[show abstract][hide abstract] ABSTRACT: A large fraction of engineered nanomaterials in consumer and commercial products will reach natural ecosystems. To date, research on the biological impacts of environmental nanomaterial exposures has largely focused on high-concentration exposures in mechanistic lab studies with single strains of model organisms. These results are difficult to extrapolate to ecosystems, where exposures will likely be at low-concentrations and which are inhabited by a diversity of organisms. Here we show adverse responses of plants and microorganisms in a replicated long-term terrestrial mesocosm field experiment following a single low dose of silver nanoparticles (0.14 mg Ag kg soil) applied via a likely route of exposure, sewage biosolid application. While total aboveground plant biomass did not differ between treatments receiving biosolids, one plant species, had 32 % less biomass in the Slurry+AgNP treatment relative to the Slurry only treatment. Microorganisms were also affected by AgNP treatment, which gave a significantly different community composition of bacteria in the Slurry+AgNPs as opposed to the Slurry treatment one day after addition as analyzed by T-RFLP analysis of 16S-rRNA genes. After eight days, NO flux was 4.5 fold higher in the Slurry+AgNPs treatment than the Slurry treatment. After fifty days, community composition and NO flux of the Slurry+AgNPs treatment converged with the Slurry. However, the soil microbial extracellular enzymes leucine amino peptidase and phosphatase had 52 and 27% lower activities, respectively, while microbial biomass was 35% lower than the Slurry. We also show that the magnitude of these responses was in all cases as large as or larger than the positive control, AgNO, added at 4-fold the Ag concentration of the silver nanoparticles.
PLoS ONE 01/2013; 8(2):e57189. · 3.73 Impact Factor
[show abstract][hide abstract] ABSTRACT: The development of antibiotics revolutionized human health, providing a simple cure for once dreaded diseases such as tuberculosis. However, widespread production, use, and mis-use of antibiotics have contributed to the next-generation concern for global public health: the emergence of multiple drug-resistant (MDR) infectious organisms (a.k.a. “superbugs”). Recently, nanotechnology, specifically the use of nanomaterials (NMs) with antimicrobial activity, has been presented as a new defense against MDR infectious organisms. We discuss the potential for NMs to either circumvent microbial resistance or induce its development in light of our current state of knowledge, finding that this question points to a need for fundamental research targeting the molecular mechanisms causing antimicrobial activity in NMs. In the context of current microbial nanotoxicology studies, particularly reductionist laboratory studies, we offer suggestions and considerations for future research, using an illustrative example from our work with silver nanoparticles.
[show abstract][hide abstract] ABSTRACT: Titanium dioxide (TiO(2)) is the most extensively used engineered nanoparticle to date, yet its fate in the soil environment has been investigated only rarely and is poorly understood. In the present study, we conducted two field-scale investigations to better describe TiO(2) nano- and larger particles in their most likely route of entry into the environment, i.e., the application of biosolids to soils. We particularly concentrated on the particles in the nano-size regime due to their novel and commercially useful properties. First, we analyzed three sewage sludge products from the US EPA TNSSS sampling inventory for the occurrence, qualitative abundance, and nature of TiO(2) nano- and larger particles by using analytical scanning electron microscopy and analytical (scanning) transmission electron microscopy. Nano- and larger particles of TiO(2) were repeatedly identified across the sewage sludge types tested, providing strong evidence of their likely concentration in sewage sludge products. The TiO(2) particles identified were as small as 40 nm, and as large as 300 nm, having faceted shapes with the rutile crystal structure, and they typically formed small, loosely packed aggregates. Second, we examined surface soils in mesocosms that had been amended with Ag nanoparticle-spiked biosolids for the occurrence of TiO(2) particles. An aggregate of TiO(2) nanoparticles with the rutile structure was again identified, but this time TiO(2) nanoparticles were found to contain Ag on their surfaces. This suggests that TiO(2) nanoparticles from biosolids can interact with toxic trace metals that would then enter the environment as a soil amendment. Therefore, the long-term behavior of TiO(2) nano- and larger particles in sewage sludge materials as well as their impacts in the soil environment need to be carefully considered.
