Shuchun Yao

Historical trends of heavy metal contamination and their sources in lacustrine sediment from Xijiu Lake, Taihu Lake Catchment, China

Concentrations of Cd, Cr, Cu, Pb, Zn and Hg in Xijiu Lake sediment from the Taihu Lake catchment, China, were analyzed. Their contamination state was investigated based on the geoaccumulation index and enrichment factors. Statistical analysis was used to differentiate the anthropogenic versus natural sources of heavy metals (HMs), and the anthropogenic accumulation fluxes were calculated to quantify anthropogenic contribution to HMs. The results indicated that the lake sediment had been heavily contaminated by Cd, enrichment of Zn and Hg was at a relatively high level, while that of Cu and Pb was in the lower-to-moderate level and Cr was in the low enrichment level. Sources of Cr in the sediment were mainly from natural inputs, while other metals, especially Cd, were predominantly derived from anthropogenic sources. In the past century, anthropogenic accumulation fluxes of Pb, Zn and Hg increased by 0.1-47.3 mg/(cm2 x yr), 2.4-398.1 mg/(cm2 x yr), and 3.7-110.3 ng/(m2 x yr), respectively, accounting for most inputs of HMs entering the sediment. The contamination state of HMs varied with industrial development of the catchment, which demonstrated that contamination started in the early 20th century, reached the maximal level between the mid-1970s and mid-1990s, and decreased a little after the implementation of constraints on high contamination industries, although the contamination of some HMs, such as Cd, Zn and Hg, is still at high levels.

Environmental changes in Lake Taihu during the past century as recorded in sediment cores

The Lake Taihu drainage basin is an economically developed area with some of the highest population densities in China. The lake has deteriorated due to ecological destruction and eutrophication. Three short sediment cores from eastern, northeastern and southwestern Lake Taihu were collected. Total organic carbon (TOC), total nitrogen (TN), pigments, elements and particle size were analyzed for the purpose of understanding past trophic status and pollution levels. Sedimentation rates were based on 137Cs or 210Pb methods. Results indicated that sediment particle size became coarser since the 1920s, and the lake was contaminated by heavy metals, such as Cu and Zn, since the 1970s. A remarkable increase in eutrophication since the 1980s due to increased loading of untreated effluents from industry, agriculture and urbanization is reflected by total organic carbon, total nitrogen and pigments in the studied cores. However the onset times of eutrophication in different parts of Lake Taihu were not synchronous.

Speciation of organic phosphorus in a sediment profile of Lake Taihu. II. Molecular species and their depth attenuation.

The understanding of organic phosphorus (P) dynamics in sediments requires information on their species at the molecular level, but such information in sediment profiles is scarce. A sediment profile was selected from a large eutrophic lake, Lake Taihu (China), and organic P species in the sediments were detected using solution phosphorus-31 nuclear magnetic resonance spectroscopy (31P NMR) following extraction of the sediments with a mixture of 0.25 mol/L NaOH and 50 mmol/L EDTA (NaOH-EDTA) solution. The results showed that P in the NaOH-EDTA extracts was mainly composed of orthophosphate, orthophosphate monoesters, phospholipids, DNA, and pyrophosphate. Concentrations of the major organic P compound groups and pyrophosphate showed a decreasing trend with the increase of depth. Their half-life times varied from 3 to 27 years, following the order of orthophosphate monoesters > phospholipids > or = DNA > pyrophosphate. Principal component analysis revealed that the detected organic P species had binding phases similar to those of humic acid-associated organic P (NaOH-NRP(HA)), a labile organic P pool that tends to transform to recalcitrant organic P pools as the early diagenetic processes proceed. This demonstrated that the depth attenuation of the organic P species could be partly attributed to their increasing immobilization by the sediment solids, while their degradation rates should be significantly lower than what were suggested in previous studies.

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.

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.

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.

Spatial–temporal patterns of methane dynamics in Lake Taihu

Lakes are important source of atmospheric methane (CH4). Especially for large and shallow lakes, accurate CH4 emission budgets must consider the spatial and seasonal heterogeneity which characterize these ecosystems. CH4 concentrations in sediment and lake water and CH4 fluxes from sediment were analysed in selected open water areas of Lake Taihu, the third largest freshwater lake in China, to test the hypothesis that CH4 concentrations and fluxes differ both spatially and temporally in relation to biological and environmental features. The results showed that Lake Taihu was a source of CH4 throughout the year. The observed CH4 concentrations and fluxes were higher in the north-western and south-eastern areas of the lake, and lower in the central area. This spatial heterogeneity in methane emissions was mainly related to local organic matter content, plant characteristics, deposition rate and sediment features. Seasonally, CH4 showed stronger emissions in summer. These results suggest that the analysis of CH4 dynamics in shallow lakes should consider the habitat heterogeneity and the different sources of organic matter. Furthermore, the CH4 emission budget should at least include high and low temperature periods to decrease temporal bias.