Release of pentachlorophenol from black carbon-inclusive sediments under different environmental conditions

To investigate the feasibility of using black carbon (BC) in the control of hydrophobic organic contaminants (HOCs) in sediment, we added BCs from various sources (rice straw charcoal (RC), fly ash (FC) and soot (SC)) to sediment to create different BC-inclusive sediments and studied the release of pentachlorophenol (PCP) in the sediments under different condition. Different pH values had no obvious effect on the release of PCP in BC-inclusive sediment, but solid/liquid ratio, temperature, salinity and dissolved organic matter (DOM) content had significant influences on the release of PCP in all sediments except the RC-inclusive sediment. Adding 2% RC to sediment resulted in a 90% decrease in PCP release, which was a greater decrease than observed with FC- and SC-inclusive sediments. Therefore, from the standpoint of HOC release, the application of RC is feasible for organic pollution control in the water environment.     

Modifications of black carbons and their influence on pyrene sorption

Sorption of pyrene on black carbons (BCs) obtained by heating sawdust at two temperatures (400 and 700 °C, denoted as 400BC and 700BC, respectively), as well as on modified BCs (via oxidation, oximation, and hydrolysis) was studied to investigate the role of BC structural characteristics in sorption of hydrophobic organic compounds. Pyrene was bound strongly by 700BC and 400BC, with organic carbon normalized distribution coefficients (K_oc) of 10^5.04-10^5.86 and 10^4.65-10^5.16, respectively, at equilibrium pyrene concentrations of 10-100 μg L⁻¹. Both chemical composition and pore distribution of the two BCs changed after modifications, which led to changes in their sorption characteristics for pyrene. After modifications, the linearity of pyrene sorption isotherm increased for 700BC but decreased for 400BC. For 700BC, both oxidation and oximation reduced pyrene sorption, with K_oc decreasing by 69.1-73.7% and 18.7-33.9%, respectively, whereas hydrolysis did not exert a significant influence. For 400BC, oxidation and hydrolysis reduced K_oc by 2.28-25.9% and 29.2-33.9%, respectively, while oximation increased K_oc. In most cases, the change in sorption capacity could be explained by the changes in C content and type, polarity, surface area, and micropore volume of the BCs; however, the role of conformation (the accessibility to sorption sites) could not be ignored.     

Effects of added PAHs and precipitated humic acid coatings on phenanthrene sorption to environmental Black carbon

Black carbon (BC; soot and charcoal) can be an extremely strong sorbent for organic compounds. In a previous study, sorption of d(10)-phenanthrene (d(10)-PHE) to BC in an unmodified contaminated sediment was found to be nine times less than that for BC isolated from this sediment. To find out the mechanism of this sorption attenuation (competition for BC sites between d(10)-PHE and native PAHs or blocking of BC sites by natural organic matter), we determined the effect on d(10)-PHE-BC sorption isotherms of additions of either PAHs or precipitated humic acid. Addition of humic acid did not significantly decrease BC sorption, whereas PAH additions (equal to the native PAH content in the original sediment) did, by about one order of magnitude. Therefore, competition between d(10)-PHE and the native PAHs could explain the whole attenuation of sorption to BC in unmodified sediments.     

Effects of black carbon and montmorillonite clay on multiphasic hexachlorobenzene desorption from sediments

The desorption kinetics of hexachlorobenzene (HCB) in four freshly spiked artificial sediments were determined using a polymeric adsorbent Tenax-mediated desorption. The sediments included a standard sediment (SS) prepared as per Organisation for Economic Cooperation and Development 218 guidelines and three derived artificial sediments prepared by supplementing the SS sediment with various levels of black carbon (lamp black soot) and/or montmorillonite clay. The desorption kinetics exhibited biphasic behavior, i.e., a fast desorbing fraction followed by a slow desorbing fraction. The addition of either lamp black soot or montmorillonite clay resulted in the reduction of the fast desorbing fraction (Ffast) of HCB in three derived sediments compared with SS sediment. Both black carbon and montmorillonite clay treatment effects on the fast desorbing fraction were statistically significant for the four artificial sediments. The black carbon treatment (i.e., addition of 0.5% wt/wt lamp black soot) effect was an average reduction of Ffast by approximately 11%, whereas the montmorillonite treatment (i.e., addition of 15% wt/wt montmorillonite clay) effect was an average reduction of Ffast by approximately 17%. The presence of soot black carbon particles reduced the desorption rate of HCB in sediments since black carbon exhibits very high sorption capacity and extremely slow diffusion rate compared with those of the natural organic matter in sediment.     

