50 organic pollutants most commonly detected in groundwater [11]
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More than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\\n\\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\\n\\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\\n\\nAdditionally, each book published by IntechOpen contains original content and research findings.
\\n\\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
Simba Information has released its Open Access Book Publishing 2020 - 2024 report and has again identified IntechOpen as the world’s largest Open Access book publisher by title count.
\n\nSimba Information is a leading provider for market intelligence and forecasts in the media and publishing industry. The report, published every year, provides an overview and financial outlook for the global professional e-book publishing market.
\n\nIntechOpen, De Gruyter, and Frontiers are the largest OA book publishers by title count, with IntechOpen coming in at first place with 5,101 OA books published, a good 1,782 titles ahead of the nearest competitor.
\n\nSince the first Open Access Book Publishing report published in 2016, IntechOpen has held the top stop each year.
\n\n\n\nMore than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\n\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\n\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\n\nAdditionally, each book published by IntechOpen contains original content and research findings.
\n\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\n\n\n\n
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This book is a part of a four volume collection (covering material aspects, physical effects, characterization and modeling, and applications) and focuses on the underlying mechanisms of ferroelectric materials, including general ferroelectric effect, piezoelectricity, optical properties, and multiferroic and magnetoelectric devices. 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After working as a post-doctoral fellow in the Center for Intelligent Material Systems and Structures (CIMSS) in Virginia Tech, Blacksburg, VA, USA in 2009, Dr. Lallart has been hired as an Associate Professor in the Laboratoire de Génie Electrique et Ferroélectricité. 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Groundwater is an important part of the water resource. It plays an irreplaceable role in supporting the national economy and social development. In China, more than 1/3 of the total water resources are utilized. As surveys shown, over 400 cities of all exploit groundwater. More seriously, many of them use groundwater as the only source of water supply.
A series of problems emerge gradually with the utilization of groundwater. Just as river waters have been over-used and polluted in many parts of the world, so have groundwater. The organic solvents and dioxins pollution of Love Canal occurred in 1978 is one of the most widely known examples, which contributes high rates of cancer and an alarming number of birth defects. Similar things occur frequently in recent decades. Governance of groundwater is so urgent a major matter of peace and prosperity. After years of researches, the nature and pollution mechanism of the contaminants in the groundwater have already got comprehended.
General scope of the organic contamination in groundwater is reviewed in this chapter. We will detail account the types of groundwater organic contamination, the pollution source of groundwater. and the fate and transport of chemicals in groundwater. Also a detailed description of the investigation and assessment method in this chapter. At last, we give some comments and suggestion on the groundwater investigation and assessment.
The figure 1 described some source of groundwater contamination, and the transport of chemicals in groundwater. We can see the landfills, leaking sewers, oil storage tanks, pesticides and fertilizer, and septic tank in the picture, all of these could be the pollution source of groundwater. We also can know the groundwater transport and flow in the unsaturated zone and saturated zone.
Diagram of the Groundwater Pollution [1].
Many studies have been conducted since 1970 to characterize concentrations of organic compounds in groundwater. In 1977, 16 drinking water wells have been closed in Gray town of Maine state because of there were at least 8 synthetic organics that were detected in drinking water wells. And in 1986, there were at least 33 organics that were detected in drinking water wells in USA [2]. It has been reported trace organic pollutants to be detected in all of 50 states. The U.S. Geological Survey(USGS) collected and assorted the test data the 1926 drinking water wells in the nation\'s rural areas from 1986 to 1999. And at least one VOCs were detected from 232 wells and the positive rate was 12%, with the highest positive rate were Chloroform, tetrachloroethylene and so on [3].
Similar conditions are to be found in other countries. In the 80s of last century, based on an inventory of the presence of halogenated substances in raw water of 232 groundwater pumping stations in The Netherlands a compilation of more than 100 organic substances identified in contaminated groundwater, the detection rate of trichloroethylene up to 67% [4]. The organic pollutants could be detected in groundwater in Britain. Flordward studied on 209 water supply wells in Britain shown that the main pollutant in the groundwater are the trichloroethylene and tetrachloroethylene. Beginning in 1974, Environment Agency of Japan conducted a nationwide comprehensive survey of chemical environmental safety. The trichloroethylene in groundwater was reported for the first time. The European Union is the largest pesticide consumer in the world, more than 600 pesticides were applied. Six of the top 10 were European countries in the pesticide application. Atrazine exists in groundwater all over the Europe, and the content always beyond the European Union drinking water standard(0.1μg/l) 10-100 times.
The research on organic pollutions of China is at starting stage, but there has serious organic contamination events in some areas. Based on a study of water pollution in sewage system in the Gaobeidian Prefecture of Beijing, 1988, organic substances identified in shallow wells and deep wells in South-east agriculture districts in Beijing. And 32 organic substances identified in deep wells, and 52 in shallow wells. Most of that are carcinogens (e.g. Chloroform and benzene) [5]. Analysis of the years groundwater monitoring data, and it is shown that the quality of groundwater is gradually worse.
A study on groundwater organic pollution in region of Beijing, Tianjin and Tangshan conducted by Institute of Chemistry of Chinese Academy of Sciences shows that the type of organic pollutants up to 133 [6]. The researchers Chen Honghan, He Jiangtao and others [7] have summed up the characteristics of organic contamination of shallow groundwater in a study area of the Taihu Lake basin. The results show that the detection probabilities of compounds in groundwater are higher but the concentrations of the compounds are lower. The concentrations of all the components of BTEX and halocarbons are lower than the standards set by the U.S. Environmental Protection Agency (EPA) for drinking water except for benzene in a few sampling sites.
Different types of groundwater contamination sources can pose different threats to human health and different problems in health risk assessment (table 1).
Volatile organic compounds (VOCs) are organic compounds with chemical and physical properties that allow the compounds to move freely between water and air. VOCs have been used extensively in industry, commerce, and households in the United States since the 1940’s. Many products contain VOCs including fuels, solvents, paints, glues, adhesives, deodorizers, refrigerants, and fumigants. In general, these compounds have low molecular weights, high vapor pressures, and low-to-medium water solubilities [8]. Many of these compounds show evidence of animal or human carcinogenicity, mutagenicity, or teratogenicity. And these compounds are quite persistent in groundwater, because of their relatively low biological and chemical reactivity. This persistence is assisted by low temperatures, absence of light and contact with the atmosphere, and comparatively low microbial concentrations typical of groundwater environments. By comparison with other organic compounds, VOCs may be transported for relatively long distances in groundwater, as a result of their relatively weak sorption affinity and their resistance to degradation. Because of human-health concerns, many VOCs have been the focus of national regulations, monitoring, and research during the past 10 to 20 years.
Pesticides consist of a large group of chemicals that are used in agriculture and residential settings to control plant and animal infestation. Pesticides are commonly applied on farms, fruit orchards, golf courses, and residential lawns and gardens. There are several different types of pesticides: Herbicides, Insecticides, Nematocides, Fungicides. Some pesticides do not break down easily in water and can remain in the groundwater for a long period of time. Likewise, the insecticide DDT, though banned for nearly twenty years, can still be found at trace levels in some groundwater. After prolonged exposure to high doses, some pesticides can cause cancer; some can also result in birth defects and damage to the nervous system. The use of pesticides and herbicides is one of the main ways of organic pollution of groundwater. Many water wells and irrigation wells have been closed for the byproducts from pesticides and herbicides be detected in shallow water in Colorado.
\n\t\t\t\tOrdering\n\t\t\t | \n\t\t\t\n\t\t\t\tComponent\n\t\t\t | \n\t\t\t\n\t\t\t\tCASRN\n\t\t\t | \n\t\t\t\n\t\t\t\tTypes\n\t\t\t | \n\t\t
1 | \n\t\t\tTrichloromethane | \n\t\t\t67-66-3 | \n\t\t\tVOCs | \n\t\t
2 | \n\t\t\tTetrachloroethylene | \n\t\t\t127-18-4 | \n\t\t\tVOCs | \n\t\t
3 | \n\t\t\t1,1,1-Trichloroethane | \n\t\t\t71-55-6 | \n\t\t\tVOCs | \n\t\t
4 | \n\t\t\tTrichloroethylene | \n\t\t\t79-01-6 | \n\t\t\tVOCs | \n\t\t
5 | \n\t\t\t1,1-Dichloroethene | \n\t\t\t75-35-4 | \n\t\t\tVOCs | \n\t\t
6 | \n\t\t\tMethyl tert-butyl ether | \n\t\t\t1634-04-4 | \n\t\t\tVOCs | \n\t\t
6* | \n\t\t\tcis-1,2-Dichloroethylene | \n\t\t\t156-59-2 | \n\t\t\tVOCs | \n\t\t
8 | \n\t\t\t1, 2, 4-Trimethylbenzene | \n\t\t\t95-63-6 | \n\t\t\tVOCs | \n\t\t
9 | \n\t\t\tToluene | \n\t\t\t108-88-3 | \n\t\t\tVOCs | \n\t\t
10 | \n\t\t\tPrometon | \n\t\t\t1610-18-0 | \n\t\t\tPesticides | \n\t\t
11 | \n\t\t\t1,1-Dichloroethane | \n\t\t\t75-34-3 | \n\t\t\tVOCs | \n\t\t
12 | \n\t\t\tBromacil | \n\t\t\t314-40-9 | \n\t\t\tPesticides | \n\t\t
13 | \n\t\t\tTebuthiuron | \n\t\t\t34014-18-1 | \n\t\t\tPesticides | \n\t\t
14 | \n\t\t\t1, 3-Dichlorobenzene | \n\t\t\t541-73-1 | \n\t\t\tVOCs | \n\t\t
15 | \n\t\t\t1,2-Dichloropropane | \n\t\t\t78-87-5 | \n\t\t\tVOCs | \n\t\t
16 | \n\t\t\tCarbon disulfide | \n\t\t\t75-15-0 | \n\t\t\tVOCs | \n\t\t
17 | \n\t\t\tDeethylatrazine | \n\t\t\t6190-65-4 | \n\t\t\tPesticides | \n\t\t
17* | \n\t\t\t1,4-Dichlorobenzene | \n\t\t\t106-46-7 | \n\t\t\tVOCs | \n\t\t
19 | \n\t\t\tSulfamethoxazole | \n\t\t\t723-46-6 | \n\t\t\tMedicine | \n\t\t
