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.     

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.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Passive samplers versus surfactant extraction for the evaluation of PAH availability in sediments with variable levels of contamination

The purpose of this study was to test the efficiency of passive solid samplers, polyoxymethylene (POM) strips and polydimethylsiloxane (PDMS) silicon tubing, to predict the bioavailability of native PAHs in contaminated sediments. Results were compared with worm bioaccumulation data and solid/liquid extraction using the surfactant Brij((R)) 700 (B700). The two passive samplers were found to act differently. The PDMS sampler overestimated the availability of PAHs in all studied sediments. The POM method provided results in accordance with those obtained with the B700 extraction. However, POM and B700 methods underestimated PAH availability in low contaminated sediments where biological factors (digestible organic matter) become important. Bioavailability of total PAHs was correctly predicted by POM and B700 in highly contaminated aluminum smelter sediments. A closer examination of individual PAH results indicated that both techniques overestimated the availability of large molecules with logK(ow)>6 suggesting a biological mechanism limiting uptake of larger PAHs which seems to be related to the molecular size of compounds.     

Effects of pig manure compost and nonionic-surfactant Tween 80 on phenanthrene and pyrene removal from soil vegetated with Agropyron elongatum

This paper evaluates the effects of pig manure compost (PMC) and Tween 80 on the removal of phenanthrene (PHE) and pyrene (PYR) from soil cultivated with Agropyron elongatum. Soils spiked with about 300mgkg(-1) of PHE and PYR were individually amended with 0%, 2.5%, 5% and 7.5% (dry wt) of PMC or 0, 20 and 100mgkg(-1) of Tween 80. Unplanted and sterile microcosms were prepared as the controls. PAH concentration, total organic matter (TOM), dissolved organic carbon (DOC), total heterotrophic and PAH degrading microbial populations in soil were quantified before and after 60d period. The results indicated that A. elongatum could significantly enhance PYR removal (from 46% to 61%) but had less impact on PHE removal (from 96% to 97%). Plant uptake of the PAHs was insignificant. Biodegradation was the key mechanism of PAH removals (<3% losses in the sterile control). Increase in PMC or Tween 80 levels increased the removal of PYR but not of PHE. Maximal PYR removal of 79% and 92% were observed in vegetated soil receiving 100mgkg(-1) Tween 80 and 7.5% PMC, respectively. Enhanced PYR removal in soil receiving PMC could be explained by the elevated levels of DOC, TOM and microbial populations as suggested by Pearson correlation test. While the positive effect of Tween 80 on PYR removal could probably due to its capacities to enhance PYR bioavailability in soil. This paper suggests that the addition of either PMC or nonionic-surfactant Tween 80 could facilitate phytoremediation of PAH contaminated soil.     

The fate of the aqueous phase polycyclic aromatic hydrocarbon fraction in a detention pond system

The concentration of dissolved polycyclic aromatic hydrocarbons (PAH) in influent, effluent, and within a detention pond system was measured. The "soluble fraction" was operationally defined as the PAHs in solution that passed through a 1.2 μm filter. The results show that influent and effluent PAH concentrations were similar, indicating that dissolved PAH moved essentially unhindered through the detention pond system. In general, low molecular weight PAH were present at the highest concentrations and the highest PAH concentrations were measured in Summer. Also, year-to-year variations in PAH concentration were observed. At the end of sufficiently large storms, the pond was comparably unpolluted. During dry periods, the dissolved PAH concentration rose, possibly due to evapoconcentration and by partitioning of PAH from trapped contaminated sediment in the detention pond system. This study provides evidence that aqueous-phase PAH concentrations in runoff water were relatively unaffected by the passage through a conventional detention pond system.     

Uptake of polycyclic aromatic hydrocarbons (PAHs) in salt marsh plants Spartina alterniflora grown in contaminated sediments

Polycyclic aromatic hydrocarbon (PAH) concentrations were measured in Spartina alterniflora plants grown in pots of contaminated sediment, plants grown in native sediment at a marsh contaminated with up to 900 microg/g total PAHs, and from plants grown in uncontaminated control sediment. The roots and leaves of the plants were separated, cleaned, and analyzed for PAHs. PAH compounds were detected at up to 43 microg/g dry weight in the root tissue of plants grown in pots of contaminated soil. PAH compounds were detected at up to 0.2 microg/g in the leaves of plants grown in pots of contaminated soil. Concentrations less than 0.004 microg/g were detected in the leaves of plants grown at a reference site. Root concentration factor (RCF) values ranged from 0.009 to 0.97 in the potted plants, and from 0.004 to 0.31 at the contaminated marsh site. Stem concentration factor (SCF) values ranged from 0.00004 to 0.03 in the potted plants and 0.0002 to 0.04 at the contaminated marsh. No correlation was found between the RCF value and PAH compound or chemical properties such as logKOW. SCF values were higher for the lighter PAHs in the potted plants, but not in the plants collected from the contaminated marsh. PAH concentrations in the roots of the potted plants are strongly correlated with soil concentrations, but there is less correlation for the roots grown in natural sediments. Additional plants were grown directly in PAH-contaminated water and analyzed for alkylated PAH homologs. No difference was found in leaf PAH concentrations between plants grown in contaminated water and control plants.     

