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 use of XAD-resins for the detection of mutagenic activity in water: II. Studies with drinking water

The combined XAD-4/8-Ames test procedure for concentrating and detecting trace amounts of organic mutagens, as already described for surface water, is shown to be suitable for drinking water as well. DMSO is as effective as acetone in eluting the adsorbed mutagens, and optimal recovery of overall mutagenic activity is observed at a flow rate of 2–4 bed volumes/min. The drinking water of 6 cities in The Netherlands, which prepare their drinking water from the rivers Rhine and Meuse, has been tested for mutagenic activity. Mutagenic activity could be demonstrated in 4 cities. Dose-related responses are observed with concentrates of as little as 500 ml of drinking water and the 4 cities clearly differ with regard to the type of mutations induced (TA 98 or TA 100) and the effect of metabolic activation. The absence of mutagenic activity in drinking water of 2 cities indicates that by a proper combination of treatment processes the organics which are responsible for the detected mutagenic activity in drinking water can be removed to a high degree.     

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.     

Chemical and biological characterization of emissions from a cereal straw burning furnace

Emissions from a cereal straw through-burning furnace have been characterized by chemical analysis and the Ames $\text{Salmonella/microsome}$ assay. The emissions of polycyclic aromatic hydrocarbons (PAH) were considerable, from 24 to 64 mg per kilo dry fuel. Most of the mutagenic activity was found in the extracts of the particles, while the condensate fractions and the XAD-2 extracts showed much lower mutagenic responses.     

Determination of mutagenic potential and organic contaminants of Great Lakes drinking water

Extracts of organic compounds were obtained, using XAD-2 macroreticular resin, from drinking water supplies in 12 Great Lakes municipalities. The extracts were tested for mutagenic potential using the Salmonella/mammalian-microsome assay and analysed for organochlorine pesticides, polyaromatic hydrocarbons, organophosphorous pesticides and trialkyl-arylphosphates. Grab samples of drinking water were also analysed for volatile organic compounds. Dose-related increases in mutagenicity were found in extracts from 11 of the drinking water supplies.     

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.     

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.     

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.     

Investigating the sources of the mutagenic activity found in a river using the Salmonella assay and different water extraction procedures

In the routine São Paulo state (Brazil) surface water quality-monitoring program, which includes the Salmonella microsome mutagenicity assay as one of its parameters, a river where water is taken and treated for drinking water purposes has repeatedly shown mutagenic activity. A textile dyeing facility employing azo-type dyes was the only identifiable source of mutagenic compounds. We extracted the river and drinking water samples with XAD4 at neutral and acidic pH and with blue rayon, which selectively adsorbs polycyclic compounds. We tested the industrial effluent, raw, and treated water and sediment samples with YG1041 and YG1042 and compared the results with the TA98 and TA100 strains. The elevated mutagenicity detected with YG-strains suggested that nitroaromatics and/or aromatic amines were causing the mutagenicity detected in the samples analyzed. Positive responses for the blue rayon extracts indicated that mutagenic polycyclic compounds were present in the water samples analyzed. The mutagen or mixture of mutagens present in the effluent and water samples cause mainly frameshift mutations and are positive with and without metabolic activation. The Salmonella assay combined with different extraction procedures proved to be very useful in the identification of the origin of the pollution and in the identification of the classes of chemical compounds causing the mutagenic activity in the river analyzed.     

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.     

