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In this study, the leaching of six phthalic acid esters (PAEs) from three common consumer plastics was investigated: low and high density polyethylene (LDPE, HDPE) and recycled polyethylene (RP). The effects of salinity, temperature, and ultraviolet irradiation (UVR) on leaching were investigated. The study of leaching of phthalates in aqueous environments in batch experiments is challenging due to their readsorption by the high hydrophobicity of PAEs, and there are no standard methods to study release processes. Here with the experiments, leaching (A) and spiking (B) using six PAEs to study the readsorption in the leaching process. PAEs were identified and quantified using GC-MS. Dibutyl phthalate (DBP) and benzyl butyl phthalate (DEHP) showed considerable leaching during the 5-day incubation: 14 ± 1 to 128 ± 14 and 25 ± 2 to 79 ± 5 ng/cm 2 , respectively, under UVR, corresponding approximately to (1.9-13%) and (12.4-22.4%) of the solvent extracted mass. The highest K d values were measured for RP polymers (0.3-9.4), followed by LDPE (0.5-5.4) and HDPE (0.2-2.2) polymers. Thus, readsorption of PAEs at the surface removed 30-80% of the leached PAEs in the dissolved phase. For example in LDPE, the calculated total release of DBP was up to 54 ± 4 ng/cm 2 , while the dissolved amount was 8.5 ± 1 ng/cm 2 during the 5-day incubation under freshwater conditions. Increasing salinity negatively affected the leaching rate, which decreased for DBP from 54 ± 4 ng/cm 2 in freshwater to 44 ± 3 and 38 ± 3 ng/cm 2 at salinity of 20 and 40 g/L, respectively, from LDPE during the 5-day incubation. Temperature and UVR had a positive effect on the leaching rate, with the release of DBP from LDPE increasing from 44 ± 3 ng/cm 2 at room temperature (25 °C) to 60 ± 6 and 128 ± 14 ng/cm 2 at high temperature (40 °C) and UVR, respectively. Overall, this study highlights the positive relationship between temperatures, UVR on the extent of leaching and surface adsorption on the leaching measurements., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Relic munitions are a hazardous legacy of the two world wars present in coastal waters worldwide. The southwest Baltic Sea has an especially high prevalence of unexploded ordnance and dumped munition material, which represent a large potential source of toxic explosive chemicals (munition compounds, MC). In the current study, diverse biota (plankton, macroalgae, tunicate, sponge, mollusc, echinoderm, polychaete, anemone, crustacea, fish) were collected from the Kiel Bight and a munitions dumpsite at Kolberger Heide, Germany, to evaluate the potential bioaccumulation of explosives and their derivatives (2,4,6-trinitrotoluene, TNT; 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dinitrotoluene, ADNT; 2,4-diamino-6-nitrotoluene and 2,6-diamino-4-nitrotoluene, DANT; 1,3-dinitrobenzene, DNB; and 1,3,5-trinitro-1,3,5-triazinane, RDX). One or more MCs were detected in >98% of organisms collected throughout the study region (n = 178), at a median level of 6 pmol/g (approximately 1 ng/g) and up to 2 × 10 7  pmol/g (TNT in Asterias rubens collected from Kolberger Heide). In most cases, TNT and its transformation product compounds ADNT and DANT were significantly higher in biota from the munitions dumpsite compared with other locations. Generally, DNB and RDX were detected less frequently and at lower concentrations than TNT, ADNT, and DANT. In commercially important fish species (plaice, flounder) from Kolberger Heide, TNT and ADNT were detected in 17 and 33% of samples, respectively. In contrast DANT was detected in every fish sample, including those outside the dumpsite. Dinitrobenzene was the second most prevalent MC in fish tissue. Fish viscera (stomach, kidney, liver) showed higher levels of DANT than edible muscle flesh, with highest DANT in liver, suggesting reduced risk to seafood consumers. This study provides some of the first environmental evidence for widespread bioaccumulation of MC in a coastal marine food web. Although tissue MC content was generally low, corrosion of munition housings may lead to greater MC release in the future, and the ecological risk of this exposure is unknown., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Marine dissolved organic matter (DOM) plays a key role in the current and future global carbon cycle, which supports life on Earth. Trace metals such as iron, an essential micronutrient, compete with protons and major ions for the binding to DOM. These competitive effects and the DOM binding capacity are related to the DOM acid-base properties, which also influence DOM transport and reactivity in marine waters. Here we present the results of a complete set of acid-base titration experiments of a pre-concentrated marine DOM sample in the range 0.01 ≤ I ≤ 0.7 M and 3 ≤ pH ≤ 10. We characterize the obtained proton binding curves using a combination of the non-ideal competitive adsorption (NICA) isotherm and Donnan electrostatic model. Within the main chemical groups of marine DOM, the carboxylic distribution was accurately characterized from the obtained data (Q maxH, 1 =2.52 mol·kg -1 , logk¯ H,1 = 3.26, m 1  = 0.69 and b = 0.70). This carboxylic mode was found to be less acidic and more homogeneous than a generic fulvic acid, but the differences are consistent with the reported variability of fulvic acids of freshwater and terrestrial origin. We find that changes in temperature (down to 5.5 °C), and the presence of calcium or magnesium (at 0.01 M) resulted in no significant modification of the proton ion binding curves obtained at 25 °C and 0.7 or 0.1 M ionic strength, respectively. We demonstrate the relevance of proton binding parameters for the modelling of the system iron/marine DOM throughout a wide range of salinity and acidity conditions in the context of different future ocean scenarios., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

