Potential release pathways, environmental fate, and ecological risks of carbon nanotubes

Carbon nanotubes (CNTs) are currently incorporated into various consumer products, and numerous new applications and products containing CNTs are expected in the future. The potential for negative effects caused by CNT release into the environment is a prominent concern and numerous research projects have investigated possible environmental release pathways, fate, and toxicity. However, this expanding body of literature has not yet been systematically reviewed. Our objective is to critically review this literature to identify emerging trends as well as persistent knowledge gaps on these topics. Specifically, we examine the release of CNTs from polymeric products, removal in wastewater treatment systems, transport through surface and subsurface media, aggregation behaviors, interactions with soil and sediment particles, potential transformations and degradation, and their potential ecotoxicity in soil, sediment, and aquatic ecosystems. One major limitation in the current literature is quantifying CNT masses in relevant media (polymers, tissues, soils, and sediments). Important new directions include developing mechanistic models for CNT release from composites and understanding CNT transport in more complex and environmentally realistic systems such as heteroaggregation with natural colloids and transport of nanoparticles in a range of soils.     

Five-stage environmental exposure assessment strategy for mixtures: gasoline as a case study

A five-stage strategy is suggested for conducting an exposure assessment of mixtures that may contain numerous chemical components. The stages are: (1) determination of mixture composition and variability, (2) selection of component groups within the mixture and documentation of criteria used for this selection, (3) compilation of relevant property data for each group, (4) assessment of environmental fate of each group, and (5) assessment of environmental and human exposure to each group and to the mixture as a whole. A subsequent step is the assessment of environmental and/or human risk associated with the individual and aggregate exposure to each group. The approach is illustrated by application to gasoline, which is treated as 24 component groups or hydrocarbon blocks. Focusing on stages 2-4, the illustration shows that the groups display widely different environmental fates as a result of their different physicochemical properties, degradation half-lives, and mode-of-entry into the environment. As a result, the relative proportions of groups in each environmental medium (such as air and water) differ greatly from that of the original mixture. It is thus important to treat gasoline and similar mixtures as a number of component groups instead of as a single substance. A generic procedure is suggested in which the model is run for unit emissions of each component group to air, water, and soil. These results are compiled into matrices that can then be conveniently scaled to actual emission rates without rerunning the model. Methods for determining subsequent exposure and risk are also briefly outlined.     

Development of a coupled reactor model for prediction of organic contaminant fate in landfills

Models describing the behavior of organic chemicals in landfills can be useful to predict their fate and transport and also to generate input data for estimates of exposure and risk. The landfill coupled-reactor (LFCR) model developed in this work simulates a landfill as a series of fully mixed reactors, each representing a daily volume of waste. The LFCR model is a numerical model allowing time-variable input parameters such as gas generation, and cover type and thickness. The model was applied to three volatile organic chemicals (acetone, toluene, benzene) as well as naphthalene and the chemical warfare agent sarin under three landfill conditions (conventional, arid, bioreactor). Sarin was rapidly hydrolyzed, whereas naphthalene was largely associated with the landfill solid phase in all scenarios. Although similar biodegradation rates were used for acetone and toluene, toluene was more persistent in the landfill due to its hydrophobicity. The cover soil moisture content had a significant impact on gaseous diffusive losses.     

Significance of xenobiotic metabolism for bioaccumulation kinetics of organic chemicals in Gammarus pulex

