Environmental Chemistry Fall 2024 PDF

PARABENS Found in about half of all personal care products, parabens and their degradation products are heavily released from waste water effluents. Chlorinated Parabens (through reaction with HClO /NaClO) are not easily removed by WWTPs. Their endocrine disrupting potential increases as their este...

PARABENS Found in about half of all personal care products, parabens and their degradation products are heavily released from waste water effluents. Chlorinated Parabens (through reaction with HClO /NaClO) are not easily removed by WWTPs. Their endocrine disrupting potential increases as their ester chain increases. Harmful to aquatic life. The list of POPs and other ubiquitous anthropogenic chemicals goes on...  Polyfluorinated organic substances (PFOS): Extrememly persistent, absorbed in the body rendering cells to be more permeable, some are endocrine (Thyroid) disruptors...  Some ethers, e.g. Methyl-tert-butyl ether (MTBE), affects nervous system, cause cancer depending on dose...  Alkyl Phenols, e.g. Nonyl-phenol, mimics oestrogen hormone, endocrine disruptor...  Bisphenol-A (BPA), used in plastic production, high EDC activity at very low doses... .... .... 66 Some of the most common PFOs, ubiquitous in the entire environment 67 An Important target of Chemical Pollutants in Body: THYROID GLAND AND THYROID HORMONES Thyroid glands and the FINE BALANCE and TIMING of the production of thyroid hormones are responsible of development of body and brain. Hormone concentrations are especially crucial in brain development of babies at prenatal stage and first years after birth. Triiodothyronine Several POPs (PCBs, Dioxins, etc.) with similar chemical structures impair the Thyroid Function by: -Impairing Iodine uptake by the gland -Blocking the hormone making enzyme -Displacing the natural hormone in blood proteins impairig Thyroxine distribution and entry. 68 Some global statistics about iodine deficiency (WHO 2004) 69  Agonist/Antagonist in Biochemistry Agonist: An endogenous (e.g. natural hormones, neurotransmitters) or exogenous (e.g. drugs, pollutants) chemical that binds to a specific receptor and activates the receptor to produce a biological response. Antagonist: A chemical that blocks a specific biological response or the activity of an agonist, by binding to and blocking its target receptor. Also called ‘blocker’. For example: -Triclosan (a common antibacterial agent) is known to disrupt thyroid systems in laboratory rats and frogs. One possible pathway is through ‘agonism or antagonism’ to specific nuclear receptors that are responsible of regulating catabolic and transport activity. -Triclosan, may be an antagonist or weak agonist of the estrogen receptor and/or a weak antagonist of the androgen receptor. All deiodinase enzymes are selenoproteins (or selenoenzymes); that is, they all contain selenium (Se). 71 Mercury, its effect on Thyroid system: Organic mercury (such as in methyl or ethyl mercury) can be converted to inorganic mercury by microorganisms in the intestine. Inorganic mercury can persist in the brain for long periods. ***Inorganic mercury interacts with selenium, forming mercury selenite, HgSe, which is thought to be the form that is retained in the central nervous system. Cadmium has similar interactions with Selenium… 72 Structural comparison of some EDCs to thyroid hormones: Note all the compounds share strong structural homology with thyroid hormone (in this case T4 is depicted). It is also pertinent to recall that TBBPA is broken down to BPA in the environment, increasing BPA load. Reference: ‘Losing Our Mind’ book by B. Demeneix 73  TRICLOSAN Antibacterial agent developed in 1960s by Ciba-Geigy (now produced by BASF), commonly found in many products such as soaps, washing gels, shampoos, personal care products, toothpastes, pesticides, etc. USA-FDA (Food and drug administration) banned its use in