Review of unsaturated-zone transport and attenuation of volatile organic compound (VOC) plumes leached from shallow source zones

Reliable prediction of the unsaturated zone transport and attenuation of dissolved-phase VOC (volatile organic compound) plumes leached from shallow source zones is a complex, multi-process, environmental problem. It is an important problem as sources, which include solid-waste landfills, aqueous-phase liquid discharge lagoons and NAPL releases partially penetrating the unsaturated zone, may persist for decades. Natural attenuation processes operating in the unsaturated zone that, uniquely for VOCs includes volatilisation, may, however, serve to protect underlying groundwater and potentially reduce the need for expensive remedial actions. Review of the literature indicates that only a few studies have focused upon the overall leached VOC source and plume scenario as a whole. These are mostly modelling studies that often involve high strength, non-aqueous phase liquid (NAPL) sources for which density-induced and diffusive vapour transport is significant. Occasional dissolved-phase aromatic hydrocarbon controlled infiltration field studies also exist. Despite this lack of focus on the overall problem, a wide range of process-based unsaturated zone - VOC research has been conducted that may be collated to build good conceptual model understanding of the scenario, particularly for the much studied aromatic hydrocarbons and chlorinated aliphatic hydrocarbons (CAHs). In general, the former group is likely to be attenuated in the unsaturated zone due to their ready aerobic biodegradation, albeit with rate variability across the literature, whereas the fate of the latter is far less likely to be dominated by a single mechanism and dependent upon the relative importance of the various attenuation processes within individual site - VOC scenarios. Analytical and numerical modelling tools permit effective process representation of the whole scenario, albeit with potential for inclusion of additional processes - e.g., multi-mechanistic sorption phase partitioning, and provide good opportunity for further sensitivity analysis and development to practitioner use. There remains a significant need to obtain intermediate laboratory-scale and particularly field-scale (actual site and controlled release) datasets that address the scenario as a whole and permit validation of the available models. Integrated assessment of the range of simultaneous processes that combine to influence leached plume generation, transport and attenuation in the unsaturated zone is required. Component process research needs are required across the problem scenario and include: the simultaneous volatilisation and dissolution of source zones; development of appropriate field-scale dispersion estimates for the unsaturated zone; assessment of transient VOC exchanges between aqueous, vapour and sorbed phases and their influence upon plume attenuation; development of improved field methods to recognise and quantify biodegradation of CAHs; establishment of the influence of co-contaminants; and, finally, translation of research findings into more robust practitioner practice.     

Economic assessment of microbial biodiesel production using heterotrophic yeasts

The production of biodiesel using oleaginous microorganisms is investigated as promising alternative to produce a truly sustainable and renewable transportation fuel. While the feasibility of this approach has been shown on the laboratory scale, a commercial scale implementation is to date inhibited due to economic restraints. In order to evaluate the current cost situation and to develop suggestions to reduce production related costs, a simple cost analysis of the proposed microbial oil production process has been carried out. For closed fermentation in large-scale fermenters a break-even price of 2,350 US$ t^–1 for microbial oil was calculated. In the context of a sensitivity analysis it was shown that especially alterations in capital cost can lead to overall cost reductions. Accordingly, an open pond cultivation approach was designed, cutting the cost for equipment almost in half and decreasing the break-even price to 1,723 US$ t^–1. However, these reductions are only feasible when stable biomass and lipid yields can be ensured in open-pond systems, because the sensitivity analysis identified these yield parameters as leading factors influencing the break-even price. Even under very optimistic assumptions, it was not possible to reduce the break-even price below that of conventional plant oils as competitive products. Therefore, economic feasibility of the process will probably only occur if on one hand considerable technical development and efficiency improvements of the production process are made while on the other hand plant and crude oil prices are continuously increasing.     

Decentralized Groundwater Recharge Systems Using Roofwater and Stormwater Runoff1

Stephens, Daniel B., Mark Miller, Stephanie J. Moore, Todd Umstot, and Deborah J. Salvato, 2011. Decentralized Groundwater Recharge Systems Using Roofwater and Stormwater Runoff. Journal of the American Water Resources Association (JAWRA) 48(1): 134‐144. DOI: 10.1111/j.1752‐1688.2011.00600.x Abstract: Stormwater capture for groundwater recharge in urban areas is usually conducted at the regional level by water agencies. Field and modeling studies in New Mexico indicate that stormwater diverted to retention basins may recharge about 50% of precipitation that falls on the developed area, even in dry climates. Comparable volumes of recharge may be expected at homes, subdivisions, or commercial properties with low‐impact development (LID) technologies for stormwater control that promote recharge over evapotranspiration. Groundwater quality has not been significantly impacted at sites that have been recharging stormwater to aquifers for decades. Distributed recharge systems may be a good alternative to centralized regional facilities where there is limited land for constructing spreading basins or little funding for new infrastructure. LID technologies borrowed from stormwater managers are important tools for groundwater managers to consider to enhance recharge.     

