Sample storage and extraction efficiencies in determination of polycyclic and nitro musks in sewage sludge

Analytical technology is continuously improving, developing better methods for isolating and concentrating trace compounds in environmental samples. Polycyclic and nitro musks (PNMs) are one group of emerging trace compounds detected in municipal wastewater. Differences in sample storage, preparation, and extraction methods for their measurement have led to variability in results. We analyzed 11 PNMs by GC/MS and compared the results of different storage times and extraction methods (supercritical fluid (SFE) or microwave-assisted (MAE)) for 202 samples of primary sludge, waste activated sludge (WAS), raw sludge, and aerobically/anaerobically digested biosolids collected from Canadian municipal wastewater treatment plants. Sixty-three air-dried samples were extracted by SFE, and 139 air-dried, centrifuged, or filtered samples were extracted by MAE. The mean surrogate recoveries were 89% (standard deviation (SD)=11%) for d(10)-anthracene by SFE and 88% (SD=14%) for d(10)-phenanthrene by MAE. Storage study results showed that PNM concentrations changed by a mean of 7% and 9% for primary sludge and WAS respectively after four weeks and decreased up to 25% after 13.5 months of storage in amber glass containers at -18 degrees C. Air-drying of sludge at room temperature caused losses of about 50% of PNM concentrations compared to centrifugation. The proportions of PNMs present in the liquid phase of sludge samples were less than 5% compared to proportions in the sludge solids. The most complete liquid-solid separation was achieved by filtration of frozen/thawed sludge samples, producing a liquid phase that contained less than 1% of the total musk content of the sample.     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

Measuring and modelling experimental densities and ultrasonic velocities of aromatic and halogenated environmental pollutants

The potential environmental impact of aromatic and halogenated chemicals from the petrochemical and steel industry is of growning concern. The present paper deals with the modelling and experimental determination of density and speed of sound at the range 278.15-323.15 of six aromatic and halogenated compounds (Benzene, Toluene, Ethylbenzene, Fluorobenzene, 2-Fluorotoluene and Chlorobenzene). Fitting equations were applied to the data in order to correlate for later computer based design. The estimation of the studied properties was made by the application of different theoretical procedures. The Mchaweh-Nasrifar-Moshfeghian model (MNM), an equation of state based on the generalized van der Waals theory which combines the Staverman-Guggenheim combinatorial term of lattice statistics with an attractive lattice gas expression and the Free Length Theory showed a good response at the studied conditions.     

Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples - impact of sources and meteorological conditions

Urban aerosol was collected in a summer and a winter campaign for 7 and 3 days, respectively. Low volume samples were taken with a time resolution of 160 min using a filter/sorption cartridge system extended by an ozone scrubber. Concentrations of mainly particle associated polycyclic aromatic hydrocarbons (PAH) and oxidised PAH (O-PAH) were determined by gas chromatography/high resolution mass spectrometry. The sampling site was located in the city centre of Augsburg, Germany, near major roads with high traffic volume. The daily concentrations and profiles were mainly governed by local emissions from traffic and domestic heating, as well as by the meteorological conditions. During the winter campaign, concentrations were more than 10 fold higher than during the summer campaign. Highest concentrations were found concurrent with low boundary layer heights and low wind speeds. Significant diurnal variation of the PAH profiles was observed. Enhanced influences of traffic related PAH on the PAH profiles were evident during daytime in summer, whereas emissions from hot water generation and domestic heating were obvious during the night time of both seasons. A general idea about the global meteorological situation was acquired using back trajectory calculations (NOAA ARL HYSPLIT4). Due to high local emissions in combination with low air exchange during the two sampling campaigns, effects of mesoscale transport were not clearly observable.     