consumer antiseptic washes, by september 2017. Ubiquitous in the environment, and found as a contaminant in human body, it is a weak endocrine disruptor an allergen. vs. Triclosan Triiodothyronine (natural hormone) Triclocarban, another antibacterial agent, with similar properties as triclosan  Triclosan (anthropogenic) Triiodothyronine (natural hormone) Both molecules share similar skeleton, major difference being presence of chlorine or iodine atoms surrounding the aromatic groups. Both chlorine and iodine are capable of forming ‘Halogen Bonds’. A parallel relationship can easily be drawn between halogen bonding and hydrogen bonding. In halogen bonding, a halogen atom is the electron acceptor. Iodine forms the strongest halogen bonds. Halogen bonds are strong, directional, and lead to specific binding angles. In the case of protein-ligand interactions, the most common charge-transfer bonds with polarizable halogens involve backbone carbonyls and/or hydroxyl and carboxylate groups of amino acid residues. Thyroid health problems result in a large range of symptoms such as obesity, depression, infertility, IQ loss…. 75  What happens when foreign chemicals in the body act together? Cocktail Effect!! Examples of ublished experiments reveal results such as: Four chemicals are tested individually for toxicity at concentrations that is below their LD50 : No harmful effect Same four chemicals at the same doses, when tested in combination: Very harmful health effects Cocktail effect is a phenomena that scientist are just beginning to study in the last years and we have very little knowledge about it.... 76 EPIGENETICS 77  EPIGENETICS: Environmental factors affect the gene functioning through activations or deactivations of genes, without a change in gene sequence. However these changes can be transmitted to next generation (heritable), if similar environmental factors continue to be present. DNA methylation and histone modification, each alters how genes are expressed without altering the underlying DNA sequence 78  Ülkemizde Atıksu Arıtma Tesisleri Çıkışında ÇKS Değerlerini Aşan Mikrokirleticilerin Listesi (TR 2017) 1 1,1-Dikloroetan 21 Asetamiprid 41 Dibutilkalay oksit 2 1-metilnaftalin 22 Azinfos-metil 42 Dieldrin 3 BBP 23 Azoksistrobin 43 Dietil Fitalat 4 1,1-Dikloroetan 24 B 44 Difenil eter; difenil oksit 5 1,2,4-trimetilbenzen 25 BBP 45 Difenilamin 6 1,3,5-trimetilbenzen; Mesitilen 26 Be 46 Diflubenzuron 7 1,3-diklorobenzen 27 Bentazon 47 Diflufenikan 8 1,4-diklorobenzen 28 Benzil benzoat 48 Diizobütil adipat 9 17-beta-estradiyol 29 Benzo(a)floren 49 Diklofenak 10 1-kloro-2,4-dinitrobenzen 30 Benzo(e)piren 50 Dimetenamid 11 1-metilnaftalin 31 Bifenil 51 Dimetoat 12 2,4-d; (2,4-diklorofenoksi)asetikasit 32 Bis(2-etilhekzil) terefitalat 52 Dimetomorf 13 2,6-di-ter-butilfenol;2,6-di-tersiyerbutilfenol 33 Bisfenol-A 53 DnOP 14 2,6-ksilenol 34 Boskalid 54 Epoksikonazol 15 2-amino-4-klorofenol 35 Bromoksinil 55 Etalfluralin 16 2-kloronaftalin 36 Buprofezin 56 Etoprofos 17 4-Kloro-3-metilfenol; Paraklorometakresol 37 DBP 57 Fenantren 18 4-kloroanilin 38 DDT Toplam 58 Fenarimol 19 Aldrin 39 Dekametilsiklopentasiloksan; Siloksan-D5 59 Feneksamid 20 Asenaften 40 Diazinon 60 Floren 61 Fludioksonil 81 Klorfenapir 101 p,p′-DDD 62 Fluopiram 82 Krisen 102 p,p'-DDE 63 Fostiazat 83 Ksilen (m) 103 p,p'-DDT 64 Hekzakonazol 84 Ksilen (o) 104 PCB 138 65 Hekzitiazoks 85 Ksilen misk 105 PCB 28 66 Imazalil 86 Lenasil 106 PCB 31 67 Imazapir 87 Linuron 107 PCB 52 68 Imidakloprid 88 MBT 108 Penkonazol 69 Isodrin 89 Metalaksil 109 Perilen 70 Izopropilbenzen 90 Metalaksil 110 Permetrin 71 Kadusafos 91 Metam potasyum 111 Piperonil butoksit 72 Karbaril 92 Metoksifenozid 112 Piren 73 Karbendazim 93 Metolaklor 113 Pirimetanil 74 Karbofuran 94 Metrafenon 114Prokloraz; N-propil-N-[2-(2,4,6-triklorofenoksi)etil]-1H-imidazol-1- karboksamid 75 Karbontetraklorür 95 Miklobutanil 115 Propamokarb HCL 