Testing the resistance of single- and multi-walled carbon nanotubes to chemothermal oxidation used to isolate soots from environmental samples

Quantification of natural and engineered carbon nanotubes (CNT) in the environment is urgently needed to study their occurrence and fate and to enable a proper risk assessment. Currently, such methods are lacking. Here, we tested the resistance of 15 structurally different CNTs to chemothermal oxidation at 375 °C (CTO-375), a method used to isolate soots from environmental samples. Depending on their structure, CNTs survived CTO-375 in proportions ranging from 26 to 93%. Standard addition of CNTs to soil and sediment yielded recoveries between 66 and 171%, demonstrating the capability of CTO-375 to isolate CNTs from complex environmental matrices. These data of pure and added CNTs correspond to recoveries obtained with “ordinary” soots under similar experimental conditions. Hence, soot fractions commonly isolated with CTO-375 from environmental matrices most probably encompass CNTs. Future work should attempt to enhance the method's selectivity, i.e., its capability to separate CNTs from other forms of soot.     

Quantification and radiocarbon source apportionment of black carbon in atmospheric aerosols using the CTO-375 method

To make progress towards linking the atmosphere and biogeosphere parts of the black carbon (BC) cycle, a chemothermal oxidation method (CTO-375), commonly applied for isolating BC from complex geomatrices such as soils, sediments and aquatic particles, was applied to investigate the BC also in atmospheric particles. Concentrations and ¹⁴C-based source apportionment of CTO-375 based BC was established for a reference aerosol (NIST RM-8785) and for wintertime aerosols collected in Stockholm and in a Swedish background area. The results were compared with thermal–optical (OC/EC) measurements. For NIST RM-8785, a good agreement was found between the BC_CTO-375 concentration and the reported elemental carbon (EC) concentration measured by the “Speciation Trends Network—National Institute of Occupational Safety and Health” method (EC_NIOSH) with BC_CTO-375 of 0.054±0.002 g g⁻¹ and EC_NIOSH of 0.067±0.008 g g⁻¹. In contrast, there was an average factor of ca. 20 difference between BC_CTO-375 and EC_NIOSH for the ambient Scandinavian wintertime aerosols, presumably reflecting a combination of BC_CTO-375 isolating only the recalcitrant soot-BC portion of the BC continuum and the EC_NIOSH metric inadvertently including some intrinsically non-pyrogenic organic matter. Isolation of BC_CTO-375 with subsequent off-line radiocarbon analysis yielded fraction modern values (fM) for total organic carbon (TOC) of 0.93 (aerosols from a Swedish background area), and 0.58 (aerosols collected in Stockholm); whereas the fM for BC_CTO-375 isolates were 1.08 (aerosols from a Swedish background area), and 0.87 (aerosols collected in Stockholm). This radiocarbon-based source apportionment suggests that contribution from biomass combustion to cold-season atmospheric BC_CTO-375 in Stockholm was 70% and in the background area 88%.     

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.     

Detection of fullerenes (C60 and C70) in commercial cosmetics

Detection methods are necessary to quantify fullerenes in commercial applications to provide potential exposure levels for future risk assessments of fullerene technologies. The fullerene concentrations of five cosmetic products were evaluated using liquid chromatography with mass spectrometry to separate and specifically detect C₆₀ and C₇₀ from interfering cosmetic substances (e.g., castor oil). A cosmetic formulation was characterized with transmission electron microscopy, which confirmed that polyvinylpyrrolidone encapsulated C₆₀. Liquid-liquid extraction of fullerenes from control samples approached 100% while solid-phase and sonication in toluene extractions yielded recoveries of 27-42%. C₆₀ was detected in four commercial cosmetics ranging from 0.04 to 1.1 μg/g, and C₇₀ was qualitatively detected in two samples. A single-use quantity of cosmetic (0.5 g) may contain up to 0.6 μg of C₆₀, demonstrating a pathway for human exposure. Steady-state modeling of fullerene adsorption to biosolids is used to discuss potential environmental releases from wastewater treatment systems.     

