Sarah E. Hale

Quantifying the Total and Bioavailable Polycyclic Aromatic Hydrocarbons and Dioxins in Biochars

Biochar soil amendment is advocated to mitigate climate change and improve soil fertility. A concern though, is that during biochar preparation PAHs and dioxins are likely formed. These contaminants can possibly be present in the biochar matrix and even bioavailable to exposed organisms. Here we quantify total and bioavailable PAHs and dioxins in a suite of over 50 biochars produced via slow pyrolysis between 250 and 900 °C, using various methods and biomass from tropical, boreal, and temperate areas. These slow pyrolysis biochars, which can be produced locally on farms with minimum resources, are also compared to biochar produced using the industrial methods of fast pyrolysis and gasification. Total concentrations were measured with a Soxhlet extraction and bioavailable concentrations were measured with polyoxymethylene passive samplers. Total PAH concentrations ranged from 0.07 μg g(-1) to 3.27 μg g(-1) for the slow pyrolysis biochars and were dependent on biomass source, pyrolysis temperature, and time. With increasing pyrolysis time and temperature, PAH concentrations generally decreased. These total concentrations were below existing environmental quality standards for concentrations of PAHs in soils. Total PAH concentrations in the fast pyrolysis and gasification biochar were 0.3 μg g(-1) and 45 μg g(-1), respectively, with maximum levels exceeding some quality standards. Concentrations of bioavailable PAHs in slow pyrolysis biochars ranged from 0.17 ng L(-1) to 10.0 ng L(-1)which is lower than concentrations reported for relatively clean urban sediments. The gasification produced biochar sample had the highest bioavailable concentration (162 ± 71 ng L(-1)). Total dioxin concentrations were low (up to 92 pg g(-1)) and bioavailable concentrations were below the analytical limit of detection. No clear pattern of how strongly PAHs were bound to different biochars was found based on the biochars physicochemical properties.

Effects of chemical, biological, and physical aging as well as soil addition on the sorption of pyrene to activated carbon and biochar.

In this study, the suitability of biochar and activated carbon (AC) for contaminated soil remediation is investigated by determining the sorption of pyrene to both materials in the presence and absence of soil and before as well as after aging. Biochar and AC were aged either alone or mixed with soil via exposure to (a) nutrients and microorganisms (biological), (b) 60 and 110 °C (chemical), and (c) freeze-thaw cycles (physical). Before and after aging, the pH, elemental composition, cation exchange capacity (CEC), microporous SA, and sorption isotherms of pyrene were quantified. Aging at 110 °C altered the physicochemical properties of all materials to the greatest extent (for example, pH increased by up to three units and CEC by up to 50% for biochar). Logarithmic K(Fr) values ranged from 7.80 to 8.21 (ng kg(-1))(ng L(-1))(-nF) for AC and 5.22 to 6.21 (ng kg(-1))(ng L(-1))(-nF) for biochar after the various aging regimes. Grinding biochar to a smaller particle size did not significantly affect the sorption of d(10) pyrene, implying that sorption processes operate on the subparticle scale. Chemical aging decreased the sorption of pyrene to the greatest extent (up to 1.8 log unit for the biochar+soil). The sorption to AC was affected more by the presence of soil than the sorption to biochar was. Our results suggest that AC and biochar have a high sorption capacity for pyrene that is maintained both in the presence of soil and during harsh aging. Both materials could therefore be considered in contaminated land remediation.

Sorption of dichlorodiphenyltrichloroethane (DDT) and its metabolites by activated carbon in clean water and sediment slurries.

Polyethylene-water partitioning coefficients (K(PE)) and mass transfer coefficients (k(PE)) for the ortho and para isomers of the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT) and its metabolites dichlorodiphenyldichloroethane (DDD), dichlorodiphenyldichloroethylene (DDE) and, dichlorodiphenylmonochloroethylene (DDMU) were measured. These data were used to derive activated carbon (AC) sorption isotherms in clean water in the sub-nanogram per litre free aqueous concentration range for a virgin and a regenerated AC. The sorption strength of AC for DDT and its metabolites was very high and logarithmic values of the AC-water partitioning coefficients, logK(AC), ranged from 8.47 to 9.26. A numerical mass transfer model was calibrated with this data to interpret previously reported reductions in DDT uptake by semipermeable membrane devices after AC amendment of sediment from Lauritzen Channel, California, USA. The activated carbon-water partitioning coefficient values (K(AC)) measured in clean water systems appear to overestimate the AC sorption capacity in sediment up to a factor 32 for DDT and its metabolites at long contact time with fine-sized AC. Modelling results show decreased attenuation of the AC sorption capacity with increased sediment-AC contact time. We infer that increased resistance in mass transfer of DDTs to sorption sites in the microporous region likely caused by deposits of dissolved organic matter in the macro- and mesopores of AC appears to be the most relevant fouling mechanism. These results suggest that DDTs may diffuse through possible deposits of dissolved organic matter over time, implying that the effects of sediment on the sorption of DDTs by AC may be more kinetic than competitive.

