Phytoremediation, Bioaugmentation, and the Plant Microbiome.

Understanding plant biology and related microbial ecology as a means to phytoremediate soil and groundwater contamination has broadened and advanced the field of environmental engineering and science over the past 30 years. Using plants to transform and degrade xenobiotic organic pollutants delivers new methods for environmental restoration. Manipulations of the plant microbiome through bioaugmentation, endophytes, adding various growth factors, genetic modification, and/or selecting the microbial community via insertion of probiotics or phages for gene transfer are future areas of research to further expand this green, cost-effective, aesthetically pleasing technology─phytoremediation.

Decadal Journey of E-Waste Recycling: What Has It Achieved?

E-waste recycling has been a hot topic around the world. This Feature revisits the issues raised by our previous Feature 10 years ago, i.e., the environmental, economic, and social benefits of e-waste recycling, using China as an example. The decadal journey of e-waste recycling has witnessed a giant leap from haphazard disposal initially to regulated disassembly presently. Specific successful stories include cleaned environment and reduced human exposure, significant advantages of urban mining over mineral mining, additional employment opportunities, and improved legislation system related to e-waste recycling. Strict legislation systems related to e-waste management based on the principle of Extended Producer Responsibility are key to the sustainable development of the e-waste recycling sector in China. The experiences and lessons learned in China would provide valuable guidelines for other developing countries.

Aerobic Bioaugmentation to Decrease Polychlorinated Biphenyl (PCB) Emissions from Contaminated Sediments to Air.

We conducted experiments to determine whether bioaugmentation with aerobic, polychlorinated biphenyl (PCB)-degrading microorganisms can mitigate polychlorinated biphenyl (PCB) emissions from contaminated sediment to air. Paraburkholderia xenovorans strain LB400 was added to bioreactors containing PCB-contaminated site sediment. PCB mass in both the headspace and aqueous bioreactor compartments was measured using passive samplers over 35 days. Time-series measurements of all 209 PCB congeners revealed a 57% decrease in total PCB mass accumulated in the vapor phase of bioaugmented treatments relative to non-bioaugmented controls, on average. A comparative congener-specific analysis revealed preferential biodegradation of lower-chlorinated PCBs (LC-PCBs) by LB400. Release of the most abundant congener (PCB 4 [2,2'-dichlorobiphenyl]) decreased by over 90%. Simulations with a PCB reactive transport model closely aligned with experimental observations. We also evaluated the effect of the phytogenic biosurfactant, saponin, on PCB bioavailability and biodegradation by LB400. Time-series qPCR measurements of biphenyl dioxygenase (bphA) genes showed that saponin better maintained bphA abundance, compared to the saponin-free treatment. These findings indicate that an active population of bioaugmented, aerobic PCB-degrading microorganisms can effectively lower PCB emissions and may therefore contribute to minimizing PCB inhalation exposure in communities surrounding PCB-contaminated sites.

Medium- and Short-Chain Chlorinated Paraffins in Mature Maize Plants and Corresponding Agricultural Soils.

For the most complex artificial chlorinated environmental contaminants, much less is known for medium-chain CPs than short-chain CPs. In this research, the spatial distributions of MCCPs and SCCPs in farmland soil and maize leaves near a CP production facility were found marginally influenced by seasonal winds. The levels of ∑MCCPs and ∑SCCPs were in the ranges of <1.51-188 and 5.41-381 ng/g dw for soils; and 77.6-52930 and 119-61999 ng/g dw for maize leaf, respectively. Bioaccumulation and tissue distributions of the CPs within maize plants were specifically analyzed. Most of the CPs were contained in the tissues directly exposed to airborne CPs. Though the estimated risk of CPs to humans through ingestion of kernels appears to be minimal, the edible safety of MCCPs in maize plants for cattle was nearly in the designated range of adverse effects. To our knowledge, this is the first report on bioaccumulation of CPs in mature maize plants, especially in the parts eaten by humans and domestic animals. It provides a baseline reference to the edible risks of CPs in agricultural food plants and alerts us to the problematic environmental behavior of MCCPs, a probable future replacement for SCCPs commercially.

