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Thursday, December 7, 2023

Chemistry

From Wikipedia, the free encyclopedia

Chemistry is the scientific study of the properties and behavior of matter. It is a physical science within the natural sciences that studies the chemical elements that make up matter and compounds made of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during reactions with other substances. Chemistry also addresses the nature of chemical bonds in chemical compounds.

In the scope of its subject, chemistry occupies an intermediate position between physics and biology. It is sometimes called the central science because it provides a foundation for understanding both basic and applied scientific disciplines at a fundamental level. For example, chemistry explains aspects of plant growth (botany), the formation of igneous rocks (geology), how atmospheric ozone is formed and how environmental pollutants are degraded (ecology), the properties of the soil on the moon (cosmochemistry), how medications work (pharmacology), and how to collect DNA evidence at a crime scene (forensics).

Chemistry has existed under various names since ancient times. Over this time frame, it has evolved, and now chemistry encompasses various areas of specialisation, or subdisciplines, that continue to increase in number and interrelate to create further interdisciplinary fields of study. The applications of various fields of chemistry are used frequently for economic purposes in the chemical industry.

Etymology

The word chemistry comes from a modification during the Renaissance of the word alchemy, which referred to an earlier set of practices that encompassed elements of chemistry, metallurgy, philosophy, astrology, astronomy, mysticism, and medicine. Alchemy is often associated with the quest to turn lead or other base metals into gold, though alchemists were also interested in many of the questions of modern chemistry.

The modern word alchemy in turn is derived from the Arabic word al-kīmīā (الكیمیاء). This may have Egyptian origins since al-kīmīā is derived from the Ancient Greek χημία, which is in turn derived from the word Kemet, which is the ancient name of Egypt in the Egyptian language.lternately, al-kīmīā may derive from χημεία 'cast together'.

Modern principles

Laboratory, Institute of Biochemistry, University of Cologne in Germany

The current model of atomic structure is the quantum mechanical model. Traditional chemistry starts with the study of elementary particles, atoms, molecules, substances, metals, crystals and other aggregates of matter. Matter can be studied in solid, liquid, gas and plasma states, in isolation or in combination. The interactions, reactions and transformations that are studied in chemistry are usually the result of interactions between atoms, leading to rearrangements of the chemical bonds which hold atoms together. Such behaviors are studied in a chemistry laboratory.

The chemistry laboratory stereotypically uses various forms of laboratory glassware. However glassware is not central to chemistry, and a great deal of experimental (as well as applied/industrial) chemistry is done without it.

Solutions of substances in reagent bottles, including ammonium hydroxide and nitric acid, illuminated in different colors

A chemical reaction is a transformation of some substances into one or more different substances. The basis of such a chemical transformation is the rearrangement of electrons in the chemical bonds between atoms. It can be symbolically depicted through a chemical equation, which usually involves atoms as subjects. The number of atoms on the left and the right in the equation for a chemical transformation is equal. (When the number of atoms on either side is unequal, the transformation is referred to as a nuclear reaction or radioactive decay.) The type of chemical reactions a substance may undergo and the energy changes that may accompany it are constrained by certain basic rules, known as chemical laws.

Energy and entropy considerations are invariably important in almost all chemical studies. Chemical substances are classified in terms of their structure, phase, as well as their chemical compositions. They can be analyzed using the tools of chemical analysis, e.g. spectroscopy and chromatography. Scientists engaged in chemical research are known as chemists. Most chemists specialize in one or more sub-disciplines.

Matter

In chemistry, matter is defined as anything that has rest mass and volume (it takes up space) and is made up of particles. The particles that make up matter have rest mass as well – not all particles have rest mass, such as the photon. Matter can be a pure chemical substance or a mixture of substances.

Atom

A diagram of an atom based on the Rutherford model

The atom is the basic unit of chemistry. It consists of a dense core called the atomic nucleus surrounded by a space occupied by an electron cloud. The nucleus is made up of positively charged protons and uncharged neutrons (together called nucleons), while the electron cloud consists of negatively charged electrons which orbit the nucleus. In a neutral atom, the negatively charged electrons balance out the positive charge of the protons. The nucleus is dense; the mass of a nucleon is approximately 1,836 times that of an electron, yet the radius of an atom is about 10,000 times that of its nucleus.

The atom is also the smallest entity that can be envisaged to retain the chemical properties of the element, such as electronegativity, ionization potential, preferred oxidation state(s), coordination number, and preferred types of bonds to form (e.g., metallic, ionic, covalent).

Element

Standard form of the periodic table of chemical elements. The colors represent different blocks of elements.

A chemical element is a pure substance which is composed of a single type of atom, characterized by its particular number of protons in the nuclei of its atoms, known as the atomic number and represented by the symbol Z. The mass number is the sum of the number of protons and neutrons in a nucleus. Although all the nuclei of all atoms belonging to one element will have the same atomic number, they may not necessarily have the same mass number; atoms of an element which have different mass numbers are known as isotopes. For example, all atoms with 6 protons in their nuclei are atoms of the chemical element carbon, but atoms of carbon may have mass numbers of 12 or 13.

The standard presentation of the chemical elements is in the periodic table, which orders elements by atomic number. The periodic table is arranged in groups, or columns, and periods, or rows. The periodic table is useful in identifying periodic trends.

Compound

Carbon dioxide (CO2), an example of a chemical compound

A compound is a pure chemical substance composed of more than one element. The properties of a compound bear little similarity to those of its elements. The standard nomenclature of compounds is set by the International Union of Pure and Applied Chemistry (IUPAC). Organic compounds are named according to the organic nomenclature system. The names for inorganic compounds are created according to the inorganic nomenclature system. When a compound has more than one component, then they are divided into two classes, the electropositive and the electronegative components. In addition the Chemical Abstracts Service has devised a method to index chemical substances. In this scheme each chemical substance is identifiable by a number known as its CAS registry number.

Molecule

A ball-and-stick representation of the caffeine molecule (C8H10N4O2)

A molecule is the smallest indivisible portion of a pure chemical substance that has its unique set of chemical properties, that is, its potential to undergo a certain set of chemical reactions with other substances. However, this definition only works well for substances that are composed of molecules, which is not true of many substances (see below). Molecules are typically a set of atoms bound together by covalent bonds, such that the structure is electrically neutral and all valence electrons are paired with other electrons either in bonds or in lone pairs.

Thus, molecules exist as electrically neutral units, unlike ions. When this rule is broken, giving the "molecule" a charge, the result is sometimes named a molecular ion or a polyatomic ion. However, the discrete and separate nature of the molecular concept usually requires that molecular ions be present only in well-separated form, such as a directed beam in a vacuum in a mass spectrometer. Charged polyatomic collections residing in solids (for example, common sulfate or nitrate ions) are generally not considered "molecules" in chemistry. Some molecules contain one or more unpaired electrons, creating radicals. Most radicals are comparatively reactive, but some, such as nitric oxide (NO) can be stable.

A 2-D structural formula of a benzene molecule (C6H6)

The "inert" or noble gas elements (helium, neon, argon, krypton, xenon and radon) are composed of lone atoms as their smallest discrete unit, but the other isolated chemical elements consist of either molecules or networks of atoms bonded to each other in some way. Identifiable molecules compose familiar substances such as water, air, and many organic compounds like alcohol, sugar, gasoline, and the various pharmaceuticals.

However, not all substances or chemical compounds consist of discrete molecules, and indeed most of the solid substances that make up the solid crust, mantle, and core of the Earth are chemical compounds without molecules. These other types of substances, such as ionic compounds and network solids, are organized in such a way as to lack the existence of identifiable molecules per se. Instead, these substances are discussed in terms of formula units or unit cells as the smallest repeating structure within the substance. Examples of such substances are mineral salts (such as table salt), solids like carbon and diamond, metals, and familiar silica and silicate minerals such as quartz and granite.

One of the main characteristics of a molecule is its geometry often called its structure. While the structure of diatomic, triatomic or tetra-atomic molecules may be trivial, (linear, angular pyramidal etc.) the structure of polyatomic molecules, that are constituted of more than six atoms (of several elements) can be crucial for its chemical nature.

Substance and mixture

Examples of pure chemical substances. From left to right: the elements tin (Sn) and sulfur (S), diamond (an allotrope of carbon), sucrose (pure sugar), and sodium chloride (salt) and sodium bicarbonate (baking soda), which are both ionic compounds.

A chemical substance is a kind of matter with a definite composition and set of properties. A collection of substances is called a mixture. Examples of mixtures are air and alloys.

Mole and amount of substance

The mole is a unit of measurement that denotes an amount of substance (also called chemical amount). One mole is defined to contain exactly 6.02214076×1023 particles (atoms, molecules, ions, or electrons), where the number of particles per mole is known as the Avogadro constant. Molar concentration is the amount of a particular substance per volume of solution, and is commonly reported in mol/dm3.

