Dustfall-bound polycyclic aromatic hydrocarbons (PAHs) over the fifth largest Chinese lake: residual levels, source apportionment, and correlations with suspended particulate matter (SPM)-bound PAHs in water.

Residual levels and temporal-spatial distribution characteristics of polycyclic aromatic hydrocarbons (PAHs) in dustfall were studied at the seasonal scale between June 2010 and May 2011 in the fifth largest shallow lake in China. PAHs flux of atmospheric deposition and the impact on the PAHs in the lake water column were estimated. The major sources of PAHs were identified by multiple methods. We found that (1) the seasonal residual levels of 16 priority controlled PAHs (PAH16) were spring (8.89 ± 3.93 µg g-1) > summer (6.68 ± 4.31 µg g-1) > winter (6.06 ± 2.95 µg g-1) > autumn (3.55 ± 2.21 µg g-1). (2) Significant positive correlations were found between the PAH levels in the dustfall and the suspended particle material (SPM) content, as well as between the deposition flux and the PAH content in the water in all four seasons. (3) Vehicle emissions, coal combustion, biomass combustion, and coke ovens were the four major sources in Lake Chaohu, accounting for 12.7%, 40.9%, 14.5%, and 31.9% of the total PAHs, respectively. (4) Compared to long-distance trajectories, short-distance trajectories played a more important role in the external sources of atmospheric PAHs in the region of Lake Chaohu.

Residual concentrations and ecological risks of neonicotinoid insecticides in the soils of tomato and cucumber greenhouses in Shouguang, Shandong Province, East China.

Neonicotinoid insecticides (NNIs) are the most widely used insecticides in China and worldwide. Continuous use of NNIs can lead to their accumulation in soil, causing potential ecological risks due to their relatively long half-life. We used liquid chromatography-tandem mass spectrometry (LC-MS/MS) to investigate the residual levels of nine neonicotinoids in greenhouse soils in Shouguang, East China, at different soil depths and with different crops (tomato and cucumber) after varying periods of cultivation. Seven neonicotinoids were detected in the soils of the tomato greenhouses and six were detected in the soils of the cucumber greenhouses, with total concentrations ranging from 0.731 to 11.383 µg kg-1 and 0.363 to 19.224 µg kg-1, respectively. In all samples, the neonicotinoid residues in the soils cultivated for 8-9 years were lower than in those cultivated for 2 years and 14-17 years. In the tomato greenhouse soils, the residual levels of NNIs were highest in the topsoil, with progressively lower concentrations found with depth. Under cucumber cultivation, the NNI residue levels were also highest in the topsoil but there was little difference between the middle and lower soil layers. Total organic carbon (TOC) decreased with soil depth while pH showed the opposite trend, showing a significant negative correlation in both types of soils (tomato soils ρ = -0.900, p = .001; cucumber soils ρ = -0.883, p = .002). Furthermore, TOC was significantly positively correlated, and pH was negatively correlated, with total NNI concentrations in both types of soils (TOC: tomato soils ρ = 0.800, p = .010; cucumber soils ρ = 0.881, p = .004; pH: tomato soils ρ = -0.850, p = .004; cucumber soils ρ = -0.643, p = .086). The results of an ecological risk analysis showed that acetamiprid represents a particularly high toxicity risk in these soils. Based on our analysis, NNI residues in the soils of tomato greenhouses and their associated ecological risks deserve more attention than those of cucumber greenhouse soils.

Impacts of anthropogenic activities on spatial variations of phthalate esters in water and suspended particulate matter from China's lakes.

