난사람 : 재물 든사람 : 지식 된사람 : 인격

초등생 가방 완구서 납-불임물질 기준치 최대 386배 초과… 21종 리콜 초등학생용 가방과 완구 등에서 불임 물질 등 유해성분이 대거 검출돼 정부가 리콜 명령을 내렸다. 산업통상자원부 산하 국가기술표준원은 학생용품과 완구 등 212개 제품을 대상으로 안전성 조사를 한 결과 위해성이 드러난 초등학생용 가방 7종과 필통 2종, 완구 10종, 아동용 섬유제품 2종에 리콜 명령을 내렸다고 24일 밝혔다. 리콜 제품에 대한 세부 정보는 ‘제품안전정보센터’ 홈페이지(www.safetykorea.kr)에서 확인할 수 있다. 초등학생 가방 7개 제품 가운데 5개 제품에서는 내분비 교란 물질로 알려진 프탈레이트 가소제가 기준치(0.1% 이하)를 74∼386배 초과해 검출됐다. 프탈레이트 가소제는 여성 불임, 정자 수 감소 등의 영향을 준다. 또 4개 제품에서는 피부염, 탈모증 등을 유발하는 납이 기준치의 최대 57.8배가 나왔다. 호흡기 장애를 일으키는 것으로 알려진 포름알데하이드가 기준치 이상으로 검출된 제품도 있었다. 아동용 완구는 7개 제품에서 프탈레이트가 기준치를 33∼235배 초과했고, 납과 카드뮴이 기준치를 넘은 제품도 발견됐다. 이 중에는 어린이에게 인기 있는 애니메이션 캐릭터인 ‘라바’, ‘또봇’ 등을 모델로 한 제품도 있었다.

프탈레이트(Phthalate) 종류 DEHP : Di-ethylhexyl phthalate DHP : Di-hexylphthalate BBP : Butyl benzyl phthalate DprP : Di-propyl phthalate DBP : Di-n-butyl phthalate DCHP : Dicyclohexyl phthalate DPP : Di-n-pentyl phthalate DEP : Diethyl phthalate DINP : Di-iso-nonylphthalate DNOP : Di-n-octylphalate DIDP : Di-iso-decylphthalate DMP : dimethylphthalate MEHP : monoethylhexylphthalate

WATER POLLUTION Chapter 7 Environmental Chemistry, 9th Edition 4 Chapter 7 WATER POLLUTION Environmental Chemistry, 9th Edition Stanley E. Manahan Taylor and Francis/CRC Press 2010 For questions, contact: manahans@missouri.edu

7.1 Nature and Types of Water Pollutants 5 7.1 Nature and Types of Water Pollutants • See list in Table 7.1 Markers of water pollution that show presence of pollution sources • Herbicides indicate agricultural runoff • Fecal coliform bacteria indicate sewage sources • Pharmaceutical metabolites in domestic wastewater Biomarkers of water pollution are organisms that indicate pollution • May accumulate pollutants that appear in analysis • May show effects from pollutant exposure • Fish lipid tissue accumulates persistent organic pollutants • Osprey at top of aquatic food web is a good biomarker

부유물질에 의한 오염 열에 의한 오염 해양오염(오일) 부영양화에 의한 오염 방사성폐기물에 의한 오염 세균에 의한 오염 중금속에 의한 오염 도시하수에 의한 오염

7 7.2 Elemental Pollutants Trace elements (harmful at a few parts per million or less) • See list in Table 7.2 Heavy metals are among most harmful • Cadmium • Mercury • Lead • Most are sulfur seekers Metalloids may be significant water pollutants • Most important is arsenic • Selenium and antimony can also be harmful

Ge

7.3 Heavy Metals Cadmium • Highly toxic 9 7.3 Heavy Metals Cadmium • Highly toxic • Chemically very similar to zinc • From mining and industrial wastes (especially metal plating Lead • Widely used and distributed in the past • Plumbing (lead pipe, solder) used to be a major source • Uses (such as in gasoline) have been greatly curtailed Mercury • Minimata Bay incident • Mobilized by bacterial methylation—HgCH3+, Hg(CH3) 2

7.4 Metalloids Arsenic is the most significant • From coal combustion 12 7.4 Metalloids Arsenic is the most significant • From coal combustion • Occurs with phosphate minerals • Byproduct of copper, gold, lead refining • Natural occurrence in some groundwaters • Formerly in pesticides: Pb3(AsO4)2, Na3AsO3, Cu3(AsO3)2 • Bangladesh tube well poisonings may have affected millions

