Organic pollution

Organic pollution has been on the rise in the Danube over the last century, as human activities have resulted in increasing loads of wastewater rich in organic matter. The most serious organic pollution problems occur in tributaries that regularly receive untreated or inadequately treated wastewater from industrial plants and municipalities. Organic pollution has been increasing in parts of the Danube Basin up till the end of the last century, as industrial production and household consumption have resulted in increasing loads of wastewater rich in organic matter. Other organic matter of natural origin includes natural soil erosion with a high organic content and the decomposition of dead plants and animals. In terms of organic pollution, water quality in the Danube ranges between Class II (moderate pollution) and Class II-III (moderate to critical pollution) of the interim ICPDR classification. The most serious organic pollution problems occur in tributaries that regularly receive untreated or inadequately treated wastewater from industrial plants and municipalities, such as on the Arges river. Organic pollution is not toxic in small quantities and may even be beneficial to the ecosystem. The problem of organic pollution is therefore one of excess - generally referred to as organic over-enrichment. The impact of the organic pollution will be dependent on factors such as the type of water body, the temperature and many other physical factors which result in the development of low oxygen or anoxic conditions. The impact of organic pollution is reversible and therefore recovery does occur. The water dissolved oxygen levels are necessary for all aerobic systems. Therefore, any wastes that directly or indirectly effect the oxygen concentration are of great importance. Aerobic bacteria utilise the oxygen present within the water to breakdown the organic matter i.e. Fig.1Authors This leads to a reduction of the oxygen content within the water. Generally this oxygen is replaced by O2 from the atmosphere, however since the diffusion of oxygen through water is relatively slow, there is a delay between reduced oxygen levels and its subsequent replacement from the atmosphere. Once the available O2 has been reduced, the aerobic system changes to an anaerobic one. Anaerobic bacteria degrade organic matter during times of limited oxygen via a slower process to produce methane (CH4) and hydrogen sulphide (H2S), compounds that are toxic to many organisms. Therefore the increased bacterial activity which is associated with the presence of excess organic matter can have a severe impact on the organisms that are present.

Many organic wastes are discharged into estuaries, especially those from sewage treatment plants, pulp and paper mills, distillery and brewing and organic chemical plants. In addition estuaries receive much natural organic matter from surrounding emergent vegetation, such as reed beds and salt marshes, as well as that brought down rivers and from the sea. Each of these contribute to high organic matter especially within the turbidity maximum zones in upper reaches of estuaries. The resulting oxygen demand creates low oxygen levels seen as dissolved oxygen sags. Organic matter being deposited and incorporated into estuarine and marine sediments will produce low oxygen levels (hypoxia) or no-oxygen levels (anoxia) in bed sediments. Methanogenic and anaerobic sulphur-reducing bacteria then produce CH4 and H2S. Click on the three different scenarios of the flow diagram to illustrate the sequence of microbially mediated redox reactions found within the sediment. On a wider scale, low oxygen areas develop in waters of restricted exchange and which receive organic and nutrient wastes such as the Baltic. Although there are many possible examples which could be looked at with respect to the affect of organic pollution, only the impact on the migratory species Salmo salar will be look at within the present case study.
Water pollution is classified into harmful substances, suspended solids (SS), organic pollution, and eutrophication. In the 1960s, serious water pollution by discharge of voluminous organic matter and following foul smell occurred in many urban and industrialized areas during the rapid economic growth in Japan (19551973) and other advanced countries(Fig. 1a).. It is known that the limit for the occurrence of a foul smell is under 10 mg O2 L1 biochemical oxygen demand (BOD) in environmental water, although this depends on the relationship with the dissolved oxygen (DO) concentration. In the 1960s, organic pollution was caused primarily by organic matter in domestic and industrial wastewater, which was made worse by delays in the construction of sewerage systems and wastewater treatment facilities. Furthermore, organic pollution was attributed to auxiliary agents used in synthetic detergents used in the 1970s.1 The auxiliary agent made of phosphates was employed to remove calcium ions (Ca2+) and magnesium ions (Mg2+) in tap water, although tap water in Japan is generally softened, unlike that in Europe and the U.S. Consequently, some phosphates remain in the sediments of closed water bodies. To solve the problem of water pollution, the government decreed a Water Quality Pollution Control Act in 1971 and revised the ministerial ordinance in 2006. With the ministerial ordinance, environmental water quality has gradually improved. Currently, organic pollution of environmental water is generally attributed to eutrophication (although surfactants from domestic water might be producing some of the recent organic pollution), especially in closed water bodies, such as lakes, marshes, reservoirs, and enclosed coastal seas (Fig. 1b). Eutrophication is caused by the release of nutritive salts, such as phosphates and nitrates. The nutritive salts are released from effluents after sewage treatment of domestic and industrial wastewater, livestock wastes, and ground water from fertilized agricultural fields. In these anthropogenic runoff sources, the influence of sewage effluents on the environmental water increases day by day due to the increase of the population in urban areas. In addition, these nutritive salts in wastewater cannot be easily removed by current sewage treatment techniques employing a conventional activated sludge method (ca. 50%) or an advanced treatment method (ca. 75%), although most organic material can be removed with the use of both methods.