Bioaccumulation and biotransformation are key toxicokinetic processes that modify toxicity of chemicals and sensitivity of organisms. Bioaccumulation kinetics vary greatly among organisms and chemicals; thus, we investigated the influence of biotransformation kinetics on bioaccumulation in a model aquatic invertebrate using fifteen (14)C-labeled organic xenobiotics from diverse chemical classes and physicochemical properties (1,2,3-trichlorobenzene, imidacloprid, 4,6-dinitro-o-cresol, ethylacrylate, malathion, chlorpyrifos, aldicarb, carbofuran, carbaryl, 2,4-dichlorophenol, 2,4,5-trichlorophenol, pentachlorophenol, 4-nitrobenzyl-chloride, 2,4-dichloroaniline, and sea-nine (4,5-dichloro-2-octyl-3-isothiazolone)). We detected and identified metabolites using HPLC with UV and radio-detection as well as high resolution mass spectrometry (LTQ-Orbitrap). Kinetics of uptake, biotransformation, and elimination of parent compounds and metabolites were modeled with a first-order one-compartment model. Bioaccumulation factors were calculated for parent compounds and metabolite enrichment factors for metabolites. Out of 19 detected metabolites, we identified seven by standards or accurate mass measurements and two via pathway analysis and analogies to other compounds. 1,2,3-Trichlorobenzene, imidacloprid, and 4,6-dinitro-o-cresol were not biotransformed. Dietary uptake contributed little to overall uptake. Differentiation between parent and metabolites increased accuracy of bioaccumulation parameters compared to total (14)C measurements. Biotransformation dominated toxicokinetics and strongly affected internal concentrations of parent compounds and metabolites. Many metabolites reached higher internal concentrations than their parents, characterized by large metabolite enrichment factors.     

Laser ablation-ICP-MS analysis of dissected tissue: a conservation-minded approach to assessing contaminant exposure

Minimally invasive sampling techniques are an essential ecotoxicological tool for continuous assessment of contaminant exposure and in instances where it is not desirable or practical to sacrifice the animal. In this paper, we report on the application of laser ablation-ICP-MS (LA-ICP-MS) for sampling of minute (approximately 1 mg, 2-3 mm) tail clips of the banded water snake, Nerodia fasciata, as a means to assess contaminant exposure. The snakes were split into three treatments (n = 8) and were fed three increasing levels (control, medium, and high) of fish contaminated with As, Se, and Sr for 24 months. LA-ICP-MS concentrations of tail clips for all three elements were significantly correlated with the remaining whole tail concentration determined by homogenization, acid digestion, and ICP-MS analysis. Additionally, LA-ICP-MS concentrations for As and Se in the tail clip were similar to the acid digestion solution analysis values for the whole tail, which suggests that these elements are homogeneously distributed. Strontium concentrations were underestimated by LA-ICP-MS when compared to whole tail concentrations. Statistical analysis showed that LA-ICP-MS tail clip concentrations differed significantly according to dietary treatment. Posterior probability error rates from nonparametric discriminant function analysis indicated that LA-ICP-MS analysis of tail clips was useful for predicting exposure to Se with only a 4% probability of misclassification among treatments. Errors associated with misclassification of As were greater (17%) but this was, in part, related to the low concentrations of As in the tail (<1 ppm for the highest treatment). Taken together, the findings from this study suggest that LA-ICP-MS of microdissected tissue shows promise as a nondestructive technique for conservation-minded ecotoxicological studies.     

Bioremediation of groundwater contaminated with gasoline hydrocarbons and oxygenates using a membrane-based reactor

The objective of this study was to operate a novel, field-scale, aerobic bioreactor and assess its performance in the ex situ treatment of groundwater contaminated with gasoline from a leaking underground storage tank in Pascoag, RI. The groundwater contained elevated concentrations of MTBE (methyl tert-butyl ether), TBA (tert-butyl alcohol), TBF (tert-butyl formate), BTEX (benzene, toluene, ethyl benzene, and xylene isomers), and other gasoline additives (tert-amyl methyl ether, di-isopropyl ether, tert-amyl alcohol, methanol, and acetone). The bioreactor was a gravity-flow membrane-based system called a Biomass Concentrator Reactor (BCR) designed to retain all biomass within the reactor. It was operated for six months at an influent flow rate that ultimately reached 5 gpm. The goal was to achieve a removal of all contaminants to <5 microg/L, which is the California Drinking Water advisory for MTBE. The concentration of TBA, an MTBE biodegradation byproduct, was consistently lower than that of MTBE. The other daughter compound detected in the influent, TBF, was degraded to concentrations below the detection limit of 0.02 microg/L. BTEX were consistently degraded to significantly lower levels in the effluent throughout the duration of the study (<1 microg/L). A similar high removal efficiency of the other gasoline oxygenates present in the groundwater (TAME, DIPE, and TAA) was also achieved. Dissolved organic carbon analysis demonstrated the ability of the bioreactor to produce high quality effluents with nonpurgeable organic carbon (NPOC) averaging approximately 50% lowerthan the NPOC concentrations in the influent contaminated groundwater.     

