Thermal DNAPL Source Zone Treatment Impact on a CVOC Plume

The tetrachloroethene (PCE) source zone at a site in Endicott, New York had caused a dissolved PCE plume. This plume was commingled with a petroleum hydrocarbon plume from an upgradient source of fuel oil. The plume required a system for hydraulic containment, using extraction wells located about 360 m downgradient of the source. The source area was remediated using in situ thermal desorption (ISTD). Approximately 1406 kilograms (kg) of PCE was removed in addition to 4082 kg of commingled petroleum‐related compounds. The ISTD treatment reduced the PCE mass discharge into the plume from an estimated 57 kg/year to 0.07 kg/year, essentially removing the source term. In the 5 years following the completion of the thermal treatment in early 2010, the PCE plume has collapsed, and the concentration of degradation products in the PCE‐series plume area has declined by two to three orders of magnitude. Anaerobic dechlorination is the suspected dominant mechanism, assisted by the presence of a fuel oil smear zone and a petroleum hydrocarbon plume from a separate source area upgradient of the PCE source. Based on the post‐thermal treatment groundwater monitoring data, the hydraulic containment system was reduced in 2014 and discontinued in early 2015.     

Trends in 1,4-Dioxane Analyses: Implications for Identification and Characterization of Contaminated Groundwater Sites

1,4-Dioxane is a contaminant of emerging concern, and there is significant uncertainty about how its environmental occurrence in groundwater is being assessed given the various analytical methods available. This study compiled public sampling records from 2000 to 2019 that included >106,000 analyses of 1,4-dioxane from 822 different U.S. sites. The 1,4-dioxane detection frequency in the entire dataset (including all methods) was 45%, and the median detected concentration was 10 μg/L, highlighting the dilute nature of 1,4-dioxane in environmental media and the importance of selecting methods with adequate sensitivity. The annual distribution of samples analyzed by each method type confirmed a shift towards methods designed for semi-volatile compounds (Method 8270 and Method 8270 SIM) that exhibited consistently lower reporting limits (median reporting limit for each year typically ≤1 μg/L). In contrast, the method designed for volatile compounds (Method 8260) exhibited less sensitivity for 1,4-dioxane (median reporting limit per year between 40 and 100 μg/L) and its use declined significantly over time with increasing use of the moderately sensitive Method 8260 SIM in later years. This shift contributed to an increase in the 1,4-dioxane detection frequency over time, with a strong correlation between the annual detection frequency and the median reporting limit. Sites where 1,4-dioxane was analyzed but not detected overwhelmingly used less-sensitive methods that may not have been adequate for the expected concentration levels. Given the sub-μg/L groundwater criteria issued for 1,4-dioxane by some regulatory agencies, more sensitive and accurate methods will be increasingly needed to assess compliance.     

Thermal Monitoring of Natural Source Zone Depletion

Natural depletion of subsurface petroleum liquids releases energy in the form of heat. The rate of natural source zone depletion (NSZD) can be derived from subsurface temperature data. An energy balance is performed to resolve NSZD‐generated energy in terms of W/m². Biodegradation rates are resolved by dividing the NSZD energy by the heat of reaction in joules/mol. Required temperature data are collected using data loggers, wireless connections, and automated data storage and analysis. Continuous thermal resolution of monthly NSZD rates at a field site indicates that apparent monthly NSZD rates vary through time, ranging from 10,000 to 77,000 L/ha/year. Temporal variations in observed apparent NSZD rates are attributed to processes governing the conversion of CH₄ to CO₂, as opposed to the actual rates of NSZD. Given a year or more of continuous NSZD rate data, it is anticipated that positive and negative biases in apparent NSZD rates will average out, and averaged apparent NSZD rates will converge to true NSZD rates. An 8.4% difference between average apparent NSZD rates over a 31‐month period using the thermal monitoring method and seven rounds of CO₂ efflux measurements using CO₂ traps supports the validity of both CO₂ trap and thermal monitoring methods. A promising aspect of thermal monitoring methods is that continuous data provide a rigorous approach to resolving the true mean NSZD rates as compared to temporally sparse CO₂ trap NSZD rate measurements. Overall, a vision is advanced of real‐time sensor‐based groundwater monitoring that can provide better data at lower costs and with greater safety, security, and sustainability.     