Optimization of analytical methods to improve detection of erythromycin from water and sediment

Analytical methods to improve the detection of erythromycin in water and sediment were developed to optimize for erythromycin's recovery of extractable and bound residues from the aquatic environment. The objective of this study was to determine optimal recovery of erythromycin from water and sediment to improve its detection in environmental samples through solid-phase extraction (SPE) and sediment-extraction methods. SPE methods examined included previously reported methods for macrolide and sulfonamide antibiotics with erythromycin recoveries ranging from 75.5 % to 94.7 %. Extraction of erythromycin was performed from sand employing various solvents and buffers to determine the best method for extraction from two sandy loam pond sediments. Various extraction times were also examined, and all extraction procedures were performed in duplicate. The greatest recovery of ¹⁴C-erythromycin in the Iowa sediment was 84 % using 0.3 M ammonium acetate at pH 4.2: acetonitrile (15:85, v/v) solution. The Oklahoma sediment yielded the greatest recovery of ¹⁴C-erythromycin at 86.7 % with 0.3 M ammonium acetate at pH 7: acetonitrile (30:70, v/v) with a 60-minute shake time. The present results demonstrate improved extraction methods for enhancing the accuracy of erythromycin detection from environmental samples.     

Contrasting effects of black carbon amendments on PAH bioaccumulation by Chironomus plumosus larvae in two distinct sediments: role of water absorption and particle ingestion

Two sediment matrices with different characteristics were amended with chars from different sources for bioaccumulation assay with filter-feeding Chironomus plumosus larvae. Chars greatly decreased porewater concentrations of PAHs (C_iw) measured using polyethylene devices in sediments. In organic rich sediment matrix-based systems where suspended char particles were absent, PAH concentrations in larvae (C_iB) were significantly correlated with C_iw, and there was no difference in water-based bioaccumulation factors (BAFs) between different treatments, suggesting that water absorption was the main contaminant uptake route for larvae. In organic poor sediment matrix-based systems where suspended char particles were present, poor Pearson correlation between C_iB and C_iw was found, but there was a significant linear increase of BAF values with char contents, which indicated that ingestion of suspended char particles could also be important for PAH bioaccumulation. Therefore, we need to rethink of the effectiveness and risks for the application of black carbon to sediment/soil remediation.     

In vitro evaluation of cellular influences induced by stable fullerene C70 medium dispersion: Induction of cellular oxidative stress

Fullerene is one of the nanocarbons that is expected to have applications to life science, such as nanomedicines. An understanding of the cellular influences of fullerene is essential for its application to life science. Although C₆₀ and C₇₀ are both known as major fullerenes, most previous reports about the cellular influences of fullerene are about C₆₀. Thus we evaluated the cellular influences caused by C₇₀. A stable and uniform C₇₀-medium dispersion was prepared. The dispersion was stable for the experimental period. Mitochondrial activity (MTT assay), colony forming ability (clonogenic assay), induction of oxidative stress (intracellular ROS and lipid peroxidation levels) and cellular uptake (TEM observation) in human keratinocyte HaCaT and lung carcinoma A549 cells exposed to C₇₀ were examined. C₇₀ did not influence mitochondrial activity. On the other hand, C₇₀ dispersion inhibited colony formation at the concentration of 25.2 μg mL⁻¹. Exposure to C₇₀ dispersion caused an increase in intracellular ROS and lipid peroxidation levels. The induction of intracellular ROS level was inhibited by pre-treatment of the cells by antioxidants. TEM observations of C₇₀ exposed cells showed cellular uptake of C₇₀. These results were similar to the cellular influences caused by C₆₀ which were reported by us previously. Although C₇₀ did not cause cell death, it caused the induction of intracellular oxidative stress.     

Numerical technique for estimating equilibrium concentrations from initial concentrations when using the freundlich adsorption equation

Abstract

The Freundlich equation, X/m = K C_e ^N, is frequently used to express the partitioning of pesticides between solid (soil, sediment) and aqueous phases. When designing adsorption‐desorption experiments, it would be useful to be able to estimate the equilibrium concentration, C_e, in terms of the initial concentration, C_o, if reasonable estimates of K and N can be made. Because of the usual non‐integer nature of N, only a numerical solution of the Freundlich equation is possible for C_e in terms of C_o. A simple computer program is presented which produces almost an exact solution for the value of C_e.     

