Creosote DNAPL Recovery‐Well Design for Mass Removal

Sites with dense nonaqueous‐phase liquid (DNAPL) contamination present significant remediation challenges in terms of technical practicability and cost. Remedial approaches to DNAPL sites often follow a management approach rather than removal or eradication approaches, particularly due to the uncertainties associated with the benefits of partial source mass removal, as complete source removal is unlikely. Mass‐removal technologies should be evaluated for all DNAPL sites, although implementation of recovery technologies will be limited to a few sites based upon site‐specific factors. Sitewide remedial strategies that employ source reduction, where applicable, and incorporate associated risk‐reduction technologies, including monitored natural attenuation, are advised. Creosote DNAPL sites are particularly challenging, as they are predominantly composed of low‐solubility polycyclic aromatic hydrocarbons that form long‐term continuing sources. Additionally, the physical properties of creosote DNAPL, including high viscosity and relatively low density, result in significant migration potential and considerable dissolved‐phase groundwater impacts. An innovative creosote DNAPL source recovery well design was developed to achieve separate‐phase removal of pooled creosote DNAPL. The design presented herein employs modified circulation‐well technology to mobilize DNAPL to the engineered recovery well, where it is gravity‐settled into a sump to permit separate‐phase mass removal of the emplaced DNAPL source without groundwater production or treatment. A discharge mass flux protocol was developed to verify dissolved‐phase plume stability and the benefit of the source mass removal. © 2013 Wiley Periodicals, Inc.     

Evaluation of heavy metal content in digestate from batch anaerobic co-digestion of sunflower hulls and poultry manure

In this experimental study, the biogas digestate from mesophilic batch anaerobic co-digestion of poultry manure and an agricultural residue, sunflower hulls, was characterized, particularly in terms of heavy metal content, in order to evaluate whether the biogas digestate was suitable for land applications. Ni, Zn, Cu, Pb, Cr, Cd, and Hg were detected in the biogas digestate in each trial, however, their concentrations were always lower than the limit values stated in Turkish regulations. The main source of heavy metals in the biogas digestate seemed to be the poultry manure, not the agricultural residue. The commercial feedstuffs that are frequently supplemented with various essential elements to promote optimum nutrient supply and optimum growth rates may have contributed to heavy metals presence in the biogas digestate. The results indicated that the biogas digestate from anaerobic co-digestion of manure and agricultural residue could be utilized as fertilizer in agricultural applications.     

Advances in the recycling of plastic wastes for metallurgical coke production

This paper aims to provide useful knowledge on the use of plastic wastes as additives to coking blends for the production of metallurgical coke. It focuses on the influence that the composition of plastic wastes has upon the development of coal fluidity, the generation of pressure during the coking process and the quality of the cokes produced in a semipilot oven. Several plastic mixtures of two types of thermoplastics, polyolefins (HDPE, LDPE and PP) and aromatic polymers such as PET, were used. The overall addition rate of plastics to a medium-fluid coal blend was 2 wt%. It is shown that polyolefins, weaker modifiers of coal fluidity, may be employed to maintain coke quality but that they have a negative effect on the generation of coking pressure, while plastics of the aromatic type such as PET, a strong modifier of coal fluidity, can be used to counteract the generation of coking pressure. From the results, it is deduced that the protocol developed is useful for determining the optimum amount of each type of polymer (polyolefins and aromatic polymers) that is needed in order to counteract the generation of pressure during the coking process and to maintain the quality of the cokes.     

Preparation and Characterization of Three Different Derivatized Potato Starches

The use of native starch as a thermoplastic polymer is limited by its fragility and high water absorption. Due to the presence of several hydroxyl groups in its structure, water acts as a natural plasticizer of starch, modifying its properties. It is necessary to chemically modify starch molecules by replacing hydroxyl groups with other functional groups to reduce water absorption. Chemical modification of starch granules also alters its swelling and gelatinization behavior. In this contribution we describe the chemical modification of starch and its influence on its hydrophilicity and heat resistance. Acetic acid, maleic anhydride and octanoyl chloride were used as derivatizing reagents. The effectiveness of the treatments was evaluated by means of infrared spectroscopy. Different tests were conducted in order to evaluate the influence of the different chemical modifications on starch structure and properties. Results showed that the treatments effectively reduced starch moisture susceptibility, while substantially altering other properties such as amylose content, swelling power, solubility, and heat resistance. Finally, films were prepared from native and derivatized starch and their surface polarity was evaluated.     

