Estimating 42 pesticide sampling rates by POCIS and POCIS-MIP samplers for groundwater monitoring: a pilot-scale calibration.

Pesticides occur in groundwater as a result of agricultural activity. Their monitoring under the Water Framework Directive is based on only a few spot-sampling measurements per year despite their temporal variability. Passive sampling, which was successfully tested in surface water to provide a more representative assessment of contamination, could be applied to groundwater for a better definition of its contamination. However, few reliable calibration data under low water flow are available. The objective of our study thus consisted in determining sampling rates by two types of passive samplers, a POCIS (polar organic chemical integrative sampler) for polar pesticides, and a POCIS-MIP sampler based on a receiving phase of molecular imprinted polymers, specific for AMPA and glyphosate under low flow conditions as exist in groundwater. To our knowledge, this is the first time that sampling rates (sampling rate represents the volume of water from which the analyte is quantitatively extracted by the sampler per unit time) are estimated for groundwater applications. Our calibrations took place in an experimental pilot filled with groundwater and with low water flow (a few metres per day). Pesticide uptake in POCIS showed good linearity, with up to 28 days before reaching equilibrium. Two types of accumulation in POCIS were noted (a linear pattern up to 28 days, and after a time lag of 7 to 14 days). Sampling rates for 38 compounds were calculated and compared with those available in the literature or obtained previously under laboratory conditions. The values obtained were lower by a factor 1 to 14 than those estimated under stirring conditions in the literature, whereas water flow velocity (m s-1) differed by a factor of 2000 to 10,000.

Reduction of endocrine disruptor emissions in the environment: the benefit of wastewater treatment.

The occurrence and fate of four estrogens and five alkylphenolic compounds were studied in thirteen plants with various treatment processes, sizes and countries. Complete load mass balance, including water and sludge phases, has shown a high reduction of the total load of hormones, around 90%. The removal of alkylphenols was more variable, due to the degradation of nonylphenol (NP) precursors - alkylphenol polyethoxylates (APnEO) - during the treatment, resulting in significant production of shorter and toxic alkylphenols (NP and short polyethoxylates) that concentrate in the sludges. Under anaerobic conditions, such as anaerobic digestion process, the load of NP was in most cases observed to increase. When considering the environmental impact, the high reduction of endocrine disrupting compounds (EDC) concentrations between raw wastewater and effluent enables to satisfy the requirements of the Water Framework Directive for NP except in very critical situations where the dilution factor of the effluent in the river would be lower than 7. For sludges, the pending European Directive on spreading of sludge on land would be complied with in all cases.

Nanoparticle stability in lake water shaped by natural organic matter properties and presence of particulate matter.

Predicting nanoparticle (NP) fate in the environment continues to remain a challenge, especially for natural surface water systems, where NPs can hetero-aggregate with natural organic and mineral suspended matter. Here we present the interactions and aggregation behavior of TiO2 NPs with natural organic matter (NOM) in a natural lake water. NP fate in a synthetic water of the same pH and ionic composition was also tested in the presence and absence of NOM analogs to gain insight into the different stabilizing effects of each NOM type. Several complementary analytical techniques were utilized to assess lake NOM composition, including pyrolysis-gas chromatography-mass spectrometry, gel permeation chromatography, the polarity rapid-assessment method, and Nanoparticle Tracking Analysis. In the natural lake water, the TiO2 NPs preferentially interacted with mostly anionic NOM of high and medium molecular weight (~1200-1450 and 400-520 Da). Specifically, strong interactions with proteins and polyhydroxy aromatics were observed. NP fate and stability were determined in both raw lake water containing mineral particulate matter and total NOM (NOMtot) and filtered lake water containing only NOM <0.8 µm (NOM<0.8), with different aggregation profiles observed over time. Additionally, three times the number of TiO2 NPs remained in suspension when only NOM<0.8 was present compared to the unfiltered water containing mineral particulate matter and NOMtot. These results demonstrate the contrasting NP fates in the aquatic environment according to the presence of NOMtot vs. NOM<0.8 and further suggest that the use of pure NOM analogs may not accurately represent NP interactions and fate in the natural system.

Use of comprehensive two-dimensional gas chromatography for the broad screening of hazardous contaminants in urban wastewaters.

