Synthetic Chemicals with Potential for Natural Attenuation

Natural attenuation of petroleum hydrocarbons is predictable and self-sustaining because bacteria able to use the contaminants as growth substrates are widely distributed. In contrast, bacteria able to grow at the expense of chlorinated aliphatic compounds are less common and the natural attenuation of such compounds is, therefore, less predictable. The purpose of this paper is to describe examples of other synthetic organic compounds that are known to be biodegradable and have the potential for natural attenuation in the field.     

Rate of Natural Attenuation of Tert-Butyl Alcohol at a Chemical Plant

Tert-butyl alcohol (TBA) may be present in groundwater as an original component of leaked gasoline, or as a degradation product of methyl tert-butyl ether (MTBE). Evidence for natural attenuation of TBA in groundwater is presented from a chemical plant in Pasadena, Texas. Shallow groundwater in several areas of the plant has been affected by historic leaks and spills of TBA. A decade of regular groundwater monitoring of one groundwater plume, consisting primarily of TBA, shows generally declining concentrations and a plume area that is shrinking. Natural attenuation mechanisms are limiting the advective transport of TBA. The principal mechanism of attenuation in this case is probably biodegradation as the other physical components of natural attenuation (dilution, dispersion, diffusion, adsorption, chemical reactions, and volatilization) cannot explain the behavior of the plume over time. Biodegradation was also indicated by the enrichment of stable carbon isotope composition (¹³C/¹²C) of TBA along the flow path. Preliminary dissolved gas and electron acceptor analyses indicate the groundwater is at least under sulfate reducing condition in the core of the plume and the process responsible for biodegradation of TBA may include fermentation under aerobic (plume fringes) and possible anaerobic conditions. This case history demonstrates that natural attenuation of TBA is important, and can be used as a groundwater management tool at this site.     

Definition, Objectives, and Evaluation of Natural Attenuation

Natural attenuation offers large benefits to owners and managers of contaminated sites, but often raises strong objections from those who live and work near a site and are asked to assume most of the long-term risks. Part of the controversy comes about because published definitions of natural attenuation do not identify a realistic end-point objective, and they also are ambiguous about the naturally occurring processes that can achieve the objective. According to guidance from the U.S. National Research Council (NRC 2000), destruction and strong immobilization are the naturally occurring processes that achieve a realistic objective: containing the contaminant relatively nears its source, thereby minimizing exposure risks. The strategy for obtaining solid evidence that the objective is being achieved requires measurements that establish a cause-and-effect relationship between contaminant loss and a destruction or strong-immobilization reaction. The cause-and-effect relationship is best documented with reaction footprints, which typically are concentration changes in reactants or products of the destruction or immobilization reaction. MTBE presents a contemporary example in which footprint evidence for biodegradation is especially crucial, since aerobic biodegradation of MTBE requires special conditions not present at all sites: a high availability of dissolved oxygen and bacteria expressing particular oxygenase enzymes.     

Selecting Remediation Goals by Assessing the Natural Attenuation Capacity of Groundwater Systems

Remediation goals for the source areas of a chlorinated ethene-contaminated groundwater plume were identified by assessing the natural attenuation capacity of the aquifer system. The redox chemistry of the site indicates that sulfate-reducing (H₂ ∼ 2 nanomoles [nM]) per liter conditions near the contaminant source grade to Fe(III)-reducing conditions (H₂ ∼ 0.5 nM) downgradient of the source. Sulfate-reducing conditions facilitate the initial reduction of perchloroethene (PCE) to trichloroethene (TCE), cis-dichloroethene (cis-DCE), and vinyl chloride (VC). Subsequently, the Fe(III)-reducing conditions drive the oxidation of cis-DCE and VC to carbon dioxide and chloride. This sequence gives the aquifer a substantial capacity for biodegrading chlorinated ethenes. Natural attenuation capacity (the slope of the steady-state contaminant concentration profile along a groundwater flowpath) is a function of biodegradation rates, aquifer dispersive characteristics, and groundwater flow velocity. The natural attenuation capacity at the Kings Bay, Georgia site was assessed by estimating groundwater flowrates (∼0.23±0.12 m/d) and aquifer dispersivity (∼1 m) from hydrologic and scale considerations. Apparent biodegradation rate constants (PCE and TCE ∼0.01 d^-1; cis-DCE and VC ∼0.025 d^-1) were estimated from observed contaminant concentration changes along aquifer flowpaths. A boundary-value problem approach was used to estimate levels to which contaminant concentrations in the source areas must be lowered (by engineered removal), or groundwater flow velocities lowered (by pumping) for the natural attenuation capacity to achieve maximum concentration limits (MCLs) prior to reaching a predetermined regulatory point of compliance.     