Incidentally, the minimal concentration of nutritive salts required for the occurrence of water bloom was 0.3 mg L1 nitrogen (N), 0.02 mg L1 phosphorus (P), 0.05 mg L1 sulfur (S), 0.02 mg L1 magnesium (Mg), and 0.002 mg L1 iron (Fe) in 1977;3 i.e., the amount of phosphorus required to induce eutrophication was fifteen times lower than that of nitrogen, although, the ratio is not close to the Redfield ratio in phytoplankton, i.e., C : N : P = 41 : 7 : 1 by mass.4 The phosphorus concentration in flowing water is considered to be an important indicator for estimating the degree of eutrophication,5 and phosphorus is considered as a limiting factor of eutrophication in lakes,6,7 although sunlight is considered to be a limiting factor of ecosystems in oligotrophic lakes.8 In fact, nitrogen is constantly supplied through many kinds of nitrogenfixation microbes, such as cyanobacteria Anabaena sp. from atmospheric nitrogen molecules. Here, cyanobacteria are blue-green algae, which belong to phytoplankton. On the other hand, phosphorus, as soluble phosphates, is not naturally supplied in any great quantity; in other words, it is mostly supplied from anthropogenic sources.9 Thus, it is known that phosphates induce accelerated eutrophication involving aberrant growth of phytoplankton as a biological producer and water bloom is formed on the surface water. The phytoplankton produces an excess of biomass by photosynthesis, involving the fixation of bicarbonate ions from atmospheric carbon dioxide. The aquatic ecosystem then deteriorates, and cyanobacteria as a principal phytoplankton produce cyanobacterial toxins (cyanotoxins), such as the neurotoxin (anatoxin-a from Anabaena sp.)10 and hepatotoxins (cylindrospermopsin from Cylindrospermopsis raciborskii11 and microcystins from Microcystis sp. and Anabaena sp.12). Further, by degradation of the biomass in the water, ill-fitted malodorous substances, such as geosmin (C12H22O, which has an earthy smell) and 2-methylisoborneol (2-MIB; C11H20O), are produced by actinomycetes (Streptomyces sp.) and cyanobacteria (Oscillatoria sp. and Phormidium sp.).13 Furthermore, excessive amounts of phytoplankton can cause death, and decomposed matter produces organic pollution. The fumes emanating from water containing decomposing organic matter are foul and contain mold, making the water not potable. Therefore, water quality in reservoirs and lakes must be carefully controlled to maintain safe supplies of drinking water. In the process of organic pollution, water goes from the oxidation to the reduction state, which leads to anoxia. Harmful heavy metal ions are then dissolved into the water from the sediments. Thus, heavy metal pollution occurs. Such polluted areas are referred to as dead zones . In summary, the causes of recent organic and heavy metal pollution following eutrophication were briefly discussed above. Subsequently, recent biosensing methods for such water pollution are introduced along with our research strategies and experiences with each type of pollution. In reviews, general biosensing methods that include fundamentals and applications were thoroughly summarized by Nakamura and Karube in 2003.14 Other reviews relevant to biosensing methods for environmental monitoring were published by Lelie et al. in 1994,15 Barcelo in 2005,16 and Rogers in 2006.

