Evaluation of a vertical frozen soil barrier at oak ridge national laboratory

Arctic Foundations, Inc. (AFI), of Anchorage, Alaska, has developed a freeze barrier system designed to hydraulically isolate a contaminant source area. The system can be used for long‐term or temporary containment of groundwater until appropriate remediation techniques can be applied. The technology was evaluated under the United States Environmental Protection Agency's (EPA's) Superfund Innovative Technology Evaluation (SITE) program at the United States Department of Energy's (DOE's) Oak Ridge National Laboratory (ORNL) facility in Oak Ridge, Tennessee. For the demonstration, an array of freeze pipes called “thermoprobes” was installed to a depth of 30 feet below ground surface around a former waste collection pond and keyed into bedrock. The system was used to establish an impermeable frozen soil barrier to hydraulically isolate the pond. Demonstration personnel collected independent data to evaluate the technology's performance. A variety of evaluation tools were used—including a groundwater dye tracing investigation, groundwater elevation measurements, and subsurface soil temperature data—to determine the effectiveness of the freeze barrier system in preventing horizontal groundwater flow beyond the limits of the frozen soil barrier. Data collected during the demonstration provided evidence that the frozen soil barrier was effective in hydraulically isolating the pond.     

Fundamental insights on when social network data are most critical for conservation planning

As declines in biodiversity accelerate, there is an urgent imperative to ensure that every dollar spent on conservation counts toward species protection. Systematic conservation planning is a widely used approach to achieve this, but there is growing concern that it must better integrate the human social dimensions of conservation to be effective. Yet, fundamental insights about when social data are most critical to inform conservation planning decisions are lacking. To address this problem, we derived novel principles to guide strategic investment in social network information for systematic conservation planning. We considered the common conservation problem of identifying which social actors, in a social network, to engage with to incentivize conservation behavior that maximizes the number of species protected. We used simulations of social networks and species distributed across network nodes to identify the optimal state-dependent strategies and the value of social network information. We did this for a range of motif network structures and species distributions and applied the approach to a small-scale fishery in Kenya. The value of social network information depended strongly on both the distribution of species and social network structure. When species distributions were highly nested (i.e., when species-poor sites are subsets of species-rich sites), the value of social network information was almost always low. This suggests that information on how species are distributed across a network is critical for determining whether to invest in collecting social network data. In contrast, the value of social network information was greatest when social networks were highly centralized. Results for the small-scale fishery were consistent with the simulations. Our results suggest that strategic collection of social network data should be prioritized when species distributions are un-nested and when social networks are likely to be centralized.     

Speciation and quantification of Hg in sediments contaminated by artisanal gold mining in the Gualaxo do Norte River,Minas Gerais,SE, Brazil

The Iron Quadrangle in SE Brazil was, in the eighteenth century, one of the most important Au producing regions of Brazil. In this region, gold is produced, even today, by artisanal methods that use Hg to increase the extraction efficiency with no control of Hg release to water systems and the atmosphere. In this context, the Gualaxo do Norte River is of particular interest; its springs are located in the Doce River basin, an important Brazilian basin that supplies water for 3.5 million people. The main goal of this work was to quantify and speciate the Hg in the sediments of the Gualaxo do Norte River using a direct mercury analyzer and gas chromatography-pyrolysis-atomic fluorescence detection system. Statistical analyses consisted of principal component analysis, aiming to assess interactions among elements and species and to group the variables in factors affecting the properties of sediment. The results show that total Hg (THg) and methylmercury (CH₃Hg⁺) concentrations in samples ranged from 209 to 1207 μg kg^?1 and from 0.07 to 1.00 μg kg^?1, respectively (methylation percentages from 0.01 to 0.27%). Thermal desorption analysis showed that mercury is mainly present in the oxidized form, and correlation analyses pointed to a relationship between THg and MnO, indicating that manganese can oxidize and/or adsorb Hg. Together, MO and CH₃Hg⁺ are important parameters in the third principal component, indicating the influence of OM on the methylation process. This first investigation on Hg methylation in this small-scale gold mining area points to the possibility of Hg bioaccumulation and to the need of better understanding the biogeochemical cycle of Hg in this area. Samples were collected in 2012, prior to the 2015 Fundão Dam disaster. The results are also a record of the characteristics of the sediment prior to that event.     

