Occurrence and prevalence of per- and polyfluoroalkyl substances in the sediment pore water of mariculture sites: Novel findings of PFASs from the Bohai and Yellow Seas using a newly established analytical method.

A new method for the determination of 26 legacy and emerging per- and polyfluoroalkyl substances (PFASs) in marine sediment pore water was developed using online solid phase extraction coupled with liquid chromatography-tandem mass spectrometry. The proposed method requires only about 1 mL of pore water samples. Satisfactory recoveries of most target PFASs (83.55-125.30 %) were achieved, with good precision (RSD of 1.09-16.53 %), linearity (R2 ≥ 0.990), and sensitivity (MDLs: 0.05 ng/L-5.00 ng/L for most PFASs). Subsequently, the method was applied to determine PFASs in the sediment pore water of five mariculture bays in the Bohai and Yellow Seas of China for the first time. Fifteen PFASs were detected with total concentrations ranging from 150.23 ng/L to 1838.48 ng/L (mean = 636.80 ng/L). The ∑PFASs and PFOA concentrations in sediment pore water were remarkably higher than those in surface seawater (tens of ng/L), indicating that the potential toxic effect of PFASs on benthic organisms may be underestimated. PFPeA was mainly distributed in pore water, and the partition of PFHpA (50.99 %) and PFOA (49.01 %) was almost equal in the solid and liquid phases. The proportions of all other PFASs partitioned in marine sediments were significantly higher than those in pore water.

Occurrence and phase distribution of lipophilic marine algal toxins in the bottom boundary layer and sediment-porewater system of two mariculture sites.

To date, understanding the fate of lipophilic marine algal toxins (LMATs) in benthic environments on which cultivated shellfish depend is still limited. In this work, the occurrence, concentration levels, and phase distributions of LMATs in the benthic environments of two mariculture sites (Sishili and Rongcheng Bays) in China were investigated for the first time. Five LMATs: okadaic acid (OA), pectenotoxin-2 (PTX2), gymnodimine, 13-desmethyl spirolide C, and azaspiracid-2 (AZA2) and three derivatives: dinophysistoxin-1 isomer (DTX1-iso), pectenotoxin-2 seco acid, and 7-epi- pectenotoxin-2 seco acid were detected in different environmental samples. OA and PTX2 were the dominant LMATs in the bottom boundary layer (BBL) and sediment, whereas AZA2 was present in the sediment only. Notably, DTX1-iso was found for the first time to be widely distributed in the benthic environments of the bays. In BBL, the average proportion of LMATs in the dissolved phase (99.20%) was much higher than in the particulate phase (0.80%). Partition of LMATs was more balanced between sediment porewater (57.80% average proportion) and sediment (42.20%). The concentrations of ∑LMATs in the BBL seawater ranged from 19.09 ng/L to 41.57 ng/L (mean of 32.67 ng/L), and the spatial distribution trend was higher in offshore than nearshore. ∑LMATs concentrations in the sediment and porewater of the two bays ranged from 17.04 ng/kg to 150.13 ng/kg (mean of 53.58 ng/kg) and from 8.29 ng/L to 120.58 ng/L (mean of 46.63 ng/L), respectively. Their spatial distributions differed from those in BBL, showing a trend of high concentrations in areas with heavy land-based inputs. ∑LMATs concentrations in porewater were significantly higher than those in BBL seawaters, suggesting that the potential hazards of LMATs to benthic organisms may be underestimated.