High-throughput analytical methodology of monoalkyl phthalate esters and the composite risk assessment with their parent phthalate esters in aquatic organisms and seawater.

A sensitive, robust, and highly efficient analytical methodology involving solid phase extraction coupled to ultra-high performance liquid chromatography tandem mass spectrometry was successfully established to detect 13 monoalkyl phthalate esters (MPAEs) in aquatic organisms and seawater. After the organisms were preprocessed using enzymatic deconjugation with ß-glucuronidase, extraction, purification, and qualitative and quantitative optimization procedures were performed. Under optimal conditions, the limits of detection varied from 0.07 to 0.88 µg/kg (wet weight) and 0.04-1.96 ng/L in organisms and seawater, respectively. Collectively, MPAEs achieved acceptable recovery values (91.0-102.7%) with relative standard deviations less than 10.4% and matrix effects ranging from 0.93 to 1.07 in the above matrix. Furthermore, MPAEs and phthalate esters were detected by the developed methodology and gas chromatography-triple quadrupole tandem mass spectrometer in practical samples, respectively. Mono-n-butyl phthalate and mono-iso-butyl phthalate were the most predominant congeners, accounting for 24.8-35.2% in aquatic organisms and seawater. Comprehensive health and ecological risks were higher after the MPAEs were incorporated than when phthalate esters were considered separately, and greater than their risk threshold. Therefore, the risks caused by substances and their metabolites in multiple media, with analogous structure-activity relationships, should be considered to ensure the safety of aquatic organisms and consumers.

Simultaneous determination and dietary intake risk assessment of 60 herbicide residues in aquatic products.

A sensitive and rugged analytical method was first established to simultaneously determine 60 herbicides in aquatic products with gas chromatography-tandem mass spectroscopy (GC-MS/MS). After extraction with acetonitrile (MeCN), NaCl and anhydrous Na2SO4 were added, concentrated supernatants were directly passed through the Carb/NH2 solid phase extraction column. Then, the cartridge was rinsed with elution solution (MeCN/toluene, 3:1, v/v), followed by GC-MS/MS analysis with multiple reaction monitoring. An excellent linearity (1.0-100.0 µg/L) with R2 value of ≥0.9991 was obtained, and the limits of quantification were 0.018-3.852 µg/kg. Satisfactory recoveries (70.8 %-117.6 %) with RSDs below 11.0 % of herbicide residues were obtained at spiked levels of 0.010-0.050 mg/kg. Furthermore, herbicide residues in actual aquatic products were analyzed, and the acute/chronic risk assessment of dietary exposure was carried out. The wide use of herbicides for controlling weed and removing moss and harmful algae may obviously increase the risk of contamination of the aquaculture environment and fishery products. Therefore, considerable attention and more research are necessary to monitor residue levels for herbicides in aquatic products and ensure the quality of marine products and consumer safety.

Occurrence, source, and ecological risk assessment of organochlorine pesticides and polychlorinated biphenyls in the water-sediment system of Hangzhou Bay and East China Sea.

The pollution characteristics, potential sources, and potential ecological risk of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were investigated in the Hangzhou Bay (HZB) and East China Sea (ECS). Total OCPs concentration ranged from 2.62 to 102.07 ng/L and 4.41 to 75.79 µg/kg in the seawater and sediment samples, with PCBs concentration in the range of 0.40-51.75 ng/L and 0.80-45.54 µg/kg, respectively. The OCPs were positively correlated with nutrients, whereas PCBs presented a negative correlation. The newly imported dichlorodiphenyltrichloroethane (DDT) in HZB is mainly the mixing of technical DDT and dicofol sources. The PCB source composition is more likely related to the mixture of Kanechlor 300, 400, Aroclor 1016, 1242, and Aroclor 1248. Risk assessment results indicate that OCPs posed low risk in seawater. The potential risk of DDTs in the sediments is a cause of concern.

Spatiotemporal occurrence, sources and risk assessment of polycyclic aromatic hydrocarbons in a typical mariculture ecosystem.

The spatiotemporal variations, influencing factors and potential sources, as well as the ecological/health risks of polycyclic aromatic hydrocarbons (PAHs) were systematically investigated in seawater, sediment, and fish from Xiangshan Bay, China, one of the most important and oldest domestic marine aquaculture bases. The average concentrations of ΣPAHs in seawater, sediment and fish were 150 ± 70.0 ng/L, 276 ± 271 µg/kg (dry weight, dw), and 434 ± 151 µg/kg (dw), respectively. Naphthalene, phenanthrene, fluoranthene, benzo(b)fluoranthene and pyrene were the dominant contaminants in all samples. The highest PAH concentrations in the seawater and sediment samples occurred in the inner bay where the mariculture and industry are clustered. Seasonal differences were observed in the seawater samples but not in the sediment samples. Among all 15 fish species, large yellow croaker (Larimichthys crocea) (775 µg/kg (dw)), red drum (Sciaenops ocellatus) (749 µg/kg (dw)), and flathead grey mullet (Mugil cephalus) (637 µg/kg (dw)) had relatively high PAH accumulation concentrations in muscle tissue. According to the molecular diagnostic ratio method, the PAHs in seawater mainly originated from a mixed source of petroleum and combustion, whereas biomass/coal combustion sources were identified for sediment. The results obtained from the risk quotient (for seawater), sediment quality guidelines and toxic equivalence quotients (for seawater and sediment) methods showed that the ecological risks posed by PAHs were generally at a low to moderate level. Potentially toxic effects existed from PAH-contaminated fish consumption, and the resulting potential carcinogenic risk was also slightly higher than the recommended guidelines (10-6).

