds to estimate mass transfer limitations for individual deployments.

Assessment of supercritical fluid extraction use in whole sediment toxicity identification evaluations.

Supercritical fluid extraction (SFE) with pure CO(2) was assessed as a confirmatory tool in phase III of whole sediment toxicity identification evaluations (TIEs). The SFE procedure was assessed on two reference sediments and three contaminated sediments by using a combination of toxicological and chemical measurements to quantify effectiveness. Sediment toxicity pre- and post-SFE treatment was quantified with a marine amphipod (Ampelisca abdita) and mysid (Americamysis bahia), and nonionic organic contaminants (NOCs) polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were measured in sediments, overlying waters, and interstitial waters. In general, use of SFE with the reference sediments was successful, with survival averaging 91% in post-SFE treatments. Substantial toxicity reductions and contaminant removal from sediments and water samples generated from extracted sediments of up to 99% in two of the contaminated sediments demonstrated SFE effectiveness. Furthermore, toxicological responses for these SFE-treated sediments showed comparable results to those from the same sediments treated with the powdered coconut charcoal addition manipulation. These data demonstrated the utility of SFE in phase III of a whole sediment TIE. Conversely, in one of the contaminated sediments, the SFE treatments had no effect on sediment toxicity, whereas sediment concentrations of PCBs and PAHs were reduced. We propose that, for some sediments, the SFE treatment may result in the release of otherwise nonbioavailable cationic metals that subsequently cause toxicity to test organisms. Overall, SFE treatment was found to be effective for reducing the toxicity and concentrations of NOCs in some contaminated sediments. However, these studies suggest that SFE treatment may enhance toxicity with some sediments, indicating that care must be taken when applying SFE and interpreting the results.

An evaluation of the ability of chemical measurements to predict polycyclic aromatic hydrocarbon-contaminated sediment toxicity to Hyalella azteca.

The present study examined the ability of three chemical estimation methods to predict toxicity and nontoxicity of polycyclic aromatic hydrocarbon (PAH) -contaminated sediment to the freshwater benthic amphipod Hyalella azteca for 192 sediment samples from 12 field sites. The first method used bulk sediment concentrations of 34 PAH compounds (PAH34), and fraction of total organic carbon, coupled with equilibrium partitioning theory to predict pore-water concentrations (KOC method). The second method used bulk sediment PAH34 concentrations and the fraction of anthropogenic (black carbon) and natural organic carbon coupled with literature-based black carbon-water and organic carbon-water partition coefficients to estimate pore-water concentrations (KOCKBC method). The final method directly measured pore-water concentrations (pore-water method). The U.S. Environmental Protection Agency's hydrocarbon narcosis model was used to predict sediment toxicity for all three methods using the modeled or measured pore-water concentration as input. The KOC method was unable to predict nontoxicity (83% of nontoxic samples were predicted to be toxic). The KOCKBC method was not able to predict toxicity (57% of toxic samples were predicted to be nontoxic) and, therefore, was not protective of the environment. The pore-water method was able to predict toxicity (correctly predicted 100% of the toxic samples were toxic) and nontoxicity (correctly predicted 71% of the nontoxic samples were nontoxic). This analysis clearly shows that direct pore-water measurement is the most accurate chemical method currently available to estimate PAH-contaminated sediment toxicity to H. azteca.

Particle-scale measurement of PAH aqueous equilibrium partitioning in impacted sediments.

This research investigated the particle-scale processes that control aqueous equilibrium partitioning of PAHs in manufactured gas plant (MGP) site sediments. Dominant particle types in impacted sediments (sand, wood, coal/coke, and pitch) were physically separated under a microscope for equilibrium assessments. Solid-phase microextraction (SPME) combined with selected ion monitoring GC/MS and perdeuterated PAH internal standards were used to determine freely dissolved PAH concentrations in small (0.1-1 mL) water samples at concentrations as low as microg/L (for lower molecular weight PAHs) to ng/L (for higher molecular weight PAHs). For every particle class the initial release of PAHs into the aqueous phase was rapid, and an apparent equilibrium was reached in a matter of days. The average ratio of aqueous total PAH concentration for pitch vs coal/coke particles for eight sediment samples was 20. Thus, sediments that had aged in the field for many decades were not at equilibrium and were still going through a slow process of contaminant mass transfer between the different particle types. A possible consequence of this slow aging process is further lowering of the activity of the chemical as mass transfer is achieved to new sorption sites with time. This study also found that the presence of black carbon even at the level of (1)/(3) of sediment organic carbon does not necessarily imply a BC-dominated sorption behavior, rather source pitch particles if present may dominate PAH partitioning. To our knowledge this is the first report of equilibrium partitioning assessment conducted at the sediment particle scale.