Sulfamethoxazole sorption by sediment fractions in comparison to pyrene and bisphenol A

The environmental behavior of antibiotics has attracted great research attention. However, their sorption mechanisms in soils/sediments are still unknown. Comparison of the sorption properties between the widely-studied hydrophobic organic contaminants (HOCs) and antibiotics may provide valuable insight to antibiotic sorption mechanisms. Thus, in this study batch experiments for pyrene (PYR), bisphenol A (BPA), and sulfamethoxazole (SMX) sorption were conducted on a sediment sample and its separated fractions. Our results showed the high sorption of PYR on black carbon and organic matter. Although high sorption of SMX was observed for both separated organic fractions (humic acids) and inorganic mineral particles, the original sediment particles showed relatively low sorption. Competitive sorption between SMX and dissolved humic acid on mineral particles was observed in this study. This competitive interaction is a unique process for antibiotic sorption in soils/sediments compared with apolar HOCs and may be one of the important factors controlling the antibiotic sorption.     

Sorption of PAHs and PCBs to activated carbon: coal versus biomass-based quality

The addition of activated carbon (AC) is an increasingly popular method for pollutant immobilization, and the AC material can be made of biomass or coal/fossil feedstock. The aim of the present study was to investigate whether there are differences between pollutant sorption to biomass and coal-based AC in the presence and absence of sediment. Through N₂ and CO₂ adsorption to probe surface area and pore size it was shown that the biomass-based AC had a stronger dominance of narrow pores in the size range 3.5-15 Å than the anthracite-based material. In the absence of sediment, sorption isotherms for the probe compounds pyrene and PCB-101 showed stronger sorption for the biomass-based AC (logarithmic Freundlich coefficients 8.15 for pyrene; 9.91 for PCB-101) than for the anthracite-based one (logarithmic Freundlich coefficients 7.20 and 9.70, respectively). In the presence of sediment, the opposite trend was observed, with the stronger sorption for anthracite-based AC. Thus, the presence of competing and/or pore-blocking sediment constituents reduces sorption to a larger extent for biomass-derived AC (factor of 5 for pyrene to almost 100 for PCB-101) than for anthracite-based AC (no reduction for pyrene to factor of 5 for PCB-101). This difference is tentatively attributed to the difference in pore size distribution, narrow pores being more prone to clogging, and could have implications for remediation feasibility with AC from different sources.     

Sorption of organic pollutants by marine sediments: implication for the role of particulate organic matter

The objective of this study was to quantify sorption properties for kerogen/black carbon (BC)-bearing sediments. Single-solute sorption isotherms were measured for five pristine marine sediments using phenanthrene, naphthalene, 1,3,5-trichlorobenzene, and 1,4-dichlorobenzene as the sorbates. The results showed that the sorption isotherms were nonlinear and that the organic carbon normalized single point K_OC values were comparable to those reported in the literature for the purified keorgen and BC, but are much higher than the data reported for HA and kerogen/BC-containing terrestrial soils and sediments. It is likely that koergen and BC associated with these pristine marine sediments may not be encapsulated with humic acids or Fe and Mn oxides and hydroxides as often do in terrestrial soils and sediments. As a result, they may be fully accessible to sorbing molecules, exhibiting higher sorption capacities. The study suggests that competition from background HOCs and reduced accessibility when kerogen and BC are associated with terrestrial sediments may dramatically increase variability of sorption reactivities of geosorbents. Such variability may lead to large uncertainties in the prediction of sorption from the contents of kerogen and/or BC along with TOC.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Development of a black carbon-inclusive multi-media model: application for PAHs in Stockholm

A multi-media model was developed for predicting the fate of organic chemicals in the Greater Stockholm Area, Sweden, and applied to selected polycyclic aromatic hydrocarbons (PAHs). Although urban models have been previously developed, this model is novel in that it includes sorption to pyrogenically-derived particles, commonly termed "black carbon" (BC), within the model structure. To examine the influence of BC sorption on environmental fate of PAHs, two versions of the model were generated and run: one in which sorption to BC was included and one in which BC sorption was excluded. The inclusion of BC sorption did not cause any significant variations to air levels, but it did cause an average 20-30% increase in sediment concentrations related to increased sediment solids partitioning. The model also predicted reduced advective losses out of the model domain, as well as chemical potential to diffuse from sediments, whilst total chemical inventory increased. In all cases, the lighter PAHs were more affected by BC inclusion than their heavier counterparts. We advocate the addition of sorption to BC in future multi-media fate and exposure models, which as well as influencing fate will also alter (lower) chemical availability and, thus, wildlife exposure to hydrophobic chemicals. A quantification of the latter was derived with the help of the soot-inclusive model version, which estimated a lowering of dissolved water concentrations between five and >200 times for the different PAHs of this study.     