Phase

Diagram showing relationships among the phases and the terms used to describe phase changes

In addition to the specific chemical properties that distinguish different chemical classifications, chemicals can exist in several phases. For the most part, the chemical classifications are independent of these bulk phase classifications; however, some more exotic phases are incompatible with certain chemical properties. A phase is a set of states of a chemical system that have similar bulk structural properties, over a range of conditions, such as pressure or temperature.

Physical properties, such as density and refractive index tend to fall within values characteristic of the phase. The phase of matter is defined by the phase transition, which is when energy put into or taken out of the system goes into rearranging the structure of the system, instead of changing the bulk conditions.

Sometimes the distinction between phases can be continuous instead of having a discrete boundary' in this case the matter is considered to be in a supercritical state. When three states meet based on the conditions, it is known as a triple point and since this is invariant, it is a convenient way to define a set of conditions.

The most familiar examples of phases are solids, liquids, and gases. Many substances exhibit multiple solid phases. For example, there are three phases of solid iron (alpha, gamma, and delta) that vary based on temperature and pressure. A principal difference between solid phases is the crystal structure, or arrangement, of the atoms. Another phase commonly encountered in the study of chemistry is the aqueous phase, which is the state of substances dissolved in aqueous solution (that is, in water).

Less familiar phases include plasmas, Bose–Einstein condensates and fermionic condensates and the paramagnetic and ferromagnetic phases of magnetic materials. While most familiar phases deal with three-dimensional systems, it is also possible to define analogs in two-dimensional systems, which has received attention for its relevance to systems in biology.

Bonding

An animation of the process of ionic bonding between sodium (Na) and chlorine (Cl) to form sodium chloride, or common table salt. Ionic bonding involves one atom taking valence electrons from another (as opposed to sharing, which occurs in covalent bonding).

Atoms sticking together in molecules or crystals are said to be bonded with one another. A chemical bond may be visualized as the multipole balance between the positive charges in the nuclei and the negative charges oscillating about them. More than simple attraction and repulsion, the energies and distributions characterize the availability of an electron to bond to another atom.

The chemical bond can be a covalent bond, an ionic bond, a hydrogen bond or just because of Van der Waals force. Each of these kinds of bonds is ascribed to some potential. These potentials create the interactions which hold atoms together in molecules or crystals. In many simple compounds, valence bond theory, the Valence Shell Electron Pair Repulsion model (VSEPR), and the concept of oxidation number can be used to explain molecular structure and composition.

An ionic bond is formed when a metal loses one or more of its electrons, becoming a positively charged cation, and the electrons are then gained by the non-metal atom, becoming a negatively charged anion. The two oppositely charged ions attract one another, and the ionic bond is the electrostatic force of attraction between them. For example, sodium (Na), a metal, loses one electron to become an Na+ cation while chlorine (Cl), a non-metal, gains this electron to become Cl. The ions are held together due to electrostatic attraction, and that compound sodium chloride (NaCl), or common table salt, is formed.

In the methane molecule (CH4), the carbon atom shares a pair of valence electrons with each of the four hydrogen atoms. Thus, the octet rule is satisfied for C-atom (it has eight electrons in its valence shell) and the duet rule is satisfied for the H-atoms (they have two electrons in their valence shells).

In a covalent bond, one or more pairs of valence electrons are shared by two atoms: the resulting electrically neutral group of bonded atoms is termed a molecule. Atoms will share valence electrons in such a way as to create a noble gas electron configuration (eight electrons in their outermost shell) for each atom. Atoms that tend to combine in such a way that they each have eight electrons in their valence shell are said to follow the octet rule. However, some elements like hydrogen and lithium need only two electrons in their outermost shell to attain this stable configuration; these atoms are said to follow the duet rule, and in this way they are reaching the electron configuration of the noble gas helium, which has two electrons in its outer shell.

Similarly, theories from classical physics can be used to predict many ionic structures. With more complicated compounds, such as metal complexes, valence bond theory is less applicable and alternative approaches, such as the molecular orbital theory, are generally used. See diagram on electronic orbitals.

Energy

In the context of chemistry, energy is an attribute of a substance as a consequence of its atomic, molecular or aggregate structure. Since a chemical transformation is accompanied by a change in one or more of these kinds of structures, it is invariably accompanied by an increase or decrease of energy of the substances involved. Some energy is transferred between the surroundings and the reactants of the reaction in the form of heat or light; thus the products of a reaction may have more or less energy than the reactants.

A reaction is said to be exergonic if the final state is lower on the energy scale than the initial state; in the case of endergonic reactions the situation is the reverse. A reaction is said to be exothermic if the reaction releases heat to the surroundings; in the case of endothermic reactions, the reaction absorbs heat from the surroundings.

Chemical reactions are invariably not possible unless the reactants surmount an energy barrier known as the activation energy. The speed of a chemical reaction (at given temperature T) is related to the activation energy E, by the Boltzmann's population factor – that is the probability of a molecule to have energy greater than or equal to E at the given temperature T. This exponential dependence of a reaction rate on temperature is known as the Arrhenius equation. The activation energy necessary for a chemical reaction to occur can be in the form of heat, light, electricity or mechanical force in the form of ultrasound.

A related concept free energy, which also incorporates entropy considerations, is a very useful means for predicting the feasibility of a reaction and determining the state of equilibrium of a chemical reaction, in chemical thermodynamics. A reaction is feasible only if the total change in the Gibbs free energy is negative, ; if it is equal to zero the chemical reaction is said to be at equilibrium.

There exist only limited possible states of energy for electrons, atoms and molecules. These are determined by the rules of quantum mechanics, which require quantization of energy of a bound system. The atoms/molecules in a higher energy state are said to be excited. The molecules/atoms of substance in an excited energy state are often much more reactive; that is, more amenable to chemical reactions.

The phase of a substance is invariably determined by its energy and the energy of its surroundings. When the intermolecular forces of a substance are such that the energy of the surroundings is not sufficient to overcome them, it occurs in a more ordered phase like liquid or solid as is the case with water (H2O); a liquid at room temperature because its molecules are bound by hydrogen bonds. Whereas hydrogen sulfide (H2S) is a gas at room temperature and standard pressure, as its molecules are bound by weaker dipole-dipole interactions.

The transfer of energy from one chemical substance to another depends on the size of energy quanta emitted from one substance. However, heat energy is often transferred more easily from almost any substance to another because the phonons responsible for vibrational and rotational energy levels in a substance have much less energy than photons invoked for the electronic energy transfer. Thus, because vibrational and rotational energy levels are more closely spaced than electronic energy levels, heat is more easily transferred between substances relative to light or other forms of electronic energy. For example, ultraviolet electromagnetic radiation is not transferred with as much efficacy from one substance to another as thermal or electrical energy.

The existence of characteristic energy levels for different chemical substances is useful for their identification by the analysis of spectral lines. Different kinds of spectra are often used in chemical spectroscopy, e.g. IR, microwave, NMR, ESR, etc. Spectroscopy is also used to identify the composition of remote objects – like stars and distant galaxies – by analyzing their radiation spectra.

Emission spectrum of iron

The term chemical energy is often used to indicate the potential of a chemical substance to undergo a transformation through a chemical reaction or to transform other chemical substances.

Reaction

During chemical reactions, bonds between atoms break and form, resulting in different substances with different properties. In a blast furnace, iron oxide, a compound, reacts with carbon monoxide to form iron, one of the chemical elements, and carbon dioxide.

When a chemical substance is transformed as a result of its interaction with another substance or with energy, a chemical reaction is said to have occurred. A chemical reaction is therefore a concept related to the "reaction" of a substance when it comes in close contact with another, whether as a mixture or a solution; exposure to some form of energy, or both. It results in some energy exchange between the constituents of the reaction as well as with the system environment, which may be designed vessels—often laboratory glassware.

Chemical reactions can result in the formation or dissociation of molecules, that is, molecules breaking apart to form two or more molecules or rearrangement of atoms within or across molecules. Chemical reactions usually involve the making or breaking of chemical bonds. Oxidation, reduction, dissociation, acid–base neutralization and molecular rearrangement are some examples of common chemical reactions.

A chemical reaction can be symbolically depicted through a chemical equation. While in a non-nuclear chemical reaction the number and kind of atoms on both sides of the equation are equal, for a nuclear reaction this holds true only for the nuclear particles viz. protons and neutrons.