Contaminant occurrence, mobility and ecological risk assessment of phthalate esters in the sediment-water system of the Hangzhou Bay.

The pollution characteristics, spatiotemporal variation, sediment-water partitioning, and potential ecological risk assessment of phthalate esters (PAEs) in the sediment-seawater system of the Hangzhou Bay (HZB) in summer and autumn were researched. The sum of the concentrations of the 10 PAEs in seawater ranges from 7305 ng/L to 22,861 ng/L in summer and from 8100 ng/L to 33,329 ng/L in autumn, with mean values of 15,567 ± 4390 and 17,884 ± 6850 ng/L, respectively. The Σ16PAEs in the sediments are between 118 and 5888 µg/kg and 145 and 4746 µg/kg in summer and autumn, respectively. The level of PAEs in seawater varies with the seasons, but it is relatively stable in the sediments. Di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DnBP), and diisobutyl phthalate (DiBP) are the predominant PAE congeners in the HZB. The DnBP and DiBP concentrations in seawater are greater than the DEHP concentration, which is the opposite in the sediments. The sediment-seawater equilibrium distribution study indicates that the PAEs with medium molecular weights, such as DiBP, butyl benzyl phthalate, and DnBP, are near dynamic equilibrium in the sediment-seawater system; PAEs with high molecular weights (e.g., di-n-octyl phthalate and DEHP) tend to transfer from water to the sediments; and PAEs with low molecular weights (e.g., dimethyl phthalate, diethyl phthalate, and diamyl phthalate) tend to spread to seawater. The risk assessment results in seawater indicate that DEHP and DiBP might pose high potential risks to sensitive organisms, and DnBP might exhibit medium ecological risks. In the sediment, DiBP might display a high potential risk to fish, and the potential risk of DEHP is high in several sites.

Highly-selective complex matrices removal via a modified QuEChERS for determination of triazine herbicide residues and risk assessment in bivalves.

A modified quick, easy, cheap, effective, rugged, and safe (QuEChERs) method for determining triazine herbicide residues in bivalves (Mussels, Scallops, Cockles) was developed. The use of molecularly imprinted polymers (MIPs) as a selective purification material during dispersive-solid phase extraction (d-SPE) increased the removal rate of pigments interference. With 4% acidic acetonitrile as the organic modifier, the modified QuEChERs method achieved good extraction rate of herbicide residues. The satisfactory recoveries (80%-118%) and RSDs (1.0%-11.6%) of herbicide residues were obtained at three spiked levels. The limits of quantification of herbicide residues ranged from 0.10 µg/kg to 1.59 µg/kg. Further, the herbicide residues in bivalves collected in the eastern coasts of China was analyzed. The developed QuEChERs procedure coupled with GC-MS/MS was successfully applied to the herbicide residues detection in bivalves, and due to the extensive use of herbicides and the large consumption of bivalves in globally, the ongoing risk evaluation is needed.

Phthalic acid esters in the sea-surface microlayer, seawater and sediments of the East China Sea: Spatiotemporal variation and ecological risk assessment.

The spatial and temporal distribution, congener profiles and ecological risk of phthalic acid esters (PAEs) were investigated in the seawater and sediment samples from the East China Sea in spring and autumn. The average concentrations of ΣPAEs in water samples were 3.16 ± 2.16 µg L-1 in autumn and 1.63 ± 1.20 µg L-1 in spring. The ΣPAEs in sediment was much higher than that in seawater, with an average value of 7.36 ± 6.70 mg kg-1 (dw). PAEs levels in the sea-surface microlayer (SML) in spring were 3.61 ± 3.36 µg L-1, indicating that the PAEs were noticeably concentrated in the SML, with an average enrichment factor of 2.10. Among the 16 PAE congeners, di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and di(2-ethylhexyl) phthalate (DEHP) were the preponderant PAEs in both sediment and seawater samples. Additionally, PAE concentrations in autumn were higher than those in spring, and this difference resulted mainly from the terrigenous input and marine transportation. The horizontal distributions of PAEs showed an opposite distribution pattern to salinity and temperature, a pattern which might be influenced by the inputs of fresh water. The vertical distributions of ΣPAEs were characterized by high concentrations in the surface waters, with a slight decrease with depth, and then an increase close to the seabed. The results of ecological risk in the water-phase showed that the level of potential risk followed the order of DEHP > DiBP and DnBP > DMP and DEP, which posed a high (DEHP), medium (DiBP and DnBP) and low (DMP and DEP) risk to the sensitive organisms, respectively. For the sediment-phase, DiBP and DnBP represented a high risk to the sensitive organisms, whereas DMP, DEP and DEHP had only a low risk.