In the largest developing country, China, plastic has become a serious environmental issue because of its overuse and non-treatment. In fact, plasticizers, such as phthalate esters (PAEs), are more toxic than plastic, and their global awareness is rising. To determine the response of sensitive PAE congeners to the anthropogenic activities in a typical lake ecosystem of China, in the present study, 12 PAEs in the water and the suspended particulate matter (SPM) phases of 46 lakes in China were measured. The concentrations of all the Σ12 PAEs in water and SPM phases ranged from 3.647 to 65.618 µg/L and 0.175 to 10.921 µg/L, respectively. Di-n-butyl phthalate (DnBP) was the predominant PAEs in the water phase, whereas diisobutyl phthalate (DIBP), DnBP, and bis(2-ethylhexyl) phthalate (DEHP) were the dominating PAEs in the SPM phase. Forty-six lakes were divided into four groups based on the anthropogenic activity intensities. The PAEs in both the water and SPM phases had increasing tendency along the human activity gradient. DIBP appears to be a sensitive PAE indicator that could distinguish the lake regions with different human industrial and agricultural activities. Dimethyl phthalate (DMP) and diethyl phthalate (DEP) are intensely affected by industrial development. DnBP and DEHP were positively correlated with agricultural activities, including the use of films and pesticides. It is suggested to control the addition and usage of PAEs in agricultural activities and improve their removal rates in industrial wastewater to reduce the PAE pollution in the water bodies in the environment management of China.

Influence of Cd exposure on H+ and Cd2+ fluxes in the leaf, stem and root of a novel aquatic hyperaccumulator - Microsorum pteropus.

Microsorum pteropus has been proven to be a potential novel aquatic Cd hyperaccumulator. In this study, Non-invasive Micro-test Technology (NMT) was used to observe the ion fluxes of different M. pteropus tissues under Cd exposure. M. pteropus can hyperaccumulate more than 1000 mg/kg Cd in roots and leaves and approximately 600 mg/kg Cd in stems after seven days of exposure to 500 µM Cd, showing that this plant have a great capacity for Cd enrichment and resistance. The NMT test found H+ fluxes increased in all tissues after Cd exposure, with the largest increases being observed in stems, followed by the leaves and roots. Cd2+ fluxes showed different accumulation levels in different tissues, with low-level Cd exposure leading to influxes into roots and leaves, and high-level Cd exposure resulting in effluxes from roots. No significant influxes or effluxes were observed in leaves under high-level Cd exposure, or in stems under low- and high-levels of Cd exposure. However, transient high-level Cd exposure showed long-term Cd2+ influxes into roots and short-term Cd2+ effluxes out of stems and leaves. The roots of M. pteropus had greater regulation mechanisms for Cd enrichment and resistance, with influxes occurring following low-level exposure and effluxes occurring from high-level exposure. When exposed to Cd, M. pteropus stems showed less transportation and absorption. Low-level Cd exposure resulted in individual leaves directly absorbing Cd from hydroponic solutions. Different Cd enrichment and resistance mechanisms were exhibited by different M. pteropus tissues.

Effects of pesticide residues on bacterial community diversity and structure in typical greenhouse soils with increasing cultivation years in Northern China.

The understanding of soil microbiome is important for sustainable cultivation, especially under greenhouse conditions. Here, we investigated the changes in soil pesticide residues and microbial diversity and community structure at different cultivation years under a greenhouse system. The 9-to-14 years sites were found to have the least diversity/rich microbial population as compared to sites under 8 years and over 16 years, as analyzed with alpha diversity index. In total, 42 bacterial phyla were identified across soils with different pesticide residues and cultivation ages. Proteobacteria, Acidobacteria, and Bacteroidetes represented the dominant phyla, that accounted for 34.2-43.4%, 9.7-19.3% and 9.2-16.5% of the total population, respectively. Our data prove that certain pesticides contribute to variation in soil microbial community and that soil bacteria respond differently to cultivation years under greenhouse conditions. Thus, this study provides an insight into microbial community structure changes by pesticides under greenhouse systems and natural biodegradation may have an important part in pesticides soil decontamination.

Comparisons of tissue distributions and health risks of perfluoroalkyl acids (PFAAs) in two fish species with different trophic levels from Lake Chaohu, China.

