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Rain that is unusually acidic

Acid rain is rain or any other form of precipitation that is unusually acidic, meaning that it has elevated levels of hydrogen ions (low pH). Most water, including drinking water, has a neutral pH that exists between 6.5 and 8.5, but acid rain has a pH level lower than this and ranges from 4–5 on average. In ecosystems, persistent acid rain reduces tree bark durability, leaving flora more susceptible to environmental stressors such as drought, heat/cold and pest infestation. Acid rain is also capable of detrimenting soil composition by stripping it of nutrients such as calcium and magnesium which play a role in plant growth and maintaining healthy soil. In terms of human infrastructure, acid rain also causes paint to peel, corrosion of steel structures such as bridges, and weathering of stone buildings and statues as well as having impacts on human health. Some governments, including those in Europe and North America, have made efforts since the 1970s to reduce the release of sulfur dioxide and nitrogen oxide into the atmosphere through air pollution regulations. These efforts have had positive results due to the widespread research on acid rain starting in the 1960s and the publicized information on its harmful effects. The main source of sulfur and nitrogen compounds that result in acid rain are anthropogenic, but nitrogen oxides can also be produced naturally by lightning strikes and sulfur dioxide is produced by volcanic eruptions.

"Acid rain" is a popular term referring to the deposition of a mixture from wet (rain, snow, sleet, fog, cloudwater, and dew) and dry (acidifying particles and gases) acidic components. Distilled water, once carbon dioxide is removed, has a neutral pH of 7. Acid deposition as an environmental issue (discussed later in the article) would include additional acids other than |H2CO3. Occasional pH readings in rain and fog water of well below 2.4 have been reported in industrialized areas. Since the Industrial Revolution, emissions of sulfur dioxide and nitrogen oxides into the atmosphere have increased. In 1852, Robert Angus Smith was the first to show the relationship between acid rain and atmospheric pollution in Manchester, England. Smith coined the term "acid rain" in 1872. In the late 1960s, scientists began widely observing and studying the phenomenon. At first, the main focus in this research lay on local effects of acid rain. Waldemar Christofer Brøgger was the first to acknowledge long distance transportation of pollutants crossing borders from the United Kingdom to Norway – a problem systematically studied by Brynjulf Ottar in the 1970s. Ottar's work was strongly influenced by Swedish soil scientist Svante Odén, who had drawn widespread attention to Europe's acid rain problem in popular newspapers and wrote a landmark paper on the subject in 1968.