As a consequence of World War II, large amounts of munition have been deposited in coastal waters. Deterioration of the mines and bombs is resulting in a release of munition compounds (MCs) like trinitrotoluene to the surrounding marine environment, with potential implications to ecosystems. Analytical methods have thus far been unable to detect these compounds reliably in seawater. We present a highly sensitive method for the analysis of MCs in the marine environment. We combine preconcentration and sample clean up by solid phase extraction with separation and detection by ultra-high performance liquid chromatography - electrospray ionisation - mass spectrometry (UHPLC-ESI-MS) for the detection of MCs dissolved in filtered (< 0.2 µm) seawater. For biota, dried and ground samples were extracted in acetonitrile and analysed after simple dilution. Eleven MCs were detected by UHPLC-ESI-MS with limits of detection between 0.01 and 25 pg. For the first time, we used heavy isotopes of trinitroluene and dinitrobenzene to improve quantification in environmental samples. We detected 7 MCs in waters sampled at a known munition disposal site in the Baltic Sea after a 1000-fold preconcentration and using an injection volume of 25 µL. Trinitrotoluene and dinitrobenzene were the most abundant MCs, occurring at concentrations between 0.1 and 11.8 ng L -1 . We observed 10 MCs at concentrations up to 24 µg g -1 dry weight in benthic organisms sampled from the site. The enhanced sensitivity of our method allowed us to detect MCs at concentrations relevant for assessment and management of munitions disposal sites in the marine environment., (Copyright © 2019 The Authors. Published by Elsevier B.V. All rights reserved.)

A rapid, automated, high-throughput analytical method capable of simultaneous analysis of multiple elements at trace and ultratrace levels is required to investigate the biogeochemical cycle of trace metals in the ocean. Here we present an analytical approach which uses a commercially available automated preconcentration device (SeaFAST) with accurate volume loading and in-line pH buffering of the sample prior to loading onto a chelating resin (WAKO) and subsequent simultaneous analysis of iron (Fe), zinc (Zn), copper (Cu), nickel (Ni), cadmium (Cd), lead (Pb), cobalt (Co) and manganese (Mn) by high-resolution inductively-coupled plasma mass spectrometry (HR-ICP-MS). Quantification of sample concentration was undertaken using isotope dilution for Fe, Zn, Cu, Ni, Cd and Pb, and standard addition for Co and Mn. The chelating resin is shown to have a high affinity for all analyzed elements, with recoveries between 83 and 100% for all elements, except Mn (60%) and Ni (48%), and showed higher recoveries for Ni, Cd, Pb, Co and Mn in direct comparison to an alternative resin (NOBIAS Chelate-PA1). The reduced recoveries for Ni and Mn using the WAKO resin did not affect the quantification accuracy. A relatively constant retention efficiency on the resin over a broad pH range (pH 5-8) was observed for the trace metals, except for Mn. Mn quantification using standard addition required accurate sample pH adjustment with optimal recoveries at pH 7.5 ± 0.3. UV digestion was necessary to increase recovery of Co and Cu in seawater by 15.6% and 11.4%, respectively, and achieved full break-down of spiked Co-containing vitamin B 12 complexes. Low blank levels and detection limits could be achieved (e.g., 0.029 nmol L -1 for Fe and 0.028 nmol L -1 for Zn) with the use of high purity reagents. Precision and accuracy were assessed using SAFe S, D1, and D2 reference seawaters, and results were in good agreement with available consensus values. The presented method is ideal for high throughput simultaneous analysis of trace elements in coastal and oceanic seawaters. We present a successful application of the analytical method to samples collected in June 2014 in the Northeast Atlantic Ocean., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A mass spectrometric (MS) method for the identification of iron protoporphyrin (IX) (FePTP, heme b) in marine particulate material and phytoplankton is described. Electrospray ionisation of FePTP produced the molecular Fe(III)PTP(+) ion (m/z=616) or the pseudomolecular [Fe(II)PTP + H](+) ion (m/z=617), depending on the oxidation state of the central iron ion. Collision induced dissociation (CID) in the ion trap mass spectrometer resulted in a single detected product ion (m/z=557) indicative of loss of ethanoic acid from a carboxylic acid side chain. Widening the isolation width to 616±3 resulted in production of a mass spectrum demonstrating the distinctive isotopic ratio of the iron containing fragment, further increasing the specificity of the analysis. Selective reactant monitoring (SRM) of the fragment ion (m/z=557) was applied to the detection of FePTP after