Simple Method for the Extraction and Determination of Ti-, Zn-, Ag-, and Au-Containing Nanoparticles in Sediments Using Single-Particle Inductively Coupled Plasma Mass Spectrometry.

The quantitative analysis of nanoparticles (NPs) in the environment is significantly important for the exploration of the occurrence, fate, and toxicological behaviors of NPs and their subsequent environmental risks. Some protocols have been recommended for the separation and extraction of NPs that are potentially dispersed in complex environmental matrixes, e.g. sediments and soils, but they remain limited. However, certain factors that may significantly affect extraction efficiency have not been comprehensively explored. In this study, on the basis of the single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS) technique, a simple standardized protocol for separating and analyzing metal-containing NPs in sediment samples was developed. On consideration of the extraction efficiencies of indigenous NPs (Ti- and Zn-NPs) and spiked NPs (Ag- and Au-NPs) in sediments, sedimentation with a settling time of 6 h is recommended for the separation of NPs and large particles, and the optimal sediment to water ratio, ultrasonication power, time, and temperature are 0.4 mg/mL, 285 W, 20 min, and 15-25 °C, respectively. On the basis of the optimized method, the recoveries of spiked Ag and Au-NPs were 71.4% and 81.1%, respectively. The applicability of the optimal protocols was verified, and TOC was proved to be an important factor controlling the separation and extraction of NPs in environmental samples. The separation and extraction of NPs in elevated TOC samples can be improved by increasing the ultrasonication power, time, and temperature.

Metal-Containing Nanoparticles in Low-Rank Coal-Derived Fly Ash from China: Characterization and Implications toward Human Lung Toxicity.

Characterization of nanoparticles (NPs) in coal fly ashes (CFAs) is critical for better understanding the potential health-related risks resulting from coal combustion. Based on single-particle (SP)-inductively coupled plasma mass spectrometry (ICP-MS) coupled with transmission electron microscopy techniques, this study is the first to determine the concentrations and sizes of metal-containing NPs in low-rank coal-derived fly ashes. Despite only comprising a minor component of the studied CFAs by mass, NPs were the dominant fraction by particle number. Fe- and Ti-containing NPs were identified as the dominant NPs with their particle number concentration ranging from 2.5 × 107 to 2.5 × 108 particles/mg. In addition, the differences of Fe-/Ti-containing NPs in various CFAs were regulated by the coalification degree of feed coals and combustion conditions of all of the low-rank CFAs tested. In the cases where these NPs in CFAs become airborne and are inhaled, they can be taken up in pulmonary interstitial fluids. This study shows that in Gamble's solution (a lung fluid simulant), 51-87% of Fe and 63-89% of Ti (ratio of the mass of Fe-/Ti-containing NPs to the total mass of Fe/Ti) exist in the NP form and remain suspended in pulmonary fluid simulants. These NPs are bioavailable and may induce lung tissue damage.

Environmental Risk Implications of Metals in Sludges from Waste Water Treatment Plants: The Discovery of Vast Stores of Metal-Containing Nanoparticles.

Nanoparticle (NP) assessment in sludge materials, although of growing importance in eco- and biotoxicity studies, is commonly overlooked and, at best, understudied. In the present study, sewage sludge samples from across the mega-city of Shanghai, China were investigated for the first time using a sequential extraction method coupled with single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) to quantify the abundance of metal-containing NPs in the extraction fractions and transmission electron microscopy to specifically identify the nanophases present. In general, most sludges observed showed high concentrations of Cr, Cu, Cd, Ni, Zn, and Pb, exceeding the maximum permitted values in the national application standard of acid soil in China. NPs in these sludges contribute little to the volume and mass but account for about half of the total particle number. Based on electron microscopy techniques, various NPs were further identified, including Ti-, Fe-, Zn-, Sn-, and Pb-containing NPs. All NPs, ignored by traditional metal risk evaluation methods, were observed at a concentration of 107 -1011 particles/g within the bioavailable fraction of metals. These results indicate the underestimate or misestimation in evaluating the environmental risks of metals based on traditional sequential extraction methods. A new approach for the environmental risk assessment of metals, including NPs, is urgently needed.

