The presence of abundant extracellular polymeric substances (EPS) play a vital role in affecting heteroaggregation process and toxicity of nanoparticles (NPs) to Microcystis aeruginosa. Interactions between n-CeO₂ and cyanobacteria with/without EPS and the toxicity of n-CeO₂ to M. aeruginosa were investigated in this study. Aggregation kinetics of n-CeO₂ under both soluble EPS (SEPS) and bound EPS (BEPS) indicated the presence of EPS could induced the formation of EPS-NPs aggregates. Heteroaggregation between cells and n-CeO₂ was confirmed through co-settling experiment and SEM-EDS observation. SEPS contributed to the observable heteroaggregation using spectral measurement. Heteroaggregation between cells and n-CeO2 under no BEPS was hardly obtained through spectral measurement, but SEM-EDS observation convinced this process. And the DLVO theory explained this heteroaggregation process under various EPS conditions, where the energy barrier decreased with gradual EPS extraction. In addition, the order for 96 h half growth inhibition concentration (IC₅₀) was Raw M9 > M9-SEPS > M9+BEPS > M9-BEPS. These results revealed that not all heteroaggregation between cell-NPs can lead to the NPs toxicity to cells. BEPS act more important role in buffering against the toxicity of NPs from ambient adverse factors, but SEPS increase the stability of NPs which could aggravate the adverse effects of NPs in the environment.

To further explore the composition and distribution of secondary organic aerosol (SOA) components from the photo-oxidation of light aromatic precursors (toluene, m-xylene, and 1,3,5-trimethylbenzene (1,3,5-TMB)) and idling gasoline exhaust, a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) was employed. Peaks of the molecular ions of the SOA components with minimum molecular fragmentation were clearly observed from the mass spectra of SOA, through the application of soft ionization methods in VUV-PIMS. The experiments comparing the exhaust-SOA and light aromatic mixture-SOA showed that the observed distributions of almost all the predominant cluster ions in the exhaust-SOA were similar to that of the mixture-SOA. Based on the characterization experiments of SOA formed from individual light aromatic precursors, the SOA components with molecular weights of 98 and 110 amu observed in the exhaust-SOA resulted from the photo-oxidation of toluene and m-xylene; the components with a molecular weight of 124 amu were derived mainly from m-xylene; and the components with molecular weights of 100, 112, 128, 138, and 156 amu were mainly derived from 1,3,5-TMB. These results suggest that C7-C9 light aromatic hydrocarbons are significant SOA precursors and that major SOA components originate from gasoline exhaust. Additionally, some new light aromatic hydrocarbon-SOA components were observed for the first time using VUV-PIMS. The corresponding reaction mechanisms were also proposed in this study to enrich the knowledge base of the formation mechanisms of light aromatic hydrocarbon-SOA compounds.

Whilst attention is increasingly being focused on embodied pollutant emissions along supply chains in China, relatively little attention has been paid to dynamic changes in this process. This study utilized environmental extended input-output analysis (EEIOA) and structural path analysis (SPA) to investigate the dynamic variation of the SO2 emissions embodied in 28 economic sectors in Chinese supply chains during 2002–2012. The main conclusions are summarized as follows: (1) The dominant SO2 emission sectors differed under production and consumption perspectives. Electricity and heat production dominated SO2 emissions from the point of view of production, while construction contributed most from the consumption perspective. (2) The embodied SO2 emissions tended to change from the path (staring from consumption side to production side): “Services→Services→Power” in 2002 to the path: “Construction and Manufacturing→Metal and Nonmetal→Power” in 2012. (3) Metal-driven emissions raised dramatically from 15% in 2002 to 22% in 2012, due to increasing demand for metal products in construction and manufacturing activities. (4) Power generation was found to result in the greatest volume of production-based emissions, a burden it tended to transfer to upstream sectors in 2012. Controlling construction activities and cutting down end-of-pipe discharges in the process of power generation represent the most radical interventions in reducing Chinese SO2 emissions. This study shed light on changes in SO2 emissions in the supply chain, providing a range of policy implications from both production and consumption perspectives.

This study investigates the occurrence of six phthalates and distribution of the three most-detected phthalates in the karst region of northern Puerto Rico (KRNPR) using data from historical records and current field measurements. Statistical data analyses, including ANOVA, Chi-Square, and logistic regression models are used to examine the major factors affecting the presence and concentrations of phthalates in the KRNPR. The most detected phthalates include DEHP, DBP, and DEP. At least one phthalate specie is detected above DL in 7% of the samples and 24% of the sampling sites. Concentrations of total phthalates average 5.08 ± 1.37 μg L−1, and range from 0.093 to 58.4 μg L−1. The analysis shows extensive spatial and temporal presence of phthalates resulting from dispersed phthalate sources throughout the karst aquifers. Hydrogeological factors are significantly more important in predicting the presence and concentrations of phthalates in eogenetic karst aquifers than anthropogenic factors. Among the hydrogeological factors, time of detection and hydraulic conductivities larger than 300 m d−1 are the most influential factors. Persistent presence through time reflects continuous sources of phthalates entering the aquifers and a high capacity of the karst aquifers to store and slowly release contaminants for long periods of time. The influence of hydraulic conductivity reveals the importance of contaminant fate and transport mechanisms from contamination sources. This study improves the understanding of factors affecting the spatial variability and fate of phthalates in karst aquifers, and allows us to better predict their occurrence based on these factors.