The sequence of steps in which the reorganization of chemical bonds may be taking place in the course of a chemical reaction is called its mechanism. A chemical reaction can be envisioned to take place in a number of steps, each of which may have a different speed. Many reaction intermediates with variable stability can thus be envisaged during the course of a reaction. Reaction mechanisms are proposed to explain the kinetics and the relative product mix of a reaction. Many physical chemists specialize in exploring and proposing the mechanisms of various chemical reactions. Several empirical rules, like the Woodward–Hoffmann rules often come in handy while proposing a mechanism for a chemical reaction.

According to the IUPAC gold book, a chemical reaction is "a process that results in the interconversion of chemical species." Accordingly, a chemical reaction may be an elementary reaction or a stepwise reaction. An additional caveat is made, in that this definition includes cases where the interconversion of conformers is experimentally observable. Such detectable chemical reactions normally involve sets of molecular entities as indicated by this definition, but it is often conceptually convenient to use the term also for changes involving single molecular entities (i.e. 'microscopic chemical events').

Ions and salts

The crystal lattice structure of potassium chloride (KCl), a salt which is formed due to the attraction of K+ cations and Cl anions. The overall charge of the ionic compound is zero.

An ion is a charged species, an atom or a molecule, that has lost or gained one or more electrons. When an atom loses an electron and thus has more protons than electrons, the atom is a positively charged ion or cation. When an atom gains an electron and thus has more electrons than protons, the atom is a negatively charged ion or anion. Cations and anions can form a crystalline lattice of neutral salts, such as the Na+ and Cl ions forming sodium chloride, or NaCl. Examples of polyatomic ions that do not split up during acid–base reactions are hydroxide (OH) and phosphate (PO43−).

Plasma is composed of gaseous matter that has been completely ionized, usually through high temperature.

Acidity and basicity

Hydrogen bromide exists in the gas phase as a diatomic molecule.

A substance can often be classified as an acid or a base. There are several different theories which explain acid–base behavior. The simplest is Arrhenius theory, which states that acid is a substance that produces hydronium ions when it is dissolved in water, and a base is one that produces hydroxide ions when dissolved in water. According to Brønsted–Lowry acid–base theory, acids are substances that donate a positive hydrogen ion to another substance in a chemical reaction; by extension, a base is the substance which receives that hydrogen ion.

A third common theory is Lewis acid–base theory, which is based on the formation of new chemical bonds. Lewis theory explains that an acid is a substance which is capable of accepting a pair of electrons from another substance during the process of bond formation, while a base is a substance which can provide a pair of electrons to form a new bond. There are several other ways in which a substance may be classified as an acid or a base, as is evident in the history of this concept.

Acid strength is commonly measured by two methods. One measurement, based on the Arrhenius definition of acidity, is pH, which is a measurement of the hydronium ion concentration in a solution, as expressed on a negative logarithmic scale. Thus, solutions that have a low pH have a high hydronium ion concentration and can be said to be more acidic. The other measurement, based on the Brønsted–Lowry definition, is the acid dissociation constant (Ka), which measures the relative ability of a substance to act as an acid under the Brønsted–Lowry definition of an acid. That is, substances with a higher Ka are more likely to donate hydrogen ions in chemical reactions than those with lower Ka values.

Redox

Redox (reduction-oxidation) reactions include all chemical reactions in which atoms have their oxidation state changed by either gaining electrons (reduction) or losing electrons (oxidation). Substances that have the ability to oxidize other substances are said to be oxidative and are known as oxidizing agents, oxidants or oxidizers. An oxidant removes electrons from another substance. Similarly, substances that have the ability to reduce other substances are said to be reductive and are known as reducing agents, reductants, or reducers.

A reductant transfers electrons to another substance and is thus oxidized itself. And because it "donates" electrons it is also called an electron donor. Oxidation and reduction properly refer to a change in oxidation number—the actual transfer of electrons may never occur. Thus, oxidation is better defined as an increase in oxidation number, and reduction as a decrease in oxidation number.

Equilibrium

Although the concept of equilibrium is widely used across sciences, in the context of chemistry, it arises whenever a number of different states of the chemical composition are possible, as for example, in a mixture of several chemical compounds that can react with one another, or when a substance can be present in more than one kind of phase.

A system of chemical substances at equilibrium, even though having an unchanging composition, is most often not static; molecules of the substances continue to react with one another thus giving rise to a dynamic equilibrium. Thus the concept describes the state in which the parameters such as chemical composition remain unchanged over time.

Chemical laws

Chemical reactions are governed by certain laws, which have become fundamental concepts in chemistry. Some of them are:

History

The history of chemistry spans a period from very old times to the present. Since several millennia BC, civilizations were using technologies that would eventually form the basis of the various branches of chemistry. Examples include extracting metals from ores, making pottery and glazes, fermenting beer and wine, extracting chemicals from plants for medicine and perfume, rendering fat into soap, making glass, and making alloys like bronze.

Chemistry was preceded by its protoscience, alchemy, which operated a non-scientific approach to understanding the constituents of matter and their interactions. Despite being unsuccessful in explaining the nature of matter and its transformations, alchemists set the stage for modern chemistry by performing experiments and recording the results. Robert Boyle, although skeptical of elements and convinced of alchemy, played a key part in elevating the "sacred art" as an independent, fundamental and philosophical discipline in his work The Sceptical Chymist (1661).

While both alchemy and chemistry are concerned with matter and its transformations, the crucial difference was given by the scientific method that chemists employed in their work. Chemistry, as a body of knowledge distinct from alchemy, became an established science with the work of Antoine Lavoisier, who developed a law of conservation of mass that demanded careful measurement and quantitative observations of chemical phenomena. The history of chemistry afterwards is intertwined with the history of thermodynamics, especially through the work of Willard Gibbs.

Definition

The definition of chemistry has changed over time, as new discoveries and theories add to the functionality of the science. The term "chymistry", in the view of noted scientist Robert Boyle in 1661, meant the subject of the material principles of mixed bodies. In 1663, the chemist Christopher Glaser described "chymistry" as a scientific art, by which one learns to dissolve bodies, and draw from them the different substances on their composition, and how to unite them again, and exalt them to a higher perfection.

The 1730 definition of the word "chemistry", as used by Georg Ernst Stahl, meant the art of resolving mixed, compound, or aggregate bodies into their principles; and of composing such bodies from those principles. In 1837, Jean-Baptiste Dumas considered the word "chemistry" to refer to the science concerned with the laws and effects of molecular forces. This definition further evolved until, in 1947, it came to mean the science of substances: their structure, their properties, and the reactions that change them into other substances – a characterization accepted by Linus Pauling. More recently, in 1998, Professor Raymond Chang broadened the definition of "chemistry" to mean the study of matter and the changes it undergoes.

Background

Democritus' atomist philosophy was later adopted by Epicurus (341–270 BCE).

Early civilizations, such as the Egyptians Babylonians and Indians amassed practical knowledge concerning the arts of metallurgy, pottery and dyes, but did not develop a systematic theory.

A basic chemical hypothesis first emerged in Classical Greece with the theory of four elements as propounded definitively by Aristotle stating that fire, air, earth and water were the fundamental elements from which everything is formed as a combination. Greek atomism dates back to 440 BC, arising in works by philosophers such as Democritus and Epicurus. In 50 BCE, the Roman philosopher Lucretius expanded upon the theory in his poem De rerum natura (On The Nature of Things). Unlike modern concepts of science, Greek atomism was purely philosophical in nature, with little concern for empirical observations and no concern for chemical experiments.

An early form of the idea of conservation of mass is the notion that "Nothing comes from nothing" in Ancient Greek philosophy, which can be found in Empedocles (approx. 4th century BC): "For it is impossible for anything to come to be from what is not, and it cannot be brought about or heard of that what is should be utterly destroyed." and Epicurus (3rd century BC), who, describing the nature of the Universe, wrote that "the totality of things was always such as it is now, and always will be".

15th-century artistic impression of Jābir ibn Hayyān (Geber), a Perso-Arab alchemist and pioneer in organic chemistry

In the Hellenistic world the art of alchemy first proliferated, mingling magic and occultism into the study of natural substances with the ultimate goal of transmuting elements into gold and discovering the elixir of eternal life. Work, particularly the development of distillation, continued in the early Byzantine period with the most famous practitioner being the 4th century Greek-Egyptian Zosimos of Panopolis. Alchemy continued to be developed and practised throughout the Arab world after the Muslim conquests, and from there, and from the Byzantine remnants, diffused into medieval and Renaissance Europe through Latin translations.

The Arabic works attributed to Jabir ibn Hayyan introduced a systematic classification of chemical substances, and provided instructions for deriving an inorganic compound (sal ammoniac or ammonium chloride) from organic substances (such as plants, blood, and hair) by chemical means. Some Arabic Jabirian works (e.g., the "Book of Mercy", and the "Book of Seventy") were later translated into Latin under the Latinized name "Geber", and in 13th-century Europe an anonymous writer, usually referred to as pseudo-Geber, started to produce alchemical and metallurgical writings under this name. Later influential Muslim philosophers, such as Abū al-Rayhān al-Bīrūnī and Avicenna disputed the theories of alchemy, particularly the theory of the transmutation of metals.