7.5 Organically Bound Metals and Metalloids 13 7.5 Organically Bound Metals and Metalloids Have metal (metalloid) bonded to carbon • Alkyl groups such as ethyl in Pb(C2H5)4 • p (pi) electron donors such as ethylene, C2H4 • Carbonyls with bound CO Tetraethyllead, C2H4, in gasoline introduced large quantities of lead into the environment until it was banned Methylation of mercury by anoxic bacteria mobilized otherwise insoluble inorganic mercury Organotin compounds were widely used as marine biocides in ship and boat paints • Tributyltin chloride commonly used industrial biocide • Endocrine disruption in shellfish and oysters • Uses now being phased out

변색된 銀제품, 색깔 되찾는 법 [출처] 본 기사는 조선닷컴에서 작성된 기사 입니다. - 치약 - 소다 가루 Enzyme-SH ---- Hg Hg HgCl2 Hg-CH3

Octane Value BTX Pb(C2H5)4 2+ Br2 n-heptane Isooctane(2,2,4-trimethylpentane) BTX Benzene Toluene Xylene (methyl tert-butyl ether) Pb(C2H5)4 2+ Br2

7.6 Inorganic Species Cyanide (HCN, CN-) • Extremely toxic 16 7.6 Inorganic Species Cyanide (HCN, CN-) • Extremely toxic • Industrial uses including metal cleaning, electroplating • Produced by coke ovens • Water pollution and fish kills from mineral processing • Concern for terrorist attacks on water supplies Ammonia • Generally as NH4+, NH3 at high pH • Added to drinking water for residual disinfection from chlorination Free carbon dioxide, CO2 • In water from decay of organic matter, geochemical sources • Makes water corrosive, harmful to aquatic life

• Foul odor, very detrimental to water quality, very toxic 17 Hydrogen sulfide, H2S • From industrial sources, decay of organosulfur compounds, geochemical sources • Foul odor, very detrimental to water quality, very toxic • Precipitates heavy metals Nitrite ion, NO2-, intermediate in reduction of NO3- • Very toxic, but rare water pollutant Sulfite ion, SO32- • Added to water as O2 scavenger[2SO3- + O2 → 2SO42-] Perchlorate ion, ClO4- • Industrial pollutant in some cases • Recognized as a pollutant fairly recently Asbestos • Causes cancer when inhaled, but unknown effects in water • Asbestos-like fibers in Lake Superior, Reserve Mining

Silicates These units can further connect into sheets or strands. Talc and asbestos are two examples of molecules containing these structures. Silicate Disilicate

7.7 Algal Nutrients and Eutrophication 19 7.7 Algal Nutrients and Eutrophication Eutrophication means “well nourished” Eutrophication in excess is detrimental causing heavy growth of biomass followed by decay • Consumes O2 • Fills shallow water bodies Of numerous algal nutrients (Table 7.3) phosphorus is generally limiting and is controlled to control eutrophication

7.8 Acidity, Alkalinity, and Salinity 20 7.8 Acidity, Alkalinity, and Salinity Acid • Pollutant acids generally strong acids • One of the most common is acid mine water (H2SO4) • Potential industrial sources of pollution Alkalinity • Generally due to NaHCO3 NaHCO3 + H+ Na+(aq) + CO2(g) + H2O(l ) • From natural geological sources • Can be worsened by irrigation practices Salinity • Salts such as NaCl and Na2SO4 • Increased in municipal water systems • Increased by irrigation • Major problem, especially in heavily irrigated areas

7.9 Oxygen, Oxidants, and Reductants 21 7.9 Oxygen, Oxidants, and Reductants Dissolved oxygen, DO, is important in water • Depleted by oxidation of NH4+, Fe2+, SO32-, and especially biodegradation of biomass, {CH2O} {CH2O} + O2 ® CO2 + H2O • Biochemical oxygen demand, BOD, refers to amount of oxygen consumed in a volume of water by the biodegradable organic matter in it • Total organic carbon, TOC, is often substituted for BOD

Substance concentration in organism Substance concentration in water 22 7.10 Organic Pollutants Bioaccumulation of Organic Pollutants Bioconcentration factor (BCF): Substance concentration in organism Substance concentration in water Bioaccumulation factor, BAF, considers pollutant concentration in food as well as water Sewage • Contains many pollutants including pathogenic microorganisms, detergents, salts, solids (Table 7.4) • Most significant pollutant in sewage is biodegradable organic material ({CH2O}) manifested as biochemical oxygen demand (BOD) • Main objective of wastewater treatment is elimination of BOD (Chapter 8)