Uptake and loss of dissolved 109Cd and 75Se in estuarine macroinvertebrates

Semaphore crabs (Heloecius cordiformis), soldier crabs (Mictyris platycheles), ghost shrimps (Trypaea australiensis), pygmy mussels (Xenostrobus securis), and polychaetes (Eunice sp.), key benthic prey items of predatory fish commonly found in estuaries throughout southeastern Australia, were exposed to dissolved (109)Cd and (75)Se for 385 h at 30 k Bq/l (uptake phase), followed by exposure to radionuclide-free water for 189 h (loss phase). The whole body uptake rates of (75)Se by pygmy mussels, semaphore crabs and soldier crabs were 1.9, 2.4 and 4.1 times higher than (109)Cd, respectively. There were no significant (P>0.05) differences between the uptake rates of (75)Se and (109)Cd for ghost shrimps and polychaetes. The uptake rates of (109)Cd and (75)Se were highest in pygmy mussels; about six times higher than in soldier crabs for (109)Cd and in polychaetes for (75)Se - the organisms with the lowest uptake rates. The loss rates of (109)Cd and (75)Se were highest in semaphore crabs; about four times higher than in polychaetes for (109)Cd and nine times higher than in ghost shrimps for (75)Se - the organisms with the lowest loss rates. The loss of (109)Cd and (75)Se in all organisms was best described by a two (i.e. short and a longer-lived) compartment model. In the short-lived, or rapidly exchanging, compartment, the biological half-lives of (75)Se (16-39 h) were about three times greater than those of (109)Cd (5-12h). In contrast, the biological half-lives of (109)Cd in the longer-lived, or slowly exchanging compartment(s), were typically greater (1370-5950 h) than those of (75)Se (161-1500 h). Semaphore crabs had the shortest biological half-lives of both radionuclides in the long-lived compartment, whereas polychaetes had the greatest biological half-life for (109)Cd (5950 h), and ghost shrimps had the greatest biological half-life for (75)Se (1500 h). This study provides the first reported data for the biological half-lives of Se in estuarine decapod crustaceans. Moreover, it emphasises the importance of determining metal(loid) accumulation and loss kinetics in keystone prey items, which consequently influences their trophic transfer potential to higher-order predators.     

Effect of soil moisture dynamics on dense nonaqueous phase liquid (DNAPL) spill zone architecture in heterogeneous porous media

The amount, location, and form of NAPL in contaminated vadose zones are controlled by the spatial distribution of water saturation and soil permeability, the NAPL spill scenario, water infiltration events, and vapor transport. To evaluate the effects of these processes, we used the three-phase flow simulator STOMP, which includes a new permeability-liquid saturation-capillary pressure (k-S-P) constitutive model. This new constitutive model considers three NAPL forms: free, residual, and trapped. A 2-D vertical cross-section with five stratigraphic layers was assumed, and simulations were performed for seven cases. The conceptual model of the soil heterogeneity was based upon the stratigraphy at the Hanford carbon tetrachloride (CT) spill site. Some cases considered co-disposal of NAPL with large volumes of wastewater, as also occurred at the Hanford CT site. In these cases, the form and location of NAPL were most strongly influenced by high water discharge rates and NAPL evaporation to the atmosphere. In order to investigate the impact of heterogeneity, the hydraulic conductivity within the lower permeability layer was modeled as a realization of a random field having three different classes. For six extreme cases of 100 realizations, the CT mass that reached the water table varied by a factor of two, and was primarily controlled by the degree of lateral connectivity of the low conductivity class within the lowest permeability layer. The grid size at the top boundary had a dramatic impact on NAPL diffusive flux just after the spill event when the NAPL was present near the ground surface. NAPL evaporation with a fine grid spacing at the top boundary decreased CT mass that reached the water table by 74%, compared to the case with a coarse grid spacing, while barometric pumping had a marginal effect for the case of a continuous NAPL spill scenario considered in this work. For low water infiltration rate scenarios, the distribution of water content prior to a NAPL spill event decreased CT mass that reached the water table by 98% and had a significant impact on the formation of trapped NAPL. For all cases simulated, use of the new constitutive model that allows the formation of residual NAPL increased the amount of NAPL retained in the vadose zone. Density-driven advective gas flow from the ground surface controlled vapor migration in strongly anisotropic layers, causing NAPL mass flux to the lower layer to be reduced. These simulations indicate that consideration of the formation of residual and trapped NAPLs and dynamic boundary conditions (e.g., areas, rates, and periods of different NAPL and water discharge and fluctuations of atmospheric pressure) in the context of full three-phase flow are needed, especially for NAPL spill events at the ground surface. In addition, NAPL evaporation, density-driven gas advection, and NAPL vertical movement enhanced by water flow must be considered in order to predict NAPL distribution and migration in the vadose zone.     

Modeling in-situ uranium(VI) bioreduction by sulfate-reducing bacteria

We present a travel-time based reactive transport model to simulate an in-situ bioremediation experiment for demonstrating enhanced bioreduction of uranium(VI). The model considers aquatic equilibrium chemistry of uranium and other groundwater constituents, uranium sorption and precipitation, and the microbial reduction of nitrate, sulfate and U(VI). Kinetic sorption/desorption of U(VI) is characterized by mass transfer between stagnant micro-pores and mobile flow zones. The model describes the succession of terminal electron accepting processes and the growth and decay of sulfate-reducing bacteria, concurrent with the enzymatic reduction of aqueous U(VI) species. The effective U(VI) reduction rate and sorption site distributions are determined by fitting the model simulation to an in-situ experiment at Oak Ridge, TN. Results show that (1) the presence of nitrate inhibits U(VI) reduction at the site; (2) the fitted effective rate of in-situ U(VI) reduction is much smaller than the values reported for laboratory experiments; (3) U(VI) sorption/desorption, which affects U(VI) bioavailability at the site, is strongly controlled by kinetics; (4) both pH and bicarbonate concentration significantly influence the sorption/desorption of U(VI), which therefore cannot be characterized by empirical isotherms; and (5) calcium-uranyl-carbonate complexes significantly influence the model performance of U(VI) reduction.     

Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.     

A synchronized amphibian metamorphosis assay as an improved tool to detect thyroid hormone disturbance by endocrine disruptors and apolar sediment extracts

Amphibian metamorphosis assays are used to evaluate potential effects of endocrine disrupting compounds on the thyroid hormone axis. In this study, Xenopus laevis tadpoles are kept in a solution of 0.2% thiourea (TU) to arrest and synchronise them in their development. The advantage of this synchronized amphibian metamorphosis assays is that synchronised tadpoles are available at any time to start metamorphosis experiments, and experimental groups are much more homogenous at the start of experimental exposure compared with groups selected from an untreated pool of animals. The water volume per animal was kept constant throughout the experimental period to overcome the influence of declining numbers of animals per aquarium due to metamorphosis and mortality on the density dependent development of the remaining tadpoles. Clophen A50 (a technical PCB mixture), the single congener 3,3',4,4'-tetrachlorobiphenyl (PCB 77) and apolar sediment extracts that were previously tested positive in the T-Screen, an in vitro proliferation assay for thyroid hormone disruption, were tested in the Synchronized Amphibian Metamorphosis Assay. Endpoints studied were mortality, malformations, body weight, and percentage of metamorphosed froglets at the end of the 60-day experimental period, percentage of tadpoles in different developmental stages, and developmental stage-dependent awarded penalty points. Dietary exposure to Clophen A50 (0.2-50mg/kg food) resulted in a significant increased percentage of tadpoles that did not pass metamorphosis at concentrations higher than 2mg/kg food. Time until metamorphosis in those animals that were able to metamorphose after the 60-days experimental period was significantly decreased. Dietary exposure to PCB 77, a congener that can be readily metabolised, did not result in significant effects in any exposure group (2-500 microg/kg food). Apolar sediment extracts from two of the three sites that are contaminated with a wide variety of chemicals significantly decreased the percentage of metamorphosed animals and significantly increased the number of tadpoles that remained in early and late metamorphic stages. These effects already occurred when the extracts where diluted more than 1000 times (on an organic carbon base) compared to environmental concentrations. The rank of potency was comparable to results obtained with the T-screen. This suggests the presence of thyroid hormone disrupting compounds in the aquatic environment and possible effects of such compounds on animal development in the wild.     

Risk assessment of linear alkylbenzene sulphonates, LAS, in agricultural soil revisited: robust chronic toxicity tests for Folsomia candida (Collembola), Aporrectodea caliginosa (Oligochaeta) and Enchytraeus crypticus (Enchytraeidae)

To obtain robust data on the toxicity of LAS, tests with the collembolan Folsomia candida L., the oligochaetes Aporrectodea caliginosa Savigny (earthworm) and Enchytraeus crypticus Westheide and Graefe (enchytraeid) were performed in a sandy loam soil. Additionally limited tests with LAS spiked to sewage sludge, and subsequently mixed into soil, were performed. For the endpoint of interest, reproduction in soil, we found an EC10 of 205 mg LAS kg(-1) soil [8.6-401] [95% confidence limits] for F. candida and an EC10 of 46 mg LAS kg(-1) soil [13-80] for A. caliginosa after 28 days. E. crypticus was not affected by concentrations up to 120 mg LAS kg(-1) soil. When adding (low contaminated) non-spiked sludge to soil, high stimulation of reproduction was observed for E. crypticus and A. caliginosa but not for F. candida. We argue that this difference in stimulative response between the tested species is related to the difference in feeding behaviour. Sludge spiked with LAS did not significantly affect the reproduction of F. candida (fertility: number of juvenile offspring) and A. caliginosa (fecundity: number of cocoons) (dose equivalent to 181 g and 91 g LAS kg(-1) sludge, respectively). Significantly reduced reproduction was observed for E. crypticus (at 120 mg LAS kg(-1) soil+sludge corresponding to 72 g LAS kg(-1) sludge) compared to non-spiked sludge. The reproduction by E. crypticus was, however, comparable to the reproduction observed in the control soil without sludge. Compared to LAS directly spiked to soil, the reproductive output of organisms exposed to spiked sludge was either not significantly different (F. candida, E. crypticus) or significantly improved (A. caliginosa). More studies are needed in order to make firm conclusions on the potential effect of artificially contaminated sludge in soil systems.