76 Klofentezin 96 Molinat 116 Propetamfos 77 Klofibrik asit 97 n-bütilkalay triklorür 117 Propilbenzen 78 Klopiralid 98 Nikosulfuron 118 Siflutrin; beta siflutrin 79 Klorantraniliprol 99 Ometoat 119 Siprodinil 80 Klordan 100 p-(1,1-dimetilpropil)fenol 120 Siromazin 121 Stiren; Vinilbenzen Ülkemizde İçme Suyu Arıtma Tesisleri Çıkışında Yüksek 122 Sülfametoksazol KonsantrasyondaTespit Edilen Mikrokirleticilerin Listesi 123 Tebukonazol (TR 2017) 124 Teflutrin 125 Tiabendazol 1 Heptaklor epoksit 126 Tiakloprid 2 Diklorometan 127 Tiametokzam 3 Benzen 128 Tidiazuron 4 Tribenuron-metil 129 Tiofanat-metil 5 Asetaklor 130 Tolfenpirad 6 Fentiyon 7 Triklosan 131 TRI 8 Sipermetrin 132 Triadimenol; α-ter-bütil-β-(4-klorofenoksi)-1H-1,2,4-triazol-1- 9 Trikloro-metan etanol 10 Vanadyum 133 Tributil fosfat 11 Perklorat 134 Tridecane 135 Trifenilkalay; Fentin 136 Vanadyum  PESTICIDE POLLUTION IN SOIL AND WHEAT: RISK ASSESSMENT OF CONTAMINATED FOOD CONSUMPTION By:Beduk, F (Beduk, Fatma)[ 1 ] ; Aydin, ME (Aydin, Mehmet Emin)[ 1 ] ; Aydin, S (Aydin, Senar)[ 1 ] ; Tekinay, A (Tekinay, Arzu)[ 1 ] ; Bahadir, M (Bahadir, Mufit)[ 2 ] FRESENIUS ENVIRONMENTAL BULLETIN Volume: 26 Issue: 3 Pages: 2330-2339 Published: 2017 View Journal Impact Abstract In this study, organochlorine pesticides (OCPs) and organophosphorus pesticides (OPPs) contamination of wheat cultivated in Konya region and soils of this region were determined. Health risk caused by the consumption of pesticide contaminated wheat was assessed. Totally, 30 soil samples and 21 wheat samples taken from the field and trade center were analyzed for OCPs (alpha-HCH, beta-HCH, gamma-HCH, delta-HCH, aldrin, dieldrin, heptachlor, heptachlor epoxide, endosulfan I, endosulfan II, endosulfan sulfate, p,p'-DDE, p,p'-DDD, p,p'-DDT, endrin, endrin aldehyde, endrin ketone, methoxychlor) and OPPs (malathion, parathion, methyl-parathion, chlorpyrifos, diazinon). Determinations of OCPs and OPPs were carried out with a GC/MSD (GC, Agilent 6890 N, MSD, Agilent 5973). Maximum concentrations of OCPs in soil samples were found for Sigma HCHs (alpha-HCH, beta-HCH, gamma-HCH, delta-HCH) and Sigma endosulfan (endosulfan I, endosulfan II, endosulfan sulfate) in the range of 8.74 - 71.8 ng g(-1) and 1.99 - 112 ng g(-1), respectively. Malathion and chlorpyrifos were the predominant OPPs in soil and wheat samples. Maximum concentrations of malathion and chlorpyrifos in soil samples were 222 ng g(-1) and 556 ng g(-1), respectively. Maximum total OCPs and total OPPs in the grain were 2.32 mu g g(-1) and 15.4 mu g g(-1), respectively. Sigma DDT was found in the range of 20 60 ng g(-1) in grain samples. Trade center samples exceeded maximum residue limits (MRL) of Turkish Food Codex (TFC) given for beta-HCH, gamma-HCH, Sigma HCH, dieldrin and chlorpyrifos, and field samples exceeded MRL given for a- HCH, beta-HCH, Sigma HCH, Sigma endosulfan, Sigma heptachlor, and all OPP compounds. There is an acute and chronic consumer health risk due to the consumption of pesticide contaminated wheat, on the basis of aHI and HQ calculation. Besides, prohibited pesticides are obviously still being used in the area. [ 1 ] Necmettin Erbakan Univ, Dept Environm Engn, Konya, Turkey Show more [ 2 ] Tech Univ Carolo Wilhelmina Braunschweig, Inst Environm & Sustainable Chem, Hagenring 30, D-38106 Braunschweig, Germany Air Pollution 83  1.Ozone Depletion A natural belt of ozone (O3, a reactive molecule ) at 15-30 km (stratosphere) above the surface, and it shields harmful UV-B radiation emmitted by sun. Ozone layer was known since 1920s-1930s. Gordon Dobson developed the ‘ozone spectrophotometer’, measuring 305 nm UV absorption by ozone (at 325 nm not absorbing). Ozone layer is 400 D.U. (Dobson Unit, 2.7x1016 molecules/cm2) which makes 4 mm thick when brought to Earth’s surface. ❖ Ozone Depletion : slow, steady decline of about 4% per decade that has been observed since 1970s. ❖ Ozone Hole : a much larger depletion (up to 65%), seasonal depletion occuring in polar regions. First discovery by Joe Farman (British Arctic Survey) in 1984. 