Lanmodulin-Functionalized Magnetic Nanoparticles as a Highly Selective Biosorbent for Recovery of Rare Earth Elements.

Recovering rare earth elements (REEs) from waste streams represents a sustainable approach to diversify REE supply while alleviating the environmental burden. However, it remains a critical challenge to selectively separate and concentrate REEs from low-grade waste streams. In this study, we developed a new type of biosorbent by immobilizing Lanmodulin-SpyCatcher (LanM-Spycatcher) on the surface of SpyTag-functionalized magnetic nanoparticles (MNPs) for selective separation and recovery of REEs from waste streams. The biosorbent, referred to as MNP-LanM, had an adsorption activity of 6.01 ± 0.11 µmol-terbium/g-sorbent and fast adsorption kinetics. The adsorbed REEs could be desorbed with >90% efficiency. The MNP-LanM selectively adsorbed REEs in the presence of a broad range of non-REEs. The protein storage stability of the MNP-LanM increased by two-fold compared to free LanM-SpyCatcher. The MNP-LanM could be efficiently separated using a magnet and reused with high stability as it retained ∼95% of the initial activity after eight adsorption-desorption cycles. Furthermore, the MNP-LanM selectively adsorbed and concentrated REEs from the leachate of coal fly ash and geothermal brine, resulting in 967-fold increase of REE purity. This study provides a scientific basis for developing innovative biosorptive materials for selective and efficient separation and recovery of REEs from low-grade feedstocks.

Tyrosinase-functionalized polyhydroxyalkanoate bio-beads as a novel biocatalyst for degradation of bisphenol analogues.

Bisphenol compounds are emerging contaminants of high concerns with known endocrine-disrupting effects. Biocatalysis provides a green chemistry alternative for advanced treatment in water reclamation. This study createda novel biocatalyst through genetically immobilizing the Bacillus megaterium tyrosinase enzyme (BmTyr) on the surface ofself-assembled polyhydroxyalkanoate (PHA) biopolymer beads (termed PHA-BmTyr) by using synthetic biology techniques and demonstrated one-pot in vivo production of the biocatalyst for effective degradation and detoxification of various bisphenol analogues for the first time. The degradation pathway of bisphenols was determined to be mediated by the monophenolase and diphenolase activity of BmTyr. Notably, biocatalytic bisphenol degradation by PHA-BmTyr could substantially reduce or eliminate estrogenic activity of the contaminants, and the degradation products had remarkably lower acute and chronic toxicity than their parent compounds. Furthermore, the PHA-BmTyr biocatalyst had high reusability for multiple bisphenol degradation reaction cycles and showed excellent stability that retained 100% and 86.6% of the initial activity when stored at 4 °C and room temperature, respectively for 30 days. Also, the PHA-BmTyr biocatalyst could efficiently degrade bisphenol analogues in real wastewater effluent matrix. This study provides a promising approach to develop innovative biocatalysis technologies for sustainable water reclamation.

Enzyme discovery and engineering for sustainable plastic recycling.

The drastically increasing amount of plastic waste is causing an environmental crisis that requires innovative technologies for recycling post-consumer plastics to achieve waste valorization while meeting environmental quality goals. Biocatalytic depolymerization mediated by enzymes has emerged as an efficient and sustainable alternative for plastic treatment and recycling. A variety of plastic-degrading enzymes have been discovered from microbial sources. Meanwhile, protein engineering has been exploited to modify and optimize plastic-degrading enzymes. This review highlights the recent trends and up-to-date advances in mining novel plastic-degrading enzymes through state-of-the-art omics-based techniques and improving the enzyme catalytic efficiency and stability via various protein engineering strategies. Future research prospects and challenges are also discussed.

Engineering Biocatalytic and Biosorptive Materials for Environmental Applications.