Perfluoroalkyl acids (PFAAs) are a type of persistent organic pollutants that are widely distributed in multiple environmental media and organisms and have a teratogenic effect on and toxicity to animals and humans. The residual levels of seventeen PFAAs in the tissues of two regular consumption fish species, Culter erythropterus and Aristichthys nobilis in Lake Chaohu were measured by a high-performance liquid chromatograph - mass spectrometer (HPLC-MS). The distributions of PFAAs and the effect of the lipid contents were analyzed, and the health risks of typical PFAAs were evaluated. The results showed that perfluorohexanoic acid (PFHxA) was the predominant contaminant (80.50 ±â€¯58.31 ng/g and 19.17 ±â€¯12.57 ng/g wet weight, ww), followed by perfluorooctanesulfonic acid (PFOS) (55.02 ±â€¯34.82 and 14.79 ±â€¯6.24 ng/g, ww) in both fish. The level of total PFAAs was the highest in the liver tissues of Culter erythropterus (359.87 ng/g, ww) and the lowest in the kidney tissues in A. nobilis (10.06 ng/g, ww). Due to the higher trophic level of C. erythropteru, the total PFAA concentrations were significantly higher in all tissues than those in A. nobilis. Liver muscle ratio of C. erythropteru was the highest, indicating the most accumulation in the liver. The concentrations of PFAAs in fish tissues were influenced by the lipid content, resulting in a difference between the lipid-normalized concentrations and the wet weight concentrations of the PFAAs. The non-carcinogenic risks of PFOS were higher than those of PFOA through the ingestion of C. erythropterus and A. nobilis. Both the carcinogenic and non-carcinogenic risks of C. erythropterus were greater than those of A. nobilis, and fish tissue intake could cause an increasing of risks up to 60%, indicating that long-term and large amount ingestion of carnivorous fish and related tissues with higher trophic level, such as C. erythropterus should be avoided.

Subcellular distribution of cadmium in a novel potential aquatic hyperaccumulator - Microsorum pteropus.

Microsorum pteropus is a novel potential Cd (cadmium) aquatic hyperaccumulator. In the present study, hydroponic experiments were conducted to assess the accumulation and subcellular distribution of Cd in the root, stem and leaf of M. pteropus. SEM (scanning electron microscopy) - EDX (energy dispersive X-ray fluorescence spectrometer) and TEM (transmission electron microscopy) were used to observe the ultrastructure of different tissues under 500 µM Cd exposure. After exposure to 500 µM Cd for 7 days, the root, stem and leaf of M. pteropus can accumulate to be > 400 mg/kg Cd in dry mass with no significant influence on the growth. In the root and leaf of M. pteropus, the Cd was more likely to store in the cell wall fraction. However, Cd in the stem was mainly stored in both the cell wall fraction and the cytoplasm fraction. Under SEM observation and EDX detection, 1) Cd was found to be sequestrated in the epidermis or chelated in the root cells, 2) no significant deposit spots were observed in the stem, 3) Cd was found in the trichome of the leaf, and the sporangium was not damaged. TEM observations revealed 1) possible Cd precipitations in the root cell and 2) no significant ultrastructure variation in the stem, and 3) the chloroplast retained its structure and was not affected by the Cd. M. pteropus showed great capacity for Cd accumulation without influencing growth. In addition, the ultrastructure of all the tissues was not damaged by the Cd. M. pteropus showed a great potential in phytoremediation in heavy metal polluted water solutions, and may provide new directions for the study of resistance mechanisms of aquatic hyperaccumulators.

Impact of organic matter and meteorological factors on the long-term trend, seasonality, and gas/particle partitioning behavior of atmospheric PBDEs.

