Effect of condensed organic matter on solvent extraction and aqueous leaching of polycyclic aromatic hydrocarbons in soils and sediments

The contents of nonhydrolyzable organic matter (NHC) and black carbon (BC) were measured in soils and sediments from the Pearl River Delta, South China. Polycyclic aromatic hydrocarbons (PAHs) were extracted respectively by Soxhlet and an accelerated solvent extraction device (ASE) using different solvents. In addition, sequential aqueous leaching at different temperatures was carried out. The PAH content extracted with the sequential three solvent ASE is two times higher than that using the Soxhlet extraction method. The relationship of the PAH content with the NHC content is very significant. The PAH concentrations measured at various temperature steps fit well to the Van't Hoff equation and the enthalpy was estimated. The investigation indicates that condensed organic matter such as kerogen carbon, aged organic matter, and BC is relevant for the extraction and distribution of native PAHs in the investigated field soils and sediments.     

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.     

Concentrations, sources and spatial distribution of polycyclic aromatic hydrocarbons in soils from Beijing, Tianjin and surrounding areas, North China

The concentrations, profiles, sources and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) were determined in 40 surface soil samples collected from Beijing, Tianjin and surrounding areas, North China in 2007, and all sampling sites were far from industrial areas, roadsides and other pollution sources, and across a range of soil types in remote, rural villages and urban areas. The total concentrations of 16 PAHs ranged from 31.6 to 1475.0 ng/g, with an arithmetic average of 336.4 ng/g. The highest PAH concentrations were measured in urban soils, followed by rural village soils and soils from remote locations. The remote-rural village-urban PAH concentration gradient was related to population density, gross domestic product (GDP), long-range atmospheric transport and different types of land use. In addition, the PAH concentration was well correlated with the total organic carbon (TOC) concentration of the soil. The PAH profile suggested that coal combustion and biomass burning were primary PAH sources.     

Microbial removal of uranium in uranium-bearing black shale

The effects of several conditional factors on efficiency of U bioleaching using an iron-oxidizer, Acidithiobacillus ferrooxidans, from U-bearing black shale (349 mg kg-1 of U) were investigated. When batch-type reactors containing black shale were initially inoculated with the cells, lower pH, higher redox potential and higher amount of aqueous Fe3+ than those of non-inoculated reactor were observed until 200 h. Such development of condition, which was facilitated by microbial activity, can enhance the rate and extent of U leaching from the solid substrate. However, under the condition of enough nutrients and energy source (Fe2+) supplied, indigenous Fe-oxidizers in the non-inoculated black shale were activated over time. They exerted almost same influence on the leaching efficiency with the inoculated samples after 250 h. Low initial Fe2+ supply (5 g l-1) and no addition of inorganic nutrients resulted in nearly identical extent of U leaching with that of 9 g l-1 of initial Fe2+ and nutrients supply. The results indicate that, in a practical process of bioleaching, the expenses for Fe2+ and nutrients addition can be reduced.     

Comparison of Laboratory Batch Methods and Large Columns for Evaluating Leachate from Monofilled Solid Wastes

Analyte concentrations in aqueous leachates from polyethylene tanks filled with five different solid wastes were compared with those in extracts from five laboratory batch procedures. Solid wastes used in the study included: electroplating sludge, electric arc furnace dust, paint Incinerator ash, mine tailings, and municipal refuse incinerator ash. Batch extraction procedures used to extract the solid wastes Included: Monofilled Waste Extraction Procedure (MWEP), U.S. EPA Extraction Procedure (EP), Ham Procedure C (HAM-C), Acetate Buffer Extraction Procedure (ABEP), and Saturated Paste Procedure (PASTE).

Analyte concentrations in leachate from the large columns were reproducible and characteristic of each solid waste. In most Instances, analytes in column leachate reached a peak concentration at a liquld-to-solid ratio of 1:1 followed by a gradual to rapid decrease with continued leaching. Analyte concentrations found in large column leachate were related qualitatively to those found in extracts from the batch procedures which used delonlzed water as the extraction medium (i.e., MWEP, HAM-C, and PASTE). Batch extraction procedures using leaching medium containing acetic acid (I.e., EP) or sodium acetate buffer (i.e., ABEP) generally did not reflect analyte concentrations in leachate from the large columns. These results suggest that batch extraction procedures using acetic acid or acetate buffer are less effective for assessing the teachability of monofilled wastes than extraction methods using deionized water as the extraction fluid.     

