Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas?

The photoenhanced uptake of nitrogen dioxide (NO₂) to the surface of commercially available self-cleaning window glass has been studied under controlled laboratory conditions. This material is one of an array of modern building products which incorporate titanium dioxide (TiO₂) nanoparticles and are finding increasing use in populated urban areas. Amongst the principal drivers for the use of these materials is that they are thought to facilitate the irreversible removal of pollutants such as NO₂ and organic molecules from the atmosphere and thus act to remediate air quality. While it appears that TiO₂ materials do indeed remove organic molecules from built environments, in this study we show that the photoenhanced uptake of NO₂ to one example material, self-cleaning window glass, is in fact accompanied by the substantial formation (50–70%) of gaseous nitrous acid (HONO). This finding has direct and serious implications for the use of these materials in urban areas. Not only is HONO a harmful respiratory irritant, it is also readily photolysed by solar radiation leading to the formation of hydroxyl radicals (OH) together with the re-release of NO_x as NO. The net effect of subsequent OH initiated chemistry can then be the further degradation of air quality through the formation of secondary pollutants such as ozone and VOC oxidation products. In summary, we suggest that a scientifically conceived technical strategy for air quality remediation based on this technology, while widely perceived as universally beneficial, could in fact have effects precisely opposite to those intended.     

Kinetics and pathways for the debromination of polybrominated diphenyl ethers by bimetallic and nanoscale zerovalent iron: effects of particle properties and catalyst

Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe⁰ slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe⁰ nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe⁰ nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe⁰ are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe⁰ reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role.     

Detecting diclofenac in livestock carcasses in India with an ELISA: a tool to prevent widespread vulture poisoning

Diclofenac, a non-steroidal anti-inflammatory drug (NSAID), has caused catastrophic vulture declines across the Indian sub-continent. Here, an indirect ELISA is used to detect and quantify diclofenac in 1251 liver samples from livestock carcasses collected across India between August 2007 and June 2008, one to two years after a ban on diclofenac manufacture and distribution for veterinary use was implemented. The ELISAs applicability was authenticated with independent data obtained using LC-ESI/MS. Of 1251 samples, 1150 (91.9%) were negative for diclofenac using both methods, and 60 (4.8%) were positive at 10-4348 and 10-4441 μg kg(-1) when analysed by ELISA and LC-ESI/MS, respectively. The residue level relationship in the 60 positive samples was highly significant (p < 0.001, r(2) = 0.644). Data suggest that this immunological assay could be used not only for cost effective sample screening, but also for residue level semi-quantification.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 1--Historical Background; Carbon Tetrachloride and Tetrachloroethylene

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. These compounds were also used in a wide variety of other applications. The history of the production and use of these four compounds is linked to the development and growth of the United States' synthetic organic chemical industry, and historical events that affected the development and use of chlorinated solvents in general. Part 1 of this article includes a discussion of the historical background common to each of the four solvents, followed by discussion on the history of CTC and PCE. In the early years of the 20th century, CTC became the first of the four solvents to come into widespread use. CTC was used as a replacement for petroleum distillates in the dry-cleaning industry, but was later replaced by PCE. In the 1990s, CTC was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

Airborne molds and mycotoxins associated with handling of corn silage and oilseed cakes in agricultural environment

In agricultural areas, the contamination of feedstuffs with molds and mycotoxins presents major environmental and health concerns. During cattle feeding, fungi and mycotoxins were monitored in corn silage, oilseed cakes and bioaerosols collected in Normandy. Most of the corn silages were found to be contaminated by deoxynivalenol (mean concentration: 1883 μg kg^?1) while a few of oilseed cakes were contaminated by alternariol, fumonisin B₁ or gliotoxin. In ambient bioaerosols, the values for fungi per cubic meter of air varied from 4.3 × 10² to 6.2 × 10⁵ cfu m^?3. Seasonal variations were observed with some species like Aspergillus fumigatus which significantly decreased between the 2 seasons (P = 0.0186) while the Penicillium roqueforti group significantly increased during the second season (P = 0.0156). In the personal bioaerosols, the values for fungi per cubic meter of air varied from 3.3 10³ to 1.7 10⁶ cfu m^?3 and the number of A. fumigatus spores significantly decreased between the 2 seasons (P = 0.0488). Gliotoxin, an immunosuppressive mycotoxin, was quantified in 3 personal filters at 3.73 μg m^?3, 1.09 μg m^?3 and 2.97 μg m^?3.     

