Technology review and evaluation of different chemical oxidation conditions on treatability of PFAS

Per‐ and polyfluoroalkyl substances (PFAS) are a class of stable compounds widely used in diverse applications. These emerging contaminants have unique properties due to carbon–fluorine (C–F) bonds, which are some of the strongest bonds in chemistry. High energy is required to break C–F bonds, which results in this class of compounds being recalcitrant to many degradation processes. Many technologies studied that have shown treatment effectiveness for PFAS cannot be implemented in situ. Chemical oxidation is a demonstrated remediation technology for in situ treatment of a wide range of organic environmental contaminants. An overview of relevant literature is presented, summarizing the use of single or combined reagent chemical oxidation processes that offer insight into oxidation–reduction chemistries potentially capable of PFAS degradation. Based on the observations and results of these studies, bench‐scale treatability tests were designed and performed to establish optimal conditions for the formation of specific free radical species, including superoxide and sulfate radicals, via various combinations of oxidants, catalysts, pH buffers, and heat to assess PFAS treatment by chemical oxidants. The study also suggests the possible abiotic transformations of some PFAS when chemical oxidation is or was used for treatment of primary organic contaminants (e.g., petroleum or chlorinated organic compounds) at a site. The bench‐scale tests utilized field‐collected samples from a firefighter training area. Much of the available data related to chemical oxidation of PFAS has only been reported for one or both of the two more commonly discussed PFAS (perfluorooctane sulfonic acid and/or perfluorooctanoic acid). In contrast, this treatability study evaluates oxidation of a diverse list of PFAS analytes. The results of this study and published literature conclude that heat‐activated persulfate is the oxidation method with the best degradation of PFAS. Limited reduction of reported PFAS concentrations in this study was observed in many oxidation reactors; however, unknown mass of PFAS (such as precursors of perfluoroalkyl acids) that cannot be identified in a field collected sample complicated quantification of how much oxidative destruction of PFAS actually occurred.     

Non-point source contribution and dynamics of soluble and particulate phosphorus from main tributaries of the Zarivar Lake watershed,Iran

The temporal variability of phosphorus (P) transport and the relationships between discharge, suspended sediment concentration and particulate (PP), and soluble (SP) phosphorus were examined. The study was conducted at the event scale in seven tributaries of the Zarivar Lake watershed in Kurdistan Province (Iran) from March 2011 to April 2012. Based on eight runoff events, 82% of the total P was the PP carried out by suspended sediment. Results showed a high variability of P transport during different runoff events. It was found that soil erosion was the source of the high P load. For all tributaries, PP was linearly related to both discharge and suspended sediment concentration. However, the relationships of SP and PP with discharge and suspended sediment concentration showed different hysteresis patterns. The relationship between PP and discharge was generally characterized by a clockwise pattern (i.e., lower part contribution of the sub-watersheds) but the patterns between SP and discharge were mainly anticlockwise (i.e., upper part contribution of the sub-watersheds or perhaps due to a subsurface flow contribution).     

Quantification of runoff in laboratory-scale chambers

Many of the variables that control transport of agrochemicals and pathogens in the field are difficult to measure because parameters such as slope, soil and plant conditions, and rainfall cannot be adequately controlled in the natural environment. This paper describes the design, construction, operation and performance of a system useful for studying surface transport of agrochemicals and pathogens under controlled slope, rainfall and soil conditions. A turntable is used to support and rotate 4 soil chambers under oscillating dripper units capable of simulating rainfall intensities from 1 to 43 mm h-1. Chambers (35 x 100 x 18 cm i.d.) were constructed with an adjustable height discharge gate to collect runoff and three drains to collect leachate. Height adjustable platforms were constructed to support and elevate the chambers up to 20% slope. The chambers were uniformly packed with 35 to 45 kg of soil (bulk density 1.18-1.27 g cm-3) and initially saturated with two low intensity rain events. The coefficient of variation of the rainfall delivery over a range of 5 to 43 mm h-1 averaged 7.5%. An experiment to determine the variability between chambers in runoff amount and uniformity indicated that at least one runoff-equilibration cycle is needed to obtain steady state conditions for conducting runoff transport evaluations. Another experiment conducted to evaluate atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] runoff under simulated crop-residue covered vs bare soil conditions indicated six times more runoff from bare than crop residue covered soil. The system is capable of precise application of simulated rain, the simultaneous collection of runoff and leachate at slopes up to 20% and can be easily modified to meet a wide range of research parameters.     

