Friday, December 29, 2023

New Major Natural Gas Discovery in North Sumatra Basin Offshore Indonesia: Mubadaba Energy’s South Andaman Find is Regionally Significant and Confirms Harbour Energy’s 2022 Discovery to the North


     Considered the world’s second-largest 2023 deepwater natural gas discovery, Abu Dhabi (UAE)-based company Mubadaba Energy announced a major natural gas discovery in December 2023. This well, the Layaran-1 Exploration well was drilled about 100km offshore Sumatra in the North Sumatra Basin. It is the first deepwater well operated by the company, drilled to a depth of 4,208 meters (13805 ft) in 1,207 meters (3959 ft) of water depth . According to Mubadaba Energy’s website:

 

 “The well encountered an extensive gas column with a thickness of over 230 meters in an Oligocene sandstone reservoir. A complete data acquisition including wireline, coring, sampling and production test (DST) were conducted. The well successfully flowed over 30mmscf/d of excellent gas quality.”

 

     Previous to this discovery there was another discovery in 2022 about 50km to the north. This well, the Timpan-1, was operated by Harbour Energy, with Mubadaba having a 40% stake. The well was drilled in a water depth of 4245 ft. From Harbour’s announcement:

 


Source: Harbour Energy


The well was drilled to a total vertical depth of 13,818 feet subsea. The well encountered a 390 foot gas column in a high net-to-gross, fine-grained sandstone reservoir with associated permeability of 1-10 mD. A full data acquisition programme has been completed including wireline logging, 240 feet of core recovered and a drill stem test.

 

The well flowed on test at 27 mmscfd of gas and 1,884 bopd of associated 58 degrees API condensate through a 56/64 inch choke. While the well has encountered a material gas accumulation, further work will be required to establish commerciality and the full potential of this play across the licence.”

 

These wells prove that the offshore Aceh part of the North Sumatra Basin has the potential for significant gas (and gas condensate) production. Based on the size of the structure Wood MacKenzie estimates the recoverable reserves at 3.3 TCF and the gas-in-place at 6 TCF. There is a possibility of multi-TCF expansion in the broader structure. The subsurface geology of the area consists of a series of small but deep syn-rift basins (a syn-rift basin indicates that faulting and deposition are synchronous).

     While the North Sumatra Basin is one of Indonesia’s most prolific hydrocarbon-producing basins with a producing history over 100 years (first hydrocarbon production in 1885), its part offshore Aceh has been underexplored according to a 2020 paper in the IOP Conference Series Materials Science and Engineering by independent geologist Muchlis – and Chris Elders of Curtin University. Previous to these two wells there was only one economic producing field along with a number of uneconomic discoveries and unsuccessful wells.

     The structural style and stratigraphy of the greater basin are shown below. The geology and tectonic history of the basin is complex strike-slip faulting and wrench faulting (Early Eocene to Early Oligocene); rotation of fault planes with more wrenching (late Oligocene to Early Miocene); regional uplift due to reactivation of older horsts and grabens, seafloor spreading, regional unconformities with widespread erosion (Middle Miocene), and finally compression stresses (Late Miocene to Recent).

 









 

The new discovery will help the region secure needed natural gas. Indonesia aims to reach a natural gas output of 12 bcf/day by 2030.

 

References:


Mubadala Energy announces major gas discovery in South Andaman. Reuters. December 20, 2023. Mubadala Energy announces major gas discovery in South Andaman (msn.com)

Harbour plans 3 exploration, appraisal wells in Andaman II block. Petromindo.com. March 9, 2023. Investments in Oil and Gas in Indonesia; Indonesia upstream oil & gas; Harbour plan Andaman drilling; Harbour drill Andaman well; Harbour plans exploration wells - Harbour plans 3 exploration, appraisal wells in Andaman II block (petromindo.com)

Mubadala Energy announces major gas discovery in South Andaman, Indonesia. Mubadala Energy. Media Release. December 19, 2023. Mubadala Energy Announces Major Gas Discovery in South Andaman, Indonesia - Mubadala Energy

A Review of Regional Geology of the North Sumatra Basin and its Paleogene Petroleum System. Ricky A. Tampubolon, Tsania Ozza, M. Tajul Arifin, A. Syauqi Hidayatillah, Aviandito Prasetio, and Terry Furqan. Indogeo Social Enterprise. No. 37, February 2017. 66 (iagi.or.id)

Structural style of the North Sumatra basin, offshore Aceh. IOP Conference Series Materials Science and Engineering 796(1):012038. Muchlis – and Chris Elders April 2020. (PDF) Structural style of the North Sumatra basin, offshore Aceh (researchgate.net)

Mubadala Petroleum discovers gas column during offshore Indonesia exploration. World Oil. July 13, 2022. Mubadala Petroleum discovers gas column during offshore Indonesia exploration (worldoil.com)

Wednesday, December 27, 2023

Fervo Energy’s Enhanced Geothermal System (EGS) Project Success and Its Implications for Future Nearfield Geothermal EGS Projects

 

     An Enhanced Geothermal System also known as an Engineered Geothermal System (EGS) involves creating a fracture system in rock via hydraulic fracturing and pumping water into and out of that system to be used for heat and electricity. The rocks chosen for EGS can vary significantly but the best areas to do EGS will be very near geothermally active areas or geothermal hotspots. This is known as nearfield geothermal. Utilizing a nearby reservoir that is artificially stimulated can have several advantages including easier drilling, less corrosion, and less seismic activity.