The impact of environmental factors in birdsong acquisition using automated recorders

The use of automatic acoustic recorders is becoming a principal method to survey birds in their natural habitats, as it is relatively noninvasive while still being informative. As with any other sound, birdsong degrades in amplitude, frequency, and temporal structure as it propagates to the recorder through the environment. Knowing how different birdsongs attenuate under different conditions is useful to, for example, develop protocols for deploying acoustic recorders and improve automated detection methods, an essential part of the research field that is becoming known as ecoacoustics. This article presents playback and recapture (record) experiments carried out under different environmental conditions using twenty bird calls from eleven New Zealand bird species in a native forest and an open area, answering five research questions: (1) How does birdsong attenuation differ between forest and open space? (2) What is the relationship between transmission height and birdsong attenuation? (3) How does frequency of birdsong impact the degradation of sound with distance? (4) Is birdsong attenuation different during the night compared to the day? and (5) what is the impact of wind on attenuation? Bird calls are complex sounds; therefore, we have chosen to use them rather than simple tones to ensure that this complexity is not missed in the analysis. The results demonstrate that birdsong transmission was significantly better in the forest than in the open site. During the night, the attenuation was at a minimum in both experimental sites. Transmission height affected the propagation of the songs of many species, particularly the flightless ones. The effect of wind was severe in the open site and attenuated lower frequencies. The reverberations due to reflective surfaces masked higher frequencies (8 kHz) in the forest even at moderate distances. The findings presented here can be applied to develop protocols for passive acoustic monitoring. Even though the attenuation can be generalized to frequency bands, the structure of the birdsong is also important. Selecting a reasonable sampling frequency avoids unnecessary data accumulation because higher frequencies attenuate more in the forest. Even at moderate distances, recorders capture significantly attenuated birdsong, and hence, automated analysis methods for field recordings need to be able to detect and recognize faint birdsong.     

Formulation of the CBC-Model for Modelling the Contaminants and Footprints in Natural Attenuation of BTEX

The Refuse Hideaway Landfill (23-acre) received municipal, commercial, and industrial waste between 1974 and 1988. It was designed as a "natural attenuation" landfill and no provision was made to collect and treat contaminated water. Natural biological degradation through sequential reductive dechlorination had been an important mechanism for natural attenuation at the site. We used the concentration of hydrogen to forecast whether reductive dechlorination would continue over time at particular locations in the plume. Based on published literature, reductive dechlorination and natural attenuation of PCE, TCE, and cis-DCE can be expected in the aquifer if the concentration of molecular hydrogen in monitoring wells are adequate (> 1 nanomolar). Reductive dechlorination can be expected to continue as the ground water moves down gradient. Natural attenuation through reductive dechlorination is not expected in flow paths that originate at down gradient monitoring wells with low concentrations of molecular hydrogen (< 1 nanomolar). In three monitoring wells at the margin of the landfill and in five monitoring wells down gradient of the landfill, ground water maintained a molecular hydrogen concentration, ranging from 1.30 to 9.17 nanomolar, that is adequate for reductive dechlorination. In three of the monitoring wells far down gradient of the landfill, the concentration of molecular hydrogen (0.33 to 0.83 nanomolar) was not adequate to support reductive dechlorination. In wells with adequate concentrations of hydrogen, the concentrations of chlorinated volatile organic compounds were attenuated over time, or concentrations of chlorinated volatile organics were below the detection limit. In wells with inadequate concentrations of hydrogen, the concentrations of chlorinated organic compounds attenuated at a slower rate over time. In wells with adequate hydrogen the first order rate of attenuation of PCE, TCE, cis-DCE and total chlorinated volatile organic compounds varies from 0.38 to 0.18 per year. In wells without adequate hydrogen the rate varies from 0.015 to 0.006 per year.     

Evaluation of Natural Attenuation of Benzene and Dichloroethanes at the KL Landfill

Natural attenuation of benzene and dichloroethanes in groundwater contaminated by leachate from the West KL Avenue landfill in Kalamazoo, Michigan, was evaluated in three phases. Existing data from the previous site investigations were used to locate a series of high-resolution vertical profile samples. By analyzing data from the discrete vertical profile samples, the rates of attenuation of benzene and dichloroethanes in the plume were forecasted. Permanent monitoring wells were installed over the depth intervals associated with high concentrations in the vertical profile sampling. These wells were monitored over time to extract independent estimates of the rates of degradation of benzene and dichloroethanes. Estimates of first-order attenuation rate constants were obtained using two methods: a method due to Buscheck and Alcantar (1995), which is based on a one-dimensional steady-state analytical solution, and the tracer correction method of Wiedemeier et al. (1996). The rates of attenuation predicted from the vertical profile sampling were found to be in good agreement with the rates obtained from the permanent monitoring well data, indicating that the long-term behavior of the contaminant plumes is consistent with the initial forecast. The results also indicated that the natural attenuation of benzene, 1,1-dichloroethane (DCA), and 1,2-DCA was statistically significant (at the 0.05 level).     

