Assessing spatial impacts of historical pulp mill effluent on trophic dynamics in a coastal marine ecosystem using stable isotope (δ13C and δ15N) analysis.

Boat Harbour, Nova Scotia was a tidal estuary that was converted into a wastewater treatment facility for pulp mill effluent in 1967. Treated effluent from Boat Harbour was discharged into the coastal Northumberland Strait, contributing significant nutrient and freshwater inputs into the coastal environment, potentially impacting local biogeochemistry and ecosystem structure. This study used stable isotope analysis of carbon (δ13C) and nitrogen (δ15N) of representative taxa to assess spatial variability in nutrient sources and trophic dynamics. Results identified stable isotope variation with depleted δ13C and δ15N values in taxa near Boat Harbour. Blue mussel (Mytilus edulis) and mummichog (Fundulus heteroclitus) were the most suitable bioindicators for identifying variation in nutrient sources. Stable isotope signatures in this study may be reflective of residual pulp mill effluent-derived nutrients, differences in marine versus terrestrial nutrient sources, and a pronounced coastal salinity gradient. The present study defined the baseline nutrient conditions of the Northumberland Strait and will be useful in assessing the effectiveness of remediation activities.

Composition and Origin of Surface Casing Fluids in a Major US Oil- and Gas-Producing Region.

Fluids leaked from oil and gas wells often originate from their surface casing─a steel pipe installed beneath the deepest underlying source of potable groundwater that serves as the final barrier around the well system. In this study, we analyze a regulatory dataset of surface casing geochemical samples collected from 2573 wells in northeastern Colorado─the only known publicly available dataset of its kind. Thermogenic gas was present in the surface casings of 96.2% of wells with gas samples. Regulatory records indicate that 73.3% of these wells were constructed to isolate the formation from which the gas originated with cement. This suggests that gas migration into the surface casing annulus predominantly occurs through compromised barriers (e.g., steel casings or cement seals), indicative of extensive integrity issues in the region. Water was collected from 22.6% of sampled surface casings. Benzene, toluene, ethylbenzene, and xylenes were detected in 99.7% of surface casing water samples tested for these compounds, which may be due to the presence of leaked oil, natural gas condensate, or oil-based drilling mud. Our findings demonstrate the value of incorporating surface casing geochemical analysis in well integrity monitoring programs to identify integrity issues and focus leak mitigation efforts.

Public data from three US states provide new insights into well integrity.

Oil and gas wells with compromised integrity are a concern because they can potentially leak hydrocarbons or other fluids into groundwater and/or the atmosphere. Most states in the United States require some form of integrity testing, but few jurisdictions mandate widespread testing and open reporting on a scale informative for leakage risk assessment. In this study, we searched 33 US state oil and gas regulatory agency databases and identified records useful for evaluating well integrity in Colorado, New Mexico, and Pennsylvania. In total, we compiled 474,621 testing records from 105,031 wells across these states into a uniform dataset. We found that 14.1% of wells tested prior to 2018 in Pennsylvania exhibited sustained casing pressure (SCP) or casing vent flow (CVF)-two indicators of compromised well integrity. Data from different hydrocarbon-producing regions within Colorado and New Mexico revealed a wider range (0.3 to 26.5%) of SCP and/or CVF occurrence than previously reported, highlighting the need to better understand regional trends in well integrity. Directional wells were more likely to exhibit SCP and/or CVF than vertical wells in Colorado and Pennsylvania, and their installation corresponded with statewide increases in SCP and/or CVF occurrence in Colorado (2005 to 2009) and Pennsylvania (2007 to 2011). Testing the ground around wells for indicators of gas leakage is not a widespread practice in the states considered. However, 3.0% of Colorado wells tested and 0.1% of New Mexico wells tested exhibited a degree of SCP sufficient to potentially induce leakage outside the well.

Occurrence and origin of groundwater methane in the Stellarton Basin, Nova Scotia, Canada.