Combustion conditions and feed coals regulating the Fe- and Ti-containing nanoparticles in various coal fly ash.

Quantitative characteristics and sizes of nanoparticles (NPs) in coal fly ash (CFA) produced in coal-fired power plants as a function of coal type and plant design will help reveal the NP emission likelihood and their environmental implications. However, little is known about how combustion conditions and types of coal regulate the NP abundance in CFAs. In this study, based on single particle (SP)-ICP-MS technology, particle number concentrations (PNCs) and sizes of Fe- and Ti-containing NPs in CFAs were determined for samples collected from power plants of different designs and burning different types of coal. The PNCs of Fe- and Ti-containing NPs in all CFAs measured were in the range of 1.3 × 107 - 3.4 × 108 and 6.8 × 106 - 2.2 × 108 particles/mg, with the average particle sizes of 111 nm and 87 nm, respectively. The highest Fe-NP PNCs likely relate to the highest contents of Fe and pyrite in the feed coal. In addition, high TOC in CFAs are associated with metal-containing NPs, resulting in elevated abundances of these NPs with relatively large sizes. Moreover, elevated PNCs of NPs were found in CFAs produced by coal-fired power plants burning low-rank coals and with small installed capacity (especially those under 100-MW units). Compared to cyclone filters, ESPs and FFs with higher removal efficiency typically retain more Fe-/Ti- containing NPs with smaller sizes. Based on a structural equation (SE) model, raw coal properties (coal rank and Fe/Ti content), boiler types, and efficiency of particulate emission control devices likely indirectly affect PNCs of Fe- and Ti-containing NPs by influencing TOC contents and their corresponding metal concentrations of CFAs. This study provides the first analytic and comprehensive information concerning the direct and indirect regulating factors on NPs in various CFAs.

Vast emission of Fe- and Ti-containing nanoparticles from representative coal-fired power plants in China and environmental implications.

Coal combustion is considered an important source of atmospheric nanoparticles (NPs). However, the underlying information on the emission of NPs from coal-fired power plants (CFPPs) is still lacking. Along these lines, in this study, coal fly ashes (CFAs) were collected from different multi-stage particulate emission control devices (PECDs) in three representative CFPPs in China. The particle size and particle number concentration (PNC) of typical metal-containing NPs (Fe- and Ti-containing NPs) were analyzed by using the single-particle inductively coupled plasma mass (SP-ICP-MS) technology. By increasing the stage of PECDs, the mean particle sizes of NPs gradually declined and the PNCs of Fe- and Ti-containing NPs increased significantly. Specifically, the PNC of final-stage CFA was 3 - 8 times that of the first-stage CFA. A comparison of the electrostatic precipitators (ESPs), fabric filters (FFs), and electrostatic-fabric-integrated precipitators (EFIPs) showed that the state-of-the-art EFIPs exhibited a relatively good NP-removal efficiency with the highest PNCs. In addition, NP hourly emissions in all coal combustion by-products (CCPs) were further calculated in a typical CFPP. The total emissions of Fe- and Ti-containing NPs in all CCPs were 1.87 × 1018 and 1.57 × 1018 particles/h, respectively. NPs were mainly enriched in CFA trapped by PECDs (80% of total emissions). Although the mass of the CFA that escaped through the stack was extremely low, it contained the highest PNCs of Fe- and Ti-containing NPs of all CCPs, accounting for 3.41% and 1.67% of the corresponding total NP emissions. These NPs may also coexist with various toxic metals, such as Zn and Pb, and be released directly into the atmosphere, where they pose a potential risk to human health.

Increasing mercury risk of fly ash generated from coal-fired power plants in China.

