Risk assessment of heavy metal and pesticide mixtures in aquatic biota using the DGT technique in sediments.

Heavy metals and pesticides (HMPs) are common contaminants due to their extensive use worldwide. Diffusive gradients in thin films (DGT) are a good method for measuring the bioavailable concentration of pollutants. This study represents the first evaluation of HMP toxicity in aquatic biota using the DGT technique in sediments. Zhelin Bay was selected as the case study site because it has been contaminated by pollutants. Nonmetric multidimensional scaling (NMS) analysis reveals that a diverse range of pollutants (V, Cr, Ni, Cu, Zn, As, Se, InHg, Mo, Cd, Sb, W, Pb, CLP, PYR) are mainly influenced by sediment characteristics. Assessment of single HMP toxicity found that the risk quotient (RQ) values for Mn, Cu, inorganic Hg (InHg), chlorpyrifos (CLP) and diuron (DIU) are significantly higher than 1, indicating that the adverse effects of these single HMPs should not be ignored. The combined toxicity of HMP mixtures based on probabilistic ecotoxicological risk assessment shows that Zhelin Bay surface sediments had a medium probability (54.6%) of toxic effects to aquatic biota.

Study on temporal and spatial differentiation of biocapacity in Shenyang from a multi-scale perspective.

Biocapacity of a region exhibits spatial differences owing to the limitations of regional scale and natural conditions. Based on the multi-scale perspective, we comprehensively studied and analyzed the temporal and spatial differences of the biocapacity of a region in an attempt to establish the groundwork for optimizing urban development and its utilization framework. By adopting the ecological footprint model along with multi-scale difference evaluation method, the municipal and county scales are incorporated into a unified analysis framework in this paper, thereby facilitating the exploration of the temporal and spatial differences in the biocapacity of Shenyang-a city in China-from 2005 to 2019. The results demonstrated that: 1) At the municipal scale, the biocapacity per capita fluctuated between 1.35 hm2/person and 2.22 hm2/person. It revealed an "up-down-up" trend, which appeared consistent with the Kuznets cycle; at the county scale, the biocapacity depicted spatial differences, while those of downtown and surrounding districts/counties developed a two-level ascending hierarchical structure. 2) The time series of footprint size and depth first ascended and then declined, and can be classified into four types: closed type, inverted U-type, S-type, and M-type. Among them, S-type and M-type have the phenomenon of over-utilizing the stock capital. 3) For a long time, the regional difference of biocapacity has mostly dwelt on two scales with an evident scale effect, and the biocapacity of Liaozhong District was the worst.

Photochemical degradation of fragrance ingredient benzyl formate in water: Mechanism and toxicity assessment.

Recently, fragrance ingredients have attracted increasing attention due to their imperceptible risks accompanying the comfortable feeling. To understand transformation mechanisms and toxicity evolution of benzyl formate (BF) in environment, its photochemical degradation in water was thoroughly studied herein. Results showed that 83.5% BF was degraded under ultraviolet (UV) irradiation for 30 min. Laser flash photolysis and quenching experiments demonstrated that triplet excited state (3BF*), O2•-, and 1O2 were three main reactive species found during BF photodegradation. Eight degradation intermediates, including benzaldehyde, benzyl alcohol, o-cresol, bibenzyl, benzyl ether, 1,2-diphenylethanol, benzoic acid, and benzylhemiformal, were mainly formed as identified by LC-Q-TOF/MS and GC-MS analyses. Furthermore, the degradation mechanism was explained as the bond cleavage of 3BF* and BF•+, O2•-/1O2 oxidation, eaq- reduction, and •OH addition reactions. Aquatic assessment suggests that except benzyl alcohol, benzoic acid, and benzylhemiformal, all the products were persistent and could result in increased aquatic toxicity compared to original BF. Consequently, these degradation products may cause more toxicity to organisms if they remain accumulated in water environment for a long time.