Pathway of anthracene modification under simulated solar radiation

Exposure of polycyclic aromatic hydrocarbons (PAHs) to sunlight results in rapid structural photomodification generally via oxidation reactions. These PAH modification products are in many cases more toxic than their parent compounds. In this study, anthracene (ANT), a rapidly photooxidized PAH, was irradiated with simulated solar radiation (SSR, 100 μmol m⁻² s⁻¹) in aqueous solution to examine the photomodification pathway. The photoproducts formed were identified by HPLC. The ANT product profile after 9 h in SSR was very complex, with more than 20 compounds detected. The photoproducts formed were anthraquinones, benzoic acids, benzaldehydes and phenols showing the process to be oxidative in nature. Some of the anthraquinones were themselves subject to photooxidation, and were thus intermediates in the product pathway. The kinetics of ANT photooxidation revealed a pseudo first-order reaction with a half-life of 2 h under the SSR source used. The kinetics of product formation allowed deduction of a probable photomodification pathway. This study indicates that PAH photooxidation products are likely to exist as complex, dynamically changing mixtures in PAH contaminated aquatic environments.     

TBT and TPhT persistence in a sludged soil

The persistence of tributyltin (TBT) and triphenyltin (TPhT) in soils was studied, taking into consideration the quantity of sewage sludge, TBT and TPhT concentrations in soil as well as the soil pH. The organotin compounds (OTC) were introduced into the soil via a spiked urban sludge, simulating agricultural practise. OTC speciation was achieved after acidic extraction of soil samples followed by gas chromatography–pulsed flame photometric analysis (GC–PFPD). Leaching tests conducted on a spiked sludge showed that more than 98% of TBT are sorbed on the sludge. TBT persistence in soil appeared to depend on its initial concentration in sludge. Thus, it was more important when concentration is over 1000 μg(Sn) kg⁻¹ of sludge. More than 50% of the initial TBT added into the soil were still present after 2 months, whatever the experimental conditions. The main degradation product appeared to be dibutyltin. About 90% of TPhT were initially sorbed on sludge, whatever the spiking concentration in sludge was. However, TPhT seemed to be quantitatively exchangeable at the solid/liquid interface, according to the leaching tests. It was also significantly degraded in sludged soil as only about 20% of TPhT remain present after 2 months, the monophenyltin being the main degradation product. pH had a significant positive effect on TBT and particularly TPhT persistence, according to the initial amounts introduced into the soil. Thus, at pH over 7 and triorganotin concentration over 100 μg(Sn) kg⁻¹, less than 10% of TBT but about 60% of TPhT were degraded. When the sludge was moderately contaminated by triorganotins (typically 50 μg(Sn) kg⁻¹ in our conditions) the pH had no effect on TBT and TPhT persistence.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

Contamination of polycyclic aromatic hydrocarbons in surface sediments of mangrove swamps

The concentrations of total polycyclic aromatic hydrocarbons (sigmaPAHs) and 15 individual PAH compounds in 20 surface sediments collected from four mangrove swamps in Hong Kong were analysed. sigmaPAH concentrations ranged from 356 to 11,098 ng g(-1) dry weight with mean and median values of 1992 and 1,142 ng g(-1), respectively. These values were significantly higher than those of marine bottom sediments of Hong Kong harbours, suggesting that more PAHs were accumulated in mangrove surface sediments. The concentrations of sigmaPAHs as well as individual PAH compound varied significantly among mangrove swamps. The swamps heavily polluted by livestock and industrial sewage, such as Ho Chung and Mai Po, had much higher concentrations of total PAHs and individual PAH than the other swamps. The PAH profiles were similar among four mangrove swamps, and were dominated by naphthalene (two-ring PAH), fluorene and phenanthrene (three-ring PAH). The mangrove sediments had higher percentages of low-molecular-weight PAHs. These indicated that PAHs in mangrove sediments might originate from oil or sewage contamination (petrogenic input). Ratio values of specific PAH compounds such as phenanthrene/anthracene and fluoranthene/ pyrene, were calculated to evaluate the possible source of PAH contamination in mangrove sediments. These ratios varied among samples, suggesting that mangrove sediments might have a mixed pattern of pyrolytic and petrogenic inputs of PAHs. Sediments collected from Ho Chung mangrove swamp appeared to be more dominated by pyrolytic input while those from Tolo showed strong petrogenic contamination.     