Transforming meadows into free surface water wetlands: Impact of increased nitrate and carbon loading on greenhouse gas production

In a laboratory study we investigated 1) the potential production of nitrous oxide (N₂O), methane (CH₄) and carbon dioxide (CO₂) and 2) the effect of nitrate (NO₃^?) and anaerobic N₂O development on CH₄ production in sediment from a recently recreated free surface water wetland (FSWW) and in soil from an adjacent meadow. We designed an experiment where production of greenhouse gases was registered at the time of maximum net development of N₂O. We made additions of biodegradable carbon (glucose) and/or NO₃^? to sediment and soil slurries and incubated them at four temperatures (4, 13, 20, 28 °C). Gas production from both substrates was positively correlated with temperature. We also found that the sediment produced more N₂O than the soil. N₂O production in sediment was NO₃^? limited, whereas in soil carbon availability was lower and only combined additions of NO₃^? and glucose supported increased N₂O development. CH₄ production was generally low and did not differ between soil and sediment. Nor did glucose addition increase CH₄ rates. The results suggest that neither soil nor sediment environment did support development of methanogenic populations. There were no clear effects of NO₃^? on CH₄ production. However, the highest records of CH₄ were found in incubations with low N₂O production, which indicates that N₂O might be toxic to methanogens. In summary, our study showed that transforming meadows into FSWWs implies a risk of increased N₂O emissions. This does not seem to be valid for CH₄. However, since N₂O is almost always produced wherever NO₃^? is denitrified, increased N₂O production in wetlands leads to reduced rates in downstream environments. Hence, we conclude that when balancing NO₃^? retention and global warming aspects, we find no reason to discourage future creation or restoration of wetlands.     

Effects of C60 nanoparticle exposure on earthworms (Lumbricus rubellus) and implications for population dynamics

Effects of C₆₀ nanoparticles (nominal concentrations 0, 15.4 and 154 mg/kg soil) on mortality, growth and reproduction of Lumbricus rubellus earthworms were assessed. C₆₀ exposure had a significant effect on cocoon production, juvenile growth rate and mortality. These endpoints were used to model effects on the population level. This demonstrated reduced population growth rate with increasing C₆₀ concentrations. Furthermore, a shift in stage structure was shown for C₆₀ exposed populations, i.e. a larger proportion of juveniles. This result implies that the lower juvenile growth rate due to exposure to C₆₀ resulted in a larger proportion of juveniles, despite increased mortality among juveniles. Overall, this study indicates that C₆₀ exposure may seriously affect earthworm populations. Furthermore, it was demonstrated that juveniles were more sensitive to C₆₀ exposure than adults.     

Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

Optimization of analytical methods to improve detection of erythromycin from water and sediment

Analytical methods to improve the detection of erythromycin in water and sediment were developed to optimize for erythromycin's recovery of extractable and bound residues from the aquatic environment. The objective of this study was to determine optimal recovery of erythromycin from water and sediment to improve its detection in environmental samples through solid-phase extraction (SPE) and sediment-extraction methods. SPE methods examined included previously reported methods for macrolide and sulfonamide antibiotics with erythromycin recoveries ranging from 75.5 % to 94.7 %. Extraction of erythromycin was performed from sand employing various solvents and buffers to determine the best method for extraction from two sandy loam pond sediments. Various extraction times were also examined, and all extraction procedures were performed in duplicate. The greatest recovery of (14)C-erythromycin in the Iowa sediment was 84 % using 0.3 M ammonium acetate at pH 4.2: acetonitrile (15:85, v/v) solution. The Oklahoma sediment yielded the greatest recovery of (14)C-erythromycin at 86.7 % with 0.3 M ammonium acetate at pH 7: acetonitrile (30:70, v/v) with a 60-minute shake time. The present results demonstrate improved extraction methods for enhancing the accuracy of erythromycin detection from environmental samples.     

