Path to autonomous soil sampling and analysis by ground-based robots.

Good site characterization is essential for the selection of remediation alternatives for impacted soils. The value of site characterization is critically dependent on the quality and quantity of the data collected. Current methods for characterizing impacted soils rely on expensive manual sample collection and off-site analysis. However, recent advances in terrestrial robotics and artificial intelligence offer a potentially revolutionary set of tools and methods that will help to autonomously explore natural environments, select sample locations with the highest value of information, extract samples, and analyze the data in real-time without exposing humans to potentially hazardous conditions. A fundamental challenge to realizing this potential is determining how to design an autonomous system for a given investigation with many, and often conflicting design criteria. This work presents a novel design methodology to navigate these criteria. Specifically, this methodology breaks the system into four components - sensing, sampling, mobility, and autonomy - and connects design variables to the investigation objectives and constraints. These connections are established for each component through a survey of existing technology, discussion of key technical challenges, and highlighting conditions where generality can promote multi-application deployment. An illustrative example of this design process is presented for the development and deployment of a robotic platform characterizing salt-impacted oil & gas reserve pits. After calibration, the relationship between the in situ robot chloride measurements and laboratory-based chloride measurements had a good linear relationship (R2-value = 0.861) and statistical significance (p-value = 0.003).

Rapid Determination of the Total Petroleum Hydrocarbon Content of Soils by Handheld Fourier Transform Near-Infrared Spectroscopy.

For successful soil remediation and hydrocarbon exploration operations, determining the total petroleum hydrocarbon (TPH) content of soils is an indispensable process step. This paper reports on the performance of a handheld Fourier transform near-infrared (FT-NIR) spectrometer for rapid and quantitative determination of TPH content of soils from two different sites by diffuse reflection measurements. For rapid decisions for exploration work or environmental site assessment projects, a quick─preferably on-site─determination of TPH content is valuable. Diffuse reflection NIR spectra were recorded from soil samples of two different sites with TPH reference values ranging from 350 to 30,000 ppm, as determined by capillary gas chromatography and flame ionization detection with hydrocarbon fingerprinting C1-C44. However, this paper not only addresses the development of site-specific partial-least squares (PLS) calibrations but also demonstrates the locally-weighted PLS (LW-PLS) technique, which can be used to develop global, site-independent PLS calibrations without significant penalty in calibration performance. As a first step, the diffuse reflection spectra were used to develop conservative, site-specific PLS calibration models with root-mean-square calibration/cross-validation errors (RMSEC/RMSECV) of 1043/1106 and 741/785 ppm TPH, respectively, and the average absolute prediction errors for samples not contained in the calibration set were 451 and 293 ppm for the two sites, respectively. In a further step, significant degradation of the RMSE values of a conservative PLS model based on the NIR spectra of both sites was then compared to the application of the LW-PLS method, with only a slight loss of the prediction accuracy relative to the site-independent models. This study confirms the ability of next-generation portable FT-NIR spectrometers to predict low TPH levels in various soil types through both─soil-specific and site-independent─calibrations, giving these spectrometers the potential to become rapid screening tools in the field.

A mechanistic derivation of the Monod bioreaction equation for a limiting nutrient.

We present a quasi-steady state mechanistic derivation of the Monod bioreaction equation based upon a conceptual model involving aqueous phase diffusive transport of substrate towards a spherical microbe; transport of the substrate across its surface membrane; and reaction depleting the substrate within the microbe. The resulting Monod coefficients [Formula: see text] and [Formula: see text] are dependent upon substrate-species pairs and the mass transfer properties of the system. Two substrate transport scenarios are investigated: (1) a constant rate model that is a function of a constant flux across the surface of the microbe; and (2) a linear rate model that is the product of a constant transport velocity and the concentration of substrate in contact with the surface of the microbe. The model is verified and parameterized using benzene, toluene, and phenol depletion and biomass growth data obtained from Reardon et al. (Biotechnol Bioeng: 385-400, 2000). Calibration results indicate a normalized surface to bulk concentration ratio of nearly unity in all simulations for benzene, toluene, and phenol when paired with P. putida F1, implying that the process is not aqueous phase diffusion limited.