The impact of infield biomass burning on PM levels and its chemical composition

In the South of Italy, it is common for farmers to burn pruning waste from olive trees in spring. In order to evaluate the impact of the biomass burning source on the physical and chemical characteristics of the particulate matter (PM) emitted by these fires, a PM monitoring campaign was carried out in an olive grove. Daily PM10 samples were collected for 1 week, when there were no open fires, and when biomass was being burned, and at two different distances from the fires. Moreover, an optical particle counter and a polycyclic aromatic hydrocarbon (PAH) analyzer were used to measure the high time-resolved dimensional distribution of particles emitted and total PAHs concentrations, respectively. Chemical analysis of PM10 samples identified organic and inorganic components such as PAHs, ions, elements, and carbonaceous fractions (OC, EC). Analysis of the collected data showed the usefulness of organic and inorganic tracer species and of PAH diagnostic ratios for interpreting the impact of biomass fires on PM levels and on its chemical composition. Finally, high time-resolved monitoring of particle numbers and PAH concentrations was performed before, during, and after biomass burning, and these concentrations were seen to be very dependent on factors such as weather conditions, combustion efficiency, and temperature (smoldering versus flaming conditions), and moisture content of the wood burned.     

Copper distribution in surface and subsurface soil horizons

The horizons of four natural soils were treated with Cu²⁺ in an acid medium to study the retention capacity of Cu. The possible mineralogical changes arising because of the treatment were also studied. The soil properties and characteristics with the greatest influence on the metal retention and its distribution among the different soil fractions were determined. Crystalline phases of each horizon were determined by X-ray diffraction (XDR). The morphology, structural distribution and particle chemical composition of soil samples were investigated using field emission scanning electron microscopy. Cu distribution in the different geochemical phases of the soil was studied using a sequential extraction. The treatment led to an increase in the amorphous phases and the formation of new crystalline phases, such as rouaite (Cu₂(NO₃)(OH)₃) and nitratine (NaNO₃). Cu was also found superficially sorbed on amorphous hydroxy compounds of Fe that interact with albite, muscovite and gibbsite, and also on spherical and curved particles of aluminium clays. The largest amount of Cu retained was in an exchangeable form, and the smallest amount associated with the crystalline Fe oxides and residual fraction. In the surface horizons, the predominant Cu retention process is complexation in organomineral associations, while in the subsurface horizons it is adsorption.     

Indoor air quality (IAQ) assessment in a multistorey shopping mall by high-spatial-resolution monitoring of volatile organic compounds (VOC)

In order to assess indoor air quality (IAQ), two 1-week monitoring campaigns of volatile organic compounds (VOC) were performed in different areas of a multistorey shopping mall. High-spatial-resolution monitoring was conducted at 32 indoor sites located in two storehouses and in different departments of a supermarket. At the same time, VOC concentrations were monitored in the mall and parking lot area as well as outdoors. VOC were sampled at 48-h periods using diffusive samplers suitable for thermal desorption. The samples were then analyzed with gas chromatography–mass spectrometry (GC–MS). The data analysis and chromatic maps indicated that the two storehouses had the highest VOC concentrations consisting principally of terpenes. These higher TVOC concentrations could be a result of the low efficiency of the air exchange and intake systems, as well as the large quantity of articles stored in these small spaces. Instead, inside the supermarket, the food department was the most critical area for VOC concentrations. To identify potential emission sources in this department, a continuous VOC analyzer was used. The findings indicated that the highest total VOC concentrations were present during cleaning activities and that these activities were carried out frequently in the food department. The study highlights the importance of conducting both high-spatial-resolution monitoring and high-temporal-resolution monitoring. The former was able to identify critical issues in environments with a complex emission scenario while the latter was useful in interpreting the dynamics of each emission source.     