We extended our knowledge of the impact of organic matter (OM) and meteorological factors on the long-term trend, seasonality and gas/particle partitioning behavior of polybrominated diphenyl ethers (PBDEs). In Lake Chaohu, PBDEs had an increasing trend, with a doubling time of 13.4 years at the urban site, and a decreasing trend, with a halving time of 6.1 years at the rural site. At the urban site, the negative association of OM with most congeners indicated that the graphene-like carbonaceous components might carry or release PBDEs, and the negative association of long-term rain fall and wind speed with most congeners was suggested to dilute or increase the transport speed of PBDEs in the atmosphere. At the rural site, the negative association with PM10 and positive association with OM indicated that the PBDEs-buried OM was mainly from non-local sources. Restricted to the temperature seasonality, the frequency of PBDE congeners decreased with seasonality from 64% and 43% to 50% and 43% at the urban and rural sites, respectively. The slope of the simplified Pankow adsorption model in samples with larger absolute OM content (>10 µgC m-3) was steeper than that with lower absolute OM content (<5 µgC m-3), indicating that OM facilitated the gas-particle partitioning equilibrium. Interestingly, the theoretic partitioning coefficients were much lower than the measured ones for less brominated BDEs, whereas the highly brominated BDEs did the opposite. The theoretic partitioning coefficient should be further modified by considering the molecular weight distribution of the OM and the corresponding activity coefficients of the target compound in a specific type of OM phase.

A general-applicable model for estimating the binding coefficient of organic pollutants with dissolved organic matter.

The binding constant (Kdoc) of organic pollutants (OPs) with dissolved organic matter (DOM) is an important parameter in determining the partitioning of OPs in the aquatic environment. Most estimation models have focused on calculating the Kdoc of a specific group of OPs but failed to obtain Kdoc values of different OPs effectively over the last three decades. In this study, we attempted to build a general-applicable Kdoc model based on various organic compounds' Kdoc values from the literature since 1973. Two multiple linear regression models, a DOM nonspecific model and an Aldrich HA model, were developed based on two solid and easy to access parameters-molecular connectivity indices (MCI) and polarity correction factors (PCF). In addition, the models' corresponding Kow-Kdoc models, which were mostly used in previous model studies, were developed for comparison. The adjusted determining coefficient (adj-R2) and standard error of the estimate (SEE) of the DOM nonspecific MCI-PCF-Kdoc model were 0.815 and 0.579, respectively, whereas the adj-R2 and SEE for the MCI-PCF-Kdoc model of Aldrich HA reached 0.907 and 0.438, respectively. The Aldrich HA model showed higher pertinence to the nonspecific model. Furthermore, both models exhibited better fit than the Kow-Kdoc models. The dipole moment modification attempts did not significantly improve either MCI-PCF-Kdoc models; hence, the two models were not altered with the dipole moment. The robustness tests by a Jackknifed method showed that the two MCI-PCF-Kdoc models exhibited higher robustness than the Kow-Kdoc. Of all of the OPs, the phenols contributed the most to their robustness. Furthermore, a sensitivity analysis showed that the two MCI-PCF-Kdoc models were sensitive to the robust parameters.

Effects of fluorescent dissolved organic matters (FDOMs) on perfluoroalkyl acids (PFAAs) in lake and river water.

This study presents the effects of fluorescent dissolved organic matters (FDOM) on perfluoroalkyl acids (PFAAs) in western Lake Chaohu and its inflow rivers. The surface water samples from the 27 sites in western Lake Chaohu and its inflow rivers were collected in March and September 2013. The contents of PFAAs and the FDOM in the water samples were measured by a high-performance liquid chromatograph - mass spectrometer (HPLC-MS) and by a fluorescence spectrophotometer, respectively. The temporal-spatial distributions of PFAAs and FDOM, as well as their interrelationships, were investigated. Eleven PFAA components were detected, and the mean concentration of total PFAAs (TPFAAs) in western Lake Chaohu and its inflow rivers were 12.93 ±â€¯5.19 ng/L and 11.84 ±â€¯9.50 ng/L, respectively. PFOA was the predominant contaminant in two regions (7.13 ±â€¯3.07 ng/L and 4.30 ±â€¯2.14 ng/L) followed by PFHxA (1.72 ±â€¯0.80 ng/L and 1.42 ±â€¯1.41 ng/L) and PFBA (1.44 ±â€¯0.78 ng/L and 1.37 ±â€¯0.78 ng/L). The mean concentration of total FDOM in western Lake Chaohu and its inflow rivers were 220.0 ±â€¯40.30 µg quinine sulfate units (Q.S.)/L and 406.3 ±â€¯213.1 µg Q.S./L, respectively. The significant, positive correlations were observed between the PFAAs and FDOMs in both the lake area and the inflow rivers. However, no significant correlation was observed between PFAAs and the dissolved organic carbon (DOC) in the lake area. This finding indicated that the residues and distributions of PFAAs were significantly dependent on the compositions of dissolved organic matters (DOM) and not on the total content of DOM.

