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

 

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