     In late September 2023, Fervo Energy announced the commencement of an exploratory drilling program to produce geothermal energy via EGS in Utah, “… at Cape Station, a next-generation geothermal energy project set to deliver 400 MW of 24/7 carbon-free electricity. Cape Station will begin delivering around-the-clock, clean power to the grid in 2026 and reach full scale production in 2028.”

     On November 28, 2023, Fervo announced that power was flowing to the local power grid to Google’s data centers from their EGS project in Nevada, begun two years previously. The project consists of “two horizontal wells and installed fiber-optic cables to capture data that shows the flow, temperature and performance of the geothermal system in real-time.” One well is an injector well and the other is a production well.

 





     Details of the Nevada project were released in a July 2023 paper by Jack Norbert and Timothy Latimer and the abstract is publicly available. The project is in north-central Nevada adjacent to an existing geothermal power plant. According to the abstract the stimulated and producing interval is a “metasedimentary and igneous formation, comprised of phyllite, quartzite, diorite, and granodiorite, representative of the geology across the most prospective geothermal areas throughout the western US.” The hole sizes in the wells are a little larger than typical oil & gas wells at 9 7/8” and 7” casing was run into them. The wells are about 3250 ft in length and just over 7000 ft in depth. The maximum temperature of the formation was recorded at 376 deg F. A vertical monitoring well was also drilled further out along the lateral sections of the doublet wells. It should perhaps be pointed out that there are sedimentary formations with temperatures nearly that high in the Louisiana Salt Basin’s Haynesville and Bossier natural gas plays at about 300 deg F. However, it would likely be more difficult to get full hydraulic containment in those formations. Stimulation and flow testing were described as follows: “A modern multistage, plug-and-perforate stimulation treatment design with proppant was used to enhance the permeability of both horizontal wells. A 37-day crossflow production test was performed in April-May 2023, confirming that the EGS wells are connected hydraulically by a highly conductive fracture network. During production testing, the system achieved flow rates of up to 63 L/s, production temperatures of up to 336 degrees F and a peak power production of 3.5 MW electric power equivalent.” This is the most productive EGS doublet in history in terms of flow rate and electric power. As a first-of-a-kind project, it is thought that improvements will come in the future. Fervo’s simulation modeling suggests that with innovation the power capacity for these types of EGS projects can be increased to 8MW per production well.

   Some slides offering details of the Nevada project from a Geothermal workshop at Stanford University in February 2023 are included below. That paper gives some background: “The geologic setting at Blue Mountain is representative of many areas throughout the Basin and Range Province with high quality geothermal resource potential. The lateral sections of the wells targeted the Grass Valley formation, a Mesozoic metasedimentary formation comprised predominantly of interbedded phyllite and quartzite, as well as intrusive diorite and dikes and sills. The horizontal wells were placed in a southern reservoir compartment believed to have relatively few large-scale faults and low intrinsic permeability.” Incidentally, I did my undergraduate geology field camp in the Basin and Range province of Central Nevada, so I am somewhat familiar with some of those rocks. I remember the dikes and sills that outcropped where I was quite well. At one, I had a peculiar experience. Dikes are volcanic intrusions that cut across the horizontally positioned sedimentary rocks while sills are the part of the intrusives that were emplaced horizontally between the sedimentary layers. The sill in question was black with reddish stripes and as I looked at it from a bit of a distance, I noticed it appeared as if part of the rocks were moving. On closer inspection I noted that lizards were running along the rock that had coloration virtually identical to those outcropping volcanic rocks, likely evolving those colors for camouflage to increase survivability.











 

 All three of the Nevada wells were outfitted with reservoir diagnostics utilizing distributed fiber optic sensing (DFOS). They deemed these reservoir diagnostic tools to be successful in determining the parameters of the hydraulic fracturing that were achieved. According to a case study presented at the SPE/AAPG/SEG Unconventional Resources Technology Conference in Denver in June 2023: “The recorded DFOS data include in-well and cross-well distributed temperature (DTS), acoustic (DAS), and strain (DSS) sensing data. We evaluated the adaptability of DFOS to geothermal applications and showcased that DFOS is a beneficial tool for optimizing multi-stage completions, characterizing the stimulated reservoir volume, and determining well placement in geothermal reservoirs.”

 

The 16-stage plug-and-perf stimulation treatment described in this study was the first of its kind in a high-temperature mixed metasedimentary and granitic formation in a fully horizontal geothermal well. To our knowledge, we recorded the first cross-well strain data during the stimulation of a geothermal well. The DFOS data acquired with three fiber-instrumented wells prove the applicability of unconventional approaches and their value for optimizing completion designs and well placement strategies in geothermal development programs. The in-well DAS data indicate that all clusters were opened during fracture initiation, and the treatment uniformity was high. Also, we found that strain change signals from induced fractures can be detected over large distances (> 1,500 ft). The DSS response recorded during the injector injection test confirmed the hydraulic communication between the injector and producer doublet before producer stimulation.”

 

     Hot granitic basement rock is considered ideal for EGS as a reservoir if it is not too deep. This is due to its characteristic lack of natural fractures. It is ideal only where faults are not present since injecting water into basement faults can trigger induced seismicity, lubricating the faults and causing them to slip. After these conditions are met the two keys to EGS are sufficient temperature and sufficient flow rates of the water after the rocks are hydraulically fractured. Granites and other basement rocks are very hard and slow to drill, often requiring drill bit changes. That makes drilling them more expensive and more time-consuming than drilling sedimentary rocks.

     Fervo’s Utah project will be adjacent to the DOE’s FORGE site that has been running for a few years now testing a similar rock, temperature, and flow configuration at about 8500 ft in vertical depth with the goal of de-risking EGS technology. This will be a much larger project and Fervo’s CEO Timothy Latimer thinks that it can be done at economic projections.

