Thomas Hartnik

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.

Persistence of the De-Icing Additive Benzotriazole at an Abandoned Airport

The environmental fate of many of the additives in the deicing agents used at airports is poorly understood. One and two years after deicing activities ceased, soil and groundwater samples were taken at an abandoned airport. Benzotriazole (BT), a corrosion and flame inhibitor, was found in low concentrations in soils along runways (mean 0.33 mg/kg), at a snow disposal site (0.66 mg/kg), as well as in sediments of a drainage ditch (13 mg/kg). Locally, high BT concentrations were found in the groundwater below the deicing pad, the regeneration plant and the snow disposal site (1.2 to 1100 μg/l). Methyl substituted triazoles or tolytriazoles (MeBT) were found in concentrations less than 10% of the BT concentration. Propylene glycol was not detected in soil samples and in only one of the groundwater samples. Microtox tests of the water samples revealed no acute toxic response, however a reduction in nitrification rate was observed (14–43%). The nitrification response could not be related directly to the BT concentration in the samples, although samples with a high BT concentration showed the largest reduction in nitrification rate. BT showed very little sorption in various soil matrices, only peat and compost with a high organic carbon content showed significant sorption. Sorption could be best described using a Freundlich isotherm. These results indicate a high mobility and possibly long persistence of BT in soil and groundwater, which may be attributed to the absence of microbial degradation of BT.

Sorption of organic compounds to fresh and field-aged activated carbons in soils and sediments.

Activated carbon (AC) amendment to polluted sediment or soil is an emerging in situ treatment technique that reduces freely dissolved porewater concentrations and subsequently reduces the ecological and human health risk of hydrophobic organic compounds (HOCs). An important question is the capacity of the amended AC after prolonged exposure in the field. To address this issue, sorption of freshly spiked and native HOCs to AC aged under natural field conditions and fresh AC amendments was compared for one soil and two sediments. After 12-32 months of field aging, all AC amendments demonstrated effectiveness for reducing pore water concentrations of both native (30-95%) and spiked (10-90%) HOCs compared to unamended sediment or soil. Values of K(AC) for field-aged AC were lower than freshly added AC for spiked HOCs up to a factor of 10, while the effect was less for native HOCs. The different behavior in sorbing native HOCs compared to freshly spiked HOCs was attributed to differences in the sorption kinetics and degree of competition for sorption sites between the contaminants and pore-clogging natural organic matter. The implications of these findings are that amended AC can still be effective in sorbing additional HOCs some years following amendment in the field. Thus, a certain level of long-term sustainability of this remediation approach is observed, but conclusions for decade-long periods cannot be drawn solely based on the present study.

Activated carbon amendment to sequester PAHs in contaminated soil: A lysimeter field trial

Activated carbon (AC) amendment is an innovative method for the in situ remediation of contaminated soils. A field-scale AC amendment of either 2% powder or granular AC (PAC and GAC) to a PAH contaminated soil was carried out in Norway. The PAH concentration in drainage water from the field plot was measured with a direct solvent extraction and by deploying polyoxymethylene (POM) passive samplers. In addition, POM samplers were dug directly in the AC amended and unamended soil in order to monitor the reduction in free aqueous PAH concentrations in the soil pore water. The total PAH concentration in the drainage water, measured by direct solvent extraction of the water, was reduced by 14% for the PAC amendment and by 59% for GAC, 12 months after amendment. Measurements carried out with POM showed a reduction of 93% for PAC and 56% for GAC. The free aqueous PAH concentration in soil pore water was reduced 93% and 76%, 17 and 28 months after PAC amendment, compared to 84% and 69% for GAC. PAC, in contrast to GAC, was more effective for reducing freely dissolved concentrations than total dissolved ones. This could tentatively be explained by leaching of microscopic AC particles from PAC. Secondary chemical effects of the AC amendment were monitored by considering concentration changes in dissolved organic carbon (DOC) and nutrients. DOC was bound by AC, while the concentrations of nutrients (NO(3), NO(2), NH(4), PO(4), P-total, K, Ca and Mg) were variable and likely affected by external environmental factors.

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.

PAH-sequestration capacity of granular and powder activated carbon amendments in soil, and their effects on earthworms and plants

A field lysimeter study was carried out to investigate whether the amendment of 2% powder and granular activated carbon (PAC and GAC) to a soil with moderate PAH contamination had an impact on the PAH bioaccumulation of earthworms and plants, since AC is known to be a strong sorbent for organic pollutants. Furthermore, secondary effects of AC on plants and earthworms were studied through growth and nutrient uptake, and survival and weight gain. Additionally, the effect of AC amendments on soil characteristics like pH, water holding capacity, and the water retention curve of the soil were investigated. Results show that the amendment of 2% PAC had a negative effect on plant growth while the GAC increased the growth rate of plants. PAC was toxic to earthworms, demonstrated by a significant weight loss, while the results for GAC were less clear due to ambiguous results of a field and a parallel laboratory study. Both kinds of AC significantly reduced biota to soil accumulation factors (BSAFs) of PAHs in earthworms and plants. The GAC reduced the BSAFs of earthworms by an average of 47 ± 44% and the PAC amendment reduced them by 72 ± 19%. For the investigated plants the BSAFs were reduced by 46 ± 36% and 53 ± 22% by the GAC and PAC, respectively.

