Evaluation of solid sorbents for sampling nitroglycerin,ethylene glycol dinitrate and isopropyl nitrate in work-room air

Activated charcoal, Amberlite XAD-2, and Amberlite XAD-7 have been evaluated for the solid sampling of airborne nitroglycerin, ethylene glycol dinitrate and isopropyl nitrate. With the use of diethyl ether for solvent desorption, XAD-2 was found superior for sampling nitroglycerin and ethylene glycol dinitrate. Both XAD-7 and activated charcoal gave high recoveries for isopropyl nitrate; charcoal had a greater capacity than XAD-7 for this compound, however.     

Sampling of epichlorohydrin and ethylene chlorohydrin in workroom air using Amberlite XAD-7 resin

Activated charcoal, Amberlite XAD-2 and Amberlite XAD-7 were evaluated for the adsorption of epichlorohydrin and ethylene chlorohydrin from air followed by desorption with solvent. Ethylene chlorohydrin was found to be unstable on activated charcoal in the presence of carbon disulfide. Recoveries from XAD-2 were low, and XAD-7 was found to be the best adsorbent for the sampling of these compounds from air.     

Evaluation of solid sorbents for sampling aliphatic and aromatic nitro compounds in work-room air

Amberlite XAD-2 and XAD-7 porous polymers were evaluated for the solid sampling of aliphatic and aromatic nitro compounds in work-room air. With the use of solvent desorption, XAD-2 gave 80–100% recovery of nitroaromatics, and XAD-7 85–100% recovery of nitroaliphatics. The compounds studied were nitromethane, nitroethane, 2-nitropropane, nitrobenzene, $\text{m}$-dinitrobenzene and 2,4,6-trinitrotoluene. All six compounds gave very poor recoveries from activated charcoal.     

Degradation of ethylene glycol using Fenton's reagent and UV

Oxidation of ethylene glycol in aqueous solutions was found to occur with the addition of Fenton's reagent with further conversion observed upon UV irradiation. The pH range studied was 2.5-9.0 with initial H2O2 concentrations ranging from 100 to 1000 mg/l. Application of this method to airport storm-water could potentially result in reduction of chemical oxygen demand by conversion of ethylene glycol to oxalic and formic acids. Although the amount of H2O2 added follows the amount of ethylene glycol degraded, smaller H2O2 doses were associated with increases in the ratio of ethylene glycol removed per unit H2O2 added indicating the potential of pulsed doses or constant H2O2 feed systems. Ethylene glycol removal was enhanced by exposure to UV light after treatment with Fenton's reagent, with rates dependent on initial H2O2 concentration. In addition to ethylene glycol, the principle products of this reaction, oxalic and formic acids, have been shown to be mineralized in other HO generating systems presenting the potential for ethylene glycol mineralization in this system with increased HO* production.     

Sorption of the herbicides diquat and difenzoquat from aqueous medium by polymeric resins in the presence of sodium dodecylsulfate: Kinetic and mechanistic study

The goal of this work was to propose a novel method for the solid-phase extraction of the herbicides diquat (DQT²⁺) and difenzoquat (DFQT⁺) from aqueous medium using polymeric Amberlite XAD-2 and XAD-4 resins in the presence of sodium dodecylsulfate (SDS). The addition of SDS to the medium was of fundamental importance in order to allow the formation of a negatively charged surface able to sorb the cationic solutes. Several factors that could influence the sorption process, such as SDS concentration in the medium, sorbent mass, pH, ionic strength, and initial concentration of the solutes were investigated. Kinetic studies were also performed to model the system and to identify the mechanisms that operate the sorption process of the herbicides. SDS concentration in the medium presented remarkable influence on the extraction efficiency, achieving maximum values when the ratios [SDS]/[herbicide] were approximately 90, for XAD-2, and 22 and 11 for DQT²⁺ and DFQT⁺, respectively, for XAD-4. The sorption process followed a pseudo second-order kinetic in all cases studied. It was also found that an intraparticle diffusion process controlled exclusively the sorption of the herbicides by the Amberlite XAD-2 and XAD-4 resins in the first 15 min, becoming less active with time.     