Journal of Environmental Monitoring 02/2012; 14(4):1129-37. · 2.09 Impact Factor
[show abstract][hide abstract] ABSTRACT: The production of the neurotoxic methylmercury in the environment is partly controlled by the bioavailability of inorganic divalent mercury (Hg(II)) to anaerobic bacteria that methylate Hg(II). In sediment porewater, Hg(II) associates with sulfides and natural organic matter to form chemical species that include organic-coated mercury sulfide nanoparticles as reaction intermediates of heterogeneous mineral precipitation. Here, we exposed two strains of sulfate-reducing bacteria to three forms of inorganic mercury: dissolved Hg and sulfide, nanoparticulate HgS, and microparticulate HgS. The bacteria cultures exposed to HgS nanoparticles methylated mercury at a rate slower than cultures exposed to dissolved forms of mercury. However, net methylmercury production in cultures exposed to nanoparticles was 6 times greater than in cultures treated with microscale particles, even when normalized to specific surface area. Furthermore, the methylation potential of HgS nanoparticles decreased with storage time of the nanoparticles in their original stock solution. In bacteria cultures amended with nano-HgS from a 16 h-old nanoparticle stock, 6-10% of total mercury was converted to methylmercury after one day. In contrast, 2-4% was methylated in cultures amended with nano-HgS that was aged for 3 days or 1 week. The methylation of mercury derived from nanoparticles (in contrast to the larger particles) would not be predicted by equilibrium speciation of mercury in the aqueous phase (<0.2 μm) and was possibly caused by the disordered structure of nanoparticles that facilitated release of chemically labile mercury species immediately adjacent to cell surfaces. Our results add new dimensions to the mechanistic understanding of mercury methylation potential by demonstrating that bioavailability is related to the geochemical intermediates of rate-limited mercury sulfide precipitation reactions. These findings could help explain observations that the "aging" of mercury in sediments reduces its methylation potential and provide a basis for assessing and remediating methylmercury hotspots in the environment.
[show abstract][hide abstract] ABSTRACT: A systematic investigation into lowered degradation rates of glyphosate in metal-contaminated soils was performed by measuring mineralization of [(14)C]glyphosate to (14)CO(2) in two mineral soils that had been spiked with Cu and/or Zn at various loadings. Cumulative (14)CO(2) release was estimated to be approximately 6% or less of the amount of [(14)C]glyphosate originally added in both soils over an 80-d incubation. For all but the highest Cu treatments (400 mg kg(-1)) in the coarse-textured Arkport soil, mineralization began without a lag phase and declined over time. No inhibition of mineralization was observed for Zn up to 400 mg kg(-1) in either soil, suggesting differential sensitivity of glyphosate mineralization to the types of metal and soil. Interestingly, Zn appeared to alleviate high-Cu inhibition of mineralization in the Arkport soil. The protective role of Zn against Cu toxicity was also observed in the pure culture study with Pseudomonas aeruginosa, suggesting that increased mineralization rates in high Cu soil with Zn additions might have been due to alleviation of cellular toxicity by Zn rather than a mineralization specific mechanism. Extensive use of glyphosate combined with its reduced degradation in Cu-contaminated, coarse-textured soils may increase glyphosate persistence in soil and consequently facilitate Cu and glyphosate mobilization in the soil environment.
Environmental Toxicology and Chemistry 03/2011; 30(3):596-601. · 2.62 Impact Factor
[show abstract][hide abstract] ABSTRACT: Nanosized silver sulfide (α-Ag(2)S) particles were identified in the final stage sewage sludge materials of a full-scale municipal wastewater treatment plant using analytical high-resolution transmission electron microscopy. The Ag(2)S nanocrystals are in the size range of 5-20 nm with ellipsoidal shape, and they form very small, loosely packed aggregates. Some of the Ag(2)S nanoparticles (NPs) have excess S on the surface of the sulfide minerals under S-rich environments, resulting in a ratio of Ag to S close to 1. Considering the current extensive production of Ag NPs and their widespread use in consumer products, it is likely that they are entering wastewater streams and the treatment facilities that process this water. This study suggests that in a reduced, S-rich environment, such as the sedimentation processes during wastewater treatment, nanosized silver sulfides are being formed. This field-scale study provides for the first time nanoparticle-level information of the Ag(2)S present in sewage sludge products, and further suggests the role of wastewater treatment processes on transformation of Ag nanoparticles and ionic Ag potentially released from them.
[show abstract][hide abstract] ABSTRACT: Common soil test methods were compared with 0.01 M CaCl2 extraction to determine their relative abilities to extract and estimate phytoavailability of Cu and Zn. In aged metal-spiked soils, all soil tests evaluated (Mehlich 3, diethylenetriaminepentaacetic acid [DTPA], Morgan, modified Morgan, CaCl2) showed a linear relationship of extractable to total Cu and Zn for both soil types studied. The fraction of total Cu and Zn extracted by aggressive tests (Mehlich 3, DTPA) was much higher than the fraction extracted by CaCl2, with the Morgan tests being intermediate. Although all extraction methods revealed Cu and Zn to be more available in the coarse-textured soil than the fine-textured soil, this texture effect was greatest for the least aggressive test (CaCl2) and least for Mehlich 3. The texture effect on soil test Cu and Zn was also reflected in bioavailability, with greater plant tissue concentrations of both metals from the coarse-textured soil in a soybean assay. Although all soil test methods provided similarly strong correlations to plant tissue concentrations of Zn for soybeans grown in the two soils, the less aggressive soil tests seemed more reliable as predictors of Cu uptake.
The efficiency of Cu and Zn extraction from field-contaminated soils was much lower than that from laboratory-spiked aged soils. For Mehlich 3 and DTPA tests, Cu and Zn in field-contaminated soils were less extractable by a factor of about 2 compared with the spiked soils. For less aggressive tests, the difference in extractability was even greater.