Adsorption of phenolic compounds from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent

A water-compatible hypercrosslinked polymeric adsorbent (NJ-8) for adsorbing and removing phenolic compounds from their aqueous solutions was prepared. This product can be used directly without a wetting process. Its adsorption property toward four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol was tested using the commercial Amberlite XAD-4 as a reference. The capacities of equilibrium adsorption for all four phenolic compounds on the NJ-8 from their aqueous solutions are around two times as high as that of Amberlite XAD4 within the temperature range 283-323 K, which may contribute to their micropore structure and the partial polarity on the network. Freundlich isotherm equations, as well as relative adsorption capacities and isosteric adsorption enthalpies for the four phenolic compounds, indicate that the adsorption of phenolic compounds on the NJ-8 resin is a physical adsorption process. Mini-column adsorption studies for phenol on Amberlite XAD4 and NJ-8 resins show that the breakthrough adsorption capacities are 0.54 and 0.99 mmol/ml, and the total capacities are 0.62 and 1.37 mmol/ml, while no extra acetone was needed to remove the adsorbed phenol from NJ-8 as from Amberlite XAD4.     

Aerosol Filtration by Sorbent Beds

Fixed beds of sorbent media are used for the evaluation of poiynuclear aromatic hydrocarbons (PAH) present in air. Twostage sampling and separate extraction and analyses of PAH associated with aerosol particles and those present in the vapor state are usually performed. The ability of commonly used sorbents to retain particulate matter introduces a potential for reducing the time and cost of PAH evaluation procedures.

The filtration efficiency of three sorbent media, Florisil, XAD-2, and polyurethanefoam (PUF), for particles in 0.1 to 1 µm size range was studied using airflow rates from 4 to 2501 /mm through a PS 1 sorbent cartridge. Theoretical considerations were used to identify the principal filtration mechanisms and to assess the predictability of the aerosol filtration performance of sorbent filters. The results of this study indicate XAD-2 to be an efficient filtration medium owing to the electrostatic enhancement of capturing and retaining aerosol particles.

As a result of theoretical considerations, Brownian diffusion and inertial deposition were found to be major filtration mechanisms accompanied by electrostatic effects. While the efficiency of the diffusional deposition mechanism was reasonably well predicted with available theories, modeling of submicron particle impaction at higher fluid velocities appeared to be inadequate. Further developments are suggested to improve our understanding of filtration phenomena in sorbent beds under high flow rate conditions.     

The mutagenic potentials of tap water samples in Shanghai

The tap water samples were collected from the users' ends in several areas of Shanghai, which is located in Taihu Lake basin, Eastern China. Source water samples were also collected from two municipal source water facilities at the same time. Samples were assayed by three different short-term mutagenicity test systems: Salmonella/microsome assay (Ames test), the Arabinose resistance test (Ara test) and the SOS/umu test. The data showed that two source water samples did not display direct mutagenic potentials. Two tap water samples from city north, which were directly from Yangtze River, were also not mutagenic. Water samples from city south and middle which used source water originating from Taihu Lake were proved to be contaminated with mutagenic potentials by three different assay techniques. The boiled water displayed an even stronger mutagenic potential compared to its original tap water. The molecular mechanism of mutagenicity was associated with a reading frame-shifting potential. GC-MS analysis of tap water extracts from city middle and corresponding source water was compared. Qualitatively similar spectra were observed except for the peaks of three chlorinated aromatic hydrocarbon compounds, which existed only in the tap water. Since the water source has been polluted, raw water was heavily chlorinated in order to sterilize. More toxic compounds, including mutagens, might form during the multi-chlorination. Caution about the possibility of elevated cancer risks in the population that consumes heavily chlorinated water should be kept in mind. A cohort study in the residents of Shanghai is required.     

Complexation of arsenate with humic substance in water extract of compost

The interactions of environmental toxicants with organic substances affect the speciation and dynamics, and subsequent toxicity, mobility, and fate of toxicants in the environment. For the purpose of understanding the complexation of As(V) with humic substances, arsenate-containing solutions with As concentrations from 1 to 8 mg l⁻¹ were prepared to react with the water extract of compost (WEC). All the reaction systems including the control were incubated for 48 h at 25 °C. The complexation of As(V) with humic substance was examined by dialysis and ion exchange techniques. From 30% to 51% of added As(V) reacted with organic substance in WEC to form an As–metal–organic complex. This was verified as a hydrophobic organic fraction after separation of As–metal–organic complex fraction from the hydrophilic fraction by XAD-8 resin. The complex substance was also identified as a humic substance by the method of proton binding formation function determination. This suggests that cations, such as Ca and Mg, and especially Fe, Al, and Mn act in cation bridging in the complexation of As(V) with humic substance. The role of metals in the complexation of As(V) with humic substance in terrestrial and especially aquatic environments thus merits close attention.     