Cadmium accumulation capacity and resistance strategies of a cadmium-hypertolerant fern - Microsorum fortunei.

Microsorum fortunei (M. fortunei), a close relative to the cadmium (Cd) hyperaccumulator Microsorum pteropus, is an epiphytic Polypodiaceae fern with strong antioxidant activity. The Cd-accumulation capacities and Cd-resistance mechanisms of M. fortunei were analyzed in this study by measuring metal contents (Cd, Fe, Mg, Ca, Zn, Mn, K and Na) and chlorophyll fluorescence parameters (Fv/Fm, qN, qP, Y(II), Y(NPQ) and Y(NO)) and by performing an RNA-sequencing analysis. M. fortunei could accumulate up to 2249.10 µg/g DW Cd in roots under a 15-day 1000 µmol/L Cd treatment, with little Cd translocated into the leaves (maximum 138.26 µg/g DW). The M. fortunei leaves could maintain their normal physiological functions with no phytosynthesis damage and few changes in metal contents or differentially expressed genes. M. fortunei roots showed a decrease in Zn concentration, with potential Cd-tolerance mechanisms such as heavy metal transporters, vesicle trafficking and fusion proteins, antioxidant systems, and primary metabolites like plant hormones, revealed by differentially expressed functional genes. In conclusion, M. fortunei may serve as a potential cadmium-hypertolerant fern that sequesters and detoxifies most cadmium in the roots, with a minimum root-to-shoot Cd translocation to guarantee the physiological functions in the more vulnerable leaves.

Differential expression of proteins in the leaves and roots of cadmium-stressed Microsorum pteropus, a novel potential aquatic cadmium hyperaccumulator.

Microsorum pteropus is a fully or partially submerged Polypodiaceae fern that has been proven to be a potential Cd aquatic hyperaccumulator. Proteomic analysis was used in this study to investigate the resistance mechanisms of M. pteropus root and leaf tissues under Cd stress. M. pteropus plants were exposed to up to 500 µM Cd in hydroponics for 7 days. The plant can accumulate >4,000 mg/kg Cd in both root and leaf dry mass. Meanwhile, the proteins in roots and leaves in the 500 µM Cd treatment were separated and analyzed by proteomics. Eight proteins with altered expression in roots and twenty proteins with altered expression in leaves were identified using MALDI-TOF/TOF-MS (matrix-assisted laser desorption/ionization time of flight mass spectrometry) in this study. The proteins were involved in energy metabolism, antioxidant activity, cellular metabolism and protein metabolism. However, just three proteins were significantly differentially expressed in both tissues, and they were all involved in basal metabolism, indicating different resistance mechanisms between roots and leaves. Root tissues of M. pteropus mainly resist Cd damage by antioxidants and the enhancement of energy metabolism, while leaf tissues of M. pteropus mainly protect themselves by maintaining photosynthetic functions and the regulation of cellular metabolism.

The spatial distribution of phosphorus and their correlations in surface sediments and pore water in Lake Chaohu, China.