Adsorption of branched alkylbenzene sulfonate onto styrene and acrylic ester resins

In this study, a series of acrylic ester resins were prepared and characterized. The adsorption behaviors of sodium 6-dodecyl benzenesulfonate (6-NaDBS) on styrene resin XAD-4 and acrylic ester resins have been studied. As compared to commercial acrylic ester resins Amberlite XAD-7 and Diaion HP2MG, YWB-38, one of the as-prepared resins, exhibits better adsorption properties toward 6-NaDBS. The experimental equilibrium data were fitted to the Langmuir and double-Langmuir models. The two models provide very good fit for all acrylic ester resins over the temperature range studied, whereas fitted results for styrene resin XAD-4 are less accurate. The investigation indicates that the adsorbate molecules are directly adsorbed on acrylic ester resins as a bi-layer, while the molecules are adsorbed on XAD-4 as monolayer formation followed by the establishment of bi-layer. Adsorption kinetics and elution processes were also investigated for further exploring the adsorption behavior and mechanism on styrene resin XAD-4 and YWB-38.     

Sampling of polychlorinated aromatics in workroom air using Amberlite XAD-2 resin

Amberlite XAD-2 porous polymer was evaluated for the solid sampling of PCBs, PCNs, tri-, tetra-and pentachlorophenol in workroom air. Using solvent desorption, the recoveries of these compounds from XAD-2 was mostly about 80%, showing this adsorbent to be an excellent medium for the sampling of polychlorinated aromatics in air.     

Fate, effects and potential environmental risks of ethylene glycol: a review

The fate, effects, and potential environmental risks of ethylene glycol (EG) in the environment were examined. EG undergoes rapid biodegradation in aerobic and anaerobic environments (approximately 100% removal of EG within 24 h to 28 days). In air, EG reacts with photo-chemically produced hydroxyl radicals with a resulting atmospheric half-life of 2 days. Acute toxicity values (LC(50)s and EC(50)s) were generally >10,000 mg/l for fish and aquatic invertebrates. The data collectively show that EG is not persistent in air, surface water, soil, or groundwater, is practically non-toxic to aquatic organisms, and does not bioaccumulate in aquatic organisms. Potential long-term, quasi-steady state regional concentrations of EG estimated with a multi-media model for air, water, soil, and sediment were all less than predicted no effect concentrations (PNECs).     

Equilibrium and kinetic studies on the adsorption of aniline compounds from aqueous phase onto bifunctional polymeric adsorbent with sulfonic groups

In the present study, a hydrophilic bifunctional polymeric resin (LS-2) with sulfonic groups was synthesized, and the adsorption performance of three aniline compounds, aniline, 4-methylaniline, and 4-nitroaniline onto LS-2 was compared with that on the commercial Amberlite XAD-4. The uptake of the aniline compounds on LS-2 is a procedure of coexistence of physisorption and chemisorption and obeys the pseudo-second order rate equation, while the uptake of the compounds on XAD-4 is merely a physical adsorption and follows the pseudo-first order rate equation. All the isothermal data fit well with the Freundlich model, and the values of K(F) of the compounds adsorbing on LS-2 are much higher than those on XAD-4 suggesting the higher adsorbing capacities on LS-2 than those on XAD-4, which may be attributed to the microporous structure and the polar groups on the network of LS-2 resin. Dynamic adsorption and desorption studies for aniline on LS-2 show that the breakthrough adsorption capacity and the total adsorption capacity are 0.96 and 1.24 mmol per milliliter resin, respectively. Nearly 100% regeneration efficiency for the adsorbent was achieved by 5% hydrochloric acid.     

The use of XAD-resins for the detection of mutagenic activity in water: I. Studies with surface water

A study of the effects of different XAD-resins, bed volume, flow rate, pH and type of eluent on the extraction of organic mutagens from surface water is presented. XAD-4/8 is as effective as XAD-2 in concentrating organic mutagens from surface water and dimethylsulfoxide (DMSO) is as efficient as acetone in eluting the adsorbed organic mutagens. The latter allows direct testing up to 0.5 ml of DMSO concentrate in the Ames test. Variation of the pH of the water after passing the XAD-4/8, followed by readsorption, shows that the majority of the mutagenic activity due to dissolved organics is adsorbed at neutral pH. Only a minor fraction is readsorbed at pH 3. Further a XAD-4/8 concentrate and a similar concentrate prepared by freeze drying gives similar mutagenic activity. This indicates that many of the organic mutagens are recovered in the XAD-4/8 concentrate.It is concluded that adsorption on XAD-4/8, followed by direct testing of the DMSO eluates in the Ames test, presents a rapid and relatively simple way to detect low concentrations of organic mutagens in surface water. The general suitability of the method is shown for different types of surface water.     