The challenges of increasing environmental contamination and scarcity of natural resources require innovative solutions to ensure a sustainable future. Recent breakthroughs in synthetic biology and protein engineering provide promising platform technologies to develop novel engineered biological materials for beneficial applications towards environmental sustainability. In particular, biocatalysis and biosorption are receiving increasing attention as sustainable approaches for environmental remediation and resource recovery from wastes. This review focuses on up-to-date advances in engineering biocatalytic and biosorptive materials that can degrade persistent organic contaminants of emerging concern, remove hazardous metal pollutants, and recover value-added metals. Opportunities and challenges for future research are also discussed.

Biocatalytic Degradation of Parabens Mediated by Cell Surface Displayed Cutinase.

Parabens are emerging environmental contaminants with known endocrine-disrupting effects. This study created a novel biocatalyst (named as SDFsC) by expressing the enzyme Fusarium solani pisi cutinase (FsC) on the cell surface of Baker's yeast Sacchromycese cerevisiae and demonstrated successful enzyme-mediated removal of parabens for the first time. Parabens with different side chain structures had different degradation rates by the SDFsC. The SDFsC preferentially degraded the parabens with relatively long alkyl or aromatic side chains. The structure-dependent degradability was in a good agreement with the binding energy between the active site of FsC and different parabens. In real wastewater effluent solution, the SDFsC effectively degraded 800 µg/L of propylparaben, butylparaben, and benzylparaben, either as a single compound or as a mixture, within 48 h. The estrogenic activity of parabens was considerably reduced as the parent parabens were degraded into 4-hydroxybenzoic acid via hydrolysis pathway by the SDFsC. The SDFsC showed superior reusability and maintained 93% of its initial catalytic activity after six rounds of paraben degradation reaction. Results from this study provide scientific basis for developing biocatalysis as a green chemistry alternative for advanced treatment of parabens in sustainable water reclamation.

Co-fermentation of cellobiose and xylose by mixed culture of recombinant Saccharomyces cerevisiae and kinetic modeling.

Efficient conversion of cellulosic sugars in cellulosic hydrolysates is important for economically viable production of biofuels from lignocellulosic biomass, but the goal remains a critical challenge. The present study reports a new approach for simultaneous fermentation of cellobiose and xylose by using the co-culture consisting of recombinant Saccharomyces cerevisiae specialist strains. The co-culture system can provide competitive advantage of modularity compared to the single culture system and can be tuned to deal with fluctuations in feedstock composition to achieve robust and cost-effective biofuel production. This study characterized fermentation kinetics of the recombinant cellobiose-consuming S. cerevisiae strain EJ2, xylose-consuming S. cerevisiae strain SR8, and their co-culture. The motivation for kinetic modeling was to provide guidance and prediction of using the co-culture system for simultaneous fermentation of mixed sugars with adjustable biomass of each specialist strain under different substrate concentrations. The kinetic model for the co-culture system was developed based on the pure culture models and incorporated the effects of product inhibition, initial substrate concentration and inoculum size. The model simulations were validated by results from independent fermentation experiments under different substrate conditions, and good agreement was found between model predictions and experimental data from batch fermentation of cellobiose, xylose and their mixtures. Additionally, with the guidance of model prediction, simultaneous co-fermentation of 60 g/L cellobiose and 20 g/L xylose was achieved with the initial cell densities of 0.45 g dry cell weight /L for EJ2 and 0.9 g dry cell weight /L SR8. The results demonstrated that the kinetic modeling could be used to guide the design and optimization of yeast co-culture conditions for achieving simultaneous fermentation of cellobiose and xylose with improved ethanol productivity, which is critically important for robust and efficient renewable biofuel production from lignocellulosic biomass.

Attenuation of bacterial cytotoxicity of carbon nanotubes by riverine suspended solids in water.

