Occurrence, sources, and ecological risks of three classes of insecticides in sediments of the Liaohe River basin, China.

The frequent and extensive use of insecticides has caused serious aquatic pollution, thus posing a great threat to ecosystems and public health. In this study, three classes of insecticides including 20 organochlorine pesticides (OCPs), 6 organophosphorus pesticides (OPs), and 8 pyrethroids were analyzed in 24 sediments from the Liaohe River basin. The results showed that all sediment samples were contaminated with insecticides, with the total concentrations ranging from 7.3 ng/g dry weight (dw) to 242.8 ng/g dw. Among them, pyrethroids (2.2-102.5 ng/g dw) contributed 55% of the total insecticide concentration, followed by OCPs (1.3-94.8 ng/g dw) and OPs (2.6-45.5 ng/g dw), representing 24% and 21% of the total concentrations, respectively. For OCPs, hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) showed the highest concentrations of 0.37-37.5 ng/g dw and 0.05-23.2 ng/g dw, respectively. Historical inputs of lindane and technical DDT were the major sources of HCHs and DDTs, respectively, as indicated by isomer or metabolite ratios. Additionally, dichlorvos (0.26-17.1 ng/g dw) was the main OP, while cypermethrin dominated the pyrethroids with the concentrations of 1.6-32.6 ng/g dw. The spatial distribution revealed that significantly higher residues of insecticides were observed in sediments from the Daliao River system than those from the Liao River. This implied that these insecticides were most likely from the discharge of highly polluted sewage and industrial wastewater from adjacent industrial and populous cities as well as urban applications (e.g., landscape maintenance and household pest control). An ecological risk assessment based on risk quotients suggested that the three classes of insecticides analyzed here pose a low risk to aquatic organisms in the study area.

[Levels, Characteristics, and Potential Source of Micro(meso)plastic Pollution of Soil in Liaohe River Basin].

With the Liaohe River basin as the research object, the morphology, abundance, and distribution characteristics of micro(meso) plastics of soil in Liaohe River basin were studied based on the density flotation principle and the technique of stereo microscope and micro-FTIR and the significant factors affecting the distribution of the micro(meso)plastics and their potential sources were reasonably speculated. The results indicated that the average abundance of the soil micro(meso)plastic is (145.83±211.46) n·kg-1. The most abundant types of micro(meso)plastics are debris (46.00%), <1000 µm (39.57%), PP (41.71%), and white (46.86%). Among them, Rayon, PES, and PET micro(meso)plastics are primarily in the shape of fibrous (>85%), PE is mostly in the shape of film and fragments (96.91%), PP is mainly in the shape of fragments (85.62%), and PS is primarily in the shape of foam. Industrial activities (express delivery companies, plastic factories, and clothing factories), agricultural activities (plastic mulch, sewage irrigation, and sludge composting), population density, and sewage treatment plants, etc, may lead to higher levels of micro(meso)plastic abundance in the soil of the study area. Plastic products (pesticide bottles, chemical fertilizer packaging bags, woven bags, and plastic agricultural films), sewage discharge and irrigation, and foam materials used for packaging and decoration are the potential sources of soil micro(meso)plastic in the region.

Responses of landscape structure to the ecological restoration programs in the farming-pastoral ecotone of Northern China.

Ecological restoration programs (ERPs) have been conducted in China since 2000 to improve ecological conditions, particularly in the farming-pastoral ecotone of Northern China. Few have studied the effects of ERPs on landscape structure. Taking West Liaohe River Basin (WLRB) as a case study, we explored how landscape dynamics were altered before and after ERPs from 1990 through 2015 by using multi-temporal Landsat TM images. We analyzed the effects of ERPs on landscape structure by exploring the relationships between landscape features and land cover change (LCC). The results indicate that dramatic changes in land cover and landscape structure occurred before and after ERPs implementation. During 2000-2015 woodlands increased with a sharper annual growth, grasslands reclamation slowed down and was restricted, whereas more croplands were converted to grasslands and woodlands. ERPs decreased landscape fragmentation and increased landscape diversity, due mostly to the portion and spatial configures of croplands, grasslands and woodlands. Landscape fragmentation was significantly correlated with mean patch size of grasslands (r = -0.677, p < 0.0001) and woodlands (r = -0.515, p < 0.0001), as well as patch number ratio of croplands to the sum of grasslands and woodlands (r = -0.414, p < 0.01). Additionally, landscape diversity had a significant negative correlation with the areal ratio of grasslands (r = -0.345, p < 0.001). Our findings indicate that the LCCs were in agreement with ERPs' key goals. The changes in landscape structure in WLRB, however, were not expected from the ERPs design. Given the importance of landscape structure in human vulnerability to environment, it seemed that EPRs from the central government should not only regulate specific land use but also focus on the health and sustainability of the landscapes. Explicit function-based local landscape management should be taken into account for the future through better design and implementations of ERPs.