Natural Attenuation Rate Clarifications: The True Picture is in the Details

The term “Natural Attenuation” (NA) has been defined as naturally occurring processes in soil and groundwater environments that act without human intervention to reduce the mass, toxicity, mobility, volume, or concentration of contaminants in those media. Monitored natural attenuation (MNA) protocols generally involve the collection of biogeochemical data from groundwater monitoring wells at sites. The data are correlated in time and space with the various chemicals of concern (COC's) to establish predominant biodegradation mechanisms. Modelers using the first-order decay expression typically use the rate coefficient as a calibration parameter and adjust it until the transport model results match field data. With this approach, uncertainties with a number of parameters (e.g., dispersion, sorption, biodegradation, etc.) are lumped together in a single calibration parameter. The problems associated with the lumped parameter approach are illustrated using two commonly used models, BIOSCREEN and Buscheck/Alcantar Analytical Solution, in a variety of practical examples. The natural attenuation decay rate estimated using the lumped parameter approach is distinguished from a biodegradation rate established by isolating processes and examining biodegradation lines of evidence. The half-life determined from empirical data using the lumped parameter approach is often mistakenly interchanged with a biodegradation half-life when it is an all-encompassing half-life based on the interaction of numerous processes. Isolation of the processes, as they are represented in the governing transport equation, and a rationale approach at parameter estimation to avoid the potential pitfalls of the all-inclusive “attenuation rate,” are provided. In closing, it is imperative to implement the following steps to dissern lumped process degradation rates from biodegradation half-lives: (a) be sure the rate/half-life processes are clarified as to what they encompass, (b) establish exactly how the rate/half-life was determined, (c) make certain other processes, such as dispersion, were estimated correctly, and (d) if the half-life is presented as a first-order biodegradation rate, examine the available lines of evidence to substantiate it.     

Monitored Natural Attenuation of Explosives

Explosives are subject to several attenuation processes that potentially reduce concentrations in groundwater over time. Some of these processes are well defined, while others are poorly understood. The objective of the project was to optimize data collection and processing procedures for evaluation and implementation of monitored natural attenuation of explosives. After conducting experiments to optimize data quality, a protocol was established for quarterly monitoring of thirty wells over a 2-year period at a former waste disposal site. Microbial biomarkers and stable isotopes of nitrogen and carbon were explored as additional approaches to tracking attenuation processes. The project included a cone penetrometry sampling event to characterize site lithology and to obtain sample material for biomarker studies. A three-dimensional groundwater model was applied to conceptualize and predict future behavior of the contaminant plume. The groundwater monitoring data demonstrated declining concentrations of explosives over the 2 years. Biomarker data showed the potential for microbial degradation and provided an estimate of the degradation rate. Measuring stable isotopic fractions of nitrogen in TNT was a promising method of monitoring TNT attenuation. Overall, results of the demonstration suggest that monitored natural attenuation is a viable option that should be among the options considered for remediation of explosives-contaminated sites.     

An Evaluation of Aerobic Trichloroethene Attenuation Using First-Order Rate Estimation

Natural attenuation of trichloroethene (TCE) was evaluated for a groundwater plume at the Idaho National Engineering and Environmental Laboratory. Significant evidence demonstrated that reductive dechlori-nation is occurring, but is limited to a small area around the contamination source. In spite of this, the plume is relatively stable. Three first-order rate estimation methods were used to help understand transport processes affecting TCE in the large, aerobic portion of the plume. Two of the methods gave attenuation half-life estimates for TCE of approximately 8 years; however, these methods do not adequately distinguish between degradation and dispersion. The third method showed TCE attenuation relative to the co-contaminants, tritium and tetrachloroethene (PCE), and used these “tracers” to distinguish between dispersion and degradation. The estimated aerobic degradation half-life for TCE was between 13 and 21 years. Aerobic cometabolism of TCE has been identified as a potential mechanism for the apparent degradation. The importance of distinguishing between dispersion and degradation was shown using an analytical model. The model demonstrated that, in general, the rate of contaminant concentration decrease due to dispersion is not constant with time after the source is removed. This has important implications for predicting the long-term effectiveness of natural attenuation for groundwater restoration.     