Equilibrium partition coefficients of diverse polar and nonpolar organic compounds to polyoxymethylene (POM) passive sampling devices.

Equilibrium passive samplers (EPS) based on polyoxymethylene (POM) are increasingly used for determining freely dissolved water and pore water concentrations of hydrophobic organic compounds in the environment. Unlike other polymeric materials commonly used as EPS, namely poly(dimethylsiloxane) (PDMS) and low-density polyethylene (PE), POM is a polar polymer, containing repeating H-bond accepting ether units. Thus, POM is expected to be a more sensitive EPS than PDMS and PE for polar, H-bond donating compounds, such as many hormones, pharmaceuticals, and biocides. To better characterize the sorption capacity of POM for diverse polar and apolar compounds, equilibrium POM-water partition coefficients, K(POM/w), were measured for 56 compounds, including several classes of polar compounds and organochlorine pesticides. Using this data set and literature data, various POM-partitioning models were calibrated and validated for their ability to predict K(POM/w). The best performing models tested were an Abraham descriptor based polyparameter linear free energy relationship (PP-LFER) (SD = 0.24 log units) and COSMOthermX (SD = 0.37 log units). The performance of SPARC (SD = 0.61 log units) and log-log correlations with K(ow) (SD = 0.49 log units) were lower. A comparison with PDMS and PE confirmed expectations that POM exhibits a higher sensitivity for H-bond donating polar compounds than PDMS and PE do for these compounds. These findings expand the domain of chemicals for which POM can be used as an EPS sampler, and demonstrate that POM is as suitable a passive sampler for many polar organic compounds as it is for hydrophobic organic compounds.

Partitioning of organochlorine pesticides from water to polyethylene passive samplers

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

Modeling the mass transfer of hydrophobic organic pollutants in briefly and continuously mixed sediment after amendment with activated carbon.

Activated carbon (AC) amendment is currently being investigated as an in situ remediation technique for sediments contaminated by persistent organic pollutants. Understanding the mass transfer of pollutants from weaker binding sites on sediment particles, to stronger binding sites inside AC particles, is important for the evaluation of this strategy. Here we study the mass transfer of polycyclic aromatic hydrocarbons (PAHs) from River Tyne sediment to polyethylene (PE) passive samplers in the presence and absence of AC under two mixing regimes. Continuously mixing and a brief initial mixing period to incorporate AC to the system, followed by unmixed conditions in settled sediments, were compared. The reduction in total PAH concentration in the PE sampler was greater than 99% after 12 months AC contact for both conditions. A numerical model based on concepts used to simulate well-mixed AC-sediment slurries was further developed to describe the briefly mixed system. These models could predict upper and lower limits for the expected remediation effectiveness for variable AC-sediment mixing regimes. It appears that mixing mode has a small impact on the treatment effectiveness for River Tyne sediment which has a strongly bound, slowly released pollutant source. However, a greater impact is anticipated for contaminated sediments containing more available pollutants.

Effect of activated carbon amendment on bacterial community structure and functions in a PAH impacted urban soil.

We collected urban soil samples impacted by polycyclic aromatic hydrocarbons (PAHs) from a sorbent-based remediation field trial to address concerns about unwanted side-effects of 2% powdered (PAC) or granular (GAC) activated carbon amendment on soil microbiology and pollutant biodegradation. After three years, total microbial cell counts and respiration rates were highest in the GAC amended soil. The predominant bacterial community structure derived from denaturing gradient gel electrophoresis (DGGE) shifted more strongly with time than in response to AC amendment. DGGE band sequencing revealed the presence of taxa with closest affiliations either to known PAH degraders, e.g. Rhodococcus jostii RHA-1, or taxa known to harbor PAH degraders, e.g. Rhodococcus erythropolis, in all soils. Quantification by real-time polymerase chain reaction yielded similar dioxygenases gene copy numbers in unamended, PAC-, or GAC-amended soil. PAH availability assessments in batch tests showed the greatest difference of 75% with and without biocide addition for unamended soil, while the lowest PAH availability overall was measured in PAC-amended, live soil. We conclude that AC had no detrimental effects on soil microbiology, AC-amended soils retained the potential to biodegrade PAHs, but the removal of available pollutants by biodegradation was most notable in unamended soil.