[Occurrence, Distribution, and Ecological Risk of Antibiotics in Surface Water in the Liaohe River Basin, China].

The pollution and ecological risk characteristics of five typical antibiotics found in the surface water of the Liaohe River Basin (LRB) were analyzed and evaluated using solid-phase extraction and high-performance liquid chromatography tandem mass spectrometry. These results showed that macrolides have the highest average concentration of all antibiotics in the surface water of the LRB of 201.88 ng·L-1, followed by quinolones, trimethoprim, and sulfonamides with average concentrations of 113.40 ng·L-1, 93.93 ng·L-1, and 124.27 ng·L-1, respectively. Tetracycline demonstrated the lowest concentration at 24.37 ng·L-1. In addition, antibiotics pollution of the Daliao River is clearly identified as being higher than that of the Liaohe River, and the highest proportion of antibiotic pollution (49.1%) is found to come from human use according to a source apportionme0nt analysis. Relatively high levels of ecological risk are identified from Trimethoprim and Erythromycin-H2O concentrations, especially for cities such as Xinmin, Shenyang, and Anshan. The risk assessment indicates that surface water of the LRB faces high ecological risk and argues for greater attention to be paid to risk management and pollution controls.

Hexabromocyclododecane and tetrabromobisphenol A in sediments and paddy soils from Liaohe River Basin, China: Levels, distribution and mass inventory.

Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are two kinds of brominated flame retardants and widely present in the environment and biota. The levels, spatial distributions and mass inventories of HBCD and TBBPA were investigated in sediments and paddy soils from the Liaohe River Basin in northeast China. The concentrations of ΣHBCD and TBBPA were in the range of not detected (nd) to 4.02ng/g dry weight (dw) and 0.03 to 4.06ng/g dw, respectively. γ-HBCD was dominated in sediments, while the abundance of α-HBCD was relatively high in paddy soils. The spatial distributions of HBCD and TBBPA in surface sediments and paddy soils indicated that the local point-input was their major source. The significant correlation between total organic carbon (TOC) contents and the HBCD levels suggested that TOC content also exerted an influence on the distribution of HBCD in sediments. Meanwhile, it was found that the irrigation with river water was not the major transportation pathway of HBCD and TBBPA in paddy soils. Based on the study, it was estimated that there were about 1.67tons HBCD and 2.20tons TBBPA deposited into sediments of the Liaohe River system every year. The total mass inventories of HBCD and TBBPA in sediments were far higher than that in paddy soils.

Occurrence and bioaccumulation of polybrominated diphenyl ethers in sediments and paddy ecosystems of Liaohe River Basin, northeast China.

Concentrations of 16 polybrominated diphenyl ether (PBDE) congeners were measured in river sediments, paddy soils and three species of paddy-field organisms (crab, loach and carp) collected from the Liaohe River Basin, northeastern China. The total contents of PBDEs (∑16PBDEs) in sediments and paddy soils were in the ranges of 273.4-3246.3pg/g dry weight (dw), and 192.1-1783.8pg/gdw, respectively. BDE 209 was the dominant congener both in sediments and paddy soils. The concentrations of ∑16PBDEs in sediments were significantly higher than those in the adjacent paddy soils, indicating a potential transport of PBDEs from river to paddy ecosystems via river water irrigation. The biota-soil accumulation factor (BSAF) was calculated as the ratio between the lipid-normalized concentration in paddy-field organisms and the total organic carbon-normalized concentration in paddy soil. The average BSAF values of ∑15PBDEs followed the sequence of crab (3.6)>loach (3.3)>carp (2.1). BDE 154 had the highest BSAF value, and a parabolic trend between BSAF values of individual PBDE congeners and their logKOW values was observed. In view of the fact that crab had the larger BSAF value and higher lipid content, the ecological risk and health risk for crab cultivation in paddy fields should be of particular concern.