Measuring low picogram per liter concentrations of freely dissolved polychlorinated biphenyls in sediment pore water using passive sampling with polyoxymethylene.

Studies into bioaccumulation of polychlorinated biphenyls (PCBs) have increasingly focused on congeners that are freely dissolved in sediment interstitial pore water. Because of their low water solubilities and their tendency to persist and concentrate as they progress in the food chain, interest has grown in methods capable of measuring individual PCB congeners at low part-per-quadrillion (picogram per liter) concentrations. Obtaining large volumes of pore water is difficult (or impossible), which makes conventional analytical approaches incapable of attaining suitable detection limits. In the present study, nondepletive sampling is used to achieve very low detection limits of freely dissolved PCBs, while requiring no separation of the sediment and water slurry. Commercially available 76 microm thick polyoxymethylene (POM) coupons were placed directly into wet sediments and left to reach equilibrium with the pore water and sediment PCBs for up to 84 days, with 28 days found to be sufficient. Freely dissolved concentrations were then calculated by dividing the PCB concentration found in the POM by its POM/water partitioning coefficient (K(POM)). The K(POM) values required for determining water concentrations were measured using two spiked sediments and two historically contaminated sediments for all 62 PCB congeners that are present at greater than trace concentrations in commercial Aroclors. Log K(POM) values ranged from ca. 4.6 for dichloro-congeners to ca. 7.0 for octachloro-congeners and correlate well with octanol/water coefficients (K(OW)) (r(2) = 0.947) so that a simple linear equation can be used to calculate dissolved concentrations within a factor of 2 or better for congeners having no measured K(POM) value. Detection limits for freely dissolved PCBs ranged from ca. 20 pg/L (part-per-quadrillion) for dichloro-congeners down to ca. 0.2 pg/L for higher-molecular-weight congeners. Sorption isotherms were found to be linear (r(2) > 0.995) over at least 3 orders of magnitude for all congeners, demonstrating good quantitative linearity of the method for determining freely dissolved PCB concentrations at environmentally relevant levels.

Solid-phase-microextraction measurement of 62 polychlorinated biphenyl congeners in milliliter sediment pore water samples and determination of K(DOC) values.

Determining dissolved concentrations of polychlorinated biphenyls (PCBs) in sediment pore (interstitial) water with conventional solvent extraction methods is problematic because obtaining large (liter) quantities of pore water, separating it from the sediment, and removing the influence of colloids can be very difficult. However, solid-phase-microextraction (SPME) can achieve similar detection limits using milliliter water samples as achieved with organic solvent extraction requiring a liter of pore water. Five different SPME sorbents were evaluated for their ability to yield the best detection limits for di- to octachlorobiphenyl congeners, both with GC/ECD and with GC/MS (both positive ion EI and negative ion CI). SPME using the 7 microm PDMS fiber with GC/MS (positive ion EI) yielded the best combination of signal-to-noise and selectivity using a 30 min extraction, although ECD was also suitable. Pore water was obtained by centrifuging wet sediment followed by flocculation to remove colloids. Quantitative calibration was simplified by adding dichloro- to hexachlorobiphenyl internal standards chosen to be compatible with either ECD or MS detection. Calibration curves and relative response factors (including the SPME and GC steps) were determined for all 62 PCB congeners that are present in above-trace quantities in commercial Aroclors. Calibrations were linear (r(2) typically >0.995) from low pg/mL to ng/mL concentrations, with near zero intercepts. Detection limits for all individual PCB congeners ranged from <1 to 3 pg/mL using 1.5 mL water samples. Dissolved organic matter (DOM) had no measurable effect on dichloro- and trichlorobiphenyls, but did contain about 10 to 25% of the tetrachlorobiphenyls and up to 60% of the hexachlorobiphenyl congeners. Log DOC/water partitioning coefficients (log K(DOC)) ranged from 3.6 to 4.6 for 2,3,5,6-tetrachlorobiphenyl and from 4.2 to 5.5 for 3,3',4,4',5,5'-hexachlorobiphenyl.