Metabolic fate of ochratoxin A as a coffee contaminant in a dynamic simulator of the human colon

Ochratoxin A (OTA) is a mycotoxin frequently encountered in coffee. The relevance of this contaminant in the colon upon digestion necessitates a study on its interaction with colon microbiota. Here, the fate of OTA during colon digestion was investigated using a dynamic simulator of the human gut. The influence of coffee as a food matrix was taken into account, as it may affect the colonic microbial ecosystem and, consequently, the fate of OTA. Biodegradation was followed by measuring OTA concentration over time, and by screening for several possible metabolites, using LC–ESI-MS and HRMS. The descending colon was found to be the main site of OTA biodegradation. Two metabolites, ochratoxin α and ochratoxin B, were identified, suggesting that biodegradation by gut microbiota is beneficial for the host, as they are considered less toxic than OTA. The extent of biodegradation was reduced in the presence of the coffee matrix, possibly due to competition for available carbon sources. Effects of OTA and the coffee matrix on the microbial ecosystem were contrasting. While OTA caused a specific, but lasting loss, of the beneficial species Lactobacillus reuteri, coffee temporarily altered the fermentation pattern towards lower ammonia and higher acetate and propionate production, likely due to its dietary fibre content.     

Practical method of assessing local and global impacts for risk-based decision making: a case study of metal degreasing processes

For risk-based decision making, local and global impacts should be considered simultaneously. In metal degreasing processes, various cleansing agents are used and a significant amount of such cleansing agents is released into the environment. An appropriate measure of reducing chemical risk associated with industrial cleaning processes should be implemented on the basis of evaluation results representing the local and global impacts. In this study, we assessed metal degreasing processes using a chlorinated solvent with an open-top washing machine and four alternative scenarios, namely, improving the settings of the machine (two cases), changing the local ventilation system, and installing a recovery system using activated carbon. The applied methods are plant-specific risk and life cycle assessments. Specifically in the risk assessment, detailed process data available for decision makers are utilized to evaluate occupational and neighborhood risks. The results of this case study indicate a tradeoff relationship between the local and global impacts in metal degreasing. Through the discussions on the practicability of the integration of the local and global impacts into actual decision making, we conclude that the way to use, select, or integrate risk and life cycle assessments should be analyzed systematically as the situation demands at decision making.     

Climate effects of emission standards: the case for gasoline and diesel cars

Passenger transport affects climate through various mechanisms involving both long-lived and short-lived climate forcers. Because diesel cars generally emit less CO(2) than gasoline cars, CO(2) emission taxes for vehicle registrations and fuels enhance the consumer preference for diesel cars over gasoline cars. However, with the non-CO(2) components, which have been changed and will be changed under the previous and upcoming vehicle emission standards, what does the shift from gasoline to diesel cars mean for the climate mitigation? By using a simple climate model, we demonstrate that, under the earlier emissions standards (EURO 3 and 4), a diesel car causes a larger warming up to a decade after the emissions than a similar gasoline car due to the higher emissions of black carbon and NO(X) (enhancing the O(3) production). Beyond a decade, the warming caused by a diesel car becomes, however, weaker because of the lower CO(2) emissions. As the latter emissions standards (EURO 5 and 6) are phased in, the short-term warming due to a diesel car becomes smaller primarily due to the lower black carbon emissions. Thus, although results are subject to restrictive assumptions and uncertainties, the switch from gasoline to diesel cars encouraged by CO(2) taxes does not contradict with the climate mitigation focusing on long-term consequences.     