Understanding the effect of natural colloidal particles (NCPs) on the photochemistry of organic pollutants is crucial to predict the environmental persistence and fate of them in surface waters, and it is, yet, scarcely elucidated. In this study, the pre-filtered surface water (through a 1 μm capsule filter) from Baiyangdian Lake was further separated into four different size NCPs: F1 (0.65–1.0 μm), F2 (100 kD-0.65 μm), F3 (10–100 kD) and F4 (1–10 kD) by cross-flow ultrafiltration (CFUF), and the photochemical kinetics and mechanisms of ofloxacin (OFL) and enrofloxacin (ENR) were investigated in the presence of those particles under simulated sunlight. Results showed that OFL and ENR underwent both direct and indirect photolysis in F1-F4 solutions, and the observed pseudo first-order rate constants (kobs) for target compounds differed depending on the size of NCPs. Direct photolysis accounted for >50% of the degradation in all cases and was the dominant degradation pathway for the two target antibiotics with the exception of OFL in F1 solution. Except for ENR in both F3 and F4 solutions, nearly all NCPs enhanced the degradation of both target compounds by indirect photolytic pathways, especially in F1 solution that showed the largest reactivity for OFL and ENR, promoting the reactions by 63% and 41%, respectively. The excited state colloidal organic matter (3COM∗) plays a significant role in the indirect photolysis, and the adsorptions of OFL and ENR to NCPs were likely to have a pronounced effect in the photochemistry process. Pearson's correlations analysis showed that the kobs(OFL) was significant positive correlated with binding of Fe (r = 0.963, P < 0.05), and the kobs(ENR) was significant positive correlated with the adsorption percentage of OFL (r = 0.999, P < 0.01).This paper has demonstrated that different size NCPs showed the different photochemical contribution to the reaction rate for OFL and ENR.

A new Land Use Regression model was built to develop pan-European 100 m resolution maps of NO2 concentrations. The model was built using NO2 concentrations from routine monitoring stations available in the Airbase database as dependent variable. Predictor variables included land use, road traffic proxies, population density, climatic and topographical variables, and distance to sea. In order to capture international and inter regional disparities not accounted for with the mentioned predictor variables, additional proxies of NO2 concentrations, like levels of activity intensity and NOx emissions for specific sectors, were also included. The model was built using Random Forest techniques. Model performance was relatively good given the EU-wide scale (R2 = 0.53). Output predictions of annual average concentrations of NO2 were in line with other existing models in terms of spatial distribution and values of concentration. The model was validated for year 2015, comparing model predictions derived from updated values of independent variables, with concentrations in monitoring stations for that year. The algorithm was then used to model future concentrations up to the year 2030, considering different emission scenarios as well as changes in land use, population distribution and economic factors assuming the most likely socio-economic trends. Levels of exposure were derived from maps of concentration. The model proved to be a useful tool for the ex-ante evaluation of specific air pollution mitigation measures, and more broadly, for impact assessment of EU policies on territorial development.

Undissolved humic acid (HA) has a great retention effect on the migration of hexavalent chromium [Cr(VI)] in soil, and HA functional groups play a predominant role in this process. However, the coupled mode between Cr(VI) retention and HA functional groups reaction is still unclear. In this study, it was found that a fair amount of Cr on HA existed in the forms of ion exchangeable and binding Cr(VI) during the reaction resulting from the ion exchange adsorption and complexation of Cr(VI). According to the results of two-dimensional correlation spectroscopic analysis (2DCOS), HA functional groups participated in the reaction with Cr(VI) in the order of carboxyl ≈ chelated carboxyl > phenol > polysaccharide > methyl, and all the functional groups were more likely to be located at aromatic domains. Based on the results of XPS spectra, rather than to be oxidized by Cr(VI), carboxyl more tended to be complexed by chromium, which is regarded as the precondition for Cr(VI) reduction. Phenol, polysaccharide and methyl with distinct reaction activities successively acted as major electron donors for Cr(VI) reduction in different reaction stages. Consequently, it was determined that the retention of Cr(VI) by undissolved HA followed an adsorption-complexation-reduction mechanism, and based on this, a multi-step kinetic model with multiple types of complexation/reduction sites was developed to simulate the retention processes resulting in a much better fitting effect (R2 > 0.99) compared with traditional first-order and second-order kinetic models (R2 < 0.95). This demonstrated that the multi-step kinetic model is of great potential in accurately simulating the migration and transformation of Cr(VI) in soil environment.