Introduction to freshwater pollution

Plants and animals cant live without freshwater, because all organisms are made up mostly by water. A tree for example is about 60% water by weight and most animals are about 50-65% water. Also each of us needs huge amounts of water. Where can freshwater be found? Only a tiny fraction of the planets abundant water is available to us as freshwater. About 97.4% by volume is found in the oceans and is too salty for drinking, irrigation, or industry (except as a coolant). Most of the remaining 2.6% water is freshwater and locked up in ice layers or glaciers or its too deep underground to be reached or too salty to be used. Thus, only about 0.014% of the earths total volume of water is easily available to us as soil moisture, usable groundwater, water vapor, and lakes and streams. Freshwater life zones Freshwater life zones occur where water with a dissolved salt concentration of less than 1% by volume accumulates on or flows through the surfaces of terrestrial biomes. Examples are lentic bodies of freshwater like lakes, ponds, and inland wetlands, and lotic systems like streams and rivers. The major components of a freshwater ecosystem are producers (plants with roots and phytoplankton), consumers (zooplankton, fish, and turtles), and decomposers (bacteria and fungi). Their interaction with abiotic components (penetration of light, water currents, dissolved nutrient concentrations, and suspended solids) forms an aquatic ecosystem. The producers supply O2 to the aquatic systems through photosynthesis. This O2 is then used by the producers, consumers and decomposers through aerobic respiration. The CO2 enters an aquatic system from the atmosphere and through aerobic respiration by producers, consumers, and decomposers and its removed by photosynthesizing producers. The concentrations of dissolved O2 and CO2 in water vary greatly with depth because of differences in the photosynthesis and aerobic respiration rates. Freshwater ecosystems and pollution The concentration of dissolved O2 highly depends also on the amount of pollutants, because most water pollutants cause low oxygen levels in freshwater. These pollutants make it difficult for species to live, and many aquatic organisms, especially fish, die when dissolved oxygen levels fall below 5 ppm. There are a few natural sources of pollutants present in aquatic ecosystems. But mostly, freshwater ecosystems may become unbalanced by factors due to human activities. Human activities affect the bioavailability of chemicals to organisms, cause temperature fluctuations, and modify rainfall, pH and salinity. Water plays a key role in diluting pollutants and because of that superiority as a solvent, it also means that water-soluble wastes pollute water easily. For instance, runoff from nearby land provides freshwater life zones with an almost constant input of organic material, inorganic nutrients, and other pollutants. Some 1500 substances have been listed as pollutants in freshwater ecosystems. Here you can find a generalized list of pollutants that occurs in freshwater, and here you can find

more information about toxicity responses and how toxicity is measured. Freshwater species The types of species that could become affected by water pollution in freshwater ecosystems are: -insects -crustaceans -fish -amphibians -arthropods -plants -fungi -bacteria -algae -viruses Insects are usually the most sensitive group, followed by crustaceans, fish and amphibians. Any changes could have harmful or disastrous effects for them. Adverse effects, such as the presence of toxic substances in industrial effluents, may affect many components of the aquatic ecosystem. The extent of which will depend on both biotic and abiotic site-specific characteristics. For more questions about water look at our water questions overview: over one hundred questions on water!