20* | \n\t\t\t1,2-Dichlorobenzene | \n\t\t\t95-50-1 | \n\t\t\tVOCs | \n\t\t
20 | \n\t\t\t2-Hydroxyatrazine | \n\t\t\t2163-68-0 | \n\t\t\tPesticides | \n\t\t
22* | \n\t\t\tTrichlorofluoromethane | \n\t\t\t75-69-4 | \n\t\t\tVOCs | \n\t\t
22 | \n\t\t\tBentazon | \n\t\t\t25057-89-0 | \n\t\t\tPesticides | \n\t\t
24 | \n\t\t\tAtrazine | \n\t\t\t1912-24-9 | \n\t\t\tPesticides | \n\t\t
25 | \n\t\t\tPicloram | \n\t\t\t1918-2-1 | \n\t\t\tPesticides | \n\t\t
26 | \n\t\t\tDiuron | \n\t\t\t330-54-1 | \n\t\t\tPesticides | \n\t\t
27* | \n\t\t\tBenzene | \n\t\t\t71-43-2 | \n\t\t\tVOCs | \n\t\t
27* | \n\t\t\tTetrachloromethane | \n\t\t\t56-23-5 | \n\t\t\tVOCs | \n\t\t
29 | \n\t\t\tChlorobenzene | \n\t\t\t108-90-7 | \n\t\t\tVOCs | \n\t\t
30* | \n\t\t\t2-Butanone | \n\t\t\t78-93-3 | \n\t\t\tVOCs | \n\t\t
30 | \n\t\t\tAcetone | \n\t\t\t67-64-1 | \n\t\t\tVOCs | \n\t\t
32* | \n\t\t\tm- + p-Xylene | \n\t\t\t106-42-3 | \n\t\t\tVOCs | \n\t\t
32* | \n\t\t\ttrans-1,2-Dichloro- ethylen | \n\t\t\t156-60-5 | \n\t\t\tVOCs | \n\t\t
32* | \n\t\t\t1,2-Dibromoethane | \n\t\t\t106-93-4 | \n\t\t\tVOCs | \n\t\t
35 | \n\t\t\tEthylbenzene | \n\t\t\t100-41-4 | \n\t\t\tVOCs | \n\t\t
36 | \n\t\t\tcaffeine | \n\t\t\t58-08-2 | \n\t\t\tMedicine | \n\t\t
37 | \n\t\t\tIsopropylbenzene | \n\t\t\t98-82-8 | \n\t\t\tVOCs | \n\t\t
38 | \n\t\t\to-Xylene | \n\t\t\t95-47-6 | \n\t\t\tVOCs | \n\t\t
38* | \n\t\t\t1,1,2-Trichloroethane | \n\t\t\t79-00-5 | \n\t\t\tVOCs | \n\t\t
38* | \n\t\t\tBromodichloromethane | \n\t\t\t75-27-4 | \n\t\t\tVOCs | \n\t\t
38* | \n\t\t\t1,1,1,2-Tetrachloroethane | \n\t\t\t630-20-6 | \n\t\t\tVOCs | \n\t\t
38* | \n\t\t\tn-Propylbenzene | \n\t\t\t103-65-1 | \n\t\t\tVOCs | \n\t\t
43 | \n\t\t\tChloromethane | \n\t\t\t74-87-3 | \n\t\t\tVOCs | \n\t\t
44 | \n\t\t\t1,1,2-Trichloro-1,2,2-trifluoroethane | \n\t\t\t76-13-1 | \n\t\t\tVOCs | \n\t\t
45 | \n\t\t\tDichlorodifluoromethane | \n\t\t\t75-71-8 | \n\t\t\tVOCs | \n\t\t
46 | \n\t\t\tMetolachlor | \n\t\t\t51218-45-2 | \n\t\t\tPesticides | \n\t\t
46* | \n\t\t\tSimazine | \n\t\t\t122-34-9 | \n\t\t\tPesticides | \n\t\t
48 | \n\t\t\tBromoform | \n\t\t\t75-25-2 | \n\t\t\tVOCs | \n\t\t
48* | \n\t\t\tImidacloprid | \n\t\t\t138261-41-3 | \n\t\t\tPesticides | \n\t\t
48* | \n\t\t\t1,3,5-Trimethylbenzene | \n\t\t\t108-67-8 | \n\t\t\tVOCs | \n\t\t
50 organic pollutants most commonly detected in groundwater [11]
*show the same detection with the front component. CASRN is the register number of chemical substances formulate by Chemical Abstracts Service, m means meta-position, p means para-position.
Tens of thousands of manmade chemicals are used in today\'s society with all having the potential to enter our water resources. There are a variety of pathways by which these organic contaminants can make their way into the aquatic environment [9]. If the groundwater is the drinking water sources, there will be potentially dangerous on human health. Pharmaceuticals and other organic contaminants are a set of compounds that are receiving an increasing amount of public and scientific attention. Water samples were collected from a network of 47 groundwater sites across 18 states in 2000 [10]. All samples collected were analyzed for 65 organic contaminants representing a wide variety of uses and origins. Thus, sites sampled were not necessarily used as a source of drinking water but provide a variety of geohydrologic environments with potential sources of organic contaminants. organic contaminants were detected in 81% of the sites sampled, with 35 of the 65 organic contaminants being found at least once. The most frequently detected compounds include N,N-diethyltoluamide (35%, insect repellant), bisphenol A (30%, plasticizer), tri(2-chloroethyl) phosphate (30%, fire retardant), sulfamethoxazole (23%, veterinary and human antibiotic), and 4-octylphenol monoethoxylate (19%, detergent metabolite).
Organic contamination includes all of natural and synthetic that could cause adverse effect on human health or ecology environment.
Naturally formed waters such as ocean water and connate brines can be sources of groundwater contamination under certain circumstances. Changes in pumping rates can cause fresh-water aquifers to be contaminated by intrusion of seawater. Similarly, changes in the groundwater flow field or leakage through imperfectly sealed wells can cause contamination of groundwater supply by naturally occurring brines or other poor-quality waters. Generally, trace amount of natural organic compounds existence in groundwater in most of regions. The major is humic acid, especially in forest and grassland. Although itself could not impair the groundwater quality, it could be enhance the heavy metal and other organic matters activities in groundwater.
As the human population grows, groundwater pollution from human activity also increases. There are a number of possible sources that could lead to groundwater contamination. Such as crude oil leakage in oil production, organic waste discharge, spills and leaks from underground storage tank and so on.
The treatment and disposal of sewage present health risks in both developed and undeveloped countries. In undeveloped countries, sewage may be directly applied to the land surface. In more developed areas, sewage is generally transported to municipal treatment plants or disposed of in septic tanks and cesspools. Groundwater contamination can result in all these cases. Sewage provides a source of pathogens, nitrates, and a variety of organic chemicals to groundwater. Land application of sewage can provide a direct contaminant source via infiltration. Treatment plants can act as contaminant sources in several ways. Leaks may occur in sewer lines and infiltration may occur from the ponds and lagoons within the treatment plants. In addition, the sewage sludge that is a product of sewage treatment processes is often disposed on land in conjunction with agricultural activity. Depending on the characteristics of the sludge, the soil characteristics, and the application process, such land application can act as a large non-point source of groundwater contamination. Land disposal of treated waste water can pose comparable risks. Depending on hydrogeologic conditions, septic tanks and cesspools may allow untreated sewage to enter the groundwater flow system. In addition, use of solvents to clean out the systems can cause groundwater contamination by synthetic organic compounds. The material cleaned out from septic tanks must eventually be disposed of, often by land application.
Industrial Wastewaters are applied to land in ponds or lagoons that are either designed to percolate the liquid into the soil or to store and/or evaporate the liquid above ground. In either case, such facilities act as potential groundwater contamination sources. Facilities designed to intentionally infiltrate into the ground include cooling ponds for power generation and for other industrial processes. The liquids in such facilities may contain potentially hazardous materials. Storage and evaporation ponds are often lined to prevent infiltration, but are likely to act as groundwater contamination sources under some circumstances, depending on surface runoff characteristics, the integrity and permeable of the liner(s), and the groundwater flow system. Poorly designed evaporation ponds may, in many cases, function as infiltration ponds.
In the United States, the big city and small town are commonly found in contaminated groundwater. An test on 39 groundwater supply in small towns conducted by the U.S. EPA, it reported that 11 VOCs could be detected in treated or untreated groundwater [12].
Land disposal of solid waste is the groundwater contamination source of most current concern to the general public in many developed countries and of most current regulatory interest.
Solid waste can be disposed in landfills, facilities engineered to safely contain the waste. While landfills may often prevent exposure of solid waste at the land surface, many landfills provide a direct connection with groundwater. In the past, landfill siting was based on the availability of inexpensive, undeveloped land requiring little modification for waste disposal, rather than on hydrogeologic suitability. Disposed materials often are very susceptible to leaching into groundwater.
Landfills may be grouped according to the type of materials they contain. Municipal landfills accept only non-hazardous materials, but are still likely to contain materials which pose potential health risks. Industrial landfills may contain either "hazardous" or "non-hazardous" materials. Until recently, little was known about how they were operated or what they contained. Open dumps and abandoned disposal sites generally have no engineering design. Their connection with the groundwater system and the type of materials present is often unknown. It is often in abandoned disposal sites that large volumes of highly toxic materials are found. The most hazardous solid waste disposal generally results from industrial and manufacturing activities as well as some governmental energy and defense activities. Populations of both developed and developing countries, where there is current or historical industrial activity, face potential health risks from solid waste disposal. It is reported that there will be the highest content and most types of organic contaminants in groundwater which is near the landfills. If there has 1 kilometers distance it still exist in the groundwater [13].
In recent years, there has been increasing awareness of the large number of potentially leaking underground storage gasoline tanks. For much of the twentieth century, underground storage tanks were constructed of unprotected carbon steel. Corrosion causes leaks in such tanks over some period of time, ranging from a few years to tens of years. Although the leakage from individual tanks is often small, it is often enough to contaminate a large volume of groundwater. In addition, the large number of buried tanks-several million in the United States-makes them a potentially significant groundwater contamination source. Above ground storage tanks pose less of a threat than underground tanks. Leak detection and maintenance is easier and the connection with the groundwater system is less direct. However leaks from such tanks may still act as groundwater contamination sources.
Numerous agricultural activities can result in non-point sources of groundwater contamination. Fertilizers, pesticides, and herbicides are applied as part of common agricultural practice throughout the world. These applications can act as sources of contamination to groundwater supplies serving large populations. Whether or not fertilizers, pesticides, and herbicides become sources of groundwater contamination depends on changing hydrogeologic conditions, application methods, and biochemical processes in the soil. In developing countries, animal and/or human waste is used for fertilizer. This is an example of the land application of sewage discussed earlier. There are the same concerns with pathogens and nitrates. The manufactured inorganic fertilizers widely used in developed countries, and finding increasing usage in all countries, also pose the threat of nitrate contamination of groundwater systems. Pesticide and herbicide application provides a source of numerous toxic organic chemicals to groundwater supplies.