Compartmentalization and Excretion of 2,4,6-Tribromophenol Sulfation and Glycosylation Conjugates in Rice Plants.

The most environmentally abundant bromophenol congener, 2,4,6-tribromophenol (2,4,6-TBP, 6.06 µmol/L), was exposed to rice for 5 d both in vivo (intact seedling) and in vitro (suspension cell) to systematically characterize the fate of its sulfation and glycosylation conjugates in rice. The 2,4,6-TBP was rapidly transformed to produce 6 [rice cells (3 h)] and 8 [rice seedlings (24 h)] sulfated and glycosylated conjugates. The predominant sulfation conjugate (TP408, 93.0-96.7%) and glycosylation conjugate (TP490, 77.1-90.2%) were excreted into the hydroponic solution after their formation in rice roots. However, the sulfation and glycosylation conjugates presented different translocation and compartmentalization behaviors during the subsequent Phase III metabolism. Specifically, the sulfated conjugate could be vertically transported into the leaf sheath and leaf, while the glycosylation conjugates were sequestered in cell vacuoles and walls, which resulted in exclusive compartmentalization within the rice roots. These results showed the micromechanisms of the different compartmentalization behaviors of 2,4,6-TBP conjugates in Phase III metabolism. Glycosylation and sulfation of the phenolic hydroxyl groups orchestrated by plant excretion and Phase III metabolism may reduce the accumulation of 2,4,6-TBP and its conjugates in rice plants.

Atropselective Disposition of 2,2',3,4',6-Pentachlorobiphenyl (PCB 91) and Identification of Its Metabolites in Mice with Liver-Specific Deletion of Cytochrome P450 Reductase.

Hepatic cytochrome P450 enzymes metabolize chiral polychlorinated biphenyls (PCBs) to hydroxylated metabolites (OH-PCBs). Animal models with impaired metabolism of PCBs are one approach to study how the atropselective oxidation of PCBs to OH-PCBs contributes to toxic outcomes, such as neurodevelopmental disorders, following PCB exposure. We investigated the disposition of PCB 91, a para-substituted PCB congener, in mice with a liver-specific deletion of the cytochrome P450 reductase (cpr) gene (KO mice). KO mice and wild-type (WT) mice were exposed orally to racemic PCB 91 (30 mg/kg b.w.). Levels and enantiomeric fractions of PCB 91 and its hydroxylated metabolites were determined in tissues 3 days after PCB exposure and in excreta on days 1-3 after PCB exposure. PCB 91, but not OH-PCB levels were higher in KO compared to WT mice. The elevated fat and protein content in the liver of KO mice resulted in the hepatic accumulation of PCB 91. OH-PCBs were detected in blood, liver, and excreta samples of KO and WT mice. 2,2',3,4',6-Pentachlorobiphenyl-5-ol (5-91) was the major metabolite. A considerable percent of the total PCB 91 dose (%TD) was excreted with the feces as 5-91 (23%TD and 31%TD in KO and WT mice, respectively). We tentatively identified glucuronide and sulfate metabolites present in urine samples. The PCB 91 atropisomer eluting first on the chiral column (E1-PCB 91) displayed genotype-dependent atropisomeric enrichment, with a more pronounced atropisomeric enrichment observed in WT compared to KO mice. E1-atropisomers of 5-91 and 2,2',3,4',6-pentachlorobiphenyl-4-ol (4-91) were enriched in blood and liver, irrespective of the genotype; however, the extent of the enrichment of E1-5-91 was genotype dependent. These differences in atropselective disposition are consistent with slower metabolism of PCB 91 in KO compared to WT mice and the accumulation of the parent PCB in the fatty liver of KO mice.

Metabolism of SCCPs and MCCPs in Suspension Rice Cells Based on Paired Mass Distance (PMD) Analysis.

