Fractal structures of single-walled carbon nanotubes in biologically relevant conditions: Role of chirality vs. media conditions

Aggregate structure of covalently functionalized chiral specific semiconducting single-walled carbon nanotubes (SWNTs) was systematically studied employing static light scattering (SLS). Fractal dimensions (D_f) of two specific chirality SWNTs—SG65 and SG76 with (6, 5) and (7, 6) chiral enrichments—were measured under four biological exposure media conditions, namely: Dulbecco’s Modified Eagle Medium (DMEM), Minimum Essential Medium (MEM), Roswell Park Memorial Institute (RPMI) 1640 medium, and 0.9% saline solution. The SWNTs exhibited chiral dependence on D_f with SG65 showing more fractal or loosely bound aggregate structures, i.e., lower D_f values (range of 2.24 ± 0.03 to 2.64 ± 0.05), compared to the SG76 sample (range of 2.58 ± 0.13 to 2.90 ± 0.08). All the D_f values reported are highly reproducible, measured from multiple SLS runs and estimated with ‘random block-effects’ statistical analysis that yielded all p values to be <0.001. The key mechanism for such difference in D_f between the SWNT samples was identified as the difference in van der Waals (VDW) interaction energies of these samples, where higher VDW of SG76 resulted in tighter packing density. Effect of medium type showed lower sensitivity; however, presence of di-valent cations (Ca²⁺) in DMEM and MEM media resulted in relatively loose or more fractal aggregates. Moreover, presence of fetal bovine serum (FBS) and bovine serum albumin (BSA), used to mimic the in vitro cell culture condition, reduced the D_f values, i.e., created more fractal structures. Steric hindrance to aggregation was identified as the key mechanism for creating the fractal structures. Also, increase in FBS concentration from 1% to 10% resulted in increasingly lower D_f values.     

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 1. Method Development

Despite the installation in the 1980s and 1990s of hydraulic containment systems around known source zones (four slurry walls and ten pump‐and‐treat systems), trichloroethene (TCE) plumes persist in the three uppermost groundwater‐bearing units at the Middlefield‐Ellis‐Whisman (MEW) Superfund Study Area in Mountain View, California. In analyzing TCE data from 15 recovery wells, the observed TCE mass discharge decreased less than an order of magnitude over a 10‐year period despite the removal of an average of 11 pore volumes of affected groundwater. Two groundwater models were applied to long‐term groundwater pump‐and‐treat data from 15 recovery wells to determine if matrix diffusion could explain the long‐term persistence of a TCE plume. The first model assumed that TCE concentrations in the plume are controlled only by advection, dispersion, and retardation (ADR model). The second model used a one‐dimensional diffusion equation in contact with two low‐permeability zones (i.e., upper and lower aquitard) to estimate the potential effects of matrix diffusion of TCE into and out of low‐permeability media in the plume. In all 15 wells, the matrix diffusion model fit the data much better than the ADR model (normalized root mean square error of 0.17 vs. 0.29; r² of 0.99 vs. 0.19), indicating that matrix diffusion is a likely contributing factor to the persistence of the TCE plume in the non‐source‐capture zones of the MEW Study Area's groundwater‐extraction wells. © 2013 Wiley Periodicals, Inc.     

Collateral benefits and hidden hazards of soil arsenic during abatement assessment of residential lead hazards

Abatement of soil-lead hazards may also reduce human exposure to other soil toxins, thereby achieving significant collateral benefits that are not accounted for today. This proposition was tested with the specific case of soil-arsenic, where 1726 residential soil samples were collected and analyzed for lead and arsenic. The study found that these two toxins coexisted in most samples, but their concentrations were weakly correlated, reflecting the differing sources for each toxin. Collateral benefits of 9% would be achieved during abatement of the lead-contaminated soils having elevated arsenic concentrations. However, a hidden hazard of 16% was observed by overlooking elevated arsenic concentrations in soils having lead concentrations not requiring abatement. This study recommends that soil samples collected under HUD programs should be collected from areas of lead and arsenic deposition and tested for arsenic as well as lead, and that soil abatement decisions consider soil-arsenic as well as soil-lead guidelines.     

H-Print: a new chemical fingerprinting approach for distinguishing primary production sources in Arctic ecosystems

The unambiguous identification of discrete sources of organic matter is critical for understanding the processes that affect ecosystem structure. Here, we demonstrate how changes in the relative proportions of highly branched isoprenoid lipids can provide a straightforward analytical method to distinguish between organic matter derived from sea ice and seawater within an Arctic ecosystem. In combination with stable isotope analysis, we reconstruct the organic matter pathway across trophic levels, thereby elucidating specific organic matter energy transfers. Combined, these methods will provide a useful analytical approach for determining ecosystem structure in the future. This is likely to become increasingly important as the Arctic continues to experience a phase of rapid climate change.     