 

 

Advantages of an Engineered Geothermal Reservoir in Meeting Power Demand and in Being a Self-Contained Artificial Hydrothermal System

 

     An EGS system provides similar benefits to a conventional geothermal power plant in terms of dispatchability and baseload power capabilities. These geothermal plants can be run continuously or ramped up and down very quickly so that they can meet power demand when it is needed. According to a May 2022 paper in Applied Energy - The value of in-reservoir energy storage for flexible dispatch of geothermal power by Wilson Ricks, Jack Norbeck, and Jesse Jenkins: “Across a range of realistic subsurface and operational conditions, our modeling demonstrates that confined, engineered geothermal reservoirs can provide large and effectively free energy storage capacity, with round-trip storage efficiencies comparable to those of leading grid-scale energy storage technologies. Optimized operational strategies indicate that flexible geothermal plants can provide both short- and long-duration energy storage, prioritizing output during periods of high electricity prices. Sensitivity analysis assesses the variation in outcomes across a range of subsurface conditions and cost scenarios.” They also point out that the low-permeability rock within which an EGS system is typically drilled can provide hydraulic confinement so that the engineered hydrothermal system is contained without losses to the surrounding rock outside of the induced fractures. This prevention of fluid leak-off is important to the stability and reliability of the system. The goal is to provide high-conductivity flow paths between an injection well and a production well and to prevent such leak-off outside the system.  

 

 

Future Potential, Some Limitations, and Optimization of EGS Systems

     Marc McClure of ResFrac has modeled and written much about EGS systems. He is bullish for EGS which utilizes convective heating vs. so-called advanced geothermal systems (AGS) which utilize conductive heating. His ResFrac Blog is a valuable source of information for reservoir stimulation of EGS systems. In a July 2023 post, he offers the following key takeaways:

 1. Thermoelastic fracture opening and propagation can have a significant negative effect on the uniformity of flow. On the other hand, interactions between fracture opening and buoyancy-driven fluid circulation cause downward fracture propagation during long-term circulation that greatly improves the thermal longevity of the system.

2. Passive inflow control design can significantly mitigate the negative effect of thermoelastic fracture opening on flow uniformity, while maintaining the positive effects of thermoelastic fracture opening and propagation on flow rate and thermal longevity.

3. Overall, simulations suggest that an EGS doublet with 8000 ft laterals at 475˚ F – using inflow control at the production well – could sustain electricity generation rates of 8-10 MWe for more than 30 years. Without inflow control, 6-8 MWe over 30 years is possible; however, there is greater risk of uncontrolled thermal breakthrough.

He notes that EGS systems will eventually be tapped out as temperature drops due to years of recycling fluids through the rocks. The upfront costs need to be balanced with the longevity of the economic electricity production of the projects. He thinks one of the keys to longevity is fracture stimulation which provides enormous surface areas of contact between the rocks and the circulating fluid. He notes: “To prevent thermal decline at the production well, heat conduction into the fractures must ‘keep up’ with the rate of fluid flow through the fractures.” Heat conduction through rock is not so great so a huge surface area of fractured rock is required. His work involves simulating the long-term circulation of fluid through the induced fracture system. He thinks the key to success is inflow control in the production well: “Because of buoyancy-driven convection and thermoelastic stress reduction and crack propagation, the simulation with inflow control in the production well exhibits outstanding reservoir performance – high flow rate and high produced temperature for more than 30 years. Designs without inflow control show strong – albeit somewhat lower –performance, but carry more risk of severe thermal breakthrough.”

     It is yet to be determined how much EGS geothermal will contribute to energy and electricity production but in time it may provide a small boost. I do not believe, however, that it will be any kind of panacea and both EGS, and particularly AGS will be difficult to economize without significant and perhaps continued subsidization. Perhaps new breakthroughs, more ideal rock, and better fracture stimulation with higher surface areas stimulated will contribute to future improvements.

 

References:

Thermoelastic fracturing and buoyancy-driven convection – Surprising sources of longevity for EGS circulation. Mark McClure. ArXiv. July 24, 2023. 2308.02761.pdf (arxiv.org)

Commercial-Scale Demonstration of a First-of-a-Kind Enhanced Geothermal System. Jack Norbeck and Timothy Latimer. July 2023. Commercial-Scale Demonstration of a First-of-a-Kind Enhanced Geothermal System (researchgate.net)

A New Type of Geothermal Power Plant Just Made the Internet a Little Greener. Gregory Barber. Wired. November 28, 2023. A New Type of Geothermal Power Plant Just Made the Internet a Little Greener | WIRED

Case Study: Completion and Well Placement Optimization Using Distributed Fiber Optic Sensing in Next-Generation Geothermal Projects. Aleksei Titov; Jack Norbeck; Sireesh Dadi; Katharine Voller; Mark Woitt; Steven Fercho; Emma McConville; Camden Lang; Saurabh Agarwal; Christian Gradl; Timothy Latimer. Paper presented at the SPE/AAPG/SEG Unconventional Resources Technology Conference, Denver, Colorado, USA, June 2023. Paper Number: URTEC-3852680-MS. Case Study: Completion and Well Placement Optimization Using Distributed Fiber Optic Sensing in Next-Generation Geothermal Projects | SPE/AAPG/SEG Unconventional Resources Technology Conference | OnePetro

The value of in-reservoir energy storage for flexible dispatch of geothermal power. Wilson Ricks, Jack Norbeck, Jesse Jenkins. Applied Energy. Volume 313, 1 May 2022, 118807. The value of in-reservoir energy storage for flexible dispatch of geothermal power - ScienceDirect