The trend in mercury (Hg) content of fly ash, the primary solid Hg waste from coal-fired power plants (CFPPs), has not been well evaluated in China. This study integrated a national sampling campaign, a literature survey, and model predictions to investigate the trend in Hg content of fly ash and associated output nationwide. The results demonstrated that Hg content of fly ash from both our campaign conducted in 2020 and the literature survey met the Weibull distribution. The best estimate for the distribution of Hg content in our campaign (401.4 µg/kg) was about two-fold higher than that from the literature survey (236.6 µg/kg). The increasing trend was mainly attributed to the increasing installation of advanced air pollution control devices (APCDs) in CFPPs. The total national Hg output by fly ash was estimated to be 217.7 tons (64.1-501.8 tons) currently. Regarding the disposal of fly ash, a total of 16.1 tons and 105.8 tons of Hg were re-emitted into the air and immobilized in materials, respectively. The increasing trend in the Hg content of fly ash suggested the need for more stringent requirements for the disposal of solid Hg waste from CFPPs in China.

Extraction and quantification of metal-containing nanoparticles in marine shellfish based on single particle inductively coupled plasma-mass spectrometry technique.

Quantitative characterization of nanoparticles (NPs) in marine shellfish is critical to understanding the risks of bio-accumulation. Based on single particle (sp)ICP-MS and electron microscopy, a standardized protocol was developed to extract Ag, Au, and indigenous Ti-containing NPs from mussels. The optimal parameters are: dry sample extraction with tetramethylammonium hydroxide (TMAH), 5% (v/v) final concentration of TMAH, extraction at 25 â„ƒ for 12 h, and separation by centrifugation (3000 rpm for 5 min). The particle number recoveries of spiked Ag and Au NPs were 88 ± 0.9% and 95 ± 1.1%, respectively, while Ti-containing NPs had a particle number concentration of 8.2 × 106 particles/mg and an average size of 70 nm in tested mussels. Furthermore, titanium oxide NPs, including rutile, anatase, and Magnéli phases (TixO2x-1) were found ubiquitously in 10 shellfish based on the optimal method. The particle number concentrations and average sizes of the Ti-containing NPs were 2.1 × 106-8.4 × 106 particles/mg and 70-80 nm, respectively. These Ti-containing NPs, such as TiO2, accounted for about half of the Ti mass in shellfish, indicating that marine shellfish may be a significant sink for Ti-containing NPs.

Titanium and zinc-containing nanoparticles in estuarine sediments: Occurrence and their environmental implications.

Understanding the behavior and risk of nanoparticles (NPs) in the aquatic environment is currently limited by the lack of quantitative characterization of NPs in the environmental matrices, such as sediments. In this study, based on the single particle (SP)-ICP-MS technique, metal-containing NPs, including Ti- and Zn-containing NPs, were analyzed in sediments taken along the Yangtze Estuary. Combined with the traditional sequential extraction method that has been widely used for metal risk assessment, different single extraction methods were used to understand the association of NPs with different chemical fractions in sediments and their potential environmental implications. Ti-containing NPs, with an average size of 81 nm, ranged from 3.02 × 107 parts/mg to 9.61 × 107 parts/mg, and Zn-containing NPs, with an average size of 41 nm, ranged from 2.47 × 106 parts/mg to 1.21 × 107 parts/mg. Both correlation and redundancy analyses showed that particle concentrations of Ti-containing NPs in sediment were significantly correlated to the Ti-containing NPs in the residual fraction and salinity, indicating that Ti-containing NPs in sediments may be dominated by Ti-containing NPs in the residue fractions of sediments. Large amounts of these NPs may be released from the residual fraction that has been considered to be not bioavailable and "environmentally safe" in the traditional environmental risk assessment of metals in sediments. Zn-containing NPs, mostly associated with carbonates, were positively correlated to all the bioavailable fractions of Zn in sediments, suggesting that these NPs may be largely presented in the bioavailable fraction. This study showed that, vast numbers of NPs with minute sizes were present in estuarine sediments, and that they were associated with different chemical fractions with different potential environmental risks. The study findings call for further research to update the traditional risk assessment method.