Under the influence of the new empirical methods propounded by Sir Francis Bacon and others, a group of chemists at Oxford, Robert Boyle, Robert Hooke and John Mayow began to reshape the old alchemical traditions into a scientific discipline. Boyle in particular questioned some commonly held chemical theories and argued for chemical practitioners to be more "philosophical" and less commercially focused in The Sceptical Chemyst. He formulated Boyle's law, rejected the classical "four elements" and proposed a mechanistic alternative of atoms and chemical reactions that could be subject to rigorous experiment.

Antoine-Laurent de Lavoisier is considered the "Father of Modern Chemistry".

In the following decades, many important discoveries were made, such as the nature of 'air' which was discovered to be composed of many different gases. The Scottish chemist Joseph Black and the Flemish Jan Baptist van Helmont discovered carbon dioxide, or what Black called 'fixed air' in 1754; Henry Cavendish discovered hydrogen and elucidated its properties and Joseph Priestley and, independently, Carl Wilhelm Scheele isolated pure oxygen. The theory of phlogiston (a substance at the root of all combustion) was propounded by the German Georg Ernst Stahl in the early 18th century and was only overturned by the end of the century by the French chemist Antoine Lavoisier, the chemical analogue of Newton in physics. Lavoisier did more than any other to establish the new science on proper theoretical footing, by elucidating the principle of conservation of mass and developing a new system of chemical nomenclature used to this day.

English scientist John Dalton proposed the modern theory of atoms; that all substances are composed of indivisible 'atoms' of matter and that different atoms have varying atomic weights.

The development of the electrochemical theory of chemical combinations occurred in the early 19th century as the result of the work of two scientists in particular, Jöns Jacob Berzelius and Humphry Davy, made possible by the prior invention of the voltaic pile by Alessandro Volta. Davy discovered nine new elements including the alkali metals by extracting them from their oxides with electric current.

In his periodic table, Dmitri Mendeleev predicted the existence of 7 new elements, and placed all 60 elements known at the time in their correct places.

British William Prout first proposed ordering all the elements by their atomic weight as all atoms had a weight that was an exact multiple of the atomic weight of hydrogen. J.A.R. Newlands devised an early table of elements, which was then developed into the modern periodic table of elements in the 1860s by Dmitri Mendeleev and independently by several other scientists including Julius Lothar Meyer. The inert gases, later called the noble gases were discovered by William Ramsay in collaboration with Lord Rayleigh at the end of the century, thereby filling in the basic structure of the table.

Top: Expected results: alpha particles passing through the plum pudding model of the atom undisturbed.
Bottom: Observed results: a small portion of the particles were deflected, indicating a small, concentrated charge.

At the turn of the twentieth century the theoretical underpinnings of chemistry were finally understood due to a series of remarkable discoveries that succeeded in probing and discovering the very nature of the internal structure of atoms. In 1897, J.J. Thomson of the University of Cambridge discovered the electron and soon after the French scientist Becquerel as well as the couple Pierre and Marie Curie investigated the phenomenon of radioactivity. In a series of pioneering scattering experiments Ernest Rutherford at the University of Manchester discovered the internal structure of the atom and the existence of the proton, classified and explained the different types of radioactivity and successfully transmuted the first element by bombarding nitrogen with alpha particles.

His work on atomic structure was improved on by his students, the Danish physicist Niels Bohr, the Englishman Henry Moseley and the German Otto Hahn, who went on to father the emerging nuclear chemistry and discovered nuclear fission. The electronic theory of chemical bonds and molecular orbitals was developed by the American scientists Linus Pauling and Gilbert N. Lewis.

The year 2011 was declared by the United Nations as the International Year of Chemistry. It was an initiative of the International Union of Pure and Applied Chemistry, and of the United Nations Educational, Scientific, and Cultural Organization and involves chemical societies, academics, and institutions worldwide and relied on individual initiatives to organize local and regional activities.

Organic chemistry was developed by Justus von Liebig and others, following Friedrich Wöhler's synthesis of urea. Other crucial 19th century advances were; an understanding of valence bonding (Edward Frankland in 1852) and the application of thermodynamics to chemistry (J. W. Gibbs and Svante Arrhenius in the 1870s).

Practice

Subdisciplines

Chemistry is typically divided into several major sub-disciplines. There are also several main cross-disciplinary and more specialized fields of chemistry.

Others subdivisions include electrochemistry, femtochemistry, flavor chemistry, flow chemistry, immunohistochemistry, hydrogenation chemistry, mathematical chemistry, molecular mechanics, natural product chemistry, organometallic chemistry, petrochemistry, photochemistry, physical organic chemistry, polymer chemistry, radiochemistry, sonochemistry, supramolecular chemistry, synthetic chemistry, and many others.

Interdisciplinary

Interdisciplinary fields include agrochemistry, astrochemistry (and cosmochemistry), atmospheric chemistry, chemical engineering, chemical biology, chemo-informatics, environmental chemistry, geochemistry, green chemistry, immunochemistry, marine chemistry, materials science, mechanochemistry, medicinal chemistry, molecular biology, nanotechnology, oenology, pharmacology, phytochemistry, solid-state chemistry, surface science, thermochemistry, and many others.

Industry

The chemical industry represents an important economic activity worldwide. The global top 50 chemical producers in 2013 had sales of US$980.5 billion with a profit margin of 10.3%.

DDT

From Wikipedia, the free encyclopedia

Dichlorodiphenyltrichloroethane
Chemical structure of DDT
Names
Preferred IUPAC name
1,1′-(2,2,2-Trichloroethane-1,1-diyl)bis(4-chlorobenzene)
Other names
Dichlorodiphenyltrichloroethane (DDT)
Clofenotane

Dichlorodiphenyltrichloroethane, commonly known as DDT, is a colorless, tasteless, and almost odorless crystalline chemical compound, an organochloride. Originally developed as an insecticide, it became infamous for its environmental impacts. DDT was first synthesized in 1874 by the Austrian chemist Othmar Zeidler. DDT's insecticidal action was discovered by the Swiss chemist Paul Hermann Müller in 1939. DDT was used in the second half of World War II to limit the spread of the insect-borne diseases malaria and typhus among civilians and troops. Müller was awarded the Nobel Prize in Physiology or Medicine in 1948 "for his discovery of the high efficiency of DDT as a contact poison against several arthropods". The WHO's anti-malaria campaign of the 1950s and 1960s relied heavily on DDT and the results were promising, though there was a resurgence in developing countries afterwards.

By October 1945, DDT was available for public sale in the United States. Although it was promoted by government and industry for use as an agricultural and household pesticide, there were also concerns about its use from the beginning. Opposition to DDT was focused by the 1962 publication of Rachel Carson's book Silent Spring. It talked about environmental impacts that correlated with the widespread use of DDT in agriculture in the United States, and it questioned the logic of broadcasting potentially dangerous chemicals into the environment with little prior investigation of their environmental and health effects. The book cited claims that DDT and other pesticides caused cancer and that their agricultural use was a threat to wildlife, particularly birds. Although Carson never directly called for an outright ban on the use of DDT, its publication was a seminal event for the environmental movement and resulted in a large public outcry that eventually led, in 1972, to a ban on DDT's agricultural use in the United States. Along with the passage of the Endangered Species Act, the United States ban on DDT is a major factor in the comeback of the bald eagle (the national bird of the United States) and the peregrine falcon from near-extinction in the contiguous United States.

The evolution of DDT resistance and the harm both to humans and the environment led many governments to curtail DDT use. A worldwide ban on agricultural use was formalized under the Stockholm Convention on Persistent Organic Pollutants, which has been in effect since 2004. Recognizing that total elimination in many malaria-prone countries is currently unfeasible in the absence of affordable/effective alternatives for disease control, the convention exempts public health use within World Health Organization (WHO) guidelines from the ban.

DDT still has limited use in disease vector control because of its effectiveness in killing mosquitos and thus reducing malarial infections, but that use is controversial due to environmental and health concerns. DDT is one of many tools to fight malaria, which remains the primary public health challenge in many countries. WHO guidelines require that absence of DDT resistance must be confirmed before using it. Resistance is largely due to agricultural use, in much greater quantities than required for disease prevention.