Even without the introduction of fertilizers, pesticides, and herbicides, irrigation activities can lead to groundwater contamination. Naturally occurring minerals in the soil can be leached at higher rates leading to hazardous concentration levels in the groundwater. Evaporation of irrigation water can cause evaporative concentration of certain chemicals in the root zone. Flushing of these chemicals can then lead to hazardous concentration levels in groundwater.
Agricultural activities related to animals also can be groundwater contamination sources. These include the feeding of animals and the storage and disposal of their waste. Animal wastes and feedlot runoff are commonly collected in some sort of pit or tank creating the contamination threat described earlier for sewage disposal.
More than 300 pesticides were applied in Asia. The Japan is a country with the largest amount of pesticide on unit area cultivated land. Indonesia, Korea, India and China are the major consumers. But, there did not have pesticides routine monitoring in the developing countries in Asia [14].
Groundwater is but one component of the hydrologie cycle. Groundwater quality is very much influenced by surface-water conditions and vice versa. Contamination of any surface water bodies that recharge the groundwater system is a source of groundwater contamination. This includes "natural" recharge sources such as lakes and rivers as well as "man-made" recharge sources such as artificial recharge ponds/injection wells and infiltration of urban runoff. More generally, it is important to consider the interaction of all environmental sources and pathways of pollution. Environmental contaminant sources cannot be divided into separate, isolated compartments. For example, atmospheric pollution can lead to deposition of hazardous fallout to surface waters and to soils, and eventually lead to groundwater contamination.
Volatilization occurs in whether the vadose zone or saturated zone when the dissolved contaminants and non-aqueous phase contaminants exposed to gas. The factors affecting volatilization include solubility of the compound, molecular weight and water-saturated state of the geological media. The evaporation rate must be measured fundamentally in order to determine pollutions transporting into the atmosphere, changes of the pollution load in the vadose zone and groundwater. The process that the contaminants of deep soil volatilize to the atmosphere can be assumed as one-dimensional diffusion, which can be described with Fick\'s second law. Volatilization of the water-soluble organic matter, such as benzene dissolved in water is generally described by Henry\'s Law [15].
Adsorption in Soil and sediment makes an important influence on the behavior of organic pollutants. The mobility and biological toxicity reduced as organics are detained in the soil and sediment. Generally, adsorption is affected by sediments and soil properties, such as organic percentage, the type and quantity of clay minerals, cation exchange, pH and the physical and chemical properties of the contaminants. During the adsorption, the organic contaminants in the water adsorbed on the surface of the soil particles by the simultaneous distribution role of both water and solid, the driving force is mainly based on principle of "like dissolves like" and electrostatic adsorption of the polar group, and the following formulas is established [15]:
The equation (1) is existed when the adsorption systems reach equilibrium. Where, Csa is the amount of organic pollutants adsorbed per unit weight of soil particles; Cwa is concentration of organic pollutants; Ka is the total sorption coefficient.
The adsorption of organic contaminants in soil or sediment usually described by Ka (soil absorption coefficient) or Koc (organic carbon absorption coefficient). The former refers to the ratio of the concentration of organic matter in the soil or sediment and its aqueous phase concentration. As well, the latter factor represents the ratio of the concentration of organic matter adsorbed by organic carbon in the soil or sediment and its aqueous phase concentration.
Microorganisms may play an important role in contamination transformations within groundwater and on the soil. They can act as catalysts for many types of reactions. When modeling biochemical reactions in groundwater, additional processes must be considered. These include the changes in the availability of substrate for the microorganisms to utilize and reactions on the particles that the microorganisms are attached to. When microbial reactions are significant, there is a possibility of clogging of pores due to precipitation reactions or to biomass accumulation [16].
Microorganisms not only influence chemical reactions, but may be contaminants themselves. There is much current uncertainty about the fate and survival time of viruses, bacteria, and larger enteric organisms in groundwater [17-18]. Distribution of microorganisms will vary greatly with depth. Potential outbreaks of waterborne diseases due to biologic pollutants are of particular concern where there is land disposal of human waste (often via septic tanks) and animal waste. The potential for transmittal of waterborne diseases in groundwater is particularly high in areas of rapid velocities such as karst regions.
Biodegradation mainly depends on two factors [19], the intrinsic characteristics of the pollutants (the structure of organics, physical and chemical properties) and microorganism (the activity of microbial populations), and the environmental factors controlling the reaction rate (temperature, pH, humidity, dissolved oxygen). As the U.S. Environmental Protection Agency researched [20], soil microbial degradation of organic pollutants can be expressed as a one-order response equation:
Where, C is the mass fraction of soil organic matter[mg/g]; X is the number of active microbial in the organic matter of soil degradation[106 /g]; t is degradation time[d]; K is the one-order biodegradation rate constant [g/(d 106)]; kr is substrate removal constant[d-1].
From the above equation,
Substituted into with half-life formula,
The half-life of degradation of residual contamination is determined.
In many cases, the receptor medium for release of a contaminant will be the unsaturated zone. In contrast to the saturated zone, pores in the unsaturated zone are not completely saturated with liquid. This fundamentally affects the processes governing flow and chemical transport. A number of processes will affect the contaminant within the unsaturated zone before it enters the saturated groundwater system and potentially is tapped by supply wells. The uncertainties in characterizing releases just described lead to uncertainties in defining the source terms and initial and boundary conditions for modeling unsaturated transport. Analogously, uncertainties in characterizing unsaturated transport processes lead to uncertainties in defining the source terms and initial and boundary conditions for modeling saturated transport.
For the most part, computer simulation of contaminant transport has focused on movement in the saturated zone. Assumptions are made regarding the time required for movement through the unsaturated zone. Often some sort of lag between source release and entry of chemicals into the saturated flow system is introduced into source terms. It is important to be aware of the unsaturated processes that are actually occurring, the uncertainty associated with these processes, and the role of monitoring in reducing these uncertainties.
Once a chemical has been released into the ground and has either moved through the unsaturated zone or directly entered the saturated zone, saturated transport processes will determine if, how fast, and at what concentration a chemical reaches a supply well. A great deal of research has been carried out on understanding and modeling these processes. There is increasing recognition that chemical transport must be viewed as a stochastic process.
The same elements of uncertainty are present for saturated transport as for unsaturated transport. The important differences are that in saturated transport, water content equals porosity, hydraulic conductivity is no longer a function of water content or head, gravity rather than suction head is the driving force, and the scale of concern may be much larger
The current situation investigation main contents are as following:
Pollution source investigation: In groundwater polluted areas, investigate the non-point-source, line-source and point-source, and the type, pollution intensity, spatial distribution of natural source.
Investigation of unsaturated zone vulnerability: Investigate the unsaturated zone of thickness, lithological composition, composition, water permeability, the capability of degradation contaminations and so on.
Investigation of the pollution condition at the groundwater: Make sure the category, quantity or concentration of the pollutants, ascertain the pollution range, variation trend and the factors relation. All of these need samples collection in filed and laboratory test.
With the developed, groundwater pollution attracted wide attention. In view of existing situation, we launched the survey of pollution sources, including the following aspects: industrial pollution sources, domestic pollution sources, agricultural pollution sources and surface polluted waters.
According to industrial pollution sources, we must investigate the situation as: the company name, position, sewage, waste residue (tailings) emissions, discharge, scale, pathways and outfall location, types of pollutants, quantity, composition and hazards, and the abandoned site of major polluting enterprises, abandoned wells, oil and survey of solvents and other underground storage facilities.
The survey include the distribution of dumps, scale, waste disposal methods and effects, the generation of dump leaching filtrate and components, geological structure of storage site; amount of sewage generated, treatment and disposal of the way, main pollutants and their concentration and hazards
Agricultural pollution sources investigation mainly include land use history and current situation, the varieties, numbers, operations, time of farmland application of chemical fertilizers and pesticides, range of sewage irrigation, main pollutants and concentration, the number of sewage irrigation and sewage irrigation amount. The scale of farms and so on.
The surface polluted waters mainly about rivers, lakes, ponds, reservoirs and drains. We survey the distribution of polluted waters, the scales, the utilizations and water quality.
The coastal areas have to survey the situation of seawater invasion and saline water distribution.
The four steps of NAS was proposed by National Academy of Sciences, United States(NAS), was an assessment method on human health risk that led by the accident, air, water, soil and other medium. The method mainly in the following aspects: the hazard identification (qualitative evaluation the degree of hazards of the chemical substances on the human health and ecological); dose-response assessment (quantitative assessment the toxicity of chemical substances, established a relationship between the dose of chemical substances and the human health hazard); exposure assessment (quantitative or qualitative estimate or calculate the exposure, exposure frequency, exposure duration and exposure mode); exposure attribute (using the data to estimate the strength of the health hazards in the different conditions or the probability of the certain health effects). This method can qualitative analysis or quantitative analysis of groundwater contamination, or combine them, the results could be quantify and analysis, and provide more detailed information to the decision-makers.
In 1989, U.S. Environmental Protection Agency (EPA) promulgated the “risk assessment guidance for superfund: Human health evaluation manual”, there was a similar assessment method to NAS method [22]. The steps following as data collection, exposure assessment, toxicity assessment, risk characterization. Contrast the two methods, NAS is more common methods, the use range wider, suitable for a variety of health risk assessment; the EPA method is more specific, it emphasis on the various parameters of the collection of contaminated sites, for the evaluation of contaminated sites, it more operational.
The MMSOILS model is multi-media model which describe the groundwater, surface water, soil and air in the migration of chemicals, exposure and food chain accumulation [23]. Contaminate sites is multi-phase, multi-media complex. The model including the migration and transformation of pollutants module and human exposure module. Migration and transformation module include: (1)atmospheric transport pathway; (2)soil erosion; (3)groundwater migration pathway; (4)surface water pathway; (5)food chain bioaccumulation. Human exposure are: (1)adopt from drinking water, animals and plants and soil; (2)atmospheric volatiles and particulate inhalation; (3)soil, surface water and groundwater contact with skin. The model could be simulate a comprehensive migration pathway and widely used in foreign countries, and the parameters could be analysis the uncertainty.
The DRASTIC method is a national standards system that developed by US EPA to evaluation aquifer vulnerability. It including: Depth to Water(D); Net Recharge(R); Aquifer media(A); Soil Media(S); Topography(T); Impact of the Unsaturated Zone Media(I); Conductivity of Aquifer Hydraulic(C). Assignment of each element from 1 to 10, and them proportional to the degree of vulnerability of groundwater. At the same time, each element is assigned a weight, the weight should be reflect the sensitivity of groundwater. The model can objectively assess the groundwater vulnerability of different areas, and its assumption that all regions of the aquifer has a uniform trend. But all the geological, hydrogeological and other conditions are different, and the model calculations defect, the DRASTIC method has some limitations.