Photochemical degradation of benzotriazole.

Abstract Benzotriazole is a commonly used additive in aircraft de-icing fluids. As a result of extensive de-icing activities the compound is detected in the groundwater below de-icing platforms at several international airports. The compound is toxic, and not biodegradable. Laboratory tests have been performed to study if UV irradiation can degrade the compound and reduce the aquatic toxicity. Benzotriazole can be degraded by UV irradiation at pH values below 7. Approximately 65% reduction in the benzotriazole concentration was achieved at a dose of 320 mWs/cm2, and almost 90% reduction was achieved at 1070 mWs/cm2, with an apparent first order relation between the logarithm to the UV dose and the reduction. Benzotriazole is not significantly mineralised by UV irradiation, but transformed into other compounds, of which aniline and phenazine were identified. The metabolites show toxic effects, but they are not as toxic as benzotriazole, resulting in a general decrease in toxicity as a result of UV irradiation.

Toxicity of the pesticide alpha‐cypermethrin to four soil nontarget invertebrates and implications for risk assessment

Alpha-cypermethrin, a synthetic pyrethroid, is used as an insecticide in agricultural settings and is increasingly replacing organophosphates and carbamates because of lower application rates and lower toxicity to mammals. Because very little is known about the acute and chronic toxicity of this compound for soil-living organisms, the present study investigated acute and sublethal toxicity of alpha-cypermethrin for four terrestrial invertebrate species in an agricultural soil from Norway. Bioassays with the earthworm Eisenia fetida, the potworm Enchytraeus crypticus, the springtail Folsomia candida, and the land snail Helix aspersa were performed according to slightly modified versions of Organization for Economic Cooperation and Development (Paris, France) or International Organization for Standardization (Geneva, Switzerland) guidelines and resulted in median lethal concentrations of greater than >1,000 to 31.4 mg/kg and sublethal no-observed-effect concentrations of 2.51 to 82 mg/kg. A high acute to chronic ratio was found, especially in the earthworms. Interspecies differences in sensitivity may be explained by differences in exposure and differences in metabolization rate. When based on measured pore-water concentrations, terrestrial species overall appear to be approximately one order of magnitude less sensitive than aquatic species. Effect assessments conducted according to European guideline for risk assessment of pesticides reveal that assessments based on acute toxicity tests are not always conservative enough to determine environmentally safe concentrations in soil. Mandatory incorporation of sublethal toxicity data will ensure that in regions with temperate climate, the effects of pesticides on populations of soil-living organisms are unlikely.

The toxicity of a ternary biocide mixture to two consecutive earthworm (Eisenia fetida) generations

The aim of the present study was to determine the toxicity of a mixture containing the biocides picoxystrobin, esfenvalerate, and triclosan to the reproduction and adult survival of two consecutive generations of Eisenia fetida (Savigny, 1826). Concentration addition and independent action were used to predict mixture toxicity. Due to degradation of mixture components during the course of the experiment, predictions were based both on the mixture composition at the beginning and the end of the exposure period. As degradations were dose-dependent, none of the calculated predictions were precise for the entire concentration range, although combining both predictions led us to conclude that lethal toxicity was well predicted by concentration addition and sublethal toxicity by independent action. Reproduction of the F1 generation was inhibited more (p < 0.0001) than reproduction of the F0 generation. Adult survival did not differ between generations. The accuracy of the mixture toxicity predictions thus depended on both the time-dependent mixture composition and the earthworm generation. The results of this study underline the need for more advanced mixture toxicity prediction models that consider degradation kinetics and changes in toxic effects over time.

Impact of Biotransformation and Bioavailability on the Toxicity of the Insecticides α-Cypermethrin and Chlorfenvinphos in Earthworm

Knowledge about the bioavailability and metabolism of pesticides in soil organisms facilitates interpretation of its toxicity in soil. The present study relates uptake kinetics and metabolism of two insecticides, the pyrethroid alpha-cypermethrin (alpha-CYP) and the organophosphate chlorfenvinphos (CFVP), in the earthworm Eisenia fetida to their lethal and sublethal toxicity. Experiments were conducted in two soils with different organic matter contents to provide media with contrasting sorption capacity for the insecticides. The results showed that organophosphate CFVP was, when taken up by earthworms, rapidly and irreversibly bound to biomolecules and the fraction of extractable parent insecticide and metabolites was low. In contrast, alpha-CYP was rapidly metabolized by earthworms but did not form conjugates. It seems that the phase II metabolism of alpha-CYP is inhibited in earthworms, resulting in an increasing accumulation of its metabolites. Instantaneous binding of non-altered CFVP to the target site presumably resulted in a higher toxicity compared to alpha-CYP and explains the small difference between lethal and reproduction toxicity. For alpha-CYP, however, accumulation of alpha-CYP metabolites in earthworms during chronic exposure may explain the large observed difference between lethal and sublethal toxicity. Bioaccumulation and toxicity of either insecticide decreased with increasing organic matter content in soil, emphasizing the role of compound sorption on bioavailability and toxicity for soil organisms.