Comparing Natural Source Zone Depletion Pathways at a Fuel Release Site

Natural source zone depletion (NSZD) refers to processes within chemically impacted vadose and saturated zones that reduce the mass of contaminants remaining in a defined source control volume. Studies of large petroleum hydrocarbon release sites have shown that the depletion rate by vapor phase migration of degradation products from the source control volume through the vadose zone (V‐NSZD) is often considerably higher than the rate of depletion from the source control volume by groundwater flow carrying dissolved petroleum hydrocarbons arising from dissolution, desorption, or back diffusion, and degradation products arising from biodegradation (GW‐NSZD). In this study, we quantified vadose zone and GW‐NSZD at a small unpaved fuel release site in California typical of those in settings with predominantly low permeability media. We estimated vadose zone using a dense network of efflux monitoring locations at four sampling events over 2 years, and GW‐NSZD using groundwater monitoring data downgradient of the source control volume in three depth intervals spanning up to 9 years. On average, vadose zone was 17 times greater than GW‐NSZD during the time interval of comparison, and vadose zone was in the range of rates quantified at other sites with petroleum hydrocarbon releases. Estimating vadose zone and GW‐NSZD rates is challenging but the vadose zone rate is the best indicator of overall source mass depletion, whereas GW‐NSZD rates may be useful as baselines to quantify progress of natural or engineered remediation in portions of the saturated zone in which there are impediments to loss of methane and other gases to the vadose zone.     

红河断裂带两侧地块地震震源参数研究

利用云南区域数字地震遥测台网资料,采用Brune圆位错模型对1998年12月至2006年8月云南境内M≥3地震和越南北部M>2地震测算震源参数。结果表明,红河断裂两侧活动块体的地震活动和震源参数存在较为明显的差异。就地震矩与震级的标度关系而言,滇西南块体与美国加州圣安德列斯断层和滇西实验场及其周边地区的结果一致,但与华南块体和越南北部地区有差异;从应力降的测算结果看,华南块体西缘的云南及越南北部地区的年均值为7.29MPa,滇西南块体为4.48MPa,两块体北部地震的应力降大于南部地区,应力降由北向南逐渐减小;就地震位错年均值而言,华南块体为12.3mm/a,滇西南块体为6.6mm/a。     

Source of Ash Zone 1 in the North Atlantic

Geochemical evidence shows that the silicic component of the widespread Ash Zone 1 in the North Atlantic is derived from a major ignimbrite-forming eruption which occurred at the Katla caldera in southern Iceland during the transition from glacial to interglacial conditions in Younger Dryas time. Both trace and major element evidence of the rhyolitic products excludes the Öræfajökull volcano as a source. The high-Ti basaltic component in the marine ash zone can also be attributed to contemporaneous eruption in the Katla volcanic complex. Dispersal of tephra from this event is primarily attributed to the generation of co-ignimbrite ash columns in the atmosphere, with ash fallout on both sea ice and on the ocean floor north and east of Iceland. Owing to the changing ocean circulation characteristics of the glacial regime, including suppression of the Irminger Current and a stronger North Atlantic Current, tephra was rafted on sea ice south into the central North Atlantic and deposited as dispersed Ash Zone 1. Sediments south of Iceland also show evidence of the formation of ash turbidites, generated either by the entrance of pyroclastic flows into the sea, or during discharge of jökulhlaups or glacier bursts from this subglacial eruption.     

Changes in Earthquake Source Properties across a Shallow Subduction Zone: Kamchatka Peninsula

—This paper studies the source properties of earthquakes originating within the shallow subduction zone near Kamchatka Peninsula. We use the regional catalog of 1962–1993 Kamchatkan earthquakes completed by the Institute of Volcanology, Russia. Our previous investigations (Zobin, 1990, 1996a) and this study allow us to show a gradual change in source properties of earthquakes from trench to coast.¶It was demonstrated that the swarm sequences change to the mainshock–aftershock sequences from trench to coast. The source area of aftershock sequences is generally smaller than the swarm areas for the same magnitude M _s of the mainshock or clue event of the swarm. Study of the M _s –K _s relation, where K _s is the energy class for Kamchatka earthquakes, reveals that the events radiate relatively higher frequencies from trench to coast.     