The fractionation of extracts of ambient particulate matter for mutagenicity testing

Extracts of air paniculate matter were fractionated by column chromatography over three different adsorbentia. It is shown that chromatography over alumina and over silicagel should be avoided, because of the low recovery of mutagenicity involved. On the other hand, fractionation over XAD-2 is strongly recommended, because of its ease of use and the superior recoveries of both mass and mutagenicity. HPLC subfractionation of the most mutagenic XAD-2 fraction showed that the mutagenicity cannot be attributed to a limited number of compounds.     

Sampling and analysis of polycyclic aromatic hydrocarbons (PAH) from two-stroke chain-saw engines

A sampling and analysis method for PAH from two-stroke engines is described. The method, which uses a standard glass fiber filter with a back-up section of Amberlite XAD-2 for sampling and GC or GC-MS for analysis, is suitable for both emission studies and occupational studies during logging. Filters and XAD-2 are desorbed with cyclohexane in an ultrasonic bath. After separation on a silica-gel micro column, the samples are submitted to analyses by capillary GC. The method is simple and covers both gaseous and particulate PAH. Naphthalene and alkyl substituted naphthalenes are also quantified.     

Influence of air humidity on sampling efficiency of some solid adsorbents used for sampling organics from work-room air

The influence of air humidity on the sampling efficiency of Amberlite XAD porous polymers and activated charcoal was studied by determining the recovery of various organics at 20% and 85% relative humidity. The sampling efficiency of XAD-7 was found to decrease with increasing relative humidity, while the sampling efficiency of XAD-2 and activated charcoal was relatively unaffected for the compounds studied. Activated charcoal had a greater capacity than Amberlite XAD for several types of compounds, however.     

Role of surface functionality in the adsorption of anionic dyes on modified polymeric sorbents

While synthetic polymeric sorbents effectively treat dye wastewaters by adsorption, the underlying mechanisms remain to be understood. This work determined the adsorption of an anionic dye by three polymers differing significantly in surface functionality. Surface functional groups of polymers were indicated in FTIR spectra and quantified by the Boehm titration. In reference to the commercial sorbent XAD-4 with a low degree of functionality, the laboratory synthesized NG-8 had primarily acidic functional groups, whereas its aminated product MN-8 had mainly basic amino groups. Electrophoresis determined the points of zero charge of 4.18, 3.23, and 4.51 for XAD-4, NG-8, and MN-8, respectively. The adsorption of Reactive Black 5 dye (RB5) by all the sorbents on a unit surface area basis increased with decreasing pH. At the same low pH (4.40), the adsorption by NG-8 was similar to that by XAD-4, indicating little influence of protonated (neutral) surface functional groups. In contrast, the adsorption by NG-8 at pH 6.05 was 75% lower than that by XAD-4, resulting apparently from the strong electrostatic repulsion between RB5 and deprotonated (negative) groups. Amination substantially enhanced RB5 adsorption by eliminating acidic groups and creating a positive charge on the surface of MN-8. The adsorptive enhancement was also achieved in the presence of CaCl2, due presumably to the neutralization of negative surface charge by Ca2+ and the RB5-Ca2+ pairing. These results manifest the important role of surface functionality in the adsorption of dyes by synthetic polymers.     

Adsorption of pesticides on resins

The objective of this work was to assess the capability of organic hydrophobic polymeric resins Amberlite XAD-4 and XAD-7 to remove the pesticides alachlor and amitrole from water. The pesticides adsorption on the two different adsorbents was measured by batch equilibrium technique and isotherm types and parameters were estimated. Two theoretical models were applied based on a Freundlich and a Langmuir isotherms. The effect of pesticides chemical composition and structure as well as the nature of solid surface on the efficiency of adsorption was evaluated. The influence of pH also was studied. In low pH solutions adsorption of amitrole was higher upon the nonionic aliphatic acrylic ester copolymer XAD-7 in comparison to the nonionic, crosslinked macroreticular copolymer of styrene divinylbenzene XAD-4. In neutral and intermediate pH solutions the polar acrylic ester copolymer XAD-7 was more effective to the retention of alachlor. The acrylic ester copolymer showed at pH 3 the lower effectiveness in alachlor removal from water. The data of the adsorption isotherms of pesticides upon the examined polymeric resins seemed to conform to both the Freundlich and the Langmuir isotherm models.     

A simplified method for sampling and analysis of high volume surface water for organic contaminants using XAD-2

A simple compressed-gas driven system for field processing and extracting water for subsequent analyses of hydrophobic organic compounds is presented. The pumping device is a pneumatically driven pump and filtration system that can easily clarify at 4 L/min. The extraction device uses compressed gas to drive filtered water through two parallel XAD-2 resin columns, at about 200 mL/min. No batteries or inverters are required for water collection or processing. Solvent extractions were performed directly in the XAD-2 glass columns. Final extracts are cleaned-up on Florisil cartridges without fractionation and contaminants analyzed by GC-MS. Method detection limits (MDLs) and recoveries for dissolved organic contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides are reported along with results of surface water analysis for the San Francisco Bay, CA.     

