Jerald L. Schnoor

Nitrogen fixation: Anthropogenic enhancement‐environmental response

In the absence of human activities, biotic fixation is the primary source of reactive N, providing about 90–130 Tg N yr−1 (Tg = 1012 g) on the continents. Human activities have resulted in the fixation of an additional ≈140 Tg N yr−1 by energy production (≈20 Tg N yr−1 ), fertilizer production (≈80 Tg N yr−1), and cultivation of crops (e.g., legumes, rice) (≈40 Tg N yr−1 ). We can only account for part of this anthropogenic N. N2O is accumulating in the atmosphere at a rate of 3 Tg N yr−1. Coastal oceans receive another 41 Tg N yr−1 via rivers, much of which is buried or denitrified. Open oceans receive 18 Tg N yr−1 by atmospheric deposition, which is incorporated into oceanic N pools (e.g., NO3−, N2). The remaining 80 Tg N yr−1 are either retained on continents in groundwater, soils, or vegetation or denitrified to N2. Field studies and calculations indicate that uncertainties about the size of each sink can account for the remaining anthropogenic N. Thus although anthropogenic N is clearly accumulating on continents, we do not know rates of individual processes. We predict the anthropogenic N-fixation rate will increase by about 60% by the year 2020, primarily due to increased fertilizer use and fossil-fuel combustion. About two-thirds of the increase will occur in Asia, which by 2020 will account for over half of the global anthropogenic N fixation.

Biodegradation of Nitro-Substituted Explosives 2,4,6-Trinitrotoluene, Hexahydro-1,3,5-Trinitro-1,3,5-Triazine, and Octahydro-1,3,5,7-Tetranitro-1,3,5-Tetrazocine by a Phytosymbiotic Methylobacterium sp. Associated with Poplar Tissues (Populus deltoides × nigra DN34)

ABSTRACT A pink-pigmented symbiotic bacterium was isolated from hybrid poplar tissues (Populus deltoides × nigra DN34). The bacterium was identified by 16S and 16S-23S intergenic spacer ribosomal DNA analysis as a Methylobacterium sp. (strain BJ001). The isolated bacterium was able to use methanol as the sole source of carbon and energy, which is a specific attribute of the genus Methylobacterium. The bacterium in pure culture was shown to degrade the toxic explosives 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazene (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5-tetrazocine (HMX). [U-ring-14C]TNT (25 mg liter−1) was fully transformed in less than 10 days. Metabolites included the reduction derivatives amino-dinitrotoluenes and diamino-nitrotoluenes. No significant release of 14CO2 was recorded from [14C]TNT. In addition, the isolated methylotroph was shown to transform [U-14C]RDX (20 mg liter−1) and [U-14C]HMX (2.5 mg liter−1) in less than 40 days. After 55 days of incubation, 58.0% of initial [14C]RDX and 61.4% of initial [14C]HMX were mineralized into 14CO2. The radioactivity remaining in solution accounted for 12.8 and 12.7% of initial [14C]RDX and [14C]HMX, respectively. Metabolites detected from RDX transformation included a mononitroso RDX derivative and a polar compound tentatively identified as methylenedinitramine. Since members of the genus Methylobacterium are distributed in a wide diversity of natural environments and are very often associated with plants, Methylobacterium sp. strain BJ001 may be involved in natural attenuation or in situ biodegradation (including phytoremediation) of explosive-contaminated sites.

Phytoremediation of Polychlorinated Biphenyls: New Trends and Promises†

Transgenic plants and associated bacteria constitute a new generation of genetically modified organisms for efficient and environment-friendly treatment of soil and water contaminated with polychlorinated biphenyls (PCBs). This review focuses on recent advances in phytoremediation for the treatment of PCBs, including the development of transgenic plants and associated bacteria. Phytoremediation, or the use of higher plants for rehabilitation of soil and groundwater, is a promising strategy for cost-effective treatment of sites contaminated by toxic compounds, including PCBs. Plants can help mitigate environmental pollution by PCBs through a range of mechanisms: besides uptake from soil (phytoextraction), plants are capable of enzymatic transformation of PCBs (phytotransformation); by releasing a variety of secondary metabolites, plants also enhance the microbial activity in the root zone, improving biodegradation of PCBs (rhizoremediation). However, because of their hydrophobicity and chemical stability, PCBs are only slowly taken up and degraded by plants and associated bacteria, resulting in incomplete treatment and potential release of toxic metabolites into the environment. Moreover, naturally occurring plant-associated bacteria may not possess the enzymatic machinery necessary for PCB degradation. To overcome these limitations, bacterial genes involved in the metabolism of PCBs, such as biphenyl dioxygenases, have been introduced into higher plants, following a strategy similar to the development of transgenic crops. Similarly, bacteria have been genetically modified that exhibit improved biodegradation capabilities and are able to maintain stable relationships with plants. Transgenic plants and associated bacteria bring hope for a broader and more efficient application of phytoremediation for the treatment of PCBs.