An important step in health risk assessment is the quantification of actual human exposure. Exposure can be expressed as either the total quantity of a substance that comes in contact with the human system or the rate at which a quantity of material comes in contact with the human system (mass per time or mass per time per unit body weight. The exposure assessment evaluates the type and magnitude of exposures to chemicals of potential concern at a site. The exposure assessment considers the source from which a chemical is released to the environment, the pathways by which chemicals are transported through the environmental medium, and the routes by which individuals are exposed. Parameters necessary to quantitatively evaluate dermal exposures, such as permeability coefficients, soil absorption factors, body surface area exposed, and soil adherence factors are developed in the exposure assessment. Exposure to chemicals in water can occur via direct ingestion, inhalation of vapors, or dermal absorption. Ingestion includes drinking of fluids as well as using water for rinsing and cooking of foods. Dermal absorption includes swimming and bathing.
Determination of average exposure levels for a particular population is quite difficult. This is due to difficulties in acquiring sufficient water-quality data, in identifying the exposed individuals, and in quantifying the concentrations in the different exposure pathways. For a given groundwater contamination problem, the U.S. Environmental Protection Agency stresses the importance of identifying both the currently affected population as well as possible changes in future land use. Subpopulations that may be especially sensitive to exposure should also be identified [24].
When attempting to estimate exposure to larger population entire countries, for example other concerns arise. Cothern [25] computed the average population exposure to volatile organic compounds in the United States, based on data from several thousand ground- and surface-water supplies. National exposure was estimated as a straight extrapolation of the concentration intervals from the original data. Best- and worst-case assumptions were applied for handling the "below detectable" category. Crouch et al. [26] applied an alternative approach to estimate population exposure levels. Rather than estimating a distribution for exposure, they made the worst-case assumption that individuals are exposed to water at the maximum measured concentration for their water supply.
According to the Risk Assessment Guidance for Superfund Volume I: Human Health Evaluation Manual (Part E, Supplemental Guidance for Dermal Risk Assessment) (U.S. EPA) [27], we calculation the dermal absorbed dose (DAD) and ingestion absorbed dose (IAD) [28].
Where:
DAD=Dermally Absorbed Dose (mg/kg-day),
DAevent=Absorbed dose per event (mg/cm2-event),
SA=Skin surface area available for contact (cm2),
EV=Event frequency (events/day),
EF=Exposure frequency (days/year),
ED=Exposure duration (years),
BW=Body weight (kg),
AT=Averaging time (days).
Where:
IAD= Ingestion absorbed dose (mg/kg-day),
ρ= Pollutant concentration in groundwater (mg/L),
U=Drinking amount per days (L/d),
EF=Exposure frequency (days/year),
ED=Exposure duration (years),
BW=Body weight (kg),
AT=Averaging time (days).
The DAD and IAD can be represent with continuous ingestion dose (CDI).
Based on the carcinogenesis of contamination, the risk could be classified into cancer risk and noncancer hazard.
Noncancer hazard: Generally, the reaction of the body to non-carcinogenic substance has a dose threshold.
Lower than the threshold, they could not affect our health adversely. The non-carcinogenic risk to represent with hazard index (HI). It is defined as a ratio that continuous ingestion dose with reference dose [28].
Where: CDI= continuous ingestion dose (mg/kg-days), RfD= reference dose (mg/kg-days).
Cancer risk: There does not have dose threshold for the carcinogenic. Once it exist in environments, it will affect human health adversely. Cancer risk will be represent with risk. It is defined as a product of continuous ingestion dose with carcinogenesis slope factor.
(If the low dose exposure risk>0.01)
Where: SF= carcinogenesis slope factor (mg-1•kg•d)
When calculating the risk of a variety of substances in a variety of ways, figure out all non-cancer risk and cancer risk respectively, then add all risks together. Regardless of synergistic effect and antagonistic effect.
Groundwater treatment technologies are mainly as follows: pump and treat, air sparging, in-situ groundwater bioremediation and in-situ reactive walls.
Pump and treat is the most common form of groundwater remediation. It is often associated with treatment technologies such as Air Stripping and Liquid-phase Granular Activated Charcoal.
Pump and treat involves pumping out contaminated groundwater with the use of a submersible or vacuum pump, and allowing the extracted groundwater to be purified by slowly proceeding through a series of vessels that contain materials designed to adsorb the contaminants from the groundwater. For petroleum-contaminated sites this material is usually activated carbon in granular form. Chemical reagents such as flocculants followed by sand filters may also be used to decrease the contamination of groundwater. Air stripping is a method that can be effective for volatile pollutants such as BTEX compounds found in gasoline.
For most biodegradable materials like BTEX, MTBE and most hydrocarbons, bioreactors can be used to clean the contaminated water to non-detectable levels. With fluidized bed bioreactors it is possible to achieve very low discharge concentrations which will meet or exceed discharge standards for most pollutants.
Depending on geology and soil type, pump and treat may be a good method to quickly reduce high concentrations of pollutants. It is more difficult to reach sufficiently low concentrations to satisfy remediation standards, due to the equilibrium of absorption (chemistry)/desorption processes in the soil.
At the figure 2, we can know how does pump and treat technology work. This system usually consists of one or more wells equipped with pumps. When the pumps are turned on, they pull the polluted groundwater into the wells and up to the surface. At the surface, the water goes into a holding tank and then on to a treatment system, where it is cleaned [29].
Pump and Treat Technology [29]
Air sparging is an in situ groundwater remediation technology that involves the injection of a gas (usually air/oxygen) under pressure into a well installed into the saturated zone. Air sparging technology extends the applicability of soil vapor extraction to saturated soils and groundwater through physical removal of volatilized groundwater contaminants and enhanced biodegradation in the saturated and unsaturated zones. Oxygen injected below the water table volatilizes contaminants that are dissolved in groundwater, existing as a separate aqueous phase, and/or sobbed onto saturated soil particles. The volatilized contaminants migrate upward in the vadose zone, where they are removed, and generally using soil vapor extraction techniques. This process of moving dissolved and non-aqueous volatile organic compounds (VOCs), originally located below the water table, into the unsaturated zone has been likened to an in situ, saturated zone, air stripping system. In addition to this air stripping process, air sparging also promotes biodegradation by increasing oxygen concentrations in the subsurface, stimulating aerobic biodegradation in the saturated and unsaturated zones(figure 3).
Air Sparging [31]
In-situ groundwater bioremediation is a technology that encourages growth and reproduction of indigenous microorganisms to enhance biodegradation of organic constituents in the saturated zone. In-situ groundwater bioremediation can effectively degrade organic constituents which are dissolved in groundwater and adsorbed onto the aquifer matrix.
In-situ groundwater bioremediation can be effective for the full range of petroleum hydrocarbons. While there are some notable exceptions (e.g., MTBE) the short-chain, low-molecular-weight, more water soluble constituents are degraded more rapidly and to lower residual levels than are long-chain, high-molecular-weight, less soluble constituents. Recoverable free product should be removed from the subsurface prior to operation of the in-situ groundwater bioremediation system. This will mitigate the major source of contaminants as well as reduce the potential for smearing or spreading high concentrations of contaminants.
In-situ bioremediation of groundwater can be combined with other saturated zone remedial technologies (e.g., air sparging) and unsaturated zone remedial operations (e.g., soil vapor extraction, bioventing).
Bioremediation generally requires a mechanism for stimulating and maintaining the activity of these microorganisms. This mechanism is usually a delivery system for providing one or more of the following: An electron acceptor (oxygen, nitrate); nutrients (nitrogen, phosphorus); and an energy source (carbon). Generally, electron acceptors and nutrients are the two most critical components of any delivery system.
In a typical in-situ bioremediation system, groundwater is extracted using one or more wells and, if necessary, treated to remove residual dissolved constituents. The treated groundwater is then mixed with an electron acceptor and nutrients, and other constituents if required, and re-injected upgradient of or within the contaminant source. Infiltration galleries or injection wells may be used to re-inject treated water. In an ideal configuration, a "closed-loop" system would be established. All water extracted would be re-injected without treatment and all remediation would occur in situ. This ideal system would continually recirculate the water until cleanup levels had been achieved. If your state does not allow re-injection of extracted groundwater, it may be feasible to mix the electron acceptor and nutrients with fresh water instead. Extracted water that is not re-injected must be discharged, typically to surface water or to publicly owned treatment works (POTW).
In-situ reactive walls are an emerging technology that have been evaluated, developed, and implemented only within the last few years. This technology is gaining widespread attention due to the increasing recognition of the limitations of pump and treat systems, and the ability to implement various treatment processes that have historically only been used in above-ground systems in an in situ environment. This technology is also known in the remediation industry as “funnel and gate systems” or “treatment walls”.
The concept of in-situ reactive walls involves the installation of impermeable barriers downgrading of the contaminated groundwater plume and hydraulic manipulation of impacted groundwater to be directed through porous reactive gates installed within the impermeable barrier. Treatment processes designed specifically to treat the target contaminants can be implemented in these reactive or treatment gates. Treated groundwater follows its natural course after exiting the treatment gates. The flow through the treatment gates is driven by natural groundwater gradients, and hence these systems are often referred to as passive treatment walls. If a groundwater plume is relatively narrow, a permeable reactive trench can be installed across the full width of the plume, and thus preclude the necessity for installation of impermeable barriers.
In-situ reactive walls eliminate or at least minimize the need for mechanical systems, thereby reducing the long-term operation and maintenance costs that so often drive up the life cycle costs of many remediation projects. In addition, groundwater monitoring and system compliance issues can be streamlined for even greater cost savings.
Bioventing, also a modification of vapor extraction technology, is briefly contrasted with air sparging. With bioventing, extraction or injection of air into the vadose zone increases subsurface oxygen concentration, promoting bioremediation of unsaturated soil contaminants. This technique is applicable to all biodegradable contaminants, but has been applied most frequently and reportedly most successfully to sites with petroleum hydrocarbon contamination
The past 40 years, groundwater subjected to pollution, it cannot be ignored that there has a serious threat to human health and ecological security problems. The research on groundwater pollution risk assessment will help understand the relationship between the soil conditions and groundwater pollution, identify the high-risk regions of groundwater pollution, provide a powerful tools for the land use and groundwater resource management, and help the policy maker and managers to develop effective management strategies and protection measures on groundwater. So we can offer some suggestions as following:
Continue to strengthen the research on the fate and transport in hydrogeological conditions. Hydrogeological conditions of the contaminated sites have a vital role in organic pollution of groundwater. We should pay attention to the impact that the thickness of the unsaturated zone, the aquifer lithology of unsaturated zone and groundwater, the groundwater runoff conditions on the organic pollution investigation and contaminated aquifer restoration. Unsaturated zone is the only avenue for the organic pollutant into the groundwater system. In the protection of groundwater quality, we should take impact of the physical, chemical, and biological characteristics of the unsaturated zone soil on the transport and degradation of organic pollutants into consideration.