Role of soil sorption and microbial degradation on dissipation of mesotrione in plant-available soil water

Mesotrione is a carotenoid biosynthesis-inhibiting herbicide labeled for pre-emergence and postemergence weed control in corn production. Understanding the factors that influence the dissipation of mesotrione in soil and in the plant-available water (PAW) is important for the environmental fate assessment and optimal weed management practices. The present research investigated the role of soil properties and microbial activities on the interrelated sorption and degradation processes of mesotrione in four soils by direct measurements of PAW. We found that mesotrione bound to the soils time dependently, with approximately 14 d to reach equilibrium. The 24-h batch-slurry equilibrium experiments provided the sorption partition coefficient ranging from 0.26 to 3.53 L kg(-1), depending on soil organic carbon and pH. The dissipation of mesotrione in the soil-bound phase was primarily attributed to desorption to the PAW. Degradation in the PAW was rapid and primarily dependent on microbial actions, with half-degradation time (DT(50)) <3 d in all four soils tested. The rapid degradation in the PAW became rate limited by sorption as more available molecules were depleted in the soil pore water, resulting in a more slowed overall process for the total soil-water system (DT(50) <26 d). The dissipation of mesotrione in the PAW was due to microbial metabolism and time-dependent sorption to the soils. A coupled kinetics model calibrated with the data from the laboratory centrifugation technique provided an effective approach to investigate the interrelated processes of sorption and degradation in realistic soil moisture conditions.     

Sampling and Analysis of Volatile Organic Compounds Evolved During Thermal Processing of Acrylonitrile Butadiene Styrene Composite Resins

Abstract

The evaluation of emissions of volatile organic compounds (VOCs) during processing of resins is of interest to resin manufacturers and resin processors. An accurate estimate of the VOCs emitted from resin processing has been difficult due to the wide variation in processing facilities. This study was designed to estimate the emissions in terms of mass of emitted VOC per mass of resin processed.

A collection and analysis method was developed and validated for the determination of VOCs present in the emissions of thermally processed acrylonitrile butadiene styrene (ABS) resins. Four composite resins were blended from automotive, general molding, pipe, and refrigeration grade ABS resins obtained from the manufacturers. Emission samples were collected in evacuated 6-L Summa canisters and then analyzed using gas chromatography/flame ionization detection/mass selective detection (GC/FID/MSD). Levels were determined for nine target analytes detected in canister samples, and for total VOCs detected by an inline GC/FID. The emissions evolved from the extrusion of each composite resin were expressed in terms of mass of VOCs per mass of processed resin. Styrene was the principal volatile emission from all the composite resins. VOCs analyzed from the pipe resin sample contained the highest level of styrene at 402 μg/g. An additional collection and detection method was used to determine the presence of aerosols in the emissions. This method involved collecting particulates on glass fiber filters, extracting them with solvents, and analyzing them using gas chromatography/mass spectrometry (GC/MS). No significant levels of any of the target analytes were detected on the filters.     

Biogenic volatile organic compounds as a potential stimulator for organic contaminant degradation by soil microorganisms

The effects of monoterpenes on the degradation of ¹⁴C-2,4-dichlorophenol (DCP) were investigated in soils collected from areas surrounding monoterpene and non-monoterpene-emitting vegetation. Indigenous microorganisms degraded ¹⁴C-2,4-DCP to ¹⁴CO₂, after 1 d contact time. Degradation was enhanced by prior exposure of the soils to 2,4-DCP for 32 d, increasing extents of mineralisation up to 60%. Monoterpene amendments further enhanced 2,4-DCP degradation, but only following pre-exposure to both 2,4-DCP and monoterpene, with total 2,4-DCP mineralisation extents of up to 71%. Degradation was greatest at the higher monoterpene concentrations (≥1 μg kg⁻¹). Total mineralisation extents were similar between concentrations, but higher than the control and the 0.1 μg kg⁻¹ amendment, indicating that increases in monoterpene concentration has a diminishing enhancing effect. We suggest that monoterpenes can stimulate the biodegradation of 2,4-DCP by indigenous soil microorganisms and that monoterpene amendment in soils is an effective strategy for removing organic contaminants.     