Assessment of the abiotic transformation of 17β-estradiol in the presence of vegetable matter--II: the role of molecular oxygen

This study characterizes the effect of oxygen in the abiotic transformation of estrogens when they are contacted with a surrogate of the vegetable wastes found in sewage. 17β-Estradiol (E2) and 17β-¹⁴C₄-estradiol (¹⁴C-E2) were utilized as model compounds. Batch experiments were run under both oxic and anoxic conditions. In order to accomplish an accurate mass balance of the target estrogen, two analyses were performed simultaneously: first, radioactivity counting, and second, quantitation of E2 and ¹⁴C-E2, as well as their transformation product estrone and ¹⁴C₄-estrone, by Liquid Chromatography tandem Mass Spectrometry. Under oxic conditions, the total concentration of ¹⁴C-E2 was found to decrease by 78% in 72 h (15% and 7% remained in the liquid and solid phases, respectively). Conversely, when the estrogens were contacted with the synthetic influent under anoxic conditions, E2 was quantitatively recovered after 72 h (70% and 22% in aqueous and solid matrices, correspondingly). These results suggest that when the concentration of dissolved oxygen is null or limited, catalysis through an oxidative coupling mechanism is halted. Moreover, it was confirmed that the catalytic reaction occurred solely in the presence of the solid phase of the model vegetable matter.     

Residue determination and dissipation of ioxynil octanoate in maize and soil

A simple and efficient residue analysis method for direct determination of ioxynil octanoate in maize and soil was developed and validated with High Performance Liquid Chromatography-Ultra Violet (HPLC-UV). The samples were extracted with mixtures of acetonitrile and deionized water followed by Solid Phase Extraction (SPE) to remove co-extractives prior to analysis by HPLC-UV. The recoveries of ioxynil octanoate extracted from maize and soil samples ranged from 86 %–104 % and 84 %–96 %, respectively, with relative standard deviation (RSD) less than 7.84% and sensitivity of 0.01 mg kg^?1. The method was applied to determine the residue of ioxynil octanoate in maize and soil samples from experimental field. Data had shown that the dissipation rate in soil was described as pseudo-first-order kinetics and the half-life (t_1/2) was less than 1.78 days. No ioxynil octanoate residue (<0.01 mg kg^?1) was detected in maize at harvest time withholding period of 60 days after treatments of the pesticide. Direct confirmation of the analytes in field trial samples was realized by Liquid Chromatography-Mass Spectrometry (LC-MS).     

Comparison of the cytotoxic responses of Escherichia coli (E. coli) AMC 198 to different fullerene suspensions (nC60)

Fullerenes are set to be produced on an industrial scale in anticipation of their wide applications. This calls for research on their environmental and health impacts. This study investigates and compares the cell toxicity of different aqueous fullerene aggregates. Popular C₆₀ dispersal methods were used to prepare four types of nC₆₀ aggregates. These aggregates were tested against the indicator species Escherichia coli (E. coli) AMC 198. With aggregates of around 150 nm in diameter, the THF/nC₆₀ suspension was very toxic and gave rise to a half maximal effective concentration (EC₅₀) of 0.54 mg L⁻¹ in E. coli. By contrast, the Tol/nC₆₀ suspension exhibited a cytoprotective role while the Aqu-N₂/nC₆₀ and Aqu-O₂/nC₆₀ suspensions enhanced the metabolism of E. coli. Although some toxicants, such as THF and THF-peroxide, were introduced into the THF/nC₆₀ suspension during the dispersion, the toxicity of nC₆₀ itself cannot be neglected.     

Short-chain chlorinated paraffins (SCCPs) in surface soil from a background area in China: occurrence, distribution, and congener profiles

Short-chain chlorinated paraffins (SCCPs) are extremely complex technical mixtures of polychlorinated n-alkanes with carbon chain lengths from C₁₀ to C₁₃ and chlorine content between 49 and 70 %. SCCPs are under consideration for inclusion in the Stockholm Convention on persistent organic pollutants. SCCPs have been used extensively in industrial production, but little is known about the pollution level in soil environment in China. In this study, levels and distribution of SCCPs in soil samples from Chongming Island were analyzed. Concentrations of total SCCPs in soil samples ranged from 0.42 to 420 ng?g^?1, with a median of 9.6 ng?g^?1. The ubiquitous occurrence of SCCPs in Chongming Island implied that long-range atmospheric transport and soil–air exchange may be the most important pathways for SCCP contamination in the background area. The localized SCCP contamination could be derived from an unidentified source. Hierarchical cluster analysis indicated that C₁₃- and C₁₁-congeners were predominant in most soils and C₁₀- and C₁₂-congeners dominated in the remaining soils. Cl₇- and Cl₈-congeners were on the average the most dominant chlorine congeners in nearly all soils. Principal component analysis suggested that the separation of even and odd carbon chain congeners occurred during long-range atmospheric transport and aging in soil in the study area.     