The earliest report about acid rain in the United States came from chemical evidence gathered from Hubbard Brook Valley; public awareness of acid rain in the US increased in the 1970s after The New York Times reported on these findings. In 1972, a group of scientists, including Gene Likens, discovered the rain that was deposited at White Mountains of New Hampshire was acidic. The pH of the sample was measured to be 4.03 at Hubbard Brook. The Hubbard Brook Ecosystem Study followed up with a series of research studies that analyzed the environmental effects of acid rain. The alumina from soils neutralized acid rain that mixed with stream water at Hubbard Brook. The result of this research indicated that the chemical reaction between acid rain and aluminium leads to an increasing rate of soil weathering. Experimental research examined the effects of increased acidity in streams on ecological species. In 1980, scientists modified the acidity of Norris Brook, New Hampshire, and observed the change in species' behaviors. There was a decrease in species diversity, an increase in community dominants, and a reduction in the food web complexity. In 1980, the US Congress passed an Acid Deposition Act. This Act established an 18 year assessment and research program under the direction of the National Acidic Precipitation Assessment Program (NAPAP). NAPAP enlarged a network of monitoring sites to determine how acidic precipitation was, seeking to determine long term trends, and established a network for dry deposition. Using a statistically based sampling design, NAPAP quantified the effects of acid rain on a regional basis by targeting research and surveys to identify and quantify the impact of acid precipitation on freshwater and terrestrial ecosystems. NAPAP also assessed the effects of acid rain on historical buildings, monuments, and building materials. It also funded extensive studies on atmospheric processes and potential control programs. From the start, policy advocates from all sides attempted to influence NAPAP activities to support their particular policy advocacy efforts, or to disparage those of their opponents. In 1981, the National Academy of Sciences was looking into research about the controversial issues regarding acid rain. President Ronald Reagan dismissed the issues of acid rain until his personal visit to Canada and confirmed that the Canadian border suffered from the drifting pollution from smokestacks originating in the US Midwest. Reagan honored the agreement to Canadian Prime Minister Pierre Trudeau's enforcement of anti pollution regulation. In 1982, Reagan commissioned William Nierenberg to serve on the National Science Board. Nierenberg selected scientists including Gene Likens to serve on a panel to draft a report on acid rain. In 1983, the panel of scientists came up with a draft report, which concluded that acid rain is a real problem and solutions should be sought. White House Office of Science and Technology Policy reviewed the draft report and sent Fred Singer's suggestions of the report, which cast doubt on the cause of acid rain. The panelists revealed rejections against Singer's positions and submitted the report to Nierenberg in April. In May 1983, the House of Representatives voted against legislation that aimed to control sulfur emissions. There was a debate about whether Nierenberg delayed to release the report. Nierenberg himself denied the saying about his suppression of the report and stated that the report was withheld after the House's vote because it was not ready to be published. In 1991, the US National Acid Precipitation Assessment Program (NAPAP) provided its first assessment of acid rain in the United States. It reported that 5% of New England Lakes were acidic, with sulfates being the most common problem. They noted that 2% of the lakes could no longer support Brook Trout, and 6% of the lakes were unsuitable for the survival of many species of minnow. Subsequent Reports to Congress have documented chemical changes in soil and freshwater ecosystems, nitrogen saturation, decreases in amounts of nutrients in soil, episodic acidification, regional haze, and damage to historical monuments. Meanwhile, in 1990, the US Congress passed a series of amendments to the Clean Air Act. Title IV of these amendments established a cap and trade system designed to control emissions of sulfur dioxide and nitrogen oxides. Both these emissions proved to cause a significant problem on U. S. citizens and their access to healthy clean air. Title IV called for a total reduction of about 10 million tons of SO2 emissions from power plants, close to a 50% reduction. Overall, the program's cap and trade program has been successful in achieving its goals. Since the 1990s, SO2 emissions have dropped 40%, and according to the Pacific Research Institute, acid rain levels have dropped 65% since 1976. Conventional regulation was used in the European Union, which saw a decrease of over 70% in SO2 emissions during the same time period. In 2007, total SO2 emissions were 8.9 million tons, achieving the program's long term goal ahead of the 2010 statutory deadline. In 2007 the EPA estimated that by 2010, the overall costs of complying with the program for businesses and consumers would be $1 billion to $2 billion a year, only one fourth of what was originally predicted. The term citizen science can be traced back as far as January 1989 to a campaign by the Audubon Society to measure acid rain. Scientist Muki Haklay cites in a policy report for the Wilson Center entitled 'Citizen Science and Policy: A European Perspective' a first use of the term 'citizen science' by R. Kerson in the magazine MIT Technology Review from January 1989. Quoting from the Wilson Center report: "The new form of engagement in science received the name "citizen science". The first recorded example of the use of the term is from 1989, describing how 225 volunteers across the US collected rain samples to assist the Audubon Society in an acid rain awareness raising campaign. The volunteers collected samples, checked for acidity, and reported back to the organization. The information was then used to demonstrate the full extent of the phenomenon." In the 1970s and 80s, acid rain was a major topic of research at the Experimental Lakes Area (ELA) in Northwestern Ontario, Canada. Researchers added sulfuric acid to whole lakes in controlled ecosystem experiments to simulate the effects of acid rain. Because its remote conditions allowed for whole ecosystem experiments, research at the ELA showed that the effect of acid rain on fish populations started at concentrations much lower than those observed in laboratory experiments. In the context of a food web, fish populations crashed earlier than when acid rain had direct toxic effects to the fish because the acidity led to crashes in prey populations (e. g. mysids). This research showed both that acidification was linked to declining fish populations and that the effects could be reversed if sulfuric acid emissions decreased, and influenced policy in Canada and the United States. The provinces agreed to limit their combined sulfur dioxide emissions to 2.3 million tonnes by 1994. The Canada US Air Quality Agreement was signed in 1991.

The most important gas which leads to acidification is sulfur dioxide. Emissions of nitrogen oxides which are oxidized to form nitric acid are of increasing importance due to stricter controls on emissions of sulfur compounds. 70 Tg(S) per year in the form of SO2 comes from fossil fuel combustion and industry, 2.8 Tg(S) from wildfires, and 7–8 Tg(S) per year from volcanoes.