Properties and chemistry

DDT is similar in structure to the insecticide methoxychlor and the acaricide dicofol. It is highly hydrophobic and nearly insoluble in water but has good solubility in most organic solvents, fats and oils. DDT does not occur naturally and is synthesised by consecutive Friedel–Crafts reactions between chloral (CCl
3
CHO
) and two equivalents of chlorobenzene (C
6
H
5
Cl
), in the presence of an acidic catalyst. DDT has been marketed under trade names including Anofex, Cezarex, Chlorophenothane, Dicophane, Dinocide, Gesarol, Guesapon, Guesarol, Gyron, Ixodex, Neocid, Neocidol and Zerdane; INN is clofenotane.

Isomers and related compounds

Commercial DDT is a mixture of several closely related compounds. Due to the nature of the chemical reaction used to synthesize DDT, several combinations of ortho and para arene substitution patterns are formed. The major component (77%) is the desired p,p' isomer. The o,p' isomeric impurity is also present in significant amounts (15%). Dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane (DDD) make up the balance of impurities in commercial samples. DDE and DDD are also the major metabolites and environmental breakdown products. DDT, DDE and DDD are sometimes referred to collectively as DDX.

Production and use

DDT has been formulated in multiple forms, including solutions in xylene or petroleum distillates, emulsifiable concentrates, water-wettable powders, granules, aerosols, smoke candles and charges for vaporizers and lotions.

From 1950 to 1980, DDT was extensively used in agriculture – more than 40,000 tonnes each year worldwide – and it has been estimated that a total of 1.8 million tonnes have been produced globally since the 1940s. In the United States, it was manufactured by some 15 companies, including Monsanto, Ciba, Montrose Chemical Company, Pennwalt, and Velsicol Chemical Corporation. Production peaked in 1963 at 82,000 tonnes per year. More than 600,000 tonnes (1.35 billion pounds) were applied in the US before the 1972 ban. Usage peaked in 1959 at about 36,000 tonnes.

In 2009, 3,314 tonnes were produced for malaria control and visceral leishmaniasis. India is the only country still manufacturing DDT, and is the largest consumer. China ceased production in 2007.

Mechanism of insecticide action

In insects, DDT opens voltage-sensitive sodium ion channels in neurons, causing them to fire spontaneously, which leads to spasms and eventual death. Insects with certain mutations in their sodium channel gene are resistant to DDT and similar insecticides. DDT resistance is also conferred by up-regulation of genes expressing cytochrome P450 in some insect species, as greater quantities of some enzymes of this group accelerate the toxin's metabolism into inactive metabolites. Genomic studies in the model genetic organism Drosophila melanogaster revealed that high level DDT resistance is polygenic, involving multiple resistance mechanisms. In the absence of genetic adaptation, Roberts and Andre 1994 find behavioral avoidance nonetheless provides insects with some protection against DDT. The M918T mutation event produces dramatic kdr for pyrethroids but Usherwood et al. 2005 find it is entirely ineffective against DDT. Scott 2019 believes this test in Drosophila oocytes holds for oocytes in general.

History

Commercial product concentrate containing 50% DDT, circa 1960s
Commercial product of Ciba-Geigy Néocide (powder box, 50 g) containing 10% DDT, made in France.

DDT was first synthesized in 1874 by Othmar Zeidler under the supervision of Adolf von Baeyer. It was further described in 1929 in a dissertation by W. Bausch and in two subsequent publications in 1930.  The insecticide properties of "multiple chlorinated aliphatic or fat-aromatic alcohols with at least one trichloromethane group" were described in a patent in 1934 by Wolfgang von Leuthold. DDT's insecticidal properties were not, however, discovered until 1939 by the Swiss scientist Paul Hermann Müller, who was awarded the 1948 Nobel Prize in Physiology and Medicine for his efforts.

Use in the 1940s and 1950s

An airplane spraying DDT over Baker County, Oregon as part of a spruce budworm control project, 1955
DDT spray log in Bosa (Sardinia)

DDT is the best-known of several chlorine-containing pesticides used in the 1940s and 1950s. During this time, the use of DDT was driven by protecting American soldiers from diseases in tropical areas. Both British and American scientists hoped to use it to control spread of malaria, typhus, dysentery, and typhoid fever among overseas soldiers, especially considering that the pyrethrum was harder to access since it came mainly from Japan. Due to the potency of DDT, it was not long before America's War Production Board placed it on military supply lists in 1942 and 1943 and encouraged its production for overseas use. Enthusiasm regarding DDT became obvious through the American government's advertising campaigns of posters depicting Americans fighting the Axis powers and insects and through media publications celebrating its military uses. In the South Pacific, it was sprayed aerially for malaria and dengue fever control with spectacular effects. While DDT's chemical and insecticidal properties were important factors in these victories, advances in application equipment coupled with competent organization and sufficient manpower were also crucial to the success of these programs.

In 1945, DDT was made available to farmers as an agricultural insecticide and played a role in the elimination of malaria in Europe and North America. Despite concerns emerging in the scientific community, and lack of research, the FDA considered it safe up to 7 parts per million in food. There was a large economic incentive to push DDT into the market and sell it to farmers, governments, and individuals to control diseases and increase food production.

DDT was also a way for American influence to reach abroad through DDT-spraying campaigns. In the 1944 issue of Life magazine there was a feature regarding the Italian program showing pictures of American public health officials in uniforms spraying DDT on Italian families.

In 1955, the World Health Organization commenced a program to eradicate malaria in countries with low to moderate transmission rates worldwide, relying largely on DDT for mosquito control and rapid diagnosis and treatment to reduce transmission. The program eliminated the disease in "North America, Europe, the former Soviet Union", and in "Taiwan, much of the Caribbean, the Balkans, parts of northern Africa, the northern region of Australia, and a large swath of the South Pacific" and dramatically reduced mortality in Sri Lanka and India.

However, failure to sustain the program, increasing mosquito tolerance to DDT, and increasing parasite tolerance led to a resurgence. In many areas early successes partially or completely reversed, and in some cases rates of transmission increased. The program succeeded in eliminating malaria only in areas with "high socio-economic status, well-organized healthcare systems, and relatively less intensive or seasonal malaria transmission".

DDT was less effective in tropical regions due to the continuous life cycle of mosquitoes and poor infrastructure. It was applied in sub-Saharan Africa by various colonial states, but the 'global' WHO eradication program didn't include the region. Mortality rates in that area never declined to the same dramatic extent, and now constitute the bulk of malarial deaths worldwide, especially following the disease's resurgence as a result of resistance to drug treatments and the spread of the deadly malarial variant caused by Plasmodium falciparum. Eradication was abandoned in 1969 and attention instead focused on controlling and treating the disease. Spraying programs (especially using DDT) were curtailed due to concerns over safety and environmental effects, as well as problems in administrative, managerial and financial implementation. Efforts shifted from spraying to the use of bednets impregnated with insecticides and other interventions.

United States ban

By October 1945, DDT was available for public sale in the United States, used both as an agricultural pesticide and as a household insecticide. Although its use was promoted by government and the agricultural industry, US scientists such as FDA pharmacologist Herbert O. Calvery expressed concern over possible hazards associated with DDT as early as 1944. In 1947, Bradbury Robinson, a physician and nutritionist practicing in St. Louis, Michigan, warned of the dangers of using the pesticide DDT in agriculture. DDT had been researched and manufactured in St. Louis by the Michigan Chemical Corporation, later purchased by Velsicol Chemical Corporation, and had become an important part of the local economy. Citing research performed by Michigan State University in 1946, Robinson, a past president of the local Conservation Club, opined that:

perhaps the greatest danger from D.D.T. is that its extensive use in farm areas is most likely to upset the natural balances, not only killing beneficial insects in great number but by bringing about the death of fish, birds, and other forms of wild life either by their feeding on insects killed by D.D.T. or directly by ingesting the poison.

As its production and use increased, public response was mixed. At the same time that DDT was hailed as part of the "world of tomorrow", concerns were expressed about its potential to kill harmless and beneficial insects (particularly pollinators), birds, fish, and eventually humans. The issue of toxicity was complicated, partly because DDT's effects varied from species to species, and partly because consecutive exposures could accumulate, causing damage comparable to large doses. A number of states attempted to regulate DDT. In the 1950s the federal government began tightening regulations governing its use. These events received little attention. Women like Dorothy Colson and Mamie Ella Plyler of Claxton, Georgia gathered evidence about DDT's effects and wrote to the Georgia Department of Public Health, the National Health Council in New York City, and other organizations.

In 1957 The New York Times reported an unsuccessful struggle to restrict DDT use in Nassau County, New York, and the issue came to the attention of the popular naturalist-author Rachel Carson. William Shawn, editor of The New Yorker, urged her to write a piece on the subject, which developed into her 1962 book Silent Spring. The book argued that pesticides, including DDT, were poisoning both wildlife and the environment and were endangering human health. Silent Spring was a best seller, and public reaction to it launched the modern environmental movement in the United States. The year after it appeared, President John F. Kennedy ordered his Science Advisory Committee to investigate Carson's claims. The committee's report "add[ed] up to a fairly thorough-going vindication of Rachel Carson's Silent Spring thesis", in the words of the journal Science, and recommended a phaseout of "persistent toxic pesticides". In 1965, the U.S. military removed DDT from the military supply system due in part to the development of resistance by body lice to DDT; it was replaced by lindane.