Evaluation of geochemical associations as a screening tool for identifying anthropogenic trace metal contamination

Geochemical association plots are used as a screening tool for environmental site assessments and use empirical log–log relationships between total trace metal concentrations and concentrations of a major (i.e., reference) soil metal constituent, such as iron (Fe), to discern sites with naturally elevated trace metal levels from sites with anthropogenic contamination. Log–log relationships have been consistently observed between trace metal and reference metal concentrations and are often considered constant. Consequently, we used a regional geochemistry data set to evaluate background trace metal/Fe log–log associations across soils with highly diverse composition. Our results indicate that, although geochemical associations may be proportional, they significantly differ across predominant United States Department of Agriculture (USDA) soil orders. This suggests that highly complex interactions between soil-forming factors and variable secondary clay mineral composition affect the ratio of trace metals to Fe concentrations in soils. Also, intra-order variability in trace metal/Fe ratios generally ranged multiple orders of magnitude which suggest that the order level of the USDA soil taxonomic system is insufficient to reasonably classify background trace metal concentrations. Consequently, geochemical association plots are a useful screening tool for environmental site assessments, but ubiquitous application of generic background metal data sets could result in erroneous conclusions. Because significantly different ratios were observed across predominant USDA soil orders, an agglomerative clustering technique was used to elucidate hierarchical patterns of association. We present these results as a mechanism to aid environmental assessors in screening candidate background metal data sets for their applicability to site-specific soil composition; although site-specific background metal data should be utilized if ample pristine reference sites with similar (i.e., sub-order) soil composition can be identified and sampled.     

Defending the scientific integrity of conservation‐policy processes

Government agencies faced with politically controversial decisions often discount or ignore scientific information, whether from agency staff or nongovernmental scientists. Recent developments in scientific integrity (the ability to perform, use, communicate, and publish science free from censorship or political interference) in Canada, Australia, and the United States demonstrate a similar trajectory. A perceived increase in scientific‐integrity abuses provokes concerted pressure by the scientific community, leading to efforts to improve scientific‐integrity protections under a new administration. However, protections are often inconsistently applied and are at risk of reversal under administrations publicly hostile to evidence‐based policy. We compared recent challenges to scientific integrity to determine what aspects of scientific input into conservation policy are most at risk of political distortion and what can be done to strengthen safeguards against such abuses. To ensure the integrity of outbound communications from government scientists to the public, we suggest governments strengthen scientific integrity policies, include scientists’ right to speak freely in collective‐bargaining agreements, guarantee public access to scientific information, and strengthen agency culture supporting scientific integrity. To ensure the transparency and integrity with which information from nongovernmental scientists (e.g., submitted comments or formal policy reviews) informs the policy process, we suggest governments broaden the scope of independent reviews, ensure greater diversity of expert input and transparency regarding conflicts of interest, require a substantive response to input from agencies, and engage proactively with scientific societies. For their part, scientists and scientific societies have a responsibility to engage with the public to affirm that science is a crucial resource for developing evidence‐based policy and regulations in the public interest.     

Longevity of rodenticide bait pellets in a tropical environment following a rat eradication program

Invasive rodents (primarily Rattus spp.) are responsible for loss of biodiversity in island ecosystems worldwide. Large-scale rodenticide applications are typically used to eradicate rats and restore ecological communities. In tropical ecosystems, environmental conditions rapidly degrade baits and competition for baits by non-target animals can result in eradication failure. Our objective was to evaluate persistence of rodenticide baits during a rat eradication program on Palmyra Atoll; a remote tropical atoll with intense competition for resources by land crabs. Following aerial application, bait condition was monitored in four terrestrial environments and in the canopy foliage of coconut palms. Ten circular PVC hoops were fixed in place in each of Palmyra’s four primary terrestrial habitats and five rodenticide pellets were placed in each hoop. Five coconut palms were selected in three distinct regions of the atoll. One rodenticide pellet was placed on each of five palm fronds in each coconut palm. Fresh baits were placed in all monitoring locations after each broadcast bait application. Bait condition and survival was monitored for 7 days after the first bait application and 6 days after second application. Bait survival curves differed between applications at most monitoring sites, suggesting a decrease in overall rat activity as a result of rodenticide treatment. One terrestrial site showed near 100 % bait survival after both applications, likely due to low localized rat and crab densities. Median days to pellet disappearance were one and two days for the first and second application, respectively. Differences in survival curves were not detected in canopy sites between bait applications. Median days to pellet disappearance in canopy sites were 2 and 4 days for the first and second application, respectively. Frequent rainfall likely contributed to rapid degradation of bait pellets in coconut palm fronds.     

APPLICATION OF ENHANCED ANNEALING TO GROUND WATER REMEDIATION DESIGN1

ABSTRACT: A methodology for ground water remediation design has been developed that interfaces ground water simulation models with an enhanced annealing optimizer. The ground water flow and transport simulators provide the ability to consider site‐specific contamination and geohydrologic conditions directly in the assessment of alternative remediation system designs. The optimizer facilitates analysis of tradeoffs between technical, environmental, regulatory, and financial risks for alternative design and operation scenarios. A ground water management model using an optimization method referred to as “enhanced annealing” (simulated annealing enhanced to include “directional search” and “memory” mechanisms) has been developed and successfully applied to an actual restoration problem. The demonstration site is the contaminated unconfined aquifer referred to as N‐Springs located at Han‐ford, Washington. Results of the demonstration show the potential for improving groundwater restoration system performance while reducing overall system cost.