chromatography of ammoniacal OGP extracts of marine samples. The detection limit for FePTP analysed by SRM after chromatography was 1.2±0.5fmol. For phytoplankton samples, reasonably good agreement was achieved between results obtained with SRM and those obtained by monitoring absorbance at λ=400nm using a diode array detector (DAD). Use of SRM for analysis of particulate material obtained from the high latitude North Atlantic allowed for the analysis of FePTP in the presence of a co-eluting compound that interfered with detection by DAD. Simultaneous collection of mass spectra from m/z=300 to 1500 resulted in identification of the pseudomolecular ion for the interfering compound. The CID fragmentation pattern and UV-visible mass spectra indicated that the interfering compound was a previously unidentified chlorin type compound. Comparison of FePTP determined by SRM and DAD on samples where this compound could not be detected showed that results collected using the two methods correlated. The use of both MS and DAD results in a powerful tool for quantifying this important biogenic component of the particulate iron pool., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Here we demonstrate the use of reverse titration - competitive ligand exchange-adsorptive cathodic stripping voltammetry (RT-CLE-ACSV) for the analysis of iron (Fe) binding ligands in seawater. In contrast to the forward titration, which examines excess ligands in solution, RT-CLE-ACSV examines the existing Fe-ligand complexes by increasing the concentration of added (electroactive) ligand (1-nitroso-2-naphthol) and analysis of the proportion of Fe bound to the added ligand. The data manipulation allows the accurate characterisation of ligands at equal or lower concentrations than Fe in seawater, and disregards electrochemically inert dissolved Fe such as some colloidal phases. The method is thus superior to the forward titration in environments with high Fe and low ligand concentrations or high concentrations of inert Fe. We validated the technique using the siderophore ligand ferrioxamine B, and observed a stability constant [Formula: see text] of 0.74-4.37×10(21) mol(-1), in agreement with previous results. We also successfully analysed samples from coastal waters and a deep ocean hydrothermal plume. Samples from these environments could not be analysed with confidence using the forward titration, highlighting the effectiveness of the RT-CLE-ACSV technique in waters with high concentrations of inert Fe., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In the period 2003-2005 a study was conducted to determine the occurrence, spatial and temporal distribution of five acidic herbicides in the Lower Fraser Valley (LFV) region of British Columbia, Canada. A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) method capable of detecting analytes at the sub ng/L level was developed for this study. Samples were collected and analyzed from two references, five agricultural, two urban and five agricultural and urban mixed sites. Only (4-chloro-2-methylphenoxy)acetic acid and triclopyr were detected at the reference sites. The highest concentration of herbicide detected at the reference sites was 0.109ng/L for (4-chloro-2-methylphenoxy)acetic acid. Varying levels of all of the herbicides monitored were detected at the urban, agricultural and the mixed sites. For the urban sites the highest concentration of herbicide detected was 66.6ng/L for 2-(4-chloro-2-methylphenoxy)propanoic acid. For the agricultural sites the highest concentration of herbicide detected was 345ng/L for (2,4-dichlorophenoxy)acetic acid (2,4-D). For the mixed sites the highest concentration of herbicide detected was 1230ng/L for 2,4-D. Overall the mixed sites showed highest concentrations and detection frequencies followed by the agricultural and urban sites. With few exceptions higher concentrations of herbicides were observed for samples collected during spring than for samples collected during fall. The detected concentrations of herbicides were evaluated against established water quality criteria. Herbicide data presented in this study provide reference levels for future pesticide monitoring programs in the region.

In this work, an isotope dilution method for determination of selected acidic herbicides by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for surface water samples. Average percent recoveries of native analytes were observed to be between 70.8 and 93.5% and average recoveries of labeled quantification standards [(13)C(6)]2,4-D and [(13)C(6)]2,4,5-T were 85.5 and 101%, respectively. Using this method, detection limits of 0.05 ng/L for dicamba, MCPA, MCPP, and triclopyr, and 0.5 ng/L for 2,4-D were routinely achieved. The method was applied to measuring the concentration of these analytes in surface water samples collected from five sampling locations in the Lower Fraser Valley region of British Columbia, Canada. All of the herbicides monitored were detected at varying levels in the surface water samples collected. The highest concentrations detected for each analyte were 345 ng/L for 2,4-D, 317 ng/L for MCPA, 271 ng/L for MCPP, 15.7 ng/L for dicamba, and 2.18 ng/L for triclopyr. Average detection frequencies of the herbicides were 95% for MCPA, 80% for MCPP, 70% for dicamba, 65% for 2,4-D, and 46% for triclopyr. Seasonal variations of herbicide levels are also discussed.