Photosynthetic control of atmospheric carbonyl sulfide during the growing season.

Climate models incorporate photosynthesis-climate feedbacks, yet we lack robust tools for large-scale assessments of these processes. Recent work suggests that carbonyl sulfide (COS), a trace gas consumed by plants, could provide a valuable constraint on photosynthesis. Here we analyze airborne observations of COS and carbon dioxide concentrations during the growing season over North America with a three-dimensional atmospheric transport model. We successfully modeled the persistent vertical drawdown of atmospheric COS using the quantitative relation between COS and photosynthesis that has been measured in plant chamber experiments. Furthermore, this drawdown is driven by plant uptake rather than other continental and oceanic fluxes in the model. These results provide quantitative evidence that COS gradients in the continental growing season may have broad use as a measurement-based photosynthesis tracer.

E-Waste Recycling: Where Does It Go from Here?

E-waste recycling has become a hotly debated global issue. This study, using China as a case study, analyzes the environmental, economic, and social implications of e-waste recycling in the developing world. More practical approaches, taking into account local economic and social conditions and the principles of Extended Producer Responsibility, are recommended to alleviate the increasing environmental disruption from improper e-waste disposal.

Degradation of TCE, Cr(VI), sulfate, and nitrate mixtures by granular iron in flow-through columns under different microbial conditions

Flow-through aquifer columns packed with a middle layer of granular iron (Fe0) were used to study the applicability and limitations of bio-enhanced Fe0 barriers for the treatment of contaminant mixtures in groundwater. Concentration profiles along the columns showed extensive degradation of hexavalent chromium Cr(VI), nitrate, sulfate, and trichloroethene (TCE), mainly in the Fe0 layer. One column was bioaugmented with Shevanella algae BRY, an iron-reducing bacterium that could enhance Fe0 reactivity by reductive dissolution of passivating iron oxides. This strain did not enhance Cr(VI), which was rapidly reduced by iron, leaving little room for improvement by microbial participation. Nevertheless, BRY-enhanced nitrate removal (from 15% to 80%), partly because this strain has a wide range of electron acceptors, including nitrate. Sulfate was removed (55%) only in a column that was bioaugmented with a mixed culture containing sulfate-reducing bacteria. Apparently, these bacteria used H2 (produced by Fe0 corrosion) as electron donor to respire sulfate. Most of the TCE was degraded in the zone containing Fe0 (50-70%), and bioaugmentation with BRY slightly increased the removal efficiency to about 80%. Microbial colonization of the Fe0 surface was confirmed by scanning electron microscopy.

Reductive dechlorination of carbon tetrachloride with elemental iron

Carbon tetrachloride (CCl4) was abiotically dechlorinated to chloroform (CHCl3) and methylene chloride (CH2Cl2) by zero valent iron (Fe0). Dechlorination of CCl4 was rapid, and approximately followed first-order kinetics in the range of concentrations tested (CCl4: 1.5–5.5 μM; Fe0 powder: 1–10 g per 265 ml distilled water). Initial dechlorination rate coefficients for anoxic batch reactors (0.290 ± 0.009 h−1 for 1 g Fe0; 1.723 ± 0.078 h−1 for 10 g Fe0) increased with iron surface area (initially 2.4 ± 0.2 m2/g). Rate coefficients also increased with time, probably because of an increase in reactive surface area due to cathodic depolarization and pitting of the iron surface. Dechlorination also occurred under oxic conditions, although the rates were significantly slower (e.g., 0.085 ± 0.041 h−1 for 1 g Fe0 and initial dissolved oxygen 7.4 mg/l). A rapid pH increase was synchronous to dissolved oxygen consumption, and the pH remained constant after the oxygen was depleted. This was attributed to the proton and oxygen consuming aerobic corrosion of the Fe0 surface. The potential for developing remediation technology with Fe0 is discussed.