In the future research, the natural attenuation of typical organic contamination in groundwater should be reinforce research, especially the organic degradation mechanism of microbes.
In recent years, the environmental hormone pollution research and prevention has begun to attract the attention of the world. Environmental hormone research has become the forefront and hot topic of environmental science research. But the mechanism of environmental hormone is not clearly, we should take more attention on these.
The research on groundwater pollution risk assessment to be carried out on the typical regions. To provide practical experience on established an reasonable and feasible groundwater pollution risk assessment system.
Exerting governmental function adequately and improving the laws, regulations and norms on groundwater quality monitor and assessment. Strengthening the cross-disciplinary exchanges and studies and establishing the groundwater pollution monitor network and the chemical toxicological database.
With entering a new era of environmental protection, the research of groundwater pollution risk assessment is bound to make new contributions to human survival and to protect and improve the natural environment, and to advance the theory research of environmental science.
This study is granted by the Specific Research on Public Service of Environmental Protection in China (No. 201009009). The authors appreciate the tutor and classmates for help.
Menstrual cycle lasts 28 ± 7 days. Just a third of patients have cycles every 28 days and 82% fluctuations among 22 and 32 days [1].
\nA cycle is known as regular when the frequency has a variation of no more than 2 days. The lasting of each cycle is calculated since the first day of menstruation until the previous day of next menstruation. The cycle frequency is regulated by the hypothalamus-pituitary-gonadal axis; hormones such as follicle stimulating hormone (FSH) and luteinizing hormone (LH) must reach their effectors at the ovarian level where a dominant follicle must be recruited and developed, secrete estradiol, in enough amounts to obtain endometrial receptivity but also participating directly in a feedback-regulated control of the cycle.
\nCycles show more irregularity in the extremes of the reproductive lifespan, during the first 2 years from the menarche and during the perimenopausal transition. The ovarian cycle has two stages separated by ovulation, the first, from the beginning of the cycle to ovulation, is called the follicular or proliferative phase. The second, between ovulation and the next menstruation, is called the luteal phase or secretory phase.
\nThe follicular phase is characterized by the maturation of the follicle containing an ovule and a retinue of follicular cells, which are responsible for transforming androstenedione into estradiol, which in turn is released and, among many other actions, stimulates endometrial renewal.
\nThe luteal phase, named because the follicular cavity that left the ovule after hatching, is transformed into a corpus luteum and continues to produce estrogen, but it also releases important amounts of progesterone. The luteal phase is preceded by a significant increase in LH, and ovulation marks its onset; then, it lasts ±14 fairly constant days when comparing different women. During this phase, the average total body temperature of women is constantly 0.5°C higher than in the follicular phase.
\nIf there is no embryo implantation, the endometrium is detached giving rise to menstrual flow, which has normal volume parameters, up to 80 mL, in duration, 3–8 days, content, absence of clots and symptoms, and absence of pain.
\nIt is considered that the conserved cyclicity expresses that the hypothalamic-pituitary-gonadal axis is healthy. The ovaries do not alternate to ovulate.
\nOvarian reserve: it corresponds to the number of follicles that a woman has and it is defined during fetal life and then the number of follicles goes slowing down gradually.
\nWhen is born, each woman counts with a fixed number of ova, which are getting lost with the past of years (atresia) Delaying maternity is nonrecommendable, since at higher age the risk of not having ovum of a good quality at the moment when a pregnancy is planned.
\nIn a woman fertility, among 38–40 years is lower than at 25–30 years. Atresia of oocytes is a continuous process that never stops not even with the use of anovulatory or pregnancy.
\nOocyte atresia:it is the mechanism of follicular apoptosis that seems to contribute to the selection of optimal ovules. During the early fetal stage, about 7,000,000 oocytes are formed in the ovary. Before birth, the ovular reserve has been reduced to one-third by mechanisms of apoptosis (programmed death).
\nAt birth, only 1–2 million oocytes remain in the ovary and during puberty, there are usually 300,000 available for eventual ovulation. In fact, they will only ovulate between 400 and 500 throughout the lifespan. Then, through the female reproductive life, between the periods of puberty and menopause, about 250,000 follicles will be destined to die, reaching less than 1000 during perimenopause (Figure 1).
\nThe number of oocytes in any woman comes defined at the moment of birth and slow down inevitably during her life during her life from 1 to 2 million at the moment of birth at 300,000 to go decreasing through her life 25,000 at 37–38 years and near 500 during the postmenopause.
Sex steroids—estrogens and progesterone: Estrogens are steroid hormones produced by the granulosa follicle, the corpus luteum, and the placenta (if there is pregnancy). Its synthesis comes from cholesterol molecules. Progesterone is synthetized by corpus luteum and placenta, if there is pregnancy.
\nOf the estrogens, the most potent is estradiol. The actions they develop are:
Female genital apparatus: they stimulate the growth and development of the female sexual organs and the proliferation of the endometrium during the sexual cycle.
Breast: they favor the growth of the mammary ducts and are, in part, responsible for the development of the mammary gland during puberty.
Bone: they regulate the osteoclastic activity and stimulate the osteoblastic activity, in such a way that they are essential to maintain adequate bone mineralization.
Cardiometabolic: estrogen relaxes the smooth muscle of arterioles, increases HDL cholesterol, and lowers LDL cholesterol, which has been associated with the lower incidence of cardiovascular disease that women have in relation to men, especially before menopause.
Progesterone is also a steroid hormone. It is responsible for the progestational changes of the endometrium. On the breasts, progesterone stimulates the development of the lobes, being its action complementary to that of the estrogens. Progesterone is thermogenic and contributes to the increase in basal temperature experienced by some women after ovulation.
\nFollicular phase begins the very first day of menstruation. The development of ovarian follicles, named folliculogenesis, begins at the last days of menstrual cycle before the release of mature follicle during ovulation (Figure 2).
\nThe menstrual cycle has two phases, follicular phase and luteal phase. The follicular phase begins with menstruation. The follicle stimulating hormone (FSH) increases released by the anterior pituitary gland and stimulates follicular growth and estradiol production. The 17 beta-estradiol produced by the follicles exerts negative feedback on the FSH. Estradiol continues to increase due to the growth of the dominant follicle. The LH increases sharply to trigger ovulation. Immediately after ovulation, the luteal phase begins. The corpus luteum produces progesterone and 17 beta-estradiol concentrations of progesterone and estradiol decrease, menstruation begins a new cycle, unless a pregnancy has been established.
When a pregnancy did not occur, the release of inhibin A and sex steroids are reduced by the end of the functional period of the corpus luteum. Both falls contribute to reduce the release of FSH by feedback at the central level, which is dependent on pulsatility of hypothalamic GnRH. This is how FSH increases during the last days of the menstrual cycle (Figures 3 and 4) [2].
\nDynamic scheme of follicular activity and the changes in gonadotropins, steroids, and inhibins during follicular phase of menstrual cycle.
The level of inhibin changes through menstrual cycle. Inhibin B dominates follicular phase during the cycle while inhibin A dominates luteal phase.
The progressive elevation of FSH allows many follicles to be recruited simultaneously. Nevertheless, only some persist, in such a way that an approximate 99% of the cycles, only a dominant follicle will be destined to ovulate, during the next menstrual cycle.
\nThe remaining 1% has codominance, that is two dominant follicles, which eventually can generate a double ovulation at the risk of a multiple pregnancy.
\nIn women from 19 to 42 years, follicular phase has an average duration of 14.6 days, however, to be precise on each woman in what step of the cycle she is very difficult because of the following reasons:
Duration of menstrual cycle is very changing, even among young women of similar ages, with variations described from 25 to 34 days.
Changes that normally occur during the fertile lifespan, between the menarche to menopause. Some women may have long and irregular cycles, many times associated to abundant uterine bleeding, at the first 2 years after to menarche and 4–6 years that precede menopause.
Besides there is a wide range of presentation for both phases of the cycle, the follicular phase may last from 10 to 23 days and luteal phases could last between 7 and 19 days. Only 10% of women with a cycle of 28 days shows follicular and luteal phase of 14 days. The variability depends more on follicular phase, which vary ±3–7 days with time, depending on the estrogen take off (ETO), at the beginning of the middle follicular phase on each cycle, which is the main explanation for the duration of cycles.
Finally, despite of normal length in their cycles, 7% of women of 25–39 years may show anovulation, even though is more frequent to observe shorter cycles or longer ones, especially in early postmenarche and premenopause (60% between 10 and 14 years and 34% older than 50 years) as seen in Figure 5.
Other environmental, ethnic, or even socioeconomic factors may affect the duration of the cycle and bleeding.
Menstrual cycle lasting variation according to age. Graphic shows the average lasting of the cycle and the range (percentiles 95 and 5) yrs. = years, d = days. Triangles indicate the group of age in the percentage of women with more than14 days of variation of a cycle during a year. From Mihm et al. [3].
At the development of dominant follicle (DF), three steps have been described namely, recruiting, selection, and dominance (Figure 6). Recruiting stage is developed during the days 1–4 of menstrual cycle.
\nTime lapse of recruiting, selection, and ovulation of dominant follicle (DF) with the beginning of atresia in the other follicles of the group. Adapted from Hodgen [4].
During the follicular phase, FSH is responsible for recruitment among those follicles that remain available. Between days 5 and 7 of the cycle, follicular selection normally occurs, to allow only one follicle, the dominant follicle (FD) to ovulate and the rest to experience atresia. Anti-müllerian hormone (AMH), which is secreted in the granular layer, also participates in the selection of FD. On day 8 of the cycle, the FD promotes its own growth, suppressing the maturation of the other ovarian follicles.
\nDuring the follicular phase, estradiol plasma levels are higher along with the growth of the number of granulosa cells and the growth of the DF. FSH receptors are found exclusively in the cell membrane of granulosa cells. The increase in FSH during the late luteal phase induces its own FSH receptors and eventually increases the secretion of estradiol by the granulosa cells by transforming androstenedione, which diffuses from the theca cells (Figure 7).
\nDiameter of dominant follicle (DF) days prior to LH peak and plasma concentration of estradiol per follicle diameter (curved lines are 95th and 5th percentiles). Adapted from Macklon and Fauser [5].
It is important to point out that the increase in the numbers of receptors of FSH is due to an increase in the population of granulosa cells and not to an increase of the concentration of receptors of FSH on them. Each granulosa cell has 1500 receptors of FSH at secondary stage of follicular development, and the number of receptors of FSH stays constant during the rest of DF growing.