Phase and size distribution of polycyclic aromatic hydrocarbons in diesel and gasoline vehicle emissions

Emission measurements were obtained for a variety of military vehicles at Hill Air Force Base (Ogden, UT) in November 2000 as part of a Strategic Environmental Research and Development Program. Aircraft ground support equipment vehicles using gasoline, diesel, and JP8 fuels were tested using chassis dynamometers under predetermined load. The exhaust from the tested vehicle was passed to a dilution tunnel where it was diluted 30-40 times and collected using Micro-Orifice Uniform Deposit Impactor (MOUDI) fitted with aluminum substrates, an XAD-coated annular denuder, and a filter followed by a solid adsorbent. All MOUDI substrates were analyzed for mass and for organic and elemental (EC) carbon by the thermal/optical reflectance method and for polycyclic aromatic hydrocarbons (PAHs) by GC/MS. Black carbon was measured with a photoacoustic instrument. The denuder and filter/solid adsorbent samples were analyzed for semivolatile PAH. Overall, there is more mass and higher EC contribution when the vehicle is run under higher load in comparison with the low load. However, older vehicles generally show more mass and EC emissions than newer vehicles, and there is a shift toward smaller particle sizes for the low load, which is most pronounced for newer vehicles. The particle-associated semivolatile PAHs and nonvolatile four-through six-ring PAHs are present predominantly on the submicron particles collected on MOUDI stages 0.1-0.18, 0.18-0.32, and 0.32-0.56 microm. For the low-load runs, the distribution of PAHs seems to be shifted toward smaller size particles. The gas-particle phase distribution of semivolatile PAHs depends also on the engine loading. For idle, not only are the more volatile two- and three-ring PAHs, from naphthalene to dimethylphenanthrenes, retained on the denuder portion, but also less volatile four-ring PAHs, such as fluoranthene and pyrene, are retained by the denuder at the 80-90% range, which implies that they are present predominantly in the gas phase. In contrast, for engines under high loads, a much larger portion of three- and four-ring PAHs are partitioned to the particle phase.     

A dynamic model of the fate of organic chemicals in a multilayered air/soil system: development and illustrative application

A new site-specific, dynamic model (SoilPlus) was developed to simulate the fate of nonionized organic chemicals in the air/litter/soil system; key features of the model are the double-layered air compartment interacting dynamically with multilayered litter and soil compartments, with seasonal dissolved organic carbon (DOC) fluxes. The model describes the soil environment calculating separate mass balances for water, chemical, and organic matter. SoilPlus underwent a process of benchmarking and evaluation in order to reach a satisfying confirmation of its predictive capability. Several simulations were performed to estimate the role of litter and DOC in affecting the fate of a model contaminant for POPs (hexachlorobenzene). The model shows that litter can behave as a buffer in the process of transferring hexachlorobenzene from air to the mineral soil and as a trap when hexachlorobenzene tends to move from a contaminated field toward clean air. DOC seems to behave as a leaching-enhancer in certain climatic conditions (heavy rainfall, high DOC concentrations), but it does not appear to move significant amounts of HCB in a year calculation.     

Environmental impact and human health risks of polychlorinated dibenzo-p-dioxins and dibenzofurans in the vicinity of a new hazardous waste incinerator: a case study

The purpose of this study was to assess the environmental impact of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the vicinity of a new hazardous waste incinerator (HWI) 4 years after regular operation of the facility. A double approach was carried out. The PCDD/F congener profiles corresponding to environmental samples, soil and herbage, collected before the HWI (baseline) and 4 years after starting regular operations, as well as PCDD/F profiles of air emission samples, were compared. The potential health risks (carcinogenic and noncarcinogenic) due to PCDD/F exposure were assessed for adults and children living in the neighborhood of the facility. Human exposure to PCDD/Fs was mainly due to dietary food intake. Comparisons between the PCDD/F congener profiles corresponding to the baseline and current surveys, as well as data concerning the human health risk assessment, indicate that the HWI in question does not cause additional risks to the environment orto the population living in the vicinity of the facility.     

