Dioxanes and dioxolanes in source waters: Occurrence, odor thresholds and behavior through upgraded conventional and advanced processes in a drinking water treatment plant.

Over the last years, the human probable carcinogen 1,4-dioxane and alkyl-1,3-dioxanes and dioxolanes have been detected and identified as the cause of several pollution episodes in the Llobregat River (Catalonia, NE Spain) and its aquifer. It is an issue of major concern to study these compounds which are released to the environment by resin manufacturing plants' spills and wastewater discharges spread along rivers and reach drinking water treatment plants (DWTPs) in order to protect the environment and public health. In this study four seasonal sampling campaigns were carried out over a year to determine the removal efficiency of the dioxanes and dioxolanes at each step of a DWTP including ozonation, granular activated carbon filters, ultrafiltration and reverse osmosis step's treatments. Additionally, a weekly sampling monitoring of 1,4-dioxane and alkyl-1,3-dioxanes and dioxolanes in raw water, groundwater and finished water was performed at a DWTP over more than two years. Aqueous odor concentration thresholds (OTCs) were established by the three-alternative forced choice method (3-AFC). Following a previous published methodology, samples were analyzed and results showed that the advanced treatment (Ultrafiltration followed by reverse osmosis) line removes more efficiently 1,4-dioxane, alkyl dioxanes and dioxolanes (80 ±â€¯6% for 1,4-dioxane, 97 ±â€¯7% for 5,5-DMD and 100 ±â€¯0% for 2,5,5-TMD) than the upgraded conventional treatment line (ozonation followed by granular activated carbon filters) (-12 ±â€¯50%, 25 ±â€¯62% and 50 ±â€¯51% respectively), where some desorption processes were eventually observed. From the monitoring study, results suggest that the presence of 1,4-dioxane is not only due to spills, but also from other sources of contamination. Whereas dioxolanes almost completely disappeared in time, 1,4-dioxane's concentrations remained low and fluctuant. A background concentration of 1,4-dioxane in surface waters (∼1 µg/L) has been determined with a relevant concentration up to 11.6 µg/L of 1,4-dioxane in groundwater. The perception values for some of the studied compounds were extremely low (few ng/L only), which confirms the relevancy of this group of compounds as malodorous agents in waters.

Simultaneous determination of the potential carcinogen 1,4-dioxane and malodorous alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes in environmental waters by solid-phase extraction and gas chromatography tandem mass spectrometry.

1,4-dioxane is a synthetic industrial solvent used in various industrial processes, and it is a probable human carcinogen whose presence in the aquatic environment is frequently reported. Alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes are compounds that have been identified as causing several odor episodes in waters over the last years, with the result of downtime of drinking water treatment plants. According to published studies, some of these episodes may be caused either by resins synthesis processes, or by industrial residues added to dehydrated sludge in wastewater treatment plants (WWTPs) in order to increase biogas production efficiency. Analytical methods based on closed loop stripping analysis (CLSA) are routinely used when taste and odor events appear, but this technique has demonstrated to be unsuitable to determine 1,4-dioxane at trace levels. In this context, drinking water companies tend to focus on determining odorous compounds, but not on those compounds that are potentially harmful. The suitability of a SPE method and further analysis by GC/MS-MS to simultaneously determine 1,4-dioxane and alkyl-1,3-dioxanes and dioxolanes has been demonstrated. Recoveries in surface waters spiked at 25ng/L ranged from 76% to 105%, whereas method quantification limits (MQLs) varied from 0.7 to 26ng/L for dioxanes, and dioxolanes and 50ng/L for 1,4-dioxane. Uncertainties were evaluated at two different concentrations, 0.02µg/L and 0.4µg/L, with values of 25% for 1,4-dioxane, and of 16-28% for alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes for the later. The methodology has been successfully applied to samples from the aquifer of the Llobregat River (NE. Spain).

Development and validation of a method for air-quality and nuisance odors monitoring of volatile organic compounds using multi-sorbent adsorption and gas chromatography/mass spectrometry thermal desorption system.