The formation, reactivity, and fate of oxygen-containing organic compounds in petroleum-contaminated groundwaters: A state of the science review and future research directions.

Hydrocarbon (HC) contamination in groundwater (GW) is a widespread environmental issue. Dissolved hydrocarbons in water are commonly utilized as an energy source by natural microbial communities, which can produce water soluble intermediate metabolite compounds, herein referred to as oxygen containing organic compounds (OCOCs), before achieving complete mineralization. This review aims to provide a comprehensive assessment of the literature focused on the state of the science for OCOCs detected and measured in GW samples collected from petroleum contaminated aquifers. In this review, we discuss and evaluate two hypotheses investigating OCOC formation, which are major points of contention in the freshwater oil spill community that need to be addressed. We reviewed over 150 articles compiling studies investigating OCOC formation and persistence to uncover knowledge gaps in the literature and studies that recommend quantitative and qualitative measurements of OCOCs in petroleum-contaminated aquifers. This review is essential because no consensus exists regarding specific compounds and related concerns. We highlight the knowledge gaps to progressing the discussion of hydrocarbon conversion products.

Portable X-ray fluorescence for autonomous in-situ characterization of chloride in oil and gas waste.

Soil salinization resulting from anthropogenic activities affects soil health and productivity. Methods that can provide rapid, inexpensive, and accurate salinity characterization over vast areas of soil and waste materials will help in managing their impacts. The objective of this work was to evaluate the accuracy and precision of portable X-ray Fluorescence (pXRF) Cl- measurements of highly saline waste material (WMs) from oil and gas production sites. We compared pXRF Cl- measurements of three unconsolidated WMs to a standard laboratory method for determining soil salinity and identified the WM properties that most affect the precision and accuracy of the pXRF Cl- measurement. Despite covering a range of several orders of magnitude in chloride concentration, calibrated pXRF measurements varied by no more than 14% compared to standard laboratory Cl- measurements for dry homogenous samples. Measurements taken of WMs that were not homogenized decreased pXRF accuracy by 75% while moisture content decreased accuracy by 15%. Field measurements made at different areas inside an oil and gas WM pit were accurate within 60% of the standard laboratory Cl- measurements, despite the samples having a wide range of moisture content and particle size distributions. This study indicates that pXRF can be used to rapidly characterize soil salinity in-situ with acceptable accuracy and precision for screening purposes, opening the door for automated robotic measurements of chloride over large areas.

Biodegradation of petroleum hydrocarbons in a weathered, unsaturated soil is inhibited by peroxide oxidants.

Field-weathered crude oil-containing soils have a residual concentration of hydrocarbons with complex chemical structure, low solubility, and high viscosity, often poorly amenable to microbial degradation. Hydrogen peroxide (H2O2)-based oxidation can generate oxygenated compounds that are smaller and/or more soluble and thus increase petroleum hydrocarbon biodegradability. In this study, we assessed the efficacy of H2O2-based oxidation under unsaturated soil conditions to promote biodegradation in a field-contaminated and weathered soil containing high concentrations of total petroleum hydrocarbons (25200 mg TPH kg-1) and total organic carbon (80900 mg TOC kg-1). Microcosms amended with three doses of 48 g H2O2 kg-1 soil (unactivated or Fe2+-activated) or 24 g sodium percarbonate kg-1 soil and nutrients did not show substantial TPH changes during the experiment. However, 7.6-41.8% of the TOC concentration was removed. Furthermore, production of DOC was enhanced and highest in the microcosms with oxidants, with approximately 20-40-fold DOC increase by the end of incubation. In the absence of oxidants, biostimulation led to > 50% TPH removal in 42 days. Oxidants limited TPH biodegradation by diminishing the viable concentration of microorganisms, altering the composition of the soil microbial communities, and/or creating inhibitory conditions in soil. Study's findings underscore the importance of soil characteristics and petroleum hydrocarbon properties and inform on potential limitations of combined H2O2 oxidation and biodegradation in weathered soils.

Complex mixture toxicology: Evaluation of toxicity to freshwater aquatic receptors from biodegradation metabolites in groundwater at a crude oil release site, recent analogous results from other authors, and implications for risk management.