The impact of solid particles on ecotoxicity of nanomaterials in water environments is poorly understood. This study investigated the effect of natural riverine suspended solids (SPS) on the cytotoxicity of single-walled carbon nanotubes (SWCNTs) towards a bacterium, Ochrobactrum sp. in water. Compared with SWCNT suspension without SPS, the presence of SPS at different concentrations ranging from 20 to 400 mg L-1 markedly increased the survival rates of bacteria exposed to 50 mg L-1 SWCNTs and bacterial survival rates increased with SPS concentrations by a power law. Sedimentation experiments and field emission scanning electron microscopy revealed the occurrence of heteroaggregation between SWCNTs and SPS, probably responsible for the reduced SWCNT toxicity. Furthermore, the extended Derjaguin-Landau-Verwey-Overbeek (ExDLVO) calculation showed the mitigated toxicity might also result from the decreased SWCNT-bacterium interaction energy with the increased SPS concentrations and the stronger SPS-SWCNT interaction than the SWCNT-bacterium interaction. This work provides new insights into our understanding of environmental hazards of engineered nanomaterials in aquatic systems.

Microbial bioavailability of 2,2',4,4'-Tetrabromodiphenyl ether (BDE-47) in natural sediments from major rivers of China.

Microbial degradation plays a crucial role in eliminating polybrominated diphenyl ethers (PBDEs) in environments. However, the microbial bioavailability of PBDEs in aquatic sediments is not well understood. In this work, the bioavailability of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), a typical PBDE congener, to PBDE-degrading microorganisms in natural sediments from six Chinese rivers under anaerobic conditions was investigated. The contents of black carbon (BC) and total organic carbon (TOC) in the six sediment samples were in the range of 0.025%-0.30% and 0.03%-3.38%, respectively. BDE-47 desorption from various sediments was fitted well with the first-order three-compartment desorption model. The desorbing fraction of sediment-associated BDE-47 at each desorption time interval exhibited a significant negative correlation with the BC content (p < 0.01). In the sediments, the anaerobic debromination of BDE-47 by microorganisms underwent a stepwise debromination pathway generating mainly three lower brominated congeners (BDE-28, -17 and -4). The microbial debromination ratio of BDE-47 ranged from 4.21% to 7.89% in various sediments after 120 d incubation anaerobically, and it negatively correlated with the content of sediment BC significantly (p < 0.01). However, the desorbing fraction and microbial debromination ratio of BDE-47 only showed weak correlations with the TOC content in sediments (p > 0.05). Furthermore, there was a significant positive correlation of desorbing fraction of BDE-47 from sediments with its microbial debromination ratio (p < 0.01) as well as with the level of its three lower brominated products (p < 0.05) after the first 20 d incubation. This study suggests that the BDE-47 bioavailability to microorganisms in anaerobic river sediments is mainly influenced by the content of sediment BC which controls the desorbing fraction of sediment-associated BDE-47.

Effects of carbonaceous materials on microbial bioavailability of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in sediments.

In this study, we investigated the influence of various types of carbonaceous materials (CMs) on the bioavailability of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) to polybrominated diphenyl ether (PBDE)-degrading microorganisms in CM-amended sediments. The microbial debromination ratio of BDE-47 was reduced by 92.8%-98.2% in the 5.0% CM-amended sediment compared with in sediment without CM amendment after 100 d of anaerobic incubation. The concentrations of lower brominated products also decreased when the content of CMs increased from 0.2% to 5.0%. The inhibitory effects of CMs on BDE-47 debromination were CM content- and characteristic-specific. The reciprocals of BDE-47 debromination ratios and lower brominated product concentrations showed positive linear correlations with CM contents in sediments (p<0.01), and the slopes of linear regression fitting generally correlated with specific surface areas (SSAs) of CMs. Desorption of BDE-47 from CMs indicated the declined desorbing fraction of BDE-47 was responsible for the reduction in BDE-47 bioavailability to microorganisms, thus decreasing its debromination in sediments amended with CMs. This study revealed that CM amendment could reduce the PBDE bioavailability to PBDE-degrading microorganisms in sediments, and it is expected to help deepen our understanding of the environmental behaviors and risks of PBDEs.

Bioconcentration of perfluoroalkyl substances by Chironomus plumosus larvae in water with different types of dissolved organic matters.