Short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) are mixtures of complex chemical compounds with intensive usage. They are frequently detected in various environmental samples. However, the interaction between CPs and plants, especially the biotransformation behaviors of CPs within plants, is poorly understood. In this study, 1,2,5,6,9,10-hexachlorodecane (CP-4, a typical standard of individual SCCP congeners) and 52%-MCCP (a commercial mixture standard of MCCPs with 52% chlorine content by mass) were selected as representative chemicals to explore the metabolic behaviors of SCCPs and MCCPs using suspension rice cell culture exposure systems. Both 79.53% and 40.70% of CP-4 and 52%-MCCP were metabolized by suspension rice cells, respectively. A complementary suspected screening strategy based on the pair mass distances (PMD) analysis algorithm was used to study the metabolism of CPs mediated by the plant cells. Forty and 25 metabolic products for CP-4 and 52%-MCCP, respectively, were identified, including (multi-) hydroxylation, dechlorination, -HCl- elimination metabolites, (hydroxylation-) sulfation, and glycosylation conjugates. Here, we propose a comprehensive metabolic molecular network and provide insight on degradation pathways of SCCPs and MCCPs in plants for the first time, aiding in further understanding of the transformation behaviors of CPs.

China's Ban on Phenylarsonic Feed Additives, A Major Step toward Reducing the Human and Ecosystem Health Risk from Arsenic.

Phenylarsonic feed additives were once widely used in poultry and swine production around the world, which brought significant and unnecessary health risk to consumers due to elevated residues of arsenic species in animal tissues. They also increased the risk to ecosystems via releases of inorganic arsenic through their environmental transformation. Out of concern for the negative impacts on human and ecosystem health, China, one of the world's largest poultry and swine producing countries, recently banned the use of phenylarsonic feed additives in food animal production. This ban, if fully enforced, will result in reduction of approximately 1160 cancer cases per year from the consumption of chicken meat alone, and avoid an annual economic loss of nearly 0.6 billion CNY according to our risk analysis. Furthermore, the inventory of anthropogenic arsenic emissions in China will be cut by approximately one-third with the phase-out of phenylarsonic feed additives. This ban is also expected to lead to significant reduction in the accumulation of arsenic in the soils of farmlands fertilized by poultry and swine wastes and, consequently, lower the accumulation of arsenic in food crops grown on them, which could have even greater public health benefits. But effective enforcement of the ban is crucial, and it will require detailed supervision of veterinary drug production and distribution, and enhanced surveillance of animal feeds and food products. Furthermore, control of other major anthropogenic sources of arsenic is also necessary to better protect human health and the environment.

Carbon Chain Decomposition of Short Chain Chlorinated Paraffins Mediated by Pumpkin and Soybean Seedlings.

Short chain chlorinated paraffins (SCCPs) are a group of complex emerging persistent organic pollutants. In this study, the uptake, translocation, and transformation of four constitutionally defined SCCP isomers were studied using whole pumpkin ( Cucurbita maxima × C. moschata) and soybean ( Glycine max L. Merrill) seedlings via hydroponic exposure. Results showed that the daughter SCCPs were C10Cl5-8 and C11-13Cl5-6. The metabolic transformation of all tested isomers included dechlorination and chlorine rearrangement. In addition, carbon chain decomposition products were found for isomers with trichlorinated carbon atoms (CCl3-groups) in both pumpkin and soybean seedlings. This study provides the first evidence of carbon chain decomposition of SCCPs in whole plants, and it suggests new metabolism pathways of SCCPs in the environment. The influence of carbon chain length and degree of chlorination of SCCPs on their fate and behavior within different plant species were also investigated. Bioaccumulation of SCCPs in pumpkin and soybean increased with increasing carbon chain length and degree of chlorination. In comparison, soybean translocated and degraded parent SCCPs faster and to a greater extent than pumpkin, but pumpkin accumulated parent SCCPs to a greater extent than soybean. After 10 days exposure, less than 4% of the initial mass of exposed chemicals remained in solution of exposure groups. The parent chemicals accumulated in roots ranging from 23.6% to 59.9% for pumpkin and 1.98% to 54.5% for soybean and in stems ranging from 0.7% to 3.81% for pumpkin and 0.50% to 2.54% for soybean. These results give new perspectives on the transport, transformation, and fate of SCCPs in the environment.