Polychlorinated Biphenyl Sorption and Availability in Field-Contaminated Sediments

Traditional and new relationships of polychlorinated biphenyl (PCB) distribution among the solid phases, the free aqueous phase, and biolipids are comprehensively reviewed using seven well-characterized freshwater and marine sediments polluted with PCBs. The traditional relationship relating free aqueous concentration and biolipid concentration to sediment total organic carbon, compound octanol−water partitioning coefficient, and solid-phase contaminant concentration overestimates measured free aqueous concentrations and biolipid concentrations by mean factors of 8 and 33, respectively. By contrast, relationships based on measured free aqueous phase concentrations or the PCB mass fraction desorbed from sediment provide reasonable predictions of biolipid concentrations. Solid-phase concentration-based predictions perform better when sorption to amorphous organic matter and black carbon (BC) is distinguished. Contrary to previously published relationships, BC sorption appears to be linear for free aqueous PCB-congener concentrations in the picogram to microgram per liter range.

Short-term effect of the soil amendments activated carbon, biochar, and ferric oxyhydroxide on bacteria and invertebrates.

The aim of the present study was to evaluate the secondary ecotoxicological effects of soil amendment materials that can be added to contaminated soils in order to sequester harmful pollutants. To this end, a nonpolluted agricultural soil was amended with 0.5, 2, and 5% of the following four amendments: powder activated carbon (PAC), granular activated carbon, corn stover biochar, and ferric oxyhydroxide powder, which have previously been proven to sequester pollutants in soil. The resulting immediate effects (i.e., without aging the mixtures before carrying out tests) on the springtail Folsomia candida, the earthworm species Aporectodea caliginosa and Eisenia fetida, the marine bacteria Vibrio fischeri, a suite of ten prokaryotic species, and a eukaryote (the yeast species Pichia anomalia) were investigated. Reproduction of F. candida was significantly increased compared to the unamended soil when 2% biochar was added to it. None of the treatments caused a negative effect on reproduction. All amendments had a deleterious effect on the growth of A. caliginosa when compared to the unamended soil, except the 0.5% amendment of biochar. In avoidance tests, E. fetida preferred biochar compared to all other amendments including the unamended soil. All amendments reduced the inhibition of luminescence to V. fischeri, i.e., were beneficial for the bacteria, with PAC showing the greatest improvement. The effects of the amendments on the suite of prokaryotic species and the eukaryote were variable, but overall the 2% biochar dose provided the most frequent positive effect on growth. It is concluded that the four soil amendments had variable but never strongly deleterious effects on the bacteria and invertebrates studied here during the respective recommended experimental test periods.

Changes in polycyclic aromatic hydrocarbon availability in River Tyne sediment following bioremediation treatments or activated carbon amendment

Bioremediation and activated carbon (AC) amendment were compared as remediation strategies for sediment from the River Tyne containing 16.4 +/- 7.3 microg/g polycyclic aromatic hydrocarbons (PAHs) and approximately 5% coal particles by total dry sediment weight. Unamended, nutrient amended (biostimulated) and nutrient and Pseudomonas putida amended (bioaugmented) sediment microcosms failed to show a significant decrease in total sediment PAH concentrations over a one month period. Polyethylene passive (PE) samplers were embedded for 21 days in these sediment microcosms in order to measure the available portion of PAHs and accumulated 4.70 +/- 0.25, 12.43 +/- 1.78, and 23.49 +/- 2.73 microg PAHs/g PE from the unamended, biostimulated, and bioaugmented microcosms, respectively. Higher PAH uptake by PE samplers in biostimulated and bioaugmented microcosms coincided with slower degradation of spiked phenanthrene in sediment-free filtrate from these microcosms compared to filtrate from the unamended microcosms. Microbial community analysis revealed changes in the bacterial community directly following the addition of nutrients, but the added P. putida community failed to establish itself. Addition of 2% by dry sediment weight activated carbon reduced PAH uptake by PE samplers to 0.28 +/- 0.01 microg PAHs/g PE, a greater than 90% reduction compared to the unamended microcosms.