Aquatic toxicity posed by the complex mixture of biodegradation metabolites and related oxygen-containing organic compounds (OCOCs) in groundwater at typical petroleum release sites is of concern to regulatory agencies; several are using results from laboratory studies in older literature that are not appropriate analogs for risk management. Recent field studies from typical sites and natural groundwater should be utilized. In this study, OCOCs downgradient of the biodegrading crude oil release at the USGS Bemidji site were tested for freshwater aquatic toxicity using unaltered whole groundwater samples. This type of testing is optimal because the entire mixture of OCOCs present is tested directly and assessment is not affected by analytical limitations. Ceriodaphnia dubia and Pimephales promelas were tested for toxicity using USEPA Methods 1002 and 1000, which estimate chronic toxicity. OCOCs in representative samples up to the maximum concentration tested of 1710 ug/L Total Petroleum Hydrocarbons (TPH) (nC10 to nC40; without silica gel cleanup) did not result in effects relative to the lab control for C. dubia survival, or for P. promelas survival or growth; and did not result in effects above background for C. dubia reproduction. This is consistent with findings using the same testing methods and species on samples from 14 biodegrading fuel release sites: OCOCs did not cause increased toxicity relative to background at a maximum tested concentration of 1800 ug/L TPH (nC10 to nC28). Based on their toxicity testing using the same species and USEPA methods on groundwater from a biodegrading diesel release site, Washington Department of Ecology recently set a freshwater screening level for OCOCs at 3000 ug/L TPH ("Weathered DRO"). These studies indicate that, in the absence of dissolved hydrocarbons, OCOCs in groundwater from typical biodegrading fuel or crude oil releases are not toxic to C. dubia or P. promelas at typical concentrations.

CO2-efflux measurements for evaluating source zone natural attenuation rates in a petroleum hydrocarbon contaminated aquifer.

In order to gain regulatory approval for source zone natural attenuation (SZNA) at hydrocarbon-contaminated sites, knowledge regarding the extent of the contamination, its tendency to spread, and its longevity is required. However, reliable quantification of biodegradation rates, an important component of SZNA, remains a challenge. If the rate of CO(2) gas generation associated with contaminant degradation can be determined, it may be used as a proxy for the overall rate of subsurface biodegradation. Here, the CO(2)-efflux at the ground surface is measured using a dynamic closed chamber (DCC) method to evaluate whether this technique can be used to assess the areal extent of the contaminant source zone and the depth-integrated rate of contaminant mineralization. To this end, a field test was conducted at the Bemidji, MN, crude oil spill site. Results indicate that at the Bemidji site the CO(2)-efflux method is able to both delineate the source zone and distinguish between the rates of natural soil respiration and contaminant mineralization. The average CO(2)-efflux associated with contaminant degradation in the source zone is estimated at 2.6 µmol m(-2) s(-1), corresponding to a total petroleum hydrocarbon mineralization rate (expressed as C(10)H(22)) of 3.3 g m(-2) day(-1).

Impacts of water table fluctuations on actual and perceived natural source zone depletion rates.

A viable means of quantifying the rate of natural source zone depletion (NSZD) at hydrocarbon contaminated sites is by the measurement of carbon dioxide (CO2) and methane (CH4) effluxes at the surface. This methodology assumes that gas effluxes are reflective of actual contaminant degradation rates in the subsurface, which is only accurate for quasi-steady state conditions. However, in reality, subsurface systems are highly dynamic, often resulting in fluctuations of the water table. To quantify the effects of water table fluctuations on NSZD rates, a simulated biodiesel spill in a 400 cm long, 100 cm wide and 150 cm tall sandtank was subjected to lowering and raising the water table, while soil-gas chemistry and surface CO2 and CH4 effluxes were measured. Results show that water table fluctuations have both short-term (perceived) and long-term (actual) effects on NSZD rates, interpreted using surface efflux measurements. When the water table was lowered, surface effluxes immediately increased up to 3 and 344 times higher than baseline for CO2 and CH4 effluxes, respectively, due to the liberation of anaerobically produced gas accumulated below the water table. After this immediate release, the system then reached quasi-steady state conditions 1.4 to 1.6 times higher for CO2 than baseline conditions, attributed to increased aerobic degradation in the broadened and exposed smear zone. When the water table was raised, quasi-steady state CO2 and CH4 effluxes declined to values of 0.9 and 0.4 times baseline effluxes, respectively, implying that contaminant degradation rates were reduced due to submergence of the smear zone. The findings of this study show that the dynamic effects of water table fluctuations and redistribution of the contaminants affect surface effluxes as well as short-term (perceived) and long-term (actual) contaminant degradation rates. Therefore, water table fluctuations need to be considered when quantifying NSZD at contaminated sites using sparse temporal rate measurements to estimate NSZD rates for extended periods of time (e.g., annual rates).

