Sarit Kaserzon

Development and calibration of a passive sampler for perfluorinated alkyl carboxylates and sulfonates in water.

Perfluorinated chemicals (PFCs) are emerging environmental contaminants with a global distribution. Due to their moderate water solubility, the majority of the environmental burden is assumed to be in the water phase. This work describes the application of the first passive sampler for the quantitative assessment of concentrations of perfluorinated alkylcarboxylates (PFCAs) and sulfonates (PFSAs) in water. The sampler is based on a modified Polar Organic Chemical Integrative Sampler (POCIS) with a weak anion exchange sorbent as a receiving phase. Sampling rates were between 0.16 and 0.37 L d(-1), and the duration of the kinetic sampling stage was between 2.2 and 13 d. A field deployment in the most urbanized estuary in Australia (Sydney Harbour) showed trace level concentrations from passive samplers (0.1-12 ng L(-1)), in good agreement with parallel grab sampling (0.2-16 ng L(-1)). A separate field comparison of the modified POCIS with standard POCIS suggests the latter may have application for PFC sampling, but with a more limited range of analytes than the modified POCIS which contains a sorbent with a mixed mode of action.

Detection of s-triazine pesticides in natural waters by modified large-volume direct injection HPLC

There is a need for simple and inexpensive methods to quantify potentially harmful persistent pesticides often found in our water-ways and water distribution systems. This paper presents a simple, relatively inexpensive method for the detection of a group of commonly used pesticides (atrazine, simazine and hexazinone) in natural waters using large-volume direct injection high performance liquid chromatography (HPLC) utilizing a monolithic column and a single wavelength ultraviolet-visible light (UV-vis) detector. The best results for this system were obtained with a mobile phase made up of acetonitrile and water in a 30:70 ratio, a flow rate of 2.0 mL min(-1), and a detector wavelength of 230 nm. Using this method, we achieved retention times of less than three minutes, and detection limits of 5.7 microg L(-1) for atrazine, 4.7 microg L(-1) for simazine and 4.0 microg L(-1) for hexazinone. The performance of this method was validated with an inter-laboratory trial against a National Association of Testing Authorities (NATA) accredited liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) method commonly used in commercial laboratories.

Monitoring Herbicide Concentrations and Loads during a Flood Event: A Comparison of Grab Sampling with Passive Sampling

The suitability of passive samplers (Chemcatcher) as an alternative to grab sampling in estimating time-weighted average (TWA) concentrations and total loads of herbicides was assessed. Grab sampling complemented deployments of passive samplers in a tropical waterway in Queensland, Australia, before, during and after a flood event. Good agreement was observed between the two sampling modes in estimating TWA concentrations that was independent of herbicide concentrations ranging over 2 orders of magnitude. In a flood-specific deployment, passive sampler TWA concentrations underestimated mean grab sampler (n = 258) derived concentrations of atrazine, diuron, ametryn, and metolachlor by an average factor of 1.29. No clear trends were evident in the ratios of load estimates from passive samplers relative to grab samples that ranged between 0.3 and 1.8 for these analytes because of the limitations of using TWA concentrations to derive flow-weighted loads. Stratification of deployments by flow however generally resulted in noticeable improvements in passive sampler load estimates. By considering the magnitude of the uncertainty (interquartile range and the root-mean-squared error) of load estimates a modeling exercise showed that passive samplers were a viable alternative to grab sampling since between 3 and 17 grab samples were needed before grab sampling results had less uncertainty.

Occurrence and distribution of brominated flame retardants and perfluoroalkyl substances in Australian landfill leachate and biosolids

The levels of perfluroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDDs) were studied in Australian landfill leachate and biosolids. Leachate was collected from 13 landfill sites and biosolids were collected from 16 wastewater treatment plants (WWTPs), across Australia. Perfluorohexanoate (PFHxA) (12-5700ng/L) was the most abundant investigated persistent, bioaccumulative and toxic (PBT) chemical in leachate. With one exception, mean concentrations of PFASs were higher in leachate of operating landfills compared to closed landfills. Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane isomers (HBCDDs) were detected typically at operating landfills in comparatively lower concentrations than the PFASs. Decabromodiphenyl ether (BDE-209) (<0.4-2300ng/g) and perfluoroctanesulfonate (PFOS) (<LOD-380ng/g) were the predominant PBTs detected in biosolids. Using data provided by sites, the volume of leachate discharged to WWTPs for treatment was small (<1% total inflow), and masses of PBTs transferred reached a maximum of 16g/yr (PFHxA). A national estimate of masses of PBTs accumulated in Australian biosolids reached 167kg/yr (BDE-209), a per capita contribution of 7.2±7.2mg/yr. Nationally, approximately 59% of biosolids are repurposed and applied to agricultural land. To our knowledge this study presents the first published data of PFASs and HBCDDs in Australian leachate and biosolids.

Aquatic Global Passive Sampling (AQUA-GAPS) Revisited: First Steps toward a Network of Networks for Monitoring Organic Contaminants in the Aquatic Environment

Organic contaminants, in particular persistent organic pollutants (POPs), adversely affect water quality and aquatic food webs across the globe. As of now, there is no globally consistent information available on concentrations of dissolved POPs in water bodies. The advance of passive sampling techniques has made it possible to establish a global monitoring program for these compounds in the waters of the world, which we call the Aquatic Global Passive Sampling (AQUA-GAPS) network. A recent expert meeting discussed the background, motivations, and strategic approaches of AQUA-GAPS, and its implementation as a network of networks for monitoring organic contaminants (e.g., POPs and others contaminants of concern). Initially, AQUA-GAPS will demonstrate its operating principle via two proof-of-concept studies focused on the detection of legacy and emerging POPs in freshwater and coastal marine sites using both polyethylene and silicone passive samplers. AQUA-GAPS is set up as a decentralized network, which is open to other participants from around the world to participate in deployments and to initiate new studies. In particular, participants are sought to initiate deployments and studies investigating the presence of legacy and emerging POPs in Africa, Central, and South America.

Passive sampling of perfluorinated chemicals in water: In-situ calibration

Perfluorinated chemicals (PFCs) have been recognised as environmental pollutants that require monitoring. A modified polar organic chemical integrative sampler (POCIS) is able to quantify aqueous PFCs. However, with varying external water velocity, PFC sampling rates (Rs) may change, affecting accuracy of derived water concentrations. To facilitate field deployment of this sampler, two methods of in-situ calibration were investigated: performance reference compounds (PRCs) and passive flow monitors (PFMs). Increased Rss (by factors of 1.2-1.9) with PFM loss rate (g d(-1)) were observed for some PFCs. Results indicate PFMs can be used to correct PFC specific Rss for more reliable estimates of environmental concentrations with a precision of about 0.01 L d(-1). Empirical models presented provide an improved means for aquatic monitoring of PFCs. The PRC approach was unsuccessful, confirming concern as to its applicability with such samplers.

Dealing with Flow Effects on the Uptake of Polar Compounds by Passive Samplers

HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés. Dealing with Flow Effects on the Uptake of Polar Compounds by Passive Samplers Vincent Fauvelle, Sarit Kaserzon, Natalia Montero, Sophie Lissalde, Ian Allan, Graham Mills, Nicolas Mazzella, Jochen Mueller, Kees Booij

Development and calibration of a passive sampler for N-nitrosodimethylamine (NDMA) in water

N-Nitrosamines such as N-nitrosodimethylamine (NDMA) are organic compounds of environmental concern in groundwater, wastewater and potable water due to their potent carcinogenicity in laboratory animal studies and probable human carcinogenicity. While passive sampling techniques have become a widely used tool for providing time-averaged estimates of trace pollutant concentration, for chemicals such as NDMA that have relatively high water solubility, the selection of a suitable sorbent is difficult. This work is a proof of principle study that investigated for the first time the use of coconut charcoal as a passive sampler sorbent. Apparent charcoal/water sorption coefficients for NDMA were >551 mL g(-1) at environmentally relevant aqueous concentrations of less than 1 μg L(-1). Under the experimental conditions employed, a sampling rate of 0.45 L d(-1) was determined and for an aqueous concentration of 1000 ng L(-1), it is predicted that the sampler remains in the linear uptake stage for approximately 4d, while equilibrium attainment would require about 26 d. The presence of humic acid, used as a surrogate for DOC, enhanced NDMA sorption on the coconut charcoal.

NORMAN interlaboratory study (ILS) on passive sampling of emerging pollutants

Passive samplers can play a valuable role in monitoring water quality within a legislative framework such as the European Union’s Water Framework Directive (WFD). The time-integrated data from these devices can be used to complement chemical monitoring of priority and emerging contaminants which are difficult to analyse by spot or bottle sampling methods, and to improve risk assessment of chemical pollution. In order to increase the acceptance of passive sampling technology amongst end users and to gain further information about the robustness of the calibration and analytical steps, several inter-laboratory field studies have recently been performed in Europe. An inter-laboratory study on the use of passive samplers for the monitoring of emerging pollutants was organised in 2011 by the NORMAN association together with the European DG Joint Research Centre to support the Common Implementation Strategy of the WFD. Thirty academic, commercial and regulatory laboratories participated in the passive sampler comparison exercise and each was allowed to select their own sampler design. All the different devices were exposed at a single sampling site to treated waste water from a large municipal treatment plant. In addition, the organisers deployed in parallel for each target analyte class multiple samplers of a single type which were subsequently distributed to the participants for analysis. This allowed an evaluation of the contribution of the different analytical laboratory procedures to the data variability. The results obtained allow an evaluation of the potential of different passive sampling methods for monitoring selected emerging organic contaminants (pharmaceuticals, polar pesticides, steroid hormones, fluorinated surfactants, triclosan, bisphenol A and brominated flame retardants). The results will be used to inform EU Member States about the potential application of passive sampling methods for monitoring organic chemicals within the framework of the WFD.

Assessment of drugs and personal care products biomarkers in the influent and effluent of two wastewater treatment plants in Ho Chi Minh City, Vietnam

Wastewater samples were collected at the influent and effluent of two wastewater treatment plants (WWTPs) in Ho Chi Minh City, Vietnam and then pooled to daily samples over multiple days using 6 hourly grab samples. The aim was to provide a first assessment of the occurrence, consumption, removal and release of a range of organic chemicals including pharmaceuticals and personal care products (PPCPs), illicit drugs, an artificial sweetener, tobacco and its metabolites and alcohol biomarkers (referred to here as DPCPBs). Nineteen DPCPBs were detected via direct measurement of filtered wastewater on LC-MS/MS with a concentration range of 0.05-38μg/L. Caffeine and paracetamol were the most prominent compounds detected in the influent, while acesulfame was found at the highest concentration in the effluent of both WWTPs. Mean concentrations of metabolites of tobacco (nicotine: 7.6μg/L, cotinine: 1.4μg/L and hydroxycotinine: 1.7μg/L) and alcohol (ethyl sulphate: 3.3μg/L) were lower than those of European countries. Consumption rates based on daily mass loads and catchment population data obtained from the WWTPs were <10g/d/1000 pp for the majority of selected PPCPs, except for caffeine (300g/d/1000 pp) and paracetamol (320g/d/1000 pp). Consumption rates for codeine and methamphetamine were 0.05g/d/1000 pp and 0.17g/d/1000 pp, respectively. Consistently across the two WWTPs most of the chemicals (10) showed >80% apparent removal rate from the wastewater, three chemicals showed apparent removal efficiency of approximately 50%; and the removal efficiency could not be assessed for 5 compounds due to their low concentrations in the influent. Based on the fraction of treated and untreated wastewater (10:90) that is released into the receiving environment we estimated a total discharge of approximately 170kg per day of DPCPBs in Ho Chi Minh City.