Spatial distribution and potential toxicity of polycyclic aromatic hydrocarbons in sediments from Liaohe River Basin, China.

The distribution and potential toxicity of polycyclic aromatic hydrocarbons (PAHs) in the sediments of Liaohe River Basin were investigated in this study. Total concentrations of 16 PAHs (∑PAH16) ranged from 82.5 to 25374.4 µg/kg averaging 3149.2 µg/kg. Three predominant PAHs were fluoranthene, phenanthrene, and pyrene. In Liao River, two-to-three-ring PAHs were dominant taking up 67.2-92.5% of ∑PAH16, whereas sediments in Daliao River system mainly contained four-to-six-ring PAHs ranging from 47.8 to 83.7%. Both petrogenic and pyrogenic sources contributed to the PAH pollution based on diagnostic ratios. The empirical and mechanistic sediment quality guidelines were used to estimate the toxicity risk of PAHs to benthic organisms. The ∑PAH16 in all sediments were significantly lower than probable effect concentrations (PEC), while ∑PAH16 at nine sites of the Daliao River system were between threshold effect concentrations (TEC) and PEC, suggesting that adverse effects were possible at the nine sites. The only individual PAH was acenaphthene whose concentrations were above PEC at some sites, indicating its potential toxicity. Based upon equilibrium partitioning theory and narcosis model, the obtained toxic units for PAH mixtures at all sites were far less than one, implying that the levels of PAH mixtures were acceptable for the protection of benthic fauna. The two evaluation methods lead to the consistent results that benthic organisms inhabiting in the sediments of Liaohe River Basin have no or low risk of adverse effects resulting from exposure to PAHs.

Concentrations and distributions of 18 organochlorine pesticides listed in the Stockholm Convention in surface sediments from the Liaohe River basin, China.

Organochlorine pesticides (OCPs) were analyzed in 26 surface sediment samples from the Liaohe River basin, and the distributions of and potential environmental risks posed by OCPs in the basin were evaluated. Eighteen OCPs listed in the Stockholm Convention were determined using isotope-dilution gas chromatography-high resolution mass spectrometry. This is the first study of hexachlorobenzene (HCB) in the Liaohe River basin sediments. The total OCP concentrations were 0.39-68.06 ng g(-1) dry weight. The total α-, ß-, γ-, and δ-hexachlorocyclohexane (HCH), the total dichlorodiphenyltrichloroethane (DDT - p,p'-dichlorodiphenyldichloroethane (DDD), p,p'-dichlorodiphenyldichloroethylene (DDE), o,p(')-DDT, and p,p'-DDT), and the HCB concentrations in the sediment samples were 0.1-28.48 ng g(-1) (mean 4.01 ng g(-1)), 0.08-6.52 ng g(-1) (mean 3.07 ng g(-1)), and 0.18-24.8 ng g(-1) (mean 4.38 ng g(-1)), respectively. The HCB concentrations were higher than the concentrations of the other OCPs, and the HCHs and HCB together were the dominant OCPs. ß-HCH was the most abundant HCH isomer. The concentrations of DDTs and other OCPs were relatively low, and the (DDE+DDD)/DDT ratios (>0.5) and DDD/DDE ratios (<1) indicated that no recent DDT inputs had occurred in the Liaohe River system. The main sources of HCHs were probably the historical production and agricultural use of HCH in the study area. The DDT and HCH concentrations were generally below or similar to the concentrations that have been found in other parts of the world. An ecotoxicological evaluation indicated that HCHs in surface sediments pose slight risks to human and ecological health in the Liaohe River basin.