Orbitrap ESI-MS evaluation of solvent extractable organics from a crude oil release site.

The concentrations of oxygen-containing organic compounds (OCOC), measured as dissolved organic carbon (DOC), in groundwater exceeds those of dissolved hydrocarbons, measured as total petroleum hydrocarbons (TPH), at a crude oil release site. Orbitrap mass spectrometry was used to characterize OCOC in samples of the oil, water from upgradient of the release, source area, and downgradient wells, and a local lake. Chemical characterization factors included carbon number, oxygen number, formulae similarity, double bond equivalents (DBE) and radiocarbon dating. Oil samples were dominated by formulae with less than 30 carbons, four or fewer oxygens, and a DBE of less than four. In water samples, formulae were identified with more than 30 carbons, more than 10 oxygens, and a DBE exceeding 30. These characteristics are consistent with DOC found in unimpacted water. Between 65% and 92% of the formulae found in samples collected within the elevated OCOC plume were also found in the upgradient or surface water samples. Evidence suggests that many of the OCOC are not petroleum degradation intermediates, but microbial products generated as a result of de novo synthesis by organisms growing on carbon supplied by the oil. Implications of these results for understanding the fate and managing the risk of hydrocarbons in the subsurface are discussed.

Predicting total petroleum hydrocarbons in field soils with Vis-NIR models developed on laboratory-constructed samples.

Accurate quantification of petroleum hydrocarbons (PHCs) is required for optimizing remedial efforts at oil spill sites. While evaluating total petroleum hydrocarbons (TPH) in soils is often conducted using costly and time-consuming laboratory methods, visible and near-infrared reflectance spectroscopy (Vis-NIR) has been proven to be a rapid and cost-effective field-based method for soil TPH quantification. This study investigated whether Vis-NIR models calibrated from laboratory-constructed PHC soil samples could be used to accurately estimate TPH concentration of field samples. To evaluate this, a laboratory sample set was constructed by mixing crude oil with uncontaminated soil samples, and two field sample sets (F1 and F2) were collected from three PHC-impacted sites. The Vis-NIR TPH models were calibrated with four different techniques (partial least squares regression, random forest, artificial neural network, and support vector regression), and two model improvement methods (spiking and spiking with extra weight) were compared. Results showed that laboratory-based Vis-NIR models could predict TPH in field sample set F1 with moderate accuracy (R2  > .53) but failed to predict TPH in field sample set F2 (R2  < .13). Both spiking and spiking with extra weight improved the prediction of TPH in both field sample sets (R2 ranged from .63 to .88, respectively); the improvement was most pronounced for F2. This study suggests that Vis-NIR models developed from laboratory-constructed PHC soil samples, spiked by a small number of field sample analyses, can be used to estimate TPH concentrations more efficiently and cost effectively compared with generating site-specific calibrations.

Towards comprehensive analysis of oxygen containing organic compounds in groundwater at a crude oil spill site using GC×GC-TOFMS and Orbitrap ESI-MS.

In this study, both GC × GC-TOFMS and Orbitrap ESI-MS were used to characterize the oxygen containing organic compounds, OCOCs, present in groundwater at a site where a crude oil pipeline ruptured decades ago. This is the only side-by-side comparison of results from these two methods analyzed by the same laboratory. GC × GC-TOFMS analysis shows OCOCs identified at the crude oil-release site are consistent with, and structurally similar to, those identified at previously studied fuel release sites. Molecular structures close to the release point differ from those found downgradient, becoming less complex and with different compound classes dominating. As with the GC × GC-TOFMS, the Orbitrap revealed that the composition of OCOCs present in groundwater close to the source area was distinctly different from that seen downgradient; however, the chemical structures increased significantly in size and complexity from wells near the source to the farthest downgradient well. Investigation into this finding suggests that the presence and structures of these non-GC-able OCOCs are consistent with organic matter resulting from biosynthesis or other processes found in natural water systems and are unlikely to be intermediates (metabolites) along petroleum biodegradation pathways.