Groundwater methane (CH4) in areas of fossil fuel development has been a recent focus of study as high CH4 concentrations pose water quality concerns and potential explosive hazards. In 2013, a provincial study in Nova Scotia identified areas with elevated groundwater CH4. However, due to limited data, the specific sources and local distribution of CH4 in those areas remain unknown. In this study, we examined the Stellarton Basin in central Nova Scotia, Canada, a region with an abundance of coal formations, numerous abandoned coal mines, and an active open pit coal mine. Methane was detected in 94% of water samples that were sampled from 45 private water wells. Six water wells exceeded the 28 mg/L hazard mitigation threshold with CH4 levels of up to 72.7 mg/L. The δ13CCH4 (-85.5 to -48.5‰) and the δ2HCH4 (-280 to -88‰) indicated that >95% of samples had CH4 of microbial origin. However, the detection of ethane (C2H6) up to 2.97 mg/L and propane (C3H8) up to 0.008 mg/L, as well as the δ13CC2H6 values (-30.1 to -15.6‰) suggested a mixture of microbial CH4 with trace thermogenic gas, likely migrated from Stellarton coals (δ13CC2H6 of -27.6 to -15.35‰). A mobile greenhouse gas analyzer survey was conducted within the perimeter of residences and off-gassing from taps had atmospheric CH4 measurements as high as 66 ppmv. This study integrates multiple sampling and monitoring methods to investigate groundwater CH4 in a coal-bearing region. The findings advance the understanding of the origin and occurrence of CH4 in complex groundwater systems. The data acquired in this study may be used as a pre-drill baseline for groundwater CH4 concentrations and origins should coal-bed methane operations in Nova Scotia proceed in the future.

Microbial and Biogeochemical Indicators of Methane in Groundwater Aquifers of the Denver Basin, Colorado.

The presence of methane and other hydrocarbons in domestic-use groundwater aquifers poses significant environmental and human health concerns. Isotopic measurements are often relied upon as indicators of groundwater aquifer contamination with methane. While these parameters are used to infer microbial metabolisms, there is growing evidence that isotopes present an incomplete picture of subsurface microbial processes. This study examined the relationships between microbiology and chemistry in groundwater wells located in the Denver-Julesburg Basin of Colorado, a rapidly urbanizing area with active oil and gas development. A primary goal was to determine if microbial data can reliably indicate the quantities and sources of groundwater methane. Comprehensive chemical and molecular analyses were performed on 39 groundwater well samples from five aquifers. Elevated methane concentrations were found in only one aquifer, and both isotopic and microbial data support a microbial origin. Microbial parameters had similar explanatory power as chemical parameters for predicting sample methane concentrations. Furthermore, a subset of samples with unique microbiology corresponded with unique chemical signatures that may be useful indicators of methane gas migration, potentially from nearby coal seams interacting with the aquifer. Microbial data may allow for more accurate determination of groundwater contamination and improved long-term water quality monitoring compared solely to isotopic and chemical data in areas with microbial methane.

Using global isotopic data to constrain the role of shale gas production in recent increases in atmospheric methane.

The accelerated increase in global methane (CH4) in the atmosphere, accompanied by a decrease in its 13C/12C isotopic ratio (δ13CCH4) from -47.1‰ to -47.3‰ observed since 2008, has been attributed to increased emissions from wetlands and cattle, as well as from shale gas and shale oil developments. To date both explanations have relied on poorly constrained δ13CCH4 source signatures. We use a dataset of δ13CCH4 from >1600 produced shale gas samples from regions that account for >97% of global shale gas production to constrain the contribution of shale gas emissions to observed atmospheric increases in the global methane burden. We find that US shale gas extracted since 2008 has volume-weighted-average δ13CCH4 of -39.6‰. The average δ13CCH4 weighted by US basin-level measured emissions in 2015 was -41.8‰. Therefore, emission increases from shale gas would contribute to an opposite atmospheric δ13CCH4 signal in the observed decrease since 2008 (while noting that the global isotopic trend is the net of all dynamic source and sink processes). This observation strongly suggests that changing emissions of other (isotopically-lighter) CH4 source terms is dominating the increase in global CH4 emissions. Although production of shale gas has increased rapidly since 2008, and CH4 emissions associated with this increased production are expected to have increased overall in that timeframe, the simultaneously-observed increase in global atmospheric CH4 is not dominated by emissions from shale gas and shale oil developments.

