Effects of burning and photochemical degradation of Macondo surrogate oil on its composition and toxicity.

Petroleum products in the environment can produce significant toxicity through photochemically driven processes. Burning surface oil and photochemical degradation were two mechanisms for oil removal after the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico. After burning, residual oil remains in the environment and may undergo further weathering, a poorly understood fate.

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.

Single-Particle ICP-MS/MS Application for Routine Screening of Nanoparticles Present in Powder-Based Facial Cosmetics.

The short- and long-term impacts of nanoparticles (NPs) in consumer products are not fully understood. Current European Union (EU) regulations enforce transparency on products containing NPs in cosmetic formulations; however, those set by the U.S.

Dispersant-enhanced photodissolution of macondo crude oil: A molecular perspective.

Previous laboratory studies developed a conceptual model based on elevated non-volatile dissolved organic carbon (NVDOC) concentrations after photodegradation and subsequent dissolution of Macondo oil following the Deepwater Horizon blowout. However, those experiments did not account for the effects of ∼1 million gallons of dispersant applied to the surface oil. Here, laboratory results show photodissolution in the presence of dispersant results in > 2x increase in NVDOC concentrations after extensive photoprocessing relative to oil without dispersant.

Photo-Enhanced Oil Toxicity to Alcid Immune Function.

Oil spills are devastating to seabirds, causing high levels of mortality and toxic physiological effects, especially to immune function. Sunlight exposure can further enhance the toxicity of oil to marine species by generating photodegradation products. Photo-enhanced oil toxicity to marine birds has not been studied.

Photochemical mobilization of dissolved hydrocarbon oxidation products from petroleum contaminated soil into a shallow aquifer activate human nuclear receptors.

Elevated non-volatile dissolved organic carbon (NVDOC) concentrations in groundwater (GW) monitoring wells under oil-contaminated hydrophobic soils originating from a pipeline rupture at the National Crude Oil Spill & Natural Attenuation Research Site near Bemidji, MN are documented. We hypothesized the elevated NVDOC is comprised of water-soluble photooxidation products transported from the surface to the aquifer. We use field and laboratory samples in combination with complementary analytical methods to test this hypothesis and determine the biological response to these products.

Emerging Chemical Methods for Petroleum and Petroleum-Derived Dissolved Organic Matter Following the Deepwater Horizon Oil Spill.

Despite the fact that oil chemistry and oils spills have been studied for many years, there are still emerging techniques and unknown processes to be explored. The 2010 Deepwater Horizon oil spill in the Gulf of Mexico resulted in a revival of oil spill research across a wide range of fields. These studies provided many new insights, but unanswered questions remain.

Dissolved organic matter production from herder application and in-situ burning of crude oil at high latitudes: Bioavailable molecular composition patterns and microbial community diversity effects.

Chemical herders and in-situ burning (ISB) are designed to mitigate the effects that oil spills may have on the high latitude marine environment. Little information exists on the water solubilization of petroleum residues stemming from chemically herded ISB and whether these bioavailable compounds have measurable impacts on marine biota. In this experiment, we investigated the effects of Siltech OP40 and crude oil ISB on a) petroleum-derived dissolved organic matter (DOM) composition and b) seawater microbial community diversity over 28 days at 4 °C in aquarium-scale mesocosms.

Hydrocarbons to carboxyl-rich alicyclic molecules: A continuum model to describe biodegradation of petroleum-derived dissolved organic matter in contaminated groundwater plumes.

Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOM) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOM from shorter to longer wavelengths.

Barium ion adduct mass spectrometry to identify carboxylic acid photoproducts from crude oil-water systems under solar irradiation.

Petroleum derived dissolved organic matter (DOMHC) samples were successfully cationized with barium, revealing many [M-H + Ba]+ peaks in both dark and simulated sunlight treatments. The DOMHC samples generated after light exposure exhibited a greater number of [M-H + Ba]+ peaks compared to the dark control. Multiple [M-H + Ba]+ peaks were investigated in the irradiated DOMHC using low resolution MS/MS in order to confirm the presence of diagnostic fragment ions, m/z 139, 155 and 196 in each treatment.