Lactational transfer of mercury and polychlorinated biphenyls in polar bears

We examined concentrations of total mercury (tHg, inorganic and methylated forms) and polychlorinated biphenyls (PCBs) in blood and milk from free-ranging Southern Beaufort-Chukchi Sea polar bears (Ursus maritimus) to assess maternal transfer of contaminants during lactation and the potential health risk to nursing young. Concentrations of contaminants in the blood of dependent and juvenile animals (ages 1-5 years) ranged from 35.9 to 52.2 μg kg(-1) ww for tHg and 13.9 to 52.2 μg kg(-1) ww (3255.81-11067.79 μg kg(-1) lw) for ΣPCB(7)s, similar to those of adult females, but greater than adult males. Contaminant concentrations in milk ranged from 5.7 to 71.8 μg tHg kg(-1)ww and 160 to 690 μg ΣPCB(11)s kg(-1) ww (547-5190 μg kg(-1) lw). The daily intake levels for tHg by milk consumption estimated for dependent young were below the tolerable daily intake level (TDIL) of tHg established for adult humans. Although the daily intake levels of PCBs through milk consumption for cubs of the year exceeded the TDIL thresholds, calculated dioxin equivalents for PCBs in milk were below adverse physiological thresholds for aquatic mammals. Relatively high concentrations of non-dioxin like PCBs in polar bear milk and blood could impact endocrine function of Southern Beaufort-Chukchi Sea polar bears, but this is uncertain. Transfer of contaminants during mid to late lactation likely limits bioaccumulation of dietary contaminants in female polar bears during spring. As polar bears respond to changes in their arctic sea ice habitat, the adverse health impacts associated with nutritional stress may be exacerbated by tHg and PCBs exposure, especially in ecologically and toxicologically sensitive polar bear cohorts such as reproductive females and young.     

Simulated use and wash-off release of decamethylcyclopentasiloxane used in anti-perspirants

The cyclic volatile methylsiloxane, decamethylcyclopentasiloxane (D₅) is used in a large variety of personal care products. Based on the physical–chemical properties of D₅, it is likely that losses due to volatilisation may strongly influence the levels entering the aquatic environment. The aim of this study was to quantify the amount of D₅ in waste wash water, after typical application and use in a range of deodorant and anti-perspirant (AP) products. Results implied significant losses after a 24 h period (>99.9%), and suggest that the use of D₅ in leave-on products, such as deodorants/AP is not likely to contribute a significant down-the-drain emission source. An illustrative example is presented, based on data reporting the use of D₅ in a range of personal care products (both wash-off and leave-on), which suggests that the contribution of D₅ used in wash-off products to the aquatic environment may be considerably more significant. Limitations associated with our understanding of the actual D₅ inclusion levels in the products, the market share of the products containing D₅, and the variability of consumer habits, are identified as data gaps that need to be addressed in order to better refine down-the-drain emission estimates.     

Filtration Properties of Fly Ash from Fluidized Bed Combustion

Some of the features of the fluidized-bed combustion (FBC) process have a direct bearing on the particulate properties that most strongly influence filtering pressure drop. A laboratory program was conducted to experimentally determine the relative pressure drop characteristics of ashes from the TVA-EPRI 20-MW bubbling bed, atmospheric pressure FBC (AFBC) pilot plant and six pulverized-coal combustion (PC) units. The combined influences of measured particle and dust cake properties on filtering pressure drop were estimated with existing filtration theories. These theories predict a higher pressure drop for a dust cake produced with the AFBC ash than for one consisting of any of the PC ashes. Laboratory measurements were made of the flow resistance of idealized, simulated dust cakes to confirm these predictions. Field operating data from the fabric filters collecting some of the tested ashes were available to validate the laboratory results. The laboratory and field data show relatively good agreement. The AFBC ash must be treated as a special case for fabric filters, and careful selection of cleaning method and fabric must be made to minimize the inherently high pressure drop characteristics of this ash.     