Influence of activated carbon amendment on the accumulation and elimination of PCBs in the earthworm Eisenia fetida

In this study we investigated the use of activated carbon (AC) as a soil amendment for reducing bioavailability of polychlorinated biphenyls (PCBs) to the earthworm Eisenia fetida. Artificial soil was contaminated with PCBs and used in bioaccumulation experiments fresh or after aging for 19 months. PCB bioaccumulation in earthworms was reduced by 68% when AC was placed as a layer without mixing and by 94% when AC was manually mixed into the soil. Aging of the same AC mixed soil for 19 months resulted in an overall reduction of 99% in PCB biouptake. AC-treated aged soil also showed two orders of magnitude lower equilibrium aqueous concentrations of PCBs compared to untreated aged soils. The findings from this study indicate that application of engineered sorbents like AC to PCB impacted soils may greatly reduce PCB uptake at the base of the terrestrial food chain.     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

Effects of biochar and greenwaste compost amendments on mobility, bioavailability and toxicity of inorganic and organic contaminants in a multi-element polluted soil

Applying amendments to multi-element contaminated soils can have contradictory effects on the mobility, bioavailability and toxicity of specific elements, depending on the amendment. Trace elements and PAHs were monitored in a contaminated soil amended with biochar and greenwaste compost over 60 days field exposure, after which phytotoxicity was assessed by a simple bio-indicator test. Copper and As concentrations in soil pore water increased more than 30 fold after adding both amendments, associated with significant increases in dissolved organic carbon and pH, whereas Zn and Cd significantly decreased. Biochar was most effective, resulting in a 10 fold decrease of Cd in pore water and a resultant reduction in phytotoxicity. Concentrations of PAHs were also reduced by biochar, with greater than 50% decreases of the heavier, more toxicologically relevant PAHs. The results highlight the potential of biochar for contaminated land remediation.     

Partitioning of chloroaromatic compounds between the aqueous phase and dissolved and particulate soil organic matter at chlorophenol contaminated sites

The retention and mobility of hydrophobic organic contaminants (HOCs) in soil is mainly determined by hydrophobic partitioning to dissolved and particulate organic matter (DOM and POM, respectively). The aqueous phase, DOM, and POM fractions were extracted and separated from soils at three sites contaminated with technical chlorophenol formulations. Concentrations of chlorophenols (CP), polychlorinated phenoxyphenols (PCPP), polychlorinated diphenyl ethers (PCDE) and polychlorinated dibenzo-p-dioxins and furans (PCDD/F) were determined. The partitioning to POM, in relation to DOM, increased in all three soils with increasing hydrophobicity in the order CP < PCPP ~ PCDE ~ PCDF < PCDD. Differences in partitioning to DOM (logK(DOC)) and POM (logK(POC)) could not be explained by differences in gross organic C chemistry. Black carbon did not contribute significantly to the sorption of PCDDs, whereas >70% wood fibre in one soil resulted in a decrease of logK(POC) of 0.5 units for CPs and PCDDs. We conclude that logK(OC) for both DOM and POM need to be explicitly determined when the retention and mobility of HOCs is described and modelled in soils.     

Effect of plant growth on copper solubility and speciation in soil solution samples

The effect of plant growth on copper solubility and speciation was studied in a 10-week pot experiment. A copper-tolerant grass variety (Agrostis capillaris L. var. Parys Mountain) was grown in pots that contained either clean (copper-total approx. 30 mg kg(-1)) or copper contaminated soil (copper-total approx. 170 mg kg(-1)) at two pH levels (4.7 and 5.5). Also, similar pots without vegetation were included in the study. Due to the addition of NH(4)NO(3) fertilizer and subsequent nitrification of ammonia to nitrate, soil pH decreased from 4.7 to 3.5 and from 5.5 to 4, respectively. In the planted pots, soil pH recovered faster after depletion of NH(4)(+). This resulted in a decrease in the calcium solution concentrations and an increase in the dissolved organic carbon (DOC) concentrations in the planted pots. However, this was only observed in the clean soil; in the contaminated soil no difference in DOC levels between bare and planted pots was observed. Copper solubility in the contaminated soil was lower in the presence of plants; in the clean soil no differences were observed between the bare and planted pots. In the planted pots, copper activities in solution in both clean and contaminated soils were two orders of magnitude lower than in the bare pots. Copper activities in the non-planted contaminated soil reached potentially toxic levels ([Cu]+/-10(-5) to 10(-6) M) in contrast to the lower levels in the planted pots ([Cu]+/-10(-7) to 10(-10) M). Data and model results show that plant growth improves pH, DOC and calcium in solution to such an extent that both the total dissolved copper concentration and the free metal activity in soils can be reduced. This stresses the potential beneficial role of plants for the immobilization and detoxification of metals in contaminated soils.     

