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A method for the determination of ultratrace amounts of Cr, Fe, Mn, Pb and Zn in seawater has been developed. It combined the low-blank magnesium hydroxide coprecipitation procedure with quadrupole inductively coupled plasma mass spectrometry and used the dynamic reaction cell technique to resolve the polyatomic interferences arising from the residual matrix, the solvent and plasma gases. Detection limits (3σ(B), n=10) for Cr, Fe, Mn, Pb and Zn were 0.02, 0.10, 0.01, 0.002 and 0.19 nM, respectively, using 50 mL of seawater sample. The accuracy of the analytical procedure was verified by the analysis of the seawater reference materials CASS-4, NASS-5, SAFe D2 and SAFe S. The analytical precision ranged from 3% to 16% (n=6), with a sample throughput of about 6 samples h(-1)., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The determination of trace pollutants in seawater is challenging, and sampling is a crucial step in the entire analytical process. Passive samplers combine in situ sampling and preconcentration, thus limiting the tedious treatment steps of the conventional sampling methods. Their use to monitor water quality in confined marine environment could bring several advantages. In this work, the presence of organic contaminants at trace and ultra-trace levels was assessed in the Genoa Aquarium supply-and-treated water using Polar Organic Integrative Samplers (POCIS). Both untargeted gas chromatography-mass spectrometry and targeted liquid chromatography-tandem mass spectrometry were employed. The untargeted approach showed the presence of hydrocarbons, diphenyl sulfone and 2,4-di-tert-butyl-phenol. Only hydrocarbons were detected in all the samples. Nineteen emerging contaminants, belonging to different classes (pharmaceuticals, UV-filters, hormones and perfluorinated compounds), were selected for the target analysis. Thirteen analytes were detected, mainly in supply water, even though the majority of them were below the quantitation limit. It is worthy to note that two of the detected UV-filters had never been reported in seawater using the POCIS samplers. The comparison of the analytes detected in supply and treated water indicated a good performance of the Aquarium water treatment system in the abatement of seawater contaminants. [ABSTRACT FROM AUTHOR]

Environmental context: Emerging contaminants such as platinum are continuously released into aquatic environments. Analytical challenges, however, have restricted information on their geochemical cycles. We examine the potential use of platinum as a tracer of anthropogenic inputs in a model industrial/urban site (Genoa Harbor, Italy), and provide a first estimate of dissolved platinum baseline concentrations in the northern Mediterranean coast. Biogeochemical cycles that include processes to control platinum (Pt) distribution remain widely unknown in aquatic environments, especially in coastal systems. Dissolved Pt concentrations in coastal seawater (PtD) and in suspended particulate matter (SPM, PtP) were measured, together with master variables comprising dissolved oxygen, dissolved and particulate organic carbon, chlorophyll-a, turbidity, and ammonium levels, along two longitudinal profiles in the industrial Genoa Harbor (north-west Italy). Concentrations and spatial distribution of PtD and PtP levels reflect distinct concentration gradients that were attributed to different Pt sources such as hospital, domestic and industrial wastewater, atmospheric deposition, and/or road runoff. Concentrations reaching up to 0.18 ng L−1 PtD and 14 ng g−1 PtP reflect the impact of Pt urban inputs to coastal sites. These first data highlight considerable anthropogenic contamination in a confined harbor compared with the proposed reference value for the western Mediterranean surface seawater measured at external sites. Identified correlations between Pt levels and human pollution signals suggest the potential use of Pt as a new tracer of anthropogenic inputs that can be applied to other urbanised coastal systems. Biogeochemical processes that induce changes in the partitioning and fate of Pt in coastal seawater reflect a spatial variability and highlight the need for comprehensive environmental monitoring at an appropriate spatial scale. Environmental context. Emerging contaminants such as platinum are continuously released into aquatic environments. Analytical challenges, however, have restricted information on their geochemical cycles. We examine the potential use of platinum as a tracer of anthropogenic inputs in a model industrial/urban site (Genoa Harbor, Italy), and provide a first estimate of dissolved platinum baseline concentrations in the northern Mediterranean coast. [ABSTRACT FROM AUTHOR]

The study of marine pollution has been traditionally addressed to persistent chemicals, generally known as priority pollutants; a current trend in environmental analysis is a shift toward “emerging pollutants,” defined as newly identified or previously unrecognized contaminants. The present review is focused on the peculiar contribution of mass spectrometry (MS) to the study of pollutants in the seawater compartment. The work is organized in five paragraphs where the most relevant groups of pollutants, both “classical” and “emerging,” are presented and discussed, highlighting the relative data obtained by the means of different MS techniques. The hyphenation of MS and separative techniques, together with the development of different ion sources, makes MS and tandem MS the analytical tool of choice for the determination of trace organic contaminants in seawater. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 37:492–512, 2018. [ABSTRACT FROM AUTHOR]

