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.     

A METHODOLOGY FOR OUTDOOR RECREATION ANALYSIS IN A STATE WATER RESOURCES PLANNING STUDY1

ABSTRACT: The paper presents a methodology for outdoor recreation analysis in a comprehensive State water resources planning study. This methodology applies to determination of recreation participation desires among the population, allocation of those desires to areas of potential resources within which they must be satisfied, comparison of the areal potential resources against the allocated desires to identify areas having recreational resource deficits or needs, and exploration of alternative solutions to the identified needs. Major elements discussed are: market area, inflow-outflow, resource desire determination and projection, resource desire allocation, facility inventory, resource desire-resource analysis and alternative solutions to identified needs of water-oriented outdoor recreation.     

Effects of chlorides on emissions of toxic compounds in waste incineration: study on partitioning characteristics of heavy metal

Chlorides derived from plastics and food residue content in MSW will affect the formation and partitioning of metal chlorides in the incineration discharges. Our study investigated the effects of waste-derived chlorides on the partitioning of heavy metals in a single-metal combustion system. The results indicate that the heavy metal partitioning behaviors are mainly affected by the presence of chloride, alkaline metals (i.e., Na, K) and moisture in the wastes. The configuration of the metal partitioning is determined by the availability of chlorine, hydrogen, and alkaline metals, or the extent to which the elements may divide from their compounds at a given combustion temperature. The effects of chlorides, including PVC, C2Cl4, FeCl3, NaCl and KCl, were also discussed.     

Improving the Synthesis Gas Quality in Catalytic Gasification of Rice Straw by an Integrated Hot-Gas Cleaning System

This research investigates an enhanced removal rate of tar and trace pollutants (e.g. hydrogen chloride and hydrogen sulfide, H₂S) in the gasification of rice straw, using an integrated in situ tar reduction and hot-gas cleaning technique. The gasification temperature was set at 900°C and equilibrium ratio (ER) was 0.30 in the gasifier. In the in situ tar reduction method, the catalyst, dolomite with an amended ratio of 0–15% was introduced to the gasifier. The integrated hot-gas cleaning system applied a multi-packed tower to remove the tar, sulfur and/or chlorine byproduct in syngas at 250°C. The packed materials composed of zeolite, calcined dolomite and activated carbon. The experimental results indicated that the tar concentration of syngas was approximately 20 g/kg. However, in catalytic gasification with 5% dolomite addition, the tar concentration reduced to 17 g/kg. The tar reduction efficiency was approximately 15% by an in situ dolomite addition. When applying the integrated hot-gas cleanup system, the tar was virtually eliminated. The total tar elimination rate was almost 100% and the cleaned syngas could be applied in other energy utilization equipment. On the other hand, the H₂S and HCl concentration were 101 ppmv and 991 ppmv, respectively. After the integrated syngas cleaning system, the H₂S and HCl were decreased to 7.9 ppmv and 410 ppmv with a removal efficiency of 92.1% and 58.6%, respectively. It can be concluded that combining the in situ method with the integrated syngas cleaning system can effectively reduce the amount of byproduct and enhance the syngas quality in the gasification of rice straw.     

Fix-Neyman model of illness-death processes

The concept of the life table originated in longevity studies of man, where it was always presented as a subject peculiar to public health, demography, and actuarial science. As a result, its development has not received sufficient attention in the field of statistics. Actually, the problems of mortality studies are similar to those of reliability theory and life testing, and they may be described in terms familiar to the statistically oriented mind. From a statistical point of view, human life is a random experiment and its outcome, survival or death, ss subject to chance. The life table systematically records the outcomes of many such experiments for a large number of individuals over a period of time. Thus, the quantities in the table are random variables subject to established statistical analysis. The purpose of this presentation is to discuss the life table from a statistical viewpoint.     

Biodegradation of nonylphenol in sewage sludge

We investigated the effects of various factors on the aerobic degradation of nonylphenol (NP) in sewage sludge. NP (5 mg/kg) degradation rate constants (k₁) calculated were 0.148 and 0.224 day⁻¹ for the batch experiment and the bioreactor experiment, respectively, and half-lives (t_1/2) were 4.7 and 3.1 days, respectively. The optimal pH value for NP degradation in sludge was 7.0 and the degradation rate was enhanced when the temperature was increased and when yeast extract (5 mg/l) and surfactants such as brij 30 or brij 35 (55 or 91 μM) were added. The addition of aluminum sulfate (200 mg/l) and hydrogen peroxide (1 mg/l) inhibited NP degradation within 28 days of incubation. Of the microorganism strains isolated from the sludge samples, we found that strain CT7 (identified as Bacillus sphaericus) manifested the best degrading ability.