The effects of four types of dissolved organic matters (DOM) on the bioconcentration of perfluoroalkyl substances (PFASs) in Chironomus plumosus larvae have been studied. The PFASs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA). The DOM included humic acid (HA), fulvic acid (FA), tannic acid (TA), and a protein, peptone (PEP), and their concentrations ranged from 0 to 50 mg L(-1). The results showed that, upon bioconcentration equilibrium, the body burdens of longer perfluoroalkyl chain PFASs (PFOS, PFDA, PFUnA and PFDoA) decreased with PEP and HA concentrations while increased with FA and TA concentrations. When FA and TA concentrations increased from 0 to 50 mg L(-1), body burdens of these PFASs increased by 7.5%-148.8% and 5.7%-37.1%, respectively. However, the DOM had no significant impact on the body burdens of shorter perfluoroalkyl chain PFASs (PFOA and PFNA). All of the four types of DOM lowered not only the uptake rate constants (ku) of PFASs due to the decrease of freely dissolved PFAS concentrations, but also the elimination rate constants (ke) due to the inhibition effect of DOM on the PFAS elimination from the larvae. The reduction in the two constants varied with both DOM and PFAS types. In the presence of PEP and HA with larger molecular weights, the ku values decreased more than ke, leading to the decreased body burdens of longer perfluoroalkyl chain PFASs. As for FA and TA with smaller molecular weights, the ke values decreased more than ku, resulting in increased body burdens of longer perfluoroalkyl chain PFASs. This study suggests that the effects of DOM on PFAS bioconcentration depend not only on the concentration but also on the molecule weight of DOM, which should be considered in the bioavailability assessment of PFASs.

Role of ingestion route in the perfluoroalkyl substance bioaccumulation by Chironomus plumosus larvae in sediments amended with carbonaceous materials.

The role of ingestion route in the bioaccumulation of six types of perfluoroalkyl substances (PFASs) by Chironomus plumosus larvae in sediments amended with four types of carbonaceous materials (CMs) was studied. The results showed that the body burden of PFASs decreased in the presence of CMs at mass ratios of 0.2-2%, regardless of ingestion. PFASs accumulated by the larvae with ingestion exposure were higher than those without ingestion, and the role of ingestion route was altered in the presence of CMs. The contribution of ingestion route to PFAS bioaccumulation was 2.7-31.6% without CMs, and it increased to more than 61.4% in the presence of fullerene at mass ratios of 0.2-2%. The enhancement of the ingestion route contribution caused by CMs is due to the fact that the CMs can be ingested and CM-associated PFASs can be partly desorbed in larvae. The maximum desorption efficiency of perfluorooctanoic acid was 20.8% from fullerene by the larval digestive juice. This study suggests that CM-associated PFASs could be accumulated partly by organisms, and the ecological risk of PFASs might increase in some cases with the presence of CMs. This should be considered when applying CMs in PFAS and other hydrophobic organic compound pollution remediation.

Bioavailability of Pyrene Associated with Suspended Sediment of Different Grain Sizes to Daphnia magna as Investigated by Passive Dosing Devices.

Suspended sediment (SPS) is widely present in rivers around the world. However, the bioavailability of hydrophobic organic compounds (HOCs) associated with SPS is not well understood. In this work, the influence of SPS grain size on the bioavailability of SPS-associated pyrene to Daphnia magna was studied using a passive dosing device, which maintained a constant freely dissolved pyrene concentration (Cfree) in the exposure systems. The immobilization and protein as well as enzymatic activities of Daphnia magna were investigated to study the bioavailability of SPS-associated pyrene. With Cfree of pyrene ranging from 20.0 to 60.0 µg L(-1), the immobilization of Daphnia magna in the presence of 1 g L(-1) SPS was 1.11-2.89 times that in the absence of SPS. The immobilization caused by pyrene associated with different grain size SPS was on the order of 50-100 µm > 0-50 µm > 100-150 µm. When pyrene Cfree was 20.0 µg L(-1), the immobilization caused by pyrene associated with 50-100 µm SPS was 1.42 and 2.43 times that with 0-50 and 100-150 µm SPS, respectively. The protein and enzymatic activities of Daphnia magna also varied with the SPS grain size. The effect of SPS grain size on the bioavailability of SPS-associated pyrene was mainly due to the difference in SPS ingestion by Daphnia magna and SPS composition, especially the organic carbon type, among the three size fractions. This study suggests that not only the concentration but also the size distribution of SPS should be considered for the development of a biological effect database and establishment of water quality criteria for HOCs in natural waters.