\nThe increase in estradiol secretion also upregulates their own receptors, increasing the total of estradiol receptors (ER) in the granulosa cells. On the other hand, in the presence of estradiol, FSH stimulates the formation of LH receptors in the same cells, which allows the secretion of small amounts of progesterone and 17-hydroxyprogesterone (17 OHP) that would exert positive feedback on the pituitary gland. Already sensitized by the increase of estrogen, thus allowing the release of luteinizing hormone (LH) and achieve its peak. FSH also stimulates many steroidogenic enzymes such as aromatase and 3β-hydroxysteroid dehydrogenase (3β-HSD).
\nThere are other signaling pathways that impact the differentiation of theca cells, not only LH but also insulin-like 3 (INSL3) that appear to modulate LH-mediated androgen biosynthesis and increased follicle cell apoptosis and luteal regression, bone morphogenetic proteins (BMPs) produced by granulosa cells, and/or oocytes who antagonized the effects of LH and INSL3, the circadian clock genes, androgens, and estrogens and (2) theca-associated vascular, immune and fibroblast cells, as well as the cytokines and matrix factors that play key roles in follicle growth [6].
\nAt Table 1, production rates are presented for sexual steroids during follicular phase, luteal phase at the moment of ovulation.
\nSex steroids* | \nEarly follicular | \nPreovulatory | \nMid-luteal | \n
---|---|---|---|
Progesterone (mg) | \n1 | \n4 | \n25 | \n
17α-Hydroxyprogesterone (mg) | \n0.5 | \n4 | \n4 | \n
17α-Hydroxyprogesterone (mg) | \n7 | \n7 | \n7 | \n
Androstenedione (mg) | \n2.6 | \n4.7 | \n3.4 | \n
Testosterone (μg) | \n144 | \n171 | \n126 | \n
Estrone (μg) | \n50 | \n350 | \n250 | \n
Estradiol (μg) | \n36 | \n380 | \n250 | \n
Production rate of sex steroids in women at different stages of the menstrual cycle.
Values are expressed in milligrams or micrograms per 24 hours.
From Baird and Fraser [7].
Differently from granulose cells, LH receptors are localized at theca cells during all of the stages of menstrual cycle. LH receptors stimulates granuloma’s cells. LH stimulates the production of androstenedione and at a lesser level the production of testosterone at the theca cells.
\nAndrostenedione is then transported to the cells of granulosa where it is aromatized, and finally, it becomes estradiol 17-β-hydroxysteroid dehydrogenase type I. This is known as the hypothesis of two cells and two gonadotropins of the regulation of synthesis on the ovary (Figure 8).
\nTwo cells and two gonadotropins, on the regulation and the synthesis of estrogens at the ovary. From: Doshi and Agarwal [8].
The normal follicular phase has been divided in two stages: (a) early and (b) middle and (c) late, to allow a better comprehension of the endocrine events that will be finally responsible of ovulation.
\nEarly follicular phase (days 1–4): it begins with the first day of menstruation. Follicular recruitment occurs due to the elevation of FSH, as a consequence of the decrease in estradiol, progesterone, and inhibin A released by the corpus luteum of the previous cycle, allowing the number of LH receptors to increase in the cells of the teak and the granulosa. The plasma levels of estradiol tend to remain low at this stage (Figure 1).
\nMedium follicular phase (days 5–7): as the recruitment and growth of follicles induced by FSH progress, estradiol increases slowly in a progressive manner thanks to the increased activity of CYP19, an FSH-dependent aromatase that is present in granulosa cells. The follicle that achieves the highest number of FSH receptors may aromatize more estradiol and become the dominant follicle. The other follicles, with fewer receptors for FSH, suffer atresia. For estrogen synthesis, it is necessary for the thecal cells to produce androgens, under the stimulus of LH, and for these to diffuse to the granulosa cells. Simultaneously, two glycoproteins, activin and inhibin, are produced in the theca and granulose, with local actions. Inhibin B exerts a negative hypophyseal feedback effect, where it potentiates the effect of estradiol and inhibits the synthesis and release of FSH [9, 10]. This would be a mechanism to achieve dominance giving an advantage to the follicle that has greater development. The estrogen take-off (ETO) marks the successful establishment of the dominance of a follicle.
\nThe FD develops its internal theca and increases receptivity to LH, which stimulates the production of androgens by degrading molecules of cholesterol to progesterone and from this to dehydroepiandrosterone, androstenedione, and testosterone.
\nAt the end of this phase, the granulosa-theca complex of the FD has almost complete functionality to enter the late follicular phase.
\nLate follicular phase (days 8–12): this period is characterized by the elevation of estrogens that come from the DF, reaching its maximum values between 40 and 50 hours, before an elevation of FSH that precedes the ovulatory peak of LH. This preovulatory follicle reaches an average diameter of 15–20 mm.
\nThe moment of greatest likelihood of successful fertilization is intercourse on the day before ovulation. However, the potentially fertile period, which depends on sperm survival, can extend from 5 days before ovulation. Those pregnancies that have been obtained after day 14, are associated with later ovulation, a normal variability in the duration of the follicular phase depending on the time of the ETO.
\nIt is believed that cycles of 30–31 days and 5 days of bleeding would have a higher probability of pregnancy [11], perhaps due to better quality of the DF, good function of the corpus luteum and optimal endometrial receptivity. The moment of the fertile window is quite variable. It has been reported that a significant number of women with regular menstrual cycles can be in their fertile window before day 10 or after day 17, of their menstrual cycle [12]. However, it seems that the possibility of pregnancy is low when the cycles are short, less than 25 days [13].
\nIn clinical practice, to determine the fertility potential of a given cycle, indirect methods are used, which require observing at least one of the three primary signs of fertility (basal body temperature, cervical mucus and position of the cervix), known as methods based on symptoms.
\nThere are kits to detect the increase in LH, which occurs 24–36 hours before ovulation named ovulation predictor kits (OPK). Those urine-based ovulation test kits are available in versions standard OPKs, digital OPKs or advanced digital OPKs, but some saliva-based ovulation tests are available also.
\nComputerized devices that interpret basal body temperature, urinary test results, or changes in saliva are called fertility monitors, and there are different types: urine-based fertility monitors, perspiration-based fertility monitors and saliva-based fertility monitors.
\nIn the monitoring of assisted fertility procedures, effective follicular follow-up with ultrasonography is preferred.
\nIn infertility treatments, ovulation inducers are used that increase endogenous levels of FSH or eleven therapeutically by administering FSH parenterally, which manages to rescue multiple follicles from atresia. So, this patient has a higher risk of multiple ovulation. It is interesting to note that when rescuing follicles from atresia, the follicular endowment remains the same, so that follicles will not be depleted in an accelerated manner.
\nAt born, woman count with primordial follicles (PF), each surrounded by one layer of cells of granulosa and are detained at the pro phase of the first meiotic division.
\nDuring adolescence, the woman has antral follicles that depend on FSH. On average, this follicle takes 14 days to mature to preovulatory FD. They are derived from a recruitment process that is independent of FSH and is mainly regulated by the anti-müllerian hormone (AMH), which is produced by the granulosa cells of the follicles in early development and inhibits the transition from the primordial to the primary follicular stage [14]. AMH levels can be measured in serum and used to measure the follicular reserve (Figures 9and10).
\nAMH is involved in the paracrine control of recruitment in the first stage, when the process is still independent of gonadotropins. AMH can not only reflect the number of early antral follicles in the process of development, but also those in earlier stages. Adapted from Ref. [1].
Clinical witnesses of the follicular development in stage pre- and postdependence of FSH: AMH and ultrasound, respectively. Adapted from Ref. [15].
Primordial follicles (PF) are independent of FSH. Their average life is 60–65 days, then they are transformed in to preantral follicles (PAF), also independent of FSH, and are surrounded by many layers of granulosa’s cells and also by theca cells. In this process, many primordial follicles suffer atresia (Figure 11).
\nFollicular dynamics and illustration of folliculogenesis process.
Due to the presence of 5α-reductase, the early preantral and antral follicles produce more androstenedione and testosterone compared to the estrogen rate. 5α-reductase is the enzyme responsible for converting testosterone to dihydrotestosterone (DHT). Once testosterone has been reduced by 5α, DHT cannot be aromatized.
\nWith the increase in age in women, the involution of granulosa cells decreases the levels of inhibin production. Because of this, when a woman approaches menopause her FSH levels become higher, a sign that her ovarian reserve has decreased. On the other hand, the perimenopausal follicles are of the worst quality, half have chromosomal alterations.
\nAs mentioned, the development of the preantral follicle is independent of FSH, so any follicle that grows beyond this point will require an interaction.
\nSecretion of gonadotropin is regulated by the releasing hormone of gonadotropin (GnRH), steroidal hormones, and diverse peptides released by dominant follicle.
\nAmong substances that can be found al follicular liquid there are steroids, pituitary hormones, plasmatic proteins, proteoglycans, and ovarian factors nonsteroidal, which regulate the micro environment of the ovary and the steroidogenesis of the granulosa.
\nFactors of growing such as the insulin growth factors 1 and 2 (IGF1, IGF2) and the epidermal growth factor (EGF) would have an important role at the development and maturity of oocytes. Concentration of ovarian steroids is higher at follicular liquid compared to plasmatic concentrations.
\nThere are two population of antral follicles: big follicles, which measure more than 6 mm diameter, and little follicles, less than 8 mm. In big follicles, concentrations of FSH are higher. Estrogen and progesterone are higher as well, while prolactin concentration is lower. Inside little follicles, prolactin and androgen levels are higher in comparison to big antral follicles.
\nIn addition, as mentioned, FSH increases during the early follicular phase and then begins to decrease until the ovulation phase, except in the short preovulatory peak. In contrast, LH is low in the early follicular phase and begins to increase in the middle follicular phase due to positive feedback of increasing levels of estrogen.
\nTo achieve positive feedback of LH release, plasma estradiol should be greater than 200 pg/ml, for at least 48 hours. The gonadotropins are secreted in a pulsatile manner in the anterior pituitary, with a frequency and widening of pulses that change according to the phase of the menstrual cycle (Figure 12).
\nPulses of LH throughout a normal cycle. Number of pulses per 24 h decreases, but total daily secretion and LH half-life are stable. The intersecretory burst interval becomes longer as the cycle progresses, being very long in the luteal phase, whereas the pulse amplitude of LH shows a dichotomous behavior, with small and high waves. Adapted from data of Sollenberger et al. [16].
During early follicular phase, secretion of LH occurs to a frequency of pulse from 60 to 90 minutes with a widening of pulse constant but variations on number of pulses intersecretory burst interval and pulse amplitude [16]. During late follicular phase, previous to ovulation, frequency of pulse increases and widening may be beginning to increase. Most of women have widening of pulse of LH beginning to increase after ovulation.
\nOnce menstruation is produced, levels of FSH begin to decrease due to negative retro alimentation on inhibin B produced by developing follicle.
\nHatching occurs 10–12 hours after peak of LH (Figure 8). Augmentation of LH is generated by significative raising of estradiol, with levels between 200 and 450 pg/mL, produced at the preovulatory follicle.