DDT became a prime target of the growing anti-chemical and anti-pesticide movements, and in 1967 a group of scientists and lawyers founded Environmental Defense (later Environmental Defense Fund, EDF) with the specific goal of enacting a ban on DDT. Victor Yannacone, Charles Wurster, Art Cooley and others in the group had all witnessed bird kills or declines in bird populations and suspected that DDT was the cause. In their campaign against the chemical, the EDF petitioned the government for a ban and filed lawsuits. Around this time, toxicologist David Peakall was measuring DDE levels in the eggs of peregrine falcons and California condors and finding that increased levels corresponded with thinner shells.

In response to an EDF suit, the U.S. District Court of Appeals in 1971 ordered the EPA to begin the de-registration procedure for DDT. After an initial six-month review process, William Ruckelshaus, the Agency's first Administrator rejected an immediate suspension of DDT's registration, citing studies from the EPA's internal staff stating that DDT was not an imminent danger. However, these findings were criticized, as they were performed mostly by economic entomologists inherited from the United States Department of Agriculture, who many environmentalists felt were biased towards agribusiness and understated concerns about human health and wildlife. The decision thus created controversy.

The EPA held seven months of hearings in 1971–1972, with scientists giving evidence for and against DDT. In the summer of 1972, Ruckelshaus announced the cancellation of most uses of DDT – exempting public health uses under some conditions. Again, this caused controversy. Immediately after the announcement, both the EDF and the DDT manufacturers filed suit against EPA. Many in the agricultural community were concerned that food production would be severely impacted, while proponents of pesticides warned of increased breakouts of insect-borne diseases and questioned the accuracy of giving animals high amounts of pesticides for cancer potential. Industry sought to overturn the ban, while the EDF wanted a comprehensive ban. The cases were consolidated, and in 1973 the United States Court of Appeals for the District of Columbia Circuit ruled that the EPA had acted properly in banning DDT. During the late 1970s, the EPA also began banning organochlorines, pesticides that were chemically similar to DDT. These included aldrin, dieldrin, chlordane, heptachlor, texaphene, and mirex.

Some uses of DDT continued under the public health exemption. For example, in June 1979, the California Department of Health Services was permitted to use DDT to suppress flea vectors of bubonic plague. DDT continued to be produced in the United States for foreign markets until 1985, when over 300 tons were exported.

International usage restrictions

In the 1970s and 1980s, agricultural use was banned in most developed countries, beginning with Hungary in 1968 – although in practice it continued to be used through at least 1970. This was followed by Norway and Sweden in 1970, West Germany and the United States in 1972, but not in the United Kingdom until 1984.

In contrast to West Germany, in the German Democratic Republic DDT was used until 1988. Especially of relevance were large-scale applications in forestry in the years 1982–1984, with the aim to combat bark beetle and pine moth. As a consequence, DDT-concentrations in eastern German forest soils are still significantly higher compared to soils in the former western German states.

By 1991, total bans, including for disease control, were in place in at least 26 countries; for example, Cuba in 1970, the US in the 1980s, Singapore in 1984, Chile in 1985, and the Republic of Korea in 1986.

The Stockholm Convention on Persistent Organic Pollutants, which took effect in 2004, put a global ban on several persistent organic pollutants, and restricted DDT use to vector control. The convention was ratified by more than 170 countries. Recognizing that total elimination in many malaria-prone countries is currently unfeasible in the absence of affordable/effective alternatives, the convention exempts public health use within World Health Organization (WHO) guidelines from the ban. Resolution 60.18 of the World Health Assembly commits WHO to the Stockholm Convention's aim of reducing and ultimately eliminating DDT. Malaria Foundation International states, "The outcome of the treaty is arguably better than the status quo going into the negotiations. For the first time, there is now an insecticide which is restricted to vector control only, meaning that the selection of resistant mosquitoes will be slower than before."

Despite the worldwide ban, agricultural use continued in India, North Korea, and possibly elsewhere. As of 2013, an estimated 3,000 to 4,000 tons of DDT were produced for disease vector control, including 2,786 tons in India. DDT is applied to the inside walls of homes to kill or repel mosquitoes. This intervention, called indoor residual spraying (IRS), greatly reduces environmental damage. It also reduces the incidence of DDT resistance. For comparison, treating 40 hectares (99 acres) of cotton during a typical U.S. growing season requires the same amount of chemical to treat roughly 1,700 homes.

Environmental impact

Degradation of DDT to form DDE (by elimination of HCl, left) and DDD (by reductive dechlorination, right)

DDT is a persistent organic pollutant that is readily adsorbed to soils and sediments, which can act both as sinks and as long-term sources of exposure affecting organisms. Depending on environmental conditions, its soil half-life can range from 22 days to 30 years. Routes of loss and degradation include runoff, volatilization, photolysis and aerobic and anaerobic biodegradation. Due to hydrophobic properties, in aquatic ecosystems DDT and its metabolites are absorbed by aquatic organisms and adsorbed on suspended particles, leaving little DDT dissolved in the water (however, its half-life in aquatic environments is listed by the National Pesticide Information Center as 150 years). Its breakdown products and metabolites, DDE and DDD, are also persistent and have similar chemical and physical properties. DDT and its breakdown products are transported from warmer areas to the Arctic by the phenomenon of global distillation, where they then accumulate in the region's food web.

Medical researchers in 1974 found a measurable and significant difference in the presence of DDT in human milk between mothers who lived in New Brunswick and mothers who lived in Nova Scotia, "possibly because of the wider use of insecticide sprays in the past".

Because of its lipophilic properties, DDT can bioaccumulate, especially in predatory birds. DDT is toxic to a wide range of living organisms, including marine animals such as crayfish, daphnids, sea shrimp and many species of fish. DDT, DDE and DDD magnify through the food chain, with apex predators such as raptor birds concentrating more chemicals than other animals in the same environment. They are stored mainly in body fat. DDT and DDE are resistant to metabolism; in humans, their half-lives are 6 and up to 10 years, respectively. In the United States, these chemicals were detected in almost all human blood samples tested by the Centers for Disease Control in 2005, though their levels have sharply declined since most uses were banned. Estimated dietary intake has declined, although FDA food tests commonly detect it.

Despite being banned for many years, in 2018 research showed that DDT residues are still present in European soils and Spanish rivers.

Eggshell thinning

The chemical and its breakdown products DDE and DDD caused eggshell thinning and population declines in multiple North American and European bird of prey species. Both laboratory experiments and field studies confirmed this effect. The effect was first conclusively proven at Bellow Island in Lake Michigan during University of Michigan-funded studies on American herring gulls in the mid-1960s. DDE-related eggshell thinning is considered a major reason for the decline of the bald eagle, brown pelican, peregrine falcon and osprey. However, birds vary in their sensitivity to these chemicals, with birds of prey, waterfowl and song birds being more susceptible than chickens and related species. Even in 2010, California condors that feed on sea lions at Big Sur that in turn feed in the Palos Verdes Shelf area of the Montrose Chemical Superfund site exhibited continued thin-shell problems, though DDT's role in the decline of the California condor is disputed.

The biological thinning mechanism is not entirely understood, but DDE appears to be more potent than DDT, and strong evidence indicates that p,p'-DDE inhibits calcium ATPase in the membrane of the shell gland and reduces the transport of calcium carbonate from blood into the eggshell gland. This results in a dose-dependent thickness reduction. Other evidence indicates that o,p'-DDT disrupts female reproductive tract development, later impairing eggshell quality. Multiple mechanisms may be at work, or different mechanisms may operate in different species.

Human health

A U.S. soldier is demonstrating DDT hand-spraying equipment. DDT was used to control the spread of typhus-carrying lice.
Spraying hospital beds with DDT, PAIGC hospital of Ziguinchor, 1973
Biomagnification is the build up of toxins in a food chain. The DDT concentration is in parts per million. As the trophic level increases in a food chain, the amount of toxic build up also increases. The X's represent the amount of toxic build up accumulating as the trophic level increases. Toxins build up in organism's tissues and fat. Predators accumulate higher toxins than the prey.

DDT is an endocrine disruptor. It is considered likely to be a human carcinogen although the majority of studies suggest it is not directly genotoxic. DDE acts as a weak androgen receptor antagonist, but not as an estrogen. p,p'-DDT, DDT's main component, has little or no androgenic or estrogenic activity. The minor component o,p'-DDT has weak estrogenic activity.