Phytostimulation of Poplars and Arabidopsis Exposed to Silver Nanoparticles and Ag+ at Sublethal Concentrations

The increasing likelihood of silver nanoparticle (AgNP) releases to the environment highlights the importance of understanding AgNP interactions with plants, which are cornerstones of most ecosystems. In this study, poplars (Populus deltoides × nigra) and Arabidopsis thaliana were exposed hydroponically to nanoparticles of different sizes (PEG-coated 5 and 10 nm AgNPs, and carbon-coated 25 nm AgNPs) or silver ions (Ag(+), added as AgNO₃) at a wide range of concentrations (0.01 to 100 mg/L). Whereas all forms of silver were phytotoxic above a specific concentration, a stimulatory effect was observed on root elongation, fresh weight, and evapotranspiration of both plants at a narrow range of sublethal concentrations (e.g., 1 mg/L of 25 nm AgNPs for poplar). Plants were most susceptible to the toxic effects of Ag(+) (1 mg/L for poplar, 0.05 mg/L for Arabidopsis), but AgNPs also showed some toxicity at higher concentrations (e.g., 100 mg/L of 25 nm AgNPs for poplar, 1 mg/L of 5 nm AgNPs for Arabidopsis) and this susceptibility increased with decreasing AgNP size. Both poplars and Arabidopsis accumulated silver, but silver distribution in shoot organs varied between plant species. Arabidopsis accumulated silver primarily in leaves (at 10-fold higher concentrations than in the stem or flower tissues), whereas poplars accumulated silver at similar concentrations in leaves and stems. Within the particle subinhibitory concentration range, silver accumulation in poplar tissues increased with exposure concentration and with smaller AgNP size. However, compared to larger AgNPs, the faster silver uptake associated with smaller AgNPs was offset by their toxic effect on evapotranspiration, which was exerted at lower concentrations (e.g., 1 mg/L of 5 nm AgNPs for poplar). Overall, the observed phytostimulatory effects preclude generalizations about the phytotoxicity of AgNPs and encourage further mechanistic research.

Barriers, pathways and processes for uptake, translocation and accumulation of nanomaterials in plants – Critical review

Abstract Uptake, transport and toxicity of engineered nanomaterials (ENMs) into plant cells are complex processes that are currently still not well understood. Parts of this problem are the multifaceted plant anatomy, and analytical challenges to visualize and quantify ENMs in plants. We critically reviewed the currently known ENM uptake, translocation, and accumulation processes in plants. A vast number of studies showed uptake, clogging, or translocation in the apoplast of plants, most notably of nanoparticles with diameters much larger than the commonly assumed size exclusion limit of the cell walls of ∼5–20 nm. Plants that tended to translocate less ENMs were those with low transpiration, drought-tolerance, tough cell wall architecture, and tall growth. In the absence of toxicity, accumulation was often linearly proportional to exposure concentration. Further important factors strongly affecting ENM internalization are the cell wall composition, mucilage, symbiotic microorganisms (mycorrhiza), the absence of a cuticle (submerged plants) and stomata aperture. Mostly unexplored are the roles of root hairs, leaf repellency, pit membrane porosity, xylem segmentation, wounding, lateral roots, nodes, the Casparian band, hydathodes, lenticels and trichomes. The next steps towards a realistic risk assessment of nanoparticles in plants are to measure ENM uptake rates, the size exclusion limit of the apoplast and to unravel plant physiological features favoring uptake.

Regional variation in water-related impacts of shale gas development and implications for emerging international plays.

The unconventional fossil fuel industry is expected to expand dramatically in coming decades as conventional reserves wane. Minimizing the environmental impacts of this energy transition requires a contextualized understanding of the unique regional issues that shale gas development poses. This manuscript highlights the variation in regional water issues associated with shale gas development in the U.S. and the approaches of various states in mitigating these impacts. The manuscript also explores opportunities for emerging international shale plays to leverage the diverse experiences of U.S. states in formulating development strategies that minimize water-related impacts within their environmental, cultural, and political ecosystem.