A Review of Drilling, Completion, and Stimulation of a Horizontal Geothermal Well System in North-Central Nevada. Jack Norbeck, Timothy Latimer, Christian Gradl, Saurabh Agarwal, Sireesh Dadi, Eric Eddy, Steven Fercho, Camden Lang, Emma McConville, Aleksei Titov, Katharine Voller, and Mark Woitt. PROCEEDINGS, 48th Workshop on Geothermal Reservoir Engineering. Stanford University, Stanford, California, February 6-8, 2023. A Review of Drilling, Completion, and Stimulation of a Horizontal Geothermal Well System in North-Central Nevada (stanford.edu)

A first-of-its-kind geothermal project is now operational. Michael Terrell. Google. November 28, 2023. Google and Fervo launch first-of-its-kind geothermal project (blog.google)

New Google geothermal electricity project could be a milestone for clean energy. Jennifer McDermott. AP News. November 28, 2023. New Google geothermal electricity project could be a milestone for clean energy | AP News

Fervo Energy Breaks Ground on the World’s Largest Next-gen Geothermal Project. Fervo Energy. September 25, 2023. Fervo Energy Breaks Ground on the World’s Largest Next-gen Geothermal Project - Fervo Energy

Monday, December 25, 2023

Harmful Algae Blooms: The Dangers of Cyanobacteria and Eutrophication, and Remediation Efforts

 

     Harmful algae blooms (HABs) are considered to be a major environmental problem throughout the U.S., in all 50 states, and throughout the world. These include so-called red tides and cyanobacteria (blue-green algae). They can impact human and animal health, aquatic ecosystems, and even economies. Not all algae blooms are harmful.  




     Harmful algae blooms are overgrowths of algae in both freshwater and saltwater. Not all are toxic but even the non-toxic ones can be harmful in other ways. The algae blooms can produce toxins that can kill people or animals. They can create “dead zones” in water bodies. They can increase water treatment costs and damage industries that rely on clean water.




     The ingredients for harmful algae blooms are sunlight, slow-moving water, and nutrients, notably nitrogen and phosphorus. The use of nitrogen and phosphorus as fertilizers and the prevalence of fertilizer runoff make HABs occur more often and with more severity. Both synthetic chemical fertilizers and natural fertilizers like animal manure contribute to the problem. Agriculture also produces gaseous nitrous oxides and ammonia that can end up in waterways and eventually contribute to HABs. Agriculture is not the only source of nutrient pollution that accumulates in waters. Stormwater runoff, wastewater from sewage systems and septic tanks, fossil fuels combustion, industrial effluents, and solid waste runoff, particularly agricultural waste from animals, also contribute. The use of fossil fuels that emit nitrogen oxides into the air in electricity generation, agriculture, and industry has led to more airborne nitrogen that can later accumulate in waters.







     Nutrient pollution in the form of nitrogen and phosphorus runoff is considered to be a major societal problem around the world. The excess nitrogen and phosphorus that accumulates in waters feeds algae to the point where the algal growth rate exceeds the ability of the water body to naturally regulate it. Water quality, food resources, and habitats are affected. Eventually, the water can become starved of oxygen. This can lead to fish kills and through time it can affect potable water and groundwater. Nutrients can move through shallow groundwater and end up in surface waters. Nitrates in potable water supplies can be elevated to dangerous levels. The graphic below gives some good information and statistics about the scope of the problem in the U.S. The Mississippi River Basin is the third largest river basin in the world and drains quite a bit of U.S. farmland. This has led to nutrient pollution in the Gulf of Mexico, often in the form of red tides due to the type of algae that is prominent.

     In the temperate areas of the U.S. HABs often occur in the warmer months from mid-June to early September. Laboratory analysis of water samples is required to identify the bacteria responsible for an algae bloom. People are advised to avoid water with possible HABs and especially to avoid letting their pets drink from such water.

     A harmful algae bloom in Western Lake Erie in August 2014 led to difficulty of the water treatment plant in Toledo, Ohio to treat the drinking water to a safe level and residents were advised not to drink it. Another bloom returned there in 2015. HABs have led to large fish kills. They have killed land animals and even whales in some cases. Livestock and pet dogs that have drunk water affected by HABs have died. People have been sickened and killed as well, largely due to eating saltwater shellfish and fish that had accumulated toxins from HABs.

     In the summer of 2015, a wet spring followed by dry hot weather along the Ohio River led to a clearing of the water and a slower-moving river. This was followed by hard rains that washed fertilizer and sewage into the river. Cattle feedlots and overloaded sewage systems were big contributors. These ideal conditions led to a cyanobacteria algae bloom along 636 miles of the 981-mile river, from Wheeling, West Virginia to Cannelton, Indiana. Oddly, the only other toxic algae bloom recorded in the river was in 2008 but by comparison that bloom only stretched 40 miles. Although I live less than 10 miles from the river I don’t seem to remember this event.