Application of surrogate methods for assessing the bioavailability of PAHs in sediments to a sediment ingesting bivalve

The usefulness of two surrogate methods for rapidly determining the bioavailability of PAHs in hydrocarbon-contaminated marine sediments was assessed. Comparisons are made between the PAHs accumulated by the benthic bivalve, Tellina deltoidalis, and the extractable-PAHs determined using a 6-h XAD-2 resin desorption method and a 4-h gut fluid mimic (GFM) extraction method. There were significant positive relationships between PAH bioaccumulation by the bivalves and sediment PAH concentrations. These relationships were not improved by normalising the sediment PAH concentrations to the organic carbon concentration. The average percentage lipid content of the bivalves was 1.47 ± 0.22% and BSAFs for total-PAHs ranged from 0.06 to 0.80 (kg OC/kg lipid). The XAD-2 and GFM methods both extracted varying amounts of PAHs from the sediments. Low concentrations of PAHs were extracted by the GFM method (0.2–3.6% of total-PAHs in sediments) and the GFM results were inadequate for generalising about the bioavailability of the PAHs in the sediments. The XAD-2 method extracted greater amounts of PAHs (3–34% of total-PAHs in sediments), however, the total-PAH concentrations in the sediments provided a better, or equally good, prediction of PAH bioaccumulation by T. deltoidalis. The results indicated that these methods required further development before they can be applied routinely as surrogate methods for assessing the bioavailability of PAHs in sediments. Future research should be directed towards lowering detection limits and obtaining comparative data for a greater range of sediment types, contaminant classes and concentrations, and organisms of different feeding guilds and with different gut chemistry.     

Sampling and analysis of particulate and gaseous polycyclic aromatic hydrocarbons from coal tar sources in the working environment

A sampling method for polycyclic aromatic hydrocarbons (PAH) in workplace atmospheres using a standard glass fiber filter with a back-up section of Amberlite XAD-2 is described. Filters and XAD are solvent-desorbed and, without further clean-up, the solutions are submitted to high performance liquid chromatographic analysis using fluorimetric detection. Recovery of PAH from XAD-2 was studied, and was found to be in the range 80–100%. The sampling method was evaluated in a coke plant, an aluminium plant and in a creosote impregnating plant. The method described is rapid and sensitive for the determination of the most important workplace PAH, and accounts for both particulate and gaseous PAH.     

Effects of ethylene glycol ethers on the reproduction of Ceriodaphnia dubia

Seven-day static renewal tests with Ceriodaphnia dubia were used to document the chronic toxicity of ethylene glycol ethers and acetates to this invertebrate. The 7-d EC10 (effective concentrations inducing an inhibition of 10% of the reproduction of the tested organisms) values ranged from 0.06 to 1025 mg/l. While a survey of the literature showed that the acute toxicity of these chemicals appeared negligible, our results clearly revealed the potential chronic effects of some of them to this organism occupying an important trophic level in the aquatic ecosystems. The usefulness of this kind of test to better estimate the adverse effects of glycol ethers was stressed.     

Validation studies of an automated preconcentration water sampler (APS) for chlorinated dibenzo-p-dioxins and dibenzofurans

An Automated Preconcentration Sampler (APS) was developed by the Ontario Ministry of the Environment (MOE) and Carleton University for the determination of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in drinking water. The APS employs a two-stage particulate filtration system followed by an XAD-2 resin column. Field and laboratory testing of the APS is required to validate the device before it is put into regular service.The capacity of the APS filtration system is 30 L for a 4 Formazin Turbidity Unit (FTU) input water turbidity and greater than 50 L for a typical treated water. Flushing of a clean XAD-2 resin column with 200 L of spiked water showed that the optimum flowrate in terms of spike breakthrough is equal to three times the resin bed volume per minute. This flowrate is used for APS operation. Testing also showed that no spike breakthrough occurred after 200 L of clean water was flushed through a spiked XAD-2 resin column at flowrates in excess of the APS operating flowrate. Spike testing was also carried out on the filters and results are pending. An analytical comparison between the present MOE sampling and analytical procedure and the proposed APS sampling and analytical procedure using a PCDD/PCDF source water is planned.