This study suggests that soil extraction methods removing smaller pools of Cu and Zn are more responsive to soil properties affecting chemical lability of the metals. Therefore, chemically nonaggressive neutral salts may be the most appropriate extractants where phytotoxicity is the concern in metal-contaminated soils.
[show abstract][hide abstract] ABSTRACT: A field pot experiment was conducted to investigate the interactive phytotoxicity of soil Cu and Zn on soybean plants [Glycine max (L.) Merr.]. Two soils (Arkport sandy loam [coarse-loamy, mixed, active, mesic Lamellic Hapludalf] and Hudson silty clay loam [fine, illitic, mesic Glossaquic Hapludalf]) spiked with Cu, Zn, and combinations of both to reach the final soil metal range of 0 to 400 mg kg(-1) were tested in a 2-yr bioassay after 1 yr of soil-metal equilibration in the field. The soluble and easily-extractable fraction of soil Zn (or Cu), estimated by dilute CaCl2, increased linearly in response to the total Zn (or Cu) added. This linearity was, however, strongly affected where soils were treated with both metals in combination, most notably for Zn, as approximately 50% more of soil Zn was extracted into solution when the Cu level was high. Consequently, added Zn is less likely to be stabilized by aging than added Cu when both metals are present in field soils. The predictive model relating soil metal extractability to plant Zn concentration also revealed a significant Cu-Zn interaction. By contrast, the interaction between the two metals contributed little to explain plant Cu uptake. The additive action of soil Cu and Zn was of considerable importance in explaining plant biomass reduction. This work clearly demonstrates the critical roles of the properties of the soil, the nature of the metal, and the level of other toxic metals present on the development of differential phytotoxicity due to soil Cu and Zn.
Journal of Environmental Quality 01/2009; 38(6):2253-9. · 2.35 Impact Factor
[show abstract][hide abstract] ABSTRACT: In the present study, the utilization of dilute CaCl2 extraction and free metal ion activity was tested for its ability to predict urease activity in soils that was measured by a simple and rapid urease assay. Two soil series (an Arkport sandy loam and a Hudson silty clay loam) were spiked with Cu and Zn, both singly and in combination, and then field aged for over a year prior to use. For both the metal-spiked Arkport and Hudson soils, much of the inhibition in measured urease activity was explained by increased CaCl2-extractable Cu, with a lesser effect from increased Zn extractability. A positive but weak interaction between Cu and Zn suggested by regression analysis indicates the toxicity of Cu-Zn mixtures to soil urease is slightly less than additive (antagonistic). Copper extractability using CaCl2 was able to predict urease activity in only one of the tested soils. By contrast, measurements of Cu2+ activity were predictive of reduced urease activity in both soils (R2adj = 0.726, p < 0.0001), indicating that Cu2+ activity is a more useful predictor of urease inhibition in soils than CaCl2-extractable Cu. The present study also highlighted the importance that clay mineral content had on controlling the availability of added metals in soils over time since a greater aging effect on Cu toxicity was found for the fine-textured Hudson than the coarse-textured Arkport soil.
Environmental Toxicology and Chemistry 08/2008; 27(12):2469-75. · 2.62 Impact Factor
[show abstract][hide abstract] ABSTRACT: Sequential extraction procedures are widely used to estimate the quantity of trace metals bound to different solid fractions in contaminated soils. However, reliability of speciation of trace metals by these procedures remains largely unexamined. In the present study, the selectivity of each extraction step was tested by observing the effect of reversing the extraction order in the procedure. Two different sequential extraction methods and their reversed modes were used for metal fractionation in sewage sludge-amended soils. Significantly increased amounts of extractable metals (Cd, Cu, Pb and Zn) were evident in the sludge-amended soils compared to control soil by all extraction schemes; however, the amounts of metals extracted by each step were strongly dependent on the order of extraction, the type of reagents and the nature of the individual metals. Caution is advised in deducing the forms of soil metals from sequential extraction results from metal-contaminated soils.
[show abstract][hide abstract] ABSTRACT: A long-term greenhouse column experiment using two soils of different textures amended with dewatered, composted and alkaline-stabilized
sludges (biosolids) tested the effect of aging on trace metal solubility, mobility and crop uptake over 15 cropping cycles.
Specifically, soil chemical properties and extractability of Cu, Zn and Mo were measured after each cropping cycle, and soybeans
(Glycine max (L.) Merr.) grown as the final crop were analyzed for those metal concentrations in the seeds. Significant Cu loss from the
surface soil through leaching, and increased Zn extractability resulting from soil acidification were evident in the early
cropping cycles shortly after sludge application, with the degree of Cu mobilization and soil acidification strongly dependent
on the type of soil and sludge. Liming to counter acidification in later cycles enhanced Mo extractability and bioavailability
substantially, with some sludge treatments producing soybean seeds with Mo concentrations up to 5 times greater than the control.
Aging effects were difficult to discern for trace metals in this long-term study, since soil pH changes caused by sludge and
liming amendments dominated metal solubility and crop uptake.
Plant and Soil 299(1):227-236. · 2.64 Impact Factor