Analyzing the contribution of climate change to long-term variations in sediment nitrogen sources for reservoirs/lakes.

We applied a mixing model based on stable isotopic δ(13)C, δ(15)N, and C:N ratios to estimate the contributions of multiple sources to sediment nitrogen. We also developed a conceptual model describing and analyzing the impacts of climate change on nitrogen enrichment. These two models were conducted in Miyun Reservoir to analyze the contribution of climate change to the variations in sediment nitrogen sources based on two (210)Pb and (137)Cs dated sediment cores. The results showed that during the past 50years, average contributions of soil and fertilizer, submerged macrophytes, N2-fixing phytoplankton, and non-N2-fixing phytoplankton were 40.7%, 40.3%, 11.8%, and 7.2%, respectively. In addition, total nitrogen (TN) contents in sediment showed significant increasing trends from 1960 to 2010, and sediment nitrogen of both submerged macrophytes and phytoplankton sources exhibited significant increasing trends during the past 50years. In contrast, soil and fertilizer sources showed a significant decreasing trend from 1990 to 2010. According to the changing trend of N2-fixing phytoplankton, changes of temperature and sunshine duration accounted for at least 43% of the trend in the sediment nitrogen enrichment over the past 50years. Regression analysis of the climatic factors on nitrogen sources showed that the contributions of precipitation, temperature, and sunshine duration to the variations in sediment nitrogen sources ranged from 18.5% to 60.3%. The study demonstrates that the mixing model provides a robust method for calculating the contribution of multiple nitrogen sources in sediment, and this study also suggests that N2-fixing phytoplankton could be regarded as an important response factor for assessing the impacts of climate change on nitrogen enrichment.

Response of PAH-degrading genes to PAH bioavailability in the overlying water, suspended sediment, and deposited sediment of the Yangtze River.

The degrading genes of hydrophobic organic compounds (HOCs) serve as indicators of in situ HOC degradation potential, and the existing forms and bioavailability of HOCs might influence the distribution of HOC-degrading genes in natural waters. However, little research has been conducted to study the relationship between them. In the present study, nahAc and nidA genes, which act as biomarkers for naphthalene- and pyrene-degrading bacteria, were selected as model genotypes to investigate the response of polycyclic aromatic hydrocarbon (PAH)-degrading genes to PAH bioavailability in the overlying water, suspended sediment (SPS), and deposited sediment of the Yangtze River. The freely dissolved concentration, typically used to reflect HOC bioavailability, and total dissolved, as well as sorbed concentrations of PAHs were determined. Phylogenetic analysis showed that all the PAH-ring hydroxylating dioxygenase gene sequences of Gram-negative bacteria (PAH-RHD[GN]) were closely related to nahAc, nagAc, nidA, and uncultured PAH-RHD genes. The PAH-RHD[GN] gene diversity as well as nahAc and nidA gene copy numbers decreased in the following order: deposited sediment>SPS>overlying water. The nahAc and nidA gene abundance was not significantly correlated with environmental parameters but was significantly correlated with the bioavailable existing forms of naphthalene and pyrene in the three phases. The nahAc gene copy numbers in the overlying water and deposited sediment were positively correlated with freely dissolved naphthalene concentrations in the overlying and pore water phases, respectively, and so were nidA gene copy numbers. This study suggests that the distribution and abundance of HOC-degrading bacterial population depend on the HOC bioavailability in aquatic environments.