Surface Casing Pressure As an Indicator of Well Integrity Loss and Stray Gas Migration in the Wattenberg Field, Colorado.

The risk of environmental contamination by oil and gas wells depends strongly on the frequency with which they lose integrity. Wells with compromised integrity typically exhibit pressure in their outermost annulus (surface casing pressure, SfCP) due to gas accumulation. SfCP is an easily measured but poorly documented gauge of well integrity. Here, we analyze SfCP data from the Colorado Oil and Gas Conservation Commission database to evaluate the frequency of well integrity loss in the Wattenberg Test Zone (WTZ), within the Wattenberg Field, Colorado. Deviated and horizontal wells were found to exhibit SfCP more frequently than vertical wells. We propose a physically meaningful well-specific critical SfCP criterion, which indicates the potential for a well to induce stray gas migration. We show that 270 of 3923 wells tested for SfCP in the WTZ exceeded critical SfCP. Critical SfCP is strongly controlled by the depth of the surface casing. Newer horizontal wells, drilled during the unconventional drilling boom, exhibited critical SfCP less frequently than other wells because they were predominantly constructed with deeper surface casings. Thus, they pose a lower risk for inducing stray gas migration than legacy vertical or deviated wells with surface casings shorter than modern standards.

Upward revision of global fossil fuel methane emissions based on isotope database.

Methane has the second-largest global radiative forcing impact of anthropogenic greenhouse gases after carbon dioxide, but our understanding of the global atmospheric methane budget is incomplete. The global fossil fuel industry (production and usage of natural gas, oil and coal) is thought to contribute 15 to 22 per cent of methane emissions to the total atmospheric methane budget. However, questions remain regarding methane emission trends as a result of fossil fuel industrial activity and the contribution to total methane emissions of sources from the fossil fuel industry and from natural geological seepage, which are often co-located. Here we re-evaluate the global methane budget and the contribution of the fossil fuel industry to methane emissions based on long-term global methane and methane carbon isotope records. We compile the largest isotopic methane source signature database so far, including fossil fuel, microbial and biomass-burning methane emission sources. We find that total fossil fuel methane emissions (fossil fuel industry plus natural geological seepage) are not increasing over time, but are 60 to 110 per cent greater than current estimates owing to large revisions in isotope source signatures. We show that this is consistent with the observed global latitudinal methane gradient. After accounting for natural geological methane seepage, we find that methane emissions from natural gas, oil and coal production and their usage are 20 to 60 per cent greater than inventories. Our findings imply a greater potential for the fossil fuel industry to mitigate anthropogenic climate forcing, but we also find that methane emissions from natural gas as a fraction of production have declined from approximately 8 per cent to approximately 2 per cent over the past three decades.

Groundwater methane in relation to oil and gas development and shallow coal seams in the Denver-Julesburg Basin of Colorado.

Unconventional oil and gas development has generated intense public concerns about potential impacts to groundwater quality. Specific pathways of contamination have been identified; however, overall rates of contamination remain ambiguous. We used an archive of geochemical data collected from 1988 to 2014 to determine the sources and occurrence of groundwater methane in the Denver-Julesburg Basin of northeastern Colorado. This 60,000-km(2) region has a 60-y-long history of hydraulic fracturing, with horizontal drilling and high-volume hydraulic fracturing beginning in 2010. Of 924 sampled water wells in the basin, dissolved methane was detected in 593 wells at depths of 20-190 m. Based on carbon and hydrogen stable isotopes and gas molecular ratios, most of this methane was microbially generated, likely within shallow coal seams. A total of 42 water wells contained thermogenic stray gas originating from underlying oil and gas producing formations. Inadequate surface casing and leaks in production casing and wellhead seals in older, vertical oil and gas wells were identified as stray gas migration pathways. The rate of oil and gas wellbore failure was estimated as 0.06% of the 54,000 oil and gas wells in the basin (lower estimate) to 0.15% of the 20,700 wells in the area where stray gas contamination occurred (upper estimate) and has remained steady at about two cases per year since 2001. These results show that wellbore barrier failure, not high-volume hydraulic fracturing in horizontal wells, is the main cause of thermogenic stray gas migration in this oil- and gas-producing basin.