An analytical method based on thermal desorption (TD) coupled to gas chromatography (GC) and mass spectrometry detection (MS) has been developed and validated for the determination of a wide range of odor nuisance and air-quality volatile organic compounds (VOC) in air. New generation isocyanates, isocyanato- and isothiocyanatocyclohexane, have been included for the first time as target compounds due to their high occurrence in air samples. A dynamic air sampling method to trap gas and vapor on multi-sorbent tubes using portable pump equipment has been also developed. Sorbent tubes were filled with Carbotrap (70mg), Carbopack X (100mg) and Carboxen-569 (90mg). Validation of the TD-GC-MS method showed good selectivity, sensibility and precision according to Compendium Method TO-17 (US Environment Protection Agency) criteria. Limits of detection (signal-to-noise=3, ng in tube) ranges were 0.004-0.03ng (alcanes), 0.001-0.1ng (aromatics), 0.03-14ng (aldehydes), 0.003-7ng (alcohols), 0.003-0.04ng (chlorides), 0.02-0.5ng (esters), 0.002-0.1ng (ketones), 0.01-0.53ng (terpenes), 14-97ng (amides), 0.2-10ng (isocyanates) and 0.001ng (carbon disulfide). The linear dynamic range was over 3-5 orders of magnitude, depending of the VOC. TD-GC-MS analysis was reproducible, with relative standard deviation (n=5) within 20%. VOCs breakthrough examination showed no significant losses when about 2000ng standard was prepared. In order to evaluate the performance of the developed method on real samples, several industrial and urban air samples were analysed. VOCs were found to be stable on the sorbent tubes for at least 1 week when stored at 4 degrees C.

Static headspace gas chromatographic method for quantitative determination of residual solvents in pharmaceutical drug substances according to european pharmacopoeia requirements.

A static headspace (HS) gas chromatographic method for quantitative determination of residual solvents in a drug substance has been developed according to European Pharmacopoeia general procedure. A water-dimethylformamide mixture is proposed as sample solvent to obtain good sensitivity and recovery. The standard addition technique with internal standard quantitation was used for ethanol, tetrahydrofuran and toluene determination. Validation was performed within the requirements of ICH validation guidelines Q2A and Q2B. Selectivity was tested for 36 solvents, and system suitability requirements described in the European Pharmacopoeia were checked. Limits of detection and quantitation, precision, linearity, accuracy, intermediate precision and robustness were determined, and excellent results were obtained.

Factors governing the atmospheric deposition of polycyclic aromatic hydrocarbons to remote areas.

Polycyclic aromatic hydrocarbons (PAH) were measured in bulk atmospheric deposition collected in three remote areas of Europe during 1997-1998. Mean total PAH fluxes over a period of 18 months were 1560 +/- 750 and 1150 +/- 630 ng m(-2) mo(-1) in the Pyrenees and the Alps, respectively. In the Caledonian mountains (Scandinavia) the observed mean fluxes were 1900 +/- 940 ng m(-2) mo(-1) (6 month collection). Similar qualitative PAH compositions (p values <0.05) in the bulk atmospheric deposition have been observed between sites, which are dominated by the more volatile parent compounds. The main differences between lakes are related to the high molecular weight compounds. Atmospheric deposition of PAH to these remote sites appears to be independent of their concentrations in the atmosphere, which are similar between sites (in the range of 1.8-3.0 ng x m(-3)), being controlled mainly by particle deposition, followed by precipitation and air temperature. A multilevel regression model including these three variables accounted for 74% of the total variability in total PAH bulk deposition; however, the contribution of each variable in the model is compound and site-dependent. The deposition of high molecular weight PAH depends more on particle deposition and precipitation, whereas air temperature is the main factor controlling the deposition fluxes of the low molecular weight PAH.

Atmospherc deposition of organochlorine compounds to remote high mountain lakes of Europe.

Bulk deposition samples were taken near three mountain lakes located in the Pyrenees (Estany Redó), Alps (Gossenköllesee), and Caledonian Mountains (Ovre Neådalsvatn) for evaluation of the atmospheric deposition load of organochlorine compounds (OC), namely, polychlorobiphenyls (PCBs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), and endosulfans, in the remote European high mountain areas. The compounds of present use in agriculture, namely, endosulfans and gamma-HCH, exhibit large differences in mean deposition fluxes between the three sites. They occur in large amounts in Estany Redó (340 and 430 ng m(-2) month(-1) for endosulfans and gamma-HCH, respectively), reflecting the impact of agricultural activities in southern Europe. This lake showed also the highest proportion of the more labile endosulfan isomers (alpha and beta = 82%) whereas only the most recalcitrant species, endosulfan sulfate, was found in Ovre Neådalsvatn. In contrast, the OC whose use is now banned exhibit a more uniform geographic distribution with deposition fluxes of 31-40, 30-100, and 1.4-15 ng m(-2) month(-1) for alpha-HCH, PCBs, and HCB. Both compounds of present and past use exhibit a clear seasonal pattern, with higher deposition in the warm periods, which is consistent with enhanced volatilization at higher temperatures. In the case of the agricultural pesticides it may also reflect higher use during application periods. The OC distributions in the atmospheric deposition of the three sites are rather uniform and highly enriched in compounds with volatilities larger than 0.0032 Pa. However, more than 90% of these compounds are not retained in the lake waters or sediments. Comparison of OC composition in atmospheric and sedimentary deposition evidences a selective trapping of the less volatile compounds. Trapping efficiencies increase at decreasing air temperatures of the lacustrine systems.