Acute toxicity

DDT is classified as "moderately toxic" by the U.S. National Toxicology Program (NTP) and "moderately hazardous" by WHO, based on the rat oral LD50 of 113 mg/kg. Indirect exposure is considered relatively non-toxic for humans.

Chronic toxicity

Primarily through the tendency for DDT to build up in areas of the body with high lipid content, chronic exposure can affect reproductive capabilities and the embryo or fetus.

  • A review article in The Lancet states: "research has shown that exposure to DDT at amounts that would be needed in malaria control might cause preterm birth and early weaning ... toxicological evidence shows endocrine-disrupting properties; human data also indicate possible disruption in semen quality, menstruation, gestational length, and duration of lactation".
  • Other studies document decreases in semen quality among men with high exposures (generally from indoor residual spraying).
  • Studies are inconsistent on whether high blood DDT or DDE levels increase time to pregnancy. In mothers with high DDE blood serum levels, daughters may have up to a 32% increase in the probability of conceiving, but increased DDT levels have been associated with a 16% decrease in one study.
  • Indirect exposure of mothers through workers directly in contact with DDT is associated with an increase in spontaneous abortions.
  • Other studies found that DDT or DDE interfere with proper thyroid function in pregnancy and childhood.
  • Mothers with high levels of DDT circulating in their blood during pregnancy were found to be more likely to give birth to children who would go on to develop autism.

Carcinogenicity

In 2015, the International Agency for Research on Cancer classified DDT as Group 2A "probably carcinogenic to humans". Previous assessments by the U.S. National Toxicology Program classified it as "reasonably anticipated to be a carcinogen" and by the EPA classified DDT, DDE and DDD as class B2 "probable" carcinogens; these evaluations were based mainly on animal studies.

A 2005 Lancet review stated that occupational DDT exposure was associated with increased pancreatic cancer risk in 2 case control studies, but another study showed no DDE dose-effect association. Results regarding a possible association with liver cancer and biliary tract cancer are conflicting: workers who did not have direct occupational DDT contact showed increased risk. White men had an increased risk, but not white women or black men. Results about an association with multiple myeloma, prostate and testicular cancer, endometrial cancer and colorectal cancer have been inconclusive or generally do not support an association. A 2017 review of liver cancer studies concluded that "organochlorine pesticides, including DDT, may increase hepatocellular carcinoma risk".

A 2009 review, whose co-authors included persons engaged in DDT-related litigation, reached broadly similar conclusions, with an equivocal association with testicular cancer. Case–control studies did not support an association with leukemia or lymphoma.

Breast cancer

The question of whether DDT or DDE are risk factors in breast cancer has not been conclusively answered. Several meta analyses of observational studies have concluded that there is no overall relationship between DDT exposure and breast cancer risk. The United States Institute of Medicine reviewed data on the association of breast cancer with DDT exposure in 2012 and concluded that a causative relationship could neither be proven nor disproven.

A 2007 case-control study using archived blood samples found that breast cancer risk was increased 5-fold among women who were born prior to 1931 and who had high serum DDT levels in 1963. Reasoning that DDT use became widespread in 1945 and peaked around 1950, they concluded that the ages of 14–20 were a critical period in which DDT exposure leads to increased risk. This study, which suggests a connection between DDT exposure and breast cancer that would not be picked up by most studies, has received variable commentary in third-party reviews. One review suggested that "previous studies that measured exposure in older women may have missed the critical period". The National Toxicology Program notes that while the majority of studies have not found a relationship between DDT exposure and breast cancer that positive associations have been seen in a "few studies among women with higher levels of exposure and among certain subgroups of women".

A 2015 case control study identified a link (odds ratio 3.4) between in-utero exposure (as estimated from archived maternal blood samples) and breast cancer diagnosis in daughters. The findings "support classification of DDT as an endocrine disruptor, a predictor of breast cancer, and a marker of high risk".

Malaria control

Malaria remains the primary public health challenge in many countries. In 2015, there were 214 million cases of malaria worldwide resulting in an estimated 438,000 deaths, 90% of which occurred in Africa. DDT is one of many tools to fight the disease. Its use in this context has been called everything from a "miracle weapon [that is] like Kryptonite to the mosquitoes", to "toxic colonialism".

Before DDT, eliminating mosquito breeding grounds by drainage or poisoning with Paris green or pyrethrum was sometimes successful. In parts of the world with rising living standards, the elimination of malaria was often a collateral benefit of the introduction of window screens and improved sanitation. A variety of usually simultaneous interventions represents best practice. These include antimalarial drugs to prevent or treat infection; improvements in public health infrastructure to diagnose, sequester and treat infected individuals; bednets and other methods intended to keep mosquitoes from biting humans; and vector control strategies such as larvaciding with insecticides, ecological controls such as draining mosquito breeding grounds or introducing fish to eat larvae and indoor residual spraying (IRS) with insecticides, possibly including DDT. IRS involves the treatment of interior walls and ceilings with insecticides. It is particularly effective against mosquitoes, since many species rest on an indoor wall before or after feeding. DDT is one of 12 WHO–approved IRS insecticides.

The WHO's anti-malaria campaign of the 1950s and 1960s relied heavily on DDT and the results were promising, though temporary in developing countries. Experts tie malarial resurgence to multiple factors, including poor leadership, management and funding of malaria control programs; poverty; civil unrest; and increased irrigation. The evolution of resistance to first-generation drugs (e.g. chloroquine) and to insecticides exacerbated the situation. Resistance was largely fueled by unrestricted agricultural use. Resistance and the harm both to humans and the environment led many governments to curtail DDT use in vector control and agriculture. In 2006 WHO reversed a longstanding policy against DDT by recommending that it be used as an indoor pesticide in regions where malaria is a major problem.

Once the mainstay of anti-malaria campaigns, as of 2008 only 12 countries used DDT, including India and some southern African states, though the number was expected to rise.

Initial effectiveness

When it was introduced in World War II, DDT was effective in reducing malaria morbidity and mortality. WHO's anti-malaria campaign, which consisted mostly of spraying DDT and rapid treatment and diagnosis to break the transmission cycle, was initially successful as well. For example, in Sri Lanka, the program reduced cases from about one million per year before spraying to just 18 in 1963 and 29 in 1964. Thereafter the program was halted to save money and malaria rebounded to 600,000 cases in 1968 and the first quarter of 1969. The country resumed DDT vector control but the mosquitoes had evolved resistance in the interim, presumably because of continued agricultural use. The program switched to malathion, but despite initial successes, malaria continued its resurgence into the 1980s.

DDT remains on WHO's list of insecticides recommended for IRS. After the appointment of Arata Kochi as head of its anti-malaria division, WHO's policy shifted from recommending IRS only in areas of seasonal or episodic transmission of malaria, to advocating it in areas of continuous, intense transmission. WHO reaffirmed its commitment to phasing out DDT, aiming "to achieve a 30% cut in the application of DDT world-wide by 2014 and its total phase-out by the early 2020s if not sooner" while simultaneously combating malaria. WHO plans to implement alternatives to DDT to achieve this goal.

South Africa continues to use DDT under WHO guidelines. In 1996, the country switched to alternative insecticides and malaria incidence increased dramatically. Returning to DDT and introducing new drugs brought malaria back under control. Malaria cases increased in South America after countries in that continent stopped using DDT. Research data showed a strong negative relationship between DDT residual house sprayings and malaria. In a research from 1993 to 1995, Ecuador increased its use of DDT and achieved a 61% reduction in malaria rates, while each of the other countries that gradually decreased its DDT use had large increases.

Mosquito resistance

In some areas, resistance reduced DDT's effectiveness. WHO guidelines require that absence of resistance must be confirmed before using the chemical. Resistance is largely due to agricultural use, in much greater quantities than required for disease prevention.

Resistance was noted early in spray campaigns. Paul Russell, former head of the Allied Anti-Malaria campaign, observed in 1956 that "resistance has appeared after six or seven years". Resistance has been detected in Sri Lanka, Pakistan, Turkey and Central America and it has largely been replaced by organophosphate or carbamate insecticides, e.g. malathion or bendiocarb.

In many parts of India, DDT is ineffective. Agricultural uses were banned in 1989 and its anti-malarial use has been declining. Urban use ended. One study concluded that "DDT is still a viable insecticide in indoor residual spraying owing to its effectivity in well supervised spray operation and high excito-repellency factor."

Studies of malaria-vector mosquitoes in KwaZulu-Natal Province, South Africa found susceptibility to 4% DDT (WHO's susceptibility standard), in 63% of the samples, compared to the average of 87% in the same species caught in the open. The authors concluded that "Finding DDT resistance in the vector An. arabiensis, close to the area where we previously reported pyrethroid-resistance in the vector An. funestus Giles, indicates an urgent need to develop a strategy of insecticide resistance management for the malaria control programmes of southern Africa."