纳米零价铁颗粒去除污染土壤HCl浸提液中的Pb

主要研究了纳米零价铁颗粒对土壤HCl浸提液中重金属Pb的去除效果。通过批实验探讨HCl浓度、纳米零价铁投入量以及处理时间对Pb去除率的影响。实验结果表明,纳米零价铁颗粒对浸提液中Pb的去除反应符合langmuir和freundlich等温吸附方程;反应遵循准一级反应动力学方程,标准化后的反应速率常数KSA=0.018 mL/(m2.min);反应30 min时,0.5 g纳米零价铁对1.0 mol/L的HCl所提取Pb(51.7 mg/L)的去除率达到91.8%。研究结果表明,纳米零价铁对土壤HCl浸提液中Pb具有良好去除效果,但相对于处理水溶液中的Pb,反应速率偏低。     

Size distribution and leaching characteristics of poly brominated diphenyl ethers (PBDEs) in the bottom ashes of municipal solid waste incinerators

The particle size distributions and leaching characteristics of polybrominated diphenyl ethers (PBDEs) in the bottom ashes of two Taiwanese municipal solid waste incinerators (MSWIs A and B) were investigated to evaluate PBDE leaching into the environment through reutilization of bottom ashes. The PBDE contents in the bottom ashes of the MSWIs (29.0–243 ng/g) could be two orders higher than those in rural and urban soils. The PBDE fraction of the bottom ashes was more distributed in larger particles (> 0.25 mm). Similar trends were found for the PBDE contents in the bottom ashes and their PBDE leaching concentrations, revealing that the elevated PBDE contents in the bottom ashes may lead to a higher PBDE leaching mass. The leaching of PBDEs is attributed to diffusion driven by the concentration gradient and effective surface area. The normalized leaching ratios (NLRs) of PBDEs for the bottom ashes of the MSWIs are about four orders greater than those of PBDE-related raw materials and products, and this may be due to their porous structures having much greater effective surface area. The elevated NLRs of PBDEs thus deserve more attention when bottom ashes are recycled and reutilized as construction materials.     

Removal of PAHs from laboratory columns simulating the humus upper layer of vertical flow constructed wetlands

Removal of three polycyclic aromatic hydrocarbons or PAHs (fluoranthene, pyrene and benzo(k)fluoranthene) from two types of PAH-contaminated effluents was investigated using four laboratory columns filled with two different organic media: a green compost and a layer coming from the first stage of vertical flow constructed wetlands. Synthetic runoff polluted by polycyclic aromatic hydrocarbons were fed through the columns during a period of two months. After a period of hydrodynamic stabilisation, the results showed a great adsorption of PAHs (>95%) on the solid media due to their large adsorption capacities. Leaching of these compounds by water was monitored. The concentrations of PAHs in leaching samples indicated that PAHs were strongly adsorbed on organic substrates and that lixiviation was limited. Fluoranthene metabolites were also investigated. Accumulation of metabolites was transitory and located in the first few cm of the media, as was observed for PAH concentrations. A toxicity test of leachates based on the inhibition of the bioluminescence of luminescent bacteria Vibrio fischeri indicated a low inhibition which can be enhanced by metal traces.     