Visual analysis to support regulators in electronic order book markets

Electronic markets and automated trading have resulted in a drastic increase in the quantity and complexity of regulatory data. Reconstructing the limit order book and analyzing order flow is an emerging challenge for financial regulators. New order types, intra-market behavior, and other exchange functionality further complicate the task of understanding market behavior at multiple levels. Data visualizations have proven to be a fundamental tool for building intuition and enabling exploratory data analysis in many fields. In this paper, we propose the incorporation of visualizations in the workflow of multiple financial regulatory roles, including market surveillance, enforcement and supporting academic research.     

Tissue heavy metal concentrations of stranded California sea lions (Zalophus californianus) in Southern California

Concentrations of nine heavy metals (As, Cd, Cu, Fe, Hg, Pb, Mn, Mo and Zn) were determined in the hepatic and renal tissues of 80 stranded California sea lions (Zalophus californianus). Significant age-dependant increases were observed in liver and kidney concentrations of cadmium and mercury, and renal zinc concentrations. Hepatic iron concentrations were significantly higher in females than males. Animals with suspected domoic acid associated pathological findings had significantly higher concentrations of liver and kidney cadmium; and significantly higher liver mercury concentrations when compared to animals classified with infectious disease or traumatic mortality. Significantly higher hepatic burdens of molybdenum and zinc were found in animals that died from infectious diseases. This is the largest study of tissue heavy metal concentrations in California sea lions to date. These data demonstrate how passive monitoring of stranded animals can provide insight into environmental impacts on marine mammals.     

Effects of HMX exposure upon metabolic rate of northern bobwhite quail (Colinus virginianus) in ovo

We evaluated the use of the gas exchange rate as an ecologically relevant indicator of chemical stress in avian embryos/eggs. Northern bobwhite quail (Colinus virginianus) were exposed to octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) via feed containing nominal concentrations of 0, 12.5, 50.0, and 125.0 mg kg(-1). Metabolic rates (oxygen consumption) of developing quail eggs were then measured via respirometry to examine potential effects of HMX exposure. Metabolic rates were examined on 5, 9, and 21 d of incubation. Next, concentrations of HMX in embryos/eggs were determined by liquid chromatography-mass spectrometry. Mean (+/-SE) concentrations of HMX in eggs were 21.0+/-5.9, 1113+/-79.0, 3864+/-154.0, and 7426+/-301.1 ng g(-1) in control, low, medium and high dose groups, respectively. There were significant differences in oxygen consumption among the three embryo ages, however differences among the ages were not consistent among dose groups (age x dose group interaction p<0.0001). Oxygen consumption rates did not vary as a function of HMX in embryos (p=0.18). No evidence was observed for alterations of in ovo metabolic rates associated with HMX exposure.     

Denitrification and the nitrogen budget of a reservoir in an agricultural landscape.

Denitrification is an important process in aquatic sediments, but its role has not been assessed in the N mass balance of upper-Midwestern (USA) reservoirs that receive large agricultural riverine N inputs. We used a 4400-ha reservoir to determine the role of denitrification in the N mass balance and effectiveness in reducing downstream transport of NO(3-)N. Sediment denitrification was (1) measured monthly (March 2002-March 2003) at eight sites in the Lake Shelbyville reservoir in central Illinois using the acetylene inhibition, chloramphenicol technique, (2) scaled to the overall reservoir and compared to N not accounted for in a mass balance, and (3) estimated indirectly using long-term (1981-2003) mass balances of N in the reservoir. Denitrification rates in the reservoir were high during spring and early summer of 2002, when maximum NO(3-)N concentrations were measured (10-14 mg NO(3-)N/L). We estimated that denitrification for the year was between 2580 and 5150 Mg N. Missing N from the mass balance was 3004 Mg N, suggesting that sediment denitrification was the sink. Areal rates of sediment denitrification in the reservoir ranged from 62 to 225 g N x m(-2) x yr(-1), with rates a function of both denitrification intensity (microg N x g dry mass x h(-1)) and the overall mass of sediment present. From 1981 to 2003 the average NO(3-)N inlet flux was 8900 Mg N/yr. About 58% of the total NO(3-)N input was removed, and annual NO(3-)N removed as a percentage of inputs was significantly related to reservoir retention time (average = 0.36 yr for the 23 years, range = 0.21-0.84 yr). By scaling denitrification in Lake Shelbyville to other reservoirs in Illinois, we estimated a sink of 48900 Mg N/yr. When combined with estimated in-stream denitrification, 60900 Mg N/yr was estimated to be removed by sediment denitrification. This reduces riverine export from Illinois to the Gulf of Mexico, where the flux during the 1990s was about 244000 Mg N/yr, and illustrates the importance of reservoir denitrification as an N sink in Midwestern agricultural landscapes.