Properties of biochars from conventional and alternative feedstocks and their suitability for metal immobilization in industrial soil

In contaminated soils, excessive concentrations of metals and their high mobility pose a serious environmental risk. A suitable soil amendment can minimize the negative effect of metals in soil. This study investigated the effect of different biochars on metal (Cu, Pb, Zn) immobilization in industrial soil. Biochars produced at 300 and 600 °C from conventional (MS, maize silage; WP, wooden pellets) and alternative (SC, sewage sludge compost; DR, digestate residue) feedstocks were used as soil amendments at a dosage of 10 % (w/w). The type of feedstock and pyrolysis temperature affected the properties of the biochars and their ability to immobilize metal in soil. Compared to production at 300 °C, all biochars produced at 600 °C had higher pH (6.2–10.7), content of ash (7.2–69.0 %) and fixed carbon (21.1–56.7 %), but lower content of volatile matter (9.7–37.2 %). All biochars except DR biochar had lower dissolved organic carbon (DOC) content (1.4–2.3 g C/L) when made at 600 °C. Only MS and SC biochars had higher cation exchange capacity (25.2 and 44.7 cmol/kg, respectively) after charring at 600 °C. All biochars contained low concentrations of Cd, Cu, Ni, Pb and Zn; Cd was volatilized to the greatest extent during pyrolysis. Based on FTIR analysis and molar ratios of H/C and O/C, biochars had a greater degree of carbonization and aromaticity after charring at 600 °C. The efficiency of the biochars in metal immobilization depended mainly on their pH, ash content, and concentration of DOC. SC and DR biochars were more effective for Cu and Zn immobilization than MS and WP biochars, which makes them attractive options for large-scale soil amendment.     

Grinding and sieving soil affects the availability of organic contaminants: a kinetic analysis

Field contaminated soils are often homogenized before application in bioassays and chemical assays that estimate the (bio)availability of their contaminants. The homogenization of the soil might affect the availability, and thereby the outcome of a bioassay might not reflect field situations. In this study, uptake kinetics of polycyclic aromatic hydrocarbons (PAH) by a negligible depletive passive sampler exposed to a ground and non-ground field contaminated soil were tested. The measurements illustrate how freely dissolved pore water concentrations of contaminants can be affected by soil treatment. It took more than a month, and over a year to reach steady state in the passive sampler exposed to the ground and non-ground soil, respectively. The uptake rate seemed to be limited by desorption from the soil, even though the fiber only extracted 0.2% of the soil-sorbed PAH at maximum. If these observations are translated to the field situation, where contaminants are not homogeneously distributed and disappear by (bio)degradation or physical transport processes, it is unlikely that pore water concentrations are solely determined by a thermodynamic equilibrium. Hence, exposure of organisms in these soils cannot always be estimated by sorption studies and an equilibrium partitioning approach.     

Reduction in uptake by rice and soybean of aromatic arsenicals from diphenylarsinic acid contaminated soil amended with activated charcoal

Activated charcoal (AC) amendment has been suggested as a promising method to immobilize organic contaminants in soil. We performed pot experiments with rice and soybean grown in agricultural soil polluted by aromatic arsenicals (AAs). The most abundant AA in rice grains and soybean seeds was methylphenylarsinic acid (MPAA). MPAA concentration in rice grains was significantly reduced to 2% and 3% in 0.2% AC treated soil compared to untreated soil in the first year of rice cultivation. In the second year, MPAA concentration in rice grains was significantly reduced to 15% in 0.2% AC treated soil compared to untreated soil. MPAA concentration in soybean seeds was significantly reduced to 44% in 0.2% AC treated soil compared to untreated soil. AC amendment was effective in reducing AAs in rice and soybean.     

Effect of catchment land use and soil type on the concentration,quality, and bacterial degradation of riverine dissolved organic matter

We studied the effects of catchment characteristics (soil type and land use) on the concentration and quality of dissolved organic matter (DOM) in river water and on the bacterial degradation of terrestrial DOM. The share of organic soil was the strongest predictor of high concentrations of dissolved organic carbon, nitrogen, and phosphorus (DOC, DON, and DOP, respectively), and was linked to DOM quality. Soil type was more important than land use in determining the concentration and quality of riverine DOM. On average, 5–9 % of the DOC and 45 % of the DON were degraded by the bacterial communities within 2–3 months. Simultaneously, the proportion of humic-like compounds in the DOM pool increased. Bioavailable DON accounted for approximately one-third of the total bioavailable dissolved nitrogen, and thus, terrestrial DON can markedly contribute to the coastal plankton dynamics and support the heterotrophic food web.     