 


 



Cyanobacteria Blooms

 

     Cyanobacteria, or blue-green algae, are microorganisms that can produce HABs in freshwater. Some freshwater cyanobacteria blooms can produce highly potent toxins known as cyanotoxins.  There are several types of cyanobacteria and some of these produce cyanotoxins. In the U.S. the most common cyano are microcystins, cylindrospermopsin, anatoxins, and saxitoxins. Microcystis is nearly always toxic. One type of cyanobacteria that produces microcystins is Dolichospermum, which forms “slimy summer blooms on the surface of eutrophic lakes and reservoirs.” These blooms can occur quickly. They look like green paint that accumulates along shores. I am guessing that the image below depicts a Dolichospermum bloom. They are less prevalent, forming smaller accumulations where nutrient loading (eutrophication) is lower.  According to the U.S. EPA: “Microcystins are the most widespread cyanobacterial toxins and can bioaccumulate in common aquatic vertebrates and invertebrates such as fish, mussels, and zooplankton. Microcystins primarily affect the liver (hepatotoxin), but can also affect the kidney and reproductive system. While there is evidence of an association between liver and colorectal cancers in humans and microcystins exposure and some evidence that microcystin-LR is a tumor promoter in mechanistic studies, EPA determined that there is inadequate information to assess carcinogenic potential of microcystins in humans due to the limitations in the few available human studies (i.e., potential co-exposure to other contaminants) and lack of long-term animal studies evaluating cancer following oral exposure.” Another cyanotoxin, Cylindrospermopsin, is known to promote liver and kidney damage and to be a possible carcinogen. It is produced by a variety of cyanobacteria genera. Anatoxins are also produced by a wide variety of cyanobacteria genera. They are a known neurotoxin since “they bind to neuronal nicotinic acetylcholine receptors affecting the central nervous system.” Saxitoxins are a large family of toxins that can accumulate in shellfish and are referred to as Paralytic Shellfish Poisoning (PSP) toxins. They mostly occur in saltwater but can also occur in freshwater.









     Favorable conditions that contribute to cyanobacteria blooms include light availability, water temperature, alteration of water flow, vertical mixing, pH changes, nutrient loading (both nitrogen and phosphorus), and trace metals. Human activities contribute to the development of cyanobacteria blooms. EPA notes that “point sources (which may include discharges from municipal and industrial wastewater treatment plants, concentrated animal feeding operations (CAFOs), Municipal Separate Storm Sewer Systems (MS4s), stormwater associated with industrial activity, and other) and non-point sources (which may include diffuse runoff from agricultural fields, roads and stormwater), may be high in nitrogen and phosphorus and can promote or cause excessive fertilization (eutrophication) of both flowing and non-flowing waters.”

 

 

Eutrophication

 

     Eutrophication refers to the condition of nutrient and mineral overloading in a body of water where the overgrowth of algae, plankton, and plants. It is also known as nutrient pollution. The excess of algae and plant growth creates problems when these organisms consume oxygen when they decompose. The pH of the water is lowered making it more acidic and oxygen supply is choked off in the water. This can result in “dead zones.” It affects freshwater and saltwater. Marine water dead zones from eutrophication are especially prominent in the Baltic Sea. There is an enduring large dead zone in the Gulf of Mexico. These are due mainly to nitrogen and phosphorus fertilizer runoff. In oceans, eutrophication also contributes to ocean acidification. The graphs below show the anthropogenic contributions to eutrophication in the Gulf of Mexico and the Chesapeake Bay. The second chart below shows the contributions of different animal foods to eutrophication.

 

 




Source of Both: Wikipedia


Phosphate-containing detergents were once the main source of phosphorous accumulating in water bodies until they were phased out in the 1970s. As the graphs above show, urban stormwater and municipal wastewater are major sources of eutrophication in the Chesapeake Bay, especially from phosphorous but also from nitrogen. Some eutrophication is natural, particularly in lakes. Geology and climate variations can influence natural eutrophication. In the geologic past, it is thought that volcanic eruptions producing ash that lands in shallow ocean or inland sea waters has led to algae proliferation. That algae decomposed in deoxygenated waters leading to deposits of organic matter at the sea floors, Where the water was deep enough that organic matter was preserved to form organic-rich black shales and mudstones, many of which later became prominent oil & gas reservoirs after deep burial created temperatures and pressures high enough to cook them into hydrocarbons.  

     Freshwater eutrophication is mainly due to phosphorus. Eutrophication in marine waters is due more to nitrogen and iron with phosphorus as a lesser contributor. Phosphate adheres tightly to soil particles, resulting in a slower journey into the water itself. A 2014 book chapter abstract Eutrophication: Challenges and Solutions in the book Eutrophication: Causes, Consequences and Control. Volume 2 explains the whole eutrophication issue concisely as follows:

 

On the hydrological map of the world eutrophication has become the primary water quality issue. The excessive enrichment of waters with anthropogenic sources of nutrients especially nitrogen (N) and phosphorus (P) lead to the transformation of oligotrophic water bodies to mesotrophic, eutrophic, and finally hypertrophic. Mesotrophic and eutrophic phases exhibit intermediate and rich levels of nutrients and show increasing and serious water quality problems, respectively. Eutrophication restricts water use for fisheries, recreation, industry, and drinking because of increased growth of undesirable algae and aquatic weeds and the oxygen shortages caused by their death and decomposition. Associated periodic surface blooms of cyanobacteria (blue-green algae) occur in drinking water supplies and may pose a serious health hazard to animals and humans. Anthropogenic activities are the worst culprit of nutrient enrichment and root cause of eutrophication of water bodies. Excess nutrient inputs to water bodies usually come from sewage, industrial discharges, agricultural runoff, construction sites, and urban areas. Eutrophication can be minimized by regulating the nutrient sources, reducing the use of fertilizers, proper soil management practices, implementing mathematical models, phytoremediation etc. Among these, public awareness of eutrophication can play an important role in preventing the eutrophication of water bodies.”

 

     Coastal eutrophication is a serious issue in many places. Increased nutrient loads lead to changes in biodiversity, proliferation of some species and suppression of others, particularly phytoplankton. Changes in the ratio of nitrogen and phosphorous to silica drive changes in phytoplankton proliferation. The map below shows areas of ocean deoxygenation caused and/or exacerbated by human activities. Some water bodies like the Baltic Sea and the Black Sea already naturally have low oxygen content and thus are more susceptible to crossing deoxygenation thresholds.   