Relation between PAH and black carbon contents in size fractions of Norwegian harbor sediments

Distributions of total organic carbon (TOC), black carbon (BC), and polycyclic aromatic hydrocarbons (PAH) were investigated in different particle size fractions for four Norwegian harbor sediments. The total PAH (16-EPA) concentrations ranged from 2 to 113 mg/kg dry weight with the greatest fraction of PAH mass in the sand fraction for three of the four sediments. TOC contents ranged from 0.84% to 14.2% and BC contents from 0.085% to 1.7%. This corresponds to organic carbon (OC = TOC - BC) contents in the range of 0.81-14% and BC:TOC ratios of 1.3-18.1%. PAH isomer ratios suggested that the PAH in all four sediments were of pyrogenic origin. Furthermore, stronger correlations between PAH versus BC (r2 = 0.85) than versus OC (r2 = 0.15) were found. For all size fractions and bulk sediments, the PAH-to-BC ratios for the total PAHs were on average 6+/-3 mg PAH/g BC. These results suggest that PAH distributions were dominated by the presence of BC, rather than OC. As sorption to BC is much stronger than sorption to OC, this may result in significantly lower dissolved concentrations of PAH than expected on the basis of organic carbon partitioning alone.     

Polycyclic aromatic hydrocarbons in lake sediments from the High Tatras

European alpine lake systems are used as indicators of air quality over the continent. Preliminary data showed high polycyclic aromatic hydrocarbons (PAH) loads in the High Tatras (Eastern Europe) in comparison to other mountain regions. Here, insight on the spatial distribution of PAH is provided from analysis of top-core sediments of 27 alpine lakes distributed along the High Tatras.Top-core sediment concentrations were higher than those in deep-cores, and they were higher than those observed in other European high mountain regions. The PAH profiles were uniform and comparable to those observed in aerosols and snow, indicating that atmospheric deposition was the predominant PAH input pathway to the lakes. Good agreement between estimated atmospheric deposition and sedimentation fluxes was observed. However, in several lakes in the western range higher sediment fluxes may correspond to higher PAH depositions levels. The higher concentrations may also reflect inputs from potential emission source areas.     

Flow Injection Analysis of MWC Fly Ash Leaching Characteristics

Abstract

A completely mixed batch reactor leaching method utilizing flow injection analysis (the CMBR-FIA method) was developed to study the lead leaching characteristics of municipal waste combustor fly ash. Flow injection analysis (FIA) coupled with atomic absorption spectrophotometry enabled the determination of lead concentrations at one minute intervals. The pH and oxidation-reduction potential of the solution were continuously monitored to characterize the leaching conditions. Automatic titration was used to alter the solution pH to defined endpoints. The CMBR-FIA method offers the ability to immediately observe alterations to the leaching solution, and grants the freedom to study a number of parameters concurrently. The CMBR-FIA method is a rapid and reliable means to investigate leaching characteristics. This paper describes the method and demonstrates its use to monitor the leaching of lead from municipal solid waste combustor fly ash as a function of pH. Soluble lead concentrations are shown to increase quickly with decreasing pH.

A maximum of 50% of the total lead concentration was available in solution at pH 2. This value gradually decreased with time to over 35% of the total.     

Pollution survey of polycyclic aromatic hydrocarbons in surface water of Hangzhou, China

The concentrations of 10 polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured for five times (July and November 1999–2002) in four water bodies of Hangzhou, China. To investigate possible sources of PAH contamination, sediments, soils, runoff water and atmospheric particles of the region were also analyzed for their PAH contents. The maximum levels of PAHs in the water bodies (34.4–67.7 μg/l) were found in July, while significantly lower PAH concentrations (4.7–15.3 μg/l) were measured in November. The contamination is substantial and it may have resulted in acute toxic effects on aquatic organisms. The measured PAH concentrations in sediments and soils (224–4222 ng/g), runoff water (8.3 μg/l) and air particles (2.3 μg/m³) are discussed in relation to concentrations and patterns found in the surface water bodies. Comparison of PAH levels in sediments and soils led to the conclusion that the erosion of soil material does not contribute significantly to the contamination of sediments. The atmospheric PAH deposition to water bodies in the city area of Hangzhou was estimated to be 530 tons/a, while the contribution of surface runoff water was estimated to be 30.7 tons/a. The ratios of selected PAH were then used to illuminate the possible origin of PAHs in the examined samples (petrogenic, pyrogenic).     

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.     