Glycosylation of Tetrabromobisphenol A in Pumpkin.

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant (BFR), and it bioaccumulates throughout the food chains. Its fate in the first trophic level, plants, is of special interest. In this study, a four-day hydroponic exposure of TBBPA at a concentration of 1 µmol L-1 to pumpkin seedlings was conducted. A nontarget screening method for hydrophilic bromine-containing metabolites was modified, based on both typical isotope patterns of bromine and mass defect, and used to process mass spectra data. A total of 20 glycosylation and malonyl glycosylation metabolites were found for TBBPA in the pumpkin plants. Representative glycosyl TBBPA reference standards were synthesized to evaluate the contribution of this glycosylation process. Approximately 86% of parent TBBPA was metabolized to form those 20 glycosyl TBBPAs, showing that glycosylation was the most dominant metabolism pathway for TBBPA in pumpkin at the tested exposure concentration.

Multiple Metabolic Pathways of 2,4,6-Tribromophenol in Rice Plants.

Bromophenols occur naturally and are used globally as man-made additives in various industrial products. They are decomposition products of many emerging organic pollutants, such as tetrabromobisphenol A, polybrominated dibenzo- p-dioxin (PBDD), polybrominated diphenyl ethers (PBDE), and others. To characterize their biotransformation pathways, bromophenol congener 2,4,6-tribromophenol, being used most frequently in the synthesis of brominated flame retardants and having the greatest environmental abundance, was selected to hydroponically expose rice plants. After exposure for 5 days, 99.2% of 2,4,6-tribromophenol was metabolized by rice. Because of the lack of relative reference standards, an effective screening strategy was used to screen for potential metabolites that were further qualitatively identified by gas and liquid chromatography combined with high-resolution mass spectrometry. Forty transformation products were confirmed or tentatively identified at different confidence levels, including 9 phase I and 31 phase II metabolites. A large number of metabolites (39) were found in rice root, and 10 of them could be translocated and detected in rice stems or leaves. Many transformation pathways were proposed, including debromination, hydroxylation, methylation, coupling reactions, sulfation, and glycosylation. It was remarkable that a total of seven hydrophobic, persistent, and toxic OH-PBDEs and PBDD/Fs were found, indicating the biotic dimeric reactions of 2,4,6-tribromophenol that occurred in the rice plants. These results improve our understanding of the transformation and environmental fates of bromophenols, and they indicate new potential sources for OH-PBDEs and PBDD/Fs in the environment, especially in food chains.

Insight into Multiple and Multilevel Structures of Biochars and Their Potential Environmental Applications: A Critical Review.

Biochar is the carbon-rich product of the pyrolysis of biomass under oxygen-limited conditions, and it has received increasing attention due to its multiple functions in the fields of climate change mitigation, sustainable agriculture, environmental control, and novel materials. To design a "smart" biochar for environmentally sustainable applications, one must understand recent advances in biochar molecular structures and explore potential applications to generalize upon structure-application relationships. In this review, multiple and multilevel structures of biochars are interpreted based on their elemental compositions, phase components, surface properties, and molecular structures. Applications such as carbon fixators, fertilizers, sorbents, and carbon-based materials are highlighted based on the biochar multilevel structures as well as their structure-application relationships. Further studies are suggested for more detailed biochar structural analysis and separation and for the combination of macroscopic and microscopic information to develop a higher-level biochar structural design for selective applications.

Sugar Cane-Converted Graphene-like Material for the Superhigh Adsorption of Organic Pollutants from Water via Coassembly Mechanisms.