The principal natural phenomena that contribute acid producing gases to the atmosphere are emissions from volcanoes. Thus, for example, fumaroles from the Laguna Caliente crater of Poás Volcano create extremely high amounts of acid rain and fog, with acidity as high as a pH of 2, clearing an area of any vegetation and frequently causing irritation to the eyes and lungs of inhabitants in nearby settlements. Acid producing gasses are also created by biological processes that occur on the land, in wetlands, and in the oceans. The major biological source of sulfur compounds is dimethyl sulfide. Nitric acid in rainwater is an important source of fixed nitrogen for plant life, and is also produced by electrical activity in the atmosphere such as lightning. Acidic deposits have been detected in glacial ice thousands of years old in remote parts of the globe. These also include power plants, which use electric power generators that account for a quarter of nitrogen oxides and two thirds of sulfur dioxide within the atmosphere. Industrial acid rain is a substantial problem in China and Russia and areas downwind from them. These areas all burn sulfur containing coal to generate heat and electricity. The problem of acid rain has not only increased with population and industrial growth, but has become more widespread. The use of tall smokestacks to reduce local pollution has contributed to the spread of acid rain by releasing gases into regional atmospheric circulation; dispersal from these taller stacks causes pollutants to be carried farther, causing widespread ecological damage. Often deposition occurs a considerable distance downwind of the emissions, with mountainous regions tending to receive the greatest deposition (because of their higher rainfall). An example of this effect is the low pH of rain which falls in Scandinavia. Regarding low pH and pH imbalances in correlation to acid rain, low levels, or those under the pH value of 7, are considered acidic. Acid rain falls at a pH value of roughly 4, making it harmful to consume for humans. When these low pH levels fall in specific regions, they not only affect the environment but also human health. With acidic pH levels in humans comes hair loss, low urinary pH, severe mineral imbalances, constipation, and many cases of chronic disorders like Fibromyalgia and Basal Carcinoma.

Combustion of fuels produces sulfur dioxide and nitric oxides. They are converted into sulfuric acid and nitric acid.

Acid deposition also occurs via dry deposition in the absence of precipitation. This can be responsible for as much as 20 to 60% of total acid deposition. This occurs when particles and gases stick to the ground, plants or other surfaces. However, the extent to which acid rain contributes directly or indirectly via runoff from the catchment to lake and river acidity (i. e., depending on characteristics of the surrounding watershed) is variable. The United States Environmental Protection Agency's (EPA) website states: "Of the lakes and streams surveyed, acid rain caused acidity in 75% of the acidic lakes and about 50% of the acidic streams". Sulfur dioxide and nitrous oxide concentration has many implication on aquatic ecosystems, including acidity change, increased nitrogen and aluminum content, and altering biogeochemical processes. Typically, sulfur dioxide and nitrous oxide do not have direct physiological effects upon exposure; most effects are developed by accumulation and prolonged exposure of these gases in the environment, modifying soil and water chemistry.

Adverse effects may be indirectly related to acid rain, like the acid's effects on soil (see above) or high concentration of gaseous precursors to acid rain. High altitude forests are especially vulnerable as they are often surrounded by clouds and fog which are more acidic than rain. Plants are capable of adapting to acid rain. On Jinyun Mountain, Chongqing, plant species were seen adapting to new environmental conditions. The affects on the species ranged from being beneficial to detrimental. With natural rainfall or mild acid rainfall, the biochemical and physiological characteristics of plant seedlings were enhanced. Once the pH increases reaches the threshold of 3.5, the acid rain can no longer be beneficial and begins to have negative affects. Acid rain can negatively impact photosynthesis in plant leaves, when leaves are exposed to a lower pH, photosynthesis is impacted due to the decline in chlorophyll. Acid rain also has the ability to cause deformation to leaves at a cellular level, examples include; tissue scaring and changes to the stomatal, epidermis and mesophyll cells. Additional impacts of acid rain includes a decline in cuticle thickness present on the leaf surface. Other plants can also be damaged by acid rain, but the effect on food crops is minimized by the application of lime and fertilizers to replace lost nutrients. In cultivated areas, limestone may also be added to increase the ability of the soil to keep the pH stable, but this tactic is largely unusable in the case of wilderness lands. When calcium is leached from the needles of red spruce, these trees become less cold tolerant and exhibit winter injury and even death. Acid rain may also affect crop productivity by necrosis or changes to soil nutrients, which ultimately prevent plants from reaching maturity.

