An examination of the physical properties,fate, ecotoxicity and potential environmental risks for a series of propylene glycol ethers

Propylene glycol ethers (PGEs) are comprised of mono-, di- and tri-PGEs and several of their acetate esters. The nature of the range of applications that use PGEs suggests that there is a potential for both intentional and unintentional entry of the materials into the environment. Selected physical/chemical properties, fate characteristics, aquatic toxicity data and calculated environmental concentrations were used to assess potential risks from the manufacture, handling, use, and disposal of PGEs. In general, the PGEs are low to moderately volatile, have high aqueous solubilities, low octanol-water partition coefficients (Kow), and bioconcentration factor values of <10, which indicate they are unlikely to accumulate in aquatic food chains. Both abiotic and biological degradation processes reduce environmental concentrations of PGEs. In air, vapor-phase PGEs react with photo-chemically produced hydroxyl radicals and have half-lives ranging from 5.5 to 34.4 h. A variety of ready and inherent biodegradation test methods, as well as tests that simulate biodegradation in wastewater treatment plants, surface water and soil have been conducted on PGEs. Significant aerobic biodegradation was generally observed, with a range of biodegradation half-lives on the order of 5-25 d. Acute aquatic toxicity studies with PGEs resulted in LC50 values ranging from approximately >100 to >20,000 mg/l for freshwater fish, the pelagic invertebrate Daphnia magna, green algae Selenastrum capricornutum (now called Pseudokirchneriella capricornutum) and bacteria. Level 3 multi-media modeling (EQC model of Mackay) was used to simulate regional-scale concentrations of PGEs in air, soil, water, and sediment. Toxicity thresholds were then compared with regional-scale water, soil and sediment concentrations to determine hazard quotients. Based upon this analysis, concentrations of PGEs are unlikely to pose adverse risks to the environment.     

Buffer zone widths for honeybees from ground and aerial spraying of insecticides

The relative field hazards of insecticides to honeybees have been estimated by considering intrinsic toxicity levels and field application rates. This approach is extended here to a consideration of buffer zones downwind of sprayed areas by estimating the distance at which bees would encounter an LD(50) dose from spray drift. 'LD(50) distances' are determined for both ground and aerial spraying of ground crops in Britain using published data on spray deposition under various weather conditions. For ground spraying at low wind speeds (< or =3 m s(-1)), this zone of risk is up to 5 m for the great majority of compounds. Aerial spraying in unstable atmospheric conditions appears to produce drift deposits of about the same order of magnitude as from ground spraying at wind speeds of about 4 m s(-1), with maximum LD(50) distances of < or =40 m for chlorpyrifos, fenitrothion and triazophos. For aerial spraying in stable atmospheric conditions these distances would be much greater. Pieris brassicae larvae are contrasted with honeybees in their relative sensitivities to insecticides and consequent LD(50) distances.     

Prediction of the vertical profile of ozone based on ground-level ozone observations and cloud cover

A number of statistical techniques have been used to develop models to predict high-elevation ozone (O3) concentrations for each discrete hour of day as a function of elevation based on ground-level O3 observations. The analyses evaluated the effect of exclusion/inclusion of cloud cover as a variable. It was found that a simple model, using the current maximum ground-level O3 concentration and no effect of cloud cover provided a reasonable prediction of the vertical profile of O3, based on data analyzed from O3 sites located in North Carolina and Tennessee. The simple model provided an approach that estimates the concentration of O3 as a function of elevation (up to 1800 m) based on the statistical results with a +/- 13.5 ppb prediction error, an R2 of 0.56, and an index of agreement, d1, of 0.66. The inclusion of cloud cover resulted in a slight improvement in the model over the simple regression model. The developed models, which consist of two matrices of 24 equations (one for each hour of day for clear to partly cloudy conditions and one for cloudy conditions), can be used to estimate the vertical O3 profile based on the inputs of the current day's 1-hr maximum ground-level O3 concentration and the level of cloud cover.     

Distribution of metals in grassland soils following surface applications of sewage sludge

In order to decide on a suitable sampling depth for grassland soil treated with sewage sludge and to assess implications for grazing animals, a field trial on two soils was designed to estimate the distribution of metals in grassland soil profiles following surface applications of sludge. Thus the sites represented permanent grassland where no form of cultivation had taken place. Soil cores were taken using specialised equipment to 30 cm depth and divided into seven sections. Movement from the soil surface to a depth of 10 cm was observed for all of the seven metals, Cd, Cr, Cu, Mo, Ni, Pb and Zn, but most of the metal (60%-100%, mean 87%) remained in the upper 5 cm of soil. It was concluded that sampling to a depth of 5 or 7.5 cm would be most suitable for monitoring long-term grassland treated with surface applications of sludge.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: characterization of microbial community structure

