Hydroxypropyl-β-cyclodextrin as non-exhaustive extractant for organochlorine pesticides and polychlorinated biphenyls in muck soil

Hydroxypropyl-β-cyclodextrin (HPCD) was used as a non-exhaustive extractant for organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in muck soil. An optimized extraction method was developed which involved using a HPCD to soil mass ratio of 5.8 with a single extraction period of 20 h. An aging experiment was performed by spiking a muck soil with ¹³C-labeled OCs and non-labeled PCBs. The soil was extracted with the optimized HPCD method and Soxhlet apparatus with dichloromethane over 550 d periodically. The HPCD extractability of the spiked OCs was greater than of the native OCs. A decreased in HPCD extractability was observed for the spiked OCs after 550 d of aging and their extractability approached those of the natives. The partition coefficient between HPCD and soil (log K_CD-Soil) was negatively correlated with the octanol-water partition coefficient (log K_OW) with r² = 0.67 and p < 0.05.     

Correlations of Eisenia fetida metabolic responses to extractable phenanthrene concentrations through time

Eisenia fetida earthworms were exposed to phenanthrene for thirty days to compare hydroxypropyl-β-cyclodextrin (HPCD) extraction of soil and ¹H NMR earthworm metabolomics as indicators of bioavailability. The phenanthrene 28-d LC₅₀ value was 750 mg/kg (632-891, 95% confidence intervals) for the peat soil tested. The initial phenanthrene concentration was 319 mg/kg, which biodegraded to 16 mg/kg within 15 days, at which time HPCD extraction suggested that phenanthrene was no longer bioavailable. Multivariate statistical analysis of ¹H NMR spectra for E. fetida tissue extracts indicated that phenanthrene exposed and control earthworms differed throughout the 30 day experiment despite the low phenanthrene concentrations present after 15 days. This metabolic response was better correlated to total phenanthrene concentrations (Q² = 0.59) than HPCD-extractable phenanthrene concentrations (Q² = 0.46) suggesting that ¹H NMR metabolomics offers considerable promise as a novel, molecular-level method to directly monitor the bioavailability of contaminants to earthworms in the environment.     

Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.     

Application of a luminescence-based biosensor for assessing naphthalene biodegradation in soils from a manufactured gas plant

Despite numerous reviews suggesting that microbial biosensors could be used in many environmental applications, in reality they have failed to be used for which they were designed. In part this is because most of these sensors perform in an aqueous phase and a buffered medium, which is in contrast to the nature of genuine environmental systems. In this study, a range of non-exhaustive extraction techniques (NEETs) were assessed for (i) compatibility with a naphthalene responsive biosensor and (ii) correlation with naphthalene biodegradation. The NEETs removed a portion of the total soil naphthalene in the order of methanol > HPCD > βCD > water. To place the biosensor performance to NEETs in context, a biodegradation experiment was carried out using historically contaminated soils. By coupling the HPCD extraction with the biosensor, it was possible to assess the fraction of the naphthalene capable of undergoing microbial degradation in soil.     

Linking chemical extraction to microbial degradation of 14C-hexadecane in soil

Chemical extractions have been shown to measure the biodegradable fraction of aromatic contaminants in soil; however, there is little research on the chemical prediction of aliphatic hydrocarbon degradation. The aim of this study was to investigate the potential for cyclodextrin extractions to predict hexadecane biodegradation in soil. Soils were amended with 10 or 100 mg kg⁻¹ of a model alkane n-hexadecane and 100 Bq g⁻¹¹⁴C-n-hexadecane. Correlations between the extents of mineralisation and extractions of the ¹⁴C-contaminant were determined. Solvent shake extractions and aqueous CaCl₂ extractions were poor predictors of hexadecane bioaccessibility. However, the novel HP-α-CD shake extraction showed close correlation (r² = 0.90, n = 36, p < 0.05) to the mineralisation data. This novel extraction technique has the potential to be used to assess the biodegradable aliphatic hydrocarbon fraction in contaminated soils.     