Soaps, Detergents, and Detergent Builders 24 Soaps, Detergents, and Detergent Builders Soaps are salts of long-chain fatty acids • Sodium stearate: C17H35CO2-Na+ • Soaps form spherical micelles which may entrain water-insoluble grease and oil particles (right) • Soap lowers water surface tension which aids its cleaning action • Soaps are biodegradable • Soaps produce insoluble salts with divalent metal ions, predominantly calcium, which removes them from water, but reduces their effectiveness as cleaning agents in hard water Calcium stearate: Ca2+(C17H35CO2-)2(s)

25 Detergents Synthetic detergents lower water surface tension and enable its cleaning action • Do not form precipitates with hardness ions • Amphiphilic structure with ionic “head” and hydrocarbon “tail” • Detergent surfactants concentrate at interfaces of water with air, solids (dirt), and immiscible greases and oils Poorly biodegradable ABS surfactants formerly used Biodegradable LAS surfactants now used

Alkyl polyethoxylate surfactants (structural formula below) 26 Alkyl polyethoxylate surfactants (structural formula below) • Used as detergents, dispersing agents, emulsifiers, solubilizers, wetting agents • Resist biodegradation • Xenoestrogens of health concern Detergent formulations have numerous components • Examples: Alkalies, anticorrosive silicates Builders added to improve performance have caused problems • Polyphosphates used in builders hydrolyze to phosphates that cause eutrophication

Naturally Occurring Chlorinated and Brominated Compounds(PCBs) 27 Naturally Occurring Chlorinated and Brominated Compounds(PCBs) Produced mostly by marine organisms • Chemical defense agents Detected in arctic samples • Air • Fish • Seabird eggs • Marine mammals • Human milk Example below

28 7.11 Pesticides in Water Numerous kinds of compounds added to soil and plants • Insecticides • Herbicides • Molluscicides • Fungicides • Bactericides • Slimicides • Avicides (birds) • Piscicides (fish) • Plant growth regulators • Plant defoliants • Plant desiccants Insecticides and fungicides most important for human exposure because of application near harvest time Herbicides most important water pollutants because of widespread application directly onto soil Table 7.4 lists numerous pesticides that may be encountered as water pollutants

Pesticides and Other Chemicals of Concern for Water Pollution 29 Pesticides and Other Chemicals of Concern for Water Pollution 1. Highly biodegradation resistant compounds 2. Known or probable carcinogens 3. Substances with adverse reproductive or developmental effects 4. Neurotoxins including cholinesterase inhibitors 5. Acutely toxic substances 6. Known groundwater contaminants

Natural Product Insecticides 30 Natural Product Insecticides • Nicotine from tobacco • Rotenone from some legume roots Pyrethrins • Products such as pyrethrum I from chrysanthum varieties grown in Kenya • Used in China 2000 years ago Pyrethroids are synthetic analogs of pyrethrins • Allethrin • Fenvalerate • Cypermethrin Sulfer

31 Figure 7.6. Common botanical insecticides and synthetic analogs of the pyrethrins.

DDT and Organochlorine Insecticides (Figure 7.7) 32 DDT and Organochlorine Insecticides (Figure 7.7) 수돗물 파동 Organochlorine insecticides have been mostly phased out of use because of persistence, harm to birds • Endosulfan one of the last to be eliminated