Source Parameters for 1999 North Anatolian Fault Zone Aftershocks

We develop a data set of aftershock recordings of the 1999, M = 7.4 Izmit and M = 7.2 Duzce (Turkey) earthquakes to study their source parameters. We combined seismograms from 44 stations maintained by several sources (organizations) to obtain a unified data set of events (2.1 ≤ M_w ≤ 5.5). We calculate source parameters of these small earthquakes by two methods that use different techniques to address the difficulty in obtaining source spectra for small earthquakes subject to interference from site response. One method (program NetMoment (NM), Hutchings, 2004) uses spectra of direct S waves in a simultaneous inversion of local high-frequency network data to estimate seismic moment, source corner frequency (f_c), site attenuation (k) and whole-path Q. This approach takes advantage of the source commonality in all recordings for a particular earthquake by fitting a common Brune source spectrum to the data with a and individual k. The second approach (Mayeda et al., 2003) uses the coda method (CM) to obtain “nonmodel-based” source spectra and moment estimates from selected broadband recording sites. We found that both methods do well for events that allow the comparison with seismic moment estimates derived from waveform modeling. Also, source spectra obtained from the two methods are very closely matched for most of the events they have in common. We use an F test to examine the trade-off between k and f_c picks identified by the direct S-wave method. About half of the events could be constrained to have less than a 50% average uncertainty in f_c and k. We used these source spectra solutions to calculate energy and apparent stress and compare these to estimates from the selected “good quality” source spectra from CM. Both studies have values mutually consistent and show a similar increase in apparent stress with increasing moment. This result has added merit due to the independent approaches to calculate apparent stress. We conclude that both methods are at least partially validated by our study, and they both have usefulness for different circumstances of recording local small earthquakes. CM would work well in studies for which there is a broad magnitude range of events and NM works well for local events recorded by band-limited recorders.     

抚顺活断层探测震源计算模型的建立及优化

本文通过对断层震源模型的讨论,明确了建立有限震源模型的方法。在考虑抚顺活断层的空间展布、错动方式、凹凸体的数量等多种参数的综合影响的基础上,建立了抚顺目标断层的震源计算模型,为同类工作的开展提供了参考。     

马边-大关构造带震源参数及应力状态研究

利用2000～2009年马边—大关构造带上的115次3级以上中小地震波形资料,计算了地震震源机制解和视应力等震源参数。根据震源机制解分析,马边—大关构造带平均主应力方向为NWW—SEE,错动类型显示,走滑型和倾滑型的地震所占比例相当。地震活动丛集的3个区段荥经—峨边、马边—盐津、鲁甸—巧家的平均主应力方向分别为NWW—SEE、NW—SE、NWW—SEE,呈现局部构造应力场方向特征。马边—大关构造带视应力分布不均匀,高值出现在云南大关—盐津一带地下20km区域,而利店断裂及以北的地区视应力值相对较低。分析认为马边—大关构造带南段未来存在潜在的强震危险性。     

Characterization and Source History Modeling Using Low‐k Zone Profiles at Two Source Areas

Like tree rings, high‐resolution soil sampling of low‐permeability (low‐k) zones can be used to evaluate the style of source history at contaminated sites (i.e., historical pattern of concentration and composition vs. time since releases occurred at the interface with the low‐k zone). This is valuable for the development of conceptual site model (CSM) and can serve as an important line of evidence supporting monitored natural attenuation (MNA) as a long‐term remedy. Source histories were successfully reconstructed at two sites at Naval Air Station Jacksonville using a simple one‐dimensional (1D) model. The plume arrival time and historical composition were reconstructed from the time initial releases that were suspected to occur decades earlier. At the first site (Building 106), the source reconstructions showed relatively constant source concentrations, but significant attenuation over time in the downgradient plume in the transmissive zone, suggesting MNA may not be an appropriate remedy if source control is a requirement, but attenuation processes are clearly helping to maintain plume stability and reduce risk. At the second site (Building 780), source concentrations in the transmissive zone showed an approximately a one order of magnitude over time, but apparently less attenuation in the downgradient plume. The source reconstruction method appeared to reflect site remediation efforts (excavation, soil vapor extraction) implemented in the 1990s. Finally, a detailed analysis using molecular biological tools, carbon isotopes, and by‐products suggests that most degradation activity is associated with high‐k zones but not with low‐k zones at these source areas. Overall, the source reconstruction methodology provided insight into historical concentration trends not obtainable otherwise given the limited long‐term monitoring data.     