Acid rain has a much less harmful effect on oceans on a global scale, but it creates an amplified impact in the shallower waters of coastal waters. Acid rain can cause the ocean's pH to fall, known as ocean acidification, making it more difficult for different coastal species to create their exoskeletons that they need to survive. These coastal species link together as part of the ocean's food chain, and without them being a source for other marine life to feed off of, more marine life will die. Coral's limestone skeleton is particularly sensitive to pH decreases, because the calcium carbonate, a core component of the limestone skeleton, dissolves in acidic (low pH) solutions. In addition to acidification, excess nitrogen inputs from the atmosphere promote increased growth of phytoplankton and other marine plants, which, in turn, may cause more frequent harmful algal blooms and eutrophication (the creation of oxygen depleted "dead zones") in some parts of the ocean. The amount of SO3 breath through the mouth is larger than the amount of SO3 breath through the nose. Additionally, OSHA has established a 5 ppm nitrogen dioxide exposure limit for 15 minutes in the workplace. The amount of sulfur dioxide that can be emitted into the atmosphere is capped by the EPA. This reduces the quantity of sulfur dioxide in the air that turns into sulfur trioxide and sulfuric acid.

Places significantly impacted by acid rain around the globe include most of eastern Europe from Poland northward into Scandinavia, the eastern third of the United States, and southeastern Canada. Other affected areas include the southeastern coast of China and Taiwan.

Many coal firing power stations use flue gas desulfurization (FGD) to remove sulfur containing gases from their stack gases. For a typical coal fired power station, FGD will remove 95% or more of the SO2 in the flue gases. An example of FGD is the wet scrubber which is commonly used. A wet scrubber is basically a reaction tower equipped with a fan that extracts hot smoke stack gases from a power plant into the tower. Lime or limestone in slurry form is also injected into the tower to mix with the stack gases and combine with the sulfur dioxide present. The calcium carbonate of the limestone produces pH neutral calcium sulfate that is physically removed from the scrubber. That is, the scrubber turns sulfur pollution into industrial sulfates. In some areas the sulfates are sold to chemical companies as gypsum when the purity of calcium sulfate is high. In others, they are placed in landfill. The effects of acid rain can last for generations, as the effects of pH level change can stimulate the continued leaching of undesirable chemicals into otherwise pristine water sources, killing off vulnerable insect and fish species and blocking efforts to restore native life. Fluidized bed combustion also reduces the amount of sulfur emitted by power production. Vehicle emissions control reduces emissions of nitrogen oxides from motor vehicles.

International treaties on the long range transport of atmospheric pollutants have been agreed upon by western countries for some time now. Beginning in 1979, European countries convened in order to ratify general principles discussed during the UNECE Convention. The purpose was to combat Long Range Transboundary Air Pollution. The 1985 Helsinki Protocol on the Reduction of Sulfur Emissions under the Convention on Long Range Transboundary Air Pollution furthered the results of the convention. Results of the treaty have already come to fruition, as evidenced by an approximate 40 percent drop in particulate matter in North America. The effectiveness of the Convention in combatting acid rain has inspired further acts of international commitment to prevent the proliferation of particulate matter. Canada and the US signed the Air Quality Agreement in 1991. Most European countries and Canada signed the treaties. Activity of the Long Range Transboundary Air Pollution Convention remained dormant after 1999, when 27 countries convened to further reduce the effects of acid rain. In 2000, foreign cooperation to prevent acid rain was sparked in Asia for the first time. Ten diplomats from countries ranging throughout the continent convened to discuss ways to prevent acid rain. Following these discussions, the Acid Deposition Monitoring Network in East Asia (EANET) was established in 2001 as an intergovernmental initiative to provide science based inputs for decision makers and promote international cooperation on acid deposition in East Asia. In 2023, the EANET member countries include Cambodia, China, Indonesia, Japan, Lao PDR, Malaysia, Mongolia, Myanmar, the Philippines, Republic of Korea, Russia, Thailand and Vietnam.

In this regulatory scheme, every current polluting facility is given or may purchase on an open market an emissions allowance for each unit of a designated pollutant it emits. Operators can then install pollution control equipment, and sell portions of their emissions allowances they no longer need for their own operations, thereby recovering some of the capital cost of their investment in such equipment. The intention is to give operators economic incentives to install pollution controls. The first emissions trading market was established in the United States by enactment of the Clean Air Act Amendments of 1990. The overall goal of the Acid Rain Program established by the Act is to achieve significant environmental and public health benefits through reductions in emissions of sulfur dioxide (SO2) and nitrogen oxides (NOx), the primary causes of acid rain. To achieve this goal at the lowest cost to society, the program employs both regulatory and market based approaches for controlling air pollution.