ALBERT

Description: Inputs of silver nanoparticles (AgNPs) to marine waters continue to increase yet mechanisms of AgNPs toxicity to marine phytoplankton are still not well resolved. This study reports a series of toxicity experiments on a representative coastal marine diatom species Chaetoceros curvisetus using the reference AgNP, NM-300K. Exposure to AgNPs resulted in photosynthetic impairment and loss of diatom biomass in proportion to the supplied AgNP dose. The underlying mechanism of toxicity was explored via comparing biological responses in parallel experiments. Diatom responses to AgNP, free Ag(I) species, and dialysis bag-retained AgNP treatments showed marked similarity, pointing towards a dominant role of Ag(I) species uptake, rather than NPs themselves, in inducing the toxic response. In marked contrast to previous studies, addition of the organic complexing agent cysteine (Cys) alongside Ag only marginally moderated toxicity, implying AgCys− complexes were bioavailable to this diatom species. A preliminary field experiment with a natural phytoplankton community in the southeast Atlantic Ocean showed no significant toxic response at a NM-300 K concentration that resulted in ~40% biomass loss in the culture studies, suggesting a modulating effect of natural seawaters on Ag toxicity.

Description: Highlights • Detection and quantification of AgNP at ppb levels in natural seawater samples. • The use of long path cells (up to 200 cm) in UV–visible spectrophotometry is proposed. • Knowledge of the molar attenuation coefficient of the NP under study in the sample matrix is required. Abstract Silver nanoparticles (AgNPs) are emerging contaminants that are difficult to detect in natural waters. UV–visible spectrophotometry is a simple technique that allows detection of AgNPs through analysis of their characteristic surface plasmon resonance band. The detection limit for nanoparticles using up to 10 cm path length cuvettes with UV–visible spectrophotometry is in the 0.1–10 ppm range. This detection limit is insufficiently low to observe AgNPs in natural environments. Here we show how the use of capillary cells with an optical path length up to 200 cm, forms an excellent technique for rapid detection and quantification of non-aggregated AgNPs at ppb concentrations in complex natural matrices such as seawater.

Description: The aggregation behaviour of polymer-coated silver nanoparticles (AgNPs) was characterized in NaCl solutions, and in two seawaters of different salinities and dissolved organic matter (DOM) contents. Representative organic coatings i.e. tannic acid (TA), alginic acid (ALG), two gum Arabic samples (GAL and GAH), branched polyethylenimine (BPEI), and non-ionic surfactants (reference material NM-300K) were selected to cover a wide range of zeta-potentials. The stability in NaCl solutions, as determined from the rate of variation in hydrodynamic size within a timeframe of one hour, followed the order BPEI ≫ NM-300K ≈ GAL ≫ ALG ≈ TA ≫ GAH. In the seawater samples the order was NM-300K ≈ GAL ≫ ALG 〉 GAH 〉 TA ≈ BPEI, and only TA, GAL and NM-300K batches behaved as expected from the NaCl experiments. Remarkably, the BPEI sample showed the largest aggregation rate in the seawater sample with the highest DOM concentration (277 μM C). The GAH sample displayed a non-monotonic variation in aggregation rate with NaCl concentration, apparently due to concomitant precipitation of AgCl. The results indicate that non-electrostatic stabilization mechanisms and DOM-coating interactions are important for the prediction of stability and persistence of polymer-coated AgNPs in seawater.

Description: Quantification of phthalates or phthalic acid esters (PAEs) might be problematic due to matrix overlap, auto-self absorbance and background scattering noise by the plastic lab materials although plastics have been reported in the release of PAEs. These materials (ambient air, reagents bottles, sampling devices, and various analytical instruments), are ubiquitous in the laboratory environment, thereby making it more difficult to reliably analyze of trace concentration of PAEs. Thus, in the current study, a straight forward and reliable protocol has been established for the analysis of PAEs including control of blank contamination, and the experimental conditions such as extraction time and temperature were optimized. The mass of PAEs in blank tests of selected materials ranged from 3±0.7 to 35±6 ng for liquid-liquid extraction (LLE) and from 5±1.8 to 63±15 ng for solid-phase extraction (SPE). For both extraction methods, higher blank values were measured for dibutyl phthalate (DBP) (35±6 ng, 12±3 ng), and DEHP (63±12 ng, 23±5 ng) in LLE and SPE, respectively. Average recoveries of PAEs in LLE were 90-97% and obtained with successive aliquots of 2 mL, 1 mL, and 1 mL dichloromethane (DCM). For SPE, recoveries up to 86-90% were achieved with successive aliquots of 5, 3, and 2 mL DCM at a sample flow rate of 5 mL min -1 . Under the optimized conditions, the method quantification limits (MQL) for PAEs was 10-20 ng L -1 for LLE and 10-35 ng L -1 for SPE. Moreover, the dissolved concentrations of PAEs from LDPE measured by the LLE method ranged 〈 1.5 to 5.83 ng cm -2, and those measured by SPE ranged from 1.0to256ngL -1 , in seawater samples of Sharm Obhur. The method has lower MQL values for LLE and SPE than average reported values of 10-100 ng L -1 and 30-100 ng L -1 , respectively.