     The term “red tides” refers mainly to the algae blooms of species of dinoflagellates, such as Karenia brevis. The term is perhaps misleading since not all are red in color. Some are also caused by other algal species, not just dinoflagellates. They are not really associated with tides at all so the term is being used less and less.

 

 

Efforts to Prevent and Reduce Harmful Algae Blooms

 

      According to Our World in Data: “…globally farmers apply around 115 million tonnes of nitrogen to our crops every year. Only around 35% of this is used by them, meaning 75 million tonnes of nitrogen runs off into our rivers, lakes, and natural environments.” China has the highest levels of fertilizer runoff. The U.S. also has high levels. Methods such as specific targeting of fertilizers and better timing of applying fertilizers can reduce runoff.

     Heavy rains are the cause of much fertilizer runoff into rivers and lakes. One very important way to prevent and reduce HABs resulting from fertilizers is to reduce fertilizer run-off. Drip irrigation using tubes and emitters for injecting fertilizer has been effective at reducing runoff. Drip irrigation is also effective at reducing water use. Other proposals include creating buffer zones of plants and wetlands that can help filter phosphorous, preventing some of it from reaching key water bodies. Conservation tillage, changing crop rotations, and wetlands restoration have also been proposed. Reduction of phosphorus applications by farmers has been successful in managing and significantly reducing dead zones in parts of the Baltic and Black Seas and the rivers that flow into them. Reduction of phosphorous runoff in particular offers hope to keep HABs under control. Chemical treatments such as algicides made from silver nitrate or copper sulfate can be very successful at killing algae but may also be toxic in themselves so care must be taken. Algae can also develop resistance to copper sulfate. Some new methods with granular sodium percarbonate that allow the algicide to float have been effective since they do not affect aquatic life below the surface.

     One of the safest natural methods under consideration includes seaweed and other aquatic plants, some of which have chemicals in them that suppress algae growth. Seaweed and kelp aquaculture in coastal waters offers a good opportunity to decrease eutrophication. “Some cultivated seaweeds have very high productivity and could absorb large quantities of N, P, CO2, producing large amounts of O2 having an excellent effect on decreasing eutrophication. It is believed that seaweed cultivation in large scale should be a good solution to the eutrophication problem in coastal waters.” This bioremediation process is referred to as nutrient bioextraction.

      Aluminum-modified clay is another promising method of reduction of HABs, specifically HABs involving the species Aureococcus. The aluminum ions create an electric charge on the surface of the clays on the bottom that can attract the algae down onto the clay sediment rather than leaving it in suspension. Studies have shown that the water can be pumped through a hydrodynamic separator leaving less algae and less phosphorus. The captured algal matter can then be biodigested for methane production.

     There is an urgent need for more sensors and monitoring devices to track algae blooms and in particular to forecast HABs. Sensors deployed in the Gulf of Mexico have likely led to a life-saving shutdown of shellfish harvesting in 2008. Satellite tracking and early warning systems for HABs are also being developed.

     Another method to reduce eutrophication and deoxygenation (hypoxia), considered to be a kind of geoengineering, involves simply pumping compressed air into the water to oxygenate it. This is standard for small waters from fish tanks to aquaculture ponds. Phosphorous can also be removed chemically by sorbents such as aluminum sulfate, which falls to the bottom of the water body. This method has been effective in shallow and deep lakes. It has been very effective in Finland.

 

 


Source: Wikipedia


     A new technology that may offer a solution involves hydrogels can sense nitrate levels in farm runoff and capture it so that it can be reused. The same lab that developed the technique also developed a hydrogel that allows soil to effectively water itself. The researchers “made a copper-based hydrogel that, when pulsed with electricity, provides a conductive reaction in a process called ‘electrocatalysis’.” Experiments showed that the nitrate in the farm field can be converted to ammonia at the surface when it runs over the gel. The process can also be used to measure the amount of nitrate and ammonia in the water and cue the farmers when fields need to be drained. The ammonia-rich water can then be recycled back into the field. This could make fertilizer use more efficiently and reduce runoff. Other potential benefits are higher plant growth rates and reduced greenhouse gas emissions due to over-fertilization. The key to the future success of the technique is “finding ways to properly drain run-off into capture areas where the hydrogel can do its magic, and then hook the ammonia-rich water up to irrigation systems.” It can be integrated into existing irrigation systems and powered by solar panels or wind turbines. The paper published in PNAS notes: “Electrocatalytic nitrate-to-ammonia conversion has been recognized as an alternative strategy to produce nitrogen fertilizer from polluted groundwater and industrial waste streams with high environmental sustainability. This work reports an electrocatalysis-enabled system for smart and precisely concentration-controlled nitrogen nutrient recycling via electrifying nitrate-rich wastewaters.” They also note: “We thus designed the Cu SAA {the hydrogel/aerogel} into a smart and sustainable fertilizing system (SSFS), a prototype device for on-site automatic recycling of nutrients with precisely controlled nitrate/ammonium concentrations. The SSFS represents a forward step toward sustainable nutrient/waste recycling, thus permitting efficient nitrogen utilization of crops and mitigating pollutant emissions. This contribution exemplifies how electrocatalysis and nanotechnology can be potentially leveraged to enable sustainable agriculture.” They think that the process may become cost-competitive with the typical Haber-Bosch process for nitrogen fertilizer production.






