Constituents of volatile organic compounds of evaporating essential oil

Essential oils containing aromatic compounds can affect air quality when used indoors. Five typical and popular essential oils—rose, lemon, rosemary, tea tree and lavender—were investigated in terms of composition, thermal characteristics, volatile organic compound (VOC) constituents, and emission factors. The activation energy was 6.3–8.6 kcal mol^?1, the reaction order was in the range of 0.6–0.8, and the frequency factor was 0.01–0.24 min^?1. Toluene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, n-undecane, p-diethylbenzene and m-diethylbenzene were the predominant VOCs of evaporating gas of essential oils at 40 °C. In addition, n-undecane, p-diethylbenzene, 1,2,4-trimethylbenzene, m-diethylbenzene, and 1,2,3-trimethylbenzene revealed high emission factors during the thermogravimetric (TG) analysis procedures. The sequence of the emission factors of 52 VOCs (137–173 mg g^?1) was rose ≈ rosemary > tea tree ≈ lemon ≈ lavender. The VOC group fraction of the emission factor of aromatics was 62–78%, paraffins were 21–37% and olefins were less than 1.5% during the TG process. Some unhealthy VOCs such as benzene and toluene were measured at low temperature; they reveal the potential effect on indoor air quality and human health.     

Microbial dechlorination of 2,4,6‐trichlorophenol in anaerobic sewage sludge

Abstract

The dechlorination of 2,4,6‐trichlorophenol (TCP) in municipal sewage sludge with a chlorophenol (CP)‐adapted consortium was investigated. Results show that dechlorination rates differed according to the source of the sludge samples used in the batch experiments. No significant differences in 2,4,6‐TCP dechlorination were observed following treatment with inoculum at densities ranging from 10% to 50% (V/V), but a significant delay was noted at 5% (V/V) density. Overall, results show that the higher the 2,4,6‐TCP concentration, the slower the dechlorination rate. The addition of acetate, lactate, pyruvate, vitamin B₁₂ or manganese dioxide did not results in a significant change in 2,4,6‐TCP dechlorination. Data collected from a bioreactor experiment revealed that pH 7.0 and a total solid concentration of 10 g/L were optimal for dechlorination. Dechlorination rates decreased significantly at higher agitation speeds. 2,4,6‐TCP dechlorination was enhanced under methanogenic conditions, but it was inhibited under denitrifying and sulfate‐reducing conditions.     

Emission factor of exhaust gas constituents during the pyrolysis of zinc chloride immersed biosolid

Pyrolysis enables ZnCl₂ immersed biosolid to be reused, but some hazardous air pollutants are emitted during this process. Physical characteristics of biosolid adsorbents were investigated in this work. In addition, the constituents of pyrolytic exhaust were determined to evaluate the exhaust characteristics. Results indicated that the pyrolytic temperature was higher than 500 °C, the specific surface area was >900 m²/g, and the total pore volume was as much as 0.8 cm³/g at 600 °C. For non-ZnCl₂ immersed biosolid pyrolytic exhaust, VOC emission factors increased from 0.677 to 3.170 mg-VOCs/g-biosolid with the pyrolytic temperature increase from 400 to 700 °C, and chlorinated VOCs and oxygenated VOCs were the dominant fraction of VOC groups. VOC emission factors increased about three to seven times, ranging from 1.813 to 21.448 mg/g for pyrolytic temperatures at 400–700 °C, corresponding to the mass ratio of ZnCl₂ and biosolid ranging from 0.25–2.5.     

Probabilistic risk assessment for personal exposure to carcinogenic polycyclic aromatic hydrocarbons in Taiwanese temples

To assess how the human exposure to airborne carcinogenic polycyclic aromatic hydrocarbons (PAHs) during working in or visiting a typical Taiwanese temple, we present a probabilistic risk model, appraised with reported empirical data. Two approaches are applied, one based on animal-derived benzo[a]pyrene (B[a]P) toxic equivalents (B[a]P(eq)) of individual PAHs and one is assumed that the potency of PAH mixtures is linked to their B[a]P level. The model integrates probabilistic exposure profiles of total-PAH and particle-bound PAH levels inside a temple from a published exploratory study with probabilistic incremental lifetime cancer risk (ILCR) models taking into account inhalation and dermal contact pathways, to quantitatively estimate the exposure risks for three age groups of adult, adolescent, and child. Risk analysis indicates that 90% probability inhalation ILCRs for three age groups have orders of magnitude around 10(-7)--10(-6); whereas for the dermal contact ILCRs ranging from 10(-5) to 10(-4), indicating high potential cancer risk. All 90% probabilities of B[a]P- and B[a]P(eq)-based total ILCRs are larger than 10(-6), indicating unacceptable probability distributions for three age groups. Sensitivity analysis indicates that to increase the accuracy of the results efforts should focus on a better definition of probability distributions for inhalation cancer slope factor, inhalation rates, and particle-bound PAH-to-skin adherence factor. We estimate risk-based visiting frequency advice for adult, adolescent, and child to a temple ranging from 5 to 7, 17 to 23, and 48 to 65 year(-1), respectively, based on an average 3h residence time.     