Description: Highlights • This study examined MP concentrations and PAE distribution in a semi-enclosed Sharm Obhur leading to the Red Sea. • DEP, DBP and DEHP are the predominant PAEs. • A positive relationship was found between PAE concentration and PDs abundance. • The ecological risk of PAEs and PDs was found from low to moderate. The abundance of plastic debris (PDs) and its correlation with phthalic acid esters (PAEs), a class of pollutants associated with plastics, is not well understood, although PDs have been reported in relation to the release and distribution of aquatic pollutants such as PAEs. Few studies have linked the distribution of these pollutants in seawater. The current study examined the abundance and relationship of PDs and PAEs in seawater from Sharm Obhur and the Red Sea. Estimates were also made of their ecological impacts. Sharm Obhur is a semi-enclosed bay on the eastern shore of the Red Sea, near Jeddah, Saudi Arabia, and is heavily impacted by human activities. Contaminants from Sharm Obhur may be transported into the deep waters of the Red Sea by the subsurface outflow. The PAEs concentrations in the study area ranged from 0.8 to 1224 ng/L. Among the six PAEs studied, diethyl phthalate (DEP) (22–1124 ng/L), di-n-butyl phthalate (DBP) (9–346 ng/L) and di (2-ethylhexyl) phthalate (DEHP) (62–640 ng/L) were the predominant additives detected across all the sampling sits. Whereas the other PAEs, dimethyl phthalate (DMP) (5–76 ng/L), benzyl butyl phthalate (BBP) (4–25 ng/L) and di-n-octyl phthalate DnOp (0.5–80 ng/L) were generally lower in most samples. The sum of the six analyzed PAEs (∑6 PAEs) was lower at Sharm Obhur (587 ± 82 ng/L) and in the Red Sea shelf (677 ± 182 ng/L) compared to the Red Sea shelf break (1266 ± 354 ng/L). This suggests that degradation and adsorption of PAEs were higher in Sharm Obhur and on the shelf than on the shelf break. In contrast, there was no difference in the abundance of PDs between Sharm Obhur (0.04 ± 0.02 PDs/m3), Red Sea shelf (0.05 ± 0.02 PDs/m3) and in the Red Sea shelf break (0.03 ± 0.1 PDs/m3). Polyethylene (32%) and polypropylene (8%) were dominant, mostly smaller than 5 mm2 (78%), with the majority consisting of white (52%) and black (24%) fragments (39%), fibers (35%) and films (24%). A positive correlation between PAE concentration and abundance of PDs, suggests either a common source or a causal link through leaching. The ecological risk of ∑4PAEs (DMP, DEP, DBP and DEHP) ranged from (0.20–0.78), indicating a low to moderate risk for the Red Sea. The pollution index of PDs ranged from (0.14–0.36), showing that the Sharm Obhur and both sites of Red Sea suffered relatively low pollution.

Description: Highlights • A high concentration BEP and DBP were detected from LDPE, HDPE and RP polymer films. • The impact salinity, temperature and UVR on leaching and re-adsorption of PaEs were investigated. • A mass balance approach was used to determine the adsorption loss of each target compounds during the leaching process. • Surface adsorption of PEs removed 40 to 80% of the leached PEs. Abstract 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/cm2, respectively, under UVR, corresponding approximately to (1.9–13%) and (12.4–22.4%) of the solvent extracted mass. The highest Kd 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/cm2, while the dissolved amount was 8.5 ± 1 ng/cm2 during the 5-day incubation under freshwater conditions. Increasing salinity negatively affected the leaching rate, which decreased for DBP from 54 ± 4 ng/cm2 in freshwater to 44 ± 3 and 38 ± 3 ng/cm2 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/cm2 at room temperature (25 °C) to 60 ± 6 and 128 ± 14 ng/cm2 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. Graphical abstract Schematic of the leaching process in experiment (A: polymer) and in Experiment B (Polymer + spikes), shows that part of leachate were re-adsorbed on the surface of the polymer were may affect the dissolution concentration. The total leached mass (adsorbed and dissolved) were estimation by compared to a treatment containing both polymer and PAEs spike (P + S; Experiment B). The influence of salinities (0.1, 20 and 40 g/L), temperature (10, 25, and 40 °C), and ultraviolet radiation (UVR 350 nm) on the leaching and re-adsorption of PEs was investigated.