Differences in the distribution, partitioning, and bioaccumulation characteristics of arsenicals between freshwater and saltwater systems remain poorly understood. To determine the characteristics of distribution and behavior of arsenicals, multimedia environmental samples including water, suspended particles, zooplankton, sediments, and porewater were collected from inner (five sites, freshwater) and outer (five sites, saltwater) regions of the estuary dike of the Youngsan River Estuary in South Korea (Nov., 2012). Six organic and inorganic forms of As were separated and measured using HPLC–ICP/MS equipped with an anion exchange column. Concentrations of arsenicals in water samples of the inner region (mean = 1.5 μg As L−1) were significantly lower than in those of the outer region (mean = 5.2 μg As L−1). Conversely, concentrations of As in suspended particles in the inner region (mean = 14 μg As g−1) were much greater than in the outer region (mean = 5.7 μg As g−1). The field-based distribution coefficient (Kd) for As depended strongly on salinity; relatively greater Kd values were found in freshwater compared with saltwater. The AsV was found to be the major form of As in all water and particle samples in both inner and outer regions. The zooplankton species were significantly distinguishable between the inner and outer regions; cladocerans were the most dominant species in freshwater and cyclopoida were predominantly found in saltwater. The As concentrations in zooplankton were shown to be particle-concentration dependent, suggesting that dietary exposure plays a substantial role in the bioaccumulation of As. Inorganic arsenicals, such as AsV and AsIII were the most dominant forms found in zooplankton. Partitioning behavior of As between porewater and sediments was similar to that in water–particle distributions. The results of the present study enhance the understanding of As biogeochemistry in river and estuarine environments.

Interactions between organic toxicants and nano-particles in the aquatic environment may modify toxicant bioavailability and consequently the toxicant's fate and toxicity. To evaluate the potential impact of nano-titanium dioxide (TiO₂) on the bio-concentration and reproductive endocrine disruption of tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) in fish, a comparative bioaccumulation study was conducted on zebrafish (Danio rerio, AB strain) treated with 0, 5.74, 23.6, or 90.7 μg L⁻¹ TDCIPP alone or co-exposed to TDCIPP and 0.09 mg L⁻¹ nano-TiO₂ for 21 days. Nano-TiO₂ can absorb TDCIPP and nano-TiO₂ is taken up into zebrafish. Chemical measurements showed that TDCIPP was bio-concentrated in zebrafish, and the highest level was detected in the liver, followed by the brain and gonads. Compared with TDCIPP treatment, increased tissue burdens of both TDCIPP were observed in the liver, brain, and gonads suggesting that nano-TiO₂ adsorbed TDCIPP and acted as a carrier facilitating the uptake and translocation of TDCIPP in tissues. Higher bio-concentration in the presence of nano-TiO₂ resulted in a significant decrease in the hepatic-somatic index, gonad-somatic index and brain-somatic index in F0 females but not F0 males. Moreover, a further gender-dependent reduction in testosterone (T), estradiol (E2), follicle-stimulating hormone (FSH) and luteinizing hormone (LH), and induction of plasma vitellogenin (VTG) concentrations in adults were observed following co-exposure. Co-exposure also inhibited egg production and caused significant developmental toxicity in F1 larvae. The results obtained using this multi-marker approach suggested that nano-TiO₂ is a carrier of TDCIPP and accelerated its bio-concentration in adult zebrafish, resulting in adverse reproduction outcomes.

The presence of pathogenic microorganisms in water is a great threat to human health, and photocatalysis is promising for disinfection. However, the research on virus inactivation with visible-light photocatalysis is still limited, especially the coexistence of virus and its host bacteria. In this study, bacteriophage f2 and its host E. coil 285 were used as the model microorganisms, and the disinfection performance of prepared Cu-TiO2 nanofibers under visible light was investigated. The result showed that the prepared Cu-TiO2 nanofibers showed a brilliant ability in terms of removing bacteriophage f2 and E. coil 285 under visible light. Series experiments indicated that the initial pH didn't affect the photocatalytic disinfection performance significantly. In the certain range, the removal efficiency of bacteriophage f2 increased with the increase of catalyst dosage, light intensity and temperature, but decreased with the increase of initial virus concentration. In virus/bacteria mixed system, bacteriophage f2 exhibited stronger resistance to photocatalytic oxidation than E. coil 285, and the removal of bacteriophage f2 was obviously affected by being mixed with E. coil 285, while the removal of E. coil 285 almost remained unchanged after being mixed with bacteriophage f2. Further research proved that competitive adsorption in mixed system played a certain role in E. coli 285 inactivation, while the free reactive oxygen species (ROSs) in the bulk phase played a crucial role in phage f2 inactivation.