Millennial-scale plankton regime shifts in the subtropical North Pacific Ocean.

Climate change is predicted to alter marine phytoplankton communities and affect productivity, biogeochemistry, and the efficacy of the biological pump. We reconstructed high-resolution records of changing plankton community composition in the North Pacific Ocean over the past millennium. Amino acid-specific δ(13)C records preserved in long-lived deep-sea corals revealed three major plankton regimes corresponding to Northern Hemisphere climate periods. Non-dinitrogen-fixing cyanobacteria dominated during the Medieval Climate Anomaly (950-1250 Common Era) before giving way to a new regime in which eukaryotic microalgae contributed nearly half of all export production during the Little Ice Age (~1400-1850 Common Era). The third regime, unprecedented in the past millennium, began in the industrial era and is characterized by increasing production by dinitrogen-fixing cyanobacteria. This picoplankton community shift may provide a negative feedback to rising atmospheric carbon dioxide concentrations.

Increasing subtropical North Pacific Ocean nitrogen fixation since the Little Ice Age.

The North Pacific subtropical gyre (NPSG) plays a major part in the export of carbon and other nutrients to the deep ocean. Primary production in the NPSG has increased in recent decades despite a reduction in nutrient supply to surface waters. It is thought that this apparent paradox can be explained by a shift in plankton community structure from mostly eukaryotes to mostly nitrogen-fixing prokaryotes. It remains uncertain, however, whether the plankton community domain shift can be linked to cyclical climate variability or a long-term global warming trend. Here we analyse records of bulk and amino-acid-specific (15)N/(14)N isotopic ratios (δ(15)N) preserved in the skeletons of long-lived deep-sea proteinaceous corals collected from the Hawaiian archipelago; these isotopic records serve as a proxy for the source of nitrogen-supported export production through time. We find that the recent increase in nitrogen fixation is the continuation of a much larger, centennial-scale trend. After a millennium of relatively minor fluctuation, δ(15)N decreases between 1850 and the present. The total shift in δ(15)N of -2 per mil over this period is comparable to the total change in global mean sedimentary δ(15)N across the Pleistocene-Holocene transition, but it is happening an order of magnitude faster. We use a steady-state model and find that the isotopic mass balance between nitrate and nitrogen fixation implies a 17 to 27 per cent increase in nitrogen fixation over this time period. A comparison with independent records suggests that the increase in nitrogen fixation might be linked to Northern Hemisphere climate change since the end of the Little Ice Age.

Nutrient regime shift in the western North Atlantic indicated by compound-specific δ15N of deep-sea gorgonian corals.

Despite the importance of the nitrogen (N) cycle on marine productivity, little is known about variability in N sources and cycling in the ocean in relation to natural and anthropogenic climate change. Beyond the last few decades of scientific observation, knowledge depends largely on proxy records derived from nitrogen stable isotopes (δ(15)N) preserved in sediments and other bioarchives. Traditional bulk δ(15)N measurements, however, represent the combined influence of N source and subsequent trophic transfers, often confounding environmental interpretation. Recently, compound-specific analysis of individual amino acids (δ(15)N-AA) has been shown as a means to deconvolve trophic level versus N source effects on the δ(15)N variability of bulk organic matter. Here, we demonstrate the first use of δ(15)N-AA in a paleoceanographic study, through analysis of annually secreted growth rings preserved in the organic endoskeletons of deep-sea gorgonian corals. In the Northwest Atlantic off Nova Scotia, coral δ(15)N is correlated with increasing presence of subtropical versus subpolar slope waters over the twentieth century. By using the new δ(15)N-AA approach to control for variable trophic processing, we are able to interpret coral bulk δ(15)N values as a proxy for nitrate source and, hence, slope water source partitioning. We conclude that the persistence of the warm, nutrient-rich regime since the early 1970s is largely unique in the context of the last approximately 1,800 yr. This evidence suggests that nutrient variability in this region is coordinated with recent changes in global climate and underscores the broad potential of δ(15)N-AA for paleoceanographic studies of the marine N cycle.