84  Stratospheric Ozone Depletion ❖ The largest hole in Antarctic (South Pole) was observed in 2006 (fall). This hole was about 10.6 million square miles (nearly the size of N. America). ❖ The largest hole in Arctic (North Pole) was observed in 2011, at the same size of the hole in South Pole that year. ❖ Holes in polar regions are expected to completely recover by 2060-2080, if ODSs were no more released. 85  Major Source of the Ozone Depletion Ozone Depleting Substances (ODS): Chlorofluorocarbon (CFCs), HCFCs, freons, halons. They are produced in large quantities to be used in air conditioning, cooling, aerosol sprays, solvents etc. in the past 50 years. (e.g. CHCl3, CCl4) CFCl3 sun radiation Cl + CFCl2 Cl + O3 ClO + O2 ClO + O3 Cl + 2O2 ❖ Cl radical reacts catalytically, single Cl radical can destroy 100.000 ozone molecules. ❖ Although Br radicals are more active, there is much less Br radical in atmosphere at present. ❖ 90 % of ODSs were emitted by industrial countries in the northern hemisphere. 86  Harmful effects of Ozone Depletion Thinner ozone leads to more UV-B radiation reaching Earth and it is suspected to result in:  Increase in skin cancer occurrence.  Increase in cataracts.  Damage to plants.  Large scale loss of phytoplanktons (especially in polar regions) 87  2. Photochemical Smog SMOG = Smoke + Fog ❖ First appearance was in England, 1883. ❖ CONTENT of Smog Aldehydes (RCHO) Nitrogen Oxides (NO2 etc.) Peroxyacetyl Nitrates (PAN) Tropospheric Ozone (O3) Volatile Organic Compounds Heavy Metals (Pb, Hg, Cd etc.) 88  Content of Photochemical Smog (cont.d) ❖ Photochemical smog is produced mainly by fuel and coal burning. Major contributors are SO2, CO and especially NO2. NO2 NO + O O + O2 O3 ❖ O3 is harmful to eyes, throat, respiratory system, agriculture etc. ❖ Incomplete combustion of carbon based fuels results in formation of volatile PAHs (they cause lung cancer). 89 Particulate Matter (PM or Aerosols) as Air Pollutant PMs are microscopic or sub-microscopic size, natural or anthropogenic, solid or liquid particles suspended in the air. PM10 : Inhalable particles with diameters that are 10 micrometers or smaller PM2.5 : Inhalable particles, with diameters that are 2.5 micrometers or smaller. They are adversely affecting ‘climate’ and ‘rain’ patterns in addition to being very harmful to human health through inhalation. They can get deep into your lungs and some may even get into your bloodstream. Smaller particles (PM2.5) pose the greatest risk to health. Common sources include power plants, industries, automobiles, construction sites, fields, fires. 90  Health Hazards of Photochemical Smog ❖In a historical example in 1952, Great Smoke killed about 4000 people in 4 days and another 8000 poeple died in the following months in London. ❖The Global Burden of Disease Study estimated that the worldwide impact of ‘outdoor’ air pollution [particulate matter (PM)2.5] was as many as 4.2 million deaths and 103 million disability-adjusted life years (DALYs) in 2015. ❖Exposure to ozone caused an additional 254 000 deaths and a loss of 4.1 million DALYs from chronic obstructive pulmonary disease in 2015. ❖In addition, high acute NO2 exposure levels are associated with a significant increase in cardiovascular mortality 91  Air Pollution Causes Premature Deaths PM is an air pollutant that causes cardiovascular and respiratory moralities, and it causes loss of life expectancy. if humans stop completely fossil fuel emissions, the global mean life expectancy would increase by 1.1 (0.9–1.2) years and 1.7 (1.4– 2.0) years It is estimated that PM2.5 exposure in India leads to about 570,000 (CI95: 320,000–730,000) premature mortalities in 2011 Just in Europe, 403000 people died because of PM 2.5 , 16000 because of tropospheric ozone, 72000 because of NO 2 in 2012. Research was conducted for 40 European countries.  