The impact of sewage sludge compost on tree peony growth and soil microbiological,and biochemical properties

In order to assess the suitability of sludge compost application for tree peony (Paeonia suffruticosa)–soil ecosystems, we determined soil microbial biomass C (C_mic), basal respiration (R_mic), enzyme activities, and tree peony growth parameters at 0–75% sludge compost amendment dosage. Soil C_mic, R_mic, C_mic as a percent of soil organic C, enzyme (invertase, urease, proteinase, phosphatase, polyphenoloxidase) activities, and plant height, flower diameter, and flower numbers per plant of tree peony significantly increased after sludge compost amendment; however, with the increasing sludge compost amendment dosage, a decreasing trend above 45% sludge compost amendment became apparent although soil organic C, total Kjeldahl N, and total P always increased with the sludge compost amendment. Soil metabolic quotient first showed a decreasing trend with the increasing sludge compost application in the range of 15–45%, and then an increasing trend from compost application of 45–75%, with the minimum found at compost application of 45%. As for the diseased plants, 50% of tree peony under the treatment without sludge compost amendment suffered from yellow leaf disease of tree peony, while no any disease was observed under the treatments with sludge compost application of 30–75%, which showed sludge compost application had significant suppressive effect on the yellow leaf disease of tree peony. This result convincingly demonstrated that ?45% sludge compost application dosage can take advantage of beneficial effect on tree peony growth and tree peony–soil ecosystems.     

Planting woody crops on dredged contaminated sediment provides both positive and negative effects in terms of remediation

There is currently a requirement for studies focusing on the long-term sustainability of phytoremediation technologies. Trace element uptake by Salix, Populus and Alnus species planted in dredged contaminated canal sediment and concentrations in sediment and pore waters were investigated, eight years after a phytoremediation trial was initiated in NW England. Soil biological activity was also measured using invertebrate and microbial assays to determine soil quality improvements. Zinc was the dominant trace metal in foliage and woody stems, and the most mobile trace element in sediment pore water (∼14 mg l⁻¹). Biological activity had improved; earthworm numbers had increased from 5 to 24, and the QBS index (an index of microarthropod groups in soil) had increased from 70 to 88. It is concluded that biological conditions had improved and natural processes appear to be enhancing soil quality, but there remains a potential risk of trace element transfer to the wider environment.     

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.     

Sorption of 17α-ethinyl estradiol, bisphenol A and phenanthrene to different size fractions of soil and sediment

The potential for negative effects caused by endocrine disrupting chemicals (EDCs) release into the environment is a prominent concern and numerous research projects have investigated possible environmental fate and toxicity. However, their sorption behavior by size fractions of soil and sediment has not been systematically represented. The sorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) by different size fractions of soil and sediment were investigated. Sorption isotherms of EE2, BPA, and Phen by size fractions of soil (SL) and sediment (ST) were well fitted to the Freundlich model. The positive correlation between EE2, BPA and Phen sorption capacity (log K_d) of size fractions and their organic carbon (OC) content suggests that OC of size fractions in SL and ST should regulate sorption, while the surface area (SA) of size fractions may not account for sorption of EE2, BPA and Phen. Each size fraction of ST had higher sorption capacity (K_d or K_OC) of EE2 and BPA than that of SL due to their difference in the polarity of organic matter (OM) between terrestrial and aquatic sources. Sorption capacity logK_d for size fractions of SL and ST did not follow the order: clay > silt > sand due to the difference in OM abundance and composition between the size fractions. Large particle fractions of ST contributed about 80% to the overall sorption for any EE2, BPA, and Phen. This study was significant to evaluate size fractions of soil and sediment as well as their associated OM affecting EE2 and BPA sorption processes.