Long-term assessment of natural attenuation: statistical approach on soils with aged PAH contamination

Natural attenuation processes valorization for PAH-contaminated soil remediation has gained increasing interest from site owners. A misunderstanding of this method and a small amount of data available does not encourage its development. However, monitored natural attenuation (MNA) offers a valuable, cheaper and environmentally friendly alternative to more classical options such as physico-chemical treatments (e.g., chemical oxidation, thermal desorption). The present work proposes the results obtained during a long-term natural attenuation assessment of historically contaminated industrial soils under real climatic conditions. This study was performed after a 10 year natural attenuation period on 60 off-ground lysimeters filled with contaminated soils from different former industrial sites (coking industry, manufactured gas plants) whose initial concentration of PAH varied between 380 and 2,077 mg kg^?1. The analysed parameters included leached water characterization, soil PAH concentrations, evaluation of vegetation cover quality and quantity. Results showed a good efficiency of the PAH dissipation and limited transfer of contaminants to the environment. It also highlighted the importance of the fine soil fractions in controlling PAH reactivity. PAH dissipation through water leaching was limited and did not present a significant risk for the environment. This PAH water concentration appeared however as a good indicator of overall dissipation rate, thereby illustrating the importance of pollutant availability in predicting its degradation potential.     

Production of reliability proven physiological data for use in automated monitoring and diagnostic systems

In recent years manufacturers of intensive care monitoring systems have introduced complex digital processing architectures that theoretically have enormous processing power. This power should allow the realization of many useful processing methodologies that up to now have only been research tools, e.g. the generation of reliable alarms, the implementation of predictive monitoring strategies and reliable diagnostic and treatment guidance to the clinical staff. However, before any of these methodologies can be successfully initiated, each must have accurate and relaible derived physiological data available to them, e.g. beat-by-beat heart rate and blood pressure. From the very nature of monitoring physiological quantities there will be much misinformation or ‘noise’ superimposed on the raw signal obtained from the patient. The major source of noise (as far as electocardiogram (ECG) monitoring is concerned) is internal to the body and is electromyographic noise. This results from the contraction of skeletal muscles producing action potentials of similar magnitude and frequency to that of the ECG. Fortunately, nursing staff are very good at ‘filtering out’ any misinformation before recording any data (on a ward chart for instance). However, in completely automated systems, if this noise is not detected and eliminated or compensated for at an early stage in the processing chain, misinformation will result with potentially serious consequences. The recognition and elimination of such noise cannot be readily achieved using standard filtering techniques without serious degradation of information. This paper discusses the potential of modern digital system architectures developed for ECG monitoring. It analyses the noise that occurs on this physiological variable and demonstrates a novel method of eliminating such noise.     

Protocols for synchronizing estrus and ovulation in buffalo (Bubalus bubalis): a review

Poor estrus expression and a prolonged intercalving interval compromise the reproductive efficiency of female buffaloes. These limitations are exacerbated during the hot season, when fertility decreases dramatically. Pregnancy rate decrease further because difficulties in detecting estrus. To improve reproductive efficiency, several protocols of estrus and ovulation synchronization have been developed. These procedures are based on manipulating the CL, either to induce premature luteolysis using prostaglandins or to prolong the luteal phase using progestagens. However, it has recently emerged that a more precise manipulation of follicular development may be needed to achieve better synchrony of ovulation and improve fertility. Researchers have therefore turned their attention to evaluating programs in which hormones such as GnRH, FSH, LH, eCG, hCG, prostaglandins, progesterone and estradiol are administered. This review considers the impacts of estrus and ovulation synchronization protocols on fertility in the buffalo. In general, it may be stated that buffaloes respond well to the exogenous administration of hormones, and artificial insemination is possible at a pre-established time after synchronizing ovulation. Most combined hormone protocols give satisfactory pregnancy rates, comparable to those achieved in animals inseminated at natural estrus.     

Natural attenuation: what does the subsurface have in store?