Human activities can drive sulfate-reducing bacteria community in Chinese intertidal sediments by affecting metal distribution.

Sulfate-reducing bacteria (SRB), which are ubiquitous in intertidal sediments, play an important role in global sulfur and carbon cycles, and in the bioremediation of toxic metalloids/metals. Pollution from human activities is now a major challenge to the sustainable development of the intertidal zone, but little is known about how and to what extent various anthropic and/or natural factors affect the SRB community. In the current study, based on the dsrB gene, we investigated the SRB community in intertidal sediment along China's coastline. The results showed that dsrB gene abundances varied among different sampling sites, with the highest average abundance of SRB at XHR (near the Bohai Sea). The SRB community structures showed obvious spatial distribution patterns with latitude along the coastal areas of China, with Desulfobulbus generally being the dominant genus. Correlation analysis and redundancy discriminant analysis revealed that total organic carbon (TOC) and pH were significantly correlated with the richness of the SRB community, and salinity, pH, sulfate and climatic parameters could be the important natural factors influencing the composition of the SRB community. Moreover, metals, especially bioavailable metals, could regulate the diversity and composition of the SRB communities. Importantly, according to structural equation model (SEM) analysis, anthropic factors (e.g., population, economy and industrial activities) could drive SRB community diversity directly or by significantly affecting the concentrations of metals. This study provides the first comprehensive investigation of the direct and indirect anthropic factors on the SRB community in intertidal sediments on a continental scale.

Time-dependent effects of ZnO nanoparticles on bacteria in an estuarine aquatic environment.

Many studies have examined the acute toxicity of nanoparticles (NPs) towards model bacteria. In this study, we report the time-dependent effects of ZnO NPs on native, selected Zn-resistant and dominant bacteria in estuarine waters. An initial inhibition of bacterial growth followed by a recovery at 24 h was observed, and this rebound phenomenon was particularly notable when the raw water samples were treated with relatively high ZnO NP concentrations (1 and 10 mg/L).By comparing the groups treated with Zn2+, Zn2+ was shown to largely explain the acute cytotoxic effect of ZnO NPs on bacteria in raw waters. Furthermore, similar to the native bacteria, especially the dominant bacteria, the viability of Escherichia coli (E. coli) decreased with the increasing treatments time and the concentrations of ZnO NPs in water with different salinities. Moreover, the expression of Zn-resistance genes including zntA and zntR in E. coli suggested that the Zn-resistance system in E. coli can be activated to defend against the stress of Zn2+ released from ZnO NPs, and salinity may promote this process in estuarine aquatic systems. Thus, the effect of ZnO NPs on bacteria in estuarine water bodies is likely determined by the synergistic effect of environmental salinity and dissolved Zn ions. As such, our findings are of high relevance and importance for understanding the ecological disturbances caused by anthropogenic NPs in estuarine environments.

Characteristics of microbial community indicate anthropogenic impact on the sediments along the Yangtze Estuary and its coastal area, China.