The pH-dependent adsorption of tributyltin to charcoals and soot

Widespread use of tributyltin (TBT) poses a serious environmental problem. Adsorption by black carbon (BC) may strongly affect its behavior. The adsorption of TBT to well characterized soot and two charcoals with specific surface area in the range of 62-111 m² g⁻¹ have been investigated with main focus on pH effects. The charcoals but not soot possess acidic functional groups. TBT adsorption reaches maximum at pH 6-7 for charcoals, and at pH > 6 for soot. Soot has between 1.5 and 15 times higher adsorption density (0.09-1.77 μmol m⁻²) than charcoals, but charcoals show up to 17 times higher sorption affinities than soot. TBT adsorption is successfully described by a new pH-dependent dual Langmuir model considering electrostatic and hydrophobic adsorption, and pH effects on TBT speciation and BC surface charge. It is inferred that strong sorption of the TBTOH species to BC may affect TBT toxicity.     

Characterization of carbonaceous combustion residues: II. Nonpolar organic compounds

Aromatic and aliphatic fractions of black carbon (BC) solvent extracts were examined by gas chromatography/mass spectrometry to determine how differences in broad chemical and physical features are correlated with the load, composition, "extractability" and bioavailability of organic compounds. Diesel soot, urban dust and chimney soot had concentrations of n-alkanes >20 microg/g and of carcinogenic polycyclic aromatic hydrocarbons (PAHs)>8 microg/g. These high levels of solvent-extractable compounds were interpreted as resulting from combustion at temperatures below optimum values for BC formation. PAH concentrations normalized to the amount of soot carbon in chimney soot were close to values for diesel soot. However, the high proportion of polar amorphous organic matter in chimney soot suggests a higher bioavailability for associated PAHs. Carbon black, vegetation fire residues, and straw and wood charcoals had only residual concentrations of n-alkanes (<9 microg/g) and PAHs (<0.2 microg/g). PAH distributions were mostly unspecific, while the overall signature of the aliphatic fraction varied with BC origin. Molecular markers among plant-derived BC included steroid and sesquiterpenoid hydrocarbons. Molecular fingerprints suggest that compounds associated with fossil BC might be more refractory than those associated with plant-derived BC.     

Characterization of carbonaceous combustion residues. I. Morphological,elemental and spectroscopic features

Scanning electron microscopy, surface area determination, elemental analysis, organic matter extraction and solid-state cross polarization/magic angle spinning and Bloch decay/magic angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy were used to investigate distinctive features among carbonaceous combustion residues. Black carbon (BC) samples included diesel soot, urban dust, carbon black, chimney soot, vegetation fire residues, wood and straw charcoals. Particles varied from small spheres (<50 nm) in fossil BC (>100 m(2)/g), to large layered structures in plant-derived BC (generally <8 m(2)/g). Chimney soot also included large (>1 micrometer) liquid-like structures, while spherules >100 nm were unique to urban dust. The ratios of amorphous to soot carbon (SC) (isolated by thermal degradation) were not necessarily correlated with the degree of aromaticity estimated from H/C ratios. In particular, values of SC in diesel soot were clearly overestimated. Solvent-extractable organic matter (SEOM) was <2% for charcoals and carbon black, but >13% for urban dust, chimney and diesel soot. SEOM is thought to clog pores or to form large waxy globules, hence reducing surface areas. The ratio of polar/nonpolar SEOM was generally <7 for fossil BC, but >30 for plant-derived BC. NMR analysis revealed essentially one chemical shift in the aromatic C region of charcoals, while diesel soot also showed important aliphatic contributions. Aliphatic and oxygenated C predominated over aryl C in urban dust and chimney soot. These morphological and chemical characteristics of the BC samples are discussed in terms of their environmental implications.     