\nThe critical concentration of estradiol needed to initiate positive feedback requires that the dominant follicle reach a size >15 mm in diameter. The increase in LH occurs 34–36 hours before ovulation and is a very reliable predictor of ovulation (Figure 9). This increase in LH is responsible for the luteinization of granulosa cells that stimulates the synthesis of progesterone and also estradiol. In addition, the LH increase resumes the second meiotic division and the chromosomal reduction in the oocyte with the release of the first polar corpuscle.
\nEstradiol levels decrease abruptly immediately before peak of LH. This can be due to regulation to down of LH from its own receptor or due to direct inhibition of estradiol synthesis because of progesterone.
\nProgesterone also participates in the stimulation of the increase in FSH in the middle of the cycle (Figure 13).
\nIncrease of LH precedes ovulation in 36 hours. Peak, on the other side, precedes ovulation in 10–12 hours.
This increase in FSH would produce the release of oocytes from their follicular junctions, to stimulate the plasminogen activator and increase the LH receptors in the granulosa. The exact mechanism responsible for the post ovulatory fall is unknown.
\nDecrease in LH would occur as the consequence of the loss of positive retro alimentation of estrogens the inhibitory retro alimentation of progesterone (Figure 14).
\nChanges in ovarian gonadotropins and steroids in the middle of the cycle, just before ovulation. The beginning of the increase of LH is at time. 0 time. Abs: E2, estrogen; P, progesterone. Adapted from Hoff et al. [17].
It takes 36 hours from the peak of estrogen until ovulation occurs. The time to ovulation measured from the peak of LH is 12 hours; considering the time of detection in urine, ovulation will take place at 24 hours since LH is measured in the urine. The hormone hCG is similar to LH and can be used as an exogenous hormone to trigger ovulation, which will occur 36 hours after administration.
\nDuring the ovulatory period, progesterone and prostaglandins are secreted inside the follicle, as well as proteolytic enzymes. This results in digestion and rupture of the follicular wall allowing hatching, commonly called ovulation [18].
\nProteolytic enzymes and prostaglandins are activated in response to LH and progesterone and digest collagen in the follicular wall, which leads to an explosive release of the cumulus-oocyte complex. Prostaglandins can also stimulate the release of oocytes, stimulating the smooth muscle within the ovary.
\nThe point of the dominant follicle closest to the ovarian surface where the rupture occurs is called a “stigma.”
\nAll the mechanisms are still not elucidated. The concentrations of prostaglandins E and F and hydroxyeicosatetraenoic acid (HETE) reach a maximum level at the follicular level just before ovulation.
\nProstaglandins stimulate proteolytic enzymes, whereas HETE stimulates angiogenesis and hyperemia. The use of high doses of prostaglandin inhibitors could hinder the follicular rupture, causing what is known as luteinized unruptured follicle syndrome, and can be observed in fertile and infertile women.
\nConsequently, it should be recommended to women in search of pregnancy and especially that with fertility problems, avoid the intake of inhibitors of prostaglandin synthesis, and inhibitors of cyclooxygenase (COX), in fact, are being investigated as an alternative to morning after pill in emergency contraception [19, 20].
\nFor ovulation to occur, a series of complex molecular mechanisms that commence after the gonadotrophin surge must be given. These include intracellular signaling, gene regulation, and remodeling of tissue structure in each of the distinct ovarian compartments, which can be summarized in (a) ovulatory mediators that exert effects through the cumulus cell complex, (b) convergence of ovulatory signals through the cumulus complex co-ordinates the mechanistic processes that control oocyte maturation and ovulation, and (c) other multiple inputs, including endocrine hormones, immune and metabolic signals, as well as intrafollicular paracrine factors from the theca, mural and cumulus granulosa cells, and the oocyte itself. Therefore, healthy and meiotically competent oocytes and the coordination and synchronization of endocrine, paracrine, immune, and metabolic signals acting mainly through the cumulus compartment exert control on oocyte maturation, developmental, and ovulation process [21].
\nMechanisms suggested implied in follicle rupture [22] are shown in Figure 15.
\nProposed mechanisms at follicular rupture. LH stimulates the expression of genes in granulosa cells (PR, PGS-2) that control the activation of matrix metalloproteinases (MMPs), leading to the breakdown and remodeling of extracellular matrices and the surface epithelium to allow rupture of the follicle and extrusion of the oocyte (ovulation). Modified from Richards et al. [22].
This phase lasts 14 days in most women after ovulation. The granulosa cells that are not released with the oocyte acquire a vacuolated appearance and a characteristic yellow color due to the concentration of a carotenoid called lutein and the incorporation of fat drops. No other function has been described for lutein than being a powerful antioxidant.
\nThe luteinized cells combine with the newly formed theca-lutein cells together with the surrounding stroma; thus, originates the transitory endocrine organ that secretes progesterone, known as the corpus luteum, whose main function is to prepare the endometrium, already proliferated by the action of follicular phase estrogens, for the implantation of the fertilized egg.
\nThe endometrium expresses adhesion molecules that make it receptive to the blastocyst and between days 7 and 9 from ovulation, a period of maximum efficiency known as the window of implantation is established; after day 9, implantation is not possible, which is why it is called the refractory phase.
\nEight or nine days after ovulation, at the time when implantation is expected, maximum vascularization is reached, the basal lamina dissolves, and the capillaries invade the granulosa cell layers in response to the secretion of angiogenic factors, both from the granulosa and from the theca cells, in harmony with the maximum levels of plasma progesterone and estradiol.
\nThe survival of the corpus luteum depends on the continuous stimulation of LH, but estradiol metabolites, acting via paracrine-autocrine pathways, affect angiogenesis or LH-mediated events also [23].
\nThe function of the corpus luteum decreases at the end of the luteal phase unless chorionic gonadotropin appears due to an eventual pregnancy. If pregnancy does not occur, the corpus luteum undergoes luteolysis. Under the action of estradiol and prostaglandins, it forms a scar tissue called corpus albicans [24].
\nAs noted, estrogen levels increase and decrease twice during the menstrual cycle, increase during the middle follicular phase, and then decrease rapidly after ovulation, followed by a further increase during the middle luteal phase, in parallel with the increase in serum levels of progesterone and 17α-hydroxyprogesterone, all falling at the end of the menstrual cycle (Figure 1).
\nThe mechanism of how the corpus luteum regulates steroid secretion is not known exactly. It may be determined in part by the pattern of LH secretion, changes in its receptor, or variations in the levels of enzymes that regulate the production of steroid hormones. The amount of granulosa cells formed during the follicular phase and the levels of LDL cholesterol that surround it may also play a role in the regulation of steroid synthesis by the corpus luteum.
\nThere are at least two types of luteal cells, large and small.
\nBoth produce progesterone but with differences. Large cells come from granulosa, are more active in steroidogenesis, produce large amounts of progesterone, and although they have numerous LH receptors, they do not elevate progesterone secretion in response to LH or cAMP. Instead, they possess receptors for PGF2a and respond to this hormone with activation of at least two second messengers. Activation of protein kinase C (PKC) decreases progesterone’s secretion.
\nAs a result of the binding of PGF2a to its receptor, the concentration of free intracellular calcium increases, which seems to be related to the induction of apoptosis and cell death.
\nThe large cells are influenced by other autocrine and paracrine factors, such as inhibin, relaxin, and oxytocin (Figure 16). The small cells are derived from the theca, contain receptors for LH, and respond to LH or cAMP by increasing the secretion of progesterone by 5–15 times [25, 26].
\nRegulation of small luteal cells (left) and large (right). In small luteal cells, the binding of LH to its receptor activates the second messenger protein kinase A (PKA) pathway, which stimulates the synthesis of progesterone. In large cells, the LH that binds to its receptor does not increase the intracellular concentrations of cAMP nor the synthesis of progesterone, but the binding of PGF2a to its receptor activates PKC, which inhibits the synthesis of progesterone and causes an influx of calcium that leads to cell degeneration. AC: adenylate cyclase, DAG: diacylglycerol, IP3: inositol 1,4,5-trisphosphate, PIP2: phosphatidylinositol 4,5-bisphosphate, and PLC: phospholipase C. From Niswender [25].
The synthesis of progesterone by the corpus luteum is essential for the establishment and maintenance of pregnancy.
\nIn addition to luteinization, that is, the conversion of an ovulatory follicle into the corpus luteum and luteal regression to allow a new cycle, there are also mechanisms of luteal maintenance and rescue to sustain pregnancy.
\nHumans preferably use circulating LDL cholesterol for steroidogenesis although the corpus luteum has the ability to synthesize its own cholesterol, in smaller amounts [27].
\nInside the cells, lipid steroid precursors are found as free cholesterol. There is also esterified cholesterol that accumulates within the rough endoplasmic reticulum and as cytoplasmic lipid droplets or lipoprotein particles. These fatty acid esters of cholesterol cannot replace free cholesterol as a structural ingredient of the plasma membrane nor serve as direct substrates for the production of steroids. They are hydrolyzed by a neutral cholesterol ester hydrolase (NCEH), also known as hormone-sensitive lipase, because their activity is tightly regulated in steroidogenic tissues by FSH, LH, and hCG.
\nProgesterone secretion and estradiol during luteal phase is tightly connected with the pulses of secretion of LH (Figure 12). The frequency and widening of secretion of LH during follicular phase regulates the function of the posterior luteal phase and is concordant with the function of LH during luteal phase.
\nThe frequency and widening of the pulses of secretion of pituitary LH affect the secretion of progesterone and estradiol during the luteal phase (Figure 12).
\nThe half-life of the corpus luteum can be reduced with the continuous administration of LH during any of the phases, follicular or luteal, as if the LH concentration is lower or its pulses are reduced.
\nThe luteal phase can suffer shortening also if the levels of FSH are inadequate or low, during the follicular phase, conditioning the development of a smaller corpus luteum.
\nThe function of the corpus luteum begins to decrease 9–11 days after ovulation. The mechanism by which the corpus luteum undergoes involution (luteolysis) is partially elucidated. Prostaglandin F2α would have a luteolytic action, through the synthesis of endothelin-1 that inhibits steroidogenesis and stimulates the release of a growth factor, the tumor necrosis factor alpha (TNFα) oxytocin, and vasopressin and would produce a luteotropic effect through an autocrine/paracrine mechanism.
\nThe ability of LH to negatively regulate its own receptor may also play a role at the end of the luteal phase; thereby, the involution of the corpus luteum must be caused by a decrease in the sensitivity of the LH receptors, rather than by a pulsatile secretion of it. Finally, the matrix metalloproteinases would also play a role in luteolysis and, therefore, in the fall of progesterone levels.