From Aminolysis Product of PET Waste to Novel Biodegradable Polyurethanes

Chemical recycling of PET has been developed by various methods. Aminolysis is one of chemical recycling methods of PET has been developed recently. The obtained product using aminolysis, Bis (2-hydroxy ethylene) terephthalamide (BHETA), has the potential for further reactions to obtain useful products. There are few reports on usage of recycled BHETA from PET waste to synthesis of polyurethanes. On the other hand, various biodegradable polyurethanes have been synthesized using polycaprolactone diol. Therefore, caprolactone is a new potential in synthesis of biodegradable polyurethanes from PET waste. In this work, novel biodegradable polyurethanes have been synthesized using BHETA. In this order, at first polyols with different molecular weights have been synthesized through ring opening polymerization of caprolactone by BHETA, then urethane linkages were formed using HDI (Hexamethylene Diisocyanate) without chain extender. Chemical, thermal, mechanical and dynamic mechanical properties, biodegradability, morphology and UV resistance of synthesized polyurethanes have been investigated.     

Impact of hairy vetch cover crop on herbicide transport under field and laboratory conditions.

This study was conducted to evaluate the effect of hairy vetch cover crop residue on runoff losses of atrazine and metolachlor under both no-till corn field plots and from a laboratory runoff system. A 2-year field study was conducted in which losses of atrazine and metolachlor from vetch and non-vetch field plots were determined from the first runoff event after application (5 and 25 days after application in 1997 and 1998, respectively). A laboratory study was conducted using soil chambers, designed to simulate field soil, water, vegetation, and herbicide treatment conditions, subjected to simulated rain events of 5, 6, 20 and 21 days after application, similar to the rainfall pattern observed in the field study. Atrazine losses ranged from 1.2 to 7.2% and 0.01 to 0.08% and metolachlor losses ranged from 0.7 to 3.1% and 0.01 to 0.1% of the amount applied for the 1997 and 1998 runoff events, respectively. In the laboratory study, atrazine runoff losses ranged from 6.7 to 22.7% and 4.2 to 8.5% and metolachlor losses ranged from 3.6 to 9.8% and 1.1 to 4.7% of the amount applied for the 5-6 and 20-21 day events, respectively. The lower losses from the field study were due to smaller rainfall amounts and a series of small rains prior to the runoff event that likely washed herbicides off crop residue and into soil where adsorption could occur. Runoff losses of both herbicides were slightly higher from non-vetch than vetch field plots. Losses from the laboratory study were related to runoff volume rather than vegetation type.     

Microbial quality and physical–chemical characteristics of thermal springs

Microbial quality and physical–chemical properties of recreational spas were surveyed to investigate the health aspect of the spas’ water. A total of 195 samples were collected from pools and springs of the spas in five sites from Ardebil Province of Iran. The effects of an independent factor defined as ‘condition’ and its component sub-factors (i.e., sampling point, location, and sampling date) on microbial quality and physical–chemical properties of the spas were studied by applying path analysis. The influence of physical–chemical properties on microbial quality was also considered. The percentage of samples exceeding the ISIRI (Swimming pool water microbiological specifications (vol 9412), Institute of Standards and Industrial Research of Iran, Tehran, 2007) limits for Staphylococcus (spp.) was up to 55.8 in the springs and 87.8 in the pools, 58.1 and 99.2 for HPC, 90.7 and 97.8 for total coliform and fecal coliform, and 9.3 and 34.4 for Pseudomonas aeruginosa, respectively. There were significant differences between the pools and springs for both physical–chemical properties and microbial quality. From the path analysis, sampling point was the most effective sub-factor of ‘condition’ on both the physical–chemical properties and microbial quality. Among the physical–chemical properties, water color had the most enhancing or additive influence on microbial pollution, while EC indicated a reducing or subtractive effect.