Effects of earthworm cast and powdered activated carbon on methane removal capacity of landfill cover soils

Landfill gases could be vented through a layer of landfill cover soil that could serve as a biofilter to oxidize methane to carbon dioxide and water. Properly managed landfill cover soil layers may reduce atmospheric CH4 emissions from landfills. In the present study, the effects of earthworm cast and powdered activated carbon (PAC) on the CH4 removal capacity of the landfill cover soil was investigated. For this purpose, column and batch tests were conducted using three different materials: typical landfill cover soil, landfill cover soil amended with earthworm cast, and landfill cover soil amended with PAC. The maximum CH4 removal rate of the columns filled with landfill cover soil amended with earthworm cast was 14.6mol m(-2)d(-1), whereas that of the columns filled with typical landfill cover soil was 7.4mol m(-2)d(-1). This result shows that amendment with earthworm cast could stimulate the CH4-oxidizing capacity of landfill cover soil. The CH4 removal rate of the columns filled with landfill cover soil amended with PAC also showed the same removal rate, but the vertical profile of gas concentrations in the columns and the methanotrophic population measured in the microbial assay suggested that the decrease of CH4 concentration in the columns is mainly due to sorption. Based on the results from this study, amendment of landfill cover soil with earthworm cast and PAC could improve its CH4 removal capacity and thus achieve a major reduction in atmospheric CH4 emission as compared with the same landfill cover soil without any amendment.     

The effects of biochars from rice residue on the formation of iron plaque and the accumulation of Cd, Zn, Pb, As in rice (Oryza sativa L.) seedlings

A historically multi-metal contaminated soil was amended with biochars produced from different parts of rice plants (straw, husk and bran) to investigate how biochar can influence the mobility of Cd, Zn, Pb and As in rice seedlings (Oryza sativa L.). Rice shoot concentrations of Cd, Zn and Pb decreased by up to 98%, 83% and 72%, respectively, due to biochar amendment, though that of As increased by up to 327%. Biochar amendments significantly decreased pore water concentrations (C_pw) of Cd and Zn and increased that of As. For Pb it depended on the amendment. Porewater pH, dissolved organic carbon, dissolved phosphorus, silicon in pore water and iron plaque formation on root surfaces all increased significantly after the amendments. The proportions of Cd and Pb in iron plaque increased by factors 1.8-5.7 and 1.4-2.8, respectively; no increase was observed for As and Zn. Straw-char application significantly and noticeably decreased the plant transfer coefficients of Cd and Pb. This study, the first to investigate changes in metal mobility and iron plaque formation in rice plants due to amending a historically contaminated soil with biochar, indicates that biochar has a potential to decrease Cd, Zn and Pb accumulations in rice shoot but increase that of As. The main cause is likely biochar decreasing the C_pw of Cd and Zn, increasing the C_pw of As, and increasing the iron plaque blocking capacity for Cd and Pb.     

Characteristics of biotic and abiotic removals of dissolved organic carbon in wastewater effluents using soil batch reactors.

Biodegradable dissolved organic carbon (BDOC) analyses and abiotic adsorption of dissolved organic carbon (DOC) from different wastewater effluent were conducted to evaluate biotic and abiotic removal mechanisms as a function of the initial DOC concentration and source of DOC using soil batch reactors. To obtain high DOC concentrations, a laboratory-scale reverse osmosis unit was used. It was found that BDOC fraction was independent of the initial DOC concentration and was dependent on the source of wastewater and/or the types of wastewater treatment. The BDOC fractions varied from 9 to 73%. Trickling filter effluent (Tucson, Arizona) showed the highest BDOC, ranging from 65 to 73% biodegradable, while wastewater treated by the soil aquifer treatment (SAT) (NW-4) was found to be most refractory, with DOC removals of 9 to 14%. For nitrified/denitrified tertiary effluent (Mesa, Arizona) and secondary effluent (Scottsdale, Arizona), 36 to 42% removal of DOC was observed during the BDOC test. The amount of BDOC in the wastewater depended not on the concentration of DOC, but on the effectiveness of pretreatment. Abiotic adsorption capacity of wastewater effluent varied from 6 to 18%. Molecular weight distribution analyses showed that more than 50% of DOC in the Scottsdale concentrate had a molecular weight of less than 1000 Da, and no significant change in distribution profiles occurred after approximately 12% abiotic adsorption with both soils with acclimated microorganisms (SAT soil) and soils without acclimated microorganisms (non-SAT soils). Hence, preferential adsorption was not observed and the presence of acclimated microbes did not influence adsorption.