Yuqiang Tao

Polycyclic aromatic hydrocarbons in surface sediments from drinking water sources of Taihu Lake, China: sources, partitioning and toxicological risk

Sources, partitioning and toxicological risk of 15 priority polycyclic aromatic hydrocarbons (PAHs) in surface sediments from drinking water sources of Taihu Lake, with an area of 2428 km(2) located in the most developed and populated area of China, were studied, and the results were compared with those in other lakes of China and the USA. Concentrations of the 15 PAHs in sediments ranged from 436.6 to 1334.9 ng g(-1) (dw). Gasoline combustion, coal combustion, diesel combustion from shipping and spillage of petroleum were apportioned to be the main sources of PAHs in this area by principal component analysis, which contributed 35.19%, 26.43%, 25.41% and 12.97% to the PAH sources estimated by further multiple linear regression. Levels of PAHs in sediments were negatively correlated with contents of clay and fine silt (<16 μm), while positively with contents of medium silt, coarse silt and sand (>16 μm). Humin with size larger than 16 μm contained the largest part of the burden of PAHs in sediments, but the specific partitioning domain (bound humic acid, lipid or insoluble residue) depended on properties of organic matter reflected by optical absorbance at 465 and 665 nm. Total toxic benzo[a]pyrene equivalent (TEQ(carc)) of the carcinogenic PAHs in sediments varied from 31.8 to 209.3 ngTEQ(carc) g(-1). Benzo[a]pyrene and dibenzo[a,h]anthracene contributed 45.36 and 25.31% to total TEQ(carc), posing high toxicological risk to this area.

Predicting bioavailability of PAHs in field-contaminated soils by passive sampling with triolein embedded cellulose acetate membranes

Triolein embedded cellulose acetate membrane (TECAM) was used for passive sampling of the fraction of naphthalene, phenanthrene, pyrene and benzo[a]pyrene in 18 field-contaminated soils. The sampling process of PAHs by TECAM fitted well with a first-order kinetics model and PAHs reached 95% of equilibrium in TECAM within 20 h. Concentrations of PAHs in TECAM (C(TECAM)) correlated well with the concentrations in soils (r(2)=0.693-0.962, p<0.001). Furthermore, concentrations of PAHs determined in the soil solution were very close to the values estimated by C(TECAM) and the partition coefficient between TECAM and water (K(TECAM-w)). After lipid normalization nearly 1:1 relationships were observed between PAH concentrations in TECAMs and earthworms exposed to the soils (r(2)=0.591-0.824, n=18, p<0.01). These results suggest that TECAM can be a useful tool to predict bioavailability of PAHs in field-contaminated soils.

Different effects of copper (II), cadmium (II) and phosphate on the sorption of phenanthrene on the biomass of cyanobacteria

Due to the large surface area and high organic carbon content of cyanobacteria, organic contaminants can be readily sorbed on cyanobacteria during algal blooms, and then be transferred to the food web. This process is likely to be affected by the coexisting metals and nutrients, however, the possible impacts remain unclear. Effects of Cu(2+), Cd(2+), and phosphate on the sorption of phenanthrene on cyanobacterial biomass collected from an algal bloom were therefore studied. Continuous decrease in phenanthrene sorption was observed in the presence of low concentrations of Cu(2+), and Cd(2+) (<0.04 mmol L(-1)), because Cu(2+) and Cd(2+) were coadsorbed with phenanthrene on the surface of cyanobacteria as suggested by scanning electron microscopy-energy dispersive X-ray (SEM-EDX) and Fourier transform infrared (FTIR) analyses. Phenanthrene sorption began to increase with the further increase in Cu(2+) concentration, but remained lower than that in the absence of Cu(2+). This increase in sorption was ascribed to the cation-π interaction between Cu(2+) and phenanthrene, as suggested by the enhanced ultraviolet absorbance at 251 nm. In contrast, sorption rebounding of phenanthrene did not occur in the presence of higher concentrations of Cd(2+). The different effects of Cu(2+) and Cd(2+) on phenanthrene sorption were attributed to that Cd(2+) required much more energy than Cu(2+) to form cation-π complexes with phenanthrene in the solutions. Phenanthrene sorption decreased continuously with the increase in phosphate concentration. Phosphate blocked the binding sites, modified the cell morphology, and increased the negative charge as well as the hydrophilicity of the cyanobacterial surface, thereby suppressing phenanthrene sorption. This study indicates that sorption of aromatic organic compounds by cyanobacteria could be significantly alerted by concentrations and properties of the coexisting transition metals and phosphates, which may subsequently affect their transfer to the food web in eutrophic waters.