Life at the Frozen Limit: Microbial Carbon Metabolism Across a Late Pleistocene Permafrost Chronosequence.

Permafrost is an extreme habitat yet it hosts microbial populations that remain active over millennia. Using permafrost collected from a Pleistocene chronosequence (19 to 33 ka), we hypothesized that the functional genetic potential of microbial communities in permafrost would reflect microbial strategies to metabolize permafrost soluble organic matter (OM) over geologic time. We also hypothesized that changes in the metagenome across the chronosequence would correlate with shifts in carbon chemistry, permafrost age, and paleoclimate at the time of permafrost formation.

DOC export is exceeded by C fixation in May Creek: A late-successional watershed of the Copper River Basin, Alaska.

Understanding the entirety of basin-scale C cycling (DOC fluxes and CO2 exchanges) are central to a holistic perspective of boreal forest biogeochemistry today. Shifts in the timing and magnitude of dissolved organic carbon (DOC) delivery in streams and eventually into oceans can be expected, while simultaneously CO2 emission may exceed CO2 fixation, leading to forests becoming stronger CO2 sources than sinks amplifying rising trace gases in the atmosphere. At May Creek, a representative late-successional boreal forest watershed at the headwaters of the Copper River Basin, Alaska, we quantified the seasonality of DOC flux and landscape-scale CO2 exchange (eddy covariance) over two seasonal cycles.

Molecular-Level Composition and Acute Toxicity of Photosolubilized Petrogenic Carbon.

To examine the molecular-level composition and acute toxicity per unit carbon of the petroleum-derived dissolved organic matter (DOM) produced via photo-oxidation, heavy and light oils were irradiated over seawater with simulated sunlight. Increases in dissolved organic carbon concentrations as a function of time were associated with changes in the DOM composition and acute toxicity per unit carbon. Parallel factor analysis showed that the fluorescent dissolved organic matter (FDOM) composition produced from the heavy oil became more blue-shifted over time, while the light oil produced a mixture of blue- and red-shifted components similar to FDOM signatures.

Examining Natural Attenuation and Acute Toxicity of Petroleum-Derived Dissolved Organic Matter with Optical Spectroscopy.

Groundwater samples containing petroleum-derived dissolved organic matter (DOM) originating from the north oil body within the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, MN, USA were analyzed by optical spectroscopic techniques (i.e., absorbance and fluorescence) to assess relationships that can be used to examine natural attenuation and toxicity of DOM in contaminated groundwater.

High fire-derived nitrogen deposition on central African forests.

Atmospheric nitrogen (N) deposition is an important determinant of N availability for natural ecosystems worldwide. Increased anthropogenic N deposition shifts the stoichiometric equilibrium of ecosystems, with direct and indirect impacts on ecosystem functioning and biogeochemical cycles. Current simulation data suggest that remote tropical forests still receive low atmospheric N deposition due to a lack of proximate industry, low rates of fossil fuel combustion, and absence of intensive agriculture.

Impact of Photooxidation and Biodegradation on the Fate of Oil Spilled During the Deepwater Horizon Incident: Advanced Stages of Weathering.

While the biogeochemical forces influencing the weathering of spilled oil have been investigated for decades, the environmental fate and effects of "oxyhydrocarbons" in sand patties deposited on beaches are not well-known. We collected sand patties deposited in the swash zone on Gulf of Mexico beaches following the Deepwater Horizon oil spill. When sand patties were exposed to simulated sunlight, a larger concentration of dissolved organic carbon was leached into seawater than the corresponding dark controls.

Sunlight creates oxygenated species in water-soluble fractions of Deepwater Horizon oil.

In order to assess the impact of sunlight on oil fate, Macondo well oil from the Deepwater Horizon (DWH) rig was mixed with pure water and irradiated with simulated sunlight. After irradiation, the water-soluble organics (WSO) from the dark and irradiated samples were extracted and characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Liquid-liquid extraction yielded two fractions from dark and irradiated water/oil mixtures: acidic WSOs (negative-ion electrospray (ESI)), and base/neutral WSOs (positive-ion ESI) coupled to FT-ICR MS to catalog molecular-level transformations that occur to Macondo-derived WSOs after solar irradiation.