Seawater passive sampling with Polar Organic Chemical Integrative Samplers (POCIS) combined with Gaschromatography-Mass Spectrometry analysis were employed as a tool for screening unknown contaminants in a complex Ligurian marine coastal area. The untargeted approach allowed recognizing different classes of compounds, mainly hydrocarbons from C 20 to C 30 . Besides, two chemicals, deriving from anthropic activities, N-butylbenzenesulfonamide (NBBS) and diphenyl sulfone (DPS), were identified and quantified in all samples. Both analytes showed decreasing concentrations from the more confined site to the outer one. The oceanographic characterization of the area performed with multiparametric probes provided useful information, in agreement with chemical analyses. The presence of NBBS and DPS in the site presenting lower continental inputs demonstrated the usefulness of the integrative sampling approach for temporal and spatial monitoring, especially for low level and/or short-term pollution events that traditional monitoring can fail to detect. [ABSTRACT FROM AUTHOR]

A focus on the studies of the Antarctic environment that have been performed by mass spectrometry is presented herein; our aim is to give evidence of the essential role of this instrumental technique in the framework of the scientific research in Antarctica, with a comprehensive review on the main literature of the last two decades. Due to the wideness of the topic, the present review is limited to the determination of organic pollutants, natural molecules and biomarkers in Antarctica, thus excluding elemental analysis and studies on inorganic species. The work has been divided into five sections, on the basis of the considered environmental compartment: air; ice and snow; seawater, pack ice and lakes; soil and sediments; and organisms and biomarkers. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Abstract The present work deals with the optimization of a magnetic solid phase extraction of polycyclic aromatic hydrocarbons (PAHs) from sea water, based on molecular imprinted microparticles, for subsequent GC–MS analysis. The extraction efficiency of the magnetic molecular imprinted polymer (MIP) was compared with that of the corresponding non-imprinted polymer; only small differences in the recovery of the extraction procedure were shown, but higher repeatability was observed using MIP. An experimental design (Plackett-Burman) allowed a fast optimization identifying the only significant factor influencing the extraction recovery, namely the ratio between the amount of microparticles and the sample volume. Two optimal ratios, based on the PAHs molecular weight, were selected for 20 mL of sea water samples: 5 mg or 20 mg of microparticles for compounds ranging from 128 to 228 and from 252 to 278 Da, respectively. The recoveries ranges were 76–104% for the low molecular weight PAHs and 95–101% for the high molecular weight PAHs. The analytical method showed satisfactory figures of merit, with detection limits ranging from 30 to 375 ng L−1 and relative standard deviations on replicate extractions from 3.7 to 12.2%. The developed method, which is fast, easy and requires very small volumes of organic solvent, was applied for the determination of PAHs in selected sea water samples. Highlights • Polycyclic aromatic hydrocarbons extracted by magnetic molecular imprinted polymer • The polymer bulk binds the analytes even if the material is not imprinted. • Main advantage of extraction with molecular imprinted polymer is repeatability. • Experimental design allowed a rational optimization of the extraction procedure. • High recoveries were achieved for all sixteen polycyclic aromatic hydrocarbons. [ABSTRACT FROM AUTHOR]

• A specific processing method, required for POCIS deployed in seawater, was optimized. • Analyte recovery significantly differed in simulated and real samples. • Optimal matrix effect and recovery from fouled POCIS extracts were attained. • Most of the investigated contaminants were detected in Italian coastal waters. 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. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • POCIS are currently the most used and sensitive passive samplers to study polar ECs in seawater. • Calibrations of passive samplers in seawater conditions are rare, but needed to obtain reliable Rs. • Quantitative results are rarely validated when applying passive sampling to seawater monitoring. • Passive sampler characteristics and deployment times should be better optimized. • Passive sampling combined to high resolution mass spectrometry is a promising approach. [ABSTRACT FROM AUTHOR]