Triolein Embedded Cellulose Acetate Membrane as a Tool to Evaluate Sequestration of PAHs in Lake Sediment Core at Large Temporal Scale

Although numerous studies have addressed sequestration of hydrophobic organic compounds (HOCs) in laboratory, little attention has been paid to its evaluation method in field at large temporal scale. A biomimetic tool, triolein embedded cellulose acetate membrane (TECAM), was therefore tested to evaluate sequestration of six PAHs with various hydrophobicity in a well-dated sediment core sampled from Nanyi Lake, China. Properties of sediment organic matter (OM) varying with aging time dominated the sequestration of PAHs in the sediment core. TECAM-sediment accumulation factors (MSAFs) of the PAHs declined with aging time, and significantly correlated with the corresponding biota-sediment accumulation factors (BSAFs) for gastropod (Bellamya aeruginosa) simultaneously incubated in the same sediment slices. Sequestration rates of the PAHs in the sediment core evaluated by TECAM were much lower than those obtained from laboratory study. The relationship between relative availability for TECAM (MSAF(t)/MSAF(0)) and aging time followed the first order exponential decay model. MSAF(t)/MSAF(0) was well-related to the minor changes of the properties of OM varying with aging time. Compared with chemical extraction, sequestration reflected by TECAM was much closer to that by B. aeruginosa. In contrast to B. aeruginosa, TECAM could avoid metabolism and the influences from feeding and other behaviors of organisms, and it is much easier to deploy and ready in laboratory. Hence TECAM provides an effective and convenient way to study sequestration of PAHs and probably other HOCs in field at large temporal scale.

Predicting bioavailability of PAHs in soils to wheat roots with triolein-embedded cellulose acetate membranes and comparison with chemical extraction.

Triolein-embedded cellulose acetate membrane (TECAM) was buried in 15 field-contaminated soils in parallel with the cultivation of wheat to predict bioavailability of naphthalene, phenanthrene, pyrene, and benzo[a]pyrene to wheat roots, and the method was compared with chemical extraction methods. Although a good linear relationship was found between PAH concentrations in chemical extractants and wheat roots, the percentage of PAH in soil removed by chemical extraction was much higher than the corresponding percentage removed by wheat roots. In contrast to chemical extraction, a nearly 1:1 relationship was found between the amount of each PAH taken up by TECAMs and wheat roots (r(2) = 0.798-0.925, P < 0.01). Furthermore, the uptake of PAHs by TECAMs and wheat roots had the same pathway of passive transport via the soil solution. Moreover, TECAM caused minimal disturbance to the soil and was easy to deploy. Therefore, TECAM is believed to be a useful tool to predict bioavailability of PAHs to wheat roots grown in contaminated soils.