The influence of Sarcocornia fruticosa on retention of PAHs in salt marsh sediments (Sado estuary, Portugal)

Depth concentration profiles of PAHs, organic carbon and dissolved oxygen in non-colonised sediments and sediments colonised by Sarcocornia fruticosa from Mitrena salt marsh (Sado, Portugal) were determined in November 2004 and April 2005. Belowground biomass and PAH levels in below and aboveground material were also determined. In both periods, colonised sediments were oxygenated until 15-cm, rich in organic carbon (max 4.4%) and presented much higher PAH concentrations (max. 7.1 microg g(-1)) than non-colonised sediments (max. 0.55 microg g(-1)). Rooting sediments contained the highest PAH concentrations. The five- and six-ring compounds accounted to 50-75% of the total PAHs in colonised sediments, while only to 30% in non-colonised sediments. The elevated concentrations of PAHs in colonised sediments may be attributed to the transfer of dissolved PAH compounds towards the roots as plant uptake water and subsequent sequestration onto organically rich particles. A phase-partitioning mechanism probably explains the higher retention of the heavier PAHs. In addition oxygenated conditions of the rooting sediments favour the degradation of the lighter PAHs and explain the elevated proportion of the heavier compounds. Below and aboveground materials presented lower PAH concentrations (0.18-0.38 microg g(-1)) than colonised sediments. Only 3- and 4-PAHs were quantified in aboveground material, reflecting either preferential translocation of lighter compounds from roots or atmospheric deposition.     

PAH removal from spiked municipal wastewater sewage sludge using biological, chemical and electrochemical treatments

Polycyclic aromatic hydrocarbons (PAHs) have been widely studied due to their presence in all the environmental media and toxicity to life. These molecules are strongly adsorbed on the particulate matters of soils, sludges or sediments because of their strong hydrophobicity which makes them less bioavailability, thus limiting their bioremediation. Different sludge treatment processes were tested to evaluate their performances for PAH removal from sludge prealably doped with 11 PAHs (5.5mg each PAH kg(-1) of dry matter (DM)): two biological processes (mesophilic aerobic digestion (MAD) and simultaneous sewage sludge digestion and metal leaching (METIX-BS)) were tested to evaluate PAH biodegradation in sewage sludge. In parallel, two chemical processes (quite similar Fenton processes: chemical metal leaching (METIX-AC) and chemical stabilization (STABIOX)) and one electrochemical process (electrochemical stabilization (ELECSTAB)) were tested to measure PAH removal by these oxidative processes. Moreover, PAH solubilisation from sludge by addition of a nonionic surfactant Tween 80 (Tw80) was also tested. The best yields of PAH removal were obtained by MAD and METIX-BS with more than 95% 3-ring PAH removal after a 21-day treatment period. Tw80 addition during MAD treatment increased 4-ring PAHs removal rate. In addition, more than 45% of 3-ring PAHs were removed from sludge by METIX-AC and during ELECSTAB process were quiet good with approximately 62% of 3-ring PAHs removal. However, little weaker removal of 3-ring PAHs (<35%) by STABIOX. None of the tested processes were efficient for the elimination of high molecular weight (> or = 5-ring) PAHs from sludge.     

PAHs associated with the leaves of three deciduous tree species. I--Concentrations and profiles

Results for the concentrations of total polycyclic aromatic hydrocarbons (Sigma PAH) and the PAH profile in leaves from three deciduous tree species from the same woodland are presented, and discussed with reference to environmental and leaf-related variables. There were significant differences between oak, ash and hazel leaves in their Sigma PAH concentrations (sum of 23 PAHs), and in the relative contribution of individual PAHs to the sum. Leaves exhibiting pubescence (hairiness) were found to have significantly higher Sigma PAH concentrations than hairless leaves, regardless of their position in the vegetation strata of the wood. Hazel leaves from the understorey had a PAH profile consisting of a greater proportion of the 4-, 5- and 6-ring PAHs than oak or ash from the canopy. This was concluded to be the result of the filtering effect of the main canopy on the air passing over and through it, with subsequent transfer of particles and attendant PAHs to the understorey below. The proportion of Sigma PAH contributed by the 6-ring PAH in hazel leaves was negatively correlated with distance from the southern edge of the canopy. It is proposed that the predominantly windward edges of the woodland, where atmospheric turbulence is likely to be greatest, favoured the deposition of particle-bound PAHs to leaves.