Long-term fate of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in an agricultural soil

Laboratory studies are useful for understanding the behavior of persistent organic pollutants (POPs) in soil, although such investigations do not always relate directly to field conditions. Outdoor lysimeter studies may be used to overcome this problem. This work aimed to investigate the behavior of two polycyclic aromatic hydrocarbons (PAHs) (fluoranthene and benzo[a]pyrene) and two polychlorinated biphenyls (PCBs; congeners 28 and 52) in soil, using lysimeters established in 1990 atthe Agrosphere Institute (Forschungszentrum Julich GmbH, Germany). The two PAHs were in one lysimeter, and the PCBs were in a second lysimeter. Afurther aim of the study was to determine soil half-lives for each of the contaminants. The overall decline in PAH concentrations was considerably greater than forthe PCBs over the 152 month study. The PCBs exhibited greater chemical extractability than the PAHs and were demonstrated to have migrated through the soil column to a greater extent than the PAHs. Loss of PCBs from surface soil was not considered to have been congener specific for the two PCB congeners in this study. The two PAHs varied in their extents of total loss and movement through the soil column. Soil half-lives were determined as 10.9 y for [12C]PCB 28, 11.2 yr for [12C]PCB 52, 2.7 yr for benzoqpyrene, and 32 d (phase 1) to 38 yr (phase 2) for fluoranthene. These are shown to disagree with some previous estimates of POP half-lives in soil, suggesting that previous studies underestimated persistence by 10-fold or more.     

Improving data quality for environmental fate models: a least-squares adjustment procedure for harmonizing physicochemical properties of organic compounds

Physicochemical properties (vapor pressure, aqueous solubility, octanol solubility, Henry's law constant, and octanol-air and octanol-water partition coefficients) and their temperature dependencies are required for fate modeling of environmental pollutants. To be internally consistent, measured values for these properties often must be adjusted. The goal of adjusting the property values for consistency is to more accurately estimate the true values. However, consistency and accuracy are not synonymous. If there are systematic errors in one property, then adjustment for consistency may reduce the accuracy of other property data. Here, we provide methods for achieving consistency and improving accuracy in the selection of partitioning properties from literature sources. First, we show that a widely used procedure does not always minimize the adjustments of property values derived from the literature when harmonizing them according to thermodynamic constraints. In such cases, the final adjusted values (FAVs) are unnecessarily different from the literature-derived values (LDVs) selected from measurements. We present an improved procedure based on the theory of least squares that minimizes the adjustment of LDVs and allows quantitative propagation of uncertainty from LDVs to FAVs. When this procedure is applied to partitioning properties for 30 organic chemicals, FAVs obtained differ by up to 30% from those calculated with the current adjustment procedure. Second, we point out that the adjustment procedure is only appropriate for correcting random errors in measurement data. Biased LDVs must be identified and corrected prior to harmonization. Using a set of 16 PCB congeners as a case study, we provide methods to identify biased data and discuss possible sources of bias. We present a new interpretation of property data for the PCBs and a new set of internally consistent properties and quantitative structure-property relationships that we recommend as the best currently available.     

Atmospheric polycyclic aromatic hydrocarbons in north China: a winter-time study

The contamination and outflow of atmospheric polycyclic aromatic hydrocarbons (PAHs) in the Chinese Northern Plain, a region with a total area of 300 000 km2 and a high PAH emission density, were investigated. Polyurethane foam (PUF) and PM10 samples were collected at 46 sites located in urban, rural (towns or villages), and control (remote mountain) areas in the winter from November 2005 to February 2006. The observed concentrations of atmospheric PAHs were generally higher than those reported for developed countries and southern Chinese cities. It was found that there was no significant difference in air PAH concentrations between the urban and the rural areas (514 +/- 563 ng/m3 and 610 +/- 645 ng/ m3, respectively), while the PAH concentrations at the control sites (57.1 +/- 12.6 ng/m3) were 1 order of magnitude lower than those at the other sites. The primary reason for the similarity in PAH concentrations between urban and rural areas was the fact that the predominant sources of biomass and domestic coal combustion were widely spread over the study area. The partition constants (K(PM10)) of PAHs were significantly correlated to the corresponding values of subcooled liquid-vapor pressure (pL0). However, the regression slopes of log K(PM10) versus log pL0 were much steeper than -1, indicating adsorption dominated over absorption. Three distinct patterns of outflow from the study area were identified by forward trajectory and cluster analysis.