Geodetic Strain Observations and Return Period of the Strongest Earthquakes of a Given Seismic Source Zone

We present the basis for a method for estimating the return period of large and medium earthquakes that is independent of current deterministic and probabilistic approaches. The two standard techniques of seismic hazard assessment??probabilistic seismic hazard assessment (PSHA) and deterministic seismic hazard assessment (DSHA)??suffer from limited knowledge of seismic prehistory. A further weakness of PSHA is its requirement of homogeneous seismic activity within a seismic zone. Moreover, PSHA and DSHA were developed for seismically active areas and, thus, cannot reliably be used in areas of medium and low activity. In this paper we propose the combined use of geodetic strain rate data and the seismic moment data set determined for past seismic events. This combination represents a new and independent approach to estimation of future seismic activity. Using a modified version of Kostrov??s (Phys Solid Earth 1:23?C40, 1974) equation and the catalogue of seismic moments, the minimum return period of the strongest earthquakes of a source area is estimated.     

Use of LIF for Real-Time In-Situ Mixed NAPL Source Zone Detection

The site characterization and analysis cone penetrometer system (SCAPS), equipped with realtime fluorophore detection capabilities, was used to delineate subsurface contaminant releases in an area where plating shop waste was temporarily stored. Records indicated that various nonaqueous phase liquids (NAPLs) were released at the site. The investigators advanced the SCAPS laser-induced fluorescence (LIF) sensor to depths beneath the water table of the principal water-bearing zone. The water table was located approximately 6 feet (1.8 m) below ground surface (bgs) across the site. Fluorescence, attributed to fuel compounds commingled with chlorinated solvents, was observed at depths ranging from 4.0 to 11.5 feet (1.2 to 3.5 m) bgs. Fluorescence, attributed to naturally occurring organic materials (by process of elimination and spectral characteristics) commingled with chlorinated solvent constituents, was observed at depths ranging from approximately 13 to 40 feet (4.0 to 12.2 m) bgs. Fluorescence responses from compounds confirmed to be commingled with chlorinated solvents indicates that the SCAPS fluorophore detection system is capable of indirectly delineating vadose zone and subaqueous chlorinated solvents and other dense nonaqueous phase liquids (DNAPLs) at contaminant release sites. This confirmation effort represents the first documented account of the successful application of LIF to identify a mixed DNAPL/LNAPL source zone.     

Methods to Estimate Source Zone Depletion of Fuel Releases by Groundwater Flow

We compare two methods for estimating the natural source zone depletion (NSZD) rate at fuel release sites that occurs by groundwater flow through the source zone due to dissolution and transport of biodegradation products. Dissolution is addressed identically in both methods. The “mass budget method”, previously proposed and applied by others, estimates the petroleum hydrocarbon biodegradation rate based on dissolved electron acceptor delivery and dissolved biodegradation product removal by groundwater flow. The mass budget method relies on assumed stoichiometry for the degradation reactions and differences in concentrations of dissolved species (oxygen, nitrate, sulfate, reduced iron, reduced manganese, nonvolatile dissolved organic carbon, methane) at monitoring locations upgradient and downgradient of the source zone. We illustrate a refinement to account for degradation reactions associated with loss of reduced iron from solution. The “carbon budget method,” a simplification of approaches applied by others, addresses carbon‐containing species in solution or lost from solution (precipitated) and does not require assumptions about stoichiometry or information about electron acceptors. We apply both methods to a fuel release site with unusually detailed monitoring data and discuss applicability to more typical and less thoroughly monitored sites. The methods, as would typically be applied, yield similar results but have different constraints and uncertainties. Overall, we conclude that the carbon budget method has greater practical utility as it is simpler, requires fewer assumptions, accounts for most iron‐reducing reactions, and does not include CO₂ that escapes from the saturated to the unsaturated zone.     