1891년 러시아 화학자 디아닌(A. P. Dianin)에 의해 처음 합성된다 1891년 러시아 화학자 디아닌(A. P. Dianin)에 의해 처음 합성된다. 1930년대에는 합성 에스트로겐으로 사용하는 데 대한 연구가 진행되었으나 실제로 사용되지는 않았다. 현재에는 폴리카보네이트나 에폭시수지 같은 플라스틱 제조의 원료로 사용한다. 폴리카보네이트는 투명하게 만들 수 있기 때문에 CD의 재료나 음식 용기로 사용되며 젖병에도 이용된다. 에폭시수지는 치과에서 사용하는 레진이나 음료수 캔을 코팅하는 데 이용된다. 비스페놀A의 위험성 강력한 세제를 사용하거나 산성 또는 고온의 액체 속에 비스페놀A로 만들어진 플라스틱을 넣으면 적은 양이 녹아 나올 수 있다. 이렇게 해서 나온 비스페놀A는 에스트로겐과 비슷한 작용을 한다. 1930년대에 난소가 없는 쥐에 비스페놀A를 주사한 실험을 통해 비스페놀A가 합성 에스트로겐으로 작용할 수 있다는 사실이 처음 밝혀졌다. 이후 세포를 이용한 실험을 통해 매우 낮은 농도에서 내분비계교란물질로 작용할 수 있다는 것이 알려졌다. 때문에 인간에게도 정자 수의 감소나 여성화 같은 건강 문제가 나타날 수 있다. 플라스틱을 만드는 업자들은 오랜 시간 동안 비스페놀A의 안전성에 대해서 주장해 왔다. 그러나 최근의 연구에 따르면 플라스틱 제조 업자들은 11개의 안전한 연구결과를 내놓았으나 104개에 걸친 독립적인 연구에서는 90% 이상 위험성이 나타났다고 한다. 또한 아주 적은 양에서도 비스페놀A가 신경 발달에 문제를 일으킨다는 연구 결과도 발표되었다. 때문에 아직까지 비스페놀A를 사용하는 것에 대해서 논란이 끊이지 않고 있다.

Polychlorinated Biphenyls (PCBs) (TCDD or “dioxin”) Bactericides

Organophosphate insecticides (Figure 7.8) 35 Organophosphate insecticides (Figure 7.8) • Though biodegradable and not generally environmentally harmful, some very toxic effects (acetycholinesterase inhibitors)

36 Malathion is a commonly used organophosphate because mammals can hydrolyze it to non-toxic products

Carbamates: Esters of Carbamic Acid (Figure 7.9) 37 Carbamates: Esters of Carbamic Acid (Figure 7.9) • Biodegradable • Acetylcholinesterase inhibitors but not unduly toxic

38 Fungicides(살진균제) Figure 7.10 Examples of widely used fungicides that can be water pollutants

Herbicides Herbicides applied to millions of acres of cropland worldwide to control weeds Herbicides commonly occur in surface water and groundwater, especially in intensely cropped areas • Especially common are atrazine, simazine, and cyanazine used for weed control on corn and soybeans • Although widely used to control weeds on crops genetically engineered to resist it, glyphosate has a very strong affinity for soil and rarely gets into water 39

40 Figure 7.12 Triazine herbicides of which atrazine is especially common in water in corn-growing areas

Figure 7.13 Chlorophenoxy herbicides 41 Figure 7.13 Chlorophenoxy herbicides • 2,4,5-T (“Agent Orange”) no longer used

Figure 7.14 Miscellaneous herbicides (others shown in text) 42 Figure 7.14 Miscellaneous herbicides (others shown in text)

Pollutants from Pesticide Manufacture 43 Pollutants from Pesticide Manufacture 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD or “dioxin”) • Badly contaminated some areas in 1970s • Highly toxic to some animals Figure 7.15 Structural formula of TCDD Kepone, manufacture of which badly contaminated the James River of Virginia in the 1970s

7.12 Polychlorinated Biphenyls (PCBs) 44 7.12 Polychlorinated Biphenyls (PCBs) Figure 7.16 Structural formula of PCBs (209 congeners) Very high chemical, thermal, and biological stability Had many uses, especially in electrical equipment Highly persistent and found in water, sediments, bird and fish tissues Contamination of Hudson River sediments from electrical equipment manufacture Now banned

7.13 Emerging Water Pollutants, Pharmaceuticals, Household Wastes 45 7.13 Emerging Water Pollutants, Pharmaceuticals, Household Wastes Emerging water pollutants are relatively new substance coming into use that may get into water and that may have undiscovered pollution effects • Nanomaterials composed of very small particles with many developing uses including pharmaceuticals • Siloxanes (silicones) used in cosmetic products, water- repellant windshield coatings, detergents • Disinfection byproducts (trihalomethanes) • Household wastes including surfactants, flame retardants, and plasticizers (bisphenol-A)

Pharmaceuticals and Partial Degradation Products 46 Pharmaceuticals and Partial Degradation Products Figure 7.17 Some pharmaceuticals and pharmaceutical metabolites found in water Feminization of male fish exposed to sewage

47 Bactericides in water Used in soaps, shampoo, deoderants, lotions, other • Triclosan and its methyl derivative found in Swiss waters