Effects of seasonal climatic variability on several toxic contaminants in urban lakes: Implications for the impacts of climate change.

Climate change is supposed to have influences on water quality and ecosystem. However, only few studies have assessed the effect of climate change on environmental toxic contaminants in urban lakes. In this research, response of several toxic contaminants in twelve urban lakes in Beijing, China, to the seasonal variations in climatic factors was studied. Fluorides, volatile phenols, arsenic, selenium, and other water quality parameters were analyzed monthly from 2009 to 2012. Multivariate statistical methods including principle component analysis, cluster analysis, and multiple regression analysis were performed to study the relationship between contaminants and climatic factors including temperature, precipitation, wind speed, and sunshine duration. Fluoride and arsenic concentrations in most urban lakes exhibited a significant positive correlation with temperature/precipitation, which is mainly caused by rainfall induced diffuse pollution. A negative correlation was observed between volatile phenols and temperature/precipitation, and this could be explained by their enhanced volatilization and biodegradation rates caused by higher temperature. Selenium did not show a significant response to climatic factor variations, which was attributed to low selenium contents in the lakes and soils. Moreover, the response degrees of contaminants to climatic variations differ among lakes with different contamination levels. On average, temperature/precipitation contributed to 8%, 15%, and 12% of the variations in volatile phenols, arsenic, and fluorides, respectively. Beijing is undergoing increased temperature and heavy rainfall frequency during the past five decades. This study suggests that water quality related to fluoride and arsenic concentrations of most urban lakes in Beijing is becoming worse under this climate change trend.

Modification of Fatty acids in membranes of bacteria: implication for an adaptive mechanism to the toxicity of carbon nanotubes.

We explored whether bacteria could respond adaptively to the presence of carbon nanotubes (CNTs) by investigating the influence of CNTs on the viability, composition of fatty acids, and cytoplasmic membrane fluidity of bacteria in aqueous medium for 24 h exposure. The CNTs included long single-walled carbon nanotubes (L-SWCNTs), short single-walled carbon nanotubes (S-SWCNTs), short carboxyl single-walled carbon nanotubes (S-SWCNT-COOH), and aligned multiwalled carbon nanotubes (A-MWCNTs). The bacteria included three common model bacteria, Staphyloccocus aureus (Gram-positive), Bacillus subtilis (Gram-positive), and Escherichia coli (Gram-negative), and one polybrominated diphenyl ether degrading strain, Ochrobactrum sp. (Gram-negative). Generally, L-SWCNTs were the most toxic to bacteria, whereas S-SWCNT-COOH showed the mildest bacterial toxicity. Ochrobactrum sp. was more susceptible to the toxic effect of CNTs than E. coli. Compared to the control in the absence of CNTs, the viability of Ochrobactrum sp. decreased from 71.6-81.4% to 41.8-70.2%, and E. coli from 93.7-104.0% to 67.7-91.0% when CNT concentration increased from 10 to 50 mg L(-1). The cytoplasmic membrane fluidity of bacteria increased with CNT concentration, and a significant negative correlation existed between the bacterial viabilities and membrane fluidity for E. coli and Ochrobactrum sp. (p < 0.05), indicating that the increase in membrane fluidity induced by CNTs was an important factor causing the inactivation of bacteria. In the presence of CNTs, E. coli and Ochrobactrum sp. showed elevation in the level of saturated fatty acids accompanied with reduction in unsaturated fatty acids, compensating for the fluidizing effect of CNTs. This demonstrated that bacteria could modify their composition of fatty acids to adapt to the toxicity of CNTs. In contrast, S. aureus and B. subtilis exposed to CNTs increased the proportion of branched-chain fatty acids and decreased the level of straight-chain fatty acids, which was also favorable to counteract the toxic effect of CNTs. This study suggests that the bacterial tolerances to CNTs are associated with both the adaptive modification of fatty acids in the membrane and the physicochemical properties of CNTs. This is the first report about the physiologically adaptive response of bacteria to CNTs, and may help to further understand the ecotoxicological effects of CNTs.