Effects of black carbon on bioturbation-induced benthic fluxes of polychlorinated biphenyls

It is unknown whether carbonaceous geosorbents, such as black carbon (BC) affect bioturbation by benthic invertebrates, thereby possibly affecting sediment-water exchange of sediment-bound contaminants. Here, we assess the effects of oil soot on polychlorinated biphenyl (PCB) mass transfer from sediment to overlying water, for sediments with and without tubificid oligochaeta as bioturbators. PCB levels were so low that toxicity to the oligochaeta played no role, whereas soot levels and binding affinity of PCBs to soot were so low that pore water PCB concentrations were not significantly affected by binding of PCBs to soot. This setup left direct effects of BC on bioturbation activity as the only explanation for any observed effects on mass transfer. Mass transfer coefficients (K_L) for benthic boundary layer transport were measured by a novel flux method using Empore™ disks as a sink for PCBs in the overlying water. For the PCBs studied (logK_ow 5.2-8.2), K_L values ranged from 0.2 to 2 cm × d⁻¹ in systems without tubificids. Systems with tubificids showed K_L values that were a factor of 10-25 higher. However, in the presence of oil soot, tubificids did not cause an increase in mass transfer coefficients. This suggests that at BC levels as encountered under field conditions, the mechanism for reduction of sediment-water transfer of contaminants may be twofold: (a) reduced mass transfer due to strong binding of the contaminants to BC, and (b) reduced mass transfer of contaminants due to a decrease in bioturbation activity.     

Effects of natural organic matter on the microporous sorption sites of black carbon in a Yangtze River sediment

Black carbon (BC), characterized by high microporosity and high specific surface area (SSA), has been demonstrated to have substantial contributions to the sorption of hydrophobic organic chemicals in soils and sediments. Other naturally occurring organic matters provide soft and penetrable sorption domains while may cling to BC and affect its original surface properties. In this work, we studied the sorption sites of a Yangtze River sediment sample with organic carbon (OC) content of 3.3 % and the preheated sediment (combusted at 375 °C) with reduced OC content (defined as BC) of 0.4 % by gas and pyrene sorption. The SSA and microporosity of the pristine and preheated sediments were characterized by N₂ and CO₂ adsorption. The results suggest that the adsorption of N₂ was hindered by amorphous organic carbon (AOC) in the pristine sediment but CO₂ was not. Instead, the uptake of CO₂ was higher in the presence of AOC, likely due to the partition of CO₂ molecules into the organic matter. The pyrene adsorptions to BC in pristine and preheated sediments show a similar adsorption capacity at high concentration, suggesting that AOC of ca. 2.9 % in the pristine sediment does not reduce the accessibility to the sorption sites on BC for pyrene.     

Adaptation, validation and application of the chemo-thermal oxidation method to quantify black carbon in soils

The chemo-thermal oxidation method at 375 °C (CTO-375) has been widely used to quantify black carbon (BC) in sediments. In the present study, CTO-375 was tested and adapted for application to soil, accounting for some matrix specific properties like high organic carbon (≤39%) and carbonate (≤37%) content. Average recoveries of standard reference material SRM-2975 ranged from 25 to 86% for nine representative Swiss and Indian samples, which is similar to literature data for sediments. The adapted method was applied to selected samples of the Swiss soil monitoring network (NABO). BC content exhibited different patterns in three soil profiles while contribution of BC to TOC was found maximum below the topsoil at all three sites, however at different depths (60-130 cm). Six different NABO sites exhibited largely constant BC concentrations over the last 25 years, with short-term (6 months) prevailing over long-term (5 years) temporal fluctuations.     

Carbonaceous particle hydration

Microgravimetric measurements of the hydration of several different black carbons or soots and a series of commercial carbon blacks have been carried out, over a relative humidity range of 20–85%, in an extension of earlier work with the model n-hexane soot. All adsorption isotherms are of type III and were analyzed by the use of the Dubinin–Radushkevich (DR) equation which, although applicable over a limited range of intermediate relative humidity values, allows identification of chemisorption limit and onset of multilayer formation. While surface area determines the maximum adsorption possible for a given type, surface functionalities are determinative at lower humidity and are characteristic of the soot-producing fuel. Aging of carbon particles and oxygen chemisorption as well as O₂ physisorption strongly influence the extent of hydration for those soots studied, such as JP-8 aviation and diesel fuels. Infrared spectra confirm the surface oxidation of JP-8 soot by its reaction with O₃, a reaction of probable atmospheric importance, as underlying its increased hydration.     