A sugar cane-converted graphene-like material (FZS900) was fabricated by carbonization and activation. The material exhibited abundant micropores, water-stable turbostratic single-layer graphene nanosheets, and a high BET-N2 surface area (2280 m2 g-1). The adsorption capacities of FZS900 toward naphthalene, phenanthrene, and 1-naphthol were 615.8, 431.2, and 2040 mg g-1, respectively, which are much higher than those of previously reported materials. The nonpolar aromatic molecules induced the turbostratic graphene nanosheets to agglomerate in an orderly manner, forming 2-11 graphene layer nanoloops, while polar aromatic compounds induced high dispersion or aggregation of the graphene nanosheets. This phase conversion of the nanosized materials after sorption occurred through coassembly of the aromatic molecules and the single-layer graphene nanosheets via large-area π-π interactions. An adsorption-induced partition mechanism was further proposed to explain the nanosize effect and nanoscale sorption sites observed. This study indicates that commonly available biomass can be converted to graphene-like material with superhigh sorption ability in order to remove pollutants from the environment via nanosize effects and a coassembly mechanism.

Effects of Polychlorinated Biphenyls (PCBs) and Their Hydroxylated Metabolites (OH-PCBs) on Arabidopsis thaliana.

Plants metabolize polychlorinated biphenyls (PCBs) into hydroxylated derivatives (OH-PCBs), which are sometimes more toxic than the parent PCBs. The objective of this research was to compare the toxicity of a suite of PCBs and OH-PCBs toward the model plant, Arabidopsis thaliana. While parent PCBs and higher-chlorinated OH-PCBs exhibited a low or nondetectable toxicity, lower-chlorinated OH-PCBs significantly inhibited the germination rate and plant growth, with inhibition concentration 50% (IC50) ranging from 1.6 to 12.0 mg L-1. The transcriptomic response of A. thaliana to 2,5-dichlorobiphenyl (2,5-DCB), and its OH metabolite, 4'-OH-2,5-DCB, was then examined using whole-genome expression microarrays (Affymetrix). Exposure to 2,5-DCB and 4'-OH-2,5-DCB resulted in different expression patterns, with the former leading to enrichment of genes involved in response to toxic stress and detoxification functions. Exposure to 2,5-DCB induced multiple xenobiotic response genes, such as cytochrome P-450 and glutathione S-transferases, potentially involved in the PCB metabolism. On the contrary, exposure to both compounds resulted in the down-regulation of genes involved in stresses not directly related to toxicity. Unlike its OH derivative, 2,5-DCB was shown to induce a transcriptomic profile similar to plant safeners, which are nontoxic chemicals stimulating detoxification pathways in plants. The differentiated induction of detoxification enzymes by 2,5-DCB may explain its lower phytotoxicity compared to 4'-OH-2,5-DCB.

Critical Uncertainties and Gaps in the Environmental- and Social-Impact Assessment of the Proposed Interoceanic Canal through Nicaragua.

The proposed interoceanic canal will connect the Caribbean Sea with the Pacific Ocean, traversing Lake Nicaragua, the major freshwater reservoir in Central America. If completed, the canal would be the largest infrastructure-related excavation project on Earth. In November 2015, the Nicaraguan government approved an environmental and social impact assessment (ESIA) for the canal. A group of international experts participated in a workshop organized by the Academy of Sciences of Nicaragua to review this ESIA. The group concluded that the ESIA does not meet international standards; essential information is lacking regarding the potential impacts on the lake, freshwater and marine environments, and biodiversity. The ESIA presents an inadequate assessment of natural hazards and socioeconomic disruptions. The panel recommends that work on the canal project be suspended until an appropriate ESIA is completed. The project should be resumed only if it is demonstrated to be economically feasible, environmentally acceptable, and socially beneficial.

Recognizing Drinking Water Pipes as Community Health Hazards.