Throughout the world, organic and inorganic substances leach intothe subsurface as a result of human activities and accidents. There, the chemicals pose director indirect threats to the environment and to increasingly scarce drinking water resources.At many contaminated sites the subsurface is able to attenuate pollutants which, potentially,lowers the costs of remediation. Natural attenuation comprises a wide range of processesof which the microbiological component, which is responsible for intrinsic bioremediation,can decrease the mass and toxicity of the contaminants and is, therefore, the mostimportant. Reliance on intrinsic bioremediation requires methods to monitor the process. Thesubject of this review is how knowledge of subsurface geology and hydrology, microbial ecologyand degradation processes is used and can be used to monitor the potential andcapacity for intrinsic bioremediation in the subsurface and to verify degradation in situ.As research on natural attenuation in the subsurface has been rather fragmented and limitedand often allows only conclusions to be drawn of the site under investigation, we providea concept based on Environmental Specimen Banking which will contribute to furtherunderstanding subsurface natural attenuation processes and will help to develop andimplement new monitoring techniques.     

Methyl-tertiary Butyl Ether Natural Attenuation Case Studies

The occurrence of methyl-tertiary butyl ether (MtBE), a gasoline additive in ground water and surface water, is causing regulatory agencies, owner/operators, environmental professionals, and researchers to reevaluate remediation strategies at sites where gasoline containing this additive has been released. Over the last 5 to 10 years, monitored natural attenuation has been applied at petroleum hydrocarbon-impacted sites with increasing frequency. The efficacy of this remediation method for releases containing MtBE is now coming under increased scrutiny. The question of natural attenuation efficacy stems from uncertainty about MtBE biodegradability and behavior in the subsurface. Researchers and applied environmental scientists have completed and are continuing studies concerning MtBE biodegradability and behavior. This article briefly summarizes the history of MtBE, its physicochemical properties, its behavior in the environmental, and the applicability of monitored natural attenuation as a remediation tool. Case studies representing past and current research are then presented and followed by a brief discussion. Results from the documented research reviewed show that MtBE does biodegrade in the laboratory and at actual release sites. “Plumathon” studies document MtBE concentration and mass reduction and/or plume stabilization over time. MtBE concentrations in monitoring wells may show declining concentrations indicating natural attenuation. The data reviewed from past and current research suggest that natural attenuation may be the appropriate remediation strategy at some release sites. Yet, the data also indicate that care must be exercised in determining the efficacy of applying monitored natural attenuation at sites impacted with MtBE.     

High surface temperatures select for individual foraging in ants

Natural selection favors signals, receptors, and signaling behaviorthat maximize the received signal relative to background noiseand that minimize signal degradation. The physical propertiesof the environment affect rates of attenuation and degradationof the signal, and thus temperature may influence the evolutionand maintenance of volatile chemical signals. We tested this hypothesis in ants, where nest mate recruitment to a food sourceby laying trail pheromones on a surface is a common phenomenon.We collected data on maximal soil surface temperatures duringthe ants' activity and mode of foraging (recruitment or solitary).By using two different comparative methodologies, we demonstrateda relationship between maximal soil temperature at which speciesare active and recruitment behavior (which is hypothesized to be related to the presence or absence of chemical signals).The species that were active at lower temperatures proved tobe those that used chemical signals to recruit nest mates duringforaging. This is also the case when comparing sympatric speciesand thereby controlling for other environmental factors. Moreover,all seven nonrecruiter species developed from recruiter ancestries,which is consistent with our hypothesis because ample evidence suggests a forest and tropical origin for ants. Thus, contraryto previous hypotheses, species that forage individually cannotbe categorically considered primitive, but rather appear tobe derived from recruiter species. Therefore, we conclude thattemperature influences the evolution and/or stability of chemicalsignals in ants by determining the recruitment of nest mates.     

Techniques for physicochemical characterization of nanomaterials

Advances in nanotechnology have opened up a new era of diagnosis, prevention and treatment of diseases and traumatic injuries. Nanomaterials, including those with potential for clinical applications, possess novel physicochemical properties that have an impact on their physiological interactions, from the molecular level to the systemic level. There is a lack of standardized methodologies or regulatory protocols for detection or characterization of nanomaterials. This review summarizes the techniques that are commonly used to study the size, shape, surface properties, composition, purity and stability of nanomaterials, along with their advantages and disadvantages. At present there are no FDA guidelines that have been developed specifically for nanomaterial based formulations for diagnostic or therapeutic use. There is an urgent need for standardized protocols and procedures for the characterization of nanoparticles, especially those that are intended for use as theranostics.     

Medical image registration: a review

This paper presents a review of automated image registration methodologies that have been used in the medical field. The aim of this paper is to be an introduction to the field, provide knowledge on the work that has been developed and to be a suitable reference for those who are looking for registration methods for a specific application. The registration methodologies under review are classified into intensity or feature based. The main steps of these methodologies, the common geometric transformations, the similarity measures and accuracy assessment techniques are introduced and described.