The paper's conclusions section summarizes the potential for this technique: “This work further highlights the SSFS with Cu SAAs as the functional unit allows on-demand ammonia production by utilizing nitrate-rich wastewaters while precisely monitoring concentrations of NO3−/NH4+ in real time. We further assessed the feasibility of the SSFS for recycling of fertigation water while controlling nitrogen nutrients with desired NO3−-N and NH4+-N ratio. Under hydroponic conditions, the SSFS achieved unattended operation with automation programs and displayed an impressive recovery rate of nitrogen from nitrate wastewater for ammonia distributions. The study of crop cultivation with the SSFS demonstrates the significantly enhanced efficiency of nutrient uptake, thus benefiting the growth of plants and reducing nitrogen losses. We believe that the SSFS with rationally designed multifunctional SAAs may open up many opportunities to advance future agriculture by integrating renewable energy and information technology.” Field trials are next on the agenda for this technology.

 

 





 

     The following is what I copied from Bing chat about an article in the Detroit Free Press that I can no longer find: According to a news article from Detroit Free Press, scientists at the Great Lakes Environmental Research Laboratory in Ann Arbor have created an uncrewed surface vehicle system that extracts algae samples and transmits data in real time. The surface vehicle, SHARC, short for Sea Harmful Algal Research Craft, will change the game for how scientists around the world understand algae in all bodies of water.

The SHARC system is designed to extract algae samples from water bodies and transmit data in real-time. The system is expected to help scientists understand why and when harmful algae blooms arise, which is important as hundreds of thousands of people travel to dip their toes in the state’s plentiful freshwater, which is a crucial economic driver for Michigan.

  

 

References:

Harmful Algal Blooms. U.S. EPA. Harmful Algal Blooms | US EPA

What are HABs? Pennsylvania Dept. of Environmental Protection. HABs (pa.gov)

Scientists hope SHARC system takes a bite out of harmful algae. Audrey Richardson. Detroit Free Press, September 5, 2023. Scientists hope SHARC system takes a bite out of harmful algae (msn.com)

Two-thirds of fertilizer is lost to run-off. This invention could recycle it. Emma Bryce. Anthropocene Magazine. July 2023. Two-thirds of fertilizer is lost to run-off. This invention could recycle it. (msn.com)

Nutrient Pollution. U.S. EPA. Nutrient Pollution | US EPA

Cyanobacterial Harmful Algal Blooms (CyanoHABs) in Water Bodies. U.S. EPA. Cyanobacterial Harmful Algal Blooms (CyanoHABs) in Water Bodies | US EPA

Cyanobacterial Harmful Algal Blooms and U.S. Geological Survey Science Capabilities. Jennifer L. Graham, Neil M. Dubrovsky, and Sandra M. Eberts. USGS. Open-File Report 2016–1174. Ver. 1.1, December 2017. Cyanobacterial Harmful Algal Blooms and U.S. Geological Survey Science Capabilities (usgs.gov)

Toxic Algae Outbreak Overwhelms a Polluted Ohio River. Michael Wines, New York Times. September 30, 2015.  Toxic Algae Outbreak Overwhelms a Polluted Ohio River - The New York Times (nytimes.com)

A multifunctional copper single-atom electrocatalyst aerogel for smart sensing and producing ammonia from nitrate. Panpan Li, Ling Liao, Zhiwei Fang, and Guihua Yu. Edited by Catherine Murphy, University of Illinois at Urbana-Champaign, Urbana, IL. June 20, 2023. PNAS. Vol. 120 | No. 26. A multifunctional copper single-atom electrocatalyst aerogel for smart sensing and producing ammonia from nitrate | PNAS

Excess fertilizer use: Which countries cause environmental damage by overapplying fertilizers? Hannah Ritchie. Our World in Data. September 7, 2021. Excess fertilizer use: Which countries cause environmental damage by overapplying fertilizers? - Our World in Data

Ocean deoxygenation. Wikipedia. Ocean deoxygenation - Wikipedia

Eutrophication. Wikipedia. Eutrophication - Wikipedia

Eutrophication: Challenges and Solutions. M. Nasir Khan & Firoz Mohammad, Chapter in the Book: Eutrophication: Causes, Consequences and Control. Volume 2. Editors: Abid A. Ansari and Sarvajeet Singh Gill. Springer. 2014. Eutrophication: Challenges and Solutions | SpringerLink

 

Friday, December 22, 2023

Rusting of Rivers in Alaska’s Brooks Range Likely Resulting from Iron Oxidation Thought to be Caused by Thawing Permafrost Exposing Bedrock and/or Thawing Wetlands Activating Iron-Rich Soil Bacteria

   Rivers in Alaska and the Yukon are turning orange due to iron oxidation. The source of this chemical alteration that is very similar to the formation of acid mine drainage is the thawing of permafrost and/or wetlands. That thawing is caused ultimately by global warming which has been significantly amplified in the Arctic as the following graphic shows. This is known as Arctic Acceleration.





Melting permafrost is thought to have several potential dangers, the biggest perhaps being the widespread release of methane that has been sequestered in the frozen ground and that if released can result in a feedback mechanism that could theoretically become a runaway feedback where that methane heats up the atmosphere even more and makes melting and methane release even more widespread. The rusting of rivers due to iron oxidation, however, was apparently not predicted.







     The issue is particularly problematic in Alaska’s Brooks Range which extends 700 miles from Alaska into Canada’s Yukon Territory. At least 75 rivers and streams have rusted in the region just over the last 5-10 years. The discoloration of the water is due to oxidizing iron and sulfuric acid, which means high concentrations of heavy metals are precipitating in the rivers. The oxidation of minerals in the soil may also be lowering the pH of the water, increasing its acidity. pH readings as low as 2.5 have been recorded which makes the issue equivalent to acid mine drainage from coal mines and some minerals mines. The level of dissolved metals as measured by electrical conductivity was roughly equivalent to that of industrial wastewater. The water is undrinkable by environmental standards. Many of the rivers before that had alkaline chemistry with pH above 7. There are obvious dangers to plant life, aquatic life, and fish in the rivers as toxic metals leach out and the rivers become strongly acidic.  