DDT can still be effective against resistant mosquitoes and the avoidance of DDT-sprayed walls by mosquitoes is an additional benefit of the chemical. For example, a 2007 study reported that resistant mosquitoes avoided treated huts. The researchers argued that DDT was the best pesticide for use in IRS (even though it did not afford the most protection from mosquitoes out of the three test chemicals) because the other pesticides worked primarily by killing or irritating mosquitoes – encouraging the development of resistance. Others argue that the avoidance behavior slows eradication. Unlike other insecticides such as pyrethroids, DDT requires long exposure to accumulate a lethal dose; however its irritant property shortens contact periods. "For these reasons, when comparisons have been made, better malaria control has generally been achieved with pyrethroids than with DDT." In India outdoor sleeping and night duties are common, implying that "the excito-repellent effect of DDT, often reported useful in other countries, actually promotes outdoor transmission".

Residents' concerns

IRS is effective if at least 80% of homes and barns in a residential area are sprayed. Lower coverage rates can jeopardize program effectiveness. Many residents resist DDT spraying, objecting to the lingering smell, stains on walls, and the potential exacerbation of problems with other insect pests. Pyrethroid insecticides (e.g. deltamethrin and lambda-cyhalothrin) can overcome some of these issues, increasing participation.

Human exposure

A 1994 study found that South Africans living in sprayed homes have levels that are several orders of magnitude greater than others. Breast milk from South African mothers contains high levels of DDT and DDE. It is unclear to what extent these levels arise from home spraying vs food residues. Evidence indicates that these levels are associated with infant neurological abnormalities.

Most studies of DDT's human health effects have been conducted in developed countries where DDT is not used and exposure is relatively low.

Illegal diversion to agriculture is also a concern as it is difficult to prevent and its subsequent use on crops is uncontrolled. For example, DDT use is widespread in Indian agriculture, particularly mango production and is reportedly used by librarians to protect books. Other examples include Ethiopia, where DDT intended for malaria control is reportedly used in coffee production, and Ghana where it is used for fishing. The residues in crops at levels unacceptable for export have been an important factor in bans in several tropical countries. Adding to this problem is a lack of skilled personnel and management.

Criticism of restrictions on DDT use

Restrictions on DDT usage have been criticized by some organizations opposed to the environmental movement, including Roger Bate of the pro-DDT advocacy group Africa Fighting Malaria and the libertarian think tank Competitive Enterprise Institute; these sources oppose restrictions on DDT and attribute large numbers of deaths to such restrictions, sometimes in the millions. These arguments were rejected as "outrageous" by former WHO scientist Socrates Litsios. May Berenbaum, University of Illinois entomologist, says, "to blame environmentalists who oppose DDT for more deaths than Hitler is worse than irresponsible". More recently, Michael Palmer, a professor of chemistry at the University of Waterloo, has pointed out that DDT is still used to prevent malaria, that its declining use is primarily due to increases in manufacturing costs, and that in Africa, efforts to control malaria have been regional or local, not comprehensive.

The question that ... malaria control experts must ask is not "Which is worse, malaria or DDT?" but rather "What are the best tools to deploy for malaria control in a given situation, taking into account the on-the-ground challenges and needs, efficacy, cost, and collateral effects – both positive and negative – to human health and the environment, as well as the uncertainties associated with all these considerations?"

Hans Herren & Charles Mbogo

Criticisms of a DDT "ban" often specifically reference the 1972 United States ban (with the erroneous implication that this constituted a worldwide ban and prohibited use of DDT in vector control). Reference is often made to Silent Spring, even though Carson never pushed for a DDT ban. John Quiggin and Tim Lambert wrote, "the most striking feature of the claim against Carson is the ease with which it can be refuted".

Investigative journalist Adam Sarvana and others characterize these notions as "myths" promoted principally by Roger Bate of the pro-DDT advocacy group Africa Fighting Malaria (AFM).

Alternatives

Insecticides

Organophosphate and carbamate insecticides, e.g. malathion and bendiocarb, respectively, are more expensive than DDT per kilogram and are applied at roughly the same dosage. Pyrethroids such as deltamethrin are also more expensive than DDT, but are applied more sparingly (0.02–0.3 g/m2 vs 1–2 g/m2), so the net cost per house per treatment is about the same. DDT has one of the longest residual efficacy periods of any IRS insecticide, lasting 6 to 12 months. Pyrethroids will remain active for only 4 to 6 months, and organophosphates and carbamates remain active for 2 to 6 months. In many malaria-endemic countries, malaria transmission occurs year-round, meaning that the high expense of conducting a spray campaign (including hiring spray operators, procuring insecticides, and conducting pre-spray outreach campaigns to encourage people to be home and to accept the intervention) will need to occur multiple times per year for these shorter-lasting insecticides.

In 2019, the related compound difluorodiphenyltrichloroethane (DFDT) was described as a potentially more effective and therefore potentially safer alternative to DDT.

Non-chemical vector control

Before DDT, malaria was successfully eliminated or curtailed in several tropical areas by removing or poisoning mosquito breeding grounds and larva habitats, for example by eliminating standing water. These methods have seen little application in Africa for more than half a century. According to CDC, such methods are not practical in Africa because "Anopheles gambiae, one of the primary vectors of malaria in Africa, breeds in numerous small pools of water that form due to rainfall ... It is difficult, if not impossible, to predict when and where the breeding sites will form, and to find and treat them before the adults emerge."

The relative effectiveness of IRS versus other malaria control techniques (e.g. bednets or prompt access to anti-malarial drugs) varies and is dependent on local conditions.

A WHO study released in January 2008 found that mass distribution of insecticide-treated mosquito nets and artemisinin–based drugs cut malaria deaths in half in malaria-burdened Rwanda and Ethiopia. IRS with DDT did not play an important role in mortality reduction in these countries.

Vietnam has enjoyed declining malaria cases and a 97% mortality reduction after switching in 1991 from a poorly funded DDT-based campaign to a program based on prompt treatment, bednets and pyrethroid group insecticides.

In Mexico, effective and affordable chemical and non-chemical strategies were so successful that the Mexican DDT manufacturing plant ceased production due to lack of demand.

A review of fourteen studies in sub-Saharan Africa, covering insecticide-treated nets, residual spraying, chemoprophylaxis for children, chemoprophylaxis or intermittent treatment for pregnant women, a hypothetical vaccine and changing front–line drug treatment, found decision making limited by the lack of information on the costs and effects of many interventions, the small number of cost-effectiveness analyses, the lack of evidence on the costs and effects of packages of measures and the problems in generalizing or comparing studies that relate to specific settings and use different methodologies and outcome measures. The two cost-effectiveness estimates of DDT residual spraying examined were not found to provide an accurate estimate of the cost-effectiveness of DDT spraying; the resulting estimates may not be good predictors of cost-effectiveness in current programs.

However, a study in Thailand found the cost per malaria case prevented of DDT spraying (US$1.87) to be 21% greater than the cost per case prevented of lambda-cyhalothrin–treated nets (US$1.54), casting some doubt on the assumption that DDT was the most cost-effective measure. The director of Mexico's malaria control program found similar results, declaring that it was 25% cheaper for Mexico to spray a house with synthetic pyrethroids than with DDT. However, another study in South Africa found generally lower costs for DDT spraying than for impregnated nets.

A more comprehensive approach to measuring the cost-effectiveness or efficacy of malarial control would not only measure the cost in dollars, as well as the number of people saved, but would also consider ecological damage and negative human health impacts. One preliminary study found that it is likely that the detriment to human health approaches or exceeds the beneficial reductions in malarial cases, except perhaps in epidemics. It is similar to the earlier study regarding estimated theoretical infant mortality caused by DDT and subject to the criticism also mentioned earlier.

A study in the Solomon Islands found that "although impregnated bed nets cannot entirely replace DDT spraying without substantial increase in incidence, their use permits reduced DDT spraying".

A comparison of four successful programs against malaria in Brazil, India, Eritrea and Vietnam does not endorse any single strategy but instead states, "Common success factors included conducive country conditions, a targeted technical approach using a package of effective tools, data-driven decision-making, active leadership at all levels of government, involvement of communities, decentralized implementation and control of finances, skilled technical and managerial capacity at national and sub-national levels, hands-on technical and programmatic support from partner agencies, and sufficient and flexible financing."

DDT resistant mosquitoes may be susceptible to pyrethroids in some countries. However, pyrethroid resistance in Anopheles mosquitoes is on the rise with resistant mosquitoes found in multiple countries.

Human extinction

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