Nitrogen isotopic records of terrestrial pollution encoded in Floridian and Bahamian gorgonian corals.

Stable nitrogen isotope (delta(15)N) analysis has proven an effective "fingerprint" of sewage contamination in coral reef environments; however, short-term variability in nitrogen cycling and isotopic fractionation may obscure long-term trends. Here, we examine delta(15)N signatures in the organic endoskeletons of long-lived (20-40 years) gorgonian corals. Specimens were collected from relatively pristine reefs off Green Turtle Cay, Bahamas, and from reefs off southeast Florida heavily impacted by multiple sources of anthropogenic nitrogen. The delta(15)N of the most recently grown skeleton (branch tips) ranged from +2 to +3 per thousand at Green Turtle Cay, and +4.5 to +10 per thousand off Florida. These values closely match the delta(15)N of macroalgae collected from the same locations, indicating that gorgonian corals are isotopically similar to primary producers, and therefore suitable for assessing sources of dissolved inorganic nitrogen. Differences in the delta(15)N between younger and older skeleton indicated an overall decline of -0.34 +/- 0.06 per thousand (1 s.e) over the last 20 - 40 years at Green Turtle Cay, reflecting a possible increase in nitrogen fixation and/or atmospheric deposition of anthropogenic nitrogen. Off southeast Florida, there was an overall increase in delta(15)N over the same time period, reflecting increasing wastewater discharges from the rapidly growing population. These results highlight the usefulness of delta(15)N recorded in gorgonians and other long-lived organisms in assessing spatiotemporal patterns of nitrogen sources to coastal marine environments.

The use of delta(15)N in assessing sewage stress on coral reefs.

While coral reefs decline, scientists argue, and effective strategies to manage land-based pollution lag behind the extent of the problem. There is need for objective, cost-effective, assessment methods. The measurement of stable nitrogen isotope ratios, delta(15)N, in tissues of reef organisms shows promise as an indicator of sewage stress. The choice of target organism will depend upon study purpose, availability, and other considerations such as conservation. Algae are usually plentiful and have been shown faithfully to track sewage input. The organic matrix of bivalve shells can provide time series spanning, perhaps, decades. Gorgonians have been shown to track sewage, and can provide records potentially centuries-long. In areas where baseline data are lacking, which is almost everywhere, delta(15)N in gorgonians can provide information on status and trends. In coral tissue, delta(15)N combined with insoluble residue determination can provide information on both sewage and sediment stress in areas lacking baseline data. In the developed world, delta(15)N provides objective assessment in a field complicated by conflicting opinions. Sample handling and processing are simple and analysis costs are low. This is a method deserving widespread application.

Clionid sponge surveys on the Florida Reef Tract suggest land-based nutrient inputs.

Bioerosion by Cliona delitrix and Cliona lampa was assessed at 43 sites along the Florida Reef Tract, USA, in the summer of 2001. Sponge abundances were estimated using rapid visual assessment. Tissue samples of sponges were taken for analysis of delta15N. Comparison samples were taken from Belize. Annual trends in sponge abundance were estimated from archived videos covering the period from 1996 to 2001. Sites with the greatest boring sponge size and cover were in the Backcountry and Lower Keys, where total nitrogen, ammonium, and delta15N levels were highest. The sites with the largest relative increase of C. delitrix and C. lampa over the 5 year period were in the Upper Keys, where the greatest relative decline in stony coral cover has occurred. Florida sponge delta15N values were 5.2(+/-0.1)%, suggesting the influence of human waste; in comparison, offshore Belize samples were 2.1(+/-0.1)%. These results suggest sewage contamination of the Florida Reef Tract, shifting the carbonate balance from construction to destruction.