Generating Synthetic Rainfall on Various Timescales—Daily, Monthly and Yearly

The main objective of this paper is to present a model for generating synthetic rainfall totals on various timescales to be applicable for a variety of uses. Many large-scale ecological and water resource models require daily, monthly and yearly rainfall data as input to the model. As historical data provides only one realisation, synthetic generated rainfall totals are needed to assess the impact of rainfall variability on water resources systems (Srikanthan, In: MODSIM2005, Melbourne, Dec. 2005, pp. 1915–1921, 2005). Thus, our preferred model should simulate rainfall for yearly, monthly and daily periods. We believe that, for water supply issues, no higher resolution is needed, although higher resolution would be useful in models designed to measure the risk of local flooding. The critical factors are daily, monthly and yearly totals and daily, monthly and yearly variation. A model for generating yearly totals will be described using traditional time series methods. This model, along with a similarly constructed daily generation model by Piantadosi et al. (A New Model for Correlated Daily Rainfall, 2008), will be cascaded to start with a synthetic yearly total, then generate a synthetic sequence of monthly totals (through selection from a large number of realisations) that match the yearly total, and subsequently perform a similar operation for sequences of daily totals to match the required monthly totals. We present a new model for the generation of synthetic monthly rainfall data, which we demonstrate for Parafield in Adelaide, South Australia. The rainfall for each month of the year is modelled as a non-negative random variable from a mixed distribution with either a zero outcome or a strictly positive outcome. We use maximum likelihood to find parameters for both the probability of a zero outcome and the gamma distribution that best matches the observed probability density for the strictly positive outcomes. We describe a new model that generates correlated monthly rainfall totals using a diagonal band copula with a single parameter to generate lag-1 correlated random numbers. Our model preserves the marginal monthly distributions and, hence, also preserves the monthly and yearly means. We show that, for Parafield, the correlation between rainfall totals for successive months is not significant, and so, it is reasonable to assume independence. This is, however, not true for daily rainfall. We describe a new model that generates correlated daily rainfall totals using a diagonal band copula with a single parameter to generate lag-1 correlated random numbers. This is an extended version of a paper presented at the 17th Biennial Congress on Modelling and Simulation, Christchurch, New Zealand, December 2007.     

An Application of the Pump-to-Fill Policy for Management of Urban Stormwater

We consider the management of urban stormwater in two connected dams. Stormwater generated by local rainfall flows into a capture dam and is subsequently pumped into a similar sized holding dam. We assume random gross inflow and constant demand. If we wish to minimise overflow from the system then the optimal management policy is to pump as much water as possible each day from the capture dam to the holding dam without allowing the holding dam to overflow. We shall refer to this policy as the pump-to-fill policy. The model is based on the Parafield stormwater management system in the City of Salisbury (CoS) but assumes constant demand instead of level dependent outflow. If there is insufficient water in the holding dam to meet the desired daily demand then all water in the holding dam is used and the shortfall is obtained from other sources. CoS, in suburban Adelaide in South Australia, is recognised in local government circles as a world leader in urban stormwater management. The water is supplied to local industry to replace regular mains water and is also used to restore and maintain urban wetlands. In mathematical terms the pump-to-fill policy defines a Markov chain with a large transition matrix and a characteristic regular block structure. We use specialised Matrix Analytic Methods to decompose the event space and find simplified equations for the steady state probability vector. In this way we enable an elementary solution procedure which we illustrate by solving the modified Parafield problem. The optimal nature of the pump-to-fill policy is established in a recent paper by Pearce et al. (JIMO 3(2):313–320, 2007). The purpose of the current study is to find optimal management policies for urban stormwater systems. Work supported by the Australian Research Council.     

Using supercritical fluid extraction to measure the desorption and bioaccessibility of phenanthrene in soils

The aim of this paper was to measure the changing desorbable fraction and bioaccessibility of phenanthrene in two different soils with increasing soil-phenanthrene contact time using supercritical fluid extractions (SFE). Both soils were spiked with 100 mg kg⁻¹ phenanthrene and aged for 28 d. Desorption profiles were measured every 7 d using selective SFE conditions and the results were compared to ¹⁴C-phenanthrene mineralisation assays. Selective SFE showed significant differences in the rates and extents of desorption in the two soils, likely to be due to different organic matter composition. Post-extraction fitting of data yielded consistent SFE extraction times within ageing soils for bioaccessibility prediction.