Sorption of naphthalene derivatives to soils from a long-term field experiment

The influence of long-term farming practices on the soil's behaviour to adsorb hydrophobic organic compounds (HOCs) over long times was investigated. Adsorption of five naphthalene derivatives (naphthalene, 1-naphthol, 1-naphthylamine, 1-hydroxy-2-naphthoic acid, 1,4-naphthoquinone) was examined on soils with varying amounts and origins of soil organic matter obtained after amendment with different organic materials over more than 40 years. Soil organic matter, pore sizes and aggregate stability were significantly altered influencing the adsorption behaviour of the soils. Samples of soil amended with peat having an organic carbon content of 3.4% sorbed naphthalene derivatives stronger than the soil treated with sewage sludge (2.6% C(org)). All other treatments, calcium nitrate, plots without nitrogen fertilizers, grassland, animal manure, green manure and the fallowed soil sorbed less and no significant difference was found between them although the organic carbon content ranged from 1.0% to 2.6%. Thus, a decrease of the carbon content of a soil does not necessarily imply a reduction of sorption capacities for hydrophobic compounds such as naphthalene derivatives. Furthermore, the importance of protonation of HOCs for the adsorption on soil surfaces was shown. Different polarities of electronic structures of HOCs distinctly influence their adsorption behaviour.     

Comparison of measurement methods for the characterization of the black carbon emissions from a T63 turboshaft engine burning conventional and Fischer-Tropsch fuels

Emission measurements of black carbon (BC) mass were conducted on a T63 turboshaft engine, operated at idle and cruise power with conventional and alternative fuels, using an Artium LII-300 laser-induced incandescence analyzer (LII) and AVL model 483 micro soot sensor (MSS) photoacoustic instrument using the manufacturer’s calibration for both instruments. These measurements were compared with elemental carbon (EC) determined by manual and semicontinuous thermal-optical transmission analyses according to National Institute for Occupational Safety and Health (NIOSH) method 5040 as the reference method. The results indicate that both the LII and MSS instruments show good linear correlation with EC for the two fuels and two engine power conditions evaluated. The LII measurements were observed to be biased high (27–49%) and the MSS measurements were biased low (24–35%) relative to EC. The agreement between the instruments and the reference method was substantially improved by applying a calibration of the instruments against a common BC aerosol source. Test data also suggest that the two instruments show some sensitivity to particle size (or properties related to size), specifically for particles with a geometric mean diameter (GMD) <30 nm. This sensitivity is problematic, since new engines or certain combustion conditions in current engines will produce smaller particles compared with the T63 model tested in this study. Further assessments of instrument performance for particles within this size range are therefore warranted.

Implications: Accurate black carbon emission measurements are needed to certify new and in-production commercial aircraft engines. Both the Artium LII-300 and AVL 483 micro soot sensor are currently approved by the International Civil Aviation Organization for this purpose. This study compares the two instruments against elemental carbon (EC) using NIOSH method 5040 as the reference using a T63 turboshaft engine. The results indicate that both instruments correlate reasonably well with EC, and the correlation substantially improved when applying a calibration against a common aerosol source. Sensitivity to particle size may be an issue for both instruments.     

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.     

Black carbon-dominated PCDD/Fs sorption to soils at a former wood impregnation site

The influence of black carbon (BC) on the sorption of 17 native polychlorinated-p-dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was studied in five soil samples from a sawmill site where wood used to be impregnated with chlorophenol preservatives. The presence of BC caused measured total organic carbon (TOC)-water distribution ratios (K(TOC)) to be a median factor of 51 (interquartile range 18-68, n=85) higher than modeled amorphous organic carbon (AOC)-water distribution ratios (K(AOC)). K(TOC) was a factor of 73+/-27 above K(AOC) for PCDFs (n=10) and a factor of 20+/-13 (n=7) for PCDDs. The reason for this difference is probably that attaining a planar configuration after sorption to BC is less thermodynamically favorable for PCDDs than for PCDFs. BC-water distribution ratios were calculated from K(TOC), K(AOC) and BC contents, and ranged from 10(9.9) (2,3,7,8-Tetra-CDD) to 10(11.5) l kg(-1) (Octa-CDF). More than 90% of the PCDD/Fs in the soil was calculated to be BC-sorbed. Dissolved organic carbon (DOC)-water distribution ratios were measured to be in the same order of magnitude as K(AOC). This study shows that strong sorption to BC should be included when assessing ecotoxicological risk or modeling transport to groundwater of PCDD/Fs in soil.