Abstract: Fast liquid chromatography coupled to triple-quadrupole tandem mass spectrometry was employed for the determination of six UV filters in seawater. The separation of the analytes was achieved in less than 5min; polarity switching was used as four of the analytes were ionized in positive mode and the remaining two in negative mode. Two ionization sources were employed and compared: atmospheric pressure chemical ionization (APCI) gave better results than electrospray ionization (ESI) for all analytes, with higher reproducibility and lower detection limits. Therefore APCI was chosen for the determination of the analytes in seawater samples using stir bar sorptive extraction-liquid desorption (SBSE-LD). Quantitative analysis was performed in multiple reaction monitoring (MRM) mode; fragmentation pathways of the analytes with regard to the formation of the MRM ions were also proposed. For the analysis of seawater samples, calibration curves were drawn using SBSE in spiked seawater. All figures of merit of the method were satisfactory; limits of detection were particularly low for the four analytes ionized in positive mode, being in the range 8–31ng/L. The method was applied to the determination of the six UV filters in seawater samples from Liguria, Italy. Only benzophenone-3 (BP-3) and ethylhexyl methoxycinnamate (EHMC) were measured in the analyzed samples; some of the remaining analytes were also detected but always below the limit of quantitation. [Copyright &y& Elsevier]

Abstract: The strong species of cadmium(II), copper(II), manganese(II) and nickel(II) in an Antarctic seawater sample are investigated by a method based on the sorption of metal ions on complexing resins. The resins compete with the ligands present in the sample to combine with the metal ions. Two resins with different adsorbing strengths were used. Very stable metal complexes were investigated with the strong sorbent Chelex 100 and weaker species with the less strong resin, Amberlite CG-50. Strong species were detected for three of the considered metal ions, but not for Mn(II). Cu(II) is completely linked to species with a side reaction coefficient as high as log α M(I) =11.6 at pH=7.3. The ligand concentration was found to be similar to that of the metal ion, and the conditional stability constant was around 1020 M−1. In the considered sample, only a fraction of the metal ions Cd(II) and Ni(II) is bound to the strong ligands, with side reaction coefficients equal to log α M(I) =5.5 and 6.5 at pH=7.3 for Cd(II) and Ni(II), respectively. These findings were confirmed by the test with the weaker sorbent Amberlite CG-50. It can be calculated from the sorption equilibria that neither Mn(II) nor Ni(II) is adsorbed on Amberlite CG-50 under the considered conditions and, in fact, only a negligible fraction of Mn(II) and Ni(II) was adsorbed. A noticeable fraction of Cd(II) was adsorbed on Amberlite CG-50, meaning that cadmium(II) is partially linked to weak ligands, possibly chloride, while no copper(II) was adsorbed on this resin, confirming that copper(II) is only combined in strong species. These results are similar, but not identical, to those obtained for other seawater samples examined in previous investigations. [Copyright &y& Elsevier]

Short-term variations of Pt concentrations and primary production indicators were compared in three contrasting coastal sites during spring bloom: (i) the Gironde Estuary mouth (SW France), (ii) the semi-enclosed Arcachon Bay (SW France), and (iii) the urbanized Genoa Harbor (NW Italy). At each site, surface seawater sampling and physical-chemical measurements were combined to study diel cycles (over 25 h) of dissolved Pt concentrations in seawater (Pt D) and master variables reflecting primary production activity (chlorophyll-a, phaeopigments, and particulate organic carbon, POC concentrations). Plankton nets were used in all sites, providing for the first time plankton Pt concentrations (Pt PK) over a whole diel cycle (Gironde Estuary mouth) and spot sampling (Arcachon Bay and Genoa Harbor) in the coastal zone. Bivalves (wild oysters or mussels), reflecting organisms at higher trophic levels, were also collected at all sites. The POC/Chl-a ratios in the collected particulate material suggested high contribution of phytoplankton to the particulate matter in the productive Gironde Estuary mouth. At this site, phytoplankton activity partly controlled Pt cycling and particle/dissolved Pt partitioning during daytime. During the night, zooplankton grazing may release Pt into the dissolved phase. These processes are partly masked by external factors such as tide or local Pt sources, especially in more confined and/or urbanized coastal water bodies such as the Arcachon Bay and the Genoa Harbor. Platinum levels in plankton and bivalves from these contrasting sites along the Atlantic and Mediterranean coasts tended to reflect the general Pt levels in seawater. These results clearly suggest that (i) Pt contamination of coastal waters and marine organisms has become a common feature in urbanized sites and (ii) Pt transfer to the marine food chain starts at the basic level of primary producers. By concentrating Pt (Bioconcentration Factor: BCF ~ 104), phytoplankton may serve as a biomonitor to assess Pt contamination in coastal environments. • Platinum was quantified in aquatic organisms from contrasting coastal environments • Results were compared to particle/dissolved Pt partitioning and master variables • Primary production activity seems to influence Pt diel cycling • Phytoplankton may be a good biomonitor of ambient seawater Pt contamination • Higher trophic level organisms (oysters/mussels) did not show Pt biomagnification [ABSTRACT FROM AUTHOR]