Applying mass transfer models for controlling organic compounds in ozonation process

Mass transfer plays a significant role in the ozonation process. The prediction models associated with the volumetric overall mass transfer coefficient (K_La) and initial fractional ozone absorption (FOA₀) during the ozonation process were developed through the use of dimensional analysis. It was found that the volumetric overall mass transfer coefficient is the function of diffusivity, agitation speed, and gas flow rate, and the parameters in the K_La equation are determined. Application of the prediction models for K_La and FOA₀ would yield information to choose the most practically feasible operating parameters. The removability of total organic carbon (TOC) can be estimated based on the mass balance relationship and kinetic expression of TOC oxidation, during continuous laboratory ozonation of humic acid solution. The reaction rate constant averaged 0.0291 L/mg·min. The developed model in combination with the mass transfer and reaction kinetics can be used successfully in forecasting the most efficient agitation speed to control the formation of organic compounds. Also, the critical value of ozone partial pressure to achieve the highest TOC removability can be determined through the use of the above developed model.     

PFAS Experts Symposium: Statements on regulatory policy,chemistry and analytics,toxicology, transport/fate,and remediation for per‐ and polyfluoroalkyl substances (PFAS) contamination issues

Sixty leading members of the scientific, engineering, regulatory, and legal communities assembled for the PFAS Experts Symposium in Arlington, Virginia on May 20 and 21, 2019 to discuss issues related to per‐ and polyfluoroalkyl substances (PFAS) based on the quickly evolving developments of PFAS regulations, chemistry and analytics, transport and fate concepts, toxicology, and remediation technologies.  The Symposium created a venue for experts with various specialized skills to provide opinions and trade perspectives on existing and new approaches to PFAS assessment and remediation in light of lessons learned managing other contaminants encountered over the past four decades. The following summarizes several consensus points developed as an outcome of the Symposium:

• Regulatory and policy issues: The response by many states and the US Environmental Protection Agency (USEPA) to media exposure and public pressure related to PFAS contamination is to relatively quickly initiate programs to regulate PFAS sites. This includes the USEPA establishing relatively low lifetime health advisory levels for PFAS in drinking water and even more stringent guidance and standards in several states. In addition, if PFAS are designated as hazardous substances at the federal level, as proposed by several Congressional bills, there could be wide‐reaching effects including listing of new Superfund sites solely for PFAS, application of stringent state standards, additional characterization and remediation at existing sites, reopening of closed sites, and cost renegotiation among PRPs.
• Chemistry and analytics: PFAS analysis is confounded by the lack of regulatory‐approved methods for most PFAS in water and all PFAS in solid media and air, interference with current water‐based analytical methods if samples contain high levels of suspended solids, and sample collection and analytical interference due to the presence of PFAS in common consumer products, sampling equipment, and laboratory materials.
• Toxicology and risk: Uncertainties remain related to human health and ecological effects for most PFAS; however, regulatory standards and guidance are being established incorporating safety factors that result in part per trillion (ppt) cleanup objectives. Given the thousands of PFAS that may be present in the environment, a more appropriate paradigm may be to develop toxicity criteria for groups of PFAS rather than individual PFAS.
• Transport and fate: The recalcitrance of many perfluoroalkyl compounds and the capability of some fluorotelomers to transform into perfluoroalkyl compounds complicate conceptual site models at many PFAS sites, particularly those involving complex mixtures, such as firefighting foams. Research is warranted to better understand the physicochemical properties and corresponding transport and fate of most PFAS, of branched and linear isomers of the same compounds, and of the interactions of PFAS with other co‐contaminants such as nonaqueous phase liquids. Many PFAS exhibit complex transport mechanisms, particularly at the air/water interface, and it is uncertain whether traditional transport principles apply to the ppt levels important to PFAS projects. Existing analytical methods are sufficient when combined with the many advances in site characterization techniques to move rapidly forward at selected sites to develop and test process‐based conceptual site models.
• Existing remediation technologies and research: Current technologies largely focus on separation (sorption, ion exchange, or sequestration). Due to diversity in PFAS properties, effective treatment will likely require treatment trains. Monitored natural attenuation will not likely involve destructive reactions, but be driven by processes such as matrix diffusion, sorption, dispersion, and dilution.