Enhancing p-cresol extraction from soil

Soil washing is a potential technology for rapid removal of organic hydrocarbons sorbed to soils. In this work, p-cresol desorption with different non-ionic surfactants (Tween 80, Brij 30 and Triton X-100) was compared to cyclodextrine and citrate as solubilizer. A series of batch extraction experiments were conducted at 20 °C using the field soil with different extracting solutions at various concentrations to investigate the removal efficiency and to optimize the concentration of the extractant. The use of the different extracting agents was very selective to p-cresol extraction, minimizing soil organic matter releasing and maintaining the natural pH of the soil. The highest asymptotic values of desorption percentages were obtained for Tween 80 and Brij 30 at 48 h. However, Brij 30 ecotoxicity (EC₅₀ = 0.5 mg L⁻¹) is in the same order of that obtained for p-cresol, being this surfactant clearly ruled out. Liquid to solid ratio of 2.5 mL g⁻¹ presented the best extraction results, while concentrations higher than 1 g L⁻¹ for Tween 80 and Citrate did not produce any significant effect on the desorption efficiency. p-Cresol extraction efficiencies higher than 70% and 60% for Tween 80 and Citrate, respectively.     

Compatibility of hydroxypropyl-beta-cyclodextrin with algal toxicity bioassays

Numerous reports have indicated that hydrophobic organic compound bioaccessibility in sediment and soil can be determined by extraction using aqueous hydroxypropyl-β-cyclodextrin (HPCD) solutions. This study establishes the compatibility of HPCD with Selenastrum capricornutum and assesses whether its presence influences the toxicity of reference toxicants. Algal growth inhibition (72 h) showed no significant (P > 0.05) difference at HPCD concentrations up to and including 20 mM. HPCD presence did not influence the toxicity of the inorganic reference toxicant (ZnSO₄), with IC50 values of 0.82 μM and 0.85 μM, in the presence and absence of HPCD (20 mM), respectively. However, HPCD presence (20 mM) reduced the toxicity of 2,4-dichlorophenol and the herbicides diuron and isoproturon. These reductions were attributed to inclusion complex formation between the toxicants and the HPCD cavity. Liberation of complexed toxicants, by sample manipulation prior to toxicity assessment, is proposed to provide a sensitive, high throughput, bioassay that reflects compound bioaccessibility.     

Bioaccumulation and bioavailability of polybrominated diphynel ethers (PBDEs) in soil

Earthworms were exposed to artificially contaminated soils of DE-71 and DE-79 to investigate the bioaccumulation and bioavailability of PBDEs in soil. All major congeners were bioavailable to earthworms. The uptake and elimination rate coefficients of PBDEs decreased with their logK_ows. The biota soil accumulation factors of PBDEs also declined with logK_ow. These may be due to the large molecular size and the high affinity of PBDEs to soil particles. The concentrations extracted by Tenax for 6 h correlated very well with those found in earthworms, suggesting that the bioavailability of PBDEs in soil is related to the fraction of rapid desorption from soil. This also indicates that 6 h Tenax extraction is a good proxy for the bioavailability of PBDEs to earthworms in soil. The BSAFs of PBDEs in aged soil decreased 22-84% compared to freshly spiked soil, indicating that aging may diminish the bioavailability of PBDEs in soil significantly.     

Sorption of sulfadiazine on Brazilian soils

Antimicrobials, among them sulfonamides are widely used in veterinary medicine and can contaminate the environment. The degree to which antimicrobials adsorb onto soil particles varies widely, as does the mobility of these drugs. Sulfadiazine (SDZ) was used to study the adsorption–desorption in Brazilian soil–water systems, using batch equilibrium experiments. Sorption of SDZ was carried out using four types of soils. Adsorption and desorption data were well fitted with Freundlich isotherms in log form (r > 0.999) and (0.984 < r < 0.999), respectively. An adsorption–desorption hysteresis phenomenon was apparent in all soils ranging from 0.517 to 0.827. The experimental results indicate that the Freundlich sorption coefficient (K_F) values for SDZ ranged from 0.45 to 2.6 μg^1?1/n (cm³)^1/n g^?1.     

Role of cosubstrate and bioaccessibility played in the enhanced anaerobic biodegradation of organochlorine pesticides (OCPs) in a paddy soil by nitrate and methyl-β-cyclodextrin amendments

The present study was conducted to investigate the anaerobic biodegradation potential of biostimulation by nitrate (KNO₃) and methyl-β-cyclodextrin (MCD) addition on an aged organochlorine pesticide (OCP)-contaminated paddy soil. After 180 days of incubation, total OCP biodegradation was highest in soil receiving the addition of nitrate and MCD simultaneously and then followed by nitrate addition, MCD addition, and control. The highest biodegradation of chlordanes, hexachlorocyclohexanes, endosulfans, and total OCPs was 74.3, 63.5, 51.2, and 65.1 %, respectively. Meanwhile, MCD addition significantly increased OCP bioaccessibility (p?<?0.05) evaluated by Tenax TA extraction and a three-compartment model method. Moreover, the addition of nitrate and MCD also obtained the highest values of soil microbial activities, including soil microbial biomass carbon and nitrogen, ATP production, denitrifying bacteria count, and nitrate reductase activity. Such similar trend between OCP biodegradation and soil-denitrifying activities suggests a close relationship between OCP biodegradation and N cycling and the indirect/direct involvement of soil microorganisms, especially denitrifying microorganisms in the anaerobic biodegradation of OCPs.     