     In 2022 the USGS and National Park Service began an investigation to map out the rusting rivers' extents and to better understand and quantify the effects. Integration of geology, hydrology, and permafrost degradation are all involved in these chemical changes. They are also studying the biological effects. We know that acid mine drainage causes massive negative effects on aquatic organisms, and this is likely to be very similar in effect. There are some people who rely on the local rivers for fish that will also likely be affected. Some of the rivers are known for spawning salmon runs downstream. Researchers think that the phenomenon is also likely to occur in other places in the Canadian and Russian Arctic regions.

     There are two prevailing theories for the phenomenon. One is that the thawing permafrost is exposing bedrock resulting in the release of iron and sulfuric acid into the streams. The other is that soil bacteria, activated by thawing wetlands, are producing the soluble iron. The acidic rivers, like acid mine drainage, also carry high sediment loads due to the precipitating metals. This creates murky water that makes it harder for fish and other aquatic creatures to find food. Iron and aluminum dissolved in the water can also accumulate on fish gills, affecting respiration. As explained below, both ideas may be contributing.




     Kobuk Valley National Park has warmed by 2.4 degrees Celsius (4.32 degrees Fahrenheit) just since 2006. Researchers think about 40% of the permafrost within the park has been thawed. Biodiversity has already been severely restricted in some of these rivers and if the phenomenon continues it seems likely that many will become devoid of life like acid mine drainage infested rivers and streams. Researchers found evidence of thawing permafrost throughout the region with the unmistakable rotting vegetable smell where microbes digest the matter and emit CO2 and methane.





     The thaw of permafrost under a wetland leads to the chemical reduction of oxidized iron that becomes soluble in water. Then, when the reduced iron particles after transport via groundwater come into contact with sufficiently oxygenated waters, they can re-oxidize and precipitate out as rust. That is the basis of the thawing wetlands theory. It is supported by findings of characteristic gray soil under reducing conditions sampled below the once frozen ground.

     The very low pH water can cause acidic “burning” of vegetation which is depicted in some of the images below. The exposed bedrock or acid-rock drainage theory better explains the high acidity. Acid-rock drainage is known to occur when streams weather the sulfide rock associated with ore deposits. The phenomenon in the Brooks Range area had actually been occurring at much lower levels well into the past but has obviously been vastly accelerated by the thawing. The acid-rock theory assumes that the thawing permafrost is allowing oxygenated water to access pyrite-rich shale for the first time in thousands of years, forming sulfuric acid and oxidizing the reduced iron that would normally precipitate out as rust, to continue downstream. The region’s rocks also contain alkaline limestones that neutralize the acid which causes precipitation of the iron. Timothy Lyons, a geochemist at the University of California, Irvine said “It's like a one-two punch. You have the shaley rocks with pyrite that source the acid and the iron, and then the limestones neutralize that acid and cause the iron to come out of solution.” Researchers think other dangerous metals including copper, zinc, cadmium, lead, and even arsenic could be leaching out.







     The whole problem may continue and expand as more permafrost is melted. Beavers have also moved north, making more summer wetlands in the area, supporting the wetlands theory. It now seems likely that both processes, acid-rock drainage and soil bacteria are contributing to the increased soluble iron content of the waters.  

     Oddly perhaps, the natural rusting of the rivers has affected the remediation of waters from The Red Dog Creek mine, one of the world’s largest zinc mines. The mine is well downstream of the affected waters, but those upstream waters had been affecting the remediation system of waters exiting the mine. The area of the mine was already affected by acid-rock leaching so when remediation began the waters actually became cleaner than they had been before the mine was built. The water became less acidic, but the total dissolved solids (TDS) increased due to the sulfates and calcium hydroxide the mine was adding to the water to remove metals. Dissolved metals from upstream due to the thawing permafrost made TDS increase in the waters downstream that the remediation project was halted for a year while the mining company constructed a $19 million reverse osmosis plant to clean up the wastewater. The bottom line is perhaps that the permafrost has become a bigger polluter than the mine. According to the Scientific American article: “Lime is often dumped into tailings ponds at old mines to buffer acid, but you can't “lime” an entire mountain stream, just as you can't refreeze the ground around it. Perhaps the only real hope is that once all the permafrost has thawed and all the iron has rusted, these wild rivers will be able to flush out the contamination and restore themselves, although that would take decades at least.”





References:

75 Alaskan Rivers Turn Bright Orange, Tainting Water Supply, Endangering Humans and Wildlife; Scientists Investigate. Marissa Papanek. Knews. December 20, 2023. 75 Alaskan Rivers Turn Bright Orange, Tainting Water Supply, Endangering Humans and Wildlife; Scientists Investigate (msn.com)

Why Are Alaska’s Rivers Turning Orange? Alec Luhn. Scientific American. January 1, 2024. Why Are Alaska's Rivers Turning Orange? | Scientific American

The Rusting of Arctic Rivers: Freshwater Ecosystems Respond to Rapidly Uptaking Metals. US Geological Survey. Alaska Science Center. November 6, 2023. The Rusting of Arctic Rivers: Freshwater Ecosystems Respond to Rapidly Uptaking Metals | U.S. Geological Survey (usgs.gov)

      Improved recycling capabilities can potentially offset part of the loss of rare earth minerals from China, but it is not a silver bull...

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