The consensus message from the Symposium participants is that PFAS present far more complex challenges to the environmental community than prior contaminants. This is because, in contrast to chlorinated solvents, PFAS are severely complicated by their mobility, persistence, toxicological uncertainties, and technical obstacles to remediation—all under the backdrop of stringent regulatory and policy developments that vary by state and will be further driven by USEPA. Concern was expressed about the time, expense, and complexity required to remediate PFAS sites and whether the challenges of PFAS warrant alternative approaches to site cleanups, including the notion that adaptive management and technical impracticability waivers may be warranted at sites with expansive PFAS plumes. A paradigm shift towards receptor protection rather than broad scale groundwater/aquifer remediation may be appropriate.     

Surface characterization of acid-oxidized multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) oxidized with sulfuric acid, nitric acid, and the mixture of sulfuric and nitric acids were characterized by thermogravimetric analysis (TGA), Raman spectroscopy, elemental analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The TGA data showed that the MWNTs were more resistant to oxidation than C₆₀ or activated carbon fibers. Catalyst particles could be removed by the oxidants containing sulfuric acid, and thus indicative of the tip opening of MWNTs. The sulfuric acid had a propensity to create defect sites and introduce the surface oxides at those defects that already exist or be newly generated on MWNTs. However, the acid mixture could open the caps of MWNTs but preserve the structure homogeneity. The treatment with nitric acid gave rise to the highest bulk oxygen content in MWNTs, while the most abundant surface oxides were provided by sulfuric acid oxidation. In addition, nitric acid exhibited the best ability to transform the phenolic groups into carboxyl groups.     

Estimating stray dog populations with the regression method versus Beck’s method: a comparison

Statistical procedures for wildlife population estimation have been greatly improved since the last decade. For estimation of stray dog population size, however, the simple methods recommended by the 1990 WHO/WSPA guidelines seem to remain the popular favorites among researchers. Although the methods are very easy to use, their usefulness relies heavily on certain assumptions that are generally unrealistic. Using simulation studies, we conclude that Beck’s method, one of the estimators recommended by the guidelines, performs fairly well and can be safely used to get a quick population estimate, as long as the underlying assumptions are not severely violated.     

Waves of intermediate length through an array of vertical cylinders

We report a semi-analytical theory of wave propagation through a vegetated water. Our aim is to construct a mathematical model for waves propagating through a lattice-like array of vertical cylinders, where the macro-scale variation of waves is derived from the dynamics in the micro-scale cells. Assuming infinitesimal waves, periodic lattice configuration, and strong contrast between the lattice spacing and the typical wavelength, the perturbation theory of homogenization (multiple scales) is used to derive the effective equations governing the macro-scale wave dynamics. The constitutive coefficients are computed from the solution of micro-scale boundary-value problem for a finite number of unit cells. Eddy viscosity in a unit cell is determined by balancing the time-averaged rate of dissipation and the rate of work done by wave force on the forest at a finite number of macro stations. While the spirit is similar to RANS scheme, less computational effort is needed. Using one fitting parameter, the theory is used to simulate three existing experiments with encouraging results. Limitations of the present theory are also pointed out.     

Pyrolytic kinetics of sludge from a petrochemical factory wastewater treatment plant--a transition state theory approach

The pyrolysis of hydrocarbon-rich sludge in an oxygen-free environment can provide useful liquefaction products and residues. When applied to sewage sludge, energy and time costs are the major factors that affect the operation. Therefore, it is important to understand how the process is affected by temperature. The pyrolysis kinetics of sludge from a petrochemical factory wastewater treatment plant was studied to reveal the effects of temperature on the reaction rate and the magnitude of deltaH and deltaS of the reaction barrier. Oven-dried sludge samples were pyrolyzed in an isothermal reactor under six different temperatures. The residues were weighed at frequent intervals within a total 30-min experiment period. Data analysis indicated that a first order reaction model could describe the pyrolysis kinetics, across all experimental temperature ranges. When transition state theory was applied, the results indicated that the major reaction barrier came from the entropy term of the activation free energy. Therefore, increasing the pyrolysis temperature to overcome the reaction barrier yielded no apparent improvement, but strategies that reduced the entropy should significantly improve the reaction.