Influence of chlorination pH and chlorine dose on the formation of mutagenic activity and the strong bacterial mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-5(2H)-furanone (MX) in water

Samples from two Dutch raw water sources were chlorinated in the laboratory at different pH:s and chlorine doses, and were analysed for mutagenic activity and the mutagenic compound 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX). Chlorination produced mutagenic activity as well as MX in both waters. The formation of MX was favoured by acidic reaction conditions and high chlorine doses, but in waters treated with excess chlorine at pH 9, no MX was detected. The mutagenicity was approximately on the same level after chlorination of both water types but the MX concentration was significantly higher in the water containing mainly humic material.

MX was found to be quantitatively extracted from acidified waters by the XAD resin adsorption technique.     

Mutagenicity and organic halogen determination in body fluids and tissues of rats treated with drinking water and pulp mill bleachery effluent concentrates

Concentrates of either drinking water or chlorination stage pulp mill effluent were injected intraperitonally into rats. Urine, feces, liver, and adipose tissues were tested for mutagenic activity and analysed for organic halogen. For both sample types nearly all the organic halogen taken up, eighteen percent from the chlorination stage sample and four percent from the drinking water sample, was excreted via the urine during the first day. Weak mutagenic activity could only be found in the urine collected the first day from animals treated with the highest dose of drinking water.     

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.     

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.     

大孔树脂吸附去除水中的2,4,6-三硝基甲苯

研究了2种大孔树脂XAD-4和NDA-804对水中的TNT的吸附行为。2种树脂对TNT的吸附等温线表明,温度的升高有利于吸附,在35℃条件下XAD-4树脂与NDA-804树脂对TNT的最高平衡吸附量分别达82.86 mg/g和94.26mg/g。采用Langmuir方程和Freundlich方程用于吸附等温线的解释,结果表明,吸附等温线更加符合Langmuir模型,相关系数均大于0.99。TNT在2种树脂上的吸附符合准二级动力学方程,TNT初始浓度越低,达到吸附平衡所需时间越短,在1 h内可达到吸附平衡。采用NDA-804处理对TNT废水,废水中TNT浓度由103.58 mg/L降至0.4 mg/L,去除率达99.6%,吸附后的树脂采用pH=2的乙醇和盐酸的混合液脱附可再生,高浓度再生溶液经蒸馏可回收TNT,实现了废水治理与资源化。     

Polycyclic organic material (POM) in urban air. Fractionation,chemical analysis and genotoxicity of particulate and vapour phases in an industrial town in Finland

Polycyclic organic material (POM) was collected by high-volume sampling on filter and on XAD-2 resin from the air of a small industrial town in Finland. Concurrent chemical analysis and the assays for genotoxic activity were performed on the particulate and the vapour phases of ambient air POM and their chemical fractions. Furthermore, correlations between seasonal meteorological parameters and POM concentrations were studied to reveal characteristic POM profiles for various emission sources. The range of total POM concentrations varied from 115 to 380 ng m⁻³ in late spring and from 17 to 83 ng m⁻³ in early winter. No direct correlation of ambient POM was seen with the temperature, but rather with the wind direction from various emission sources. Especially the low molecular weight compounds were associated with wind direction from industrial sources. Genotoxic activity, as detected by the Ames Salmonella/microsome test and the SCE assay in CHO cells, was found not only in the paniculate phase samples but also in the vapour phase. The polar fractions of some of the samples showed genotoxic activity, and also direct mutagenicity was observed with both the assay systems; these facts support the significance of compounds other than conventional polycyclic aromatic hydrocarbons (PAH) in the samples.