Toxicity to aquatic life

How does the aquatic ecosystem react on pollutants The harmful effects that chemicals have upon individual organisms depend on many different factors. Not only the difference between the freshwater species, but also the form in which pollutants occur, and if the pollutant shows up in lentic or lotic systems. To measure the toxicity there has to get done some toxicity tests. Then there is clarity what the dose is of a chemical that a type of specie will die, which will be expressed in a LC50 or LD50. What can be the toxicity of the different pollutants on aquatic ecosystems? The effects of pollutants on the whole organism are considered under three main headings, namely neurophysiological, behavioural and reproductive effects. These effects can often be inter-related: neurological changes can affect behaviour; changes in behaviour can affect reproduction and so on. A compound doesn't always exert an effect on a target organism or a community. It always depends on the concentration of that compound and the time of exposure to it. These effects eventually can be either acute or chronic. Acute toxicity occurs rapidly, are clearly defined, often fatal and rarely reversible. Chronic effects develop after long exposure to low doses or long after exposure and may ultimately cause death. A poison is lethal when it causes death, or sufficient to cause it, by direct action. And it is sub

lethal when the poison is below the level that directly causes death. Then it results in the regression of the physiological or behavioural processes of the organism, and its overall fitness is reduced. Only in the case of radioactive pollution, it is likely that it will cause irreversible effects at the ecosystem. The effects of pollution on freshwater species are registered in the loss of some species, with maybe some profits for some of them. There normally is a reduction in diversity but not necessarily numbers of individual species, and a change in the balance of such processes as predation, competition and materials cycling. Because of the complexity of pollution, the effects of take-up in the aquatic life are also depended on the pollutants characteristic feature. If two or more poisons are present together in an effluent they may exert a combined effect to an organism, which can be additive, antagonistic or synergistic. An example of an additive interaction is the combined toxicity of zinc and cadmium to fish. Calcium in antagonistic to lead, zinc and aluminium. Copper is more than additive with chlorine, zinc, cadmium and mercury, while its decreases the toxicity of cyanide. The toxicity to the mayfly Baetis rhodani of phenol and ammonia at low concentrations is additive, but at higher concentrations the effect is more than additive. In the following overview, you can see what the fate of wastes in the aquatic environment is and how their community responses. Toxicity testing Aquatic systems reflects perturbations in the environment. So fish and invertebrates can often be used to indicate the health of an aquatic system because chemicals can accumulate in invertebrates from the water and sediment and in fish from water, sediment, and the food chain. The monitoring of these effects is extremely important to regulate and remediate pollution. To test the toxicity, they can apply biomarkers to detect low-level pollution in aquatic systems. First there has to be developed the right biomarkers, and then they can be applied in the Daphnia magna (fig2.) to detect pollution in contaminated groundwater with an aim to develop measures of toxic hazard and risk.

Acids & alkalis in freshwater

Effects of changes in pH on freshwater ecosystems Unpolluted deposition (or rain), in balance with atmospheric carbon dioxide, has a pH of 5.6. Almost everywhere in the world the pH of rain is lower than this. The main pollutants responsible for acid deposition (or acid rain) are sulfur dioxide (SO2) and nitrogen oxides (NOx). Acid deposition influences mainly the pH of freshwater. Nitrogen and sulfuric emissions come from natural and anthropogenic sources. Natural emissions include e.g. volcano emissions, lightning, and microbial processes. Power stations and industrial plants, like the mining and smelting of high-sulfur ores and the combustion of fossil fuels, emit the largest quantities of sulfur and nitrogen oxides and other acidic compounds. These compounds mix with water vapor at unusual proportions to cause acid deposition with a pH of 4.2 to 4.7. That is 10 or more times the acidity of natural deposition.

The acidification of freshwater in an area is dependent on the quantity of calcium carbonate (limestone) in the soil. Limestone can buffer (neutralize) the acidification of freshwater. The effects of acid deposition are much greater on lakes with little buffering capacity. Much of the damage to aquatic life in sensitive areas with this little buffering capacity is a result of acid shock. This is caused by the sudden runoff of large amounts of highly acidic water and aluminium ions into lakes and streams, when snow melts in the spring or after unusually heavy rains. Effects on aquatic life Most freshwater lakes, streams, and ponds have a natural pH in the range of 6 to 8. Acid deposition has many harmful ecological effects when the pH of most aquatic systems falls below 6 and especially below 5. Here are some effects of increased acidity on aquatic systems: - As the pH approaches 5, non-desirable species of plankton and mosses may begin to invade, and populations of fish such as smallmouth bass disappear.