In the contaminated coastal sediments, variations of microbial community can reflect the impact of anthropogenic activities. The identification, evaluation and monitoring of the potential bio-indicator species and biomarker communities are vital for the ecological studies in sedimentary environments. Based on the high-throughput sequencing, the microbial communities were characterized in the sediments along the Yangtze Estuary and its coastal area. The results showed that the structure and composition of microbial communities varied greatly among different sampling sites at the phyla level, especially for Euryarchaeota. Metabolic pathway and quantitative PCR analyses suggested that the methane metabolism-related microbes were mainly included in the phylum of Euryarchaeota. Elevated abundances of methane metabolism-related microbes were found at Shidongkou (SDK) and Wusongkou (WSK), where microbes were seriously impacted by the wastewater treatment plant (WWTP) effluent and urban runoff. By comparing with the Euryarchaeota in WWTP sludge, the relatively high abundance of Euryarchaeota in sediment at SDK may be mainly related to the massive growth of indigenous species, promoted by anthropogenic nutrients. Moreover, redundancy discriminant analysis and correlation analysis revealed that methanogens and methanotrophs mainly respond to the nutrients and metals, such as total organic carbon, total phosphorus, total nitrogen, SO42-, NO2-, NH4+, Cr, and Zn, which were often related to human activities. Network analyses showed that the species related to the metabolism of methane may play a vital role in the interassociation among different microbial communities. Therefore, methanogens, methanotrophs and their community compositions could be considered as potential bio-indicator species and biomarker communities, indicating anthropogenic activities in the sediments along the Yangtze Estuary and its coastal area.

Biofilms as a sink for antibiotic resistance genes (ARGs) in the Yangtze Estuary.

Biofilms are ubiquitous throughout aquatic environments and they are thought to promote the acquisition and dissemination of antibiotic resistant genes (ARGs). This study focused on the occurrence and distribution of five types of ARG in naturally-occurring biofilms, in comparison to associated sediment and water samples, from the Yangtze Estuary, which borders the meta-city of Shanghai, China. The detection frequency and abundances of most ARGs showed the following order: biofilm > sediment > water, which can be attributed to a high level of antibiotics and metals that can accelerate the generation and propagation of ARGs in biofilms. Most of ARG abundances were contributed by extracellular DNA (eDNA) in biofilm and sediment samples. ARGs (sul1, sul2, tetA and tetW) in eDNA were significantly correlated with TOC in both biofilm and sediment samples. Furthermore, both intracellular DNA-associated ARGs per gram of microbial biomass carbon (MBC) and eDNA-associated ARGs per gram of non-MBC and were higher in biofilms than sediments, and the partitioning coefficients of ARGs in eDNA between biofilm and water were higher than those between sediment and water. Our results provide new insight for evaluating the occurrence and abundance of ARGs in aquatic environments, confirming that biofilms are a significant sink for ARGs in the estuarine environment.

Sulphate-reducing bacteria (SRB) in the Yangtze Estuary sediments: Abundance, distribution and implications for the bioavailibility of metals.

Ubiquitous in the aquatic environment, sulphate-reducing bacteria (SRB) are considered one of the dominant microorganisms involved in the degradation of sulphate. This study focused on the spatial and temporal distributions of SRB in the Scirpus triquter rhizosphere sediments with a comparison to non-rhizosphere sediments and evaluated the implication of SRB to the bioavailability of metals in the Yangtze Estuary. The results showed that taking dsrB as the target gene, SRB abundances in rhizosphere sediments were significantly higher than those in non-rhizosphere sediments (P<0.01). SRB abundances were relatively higher in April and January than other seasons. Moreover, redundancy discriminate analysis (RDA) results indicated that sulphate, pH and TOC were the major environmental factors affecting the SRB abundance in rhizosphere sediments. The concentrations of most metals were significantly related to SRB abundance, and sulphide concentrations showed a significantly positive correlation to metal concentrations, indicating metal sulphide/metal associated sulphide could be regulated by SRB. Furthermore, electron microscope analysis found that nano-sized metal sulphide particles were ubiquitous in rhizosphere sediments and could be further taken up by plants. This study provides new insights into the immobilization and removal of heavy metals and the ecological value of the sulphate-reducing bacteria in the Yangtze Estuary.

Bacterial community structure in response to environmental impacts in the intertidal sediments along the Yangtze Estuary, China.