The study presents the spatial distribution of different forms of phosphorus in the sediments in Lake Chaohu, a large eutrophic Chinese lake, and their correlation with phosphorus content in pore water. The sediment and pore water samples were taken from 19 sampling sites. A sequential extraction was used to determine the contents of different forms of phosphorus in the sediments. The compositions and spatial distribution of different forms of phosphorus in the sediments and their correlation with orthophosphate and total phosphorus content in the pore water were studied. The following results were obtained: (1) the mean content of total phosphorus was 474.7 ± 20.5 mg/kg, with 390.8 ± 82.4 mg/kg for the eastern lake (N = 5), 469.0 ± 53.9 mg/kg for the western lake (N = 5), and 524.5 ± 185.3 mg/kg for rivers (N = 9); (2) the order of the proportions of the different forms of phosphorus was occluded phosphorus (Oc-P, 52.4%) > debris phosphorus (De-P, 14.2%) > auto-calcium-bound phosphorus (ACa-P, 13.5%) > aluminum-bound phosphorus (Al-P, 9.8%) > organic phosphorus (Or-P, 6.8%) > exchangeable phosphorus (Ex-P, 2.1%) > iron-bound phosphorus (Fe-P, 1.3%); (3) Ex-P, Al-P, and Fe-P had significantly positive correlations with orthophosphate and total phosphorus content in pore water, which showed that these forms of phosphorus were released more easily and had an indirect impact on lake eutrophication.

Comparisons of cadmium bioaccumulation potentials and resistance physiology of Microsorum pteropus and Echinodorus grisebachii.

To better monitor and remediate environments contaminated by cadmium (Cd), plants are used as hyperaccumulators or biomonitors; however, few have been identified for aquatic Cd pollution. In our study, two aquatic ornamental plants, Microsorum pteropus (Blume) Copel. and Echinodorus grisebachii Small, were studied for their Cd accumulation capacity, morphological characteristics, and leaf physiological indexes. Microsorum pteropus (Blume) Copel. leaf has the potential to hyperaccumulate Cd (166 mg/kg dry weight for 1 mg/L exposure), with no significant physiological difference under exposure. Echinodorus grisebachii Small had sensitive diagnostic responses to Cd toxicity, such as significant decreases in Chl (a + b) and Chl-a/b, increased peroxidase (POD) activity, greater malondialdehyde (MDA) content, and increased soluble sugar content. These results suggest that Microsorum pteropus (Blume) Copel. could have the potential to be a Cd hyperaccumulator, while Echinodorus grisebachii Small could serve as a biomonitor for Cd-contaminated water bodies.

Resistance mechanisms and their difference between the root and leaf of Microsorum pteropus - A novel potential aquatic cadmium hyperaccumulator.

Microsorum pteropus (M. pteropus), an aquatic Polypodiaceae fern, was identified as a novel potential cadmium (Cd) hyperaccumulator in our previous study. This study reveals the Cd-resistance mechanisms and their difference between the root and leaf of M. pteropus based on analyses of photosynthesis, antioxidant systems and gene expression. A high level of Cd at 500µM was used to treat the samples to test the effects of this compound. Superoxide dismutase (SOD), peroxidase (POD), malondialdehyde (MDA) and flavonoids were used as indicators for antioxidant system changes. Five chlorophyll fluorescent parameters including the maximal photochemical efficiency of photosystem II (Fv/Fm), effective quantum yield of photosystem II (Y(II)), photochemical quenching (qP), nonphotochemical quenching (qN) and electron transport rate (ETR) were measured to determine the photosynthetic changes. RNA-sequencing analysis was used to study the changes in gene expression. The results showed that after exposure to high levels of Cd, the concentrations of enzymatic oxidants (SOD and POD) were significantly increased, while the MDA levels were significantly decreased. There were no significant changes for the chlorophyll fluorescent parameters during Cd stress, which indicates that M. pteropus is highly effective at protecting itself. Certain functional genes, including photosystem genes and secondary metabolites, had significantly altered levels of expression. Different Cd-resistance mechanisms were found between the root and leaf tissues of M. pteropus. The root tissues of M. pteropus resist Cd damage using antioxidants, while its leaf tissues mainly protect themselves using photosystem self-protection.

Bias and association of sediment organic matter source apportionment indicators: A case study in a eutrophic Lake Chaohu, China.