Human and Aquatic Toxicity Potential of Petroleum Biodegradation Metabolite Mixtures in Groundwater from Fuel Release Sites.

The potential toxicity to human and aquatic receptors of petroleum fuel biodegradation metabolites (oxygen-containing organic compounds [OCOCs]) in groundwater has been investigated as part of a multi-year research program. Whole mixtures collected from locations upgradient and downgradient of multiple fuel release sites were tested using: 1) in vitro screening assays for human genotoxicity (the gamma-H2AX assay) and estrogenic effects (estrogen receptor transcriptional activation assay), and 2) chronic aquatic toxicity tests in 3 species (Ceriodaphnia dubia, Raphidocelis subcapitata, and Pimephales promelas). In vitro screening assay results demonstrated that the mixtures did not cause genotoxic or estrogenic effects. No OCOC-related aquatic toxicity was observed and when aquatic toxicity did occur, upgradient samples typically had the same response as samples downgradient of the release, indicating that background water quality was impacting the results. This information provides additional support for previous work that focused on the individual compounds and, taken together, indicates that OCOCs from petroleum degradation at fuel release sites are unlikely to cause toxicity to human or freshwater receptors at the concentrations present. Environ Toxicol Chem 2020;39:1634-1645. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Biochar amendment as a remediation strategy for surface soils impacted by crude oil.

The impact of organic bulking agents on the biodegradation of petroleum hydrocarbons in crude oil impacted soils was evaluated in batch laboratory experiments. Crude oil impacted soils from three separate locations were amended with fertilizer and bulking agents consisting of biochars derived from walnut shells or ponderosa pine wood chips produced at 900 °C. The batch reactors were incubated at 25 °C and sampled at pre-determined intervals to measure changes in total petroleum hydrocarbons (TPH) over time. For the duration of the incubation, the soil moisture content was adjusted to 75% of the maximum water holding capacity (MWHC) and prior to each sampling event, the sample was manually stirred. Results show that the addition of fertilizer and bulking agents increased biodegradation rates of TPH. Soil samples amended with ponderosa pine wood biochar achieved the highest biodegradation rate, whereas the walnut shell biochar was inhibitory to TPH biodegradation. The beneficial impact of biochars on TPH biodegredation was more pronounced for a soil impacted with lighter hydrocarbons compared to a soil impacted with heavier hydrocarbons. This study demonstrates that some biochars, in combination with fertilizer, have the potential to be a low-technology and eco-friendly remediation strategy for crude oil impacted soils.

Comparison of surficial CO2 efflux to other measures of subsurface crude oil degradation.

At a spill site near Bemidji, Minnesota, crude oil at the water table has been undergoing anaerobic biodegradation for over 30years. Previous work at this site has shown that methane produced from biodegradation of the oil migrates upward and is oxidized in a methanotrophic zone midway between the water table and the surface. To compare microbial activity measurement methods from multiple locations in the oil body, surficial carbon dioxide efflux, methanogen and methanotroph concentrations, and oil degradation state were collected. Carbon dioxide effluxes over the oil body averaged more than four times those at the background site. Methanotrophic bacteria concentrations measured using pmoA were over 10(5) times higher above the oil-contaminated sediments compared with the background site. Methanogenic archaea measured using mcrA ranged from 10(5) to over 10(7) in the oil and were below detection in the background. Methanogens correlated very well with methanotroph concentrations (r=0.99), n-alkylcyclohexane losses as a proxy for degradation state (r=-0.96), and somewhat less well with carbon dioxide efflux (r=0.92). Carbon dioxide efflux similarly correlated to methanotroph concentrations (r=0.90) and n-alkylcyclohexane losses (r=-0.91).

Methane emissions and contaminant degradation rates at sites affected by accidental releases of denatured fuel-grade ethanol.

The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation-related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur-even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 µmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 9 µmol m(-2) s(-1). At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 µmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 393 µmol m(-2) s(-1). Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions.