Wastewater and seawater monitoring in Antarctica: Passive sampling as a powerful strategy to evaluate emerging pollution.

The Ross Sea, among the least human-impacted marine environments worldwide, recently became the first marine protected area in Antarctica. To assess the impact of the Italian research station Mario Zucchelli (MZS) on the surrounding waters, passive sampling - as well as spot sampling for comparison - took place in the effluent of the wastewater treatment plant (WWTP) and the receiving surface marine waters. Polar Organic Chemical Integrative Samplers (POCIS) were deployed for six consecutive 2-week periods from November to February in a reservoir collecting the wastewater effluent. Passive samplers were also deployed at shallow depth offshore from the wastewater effluent outlet from MZS for two separate 3-week periods (November 2021 and January 2022). Grab water samples were collected alongside each POCIS deployment, for comparison with passive sampling results. POCIS, used for the first time in Antarctica, demonstrated to be advantageous to estimate time-averaged concentrations in waters and the results were comparable to those obtained by repeated spot samplings. Among the 23 studied ECs - including drugs, UV-filters, perfluorinated substances, caffeine - 15 were detected in both grab and passive sampling in the WWTP effluent and followed similar concentration profiles in both types of sampling. High concentrations of caffeine, naproxen and ketoprofen in the dozens of µg L-1 were detected. Other compounds, including drugs and several UV filters, were detected down to sub- µg L-1 concentrations. In marine waters close to the effluent output, only traces of a drug (4.8 ng L-1) and two UV filters (up to 0.04 µg L-1) were quantified.

A Review on Polyethersulfone Membranes in Polar Organic Chemical Integrative Samplers: Preparation, Characterization and Innovation.

The membranes in polar organic chemical integrative samplers (POCIS) enclose the receiving sorbent and protect it from coming into direct contact with the environmental matrix. They have a crucial role in extending the kinetic regime of contaminant uptake, by slowing down their diffusion between the water phase and the receiving phase. The drive to improve passive sampling requires membranes with better design and enhanced performances. In this review, the preparation of standard polyethersulfone (PES) membranes for POCIS is presented, as well as methods to evaluate their composition, morphology, structure, and performance. Generally, only supplier-related morphological and structural data are provided, such as membrane type, thickness, surface area, and pore diameter. The issues related to the use of PES membranes in POCIS applications are exposed. Finally, alternative membranes to PES in POCIS are also discussed, although no better membrane has yet been developed. This review highlights the urge for more membrane characterization details and a better comprehension of the mechanisms which underlay their behavior and performance, to improve membrane selection and optimize passive sampler development.

An optimized processing method for polar organic chemical integrative samplers deployed in seawater: Toward a maximization of the analysis accuracy for trace emerging contaminants.

Passive sampling of emerging contaminants (ECs) in seawater represents a challenge in environmental monitoring. A specific protocol for Polar Organic Chemical Integrative Sampler (POCIS) processing may be necessary when dealing with marine applications, due to the peculiarity of the considered matrix. Herein, both the instrumental LC-MS/MS analysis and the sampler processing for the determination of 22 ECs in seawater were carefully optimized. The study entailed a test simulating POCIS sorbent exposure to seawater as well as the processing of replicated field POCIS with different elution solvents. The final method involved washing the sorbent with water, to eliminate most salts, and a two-step elution, by using methanol and a small volume of a dichloromethane-isopropanol mixture. With this protocol, recoveries between 58 and 137% (average 106%) were obtained for most analytes, including non-steroidal anti-inflammatory drugs, UV-filters, perfluorinated substances and caffeine. Still, the protocol was not suitable for very hydrophilic compounds (recovery under 20% for artificial sweeteners and the pharmaceutical salbutamol), which also showed remarkable ion suppression (matrix effects in the range 4-46%). For all other chemicals, the matrix effects were in the range 67-103% (average 86%), indicating satisfactory accuracy. Also, the overall method showed high sensitivity (detection limits in the range 0.04-9 ng g-1 of POCIS sorbent) and excellent specificity, thanks to the monitoring of two "precursor ion-product ion" MS transitions for identity confirmation. The method was applied to samplers deployed in the Ligurian coast (Italy), detecting caffeine, bisphenol A, ketoprofen and two UV-filters as the most concentrated in the POCIS sorbent.

The study of polar emerging contaminants in seawater by passive sampling: A review.

Emerging Contaminants (ECs) in marine waters include different classes of compounds, such as pharmaceuticals and personal care products, showing "emerging concern" related to the environment and human health. Their measurement in seawater is challenging mainly due to the low concentration levels and the possible matrix interferences. Mass spectrometry combined with chromatographic techniques represents the method of choice to study seawater ECs, due to its sensitivity and versatility. Nevertheless, these instrumental techniques have to be preceded by suitable sample collection and pre-treatment: passive sampling represents a powerful approach in this regard. The present review compiles the existing occurrence studies on passive sampling coupled to mass spectrometry for the monitoring of polar ECs in seawater and discusses the availability of calibration data that enabled quantitative estimations. A vast majority of the published studies carried out during the last two decades describe the use of integrative samplers, while applications of equilibrium samplers represent approximately 10%. The polar Chemcatcher was the first applied to marine waters, while the more sensitive Polar Organic Chemical Integrative Sampler rapidly became the most widely employed passive sampler. The organic Diffusive Gradients in Thin film technology is a recently introduced and promising device, due to its more reliable sampling rates. The best passive sampler selection for the monitoring of ECs in the marine environment as well as future research and development needs in this area are further discussed. On the instrumental side, combining passive sampling with high resolution mass spectrometry to better assess polar ECs is strongly advocated, despite the current challenges associated.

Iodide sources in the aquatic environment and its fate during oxidative water treatment - A critical review.

Iodine is a naturally-occurring halogen in natural waters generally present in concentrations between 0.5 and 100 µg L-1. During oxidative drinking water treatment, iodine-containing disinfection by-products (I-DBPs) can be formed. The formation of I-DBPs was mostly associated to taste and odor issues in the produced tap water but has become a potential health problem more recently due to the generally more toxic character of I-DBPs compared to their chlorinated and brominated analogues. This paper is a systematic and critical review on the reactivity of iodide and on the most common intermediate reactive iodine species HOI. The first step of oxidation of I- to HOI is rapid for most oxidants (apparent second-order rate constant, kapp > 103 M-1s-1 at pH 7). The reactivity of hypoiodous acid with inorganic and organic compounds appears to be intermediate between chlorine and bromine. The life times of HOI during oxidative treatment determines the extent of the formation of I-DBPs. Based on this assessment, chloramine, chlorine dioxide and permanganate are of the highest concern when treating iodide-containing waters. The conditions for the formation of iodo-organic compounds are also critically reviewed. From an evaluation of I-DBPs in more than 650 drinking waters, it can be concluded that one third show low levels of I-THMs (<1 µg L-1), and 18% exhibit concentrations > 10 µg L-1. The most frequently detected I-THM is CHCl2I followed by CHBrClI. More polar I-DBPs, iodoacetic acid in particular, have been reviewed as well. Finally, the transformation of iodide to iodate, a safe iodine-derived end-product, has been proposed to mitigate the formation of I-DBPs in drinking water processes. For this purpose a pre-oxidation step with either ozone or ferrate(VI) to completely oxidize iodide to iodate is an efficient process. Activated carbon has also been shown to be efficient in reducing I-DBPs during drinking water oxidation.

Unravelling the role of membrane pore size in polar organic chemical integrative samplers (POCIS) to broaden the polarity range of sampled analytes.

Polar organic chemical integrative samplers (POCIS) are widely used in their standard configuration for sampling contaminants in water bodies. A wider polyethersulfone (PES) membrane pore size was employed in POCIS exposed in a static calibration experiment to investigate the uptake of 21 emerging contaminants ranging from hydrophilic (perfluoroalkyl compounds, xanthines, an artificial sweetener) to more hydrophobic compounds (pharmaceuticals, oestrogens, UV filters). Compared to standard POCIS with 0.1-µm pore size PES membranes, the POCIS with 5-µm pore size PES membranes did not increase sampling rates for compounds of relatively low and mid-hydrophobicity. However, the uptake of more hydrophobic and anionic compounds, which either poorly diffuse through or are retained within the standard 0.1-µm PES membrane, showed a marked increase. This led to the first ever recorded sampling rates for triclosan (0.249 L day-1) and two UV filters (0.075-0.123 L day-1). Based on these results, more attention should be placed on the choice of the appropriate membrane for each POCIS application. The most suitable configuration depends on the studied compound physico-chemical characteristics-such as the polarity and the compound membrane-to-sorbent partitioning coefficient-but also on the site conditions (deployment time, fouling, flow variations, et.).

Formation and removal of disinfection by-products in a full scale drinking water treatment plant.

In this case study, high sensitivity simple methods for the analysis of trihalomethanes (THM4), iodinated-trihalomethanes (I-THMs), haloacetic acids (HAAs), bromide, iodide and iodate have been developed. A one-step procedure for the analysis of haloacetic acids by head-space GC-MS provides good reproducibility and low limits of quantification (≤50 ng L-1). These methods were applied to characterize the formation of disinfection by-products (DBPs) in a full scale drinking water treatment plant. In this treatment plant, the incorporation of bromine into THMs increases throughout the water treatment line, due to the formation of bromine reactive species favored by the decrease of competition between dissolved organic carbon (DOC) and bromide towards chlorine. A linear correlation has been observed between the bromine incorporation factor and the Br-/DOC mass ratio. The conversion of iodine to iodate by chlorination occurs in this water due to the relatively high bromide concentration. Moreover, a higher formation of iodate compared to iodide levels in the raw water is observed indicating a degradation of organic iodinated compounds. The formation of I-THMs was constant in terms of quantity and speciation between campaigns despite fluctuating concentrations of DOC and total iodine in the raw water. A preferential removal of DBPs formed by the intermediate chlorination in the order I-DBPs > Br-DBPs > Cl-DBPs occurs during the subsequent activated carbon filtration. The removal rates range from 25 to 36% for the regulated THM4, from 82 to 93% for the ∑I-THMs and 95% for haloacetic acids. The assessment of the relative toxicity shows that despite a much lower concentration of HAAs (<10% of the total mass of measured DBPs) compared to THMs, these compounds are responsible for 75% of the relative cytotoxicity of the treated water. Bromoacetic acid on its own accounts for more than 60% of the overall toxicity of the 17 compounds included in this study.