Estrogenic Substances in Wastewater 48 Estrogenic Substances in Wastewater Disrupt endocrine gland activities regulating metabolism and reproductive functions of organisms Aquatic organisms (fish, frogs, alligators) exhibit • Reproductive dysfunction • Altered sex characteristic • Abnormal serum steroid levels Substances include • Oral contraceptives • Hormonal treatments • Cancer treatments Nonionic surfactant polyethoxylates are estrogenic substances • Much less potent than hormonal substances • But released in enormous quantities

Biorefractory Organic Pollutants 49 Biorefractory Organic Pollutants • Poorly biodegradable organics • Also called persistent organic pollutants, POP • Include prominently chlorinated hydrocarbons • Examples are benzene, chloroform, tetrachloroethylene Biorefractory compounds are not well removed by biological treatment and may require physical means such as carbon adsorption

Perfluorinated Compounds as POPs 50 Perfluorinated Compounds as POPs Brominated Compounds as POPs Benzotriazole, tolyltriazoles and naphthenic acids are POPs POPs : persistent organic pollutant

7.14 Radionuclides in the Aquatic Environment 51 7.14 Radionuclides in the Aquatic Environment Figure 7.18 Production of fission products from uranium fission(fusion) Radionuclides produce ionizing radiation as alpha particles, beta particles, gamma rays 숙제(성질 및 특성)

See Table 7.5, Radionuclides that may be in water 52 See Table 7.5, Radionuclides that may be in water Carbon-14 from cosmic processes Radium-226 from uranium • Especially significant water pollutant in some areas Fission products important in health • Strontium-90 that substitutes for calcium in bone • Iodine-131 that affects thyroid • Cesium-137 that substitutes for sodium Radionuclides are characterized by half-lives in which half of the radioisotopes decay Radiation from radionuclides damages living organisms by breaking bonds in biological macromolecules • Bone marrow may be damaged in acute cases • Genetic effects (damage to DNA) is of particular concern

53 PAHs Benzo[a]pyrene Benzo[e]pyrene (성질조사?)

54 라면스프에서 검출된 벤조피렌이 과연 얼마나 위험하냐를 놓고 의문이 일고 있다. 생생우동, 얼큰한 너구리 등에서 검출된 벤조피렌은 최대 4.7㎍/㎏(ppb). (기준치 2ppb) 식약청에 따르면 스프제품은 모두 30개. 이 제품들에서 나온 벤조피렌 검출량을 우리나라 국민이 하루 평균 섭취하는 라면스프의 양으로 환산하면, 하루에 라면스프를 통해 우리국민은 0.000005㎍의 벤조피렌을 섭취한다. 반면 구운 소고기, 돼지고기, 닭고기 등을 통해 우리국민이 하루 평균 섭취하는 벤조피렌의 양은 0.08㎍으로 스프로 인한 섭취보다 1만6,000배나 많다. 라면스프에서 벤조피렌이 검출됐다는 사실을 처음 공개한 정치권과 보건당국의 입장 차는 크게 갈린다. 식약청은 "안전한 수준"이라는 입장이다. 반면 "벤조피렌이 검출된 가쓰오부시 원료의 양은 스프의 3%밖에 안 되지만 스프에서 검출된 벤조피렌은 가쓰오부시에서 검출된 양(10.6㎍/㎏)의 절반에 가깝다"며 위해성을 무시할 수 없다는 입장이다. 임종한 인하대 의대교수는 "자료가 축적돼 있지 않아 위험성을 판단하기는 어렵다"면서 "어린이들이 많이 먹는 만큼 엄격한 잣대로 볼 필요는 있다"는 입장을 밝혔다. 가공식품 중 분유 등 영ㆍ유아식의 벤조피렌 허용량이 1ppb(1㎍/㎏)로 가장 엄격하다.

가습기 살균제 5시간 사용때 나오는 독성물질 ‘CMIT’ 총량 시판 16종중 5종 CMIT-MIT 함유… 美화학사 “과다 노출땐 사망” 경고

CAS [Chemical Abstract Service] 1907년에 설립되었으며 현재는 사실상 전 세계 화학정보 센터 역할을 하고 있으며, 따라서 CAS가 작성하는 화학정보 데이터 베이스는 세계 최대이다. 또 CAS는 세계의 화학문헌을 망라한 Chemical Abstracts를 발행하고 있다. 보통 화학상품에는 CAS넘버(번호)가 부여되고 있다.