The sources of sediment organic matter (SOM) could be explained by various indicators. To test their biases and associations, the present study determined multiple indicators for SOM source apportionment, including elemental analysis (carbon and nitrogen, and their stable isotope δ13C and δ15N), n-alkanes compositions as well as derivative indicators (e.g., terrigenous to aquatic ratio), and carbon isotopes of n-alkane in Lake Chaohu, a eutrophic lake. The spatial variation of anthropogenic effects could be revealed by SOM elemental variations. The n-alkanes of all samples had a bimodal distribution with the 1st peak at n-alkane with 17 carbons (C17) and the 2nd predominant peak at C29. The parity advantage index of n-alkanes indicated that the sediments had mixed characteristics of both endogenous and terrigenous sources. Some n-alkanes indicators also revealed eutrophication characteristics of dominant algae in Lake Chaohu. SOM received a mixed contribution of plankton (I), low-latitude terrestrial high-grade plants (II) and microbial material (III) as indicated by isotopic compositions of long-chain n-alkane. Multiport element model (MEM) showed the contribution of self-generated sources of organic matter in Lake Chaohu is >50%, indicating the historic serious eutrophication in Lake Chaohu. The main sources of SOM in the eastern part of the lake were algae and terrestrial input, with little input from microbes, and the contribution from algae decreased from west to east. The multiple indicators' judgment by MEM and principle component analysis (PCA) was of ecological significance and proposed because they offered scientific tools for disclosing the historic variations of SOM as well as their sources.

Current status and historical variations of DDT-related contaminants in the sediments of Lake Chaohu in China and their influencing factors.

The temporal-spatial distributions of DDT-related contaminants (DDXs), including DDT (dichlorodiphenyltrichloroethane), DDE (dichlorodiphenyldichloroethylene) and DDD (dichlorodiphenyldichloroethane), in the sediments of Lake Chaohu and their influencing factors were studied. p,p-DDE and p,p-DDD were found to be the two dominant components of DDXs in both surface and core sediments. The parent DDT compounds were still detectable in sediment cores after the late 1930s. Historical usage of technical DDT was identified as the primary source of DDXs in sediments, as indicated by DDT/(DDD + DDE) ratios of less than one. The residual levels of DDXs were higher in the surface and core sediments in the western lake area than in other lake areas, which might be due to the combined inflow effects of municipal sewage, industrial wastewater and agricultural runoff. The DDX residues in the sediment cores reached peak values in the late 1970s or early 1980s. There were significant positive relationships between DDX residues in sediment cores with annual DDT production and with fine particulate sizes (<4.5 µm). The relationship between the DDXs and TOC in sediment was complex, as indicated by the significant differences among the surface and core sediments. The algae-derived organic matter significantly influenced the amount of residue, composition and distribution of DDXs in the sediments. The DDD/DDE ratios responded well to the anaerobic conditions in the sediments that were caused by algal blooms after the late 1970s in the western lake area. This suggests that the algae-derived organic matter was an important factor and served as a biomarker of eutrophication and also affected the DDX residues and lifecycle in the lake ecosystem.

Occurrence, spatial distribution, sources, and risks of polychlorinated biphenyls and heavy metals in surface sediments from a large eutrophic Chinese lake (Lake Chaohu).

Surface sediment from large and eutrophic Lake Chaohu was investigated to determine the occurrence, spatial distribution, sources, and risks of polychlorinated biphenyls (PCBs) and heavy metals in one of the five biggest freshwater lakes in China. Total concentration of PCBs (Σ34PCBs) in Lake Chaohu was 672 pg g(-1) dry weight (dw), with a range of 7 to 3999 pg g(-1) dw, which was lower than other water bodies worldwide. The majority of heavy metals were detected at all sampling locations, except for Sr, B, and In. Concentrations of Al, Fe, Ca, Mn, Sr, Co, Zn, Cd, Pb, and Hg were similar to that reported for other lakes globally. Concentrations of K, Mg, Na, Li, Ga, and Ag were greater than the average, whereas those of Cr, Ni, and Cu were lower. Cluster analysis (CA) and positive matrix factorization (PMF) yielded accordant results for the source apportionment of PCBs. The technical PCBs and microbial degradation accounted for 34.2 % and 65.8 % of total PCBs using PMF, and PMF revealed that natural and anthropogenic sources of heavy metals accounted for 38.1 % and 61.8 %, respectively. CA indicated that some toxic heavy metals (e.g., Cd, In, Tl, and Hg) were associated with Ca-Na-Mg minerals rather than Fe-Mn minerals. The uncorrelated results between organic matter revealed by pyrolysis technology and heavy metals might be caused by the existence of competitive adsorption between organic matter and minerals. PCBs and heavy metals were coupling discharge without organochlorine pesticides (OCPs), but with polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers (PBDEs). No sediment sample exceeded the toxic threshold for dioxin-like PCBs (dl-PCBs) set at 20 pg toxicity equivalency quantity (TEQ) g(-1), (max dl-PCBs, 10.9 pg TEQ g(-1)). However, concentrations of Ag, Cd, and Hg were at levels of environmental concern. The sediment in the drinking water source area (DWSA) was threatened by heavy metals from other areas, and some fundamental solutions were proposed to protect the DWSA.