A comparative evaluation of passive and active samplers for measurements of gaseous semi-volatile organic compounds in the tropical atmosphere

The polyurethane foam (PUF) disk-based passive air samplers (PAS), mounted inside two aluminium bowls to buffer the air flow to the disk and to shield it from precipitation and sunlight, were used for the collection of atmospheric SVOCs in Singapore during April 2008–June 2008. Data obtained from PAS measurements are compared to those from active high-volume air sampling (AAS). Single factor ANOVA tests show that there were no significant differences in chemical distribution profiles between actively and passively collected samples (PAHs, F = 3.38 × 10^?8 < F_critical = 4.17 with p > 0.05; OCPs, F = 2.71 × 10^?8 < F_critical = 4.75 with p > 0.05). The average air-side mass transfer coefficient (k_A) for PAS, determined from the loss of depuration compounds such as 13C₆ – HCB (1000 ng), 13C₁₂ – 4,4′ DDT (1000 ng) and 13C₁₂ – PCB 101 (1000 ng)spiked on the disks prior to deployment, was 0.12 ± 0.04 m s^?1. These values are comparable to those reported previously in the literature. The average sampling rate was 3.78 ± 1.83 m³ d^?1 for the 365 cm² PUF disk. Throughout the entire sampling period (～68 d), most of the PAHs and all OCPs exhibited a linear uptake trend on PAS, while naphthalene, acenaphthylene, acenaphthene and fluorene reached the curvilinear phase after the first ～30 d exposure. Theoretically estimated times to equilibrium (t_eq) ranged from around one month for Acy to hundreds of years for DB(ah)A. Sampling rates, based on the time integrated active sampling-derived concentrations and masses collected by PUF disks during the linear uptake phase, were determined for all target compounds with the average values of 2.50 m³ d^?1 and 3.43 m³ d^?1 for PAHs and OCPs, respectively. More variations were observed as compared to those from the depuration study. These variation were most likely due to the difference of physicochemical properties of individual species. Lastly, multiple linear regression models were developed to estimate the log-transformed gaseous concentration of an individual compound in air based on the mass collection rate of the gaseous SVOCs measured using the PAS and the molecular weight (MW) of the particular compound for both PAHs and OCPs, respectively.     

Comparing the desorption and biodegradation of low concentrations of phenanthrene sorbed to activated carbon,biochar and compost

Carbonaceous soil amendments are applied to contaminated soils and sediments to strongly sorb hydrophobic organic contaminants (HOCs) and reduce their freely dissolved concentrations. This limits biouptake and toxicity, but also biodegradation. To investigate whether HOCs sorbed to such amendments can be degraded at all, the desorption and biodegradation of low concentrations of ¹⁴C-labelled phenanthrene (?5 μg L^?1) freshly sorbed to suspensions of the pure soil amendments activated carbon (AC), biochar (charcoal) and compost were compared. Firstly, the maximum abiotic desorption of phenanthrene from soil amendment suspensions in water, minimal salts medium (MSM) or tryptic soy broth (TSB) into a dominating silicone sink were measured. Highest fractions remained sorbed to AC (84 ± 2.3%, 87 ± 4.1%, and 53 ± 1.2% for water, MSM and TSB, respectively), followed by charcoal (35 ± 2.2%, 32 ± 1.7%, and 12 ± 0.3%, respectively) and compost (1.3 ± 0.21%, similar for all media). Secondly, the mineralization of phenanthrene sorbed to AC, charcoal and compost by Sphingomonas sp. 10-1 (DSM 12247) was determined. In contrast to the amounts desorbed, phenanthrene mineralization was similar for all the soil amendments at about 56 ± 11% of the initially applied radioactivity. Furthermore, HPLC analyses showed only minor amounts (<5%) of residual phenanthrene remaining in the suspensions, indicating almost complete biodegradation. Fitting the data to a coupled desorption and biodegradation model revealed that desorption did not limit biodegradation for any of the amendments, and that degradation could proceed due to the high numbers of bacteria and/or the production of biosurfactants or biofilms. Therefore, reduced desorption of phenanthrene from AC or charcoal did not inhibit its biodegradation, which implies that under the experimental conditions these amendments can reduce freely dissolved concentration without hindering biodegradation. In contrast, phenanthrene sorbed to compost was fully desorbed and biodegraded.     