3. Acid Rain ❖ The pH of natural rain is approximately 5.7. Acid rain decreases the pH to 2.4. Major source of the acidity in the rain is SO2 and NOx which is mainly coming from coal burning and other fossil-fuels. Globally an approximate of 150 million tonnes SO2/year was discharged into atmosphere. H2O + CO2 H2CO3 (Natural source for acidity) SO2 + OH HOSO2 HOSO2 + O2 HO2 + SO3 (Man-released sources) SO3 + H2O H2SO4 NO2 + OH HNO3 ❖ Acid rain was discovered in UK in 1882. However, it was first started to be studied in 1960. 93  Precautions and Results ❖ Reduction of SO2 emission was targeted in 1980 via Acid Deposition Act and in 1990 with a series of amendments. ❖ Total reduction of 10 million tons of SO2 was targeteded in 1990. The second phase of reduction was started in 2000. ❖ Since 1990, SO2 emission dropped as 40 % in USA, thus acid rain dropped 65 % in USA (70 % in Europe). 94  4. Global Climate Change- Warming and Dimming ❖ Global Warming is the rise in the average temperature of Earth’s atmosphere and oceans since the late 19th century and it is projected to continue. Increase in the greenhouse gases concentration especially in the CO2 is the major factor of warming. Since the beginning of the industrial revolution, CO2 concentration has raised from 280 ppm to 400 ppm today. CO2 mainly comes from fossil fuel burning (Coal 35%, Oil 36%, Natural gas 20%) Meanwhile, many other anthropogenic gases with much higher warming potential are also being released to the atmosphere (N20, CCl2F2, CF4, hexafluoroethane, SF6, etc.) 95 Livestock accounts for about 14.5% of ’Anthropogenic Greenhouse Gas Emisions’ estimated as 100-year CO2 equivalents GWP (Global Warming Potential) for CO2 is taken as exactly ‘1’ 96 97 ❖ Global Dimming is the gradual reduction in the amount of global direct irradiance at the Earth’s surface that was observed since 1950s. Today there is an average of 10% to 30% less solar radiation reaching Earth’s surface.  Artificial clouds are formed by aerosols which are industrial dust, mainly consisting of SO2 particulates. SO2 is mainly release by coal burning.  Pollution driven formation of artificial clouds leads to dangerous disruption in Earth’s atmospheric hydrological cycles, leading to drastic changes in weather patterns. One important example is the 1980’s subsaharan drought, killing more than a million people in Ethiopian region.  If pollutant aerosols are cleaned from atmosphere but the green house emissions continue than an increased effect of atmospheric warming occurs leading to extremely warm temperatures. One example is ‘European brightening’ that occured after limiting SO2 emissions in Europe, thousands of people died in France in summers of early 2000s. 98  Ocean Acidification An estimated 30–40% of the carbon dioxide from human activity released into the atmosphere dissolves into seas, lakes and rivers. Dissolved CO2 reacts with water to release carbonic acid (H2CO3), which increase H+ ion concentration in oceans by about 35%, decreasing pH from 8,25 to 8,14 between 1751 and 1996. Increased acidity is already being detrimental to aquatic life, especially for calcifying organisms (coccolithophores, corals, foraminifera, echinoderms, crustaceans and molluscs), as the pH goes down, consequently carbonate becomes undersaturated, then aquatic species that contain shells made of calcium carbonate become vulnerable to dissolution. Severe consequences of multi-faced alteration of natural environmental conditions: In its 2014 Living Planet Report, WWF has recently announced that Living Planet Index (LPI), which measures more than 10,000 representative populations of mammals, birds, reptiles, amphibians and fish, has declined by 52 per cent since 1970! (about 60% by 2017) Severe fall in insect populations are also well documented… 100