Using Linoleic Acid Embedded Cellulose Acetate Membranes to in Situ Monitor Polycyclic Aromatic Hydrocarbons in Lakes and Predict Their Bioavailability to Submerged Macrophytes

To date no passive sampler has been used to predict bioavailability of contaminants to macrophytes. Here a novel passive sampler, linoleic acid embedded cellulose acetate membrane (LAECAM), was developed and used to in situ measure the freely dissolved concentrations of ten polycyclic aromatic hydrocarbons in the sediment porewaters and the water columns of two lakes in both winter and summer and predict their bioavailability to the shoots of resident submerged macrophytes (Potamogeton malainus, Myriophyllum spicata, Najas minor All., and Vallisneria natans (Lour.) Hara). PAH sampling by LAECAMs could reach equilibrium within 21 days. The influence of temperature on LAECAM-water partition coefficients was 0.0008-0.0116 log units/°C. The method of LAECAM was comparable with the active sampling methods of liquid-liquid extraction combined with fDOC adjustment, centrifugation/solid-phase extraction (SPE), and filtration/SPE but had several advantages. After lipid normalization, concentrations of the PAHs in LAECAMs were not significantly different from those in the macrophytes. In contrast, concentrations of the PAHs in the triolein containing passive sampler (TECAM) deployed simultaneously with LAECAM were much higher. The results suggest that linoleic acid is more suitable than triolein as the model lipid for passive samplers to predict bioavailability of PAHs to submerged macrophytes.

Effects of metals on the uptake of polycyclic aromatic hydrocarbons by the cyanobacterium Microcystis aeruginosa

Effects of Cu(2+), Zn(2+), Cd(2+), and Ag(+) on the uptake of phenanthrene, pyrene, and benzo[a]pyrene by Microcystis aeruginosa were investigated. A biomimic passive sampler, triolein embedded cellulose acetate membrane (TECAM) was used to help to study the related mechanisms. The facilitation effects of the metals on the uptake of the PAHs by M. aeruginosa increased with the softness order of the metals (Zn(2+)≈Cd(2+)<Cu(2+)<Ag(+)) and the π donor strength of the PAHs (phenanthrene<pyrene<benzo[a]pyrene). The cation-π interactions between Cu(2+), Ag(+) and the PAHs increased the freely dissolved concentrations of the PAHs, and consequently their uptake by M. aeruginosa. The increase in aromaticity of dissolved organic matter (DOM) caused by Cu(2+), and Ag(+) also enhanced the uptake of the PAHs. The facilitation effects of Cu(2+), and Ag(+) exceeded their toxic effects, uptake of the PAHs was thereby enhanced. In the presence of Zn(2+), and Cd(2+), no cation-π interactions between Zn(2+), Cd(2+) and the PAHs formed in solutions. Aromaticity of DOM was reduced, the diffusive mass transfer of the PAHs was not enhanced. Uptake of the PAHs was thereby reduced. This study suggests that uptake of PAHs by phytoplankton can be significantly influenced by the properties of both metals and PAHs, which will help to understand the fate and risks of PAHs in eutrophic waters co-contaminated with metals.

Influences of pH, heavy metals and phosphate and their co-influences on the sorption of pentachlorophenol on cyanobacterial biomass

Influences of pH, two types of ions of transition metals (Cu²⁺, Cd²⁺), Na₃PO₄ and their co-influences on the sorption of pentachlorophenol (PCP) on cyanobacterial biomass derived from natural bloom were studied. Sorption of PCP significantly decreases with pH in the range of 3.25-9.00. Although sorption coefficient of ionized PCP is 8.51 times lower than that of neutral species, it is the dominant species at environmentally relevant pH and contributes more to the total sorption of PCP. In the presence of low concentration of Cu²⁺ (≤ 40 μmol L⁻¹), sorption of PCP was much lower than that of the blank. However, it increased gradually with Cu²⁺, and overpassed the blank when concentration of Cu²⁺ was higher than 50 μmol L⁻¹. Compared with the sole influence of pH, coexisted Cu²⁺ inhibited the sorption of PCP at pH of 3.25 and 4.35, but enhanced it in the pH range of 5.00-9.00. In the presence of Cd²⁺, sorption of PCP first increased then decreased rapidly and finally increased slightly again with Cd²⁺. Except for at pH of 9.00, sorption of PCP at other pH in the presence of Cd²⁺ was much lower than that solely affected by pH. In the presence of Na₃PO₄, sorption of PCP increased rapidly then maintained with Na₃PO₄. Under the influence of both Na₃PO₄ and pH, sorption of PCP at pH from 3.25 to 5.00 was lower than that solely affected by pH, while it increased with pH in the range of 5.00-9.00 and was higher than that solely affected by pH in the range of 6.00-9.00. Ion pairs of pentachlorophenolate-metal facilitated the sorption of PCP, which was largely dependent on pH illustrated by UV-visible and FTIR spectra. Speciations of metals and PCP and the stability constants of ion pairs of pentachlorophenolate-metal greatly affected the sorption. Ionic strength also played an important role for the sorption of PCP.