Sorption and transport of trichloroethylene in caliche soil

Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co = 122-1300 mg L⁻¹) but Freundlich isotherm at the low concentration range (1-122 mg L⁻¹). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6 × 10⁻⁴ s⁻¹), then continued at a 100-fold slower rate (7.7 × 10⁻⁶ s⁻¹). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R = 1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r² = 0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co = 1300 mg L⁻¹). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L⁻¹), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.     

H NMR metabolomics of earthworm exposure to sub-lethal concentrations of phenanthrene in soil

¹H NMR metabolomics was used to monitor earthworm responses to sub-lethal (50-1500 mg/kg) phenanthrene exposure in soil. Total phenanthrene was analyzed via soxhlet extraction, bioavailable phenanthrene was estimated by hydroxypropyl-β-cyclodextrin (HPCD) and 1-butanol extractions and sorption to soil was assessed by batch equilibration. Bioavailable phenanthrene (HPCD-extracted) comprised ∼65-97% of total phenanthrene added to the soil. Principal component analysis (PCA) showed differences in responses between exposed earthworms and controls after 48 h exposure. The metabolites that varied with exposure included amino acids (isoleucine, alanine and glutamine) and maltose. PLS models indicated that earthworm response is positively correlated to both total phenanthrene concentration and bioavailable (HPCD-extracted) phenanthrene in a freshly spiked, unaged soil. These results show that metabolomics is a powerful, direct technique that may be used to monitor contaminant bioavailability and toxicity of sub-lethal concentrations of contaminants in the environment. These initial findings warrant further metabolomic studies with aged contaminated soils.     

Organochlorine pesticides in soils of Mexico and the potential for soil-air exchange

The spatial distribution of organochlorine pesticides (OCs) in soils and their potential for soil-air exchange was examined. The most prominent OCs were the DDTs (Geometric Mean, GM = 1.6 ng g⁻¹), endosulfans (0.16 ng g⁻¹), and toxaphenes (0.64 ng g⁻¹). DDTs in soils of southern Mexico showed fresher signatures with higher F_DDTe = p,p′-DDT/(p,p′-DDT + p,p′-DDE) and more racemic o,p′-DDT, while the signatures in the central and northern part of Mexico were more indicative of aged residues. Soil-air fugacity fractions showed that some soils are net recipients of DDTs from the atmosphere, while other soils are net sources. Toxaphene profiles in soils and air showed depletion of Parlar 39 and 42 which suggests that soil is the source to the atmosphere. Endosulfan was undergoing net deposition at most sites as it is a currently used pesticide. Other OCs showed wide variability in fugacity, suggesting a mix of net deposition and volatilization.     

Ambient TSP concentration and dustfall in major cities of China: Spatial distribution and temporal variability

Based on environmental monitoring data in 93 major cities and meteorological records at 398 weather stations in China from 1981 to 2007, total suspended particle (TSP) concentration, the intensity of dustfall, and sand and dust storm frequency (F_d) were analysed. During the past 27 years, the annual average TSP concentration (C_TSP) in 93 cities was 402 μg m^?3. Annual average C_TSP decreased from the north to the south and from inland to the coast areas with a peak value of 628.8 μg m^?3 in Lanzhou. In the 1980s, 1990s and 2000s, annual average C_TSP was 628.7, 319.2, and 250.1 μg m^?3, respectively. Annual average intensity of dustfall (I_d) was 240.5 t km^?2 a^?1, decreased from northern to southern China and from inland to the coast areas with the maximum value of 717.2 t km^?2 a^?1 in Baotou. In the 1980s, 1990s and 2000s, annual average I_d was 334.8, 220.9, 146 t km^?2 a^?1 respectively. Annual average I_d in the Loess Plateau region was commonly higher than 200 t km^?2 a^?1. The annual average F_d decreased from arid regions in northwestern China to humid areas in southeastern China with two sand and sand storm centers existing in Xinjiang Taklamakan Desert and western Inner Mongolia. The annual average F_d in the 1980s, 1990s, 2000s was 16, 8, 6 days respectively, decreased steadily from 18 days in 1981–5 days in 2007. Annual average I_d had a positive linear relation to annual average C_TSP (R² = 0.96). Annual average F_d had a positive relation with annual average C_TSP (R² = 0.97) as well as annual average I_d (R² = 0.94). TSP was the chief pollutant influencing Air Pollution Index (API) in northern China in spring and winter seasons. Sand and dust storm might be a major factor affecting the temporal variability and spatial distribution of TSP and dustfall in China.     