Laser-induced fluorescence coupled with solid-phase microextraction for in situ determination of PAHs in sediment pore water.

In situ sampling with solid-phase microextraction (SPME) was coupled with laser-induced fluorescence (LIF) in an effort to develop a simple field-portable method to determine total dissolved PAH (polycyclic aromatic hydrocarbon) concentrations in sediment pore water. Glass fiber rods with a 50 microm coating of optically clear polydimethylsiloxane (PDMS) were inserted directly into sediment/water slurries. After 1-140 h (typically 18 h), the coated rods were recovered, rinsed with water, and their LIF response was measured with excitation wavelength (308 nm) and emission wavelengths (350-500 nm) chosen to monitor 2- to 6-ring PAHs. SPME-UF response was independent of sediment sample size, as is required for equilibrium sampling methods to be used in situ in the field. Potential interferences from high and variable background fluorescence from dissolved organic matter were eliminated by the use of the nonpolar PDMS sorbent. The detection limit in pore water was ca. 2 ng/mL (as total PAH-34), which corresponds to ca. 0.2 EPA PAH toxic units. Good quantitative agreement (r2 = 0.96) for total PAH-34 pore water concentrations with conventional GC/MS determinations was obtained for 33 surface sediments collected from former manufactured gas plant (MGP) and related sites. Quantitative agreement between SPME-LIF and GC/MS total PAH-34 concentrations was also good for 11 sediment cores (r2 = 0.87), but the predominance of 2-ring PAHs (compared to the other sites) resulted in a lower relative SPME-LIF response compared to the surface sediment samples. The method is very simple to perform, and should be directly applicable to field surveys.

Interaction of soil, water and TNT during degradation of TNT on contaminated soil using subcritical water.

Subcritical water was used at laboratory scale to reveal information with respect to the degradation mechanism of TNT on contaminated soil. Highly contaminated soil (12% TNT) was heated with water at four different temperatures, 150, 175, 200 and 225 degrees C and samples were obtained at appropriate time intervals. At the same time, similar experiments were performed with TNT spiked on to clean soil, sand and pure water in order to compare and eliminate various factors that may be present in the more complex contaminated soil system. Subcritical water was successful at remediating TNT-contaminated soil. TNT destruction percentages ranged between 98 and 100%. The aim of this work was to study the soil-water-contaminant interaction and determine the main physical parameters that affect TNT degradation. It was shown that the rate-limiting step of the process is the extraction/diffusion of TNT molecules from the soil core to the soil surface, where they degrade. Additionally, it was determined that the soil matrix also catalyses degradation to a lesser extent. Autocatalytic effects were not clearly observed.

Predicting PAH bioaccumulation and toxicity in earthworms exposed to manufactured gas plant soils with solid-phase microextraction.

Soils from former manufactured gas plant (MGP) sites are often heavily contaminated with polycyclic aromatic hydrocarbons (PAHs). Current risk assessment methods that rely on total PAH concentrations likely overstate adverse effects of such soils since bioavailability is ignored. In this study, solid-phase microextraction (SPME) was applied to estimate bioavailable PAH concentrations and toxicity in earthworms exposed to 15 MGP soils. In addition, PAH sorption to all soils (K0o values) was determined. The results showed a several orders of magnitude variation in Koc values, demonstrating that generic organic carbon-normalized sorption coefficients will typically be overconservative at MGP sites. SPME-predicted bioaccumulation generally was within a factor of 10 of measured bioaccumulation (in earthworm bioassays), in contrast to current risk assessment model estimates that overpredicted bioaccumulation 10-10 000 times. Furthermore, on the basis of estimated total body residues of narcotic PAHs, SPME correctly predicted worm mortality observed during bioassays in the majority of cases. For MGP sites where current risk assessment procedures indicate concerns, SPME thus provides a useful tool for performing a refined, site-specific assessment.