Precipitation and temperature drive seasonal variation in bioaccumulation of polycyclic aromatic hydrocarbons in the planktonic food webs of a subtropical shallow eutrophic lake in China

Hydrophobic organic contaminants (HOCs) are toxic and ubiquitous in aquatic environments and pose great risks to aquatic organisms. Bioaccumulation by plankton is the first step for HOCs to enter aquatic food webs. Trophic status is considered to dominate variations in bioaccumulation of HOCs in plankton in temperate and frigid deep oligotrophic waters. However, long-term driving factors for bioaccumulation of HOCs in planktonic food webs of subtropical shallow eutrophic waters have not been well investigated. China has the largest subtropical lake density in the Northern Hemisphere. Due to limited field data, long-term variations in the bioaccumulation of HOCs in these lakes are almost unknown. Here we take Lake Xuanwu as an example to investigate long-term variations in the bioaccumulation, and biomagnification of polycyclic aromatic hydrocarbon (PAHs) in planktonic food webs of subtropical shallow eutrophic lakes in China, and elucidate the driving factors. Our results indicate that temperature rather than nutrients dominates long-term dynamics of planktonic biomass in this lake. Precipitation significantly enhances the concentrations of the PAHs, and total suspended particles, and consequently affects the distribution of the PAHs in the water column. Biomass dilution induced by temperature dominates bioaccumulation of the PAHs by both phytoplankton and zooplankton (copepods and cladocerans). Biomagnification of the PAHs from phytoplankton to zooplankton is positively correlated with temperature. Our study suggests that temperature and precipitation drive long-term variations in the bioaccumulation of the PAHs in the planktonic food webs of this subtropical shallow eutrophic lake. Lake Xuanwu has a similar mean annual temperature, annual precipitation, sunshine duration, and nutrient levels as other subtropical shallow eutrophic lakes in China. This study may also help to understand the bioaccumulation of HOCs in planktonic food webs of other subtropical shallow eutrophic lakes.

Effects of Heavy Metals on the Sorption of Polycyclic Aromatic Hydrocarbons by Microcystis aeruginosa

To date, little is known about the effects of heavy metals on the sorption of organic contaminants by phytoplankton. In this study, the effects of Cu, Cd, and Ag on the sorption of polycyclic aromatic hydrocarbons (PAHs) by were studied. Phenanthrene sorption was facilitated by low concentrations of metal salts (≤20 μmol L) and was significantly suppressed in the presence of 50 to 200 μmol L metal salts and rebounded and exceeded the control in the presence of 500 to 5000 μmol L Cu(NO) and AgNO, respectively. Although the ionic strengths of the solutions were the same, phenanthrene sorption was different in the presence of the same concentrations of Cu(NO) and Cd(NO) especially in the high concentration range. In the high concentration range, Ag was much more effective than Cu and Cd to increase phenanthrene sorption. In contrast to phenanthrene, sorption of both pyrene and benzo[a]pyrene increased dramatically in the presence of Cu(NO). The cation-π interactions between the metal cations and PAHs facilitated the sorption of the PAHs. Sorption enhancement of the PAHs caused by the cation-π interactions increased with the softness order of the metals (Cd < Cu < Ag) and the π donor strength order of the PAHs (phenanthrene < pyrene < benzo[a]pyrene). This study suggests that sorption of PAHs by cyanobacteria can be significantly altered by concentrations and properties of both heavy metals and PAHs.