Study on the coupling relationship between urban resilience and urbanization quality-A case study of 14 cities of Liaoning Province in China.

In this paper, entropy, coupling coordination degree, spatial auto-analysis, LISA time path, and other methods have been used to analyze the coupling coordination degree of urban resilience and urbanization quality of 14 cities in Liaoning Province from 2009 to 2019. The results show that: 1. The number of highly resilient cities accounts for 14.3% of the total number of cities in Liaoning Province, and the overall resilience degree is low; the spatial distribution shrinks along the Shenyang-Dalian Economic Belt toward both sides, with obvious "core-margin" characteristics. 2. The average score of urbanization quality increased from 0.0574 to 0.0966, showing a fluctuating upward trend; the regional difference was significant, and the "dual-core" characteristic was prominent. 3. During the study period, the 14 cities of Liaoning Province were in a state of imbalance, and there was a positive correlation between the coupling degree and the coordination degree. Moran's I decreased from 0.237 to 0.220 and the spatial agglomeration characteristics also weakened. Further analysis of the spatial and temporal linkage characteristics of the coupling relationship shows that the relative length of LISA time path presents characteristics of protrusion in the central region and shrinkage on the East and West sides, and the curvature presents characteristics that are smaller in the North and larger in the South.

Mechanism, kinetics and toxicity assessment of OH-initiated transformation of triclosan in aquatic environments.

The mechanisms and kinetics of OH-initiated transformation of triclosan (TCS) in aquatic environments were modeled using high-accuracy molecular orbital theory. TCS can be initially attacked by OH in two ways, OH-addition and H-abstraction. Twelve OH-addition routes were reported, and the C atom adjacent to the ether bond in the benzene ring (RaddB1) was found as the most easily attacked position by OH, producing TCS-OHB1. Seven H-abstraction routes were reported, and the OH exclusively abstracted the phenolic hydroxyl (RabsOH) H atom, to form TCS(-H). The kinetics results showed that the RaddB1 and RabsOH routes would occur preferentially in aquatic environments, and the half-life depended on the OH concentration ([OH]). At low [OH], the main intermediates, TCS-OHB1 and TCS(-H), can be converted into 2,4-dichlorophenol and polychlorinated dibenzo-p-dioxins, respectively. However, when enough OH is present, such as in advanced oxidation process (AOP) systems, they would be fully decomposed. The acute and chronic toxicities of TCS and its products were assessed at three trophic levels using the "ecological structure-activity relationships" program. The toxicity of the products decreased through the RaddB1 route, while the toxicity of the products first increased and then decreased through the other degradation routes. These results should help reveal the mechanism of TCS transformation as well as risk assessment in aquatic environments, and will help design further experimental studies and industrial application of AOPs.

Advanced oxidation kinetics and mechanism of preservative propylparaben degradation in aqueous suspension of TiO2 and risk assessment of its degradation products.

The absolute kinetic rate constants of propylparaben (PPB) in water with different free radicals were investigated, and it was found that both hydroxyl radicals (HO(•)) and hydrated electrons could rapidly react with PPB. The advanced oxidation kinetics and mechanisms of PPB were investigated using photocatalytic process as a model technology, and the degradation was found to be a pseudo-first-order model. Oxidative species, particularly HO(•), were the most important reactive oxygen species mediating photocatalytic degradation of PPB, and PPB degradation was found to be significantly affected by pH because it was controlled by the radical reaction mechanism and was postulated to occur primarily via HO(•)-addition or H-abstraction reactions on the basis of pulse radiolysis measurements and observed reaction products. To investigate potential risk of PPB to humans and aqueous organisms, the estrogenic assays and bioassays were performed using 100 µM PPB solution degraded by photocatalysis at specific intervals. The estrogenic activity decreased as PPB was degraded, while the acute toxicity at three trophic levels first increased slowly and then decreased rapidly as the total organic carbon decreased during photocatalytic degradation.