Trace element concentration and speciation in selected urban soils in New York City

A long history of urbanization and industrialization has affected trace elements in New York City (NYC) soils. Selected NYC pedons were analyzed by aqua regia microwave digestion and sequential chemical extraction as follows: water soluble (WS); exchangeable (EX); specifically sorbed/carbonate bound (SS/CAR); oxide-bound (OX); organic/sulfide bound (OM/S). Soils showed a range in properties (e.g., pH 3.9 to 7.4). Sum of total extractable (SUM_TE) trace elements was higher in NYC parks compared to Bronx River watershed sites. NYC surface horizons showed higher total extractable (TE) levels compared to US non-anthropogenic soils. TE levels increased over 10 year in some of the relatively undisturbed and mostly wooded park sites. Surface horizons of park sites with long-term anthropogenic inputs showed elevated TE levels vs. subsurface horizons. Conversely, some Bronx River watershed soils showed increased concentrations with depth, reflective of their formation in a thick mantle of construction debris increasing with depth and intermingled with anthrotransported soil materials. Short-range variability was evident in primary pedons and satellite samples (e.g., Pb 253?±?143 mg/kg). Long-range variability was indicated by Pb_TE (348 versus 156 mg/kg) and Hg_TE (1 versus 0.3 mg/kg) concentrations varying several-fold in the same soil but in different geographic locations. Relative predominance of fractions: RES (37 %)?>?SS/CAR (22 %)?>?OX (20 %)?>?OM/S (10 %)?>?EX (7 %)?>?WS (4 %). WS and EX fractions were greatest for Hg (7 %) and Cd (14 %), respectively. RES was predominant fraction for Co, Cr, Ni, and Zn (41 to 51 %); SS/CAR for Cd and Pb (40 and 63 %); OM/S for Cu and Hg (36 and 37 %); and OX for As (59 %).     

Bioremediation of petroleum hydrocarbons in contaminated soils: comparison of biosolids addition, carbon supplementation, and monitored natural attenuation

Two methods of biostimulation were compared in a laboratory incubation study with monitored natural attenuation (MNA) for total petroleum hydrocarbon (TPH) degradation in diesel-contaminated Tarpley clay soil with low carbon content. One method utilized rapid-release inorganic fertilizers rich in N and P, and the other used sterilized, slow-release biosolids, which added C in addition to N and P. After 8 weeks of incubation, both biostimulation methods degraded approximately 96% of TPH compared to MNA, which degraded 93.8%. However, in the first week of incubation, biosolids-amended soils showed a linear two orders of magnitude increase in microbial population compared to MNA, whereas, in the fertilizer-amended soils, only a one order of magnitude increase was noted. In the following weeks, microbial population in the fertilizer-amended soils dropped appreciably, suggesting a toxic effect owing to fertilizer-induced acidity and/or NH(3) overdosing. Results suggest that biosolids addition is a more effective soil amendment method for biostimulation than the commonly practiced inorganic fertilizer application, because of the abilities of biosolids to supplement carbon. No statistically significant difference was observed between the biostimulation methods and MNA, suggesting that MNA can be a viable remediation strategy in certain soils with high native microbial population.     

Effects of oxygen exposure on anaerobic digester sludge.

Recuperative thickening of anaerobic digester sludge (thickening with solids return) yields increased digester capacity. Common thickening methods cause oxygen exposure to the digester sludge. This study evaluated the effects of various levels of oxygen exposure on the acetoclastic methanogens. Gravity belt thickening had no detrimental effect on the acetoclastic activity. From a 7-day batch test with continuous oxygen exposure of digester sludge, a 12% loss in acetoclastic activity was predicted for a digester with a 20-day solids retention time (SRT) and 100% recycle with recuperative thickening via dissolved air flotation thickening. However, a greater loss (27%) was found from a long-term, bench-scale digester operated under similar conditions. This loss did not affect the digester performance, as measured by volatile solids destruction. This research suggests that recuperative thickening may not affect digester performance at a long SRT with constant operation, but may change the reserve capacity of the anaerobic community.     

Use of Flyash as Environmental and Agronomic Amendments

Coal combustion power plant flyash materials have been reported as useful soil amendments with agronomic and environmental benefits. This paper reports the efficacy of fluidized bed combustion (FBC) and flue gas desulfurization (FGD) byproducts, when amended with dairy, swine, and broiler litter manures, in reducing phosphorus (P) solubility and potential impact on water quality. At a rate of 400 g/kg, FBC reduced water soluble P by 60% for dairy and swine and 50% for broiler litter, as compared to un-treated control samples. Byproduct FGD had little effect when amended into dairy manure, but reduced water soluble P by nearly 80% when amended into swine and broiler manure at a rate of 250 g/kg. The amount of Ca added in the amendments together with pH of the mixture is the major contributing factor in soluble P reduction. Sequential extraction results showed that the flyash treatments shifted water soluble P into mainly bicarbonate extractable P. The latter is still considered available for crop uptake but less vulnerable for environmental losses. Coal combustion byproducts, when amended into manure and used properly, can provide a useful and viable option for improving nutrient management on animal farms.     

Low-manpower checkpoints: can they provide effective DUI enforcement in small communities?

OBJECTIVE: Sobriety checkpoints can be effective in reducing alcohol-impaired driving. Checkpoints are underutilized, however, partially because police believe a large number of officers are required. This study evaluated the feasibility and impact of conducting small-scale checkpoints in rural communities. METHODS: Law enforcement agencies in two counties agreed to conduct weekly checkpoints for one year. Two nonadjacent counties did not undertake additional checkpoints. Evaluation included public-awareness surveys and roadside surveys (including blood alcohol concentration [BAC] measurements) of weekend nighttime drivers. RESULTS: Relative to drivers in the comparison counties, the proportion of drivers in the experimental counties with BACs >0.05% was 70% lower. Drivers surveyed at driver's license offices in the experimental counties after program implementation were more likely to report seeing or passing through a checkpoint and were more aware of publicity on driving under the influence (DUI) enforcement. CONCLUSIONS: Small rural communities can safely and effectively conduct low-staff sobriety checkpoints on a weekly basis. Such programs can be expected to result in large reductions in drivers operating at higher BACs.