Current status and historical variations of phthalate ester (PAE) contamination in the sediments from a large Chinese lake (Lake Chaohu).

The residual levels of phthalate esters (PAEs) in the surface and two core sediments from Lake Chaohu were measured with a gas chromatograph-mass spectrometer (GC-MS). The temporal-spatial distributions, compositions of PAEs, and their effecting factors were investigated. The results indicated that di-n-butyl phthalate (DnBP), diisobutyl phthalate (DIBP), and di(2-ethylhexyl) phthalate (DEHP) were three dominant PAE components in both the surface and core sediments. The residual level of total detected PAEs (∑PAEs) in the surface sediments (2.146 ± 2.255 µg/g dw) was lower than that in the western core sediments (10.615 ± 9.733 µg/g) and in the eastern core sediments (5.109 ± 4.741 µg/g). The average content of ∑PAEs in the surface sediments from the inflow rivers (4.128 ± 1.738 µg/g dw) was an order of magnitude higher than those from the lake (0.323 ± 0.093 µg/g dw), and there were similar PAE compositions between the lake and inflow rivers. This finding means that there were important effects of PAE input from the inflow rivers on the compositions and distributions of PAEs in the surface sediments. An increasing trend was found for the residual levels of ΣPAEs, DnBP, and DIBP from the bottom to the surface in both the western and eastern core sediments. Increasing PAE usage with the population growth, urbanization, and industrial and agricultural development in Lake Chaohu watershed would result in the increasing production of PAEs and their resulting presence in the sediments. The significant positive relationships were also found between the PAE contents and the percentage of sand particles, as well as TOC contents in the sediment cores.

Influences of binding to dissolved organic matter on hydrophobic organic compounds in a multi-contaminant system: Coefficients, mechanisms and ecological risks.

The complexation flocculation (CF) method was successfully employed to identify binding coefficients (Kdoc) of specific organic contaminants to dissolved organic matter (DOM, often indicated by dissolved organic carbon, DOC) in a multi-contaminant hydrophobic organic contaminant (HOC) system. Kdoc values were obtained for most of the evaluated 33 HOCs, indicating the feasibility and applicability of the CF method in a multi-contaminant system. Significant positive correlations were observed between binding coefficients and octanol-water partition coefficients (Kow) for organic halogen compounds, such as polybrominated diphenyl ethers (PBDEs) (R(2) = 0.95, p < 0.05) and organic chlorine pesticides (OCPs) (methoxychlor excluded, R(2) = 0.82, p < 0.05). The positive correlations identified between the lgKdoc and lgBCF (bioconcentration factor) for PBDEs and OCPs, as well as the negative correlation observed for polycyclic aromatic hydrocarbons (PAHs), indicated that different binding or partition mechanisms between PAHs and organic halogen compounds exist. These differences further result in discriminative competition partitions of HOCs between DOM and organisms. Assuming that only freely dissolved HOCs are bioconcentrative, the results of DOM-influenced bioconcentration factor (BCFDOM) and DOM-influenced lowest observed effect level (LOELDOM) indicate that the ecological risk of HOCs is decreased by DOM.