This study was designed to investigate the characteristics of bacterial communities in intertidal sediments along the Yangtze Estuary and their responses to environmental factors. The results showed that bacterial abundance was significantly correlated with salinity, SO42- and total organic carbon, while bacterial diversity was significantly correlated with SO42- and total nitrogen. At different taxonomic levels, both the dominant taxa and their abundances varied among the eight samples, with Proteobacteria being the most dominant phylum in general. Cluster analysis revealed that the bacterial community structure was influenced by river runoff and sewerage discharge. Moreover, SO42-, salinity and total phosphorus were the vital environmental factors that influenced the bacterial community structure. Quantitative PCR and sequencing of sulphate-reducing bacteria indicated that the sulphate reduction process occurs frequently in intertidal sediments. These findings are important to understand the microbial ecology and biogeochemical cycles in estuarine environments.

Seasonal and spatial distribution of antibiotic resistance genes in the sediments along the Yangtze Estuary, China.

Antibiotics resistance genes (ARGs) are considered as an emerging pollutant among various environments. As a sink of ARGs, a comprehensive study on the spatial and temporal distribution of ARGs in the estuarine sediments is needed. In the present study, six ARGs were determined in sediments taken along the Yangtze Estuary temporally and spatially. The sulfonamides, tetracyclines and fluoroquinolones resistance genes including sul1, sul2, tetA, tetW, aac(6')-Ib, and qnrS, were ubiquitous, and the average abundances of most ARGs showed significant seasonal differences, with relative low abundances in winter and high abundances in summer. Moreover, the relative high abundances of ARGs were found at Shidongkou (SDK) and Wusongkou (WSK), which indicated that the effluents from the wastewater treatment plant upstream and inland river discharge could influence the abundance of ARGs in sediments. The positive correlation between intI1 and sul1 implied intI1 may be related to the occurrence and propagation of sulfonamides resistance genes. Correlation analysis and redundancy discriminant analysis showed that antibiotic concentrations had no significant correlation to their corresponding ARGs, while the total extractable metal, especially the bioavailable metals, as well as other environmental factors including temperature, clay, total organic carbon and total nitrogen, could regulate the occurrence and distribution of ARGs temporally and spatially. Our findings suggested the comprehensive effects of multiple pressures on the distribution of ARGs in the sediments, providing new insight into the distribution and dissemination of ARGs in estuarine sediments, spatially and temporally.

Bacterial community structure in the intertidal biofilm along the Yangtze Estuary, China.

In this study, the 16S rRNA-based Illumina MiSeq sequencing was used to investigate the bacterial community structure and composition of intertidal biofilm taken along the Yangtze Estuary. The results showed that 680,721 valid sequences of seven samples were assigned to 147,239 operational taxonomic units, which belonged to 49 phyla, 246 family and 314 genera. Compared to other studies on water and sediments in the study area, biofilms showed highest index of bacterial diversity and abundances. At different taxonomic levels, both dominant taxa and their abundances varied among the seven samples, with Proteobacteria as the dominant phylum in general. Principal component analysis and cluster analysis revealed that bacterial communities at WSK differed from those at other sampling sites. Salinity, dissolved oxygen, pH and nutrients were the vital environmental factors to influence the bacterial community structure of biofilms. These results may provide a new insight into the microbial ecology in estuarine environments.

PCBs and OCPs in fish along coastal fisheries in China: Distribution and health risk assessment.

PCBs and OCPs were analyzed in fish (bass) taken along Chinese coastal fisheries. In the bass muscle, PCB, DDT and HCH concentrations were in the range of 1.02-2.2ng/g, 0.44-1.74 and 2.84-106.11ng/gww, respectively. Spatial distribution showed that the concentrations of target contaminants in bass from south fisheries were in general much lower than those from north fisheries in China. The ratios of OCP congeners suggested that technical DDT was not the main input and a recent usage of lindane or old technical HCH residuals could be the source of HCHs. The OCC concentrations in liver (127-442.43ng/gww) from selected samples were 8-12 and 10-14 times higher than those in gills and muscles, respectively. Based on the maximum allowable fish assumption rate (CRlim and CRmm), it could cause human health risk, by consuming bass samples taken from highly contaminated fisheries including QD and ST.