\nIn the absence of pregnancy, the levels of progesterone and estradiol begin to decrease as a result of the corpus luteum decreasing. The fall of progesterone increases in degree of coiling and the constriction of the spiraled arterioles. This finally produces tissue ischemia due to decreased blood flow from the superficial, spongy, and compact endometrial layers. After the fall of serum concentrations of ovarian steroids, matrix metalloproteinases play a key role in the onset of menstrual bleeding in the human endometrium, by inducing the degradation of the extracellular matrix of this mucosa [28]. Endometrial prostaglandins cause contractions of the uterine smooth muscle and detachment of degraded tissue.
\nThe release of prostaglandins may appear due to instability of the lysosomal membranes in the endometrial cells. The magnitude of this effect is such that inhibitors of prostaglandin synthesis can be used as a therapy in women with excessive uterine bleeding. Menstrual flow is composed of detachment of endometrial tissue, red blood cells, inflammatory exudates, and proteolytic enzymes.
\nTwo days after the start of menstruation and while the shedding of the endometrium still occurs, the estrogen produced by the new growing follicles begins to stimulate the regeneration of the superficial layers of the endometrium. The estrogen secreted by the growing follicles causes a long constriction of the vessel facilitating the formation of a veil over the denuded endometrial vessels.
\nThe average duration of menstruation is 4–6 days, but the normal range can be 2–8 days. As mentioned above, the average amount of bleeding loss is 30 ml and more than 80 ml is considered abnormal. A few years ago, a classification has been generalized to describe the abnormalities of bleeding suggested by the International Federation of Gynecology and Obstetrics [29].
\nThe characteristics of the endometrium in gynecological ultrasound change depending on the period of the menstrual cycle, presenting different thicknesses according to the stage of the menstrual cycle (Figure 17).
\nThe main substrate for human steroidogenesis is LDL cholesterol: it is incorporated by endocytosis and stored as free cholesterol or as ester. Esterified cholesterol is hydrolyzed cholesterol esterases (CE) and transported as free cholesterol to the mitochondria. It passes from the outer mitochondrial membrane to the internal membrane, with the concurrence of the steroidogenic acute regulatory protein (StAR), peripheral type benzodiazepine receptors and endozepine. In mitochondria, cholesterol is converted to pregnenolone by cytochrome P450scc, which is transported out of the mitochondria and converted to progesterone by 3b-hydroxysteroid dehydrogenase, D5, D4 isomerase (3b-HSD), which is present in the smooth endoplasmic reticulum (The cell nucleus is not shown.).
Endometrium type 0, postmenstrual: it is characterized because only a fine refractive line can be seen. It is the endometrium typical of postmenopause, postpartum, or after a uterine scraping. Most postmenopausal women are between 3 and 5 mm thick, but it is normal up to 8 mm if there has been no unexpected bleeding.
\nEndometrium type 1, preovulatory: trilaminar endometrium, refers to the observation of three refractive lines. This stage corresponds to the proliferative or estrogenic phase. In an early follicular stage, the size of the endometrium is between 3 and 4 mm thick, while in the stage close to ovulation, it can reach 9–11 mm.
\nEndometrium type 2, postovulatory: in this stage, the progesterone matures the already proliferated endometrium, especially in its glandular and vascular structures, thickening the endometrium. The ultrasound image becomes whiter to the extent that it contains more water and glycogen. This layer of refringency represents most of the endometrium toward the end of the luteal phase.
\nEndometrium type 3, premenstrual: in this stage, there is only one large refractive line and corresponds to the late secretory phase.
\nWhen the gonadal axis has reached maturity, the neurons of the preoptic area and the infundibular and arcuate nuclei in the hypothalamus secrete GnRh in a pulsatile fashion, every 60–90 minutes, to the pituitary portal system.
\nFrequency and amplitude are essential to produce and maintain the effect on the gonadotropic cells of the anterior part of the pituitary gland, which consists of releasing both LH and FSH. The secreted amounts of each will depend not only on the pulsatility of GnRH, but also on the positive and negative feedbacks mechanisms of sex steroids.
\nIn general, estrogen sensitizes and counter-regulates FSH, at both levels, the hypothalamus and the adenohypophysis, selectively modulated by other factors such as inhibins A and B. LH is sensitive to positive feedback, while there are estrogens in the late follicular phase and in the luteal phase, but the feedback becomes negative when estrogen levels fall at the end of the cycle.
\nRecent evidence indicates that the administration of progesterone in the late well-estrogenized follicular phase does not prevent the LH surge, which is of great importance because it would have no interference with ovulation [30, 31].
\nRelatively, low levels of estradiol, in early follicular and luteal phases, decrease kisspeptin expression, which reduces the amplitude of GnRH pulses [32]. On the other hand, progesterone would increase the dynorphin expression, which in turn reduces that of kisspeptin. These changes have been associated with the lower frequency of GnRH pulses in the luteal phase.
\nOther modulators that stimulate the pulsatile secretion of GnRH are glutamate and norepinephrine, while GABA and endogenous opioids inhibit it.
\nNeurokinin B and dynorphin neuropeptides act in an auto-synaptic fashion in the arcuate/infundibular nucleus, so that an increase in the expression of neurokinin B (NKB) stimulates the secretion of and, therefore, of GnRH, while an increase in dynorphin (Dyn) expression decreases kisspeptin secretion by inhibiting the pulsatility of GnRH. This system is known as KNDy [33].
\nAt the beginning of the menstrual cycle, estradiol levels are low and FSH levels are slightly elevated. This ratio manages to recruit follicles and as that happens, not only estradiol increases but also inhibin A, due to the empowerment of FD, which generates a continuous decrease in FSH in the follicular phase.
\nThe concentrations of FSH reach the maximum levels on the day when the FD is defined, followed by a slow decrease during the follicular phase, from day 5 to 13, reaching a nadir and then a peak just before ovulation (Figure 14). There comes a time when estradiol levels are such that they trigger the peak of FSH and LH, producing ovulation.
\nAs the luteal phase advance in time, inhibin A, estradiol, and progesterone fall together with the increase in activin A. FSH increases in the transition from the luteal phase to the next follicular phase, beginning 4 days before menstruation, a stage in which inhibin B increases during follicular recruitment.
\nThe concentration of activin A secreted by the follicles increases in the second half of the luteal phase [34] (Figure 18), decreases at the beginning of the follicular phase, increases during the early follicular phase, and then increases during the middle follicular phase in parallel with estradiol and inhibin A (Figure 19).
\nTypes of endometrium in transvaginal ultrasound. The endometrium was classified into four types (0, 1, 2, and 3) according to the appearance of the myometrium-endometrium and endometrium-endometrium interfaces, the texture, and the thickness of the functional layer. Type 0: smooth, thin as a pencil line; type 1: trilaminar structure with an iso- or hypoechoic functional layer; type 2: also trilaminar, but the myometrium-endometrium interfaces are thicker than those of type 1; and type 3: thick and homogeneous echogenic image. The type of endometrium correlates with the day of the menstrual cycle. Ultrasound is defined on day 0 as the day of the follicle break. Type 0 is usually found on day −11, during and immediately after menstruation. Type 1 is observed during the middle follicular phase and until day +2. Types 2 and 3 are observed after the ovulatory days. The endometrium increases more thickness during the preovulatory phase (average +5.5 mm), and in the luteal phase, the average is +2.6 mm.
Scheme composed shows luteal events, follicular ones and hormonals during luteal phase of woman CL = corpus luteum; DF = dominant follicle; WEM1–3 = wave emergency 1, 2, or 3 at the cycle; the waves of follicle of light gray color indicates the low frequency of the principal waves (selection of DF) during luteal phase or early follicular ones in women of 2 or 3 waves. The estradiol rise in the follicular phase begins after the emergence of the ovulatory DF and becomes more rapid following DF selection, and occurs earlier in women with 2 versus 3 follicle waves per cycle. After ovulation, estradiol concentrations increase to the mid-luteal phase (days 7–9 after ovulation) and then decline, and this is due to luteal estradiol secretion and is unaffected by minor or major anovulatory waves. Adapted from Macklon and Fauser [5].
In older women, FSH is higher, even during nadir, and the increase occurs early during the luteal phase. Recruitment of a group of follicles begins early, but the selection of DF is altered and can either advance or delay. The result is the variability of the cycle at the expense of a variable follicular phase, called “lag phase,” which ends when the ETO is produced [35].
\nThe ETO is when the estradiol overt elevation is achieved, which marks the selection of the FD. If an FD capable of ovulating was not achieved, the woman can go through a hyperestrogenic state without establishing a corpus luteum, so at the endometrial level, the cycle is hormonally monophasic. This is the pathophysiological basis that explains the monophasic hyperestrogenism that affects approximately one-third of women in perimenopause (Figure 20).
\nThe variability in perimenopause depends on the lag phase, a delayed recruitment process. Adapted from Hale et al. [35].
A chronic negative energy imbalance reduces the pulsatility of LH, generates atresia of FD and, consequently, anovulation and amenorrhea. Weight loss is associated with a reduction in LH pulses, which generates functional, reversible hypothalamic amenorrhea. On the contrary, the pulsatility of LH is increased in adolescents with irregular cycles or in women with polycystic ovary syndrome, associated with anovulation also, but here the selection of DF is absent.
\nHuman reproduction depends on the integrity of a system of intracrine and paracrine signals within the ovaries, in which those recruited follicles that have reached a level of differentiation that make them sensitive to the endocrine control of the other distant and great actor, the hypothalamus axis participate pituitary. Once a dominant follicle has been achieved, the elevations of the circulating levels of estradiol and inhibin B produced by it will modulate FSH levels and will allow, on the one hand, the atresia of the other follicles, and on the other, they will facilitate the LH surge, necessary to trigger ovulation. After hatching, the surrounding theca and granulosa cells from the follicular bed abandoned by the newly ovulated egg interact to produce a corpus luteum, which retains sufficient steroidogenic properties to produce progesterone at the concentration required to regulate the endometrium, till the implantation of a fertilized egg. If pregnancy does not occur, since the end of the luteal phase, gonadotropic changes are prepared to allow the development of a follicular recruitment phase.
\nBeing such a complex process, dependent on so many variables and exposed to so many actions, reactions and interferences, the sequences of the menstrual cycle are remarkably predictable within not very wide ranges of variability. In general, the duration standards of each cycle, 25–35 days, coincide with the ovulation presumption criteria accepted for women with ovulatory anomalies such as in the polycystic ovarian syndrome. The detailed understanding of the mechanisms allow to improve the efficiency in the clinical management when it is intended to give assistance to obtain a pregnancy, as well as to avoid it when the goal is contraception, or to correct bleeding anomalies that may result from ovulatory disorders with luteal insufficiency. There are still many aspects to investigate.
\nThe authors declare no conflict of interest in relation to this publication.
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