A polyphasic approach based on cultivation and direct recovery of 16S rRNA gene sequences was utilized for microbial characterization of an aquifer contaminated with chlorinated ethenes. This work was conducted in order to support the evaluation of natural attenuation of chlorinated ethenes in groundwater at Area 6 at Dover Air Force Base (Dover, DE). Results from these studies demonstrated the aquifer contained relatively low biomass (e.g. direct microscopic counts of < 10(7) bacteria/g of sediment) comprised of a physiologically diverse group of microorganisms including iron reducers, acetogens, sulfate reducers, denitrifiers, aerobic and anaerobic heterotrophs. Laboratory microcosms prepared with authentic sediment and groundwater provided direct microbiological evidence that the mineralization of vinyl chloride and cis-dichloroethene as well as each step in the complete reductive dechlorination of tetracloroethene to ethene can occur in the Area 6 aquifer. Enrichment cultures capable of the oxidative degradation of cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were obtained from groundwater across the aquifer demonstrating the possible importance of direct, non-cometabolic oxidation of cis-DCE and VC in natural attenuation. Culture-independent analyses based upon recovery of 16S rRNA gene sequences revealed the presence of anaerobic organisms distributed primarily between two major bacterial divisions: the delta subdivision of the Proteobacteria and low-G + C gram positive. Recovery of sequences affiliated with phylogenetic groups containing known anaerobic-halorespiring organisms such as Desulfitobacterium, Dehalobacter, and certain groups of iron reducers provided qualitative support for a role of reductive dechlorination processes in the aquifer. This molecular data is suggestive of a functional linkage between the microbiology of the site and the apparent natural attenuation process. The presence and distribution of microorganisms were found to be consistent with a microbially driven attenuation of chlorinated ethenes within the aquifer and in accord with a conceptual model of aquifer geochemistry which suggest that both reductive and oxidative mechanisms are involved in heterogeneous, spatially distributed processes across the aquifer.     

ERD of Residual TCE DNAPL Achieving Nondetect from a Single Injection of Food‐Grade Waste

Residual dense nonaqueous phase liquid (DNAPL) composed of trichloroethene (TCE) was identified in a deeper interval of an overburden groundwater system at a manufacturing facility located in northern New England. Site hydrostratigraphy is characterized by two laterally continuous and transmissive zones consisting of fully‐saturated fine sand with silt and clay. The primary DNAPL source was identified as a former dry well with secondary contributions from a proximal aboveground TCE storage tank. A single additive‐injection mobilization in 2001 utilizing a food‐grade injectate formulated with waste dairy product and inactive yeast enhanced residual TCE DNAPL destruction in situ by stimulating biotic reductive dechlorination. The baseline TCE concentration was detected up to 97,400 μg/L in the deeper interval of the overburden groundwater system, and enhanced reductive dechlorination (ERD) achieved >99 percent reduction in TCE concentrations in groundwater over nine years with no evidence of sustained rebound. TCE concentrations have remained nondetect below 2.0 μg/L for the last five consecutive sampling rounds between 2013 and 2015. ERD utilizing a food‐grade injectate is a green remediation technology that has destroyed residual DNAPL at the site and achieved similar results at other residual DNAPL sites during both pilot‐ and full‐scale applications. ©2016 Wiley Periodicals, Inc.     

New investigation findings on the 2006 Danvers,MA explosion

On November 22, 2006 the largest explosion in the history of Massachusetts occurred in Danvers, MA at approximately 2:46 am. This paper presents a detailed analysis into the potential causes and lessons learned from the Danvers explosion. Other investigative groups concluded that the cause of the explosion was an overheated production tank. However, the analyses presented here demonstrate that their proposed scenario could not have occurred and that other potential causes are more likely.Using the computational fluid dynamics tool FLACS, it was possible to investigate the chain of events leading to the explosion, including: (1) evaluating various leak scenarios by modeling the dispersion and mixing of gases and vapors within the facility, (2) evaluating potential ignition sources within the facility of the flammable fuel–air mixture, and (3) evaluating the explosion itself by comparing the resulting overpressures of the exploding fuel–air cloud with the structural response of the facility and the observed near-field and far-field blast damage. These results, along with key witness statements and other analyses, provide valuable insight into the likely cause of this incident. Based on the results of our detailed analysis, lessons learned regarding the investigative procedure and methods for mitigating this and future explosions are discussed.     

Using computational fluid dynamics (CFD) for blast wave predictions

Explosions will, in most cases, generate blast waves. While simple models (e.g., Multi Energy Method) are useful for simple explosion geometries, most practical explosions are far from trivial and require detailed analyses. For a reliable estimate of the blast from a gas explosion it is necessary to know the explosion strength. The source explosion may not be symmetric; the pressure waves will be reflected or deflected when hitting objects, or even worse, the blast waves may propagate inside buildings or tunnels with a very low rate of decay. The use of computational fluid dynamics (CFD) explosion models for near and far field blast wave predictions has many advantages. These include more precise estimates of the energy and resulting pressure of the blast wave, as well as the ability to evaluate non-symmetrical effects caused by realistic geometries, gas cloud variations and ignition locations. This is essential when evaluating the likelihood of a given leak source as cause of an explosion or equally when evaluating the potential risk associated with a given leak source for a consequence analysis.In addition, unlike simple methods, CFD explosion models can also evaluate detailed dynamic effects in the near and far field, which include time dependent pressure loads as well as reflection and focusing of the blast waves. This is particularly valuable when assessing actual near-field blast damage during an explosion investigation or potential near-field damage during a risk analysis for a facility. One main challenge in applying CFD, however, is that these models require more information about the actual facility, including geometry details and process information. Collecting the necessary geometry and process data may be quite time consuming. This paper will show some blast prediction validation examples for the CFD model FLACS. It will also provide examples of how directional effects or interaction with objects can significantly influence the dynamics of the blast wave. Finally, the challenge of obtaining useful predictions with insufficient details regarding the geometry will also be addressed.     

Compilation of EINECS: Descriptions and definitions used for substances,impurities and mixtures

The European INventory of Existing commercial Chemical Substances (EINECS) lists all substances which were on the European Community Market between 1 January 1971 and 18 September 1981. Substances on EINECS are known as ‘existing’ substances. The EINECS inventory was drawn up by the European Commission to meet the requirements of article 13 of Directive 79/831/EEC [1]. EINECS was published in the Official Journal of the European Communities in 1990 [2]. This paper describes how individual substances, impurities and mixtures were defined and dealt with when registered for the EINECS inventory. It is the first in a series of such papers.