Field Tracer Test for the Design of LNAPL Source Zone Surfactant Flushing

A field tracer test was carried out in a light nonaqueous phase liquid (LNAPL) source zone using a well pattern consisting of one injection well surrounded by four extraction wells (5‐spot well pattern). Multilevel sampling was carried out in two observation wells located inside the test cell characterized by heterogeneous lithology. Tracer breakthrough curves showed relatively uniform flow within soil layers. A numerical flow and solute transport model was calibrated on hydraulic heads and tracer breakthrough curves. The model was used to estimate an average accessible porosity of 0.115 for the swept zone and an average longitudinal dispersivity of 0.55 m. The model was further used to optimize the relative effects of viscous forces versus capillary forces under realistic imposed hydraulic gradients and to establish optimal surfactant solution properties. Maximum capillary number (N_Ca) values between injection and extraction wells were obtained for an injection flow rate of 16 L/min, a total extraction flow rate of 20 L/min, and a surfactant solution with a viscosity of 0.005 Pa?s. The unconfined nature of the aquifer limited further flow rate or viscosity increases that would have led to unrealistic hydraulic gradients. An N_Ca range of 3.8 × 10^?4 to 7.6 × 10^?3 was obtained depending on the magnitude of the simulated LNAPL‐water interfacial tension reduction. Finally, surfactant and chase water slug sizing was optimized with a radial form of the simplified Ogata‐Banks analytical solution (Ogata and Banks 1961) so that injected concentrations could be maintained in the entire 5‐spot cell.     

Effect of NAPL Source Morphology on Mass Transfer in the Vadose Zone

The generation of vapor‐phase contaminant plumes within the vadose zone is of interest for contaminated site management. Therefore, it is important to understand vapor sources such as non‐aqueous‐phase liquids (NAPLs) and processes that govern their volatilization. The distribution of NAPL, gas, and water phases within a source zone is expected to influence the rate of volatilization. However, the effect of this distribution morphology on volatilization has not been thoroughly quantified. Because field quantification of NAPL volatilization is often infeasible, a controlled laboratory experiment was conducted in a two‐dimensional tank (28 cm × 15.5 cm × 2.5 cm) with water‐wet sandy media and an emplaced trichloroethylene (TCE) source. The source was emplaced in two configurations to represent morphologies encountered in field settings: (1) NAPL pools directly exposed to the air phase and (2) NAPLs trapped in water‐saturated zones that were occluded from the air phase. Airflow was passed through the tank and effluent concentrations of TCE were quantified. Models were used to analyze results, which indicated that mass transfer from directly exposed NAPL was fast and controlled by advective‐dispersive‐diffusive transport in the gas phase. However, sources occluded by pore water showed strong rate limitations and slower effective mass transfer. This difference is explained by diffusional resistance within the aqueous phase. Results demonstrate that vapor generation rates from a NAPL source will be influenced by the soil water content distribution within the source. The implications of the NAPL morphology on volatilization in the context of a dynamic water table or climate are discussed.     

Experimental and Economic Assessment of Two Surfactant Formulations for Source Zone Remediation at a Former Dry Cleaning Facility

Treatability tests and cost analyses were conducted to provide objective criteria for selection of a surfactant formulation to be used for surfactant enhanced aquifer remediation (SEAR) of a tetrachloroethene (PCE)-contaminated site in Oscoda, Michigan. Two surfactant formulations, 4% Tween 80 + 500 mg/L CaCl₂ and 8% Aerosol MA/IPA +15,000 mg/L NaCl + 1000 mg/L CaCl₂, were considered based on their capacity to solubilize PCE and prior use in SEAR applications. Results of a two-dimensional aquifer cell experiment indicated that 53% of the released PCE was recovered after flushing with approximately 8 pore volumes of 4% Tween 80. In contrast, only 3 pore volumes of 8% Aerosol MA/IPA solution were required to recover 78% of the PCE from the two-dimensional aquifer cell, although the greater recovery of PCE was attributed, in large part, to the higher concentration of Aerosol MA. However, mobilization of PCE as free product was observed during the 8% Aerosol MA/IPA flood, which was consistent with total trapping number (N_T) calculations. At the pilot-scale, SEAR treatment costs were estimated to be $222,000 and $244,000 for 4% Tween 80 and 8% Aerosol MA/IPA, respectively, which compared favorably to the estimated pump-and-treat cost of $316,000. Projected full-scale costs, based on a line-drive flushing system, were $382,000 for 4% Tween 80 and $443,000 for 8% Aerosol MA/IPA. In contrast, full-scale pump-and-treat costs were estimated to be $1,167,000. Surfactant recycling was shown to be logistically and economically infeasible at the pilot scale, and provided only a minimal cost benefit for 4% Tween 80 at the full scale. Based on the similarities in solubilization capacity and treatment cost, but substantially lower risk of PCE displacement, Tween 80 was recommended over Aerosol MA/IPA for pilot-scale testing of SEAR.