A review of plant–pharmaceutical interactions: from uptake and effects in crop plants to phytoremediation in constructed wetlands

Pharmaceuticals are commonly found both in the aquatic and the agricultural environments as a consequence of the human activities and associated discharge of wastewater effluents to the environment. The utilization of treated effluent for crop irrigation, along with land application of manure and biosolids, accelerates the introduction of these compounds into arable lands and crops. Despite the low concentrations of pharmaceuticals usually found, the continuous introduction into the environment from different pathways makes them ‘pseudo-persistent’. Several reviews have been published regarding the potential impact of veterinary and human pharmaceuticals on arable land. However, plant uptake as well as phytotoxicity data are scarcely studied. Simultaneously, phytoremediation as a tool for pharmaceutical removal from soils, sediments and water is starting to be researched, with promising results. This review gives an in-depth overview of the phytotoxicity of pharmaceuticals, their uptake and their removal by plants. The aim of the current work was to map the present knowledge concerning pharmaceutical interactions with plants in terms of uptake and the use of plant-based systems for phytoremediation purposes.     

An exploratory study of air emissions associated with shale gas development and production in the Barnett Shale

Information regarding air emissions from shale gas extraction and production is critically important given production is occurring in highly urbanized areas across the United States. Objectives of this exploratory study were to collect ambient air samples in residential areas within 61 m (200 feet) of shale gas extraction/production and determine whether a “fingerprint” of chemicals can be associated with shale gas activity. Statistical analyses correlating fingerprint chemicals with methane, equipment, and processes of extraction/production were performed. Ambient air sampling in residential areas of shale gas extraction and production was conducted at six counties in the Dallas/Fort Worth (DFW) Metroplex from 2008 to 2010. The 39 locations tested were identified by clients that requested monitoring. Seven sites were sampled on 2 days (typically months later in another season), and two sites were sampled on 3 days, resulting in 50 sets of monitoring data. Twenty-four-hour passive samples were collected using summa canisters. Gas chromatography/mass spectrometer analysis was used to identify organic compounds present. Methane was present in concentrations above laboratory detection limits in 49 out of 50 sampling data sets. Most of the areas investigated had atmospheric methane concentrations considerably higher than reported urban background concentrations (1.8–2.0 ppm_v). Other chemical constituents were found to be correlated with presence of methane. A principal components analysis (PCA) identified multivariate patterns of concentrations that potentially constitute signatures of emissions from different phases of operation at natural gas sites. The first factor identified through the PCA proved most informative. Extreme negative values were strongly and statistically associated with the presence of compressors at sample sites. The seven chemicals strongly associated with this factor (o-xylene, ethylbenzene, 1,2,4-trimethylbenzene, m- and p-xylene, 1,3,5-trimethylbenzene, toluene, and benzene) thus constitute a potential fingerprint of emissions associated with compression.

Implications: Information regarding air emissions from shale gas development and production is critically important given production is now occurring in highly urbanized areas across the United States. Methane, the primary shale gas constituent, contributes substantially to climate change; other natural gas constituents are known to have adverse health effects. This study goes beyond previous Barnett Shale field studies by encompassing a wider variety of production equipment (wells, tanks, compressors, and separators) and a wider geographical region. The principal components analysis, unique to this study, provides valuable information regarding the ability to anticipate associated shale gas chemical constituents.     

Recharge and Flow in the Medicine Lake Volcano–Fall River Springs Groundwater Basin,California

Isotopic measurements of the 34 m³/s discharge from the Fall River Springs of northern California indicate recharge from 50 km upgradient in high elevation regions of Medicine Lake Volcano. Age determinations suggest less than 20-year travel time. Data demonstrate Klamath Basin further north cannot be a recharge source. Mass balance calculations support that annual precipitation on the volcano supplies observed spring discharge, requiring 50%–75% recharge rates. Radiocarbon and δ¹³C of dissolved inorganic carbon indicate 30%–40% is derived from magmatic CO₂. Measured excess ³He is also consistent with the presence of magmatic gas derived from the Quaternary Age Medicine Lake Volcano.