- Below a pH of 5, fish populations begin to disappear, the bottom is covered with undecayed material, and mosses may dominate nearshore areas. - Below a pH of 4.5, the water is essentially devoid of fish. - Aluminium ions (Al3+) attached to minerals in nearby soil can be released into lakes, where they can kill many kinds of fish by stimulating excessive mucus formation. This asphyxiates the fish by clogging their gills. It can also cause chronic stress that may not kill individual fish, but leads to lower body weight and smaller size and makes fish less able to compete for food and habitat. - The most serious chronic effect of increased acidity in surface waters appears to be interference with the fish reproductive cycle. Calcium levels in the female fish may be lowered to the point where she cannot produce eggs or the eggs fail to pass from the ovaries or if fertilized, the eggs and/or larvae develop abnormally (EPA, 1980). See also metals in freshwater. Extreme pH can kill adult fish and invertebrate life directly and can also damage developing juvenile fish. It will strip a fish of its slime coat and high pH level chaps the skin of fish because of its alkalinity. When the pH of freshwater becomes highly alkaline (e.g. 9.6), the effects on fish may include: death, damage to outer surfaces like gills, eyes, and skin and an inability to dispose of metabolic wastes. High pH may also increase the toxicity of other substances. For example, the toxicity of ammonia is ten times more severe at a pH of 8 than it is at pH 7. It is directly toxic to aquatic life when it appears in alkaline conditions. Low concentrations of ammonia are generally permitted for discharge.

Thermal pollution
The problems in freshwater ecosystems caused by heat (thermal pollution) There are various effects on the biology of the ecosystems when heated effluents reach the receiving waters. The species that are intolerant to warm conditions may disappear, while others, rare in unheated water, may thrive so that the structure of the community changes. Thermal pollution can have a great influence on the aquatic ecosystem. Species that are restricted to heated waters, can build up large populations in the receiving waters. Respiration and growth rates may be changed and these may alter the feeding rates of organisms. The reproduction period may be brought forward and development may be speeded up. Parasites and diseases may also be affected. An increase of temperature also means a decrease in oxygen solubility. Any reduction in the oxygen concentration of the water, particularly when organic pollution is also present, may result in the loss of sensitive species. Where does heated water come from? Possibly the most damaging environmental effect of a power station is the many organisms that may be sucked in through the water intake. Larger creatures, such as fish, are killed on the intake screens while smaller species pass through the plant. Even algae may be damaged, with permanent impairment of the photosynthetic mechanism. Liquid water changes temperature

slowly because it can store a large amount of heat without a large change in temperature. This high heat capacity helps protect living organisms from temperature fluctuations, moderates the earths climate and makes water an excellent coolant for car engines, power plants and heatproducing industrial processes. But when water is used in the industry, it is hot and it will be spilled through a discharge pipe into a river. This increase in temperature will reduce the amount of oxygen in the river. That can affect the level of oxygen freely available to organisms, which in turn affects respiration and essentially their way of life. For example, the metabolism rate is largely dependent upon the temperature of an animal's body. Animals display several different types of thermal adaptations to their environment. Two particularly prevalent types include ectotherms and endotherms. In ectotherms (an animal whose body temperature varies with the temperature of its surroundings; any animal except birds and mammals), the body temperature will be low in a cold environment and high in a warm environment. For example, in summer fish may have high metabolic rates because their body temperatures are elevated in the warm water. At the same time they are faced with relatively low oxygen availability because warm water holds less dissolved oxygen than cold water. The interaction of these factors may prove critical. For this reason there is a growing concern among ecologists about the heating of aquatic habitats by effluents from industrial and nuclear generating facilities. Heated water can kill animals and plants that are accustomed to living at lower temperatures.