On this Earth Day, let us begin to recognize that aging water infrastructure, particularly lead pipes, solder, and faucets, represents a community health hazard of enduring significance. Causes of the crisis in Flint, Michigan, are discussed, but such scenarios could take place in thousands of similar communities. Recommendations are offered to the public as taxpayers, the U.S. Environmental Protection Agency, and to chemical educators and water engineers. Old water infrastructure needs maintenance, repair, and replacement, and funds should be established now to accomplish the task.

Charge, size, and cellular selectivity for multiwall carbon nanotubes by maize and soybean.

Maize (Zea mays) and soybean (Glycine max) were used as model food-chain plants to explore vegetative uptake of differently charged multiwall carbon nanotubes (MWCNTs). Three types of MWCNTs, including neutral pristine MWCNT (p-MWCNT), positively charged MWCNT-NH2, and negatively charged MWCNT-COOH, were directly taken-up and translocated from hydroponic solution to roots, stems, and leaves of maize and soybean plants at the MWCNT concentrations ranging from 10.0 to 50.0 mg/L during 18-day exposures. MWCNTs accumulated in the xylem and phloem cells and within specific intracellular sites like the cytoplasm, cell wall, cell membrane, chloroplast, and mitochondria, which was observed by transmission electron microscopy. MWCNTs stimulated the growth of maize and inhibited the growth of soybean at the exposed doses. The cumulative transpiration of water in maize exposed to 50 mg/L of MWCNT-COOHs was almost twice as much as that in the maize control. Dry biomass of maize exposed to MWCNTs was greater than that of maize control. In addition, the uptake and translocation of these MWCNTs clearly exhibited cellular, charge, and size selectivity in maize and soybean, which could be important properties for nanotransporters. This is the first report of cellular, charge, and size selectivity on the uptake by whole food plants for three differently charged MWCNTs.

Scientists raise alarms about fast tracking of transoceanic canal through Nicaragua.

Seeking economic growth and job creation to tackle the nation's extreme poverty, the Nicaraguan government awarded a concession to build an interoceanic canal and associated projects to a recently formed Hong Kong based company with no track record or related expertise. This concession was awarded without a bidding process and in advance of any feasibility, socio-economic or environmental impact assessments; construction has begun without this information. The 278 km long interoceanic canal project may result in significant environmental and social impairments. Of particular concern are damage to Lake Cocibolca, a unique freshwater tropical lake and Central America's main freshwater reservoir; damage to regional biodiversity and ecosystems; and socio-economic impacts. Concerned about the possibly irreparable damage to the environment and to native communities, conservationists and the scientific community at large are urging the Nicaraguan government to devise and reveal an action plan to address and mitigate the possible negative repercussions of this interoceanic canal and associated projects. Critical research needs for preparation of a comprehensive benefit-cost analysis for this megaproject are presented.

Microbial community analysis of switchgrass planted and unplanted soil microcosms displaying PCB dechlorination.

Polychlorinated biphenyls (PCBs) pose potential risks to human and environmental health because they are carcinogenic, persistent, and bioaccumulative. In this study, we investigated bacterial communities in soil microcosms spiked with PCB 52, 77, and 153. Switchgrass (Panicum virgatum) was employed to improve overall PCB removal, and redox cycling (i.e., sequential periods of flooding followed by periods of no flooding) was performed in an effort to promote PCB dechlorination. Lesser chlorinated PCB transformation products were detected in all microcosms, indicating the occurrence of PCB dechlorination. Terminal restriction fragment length polymorphism (T-RFLP) and clone library analysis showed that PCB spiking, switchgrass planting, and redox cycling affected the microbial community structure. Putative organohalide-respiring Chloroflexi populations, which were not found in unflooded microcosms, were enriched after 2 weeks of flooding in the redox-cycled microcosms. Sequences classified as Geobacter sp. were detected in all microcosms and were most abundant in the switchgrass-planted microcosm spiked with PCB congeners. The presence of possible organohalide-respiring bacteria in these soil microcosms suggests that they play a role in PCB dechlorination therein.