The list of priority chemicals included in various regulations such as the European Water Framework Directive, as well as the list of hazardous contaminants identified in the aquatic environment, are increasing at an accelerated pace. Therefore, there is a need for broad spectrum methods capable of simultaneously determining hundreds, if not thousands, of contaminants. For the analysis of non-polar or semi-polar contaminants, comprehensive two-dimensional gas chromatography (GC x GC) is more powerful than conventional gas chromatography thanks to a separation on two different stationary phases. This paper reports the use of GC x GC for a broad screening of hazardous contaminants in an urban wastewater plant. Comparison between the raw and treated wastewater has been carried out using a semi-quantitative approach. A variety of drugs, personal care products, pesticides, carcinogens and compounds toxic for reproduction, were identified. Most of these compounds were removed or decreased by this wastewater treatment plant. Preliminary results from this single plant will need to be confirmed by a more extensive study before drawing conclusions on the removal efficiency of 2D-GC amenable compounds.

Analysis of endocrine activity in drinking water, surface water and treated wastewater from six countries.

The aquatic environment can contain numerous micropollutants and there are concerns about endocrine activity in environmental waters and the potential impacts on human and ecosystem health. In this study a complementary chemical analysis and in vitro bioassay approach was applied to evaluate endocrine activity in treated wastewater, surface water and drinking water samples from six countries (Germany, Australia, France, South Africa, the Netherlands and Spain). The bioassay test battery included assays indicative of seven endocrine pathways, while 58 different chemicals, including pesticides, pharmaceuticals and industrial compounds, were analysed by targeted chemical analysis. Endocrine activity was below the limit of quantification for most water samples, with only two of six treated wastewater samples and two of six surface water samples exhibiting estrogenic, glucocorticoid, progestagenic and/or anti-mineralocorticoid activity above the limit of quantification. Based on available effect-based trigger values (EBT) for estrogenic and glucocorticoid activity, some of the wastewater and surface water samples were found to exceed the EBT, suggesting these environmental waters may pose a potential risk to ecosystem health. In contrast, the lack of bioassay activity and low detected chemical concentrations in the drinking water samples do not suggest a risk to human endocrine health, with all samples below the relevant EBTs.

Simultaneous determination of "earthy-musty" odorous haloanisoles and their corresponding halophenols in water samples using solid-phase microextraction coupled to gas chromatography with electron-capture detection.

Certain haloanisoles present at trace levels cause a large part of earthy-musty off-flavor problems in drinking water. These potent odorous chemicals come mainly through biomethylation of their corresponding halopenols. To enable the investigation of both families of compounds, a method involving solid-phase microextraction (SPME) was developed and the main parameters governing SPME were optimized. This method allows the simultaneous quantification of haloanisoles and halophenols at levels ranging from 1 to 100 or 250 ng/l, with detection limits of about 0.5 ng/l and could be applied to potable as well as raw surface waters.

Multiresidue determination of pesticides in drinking and related waters by solid-phase extraction and liquid chromatography with ultraviolet detection: interlaboratory study.

As part of a project funded by the European Commission (EC) for the development and evaluation of multiresidue methods for analysis of drinking and related waters, 17 European laboratories evaluated a method using styrene-divinylbenzene copolymer solid-phase extraction followed by liquid chromatography with diode array detection. The main aim of the study was to evaluate whether the method meets the requirements of EC Drinking Water Directive 98/83 in terms of accuracy, precision, and detection limit for 21 pesticides according to the following requirements: limit of detection, < or =0.025 microg/L; accuracy expressed as recovery, between 75 and 125%; and precision expressed as repeatability relative standard deviation of the method, <12.5%, and as reproducibility relative standard deviation of the method, <25%. Analyses for unknown concentrations were performed with commercial bottled and tap waters. All laboratories were able to achieve detection limits of 0.01 microg/L for all pesticides except pirimicarb (0.02 microg/L). The criteria for repeatability were met for all compounds. Terbutryn in bottled water and carbendazim in tap water did not meet the criteria for reproducibility. In terms of accuracy, the method met the requirements for all pesticides in both matrixes, except for metamitron. However, several compounds (linuron, terbutryn, propazine, metobromuron, and isoproturon) showed recoveries slightly below 75%.

Convex hull: a new method to determine the separation space used and to optimize operating conditions for comprehensive two-dimensional gas chromatography.

It is important to develop methods of optimizing the selection of column sets and operating conditions for comprehensive two-dimensional gas chromatography. A new method for the calculation of the percentage of separation space used was developed using Delaunay's triangulation algorithms (convex hull). This approach was compared with an existing method and showed better precision and accuracy. It was successfully applied to the selection of the most convenient column set and the geometrical parameters of second column for the analysis of 49 target compounds in wastewater.