Determinants of indoor and personal exposure to PM2.5 of indoor and outdoor origin during the RIOPA study

Effects of physical/environmental factors on fine particle (PM_2.5) exposure, outdoor-to-indoor transport and air exchange rate (AER) were examined. The fraction of ambient PM_2.5 found indoors (F_INF) and the fraction to which people are exposed (α) modify personal exposure to ambient PM_2.5. Because F_INF, α, and AER are infrequently measured, some have used air conditioning (AC) as a modifier of ambient PM_2.5 exposure. We found no single variable that was a good predictor of AER. About 50% and 40% of the variation in F_INF and α, respectively, was explained by AER and other activity variables. AER alone explained 36% and 24% of the variations in F_INF and α, respectively. Each other predictor, including Central AC Operation, accounted for less than 4% of the variation. This highlights the importance of AER measurements to predict F_INF and α. Evidence presented suggests that outdoor temperature and home ventilation features affect particle losses as well as AER, and the effects differ.Total personal exposures to PM_2.5 mass/species were reconstructed using personal activity and microenvironmental methods, and compared to direct personal measurement. Outdoor concentration was the dominant predictor of (partial R² = 30–70%) and the largest contributor to (20–90%) indoor and personal exposures for PM_2.5 mass and most species. Several activities had a dramatic impact on personal PM_2.5 mass/species exposures for the few study participants exposed to or engaged in them, including smoking and woodworking. Incorporating personal activities (in addition to outdoor PM_2.5) improved the predictive power of the personal activity model for PM_2.5 mass/species; more detailed information about personal activities and indoor sources is needed for further improvement (especially for Ca, K, OC). Adequate accounting for particle penetration and persistence indoors and for exposure to non-ambient sources could potentially increase the power of epidemiological analyses linking health effects to particulate exposures.     

Environmental monitoring of complex hydrocarbon mixtures in water and soil samples after solid phase microextraction using PVC/MWCNTs nanocomposite fiber

A novel nanocomposite based on incorporation of multiwalled carbon nanotubes (MWCNTs) in polyvinyl chloride (PVC) was prepared. Proposed nanocomposite was coated on stainless steel wire by deep coating. Composition of nanocomposite was optimized based on results of morphological studies using scanning electron microscopy. The best composition (83% MWCNTs:17% PVC) was applied as a solid phase microextraction fiber. Complex mixture of aromatic (BTEX) and aliphatic hydrocarbons (C₅–C₃₄) were selected as model analytes, and performance of proposed fiber in extraction of the studied compounds from water and soil samples was evaluated. Analytical merits of the method for water samples (LODs = 0.10–1.10 ng L⁻¹, r² = 0.9940–0.9994) and for soil samples (LODs = 0.10–0.77 ng kg⁻¹, r² = 0.9946–0.9994) showed excellent characteristics of it in ultra trace determination of petroleum type environmental pollutants. Finally, the method was used for determination of target analytes in river water, industrial effluent and soil samples.     

Radon exhalation and ultrafine fraction of radon progeny in closed room air

The influence of ²²²Rn exhalation from walls and air exchange (low ventilation rates ν<0.3 h^-1) upon its concentration in room air has been considered. It was found that the radon concentration reachs 84 Bq m^-3 at exhalation and ventilation rates of 66 Bq hm^-2 and 0.28 h^-1, respectively. The radon concentration and the ultrafine fraction f_p of potential α energy concentration as well as the equilibrium factor F of the short-lived radon progeny were also determined in three different completely closed rooms. An electroprecipitation method was applied for determining the ²²²Rn concentration while a single wire-screen technique was used for the determination of ultrafine radon progeny. During the measurements, the radon concentrations were varied between 33 and 134 with a mean value 89 Bq m^-3. A mean ultrafine fraction (f_p) of 0.16 was obtained at a mean aerosol particle concentration (Z) of 1700 cm^-3 and a mean equilibrium factor (F) of 0.33. The obtained mean value of f_p was found to be about five times higher than the value reported in the ICRP publication (f_p=0.03). The attachment rate (X), the deposition rate (q^f) and the deposition velocity (v^f_d) of the ultrafine radionuclide ²¹⁸Po were calculated. A mean value of X was found to be 49 h^-1 at a mean q^f of 46 h^-1 and a mean v^f_d of 4.6 m h^-1. The attachment coefficient β of ²¹⁸Po was found to vary between 0.016 and 0.047 with a mean value 0.028 cm³ h^-1.